Crystal structure of 1,3-bis­(1H-benzotriazol-1-yl­meth­yl)benzene

Macías, M.A.; Nuñez-Dallos, N.; Hurtado, J.; Suescun, L.

doi:10.1107/S2056989016007805

research communications

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ISSN: 2056-9890

Volume 72| Part 6| June 2016| Pages 815-818

https://doi.org/10.1107/S2056989016007805

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Crystal structure of 1,3-bis(1H-benzotriazol-1-ylmethyl)benzene

Mario A. Macías,^a,^b Nelson Nuñez-Dallos,^c John Hurtado ^c ^* and Leopoldo Suescun ^a ^*

^aCryssmat-Lab/Cátedra de Física/DETEMA, Facultad de Química, Universidad de la República, Montevideo, Uruguay, ^bGrupo INTERFASE, Universidad Industrial de Santander, Carrera 27, Calle 9, Ciudad Universitaria, Bucaramanga, Colombia, and ^cDepartamento de Química, Universidad de los Andes, Carrera 1 No 18A-12, Bogotá, Colombia
^*Correspondence e-mail: jj.hurtado@uniandes.edu.co, leopoldo@fq.edu.uy

Edited by R. F. Baggio, Comisión Nacional de Energía Atómica, Argentina (Received 4 May 2016; accepted 11 May 2016; online 17 May 2016)

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.

Keywords: crystal structure; benzotriazole derivative; benzotriazolophanes; bis(1H-benzotriazol-1-ylmethyl)arene ligands.

CCDC reference: 1479416

1. 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.

2. 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.

3. 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⋯N3Aⁱ [symmetry code: (i) −x + 1, −y + 1, −z + 1] interactions form slabs of infinite chains of molecules running along [ $[\overline{1}]$ 10]. Each molecule in a slab connects to two translation-equivalent molecules through C4A—H4A⋯N3Bⁱⁱ [symmetry code: (ii) x − 1, y + 1, z] interactions (Fig. 2a). 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. 2b). 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. 2c). This orthogonal chain interacts with the initial one through C4B—H4B⋯Cg2^iv [Cg2 is the centroid of the C4A-C3A-C2A-C7A-C6A-C5A ring; symmetry code: (iv) $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z] (Fig. 2b). 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⋯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⋯Cg2^iv	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) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
The crystal structure of the title compound showing the hydrogen-bond interactions: (a) C—H⋯N along [ $[\overline{1}]$ 10], (b) C—H⋯π and (c) orthogonal chains viewed along [001].

4. 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.

5. 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]⁺.

6. 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[F² > 2σ(F²)], wR(F²), S	0.067, 0.160, 1.42
No. of reflections	3480
No. of parameters	236
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.27
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS2014 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and Mercury (Macrae et al., 2008 ).

Supporting information

CCDC reference: 1479416

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016007805/bg2585sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016007805/bg2585Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016007805/bg2585Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

1,3-Bis(1H-benzotriazol-1-ylmethyl)benzene top

Crystal data top

C₂₀H₁₆N₆	F(000) = 712
M_r = 340.39	D_x = 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 top

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	R_int = 0.035
φ and ω scans	θ_max = 26.4°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2013)	h = −11→11
T_min = 0.666, T_max = 0.746	k = −11→11
28764 measured reflections	l = −24→24

Refinement top

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(F_o²) + (0.036P)² + 0.9412P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.160	(Δ/σ)_max < 0.001
S = 1.42	Δρ_max = 0.24 e Å⁻³
3480 reflections	Δρ_min = −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 top

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) top

	x	y	z	U_iso*/U_eq
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) top

	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) top

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···Cg2^iv	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) top

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···Cg2^iv	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.

Acknowledgements

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).

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