3-[(Furan-2-yl­methyl­idene)amino]-1-(4-methyl­phen­yl)thio­urea

Zhang, Y.-L.; Zhang, F.-J.; Xu, Z.-H.; Yang, F.-L.

doi:10.1107/S1600536811000110

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o275

doi:10.1107/S1600536811000110

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3-[(Furan-2-ylmethylidene)amino]-1-(4-methylphenyl)thiourea

Yan-Ling Zhang,^a Fu-Juan Zhang,^a Zhi-Hong Xu ^a and Feng-Ling Yang ^a ^*

^aCollege of Chemistry and Chemical Engineering, Xuchang University, Xuchang, Henan Province 461000, People's Republic of China
^*Correspondence e-mail: zhangyanling315@126.com

(Received 9 December 2010; accepted 4 January 2011; online 8 January 2011)

There are two independent molecules in the asymmetric unit of the title compound, C₁₃H₁₃N₃OS, which was obtained from a condensation reaction of N-(p-tolyl)hydrazinecarbothioamide and furfural. The dihedral angles between the mean planes of the tolyl ring and the (furan-2-ylmethylene)hydrazine unit are 39.83 (8) and 48.95 (7)° in the two molecules. The molecules both exhibit an E configuration. In the crystal, intermolecular N—H⋯N and N—H⋯S hydrogen bonds connect the two independent molecules.

Related literature

For biological applications of thiosemicarbazones, see: Okabe et al. (1993 ); Hu et al. (2006 ). For related structures, see: Zhang et al. (2005 ); Shan et al. (2006 ).

Experimental

Crystal data

C₁₃H₁₃N₃OS
M_r = 259.32
Monoclinic, P 2₁ /c
a = 12.9464 (3) Å
b = 13.8613 (3) Å
c = 16.6155 (5) Å
β = 118.028 (2)°
V = 2632.01 (12) Å³
Z = 8
Cu Kα radiation
μ = 2.12 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.677, T_max = 0.677
19253 measured reflections
4697 independent reflections
3878 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.147
S = 1.03
4697 reflections
328 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1Aⁱ	0.86	2.59	3.4397 (19)	171
N2A—H2A⋯S1ⁱⁱ	0.86	2.66	3.3696 (17)	141
N3A—H3A⋯N1A	0.86	2.20	2.628 (2)	111
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811000110/kp2296sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811000110/kp2296Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazones have attracted our attention because of their biological applications (Okabe et al., 1993; Hu et al., 2006). A few single-crystal structres (Zhang et al., 2005; Shan et al., 2006) were reported. For understanding their anticancer activity, it is necessary to have detailed information on their molecular geometries. Both molecules of the asymmetric unit (I) (Fig. 1) reveal an E-configuration. these molecules are related by a pseudo-inversion symmetry. The dihedral angles between the mean planes of the tolyl ring and the (furan-2-ylmethylene)hydrazine unit are 39.83 (8) and 48.95 (7)°. A dominant motif in a crystal packing are hydrogen bonded dimers via intermolecular N(2)—H(2)···S(1 A)and N(2 A)—H(2 A)···S(1), interactions (Table 1 and Fig. 1). Intramolecular hydrogen bond N3A-H3A···N1A is observed (Table 1) whereas the other molecule of asymmetric unit does not meet the angle criterium (N-H···N angle is 108 °) for intramolecular hydrogen bond. The value of this angle might be affected by lower accuracy of hydrogen atom position or slight difference between molecular conformations of these two molecules.

Related literature top

For biological applications of thiosemicarbazones, see: Okabe et al. (1993); Hu et al. (2006). For related structures, see: Zhang et al. (2005); Shan et al. (2006).

Experimental top

N-(p-Tolyl)hydrazinecarbothioamide (1.8 g,10 mmol) and furfural (0.96 g, 10 mmol) was dissolved in 95% ethanol (15 mL) and the solution was refluxed for 2.5 h. Fine colourless crystals appeared on cooling. They were filtered and washed by 95% ethanol to give 2.06 g of the title compound in 79.5% yield. Single crystals of (I) were obtained by recrystallisation from acetone.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at 30% probability level. The two molecules of the asymmetric unit are connected by hydrogen bonds N-H···S (dashed lines).

3-[(Furan-2-ylmethylidene)amino]-1-(4-methylphenyl)thiourea top

Crystal data top

C₁₃H₁₃N₃OS	F(000) = 1088
M_r = 259.32	D_x = 1.309 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 7546 reflections
a = 12.9464 (3) Å	θ = 3.0–72.2°
b = 13.8613 (3) Å	µ = 2.12 mm⁻¹
c = 16.6155 (5) Å	T = 293 K
β = 118.028 (2)°	Prismatic, colorless
V = 2632.01 (12) Å³	0.20 × 0.20 × 0.20 mm
Z = 8

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	4697 independent reflections
Radiation source: fine-focus sealed tube	3878 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ω scans	θ_max = 67.1°, θ_min = 3.9°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −15→15
T_min = 0.677, T_max = 0.677	k = −16→16
19253 measured reflections	l = −19→13

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)] = 0.043	H-atom parameters constrained
wR(F²) = 0.147	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
4697 reflections	Δρ_max = 0.19 e Å⁻³
328 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0044 (4)

Crystal data top

C₁₃H₁₃N₃OS	V = 2632.01 (12) Å³
M_r = 259.32	Z = 8
Monoclinic, P2₁/c	Cu Kα radiation
a = 12.9464 (3) Å	µ = 2.12 mm⁻¹
b = 13.8613 (3) Å	T = 293 K
c = 16.6155 (5) Å	0.20 × 0.20 × 0.20 mm
β = 118.028 (2)°

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	4697 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	3878 reflections with I > 2σ(I)
T_min = 0.677, T_max = 0.677	R_int = 0.042
19253 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.147	H-atom parameters constrained
S = 1.03	Δρ_max = 0.19 e Å⁻³
4697 reflections	Δρ_min = −0.24 e Å⁻³
328 parameters

Special details top

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	0.12468 (5)	0.04591 (4)	0.57517 (3)	0.05268 (19)
S1A	0.30556 (5)	0.53789 (4)	0.36034 (4)	0.0548 (2)
O1	0.63171 (13)	0.26407 (12)	0.80209 (9)	0.0551 (4)
O1A	−0.24494 (16)	0.36883 (14)	0.18097 (11)	0.0676 (5)
N1	0.42256 (15)	0.16907 (13)	0.73490 (11)	0.0482 (4)
N1A	−0.02089 (16)	0.45411 (12)	0.24339 (12)	0.0466 (4)
N2	0.32088 (16)	0.11669 (14)	0.70435 (12)	0.0526 (4)
H2	0.3089	0.0811	0.7415	0.063*
N2A	0.08617 (16)	0.48994 (14)	0.25989 (11)	0.0488 (4)
H2A	0.0953	0.5122	0.2153	0.059*
N3	0.26010 (16)	0.18718 (14)	0.56597 (12)	0.0534 (4)
H3	0.3172	0.2263	0.5953	0.064*
N3A	0.15430 (16)	0.45539 (14)	0.40998 (12)	0.0516 (4)
H3A	0.0848	0.4331	0.3913	0.062*
C1	0.7393 (2)	0.3023 (2)	0.85542 (18)	0.0656 (6)
H1	0.7772	0.3453	0.8351	0.079*
C1A	−0.3614 (3)	0.3434 (2)	0.12705 (19)	0.0734 (7)
H1A	−0.4045	0.3037	0.1453	0.088*
C2	0.7830 (2)	0.2704 (2)	0.93994 (16)	0.0684 (7)
H2B	0.8552	0.2864	0.9884	0.082*
C2A	−0.4018 (2)	0.3844 (2)	0.04573 (17)	0.0697 (7)
H2AA	−0.4772	0.3789	−0.0025	0.084*
C3	0.6988 (2)	0.20724 (19)	0.94272 (15)	0.0600 (6)
H3B	0.7047	0.1737	0.9932	0.072*
C3A	−0.3098 (2)	0.43732 (19)	0.04610 (15)	0.0568 (5)
H3AA	−0.3126	0.4738	−0.0019	0.068*
C4	0.60805 (18)	0.20553 (15)	0.85729 (13)	0.0456 (4)
C4A	−0.2166 (2)	0.42593 (15)	0.12823 (14)	0.0488 (5)
C5	0.49801 (19)	0.15645 (15)	0.81887 (13)	0.0478 (5)
H5	0.4809	0.1150	0.8550	0.057*
C5A	−0.10118 (19)	0.46325 (15)	0.16071 (14)	0.0475 (5)
H5A	−0.0833	0.4958	0.1199	0.057*
C6	0.23996 (18)	0.12135 (15)	0.61564 (13)	0.0457 (4)
C6A	0.17739 (18)	0.49072 (14)	0.34471 (13)	0.0434 (4)
C7	0.19719 (18)	0.19935 (14)	0.46945 (14)	0.0468 (4)
C7A	0.22866 (19)	0.45001 (15)	0.50532 (14)	0.0463 (5)
C8	0.2592 (2)	0.20326 (18)	0.42067 (16)	0.0570 (5)
H8	0.3405	0.1996	0.4512	0.068*
C8A	0.1803 (2)	0.4686 (2)	0.56153 (17)	0.0674 (7)
H8A	0.1016	0.4851	0.5362	0.081*
C9	0.2013 (2)	0.21261 (18)	0.32708 (17)	0.0622 (6)
H9	0.2443	0.2155	0.2954	0.075*
C9A	0.2462 (3)	0.4631 (2)	0.65487 (17)	0.0696 (7)
H9A	0.2114	0.4764	0.6915	0.084*
C10	0.0806 (2)	0.21771 (16)	0.27934 (15)	0.0572 (6)
C10A	0.3629 (2)	0.43844 (17)	0.69498 (15)	0.0535 (5)
C11	0.0199 (2)	0.21777 (18)	0.32891 (16)	0.0602 (6)
H11A	−0.0612	0.2233	0.2983	0.072*
C11A	0.41067 (19)	0.41712 (16)	0.63797 (14)	0.0508 (5)
H11	0.4888	0.3987	0.6634	0.061*
C12	0.07673 (19)	0.20985 (17)	0.42347 (15)	0.0550 (5)
H12A	0.0341	0.2116	0.4555	0.066*
C12A	0.34502 (19)	0.42261 (16)	0.54403 (14)	0.0485 (5)
H12	0.3790	0.4079	0.5071	0.058*
C13	0.0164 (3)	0.2217 (2)	0.17613 (17)	0.0784 (8)
H13D	0.0540	0.2675	0.1551	0.118*
H13E	−0.0632	0.2410	0.1560	0.118*
H13F	0.0177	0.1591	0.1519	0.118*
C13A	0.4365 (3)	0.4347 (2)	0.79706 (17)	0.0710 (7)
H13A	0.3925	0.4598	0.8255	0.106*
H13B	0.5058	0.4728	0.8149	0.106*
H13C	0.4581	0.3691	0.8159	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0500 (3)	0.0630 (3)	0.0400 (3)	−0.0190 (2)	0.0169 (2)	−0.0050 (2)
S1A	0.0495 (3)	0.0691 (4)	0.0465 (3)	−0.0145 (2)	0.0231 (2)	−0.0043 (2)
O1	0.0478 (8)	0.0680 (10)	0.0420 (7)	−0.0072 (7)	0.0149 (6)	0.0030 (6)
O1A	0.0630 (11)	0.0806 (12)	0.0538 (9)	−0.0012 (9)	0.0230 (8)	0.0119 (8)
N1	0.0433 (9)	0.0527 (9)	0.0410 (8)	−0.0064 (7)	0.0135 (7)	−0.0019 (7)
N1A	0.0440 (9)	0.0521 (9)	0.0412 (9)	0.0009 (7)	0.0178 (8)	0.0003 (7)
N2	0.0482 (10)	0.0609 (10)	0.0411 (9)	−0.0140 (8)	0.0148 (8)	0.0005 (7)
N2A	0.0448 (9)	0.0615 (10)	0.0390 (8)	−0.0020 (8)	0.0188 (7)	0.0046 (7)
N3	0.0454 (9)	0.0605 (11)	0.0422 (9)	−0.0160 (8)	0.0107 (7)	0.0014 (7)
N3A	0.0401 (9)	0.0709 (12)	0.0401 (9)	−0.0100 (8)	0.0156 (8)	0.0018 (7)
C1	0.0520 (13)	0.0771 (16)	0.0630 (14)	−0.0173 (12)	0.0232 (11)	−0.0052 (12)
C1A	0.0677 (16)	0.0854 (18)	0.0701 (16)	−0.0179 (14)	0.0349 (14)	0.0011 (14)
C2	0.0456 (12)	0.0907 (19)	0.0490 (12)	−0.0128 (12)	0.0056 (10)	−0.0063 (12)
C2A	0.0501 (13)	0.0953 (19)	0.0528 (13)	−0.0161 (13)	0.0151 (11)	−0.0055 (12)
C3	0.0540 (13)	0.0713 (14)	0.0393 (10)	−0.0026 (11)	0.0091 (9)	0.0042 (10)
C3A	0.0462 (12)	0.0749 (14)	0.0402 (10)	−0.0061 (11)	0.0127 (9)	0.0084 (10)
C4	0.0442 (11)	0.0475 (10)	0.0390 (10)	0.0015 (8)	0.0145 (8)	−0.0006 (8)
C4A	0.0487 (11)	0.0518 (11)	0.0423 (10)	0.0035 (9)	0.0183 (9)	−0.0001 (8)
C5	0.0480 (11)	0.0466 (10)	0.0431 (10)	−0.0004 (9)	0.0168 (9)	0.0010 (8)
C5A	0.0450 (11)	0.0540 (11)	0.0390 (10)	0.0036 (8)	0.0161 (9)	0.0031 (8)
C6	0.0438 (10)	0.0498 (10)	0.0411 (10)	−0.0050 (8)	0.0181 (8)	−0.0058 (8)
C6A	0.0444 (10)	0.0465 (10)	0.0398 (9)	0.0004 (8)	0.0201 (8)	−0.0028 (8)
C7	0.0434 (10)	0.0448 (10)	0.0435 (10)	−0.0038 (8)	0.0132 (9)	0.0027 (8)
C7A	0.0431 (10)	0.0542 (11)	0.0392 (10)	−0.0071 (8)	0.0172 (9)	−0.0004 (8)
C8	0.0431 (11)	0.0670 (14)	0.0569 (12)	0.0036 (10)	0.0203 (10)	0.0062 (10)
C8A	0.0452 (12)	0.109 (2)	0.0491 (13)	0.0111 (12)	0.0232 (11)	0.0067 (12)
C9	0.0703 (15)	0.0666 (14)	0.0552 (13)	0.0088 (12)	0.0341 (12)	0.0059 (11)
C9A	0.0627 (15)	0.105 (2)	0.0467 (13)	0.0066 (14)	0.0306 (12)	0.0004 (12)
C10	0.0662 (14)	0.0475 (11)	0.0450 (11)	0.0019 (10)	0.0155 (10)	0.0034 (9)
C10A	0.0554 (13)	0.0565 (12)	0.0429 (11)	−0.0058 (10)	0.0183 (10)	−0.0015 (9)
C11	0.0450 (12)	0.0625 (13)	0.0554 (13)	−0.0003 (10)	0.0090 (10)	0.0104 (10)
C11A	0.0441 (11)	0.0530 (11)	0.0490 (11)	0.0009 (9)	0.0166 (9)	0.0041 (9)
C12	0.0434 (11)	0.0656 (13)	0.0532 (12)	−0.0014 (10)	0.0204 (10)	0.0076 (10)
C12A	0.0465 (11)	0.0553 (11)	0.0440 (10)	0.0015 (9)	0.0217 (9)	0.0022 (8)
C13	0.095 (2)	0.0716 (16)	0.0469 (13)	0.0048 (15)	0.0153 (13)	0.0059 (11)
C13A	0.0754 (17)	0.0839 (17)	0.0437 (12)	−0.0012 (14)	0.0197 (12)	−0.0006 (11)

Geometric parameters (Å, º) top

S1—C6	1.682 (2)	C4—C5	1.430 (3)
S1A—C6A	1.686 (2)	C4A—C5A	1.427 (3)
O1—C1	1.359 (3)	C5—H5	0.9300
O1—C4	1.363 (3)	C5A—H5A	0.9300
O1A—C4A	1.353 (3)	C7—C12	1.385 (3)
O1A—C1A	1.389 (3)	C7—C8	1.385 (3)
N1—C5	1.285 (3)	C7A—C8A	1.371 (3)
N1—N2	1.375 (2)	C7A—C12A	1.384 (3)
N1A—C5A	1.281 (3)	C8—C9	1.379 (3)
N1A—N2A	1.373 (2)	C8—H8	0.9300
N2—C6	1.350 (3)	C8A—C9A	1.377 (4)
N2—H2	0.8599	C8A—H8A	0.9300
N2A—C6A	1.348 (3)	C9—C10	1.382 (4)
N2A—H2A	0.8600	C9—H9	0.9300
N3—C6	1.336 (3)	C9A—C10A	1.377 (4)
N3—C7	1.427 (3)	C9A—H9A	0.9300
N3—H3	0.8600	C10—C11	1.380 (4)
N3A—C6A	1.345 (3)	C10—C13	1.515 (3)
N3A—C7A	1.417 (3)	C10A—C11A	1.385 (3)
N3A—H3A	0.8600	C10A—C13A	1.506 (3)
C1—C2	1.320 (4)	C11—C12	1.391 (3)
C1—H1	0.9300	C11—H11A	0.9300
C1A—C2A	1.326 (4)	C11A—C12A	1.385 (3)
C1A—H1A	0.9300	C11A—H11	0.9300
C2—C3	1.415 (4)	C12—H12A	0.9300
C2—H2B	0.9300	C12A—H12	0.9300
C2A—C3A	1.397 (3)	C13—H13D	0.9600
C2A—H2AA	0.9300	C13—H13E	0.9600
C3—C4	1.352 (3)	C13—H13F	0.9600
C3—H3B	0.9300	C13A—H13A	0.9600
C3A—C4A	1.340 (3)	C13A—H13B	0.9600
C3A—H3AA	0.9300	C13A—H13C	0.9600

C1—O1—C4	106.22 (18)	N3A—C6A—S1A	126.32 (16)
C4A—O1A—C1A	105.83 (19)	N2A—C6A—S1A	118.65 (15)
C5—N1—N2	115.88 (17)	C12—C7—C8	119.1 (2)
C5A—N1A—N2A	114.36 (17)	C12—C7—N3	122.2 (2)
C6—N2—N1	119.67 (17)	C8—C7—N3	118.73 (19)
C6—N2—H2	120.2	C8A—C7A—C12A	118.7 (2)
N1—N2—H2	120.1	C8A—C7A—N3A	117.6 (2)
C6A—N2A—N1A	121.19 (16)	C12A—C7A—N3A	123.58 (19)
C6A—N2A—H2A	119.4	C9—C8—C7	120.4 (2)
N1A—N2A—H2A	119.5	C9—C8—H8	119.8
C6—N3—C7	126.95 (18)	C7—C8—H8	119.8
C6—N3—H3	116.5	C7A—C8A—C9A	121.1 (2)
C7—N3—H3	116.5	C7A—C8A—H8A	119.4
C6A—N3A—C7A	128.95 (18)	C9A—C8A—H8A	119.4
C6A—N3A—H3A	115.5	C8—C9—C10	121.4 (2)
C7A—N3A—H3A	115.5	C8—C9—H9	119.3
C2—C1—O1	111.0 (2)	C10—C9—H9	119.3
C2—C1—H1	124.5	C10A—C9A—C8A	121.2 (2)
O1—C1—H1	124.5	C10A—C9A—H9A	119.4
C2A—C1A—O1A	109.7 (2)	C8A—C9A—H9A	119.4
C2A—C1A—H1A	125.1	C11—C10—C9	117.7 (2)
O1A—C1A—H1A	125.1	C11—C10—C13	120.8 (2)
C1—C2—C3	106.9 (2)	C9—C10—C13	121.5 (3)
C1—C2—H2B	126.5	C9A—C10A—C11A	117.6 (2)
C3—C2—H2B	126.5	C9A—C10A—C13A	121.6 (2)
C1A—C2A—C3A	107.0 (2)	C11A—C10A—C13A	120.9 (2)
C1A—C2A—H2AA	126.5	C10—C11—C12	121.8 (2)
C3A—C2A—H2AA	126.5	C10—C11—H11A	119.1
C4—C3—C2	106.2 (2)	C12—C11—H11A	119.1
C4—C3—H3B	126.9	C12A—C11A—C10A	121.6 (2)
C2—C3—H3B	126.9	C12A—C11A—H11	119.2
C4A—C3A—C2A	107.5 (2)	C10A—C11A—H11	119.2
C4A—C3A—H3AA	126.3	C7—C12—C11	119.5 (2)
C2A—C3A—H3AA	126.3	C7—C12—H12A	120.3
C3—C4—O1	109.7 (2)	C11—C12—H12A	120.3
C3—C4—C5	132.0 (2)	C7A—C12A—C11A	119.75 (19)
O1—C4—C5	118.33 (17)	C7A—C12A—H12	120.1
C3A—C4A—O1A	109.9 (2)	C11A—C12A—H12	120.1
C3A—C4A—C5A	128.6 (2)	C10—C13—H13D	109.5
O1A—C4A—C5A	121.45 (19)	C10—C13—H13E	109.5
N1—C5—C4	120.63 (19)	H13D—C13—H13E	109.5
N1—C5—H5	119.7	C10—C13—H13F	109.5
C4—C5—H5	119.7	H13D—C13—H13F	109.5
N1A—C5A—C4A	123.2 (2)	H13E—C13—H13F	109.5
N1A—C5A—H5A	118.4	C10A—C13A—H13A	109.5
C4A—C5A—H5A	118.4	C10A—C13A—H13B	109.5
N3—C6—N2	115.50 (18)	H13A—C13A—H13B	109.5
N3—C6—S1	124.88 (16)	C10A—C13A—H13C	109.5
N2—C6—S1	119.62 (16)	H13A—C13A—H13C	109.5
N3A—C6A—N2A	115.00 (18)	H13B—C13A—H13C	109.5

C5—N1—N2—C6	−176.10 (19)	C7A—N3A—C6A—S1A	0.8 (3)
C5A—N1A—N2A—C6A	176.01 (19)	N1A—N2A—C6A—N3A	−0.8 (3)
C4—O1—C1—C2	0.2 (3)	N1A—N2A—C6A—S1A	−178.76 (15)
C4A—O1A—C1A—C2A	−0.7 (3)	C6—N3—C7—C12	53.4 (3)
O1—C1—C2—C3	−0.2 (3)	C6—N3—C7—C8	−128.4 (3)
O1A—C1A—C2A—C3A	0.3 (4)	C6A—N3A—C7A—C8A	140.9 (3)
C1—C2—C3—C4	0.1 (3)	C6A—N3A—C7A—C12A	−42.4 (3)
C1A—C2A—C3A—C4A	0.2 (3)	C12—C7—C8—C9	−3.2 (4)
C2—C3—C4—O1	0.0 (3)	N3—C7—C8—C9	178.4 (2)
C2—C3—C4—C5	−178.9 (2)	C12A—C7A—C8A—C9A	2.0 (4)
C1—O1—C4—C3	−0.1 (3)	N3A—C7A—C8A—C9A	178.8 (3)
C1—O1—C4—C5	179.0 (2)	C7—C8—C9—C10	−0.4 (4)
C2A—C3A—C4A—O1A	−0.6 (3)	C7A—C8A—C9A—C10A	−0.3 (5)
C2A—C3A—C4A—C5A	177.9 (2)	C8—C9—C10—C11	3.0 (4)
C1A—O1A—C4A—C3A	0.8 (3)	C8—C9—C10—C13	−176.1 (2)
C1A—O1A—C4A—C5A	−177.9 (2)	C8A—C9A—C10A—C11A	−1.5 (4)
N2—N1—C5—C4	178.51 (19)	C8A—C9A—C10A—C13A	178.5 (3)
C3—C4—C5—N1	177.4 (2)	C9—C10—C11—C12	−2.1 (4)
O1—C4—C5—N1	−1.5 (3)	C13—C10—C11—C12	177.1 (2)
N2A—N1A—C5A—C4A	176.32 (19)	C9A—C10A—C11A—C12A	1.6 (4)
C3A—C4A—C5A—N1A	174.2 (2)	C13A—C10A—C11A—C12A	−178.3 (2)
O1A—C4A—C5A—N1A	−7.4 (3)	C8—C7—C12—C11	4.1 (3)
C7—N3—C6—N2	171.9 (2)	N3—C7—C12—C11	−177.6 (2)
C7—N3—C6—S1	−7.4 (3)	C10—C11—C12—C7	−1.5 (4)
N1—N2—C6—N3	−7.8 (3)	C8A—C7A—C12A—C11A	−1.8 (3)
N1—N2—C6—S1	171.49 (16)	N3A—C7A—C12A—C11A	−178.48 (19)
C7A—N3A—C6A—N2A	−177.0 (2)	C10A—C11A—C12A—C7A	0.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1Aⁱ	0.86	2.59	3.4397 (19)	171
N2A—H2A···S1ⁱⁱ	0.86	2.66	3.3696 (17)	141
N3A—H3A···N1A	0.86	2.20	2.628 (2)	111

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃N₃OS
M_r	259.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.9464 (3), 13.8613 (3), 16.6155 (5)
β (°)	118.028 (2)
V (Å³)	2632.01 (12)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	2.12
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.677, 0.677
No. of measured, independent and observed [I > 2σ(I)] reflections	19253, 4697, 3878
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.147, 1.03
No. of reflections	4697
No. of parameters	328
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.24

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1Aⁱ	0.86	2.59	3.4397 (19)	171
N2A—H2A···S1ⁱⁱ	0.86	2.66	3.3696 (17)	141
N3A—H3A···N1A	0.86	2.20	2.628 (2)	111

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

Acknowledgements

The authors thank the Natural Science Foundation of the Education Department of Henan Province, China (2010B150029), the Science Foundation of Henan Province, China (082300420110) and the Scientific Research Foundation of Xuchang University of Henan Province, China (2009086) for supporting this work.

References

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Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England. Google Scholar
Shan, S. & Zhang, Y.-L. (2006). Acta Cryst. E62, o2051–o2052. Web of Science CSD CrossRef IUCr Journals Google Scholar
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