Benzyl N′-(2-chloro­benzyl­idene)hydrazinecarbodithio­ate

Shi, Z.-Q.; Ji, N.-N.; Ji, Q.-Q.

doi:10.1107/S1600536808034892

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2249

doi:10.1107/S1600536808034892

Open

access

Benzyl N′-(2-chlorobenzylidene)hydrazinecarbodithioate

Zhi-Qiang Shi,^a ^* Ning-Ning Ji ^b and Qin-Qin Ji ^c

^aDepartment of Materials Science and Chemical Engineering, Taishan University, 271021 Taian, Shandong, People's Republic of China, ^bDepartment of Chemistry, Taishan University, 271021 Taian, Shandong, People's Republic of China, and ^cDepartment of Chemical Engineering and Technology, School of Chemical Engineering and Technology, China University of Mining and Technology, 221116 Xuzhou, Jiangsu, People's Republic of China
^*Correspondence e-mail: kobeecho@163.com

(Received 20 September 2008; accepted 27 October 2008; online 8 November 2008)

The asymmetric unit of the title compound, C₁₅H₁₃ClN₂S₂, contains two independent molecules, which are linked into a pseudo-centrosymmetric dimer by intermolecular N—H⋯S hydrogen bonds. The aromatic rings form dihedral angles of 67.06 (3) and 81.85 (2)° in the two independent molecules.

Related literature

For the biomedical properties of ligands derived from S-benzyldithiocarbazate, see: Ali et al. (2001 , 2002 ); Tarafder et al. (2001 , 2008 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₅H₁₃ClN₂S₂
M_r = 320.84
Triclinic, $[P \overline 1]$
a = 11.877 (2) Å
b = 11.906 (2) Å
c = 12.623 (3) Å
α = 68.242 (3)°
β = 71.116 (4)°
γ = 82.335 (4)°
V = 1568.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 295 (2) K
0.12 × 0.10 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.942, T_max = 0.971
8397 measured reflections
5524 independent reflections
3436 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.127
S = 0.97
5524 reflections
361 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S4	0.86	2.56	3.405 (3)	166
N3—H3A⋯S2	0.86	2.60	3.451 (3)	169

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 and SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL .

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808034892/cv2453sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808034892/cv2453Isup2.hkl

checkCIF report

Comment top

In recent years, the intriguing coordination chemistry and increasingly important biomedical properties of ligands derived from S-benzyldithiocarbazate(SBDTC) have received much attention (Ali et al., 2001, 2002; Tarafder et al., 2001, 2008). In order to search for new ligands derived from SBDTC, the title compound, (I), was synthesized. Herewith we present its crystal structure.

In (I), all bond lengths and angles are normal (Allen et al., 1987). The C=N bond length in the independent molecules are 1.279 (3) Å(C7=N2) and 1.271 (4) Å(C22=N4), respectively, showing the double-bond character. The C=S bond lengths of 1.656 (3) Å(S2=C8) and 1.661 (3) Å(S4=C23) are intermediate between the values of 1.82Å for a C—S single bond and 1.56Å for a C=S double bond. The C=N—N angles in the independent molecule of 115.5 (2)° and 115.6 (3)° are significantly smaller than the ideal value of 120° expected for sp²-hybridized N atoms. This is probably a consequence of repulsion between the nitrogen lone pairs and the adjacent N bonds.

Two independent molecules are linked by N—H···S hydrogen bonds (Table 1) into pseudo-centrosymmetric dimers (Fig. 1).

Related literature top

For the biomedical properties of ligands derived from

S-benzyldithiocarbazaterelated literature, see: Ali et al. (2001, 2002); Tarafder et al. (2001, 2008). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was synthesized by the reaction of hydrazinecarbodithioic acid benzyl ester(1 mmol, 198.3 mg) with 2-chloro-benzaldehyde(1 mmol, 140.6 mg) in ethanol(20 ml) under reflux conditions (343 K) for 6 h. The solvent was removed and the solid product recrystallized from tetrahydrofuran. After five days yellow crystals suitable for X-ray diffraction study were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005) and SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level. Dashed lines indicate hydrogen bonds.

Benzyl N'-(2-chlorobenzylidene)hydrazinecarbodithioate top

Crystal data top

C₁₅H₁₃ClN₂S₂	Z = 4
M_r = 320.84	F(000) = 664
Triclinic, P1	D_x = 1.359 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.877 (2) Å	Cell parameters from 1618 reflections
b = 11.906 (2) Å	θ = 2.6–24.6°
c = 12.623 (3) Å	µ = 0.50 mm⁻¹
α = 68.242 (3)°	T = 295 K
β = 71.116 (4)°	Block, yellow
γ = 82.335 (4)°	0.12 × 0.10 × 0.06 mm
V = 1568.4 (5) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	5524 independent reflections
Radiation source: fine-focus sealed tube	3436 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→14
T_min = 0.942, T_max = 0.971	k = −14→13
8397 measured reflections	l = −14→14

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0533P)² + 0.4623P] where P = (F_o² + 2F_c²)/3
5524 reflections	(Δ/σ)_max = 0.001
361 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₁₅H₁₃ClN₂S₂	γ = 82.335 (4)°
M_r = 320.84	V = 1568.4 (5) Å³
Triclinic, P1	Z = 4
a = 11.877 (2) Å	Mo Kα radiation
b = 11.906 (2) Å	µ = 0.50 mm⁻¹
c = 12.623 (3) Å	T = 295 K
α = 68.242 (3)°	0.12 × 0.10 × 0.06 mm
β = 71.116 (4)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	5524 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3436 reflections with I > 2σ(I)
T_min = 0.942, T_max = 0.971	R_int = 0.026
8397 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 0.97	Δρ_max = 0.44 e Å⁻³
5524 reflections	Δρ_min = −0.46 e Å⁻³
361 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
Cl2	0.61916 (10)	0.15814 (11)	0.57081 (9)	0.0994 (4)
S3	0.36389 (7)	0.66976 (8)	0.21058 (7)	0.0541 (3)
S4	0.15028 (7)	0.61729 (8)	0.43141 (7)	0.0566 (3)
N3	0.3563 (2)	0.5043 (2)	0.4167 (2)	0.0514 (7)
H3A	0.3270	0.4634	0.4914	0.062*
N4	0.4704 (2)	0.4789 (2)	0.3570 (2)	0.0478 (7)
C16	0.6959 (3)	0.2483 (3)	0.4266 (3)	0.0544 (9)
C17	0.6419 (3)	0.3506 (3)	0.3648 (3)	0.0455 (8)
C18	0.7096 (3)	0.4188 (3)	0.2498 (3)	0.0554 (9)
H18	0.6770	0.4888	0.2056	0.066*
C19	0.8242 (3)	0.3835 (3)	0.2014 (3)	0.0606 (10)
H19	0.8678	0.4290	0.1244	0.073*
C20	0.8742 (3)	0.2812 (4)	0.2663 (3)	0.0617 (10)
H20	0.9518	0.2584	0.2332	0.074*
C21	0.8112 (3)	0.2133 (3)	0.3785 (3)	0.0631 (10)
H21	0.8452	0.1443	0.4224	0.076*
C22	0.5211 (3)	0.3882 (3)	0.4168 (3)	0.0504 (8)
H22	0.4802	0.3449	0.4955	0.061*
C23	0.2902 (3)	0.5914 (3)	0.3608 (3)	0.0441 (8)
C24	0.2502 (3)	0.7786 (3)	0.1668 (3)	0.0612 (10)
H24A	0.1772	0.7372	0.1861	0.073*
H24B	0.2335	0.8347	0.2097	0.073*
C25	0.2944 (3)	0.8461 (3)	0.0345 (3)	0.0480 (8)
C26	0.3717 (3)	0.9404 (3)	−0.0123 (3)	0.0609 (10)
H26	0.3981	0.9628	0.0389	0.073*
C27	0.4111 (3)	1.0026 (3)	−0.1335 (3)	0.0689 (11)
H27	0.4636	1.0661	−0.1634	0.083*
C28	0.3730 (3)	0.9712 (4)	−0.2098 (3)	0.0684 (11)
H28	0.3994	1.0132	−0.2916	0.082*
C29	0.2967 (3)	0.8785 (4)	−0.1655 (3)	0.0716 (11)
H29	0.2702	0.8573	−0.2172	0.086*
C30	0.2579 (3)	0.8152 (3)	−0.0442 (3)	0.0623 (10)
H30	0.2065	0.7509	−0.0151	0.075*
Cl1	−0.22425 (9)	0.74778 (9)	0.55632 (8)	0.0702 (3)
S1	0.06032 (8)	0.28590 (8)	0.93397 (7)	0.0589 (3)
S2	0.25595 (8)	0.30266 (9)	0.70505 (7)	0.0619 (3)
N1	0.0603 (2)	0.4336 (2)	0.7232 (2)	0.0497 (7)
H1	0.0857	0.4679	0.6469	0.060*
N2	−0.0472 (2)	0.4698 (2)	0.7859 (2)	0.0466 (7)
C1	−0.2804 (3)	0.6881 (3)	0.7111 (3)	0.0492 (8)
C2	−0.2159 (3)	0.6018 (3)	0.7786 (3)	0.0444 (8)
C3	−0.2674 (3)	0.5582 (3)	0.9025 (3)	0.0577 (9)
H3	−0.2269	0.5002	0.9504	0.069*
C4	−0.3772 (3)	0.5999 (4)	0.9548 (3)	0.0728 (11)
H4	−0.4098	0.5708	1.0375	0.087*
C5	−0.4383 (3)	0.6844 (4)	0.8849 (4)	0.0804 (13)
H5	−0.5128	0.7118	0.9205	0.097*
C6	−0.3909 (3)	0.7286 (4)	0.7634 (3)	0.0669 (10)
H6	−0.4329	0.7857	0.7164	0.080*
C7	−0.1006 (3)	0.5565 (3)	0.7233 (3)	0.0461 (8)
H7	−0.0652	0.5910	0.6413	0.055*
C8	0.1257 (3)	0.3461 (3)	0.7791 (3)	0.0446 (8)
C9	0.1668 (3)	0.1677 (3)	0.9769 (3)	0.0613 (10)
H9A	0.1802	0.1150	0.9308	0.074*
H9B	0.2421	0.2030	0.9614	0.074*
C10	0.1176 (3)	0.0961 (3)	1.1086 (3)	0.0476 (8)
C11	0.1692 (3)	0.1043 (3)	1.1888 (3)	0.0572 (9)
H11	0.2325	0.1561	1.1620	0.069*
C12	0.1273 (3)	0.0359 (3)	1.3090 (3)	0.0639 (10)
H12	0.1632	0.0415	1.3622	0.077*
C13	0.0338 (3)	−0.0398 (3)	1.3501 (3)	0.0632 (10)
H13	0.0060	−0.0854	1.4310	0.076*
C14	−0.0190 (3)	−0.0484 (3)	1.2711 (3)	0.0672 (11)
H14	−0.0827	−0.0999	1.2983	0.081*
C15	0.0231 (3)	0.0200 (3)	1.1512 (3)	0.0617 (10)
H15	−0.0132	0.0144	1.0982	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl2	0.0801 (8)	0.0990 (9)	0.0654 (7)	0.0195 (6)	−0.0101 (6)	0.0142 (6)
S3	0.0454 (5)	0.0542 (6)	0.0410 (5)	0.0071 (4)	−0.0009 (4)	−0.0054 (4)
S4	0.0451 (5)	0.0626 (6)	0.0416 (5)	0.0100 (4)	−0.0017 (4)	−0.0085 (4)
N3	0.0410 (16)	0.0570 (18)	0.0386 (15)	0.0077 (13)	−0.0044 (12)	−0.0063 (13)
N4	0.0396 (15)	0.0508 (17)	0.0441 (16)	0.0053 (13)	−0.0071 (13)	−0.0135 (13)
C16	0.046 (2)	0.064 (2)	0.0444 (19)	0.0060 (17)	−0.0116 (16)	−0.0131 (17)
C17	0.0387 (18)	0.050 (2)	0.0456 (18)	0.0053 (15)	−0.0141 (15)	−0.0155 (16)
C18	0.051 (2)	0.056 (2)	0.054 (2)	0.0006 (17)	−0.0130 (17)	−0.0162 (17)
C19	0.056 (2)	0.069 (3)	0.052 (2)	−0.005 (2)	−0.0029 (18)	−0.0267 (19)
C20	0.045 (2)	0.077 (3)	0.070 (3)	0.012 (2)	−0.0156 (19)	−0.040 (2)
C21	0.057 (2)	0.071 (3)	0.063 (2)	0.019 (2)	−0.027 (2)	−0.025 (2)
C22	0.047 (2)	0.052 (2)	0.0402 (18)	0.0013 (17)	−0.0081 (16)	−0.0086 (16)
C23	0.0441 (18)	0.0427 (19)	0.0399 (17)	0.0017 (15)	−0.0081 (15)	−0.0126 (15)
C24	0.049 (2)	0.059 (2)	0.051 (2)	0.0140 (17)	−0.0038 (17)	−0.0065 (17)
C25	0.0372 (18)	0.045 (2)	0.0478 (19)	0.0061 (15)	−0.0070 (15)	−0.0073 (16)
C26	0.064 (2)	0.065 (2)	0.051 (2)	−0.010 (2)	−0.0216 (18)	−0.0108 (19)
C27	0.073 (3)	0.062 (3)	0.057 (2)	−0.020 (2)	−0.014 (2)	−0.002 (2)
C28	0.064 (2)	0.075 (3)	0.048 (2)	0.002 (2)	−0.0136 (19)	−0.004 (2)
C29	0.064 (2)	0.093 (3)	0.060 (2)	0.000 (2)	−0.026 (2)	−0.024 (2)
C30	0.044 (2)	0.060 (2)	0.077 (3)	−0.0071 (18)	−0.0144 (19)	−0.019 (2)
Cl1	0.0795 (7)	0.0724 (7)	0.0449 (5)	0.0055 (5)	−0.0195 (5)	−0.0065 (4)
S1	0.0544 (5)	0.0630 (6)	0.0368 (5)	0.0098 (4)	−0.0037 (4)	−0.0044 (4)
S2	0.0575 (6)	0.0645 (6)	0.0414 (5)	0.0168 (5)	−0.0038 (4)	−0.0092 (4)
N1	0.0471 (16)	0.0566 (18)	0.0324 (14)	0.0087 (14)	−0.0064 (12)	−0.0090 (13)
N2	0.0382 (15)	0.0541 (17)	0.0400 (15)	0.0016 (13)	−0.0064 (12)	−0.0133 (13)
C1	0.050 (2)	0.053 (2)	0.0430 (19)	0.0028 (17)	−0.0150 (16)	−0.0158 (16)
C2	0.0414 (18)	0.048 (2)	0.0406 (18)	−0.0013 (15)	−0.0083 (15)	−0.0144 (15)
C3	0.056 (2)	0.061 (2)	0.045 (2)	0.0045 (18)	−0.0118 (17)	−0.0111 (17)
C4	0.058 (2)	0.092 (3)	0.049 (2)	0.005 (2)	−0.0011 (19)	−0.019 (2)
C5	0.050 (2)	0.108 (4)	0.075 (3)	0.021 (2)	−0.010 (2)	−0.038 (3)
C6	0.057 (2)	0.078 (3)	0.065 (3)	0.019 (2)	−0.025 (2)	−0.025 (2)
C7	0.0427 (18)	0.050 (2)	0.0369 (17)	0.0004 (16)	−0.0086 (15)	−0.0086 (15)
C8	0.0452 (18)	0.0440 (19)	0.0380 (17)	0.0020 (15)	−0.0105 (15)	−0.0095 (15)
C9	0.059 (2)	0.061 (2)	0.044 (2)	0.0099 (18)	−0.0101 (17)	−0.0044 (17)
C10	0.053 (2)	0.044 (2)	0.0389 (17)	0.0089 (16)	−0.0134 (16)	−0.0101 (15)
C11	0.065 (2)	0.049 (2)	0.053 (2)	−0.0041 (18)	−0.0205 (18)	−0.0095 (17)
C12	0.076 (3)	0.070 (3)	0.047 (2)	0.009 (2)	−0.026 (2)	−0.0189 (19)
C13	0.077 (3)	0.060 (2)	0.0364 (19)	0.010 (2)	−0.0092 (19)	−0.0085 (17)
C14	0.066 (2)	0.065 (3)	0.055 (2)	−0.011 (2)	−0.007 (2)	−0.011 (2)
C15	0.066 (2)	0.069 (3)	0.050 (2)	−0.003 (2)	−0.0174 (19)	−0.0199 (19)

Geometric parameters (Å, º) top

Cl2—C16	1.742 (3)	Cl1—C1	1.738 (3)
S3—C23	1.750 (3)	S1—C8	1.751 (3)
S3—C24	1.815 (3)	S1—C9	1.810 (3)
S4—C23	1.662 (3)	S2—C8	1.657 (3)
N3—C23	1.337 (4)	N1—C8	1.334 (4)
N3—N4	1.376 (3)	N1—N2	1.375 (3)
N3—H3A	0.8600	N1—H1	0.8600
N4—C22	1.271 (4)	N2—C7	1.279 (4)
C16—C17	1.384 (4)	C1—C6	1.377 (5)
C16—C21	1.384 (5)	C1—C2	1.390 (4)
C17—C18	1.399 (4)	C2—C3	1.398 (4)
C17—C22	1.458 (4)	C2—C7	1.455 (4)
C18—C19	1.380 (5)	C3—C4	1.376 (5)
C18—H18	0.9300	C3—H3	0.9300
C19—C20	1.375 (5)	C4—C5	1.371 (5)
C19—H19	0.9300	C4—H4	0.9300
C20—C21	1.358 (5)	C5—C6	1.366 (5)
C20—H20	0.9300	C5—H5	0.9300
C21—H21	0.9300	C6—H6	0.9300
C22—H22	0.9300	C7—H7	0.9300
C24—C25	1.503 (4)	C9—C10	1.512 (4)
C24—H24A	0.9700	C9—H9A	0.9700
C24—H24B	0.9700	C9—H9B	0.9700
C25—C26	1.373 (4)	C10—C15	1.374 (4)
C25—C30	1.379 (5)	C10—C11	1.378 (4)
C26—C27	1.377 (5)	C11—C12	1.384 (5)
C26—H26	0.9300	C11—H11	0.9300
C27—C28	1.366 (5)	C12—C13	1.364 (5)
C27—H27	0.9300	C12—H12	0.9300
C28—C29	1.355 (5)	C13—C14	1.377 (5)
C28—H28	0.9300	C13—H13	0.9300
C29—C30	1.381 (5)	C14—C15	1.382 (5)
C29—H29	0.9300	C14—H14	0.9300
C30—H30	0.9300	C15—H15	0.9300

C23—S3—C24	101.41 (15)	C8—S1—C9	101.13 (15)
C23—N3—N4	121.2 (2)	C8—N1—N2	121.0 (2)
C23—N3—H3A	119.4	C8—N1—H1	119.5
N4—N3—H3A	119.4	N2—N1—H1	119.5
C22—N4—N3	115.6 (3)	C7—N2—N1	115.5 (3)
C17—C16—C21	122.5 (3)	C6—C1—C2	121.8 (3)
C17—C16—Cl2	120.3 (3)	C6—C1—Cl1	117.5 (3)
C21—C16—Cl2	117.3 (3)	C2—C1—Cl1	120.7 (3)
C16—C17—C18	116.9 (3)	C1—C2—C3	117.1 (3)
C16—C17—C22	122.2 (3)	C1—C2—C7	121.8 (3)
C18—C17—C22	120.9 (3)	C3—C2—C7	121.0 (3)
C19—C18—C17	120.8 (3)	C4—C3—C2	121.1 (3)
C19—C18—H18	119.6	C4—C3—H3	119.5
C17—C18—H18	119.6	C2—C3—H3	119.5
C20—C19—C18	120.3 (3)	C5—C4—C3	119.9 (4)
C20—C19—H19	119.9	C5—C4—H4	120.1
C18—C19—H19	119.9	C3—C4—H4	120.1
C21—C20—C19	120.5 (3)	C6—C5—C4	120.6 (4)
C21—C20—H20	119.8	C6—C5—H5	119.7
C19—C20—H20	119.8	C4—C5—H5	119.7
C20—C21—C16	119.2 (3)	C5—C6—C1	119.5 (4)
C20—C21—H21	120.4	C5—C6—H6	120.3
C16—C21—H21	120.4	C1—C6—H6	120.3
N4—C22—C17	121.6 (3)	N2—C7—C2	120.9 (3)
N4—C22—H22	119.2	N2—C7—H7	119.6
C17—C22—H22	119.2	C2—C7—H7	119.6
N3—C23—S4	121.1 (2)	N1—C8—S2	121.6 (2)
N3—C23—S3	114.0 (2)	N1—C8—S1	113.4 (2)
S4—C23—S3	124.88 (19)	S2—C8—S1	125.03 (19)
C25—C24—S3	108.6 (2)	C10—C9—S1	108.5 (2)
C25—C24—H24A	110.0	C10—C9—H9A	110.0
S3—C24—H24A	110.0	S1—C9—H9A	110.0
C25—C24—H24B	110.0	C10—C9—H9B	110.0
S3—C24—H24B	110.0	S1—C9—H9B	110.0
H24A—C24—H24B	108.4	H9A—C9—H9B	108.4
C26—C25—C30	117.7 (3)	C15—C10—C11	118.4 (3)
C26—C25—C24	121.6 (3)	C15—C10—C9	121.5 (3)
C30—C25—C24	120.8 (3)	C11—C10—C9	120.0 (3)
C25—C26—C27	121.3 (3)	C10—C11—C12	120.4 (3)
C25—C26—H26	119.4	C10—C11—H11	119.8
C27—C26—H26	119.4	C12—C11—H11	119.8
C28—C27—C26	120.1 (3)	C13—C12—C11	120.6 (3)
C28—C27—H27	119.9	C13—C12—H12	119.7
C26—C27—H27	119.9	C11—C12—H12	119.7
C29—C28—C27	119.6 (3)	C12—C13—C14	119.6 (3)
C29—C28—H28	120.2	C12—C13—H13	120.2
C27—C28—H28	120.2	C14—C13—H13	120.2
C28—C29—C30	120.5 (4)	C13—C14—C15	119.6 (3)
C28—C29—H29	119.8	C13—C14—H14	120.2
C30—C29—H29	119.8	C15—C14—H14	120.2
C25—C30—C29	120.9 (3)	C10—C15—C14	121.3 (3)
C25—C30—H30	119.6	C10—C15—H15	119.3
C29—C30—H30	119.6	C14—C15—H15	119.3

C23—N3—N4—C22	−174.7 (3)	C8—N1—N2—C7	178.3 (3)
C21—C16—C17—C18	−0.1 (5)	C6—C1—C2—C3	−0.5 (5)
Cl2—C16—C17—C18	179.5 (3)	Cl1—C1—C2—C3	−179.9 (3)
C21—C16—C17—C22	−178.8 (3)	C6—C1—C2—C7	178.3 (3)
Cl2—C16—C17—C22	0.8 (5)	Cl1—C1—C2—C7	−1.0 (4)
C16—C17—C18—C19	0.7 (5)	C1—C2—C3—C4	−0.3 (5)
C22—C17—C18—C19	179.4 (3)	C7—C2—C3—C4	−179.2 (3)
C17—C18—C19—C20	−0.9 (5)	C2—C3—C4—C5	0.8 (6)
C18—C19—C20—C21	0.5 (6)	C3—C4—C5—C6	−0.6 (6)
C19—C20—C21—C16	0.1 (6)	C4—C5—C6—C1	−0.2 (6)
C17—C16—C21—C20	−0.3 (6)	C2—C1—C6—C5	0.8 (6)
Cl2—C16—C21—C20	−179.9 (3)	Cl1—C1—C6—C5	−179.8 (3)
N3—N4—C22—C17	179.8 (3)	N1—N2—C7—C2	179.0 (3)
C16—C17—C22—N4	−176.4 (3)	C1—C2—C7—N2	−174.0 (3)
C18—C17—C22—N4	5.0 (5)	C3—C2—C7—N2	4.8 (5)
N4—N3—C23—S4	176.9 (2)	N2—N1—C8—S2	−179.3 (2)
N4—N3—C23—S3	−2.0 (4)	N2—N1—C8—S1	0.3 (4)
C24—S3—C23—N3	−179.2 (3)	C9—S1—C8—N1	177.0 (2)
C24—S3—C23—S4	1.8 (3)	C9—S1—C8—S2	−3.5 (3)
C23—S3—C24—C25	−174.0 (2)	C8—S1—C9—C10	−174.1 (2)
S3—C24—C25—C26	−80.4 (4)	S1—C9—C10—C15	71.2 (4)
S3—C24—C25—C30	99.9 (3)	S1—C9—C10—C11	−110.1 (3)
C30—C25—C26—C27	0.4 (5)	C15—C10—C11—C12	0.9 (5)
C24—C25—C26—C27	−179.4 (3)	C9—C10—C11—C12	−177.8 (3)
C25—C26—C27—C28	0.2 (6)	C10—C11—C12—C13	−0.6 (6)
C26—C27—C28—C29	−0.1 (6)	C11—C12—C13—C14	0.2 (6)
C27—C28—C29—C30	−0.5 (6)	C12—C13—C14—C15	−0.1 (6)
C26—C25—C30—C29	−0.9 (5)	C11—C10—C15—C14	−0.9 (6)
C24—C25—C30—C29	178.8 (3)	C9—C10—C15—C14	177.8 (3)
C28—C29—C30—C25	1.0 (6)	C13—C14—C15—C10	0.5 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S4	0.86	2.56	3.405 (3)	166
N3—H3A···S2	0.86	2.60	3.451 (3)	169

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃ClN₂S₂
M_r	320.84
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	11.877 (2), 11.906 (2), 12.623 (3)
α, β, γ (°)	68.242 (3), 71.116 (4), 82.335 (4)
V (Å³)	1568.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.50
Crystal size (mm)	0.12 × 0.10 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.942, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	8397, 5524, 3436
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.127, 0.97
No. of reflections	5524
No. of parameters	361
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.46

Computer programs: , APEX2 (Bruker, 2005) and SAINT (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S4	0.86	2.56	3.405 (3)	166.1
N3—H3A···S2	0.86	2.60	3.451 (3)	168.6

Acknowledgements

This project was supported by the Postgraduate Foundation of Taishan University (grant No. Y06–2–08).

References

Ali, M. A., Mirza, A. H., Butcher, R. J., Tarafder, M. T. H., Ali, A. M. & Manaf, A. (2001). Inorg. Chim. Acta, 320, 1–6. Google Scholar
Ali, M. A., Mirza, A. H., Butcher, R. J., Tarafder, M. T. H., Keat, T. B., Ali, A. M. & &Manaf, A. (2002). J. Inorg. Biochem. 92, 141–148. PubMed Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tarafder, M. T. H., Islam, M. T., Islam, M. A. A. A. A., Chantrapromma, S. & Fun, H.-K. (2008). Acta Cryst. E64, m416–m417. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Tarafder, M. T. H., Kasbollah, A., Crouse, K. A., Ali, A. M., Yamin, B. M. & Fun, H.-K. (2001). Polyhedron, 20, 2363–2370. Web of Science CSD CrossRef CAS Google Scholar