In the crystal, the crystal packing is ordered via synergetic contributions from N—H⋯Cl, O—H⋯Cl and N—H⋯O hydrogen bonds, which together assemble the cations and anions into a three-dimensional framework.
Keywords: crystal structure, imidazol, ethanaminium, ethanaminium chloride, Hirshfeld surface
Abstract
The asymmetric unit of the title compound, C8H11N3 2+·2Cl−·H2O, contains three organic cations, six chloride anions and three water molecules of crystallization, which are connected by extensive hydrogen-bonding interactions into a three-dimensional supramolecular architecture. Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the most important contributions to the crystal packing are from H⋯H (37.4%), Cl⋯H/H⋯Cl (35.5%), C⋯H/H⋯C (9.5%) and C⋯C (6.9%) interactions.
Chemical context
Heterocyclic compounds containing nitrogen such as benzimidazoles and their derivatives have attracted attention because of their medicinal applications as antiulcer, anticancer, antifungal, antimycobacterial and anti-inflammatory agents (El-masry et al., 2000 ▸). Besides being important pharmacophores, in particular amine-substituted benzimidazoles are good intermediates for the synthesis of different organic compounds (Maurya et al., 2007 ▸). General methods for the preparation of benzimidazoles involve the reaction of o-phenylenediamine and carboxylic acid or its derivatives under harsh dehydrating conditions or with aldehydes followed by oxidation (Peng et al., 2014 ▸).
We report herein the compound 2-aminomethylbenzimidazole dihydrochloride (ambmz·2HCl) prepared as described previously (Wu et al., 2008 ▸)
Structural commentary
The asymmetric unit of the title compound contains three organic cations, six chloride anions and three water molecules of crystallization, which are connected by O—H⋯Cl, N—H⋯O and N—H⋯Cl hydrogen bonds (Fig. 1 ▸). The r.m.s. deviations of the benzimidazolium ring systems are 0.0085 Å for N1/N2/C1–C7, 0.0076 Å for N4/N5/C9–C15, 0.0063 Å for N7/N8/C17–C23 with maximum deviations from planarity of 0.0169 (13) Å for atom C7, 0.0149 (13) Å for atom C15 and 0.0132 (13) Å for atom C23, respectively. The observed bond lengths are in good agreement with previously reported values (Cui, 2011 ▸).
Figure 1.
The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 20% probability level.
Supramolecular features
The crystal packing of the title compound features extensive hydrogen bonding (Table 1 ▸ and Fig. and 2) involving all three O atoms and all nine N atoms. N5—H5A⋯Cl5, N8—H8⋯Cl4, N2—H2⋯Cl1ii, N9—H9C⋯Cl5vi and N6—H6B⋯Cl1v hydrogen bonds link the ions into chains along the c-axis direction. These chains are linked by O–H⋯Cl and N—H⋯O hydrogen bonds, generating a three-dimensional network (Fig. 2 ▸).
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O1—H1A⋯Cl4i | 0.82 (2) | 2.63 (2) | 3.4431 (15) | 168 (3) |
| O1—H2B⋯Cl2 | 0.81 (2) | 2.36 (2) | 3.1598 (18) | 169 (3) |
| O2—H2C⋯Cl3 | 0.82 (2) | 2.33 (2) | 3.1244 (17) | 165 (2) |
| O2—H2D⋯Cl1 | 0.81 (1) | 2.64 (1) | 3.4492 (15) | 171 (3) |
| O3—H3D⋯Cl5ii | 0.80 (2) | 2.69 (2) | 3.4586 (15) | 164 (3) |
| O3—H3E⋯Cl6ii | 0.82 (2) | 2.32 (2) | 3.1364 (18) | 173 (3) |
| N1—H1⋯O1 | 0.83 (2) | 1.92 (2) | 2.746 (2) | 174 (2) |
| N2—H2⋯Cl1iii | 0.71 (2) | 2.44 (2) | 3.1519 (17) | 175 (2) |
| N3—H3⋯Cl3 | 0.88 (3) | 2.30 (3) | 3.105 (2) | 153 (2) |
| N3—H3A⋯Cl1 | 0.86 (4) | 2.26 (3) | 3.119 (2) | 173 (3) |
| N3—H3B⋯Cl4iv | 0.99 (3) | 2.33 (2) | 3.267 (2) | 156.8 (19) |
| N4—H4A⋯O2 | 0.85 (2) | 1.91 (2) | 2.754 (2) | 171 (2) |
| N5—H5A⋯Cl5 | 0.83 (2) | 2.31 (2) | 3.1205 (17) | 165 (2) |
| N6—H6A⋯Cl2 | 0.87 (3) | 2.33 (3) | 3.107 (2) | 150 (2) |
| N6—H6B⋯Cl1v | 0.98 (3) | 2.36 (2) | 3.287 (2) | 158.2 (18) |
| N6—H6C⋯Cl4i | 0.79 (3) | 2.35 (4) | 3.1347 (19) | 176 (3) |
| N7—H7⋯O3 | 0.85 (3) | 1.89 (3) | 2.742 (2) | 175 (3) |
| N8—H8⋯Cl4 | 0.81 (2) | 2.31 (2) | 3.1049 (17) | 172 (2) |
| N9—H9A⋯Cl6 | 0.83 (3) | 2.35 (3) | 3.100 (2) | 151 (2) |
| N9—H9B⋯Cl5 | 0.80 (3) | 2.32 (2) | 3.120 (2) | 176 (2) |
| N9—H9C⋯Cl5vi | 0.99 (3) | 2.34 (3) | 3.270 (2) | 157 (2) |
| C4—H4⋯Cl1i | 0.92 (2) | 2.81 (2) | 3.535 (2) | 136.7 (16) |
| C8—H8B⋯Cl3vii | 0.93 (3) | 2.65 (3) | 3.544 (2) | 162 (2) |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
; (v) 
; (vi) 
; (vii) 
.
Figure 2.
The view of the crystal packing of the title compound. Dashed lines denote the hydrogen bonds.
Hirshfeld surface analysis
The Hirshfeld surface analysis was performed using Crystal Explorer (Turner et al., 2017 ▸). The Hirshfeld surfaces, illustrated in Fig. 3 ▸, and their associated two-dimensional fingerprint plots were used to quantify the various intermolecular interactions in the synthesized complex. Red spots on the Hirshfeld surfaces indicate the intermolecular contacts involved in strong hydrogen bonds and interatomic contacts (Gümüş et al., 2018 ▸; Kansız et al., 2018 ▸; Kansız & Dege, 2018 ▸). The red spots in Fig. 4 ▸ correspond to the H⋯Cl contacts resulting from the N—H⋯Cl and O—H⋯Cl hydrogen bonds. The Hirshfeld surfaces were mapped using a standard (high) surface resolution with the three-dimensional dnorm surfaces mapped over a fixed colour scale of −0.518 (red) to 1.174 (blue) a.u..
Figure 3.
The Hirshfeld surface of the title compound mapped over d norm, d i and d e.
Figure 4.
Hirshfeld surface mapped over d norm to visualize the intermolecular interactions of the title compound.
Fig. 5 ▸ shows the two-dimensional fingerprint plot of all the contacts contributing to the Hirshfeld surface represented in normal mode. Fig. 6 ▸ shows the two-dimensional fingerprint plots of the (d i, d e) points associated with various atoms. H⋯H contacts contribute 37.4% to the Hirshfeld surface. The graph for Cl⋯H/H⋯Cl shows the contacts between the chlorine atoms inside the Hirshfeld surface and the hydrogen atoms outside the surface and vice versa, and has two symmetrical wings on the left and right sides (35.5%). Further, there are C⋯H/H⋯C (9.5%), C⋯C (6.9%), O⋯H/H⋯O (4.1%) and N⋯H/H⋯N (3.4%) contacts.
Figure 5.
Fingerprint plot of all the contacts.
Figure 6.
Two-dimensional fingerprint plots with a d norm view of the H⋯H (37.4%), Cl⋯H/H⋯Cl (35.5%), C⋯H/H⋯C (9.5%) and C⋯C (6.9%) contacts in the title compound.
Synthesis and crystallization
o-Phenylenediamine (10.8 g, 99.87 mmol) and glycine (10.00 g, 133.2 mmol) were dissolved in 5.5 M HCl (150 mL) . The reaction mixture was purged by argon at room temperature and heated up to reflux temperature for 12 h. The reaction was monitored by TLC. After completion of the reaction, the mixture was concentrated to 50 mL and kept at 269 K for 2 d. The crystals were filtered off and washed twice with acetone and dried to give the desired product (Fig. 7 ▸).
Figure 7.
The synthesis of the title compound.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. C-bound H atoms were positioned geometrically with C—H distances of 0.93–0.97 Å. and refined as riding, with U iso(H) = 1.2U eq(C). N-bound H atoms were located in difference-Fourier maps and refined isotropically. The coordinates of the water H atoms were determined from a difference-Fourier map and refined isotropically subject to a restraint of O—H = 0.82 (4) Å.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C8H11N3 +·2Cl−·H2O· |
| M r | 238.11 |
| Crystal system, space group | Triclinic, P
|
| Temperature (K) | 296 |
| a, b, c (Å) | 6.9340 (4), 12.1198 (7), 19.2128 (11) |
| α, β, γ (°) | 99.859 (5), 90.647 (5), 90.247 (5) |
| V (Å3) | 1590.64 (16) |
| Z | 6 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.58 |
| Crystal size (mm) | 0.57 × 0.50 × 0.46 |
| Data collection | |
| Diffractometer | Stoe IPDS 2 |
| Absorption correction | Integration (X-RED32; Stoe & Cie, 2002 ▸) |
| T min, T max | 0.788, 0.828 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 16045, 6254, 5000 |
| R int | 0.064 |
| (sin θ/λ)max (Å−1) | 0.617 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.035, 0.092, 0.96 |
| No. of reflections | 6254 |
| No. of parameters | 536 |
| No. of restraints | 9 |
| H-atom treatment | All H-atom parameters refined |
| Δρmax, Δρmin (e Å−3) | 0.34, −0.28 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S205698901801335X/xu5941sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901801335X/xu5941Isup2.hkl
Supporting information file. DOI: 10.1107/S205698901801335X/xu5941Isup3.cml
CCDC reference: 1868580
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund).
supplementary crystallographic information
Crystal data
| C8H11N3+·2Cl−·H2O· | Z = 6 |
| Mr = 238.11 | F(000) = 744 |
| Triclinic, P1 | Dx = 1.491 Mg m−3 |
| a = 6.9340 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 12.1198 (7) Å | Cell parameters from 18110 reflections |
| c = 19.2128 (11) Å | θ = 1.7–27.4° |
| α = 99.859 (5)° | µ = 0.58 mm−1 |
| β = 90.647 (5)° | T = 296 K |
| γ = 90.247 (5)° | Prism, brown |
| V = 1590.64 (16) Å3 | 0.57 × 0.50 × 0.46 mm |
Data collection
| Stoe IPDS 2 diffractometer | 6254 independent reflections |
| Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 5000 reflections with I > 2σ(I) |
| Detector resolution: 6.67 pixels mm-1 | Rint = 0.064 |
| rotation method scans | θmax = 26.0°, θmin = 1.7° |
| Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | h = −8→8 |
| Tmin = 0.788, Tmax = 0.828 | k = −14→14 |
| 16045 measured reflections | l = −23→23 |
Refinement
| Refinement on F2 | Hydrogen site location: difference Fourier map |
| Least-squares matrix: full | All H-atom parameters refined |
| R[F2 > 2σ(F2)] = 0.035 | w = 1/[σ2(Fo2) + (0.056P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.092 | (Δ/σ)max = 0.001 |
| S = 0.96 | Δρmax = 0.34 e Å−3 |
| 6254 reflections | Δρmin = −0.28 e Å−3 |
| 536 parameters | Extinction correction: SHELXL-2017/1 (Sheldrick 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 9 restraints | Extinction coefficient: 0.0327 (17) |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 1.44783 (7) | 0.25544 (4) | 0.93231 (2) | 0.04012 (12) | |
| Cl4 | 0.55220 (7) | 0.93572 (4) | 0.73215 (2) | 0.03912 (12) | |
| Cl5 | 0.44034 (7) | 0.39635 (4) | 0.59956 (2) | 0.04089 (13) | |
| Cl3 | 0.85067 (7) | 0.04098 (4) | 0.91238 (3) | 0.04840 (14) | |
| Cl6 | −0.13546 (8) | 0.60301 (5) | 0.58937 (3) | 0.05432 (15) | |
| Cl2 | 1.13465 (8) | 0.15568 (5) | 0.74387 (3) | 0.05337 (15) | |
| O2 | 0.9557 (2) | 0.29533 (13) | 0.93050 (9) | 0.0492 (3) | |
| O1 | 1.0439 (2) | −0.10288 (14) | 0.73035 (9) | 0.0517 (4) | |
| N4 | 0.7622 (2) | 0.41261 (12) | 0.84094 (8) | 0.0332 (3) | |
| O3 | 0.0525 (2) | 0.64579 (14) | 0.39493 (9) | 0.0553 (4) | |
| N7 | 0.2335 (2) | 0.81071 (13) | 0.48888 (8) | 0.0333 (3) | |
| N5 | 0.6592 (2) | 0.46067 (13) | 0.74372 (9) | 0.0347 (3) | |
| N1 | 1.2273 (2) | −0.21584 (13) | 0.82407 (8) | 0.0334 (3) | |
| N2 | 1.3362 (2) | −0.25722 (14) | 0.92226 (9) | 0.0376 (4) | |
| N8 | 0.3400 (2) | 0.90994 (13) | 0.58704 (9) | 0.0358 (3) | |
| N6 | 0.7067 (3) | 0.17781 (15) | 0.79023 (10) | 0.0427 (4) | |
| N9 | 0.2868 (3) | 0.60170 (15) | 0.53791 (10) | 0.0447 (4) | |
| N3 | 1.2803 (3) | 0.02017 (15) | 0.86850 (10) | 0.0421 (4) | |
| C14 | 0.7037 (2) | 0.55975 (14) | 0.78881 (9) | 0.0314 (4) | |
| C22 | 0.2942 (2) | 0.98527 (15) | 0.54300 (9) | 0.0323 (4) | |
| C9 | 0.7708 (2) | 0.52904 (14) | 0.85148 (9) | 0.0315 (4) | |
| C15 | 0.6935 (2) | 0.37525 (15) | 0.77671 (9) | 0.0335 (4) | |
| C1 | 1.2214 (2) | −0.33227 (14) | 0.81587 (9) | 0.0324 (4) | |
| C17 | 0.2255 (2) | 0.92225 (14) | 0.48021 (9) | 0.0319 (4) | |
| C10 | 0.8268 (3) | 0.60738 (16) | 0.90934 (10) | 0.0369 (4) | |
| C18 | 0.1652 (2) | 0.97150 (16) | 0.42385 (10) | 0.0355 (4) | |
| C7 | 1.2981 (2) | −0.17423 (15) | 0.88773 (9) | 0.0339 (4) | |
| C2 | 1.1642 (3) | −0.41361 (16) | 0.75996 (10) | 0.0377 (4) | |
| C6 | 1.2930 (2) | −0.35839 (15) | 0.87927 (10) | 0.0349 (4) | |
| C13 | 0.6926 (3) | 0.67112 (16) | 0.78093 (11) | 0.0385 (4) | |
| C23 | 0.3047 (2) | 0.80652 (15) | 0.55283 (9) | 0.0342 (4) | |
| C20 | 0.2469 (3) | 1.15029 (16) | 0.49646 (11) | 0.0392 (4) | |
| C21 | 0.3055 (3) | 1.10154 (16) | 0.55279 (11) | 0.0382 (4) | |
| C12 | 0.7490 (3) | 0.74911 (16) | 0.83844 (11) | 0.0394 (4) | |
| C5 | 1.3092 (3) | −0.46915 (17) | 0.88878 (11) | 0.0421 (4) | |
| C19 | 0.1785 (3) | 1.08684 (16) | 0.43313 (10) | 0.0389 (4) | |
| C4 | 1.2532 (3) | −0.54982 (17) | 0.83351 (12) | 0.0443 (5) | |
| C11 | 0.8145 (3) | 0.71817 (16) | 0.90146 (11) | 0.0401 (4) | |
| C8 | 1.3424 (3) | −0.05475 (17) | 0.91637 (11) | 0.0414 (4) | |
| C16 | 0.6469 (3) | 0.25681 (17) | 0.74466 (11) | 0.0428 (4) | |
| C3 | 1.1819 (3) | −0.52313 (17) | 0.77020 (12) | 0.0423 (4) | |
| C24 | 0.3525 (3) | 0.70519 (18) | 0.58323 (12) | 0.0458 (5) | |
| H2 | 1.384 (3) | −0.2526 (17) | 0.9558 (11) | 0.028 (5)* | |
| H18 | 0.111 (3) | 0.9325 (18) | 0.3840 (12) | 0.044 (6)* | |
| H10 | 0.873 (3) | 0.5879 (16) | 0.9522 (11) | 0.033 (5)* | |
| H2A | 1.108 (3) | −0.3947 (17) | 0.7161 (11) | 0.039 (5)* | |
| H11 | 0.854 (3) | 0.7742 (19) | 0.9433 (11) | 0.046 (6)* | |
| H19 | 0.136 (3) | 1.1218 (17) | 0.3927 (11) | 0.039 (5)* | |
| H20 | 0.255 (3) | 1.223 (2) | 0.5012 (12) | 0.048 (6)* | |
| H13 | 0.649 (3) | 0.6891 (17) | 0.7361 (11) | 0.039 (5)* | |
| H12 | 0.740 (3) | 0.816 (2) | 0.8342 (12) | 0.050 (6)* | |
| H21 | 0.350 (3) | 1.1439 (19) | 0.5987 (12) | 0.047 (6)* | |
| H5 | 1.355 (3) | −0.4842 (19) | 0.9333 (12) | 0.050 (6)* | |
| H4 | 1.264 (3) | −0.6238 (19) | 0.8385 (11) | 0.040 (5)* | |
| H5A | 0.608 (3) | 0.4556 (18) | 0.7041 (12) | 0.041 (6)* | |
| H1 | 1.179 (3) | −0.179 (2) | 0.7956 (13) | 0.055 (7)* | |
| H4A | 0.811 (3) | 0.372 (2) | 0.8683 (12) | 0.052 (6)* | |
| H8 | 0.393 (3) | 0.9236 (17) | 0.6251 (12) | 0.036 (5)* | |
| H24A | 0.291 (3) | 0.710 (2) | 0.6289 (13) | 0.058 (7)* | |
| H24B | 0.491 (5) | 0.697 (3) | 0.5884 (17) | 0.101 (10)* | |
| H7 | 0.183 (4) | 0.757 (2) | 0.4601 (14) | 0.063 (7)* | |
| H9A | 0.167 (4) | 0.600 (2) | 0.5354 (13) | 0.058 (7)* | |
| H16A | 0.518 (4) | 0.253 (2) | 0.7334 (15) | 0.076 (8)* | |
| H9B | 0.325 (4) | 0.551 (2) | 0.5559 (13) | 0.055 (7)* | |
| H9C | 0.336 (4) | 0.593 (2) | 0.4891 (16) | 0.080 (9)* | |
| H16B | 0.709 (3) | 0.2385 (19) | 0.7019 (13) | 0.052 (6)* | |
| H3C | 1.143 (3) | −0.581 (2) | 0.7340 (12) | 0.050 (6)* | |
| H8A | 1.472 (4) | −0.045 (2) | 0.9269 (13) | 0.061 (7)* | |
| H8B | 1.282 (4) | −0.035 (2) | 0.9596 (14) | 0.066 (7)* | |
| H6A | 0.831 (4) | 0.176 (2) | 0.7947 (13) | 0.061 (8)* | |
| H6B | 0.660 (3) | 0.194 (2) | 0.8388 (14) | 0.059 (7)* | |
| H6C | 0.667 (4) | 0.118 (3) | 0.7738 (15) | 0.065 (8)* | |
| H2C | 0.920 (3) | 0.2322 (16) | 0.9337 (14) | 0.063 (8)* | |
| H2D | 1.072 (2) | 0.289 (2) | 0.9267 (17) | 0.098 (12)* | |
| H3A | 1.316 (4) | 0.087 (3) | 0.8871 (16) | 0.086 (10)* | |
| H3B | 1.330 (3) | 0.000 (2) | 0.8197 (14) | 0.060 (7)* | |
| H3 | 1.154 (4) | 0.022 (2) | 0.8652 (12) | 0.056 (7)* | |
| H3D | −0.062 (3) | 0.649 (3) | 0.3941 (19) | 0.106 (12)* | |
| H3E | 0.082 (4) | 0.5804 (16) | 0.3962 (15) | 0.071 (9)* | |
| H1A | 0.926 (3) | −0.102 (3) | 0.7339 (18) | 0.100 (12)* | |
| H2B | 1.076 (4) | −0.0391 (16) | 0.7286 (15) | 0.069 (9)* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0439 (2) | 0.0399 (2) | 0.0360 (2) | 0.00037 (18) | −0.00373 (18) | 0.00530 (18) |
| Cl4 | 0.0430 (2) | 0.0388 (2) | 0.0348 (2) | −0.00156 (18) | −0.00346 (18) | 0.00436 (18) |
| Cl5 | 0.0447 (3) | 0.0395 (2) | 0.0378 (2) | −0.00330 (18) | −0.00542 (18) | 0.00547 (18) |
| Cl3 | 0.0486 (3) | 0.0458 (3) | 0.0518 (3) | −0.0026 (2) | 0.0038 (2) | 0.0112 (2) |
| Cl6 | 0.0503 (3) | 0.0508 (3) | 0.0615 (3) | 0.0005 (2) | −0.0013 (2) | 0.0085 (2) |
| Cl2 | 0.0491 (3) | 0.0519 (3) | 0.0600 (3) | −0.0049 (2) | −0.0007 (2) | 0.0126 (2) |
| O2 | 0.0490 (9) | 0.0458 (9) | 0.0538 (9) | −0.0016 (7) | −0.0076 (7) | 0.0121 (7) |
| O1 | 0.0475 (9) | 0.0546 (9) | 0.0566 (9) | −0.0045 (7) | −0.0098 (7) | 0.0209 (8) |
| N4 | 0.0346 (7) | 0.0320 (7) | 0.0337 (8) | 0.0003 (6) | −0.0023 (6) | 0.0071 (6) |
| O3 | 0.0496 (9) | 0.0456 (9) | 0.0652 (10) | 0.0011 (7) | −0.0110 (8) | −0.0056 (7) |
| N7 | 0.0323 (7) | 0.0331 (8) | 0.0331 (8) | −0.0025 (6) | −0.0008 (6) | 0.0017 (6) |
| N5 | 0.0336 (8) | 0.0387 (8) | 0.0314 (8) | 0.0013 (6) | −0.0032 (6) | 0.0047 (6) |
| N1 | 0.0317 (7) | 0.0359 (8) | 0.0341 (8) | −0.0008 (6) | −0.0022 (6) | 0.0106 (6) |
| N2 | 0.0333 (8) | 0.0494 (10) | 0.0314 (9) | −0.0017 (7) | −0.0053 (7) | 0.0107 (7) |
| N8 | 0.0342 (8) | 0.0420 (9) | 0.0298 (8) | −0.0059 (6) | −0.0038 (6) | 0.0028 (6) |
| N6 | 0.0505 (11) | 0.0310 (9) | 0.0451 (10) | −0.0057 (8) | 0.0012 (8) | 0.0025 (7) |
| N9 | 0.0501 (11) | 0.0375 (9) | 0.0485 (11) | 0.0051 (8) | 0.0010 (8) | 0.0128 (8) |
| N3 | 0.0469 (10) | 0.0358 (9) | 0.0426 (10) | −0.0042 (7) | 0.0018 (8) | 0.0034 (7) |
| C14 | 0.0264 (8) | 0.0346 (9) | 0.0331 (9) | 0.0007 (6) | 0.0018 (7) | 0.0052 (7) |
| C22 | 0.0265 (8) | 0.0378 (9) | 0.0315 (9) | −0.0035 (7) | 0.0011 (7) | 0.0027 (7) |
| C9 | 0.0275 (8) | 0.0312 (8) | 0.0357 (9) | −0.0003 (6) | 0.0023 (7) | 0.0054 (7) |
| C15 | 0.0295 (8) | 0.0347 (9) | 0.0353 (9) | 0.0001 (7) | 0.0003 (7) | 0.0029 (7) |
| C1 | 0.0266 (8) | 0.0355 (9) | 0.0361 (9) | −0.0010 (7) | 0.0026 (7) | 0.0093 (7) |
| C17 | 0.0274 (8) | 0.0337 (9) | 0.0334 (9) | −0.0023 (6) | 0.0034 (7) | 0.0019 (7) |
| C10 | 0.0349 (9) | 0.0406 (10) | 0.0343 (9) | −0.0015 (7) | 0.0003 (7) | 0.0042 (8) |
| C18 | 0.0306 (8) | 0.0423 (10) | 0.0320 (9) | −0.0003 (7) | 0.0002 (7) | 0.0016 (8) |
| C7 | 0.0287 (8) | 0.0391 (9) | 0.0343 (9) | −0.0018 (7) | 0.0006 (7) | 0.0073 (7) |
| C2 | 0.0319 (9) | 0.0440 (10) | 0.0371 (10) | −0.0025 (7) | 0.0017 (7) | 0.0066 (8) |
| C6 | 0.0269 (8) | 0.0417 (10) | 0.0378 (9) | 0.0014 (7) | 0.0008 (7) | 0.0112 (8) |
| C13 | 0.0334 (9) | 0.0399 (10) | 0.0442 (11) | 0.0032 (7) | 0.0036 (8) | 0.0130 (8) |
| C23 | 0.0291 (8) | 0.0384 (9) | 0.0353 (9) | −0.0026 (7) | 0.0008 (7) | 0.0066 (7) |
| C20 | 0.0344 (9) | 0.0343 (10) | 0.0485 (11) | −0.0028 (8) | 0.0075 (8) | 0.0051 (8) |
| C21 | 0.0318 (9) | 0.0384 (10) | 0.0408 (10) | −0.0061 (7) | 0.0020 (8) | −0.0030 (8) |
| C12 | 0.0359 (9) | 0.0307 (9) | 0.0519 (12) | 0.0024 (7) | 0.0068 (8) | 0.0076 (8) |
| C5 | 0.0339 (9) | 0.0470 (11) | 0.0498 (12) | 0.0041 (8) | 0.0033 (8) | 0.0202 (9) |
| C19 | 0.0349 (9) | 0.0419 (10) | 0.0412 (10) | 0.0012 (7) | 0.0053 (8) | 0.0100 (8) |
| C4 | 0.0354 (10) | 0.0389 (10) | 0.0608 (13) | 0.0044 (8) | 0.0106 (9) | 0.0146 (10) |
| C11 | 0.0351 (9) | 0.0367 (10) | 0.0457 (11) | −0.0036 (7) | 0.0058 (8) | −0.0013 (8) |
| C8 | 0.0423 (11) | 0.0437 (11) | 0.0362 (10) | −0.0059 (8) | −0.0033 (9) | 0.0017 (8) |
| C16 | 0.0494 (12) | 0.0369 (10) | 0.0398 (11) | −0.0013 (8) | −0.0073 (9) | −0.0001 (8) |
| C3 | 0.0349 (9) | 0.0401 (10) | 0.0509 (12) | −0.0025 (8) | 0.0069 (8) | 0.0044 (9) |
| C24 | 0.0478 (11) | 0.0460 (11) | 0.0456 (12) | −0.0031 (9) | −0.0062 (9) | 0.0141 (9) |
Geometric parameters (Å, º)
| O2—H2C | 0.817 (16) | C22—C17 | 1.391 (2) |
| O2—H2D | 0.812 (17) | C22—C21 | 1.391 (3) |
| O1—H1A | 0.819 (17) | C9—C10 | 1.383 (3) |
| O1—H2B | 0.810 (16) | C15—C16 | 1.494 (3) |
| N1—C7 | 1.328 (2) | C1—C2 | 1.381 (3) |
| N1—C1 | 1.393 (2) | C1—C6 | 1.396 (2) |
| N1—H1 | 0.83 (2) | C17—C18 | 1.384 (2) |
| N2—C7 | 1.322 (2) | C10—C11 | 1.380 (3) |
| N2—C6 | 1.386 (3) | C10—H10 | 0.95 (2) |
| N2—H2 | 0.71 (2) | C18—C19 | 1.381 (3) |
| N3—C8 | 1.461 (3) | C18—H18 | 0.91 (2) |
| N3—H3A | 0.87 (4) | C7—C8 | 1.488 (3) |
| N3—H3B | 0.99 (3) | C2—C3 | 1.381 (3) |
| N3—H3 | 0.88 (3) | C2—H2A | 0.99 (2) |
| N4—C15 | 1.322 (2) | C6—C5 | 1.390 (3) |
| N4—C9 | 1.392 (2) | C13—C12 | 1.377 (3) |
| N4—H4A | 0.85 (2) | C13—H13 | 0.97 (2) |
| N5—C15 | 1.324 (2) | C23—C24 | 1.484 (3) |
| N5—C14 | 1.386 (2) | C20—C21 | 1.377 (3) |
| N5—H5A | 0.83 (2) | C20—C19 | 1.400 (3) |
| N6—C16 | 1.462 (3) | C20—H20 | 0.87 (2) |
| N6—H6A | 0.86 (3) | C21—H21 | 0.99 (2) |
| N6—H6B | 0.98 (3) | C12—C11 | 1.399 (3) |
| N6—H6C | 0.79 (3) | C12—H12 | 0.83 (2) |
| O3—H3D | 0.796 (17) | C5—C4 | 1.366 (3) |
| O3—H3E | 0.822 (16) | C5—H5 | 0.96 (2) |
| N7—C23 | 1.328 (2) | C19—H19 | 0.99 (2) |
| N7—C17 | 1.391 (2) | C4—C3 | 1.397 (3) |
| N7—H7 | 0.85 (3) | C4—H4 | 0.92 (2) |
| N8—C23 | 1.332 (2) | C11—H11 | 0.99 (2) |
| N8—C22 | 1.383 (2) | C8—H8A | 0.92 (3) |
| N8—H8 | 0.80 (2) | C8—H8B | 0.93 (3) |
| N9—C24 | 1.467 (3) | C16—H16A | 0.92 (3) |
| N9—H9A | 0.83 (3) | C16—H16B | 0.93 (2) |
| N9—H9B | 0.80 (3) | C3—H3C | 0.93 (2) |
| N9—H9C | 0.99 (3) | C24—H24A | 0.97 (2) |
| C14—C13 | 1.386 (2) | C24—H24B | 0.97 (3) |
| C14—C9 | 1.395 (2) | ||
| H2C—O2—H2D | 104 (2) | C19—C18—C17 | 116.33 (18) |
| H1A—O1—H2B | 106 (2) | C19—C18—H18 | 120.3 (14) |
| C15—N4—C9 | 108.99 (15) | C17—C18—H18 | 123.2 (14) |
| C15—N4—H4A | 124.8 (16) | N2—C7—N1 | 109.33 (16) |
| C9—N4—H4A | 125.4 (16) | N2—C7—C8 | 123.45 (17) |
| H3D—O3—H3E | 107 (2) | N1—C7—C8 | 127.11 (16) |
| C23—N7—C17 | 108.55 (16) | C3—C2—C1 | 116.08 (18) |
| C23—N7—H7 | 126.6 (17) | C3—C2—H2A | 121.8 (12) |
| C17—N7—H7 | 124.0 (17) | C1—C2—H2A | 122.0 (12) |
| C15—N5—C14 | 109.14 (15) | N2—C6—C5 | 132.85 (18) |
| C15—N5—H5A | 124.9 (15) | N2—C6—C1 | 106.35 (15) |
| C14—N5—H5A | 125.6 (15) | C5—C6—C1 | 120.80 (18) |
| C7—N1—C1 | 109.27 (15) | C12—C13—C14 | 116.35 (17) |
| C7—N1—H1 | 125.7 (17) | C12—C13—H13 | 124.6 (12) |
| C1—N1—H1 | 124.5 (17) | C14—C13—H13 | 119.1 (12) |
| C7—N2—C6 | 109.38 (16) | N7—C23—N8 | 109.72 (16) |
| C7—N2—H2 | 126.4 (17) | N7—C23—C24 | 127.55 (18) |
| C6—N2—H2 | 123.7 (17) | N8—C23—C24 | 122.63 (17) |
| C23—N8—C22 | 108.85 (15) | C21—C20—C19 | 122.08 (18) |
| C23—N8—H8 | 123.7 (15) | C21—C20—H20 | 117.6 (16) |
| C22—N8—H8 | 127.0 (15) | C19—C20—H20 | 120.3 (15) |
| C16—N6—H6A | 111.4 (17) | C20—C21—C22 | 116.12 (18) |
| C16—N6—H6B | 115.5 (14) | C20—C21—H21 | 124.1 (13) |
| H6A—N6—H6B | 104 (2) | C22—C21—H21 | 119.7 (13) |
| C16—N6—H6C | 109 (2) | C13—C12—C11 | 122.09 (18) |
| H6A—N6—H6C | 110 (3) | C13—C12—H12 | 116.6 (16) |
| H6B—N6—H6C | 107 (2) | C11—C12—H12 | 121.3 (16) |
| C24—N9—H9A | 110.4 (18) | C4—C5—C6 | 116.97 (18) |
| C24—N9—H9B | 106.7 (18) | C4—C5—H5 | 124.2 (14) |
| H9A—N9—H9B | 109 (2) | C6—C5—H5 | 118.8 (14) |
| C24—N9—H9C | 113.6 (17) | C18—C19—C20 | 121.68 (18) |
| H9A—N9—H9C | 108 (2) | C18—C19—H19 | 116.2 (12) |
| H9B—N9—H9C | 109 (2) | C20—C19—H19 | 122.1 (12) |
| C8—N3—H3A | 108 (2) | C5—C4—C3 | 121.94 (19) |
| C8—N3—H3B | 114.2 (14) | C5—C4—H4 | 118.4 (13) |
| H3A—N3—H3B | 111 (2) | C3—C4—H4 | 119.6 (13) |
| C8—N3—H3 | 111.0 (16) | C10—C11—C12 | 121.71 (19) |
| H3A—N3—H3 | 106 (3) | C10—C11—H11 | 115.9 (12) |
| H3B—N3—H3 | 107 (2) | C12—C11—H11 | 122.3 (12) |
| C13—C14—N5 | 132.44 (17) | N3—C8—C7 | 112.34 (16) |
| C13—C14—C9 | 121.46 (17) | N3—C8—H8A | 110.4 (16) |
| N5—C14—C9 | 106.11 (15) | C7—C8—H8A | 110.8 (16) |
| N8—C22—C17 | 106.45 (15) | N3—C8—H8B | 109.5 (16) |
| N8—C22—C21 | 131.74 (17) | C7—C8—H8B | 109.3 (16) |
| C17—C22—C21 | 121.81 (17) | H8A—C8—H8B | 104 (2) |
| C10—C9—N4 | 131.77 (16) | N6—C16—C15 | 112.13 (17) |
| C10—C9—C14 | 122.19 (16) | N6—C16—H16A | 113.4 (18) |
| N4—C9—C14 | 106.02 (15) | C15—C16—H16A | 108.1 (18) |
| N4—C15—N5 | 109.73 (16) | N6—C16—H16B | 108.5 (14) |
| N4—C15—C16 | 127.44 (16) | C15—C16—H16B | 109.5 (15) |
| N5—C15—C16 | 122.72 (16) | H16A—C16—H16B | 105 (2) |
| C2—C1—N1 | 131.96 (16) | C2—C3—C4 | 121.8 (2) |
| C2—C1—C6 | 122.37 (17) | C2—C3—H3C | 118.8 (14) |
| N1—C1—C6 | 105.66 (16) | C4—C3—H3C | 119.4 (14) |
| C18—C17—C22 | 121.97 (16) | N9—C24—C23 | 112.39 (17) |
| C18—C17—N7 | 131.61 (17) | N9—C24—H24A | 108.5 (15) |
| C22—C17—N7 | 106.41 (15) | C23—C24—H24A | 109.0 (14) |
| C11—C10—C9 | 116.19 (17) | N9—C24—H24B | 105 (2) |
| C11—C10—H10 | 120.6 (12) | C23—C24—H24B | 112 (2) |
| C9—C10—H10 | 123.2 (12) | H24A—C24—H24B | 110 (2) |
| C15—N5—C14—C13 | −179.30 (18) | C7—N2—C6—C5 | 178.55 (18) |
| C15—N5—C14—C9 | 0.93 (19) | C7—N2—C6—C1 | −1.15 (19) |
| C23—N8—C22—C17 | 1.03 (19) | C2—C1—C6—N2 | 179.60 (15) |
| C23—N8—C22—C21 | −179.49 (17) | N1—C1—C6—N2 | 0.52 (18) |
| C15—N4—C9—C10 | 178.27 (18) | C2—C1—C6—C5 | −0.1 (3) |
| C15—N4—C9—C14 | −0.41 (18) | N1—C1—C6—C5 | −179.23 (15) |
| C13—C14—C9—C10 | 1.1 (3) | N5—C14—C13—C12 | 179.48 (17) |
| N5—C14—C9—C10 | −179.15 (15) | C9—C14—C13—C12 | −0.8 (2) |
| C13—C14—C9—N4 | 179.89 (15) | C17—N7—C23—N8 | 1.29 (19) |
| N5—C14—C9—N4 | −0.31 (18) | C17—N7—C23—C24 | −175.17 (18) |
| C9—N4—C15—N5 | 1.02 (19) | C22—N8—C23—N7 | −1.5 (2) |
| C9—N4—C15—C16 | −175.38 (18) | C22—N8—C23—C24 | 175.21 (16) |
| C14—N5—C15—N4 | −1.22 (19) | C19—C20—C21—C22 | 0.5 (3) |
| C14—N5—C15—C16 | 175.38 (16) | N8—C22—C21—C20 | 179.87 (17) |
| C7—N1—C1—C2 | −178.68 (18) | C17—C22—C21—C20 | −0.7 (2) |
| C7—N1—C1—C6 | 0.28 (18) | C14—C13—C12—C11 | 0.2 (3) |
| N8—C22—C17—C18 | 179.76 (15) | N2—C6—C5—C4 | −179.37 (18) |
| C21—C22—C17—C18 | 0.2 (2) | C1—C6—C5—C4 | 0.3 (3) |
| N8—C22—C17—N7 | −0.25 (17) | C17—C18—C19—C20 | −0.8 (3) |
| C21—C22—C17—N7 | −179.79 (15) | C21—C20—C19—C18 | 0.3 (3) |
| C23—N7—C17—C18 | 179.37 (18) | C6—C5—C4—C3 | −0.3 (3) |
| C23—N7—C17—C22 | −0.62 (18) | C9—C10—C11—C12 | 0.0 (3) |
| N4—C9—C10—C11 | −179.14 (17) | C13—C12—C11—C10 | 0.2 (3) |
| C14—C9—C10—C11 | −0.6 (2) | N2—C7—C8—N3 | −178.27 (17) |
| C22—C17—C18—C19 | 0.5 (2) | N1—C7—C8—N3 | 6.0 (3) |
| N7—C17—C18—C19 | −179.44 (17) | N4—C15—C16—N6 | −6.7 (3) |
| C6—N2—C7—N1 | 1.4 (2) | N5—C15—C16—N6 | 177.37 (17) |
| C6—N2—C7—C8 | −175.02 (16) | C1—C2—C3—C4 | 0.1 (3) |
| C1—N1—C7—N2 | −1.02 (19) | C5—C4—C3—C2 | 0.1 (3) |
| C1—N1—C7—C8 | 175.20 (17) | N7—C23—C24—N9 | −8.3 (3) |
| N1—C1—C2—C3 | 178.75 (17) | N8—C23—C24—N9 | 175.69 (17) |
| C6—C1—C2—C3 | −0.1 (2) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1A···Cl4i | 0.82 (2) | 2.63 (2) | 3.4431 (15) | 168 (3) |
| O1—H2B···Cl2 | 0.81 (2) | 2.36 (2) | 3.1598 (18) | 169 (3) |
| O2—H2C···Cl3 | 0.82 (2) | 2.33 (2) | 3.1244 (17) | 165 (2) |
| O2—H2D···Cl1 | 0.81 (1) | 2.64 (1) | 3.4492 (15) | 171 (3) |
| O3—H3D···Cl5ii | 0.80 (2) | 2.69 (2) | 3.4586 (15) | 164 (3) |
| O3—H3E···Cl6ii | 0.82 (2) | 2.32 (2) | 3.1364 (18) | 173 (3) |
| N1—H1···O1 | 0.83 (2) | 1.92 (2) | 2.746 (2) | 174 (2) |
| N2—H2···Cl1iii | 0.71 (2) | 2.44 (2) | 3.1519 (17) | 175 (2) |
| N3—H3···Cl3 | 0.88 (3) | 2.30 (3) | 3.105 (2) | 153 (2) |
| N3—H3A···Cl1 | 0.86 (4) | 2.26 (3) | 3.119 (2) | 173 (3) |
| N3—H3B···Cl4iv | 0.99 (3) | 2.33 (2) | 3.267 (2) | 156.8 (19) |
| N4—H4A···O2 | 0.85 (2) | 1.91 (2) | 2.754 (2) | 171 (2) |
| N5—H5A···Cl5 | 0.83 (2) | 2.31 (2) | 3.1205 (17) | 165 (2) |
| N6—H6A···Cl2 | 0.87 (3) | 2.33 (3) | 3.107 (2) | 150 (2) |
| N6—H6B···Cl1v | 0.98 (3) | 2.36 (2) | 3.287 (2) | 158.2 (18) |
| N6—H6C···Cl4i | 0.79 (3) | 2.35 (4) | 3.1347 (19) | 176 (3) |
| N7—H7···O3 | 0.85 (3) | 1.89 (3) | 2.742 (2) | 175 (3) |
| N8—H8···Cl4 | 0.81 (2) | 2.31 (2) | 3.1049 (17) | 172 (2) |
| N9—H9A···Cl6 | 0.83 (3) | 2.35 (3) | 3.100 (2) | 151 (2) |
| N9—H9B···Cl5 | 0.80 (3) | 2.32 (2) | 3.120 (2) | 176 (2) |
| N9—H9C···Cl5vi | 0.99 (3) | 2.34 (3) | 3.270 (2) | 157 (2) |
| C4—H4···Cl1i | 0.92 (2) | 2.81 (2) | 3.535 (2) | 136.7 (16) |
| C8—H8B···Cl3vii | 0.93 (3) | 2.65 (3) | 3.544 (2) | 162 (2) |
Symmetry codes: (i) x, y−1, z; (ii) −x, −y+1, −z+1; (iii) −x+3, −y, −z+2; (iv) x+1, y−1, z; (v) x−1, y, z; (vi) −x+1, −y+1, −z+1; (vii) −x+2, −y, −z+2.
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) I. DOI: 10.1107/S205698901801335X/xu5941sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901801335X/xu5941Isup2.hkl
Supporting information file. DOI: 10.1107/S205698901801335X/xu5941Isup3.cml
CCDC reference: 1868580
Additional supporting information: crystallographic information; 3D view; checkCIF report