The crystal structures of ligand precursor bis(imidaozolium) salts 1,1′-methylenebis(3-tert-butylimidazolium) dibromide monohydrate, C15H26N4 +·2Br−·H2O or [ tBuNHC2Me][Br]2·H2O, 1,1′-(ethane-1,2-diyl)bis(3-tert-butylimidazolium) dibromide dihydrate, C16H28N4 +·2Br−·2H2O or [ tBuNHC2Et][Br]2·2H2O, 1,1′-methylenebis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide dihydrate, C25H30N4 2+·2Br−·2H2O or [MesNHC2Me][Br]2·2H2O, and 1,1′-1,1′-(ethane-1,2-diyl)bis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide tetrahydrate, C26H32N4 2+·2Br−·4H2O or [MesNHC2Et][Br]2·4H2O, are reported. At 293 K, [ tBuNHC2Me][Br]2·H2O crystallizes in the P21/c space group, while [ tBuNHC2Et][Br]2·2H2O crystallizes in the P21/n space group at 100 K. At 112 K, [MesNHC2Me][Br]2·2H2O crystallizes in the orthorhombic space group Pccn while [MesNHC2Et][Br]2·4H2O crystallizes in the P21/c space group at 100 K.
Keywords: crystal structure, bis(imidazolium), bidentate NHC, N-heterocyclic carbene
Abstract
The crystal structures of ligand precursor bis(imidazolium) salts 1,1′-methylenebis(3-tert-butylimidazolium) dibromide monohydrate, C15H26N4 +·2Br−·H2O or [ tBuNHC2Me][Br]2·H2O, 1,1′-(ethane-1,2-diyl)bis(3-tert-butylimidazolium) dibromide dihydrate, C16H28N4 +·2Br−·2H2O or [ tBuNHC2Et][Br]2·2H2O, 1,1′-methylenebis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide dihydrate, C25H30N4 2+·2Br−·2H2O or [MesNHC2Me][Br]2·2H2O, and 1,1′-(ethane-1,2-diyl)bis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide tetrahydrate, C26H32N4 2+·2Br−·4H2O or [MesNHC2Et][Br]2·4H2O, are reported. At 293 K, [ tBuNHC2Me][Br]2·H2O crystallizes in the P21/c space group, while [ tBuNHC2Et][Br]2·2H2O crystallizes in the P21/n space group at 100 K. At 112 K, [MesNHC2Me][Br]2·2H2O crystallizes in the orthorhombic space group Pccn while [MesNHC2Et][Br]2·4H2O crystallizes in the P21/c space group at 100 K. Bond distances and angles within the imidazolium rings are generally comparable among the four structures. All four bis(imidazolium) salts co-crystallize with one to four molecules of water.
1. Chemical context
Bis(imidazolium) salts are common precursors for the synthesis of bidentate N-heterocyclic carbene (NHC2) ligands, which can be used to stabilize a variety of metal complexes and catalysts. Bis(imidazolium) salts, [ R NHC2 R 1][X]2 are relatively modular in that modifications can be relatively easily made to exterior groups attached to each NHC (R), the moiety linking the two NHC groups (R 1), and the counter-ion (X). One general synthetic approach for synthesizing bis(imidazolium) salts is where two equivalents of an alkyl or aryl imidazole are combined with one equivalent of an organic dihalide reagent and refluxed to afford the final product (Gardiner et al., 1999 ▸). A simplified procedure for a variety of ligand salts using pressure tubes resulting in yields that were generally over 80% was also reported (Scherg et al., 2006 ▸). Some reports have gone even further to minimize solvent in the synthesis of these ligand precursors, including a solvent-free synthesis (Cao et al., 2011 ▸, 2012 ▸). This implies that the exterior R groups can easily be modified by changing the alkyl or aryl group on the starting imidazole. The linking group R 1 and counter-ion X can be modified by changing the organic dihalide reagent. In this fashion, a library of bis(imidazolium) salts can be relatively easily synthesized from alkyl or aryl imidazoles, and some are also commercially available.
Some of the most widely reported bis(imidazolium) salts are those with tert-butyl ( t Bu) and mesityl (Mes) exterior R groups and methylene (Me) or ethylene (Et) linking R 1 groups. [MesNHC2Et][Br]2 was even reported to be a stand-alone catalyst for the conversion of arylaldehydes to carboxylic acids in combination with water and K2CO3 in DMSO (Yang et al., 2013 ▸). Methylene linkers are quite commonly used for complexing to metals, and although examples with ethylene linkers are fewer, comparative studies report that changing the linker affects catalysis. For example, shorter methylene linkers (R 1) were reported to be more effective for hydrosilylation reactions with RhI complexes than ethylene linkers (Riederer et al., 2010 ▸).
The bidentate NHC ligand system is highly versatile for stabilizing a range of metals, some of which result in catalytically active systems. For example, [ tBuNHC2Me][Br]2 and [ tBuNHC2Et][Br]2 were used as precursors for synthesis of rhodium complexes (Leung et al., 2006 ▸). [ tBuNHC2Et][Cl]2 was used for synthesis of aluminum, gallium, and indium complexes (Baker et al., 2002 ▸). [MesNHC2Et][Br]2 was reported for synthesizing rhenium complexes (Hock et al., 2014 ▸; Hiltner et al., 2010 ▸), palladium complexes via Pd(OAc)2-assisted deprotometalation (Wierenga et al., 2019 ▸), palladium complexes via silver transmetallation (Sluijter et al., 2013 ▸), and for palladium catalysts for Suzuki and Heck coupling reactions (Lee et al., 2004 ▸). Other reported palladium complexes were active for dehalogenation of aryl halides (Viciu et al., 2001 ▸).
Examples with first row transition metals are fewer, with nickel being the most commonly reported. Nickel carbonato complexes were synthesized with [MesNHC2Me][Cl]2 and [MesNHC2Et][Cl]2 ligand precursors (Guo et al., 2013 ▸). Iron complexes for use in aryl Grignard-alkyl halide cross-coupling reactions were synthesized using various bis(imidazolium) salts including [ tBuNHC2Me][Cl]2, [ tBuNHC2Me][Br]2, [MesNHC2Me][Cl]2, [MesNHC2Me][Br]2, and [MesNHC2Et][Br]2 (Meyer et al., 2011 ▸).
When used for stabilizing bimetallic systems, [
tBuNHC2Et][Cl]2 and [MesNHC2Et][Cl]2 have been used as precursors for dipalladium complexes for Heck reactions (Li et al., 2013 ▸; Yang et al., 2012 ▸; Cao et al., 2010 ▸), while [
tBuNHC2Et][Br]2 was a precursor for dimetallic Rh complexes (Wells et al., 2008 ▸) and mixed-metal Rh/Pd (Zamora et al., 2009 ▸) and Ir/Rh (Frey et al., 2006 ▸). Similarly, [MesNHC2Me][Br]2 and [MesNHC2Et][Br]2 were used to synthesize bimetallic gold catalysts for cross-coupling and hydroamination reactions (Baron et al., 2018 ▸).
While bis(imidazolium) salts are common ligand precursors, few have been structurally characterized (Rheingold, 2019 ▸). This work presents structural characterization and a comparison of supramolecular features for methylene- versus ethylene-linked bis(imidazolium) salts with tert-butyl and mesityl ancillary groups.
2. Structural commentary
All four bis(imidazolium) salts were recrystallized from hot methanol and each compound co-crystallizes with one or more molecules of water. Fig. 1 ▸ depicts [ tBuNHC2Me][Br]2·H2O while Fig. 2 ▸ depicts [ tBuNHC2Et][Br]2·2H2O.
Figure 1.
View of [ tBuNHC2Me][Br]2·H2O with 50% probability ellipsoids.
Figure 2.
View of [ tBuNHC2Et][Br]2·2H2O with 50% probability ellipsoids.
Bond distances in the imidazolium rings of [ tBuNHC2Me][Br]2·H2O and [ tBuNHC2Et][Br]2·2H2O are mostly the same within experimental error, with backbone C2—C3 distances of 1.348 (4) and 1.349 (3) Å, respectively. The N—C distances are also mostly comparable with [ tBuNHC2Me][Br]2·H2O having an N1—C2 and an N2—C3 distance of 1.389 (3) Å and N1—C1 and N2—C1 distances both being 1.337 (3) Å, while [ tBuNHC2Et][Br]2·2H2O has an N1—C2 distance of 1.388 (3) Å, an N2—C3 distance of 1.384 (3) Å, an N1—C1 distance of 1.327 (3) Å and an N2—C1 distance of 1.331 (3) Å. For the linker, the N2—C7 distance is 1.463 (3) Å for [ tBuNHC2Me][Br]2·H2O and 1.468 (3) Å for [ tBuNHC2Et][Br]2·2H2O.
Bond angles in the imidazolium rings are also quite similar in [ tBuNHC2Me][Br]2·H2O and [ tBuNHC2Et][Br]2·2H2O. For [ tBuNHC2Me][Br]2·H2O, bond angles include C1—N1—C2 at 108.2 (2)°, N1—C2—C3 at 107.6 (2)°, C2—C3—N2 at 106.9 (2)°, C3—N2—C1 at 108.6 (2)°, and N2—C1—N1 at 108.7 (2)°. For [ tBuNHC2Et][Br]2·H2O, bond angles include C1—N1—C2 at 108.21 (19)°, N1—C2—C3 at 107.3 (2)°, C2—C3—N2 at 106.9 (2)°, C3—N2—C1 at 108.54 (19)°, and N2—C1—N1 at 109.02 (19)°.
Fig. 3 ▸ depicts [MesNHC2Me][Br]2·2H2O while Fig. 4 ▸ depicts [MesNHC2Et][Br]2·4H2O. Notably, [MesNHC2Et][Br]2·4H2O is the only compound of the four for which the asymmetric unit contains only half of the molecule.
Figure 3.
View of [MesNHC2Me][Br]2·2H2O with 50% probability ellipsoids.
Figure 4.
View of [MesNHC2Et][Br]2·4H2O with 50% probability ellipsoids.
Bond distances in the imidazolium rings of [MesNHC2Me][Br]2·2H2O and [MesNHC2Et][Br]2·4H2O are mostly the same within experimental error, with backbone C2—C3 distances of 1.344 (3) and 1.3506 (19) Å, respectively. N—C distances are also mostly the same with [MesNHC2Me][Br]2·2H2O having an N1—C2 distance of 1.387 (3) Å, an N2—C3 distance of 1.380 (3) Å, an N1—C1 distance of 1.326 (3) Å, and an N2—C1 distance of 1.341 (3) Å. Similarly, [MesNHC2Et][Br]2·4H2O has an N1—C2 distance of 1.3872 (16) Å, an N2—C3 distance of 1.3841 (16) Å, an N1—C1 distance of 1.3322 (16) Å and an N2—C1 distance of 1.3314 (16) Å. For the linker, the N2—C7 distance is 1.457 (3) Å for [MesNHC2Me][Br]2·2H2O and 1.4653 (16) Å for [MesNHC2Et][Br]2·4H2O.
Bond angles in the imidazolium rings are also mostly the same for [MesNHC2Me][Br]2·2H2O and [MesNHC2Et][Br]2·4H2O. For [MesNHC2Me][Br]2·2H2O, bond angles include C1—N1—C2 at 108.92 (17)°, N1—C2—C3 at 107.20 (19)°, C2—C3—N2 at 106.95 (19)°, C3—N2—C1 at 108.96 (17)°, and N2—C1—N1 at 107.96 (18)°. For [MesNHC2Et][Br]2·4H2O, bond angles include C1—N1—C2 at 108.51 (11)°, N1—C2—C3 at 107.19 (11)°, C2—C3—N2 at 106.87 (11)°, C3—N2—C1 at 108.89 (11)°, and N2—C1—N1 at 108.54 (11)°. Overall, these data support that changing the linker R 1 group from methylene to ethylene does not significantly affect the imidazolium ring structures.
3. Supramolecular features
The supramolecular structure of [ tBuNHC2Me][Br]2·H2O is stabilized by hydrogen bonding (Fig. 5 ▸, Table 1 ▸). Distances between centroids of neighboring imidazoles are greater than 5 Å, suggesting no π-stacking interactions (Janiak, 2000 ▸). Hydrogen bonding between one bromide atom and one water molecule is found with Br1⋯H1D having a distance of 2.575 (4) Å. One tert-butyl group has positional disorder.
Figure 5.
View of four molecules of [ tBuNHC2Me][Br]2·H2O with 50% probability ellipsoids, highlighting intermolecular distances. Disordered tert-butyl groups are omitted for clarity.
Table 1. Intermolecular distances (Å) in the unit cells of [ R NHC2 R 1][X]2·nH2O.
Standard deviations for distances including some H atoms are omitted where H atoms were positionally fixed.
| Compound | Atoms | Distance |
|---|---|---|
| [ t BuNHC2Me][Br]2·H2O | Br1⋯H1D | 2.575 (4) |
| [ t BuNHC2Et][Br]2·2H2O | Br1⋯H1A | 2.398 |
| Br2⋯H1B | 2.439 | |
| [MesNHC2Me][Br]2·2H2O | Br1⋯H2A | 2.413 |
| Br2⋯H1A | 2.463 | |
| O1A⋯H2B | 2.125 | |
| [MesNHC2Et][Br]2·4H2O | O1⋯H2B | 1.994 (2) |
| O2⋯H1E | 2.001 (3) | |
| Br1⋯H1D | 2.585 (2) |
The supramolecular structure of [ tBuNHC2Et][Br]2·2H2O is stabilized by extensive hydrogen bonding (Fig. 6 ▸, Table 1 ▸). Distances between centroids of neighboring imidazoles are greater than 5 Å, suggesting no π-stacking interactions (Janiak, 2000 ▸). Several hydrogen-bonding interactions are found between bromide ions and water molecules, including Br2⋯H1B (2.439 Å) and Br1⋯H1A (2.398 Å).
Figure 6.
View of four molecules of [ tBuNHC2Et][Br]2·2H2O with 50% probability ellipsoids, highlighting intermolecular distances.
The supramolecular structure of [MesNHC2Me][Br]2·2H2O is also stabilized by hydrogen bonding (Fig. 7 ▸, Table 1 ▸). No π-stacking interactions were found as distances between centroids of aromatic rings of neighboring molecules are greater than 5 Å (Janiak, 2000 ▸). Several hydrogen-bonding interactions are observed between bromide ions and water molecules as well as neighboring water molecules, including Br1⋯H2A at 2.413 Å, Br2⋯H1A at 2.463 Å, and O1A⋯H2B at 2.125 Å.
Figure 7.
View of eight molecules of [MesNHC2Me][Br]2·2H2O with 50% probability ellipsoids, highlighting intermolecular distances.
The supramolecular structure of [MesNHC2Et][Br]2·4H2O is also stabilized by hydrogen bonding (Fig. 8 ▸, Table 1 ▸). No π-stacking is observed between mesityl groups, similar to [MesNHC2Me][Br]2·2H2O as the distance between centroids of the mesityl groups of neighboring fragments is greater than 4.5 Å (Janiak, 2000 ▸). Hydrogen-bonding interactions include O1⋯H2B at 1.994 (2) Å, O2⋯H1E at 2.001 (3) Å, and Br1⋯H1D at 2.585 (2) Å.
Figure 8.
View of eight molecules of [MesNHC2Et][Br]2·4H2O with 50% probability ellipsoids, highlighting intermolecular distances.
4. Database survey
A survey of the Cambridge Structural Database (Web accessed March 24, 2022; Groom et al., 2016 ▸) and SciFinder (SciFinder, 2022 ▸) yielded no exact matches for the unit cells of [ tBuNHC2Me][Br]2·H2O, [ tBuNHC2Et][Br]2·2H2O, or [MesNHC2Et][Br]2·4H2O. A deposited dataset for [MesNHC2Me][Br]2·2H2O was found (Rheingold, 2019 ▸) with a slightly higher R1 of 3.94% and data collection at a higher temperature of 150 K, as compared to R1 of 3.18% and temperature of 112 K in the current report. As discussed in the introduction, the syntheses of all of the reported structures are reported based on the SciFinder search; however, no additional structural data were found.
5. Synthesis and crystallization
General considerations. All reagents were purchased from commercial suppliers and used without further purification. 1H NMR data were collected on a Varian 400 MHz spectrometer and referenced to residual CHCl3.
Synthesis of 1- tert -butyl-1 H -imidazole, ( t BuIm). The procedure was adapted from a literature procedure (Liu et al., 2003 ▸). A round-bottom flask was charged with 10.0 mL (95 mmol, 1 eq.) of tert-butylamine, 11.0 mL of 40% glyoxal (95 mmol, 1 eq.), approximately 100 mL of methanol, and approximately 25 mL of deionized water and a stir bar, then heated to 343 K under reflux. 7.81 mL of 37% formaldehyde (95 mmol, 1 eq.) were added, followed by 3.70 mL of ammonium hydroxide (95 mmol, 1 eq.) added dropwise over 5 minutes while stirring. The solution was refluxed at 343 K for 5 h, resulting in a light red–orange solution. Excess solvent was removed in vacuo, and the resulting product was diluted with approximately 150 mL of dichloromethane and washed twice with 50 mL of deionized H2O until the aqueous layers ran clear. The product was vacuum distilled at ∼373 K, yielding a clear liquid, which was weighed in a tared vial, resulting in 7.95 g (34% yield) of tBuIm, and characterized by 1H NMR spectroscopy in CDCl3.
Synthesis of 1-(2,4,6-trimethylphenyl)-1 H -imidazole, (MesIm). The procedure was adapted from a literature procedure (Liu et al., 2003; Gardiner et al., 1999 ▸). A 250 mL three-neck round-bottom flask was charged with 15.000 g (110.9 mmol, 1 eq.) of 2,4,6-trimethylaniline, 16.090 g (110.9 mmol, 1 eq) of 40% glyoxal, and ∼75 mL of methanol and stirred for 24 h after which the solution turned orange with a yellow precipitate. 11.86 g (221.8 mmol, 2 eq.) of ammonium chloride, 18.00 g (221.8 mmol, 2 eq.) of 37% formaldehyde, and 300 mL of methanol were added, and the solution was refluxed for 24 h at 373 K, at which point the solution was deep brown. After being cooled to room temperature, 25.57 g (221.8 mmol, 2 eq.) of 85% phosphoric acid were added dropwise over ten minutes and the solution was refluxed for 16 h at 368 K. Excess solvent was removed in vacuo at 313 K, and the viscous brown residue was poured over ∼300 g of ice and neutralized to pH 10 with a saturated solution of potassium hydroxide, resulting in a clear solution with a chunky brown precipitate. The product was taken into diethyl ether by washing the solution three times with ∼100 mL of diethyl ether. The diethyl ether solution was washed thrice with ∼100 mL of water, thrice with ∼100 mL of brine, and dried overnight over sodium sulfate. Sodium sulfate solids were gravity filtered from the solution and the solvent was removed in vacuo resulting in a brown solid. The product was recrystallized from hot ethyl acetate, resulting in 9.49 g (46% yield) of tan crystals, which were characterized by 1H NMR spectroscopy and identified as MesIm.
Synthesis of 1,1′-di( tert -butyl)-3,3′-methylene-diimidazolium dibromide, [ t BuNHC2Me][Br]2. 1.850 g (14.9 mmol, 2.5 eq.) of tbuIm and 0.4194 mL (5.9 mmol, 1 eq.) of dibromomethane, a stir bar, and ∼20 mL of toluene were stirred in a 50 mL round-bottomed flask. The solution was then heated to 423 K and refluxed for 46 h, resulting in the formation of a dark orange–brown solution. The solution was cooled in an ice bath, resulting in a fine white precipitate which was collected via vacuum filtration, washed twice with ∼5 mL of cold toluene, filtered and dried. 1.120 g (78.02% yield) of a fine white solid identified as [ tBuNHC2Me][Br]2 were isolated. Crystals suitable for X-ray diffraction were obtained by recrystallization from hot methanol. The product was characterized by 1H NMR spectroscopy. The 1H NMR data were consistent with those previously reported (Scherg et al., 2006 ▸).
Synthesis of 1,1′-di( tert- butyl)-3,3′-ethylene-diimidazolium dibromide [ t BuNHC2Et][Br]2. A 250 mL round-bottomed flask was charged with 2.017 g (16.2 mmol, 2.5 eq.) of tbuIm, 0.562 mL (6.45 mmol, 1 eq.) of dibromoethane, a stir bar, and ∼20 mL of toluene. The mixture was refluxed at 423 K and stirred for 46 h, at which point the solution was a rusty brown color. The flask was then placed in an ice bath, and the resulting precipitate was collected via vacuum filtration and washed twice with ∼5 mL of cold toluene. The resulting solids were dried and weighed, yielding 1.727 g (61% yield) of [ tBuNHC2Et][Br]2 and single crystals suitable for X-ray diffraction were obtained via recrystallization from hot methanol. 1H NMR data were consistent with those previously reported (Scherg et al., 2006 ▸).
Synthesis of 1,1′-di(mesityl)-3,3′-methylene-diimidazolium dibromide, [MesNHC2Me][Br]2. The procedure was adapted from a literature procedure (Gardiner et al., 1999 ▸). 5.00 g (26.8 mmol, 2.5 eq.) of MesIm we added to a 50 mL round-bottomed flask with a stir bar and ∼20 mL of toluene. 0.754 mL (10.72 mmol, 1 eq.) of dibromomethane were added and the solution was refluxed at 423 K for 20 h. The solution was cooled in an ice bath, resulting in a white precipitate. The white solid was recrystallized from ∼12 mL of hot methanol. The product was obtained in 17% yield (1.10 g) as tan crystals identified as [MesNHC2Me][Br]2 suitable for X-ray diffraction and characterized by 1H NMR.
Synthesis of 1,1′-di(mesityl)-3,3′-ethylene-diimidazolium dibromide, [MesNHC2Et][Br]2. A 250 mL three-neck round-bottom flask was charged with 4.438 g (23.8 mmol, 2.5 eq.) of MesIm, 0.824 mL (9.52 mmol, 1 eq.) of 1,2-dibromoethane, and ∼20 mL of toluene. The reaction mixture was heated to 423 K and refluxed for 19 h, resulting in a cloudy yellow solution. The solution was cooled in an ice bath and the precipitate was collected and recrystallized from ∼25 mL of hot methanol, resulting in 2.962 g (55% yield) of tan crystals which were analyzed via 1H NMR spectroscopy and identified as [MesNHC2Et][Br]2.
6. Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. Most hydrogen atoms were placed in calculated positions using the AFIX commands of SHELXL and included as riding contributions with distances of 0.95 Å for C—H, 0.99 Å for CH2 and 0.98 Å for CH3. Methyl H atoms were allowed to rotate but not to tip to best fit the experimental electron density. U iso values of riding H atoms were set to 1.2 times U eq(C) for CH and CH2, and 1.5 times U eq(C) for CH3 and H2O. For [ tBuNHC2Me][Br]2, the SADI command of SHELX was used to model disorder in one of the tert-butyl moieties for N4—C0AA and N4—C12, C0AA—C00N and C14—C12, and C1AA—C0AA and C13—C12 to restrain distances within a sigma of 0.02 Å. The population parameters for the disordered tert-butyl groups are 0.54019 for C12–C14, and 0.45981 for C00N, C0AA, and C1AA. The highest peak and deepest hole are both near a heavy atom Br1 with a distance of 0.88 Å from the highest peak of 1.49 e Å−3 and a distance of 0.73 Å from the deepest hole of −1.10 e Å−3.
Table 2. Experimental details.
| [MesNHC2Me][Br]2·2H2O | [ tBuNHC2Me][Br]2·H2O | [ tBuNHC2Et][Br]2·2H2O | [MesNHC2Et][Br]2·4H2O | |
|---|---|---|---|---|
| Crystal data | ||||
| Chemical formula | C25H30N4 2+·2Br−·2H2O | C15H26N4 +·2Br−·H2O | C16H28N4 2+·2Br−·2H2O | C26H32N4 2+·2Br−·4H2O |
| M r | 582.38 | 440.23 | 472.27 | 632.42 |
| Crystal system, space group | Orthorhombic, P c c n | Monoclinic, P21/c | Monoclinic, P21/n | Monoclinic, P21/c |
| Temperature (K) | 112 | 293 | 100 | 100 |
| a, b, c (Å) | 21.5695 (6), 28.3385 (6), 8.9401 (2) | 7.211 (5), 18.311 (17), 15.409 (5) | 17.1577 (6), 7.3180 (2), 18.2712 (6) | 12.4230 (3), 13.1447 (3), 9.2780 (2) |
| α, β, γ (°) | 90, 90, 90 | 90, 101.35 (3), 90 | 90, 112.786 (1), 90 | 90, 108.379 (1), 90 |
| V (Å3) | 5464.6 (2) | 1995 (2) | 2115.09 (12) | 1437.78 (6) |
| Z | 8 | 4 | 4 | 2 |
| Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
| μ (mm−1) | 2.99 | 4.07 | 3.85 | 2.86 |
| Crystal size (mm) | 0.4 × 0.3 × 0.25 | 0.3 × 0.15 × 0.1 | 0.2 × 0.1 × 0.05 | 0.15 × 0.15 × 0.05 |
| Data collection | ||||
| Diffractometer | Bruker Venture D8 Kappa | Bruker APEXII CCD | Bruker Venture D8 Kappa | Bruker Venture D8 Kappa |
| Absorption correction | Multi-scan (SADABS; Bruker, 2016 ▸) | Multi-scan (SADABS; Bruker, 2016 ▸) | Multi-scan (SADABS; Bruker, 2016 ▸) | Multi-scan (SADABS; Bruker, 2016 ▸) |
| T min, T max | 0.386, 0.748 | 0.544, 0.747 | 0.496, 0.748 | 0.544, 0.750 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 39085, 5954, 5530 | 33565, 4402, 3780 | 31474, 4664, 4168 | 28199, 3165, 3028 |
| R int | 0.035 | 0.043 | 0.059 | 0.025 |
| (sin θ/λ)max (Å−1) | 0.641 | 0.641 | 0.641 | 0.641 |
| Refinement | ||||
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.032, 0.066, 1.19 | 0.035, 0.068, 1.08 | 0.031, 0.066, 1.11 | 0.018, 0.044, 1.10 |
| No. of reflections | 5954 | 4402 | 4664 | 3165 |
| No. of parameters | 338 | 259 | 253 | 194 |
| No. of restraints | 0 | 3 | 0 | 0 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.42, −0.54 | 1.49, −1.10 | 0.60, −0.61 | 0.33, −0.29 |
Supplementary Material
Crystal structure: contains datablock(s) sces01006_0m, est01043_0m, at01019_0ma, est01041d_0ma, global. DOI: 10.1107/S2056989022008003/mw2188sup1.cif
Structure factors: contains datablock(s) sces01006_0m. DOI: 10.1107/S2056989022008003/mw2188sces01006_0msup2.hkl
Structure factors: contains datablock(s) est01043_0m. DOI: 10.1107/S2056989022008003/mw2188est01043_0msup3.hkl
Structure factors: contains datablock(s) at01019_0ma. DOI: 10.1107/S2056989022008003/mw2188at01019_0masup4.hkl
Structure factors: contains datablock(s) est01041d_0ma. DOI: 10.1107/S2056989022008003/mw2188est01041d_0masup5.hkl
Supporting information file. DOI: 10.1107/S2056989022008003/mw2188sces01006_0msup6.cml
Supporting information file. DOI: 10.1107/S2056989022008003/mw2188est01043_0msup7.cml
Supporting information file. DOI: 10.1107/S2056989022008003/mw2188at01019_0masup8.cml
Supporting information file. DOI: 10.1107/S2056989022008003/mw2188est01041d_0masup9.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
1,1'-Methylenebis(3-tert-butylimidazolium) dibromide monohydrate (sces01006_0m) . Crystal data
| C15H26N4+·2Br−·H2O | F(000) = 896 |
| Mr = 440.23 | Dx = 1.466 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.211 (5) Å | Cell parameters from 9889 reflections |
| b = 18.311 (17) Å | θ = 2.6–30.2° |
| c = 15.409 (5) Å | µ = 4.07 mm−1 |
| β = 101.35 (3)° | T = 293 K |
| V = 1995 (2) Å3 | Prism, clear colourless |
| Z = 4 | 0.3 × 0.15 × 0.1 mm |
1,1'-Methylenebis(3-tert-butylimidazolium) dibromide monohydrate (sces01006_0m) . Data collection
| Bruker APEXII CCD diffractometer | 3780 reflections with I > 2σ(I) |
| φ and ω scans | Rint = 0.043 |
| Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 27.1°, θmin = 2.7° |
| Tmin = 0.544, Tmax = 0.747 | h = −9→8 |
| 33565 measured reflections | k = −23→23 |
| 4402 independent reflections | l = −19→19 |
1,1'-Methylenebis(3-tert-butylimidazolium) dibromide monohydrate (sces01006_0m) . Refinement
| Refinement on F2 | Primary atom site location: dual |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.035 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.068 | w = 1/[σ2(Fo2) + (0.0006P)2 + 4.1194P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.08 | (Δ/σ)max = 0.001 |
| 4402 reflections | Δρmax = 1.49 e Å−3 |
| 259 parameters | Δρmin = −1.10 e Å−3 |
| 3 restraints |
1,1'-Methylenebis(3-tert-butylimidazolium) dibromide monohydrate (sces01006_0m) . Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
1,1'-Methylenebis(3-tert-butylimidazolium) dibromide monohydrate (sces01006_0m) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Br2 | 0.83773 (4) | 0.86331 (2) | 0.55378 (2) | 0.03323 (9) | |
| Br1 | 1.05299 (4) | 0.61882 (2) | 0.35706 (2) | 0.03727 (10) | |
| N3 | 0.4514 (3) | 0.71177 (11) | 0.18236 (13) | 0.0175 (4) | |
| N1 | 0.5823 (3) | 0.48054 (11) | 0.16964 (13) | 0.0162 (4) | |
| O1 | 0.8362 (4) | 0.78047 (16) | 0.35775 (17) | 0.0419 (6) | |
| N2 | 0.4742 (3) | 0.58205 (11) | 0.21324 (13) | 0.0170 (4) | |
| N4 | 0.5288 (3) | 0.80162 (12) | 0.10500 (14) | 0.0225 (5) | |
| C1 | 0.6311 (4) | 0.54357 (13) | 0.21172 (16) | 0.0181 (5) | |
| H5 | 0.753852 | 0.558228 | 0.235943 | 0.022* | |
| C5 | 0.2905 (4) | 0.73014 (14) | 0.12095 (18) | 0.0221 (5) | |
| C4 | 0.5935 (4) | 0.75572 (14) | 0.17061 (16) | 0.0211 (5) | |
| H9 | 0.716674 | 0.754245 | 0.203041 | 0.025* | |
| C7 | 0.4681 (4) | 0.65531 (14) | 0.25048 (16) | 0.0212 (5) | |
| H8A | 0.361201 | 0.658686 | 0.279890 | 0.025* | |
| H8B | 0.582372 | 0.663573 | 0.294434 | 0.025* | |
| C8 | 0.7152 (4) | 0.42139 (14) | 0.15085 (18) | 0.0207 (5) | |
| C6 | 0.3396 (4) | 0.78602 (15) | 0.07277 (19) | 0.0251 (6) | |
| C2 | 0.3869 (4) | 0.47957 (15) | 0.14242 (18) | 0.0216 (5) | |
| C3 | 0.3195 (4) | 0.54263 (15) | 0.16910 (19) | 0.0239 (6) | |
| C13 | 0.5981 (4) | 0.86039 (16) | −0.02694 (18) | 0.0290 (6) | |
| H15A | 0.613085 | 0.812884 | −0.050991 | 0.043* | 0.54 (3) |
| H15B | 0.674562 | 0.895007 | −0.050884 | 0.043* | 0.54 (3) |
| H15C | 0.467761 | 0.874789 | −0.042171 | 0.043* | 0.54 (3) |
| H15D | 0.641328 | 0.812747 | −0.039773 | 0.043* | 0.46 (3) |
| H15E | 0.674290 | 0.896891 | −0.047847 | 0.043* | 0.46 (3) |
| H15F | 0.468475 | 0.866370 | −0.055952 | 0.043* | 0.46 (3) |
| C12 | 0.6629 (17) | 0.8579 (5) | 0.0781 (8) | 0.014 (2) | 0.54 (3) |
| C11 | 0.6634 (5) | 0.35011 (16) | 0.1920 (2) | 0.0402 (8) | |
| H3A | 0.676730 | 0.356294 | 0.254815 | 0.060* | |
| H3B | 0.746068 | 0.311841 | 0.180278 | 0.060* | |
| H3C | 0.534897 | 0.337462 | 0.166825 | 0.060* | |
| C10 | 0.9155 (4) | 0.44460 (17) | 0.1903 (3) | 0.0408 (8) | |
| H1A | 0.944282 | 0.489150 | 0.162880 | 0.061* | |
| H1B | 1.002017 | 0.407121 | 0.180300 | 0.061* | |
| H1C | 0.927348 | 0.452256 | 0.252799 | 0.061* | |
| C9 | 0.6908 (5) | 0.4157 (2) | 0.0510 (2) | 0.0399 (8) | |
| H4A | 0.564299 | 0.400122 | 0.026305 | 0.060* | |
| H4B | 0.779299 | 0.380851 | 0.036360 | 0.060* | |
| H4C | 0.713383 | 0.462547 | 0.027048 | 0.060* | |
| C15 | 0.8712 (15) | 0.8362 (6) | 0.1050 (8) | 0.0245 (19) | 0.54 (3) |
| H13A | 0.906281 | 0.834192 | 0.168381 | 0.037* | 0.54 (3) |
| H13B | 0.948184 | 0.871611 | 0.082775 | 0.037* | 0.54 (3) |
| H13C | 0.889802 | 0.789067 | 0.080737 | 0.037* | 0.54 (3) |
| C14 | 0.6197 (18) | 0.9291 (5) | 0.1206 (7) | 0.025 (2) | 0.54 (3) |
| H14A | 0.487306 | 0.939908 | 0.103235 | 0.038* | 0.54 (3) |
| H14B | 0.692055 | 0.967891 | 0.101603 | 0.038* | 0.54 (3) |
| H14C | 0.652454 | 0.924641 | 0.183859 | 0.038* | 0.54 (3) |
| H1D | 0.905 (6) | 0.746 (2) | 0.365 (3) | 0.061 (15)* | |
| C14A | 0.530 (3) | 0.9398 (5) | 0.0928 (10) | 0.034 (3) | 0.46 (3) |
| H00A | 0.398530 | 0.942603 | 0.064831 | 0.050* | 0.46 (3) |
| H00B | 0.596718 | 0.980230 | 0.074007 | 0.050* | 0.46 (3) |
| H00C | 0.540922 | 0.941501 | 0.155917 | 0.050* | 0.46 (3) |
| C12A | 0.614 (2) | 0.8681 (6) | 0.0668 (11) | 0.021 (3) | 0.46 (3) |
| C15A | 0.823 (2) | 0.8614 (11) | 0.1096 (10) | 0.038 (3) | 0.46 (3) |
| H1AA | 0.837624 | 0.866529 | 0.172622 | 0.057* | 0.46 (3) |
| H1AB | 0.893103 | 0.898947 | 0.087072 | 0.057* | 0.46 (3) |
| H1AC | 0.868755 | 0.814380 | 0.096076 | 0.057* | 0.46 (3) |
| H1E | 0.839 (5) | 0.800 (2) | 0.399 (3) | 0.041 (12)* | |
| H6 | 0.331 (4) | 0.4388 (16) | 0.1108 (19) | 0.023 (7)* | |
| H11 | 0.270 (5) | 0.8115 (18) | 0.027 (2) | 0.035 (9)* | |
| H10 | 0.175 (5) | 0.7062 (18) | 0.118 (2) | 0.037 (9)* | |
| H7 | 0.201 (5) | 0.5612 (17) | 0.164 (2) | 0.034 (9)* |
1,1'-Methylenebis(3-tert-butylimidazolium) dibromide monohydrate (sces01006_0m) . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br2 | 0.02663 (15) | 0.03928 (17) | 0.02985 (16) | 0.01469 (13) | −0.00401 (11) | −0.00144 (13) |
| Br1 | 0.02382 (15) | 0.0520 (2) | 0.03702 (18) | −0.01154 (13) | 0.00837 (12) | −0.02086 (14) |
| N3 | 0.0203 (11) | 0.0185 (10) | 0.0146 (10) | −0.0049 (8) | 0.0058 (8) | −0.0011 (8) |
| N1 | 0.0134 (10) | 0.0203 (11) | 0.0140 (10) | −0.0024 (8) | 0.0008 (8) | 0.0046 (8) |
| O1 | 0.0559 (17) | 0.0417 (15) | 0.0233 (13) | −0.0041 (13) | −0.0040 (11) | 0.0034 (11) |
| N2 | 0.0182 (11) | 0.0207 (11) | 0.0125 (10) | −0.0039 (8) | 0.0040 (8) | 0.0026 (8) |
| N4 | 0.0315 (13) | 0.0209 (11) | 0.0153 (11) | −0.0117 (9) | 0.0053 (9) | −0.0034 (8) |
| C1 | 0.0149 (12) | 0.0223 (13) | 0.0156 (12) | −0.0039 (10) | −0.0009 (9) | 0.0041 (10) |
| C5 | 0.0210 (14) | 0.0194 (13) | 0.0241 (14) | −0.0026 (10) | 0.0002 (11) | −0.0025 (10) |
| C4 | 0.0243 (14) | 0.0283 (14) | 0.0106 (12) | −0.0092 (11) | 0.0035 (10) | −0.0022 (10) |
| C7 | 0.0285 (14) | 0.0233 (13) | 0.0135 (12) | −0.0036 (11) | 0.0083 (10) | 0.0014 (10) |
| C8 | 0.0176 (13) | 0.0180 (12) | 0.0271 (14) | −0.0015 (10) | 0.0060 (11) | 0.0024 (10) |
| C6 | 0.0304 (15) | 0.0196 (13) | 0.0227 (14) | −0.0033 (11) | −0.0010 (12) | −0.0013 (11) |
| C2 | 0.0126 (12) | 0.0246 (14) | 0.0266 (14) | −0.0068 (10) | 0.0016 (10) | 0.0013 (11) |
| C3 | 0.0136 (13) | 0.0256 (14) | 0.0328 (16) | −0.0051 (11) | 0.0053 (11) | 0.0022 (11) |
| C13 | 0.0353 (16) | 0.0344 (16) | 0.0195 (14) | −0.0012 (13) | 0.0109 (12) | 0.0030 (12) |
| C12 | 0.023 (5) | 0.011 (3) | 0.008 (4) | −0.003 (3) | 0.002 (4) | 0.000 (3) |
| C11 | 0.0429 (19) | 0.0235 (15) | 0.060 (2) | 0.0033 (13) | 0.0254 (17) | 0.0115 (14) |
| C10 | 0.0166 (15) | 0.0285 (16) | 0.072 (2) | 0.0027 (12) | −0.0039 (15) | −0.0055 (16) |
| C9 | 0.0406 (19) | 0.050 (2) | 0.0316 (17) | 0.0052 (15) | 0.0133 (14) | −0.0072 (15) |
| C15 | 0.014 (4) | 0.028 (5) | 0.031 (3) | −0.009 (3) | 0.003 (3) | 0.000 (3) |
| C14 | 0.032 (5) | 0.020 (3) | 0.028 (4) | −0.006 (3) | 0.014 (3) | −0.002 (3) |
| C14A | 0.066 (9) | 0.011 (3) | 0.030 (5) | −0.003 (4) | 0.026 (6) | 0.000 (3) |
| C12A | 0.025 (6) | 0.022 (5) | 0.014 (4) | −0.005 (4) | −0.004 (4) | 0.008 (3) |
| C15A | 0.028 (6) | 0.047 (8) | 0.032 (5) | −0.018 (5) | −0.010 (5) | 0.022 (5) |
1,1'-Methylenebis(3-tert-butylimidazolium) dibromide monohydrate (sces01006_0m) . Geometric parameters (Å, º)
| N3—C5 | 1.387 (3) | C13—H15D | 0.9600 |
| N3—C4 | 1.343 (3) | C13—H15E | 0.9600 |
| N3—C7 | 1.461 (3) | C13—H15F | 0.9600 |
| N1—C1 | 1.337 (3) | C13—C12 | 1.595 (13) |
| N1—C8 | 1.512 (3) | C13—C12A | 1.434 (16) |
| N1—C2 | 1.389 (3) | C12—C15 | 1.530 (10) |
| O1—H1D | 0.80 (4) | C12—C14 | 1.519 (10) |
| O1—H1E | 0.73 (4) | C11—H3A | 0.9600 |
| N2—C1 | 1.337 (3) | C11—H3B | 0.9600 |
| N2—C7 | 1.463 (3) | C11—H3C | 0.9600 |
| N2—C3 | 1.389 (3) | C10—H1A | 0.9600 |
| N4—C4 | 1.327 (3) | C10—H1B | 0.9600 |
| N4—C6 | 1.387 (4) | C10—H1C | 0.9600 |
| N4—C12 | 1.525 (9) | C9—H4A | 0.9600 |
| N4—C12A | 1.531 (11) | C9—H4B | 0.9600 |
| C1—H5 | 0.9300 | C9—H4C | 0.9600 |
| C5—C6 | 1.352 (4) | C15—H13A | 0.9600 |
| C5—H10 | 0.94 (3) | C15—H13B | 0.9600 |
| C4—H9 | 0.9300 | C15—H13C | 0.9600 |
| C7—H8A | 0.9700 | C14—H14A | 0.9600 |
| C7—H8B | 0.9700 | C14—H14B | 0.9600 |
| C8—C11 | 1.529 (4) | C14—H14C | 0.9600 |
| C8—C10 | 1.514 (4) | C14A—H00A | 0.9600 |
| C8—C9 | 1.518 (4) | C14A—H00B | 0.9600 |
| C6—H11 | 0.91 (3) | C14A—H00C | 0.9600 |
| C2—C3 | 1.348 (4) | C14A—C12A | 1.531 (12) |
| C2—H6 | 0.94 (3) | C12A—C15A | 1.527 (11) |
| C3—H7 | 0.91 (3) | C15A—H1AA | 0.9600 |
| C13—H15A | 0.9600 | C15A—H1AB | 0.9600 |
| C13—H15B | 0.9600 | C15A—H1AC | 0.9600 |
| C13—H15C | 0.9600 | ||
| C5—N3—C7 | 127.0 (2) | C12A—C13—H15F | 109.5 |
| C4—N3—C5 | 108.7 (2) | N4—C12—C13 | 102.7 (7) |
| C4—N3—C7 | 124.3 (2) | N4—C12—C15 | 113.1 (8) |
| C1—N1—C8 | 126.5 (2) | C15—C12—C13 | 111.0 (8) |
| C1—N1—C2 | 108.2 (2) | C14—C12—N4 | 105.6 (7) |
| C2—N1—C8 | 125.2 (2) | C14—C12—C13 | 111.6 (6) |
| H1D—O1—H1E | 112 (4) | C14—C12—C15 | 112.4 (7) |
| C1—N2—C7 | 125.5 (2) | C8—C11—H3A | 109.5 |
| C1—N2—C3 | 108.6 (2) | C8—C11—H3B | 109.5 |
| C3—N2—C7 | 125.8 (2) | C8—C11—H3C | 109.5 |
| C4—N4—C6 | 108.4 (2) | H3A—C11—H3B | 109.5 |
| C4—N4—C12 | 119.2 (6) | H3A—C11—H3C | 109.5 |
| C4—N4—C12A | 133.6 (7) | H3B—C11—H3C | 109.5 |
| C6—N4—C12 | 132.4 (6) | C8—C10—H1A | 109.5 |
| C6—N4—C12A | 117.7 (7) | C8—C10—H1B | 109.5 |
| N1—C1—N2 | 108.7 (2) | C8—C10—H1C | 109.5 |
| N1—C1—H5 | 125.6 | H1A—C10—H1B | 109.5 |
| N2—C1—H5 | 125.6 | H1A—C10—H1C | 109.5 |
| N3—C5—H10 | 123 (2) | H1B—C10—H1C | 109.5 |
| C6—C5—N3 | 106.5 (2) | C8—C9—H4A | 109.5 |
| C6—C5—H10 | 131 (2) | C8—C9—H4B | 109.5 |
| N3—C4—H9 | 125.7 | C8—C9—H4C | 109.5 |
| N4—C4—N3 | 108.6 (2) | H4A—C9—H4B | 109.5 |
| N4—C4—H9 | 125.7 | H4A—C9—H4C | 109.5 |
| N3—C7—N2 | 111.8 (2) | H4B—C9—H4C | 109.5 |
| N3—C7—H8A | 109.3 | C12—C15—H13A | 109.5 |
| N3—C7—H8B | 109.3 | C12—C15—H13B | 109.5 |
| N2—C7—H8A | 109.3 | C12—C15—H13C | 109.5 |
| N2—C7—H8B | 109.3 | H13A—C15—H13B | 109.5 |
| H8A—C7—H8B | 107.9 | H13A—C15—H13C | 109.5 |
| N1—C8—C11 | 108.4 (2) | H13B—C15—H13C | 109.5 |
| N1—C8—C10 | 108.2 (2) | C12—C14—H14A | 109.5 |
| N1—C8—C9 | 107.0 (2) | C12—C14—H14B | 109.5 |
| C10—C8—C11 | 111.4 (3) | C12—C14—H14C | 109.5 |
| C10—C8—C9 | 109.7 (3) | H14A—C14—H14B | 109.5 |
| C9—C8—C11 | 111.9 (3) | H14A—C14—H14C | 109.5 |
| N4—C6—H11 | 122 (2) | H14B—C14—H14C | 109.5 |
| C5—C6—N4 | 107.7 (2) | H00A—C14A—H00B | 109.5 |
| C5—C6—H11 | 131 (2) | H00A—C14A—H00C | 109.5 |
| N1—C2—H6 | 118.1 (18) | H00B—C14A—H00C | 109.5 |
| C3—C2—N1 | 107.6 (2) | C12A—C14A—H00A | 109.5 |
| C3—C2—H6 | 134.3 (18) | C12A—C14A—H00B | 109.5 |
| N2—C3—H7 | 120 (2) | C12A—C14A—H00C | 109.5 |
| C2—C3—N2 | 106.9 (2) | N4—C12A—C14A | 111.9 (9) |
| C2—C3—H7 | 133 (2) | C13—C12A—N4 | 110.5 (9) |
| H15A—C13—H15B | 109.5 | C13—C12A—C14A | 113.1 (8) |
| H15A—C13—H15C | 109.5 | C13—C12A—C15A | 107.5 (10) |
| H15B—C13—H15C | 109.5 | C15A—C12A—N4 | 101.8 (9) |
| H15D—C13—H15E | 109.5 | C15A—C12A—C14A | 111.4 (10) |
| H15D—C13—H15F | 109.5 | C12A—C15A—H1AA | 109.5 |
| H15E—C13—H15F | 109.5 | C12A—C15A—H1AB | 109.5 |
| C12—C13—H15A | 109.5 | C12A—C15A—H1AC | 109.5 |
| C12—C13—H15B | 109.5 | H1AA—C15A—H1AB | 109.5 |
| C12—C13—H15C | 109.5 | H1AA—C15A—H1AC | 109.5 |
| C12A—C13—H15D | 109.5 | H1AB—C15A—H1AC | 109.5 |
| C12A—C13—H15E | 109.5 | ||
| N3—C5—C6—N4 | −0.3 (3) | C7—N2—C1—N1 | −177.6 (2) |
| N1—C2—C3—N2 | −0.4 (3) | C7—N2—C3—C2 | 177.5 (2) |
| C1—N1—C8—C11 | 122.5 (3) | C8—N1—C1—N2 | 178.4 (2) |
| C1—N1—C8—C10 | 1.6 (3) | C8—N1—C2—C3 | −177.9 (2) |
| C1—N1—C8—C9 | −116.6 (3) | C6—N4—C4—N3 | −0.8 (3) |
| C1—N1—C2—C3 | −0.3 (3) | C6—N4—C12—C13 | −36.8 (9) |
| C1—N2—C7—N3 | 97.2 (3) | C6—N4—C12—C15 | −156.5 (6) |
| C1—N2—C3—C2 | 0.9 (3) | C6—N4—C12—C14 | 80.3 (8) |
| C5—N3—C4—N4 | 0.6 (3) | C6—N4—C12A—C13 | −59.5 (11) |
| C5—N3—C7—N2 | 75.7 (3) | C6—N4—C12A—C14A | 67.4 (12) |
| C4—N3—C5—C6 | −0.2 (3) | C6—N4—C12A—C15A | −173.5 (9) |
| C4—N3—C7—N2 | −105.5 (3) | C2—N1—C1—N2 | 0.8 (3) |
| C4—N4—C6—C5 | 0.7 (3) | C2—N1—C8—C11 | −60.3 (3) |
| C4—N4—C12—C13 | 142.2 (5) | C2—N1—C8—C10 | 178.8 (3) |
| C4—N4—C12—C15 | 22.6 (10) | C2—N1—C8—C9 | 60.6 (3) |
| C4—N4—C12—C14 | −100.7 (6) | C3—N2—C1—N1 | −1.0 (3) |
| C4—N4—C12A—C13 | 127.1 (8) | C3—N2—C7—N3 | −78.8 (3) |
| C4—N4—C12A—C14A | −105.9 (8) | C12—N4—C4—N3 | 179.9 (5) |
| C4—N4—C12A—C15A | 13.1 (14) | C12—N4—C6—C5 | 179.8 (6) |
| C7—N3—C5—C6 | 178.7 (2) | C12A—N4—C4—N3 | 173.0 (8) |
| C7—N3—C4—N4 | −178.3 (2) | C12A—N4—C6—C5 | −174.3 (7) |
1,1'-(Ethane-1,2-diyl)bis(3-tert-butylimidazolium) dibromide dihydrate (est01043_0m) . Crystal data
| C16H28N42+·2Br−·2H2O | F(000) = 968 |
| Mr = 472.27 | Dx = 1.483 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| a = 17.1577 (6) Å | Cell parameters from 9074 reflections |
| b = 7.3180 (2) Å | θ = 2.4–38.4° |
| c = 18.2712 (6) Å | µ = 3.85 mm−1 |
| β = 112.786 (1)° | T = 100 K |
| V = 2115.09 (12) Å3 | Prism, clear colourless |
| Z = 4 | 0.2 × 0.1 × 0.05 mm |
1,1'-(Ethane-1,2-diyl)bis(3-tert-butylimidazolium) dibromide dihydrate (est01043_0m) . Data collection
| Bruker Venture D8 Kappa diffractometer | 4168 reflections with I > 2σ(I) |
| φ and ω scans | Rint = 0.059 |
| Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 27.1°, θmin = 2.6° |
| Tmin = 0.496, Tmax = 0.748 | h = −21→21 |
| 31474 measured reflections | k = −9→9 |
| 4664 independent reflections | l = −23→23 |
1,1'-(Ethane-1,2-diyl)bis(3-tert-butylimidazolium) dibromide dihydrate (est01043_0m) . Refinement
| Refinement on F2 | Primary atom site location: dual |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.013P)2 + 2.745P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.11 | (Δ/σ)max = 0.001 |
| 4664 reflections | Δρmax = 0.60 e Å−3 |
| 253 parameters | Δρmin = −0.61 e Å−3 |
| 0 restraints |
1,1'-(Ethane-1,2-diyl)bis(3-tert-butylimidazolium) dibromide dihydrate (est01043_0m) . Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
1,1'-(Ethane-1,2-diyl)bis(3-tert-butylimidazolium) dibromide dihydrate (est01043_0m) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| Br2 | 0.42021 (2) | 1.06846 (3) | 0.17436 (2) | 0.01794 (7) | |
| Br1 | 0.64204 (2) | 1.22356 (3) | 0.46410 (2) | 0.01716 (7) | |
| O2 | 0.60635 (11) | 0.9669 (3) | 0.30798 (12) | 0.0253 (4) | |
| H2C | 0.612198 | 1.048204 | 0.344458 | 0.038* | |
| H2D | 0.556728 | 0.988924 | 0.271398 | 0.038* | |
| O1 | 0.84726 (12) | 1.2201 (3) | 0.50226 (12) | 0.0273 (4) | |
| H1C | 0.874519 | 1.260282 | 0.550269 | 0.041* | |
| H1D | 0.793229 | 1.222132 | 0.491369 | 0.041* | |
| N1 | 0.63968 (11) | 0.5405 (3) | 0.63652 (11) | 0.0097 (4) | |
| N2 | 0.70265 (12) | 0.7072 (3) | 0.57816 (11) | 0.0111 (4) | |
| N3 | 0.79306 (12) | 0.7383 (3) | 0.42286 (12) | 0.0113 (4) | |
| N4 | 0.86030 (11) | 0.8912 (2) | 0.36416 (11) | 0.0103 (4) | |
| C1 | 0.70549 (14) | 0.5497 (3) | 0.61555 (13) | 0.0100 (4) | |
| C9 | 0.61678 (14) | 0.3834 (3) | 0.67751 (14) | 0.0119 (5) | |
| C7 | 0.76212 (14) | 0.7620 (3) | 0.54214 (14) | 0.0123 (5) | |
| H1A | 0.818644 | 0.709890 | 0.572987 | 0.015* | |
| H1B | 0.767285 | 0.896775 | 0.543092 | 0.015* | |
| C4 | 0.79441 (14) | 0.8939 (3) | 0.38544 (13) | 0.0108 (4) | |
| C3 | 0.63152 (15) | 0.8025 (3) | 0.57441 (15) | 0.0152 (5) | |
| C10 | 0.68416 (16) | 0.2364 (3) | 0.69468 (15) | 0.0165 (5) | |
| H9A | 0.688285 | 0.198067 | 0.644913 | 0.025* | |
| H9B | 0.668875 | 0.131113 | 0.719524 | 0.025* | |
| H9C | 0.738750 | 0.285198 | 0.730682 | 0.025* | |
| C2 | 0.59238 (15) | 0.6988 (3) | 0.61096 (15) | 0.0154 (5) | |
| C8 | 0.73079 (14) | 0.6942 (3) | 0.45708 (14) | 0.0133 (5) | |
| H2A | 0.721968 | 0.560336 | 0.455808 | 0.016* | |
| H2B | 0.676038 | 0.752701 | 0.425349 | 0.016* | |
| C11 | 0.61411 (16) | 0.4549 (3) | 0.75498 (15) | 0.0176 (5) | |
| H7A | 0.670172 | 0.500229 | 0.789205 | 0.026* | |
| H7B | 0.597527 | 0.355834 | 0.782054 | 0.026* | |
| H7C | 0.572921 | 0.554573 | 0.743410 | 0.026* | |
| C5 | 0.86096 (15) | 0.6322 (3) | 0.42626 (15) | 0.0155 (5) | |
| C12 | 0.53083 (15) | 0.3119 (4) | 0.62096 (16) | 0.0196 (5) | |
| H8A | 0.488167 | 0.407825 | 0.611530 | 0.029* | |
| H8B | 0.515078 | 0.205199 | 0.644608 | 0.029* | |
| H8C | 0.534144 | 0.276943 | 0.570466 | 0.029* | |
| C16 | 0.81928 (16) | 1.1913 (3) | 0.30107 (15) | 0.0170 (5) | |
| H16A | 0.764854 | 1.140422 | 0.265770 | 0.025* | |
| H16B | 0.835344 | 1.291111 | 0.273954 | 0.025* | |
| H16C | 0.814374 | 1.238204 | 0.349352 | 0.025* | |
| C13 | 0.88640 (14) | 1.0428 (3) | 0.32301 (14) | 0.0126 (5) | |
| C15 | 0.89362 (16) | 0.9645 (3) | 0.24873 (15) | 0.0186 (5) | |
| H15A | 0.935772 | 0.866340 | 0.263706 | 0.028* | |
| H15B | 0.911020 | 1.061099 | 0.221125 | 0.028* | |
| H15C | 0.838699 | 0.915498 | 0.213542 | 0.028* | |
| C6 | 0.90270 (15) | 0.7277 (3) | 0.38943 (15) | 0.0157 (5) | |
| C14 | 0.97108 (15) | 1.1159 (4) | 0.38186 (16) | 0.0195 (5) | |
| H14A | 0.964657 | 1.157067 | 0.430264 | 0.029* | |
| H14B | 0.989184 | 1.218801 | 0.357887 | 0.029* | |
| H14C | 1.013621 | 1.018734 | 0.395112 | 0.029* | |
| H5 | 0.7461 (15) | 0.464 (3) | 0.6249 (15) | 0.006 (6)* | |
| H4 | 0.5430 (18) | 0.717 (4) | 0.6210 (17) | 0.023 (8)* | |
| H12 | 0.7552 (15) | 0.985 (3) | 0.3754 (14) | 0.003 (6)* | |
| H11 | 0.9505 (17) | 0.698 (4) | 0.3796 (16) | 0.018 (7)* | |
| H3 | 0.6180 (17) | 0.910 (4) | 0.5485 (17) | 0.018 (7)* | |
| H10 | 0.8680 (18) | 0.521 (4) | 0.4505 (18) | 0.028 (8)* |
1,1'-(Ethane-1,2-diyl)bis(3-tert-butylimidazolium) dibromide dihydrate (est01043_0m) . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br2 | 0.01224 (11) | 0.01866 (13) | 0.02260 (14) | −0.00149 (9) | 0.00642 (10) | 0.00053 (10) |
| Br1 | 0.02064 (13) | 0.01617 (12) | 0.01448 (13) | −0.00222 (9) | 0.00658 (10) | 0.00156 (9) |
| O2 | 0.0199 (9) | 0.0299 (11) | 0.0227 (11) | 0.0067 (8) | 0.0046 (8) | −0.0070 (8) |
| O1 | 0.0261 (10) | 0.0346 (11) | 0.0234 (11) | 0.0008 (9) | 0.0120 (8) | −0.0035 (9) |
| N1 | 0.0115 (9) | 0.0117 (9) | 0.0082 (9) | −0.0001 (7) | 0.0063 (7) | 0.0017 (7) |
| N2 | 0.0120 (9) | 0.0141 (9) | 0.0088 (10) | −0.0008 (7) | 0.0059 (8) | 0.0006 (8) |
| N3 | 0.0135 (9) | 0.0113 (9) | 0.0118 (10) | −0.0022 (7) | 0.0078 (8) | 0.0015 (7) |
| N4 | 0.0129 (9) | 0.0103 (9) | 0.0098 (10) | −0.0010 (7) | 0.0068 (8) | 0.0018 (7) |
| C1 | 0.0114 (10) | 0.0116 (11) | 0.0084 (11) | 0.0009 (9) | 0.0054 (9) | 0.0002 (8) |
| C9 | 0.0148 (11) | 0.0132 (11) | 0.0103 (11) | −0.0025 (9) | 0.0078 (9) | 0.0027 (9) |
| C7 | 0.0146 (11) | 0.0155 (11) | 0.0094 (11) | −0.0034 (9) | 0.0075 (9) | 0.0031 (9) |
| C4 | 0.0125 (10) | 0.0127 (11) | 0.0087 (11) | −0.0010 (9) | 0.0056 (9) | 0.0005 (9) |
| C3 | 0.0170 (12) | 0.0142 (12) | 0.0157 (13) | 0.0041 (9) | 0.0079 (10) | 0.0038 (10) |
| C10 | 0.0214 (12) | 0.0145 (11) | 0.0168 (13) | 0.0004 (9) | 0.0110 (10) | 0.0029 (10) |
| C2 | 0.0150 (11) | 0.0157 (12) | 0.0182 (13) | 0.0048 (9) | 0.0094 (10) | 0.0032 (10) |
| C8 | 0.0135 (11) | 0.0177 (12) | 0.0121 (12) | −0.0047 (9) | 0.0085 (9) | 0.0008 (9) |
| C11 | 0.0228 (12) | 0.0200 (12) | 0.0166 (13) | 0.0004 (10) | 0.0149 (10) | 0.0027 (10) |
| C5 | 0.0192 (12) | 0.0108 (11) | 0.0182 (13) | 0.0020 (9) | 0.0092 (10) | 0.0024 (9) |
| C12 | 0.0157 (12) | 0.0218 (13) | 0.0207 (14) | −0.0074 (10) | 0.0065 (10) | 0.0012 (10) |
| C16 | 0.0217 (12) | 0.0160 (12) | 0.0179 (13) | 0.0024 (10) | 0.0127 (10) | 0.0053 (10) |
| C13 | 0.0143 (11) | 0.0132 (11) | 0.0133 (12) | −0.0032 (9) | 0.0085 (9) | 0.0034 (9) |
| C15 | 0.0240 (13) | 0.0212 (13) | 0.0166 (13) | −0.0010 (10) | 0.0144 (11) | 0.0019 (10) |
| C6 | 0.0173 (12) | 0.0140 (11) | 0.0200 (13) | 0.0027 (9) | 0.0120 (10) | 0.0014 (10) |
| C14 | 0.0164 (12) | 0.0215 (13) | 0.0199 (13) | −0.0055 (10) | 0.0063 (10) | 0.0031 (10) |
1,1'-(Ethane-1,2-diyl)bis(3-tert-butylimidazolium) dibromide dihydrate (est01043_0m) . Geometric parameters (Å, º)
| O2—H2C | 0.8695 | C10—H9B | 0.9800 |
| O2—H2D | 0.8698 | C10—H9C | 0.9800 |
| O1—H1C | 0.8699 | C2—H4 | 0.94 (3) |
| O1—H1D | 0.8697 | C8—H2A | 0.9900 |
| N1—C1 | 1.327 (3) | C8—H2B | 0.9900 |
| N1—C9 | 1.505 (3) | C11—H7A | 0.9800 |
| N1—C2 | 1.388 (3) | C11—H7B | 0.9800 |
| N2—C1 | 1.331 (3) | C11—H7C | 0.9800 |
| N2—C7 | 1.468 (3) | C5—C6 | 1.352 (3) |
| N2—C3 | 1.384 (3) | C5—H10 | 0.91 (3) |
| N3—C4 | 1.333 (3) | C12—H8A | 0.9800 |
| N3—C8 | 1.468 (3) | C12—H8B | 0.9800 |
| N3—C5 | 1.381 (3) | C12—H8C | 0.9800 |
| N4—C4 | 1.330 (3) | C16—H16A | 0.9800 |
| N4—C13 | 1.503 (3) | C16—H16B | 0.9800 |
| N4—C6 | 1.384 (3) | C16—H16C | 0.9800 |
| C1—H5 | 0.91 (2) | C16—C13 | 1.520 (3) |
| C9—C10 | 1.520 (3) | C13—C15 | 1.522 (3) |
| C9—C11 | 1.526 (3) | C13—C14 | 1.531 (3) |
| C9—C12 | 1.528 (3) | C15—H15A | 0.9800 |
| C7—H1A | 0.9900 | C15—H15B | 0.9800 |
| C7—H1B | 0.9900 | C15—H15C | 0.9800 |
| C7—C8 | 1.518 (3) | C6—H11 | 0.93 (3) |
| C4—H12 | 0.91 (2) | C14—H14A | 0.9800 |
| C3—C2 | 1.349 (3) | C14—H14B | 0.9800 |
| C3—H3 | 0.90 (3) | C14—H14C | 0.9800 |
| C10—H9A | 0.9800 | ||
| H2C—O2—H2D | 104.5 | N3—C8—H2B | 109.7 |
| H1C—O1—H1D | 109.5 | C7—C8—H2A | 109.7 |
| C1—N1—C9 | 126.71 (19) | C7—C8—H2B | 109.7 |
| C1—N1—C2 | 108.21 (19) | H2A—C8—H2B | 108.2 |
| C2—N1—C9 | 125.02 (18) | C9—C11—H7A | 109.5 |
| C1—N2—C7 | 124.95 (19) | C9—C11—H7B | 109.5 |
| C1—N2—C3 | 108.54 (19) | C9—C11—H7C | 109.5 |
| C3—N2—C7 | 126.4 (2) | H7A—C11—H7B | 109.5 |
| C4—N3—C8 | 124.51 (19) | H7A—C11—H7C | 109.5 |
| C4—N3—C5 | 108.75 (19) | H7B—C11—H7C | 109.5 |
| C5—N3—C8 | 126.7 (2) | N3—C5—H10 | 118.4 (19) |
| C4—N4—C13 | 125.94 (19) | C6—C5—N3 | 106.7 (2) |
| C4—N4—C6 | 108.16 (19) | C6—C5—H10 | 134.9 (19) |
| C6—N4—C13 | 125.85 (19) | C9—C12—H8A | 109.5 |
| N1—C1—N2 | 109.02 (19) | C9—C12—H8B | 109.5 |
| N1—C1—H5 | 126.1 (16) | C9—C12—H8C | 109.5 |
| N2—C1—H5 | 124.9 (16) | H8A—C12—H8B | 109.5 |
| N1—C9—C10 | 108.60 (18) | H8A—C12—H8C | 109.5 |
| N1—C9—C11 | 107.87 (18) | H8B—C12—H8C | 109.5 |
| N1—C9—C12 | 107.13 (18) | H16A—C16—H16B | 109.5 |
| C10—C9—C11 | 110.2 (2) | H16A—C16—H16C | 109.5 |
| C10—C9—C12 | 110.8 (2) | H16B—C16—H16C | 109.5 |
| C11—C9—C12 | 112.13 (19) | C13—C16—H16A | 109.5 |
| N2—C7—H1A | 109.7 | C13—C16—H16B | 109.5 |
| N2—C7—H1B | 109.7 | C13—C16—H16C | 109.5 |
| N2—C7—C8 | 109.74 (18) | N4—C13—C16 | 108.52 (18) |
| H1A—C7—H1B | 108.2 | N4—C13—C15 | 108.11 (19) |
| C8—C7—H1A | 109.7 | N4—C13—C14 | 107.00 (19) |
| C8—C7—H1B | 109.7 | C16—C13—C15 | 110.4 (2) |
| N3—C4—H12 | 124.6 (15) | C16—C13—C14 | 110.6 (2) |
| N4—C4—N3 | 108.8 (2) | C15—C13—C14 | 112.0 (2) |
| N4—C4—H12 | 126.5 (15) | C13—C15—H15A | 109.5 |
| N2—C3—H3 | 120.5 (17) | C13—C15—H15B | 109.5 |
| C2—C3—N2 | 106.9 (2) | C13—C15—H15C | 109.5 |
| C2—C3—H3 | 132.5 (17) | H15A—C15—H15B | 109.5 |
| C9—C10—H9A | 109.5 | H15A—C15—H15C | 109.5 |
| C9—C10—H9B | 109.5 | H15B—C15—H15C | 109.5 |
| C9—C10—H9C | 109.5 | N4—C6—H11 | 121.8 (17) |
| H9A—C10—H9B | 109.5 | C5—C6—N4 | 107.6 (2) |
| H9A—C10—H9C | 109.5 | C5—C6—H11 | 130.7 (17) |
| H9B—C10—H9C | 109.5 | C13—C14—H14A | 109.5 |
| N1—C2—H4 | 120.4 (18) | C13—C14—H14B | 109.5 |
| C3—C2—N1 | 107.3 (2) | C13—C14—H14C | 109.5 |
| C3—C2—H4 | 132.3 (17) | H14A—C14—H14B | 109.5 |
| N3—C8—C7 | 109.68 (18) | H14A—C14—H14C | 109.5 |
| N3—C8—H2A | 109.7 | H14B—C14—H14C | 109.5 |
| N2—C7—C8—N3 | −176.23 (18) | C4—N4—C6—C5 | 0.0 (3) |
| N2—C3—C2—N1 | −0.2 (3) | C3—N2—C1—N1 | −0.5 (3) |
| N3—C5—C6—N4 | 0.2 (3) | C3—N2—C7—C8 | −86.8 (3) |
| C1—N1—C9—C10 | 2.3 (3) | C2—N1—C1—N2 | 0.4 (3) |
| C1—N1—C9—C11 | 121.7 (2) | C2—N1—C9—C10 | 179.3 (2) |
| C1—N1—C9—C12 | −117.4 (2) | C2—N1—C9—C11 | −61.3 (3) |
| C1—N1—C2—C3 | −0.1 (3) | C2—N1—C9—C12 | 59.6 (3) |
| C1—N2—C7—C8 | 88.3 (3) | C8—N3—C4—N4 | 178.2 (2) |
| C1—N2—C3—C2 | 0.5 (3) | C8—N3—C5—C6 | −178.1 (2) |
| C9—N1—C1—N2 | 177.7 (2) | C5—N3—C4—N4 | 0.4 (3) |
| C9—N1—C2—C3 | −177.5 (2) | C5—N3—C8—C7 | 88.4 (3) |
| C7—N2—C1—N1 | −176.37 (19) | C13—N4—C4—N3 | −177.8 (2) |
| C7—N2—C3—C2 | 176.3 (2) | C13—N4—C6—C5 | 177.6 (2) |
| C4—N3—C8—C7 | −88.9 (3) | C6—N4—C4—N3 | −0.3 (3) |
| C4—N3—C5—C6 | −0.4 (3) | C6—N4—C13—C16 | 176.4 (2) |
| C4—N4—C13—C16 | −6.5 (3) | C6—N4—C13—C15 | 56.6 (3) |
| C4—N4—C13—C15 | −126.3 (2) | C6—N4—C13—C14 | −64.3 (3) |
| C4—N4—C13—C14 | 112.8 (2) |
1,1'-Methylenebis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide dihydrate (at01019_0ma). Crystal data
| C25H30N42+·2Br−·2H2O | Dx = 1.416 Mg m−3 |
| Mr = 582.38 | Mo Kα radiation, λ = 0.71073 Å |
| Orthorhombic, Pccn | Cell parameters from 9959 reflections |
| a = 21.5695 (6) Å | θ = 2.6–39.4° |
| b = 28.3385 (6) Å | µ = 2.99 mm−1 |
| c = 8.9401 (2) Å | T = 112 K |
| V = 5464.6 (2) Å3 | Prism, clear colourless |
| Z = 8 | 0.4 × 0.3 × 0.25 mm |
| F(000) = 2384 |
1,1'-Methylenebis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide dihydrate (at01019_0ma). Data collection
| Bruker Venture Kappa D diffractometer | 5530 reflections with I > 2σ(I) |
| φ and ω scans | Rint = 0.035 |
| Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 27.1°, θmin = 2.6° |
| Tmin = 0.386, Tmax = 0.748 | h = −24→27 |
| 39085 measured reflections | k = −31→36 |
| 5954 independent reflections | l = −11→11 |
1,1'-Methylenebis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide dihydrate (at01019_0ma). Refinement
| Refinement on F2 | Primary atom site location: iterative |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.0149P)2 + 6.9269P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.19 | (Δ/σ)max = 0.002 |
| 5954 reflections | Δρmax = 0.42 e Å−3 |
| 338 parameters | Δρmin = −0.54 e Å−3 |
| 0 restraints |
1,1'-Methylenebis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide dihydrate (at01019_0ma). Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
1,1'-Methylenebis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide dihydrate (at01019_0ma). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Br1 | 0.32147 (2) | 0.59206 (2) | 0.51936 (2) | 0.01792 (6) | |
| Br2 | 0.33241 (2) | 0.42996 (2) | 0.77256 (2) | 0.01874 (6) | |
| N2 | 0.14868 (8) | 0.40218 (6) | 0.76624 (19) | 0.0134 (3) | |
| N3 | 0.17753 (8) | 0.54615 (6) | 0.5774 (2) | 0.0167 (4) | |
| N1 | 0.17956 (8) | 0.47256 (6) | 0.7130 (2) | 0.0158 (4) | |
| N4 | 0.14048 (8) | 0.61532 (6) | 0.53485 (19) | 0.0151 (3) | |
| C4 | 0.17963 (9) | 0.42757 (7) | 0.6667 (2) | 0.0165 (4) | |
| H4 | 0.198554 | 0.415943 | 0.578146 | 0.020* | |
| C16 | 0.17313 (9) | 0.59006 (7) | 0.6302 (2) | 0.0154 (4) | |
| H16 | 0.190588 | 0.601214 | 0.721117 | 0.018* | |
| C17 | 0.12153 (9) | 0.66386 (7) | 0.5581 (2) | 0.0146 (4) | |
| C5 | 0.13900 (9) | 0.35172 (7) | 0.7556 (2) | 0.0141 (4) | |
| O2A | 0.4650 (10) | 0.5643 (7) | 0.601 (3) | 0.037 (3) | 0.47 (9) |
| H2AA | 0.482702 | 0.563311 | 0.513609 | 0.055* | 0.47 (9) |
| H2AB | 0.427586 | 0.574062 | 0.582766 | 0.055* | 0.47 (9) |
| C12 | 0.22444 (10) | 0.34048 (8) | 0.9479 (2) | 0.0201 (4) | |
| H12A | 0.256440 | 0.357156 | 0.890780 | 0.030* | |
| H12B | 0.243324 | 0.314106 | 1.002226 | 0.030* | |
| H12C | 0.205240 | 0.362270 | 1.019314 | 0.030* | |
| C14 | 0.14765 (13) | 0.54398 (8) | 0.4406 (3) | 0.0275 (5) | |
| C18 | 0.07474 (9) | 0.67224 (7) | 0.6624 (2) | 0.0150 (4) | |
| C22 | 0.15021 (10) | 0.69938 (7) | 0.4754 (2) | 0.0179 (4) | |
| C6 | 0.17572 (9) | 0.32189 (7) | 0.8424 (2) | 0.0153 (4) | |
| C24 | 0.04581 (10) | 0.63259 (7) | 0.7507 (2) | 0.0190 (4) | |
| H24A | 0.037277 | 0.605939 | 0.683916 | 0.028* | |
| H24B | 0.006967 | 0.643518 | 0.795745 | 0.028* | |
| H24C | 0.074401 | 0.622543 | 0.829693 | 0.028* | |
| C3 | 0.12848 (12) | 0.43164 (8) | 0.8801 (3) | 0.0244 (5) | |
| C10 | 0.09279 (10) | 0.33558 (7) | 0.6589 (2) | 0.0163 (4) | |
| C15 | 0.12434 (13) | 0.58713 (8) | 0.4143 (3) | 0.0272 (5) | |
| C1 | 0.21637 (10) | 0.50965 (7) | 0.6432 (3) | 0.0231 (5) | |
| H1A | 0.243891 | 0.524043 | 0.719194 | 0.028* | |
| H1B | 0.242843 | 0.495638 | 0.564401 | 0.028* | |
| C19 | 0.05623 (10) | 0.71864 (7) | 0.6822 (2) | 0.0174 (4) | |
| H19 | 0.024420 | 0.725449 | 0.752452 | 0.021* | |
| C11 | 0.05222 (11) | 0.36931 (8) | 0.5741 (3) | 0.0242 (5) | |
| H11A | 0.036347 | 0.393487 | 0.642452 | 0.036* | |
| H11B | 0.017393 | 0.352060 | 0.529724 | 0.036* | |
| H11C | 0.076445 | 0.384406 | 0.494617 | 0.036* | |
| O1A | 0.47220 (10) | 0.47135 (8) | 0.6838 (4) | 0.0715 (9) | |
| H1AA | 0.487824 | 0.450597 | 0.622561 | 0.107* | |
| H1AB | 0.436751 | 0.459386 | 0.710574 | 0.107* | |
| C7 | 0.16563 (9) | 0.27361 (7) | 0.8269 (2) | 0.0175 (4) | |
| H7 | 0.189642 | 0.252345 | 0.885177 | 0.021* | |
| C2 | 0.14808 (12) | 0.47542 (8) | 0.8472 (3) | 0.0245 (5) | |
| C20 | 0.08292 (10) | 0.75565 (7) | 0.6021 (2) | 0.0182 (4) | |
| C23 | 0.20108 (11) | 0.68858 (8) | 0.3644 (3) | 0.0263 (5) | |
| H23A | 0.236552 | 0.674719 | 0.416963 | 0.040* | |
| H23B | 0.214017 | 0.717788 | 0.314740 | 0.040* | |
| H23C | 0.185662 | 0.666212 | 0.289523 | 0.040* | |
| C8 | 0.12146 (10) | 0.25546 (7) | 0.7288 (2) | 0.0184 (4) | |
| C9 | 0.08556 (10) | 0.28686 (7) | 0.6465 (2) | 0.0179 (4) | |
| H9 | 0.055181 | 0.274754 | 0.579845 | 0.021* | |
| C13 | 0.11192 (11) | 0.20288 (7) | 0.7166 (3) | 0.0243 (5) | |
| H13A | 0.152068 | 0.186833 | 0.723425 | 0.036* | |
| H13B | 0.092477 | 0.195470 | 0.620360 | 0.036* | |
| H13C | 0.085012 | 0.192160 | 0.798149 | 0.036* | |
| C21 | 0.12978 (10) | 0.74543 (7) | 0.5009 (2) | 0.0197 (4) | |
| H21 | 0.148577 | 0.770574 | 0.447203 | 0.024* | |
| C25 | 0.06032 (11) | 0.80563 (7) | 0.6251 (3) | 0.0256 (5) | |
| H25A | 0.020408 | 0.809802 | 0.574412 | 0.038* | |
| H25B | 0.090640 | 0.827784 | 0.583474 | 0.038* | |
| H25C | 0.055261 | 0.811696 | 0.732324 | 0.038* | |
| H2 | 0.1460 (13) | 0.5020 (10) | 0.892 (3) | 0.031* | |
| H15 | 0.1018 (13) | 0.5989 (9) | 0.332 (3) | 0.031* | |
| H3 | 0.1080 (13) | 0.4191 (10) | 0.963 (3) | 0.031* | |
| H14 | 0.1479 (13) | 0.5182 (10) | 0.388 (3) | 0.031* | |
| O2 | 0.4729 (8) | 0.5614 (8) | 0.556 (4) | 0.043 (5) | 0.53 (9) |
| H2A | 0.438 (4) | 0.569 (4) | 0.542 (11) | 0.064* | 0.53 (9) |
| H2B | 0.465 (4) | 0.542 (3) | 0.606 (11) | 0.064* | 0.53 (9) |
1,1'-Methylenebis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide dihydrate (at01019_0ma). Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.01793 (11) | 0.01900 (10) | 0.01682 (11) | −0.00262 (8) | 0.00203 (8) | −0.00139 (8) |
| Br2 | 0.02215 (11) | 0.01532 (10) | 0.01876 (11) | −0.00184 (8) | 0.00044 (8) | −0.00160 (8) |
| N2 | 0.0173 (8) | 0.0108 (8) | 0.0120 (8) | −0.0006 (6) | 0.0010 (6) | −0.0006 (6) |
| N3 | 0.0177 (9) | 0.0101 (8) | 0.0222 (9) | 0.0009 (6) | 0.0016 (7) | 0.0035 (7) |
| N1 | 0.0145 (8) | 0.0116 (8) | 0.0213 (9) | 0.0005 (6) | 0.0008 (7) | 0.0025 (7) |
| N4 | 0.0207 (9) | 0.0114 (8) | 0.0133 (8) | 0.0006 (6) | −0.0008 (7) | 0.0006 (7) |
| C4 | 0.0157 (10) | 0.0147 (9) | 0.0190 (10) | 0.0021 (8) | 0.0023 (8) | 0.0000 (8) |
| C16 | 0.0150 (10) | 0.0125 (9) | 0.0186 (10) | −0.0017 (7) | −0.0002 (8) | 0.0012 (8) |
| C17 | 0.0179 (10) | 0.0113 (9) | 0.0147 (10) | 0.0014 (7) | −0.0043 (8) | −0.0008 (8) |
| C5 | 0.0186 (10) | 0.0101 (9) | 0.0135 (10) | −0.0020 (7) | 0.0038 (8) | 0.0000 (7) |
| O2A | 0.026 (5) | 0.040 (4) | 0.045 (6) | 0.008 (4) | 0.005 (4) | 0.005 (5) |
| C12 | 0.0208 (11) | 0.0196 (10) | 0.0200 (11) | −0.0019 (8) | −0.0023 (9) | 0.0016 (9) |
| C14 | 0.0443 (15) | 0.0135 (10) | 0.0248 (12) | 0.0035 (10) | −0.0058 (11) | −0.0070 (9) |
| C18 | 0.0174 (10) | 0.0128 (9) | 0.0148 (10) | −0.0008 (7) | −0.0047 (8) | 0.0020 (8) |
| C22 | 0.0198 (11) | 0.0149 (10) | 0.0192 (10) | −0.0008 (8) | −0.0009 (8) | 0.0011 (8) |
| C6 | 0.0135 (10) | 0.0168 (9) | 0.0157 (10) | −0.0010 (7) | 0.0034 (8) | 0.0016 (8) |
| C24 | 0.0206 (11) | 0.0157 (10) | 0.0205 (11) | 0.0016 (8) | 0.0014 (9) | 0.0045 (8) |
| C3 | 0.0376 (14) | 0.0183 (11) | 0.0174 (11) | 0.0000 (9) | 0.0088 (10) | −0.0005 (9) |
| C10 | 0.0177 (10) | 0.0163 (10) | 0.0150 (10) | −0.0026 (8) | 0.0008 (8) | 0.0027 (8) |
| C15 | 0.0446 (15) | 0.0182 (11) | 0.0188 (11) | 0.0055 (10) | −0.0107 (11) | −0.0043 (9) |
| C1 | 0.0170 (11) | 0.0122 (10) | 0.0402 (14) | 0.0011 (8) | 0.0022 (10) | 0.0103 (9) |
| C19 | 0.0182 (10) | 0.0151 (10) | 0.0188 (10) | 0.0023 (8) | −0.0018 (8) | −0.0007 (8) |
| C11 | 0.0257 (12) | 0.0202 (11) | 0.0266 (12) | −0.0037 (9) | −0.0083 (10) | 0.0042 (9) |
| O1A | 0.0296 (12) | 0.0545 (14) | 0.130 (3) | 0.0055 (10) | 0.0180 (14) | 0.0468 (16) |
| C7 | 0.0168 (10) | 0.0147 (9) | 0.0208 (10) | 0.0018 (8) | 0.0026 (8) | 0.0041 (8) |
| C2 | 0.0364 (14) | 0.0154 (10) | 0.0216 (12) | 0.0015 (9) | 0.0050 (10) | −0.0040 (9) |
| C20 | 0.0212 (11) | 0.0107 (9) | 0.0227 (11) | 0.0007 (8) | −0.0062 (9) | −0.0007 (8) |
| C23 | 0.0283 (13) | 0.0216 (11) | 0.0291 (13) | 0.0004 (9) | 0.0091 (10) | 0.0042 (10) |
| C8 | 0.0202 (10) | 0.0147 (10) | 0.0201 (10) | −0.0028 (8) | 0.0083 (8) | −0.0002 (8) |
| C9 | 0.0203 (11) | 0.0170 (10) | 0.0164 (10) | −0.0057 (8) | 0.0002 (8) | −0.0013 (8) |
| C13 | 0.0267 (12) | 0.0148 (10) | 0.0313 (13) | −0.0033 (8) | 0.0054 (10) | −0.0026 (9) |
| C21 | 0.0225 (11) | 0.0125 (9) | 0.0242 (11) | −0.0027 (8) | −0.0021 (9) | 0.0036 (9) |
| C25 | 0.0283 (12) | 0.0120 (10) | 0.0366 (14) | 0.0028 (9) | 0.0002 (10) | −0.0008 (10) |
| O2 | 0.023 (4) | 0.045 (5) | 0.060 (13) | 0.013 (3) | 0.006 (5) | 0.026 (7) |
1,1'-Methylenebis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide dihydrate (at01019_0ma). Geometric parameters (Å, º)
| N2—C4 | 1.325 (3) | C3—C2 | 1.343 (3) |
| N2—C5 | 1.448 (2) | C3—H3 | 0.93 (3) |
| N2—C3 | 1.387 (3) | C10—C11 | 1.502 (3) |
| N3—C16 | 1.334 (3) | C10—C9 | 1.394 (3) |
| N3—C14 | 1.384 (3) | C15—H15 | 0.94 (3) |
| N3—C1 | 1.455 (3) | C1—H1A | 0.9900 |
| N1—C4 | 1.340 (3) | C1—H1B | 0.9900 |
| N1—C1 | 1.458 (3) | C19—H19 | 0.9500 |
| N1—C2 | 1.380 (3) | C19—C20 | 1.394 (3) |
| N4—C16 | 1.317 (3) | C11—H11A | 0.9800 |
| N4—C17 | 1.450 (2) | C11—H11B | 0.9800 |
| N4—C15 | 1.386 (3) | C11—H11C | 0.9800 |
| C4—H4 | 0.9500 | O1A—H1AA | 0.8712 |
| C16—H16 | 0.9500 | O1A—H1AB | 0.8701 |
| C17—C18 | 1.394 (3) | C7—H7 | 0.9500 |
| C17—C22 | 1.394 (3) | C7—C8 | 1.394 (3) |
| C5—C6 | 1.394 (3) | C2—H2 | 0.86 (3) |
| C5—C10 | 1.396 (3) | C20—C21 | 1.387 (3) |
| O2A—H2AA | 0.8694 | C20—C25 | 1.512 (3) |
| O2A—H2AB | 0.8679 | C23—H23A | 0.9800 |
| C12—H12A | 0.9800 | C23—H23B | 0.9800 |
| C12—H12B | 0.9800 | C23—H23C | 0.9800 |
| C12—H12C | 0.9800 | C8—C9 | 1.390 (3) |
| C12—C6 | 1.507 (3) | C8—C13 | 1.508 (3) |
| C14—C15 | 1.343 (3) | C9—H9 | 0.9500 |
| C14—H14 | 0.87 (3) | C13—H13A | 0.9800 |
| C18—C24 | 1.508 (3) | C13—H13B | 0.9800 |
| C18—C19 | 1.386 (3) | C13—H13C | 0.9800 |
| C22—C23 | 1.511 (3) | C21—H21 | 0.9500 |
| C22—C21 | 1.396 (3) | C25—H25A | 0.9800 |
| C6—C7 | 1.392 (3) | C25—H25B | 0.9800 |
| C24—H24A | 0.9800 | C25—H25C | 0.9800 |
| C24—H24B | 0.9800 | O2—H2A | 0.79 (9) |
| C24—H24C | 0.9800 | O2—H2B | 0.74 (11) |
| C4—N2—C5 | 124.39 (17) | C14—C15—N4 | 107.1 (2) |
| C4—N2—C3 | 108.93 (17) | C14—C15—H15 | 130.8 (17) |
| C3—N2—C5 | 126.68 (17) | N3—C1—N1 | 111.83 (17) |
| C16—N3—C14 | 108.72 (18) | N3—C1—H1A | 109.3 |
| C16—N3—C1 | 124.13 (19) | N3—C1—H1B | 109.3 |
| C14—N3—C1 | 126.41 (19) | N1—C1—H1A | 109.3 |
| C4—N1—C1 | 123.56 (19) | N1—C1—H1B | 109.3 |
| C4—N1—C2 | 108.94 (18) | H1A—C1—H1B | 107.9 |
| C2—N1—C1 | 126.71 (19) | C18—C19—H19 | 119.0 |
| C16—N4—C17 | 124.98 (17) | C18—C19—C20 | 122.0 (2) |
| C16—N4—C15 | 108.91 (17) | C20—C19—H19 | 119.0 |
| C15—N4—C17 | 126.00 (18) | C10—C11—H11A | 109.5 |
| N2—C4—N1 | 107.98 (18) | C10—C11—H11B | 109.5 |
| N2—C4—H4 | 126.0 | C10—C11—H11C | 109.5 |
| N1—C4—H4 | 126.0 | H11A—C11—H11B | 109.5 |
| N3—C16—H16 | 125.8 | H11A—C11—H11C | 109.5 |
| N4—C16—N3 | 108.43 (19) | H11B—C11—H11C | 109.5 |
| N4—C16—H16 | 125.8 | H1AA—O1A—H1AB | 104.5 |
| C18—C17—N4 | 117.50 (17) | C6—C7—H7 | 118.9 |
| C22—C17—N4 | 118.93 (18) | C6—C7—C8 | 122.13 (19) |
| C22—C17—C18 | 123.56 (18) | C8—C7—H7 | 118.9 |
| C6—C5—N2 | 118.71 (18) | N1—C2—H2 | 119.2 (19) |
| C6—C5—C10 | 123.44 (18) | C3—C2—N1 | 106.9 (2) |
| C10—C5—N2 | 117.85 (18) | C3—C2—H2 | 133.8 (19) |
| H2AA—O2A—H2AB | 104.6 | C19—C20—C25 | 120.1 (2) |
| H12A—C12—H12B | 109.5 | C21—C20—C19 | 118.61 (19) |
| H12A—C12—H12C | 109.5 | C21—C20—C25 | 121.3 (2) |
| H12B—C12—H12C | 109.5 | C22—C23—H23A | 109.5 |
| C6—C12—H12A | 109.5 | C22—C23—H23B | 109.5 |
| C6—C12—H12B | 109.5 | C22—C23—H23C | 109.5 |
| C6—C12—H12C | 109.5 | H23A—C23—H23B | 109.5 |
| N3—C14—H14 | 121.0 (18) | H23A—C23—H23C | 109.5 |
| C15—C14—N3 | 106.8 (2) | H23B—C23—H23C | 109.5 |
| C15—C14—H14 | 132.2 (19) | C7—C8—C13 | 120.2 (2) |
| C17—C18—C24 | 121.48 (18) | C9—C8—C7 | 118.53 (19) |
| C19—C18—C17 | 117.11 (19) | C9—C8—C13 | 121.2 (2) |
| C19—C18—C24 | 121.41 (19) | C10—C9—H9 | 119.0 |
| C17—C22—C23 | 121.64 (19) | C8—C9—C10 | 122.0 (2) |
| C17—C22—C21 | 116.6 (2) | C8—C9—H9 | 119.0 |
| C21—C22—C23 | 121.72 (19) | C8—C13—H13A | 109.5 |
| C5—C6—C12 | 122.16 (18) | C8—C13—H13B | 109.5 |
| C7—C6—C5 | 116.87 (19) | C8—C13—H13C | 109.5 |
| C7—C6—C12 | 120.96 (19) | H13A—C13—H13B | 109.5 |
| C18—C24—H24A | 109.5 | H13A—C13—H13C | 109.5 |
| C18—C24—H24B | 109.5 | H13B—C13—H13C | 109.5 |
| C18—C24—H24C | 109.5 | C22—C21—H21 | 118.9 |
| H24A—C24—H24B | 109.5 | C20—C21—C22 | 122.1 (2) |
| H24A—C24—H24C | 109.5 | C20—C21—H21 | 118.9 |
| H24B—C24—H24C | 109.5 | C20—C25—H25A | 109.5 |
| N2—C3—H3 | 120.2 (17) | C20—C25—H25B | 109.5 |
| C2—C3—N2 | 107.2 (2) | C20—C25—H25C | 109.5 |
| C2—C3—H3 | 132.4 (17) | H25A—C25—H25B | 109.5 |
| C5—C10—C11 | 121.33 (18) | H25A—C25—H25C | 109.5 |
| C9—C10—C5 | 116.98 (19) | H25B—C25—H25C | 109.5 |
| C9—C10—C11 | 121.68 (19) | H2A—O2—H2B | 94 (10) |
| N4—C15—H15 | 122.0 (17) | ||
| N2—C5—C6—C12 | 0.8 (3) | C18—C17—C22—C23 | 179.6 (2) |
| N2—C5—C6—C7 | −178.95 (18) | C18—C17—C22—C21 | −0.1 (3) |
| N2—C5—C10—C11 | −2.9 (3) | C18—C19—C20—C21 | −0.7 (3) |
| N2—C5—C10—C9 | 177.94 (18) | C18—C19—C20—C25 | 178.7 (2) |
| N2—C3—C2—N1 | 0.5 (3) | C22—C17—C18—C24 | −179.1 (2) |
| N3—C14—C15—N4 | 0.3 (3) | C22—C17—C18—C19 | 0.4 (3) |
| N4—C17—C18—C24 | 1.4 (3) | C6—C5—C10—C11 | 176.7 (2) |
| N4—C17—C18—C19 | −178.99 (18) | C6—C5—C10—C9 | −2.5 (3) |
| N4—C17—C22—C23 | −1.0 (3) | C6—C7—C8—C9 | −1.5 (3) |
| N4—C17—C22—C21 | 179.30 (18) | C6—C7—C8—C13 | −179.6 (2) |
| C4—N2—C5—C6 | 101.6 (2) | C24—C18—C19—C20 | 179.5 (2) |
| C4—N2—C5—C10 | −78.8 (3) | C3—N2—C4—N1 | −0.4 (2) |
| C4—N2—C3—C2 | −0.1 (3) | C3—N2—C5—C6 | −77.5 (3) |
| C4—N1—C1—N3 | 116.6 (2) | C3—N2—C5—C10 | 102.1 (3) |
| C4—N1—C2—C3 | −0.8 (3) | C10—C5—C6—C12 | −178.8 (2) |
| C16—N3—C14—C15 | −1.2 (3) | C10—C5—C6—C7 | 1.5 (3) |
| C16—N3—C1—N1 | 110.9 (2) | C15—N4—C16—N3 | −1.4 (2) |
| C16—N4—C17—C18 | −72.6 (3) | C15—N4—C17—C18 | 103.3 (3) |
| C16—N4—C17—C22 | 108.0 (2) | C15—N4—C17—C22 | −76.2 (3) |
| C16—N4—C15—C14 | 0.7 (3) | C1—N3—C16—N4 | 172.30 (18) |
| C17—N4—C16—N3 | 175.03 (18) | C1—N3—C14—C15 | −171.6 (2) |
| C17—N4—C15—C14 | −175.7 (2) | C1—N1—C4—N2 | 171.14 (19) |
| C17—C18—C19—C20 | 0.0 (3) | C1—N1—C2—C3 | −170.8 (2) |
| C17—C22—C21—C20 | −0.6 (3) | C19—C20—C21—C22 | 1.0 (3) |
| C5—N2—C4—N1 | −179.63 (18) | C11—C10—C9—C8 | −177.7 (2) |
| C5—N2—C3—C2 | 179.1 (2) | C7—C8—C9—C10 | 0.4 (3) |
| C5—C6—C7—C8 | 0.6 (3) | C2—N1—C4—N2 | 0.7 (2) |
| C5—C10—C9—C8 | 1.5 (3) | C2—N1—C1—N3 | −74.7 (3) |
| C12—C6—C7—C8 | −179.16 (19) | C23—C22—C21—C20 | 179.7 (2) |
| C14—N3—C16—N4 | 1.6 (2) | C13—C8—C9—C10 | 178.5 (2) |
| C14—N3—C1—N1 | −80.1 (3) | C25—C20—C21—C22 | −178.4 (2) |
1,1'-(Ethane-1,2-diyl)bis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide tetrahydrate (est01041d_0ma). Crystal data
| C26H32N42+·2Br−·4H2O | F(000) = 652 |
| Mr = 632.42 | Dx = 1.461 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 12.4230 (3) Å | Cell parameters from 9565 reflections |
| b = 13.1447 (3) Å | θ = 2.3–44.6° |
| c = 9.2780 (2) Å | µ = 2.86 mm−1 |
| β = 108.379 (1)° | T = 100 K |
| V = 1437.78 (6) Å3 | Prism, clear colourless |
| Z = 2 | 0.15 × 0.15 × 0.05 mm |
1,1'-(Ethane-1,2-diyl)bis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide tetrahydrate (est01041d_0ma). Data collection
| Bruker Venture D8 Kappa diffractometer | 3028 reflections with I > 2σ(I) |
| φ and ω scans | Rint = 0.025 |
| Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 27.1°, θmin = 2.8° |
| Tmin = 0.544, Tmax = 0.750 | h = −15→15 |
| 28199 measured reflections | k = −16→16 |
| 3165 independent reflections | l = −11→11 |
1,1'-(Ethane-1,2-diyl)bis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide tetrahydrate (est01041d_0ma). Refinement
| Refinement on F2 | Primary atom site location: dual |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.018 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.044 | w = 1/[σ2(Fo2) + (0.0151P)2 + 0.8539P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.10 | (Δ/σ)max < 0.001 |
| 3165 reflections | Δρmax = 0.33 e Å−3 |
| 194 parameters | Δρmin = −0.29 e Å−3 |
| 0 restraints |
1,1'-(Ethane-1,2-diyl)bis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide tetrahydrate (est01041d_0ma). Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
1,1'-(Ethane-1,2-diyl)bis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide tetrahydrate (est01041d_0ma). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| Br01 | −0.19328 (2) | 0.01828 (2) | 0.22033 (2) | 0.01558 (5) | |
| O1 | −0.07000 (10) | 0.23627 (9) | 0.37843 (13) | 0.0268 (2) | |
| H1D | −0.1073 (18) | 0.1876 (18) | 0.340 (2) | 0.036 (5)* | |
| H1E | −0.0360 (18) | 0.2528 (17) | 0.326 (3) | 0.039 (6)* | |
| N1 | 0.28176 (8) | 0.55577 (8) | 0.81318 (11) | 0.0117 (2) | |
| N2 | 0.12491 (9) | 0.48768 (8) | 0.67428 (12) | 0.0123 (2) | |
| O2 | 0.04964 (10) | 0.29104 (10) | 0.18398 (14) | 0.0276 (2) | |
| H2A | 0.0823 (18) | 0.3420 (18) | 0.200 (2) | 0.036 (6)* | |
| H2B | 0.016 (2) | 0.2902 (19) | 0.096 (3) | 0.051 (7)* | |
| C12 | 0.71245 (12) | 0.75891 (11) | 0.97675 (18) | 0.0250 (3) | |
| H1A | 0.736386 | 0.766617 | 0.886291 | 0.037* | |
| H1B | 0.768542 | 0.718094 | 1.052694 | 0.037* | |
| H1C | 0.706272 | 0.826152 | 1.019087 | 0.037* | |
| C6 | 0.59853 (11) | 0.70628 (10) | 0.93381 (15) | 0.0166 (3) | |
| C10 | 0.51141 (11) | 0.74146 (10) | 0.98445 (14) | 0.0166 (3) | |
| H3 | 0.523920 | 0.800361 | 1.046905 | 0.020* | |
| C8 | 0.40605 (11) | 0.69326 (10) | 0.94673 (14) | 0.0148 (2) | |
| C9 | 0.39084 (10) | 0.60639 (9) | 0.85679 (13) | 0.0117 (2) | |
| C1 | 0.21894 (10) | 0.53490 (9) | 0.67103 (14) | 0.0126 (2) | |
| H6 | 0.2362 (13) | 0.5503 (13) | 0.5832 (19) | 0.015 (4)* | |
| C7 | 0.03385 (10) | 0.45390 (10) | 0.53959 (14) | 0.0132 (2) | |
| H7A | −0.016689 | 0.406014 | 0.569818 | 0.016* | |
| H7B | 0.066579 | 0.418089 | 0.469255 | 0.016* | |
| C4 | 0.47678 (10) | 0.56704 (10) | 0.80436 (13) | 0.0128 (2) | |
| C5 | 0.57920 (10) | 0.61949 (10) | 0.84337 (14) | 0.0147 (2) | |
| H9 | 0.637928 | 0.595239 | 0.807044 | 0.018* | |
| C13 | 0.46334 (11) | 0.47141 (10) | 0.71025 (16) | 0.0183 (3) | |
| H10A | 0.418593 | 0.486447 | 0.604922 | 0.027* | |
| H10B | 0.424390 | 0.419506 | 0.751255 | 0.027* | |
| H10C | 0.538291 | 0.446186 | 0.713460 | 0.027* | |
| C11 | 0.31461 (12) | 0.73712 (11) | 1.00412 (16) | 0.0225 (3) | |
| H11A | 0.240263 | 0.726481 | 0.927945 | 0.034* | |
| H11B | 0.327739 | 0.810168 | 1.022662 | 0.034* | |
| H11C | 0.316568 | 0.703141 | 1.098930 | 0.034* | |
| C3 | 0.12649 (11) | 0.47941 (11) | 0.82365 (15) | 0.0166 (3) | |
| H12 | 0.0660 (15) | 0.4502 (14) | 0.8469 (19) | 0.023 (4)* | |
| C2 | 0.22470 (11) | 0.52150 (11) | 0.91051 (15) | 0.0162 (3) | |
| H13 | 0.2517 (15) | 0.5293 (13) | 1.016 (2) | 0.022 (4)* |
1,1'-(Ethane-1,2-diyl)bis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide tetrahydrate (est01041d_0ma). Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br01 | 0.01802 (7) | 0.01898 (8) | 0.01231 (7) | −0.00240 (5) | 0.00847 (5) | −0.00121 (5) |
| O1 | 0.0320 (6) | 0.0288 (6) | 0.0207 (5) | −0.0124 (5) | 0.0100 (5) | −0.0066 (5) |
| N1 | 0.0124 (5) | 0.0137 (5) | 0.0093 (5) | 0.0009 (4) | 0.0037 (4) | 0.0012 (4) |
| N2 | 0.0122 (5) | 0.0141 (5) | 0.0108 (5) | −0.0002 (4) | 0.0039 (4) | 0.0020 (4) |
| O2 | 0.0332 (6) | 0.0284 (6) | 0.0201 (6) | −0.0086 (5) | 0.0068 (5) | 0.0010 (5) |
| C12 | 0.0165 (6) | 0.0195 (7) | 0.0338 (8) | −0.0033 (5) | 0.0007 (6) | −0.0009 (6) |
| C6 | 0.0159 (6) | 0.0141 (6) | 0.0158 (6) | −0.0007 (5) | −0.0005 (5) | 0.0031 (5) |
| C10 | 0.0206 (6) | 0.0125 (6) | 0.0133 (6) | 0.0006 (5) | 0.0003 (5) | −0.0027 (5) |
| C8 | 0.0168 (6) | 0.0150 (6) | 0.0112 (5) | 0.0045 (5) | 0.0024 (4) | 0.0008 (5) |
| C9 | 0.0116 (5) | 0.0134 (6) | 0.0087 (5) | −0.0002 (4) | 0.0012 (4) | 0.0018 (4) |
| C1 | 0.0141 (6) | 0.0132 (6) | 0.0109 (6) | −0.0006 (4) | 0.0046 (5) | 0.0007 (4) |
| C7 | 0.0125 (5) | 0.0136 (6) | 0.0120 (5) | −0.0024 (5) | 0.0021 (4) | −0.0005 (5) |
| C4 | 0.0153 (6) | 0.0127 (6) | 0.0094 (5) | 0.0015 (5) | 0.0027 (4) | 0.0008 (5) |
| C5 | 0.0136 (5) | 0.0161 (6) | 0.0140 (6) | 0.0018 (5) | 0.0036 (4) | 0.0020 (5) |
| C13 | 0.0178 (6) | 0.0179 (7) | 0.0200 (6) | −0.0004 (5) | 0.0070 (5) | −0.0070 (5) |
| C11 | 0.0222 (7) | 0.0238 (7) | 0.0219 (7) | 0.0057 (5) | 0.0076 (5) | −0.0074 (6) |
| C3 | 0.0155 (6) | 0.0228 (7) | 0.0127 (6) | 0.0005 (5) | 0.0064 (5) | 0.0050 (5) |
| C2 | 0.0164 (6) | 0.0224 (7) | 0.0109 (6) | 0.0025 (5) | 0.0059 (5) | 0.0036 (5) |
1,1'-(Ethane-1,2-diyl)bis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide tetrahydrate (est01041d_0ma). Geometric parameters (Å, º)
| O1—H1D | 0.80 (2) | C8—C11 | 1.5126 (17) |
| O1—H1E | 0.77 (2) | C9—C4 | 1.4042 (17) |
| N1—C9 | 1.4481 (15) | C1—H6 | 0.928 (17) |
| N1—C1 | 1.3322 (16) | C7—C7i | 1.525 (2) |
| N1—C2 | 1.3872 (16) | C7—H7A | 0.9900 |
| N2—C1 | 1.3314 (16) | C7—H7B | 0.9900 |
| N2—C7 | 1.4653 (16) | C4—C5 | 1.3909 (17) |
| N2—C3 | 1.3841 (16) | C4—C13 | 1.5095 (17) |
| O2—H2A | 0.77 (2) | C5—H9 | 0.9500 |
| O2—H2B | 0.79 (3) | C13—H10A | 0.9800 |
| C12—H1A | 0.9800 | C13—H10B | 0.9800 |
| C12—H1B | 0.9800 | C13—H10C | 0.9800 |
| C12—H1C | 0.9800 | C11—H11A | 0.9800 |
| C12—C6 | 1.5114 (18) | C11—H11B | 0.9800 |
| C6—C10 | 1.3880 (19) | C11—H11C | 0.9800 |
| C6—C5 | 1.3915 (18) | C3—H12 | 0.928 (18) |
| C10—H3 | 0.9500 | C3—C2 | 1.3506 (19) |
| C10—C8 | 1.3959 (18) | C2—H13 | 0.932 (19) |
| C8—C9 | 1.3915 (18) | ||
| H1D—O1—H1E | 107 (2) | N2—C7—H7A | 109.8 |
| C1—N1—C9 | 125.15 (10) | N2—C7—H7B | 109.8 |
| C1—N1—C2 | 108.51 (11) | C7i—C7—H7A | 109.8 |
| C2—N1—C9 | 126.34 (10) | C7i—C7—H7B | 109.8 |
| C1—N2—C7 | 124.67 (11) | H7A—C7—H7B | 108.3 |
| C1—N2—C3 | 108.89 (11) | C9—C4—C13 | 123.34 (11) |
| C3—N2—C7 | 126.41 (11) | C5—C4—C9 | 117.41 (11) |
| H2A—O2—H2B | 106 (2) | C5—C4—C13 | 119.25 (11) |
| H1A—C12—H1B | 109.5 | C6—C5—H9 | 118.9 |
| H1A—C12—H1C | 109.5 | C4—C5—C6 | 122.21 (12) |
| H1B—C12—H1C | 109.5 | C4—C5—H9 | 118.9 |
| C6—C12—H1A | 109.5 | C4—C13—H10A | 109.5 |
| C6—C12—H1B | 109.5 | C4—C13—H10B | 109.5 |
| C6—C12—H1C | 109.5 | C4—C13—H10C | 109.5 |
| C10—C6—C12 | 121.57 (12) | H10A—C13—H10B | 109.5 |
| C10—C6—C5 | 118.20 (12) | H10A—C13—H10C | 109.5 |
| C5—C6—C12 | 120.23 (12) | H10B—C13—H10C | 109.5 |
| C6—C10—H3 | 118.9 | C8—C11—H11A | 109.5 |
| C6—C10—C8 | 122.24 (12) | C8—C11—H11B | 109.5 |
| C8—C10—H3 | 118.9 | C8—C11—H11C | 109.5 |
| C10—C8—C11 | 119.19 (12) | H11A—C11—H11B | 109.5 |
| C9—C8—C10 | 117.53 (12) | H11A—C11—H11C | 109.5 |
| C9—C8—C11 | 123.28 (12) | H11B—C11—H11C | 109.5 |
| C8—C9—N1 | 118.87 (11) | N2—C3—H12 | 120.6 (11) |
| C8—C9—C4 | 122.39 (11) | C2—C3—N2 | 106.87 (11) |
| C4—C9—N1 | 118.73 (11) | C2—C3—H12 | 132.6 (11) |
| N1—C1—H6 | 126.8 (10) | N1—C2—H13 | 123.8 (11) |
| N2—C1—N1 | 108.54 (11) | C3—C2—N1 | 107.19 (11) |
| N2—C1—H6 | 124.6 (10) | C3—C2—H13 | 129.0 (11) |
| N2—C7—C7i | 109.28 (13) | ||
| N1—C9—C4—C5 | 177.64 (10) | C1—N1—C9—C4 | −53.80 (17) |
| N1—C9—C4—C13 | −2.91 (18) | C1—N1—C2—C3 | 0.17 (15) |
| N2—C3—C2—N1 | 0.44 (15) | C1—N2—C7—C7i | −73.94 (17) |
| C12—C6—C10—C8 | −179.51 (12) | C1—N2—C3—C2 | −0.90 (15) |
| C12—C6—C5—C4 | 178.27 (12) | C7—N2—C1—N1 | 179.04 (11) |
| C6—C10—C8—C9 | 0.85 (19) | C7—N2—C3—C2 | −178.88 (12) |
| C6—C10—C8—C11 | −179.00 (12) | C5—C6—C10—C8 | −0.48 (19) |
| C10—C6—C5—C4 | −0.78 (19) | C13—C4—C5—C6 | −177.92 (12) |
| C10—C8—C9—N1 | −178.79 (11) | C11—C8—C9—N1 | 1.04 (18) |
| C10—C8—C9—C4 | 0.00 (18) | C11—C8—C9—C4 | 179.84 (12) |
| C8—C9—C4—C5 | −1.16 (18) | C3—N2—C1—N1 | 1.01 (14) |
| C8—C9—C4—C13 | 178.30 (12) | C3—N2—C7—C7i | 103.73 (16) |
| C9—N1—C1—N2 | 179.64 (11) | C2—N1—C9—C8 | −54.53 (17) |
| C9—N1—C2—C3 | 179.79 (12) | C2—N1—C9—C4 | 126.64 (13) |
| C9—C4—C5—C6 | 1.56 (18) | C2—N1—C1—N2 | −0.73 (14) |
| C1—N1—C9—C8 | 125.04 (13) |
Symmetry code: (i) −x, −y+1, −z+1.
Funding Statement
Funding for this research was provided by: National Science Foundation, Directorate for Mathematical and Physical Sciences (award No. 1847926 to S. Chantal E. Stieber); National Science Foundation, Directorate for Education and Human Resources (scholarship No. 1834186 to Elisa M. Olivas; scholarship No. 1826490 to Emily S. Thompson, Adrian Torres, Briana C. Arreaga, Hector L. Alarcon); U.S. Department of Defense, U.S. Army (award No. W911NF-17-1-0537 to S. Chantal E. Stieber); National Institutes of Health, National Institute of General Medical Sciences (scholarship No. 5R25GM113748-03 to Briana C. Arreaga).
References
- Baker, R. J., Cole, M. L., Jones, C. & Mahon, M. F. (2002). J. Chem. Soc. Dalton Trans. pp. 1992–1996.
- Baron, M., Battistel, E., Tubaro, C., Biffis, A., Armelao, L., Rancan, M. & Graiff, C. (2018). Organometallics, 37, 4213–4223.
- Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2015). Acta Cryst. A71, 59–75. [DOI] [PMC free article] [PubMed]
- Bruker (2016). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
- Cao, C., Zhuang, Y., Zhao, J., Liu, H., Geng, P., Pang, G. & Shi, Y. (2012). Synth. Commun. 42, 380–387.
- Cao, C., Zhuang, Y., Zhao, J., Pang, G. & Shi, Y. (2011). J. Chem. Res. 35, 320–322.
- Cao, C., Zhuang, Y., Zhao, J., Peng, Y., Li, X., Shi, Z., Pang, G. & Shi, Y. (2010). Inorg. Chim. Acta, 363, 3914–3918.
- Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.
- Frey, G. D., Rentzsch, C. F., von Preysing, D., Scherg, T., Mühlhofer, M., Herdtweck, E. & Herrmann, W. A. (2006). J. Organomet. Chem. 691, 5725–5738.
- Gardiner, M. G., Herrmann, W. A., Reisinger, C.-P., Schwarz, J. & Spiegler, M. (1999). J. Organomet. Chem. 572, 239–247.
- Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. [DOI] [PMC free article] [PubMed]
- Guo, J., Lv, L., Wang, X., Cao, C., Pang, G. & Shi, Y. (2013). Inorg. Chem. Commun. 31, 74–78.
- Hiltner, O., Boch, F. J., Brewitz, L., Härter, P., Drees, M., Herdtweck, E., Herrmann, W. A. & Kühn, F. E. (2010). Eur. J. Inorg. Chem. pp. 5284–5293.
- Hock, S. J., Schaper, L.-A., Pöthig, A., Drees, M., Herdtweck, E., Hiltner, O., Herrmann, W. A. & Kühn, F. E. (2014). Dalton Trans. 43, 2259–2271. [DOI] [PubMed]
- Janiak, D. (2000). J. Chem. Soc. Dalton Trans. pp. 3885–3896.
- Lee, H. M., Lu, C. Y., Chen, C. Y. C. W. L., Chen, W. L., Lin, H. C., Chiu, P. L. & Cheng, P. Y. (2004). Tetrahedron, 60, 5807–5825.
- Leung, C. H., Incarvito, C. D. & Crabtree, R. H. (2006). Organometallics, 25, 6099–6107.
- Li, Y., Liu, G., Cao, C., Wang, S., Li, Y., Pang, G. & Shi, Y. (2013). Tetrahedron, 69, 6241–6250.
- Liu, J., Chen, J., Zhao, J., Zhao, Y., Li, L. & Zhang, H. (2003). Synthesis, pp. 2661–2666.
- Meyer, S., Orben, C. M., Demeshko, S., Dechert, S. & Meyer, F. (2011). Organometallics, 30, 6692–6702.
- Rheingold, A. L. (2019). CSD Communication (CCDC 1953445). CCDC, Cambridge, England. https://doi.org/10.5517/ccdc.csd.cc23kqcs
- Riederer, S. K. U., Gigler, P., Högerl, M. P., Herdtweck, E., Bechlars, B., Herrmann, W. A. & Kühn, F. E. (2010). Organometallics, 29, 5681–5692.
- Scherg, T., Schneider, S. K., Frey, G. D., Schwarz, J., Herdtweck, E. & Herrmann, W. A. (2006). Synlett, pp. 2894–2907.
- SciFinder (2022). Chemical Abstracts Service: Colombus, OH, 2010; RN 58-08-2 (accessed March 24, 2022). https://www.cas.org/products/scifinder
- Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8.
- Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.
- Sluijter, S. N., Warsink, S., Lutz, M. & Elsevier, C. J. (2013). Dalton Trans. 42, 7365–7372. [DOI] [PubMed]
- Viciu, M. S., Grasa, G. A. & Nolan, S. P. (2001). Organometallics, 20, 3607–3612.
- Wells, K. D., Ferguson, M. J., McDonald, R. & Cowie, M. (2008). Organometallics, 27, 691–703.
- Wierenga, T. S., Vanston, C. R., Ariafard, A., Gardiner, M. G. & Ho, C. C. (2019). Organometallics, 38, 3032–3038.
- Yang, L., Zhao, J., Li, Y., Ge, K., Zhuang, Y., Cao, C. & Shi, Y. (2012). Inorg. Chem. Commun. 22, 33–36.
- Yang, W., Gou, G.-Z., Wang, Y. & Fu, W.-F. (2013). RSC Adv. 3, 6334–6338.
- Zamora, M. T., Ferguson, M. J., McDonald, R. & Cowie, M. (2009). Dalton Trans. pp. 7269–7287 [DOI] [PubMed]
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) sces01006_0m, est01043_0m, at01019_0ma, est01041d_0ma, global. DOI: 10.1107/S2056989022008003/mw2188sup1.cif
Structure factors: contains datablock(s) sces01006_0m. DOI: 10.1107/S2056989022008003/mw2188sces01006_0msup2.hkl
Structure factors: contains datablock(s) est01043_0m. DOI: 10.1107/S2056989022008003/mw2188est01043_0msup3.hkl
Structure factors: contains datablock(s) at01019_0ma. DOI: 10.1107/S2056989022008003/mw2188at01019_0masup4.hkl
Structure factors: contains datablock(s) est01041d_0ma. DOI: 10.1107/S2056989022008003/mw2188est01041d_0masup5.hkl
Supporting information file. DOI: 10.1107/S2056989022008003/mw2188sces01006_0msup6.cml
Supporting information file. DOI: 10.1107/S2056989022008003/mw2188est01043_0msup7.cml
Supporting information file. DOI: 10.1107/S2056989022008003/mw2188at01019_0masup8.cml
Supporting information file. DOI: 10.1107/S2056989022008003/mw2188est01041d_0masup9.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report