The title structure consists of 3-aminopyridinium cations and 1′-carboxyferrocene-1-carboxylate monoanions held together by N—H⋯O and O—H⋯O hydrogen bonds.
Keywords: crystal structure; ferrocene-1,1′-dicarboxylic acid; ferrocene conformation
Abstract
The structure of the title salt, (C5H7N2)[Fe(C6H4O2)(C6H5O2)], consists of 3-aminopyridinium cations and 1′-carboxyferrocene-1-carboxylate monoanions. The ferrocenyl moiety of the anion adopts a typical sandwich structure, with Fe—C distances in the range 2.0270 (15)–2.0568 (17) Å. The anion possesses an eclipsed conformation, with the torsion angle φ (Csubst—Cpcent—Cpcent— Csubst) equal to 66.0°. The conformations of other 1′-carboxyferrocene-1-carboxylate monoanions are compared and analyzed on the basis of literature data.
Chemical context
The idea behind this research was to use ferrocenedicarboxylic acid as a dianionic building block in supramolecular polymer and conventional polymer design (Amer et al., 2013 ▸; Sun et al., 2016 ▸; Zheng et al., 2016 ▸).
We tried to apply the trio of available aminopyridines, namely 2-, 3- and 4-aminopyridine, as basic counterparts to ferrocenedicarboxylic diacid. One of the ideas was to check the possibility of obtaining gels with a supramolecular arrangement of the constituents in alcoholic media. All those reactions were carried out in a 1:2 ratio of acid–amine in order to exploit both carboxylic acid groups of the diacid. The experiments revealed, however, that while in cases of 2- and 4-aminopyridine, only amorphous powders could be obtained, the reaction of 3-aminopyridine led to a crystalline salt, 3-aminopyridinium 1′-carboxyferrocene-1-carboxylate, (1), but with a 1:1 composition.
Structural commentary
The crystal structure of (1) consists of one 3-aminopyridinium cation and one 1′-carboxyferrocene-1-carboxylate monoanion (Fig. 1 ▸). In the cation, the pyridine N atom is protonated. The ferrocenyl moieties adopt the characteristic sandwich structure, with typical Fe—C distances in the range 2.0270 (15)–2.0568 (17) Å (Table 1 ▸). The FeII atom is slightly (∼0.01 Å) shifted towards the substituted C11 and C21 atoms. The C16—O bond lengths within the carboxylate anion are almost equal [1.2604 (19) and 1.2636 (19) Å], whereas, in contrast, they differ greatly within the carboxylic acid group, with C26=O22 = 1.2128 (19) Å and C26—O21 = 1.326 (2) Å, the latter involving the OH group. The planes of the cyclopentadienyl (Cp) rings are almost parallel to the planes of the corresponding carboxy/carboxylate groups, with O—C—C—C torsion angles less than 13°. The conformation of 1,1′-disubstituted ferrocenes is described by the torsion angle Csubst—Cpcent—Cpcent—Csubst, where Csubst stands for a ferrocene C atom with an additional bonding partner and Cpcent for the centre of gravity of the C atoms of the ring; this angle is hereafter referred to as φ. In (1), the anion possesses an eclipsed conformation with φ = 66.0° (ideal value 72°) (Fig. 2 ▸).
Figure 1.
The structures of the molecular components in (1). Displacement ellipsoids are shown at the 50% probability level. Hydrogen bonding is shown as dashed lines.
Table 1. Selected geometric parameters (Å, °).
| Fe1—C21 | 2.0270 (15) | Fe1—C24 | 2.0515 (16) |
| Fe1—C15 | 2.0341 (16) | Fe1—C13 | 2.0517 (18) |
| Fe1—C11 | 2.0359 (16) | Fe1—C23 | 2.0568 (17) |
| Fe1—C22 | 2.0414 (17) | O11—C16 | 1.2604 (19) |
| Fe1—C25 | 2.0451 (16) | O12—C16 | 1.2636 (19) |
| Fe1—C12 | 2.0459 (17) | O21—C26 | 1.326 (2) |
| Fe1—C14 | 2.0496 (17) | O22—C26 | 1.2128 (19) |
| C12—C11—C16—O11 | 14.1 (2) | C25—C21—C26—O21 | 10.2 (2) |
Figure 2.
The four known conformations of the (HO2C-η5-C5H4)Fe(η5-C5H4—CO2 −) anion.
Supramolecular features
In the title crystal, adjacent cationic and anionic units are combined into a layered arrangement parallel to (100) by charge-supported NH⋯−O2C hydrogen bonds of medium–strong-to-weak nature and of CO2H⋯−O2C hydrogen bonds of strong nature (Table 2 ▸ and Fig. 3 ▸).
Table 2. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| N1—H11⋯O12 | 0.87 (3) | 2.08 (3) | 2.918 (2) | 161 (2) |
| N1—H10⋯O11i | 0.84 (3) | 2.07 (3) | 2.906 (2) | 171 (3) |
| N2—H2⋯O11ii | 0.89 (2) | 1.79 (2) | 2.675 (2) | 177 (2) |
| O21—H21⋯O12iii | 0.81 (2) | 1.77 (2) | 2.5621 (16) | 164 (2) |
Symmetry codes: (i) 
; (ii) 
; (iii) 
.
Figure 3.
The formation of hydrogen-bonded layers parallel to (100) in the crystal. Hydrogen bonds are drawn as dashed lines.
Database survey
The Cambridge Structural Database (CSD, Version 5.38 of February 2017; Groom et al., 2016 ▸) contains data for 11 structures comprising (HO2C-η5-C5H4)Fe(η5-C5H4-CO2 −) units from 14 crystallographically independent monoanions. Among these 14 fragments, three adopt a trans-staggered conformation, with m = 5 (as defined in Zakaria et al., 2002 ▸). Others adopt three eclipsed conformations with m = 0, 2 and 4 (3, 4 and 4 cases, respectively; Fig. 2 ▸). Surprisingly, two staggered conformations with m = 1 and 3 (Fig. 4 ▸) were not observed.
Figure 4.
Unobserved staggered conformations in the structures containing a 1′-carboxyferrocene-1-carboxylate acid monoanion.
Synthesis and crystallization
Preparation of ferrocene-1,1′-dicarboxylic acid (Gao et al., 2009 ▸)
An 8% NaOCl aqueous solution (100 ml) was added dropwise to 1,1′-diacetylferrocene (5.37 g, 20 mmol) under stirring at a temperature of 317–320 K. The solution was stirred at this temperature for 2 h. Three more 25 ml portions of NaOCl solution were added every 2 h. The reaction mixture was filtered and acidified to a pH of 1.1 with 10% hydrochloric acid and cooled to 277 K overnight. The yellow precipitate which formed was filtered off and recrystallized from ethanol to give an orange microcrystalline powder (yield 2.18 g, 40%).
Preparation of 3-aminopyridinium 1′-carboxyferrocene-1-carboxylate, (1)
Ferrocene-1,1′-dicarboxylic acid (50 mg, 0.18 mmol) was dissolved in methanol and mixed with a methanolic solution of 3-aminopyridine (33.8 mg, 0.36 mmol). The reaction mixture was filtered and subjected to slow evaporation at room temperature to give orange crystals of the title salt.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. All H atoms were located from a difference Fourier synthesis and refined isotropically without constraints or restraints.
Table 3. Experimental details.
| Crystal data | |
| Chemical formula | (C5H7N2)[Fe(C6H4O2)(C6H5O2)] |
| M r | 368.17 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 150 |
| a, b, c (Å) | 13.2246 (10), 10.3040 (8), 11.7402 (9) |
| β (°) | 101.703 (1) |
| V (Å3) | 1566.5 (2) |
| Z | 4 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.99 |
| Crystal size (mm) | 0.22 × 0.20 × 0.02 |
| Data collection | |
| Diffractometer | Bruker SMART APEXII |
| Absorption correction | Multi-scan (SADABS; Bruker, 2008 ▸) |
| T min, T max | 0.812, 0.981 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 14616, 3409, 2812 |
| R int | 0.026 |
| (sin θ/λ)max (Å−1) | 0.638 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.027, 0.073, 1.03 |
| No. of reflections | 3409 |
| No. of parameters | 281 |
| H-atom treatment | All H-atom parameters refined |
| Δρmax, Δρmin (e Å−3) | 0.37, −0.23 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017007058/wm5388sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017007058/wm5388Isup2.hkl
CCDC reference: 1444115
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
X-ray diffraction studies were performed at the Centre of Shared Equipment of IGIC RAS.
supplementary crystallographic information
Crystal data
| (C5H7N2)[Fe(C6H4O2)(C6H5O2)] | F(000) = 760 |
| Mr = 368.17 | Dx = 1.561 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 5525 reflections |
| a = 13.2246 (10) Å | θ = 2.5–30.1° |
| b = 10.3040 (8) Å | µ = 0.99 mm−1 |
| c = 11.7402 (9) Å | T = 150 K |
| β = 101.703 (1)° | Plate, orange |
| V = 1566.5 (2) Å3 | 0.22 × 0.20 × 0.02 mm |
| Z = 4 |
Data collection
| Bruker SMART APEXII diffractometer | 3409 independent reflections |
| Radiation source: fine-focus sealed tube | 2812 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.026 |
| ω scans | θmax = 27.0°, θmin = 2.5° |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −16→16 |
| Tmin = 0.812, Tmax = 0.981 | k = −13→13 |
| 14616 measured reflections | l = −14→14 |
Refinement
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.027 | Hydrogen site location: difference Fourier map |
| wR(F2) = 0.073 | All H-atom parameters refined |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.0395P)2 + 0.5357P] where P = (Fo2 + 2Fc2)/3 |
| 3409 reflections | (Δ/σ)max = 0.001 |
| 281 parameters | Δρmax = 0.37 e Å−3 |
| 0 restraints | Δρmin = −0.23 e Å−3 |
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. |
| Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| Fe1 | 0.374096 (17) | 0.50216 (2) | 0.671077 (19) | 0.01937 (8) | |
| O11 | 0.09010 (9) | 0.36772 (12) | 0.61033 (10) | 0.0311 (3) | |
| O12 | 0.16389 (8) | 0.34091 (11) | 0.45865 (10) | 0.0257 (3) | |
| O21 | 0.30237 (9) | 0.21837 (12) | 0.84337 (11) | 0.0277 (3) | |
| O22 | 0.35822 (10) | 0.38212 (12) | 0.96535 (10) | 0.0291 (3) | |
| C11 | 0.22302 (12) | 0.51243 (15) | 0.58942 (14) | 0.0228 (3) | |
| C12 | 0.23757 (13) | 0.57474 (17) | 0.70015 (15) | 0.0272 (4) | |
| C13 | 0.30979 (14) | 0.67653 (17) | 0.70209 (17) | 0.0321 (4) | |
| C14 | 0.34025 (14) | 0.67928 (17) | 0.59322 (17) | 0.0311 (4) | |
| C15 | 0.28745 (13) | 0.57799 (16) | 0.52300 (15) | 0.0254 (4) | |
| C16 | 0.15563 (12) | 0.39937 (16) | 0.55094 (13) | 0.0219 (3) | |
| C21 | 0.42157 (12) | 0.36219 (15) | 0.79136 (13) | 0.0210 (3) | |
| C22 | 0.49364 (13) | 0.46741 (16) | 0.80757 (15) | 0.0234 (3) | |
| C23 | 0.53193 (13) | 0.48018 (16) | 0.70361 (16) | 0.0255 (4) | |
| C24 | 0.48348 (13) | 0.38427 (16) | 0.62345 (15) | 0.0248 (3) | |
| C25 | 0.41579 (12) | 0.31077 (15) | 0.67722 (14) | 0.0214 (3) | |
| C26 | 0.35821 (12) | 0.32398 (15) | 0.87553 (13) | 0.0212 (3) | |
| H12 | 0.2043 (15) | 0.5490 (19) | 0.7600 (17) | 0.029 (5)* | |
| H13 | 0.3336 (15) | 0.727 (2) | 0.7642 (18) | 0.037 (5)* | |
| H14 | 0.3905 (16) | 0.737 (2) | 0.5730 (17) | 0.037 (5)* | |
| H15 | 0.2915 (15) | 0.555 (2) | 0.4446 (18) | 0.035 (5)* | |
| H21 | 0.2655 (18) | 0.207 (2) | 0.8897 (19) | 0.048 (7)* | |
| H22 | 0.5128 (15) | 0.5176 (18) | 0.8710 (18) | 0.030 (5)* | |
| H23 | 0.5770 (15) | 0.543 (2) | 0.6893 (16) | 0.030 (5)* | |
| H24 | 0.4920 (14) | 0.3759 (18) | 0.5428 (18) | 0.030 (5)* | |
| H25 | 0.3712 (14) | 0.2455 (18) | 0.6409 (15) | 0.023 (5)* | |
| N1 | 0.04432 (16) | 0.4901 (2) | 0.26631 (16) | 0.0457 (5) | |
| N2 | 0.03611 (12) | 0.69407 (15) | 0.01507 (13) | 0.0281 (3) | |
| C1 | 0.01186 (13) | 0.64261 (17) | 0.11058 (15) | 0.0288 (4) | |
| C2 | 0.07267 (14) | 0.54610 (19) | 0.17299 (15) | 0.0303 (4) | |
| C3 | 0.16037 (14) | 0.50701 (18) | 0.13113 (17) | 0.0324 (4) | |
| C4 | 0.18291 (14) | 0.56395 (19) | 0.03310 (17) | 0.0340 (4) | |
| C5 | 0.11970 (14) | 0.65834 (19) | −0.02507 (17) | 0.0321 (4) | |
| H1 | −0.0489 (15) | 0.6761 (19) | 0.1314 (16) | 0.030 (5)* | |
| H2 | −0.0059 (17) | 0.753 (2) | −0.0242 (19) | 0.044 (6)* | |
| H3 | 0.2027 (15) | 0.446 (2) | 0.1703 (17) | 0.033 (5)* | |
| H4 | 0.2411 (17) | 0.538 (2) | 0.0051 (19) | 0.041 (6)* | |
| H5 | 0.1301 (16) | 0.700 (2) | −0.0915 (18) | 0.039 (6)* | |
| H10 | 0.000 (2) | 0.529 (3) | 0.296 (2) | 0.058 (8)* | |
| H11 | 0.0872 (19) | 0.439 (2) | 0.311 (2) | 0.049 (6)* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Fe1 | 0.01955 (13) | 0.01805 (13) | 0.02010 (13) | −0.00017 (9) | 0.00306 (9) | 0.00002 (9) |
| O11 | 0.0287 (6) | 0.0375 (7) | 0.0308 (6) | −0.0076 (5) | 0.0146 (5) | −0.0072 (5) |
| O12 | 0.0222 (6) | 0.0317 (6) | 0.0240 (6) | −0.0020 (5) | 0.0063 (5) | −0.0074 (5) |
| O21 | 0.0306 (6) | 0.0273 (6) | 0.0291 (6) | −0.0060 (5) | 0.0153 (5) | −0.0031 (5) |
| O22 | 0.0395 (7) | 0.0296 (6) | 0.0189 (6) | −0.0017 (5) | 0.0073 (5) | −0.0024 (5) |
| C11 | 0.0204 (7) | 0.0244 (8) | 0.0233 (8) | 0.0044 (6) | 0.0035 (6) | −0.0004 (6) |
| C12 | 0.0243 (8) | 0.0291 (9) | 0.0281 (9) | 0.0045 (7) | 0.0051 (7) | −0.0057 (7) |
| C13 | 0.0309 (9) | 0.0233 (9) | 0.0389 (10) | 0.0050 (7) | −0.0008 (8) | −0.0088 (8) |
| C14 | 0.0290 (9) | 0.0203 (8) | 0.0417 (10) | 0.0020 (7) | 0.0015 (8) | 0.0071 (8) |
| C15 | 0.0242 (8) | 0.0253 (8) | 0.0255 (9) | 0.0020 (7) | 0.0020 (7) | 0.0059 (7) |
| C16 | 0.0182 (7) | 0.0256 (8) | 0.0211 (8) | 0.0037 (6) | 0.0026 (6) | 0.0003 (6) |
| C21 | 0.0218 (7) | 0.0202 (8) | 0.0202 (8) | 0.0020 (6) | 0.0026 (6) | 0.0015 (6) |
| C22 | 0.0214 (8) | 0.0225 (8) | 0.0242 (8) | −0.0007 (6) | −0.0004 (6) | 0.0003 (7) |
| C23 | 0.0204 (8) | 0.0245 (9) | 0.0316 (9) | −0.0005 (6) | 0.0053 (7) | 0.0045 (7) |
| C24 | 0.0243 (8) | 0.0259 (8) | 0.0256 (9) | 0.0040 (7) | 0.0083 (7) | 0.0019 (7) |
| C25 | 0.0233 (8) | 0.0186 (8) | 0.0226 (8) | 0.0028 (6) | 0.0050 (6) | −0.0008 (6) |
| C26 | 0.0221 (8) | 0.0207 (7) | 0.0199 (8) | 0.0043 (6) | 0.0021 (6) | 0.0034 (6) |
| N1 | 0.0483 (11) | 0.0575 (12) | 0.0334 (9) | 0.0270 (9) | 0.0135 (8) | 0.0118 (9) |
| N2 | 0.0255 (7) | 0.0261 (8) | 0.0313 (8) | 0.0006 (6) | 0.0024 (6) | −0.0017 (6) |
| C1 | 0.0254 (9) | 0.0313 (9) | 0.0292 (9) | 0.0046 (7) | 0.0047 (7) | −0.0042 (7) |
| C2 | 0.0296 (9) | 0.0342 (9) | 0.0260 (9) | 0.0049 (8) | 0.0028 (7) | −0.0042 (7) |
| C3 | 0.0280 (9) | 0.0323 (10) | 0.0343 (10) | 0.0078 (8) | 0.0001 (8) | −0.0053 (8) |
| C4 | 0.0243 (9) | 0.0366 (10) | 0.0422 (11) | 0.0010 (8) | 0.0096 (8) | −0.0093 (9) |
| C5 | 0.0295 (9) | 0.0324 (10) | 0.0356 (10) | −0.0045 (8) | 0.0092 (8) | −0.0060 (8) |
Geometric parameters (Å, º)
| Fe1—C21 | 2.0270 (15) | C21—C25 | 1.429 (2) |
| Fe1—C15 | 2.0341 (16) | C21—C22 | 1.431 (2) |
| Fe1—C11 | 2.0359 (16) | C21—C26 | 1.473 (2) |
| Fe1—C22 | 2.0414 (17) | C22—C23 | 1.419 (2) |
| Fe1—C25 | 2.0451 (16) | C22—H22 | 0.90 (2) |
| Fe1—C12 | 2.0459 (17) | C23—C24 | 1.424 (2) |
| Fe1—C14 | 2.0496 (17) | C23—H23 | 0.92 (2) |
| Fe1—C24 | 2.0515 (16) | C24—C25 | 1.415 (2) |
| Fe1—C13 | 2.0517 (18) | C24—H24 | 0.98 (2) |
| Fe1—C23 | 2.0568 (17) | C25—H25 | 0.938 (19) |
| O11—C16 | 1.2604 (19) | N1—C2 | 1.357 (3) |
| O12—C16 | 1.2636 (19) | N1—H10 | 0.84 (3) |
| O21—C26 | 1.326 (2) | N1—H11 | 0.87 (3) |
| O21—H21 | 0.81 (2) | N2—C1 | 1.337 (2) |
| O22—C26 | 1.2128 (19) | N2—C5 | 1.338 (2) |
| C11—C12 | 1.427 (2) | N2—H2 | 0.89 (2) |
| C11—C15 | 1.435 (2) | C1—C2 | 1.391 (3) |
| C11—C16 | 1.481 (2) | C1—H1 | 0.95 (2) |
| C12—C13 | 1.416 (3) | C2—C3 | 1.407 (3) |
| C12—H12 | 0.94 (2) | C3—C4 | 1.377 (3) |
| C13—C14 | 1.416 (3) | C3—H3 | 0.91 (2) |
| C13—H13 | 0.90 (2) | C4—C5 | 1.371 (3) |
| C14—C15 | 1.422 (3) | C4—H4 | 0.94 (2) |
| C14—H14 | 0.96 (2) | C5—H5 | 0.92 (2) |
| C15—H15 | 0.96 (2) | ||
| C21—Fe1—C15 | 155.49 (7) | C13—C14—H14 | 125.0 (12) |
| C21—Fe1—C11 | 120.05 (6) | C15—C14—H14 | 126.7 (12) |
| C15—Fe1—C11 | 41.30 (7) | Fe1—C14—H14 | 124.5 (12) |
| C21—Fe1—C22 | 41.17 (6) | C14—C15—C11 | 107.83 (15) |
| C15—Fe1—C22 | 161.90 (7) | C14—C15—Fe1 | 70.20 (10) |
| C11—Fe1—C22 | 155.29 (7) | C11—C15—Fe1 | 69.42 (9) |
| C21—Fe1—C25 | 41.07 (6) | C14—C15—H15 | 128.3 (12) |
| C15—Fe1—C25 | 120.11 (7) | C11—C15—H15 | 123.9 (12) |
| C11—Fe1—C25 | 107.37 (6) | Fe1—C15—H15 | 126.2 (12) |
| C22—Fe1—C25 | 69.07 (7) | O11—C16—O12 | 122.66 (15) |
| C21—Fe1—C12 | 107.64 (7) | O11—C16—C11 | 118.27 (14) |
| C15—Fe1—C12 | 68.83 (7) | O12—C16—C11 | 119.03 (14) |
| C11—Fe1—C12 | 40.94 (6) | C25—C21—C22 | 108.26 (14) |
| C22—Fe1—C12 | 120.15 (7) | C25—C21—C26 | 126.92 (15) |
| C25—Fe1—C12 | 125.97 (7) | C22—C21—C26 | 124.58 (14) |
| C21—Fe1—C14 | 162.37 (7) | C25—C21—Fe1 | 70.14 (9) |
| C15—Fe1—C14 | 40.76 (7) | C22—C21—Fe1 | 69.95 (9) |
| C11—Fe1—C14 | 68.84 (7) | C26—C21—Fe1 | 121.30 (11) |
| C22—Fe1—C14 | 124.79 (7) | C23—C22—C21 | 107.47 (15) |
| C25—Fe1—C14 | 155.14 (7) | C23—C22—Fe1 | 70.32 (10) |
| C12—Fe1—C14 | 68.20 (8) | C21—C22—Fe1 | 68.87 (9) |
| C21—Fe1—C24 | 68.45 (6) | C23—C22—H22 | 124.7 (13) |
| C15—Fe1—C24 | 107.50 (7) | C21—C22—H22 | 127.9 (13) |
| C11—Fe1—C24 | 125.54 (7) | Fe1—C22—H22 | 126.3 (13) |
| C22—Fe1—C24 | 68.50 (7) | C22—C23—C24 | 108.23 (15) |
| C25—Fe1—C24 | 40.42 (6) | C22—C23—Fe1 | 69.16 (9) |
| C12—Fe1—C24 | 163.10 (7) | C24—C23—Fe1 | 69.52 (9) |
| C14—Fe1—C24 | 120.53 (7) | C22—C23—H23 | 125.5 (12) |
| C21—Fe1—C13 | 125.48 (7) | C24—C23—H23 | 126.2 (12) |
| C15—Fe1—C13 | 68.49 (7) | Fe1—C23—H23 | 124.0 (12) |
| C11—Fe1—C13 | 68.63 (7) | C25—C24—C23 | 108.49 (15) |
| C22—Fe1—C13 | 107.28 (7) | C25—C24—Fe1 | 69.55 (9) |
| C25—Fe1—C13 | 163.08 (7) | C23—C24—Fe1 | 69.92 (10) |
| C12—Fe1—C13 | 40.42 (7) | C25—C24—H24 | 126.2 (11) |
| C14—Fe1—C13 | 40.40 (8) | C23—C24—H24 | 125.1 (11) |
| C24—Fe1—C13 | 155.15 (7) | Fe1—C24—H24 | 122.7 (11) |
| C21—Fe1—C23 | 68.47 (6) | C24—C25—C21 | 107.56 (14) |
| C15—Fe1—C23 | 125.14 (7) | C24—C25—Fe1 | 70.04 (9) |
| C11—Fe1—C23 | 162.78 (7) | C21—C25—Fe1 | 68.79 (9) |
| C22—Fe1—C23 | 40.52 (7) | C24—C25—H25 | 125.2 (11) |
| C25—Fe1—C23 | 68.35 (7) | C21—C25—H25 | 127.0 (11) |
| C12—Fe1—C23 | 154.95 (7) | Fe1—C25—H25 | 122.4 (11) |
| C14—Fe1—C23 | 107.61 (7) | O22—C26—O21 | 123.69 (15) |
| C24—Fe1—C23 | 40.57 (7) | O22—C26—C21 | 123.47 (15) |
| C13—Fe1—C23 | 120.33 (7) | O21—C26—C21 | 112.83 (14) |
| C26—O21—H21 | 107.7 (17) | C2—N1—H10 | 117.7 (18) |
| C12—C11—C15 | 107.33 (15) | C2—N1—H11 | 119.6 (15) |
| C12—C11—C16 | 126.40 (15) | H10—N1—H11 | 117 (2) |
| C15—C11—C16 | 126.26 (15) | C1—N2—C5 | 122.83 (17) |
| C12—C11—Fe1 | 69.91 (9) | C1—N2—H2 | 118.5 (14) |
| C15—C11—Fe1 | 69.29 (9) | C5—N2—H2 | 118.7 (14) |
| C16—C11—Fe1 | 125.12 (11) | N2—C1—C2 | 120.94 (16) |
| C13—C12—C11 | 108.29 (16) | N2—C1—H1 | 115.5 (11) |
| C13—C12—Fe1 | 70.01 (10) | C2—C1—H1 | 123.6 (11) |
| C11—C12—Fe1 | 69.15 (9) | N1—C2—C1 | 120.30 (17) |
| C13—C12—H12 | 127.9 (12) | N1—C2—C3 | 122.88 (18) |
| C11—C12—H12 | 123.8 (12) | C1—C2—C3 | 116.76 (17) |
| Fe1—C12—H12 | 125.8 (12) | C4—C3—C2 | 120.22 (18) |
| C12—C13—C14 | 108.35 (16) | C4—C3—H3 | 120.3 (13) |
| C12—C13—Fe1 | 69.57 (10) | C2—C3—H3 | 119.4 (13) |
| C14—C13—Fe1 | 69.72 (10) | C5—C4—C3 | 120.33 (17) |
| C12—C13—H13 | 124.4 (13) | C5—C4—H4 | 119.4 (14) |
| C14—C13—H13 | 127.2 (13) | C3—C4—H4 | 120.3 (14) |
| Fe1—C13—H13 | 124.1 (13) | N2—C5—C4 | 118.91 (18) |
| C13—C14—C15 | 108.20 (16) | N2—C5—H5 | 116.4 (13) |
| C13—C14—Fe1 | 69.88 (10) | C4—C5—H5 | 124.7 (13) |
| C15—C14—Fe1 | 69.04 (10) | ||
| C21—Fe1—C11—C12 | 82.37 (11) | C14—Fe1—C21—C25 | −161.7 (2) |
| C15—Fe1—C11—C12 | −118.52 (14) | C24—Fe1—C21—C25 | −37.55 (10) |
| C22—Fe1—C11—C12 | 47.8 (2) | C13—Fe1—C21—C25 | 166.01 (10) |
| C25—Fe1—C11—C12 | 125.35 (10) | C23—Fe1—C21—C25 | −81.32 (10) |
| C14—Fe1—C11—C12 | −80.70 (11) | C15—Fe1—C21—C22 | 166.56 (15) |
| C24—Fe1—C11—C12 | 166.16 (10) | C11—Fe1—C21—C22 | −158.87 (10) |
| C13—Fe1—C11—C12 | −37.20 (11) | C25—Fe1—C21—C22 | 119.10 (14) |
| C23—Fe1—C11—C12 | −161.9 (2) | C12—Fe1—C21—C22 | −115.91 (10) |
| C21—Fe1—C11—C15 | −159.11 (10) | C14—Fe1—C21—C22 | −42.6 (3) |
| C22—Fe1—C11—C15 | 166.30 (15) | C24—Fe1—C21—C22 | 81.55 (10) |
| C25—Fe1—C11—C15 | −116.13 (10) | C13—Fe1—C21—C22 | −74.89 (12) |
| C12—Fe1—C11—C15 | 118.52 (14) | C23—Fe1—C21—C22 | 37.79 (10) |
| C14—Fe1—C11—C15 | 37.82 (10) | C15—Fe1—C21—C26 | −74.4 (2) |
| C24—Fe1—C11—C15 | −75.32 (12) | C11—Fe1—C21—C26 | −39.84 (15) |
| C13—Fe1—C11—C15 | 81.31 (11) | C22—Fe1—C21—C26 | 119.03 (17) |
| C23—Fe1—C11—C15 | −43.4 (3) | C25—Fe1—C21—C26 | −121.87 (17) |
| C21—Fe1—C11—C16 | −38.63 (16) | C12—Fe1—C21—C26 | 3.12 (14) |
| C15—Fe1—C11—C16 | 120.48 (18) | C14—Fe1—C21—C26 | 76.5 (3) |
| C22—Fe1—C11—C16 | −73.2 (2) | C24—Fe1—C21—C26 | −159.42 (15) |
| C25—Fe1—C11—C16 | 4.35 (15) | C13—Fe1—C21—C26 | 44.14 (16) |
| C12—Fe1—C11—C16 | −121.01 (18) | C23—Fe1—C21—C26 | 156.82 (15) |
| C14—Fe1—C11—C16 | 158.29 (16) | C25—C21—C22—C23 | −0.07 (18) |
| C24—Fe1—C11—C16 | 45.16 (17) | C26—C21—C22—C23 | −174.85 (14) |
| C13—Fe1—C11—C16 | −158.21 (16) | Fe1—C21—C22—C23 | −60.00 (11) |
| C23—Fe1—C11—C16 | 77.1 (3) | C25—C21—C22—Fe1 | 59.92 (11) |
| C15—C11—C12—C13 | −0.16 (19) | C26—C21—C22—Fe1 | −114.85 (15) |
| C16—C11—C12—C13 | 178.69 (15) | C21—Fe1—C22—C23 | 118.68 (14) |
| Fe1—C11—C12—C13 | 59.27 (12) | C15—Fe1—C22—C23 | −43.2 (3) |
| C15—C11—C12—Fe1 | −59.42 (11) | C11—Fe1—C22—C23 | 166.96 (14) |
| C16—C11—C12—Fe1 | 119.42 (16) | C25—Fe1—C22—C23 | 80.76 (10) |
| C21—Fe1—C12—C13 | 124.47 (11) | C12—Fe1—C22—C23 | −158.90 (10) |
| C15—Fe1—C12—C13 | −81.27 (12) | C14—Fe1—C22—C23 | −75.76 (12) |
| C11—Fe1—C12—C13 | −119.72 (15) | C24—Fe1—C22—C23 | 37.27 (10) |
| C22—Fe1—C12—C13 | 81.25 (13) | C13—Fe1—C22—C23 | −116.74 (11) |
| C25—Fe1—C12—C13 | 166.16 (11) | C15—Fe1—C22—C21 | −161.9 (2) |
| C14—Fe1—C12—C13 | −37.32 (11) | C11—Fe1—C22—C21 | 48.28 (19) |
| C24—Fe1—C12—C13 | −161.8 (2) | C25—Fe1—C22—C21 | −37.92 (9) |
| C23—Fe1—C12—C13 | 47.7 (2) | C12—Fe1—C22—C21 | 82.42 (11) |
| C21—Fe1—C12—C11 | −115.81 (10) | C14—Fe1—C22—C21 | 165.56 (10) |
| C15—Fe1—C12—C11 | 38.45 (10) | C24—Fe1—C22—C21 | −81.42 (10) |
| C22—Fe1—C12—C11 | −159.02 (10) | C13—Fe1—C22—C21 | 124.58 (10) |
| C25—Fe1—C12—C11 | −74.12 (12) | C23—Fe1—C22—C21 | −118.68 (14) |
| C14—Fe1—C12—C11 | 82.40 (11) | C21—C22—C23—C24 | 0.38 (18) |
| C24—Fe1—C12—C11 | −42.0 (3) | Fe1—C22—C23—C24 | −58.70 (12) |
| C13—Fe1—C12—C11 | 119.72 (15) | C21—C22—C23—Fe1 | 59.08 (11) |
| C23—Fe1—C12—C11 | 167.44 (14) | C21—Fe1—C23—C22 | −38.38 (10) |
| C11—C12—C13—C14 | 0.4 (2) | C15—Fe1—C23—C22 | 164.92 (10) |
| Fe1—C12—C13—C14 | 59.12 (12) | C11—Fe1—C23—C22 | −161.4 (2) |
| C11—C12—C13—Fe1 | −58.73 (12) | C25—Fe1—C23—C22 | −82.70 (10) |
| C21—Fe1—C13—C12 | −74.75 (13) | C12—Fe1—C23—C22 | 47.3 (2) |
| C15—Fe1—C13—C12 | 82.19 (11) | C14—Fe1—C23—C22 | 123.37 (10) |
| C11—Fe1—C13—C12 | 37.67 (10) | C24—Fe1—C23—C22 | −119.96 (14) |
| C22—Fe1—C13—C12 | −116.48 (11) | C13—Fe1—C23—C22 | 81.10 (12) |
| C25—Fe1—C13—C12 | −41.7 (3) | C21—Fe1—C23—C24 | 81.58 (10) |
| C14—Fe1—C13—C12 | 119.72 (15) | C15—Fe1—C23—C24 | −75.12 (12) |
| C24—Fe1—C13—C12 | 167.49 (15) | C11—Fe1—C23—C24 | −41.5 (3) |
| C23—Fe1—C13—C12 | −158.72 (10) | C22—Fe1—C23—C24 | 119.96 (14) |
| C21—Fe1—C13—C14 | 165.53 (10) | C25—Fe1—C23—C24 | 37.26 (9) |
| C15—Fe1—C13—C14 | −37.53 (10) | C12—Fe1—C23—C24 | 167.30 (15) |
| C11—Fe1—C13—C14 | −82.05 (11) | C14—Fe1—C23—C24 | −116.67 (11) |
| C22—Fe1—C13—C14 | 123.80 (11) | C13—Fe1—C23—C24 | −158.94 (10) |
| C25—Fe1—C13—C14 | −161.4 (2) | C22—C23—C24—C25 | −0.55 (19) |
| C12—Fe1—C13—C14 | −119.72 (15) | Fe1—C23—C24—C25 | −59.03 (11) |
| C24—Fe1—C13—C14 | 47.8 (2) | C22—C23—C24—Fe1 | 58.48 (11) |
| C23—Fe1—C13—C14 | 81.56 (12) | C21—Fe1—C24—C25 | 38.14 (10) |
| C12—C13—C14—C15 | −0.5 (2) | C15—Fe1—C24—C25 | −116.18 (10) |
| Fe1—C13—C14—C15 | 58.56 (12) | C11—Fe1—C24—C25 | −74.16 (12) |
| C12—C13—C14—Fe1 | −59.03 (12) | C22—Fe1—C24—C25 | 82.56 (10) |
| C21—Fe1—C14—C13 | −42.2 (3) | C12—Fe1—C24—C25 | −41.5 (3) |
| C15—Fe1—C14—C13 | 119.78 (15) | C14—Fe1—C24—C25 | −158.78 (10) |
| C11—Fe1—C14—C13 | 81.48 (11) | C13—Fe1—C24—C25 | 167.36 (15) |
| C22—Fe1—C14—C13 | −75.05 (13) | C23—Fe1—C24—C25 | 119.78 (14) |
| C25—Fe1—C14—C13 | 167.24 (15) | C21—Fe1—C24—C23 | −81.64 (10) |
| C12—Fe1—C14—C13 | 37.33 (11) | C15—Fe1—C24—C23 | 124.04 (10) |
| C24—Fe1—C14—C13 | −158.82 (10) | C11—Fe1—C24—C23 | 166.06 (10) |
| C23—Fe1—C14—C13 | −116.40 (11) | C22—Fe1—C24—C23 | −37.23 (10) |
| C21—Fe1—C14—C15 | −162.0 (2) | C25—Fe1—C24—C23 | −119.78 (14) |
| C11—Fe1—C14—C15 | −38.30 (10) | C12—Fe1—C24—C23 | −161.3 (2) |
| C22—Fe1—C14—C15 | 165.18 (10) | C14—Fe1—C24—C23 | 81.43 (12) |
| C25—Fe1—C14—C15 | 47.5 (2) | C13—Fe1—C24—C23 | 47.6 (2) |
| C12—Fe1—C14—C15 | −82.44 (11) | C23—C24—C25—C21 | 0.50 (18) |
| C24—Fe1—C14—C15 | 81.40 (12) | Fe1—C24—C25—C21 | −58.76 (11) |
| C13—Fe1—C14—C15 | −119.78 (15) | C23—C24—C25—Fe1 | 59.26 (11) |
| C23—Fe1—C14—C15 | 123.83 (11) | C22—C21—C25—C24 | −0.27 (18) |
| C13—C14—C15—C11 | 0.36 (19) | C26—C21—C25—C24 | 174.35 (15) |
| Fe1—C14—C15—C11 | 59.45 (11) | Fe1—C21—C25—C24 | 59.54 (11) |
| C13—C14—C15—Fe1 | −59.09 (12) | C22—C21—C25—Fe1 | −59.81 (11) |
| C12—C11—C15—C14 | −0.13 (18) | C26—C21—C25—Fe1 | 114.81 (16) |
| C16—C11—C15—C14 | −178.98 (15) | C21—Fe1—C25—C24 | −119.03 (14) |
| Fe1—C11—C15—C14 | −59.94 (11) | C15—Fe1—C25—C24 | 81.66 (11) |
| C12—C11—C15—Fe1 | 59.82 (11) | C11—Fe1—C25—C24 | 124.90 (10) |
| C16—C11—C15—Fe1 | −119.03 (16) | C22—Fe1—C25—C24 | −81.02 (11) |
| C21—Fe1—C15—C14 | 166.96 (14) | C12—Fe1—C25—C24 | 166.22 (10) |
| C11—Fe1—C15—C14 | 118.87 (15) | C14—Fe1—C25—C24 | 47.9 (2) |
| C22—Fe1—C15—C14 | −42.6 (3) | C13—Fe1—C25—C24 | −161.6 (2) |
| C25—Fe1—C15—C14 | −159.02 (10) | C23—Fe1—C25—C24 | −37.39 (10) |
| C12—Fe1—C15—C14 | 80.74 (11) | C15—Fe1—C25—C21 | −159.31 (9) |
| C24—Fe1—C15—C14 | −116.75 (11) | C11—Fe1—C25—C21 | −116.08 (10) |
| C13—Fe1—C15—C14 | 37.21 (11) | C22—Fe1—C25—C21 | 38.01 (10) |
| C23—Fe1—C15—C14 | −75.53 (13) | C12—Fe1—C25—C21 | −74.75 (11) |
| C21—Fe1—C15—C11 | 48.1 (2) | C14—Fe1—C25—C21 | 166.90 (15) |
| C22—Fe1—C15—C11 | −161.4 (2) | C24—Fe1—C25—C21 | 119.03 (14) |
| C25—Fe1—C15—C11 | 82.11 (11) | C13—Fe1—C25—C21 | −42.6 (3) |
| C12—Fe1—C15—C11 | −38.13 (10) | C23—Fe1—C25—C21 | 81.64 (10) |
| C14—Fe1—C15—C11 | −118.87 (15) | C25—C21—C26—O22 | −170.69 (15) |
| C24—Fe1—C15—C11 | 124.38 (10) | C22—C21—C26—O22 | 3.1 (2) |
| C13—Fe1—C15—C11 | −81.66 (11) | Fe1—C21—C26—O22 | −83.00 (18) |
| C23—Fe1—C15—C11 | 165.60 (9) | C25—C21—C26—O21 | 10.2 (2) |
| C12—C11—C16—O11 | 14.1 (2) | C22—C21—C26—O21 | −176.01 (15) |
| C15—C11—C16—O11 | −167.29 (15) | Fe1—C21—C26—O21 | 97.89 (14) |
| Fe1—C11—C16—O11 | 103.88 (16) | C5—N2—C1—C2 | −1.0 (3) |
| C12—C11—C16—O12 | −167.90 (15) | N2—C1—C2—N1 | −176.66 (18) |
| C15—C11—C16—O12 | 10.7 (2) | N2—C1—C2—C3 | 0.5 (3) |
| Fe1—C11—C16—O12 | −78.10 (18) | N1—C2—C3—C4 | 177.35 (19) |
| C15—Fe1—C21—C25 | 47.46 (19) | C1—C2—C3—C4 | 0.3 (3) |
| C11—Fe1—C21—C25 | 82.02 (11) | C2—C3—C4—C5 | −0.6 (3) |
| C22—Fe1—C21—C25 | −119.10 (14) | C1—N2—C5—C4 | 0.7 (3) |
| C12—Fe1—C21—C25 | 124.98 (10) | C3—C4—C5—N2 | 0.1 (3) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H11···O12 | 0.87 (3) | 2.08 (3) | 2.918 (2) | 161 (2) |
| N1—H10···O11i | 0.84 (3) | 2.07 (3) | 2.906 (2) | 171 (3) |
| N2—H2···O11ii | 0.89 (2) | 1.79 (2) | 2.675 (2) | 177 (2) |
| O21—H21···O12iii | 0.81 (2) | 1.77 (2) | 2.5621 (16) | 164 (2) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, y+1/2, −z+1/2; (iii) x, −y+1/2, z+1/2.
References
- Amer, W. A., Yu, H., Wang, L., Vatsadze, S. & Tong, R. (2013). J. Inorg. Organomet. Polym. 23, 1431–1444.
- Bruker (2008). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
- Gao, B., Yang, B., Li, T. & Zhang, B. (2009). Synth. Commun. 39, 2973–2981.
- Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. [DOI] [PMC free article] [PubMed]
- Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
- Sun, R., Wang, L., Yu, H., Zain-ul-Abdin Chen, Y., Khalid, H., Abbasi, N., Akram, M., Vatsadze, S. Z. & Lemenovskii, D. A. (2016). J. Inorg. Organomet. Polym. 26, 545–554.
- Zakaria, C. M., Ferguson, G., Lough, A. J. & Glidewell, C. (2002). Acta Cryst. B58, 786–802. [DOI] [PubMed]
- Zheng, D., Haojie, Y., Li, W., Xiaoting, Z., Yongsheng, C. & Vatsadze, S. Z. (2016). J. Organomet. Chem. 821, 48–53.
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) I. DOI: 10.1107/S2056989017007058/wm5388sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017007058/wm5388Isup2.hkl
CCDC reference: 1444115
Additional supporting information: crystallographic information; 3D view; checkCIF report