1-Benzothio­phene-2-carbaldehyde 4-ethyl­thio­semicarbazone

Kayed, S.F.; Farina, Y.; Simpson, J.

doi:10.1107/S1600536808042797

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Pages o180-o181

doi:10.1107/S1600536808042797

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1-Benzothiophene-2-carbaldehyde 4-ethylthiosemicarbazone

Safa'a Fares Kayed,^a Yang Farina ^a ^* and Jim Simpson ^b

^aSchool of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia, and ^bDepartment of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
^*Correspondence e-mail: farina@pkrisc.cc.ukm.my

(Received 19 November 2008; accepted 16 December 2008; online 20 December 2008)

The title compound, C₁₃H₁₅N₃S₂, crystallizes with two unique molecules, A and B, in the asymmetric unit. These differ principally in that the methyl group of the 4-ethylthiosemicarbazone moiety is ordered in molecule A but disordered over two positions with equal occupancies in molecule B. The benzothiophene group and the semicarbazone unit are inclined at dihedral angles of 11.78 (8)° for molecule A and 8.18 (13)° for molecule B. Weak intramolecular N—H⋯N interactions contribute to the planarity of the semicarbazone units in both molecules and each molecule adopts an E configuration with respect to the C=N bonds. In the crystal structure, molecules form centrosymmetric dimers as a result of N—H⋯S hydrogen bonds, augmented by C—H⋯S interactions for molecule A and C—H⋯S interactions for molecule B. Weak C—H⋯π interactions stack the dimers of both molecules 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_r = 277.40
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.042
wR(F²) = 0.111
S = 1.05
5907 reflections
354 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.41 e Å⁻³

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⋯Cg2^iv	0.98	2.72	3.600 (2)	150
Symmetry codes: (i) -x, -y, -z+2; (ii) -x+3, -y+2, -z+1; (iii) x+1, y, z; (iv) x-1, y, z. Cg1 and Cg2 are the centroids of the S1A/C1A/C2A/C3A/C8A and S1B/C1B/C2B/C3B/C8B rings, respectively.

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 ).

Supporting information

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

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

checkCIF report

Comment top

Thiosemicarbazones are a class of compounds that have been investigated because of their biological activity (de Sousa et al., 2007). As a continuation of our work on thiosemicarbazone compounds as potential ligands in transition metal chemistry (Kayed et al., 2008;) we report here the structure of the title compound (Fig. 1), which crystallizes with two unique molecules, A and B, in the asymmetric unit. The two molecules are closely similar with the exception of the methyl C atom of the ethyl group which is disordered over two positions C131 and C132, with equal occupancies. The similarities of the remainder of the two molecules are demonstrated by the fact that the non-hydrogen atoms of molecules A and B overlay in Mercury (Macrae et al., 2006) with an r.m.s. deviation of 0.077 Å, when the C132 disorder component is excluded. The molecules are each reasonably planar with r.m.s. deviations of 0.137 Å and 0.128 Å from the planes through all non-hydrogen atoms of the two molecules excluding the C132 disorder component. The planarity of the N1/N2/C11/S2/N3 segments of both molecules (r.m.s. deviations 0.050 Å for molecule A and 0.037 Å for molecule B) is aided by weak intramolecular N3—H3N···N1 interactions. The benzothiophene groups and the semicarbazone groups are inclined at dihedral angles of 11.78 (8)° for molecule A and 8.18 (13)° for molecule B. Both molecules adopt an E configuration with respect to the C═N bonds, bond distances are normal (Allen et al., 1987) and comparable to those in similar structures (Chuev et al. 1992; de Lima et al. 2002; Isik et al. 2006; Kayed et al. 2008).

In the crystal structure, a centrosymmetric dimer with an R²₂(8) ring motif (Bernstein et al., 1995) is formed by through N2A—H2NA···S2A hydrogen bonds strengthened by additional C10A—H10A···S2A interactions for molecule A. A second dimer forms via C10B—H10D···S2B interactions for molecule B (Table 1 and Fig. 2). The dimers are further aggregated into columns down the a axis by weak C—H···π interactions involving the C10A and C10B methyl groups and the thiophene rings of adjacent molecules, Fig. 3.

Related literature top

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 top

The title compound was prepared by heating 35 ml of an ethanolic solution of 2-acetylbenzothiophene (1.76 g, 10 mmol) and 4-ethyl-3-thiosemicarbazide (1.2 g, 10 mmol) under reflux for 2 h. Three drops of concentrated H₂SO₄ were added. The resulting product was isolated and recrystallized from acetonitrile to afford yellow needles of the title compound in 63.5% yield (m.p. 448–450 K).

Computing details top

Data collection: APEX2 (Bruker 2006); cell refinement: APEX2 and SAINT (Bruker 2006); data reduction: SAINT (Bruker 2006); 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).

Figures top

	Fig. 1. The asymmetric unit of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms. For clarity, only one disorder component is shown.
	Fig. 2. Formation of dimers in the crystal structure of the title compound, through N—H···S and C—H···S hydrogen bonds, shown as dashed lines. H atoms not involved in hydrogen bonding and atoms of one of the disorder components have been omitted for clarity.
	Fig. 3. C—H···π interactions between dimers in the title compound. Cg1 is the centroid of the S1A/C1A/C2A/C3A/C8A ring and Cg2 that of the S1B/C1B/C2B/C3B/C8B ring. H···Cg interactions are drawn as dotted lines and hydrogen bonds as dashed lines. H atoms not involved in these interactions and atoms of one of the disorder components have been omitted for clarity.

1-Benzothiophene-2-carbaldehyde 4-ethylthiosemicarbazone top

Crystal data top

C₁₃H₁₅N₃S₂	Z = 4
M_r = 277.40	F(000) = 584
Triclinic, P1	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0519P)²] where P = (F_o² + 2F_c²)/3
5907 reflections	(Δ/σ)_max = 0.001
354 parameters	Δρ_max = 0.49 e Å⁻³
6 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₁₃H₁₅N₃S₂	γ = 76.298 (5)°
M_r = 277.40	V = 1359.4 (2) Å³
Triclinic, P1	Z = 4
a = 5.5343 (5) Å	Mo Kα radiation
b = 10.9943 (10) Å	µ = 0.38 mm⁻¹
c = 23.443 (2) Å	T = 92 K
α = 78.825 (5)°	0.37 × 0.10 × 0.05 mm
β = 88.175 (5)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	5907 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	4307 reflections with I > 2σ(I)
T_min = 0.873, T_max = 0.981	R_int = 0.051
18044 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	6 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.49 e Å⁻³
5907 reflections	Δρ_min = −0.41 e Å⁻³
354 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq	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

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···Cg2^iv	0.98	2.72	3.600 (2)	150

Symmetry codes: (i) −x, −y, −z+2; (ii) −x+3, −y+2, −z+1; (iii) x+1, y, z; (iv) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₅N₃S₂
M_r	277.40
Crystal system, space group	Triclinic, P1
Temperature (K)	92
a, b, c (Å)	5.5343 (5), 10.9943 (10), 23.443 (2)
α, β, γ (°)	78.825 (5), 88.175 (5), 76.298 (5)
V (Å³)	1359.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.37 × 0.10 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.873, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	18044, 5907, 4307
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.111, 1.05
No. of reflections	5907
No. of parameters	354
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.41

Computer programs: APEX2 (Bruker 2006), APEX2 and SAINT (Bruker 2006), SAINT (Bruker 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXL97, enCIFer (Allen et al., 2004), PLATON (Spek, 2003) and publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

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···Cg2^iv	0.98	2.72	3.600 (2)	150

Symmetry codes: (i) −x, −y, −z+2; (ii) −x+3, −y+2, −z+1; (iii) x+1, y, z; (iv) x−1, y, z.

Acknowledgements

The authors thank the Universiti Kebangsaan Malaysia and the Ministry of Higher Education, Malaysia, for supporting this research through grants UKM-ST-01-FRGS0022–2006 and UKM-GUP-NBT-08–27-112. The authors also thank the University of Otago for purchase of the diffractometer.

References

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