The crystal structure of 1,3-bis(1H-benzotriazol-1-ylmethyl)benzene shows an interesting three-dimensional assembly influenced by its non-planar molecular conformation.
Keywords: crystal structure, benzotriazole derivative, benzotriazolophanes, bis(1H-benzotriazol-1-ylmethyl)arene ligands
Abstract
The molecular structure of the title compound, C20H16N6, contains two benzotriazole units bonded to a benzene nucleus in a meta configuration, forming dihedral angles of 88.74 (11) and 85.83 (10)° with the central aromatic ring and 57.08 (9)° with each other. The three-dimensional structure is controlled mainly by weak C—H⋯N and C—H⋯π interactions. The molecules are connected in inversion-related pairs, forming the slabs of infinite chains that run along the [-110] and [110] directions.
Chemical context
Bis(1H-benzotriazol-1-ylmethyl)arene compounds are used as precursors for the synthesis of benzotriazolophanes, a class of positively charged cyclophanes that have the potential ability to trap anions and guest molecules with high electron density (Rajakumar & Murali, 2000 ▸). On the other hand, the study of the self-assembly of helicates from the reaction of metal ions with bis(1H-benzotriazol-1-ylmethyl)arene ligands has been of great interest. In these complexes, the metal center coordinates through the N3-nitrogen of the benzotriazole ring (O’Keefe & Steel, 2000 ▸). We have been interested in the synthesis of metal complexes with ligands derived from benzotriazole, which show high activity as catalysts for oxidative amination of allyl butyl ether (Hurtado et al., 2013 ▸).The crystal structures for a number of bis(1H-benzotriazol-1-ylmethyl)arene ligands have been determined: 2,6-bis(1H-benzotriazol-1-ylmethyl)pyridine (Selvanayagam et al., 2002 ▸), 1,4-bis(1H-benzotriazol-1-ylmethyl)benzene tetrahydrate (Cai et al., 2004 ▸) and benzyl 3,5-bis(1H-benzotriazol-1-ylmethyl)phenyl ether (Selvanayagam et al., 2004 ▸). As part of structural studies of the self-assembly process of metal ions with ligands derived from benzotriazole, we report here the crystal structure of the ligand 1,3-bis(1H-benzotriazol-1-ylmethyl)benzene.
Structural commentary
Fig. 1 ▸ shows the molecule of the title compound. The molecular structure is built by two benzotriazole groups describing a meta substitution of the central benzene ring. The dihedral angle between the two benzotriazole units is 57.08 (9)° and those between each benzotriazole moiety (N1–N3/C2–C7) and the central benzene ring are 88.74 (11) and 85.83 (10)° for the A and B groups, respectively. These values differ from the related structures 2,6-bis(N,N′-benzotriazol-1-ylmethyl)pyridine, with a pyridine central ring, where the angle between the two benzotriazole units is 72.49 (6)° and those between the pyridine ring and the two benzotriazole units are 70.26 (6) and 57.70 (7)° (Selvanayagam et al., 2002 ▸), and from the 1,4-bis(1H-benzotriazol-1-ylmethyl)benzene tetrahydrate, with para substitution, where the two benzotriazole units are parallel and the dihedral angle between each benzotriazole unit and the central benzene ring is 74.95 (9)° (Cai et al., 2004 ▸).
Figure 1.
The molecular structure of the title compound, showing anisotropic displacement ellipsoids drawn at the 50% probability level.
Supramolecular features
The packing is directed by weak C—H⋯N and C—H⋯π interactions as shown in Table 1 ▸. Pairs of inversion-related molecules, connected by two equivalent weak C1B—H1BA⋯N3A
i [symmetry code: (i) −x + 1, −y + 1, −z + 1] interactions form slabs of infinite chains of molecules running along [
10]. Each molecule in a slab connects to two translation-equivalent molecules through C4A—H4A⋯N3B
ii [symmetry code: (ii) x − 1, y + 1, z] interactions (Fig. 2 ▸
a). Parallel chains interact through C7A—H7A⋯Cg1iii [Cg1 is the centroid of the N2B–N1B–C2B–C3B–N3B ring; symmetry code: (iii) 1 − x, y, z] (Fig. 2 ▸
b). Since the chains run along the diagonal of the ab plane and a≃b, the 21 screw axis parallel to b transforms each chain into an orthogonal one, running along [110] (Fig. 2 ▸
c). This orthogonal chain interacts with the initial one through C4B—H4B⋯Cg2iv [Cg2 is the centroid of the C4A-C3A-C2A-C7A-C6A-C5A ring; symmetry code: (iv) 
− x, −
+ y, − z] (Fig. 2 ▸
b). In this way, each molecule displays four pairs of interactions with seven neighbouring molecules. This crystallographic three-dimensional organization differs from the related 1,4-bis(1H-benzotriazol-1-ylmethyl)benzene tetrahydrate where a two-dimensional network is observed (Cai et al., 2004 ▸).
Table 1. Hydrogen-bond geometry (Å, °).
Cg1 and Cg2 are the centroids of the N1B–N3B/C2B/C3B C2A–C7A rings, respectively.
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C1B—H1BA⋯N3A i | 0.97 | 2.59 | 3.409 (4) | 142 |
| C4A—H4A⋯N3B ii | 0.93 | 2.66 | 3.443 (4) | 143 |
| C7A—H7A⋯Cg1iii | 0.93 | 2.69 | 3.423 (3) | 136 |
| C4B—H4B⋯Cg2iv | 0.93 | 2.89 | 3.481 (3) | 132 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
.
Figure 2.
The crystal structure of the title compound showing the hydrogen-bond interactions: (a) C—H⋯N along [10], (b) C—H⋯π and (c) orthogonal chains viewed along [001].
Database survey
A search of the Cambridge Structural Database (CSD Version 5.36 with one update; Groom et al., 2016 ▸) for the 1,3-bis(1H-benzotriazol-1-ylmethyl)benzene molecular structure with the possibility of any group replacing the 2,4,5,6-H atoms in the central benzene ring gave four hits, from which two have one additional arene substituent (Br, -OCH2Ph), one has the bis(1H-benzotriazole-1-ylmethanone) moiety instead of bis(1H-benzotriazol-1-ylmethyl) and the last one corresponds to a more complex molecular structure. When the search also considers heterocyclic compounds, two new hits (in addition to the first four structures) appear, one cyclic bipyridine and the related molecular structure 2,6-bis(1H-benzotriazol-1-ylmethyl)pyridine. A search for the 1,4-bis(1H-benzotriazol-1-ylmethyl)-substituted benzene ring gave four hits, one of which corresponds to a ligand with additional methyl groups at the 1,3,5,6-sites of the central benzene ring and the other to its corresponding palladium complex. The remaining two relate to the same compound, viz. 1,4-bis(1H-benzotriazol-1-ylmethyl)benzene tetrahydrate, a related molecular structure.
Synthesis and crystallization
m-Xylylene dibromide (1.16 g, 4.4 mmol) was added to a solution of 1H-benzotriazole (1.04 g, 8.7 mmol) in toluene (60 mL), and the mixture was heated at reflux for 72 h. The resulting mixture was filtered, and the toluene solution was concentrated and cooled to give a white solid. Single crystals suitable for X-ray structure analysis were obtained by dissolving the compound in the minimum volume of dichloromethane, adding diethyl ether and cooling the solution to 277 K. The title compound formed colorless parallelepipeds. Yield: 668 mg (45%). M.p. 423–424 K. IR (KBr, cm−1): ν 3058 (w), 3031 (w), 2979 (w), 2944 (w), 1613 (m), 1494 (m), 1452 (s), 1228 (s), 1159 (m), 1080 (s), 781 (s), 754 (s), 743 (s). 1H NMR (400 MHz, DMSO-d6): δ (p.p.m.) 8.04 (d, J = 8.3 Hz, 2H), 7.72 (d, J = 8.3 Hz, 2H), 7.47 (t, J = 8.1 Hz, 2H), 7.38 (t, J = 8.2 Hz, 2H), 7.36 (s, 1H), 7.32 (dd, J = 8.5, 6.6 Hz, 1H), 7.25 (d, J = 8.2 Hz, 2H), 5.95 (s, 4H). 13C NMR (100 MHz, DMSO-d6): δ (p.p.m.) 145.3 (C), 136.5 (C), 132.6 (C), 129.3 (CH), 127.5 (CH), 127.4 (CH), 127.2 (CH), 124.0 (CH), 119.2 (CH), 110.6 (CH), 50.7 (CH2). HRMS m/z (ESI) calculated for [C20H16N6+H]+: 341.1509; found 341.1532 [M+H]+.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. H atoms were placed in calculated positions (C—H: 0.93–0.97 Å) and included as riding contributions with isotropic displacement parameters set at 1.2–1.5 times the U eq value of the parent atom.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C20H16N6 |
| M r | 340.39 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 293 |
| a, b, c (Å) | 9.3050 (5), 9.4479 (5), 19.5429 (9) |
| β (°) | 99.205 (2) |
| V (Å3) | 1695.94 (15) |
| Z | 4 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.08 |
| Crystal size (mm) | 0.40 × 0.39 × 0.18 |
| Data collection | |
| Diffractometer | Bruker D8 Venture/Photon 100 CMOS |
| Absorption correction | Multi-scan (SADABS; Bruker, 2013 ▸) |
| T min, T max | 0.666, 0.746 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 28764, 3480, 2830 |
| R int | 0.035 |
| (sin θ/λ)max (Å−1) | 0.626 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.067, 0.160, 1.42 |
| No. of reflections | 3480 |
| No. of parameters | 236 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.24, −0.27 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016007805/bg2585sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016007805/bg2585Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989016007805/bg2585Isup3.cml
CCDC reference: 1479416
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The financial support from the Departamento de Química, Facultad de Ciencias and Vicerrectoría de Investigaciones of the Universidad de los Andes is gratefully acknowledged. NND is also grateful to COLCIENCIAS for his doctoral scholarship (Conv. 617). The authors wish to thank ANII (EQC_2012_07), CSIC and Facultad de Química for the funds to purchase the diffractometer. MAM also thanks ANII for his post-doctoral contract (PD_NAC_2014_1_102409).
supplementary crystallographic information
Crystal data
| C20H16N6 | F(000) = 712 |
| Mr = 340.39 | Dx = 1.333 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| a = 9.3050 (5) Å | Cell parameters from 9846 reflections |
| b = 9.4479 (5) Å | θ = 3.0–27.1° |
| c = 19.5429 (9) Å | µ = 0.08 mm−1 |
| β = 99.205 (2)° | T = 293 K |
| V = 1695.94 (15) Å3 | Parallelepiped, colorless |
| Z = 4 | 0.40 × 0.39 × 0.18 mm |
Data collection
| Bruker D8 Venture/Photon 100 CMOS diffractometer | 3480 independent reflections |
| Radiation source: Mo sealed tube | 2830 reflections with I > 2σ(I) |
| Detector resolution: 10.4167 pixels mm-1 | Rint = 0.035 |
| φ and ω scans | θmax = 26.4°, θmin = 3.0° |
| Absorption correction: multi-scan (SADABS; Bruker, 2013) | h = −11→11 |
| Tmin = 0.666, Tmax = 0.746 | k = −11→11 |
| 28764 measured reflections | l = −24→24 |
Refinement
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.067 | w = 1/[σ2(Fo2) + (0.036P)2 + 0.9412P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.160 | (Δ/σ)max < 0.001 |
| S = 1.42 | Δρmax = 0.24 e Å−3 |
| 3480 reflections | Δρmin = −0.27 e Å−3 |
| 236 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.0162 (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 | ||
| C1 | 0.2899 (2) | 0.1606 (3) | 0.54469 (11) | 0.0400 (5) | |
| C2 | 0.2736 (3) | 0.0198 (3) | 0.56154 (13) | 0.0475 (6) | |
| H2 | 0.1814 | −0.0207 | 0.5552 | 0.057* | |
| C3 | 0.3936 (3) | −0.0607 (3) | 0.58775 (13) | 0.0499 (6) | |
| H3 | 0.3820 | −0.1554 | 0.5985 | 0.060* | |
| C4 | 0.5308 (3) | −0.0010 (3) | 0.59803 (13) | 0.0454 (6) | |
| H4 | 0.6109 | −0.0560 | 0.6159 | 0.054* | |
| C5 | 0.5505 (2) | 0.1396 (2) | 0.58204 (11) | 0.0366 (5) | |
| C6 | 0.4286 (2) | 0.2197 (3) | 0.55500 (12) | 0.0401 (5) | |
| H6 | 0.4403 | 0.3141 | 0.5437 | 0.048* | |
| C1A | 0.1582 (3) | 0.2463 (3) | 0.51371 (14) | 0.0516 (7) | |
| H1AA | 0.1547 | 0.2522 | 0.4639 | 0.062* | |
| H1AB | 0.0708 | 0.1981 | 0.5223 | 0.062* | |
| N1A | 0.1601 (2) | 0.3890 (2) | 0.54221 (10) | 0.0433 (5) | |
| C2A | 0.1399 (2) | 0.4294 (2) | 0.60655 (12) | 0.0380 (5) | |
| N2A | 0.1856 (3) | 0.5036 (3) | 0.50437 (13) | 0.0606 (6) | |
| C1B | 0.6995 (3) | 0.2062 (3) | 0.59004 (13) | 0.0457 (6) | |
| H1BA | 0.7311 | 0.2092 | 0.5451 | 0.055* | |
| H1BB | 0.6932 | 0.3030 | 0.6059 | 0.055* | |
| N1B | 0.8073 (2) | 0.1311 (2) | 0.63824 (10) | 0.0408 (5) | |
| C3A | 0.1528 (3) | 0.5760 (3) | 0.60636 (14) | 0.0458 (6) | |
| N3A | 0.1814 (3) | 0.6171 (3) | 0.54235 (14) | 0.0621 (7) | |
| C2B | 0.8262 (2) | 0.1272 (2) | 0.70871 (12) | 0.0400 (5) | |
| N2B | 0.9063 (2) | 0.0455 (2) | 0.61519 (12) | 0.0530 (6) | |
| C4A | 0.1384 (3) | 0.6549 (3) | 0.66532 (18) | 0.0633 (8) | |
| H4A | 0.1454 | 0.7531 | 0.6658 | 0.076* | |
| C3B | 0.9426 (3) | 0.0367 (3) | 0.72765 (14) | 0.0455 (6) | |
| N3B | 0.9888 (2) | −0.0122 (2) | 0.66848 (14) | 0.0589 (6) | |
| C5A | 0.1133 (4) | 0.5806 (4) | 0.72234 (18) | 0.0716 (9) | |
| H5A | 0.1039 | 0.6297 | 0.7626 | 0.086* | |
| C4B | 0.9949 (3) | 0.0093 (3) | 0.79741 (17) | 0.0656 (9) | |
| H4B | 1.0748 | −0.0492 | 0.8108 | 0.079* | |
| C6A | 0.1013 (4) | 0.4324 (4) | 0.72188 (15) | 0.0654 (8) | |
| H6A | 0.0840 | 0.3864 | 0.7618 | 0.078* | |
| C5B | 0.9239 (4) | 0.0719 (4) | 0.84490 (18) | 0.0782 (11) | |
| H5B | 0.9553 | 0.0550 | 0.8918 | 0.094* | |
| C7A | 0.1143 (3) | 0.3539 (3) | 0.66457 (13) | 0.0504 (6) | |
| H7A | 0.1065 | 0.2557 | 0.6643 | 0.060* | |
| C7B | 0.7529 (3) | 0.1924 (3) | 0.75700 (15) | 0.0589 (7) | |
| H7B | 0.6744 | 0.2529 | 0.7439 | 0.071* | |
| C6B | 0.8042 (4) | 0.1616 (4) | 0.82488 (16) | 0.0756 (10) | |
| H6B | 0.7580 | 0.2015 | 0.8591 | 0.091* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0383 (12) | 0.0479 (14) | 0.0339 (11) | 0.0014 (10) | 0.0059 (9) | −0.0096 (10) |
| C2 | 0.0445 (13) | 0.0528 (15) | 0.0460 (14) | −0.0082 (12) | 0.0102 (11) | −0.0078 (11) |
| C3 | 0.0537 (15) | 0.0423 (14) | 0.0545 (15) | −0.0078 (12) | 0.0106 (12) | 0.0013 (12) |
| C4 | 0.0477 (13) | 0.0418 (13) | 0.0466 (13) | 0.0024 (11) | 0.0074 (11) | 0.0043 (11) |
| C5 | 0.0393 (12) | 0.0386 (12) | 0.0324 (11) | 0.0002 (10) | 0.0067 (9) | −0.0014 (9) |
| C6 | 0.0422 (12) | 0.0378 (12) | 0.0396 (12) | 0.0009 (10) | 0.0048 (10) | −0.0001 (10) |
| C1A | 0.0419 (13) | 0.0631 (17) | 0.0472 (14) | 0.0063 (12) | −0.0009 (11) | −0.0123 (12) |
| N1A | 0.0405 (11) | 0.0486 (12) | 0.0407 (11) | 0.0041 (9) | 0.0059 (9) | 0.0062 (9) |
| C2A | 0.0316 (11) | 0.0408 (12) | 0.0414 (12) | 0.0029 (9) | 0.0052 (9) | 0.0043 (10) |
| N2A | 0.0552 (14) | 0.0708 (17) | 0.0561 (14) | 0.0028 (12) | 0.0096 (11) | 0.0247 (13) |
| C1B | 0.0420 (13) | 0.0432 (13) | 0.0502 (14) | −0.0009 (11) | 0.0027 (11) | 0.0070 (11) |
| N1B | 0.0351 (10) | 0.0399 (11) | 0.0474 (11) | 0.0040 (8) | 0.0071 (8) | −0.0005 (9) |
| C3A | 0.0370 (12) | 0.0391 (13) | 0.0600 (16) | 0.0051 (10) | 0.0041 (11) | 0.0074 (11) |
| N3A | 0.0586 (14) | 0.0537 (14) | 0.0725 (16) | 0.0015 (12) | 0.0062 (12) | 0.0232 (13) |
| C2B | 0.0373 (12) | 0.0360 (12) | 0.0466 (13) | −0.0016 (10) | 0.0061 (10) | −0.0005 (10) |
| N2B | 0.0445 (12) | 0.0517 (13) | 0.0651 (14) | 0.0055 (10) | 0.0155 (11) | −0.0103 (11) |
| C4A | 0.0559 (17) | 0.0421 (15) | 0.091 (2) | 0.0059 (13) | 0.0083 (16) | −0.0118 (15) |
| C3B | 0.0354 (12) | 0.0368 (12) | 0.0615 (16) | −0.0022 (10) | −0.0006 (11) | 0.0035 (11) |
| N3B | 0.0445 (12) | 0.0496 (13) | 0.0823 (17) | 0.0103 (10) | 0.0087 (12) | −0.0032 (12) |
| C5A | 0.067 (2) | 0.078 (2) | 0.073 (2) | 0.0010 (17) | 0.0205 (16) | −0.0281 (18) |
| C4B | 0.0582 (17) | 0.0525 (17) | 0.077 (2) | −0.0098 (14) | −0.0182 (15) | 0.0150 (16) |
| C6A | 0.077 (2) | 0.072 (2) | 0.0515 (16) | −0.0086 (17) | 0.0232 (15) | −0.0035 (15) |
| C5B | 0.100 (3) | 0.071 (2) | 0.0560 (19) | −0.028 (2) | −0.0110 (18) | 0.0139 (17) |
| C7A | 0.0571 (15) | 0.0460 (14) | 0.0490 (14) | −0.0057 (12) | 0.0119 (12) | 0.0020 (11) |
| C7B | 0.0622 (17) | 0.0583 (17) | 0.0587 (17) | 0.0045 (14) | 0.0176 (14) | −0.0055 (14) |
| C6B | 0.102 (3) | 0.076 (2) | 0.0519 (18) | −0.012 (2) | 0.0221 (18) | −0.0090 (16) |
Geometric parameters (Å, º)
| C1—C2 | 1.384 (4) | N1B—N2B | 1.355 (3) |
| C1—C6 | 1.391 (3) | N1B—C2B | 1.361 (3) |
| C1—C1A | 1.513 (3) | C3A—N3A | 1.376 (3) |
| C2—C3 | 1.380 (4) | C3A—C4A | 1.397 (4) |
| C2—H2 | 0.9300 | C2B—C3B | 1.383 (3) |
| C3—C4 | 1.380 (4) | C2B—C7B | 1.394 (4) |
| C3—H3 | 0.9300 | N2B—N3B | 1.310 (3) |
| C4—C5 | 1.384 (3) | C4A—C5A | 1.369 (5) |
| C4—H4 | 0.9300 | C4A—H4A | 0.9300 |
| C5—C6 | 1.395 (3) | C3B—N3B | 1.376 (4) |
| C5—C1B | 1.507 (3) | C3B—C4B | 1.396 (4) |
| C6—H6 | 0.9300 | C5A—C6A | 1.404 (5) |
| C1A—N1A | 1.457 (3) | C5A—H5A | 0.9300 |
| C1A—H1AA | 0.9700 | C4B—C5B | 1.358 (5) |
| C1A—H1AB | 0.9700 | C4B—H4B | 0.9300 |
| N1A—N2A | 1.354 (3) | C6A—C7A | 1.365 (4) |
| N1A—C2A | 1.355 (3) | C6A—H6A | 0.9300 |
| C2A—C3A | 1.390 (3) | C5B—C6B | 1.405 (5) |
| C2A—C7A | 1.392 (3) | C5B—H5B | 0.9300 |
| N2A—N3A | 1.308 (4) | C7A—H7A | 0.9300 |
| C1B—N1B | 1.447 (3) | C7B—C6B | 1.367 (4) |
| C1B—H1BA | 0.9700 | C7B—H7B | 0.9300 |
| C1B—H1BB | 0.9700 | C6B—H6B | 0.9300 |
| H1BA···N3Ai | 2.59 | H7A···Cg1iii | 2.69 |
| H4A···N3Bii | 2.66 | H4B···Cg2iv | 2.79 |
| C2—C1—C6 | 119.1 (2) | N2B—N1B—C1B | 120.9 (2) |
| C2—C1—C1A | 119.8 (2) | C2B—N1B—C1B | 129.5 (2) |
| C6—C1—C1A | 121.1 (2) | N3A—C3A—C2A | 108.2 (2) |
| C3—C2—C1 | 120.3 (2) | N3A—C3A—C4A | 131.1 (3) |
| C3—C2—H2 | 119.8 | C2A—C3A—C4A | 120.7 (3) |
| C1—C2—H2 | 119.8 | N2A—N3A—C3A | 108.2 (2) |
| C2—C3—C4 | 120.2 (2) | N1B—C2B—C3B | 104.9 (2) |
| C2—C3—H3 | 119.9 | N1B—C2B—C7B | 132.5 (2) |
| C4—C3—H3 | 119.9 | C3B—C2B—C7B | 122.6 (2) |
| C3—C4—C5 | 120.8 (2) | N3B—N2B—N1B | 109.1 (2) |
| C3—C4—H4 | 119.6 | C5A—C4A—C3A | 116.7 (3) |
| C5—C4—H4 | 119.6 | C5A—C4A—H4A | 121.7 |
| C4—C5—C6 | 118.5 (2) | C3A—C4A—H4A | 121.7 |
| C4—C5—C1B | 122.0 (2) | N3B—C3B—C2B | 108.6 (2) |
| C6—C5—C1B | 119.4 (2) | N3B—C3B—C4B | 130.7 (3) |
| C1—C6—C5 | 121.1 (2) | C2B—C3B—C4B | 120.8 (3) |
| C1—C6—H6 | 119.4 | N2B—N3B—C3B | 107.8 (2) |
| C5—C6—H6 | 119.4 | C4A—C5A—C6A | 122.0 (3) |
| N1A—C1A—C1 | 112.5 (2) | C4A—C5A—H5A | 119.0 |
| N1A—C1A—H1AA | 109.1 | C6A—C5A—H5A | 119.0 |
| C1—C1A—H1AA | 109.1 | C5B—C4B—C3B | 117.1 (3) |
| N1A—C1A—H1AB | 109.1 | C5B—C4B—H4B | 121.5 |
| C1—C1A—H1AB | 109.1 | C3B—C4B—H4B | 121.5 |
| H1AA—C1A—H1AB | 107.8 | C7A—C6A—C5A | 122.0 (3) |
| N2A—N1A—C2A | 110.1 (2) | C7A—C6A—H6A | 119.0 |
| N2A—N1A—C1A | 121.6 (2) | C5A—C6A—H6A | 119.0 |
| C2A—N1A—C1A | 128.3 (2) | C4B—C5B—C6B | 121.5 (3) |
| N1A—C2A—C3A | 104.7 (2) | C4B—C5B—H5B | 119.2 |
| N1A—C2A—C7A | 132.7 (2) | C6B—C5B—H5B | 119.2 |
| C3A—C2A—C7A | 122.6 (2) | C6A—C7A—C2A | 116.0 (3) |
| N3A—N2A—N1A | 108.8 (2) | C6A—C7A—H7A | 122.0 |
| N1B—C1B—C5 | 113.11 (19) | C2A—C7A—H7A | 122.0 |
| N1B—C1B—H1BA | 109.0 | C6B—C7B—C2B | 115.5 (3) |
| C5—C1B—H1BA | 109.0 | C6B—C7B—H7B | 122.3 |
| N1B—C1B—H1BB | 109.0 | C2B—C7B—H7B | 122.3 |
| C5—C1B—H1BB | 109.0 | C7B—C6B—C5B | 122.5 (3) |
| H1BA—C1B—H1BB | 107.8 | C7B—C6B—H6B | 118.8 |
| N2B—N1B—C2B | 109.6 (2) | C5B—C6B—H6B | 118.8 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y+1, z; (iii) x−1, y, z; (iv) −x+3/2, y−1/2, −z+3/2.
Hydrogen-bond geometry (Å, º)
Cg1 and Cg2 are the centroids of the N1B–N3B/C2B/C3B C2A–C7A rings, respectively.
| D—H···A | D—H | H···A | D···A | D—H···A |
| C1B—H1BA···N3Ai | 0.97 | 2.59 | 3.409 (4) | 142 |
| C4A—H4A···N3Bii | 0.93 | 2.66 | 3.443 (4) | 143 |
| C7A—H7A···Cg1iii | 0.93 | 2.69 | 3.423 (3) | 136 |
| C4B—H4B···Cg2iv | 0.93 | 2.89 | 3.481 (3) | 132 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y+1, z; (iii) x−1, y, z; (iv) −x+3/2, y−1/2, −z+3/2.
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/S2056989016007805/bg2585sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016007805/bg2585Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989016007805/bg2585Isup3.cml
CCDC reference: 1479416
Additional supporting information: crystallographic information; 3D view; checkCIF report