Benzyl 2-methyl-3-[(E)-(thio-phen-2-yl)methyl-idene]dithio-carbazate.

In the title compound, C(14)H(14)N(2)S(3), the thione S atom and methyl group are syn, as are the two thio-ether S atoms. The mol-ecule is twisted, the dihedral angles between the central (C(2)N(2)S(2)) residue and the pendent 2-thienyl and phenyl rings being 21.57 (6) and 77.54 (3)°, respectively. In the crystal, mol-ecules assemble into a three-dimensional architecture via C-H⋯π inter-actions, involving both the five- and six-membered rings as acceptors, as well as S⋯S inter-actions [3.3406 (5) Å] between centrosymmetrically related 2-thienyl rings.

Related literature

For the biological activity of related Schiff base compounds, see: Hazari et al. (2002 ▶). For a related structure, see: Scovill & Silverton (1980 ▶).

Experimental

Crystal data

C14H14N2S3

M = 306.45

Monoclinic,

a = 6.0585 (1) Å

b = 19.3774 (5) Å

c = 12.5769 (3) Å

β = 103.200 (2)°

V = 1437.49 (6) Å3

Z = 4

Cu Kα radiation

μ = 4.60 mm−1

T = 100 K

0.15 × 0.15 × 0.15 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.871, T max = 1.000

5742 measured reflections

2958 independent reflections

2746 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.080

S = 1.04

2958 reflections

173 parameters

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.50 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); 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: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812012652/hg5198sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812012652/hg5198Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812012652/hg5198Isup3.cml

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

C14H14N2S3	F(000) = 640
Mr = 306.45	Dx = 1.416 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 3411 reflections
a = 6.0585 (1) Å	θ = 3.6–76.3°
b = 19.3774 (5) Å	µ = 4.60 mm−1
c = 12.5769 (3) Å	T = 100 K
β = 103.200 (2)°	Block, yellow-green
V = 1437.49 (6) Å3	0.15 × 0.15 × 0.15 mm
Z = 4

Agilent SuperNova Dual diffractometer with an Atlas detector	2958 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2746 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.017
Detector resolution: 10.4041 pixels mm-1	θmax = 76.5°, θmin = 4.3°
ω scan	h = −7→6
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −21→24
Tmin = 0.871, Tmax = 1.000	l = −14→15
5742 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0498P)2 + 0.373P] where P = (Fo2 + 2Fc2)/3
2958 reflections	(Δ/σ)max = 0.001
173 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.50 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
S1	0.38152 (6)	0.42510 (2)	0.02208 (3)	0.02374 (11)
S2	0.98715 (5)	0.412867 (18)	0.30849 (3)	0.01609 (10)
S3	1.13698 (6)	0.28550 (2)	0.44362 (3)	0.02327 (11)
N1	0.6131 (2)	0.34137 (6)	0.21795 (9)	0.0164 (2)
N2	0.7444 (2)	0.30069 (6)	0.29841 (9)	0.0173 (2)
C1	0.1243 (3)	0.43987 (9)	−0.06539 (13)	0.0309 (4)
H1	0.0995	0.4737	−0.1215	0.037*
C2	−0.0402 (3)	0.39739 (10)	−0.04503 (13)	0.0308 (4)
H2	−0.1931	0.3985	−0.0855	0.037*
C3	0.0401 (3)	0.35160 (8)	0.04254 (12)	0.0226 (3)
H3	−0.0520	0.3185	0.0677	0.027*
C4	0.2703 (2)	0.36066 (8)	0.08760 (11)	0.0176 (3)
C5	0.4082 (2)	0.32207 (7)	0.17652 (11)	0.0171 (3)
H5	0.3479	0.2825	0.2044	0.020*
C6	0.6657 (3)	0.23282 (8)	0.32401 (13)	0.0230 (3)
H6A	0.7881	0.2090	0.3753	0.035*
H6B	0.6211	0.2057	0.2568	0.035*
H6C	0.5352	0.2382	0.3571	0.035*
C7	0.9478 (2)	0.32789 (7)	0.35022 (11)	0.0161 (3)
C8	1.2618 (2)	0.43443 (8)	0.39547 (11)	0.0182 (3)
H8A	1.2569	0.4301	0.4733	0.022*
H8B	1.3797	0.4028	0.3809	0.022*
C9	1.3146 (2)	0.50761 (8)	0.36994 (11)	0.0167 (3)
C10	1.4672 (2)	0.52084 (8)	0.30438 (11)	0.0186 (3)
H10	1.5329	0.4834	0.2737	0.022*
C11	1.5239 (3)	0.58827 (8)	0.28352 (12)	0.0212 (3)
H11	1.6290	0.5967	0.2393	0.025*
C12	1.4274 (3)	0.64340 (8)	0.32713 (12)	0.0217 (3)
H12	1.4663	0.6894	0.3129	0.026*
C13	1.2733 (3)	0.63085 (8)	0.39186 (12)	0.0217 (3)
H13	1.2065	0.6684	0.4217	0.026*
C14	1.2175 (2)	0.56349 (8)	0.41276 (11)	0.0204 (3)
H14	1.1120	0.5553	0.4568	0.025*

	U11	U22	U33	U12	U13	U23
S1	0.0266 (2)	0.0239 (2)	0.01970 (19)	0.00074 (14)	0.00326 (14)	0.00408 (13)
S2	0.01503 (17)	0.01798 (18)	0.01359 (17)	−0.00058 (12)	−0.00020 (12)	0.00121 (11)
S3	0.02006 (18)	0.0231 (2)	0.0235 (2)	0.00380 (13)	−0.00161 (14)	0.00613 (14)
N1	0.0182 (6)	0.0174 (6)	0.0126 (5)	0.0008 (4)	0.0012 (4)	0.0017 (4)
N2	0.0183 (6)	0.0169 (6)	0.0151 (5)	−0.0003 (5)	0.0005 (4)	0.0031 (4)
C1	0.0414 (10)	0.0315 (9)	0.0169 (7)	0.0162 (7)	0.0005 (7)	−0.0005 (6)
C2	0.0237 (8)	0.0413 (10)	0.0227 (8)	0.0135 (7)	−0.0043 (6)	−0.0136 (7)
C3	0.0194 (7)	0.0290 (8)	0.0188 (7)	−0.0013 (6)	0.0030 (5)	−0.0106 (6)
C4	0.0180 (6)	0.0198 (7)	0.0145 (6)	−0.0010 (5)	0.0028 (5)	−0.0048 (5)
C5	0.0180 (6)	0.0176 (6)	0.0157 (6)	−0.0028 (5)	0.0041 (5)	−0.0016 (5)
C6	0.0237 (7)	0.0184 (7)	0.0254 (7)	−0.0028 (6)	0.0025 (6)	0.0057 (6)
C7	0.0160 (6)	0.0190 (6)	0.0139 (6)	0.0016 (5)	0.0044 (5)	−0.0009 (5)
C8	0.0153 (6)	0.0211 (7)	0.0162 (6)	0.0000 (5)	−0.0008 (5)	0.0001 (5)
C9	0.0136 (6)	0.0208 (7)	0.0130 (6)	0.0006 (5)	−0.0023 (5)	−0.0002 (5)
C10	0.0168 (6)	0.0221 (7)	0.0161 (6)	0.0031 (5)	0.0023 (5)	−0.0032 (5)
C11	0.0201 (7)	0.0270 (8)	0.0171 (7)	−0.0013 (6)	0.0056 (5)	0.0003 (6)
C12	0.0229 (7)	0.0215 (7)	0.0186 (7)	0.0000 (6)	0.0007 (6)	0.0014 (6)
C13	0.0234 (7)	0.0217 (7)	0.0194 (7)	0.0051 (6)	0.0038 (6)	−0.0023 (5)
C14	0.0191 (7)	0.0267 (8)	0.0161 (6)	0.0026 (6)	0.0055 (5)	−0.0007 (5)

S1—C1	1.7139 (17)	C6—H6A	0.9800
S1—C4	1.7164 (15)	C6—H6B	0.9800
S2—C7	1.7610 (15)	C6—H6C	0.9800
S2—C8	1.8188 (14)	C8—C9	1.504 (2)
S3—C7	1.6594 (14)	C8—H8A	0.9900
N1—C5	1.2876 (18)	C8—H8B	0.9900
N1—N2	1.3821 (16)	C9—C10	1.3960 (19)
N2—C7	1.3615 (18)	C9—C14	1.398 (2)
N2—C6	1.4597 (18)	C10—C11	1.391 (2)
C1—C2	1.362 (3)	C10—H10	0.9500
C1—H1	0.9500	C11—C12	1.389 (2)
C2—C3	1.412 (2)	C11—H11	0.9500
C2—H2	0.9500	C12—C13	1.393 (2)
C3—C4	1.3915 (19)	C12—H12	0.9500
C3—H3	0.9500	C13—C14	1.388 (2)
C4—C5	1.443 (2)	C13—H13	0.9500
C5—H5	0.9500	C14—H14	0.9500
C1—S1—C4	91.75 (8)	N2—C7—S3	123.41 (11)
C7—S2—C8	101.72 (7)	N2—C7—S2	112.87 (10)
C5—N1—N2	118.12 (12)	S3—C7—S2	123.72 (8)
C7—N2—N1	115.86 (11)	C9—C8—S2	107.34 (9)
C7—N2—C6	123.27 (12)	C9—C8—H8A	110.2
N1—N2—C6	120.86 (11)	S2—C8—H8A	110.2
C2—C1—S1	112.07 (13)	C9—C8—H8B	110.2
C2—C1—H1	124.0	S2—C8—H8B	110.2
S1—C1—H1	124.0	H8A—C8—H8B	108.5
C1—C2—C3	112.96 (14)	C10—C9—C14	118.61 (14)
C1—C2—H2	123.5	C10—C9—C8	120.07 (13)
C3—C2—H2	123.5	C14—C9—C8	121.30 (13)
C4—C3—C2	111.92 (15)	C11—C10—C9	120.62 (13)
C4—C3—H3	124.0	C11—C10—H10	119.7
C2—C3—H3	124.0	C9—C10—H10	119.7
C3—C4—C5	126.83 (14)	C12—C11—C10	120.22 (14)
C3—C4—S1	111.30 (11)	C12—C11—H11	119.9
C5—C4—S1	121.87 (11)	C10—C11—H11	119.9
N1—C5—C4	119.83 (13)	C11—C12—C13	119.67 (14)
N1—C5—H5	120.1	C11—C12—H12	120.2
C4—C5—H5	120.1	C13—C12—H12	120.2
N2—C6—H6A	109.5	C14—C13—C12	119.97 (14)
N2—C6—H6B	109.5	C14—C13—H13	120.0
H6A—C6—H6B	109.5	C12—C13—H13	120.0
N2—C6—H6C	109.5	C13—C14—C9	120.90 (13)
H6A—C6—H6C	109.5	C13—C14—H14	119.6
H6B—C6—H6C	109.5	C9—C14—H14	119.6
C5—N1—N2—C7	−171.17 (12)	C6—N2—C7—S2	−175.83 (11)
C5—N1—N2—C6	9.13 (19)	C8—S2—C7—N2	177.56 (10)
C4—S1—C1—C2	0.23 (13)	C8—S2—C7—S3	−1.90 (10)
S1—C1—C2—C3	−0.11 (18)	C7—S2—C8—C9	−178.59 (9)
C1—C2—C3—C4	−0.10 (19)	S2—C8—C9—C10	−102.29 (13)
C2—C3—C4—C5	−178.82 (13)	S2—C8—C9—C14	79.22 (14)
C2—C3—C4—S1	0.27 (16)	C14—C9—C10—C11	0.9 (2)
C1—S1—C4—C3	−0.28 (12)	C8—C9—C10—C11	−177.58 (13)
C1—S1—C4—C5	178.86 (12)	C9—C10—C11—C12	−0.5 (2)
N2—N1—C5—C4	−176.07 (12)	C10—C11—C12—C13	0.0 (2)
C3—C4—C5—N1	−172.02 (13)	C11—C12—C13—C14	0.2 (2)
S1—C4—C5—N1	8.98 (19)	C12—C13—C14—C9	0.2 (2)
N1—N2—C7—S3	−176.06 (9)	C10—C9—C14—C13	−0.8 (2)
C6—N2—C7—S3	3.63 (19)	C8—C9—C14—C13	177.73 (13)
N1—N2—C7—S2	4.48 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···Cg1i	0.98	2.85	3.4021 (17)	117
C8—H8A···Cg2ii	0.99	2.80	3.4795 (15)	127

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the S1,C1–C4 and C9–C14 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯Cg1i	0.98	2.85	3.4021 (17)	117
C8—H8A⋯Cg2ii	0.99	2.80	3.4795 (15)	127

Symmetry codes: (i) ; (ii) .