1-Benzothio-phene-2-carbaldehyde 4-ethyl-thio-semicarbazone.

The title compound, C(13)H(15)N(3)S(2), crystallizes with two unique mol-ecules, A and B, in the asymmetric unit. These differ principally in that the methyl group of the 4-ethyl-thio-semicarbazone moiety is ordered in mol-ecule A but disordered over two positions with equal occupancies in mol-ecule B. The benzothio-phene group and the semicarbazone unit are inclined at dihedral angles of 11.78 (8)° for mol-ecule A and 8.18 (13)° for mol-ecule B. Weak intra-molecular N-H⋯N inter-actions contribute to the planarity of the semicarbazone units in both mol-ecules and each mol-ecule adopts an E configuration with respect to the C=N bonds. In the crystal structure, mol-ecules form centrosymmetric dimers as a result of N-H⋯S hydrogen bonds, augmented by C-H⋯S inter-actions for mol-ecule A and C-H⋯S inter-actions for mol-ecule B. Weak C-H⋯π inter-actions stack the dimers of both mol-ecules into columns down the a axis.

Related literature

For background to the biological activity of thio­semicarbazones, see: de Sousa et al. (2007 ▶). For related structures, see: Chuev et al. (1992 ▶); de Lima et al. (2002 ▶); Isik et al. (2006 ▶); Kayed et al. (2008 ▶). For details of graph-set analysis of hydrogen-bonding patterns, see: Bernstein et al. (1995 ▶). For reference structural data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C13H15N3S2

M = 277.40

Triclinic,

a = 5.5343 (5) Å

b = 10.9943 (10) Å

c = 23.443 (2) Å

α = 78.825 (5)°

β = 88.175 (5)°

γ = 76.298 (5)°

V = 1359.4 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.38 mm−1

T = 92 (2) K

0.37 × 0.10 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T min = 0.873, T max = 0.981

18044 measured reflections

5907 independent reflections

4307 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.111

S = 1.05

5907 reflections

354 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.49 e Å−3

Δρmin = −0.41 e Å−3

Data collection: APEX2 (Bruker 2006 ▶); cell refinement: APEX2 and SAINT (Bruker 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and TITAN (Hunter & Simpson, 1999 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ▶), PLATON (Spek, 2003 ▶) and publCIF (Westrip, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808042797/ci2731sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808042797/ci2731Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C13H15N3S2	Z = 4
Mr = 277.40	F(000) = 584
Triclinic, P1	Dx = 1.355 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.5343 (5) Å	Cell parameters from 3088 reflections
b = 10.9943 (10) Å	θ = 4.7–52.7°
c = 23.443 (2) Å	µ = 0.38 mm−1
α = 78.825 (5)°	T = 92 K
β = 88.175 (5)°	Needle, yellow
γ = 76.298 (5)°	0.37 × 0.10 × 0.05 mm
V = 1359.4 (2) Å3

Bruker APEXII CCD area-detector diffractometer	5907 independent reflections
Radiation source: fine-focus sealed tube	4307 reflections with I > 2σ(I)
graphite	Rint = 0.051
ω scans	θmax = 27.1°, θmin = 0.9°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −7→6
Tmin = 0.873, Tmax = 0.981	k = −14→14
18044 measured reflections	l = −30→29

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0519P)2] where P = (Fo2 + 2Fc2)/3
5907 reflections	(Δ/σ)max = 0.001
354 parameters	Δρmax = 0.49 e Å−3
6 restraints	Δρmin = −0.41 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1A	0.93115 (11)	0.05062 (5)	0.82595 (2)	0.01751 (15)
S2A	0.13864 (11)	−0.19901 (5)	0.99817 (3)	0.02041 (15)
N1A	0.5271 (3)	0.01724 (17)	0.90359 (8)	0.0153 (4)
N2A	0.3543 (3)	−0.02135 (17)	0.94186 (8)	0.0163 (4)
H2NA	0.225 (3)	0.0337 (19)	0.9488 (10)	0.028 (7)*
N3A	0.5742 (4)	−0.22703 (18)	0.94436 (8)	0.0170 (4)
H3NA	0.691 (3)	−0.195 (2)	0.9300 (10)	0.022 (7)*
C1A	0.6844 (4)	0.1718 (2)	0.84181 (9)	0.0150 (5)
C2A	0.6914 (4)	0.2885 (2)	0.80979 (9)	0.0182 (5)
H2A	0.5730	0.3648	0.8132	0.022*
C3A	0.8956 (4)	0.2843 (2)	0.77044 (9)	0.0175 (5)
C4A	0.9572 (5)	0.3831 (2)	0.72958 (10)	0.0238 (6)
H4A	0.8591	0.4678	0.7260	0.029*
C5A	1.1606 (5)	0.3570 (2)	0.69452 (10)	0.0253 (6)
H5A	1.2001	0.4241	0.6665	0.030*
C6A	1.3095 (5)	0.2332 (2)	0.69971 (10)	0.0241 (6)
H6A	1.4497	0.2169	0.6755	0.029*
C7A	1.2534 (4)	0.1345 (2)	0.73997 (10)	0.0222 (5)
H7A	1.3555	0.0506	0.7440	0.027*
C8A	1.0452 (4)	0.1596 (2)	0.77463 (9)	0.0162 (5)
C9A	0.4991 (4)	0.1378 (2)	0.88361 (9)	0.0148 (5)
C10A	0.2935 (4)	0.2411 (2)	0.89979 (10)	0.0203 (5)
H10A	0.2988	0.2372	0.9419	0.030*
H10B	0.1328	0.2289	0.8887	0.030*
H10C	0.3146	0.3244	0.8793	0.030*
C11A	0.3697 (4)	−0.1483 (2)	0.95961 (9)	0.0154 (5)
C12A	0.6216 (4)	−0.3666 (2)	0.95906 (10)	0.0194 (5)
H12A	0.4719	−0.3938	0.9496	0.023*
H12B	0.6555	−0.3954	1.0013	0.023*
C13A	0.8407 (4)	−0.4280 (2)	0.92596 (11)	0.0253 (6)
H13A	0.8674	−0.5210	0.9362	0.038*
H13B	0.9899	−0.4029	0.9361	0.038*
H13C	0.8068	−0.4000	0.8841	0.038*
S1B	0.67836 (11)	0.71828 (5)	0.64398 (3)	0.01964 (15)
S2B	1.51802 (11)	0.85218 (6)	0.44850 (3)	0.02281 (16)
N1B	1.0500 (3)	0.82960 (18)	0.57598 (8)	0.0180 (4)
N2B	1.2186 (4)	0.87090 (19)	0.53790 (8)	0.0187 (4)
H2NB	1.300 (4)	0.9225 (19)	0.5457 (11)	0.028 (8)*
N3B	1.1624 (4)	0.72808 (19)	0.48311 (9)	0.0205 (5)
H3NB	1.040 (3)	0.721 (2)	0.5042 (9)	0.022 (7)*
C1B	0.8201 (4)	0.8337 (2)	0.66072 (10)	0.0159 (5)
C2B	0.7499 (4)	0.8626 (2)	0.71398 (9)	0.0163 (5)
H2B	0.8087	0.9234	0.7301	0.020*
C3B	0.5797 (4)	0.7926 (2)	0.74310 (9)	0.0161 (5)
C4B	0.4694 (4)	0.7975 (2)	0.79772 (10)	0.0207 (5)
H4B	0.5074	0.8524	0.8210	0.025*
C5B	0.3050 (4)	0.7218 (2)	0.81723 (11)	0.0241 (6)
H5B	0.2285	0.7258	0.8539	0.029*
C6B	0.2499 (4)	0.6392 (2)	0.78363 (11)	0.0256 (6)
H6B	0.1380	0.5872	0.7979	0.031*
C7B	0.3576 (4)	0.6328 (2)	0.72976 (11)	0.0234 (6)
H7B	0.3197	0.5771	0.7069	0.028*
C8B	0.5215 (4)	0.7090 (2)	0.70985 (10)	0.0179 (5)
C9B	0.9933 (4)	0.8839 (2)	0.62066 (9)	0.0156 (5)
C10B	1.0962 (4)	0.9905 (2)	0.63256 (10)	0.0204 (5)
H10D	1.0649	1.0607	0.5988	0.031*
H10E	1.2757	0.9602	0.6400	0.031*
H10F	1.0154	1.0207	0.6667	0.031*
C11B	1.2880 (4)	0.8130 (2)	0.49148 (9)	0.0163 (5)
C12B	1.1924 (5)	0.6655 (2)	0.43327 (12)	0.0370 (7)
H12C	1.3697	0.6441	0.4224	0.044*	0.50
H12D	1.0953	0.7219	0.3995	0.044*	0.50
H12E	1.2155	0.7286	0.4004	0.044*	0.50
H12F	1.0372	0.6450	0.4271	0.044*	0.50
C131	1.0968 (10)	0.5437 (4)	0.4516 (2)	0.0281 (12)	0.50
H13D	0.9176	0.5667	0.4586	0.042*	0.50
H13E	1.1834	0.4928	0.4873	0.042*	0.50
H13F	1.1282	0.4939	0.4205	0.042*	0.50
C132	1.3847 (8)	0.5534 (4)	0.4312 (2)	0.0265 (12)	0.50
H13G	1.5473	0.5719	0.4354	0.040*	0.50
H13H	1.3754	0.5271	0.3939	0.040*	0.50
H13I	1.3629	0.4846	0.4630	0.040*	0.50

	U11	U22	U33	U12	U13	U23
S1A	0.0177 (3)	0.0162 (3)	0.0184 (3)	−0.0042 (2)	0.0046 (2)	−0.0031 (2)
S2A	0.0159 (3)	0.0207 (3)	0.0252 (3)	−0.0071 (2)	0.0071 (3)	−0.0033 (2)
N1A	0.0121 (10)	0.0206 (10)	0.0135 (9)	−0.0053 (8)	0.0028 (8)	−0.0022 (8)
N2A	0.0129 (10)	0.0169 (10)	0.0190 (10)	−0.0034 (8)	0.0034 (8)	−0.0042 (8)
N3A	0.0145 (11)	0.0188 (10)	0.0180 (10)	−0.0069 (8)	0.0055 (9)	−0.0011 (8)
C1A	0.0115 (11)	0.0185 (11)	0.0149 (11)	−0.0025 (9)	−0.0003 (9)	−0.0044 (9)
C2A	0.0169 (12)	0.0198 (12)	0.0175 (12)	−0.0041 (10)	0.0010 (10)	−0.0034 (9)
C3A	0.0202 (13)	0.0192 (11)	0.0146 (11)	−0.0078 (10)	−0.0017 (10)	−0.0026 (9)
C4A	0.0294 (15)	0.0218 (12)	0.0206 (13)	−0.0090 (11)	0.0038 (11)	−0.0015 (10)
C5A	0.0333 (15)	0.0294 (14)	0.0180 (12)	−0.0185 (12)	0.0049 (11)	−0.0028 (10)
C6A	0.0246 (14)	0.0380 (15)	0.0162 (12)	−0.0153 (12)	0.0069 (11)	−0.0120 (11)
C7A	0.0215 (13)	0.0277 (13)	0.0209 (13)	−0.0097 (11)	0.0038 (11)	−0.0088 (10)
C8A	0.0205 (13)	0.0189 (11)	0.0123 (11)	−0.0095 (10)	0.0015 (10)	−0.0050 (9)
C9A	0.0134 (12)	0.0183 (11)	0.0124 (11)	−0.0042 (9)	−0.0022 (9)	−0.0014 (9)
C10A	0.0183 (13)	0.0209 (12)	0.0220 (13)	−0.0058 (10)	0.0054 (10)	−0.0045 (10)
C11A	0.0163 (12)	0.0186 (11)	0.0120 (11)	−0.0052 (9)	−0.0026 (9)	−0.0026 (9)
C12A	0.0212 (13)	0.0154 (11)	0.0196 (12)	−0.0039 (10)	0.0024 (10)	0.0005 (9)
C13A	0.0211 (13)	0.0227 (13)	0.0300 (14)	−0.0013 (10)	0.0028 (11)	−0.0050 (11)
S1B	0.0211 (3)	0.0214 (3)	0.0196 (3)	−0.0081 (2)	0.0061 (3)	−0.0087 (2)
S2B	0.0208 (3)	0.0305 (3)	0.0218 (3)	−0.0125 (3)	0.0100 (3)	−0.0099 (3)
N1B	0.0152 (10)	0.0216 (10)	0.0163 (10)	−0.0047 (8)	0.0034 (8)	−0.0017 (8)
N2B	0.0176 (11)	0.0252 (11)	0.0170 (10)	−0.0100 (9)	0.0050 (9)	−0.0074 (9)
N3B	0.0204 (12)	0.0247 (11)	0.0203 (11)	−0.0109 (9)	0.0112 (9)	−0.0084 (9)
C1B	0.0125 (12)	0.0153 (11)	0.0186 (12)	−0.0003 (9)	−0.0018 (10)	−0.0036 (9)
C2B	0.0152 (12)	0.0193 (11)	0.0145 (11)	−0.0038 (9)	0.0002 (9)	−0.0039 (9)
C3B	0.0130 (12)	0.0168 (11)	0.0157 (11)	0.0002 (9)	−0.0010 (9)	−0.0008 (9)
C4B	0.0204 (13)	0.0255 (13)	0.0145 (12)	−0.0033 (10)	0.0027 (10)	−0.0027 (10)
C5B	0.0191 (13)	0.0280 (13)	0.0196 (12)	0.0006 (10)	0.0041 (11)	0.0009 (10)
C6B	0.0183 (13)	0.0212 (12)	0.0315 (14)	−0.0020 (10)	0.0062 (11)	0.0048 (11)
C7B	0.0214 (13)	0.0211 (12)	0.0289 (14)	−0.0070 (10)	0.0051 (11)	−0.0059 (10)
C8B	0.0143 (12)	0.0177 (11)	0.0183 (12)	0.0004 (9)	0.0035 (10)	−0.0007 (9)
C9B	0.0126 (12)	0.0195 (11)	0.0136 (11)	−0.0013 (9)	−0.0020 (9)	−0.0033 (9)
C10B	0.0199 (13)	0.0264 (13)	0.0195 (12)	−0.0118 (10)	0.0066 (10)	−0.0083 (10)
C11B	0.0130 (12)	0.0200 (12)	0.0149 (11)	−0.0018 (9)	0.0011 (9)	−0.0037 (9)
C12B	0.0458 (18)	0.0446 (17)	0.0388 (16)	−0.0330 (14)	0.0295 (14)	−0.0292 (14)
C131	0.038 (3)	0.025 (3)	0.028 (3)	−0.011 (2)	0.005 (2)	−0.015 (2)
C132	0.027 (3)	0.029 (3)	0.021 (3)	−0.001 (2)	0.006 (2)	−0.004 (2)

S1A—C8A	1.741 (2)	N1B—N2B	1.365 (3)
S1A—C1A	1.754 (2)	N2B—C11B	1.365 (3)
S2A—C11A	1.683 (2)	N2B—H2NB	0.852 (10)
N1A—C9A	1.291 (3)	N3B—C11B	1.334 (3)
N1A—N2A	1.375 (3)	N3B—C12B	1.453 (3)
N2A—C11A	1.360 (3)	N3B—H3NB	0.835 (10)
N2A—H2NA	0.852 (10)	C1B—C2B	1.369 (3)
N3A—C11A	1.337 (3)	C1B—C9B	1.449 (3)
N3A—C12A	1.467 (3)	C2B—C3B	1.429 (3)
N3A—H3NA	0.839 (10)	C2B—H2B	0.95
C1A—C2A	1.363 (3)	C3B—C4B	1.406 (3)
C1A—C9A	1.459 (3)	C3B—C8B	1.411 (3)
C2A—C3A	1.434 (3)	C4B—C5B	1.384 (3)
C2A—H2A	0.95	C4B—H4B	0.95
C3A—C4A	1.402 (3)	C5B—C6B	1.400 (4)
C3A—C8A	1.411 (3)	C5B—H5B	0.95
C4A—C5A	1.380 (3)	C6B—C7B	1.386 (3)
C4A—H4A	0.95	C6B—H6B	0.95
C5A—C6A	1.399 (3)	C7B—C8B	1.387 (3)
C5A—H5A	0.95	C7B—H7B	0.95
C6A—C7A	1.381 (3)	C9B—C10B	1.493 (3)
C6A—H6A	0.95	C10B—H10D	0.98
C7A—C8A	1.393 (3)	C10B—H10E	0.98
C7A—H7A	0.95	C10B—H10F	0.98
C9A—C10A	1.502 (3)	C12B—C132	1.432 (4)
C10A—H10A	0.98	C12B—C131	1.535 (4)
C10A—H10B	0.98	C12B—H12C	0.99
C10A—H10C	0.98	C12B—H12D	0.99
C12A—C13A	1.511 (3)	C12B—H12E	0.96
C12A—H12A	0.99	C12B—H12F	0.96
C12A—H12B	0.99	C131—H12F	1.13
C13A—H13A	0.98	C131—H13D	0.98
C13A—H13B	0.98	C131—H13E	0.98
C13A—H13C	0.98	C131—H13F	0.98
S1B—C8B	1.745 (2)	C132—H13G	0.98
S1B—C1B	1.750 (2)	C132—H13H	0.98
S2B—C11B	1.683 (2)	C132—H13I	0.98
N1B—C9B	1.298 (3)
C8A—S1A—C1A	91.23 (11)	C9B—C1B—S1B	120.17 (17)
C9A—N1A—N2A	118.26 (18)	C1B—C2B—C3B	113.6 (2)
C11A—N2A—N1A	118.93 (18)	C1B—C2B—H2B	123.2
C11A—N2A—H2NA	120.8 (18)	C3B—C2B—H2B	123.2
N1A—N2A—H2NA	119.2 (18)	C4B—C3B—C8B	118.8 (2)
C11A—N3A—C12A	123.92 (19)	C4B—C3B—C2B	129.2 (2)
C11A—N3A—H3NA	117.9 (17)	C8B—C3B—C2B	111.9 (2)
C12A—N3A—H3NA	117.6 (17)	C5B—C4B—C3B	119.5 (2)
C2A—C1A—C9A	128.8 (2)	C5B—C4B—H4B	120.3
C2A—C1A—S1A	112.27 (17)	C3B—C4B—H4B	120.3
C9A—C1A—S1A	118.84 (16)	C4B—C5B—C6B	120.9 (2)
C1A—C2A—C3A	113.2 (2)	C4B—C5B—H5B	119.6
C1A—C2A—H2A	123.4	C6B—C5B—H5B	119.6
C3A—C2A—H2A	123.4	C7B—C6B—C5B	120.5 (2)
C4A—C3A—C8A	118.6 (2)	C7B—C6B—H6B	119.8
C4A—C3A—C2A	129.4 (2)	C5B—C6B—H6B	119.8
C8A—C3A—C2A	111.9 (2)	C6B—C7B—C8B	118.9 (2)
C5A—C4A—C3A	119.9 (2)	C6B—C7B—H7B	120.6
C5A—C4A—H4A	120.1	C8B—C7B—H7B	120.6
C3A—C4A—H4A	120.1	C7B—C8B—C3B	121.5 (2)
C4A—C5A—C6A	120.9 (2)	C7B—C8B—S1B	127.42 (19)
C4A—C5A—H5A	119.5	C3B—C8B—S1B	111.11 (17)
C6A—C5A—H5A	119.5	N1B—C9B—C1B	115.7 (2)
C7A—C6A—C5A	120.2 (2)	N1B—C9B—C10B	124.4 (2)
C7A—C6A—H6A	119.9	C1B—C9B—C10B	119.94 (19)
C5A—C6A—H6A	119.9	C9B—C10B—H10D	109.5
C6A—C7A—C8A	119.2 (2)	C9B—C10B—H10E	109.5
C6A—C7A—H7A	120.4	H10D—C10B—H10E	109.5
C8A—C7A—H7A	120.4	C9B—C10B—H10F	109.5
C7A—C8A—C3A	121.2 (2)	H10D—C10B—H10F	109.5
C7A—C8A—S1A	127.48 (18)	H10E—C10B—H10F	109.5
C3A—C8A—S1A	111.36 (17)	N3B—C11B—N2B	116.2 (2)
N1A—C9A—C1A	115.43 (19)	N3B—C11B—S2B	124.21 (18)
N1A—C9A—C10A	125.1 (2)	N2B—C11B—S2B	119.61 (18)
C1A—C9A—C10A	119.50 (19)	C132—C12B—N3B	122.0 (3)
C9A—C10A—H10A	109.5	C132—C12B—C131	68.4 (3)
C9A—C10A—H10B	109.5	N3B—C12B—C131	106.5 (3)
H10A—C10A—H10B	109.5	N3B—C12B—H12C	110.4
C9A—C10A—H10C	109.5	C131—C12B—H12C	110.4
H10A—C10A—H10C	109.5	C132—C12B—H12D	125.7
H10B—C10A—H10C	109.5	N3B—C12B—H12D	110.4
N3A—C11A—N2A	116.3 (2)	C131—C12B—H12D	110.4
N3A—C11A—S2A	123.46 (17)	H12C—C12B—H12D	108.6
N2A—C11A—S2A	120.25 (17)	C132—C12B—H12E	106.6
N3A—C12A—C13A	111.06 (19)	N3B—C12B—H12E	106.2
N3A—C12A—H12A	109.4	C131—C12B—H12E	143.4
C13A—C12A—H12A	109.4	H12C—C12B—H12E	72.4
N3A—C12A—H12B	109.4	C132—C12B—H12F	107.0
C13A—C12A—H12B	109.4	N3B—C12B—H12F	107.2
H12A—C12A—H12B	108.0	C131—C12B—H12F	47.0
C12A—C13A—H13A	109.5	H12C—C12B—H12F	140.9
C12A—C13A—H13B	109.5	H12D—C12B—H12F	66.4
H13A—C13A—H13B	109.5	H12E—C12B—H12F	106.9
C12A—C13A—H13C	109.5	C12B—C131—H13D	109.5
H13A—C13A—H13C	109.5	H12F—C131—H13D	76.5
H13B—C13A—H13C	109.5	C12B—C131—H13E	109.5
C8B—S1B—C1B	91.60 (11)	H12F—C131—H13E	141.6
C9B—N1B—N2B	117.9 (2)	C12B—C131—H13F	109.5
C11B—N2B—N1B	119.3 (2)	H12F—C131—H13F	103.3
C11B—N2B—H2NB	118.7 (18)	C12B—C132—H13G	109.5
N1B—N2B—H2NB	121.0 (18)	C12B—C132—H13H	109.5
C11B—N3B—C12B	124.4 (2)	H13G—C132—H13H	109.5
C11B—N3B—H3NB	117.9 (17)	C12B—C132—H13I	109.5
C12B—N3B—H3NB	116.7 (17)	H13G—C132—H13I	109.5
C2B—C1B—C9B	128.1 (2)	H13H—C132—H13I	109.5
C2B—C1B—S1B	111.75 (18)
C9A—N1A—N2A—C11A	174.7 (2)	C8B—S1B—C1B—C2B	0.07 (17)
C8A—S1A—C1A—C2A	−0.36 (18)	C8B—S1B—C1B—C9B	178.56 (17)
C8A—S1A—C1A—C9A	177.19 (18)	C9B—C1B—C2B—C3B	−178.3 (2)
C9A—C1A—C2A—C3A	−176.5 (2)	S1B—C1B—C2B—C3B	0.1 (2)
S1A—C1A—C2A—C3A	0.8 (3)	C1B—C2B—C3B—C4B	−179.9 (2)
C1A—C2A—C3A—C4A	177.4 (2)	C1B—C2B—C3B—C8B	−0.2 (3)
C1A—C2A—C3A—C8A	−0.9 (3)	C8B—C3B—C4B—C5B	−0.7 (3)
C8A—C3A—C4A—C5A	0.1 (4)	C2B—C3B—C4B—C5B	179.0 (2)
C2A—C3A—C4A—C5A	−178.1 (2)	C3B—C4B—C5B—C6B	0.9 (3)
C3A—C4A—C5A—C6A	−1.0 (4)	C4B—C5B—C6B—C7B	−0.6 (3)
C4A—C5A—C6A—C7A	0.5 (4)	C5B—C6B—C7B—C8B	0.3 (3)
C5A—C6A—C7A—C8A	0.9 (4)	C6B—C7B—C8B—C3B	−0.2 (3)
C6A—C7A—C8A—C3A	−1.8 (4)	C6B—C7B—C8B—S1B	−179.72 (17)
C6A—C7A—C8A—S1A	177.30 (18)	C4B—C3B—C8B—C7B	0.4 (3)
C4A—C3A—C8A—C7A	1.3 (3)	C2B—C3B—C8B—C7B	−179.4 (2)
C2A—C3A—C8A—C7A	179.8 (2)	C4B—C3B—C8B—S1B	−179.99 (16)
C4A—C3A—C8A—S1A	−177.92 (18)	C2B—C3B—C8B—S1B	0.2 (2)
C2A—C3A—C8A—S1A	0.6 (3)	C1B—S1B—C8B—C7B	179.4 (2)
C1A—S1A—C8A—C7A	−179.3 (2)	C1B—S1B—C8B—C3B	−0.18 (17)
C1A—S1A—C8A—C3A	−0.14 (18)	N2B—N1B—C9B—C1B	−178.00 (18)
N2A—N1A—C9A—C1A	−178.12 (18)	N2B—N1B—C9B—C10B	1.4 (3)
N2A—N1A—C9A—C10A	1.3 (3)	C2B—C1B—C9B—N1B	172.1 (2)
C2A—C1A—C9A—N1A	173.7 (2)	S1B—C1B—C9B—N1B	−6.1 (3)
S1A—C1A—C9A—N1A	−3.4 (3)	C2B—C1B—C9B—C10B	−7.3 (3)
C2A—C1A—C9A—C10A	−5.8 (4)	S1B—C1B—C9B—C10B	174.51 (16)
S1A—C1A—C9A—C10A	177.12 (16)	C12B—N3B—C11B—N2B	174.0 (2)
C12A—N3A—C11A—N2A	−179.3 (2)	C12B—N3B—C11B—S2B	−5.2 (3)
C12A—N3A—C11A—S2A	0.3 (3)	N1B—N2B—C11B—N3B	7.4 (3)
N1A—N2A—C11A—N3A	8.8 (3)	N1B—N2B—C11B—S2B	−173.36 (15)
N1A—N2A—C11A—S2A	−170.77 (15)	C11B—N3B—C12B—C132	84.2 (4)
C11A—N3A—C12A—C13A	168.7 (2)	C11B—N3B—C12B—C131	158.7 (3)
C9B—N1B—N2B—C11B	177.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3A—H3NA···N1A	0.84 (1)	2.27 (2)	2.623 (3)	106 (2)
N3B—H3NB···N1B	0.83 (1)	2.26 (2)	2.627 (3)	107 (2)
C10A—H10A···S2Ai	0.98	2.84	3.374 (2)	115
N2A—H2NA···S2Ai	0.85 (1)	2.81 (1)	3.638 (2)	164 (2)
C10B—H10D···S2Bii	0.98	2.82	3.373 (2)	117
C10A—H10B···Cg1iii	0.98	2.71	3.577 (2)	147
C10B—H10E···Cg2iv	0.98	2.72	3.600 (2)	150

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3A—H3NA⋯N1A	0.84 (1)	2.27 (2)	2.623 (3)	106 (2)
N3B—H3NB⋯N1B	0.83 (1)	2.26 (2)	2.627 (3)	107 (2)
C10A—H10A⋯S2Ai	0.98	2.84	3.374 (2)	115
N2A—H2NA⋯S2Ai	0.85 (1)	2.81 (1)	3.638 (2)	164 (2)
C10B—H10D⋯S2Bii	0.98	2.82	3.373 (2)	117
C10A—H10B⋯Cg1iii	0.98	2.71	3.577 (2)	147
C10B—H10E⋯Cg2iv	0.98	2.72	3.600 (2)	150

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) . Cg1 and Cg2 are the centroids of the S1A/C1A/C2A/C3A/C8A and S1B/C1B/C2B/C3B/C8B rings, respectively.