2,8-Dimethyl-5,11-bis­[3-(methyl­sulfan­yl)prop­yl]-1H,7H-diimidazo[c,h][1,6]diazecine

Gasque, L.; Zermeño, E.; Bernès, S.

doi:10.1107/S2414314619004413

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 4| April 2019| x190441

https://doi.org/10.1107/S2414314619004413

Open

access

2,8-Dimethyl-5,11-bis[3-(methylsulfanyl)propyl]-1H,7H-diimidazo[c,h][1,6]diazecine

Laura Gasque,^a Edgar Zermeño ^a and Sylvain Bernès ^b ^*

^aFacultad de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, 04510 México D.F., Mexico, and ^bInstituto de Física, Benemérita Universidad Autónoma de Puebla, Av. San Claudio y 18 Sur, 72570 Puebla, Pue., Mexico
^*Correspondence e-mail: sylvain_bernes@hotmail.com

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 25 March 2019; accepted 1 April 2019; online 5 April 2019)

The refinement of the crystal structure of the title compound, C₂₀H₃₄N₆S₂, was challenging, as a consequence of three issues: crystals are twinned, disordered, and include large empty voids corresponding to ca 8% of the unit-cell volume. A satisfactory model was obtained using data collected at 153 K. The diazecine ring is centrosymmetric, and displays the expected boat–chair–boat conformation. The 3-(methylsulfanyl)propyl chain is disordered over two sites with equal occupancies, and different conformations, i.e. trans–gauche–gauche for the first chain [N_diaz—C_meth—C_meth—C_meth torsion angles: 169.9 (4), 66.8 (5), 62.4 (5)°; diaz = diazecine and meth = methylene] and trans–trans–gauche for the second component [torsion angles: 169.9 (4), −177.6 (4), 64.4 (5)°]. In the crystal, N—H⋯N hydrogen bonds between imidazole rings are evident; weak intermolecular C—H⋯S contacts are also noted. The crystal studied was modelled as a two-component twin.

Keywords: crystal structure; diazecine; twinning; disorder; SQUEEZE algorithm.

CCDC reference: 1907206

Structure description

The chemistry of [1,6]diazecine derivatives bearing imidazole rings started in the 1990′s, through a collaboration between groups from Mexico and The Netherlands (Mendoza-Díaz et al., 1996 ), when a suitable methodology was established for their preparation, based on the Mannich reaction. Here, the one-pot reaction between propylamine, formaldehyde and 2-methylimidazole resulted in the double addition of formaldehyde on the imidazole, followed by condensation with propylamine, to afford the ten-membered ring characterizing the diazecines. Some other related structures were characterized by X-ray diffraction, upon modification of the group substituting the N sites in positions 1 and 6 in the ring (Mendoza-Díaz et al., 2002 , 2010 ). On the other hand, the coordination chemistry of Cu^II with these molecules was studied, which has been relevant towards bioinorganic topics, including the modelling of the active site of catecholases (Mendoza-Díaz et al., 2002; Mendoza-Quijano et al., 2012 ; Zerón et al., 2017 ).

Although the bioinorganic chemistry has grown steadily for this class of compound, it is clear that the chemical crystallography of the corresponding free ligands is rather poor, with very few structures deposited in the Cambridge Structural Database (Groom et al., 2016 ). The reason probably stems in part from the fact that the refinement of these crystal structures is not always routine. In the case of the title compound, three issues made the refinement challenging: (i) crystals are systematically twinned, a rather common feature for the tetragonal system. In the present case, a rotation axis about (110) is swapping unit cell vectors a and b in the Laue class 4/m (class I of twins by merohedry), to form an almost perfect twin; for the studied crystal, fractional contributions for the two-component twin were k₁ = 0.486 (2) and k₂ = 0.514 (2). (ii) A disorder is observed for the lateral 3-(methylsulfanyl)propyl chain, involving the S atom, which is the main scatterer in the crystal (see Fig. 1, inset). Indeed, this disorder could not be solved using room-temperature diffraction data. (iii) The packing efficiency of the molecules in the crystal is very poor, leaving ca 8% of the cell empty (Fig. 2). Apparently, each individual void of ca 100 Å³ is not filled with disordered solvent (ethanol or water), as evidenced by unsuccessful attempts to include the contribution of disordered solvents to structure factors using the SQUEEZE tool in PLATON (Spek, 2015 ); a non-significant density of 12 e⁻ per unit cell was recovered, corresponding to 1.5 e⁻/molecule.

Figure 1
Molecular structure of the title compound, with 50% displacement ellipsoids for non-H atoms. Disordered sites B were omitted for clarity. The complete asymmetric unit is represented in the inset, including A and B disordered sites.

Figure 2
Part of the crystal structure of the title compound, viewed along the b axis. The minor part of the disorder and H atoms were omitted. The red molecule in the top-left unit cell includes the asymmetric unit. Void spaces in the crystal are delimited by gold surfaces calculated using the `contact surface' tool in Mercury, with a probe radius of 1.2 Å and a grid spacing of 0.3 Å (Macrae et al., 2008

Although these issues are decreased dramatically the scattering power of the crystals, data collected on a large sample at 153 K were suitable for refining the structure satisfactorily. The asymmetric unit contains half the formula, with the molecule lying on an inversion centre (Fig. 1). Atoms C10/S1/C11 belonging to the lateral chain are disordered over two sites, with occupancies equal to 0.5 for each part (sites A and B, Fig. 1, inset). The conformation of this chain is different for each disordered part: trans–gauche–gauche for part A [torsion angles starting from N7: 169.9 (4), 66.8 (5), 62.4 (5)°] and trans–trans–gauche for part B [torsion angles starting from N7: 169.9 (4), −177.6 (4), 64.4 (5)°]. The diazecine ten-membered ring adopts the skewed boat-chair-boat conformation, invariably found in other related derivatives (idealized symmetry: C_2h). In the imidazole ring, π-bonds are localized, with normal bond lengths C2=N3 [1.320 (3) Å] and C3=C4 [1.369 (3) Å]. As a consequence, the imidazolic H atom is localized on N1. This group serves as donor group for the formation of N1—H1⋯N3 hydrogen bonds with a symmetry-related imidazole ring. Other potentially stabilizing hydrogen bonds are weak intermolecular C—H⋯S contacts (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N3ⁱ	0.68 (3)	2.15 (3)	2.825 (2)	169 (3)
C6—H6B⋯S1Aⁱⁱ	0.99	2.93	3.837 (3)	153
C12—H12A⋯S1Aⁱⁱⁱ	0.98	3.01	3.926 (3)	156
C11B—H11D⋯S1B^iv	0.98	1.97	2.767 (6)	137
Symmetry codes: (i) $[y-{\script{1\over 4}}, -x+{\script{3\over 4}}, z-{\script{1\over 4}}]$ ; (ii) $[-y+{\script{5\over 4}}, x-{\script{1\over 4}}, z-{\script{1\over 4}}]$ ; (iii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z+1.

Synthesis and crystallization

2-Methylimidazole (20 mmol, 1.64 g) was dissolved in water (100 ml). To this solution, with vigorous stirring, 3(methylthio)propylamine (20 mmol, 2.1 g) was added dropwise. This mixture formed an emulsion which was broken with the addition of EtOH (ca 20 ml). Without pausing the agitation, formaldehyde (60 mmol, 37% aqueous solution) was added dropwise. This mixture was allowed to react at 333 K for approximately two days when the appearance of a white precipitate indicated the presence of the product. Analysis calculated (%) for C₂₀H₃₄N₆S₂: C, 56.37; H, 8.11; N, 19.88; S, 15.17. Found: C, 57.15; H, 8.25; N, 19.68, S, 15.30. ¹H-NMR (400 MHz, CD₃OD, p.p.m.) δ: 2.34 (s, 6H, CH₃-Im), 3.36 (s, 8H, Im–CH₂–N—R), 1.93 (q, 4H, –CH₂-CH₂-CH₂—S—CH₃), 2.12 (s, 6H, CH₃-S–), 2.92 (t, 4H, –CH₂—CH₂–CH₂–N–), 2.66 (t, 4H, –S–CH₂–CH₂—CH₂—N–). Crystalline samples were obtained from the slow evaporation of ethanolic solutions of the compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The crystal was modelled as a two-component twin, using the twin matrix (0 1 0, 1 0 0, 0 0 $[\overline{1}]$ ) and one batch scale factor, which converged to 0.486 (2) (Sheldrick, 2015b ). Occupancies for disordered sites A and B (atoms C10/S1/C11) were first refined, and since they converged towards a value very close to 1/2, they were fixed to 0.5 in the last cycles of refinement.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₀H₃₄N₆S₂
M_r	422.65
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	153
a, c (Å)	16.8114 (6), 17.8288 (6)
V (Å³)	5038.8 (4)
Z	8
Radiation type	Ag Kα, λ = 0.56083 Å
μ (mm⁻¹)	0.12
Crystal size (mm)	0.30 × 0.25 × 0.25

Data collection
Diffractometer	Stoe Stadivari
Absorption correction	Multi-scan (X-AREA; Stoe & Cie, 2018 )
T_min, T_max	0.326, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	50278, 2943, 2296
R_int	0.098
(sin θ/λ)_max (Å⁻¹)	0.653

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.138, 0.97
No. of reflections	2943
No. of parameters	159
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.19
Computer programs: X-AREA, SHELXT2018 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b), XP in SHELXTL-Plus (Sheldrick, 2008 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1907206

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619004413/tk4057sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619004413/tk4057Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619004413/tk4057Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2018); cell refinement: X-AREA (Stoe & Cie, 2018; data reduction: X-AREA (Stoe & Cie, 2018; program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

2,8-Dimethyl-5,11-bis[3-(methylsulfanyl)propyl]-1H,7H-diimidazo[c,h][1,6]diazecine top

Crystal data top

C₂₀H₃₄N₆S₂	D_x = 1.114 Mg m⁻³
M_r = 422.65	Ag Kα radiation, λ = 0.56083 Å
Tetragonal, I4₁/a	Cell parameters from 29151 reflections
a = 16.8114 (6) Å	θ = 2.3–25.6°
c = 17.8288 (6) Å	µ = 0.12 mm⁻¹
V = 5038.8 (4) Å³	T = 153 K
Z = 8	Prism, yellow
F(000) = 1824	0.30 × 0.25 × 0.25 mm

Data collection top

Stoe Stadivari diffractometer	2943 independent reflections
Radiation source: Sealed X-ray tube, Axo Astix-f Microfocus source	2296 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	R_int = 0.098
Detector resolution: 5.81 pixels mm^-1	θ_max = 21.5°, θ_min = 2.3°
ω scans	h = −21→21
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2018)	k = −21→21
T_min = 0.326, T_max = 1.000	l = −23→19
50278 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: mixed
wR(F²) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ²(F_o²) + (0.0946P)²] where P = (F_o² + 2F_c²)/3
2943 reflections	(Δ/σ)_max < 0.001
159 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³
0 constraints

Special details top

Refinement. Refined as a 2-component twin, rotation axis (1 1 0). TWIN 0 1 0 1 0 0 0 0 -1 2 BASF 0.48572

All C-bound H atoms were placed in calculated positions and refined as riding to their carrier C atoms with isotropic displacement parameters. The atomic coordinates for the N-bound H atom were refined; U_iso = 1.2U_eq(N).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C10A	0.5232 (4)	0.5267 (4)	0.3420 (3)	0.0508 (13)	0.5
H10A	0.559442	0.480455	0.338174	0.061*	0.5
H10B	0.482368	0.515233	0.380508	0.061*	0.5
S1A	0.57758 (8)	0.61513 (10)	0.36542 (7)	0.0531 (4)	0.5
C11A	0.5021 (6)	0.6863 (5)	0.3722 (7)	0.126 (4)	0.5
H11A	0.525322	0.737967	0.385065	0.189*	0.5
H11B	0.474258	0.690329	0.324065	0.189*	0.5
H11C	0.464325	0.670403	0.411337	0.189*	0.5
C10B	0.5452 (3)	0.5766 (5)	0.3314 (3)	0.0541 (14)	0.5
H10C	0.557718	0.633326	0.322144	0.065*	0.5
H10D	0.595553	0.546074	0.329966	0.065*	0.5
S1B	0.49849 (9)	0.56555 (13)	0.42257 (7)	0.0728 (5)	0.5
C11B	0.4927 (5)	0.4626 (7)	0.4248 (4)	0.099 (3)	0.5
H11D	0.467977	0.445643	0.471933	0.149*	0.5
H11E	0.460470	0.443912	0.382466	0.149*	0.5
H11F	0.546275	0.439992	0.421161	0.149*	0.5
N1	0.33547 (11)	0.45749 (11)	−0.05949 (9)	0.0340 (4)
H1	0.3217 (17)	0.4482 (17)	−0.0945 (15)	0.041*
C2	0.28871 (13)	0.49400 (12)	−0.00916 (11)	0.0337 (4)
N3	0.32672 (11)	0.50618 (11)	0.05457 (9)	0.0342 (4)
C3	0.40212 (12)	0.47426 (12)	0.04372 (11)	0.0308 (4)
C4	0.40840 (12)	0.44355 (12)	−0.02712 (11)	0.0316 (4)
C5	0.47564 (13)	0.40230 (13)	−0.06585 (12)	0.0369 (5)
H5A	0.516715	0.390068	−0.027772	0.044*
H5B	0.455497	0.350876	−0.085133	0.044*
C6	0.46077 (13)	0.47487 (14)	0.10598 (10)	0.0361 (5)
H6A	0.437275	0.447824	0.150050	0.043*
H6B	0.508375	0.444327	0.090521	0.043*
N7	0.48549 (11)	0.55613 (12)	0.12799 (8)	0.0373 (4)
C8	0.53467 (15)	0.5544 (2)	0.19642 (12)	0.0559 (8)
H8A	0.564999	0.604701	0.200290	0.067*
H8B	0.573358	0.510160	0.192816	0.067*
C9	0.48435 (19)	0.5437 (2)	0.26668 (12)	0.0732 (10)
H9A	0.452184	0.592605	0.272717	0.088*	0.5
H9B	0.446619	0.499762	0.256607	0.088*	0.5
H9C	0.470416	0.487153	0.274937	0.088*	0.5
H9D	0.435047	0.575808	0.264417	0.088*	0.5
C12	0.20352 (15)	0.51376 (16)	−0.02429 (14)	0.0481 (6)
H12A	0.184832	0.552542	0.012768	0.072*
H12B	0.171306	0.465312	−0.020832	0.072*
H12C	0.198561	0.536381	−0.074737	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C10A	0.052 (3)	0.072 (4)	0.028 (2)	−0.006 (3)	−0.007 (2)	−0.006 (2)
S1A	0.0488 (7)	0.0725 (9)	0.0379 (6)	0.0006 (7)	−0.0083 (5)	−0.0032 (6)
C11A	0.088 (6)	0.083 (6)	0.206 (10)	0.033 (5)	−0.044 (7)	−0.028 (7)
C10B	0.042 (3)	0.089 (5)	0.031 (2)	−0.013 (3)	−0.009 (2)	−0.020 (3)
S1B	0.0529 (8)	0.1376 (17)	0.0279 (5)	0.0111 (9)	0.0017 (5)	−0.0087 (7)
C11B	0.060 (4)	0.187 (10)	0.051 (3)	0.018 (5)	0.011 (3)	0.024 (4)
N1	0.0360 (9)	0.0387 (10)	0.0274 (8)	−0.0039 (8)	−0.0013 (7)	−0.0085 (7)
C2	0.0360 (11)	0.0316 (10)	0.0334 (10)	−0.0034 (8)	0.0016 (8)	−0.0043 (8)
N3	0.0362 (9)	0.0382 (9)	0.0282 (8)	−0.0026 (7)	0.0042 (7)	−0.0056 (7)
C3	0.0361 (11)	0.0300 (10)	0.0262 (8)	−0.0025 (8)	0.0028 (8)	−0.0002 (7)
C4	0.0349 (10)	0.0305 (10)	0.0295 (9)	−0.0045 (8)	0.0016 (7)	−0.0035 (8)
C5	0.0379 (12)	0.0345 (11)	0.0384 (10)	−0.0016 (9)	0.0009 (8)	−0.0108 (9)
C6	0.0398 (12)	0.0459 (12)	0.0227 (8)	−0.0001 (9)	0.0014 (8)	0.0035 (8)
N7	0.0384 (10)	0.0520 (12)	0.0216 (7)	−0.0023 (8)	−0.0016 (7)	−0.0124 (7)
C8	0.0432 (13)	0.099 (2)	0.0256 (10)	0.0152 (13)	−0.0079 (9)	−0.0217 (12)
C9	0.0659 (18)	0.131 (3)	0.0225 (10)	0.0355 (19)	−0.0047 (11)	−0.0117 (13)
C12	0.0383 (13)	0.0531 (14)	0.0529 (13)	0.0028 (11)	−0.0022 (10)	−0.0120 (11)

Geometric parameters (Å, º) top

C10A—C9	1.520 (5)	N3—C3	1.390 (3)
C10A—S1A	1.795 (7)	C3—C4	1.369 (3)
C10A—H10A	0.9900	C3—C6	1.485 (3)
C10A—H10B	0.9900	C4—C5	1.495 (3)
S1A—C11A	1.748 (8)	C5—N7ⁱ	1.464 (3)
C11A—H11A	0.9800	C5—H5A	0.9900
C11A—H11B	0.9800	C5—H5B	0.9900
C11A—H11C	0.9800	C6—N7	1.481 (3)
C10B—C9	1.639 (6)	C6—H6A	0.9900
C10B—S1B	1.815 (6)	C6—H6B	0.9900
C10B—H10C	0.9900	N7—C8	1.474 (3)
C10B—H10D	0.9900	C8—C9	1.522 (4)
S1B—C11B	1.734 (11)	C8—H8A	0.9900
C11B—H11D	0.9800	C8—H8B	0.9900
C11B—H11E	0.9800	C9—H9A	0.9900
C11B—H11F	0.9800	C9—H9B	0.9900
N1—C2	1.341 (3)	C9—H9C	0.9900
N1—C4	1.375 (3)	C9—H9D	0.9900
N1—H1	0.68 (3)	C12—H12A	0.9800
C2—N3	1.320 (3)	C12—H12B	0.9800
C2—C12	1.495 (3)	C12—H12C	0.9800

C9—C10A—S1A	105.6 (4)	N7ⁱ—C5—C4	117.74 (18)
C9—C10A—H10A	110.6	N7ⁱ—C5—H5A	107.9
S1A—C10A—H10A	110.6	C4—C5—H5A	107.9
C9—C10A—H10B	110.6	N7ⁱ—C5—H5B	107.9
S1A—C10A—H10B	110.6	C4—C5—H5B	107.9
H10A—C10A—H10B	108.8	H5A—C5—H5B	107.2
C11A—S1A—C10A	102.3 (4)	N7—C6—C3	113.01 (18)
S1A—C11A—H11A	109.5	N7—C6—H6A	109.0
S1A—C11A—H11B	109.5	C3—C6—H6A	109.0
H11A—C11A—H11B	109.5	N7—C6—H6B	109.0
S1A—C11A—H11C	109.5	C3—C6—H6B	109.0
H11A—C11A—H11C	109.5	H6A—C6—H6B	107.8
H11B—C11A—H11C	109.5	C5ⁱ—N7—C8	112.67 (19)
C9—C10B—S1B	109.0 (4)	C5ⁱ—N7—C6	111.42 (14)
C9—C10B—H10C	109.9	C8—N7—C6	111.0 (2)
S1B—C10B—H10C	109.9	N7—C8—C9	111.8 (2)
C9—C10B—H10D	109.9	N7—C8—H8A	109.3
S1B—C10B—H10D	109.9	C9—C8—H8A	109.3
H10C—C10B—H10D	108.3	N7—C8—H8B	109.3
C11B—S1B—C10B	98.5 (3)	C9—C8—H8B	109.3
S1B—C11B—H11D	109.5	H8A—C8—H8B	107.9
S1B—C11B—H11E	109.5	C10A—C9—C8	120.7 (3)
H11D—C11B—H11E	109.5	C8—C9—C10B	101.1 (3)
S1B—C11B—H11F	109.5	C10A—C9—H9A	107.2
H11D—C11B—H11F	109.5	C8—C9—H9A	107.2
H11E—C11B—H11F	109.5	C10A—C9—H9B	107.2
C2—N1—C4	108.65 (16)	C8—C9—H9B	107.2
C2—N1—H1	121 (2)	H9A—C9—H9B	106.8
C4—N1—H1	130 (2)	C8—C9—H9C	111.6
N3—C2—N1	111.29 (19)	C10B—C9—H9C	111.6
N3—C2—C12	125.80 (19)	C8—C9—H9D	111.6
N1—C2—C12	122.85 (19)	C10B—C9—H9D	111.6
C2—N3—C3	105.19 (17)	H9C—C9—H9D	109.4
C4—C3—N3	110.15 (18)	C2—C12—H12A	109.5
C4—C3—C6	129.9 (2)	C2—C12—H12B	109.5
N3—C3—C6	119.93 (17)	H12A—C12—H12B	109.5
C3—C4—N1	104.72 (18)	C2—C12—H12C	109.5
C3—C4—C5	131.3 (2)	H12A—C12—H12C	109.5
N1—C4—C5	124.00 (17)	H12B—C12—H12C	109.5

C9—C10A—S1A—C11A	62.4 (5)	C2—N1—C4—C5	178.75 (19)
C9—C10B—S1B—C11B	64.4 (5)	C3—C4—C5—N7ⁱ	−111.7 (3)
C4—N1—C2—N3	0.9 (3)	N1—C4—C5—N7ⁱ	69.1 (3)
C4—N1—C2—C12	−176.4 (2)	C4—C3—C6—N7	117.0 (2)
N1—C2—N3—C3	−0.8 (2)	N3—C3—C6—N7	−65.4 (2)
C12—C2—N3—C3	176.4 (2)	C3—C6—N7—C5ⁱ	−61.5 (2)
C2—N3—C3—C4	0.4 (2)	C3—C6—N7—C8	172.04 (17)
C2—N3—C3—C6	−177.72 (19)	C5ⁱ—N7—C8—C9	156.2 (3)
N3—C3—C4—N1	0.2 (2)	C6—N7—C8—C9	−78.0 (3)
C6—C3—C4—N1	178.0 (2)	S1A—C10A—C9—C8	66.8 (5)
N3—C3—C4—C5	−179.1 (2)	N7—C8—C9—C10A	169.9 (4)
C6—C3—C4—C5	−1.3 (4)	N7—C8—C9—C10B	−159.8 (3)
C2—N1—C4—C3	−0.6 (2)	S1B—C10B—C9—C8	−177.6 (4)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3ⁱⁱ	0.68 (3)	2.15 (3)	2.825 (2)	169 (3)
C6—H6B···S1Aⁱⁱⁱ	0.99	2.93	3.837 (3)	153
C12—H12A···S1A^iv	0.98	3.01	3.926 (3)	156
C11B—H11D···S1B^v	0.98	1.97	2.767 (6)	137

Symmetry codes: (ii) y−1/4, −x+3/4, z−1/4; (iii) −y+5/4, x−1/4, z−1/4; (iv) x−1/2, y, −z+1/2; (v) −x+1, −y+1, −z+1.

Funding information

Funding for this research was provided by: Consejo Nacional de Ciencia y Tecnología (grant No. 268178).

References

Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Mendoza-Díaz, G., Betancourt-Mendiola, M. de L. & Bernès, S. (2010). Acta Cryst. E66, o1958–o1959. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mendoza-Díaz, G., Driessen, W. L. & Reedijk, J. (1996). Acta Cryst. C52, 960–962. CSD CrossRef Web of Science IUCr Journals Google Scholar
Mendoza-Díaz, G., Driessen, W. L., Reedijk, J., Gorter, S., Gasque, L. & Thompson, K. R. (2002). Inorg. Chim. Acta, 339, 51–59. Web of Science CSD CrossRef CAS Google Scholar
Mendoza-Quijano, M. R., Ferrer-Sueta, G., Flores-Álamo, M., Aliaga-Alcalde, N., Gómez-Vidales, V., Ugalde-Saldívar, V. M. & Gasque, L. (2012). Dalton Trans. 41, 4985–4997. Web of Science CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2015). Acta Cryst. C71, 9–18. Web of Science CrossRef IUCr Journals Google Scholar
Stoe & Cie (2018). X-AREA and X-RED32, Stoe & Cie, Darmstadt, Germany. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zerón, P., Westphal, M., Comba, P., Flores-Álamo, M., Stueckl, A. C., Leal-Cervantes, C., Ugalde-Saldívar, V. M. & Gasque, L. (2017). Eur. J. Inorg. Chem. pp. 56–62. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.