The crystal of the isomorphous anhydrous ammonium salts of phenoxyacetic acid and (4-fluorophenoxy)acetic acid and that of the hemihydrate ammonium salt of 4-chloro-2-methylphenoxy)acetic acid show two-dimensional layered structures based on conjoined cyclic hydrogen-bonded motifs.
Keywords: crystal structure, phenoxyacetic acid salts, MCPA, herbicides, ammonium carboxylates, hydrogen bonding
Abstract
The structures of the ammonium salts of phenoxyacetic acid, NH4 +·C8H6O3 −, (I), (4-fluorophenoxy)acetic acid, NH4 +·C8H5FO3 −, (II), and the herbicidally active (4-chloro-2-methylphenoxy)acetic acid (MCPA), NH4 +·C9H8ClO3 −·0.5H2O, (III) have been determined. All have two-dimensional layered structures based on inter-species ammonium N—H⋯O hydrogen-bonding associations, which give core substructures consisting primarily of conjoined cyclic motifs. The crystals of (I) and (II) are isomorphous with the core comprising R 1 2(5), R 1 2(4) and centrosymmetric R 4 2(8) ring motifs, giving two-dimensional layers lying parallel to (100). In (III), the water molecule of solvation lies on a crystallographic twofold rotation axis and bridges two carboxyl O atoms in an R 4 4(12) hydrogen-bonded motif, creating two R 4 3(10) rings, which together with a conjoined centrosymmetric R 4 2(8) ring incorporating both ammonium cations, generate two-dimensional layers lying parallel to (100). No π–π ring associations are present in any of the structures.
Chemical context
The crystal structures of the ammonium salts of carboxylic acids are, despite their simple formulae, characterized by the presence of a complex array of hydrogen-bonding interactions. From a study of the packing motifs of the these ammonium carboxylate salts from examples in the Cambridge Structural Database (Groom & Allen, 2014 ▶), Odendal et al. (2010 ▶) found that two-dimensional hydrogen-bonded nets, ladders or cubane-type structures could be predicted on the basis of the size and conformation of the anions. These structures are often stabilized by π–π aromatic ring interactions. With the benzoic acid analogues, two-dimensional sheet structures are common with interactions involving the ammonium cations and the carboxylate anions in N—H⋯O hydrogen bonding, forming core layer structures, with the aromatic rings occupying the interstitial cell regions, e.g. with benzoic acid (Odendal et al., 2010 ▶), 3-nitrobenzoic acid (Eppel & Bernstein, 2009 ▶) and 2,4-dichlorobenzoic acid (Smith, 2014 ▶). Three-dimensional structures are usually only formed when interactive substituent groups are present on the benzoate rings, interlinking the layers e.g. with 3,5-dinitrobenzoic acid (Smith, 2014 ▶). The presence of water molecules of solvation may also produce a similar effect, although these are usually confined to the primary cation–anion layers.
With the phenoxyacetic acid analogues, which comprise a number of herbicidally active commercial herbicides (Zumdahl, 2010 ▶), this should also be the case. In the only reported structure of an ammonium salt of a phenoxyacetic acid [with the commercially important herbicide, the 2,4-dichloro-substituted analogue (2,4-D) (a hemihydrate) (Liu et al., 2009 ▶)], the expected two-dimensional layered structure is found. Herein are reported the preparation and structures of the anhydrous ammonium salts of the parent phenoxyacetic acid, NH4
+·C8H6O3
− (I) and (4-fluorophenoxy)acetic acid, NH4
+·C8H5FO3
− (II) and the hemihydrate salt of the herbicidally active (4-chloro-2-methylphenoxy)acetic acid (MCPA), NH4
+·C9H8ClO3
−·0.5H2O (III). The structure of a hydrated chloromethylammonium salt of MCPA is known (Pernak et al., 2011 ▶).
Structural commentary
In the structures of the isomorphous ammonium phenoxyacetate (I) and (4-fluorophenoxy)acetate (II) (Figs. 1 ▶ and 2 ▶, respectively), the anionic species are essentially planar; the comparative defining torsion angles in the phenoxyacetate side chain (C2—C1—O11—C12, C1—O11—C12—C13 and O11—C12—C13—O14) are 178.93 (19), −177.48 (18) and −173.58 (18)°, respectively, for (I) and −179.05 (18), −178.98 (17) and −174.13 (17)°, respectively, for (II). This planarity is also found in the MCPA anion in (III) (Fig. 3 ▶) where the corresponding torsion angles are −179.13 (15), −173.34 (14) and −178.71 (15)° and is also the case with the parent acids [for (I): Kennard et al. (1982 ▶), for (II): Smith et al. (1992 ▶) and for (III): Smith & Kennard (1981 ▶); Sieron et al. (2011 ▶)]. In (III), the water molecule of solvation lies on a crystallographic twofold rotation axis.
Figure 1.
Molecular conformation and atom labelling for (I), with inter-species hydrogen bonds shown as a dashed lines (see Table 1 ▶ for details). Non-H atoms are shown as 40% probability displacement ellipsoids.
Figure 2.
Molecular conformation and atom labelling for (II), with inter-species hydrogen bonds shown as dashed lines (see Table 2 ▶ for details). Non-H atoms are shown as 40% probability displacement ellipsoids.
Figure 3.
Molecular conformation and atom labelling for (III), with inter-species hydrogen bonds shown as dashed lines (see Table 3 ▶ for details). Non-H atoms are shown as 40% probability displacement ellipsoids.
Supramolecular features
In the crystals of (I) and (II), two H atoms of the ammonium group give cyclic asymmetric three-centre (bifurcated) N—H⋯(O,O) hydrogen-bonding interactions with the anion (Tables 1 ▶ and 2 ▶, respectively). One of these is with two O-atom acceptors of the carboxyl group (O13, O14) [graph set 
(4)], the other is with the carboxyl and phenoxy O-atom acceptors (O13ii, O11ii) of an inversion-related anion [graph set (5)]. These, together with a third N1—H13⋯O13ii hydrogen bond, give a cyclic 
(8) ring motif, forming a series of conjoined rings which extend the structures along c. The other H atom gives structure extension through an N—H⋯O hydrogen bond to a carboxyl O atom (O14iii), forming a two-dimensional sheet-like structure which lies parallel to (100). Present in the crystal are short inversion-related intermolecular F4⋯F4iv contacts of 2.793 (2) Å [symmetry code: (iv) −x + 2, −y + 1, −z − 1]. The crystal packing and hydrogen-bonding in (I) is identical to that in isostructural (II), as shown in Fig. 4 ▶.
Table 1. Hydrogen-bond geometry (, ) for (I) .
| DHA | DH | HA | D A | DHA |
|---|---|---|---|---|
| N1H11O13 | 0.96 | 1.92 | 2.849(3) | 163 |
| N1H11O14 | 0.96 | 2.55 | 3.330(3) | 138 |
| N1H12O13i | 0.85 | 2.03 | 2.867(3) | 172 |
| N1H13O11ii | 0.90 | 2.39 | 3.202(3) | 150 |
| N1H13O13ii | 0.90 | 2.15 | 2.869(3) | 136 |
| N1H14O14iii | 0.84 | 1.95 | 2.788(3) | 178 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
.
Table 2. Hydrogen-bond geometry (, ) for (II) .
| DHA | DH | HA | D A | DHA |
|---|---|---|---|---|
| N1H11O13 | 0.90 | 1.95 | 2.847(2) | 177 |
| N1H11O14 | 0.90 | 2.55 | 3.347(2) | 135 |
| N1H12O13i | 0.97 | 1.88 | 2.847(3) | 173 |
| N1H13O11ii | 0.96 | 2.36 | 3.172(2) | 142 |
| N1H13O13ii | 0.96 | 2.13 | 2.892(2) | 135 |
| N1H14O14iii | 0.89 | 1.91 | 2.793(2) | 173 |
Symmetry codes: (i) ; (ii) ; (iii) .
Figure 4.
The two-dimensional hydrogen-bonded network structure of (I), which is equivalent to that of the isomorphous compound (II). Hydrogen bonds are shown as dashed lines and non-associative H-atoms have been omitted [for symmetry codes see Tables 1 ▶ and 2 ▶].
In the crystal of (III), centrosymmetric inter-ion (8) rings are formed between two ammonium cations and two O13 carboxyl O-atom acceptors and are bridged by a third ammonium H donor through O13iii, extending the structure down b (Table 3 ▶ and Fig. 5 ▶). The fourth H atom gives extension along a through N1—H12⋯O14ii forming an enlarged conjoined 
(12) ring, which is bridged by the water molecule of solvation lying on the twofold rotation axis, through O1W—H11W⋯O14 hydrogen bonds. This link effectively generates two separate 
(10) ring motifs, extending the structure along a and giving the overall two-dimensional layers lying parallel to (100) (Fig. 6 ▶). In (III), no three-centre (4) or (5) motifs to carboxyl (O,O′) or carboxyl-phenoxy (O,O
1) acceptors such as are present in (I) and (II) are found. The structure of (III) is essentially isostructural with that of ammonium (2,4-dichlorophenoxy)acetate hemihydrate (Liu et al., 2009 ▶), with isomorphous crystals [a = 37.338 (8), b = 4.388 (9), c = 12.900 (3) Å, β = 103.82 (3)°, V = 2074.7 (8) Å3, Z = 8, space group C2/c].
Table 3. Hydrogen-bond geometry (, ) for (III) .
| DHA | DH | HA | D A | DHA |
|---|---|---|---|---|
| N1H11O13i | 0.82 | 2.21 | 2.998(4) | 161 |
| N1H12O14ii | 0.82 | 2.09 | 2.886(4) | 166 |
| N1H13O13iii | 0.84 | 2.04 | 2.877(4) | 173 |
| N1H14O13 | 0.82 | 2.00 | 2.798(4) | 163 |
| O1WH11WO14 | 0.88 | 1.95 | 2.809(4) | 165 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
.
Figure 5.
A partial extension of the basic cation–anion hydrogen-bonding associations in the structure of (III), showing conjoined cyclic (12), (10) and (8) ring motifs. [Symmetry code: (iv) −x + 1, y, −z + 
. For other codes, see Table 3 ▶].
Figure 6.
The two-dimensional hydrogen-bonded network structure of (III) in the unit cell, viewed along b.
No π–π interactions are found in any of the structures reported here [minimum ring centroid separation = 4.8849 (16) (I), 4.8919 (15) (II) and 4.456 (5) Å (III) (the b unit-cell parameter)].
Synthesis and crystallization
The title compounds were prepared by the addition of excess 5 M aqueous ammonia solution to 1 mmol of either phenoxyacetic acid [150 mg for (I)], (4-fluorophenoxy)acetic acid [170 mg for (II)] or (4-chloro-2-methylphenoxy)acetic acid [200 mg for (III)] in 10 mL of 10% ethanol–water. Room-temperature evaporation of the solvent gave colourless plate-like crystals of (I), (II) and (III) from which specimens were cleaved for the X-ray analyses.
Refinement details
Crystal data, data collection and structure refinement details are summarized in Table 4 ▶. Hydrogen atoms potentially involved in hydrogen-bonding interactions were located in difference Fourier maps but were subsequently included in the refinements with positional parameters fixed and with U iso(H) = 1.2U eq(N) or = 1.5U eq(O). Other H atoms were included at calculated positions [C—H(aromatic) = 0.95, C—H(methylene) = 0.98, C—H(methyl) = 0.97 Å] and also treated as riding, with U iso(H) = 1.5U eq(C) for methyl H atoms and = 1.2U eq(C) for other H atoms. In (III), the methyl group was found to be rotationally disordered, with the H atoms distributed over six equivalent half-sites, and was treated accordingly.
Table 4. Experimental details.
| (I) | (II) | (III) | |
|---|---|---|---|
| Crystal data | |||
| Chemical formula | NH4 +C8H7O3 | NH4 +C8H6FO3 | NH4 +C9H8ClNO3 0.5H2O |
| M r | 169.17 | 187.17 | 226.65 |
| Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c | Monoclinic, C2/c |
| Temperature (K) | 200 | 200 | 200 |
| a, b, c () | 17.824(2), 7.1453(6), 6.7243(7) | 18.386(2), 7.1223(6), 6.7609(6) | 38.0396(9), 4.4560(8), 12.944(5) |
| () | 90.321(9) | 93.399(8) | 104.575(5) |
| V (3) | 856.38(15) | 883.79(14) | 2123.5(9) |
| Z | 4 | 4 | 8 |
| Radiation type | Mo K | Mo K | Mo K |
| (mm1) | 0.10 | 0.12 | 0.35 |
| Crystal size (mm) | 0.35 0.25 0.10 | 0.26 0.20 0.05 | 0.35 0.35 0.10 |
| Data collection | |||
| Diffractometer | Oxford Diffraction Gemini-S CCD detector | Oxford Diffraction Gemini-S CCD detector | Oxford Diffraction Gemini-S CCD detector |
| Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2013 ▶) | Multi-scan (CrysAlis PRO; Agilent, 2013 ▶) | Multi-scan (CrysAlis PRO; Agilent, 2013 ▶) |
| T min, T max | 0.920, 0.980 | 0.960, 0.980 | 0.913, 0.980 |
| No. of measured, independent and observed [I > 2(I)] reflections | 5450, 1686, 1218 | 5619, 1738, 1304 | 6215, 2087, 1771 |
| R int | 0.052 | 0.033 | 0.030 |
| (sin /)max (1) | 0.617 | 0.617 | 0.617 |
| Refinement | |||
| R[F 2 > 2(F 2)], wR(F 2), S | 0.063, 0.163, 1.10 | 0.053, 0.116, 1.10 | 0.036, 0.091, 1.03 |
| No. of reflections | 1686 | 1738 | 2087 |
| No. of parameters | 109 | 118 | 132 |
| H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
| max, min (e 3) | 0.29, 0.24 | 0.16, 0.22 | 0.32, 0.28 |
Supplementary Material
Crystal structure: contains datablock(s) global, I, II, III. DOI: 10.1107/S160053681402488X/su5018sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681402488X/su5018Isup2.hkl
Structure factors: contains datablock(s) II. DOI: 10.1107/S160053681402488X/su5018IIsup3.hkl
Structure factors: contains datablock(s) III. DOI: 10.1107/S160053681402488X/su5018IIIsup4.hkl
Supporting information file. DOI: 10.1107/S160053681402488X/su5018Isup5.cml
Supporting information file. DOI: 10.1107/S160053681402488X/su5018IIsup6.cml
Supporting information file. DOI: 10.1107/S160053681402488X/su5018IIIsup7.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The author acknowledges financial support from the Science and Engineering Faculty, Queensland University of Technology.
supplementary crystallographic information
Crystal data
| NH4+·C9H8ClNO3−·0.5H2O | F(000) = 952 |
| Mr = 226.65 | Dx = 1.418 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 1819 reflections |
| a = 38.0396 (9) Å | θ = 4.4–28.1° |
| b = 4.4560 (8) Å | µ = 0.35 mm−1 |
| c = 12.944 (5) Å | T = 200 K |
| β = 104.575 (5)° | Plate, colourless |
| V = 2123.5 (9) Å3 | 0.35 × 0.35 × 0.10 mm |
| Z = 8 |
Data collection
| Oxford Diffraction Gemini-S CCD-detector diffractometer | 2087 independent reflections |
| Radiation source: Enhance (Mo) X-ray source | 1771 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.030 |
| Detector resolution: 16.077 pixels mm-1 | θmax = 26.0°, θmin = 3.2° |
| ω scans | h = −46→46 |
| Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) | k = −5→5 |
| Tmin = 0.913, Tmax = 0.980 | l = −15→15 |
| 6215 measured reflections |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.091 | H-atom parameters constrained |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.0409P)2 + 1.4504P] where P = (Fo2 + 2Fc2)/3 |
| 2087 reflections | (Δ/σ)max < 0.001 |
| 132 parameters | Δρmax = 0.32 e Å−3 |
| 0 restraints | Δρmin = −0.28 e Å−3 |
Special details
| Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
| 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 > σ(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 | Occ. (<1) | |
| Cl4 | 0.24818 (1) | 0.32330 (12) | 0.36021 (4) | 0.0372 (2) | |
| O11 | 0.39197 (3) | 0.8996 (3) | 0.46961 (9) | 0.0262 (4) | |
| O13 | 0.45425 (3) | 1.2161 (3) | 0.49906 (10) | 0.0296 (4) | |
| O14 | 0.44789 (4) | 1.4021 (3) | 0.65332 (10) | 0.0339 (4) | |
| C1 | 0.35808 (5) | 0.7686 (4) | 0.44981 (13) | 0.0224 (5) | |
| C2 | 0.34876 (5) | 0.5869 (4) | 0.35836 (13) | 0.0246 (5) | |
| C3 | 0.31491 (5) | 0.4496 (4) | 0.33324 (14) | 0.0269 (5) | |
| C4 | 0.29091 (5) | 0.4918 (4) | 0.39679 (14) | 0.0264 (5) | |
| C5 | 0.30027 (5) | 0.6675 (4) | 0.48684 (14) | 0.0275 (6) | |
| C6 | 0.33390 (5) | 0.8070 (4) | 0.51321 (14) | 0.0258 (5) | |
| C12 | 0.40205 (5) | 1.0812 (4) | 0.56298 (14) | 0.0242 (5) | |
| C13 | 0.43762 (5) | 1.2444 (4) | 0.57156 (14) | 0.0234 (5) | |
| C21 | 0.37517 (5) | 0.5430 (5) | 0.29002 (15) | 0.0370 (6) | |
| O1W | 0.50000 | 1.8306 (4) | 0.75000 | 0.0464 (7) | |
| N1 | 0.46781 (3) | 0.7274 (3) | 0.37900 (10) | 0.0156 (4) | |
| H3 | 0.30820 | 0.32800 | 0.27310 | 0.0320* | |
| H5 | 0.28420 | 0.69260 | 0.52960 | 0.0330* | |
| H6 | 0.34030 | 0.92710 | 0.57380 | 0.0310* | |
| H121 | 0.40420 | 0.95550 | 0.62550 | 0.0290* | |
| H122 | 0.38300 | 1.22720 | 0.56190 | 0.0290* | |
| H211 | 0.39700 | 0.65450 | 0.31980 | 0.0550* | 0.500 |
| H212 | 0.36440 | 0.61300 | 0.21890 | 0.0550* | 0.500 |
| H213 | 0.38090 | 0.33380 | 0.28790 | 0.0550* | 0.500 |
| H214 | 0.36460 | 0.41300 | 0.23130 | 0.0550* | 0.500 |
| H215 | 0.39710 | 0.45450 | 0.33210 | 0.0550* | 0.500 |
| H216 | 0.38060 | 0.73370 | 0.26320 | 0.0550* | 0.500 |
| H11W | 0.48390 | 1.71260 | 0.70860 | 0.0700* | |
| H11 | 0.49010 | 0.73870 | 0.39810 | 0.0190* | |
| H12 | 0.45970 | 0.71470 | 0.31450 | 0.0190* | |
| H13 | 0.46250 | 0.57360 | 0.40950 | 0.0190* | |
| H14 | 0.45930 | 0.86670 | 0.40680 | 0.0190* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl4 | 0.0264 (3) | 0.0466 (3) | 0.0378 (3) | −0.0121 (2) | 0.0064 (2) | −0.0044 (2) |
| O11 | 0.0233 (7) | 0.0335 (7) | 0.0230 (6) | −0.0071 (5) | 0.0083 (5) | −0.0075 (5) |
| O13 | 0.0293 (7) | 0.0279 (6) | 0.0355 (7) | −0.0036 (6) | 0.0155 (6) | −0.0015 (6) |
| O14 | 0.0340 (8) | 0.0378 (7) | 0.0268 (7) | −0.0094 (6) | 0.0020 (6) | −0.0054 (6) |
| C1 | 0.0215 (9) | 0.0222 (8) | 0.0224 (9) | −0.0010 (7) | 0.0037 (7) | 0.0028 (7) |
| C2 | 0.0253 (9) | 0.0277 (9) | 0.0198 (8) | 0.0005 (7) | 0.0041 (7) | 0.0002 (7) |
| C3 | 0.0278 (10) | 0.0287 (9) | 0.0223 (9) | −0.0021 (8) | 0.0027 (8) | −0.0023 (8) |
| C4 | 0.0217 (9) | 0.0277 (9) | 0.0277 (9) | −0.0031 (7) | 0.0023 (8) | 0.0037 (8) |
| C5 | 0.0230 (10) | 0.0332 (10) | 0.0282 (9) | 0.0003 (8) | 0.0099 (8) | 0.0017 (8) |
| C6 | 0.0259 (10) | 0.0281 (9) | 0.0234 (9) | −0.0011 (8) | 0.0062 (7) | −0.0022 (8) |
| C12 | 0.0244 (9) | 0.0276 (9) | 0.0208 (8) | −0.0026 (7) | 0.0059 (7) | −0.0033 (7) |
| C13 | 0.0247 (9) | 0.0215 (8) | 0.0232 (9) | 0.0029 (7) | 0.0045 (7) | 0.0042 (7) |
| C21 | 0.0331 (11) | 0.0520 (12) | 0.0278 (10) | −0.0083 (10) | 0.0114 (9) | −0.0126 (9) |
| O1W | 0.0421 (13) | 0.0259 (10) | 0.0667 (15) | 0.0000 | 0.0053 (11) | 0.0000 |
| N1 | 0.0141 (7) | 0.0159 (6) | 0.0179 (6) | −0.0006 (5) | 0.0060 (5) | −0.0004 (5) |
Geometric parameters (Å, º)
| Cl4—C4 | 1.744 (3) | C3—C4 | 1.387 (3) |
| O11—C1 | 1.379 (3) | C4—C5 | 1.375 (3) |
| O11—C12 | 1.425 (3) | C5—C6 | 1.386 (3) |
| O13—C13 | 1.263 (3) | C12—C13 | 1.515 (3) |
| O14—C13 | 1.248 (3) | C3—H3 | 0.9300 |
| O1W—H11W | 0.8800 | C5—H5 | 0.9300 |
| O1W—H11Wi | 0.8800 | C6—H6 | 0.9300 |
| N1—H12 | 0.8200 | C12—H121 | 0.9700 |
| N1—H11 | 0.8200 | C12—H122 | 0.9700 |
| N1—H13 | 0.8400 | C21—H216 | 0.9600 |
| N1—H14 | 0.8200 | C21—H211 | 0.9600 |
| C1—C2 | 1.404 (3) | C21—H212 | 0.9600 |
| C1—C6 | 1.389 (3) | C21—H213 | 0.9600 |
| C2—C21 | 1.509 (3) | C21—H214 | 0.9600 |
| C2—C3 | 1.388 (3) | C21—H215 | 0.9600 |
| C1—O11—C12 | 115.95 (13) | C2—C3—H3 | 120.00 |
| H11W—O1W—H11Wi | 107.00 | C4—C3—H3 | 120.00 |
| H12—N1—H14 | 114.00 | C4—C5—H5 | 120.00 |
| H13—N1—H14 | 104.00 | C6—C5—H5 | 120.00 |
| H11—N1—H12 | 114.00 | C5—C6—H6 | 120.00 |
| H11—N1—H13 | 105.00 | C1—C6—H6 | 120.00 |
| H11—N1—H14 | 108.00 | C13—C12—H122 | 109.00 |
| H12—N1—H13 | 111.00 | C13—C12—H121 | 109.00 |
| O11—C1—C2 | 115.26 (16) | O11—C12—H121 | 109.00 |
| O11—C1—C6 | 124.41 (15) | O11—C12—H122 | 109.00 |
| C2—C1—C6 | 120.33 (17) | H121—C12—H122 | 108.00 |
| C1—C2—C21 | 120.32 (17) | C2—C21—H211 | 109.00 |
| C1—C2—C3 | 118.30 (17) | C2—C21—H212 | 109.00 |
| C3—C2—C21 | 121.37 (16) | C2—C21—H213 | 109.00 |
| C2—C3—C4 | 120.77 (16) | C2—C21—H214 | 110.00 |
| C3—C4—C5 | 120.76 (18) | C2—C21—H215 | 109.00 |
| Cl4—C4—C3 | 119.22 (14) | C2—C21—H216 | 109.00 |
| Cl4—C4—C5 | 120.01 (15) | H214—C21—H215 | 109.00 |
| C4—C5—C6 | 119.37 (17) | H214—C21—H216 | 109.00 |
| C1—C6—C5 | 120.46 (16) | H215—C21—H216 | 110.00 |
| O11—C12—C13 | 112.31 (15) | H211—C21—H212 | 109.00 |
| O13—C13—O14 | 125.29 (18) | H211—C21—H213 | 110.00 |
| O13—C13—C12 | 120.17 (16) | H212—C21—H213 | 109.00 |
| O14—C13—C12 | 114.55 (16) | ||
| C12—O11—C1—C2 | −179.13 (15) | C1—C2—C3—C4 | 0.2 (3) |
| C12—O11—C1—C6 | 1.0 (2) | C21—C2—C3—C4 | 179.98 (17) |
| C1—O11—C12—C13 | −173.34 (14) | C2—C3—C4—Cl4 | 178.25 (14) |
| O11—C1—C2—C3 | −179.57 (15) | C2—C3—C4—C5 | −0.8 (3) |
| O11—C1—C2—C21 | 0.6 (2) | Cl4—C4—C5—C6 | −178.13 (14) |
| C6—C1—C2—C3 | 0.3 (3) | C3—C4—C5—C6 | 0.9 (3) |
| C6—C1—C2—C21 | −179.46 (17) | C4—C5—C6—C1 | −0.4 (3) |
| O11—C1—C6—C5 | 179.67 (16) | O11—C12—C13—O13 | 1.7 (2) |
| C2—C1—C6—C5 | −0.2 (3) | O11—C12—C13—O14 | −178.71 (15) |
Symmetry code: (i) −x+1, y, −z+3/2.
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H11···O13ii | 0.82 | 2.21 | 2.998 (4) | 161 |
| N1—H12···O14iii | 0.82 | 2.09 | 2.886 (4) | 166 |
| N1—H13···O13iv | 0.84 | 2.04 | 2.877 (4) | 173 |
| N1—H14···O13 | 0.82 | 2.00 | 2.798 (4) | 163 |
| O1W—H11W···O14 | 0.88 | 1.95 | 2.809 (4) | 165 |
Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) x, −y+2, z−1/2; (iv) x, y−1, z.
References
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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) global, I, II, III. DOI: 10.1107/S160053681402488X/su5018sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681402488X/su5018Isup2.hkl
Structure factors: contains datablock(s) II. DOI: 10.1107/S160053681402488X/su5018IIsup3.hkl
Structure factors: contains datablock(s) III. DOI: 10.1107/S160053681402488X/su5018IIIsup4.hkl
Supporting information file. DOI: 10.1107/S160053681402488X/su5018Isup5.cml
Supporting information file. DOI: 10.1107/S160053681402488X/su5018IIsup6.cml
Supporting information file. DOI: 10.1107/S160053681402488X/su5018IIIsup7.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report