Benzyl 3-[(E)-1-(pyrazin-2-yl)ethyl­idene]dithio­carbazate

Shan, S.; Huang, Y.-L.; Guo, H.-Q.; Li, D.-F.; Sun, J.

doi:10.1107/S1600536811028480

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2105

doi:10.1107/S1600536811028480

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Benzyl 3-[(E)-1-(pyrazin-2-yl)ethylidene]dithiocarbazate

Shang Shan,^a ^* Yan-Lan Huang,^a Han-Qi Guo,^a Deng-Feng Li ^a and Jian Sun ^a

^aCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, People's Republic of China
^*Correspondence e-mail: shanshang@mail.hz.zj.cn

(Received 9 July 2011; accepted 15 July 2011; online 23 July 2011)

The title compound, C₁₄H₁₄N₄S₂, was obtained from a condensation reaction of benzyl dithiocarbazate and acetylpyrazine. The asymmetric unit contains two independent molecules, in each of which the pyrazine ring and dithiocarbazate unit are approximately co-planar, the r.m.s. deviations being 0.0304 and 0.0418 Å. The mean plane is oriented with respect to the benzene ring at 49.22 (4)° in one molecule and at 69.76 (7)° in the other. In the crystal, the molecules are linked to each other via intermolecular N—H⋯S hydrogen bonds, forming centrosymmetric supramolecular dimers.

Related literature

For applications of hydrazone and its derivatives in the biological field, see: Okabe et al. (1993 ); Hu et al. (2001 ). For related structures, see: Shan et al. (2006 , 2008a ,b ). For the synthesis, see: Hu et al. (2001).

Experimental

Crystal data

C₁₄H₁₄N₄S₂
M_r = 302.41
Triclinic, $[P \overline 1]$
a = 9.511 (3) Å
b = 9.786 (3) Å
c = 17.144 (5) Å
α = 90.688 (4)°
β = 100.178 (6)°
γ = 111.006 (6)°
V = 1461.2 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 294 K
0.45 × 0.23 × 0.22 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.88, T_max = 0.90
9171 measured reflections
5249 independent reflections
3005 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.111
S = 0.94
5249 reflections
364 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4N⋯S3ⁱ	0.86	2.75	3.611 (2)	175
N8—H8N⋯S1ⁱ	0.86	2.77	3.622 (2)	174
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811028480/xu5267sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028480/xu5267Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811028480/xu5267Isup3.cml

checkCIF report

Comment top

Hydrazone and its derivatives have shown the potential application in the biological field (Okabe et al., 1993; Hu et al., 2001). As part of the ongoing investigation on anti-cancer compounds, the title compound has recently been prepared in our laboratory and its crystal structure is presented here.

The molecular structure of the title compound is shown in Fig. 1. The asymmetric unit contains two independent molecules. In each, the pyrazine ring and dithiocarbazate moiety are approximately co-planer, r.m.s. deviation being 0.0304 and 0.0418 Å, respectively. The mean plane is oriented with respect to the benzene ring at 49.22 (4)° in one molecule while at 69.76 (7)° in the other. The N3—C5 bond length of 1.284 (3) Å and the N7—C19 bond length of 1.282 (3) Å indicate the typical C═N double bonds. The pyrazine ring and dithiocarbazate moieties are located on the opposite positions of the C═N bonds, showing the E-configuration, which agrees with those found in related compounds (Shan et al., 2006; Shan et al., 2008a,b).

In the crystal the two independent molecules are linked to each other via intermolecular N—H···S hydrogen bonding to form the centro-symmetric supramolecular dimer (Table 1).

Related literature top

For applications of hydrazone and its derivatives in the biological field, see: Okabe et al. (1993); Hu et al. (2001). For related structures, see: Shan et al. (2006, 2008a,b). For the synthesis, see: Hu et al. (2001).

Experimental top

Benzyl dithiocarbazate was synthesized as described previously (Hu et al., 2001). Benzyl dithiocarbazate (0.4 g, 2 mmol) and acetylpyrazine (0.24 g, 2 mmol) were dissolved in ethanol (20 ml), then acetic acid (0.2 ml) was added to the ethanol solution with stirring. The mixture solution was refluxed for 6 h. After cooling to room temperature, yellow microcrystals appeared. The microcrystals were separated from the solution and washed with cold water three times. Recrystallization was performed twice with absolute methanol to obtain single crystals of the title compound.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of the title compound with 40% probability displacement (arbitrary spheres for H atoms).

Benzyl 3-[(E)-1-(pyrazin-2-yl)ethylidene]dithiocarbazate top

Crystal data top

C₁₄H₁₄N₄S₂	Z = 4
M_r = 302.41	F(000) = 632
Triclinic, P1	D_x = 1.375 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.511 (3) Å	Cell parameters from 5249 reflections
b = 9.786 (3) Å	θ = 3.3–25.2°
c = 17.144 (5) Å	µ = 0.36 mm⁻¹
α = 90.688 (4)°	T = 294 K
β = 100.178 (6)°	Needle, yellow
γ = 111.006 (6)°	0.45 × 0.23 × 0.22 mm
V = 1461.2 (8) Å³

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	5249 independent reflections
Radiation source: fine-focus sealed tube	3005 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 10.0 pixels mm^-1	θ_max = 25.2°, θ_min = 3.4°
ω scans	h = −11→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −10→11
T_min = 0.88, T_max = 0.90	l = −17→20
9171 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0442P)²] where P = (F_o² + 2F_c²)/3
S = 0.94	(Δ/σ)_max < 0.001
5249 reflections	Δρ_max = 0.21 e Å⁻³
364 parameters	Δρ_min = −0.22 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0051 (7)

Crystal data top

C₁₄H₁₄N₄S₂	γ = 111.006 (6)°
M_r = 302.41	V = 1461.2 (8) Å³
Triclinic, P1	Z = 4
a = 9.511 (3) Å	Mo Kα radiation
b = 9.786 (3) Å	µ = 0.36 mm⁻¹
c = 17.144 (5) Å	T = 294 K
α = 90.688 (4)°	0.45 × 0.23 × 0.22 mm
β = 100.178 (6)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	5249 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3005 reflections with I > 2σ(I)
T_min = 0.88, T_max = 0.90	R_int = 0.027
9171 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 0.94	Δρ_max = 0.21 e Å⁻³
5249 reflections	Δρ_min = −0.22 e Å⁻³
364 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
S1	0.37949 (8)	0.30497 (8)	0.39964 (4)	0.0577 (2)
S2	0.47351 (8)	0.22593 (7)	0.25099 (4)	0.0478 (2)
S3	0.36950 (8)	0.79605 (8)	0.39238 (4)	0.0576 (2)
S4	0.47142 (8)	0.73081 (7)	0.24347 (4)	0.0475 (2)
N1	0.9596 (3)	−0.0100 (2)	0.37093 (13)	0.0612 (6)
N2	0.9043 (3)	0.0108 (3)	0.20740 (14)	0.0678 (7)
N3	0.6706 (2)	0.1393 (2)	0.35110 (11)	0.0440 (5)
N4	0.5883 (2)	0.1903 (2)	0.39383 (12)	0.0462 (5)
H4N	0.6029	0.1905	0.4448	0.055*
N5	0.9564 (3)	0.4878 (2)	0.37052 (13)	0.0579 (6)
N6	0.9118 (3)	0.5081 (3)	0.20683 (14)	0.0700 (7)
N7	0.6718 (2)	0.6436 (2)	0.34506 (12)	0.0451 (5)
N8	0.5870 (2)	0.6937 (2)	0.38655 (12)	0.0475 (5)
H8N	0.6022	0.6962	0.4376	0.057*
C1	0.8542 (3)	0.0416 (2)	0.33694 (14)	0.0419 (6)
C2	0.8283 (3)	0.0504 (3)	0.25545 (16)	0.0575 (7)
H2	0.7532	0.0862	0.2331	0.069*
C3	1.0097 (3)	−0.0394 (3)	0.24298 (18)	0.0623 (8)
H3	1.0675	−0.0680	0.2124	0.075*
C4	1.0353 (3)	−0.0503 (3)	0.32220 (18)	0.0664 (8)
H4	1.1094	−0.0878	0.3439	0.080*
C5	0.7692 (3)	0.0897 (2)	0.38862 (14)	0.0421 (6)
C6	0.8013 (3)	0.0798 (3)	0.47576 (15)	0.0646 (8)
H6A	0.8297	0.1752	0.5026	0.097*
H6B	0.8838	0.0445	0.4894	0.097*
H6C	0.7110	0.0132	0.4917	0.097*
C7	0.4838 (3)	0.2402 (2)	0.35357 (14)	0.0420 (6)
C8	0.3348 (3)	0.3081 (3)	0.21370 (14)	0.0513 (7)
H8A	0.2407	0.2609	0.2333	0.062*
H8B	0.3751	0.4118	0.2314	0.062*
C9	0.3036 (3)	0.2880 (2)	0.12422 (15)	0.0443 (6)
C10	0.1556 (3)	0.2220 (3)	0.08232 (16)	0.0591 (8)
H10	0.0749	0.1883	0.1095	0.071*
C11	0.1261 (4)	0.2054 (3)	0.00069 (19)	0.0731 (9)
H11	0.0254	0.1628	−0.0270	0.088*
C12	0.2447 (4)	0.2513 (3)	−0.04033 (18)	0.0697 (9)
H12	0.2246	0.2382	−0.0956	0.084*
C13	0.3914 (4)	0.3160 (3)	0.00040 (18)	0.0670 (8)
H13	0.4720	0.3470	−0.0271	0.080*
C14	0.4215 (3)	0.3359 (3)	0.08218 (17)	0.0590 (8)
H14	0.5221	0.3819	0.1094	0.071*
C15	0.8569 (3)	0.5450 (2)	0.33416 (14)	0.0401 (6)
C16	0.8372 (3)	0.5543 (3)	0.25265 (15)	0.0568 (7)
H16	0.7676	0.5954	0.2289	0.068*
C17	1.0091 (3)	0.4506 (3)	0.24458 (18)	0.0620 (8)
H17	1.0642	0.4153	0.2153	0.074*
C18	1.0308 (3)	0.4415 (3)	0.32380 (18)	0.0623 (8)
H18	1.1013	0.4010	0.3470	0.075*
C19	0.7713 (3)	0.5969 (2)	0.38395 (14)	0.0430 (6)
C20	0.8037 (3)	0.5919 (3)	0.47198 (15)	0.0620 (8)
H20A	0.8294	0.6881	0.4972	0.093*
H20B	0.8882	0.5596	0.4869	0.093*
H20C	0.7145	0.5247	0.4884	0.093*
C21	0.4789 (3)	0.7394 (2)	0.34580 (14)	0.0416 (6)
C22	0.3174 (3)	0.7955 (3)	0.20720 (14)	0.0487 (7)
H22A	0.2249	0.7366	0.2254	0.058*
H22B	0.3457	0.8969	0.2271	0.058*
C23	0.2895 (3)	0.7829 (3)	0.11759 (14)	0.0428 (6)
C24	0.2221 (3)	0.6467 (3)	0.07488 (16)	0.0533 (7)
H24	0.1938	0.5621	0.1018	0.064*
C25	0.1965 (3)	0.6353 (3)	−0.00675 (17)	0.0605 (8)
H25	0.1516	0.5432	−0.0347	0.073*
C26	0.2366 (3)	0.7584 (3)	−0.04698 (16)	0.0632 (8)
H26	0.2194	0.7505	−0.1022	0.076*
C27	0.3021 (4)	0.8932 (3)	−0.00586 (17)	0.0677 (8)
H27	0.3283	0.9775	−0.0331	0.081*
C28	0.3295 (3)	0.9046 (3)	0.07592 (17)	0.0599 (8)
H28	0.3761	0.9970	0.1034	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0636 (5)	0.0886 (5)	0.0419 (4)	0.0505 (4)	0.0153 (4)	0.0049 (4)
S2	0.0585 (5)	0.0617 (4)	0.0362 (4)	0.0382 (3)	0.0076 (3)	0.0020 (3)
S3	0.0596 (5)	0.0915 (5)	0.0420 (4)	0.0499 (4)	0.0142 (3)	0.0052 (4)
S4	0.0525 (4)	0.0643 (4)	0.0365 (4)	0.0341 (3)	0.0091 (3)	0.0026 (3)
N1	0.0642 (16)	0.0921 (16)	0.0485 (14)	0.0546 (14)	0.0094 (12)	0.0079 (12)
N2	0.0755 (18)	0.1014 (18)	0.0466 (15)	0.0511 (15)	0.0225 (13)	0.0082 (13)
N3	0.0461 (13)	0.0598 (12)	0.0379 (12)	0.0323 (11)	0.0103 (10)	0.0047 (10)
N4	0.0507 (13)	0.0675 (13)	0.0327 (11)	0.0351 (11)	0.0105 (10)	0.0069 (10)
N5	0.0585 (15)	0.0868 (15)	0.0464 (14)	0.0465 (13)	0.0135 (12)	0.0071 (12)
N6	0.0879 (19)	0.0954 (17)	0.0469 (15)	0.0527 (16)	0.0235 (14)	0.0005 (13)
N7	0.0465 (13)	0.0607 (12)	0.0394 (12)	0.0327 (11)	0.0092 (10)	0.0033 (10)
N8	0.0505 (13)	0.0693 (13)	0.0345 (12)	0.0355 (11)	0.0090 (10)	0.0047 (10)
C1	0.0427 (15)	0.0487 (13)	0.0382 (15)	0.0213 (12)	0.0080 (12)	0.0037 (11)
C2	0.065 (2)	0.0804 (18)	0.0451 (17)	0.0451 (16)	0.0155 (15)	0.0124 (14)
C3	0.062 (2)	0.0807 (19)	0.059 (2)	0.0377 (16)	0.0260 (16)	0.0021 (16)
C4	0.064 (2)	0.095 (2)	0.063 (2)	0.0555 (17)	0.0150 (17)	0.0080 (17)
C5	0.0412 (15)	0.0532 (14)	0.0360 (14)	0.0225 (12)	0.0064 (12)	0.0055 (11)
C6	0.069 (2)	0.107 (2)	0.0379 (16)	0.0568 (17)	0.0089 (14)	0.0074 (15)
C7	0.0450 (15)	0.0468 (13)	0.0385 (14)	0.0217 (12)	0.0088 (12)	0.0036 (11)
C8	0.0585 (17)	0.0630 (15)	0.0456 (16)	0.0384 (14)	0.0090 (13)	0.0040 (12)
C9	0.0510 (17)	0.0437 (14)	0.0449 (16)	0.0264 (12)	0.0065 (13)	0.0077 (12)
C10	0.0509 (18)	0.0758 (18)	0.0556 (19)	0.0294 (15)	0.0090 (15)	0.0125 (15)
C11	0.062 (2)	0.088 (2)	0.058 (2)	0.0224 (17)	−0.0059 (18)	0.0055 (17)
C12	0.090 (3)	0.077 (2)	0.0420 (18)	0.0338 (18)	0.0051 (18)	0.0095 (15)
C13	0.069 (2)	0.0793 (19)	0.056 (2)	0.0275 (17)	0.0208 (17)	0.0164 (16)
C14	0.0530 (18)	0.0644 (17)	0.0540 (19)	0.0167 (14)	0.0058 (15)	0.0106 (14)
C15	0.0398 (15)	0.0486 (13)	0.0346 (14)	0.0195 (12)	0.0067 (12)	0.0027 (11)
C16	0.066 (2)	0.0785 (18)	0.0397 (16)	0.0432 (16)	0.0096 (14)	0.0060 (14)
C17	0.068 (2)	0.0739 (18)	0.062 (2)	0.0402 (16)	0.0272 (16)	0.0011 (15)
C18	0.063 (2)	0.090 (2)	0.0549 (19)	0.0510 (17)	0.0162 (15)	0.0061 (16)
C19	0.0440 (16)	0.0530 (14)	0.0381 (15)	0.0243 (12)	0.0092 (12)	0.0046 (11)
C20	0.0646 (19)	0.101 (2)	0.0391 (16)	0.0539 (17)	0.0077 (14)	0.0021 (14)
C21	0.0421 (15)	0.0479 (13)	0.0388 (14)	0.0217 (11)	0.0071 (12)	0.0020 (11)
C22	0.0529 (17)	0.0579 (15)	0.0446 (16)	0.0318 (13)	0.0081 (13)	0.0048 (12)
C23	0.0401 (15)	0.0526 (15)	0.0421 (15)	0.0252 (12)	0.0065 (12)	0.0051 (12)
C24	0.0583 (18)	0.0520 (16)	0.0512 (18)	0.0229 (13)	0.0085 (14)	0.0069 (13)
C25	0.0604 (19)	0.0646 (18)	0.0541 (19)	0.0246 (15)	0.0020 (15)	−0.0082 (15)
C26	0.071 (2)	0.086 (2)	0.0405 (17)	0.0403 (17)	0.0041 (15)	0.0041 (16)
C27	0.085 (2)	0.0684 (19)	0.055 (2)	0.0332 (16)	0.0161 (17)	0.0223 (16)
C28	0.073 (2)	0.0510 (15)	0.0564 (19)	0.0264 (14)	0.0073 (15)	0.0055 (14)

Geometric parameters (Å, º) top

S1—C7	1.651 (2)	C9—C10	1.376 (3)
S2—C7	1.745 (2)	C9—C14	1.383 (4)
S2—C8	1.808 (2)	C10—C11	1.374 (4)
S3—C21	1.650 (2)	C10—H10	0.9300
S4—C21	1.743 (3)	C11—C12	1.376 (4)
S4—C22	1.813 (2)	C11—H11	0.9300
N1—C1	1.327 (3)	C12—C13	1.360 (4)
N1—C4	1.335 (3)	C12—H12	0.9300
N2—C2	1.325 (3)	C13—C14	1.377 (4)
N2—C3	1.327 (3)	C13—H13	0.9300
N3—C5	1.284 (3)	C14—H14	0.9300
N3—N4	1.368 (3)	C15—C16	1.385 (3)
N4—C7	1.348 (3)	C15—C19	1.477 (3)
N4—H4N	0.8600	C16—H16	0.9300
N5—C18	1.330 (3)	C17—C18	1.346 (4)
N5—C15	1.333 (3)	C17—H17	0.9300
N6—C16	1.321 (3)	C18—H18	0.9300
N6—C17	1.328 (3)	C19—C20	1.491 (3)
N7—C19	1.282 (3)	C20—H20A	0.9600
N7—N8	1.370 (3)	C20—H20B	0.9600
N8—C21	1.352 (3)	C20—H20C	0.9600
N8—H8N	0.8600	C22—C23	1.508 (3)
C1—C2	1.384 (3)	C22—H22A	0.9700
C1—C5	1.475 (3)	C22—H22B	0.9700
C2—H2	0.9300	C23—C28	1.366 (3)
C3—C4	1.349 (4)	C23—C24	1.386 (3)
C3—H3	0.9300	C24—C25	1.374 (4)
C4—H4	0.9300	C24—H24	0.9300
C5—C6	1.482 (3)	C25—C26	1.362 (4)
C6—H6A	0.9600	C25—H25	0.9300
C6—H6B	0.9600	C26—C27	1.363 (3)
C6—H6C	0.9600	C26—H26	0.9300
C8—C9	1.507 (3)	C27—C28	1.376 (4)
C8—H8A	0.9700	C27—H27	0.9300
C8—H8B	0.9700	C28—H28	0.9300

C7—S2—C8	102.79 (11)	C11—C12—H12	120.2
C21—S4—C22	102.13 (11)	C12—C13—C14	120.3 (3)
C1—N1—C4	116.0 (2)	C12—C13—H13	119.8
C2—N2—C3	115.1 (3)	C14—C13—H13	119.8
C5—N3—N4	118.6 (2)	C13—C14—C9	120.7 (3)
C7—N4—N3	117.9 (2)	C13—C14—H14	119.7
C7—N4—H4N	121.0	C9—C14—H14	119.7
N3—N4—H4N	121.0	N5—C15—C16	120.0 (2)
C18—N5—C15	115.9 (2)	N5—C15—C19	117.5 (2)
C16—N6—C17	115.0 (3)	C16—C15—C19	122.4 (2)
C19—N7—N8	118.4 (2)	N6—C16—C15	123.6 (3)
C21—N8—N7	118.8 (2)	N6—C16—H16	118.2
C21—N8—H8N	120.6	C15—C16—H16	118.2
N7—N8—H8N	120.6	N6—C17—C18	122.3 (3)
N1—C1—C2	119.9 (2)	N6—C17—H17	118.8
N1—C1—C5	118.0 (2)	C18—C17—H17	118.8
C2—C1—C5	122.1 (2)	N5—C18—C17	123.2 (3)
N2—C2—C1	123.7 (3)	N5—C18—H18	118.4
N2—C2—H2	118.1	C17—C18—H18	118.4
C1—C2—H2	118.1	N7—C19—C15	114.5 (2)
N2—C3—C4	122.0 (3)	N7—C19—C20	125.4 (2)
N2—C3—H3	119.0	C15—C19—C20	120.1 (2)
C4—C3—H3	119.0	C19—C20—H20A	109.5
N1—C4—C3	123.2 (3)	C19—C20—H20B	109.5
N1—C4—H4	118.4	H20A—C20—H20B	109.5
C3—C4—H4	118.4	C19—C20—H20C	109.5
N3—C5—C1	113.9 (2)	H20A—C20—H20C	109.5
N3—C5—C6	125.6 (2)	H20B—C20—H20C	109.5
C1—C5—C6	120.5 (2)	N8—C21—S3	120.95 (19)
C5—C6—H6A	109.5	N8—C21—S4	113.05 (18)
C5—C6—H6B	109.5	S3—C21—S4	126.01 (14)
H6A—C6—H6B	109.5	C23—C22—S4	108.01 (16)
C5—C6—H6C	109.5	C23—C22—H22A	110.1
H6A—C6—H6C	109.5	S4—C22—H22A	110.1
H6B—C6—H6C	109.5	C23—C22—H22B	110.1
N4—C7—S1	121.67 (19)	S4—C22—H22B	110.1
N4—C7—S2	112.47 (18)	H22A—C22—H22B	108.4
S1—C7—S2	125.85 (14)	C28—C23—C24	117.9 (2)
C9—C8—S2	107.72 (16)	C28—C23—C22	121.3 (2)
C9—C8—H8A	110.2	C24—C23—C22	120.8 (2)
S2—C8—H8A	110.2	C25—C24—C23	120.8 (2)
C9—C8—H8B	110.2	C25—C24—H24	119.6
S2—C8—H8B	110.2	C23—C24—H24	119.6
H8A—C8—H8B	108.5	C26—C25—C24	120.2 (2)
C10—C9—C14	118.4 (2)	C26—C25—H25	119.9
C10—C9—C8	120.3 (3)	C24—C25—H25	119.9
C14—C9—C8	121.3 (2)	C25—C26—C27	119.7 (3)
C11—C10—C9	120.6 (3)	C25—C26—H26	120.1
C11—C10—H10	119.7	C27—C26—H26	120.1
C9—C10—H10	119.7	C26—C27—C28	120.1 (3)
C10—C11—C12	120.4 (3)	C26—C27—H27	120.0
C10—C11—H11	119.8	C28—C27—H27	120.0
C12—C11—H11	119.8	C23—C28—C27	121.3 (2)
C13—C12—C11	119.6 (3)	C23—C28—H28	119.3
C13—C12—H12	120.2	C27—C28—H28	119.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···S3ⁱ	0.86	2.75	3.611 (2)	175
N8—H8N···S1ⁱ	0.86	2.77	3.622 (2)	174

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄N₄S₂
M_r	302.41
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	9.511 (3), 9.786 (3), 17.144 (5)
α, β, γ (°)	90.688 (4), 100.178 (6), 111.006 (6)
V (Å³)	1461.2 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.45 × 0.23 × 0.22

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.88, 0.90
No. of measured, independent and observed [I > 2σ(I)] reflections	9171, 5249, 3005
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.111, 0.94
No. of reflections	5249
No. of parameters	364
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.22

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···S3ⁱ	0.86	2.75	3.611 (2)	175
N8—H8N···S1ⁱ	0.86	2.77	3.622 (2)	174

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The work was supported by the Natural Science Foundation of Zhejiang Province, China (No. M203027).

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Hu, W., Sun, N. & Yang, Z. (2001). Chem. J. Chin. Univ. 22, 2014–2017. CAS Google Scholar
Okabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678–1680. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Shan, S., Tian, Y.-L., Wang, S.-H., Wang, W.-L. & Xu, Y.-L. (2008a). Acta Cryst. E64, o1014. Web of Science CSD CrossRef IUCr Journals Google Scholar
Shan, S., Tian, Y.-L., Wang, S.-H., Wang, W.-L. & Xu, Y.-L. (2008b). Acta Cryst. E64, o1024. Web of Science CSD CrossRef IUCr Journals Google Scholar
Shan, S., Zhang, Y.-L. & Xu, D.-J. (2006). Acta Cryst. E62, o1567–o1569. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar