Benzyl 3-(2-methyl-phen-yl)dithio-carbazate.

In the title compound, C(15)H(16)N(2)S(2), the central C(2)N(2)S(2) unit is essentially planar (r.m.s. deviation = 0.047 Å) and forms dihedral angles of 68.26 (4) and 65.99 (4)° with the phenyl and benzene rings, respectively, indicating a twisted mol-ecule. Supra-molecular chains with a step topology and propagating along [100] feature in the crystal packing, mediated through N-H⋯S hydrogen bonds. The chains are consolidated into a three-dimensional architecture by C-H⋯π inter-actions.

Related literature

For background to the coordination chemistry and bio-activity of hydrazinecarbodithio­ates, see: Khoo et al. (2005 ▶); Chan et al. (2008 ▶); Ravoof et al. (2010 ▶). For related structures, see: Paulus et al. (2011 ▶); Manan et al. (2012 ▶). For the synthesis, see: Tarafder et al. (2002 ▶).

Experimental

Crystal data

C15H16N2S2

M = 288.42

Monoclinic,

a = 5.7000 (1) Å

b = 11.0136 (2) Å

c = 22.7545 (4) Å

β = 95.198 (2)°

V = 1422.60 (4) Å3

Z = 4

Cu Kα radiation

μ = 3.27 mm−1

T = 100 K

0.22 × 0.14 × 0.08 mm

Data collection

Oxford Diffraction Xcaliber Eos Gemini diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.63, T max = 0.77

15011 measured reflections

2725 independent reflections

2560 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.097

S = 1.03

2725 reflections

179 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 e Å−3

Δρmin = −0.23 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/S160053681201567X/hg5209sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681201567X/hg5209Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681201567X/hg5209Isup3.cml

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

C15H16N2S2	F(000) = 608
Mr = 288.42	Dx = 1.347 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2yn	Cell parameters from 8863 reflections
a = 5.7000 (1) Å	θ = 4–71°
b = 11.0136 (2) Å	µ = 3.27 mm−1
c = 22.7545 (4) Å	T = 100 K
β = 95.198 (2)°	Prism, dark-yellow
V = 1422.60 (4) Å3	0.22 × 0.14 × 0.08 mm
Z = 4

Oxford Diffraction Xcaliber Eos Gemini diffractometer	2725 independent reflections
Radiation source: fine-focus sealed tube	2560 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 16.1952 pixels mm-1	θmax = 71.5°, θmin = 3.9°
ω/2θ scans	h = −6→6
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −13→13
Tmin = 0.63, Tmax = 0.77	l = −27→25
15011 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0646P)2 + 0.6201P] where P = (Fo2 + 2Fc2)/3
2725 reflections	(Δ/σ)max = 0.001
179 parameters	Δρmax = 0.44 e Å−3
2 restraints	Δρmin = −0.23 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.96691 (6)	0.83305 (3)	0.582743 (16)	0.02154 (13)
S2	0.73047 (7)	0.64766 (4)	0.498745 (16)	0.02497 (14)
N1	1.1403 (2)	0.62113 (12)	0.56054 (6)	0.0234 (3)
H1n	1.153 (3)	0.5503 (11)	0.5436 (8)	0.028*
N2	1.3086 (2)	0.65256 (12)	0.60680 (6)	0.0226 (3)
H2n	1.446 (2)	0.6572 (17)	0.5924 (8)	0.027*
C1	0.6928 (3)	0.90389 (14)	0.55250 (7)	0.0247 (3)
H1A	0.6944	0.9153	0.5094	0.030*
H1B	0.5571	0.8516	0.5597	0.030*
C2	0.6713 (3)	1.02493 (14)	0.58237 (6)	0.0216 (3)
C3	0.8217 (3)	1.12038 (16)	0.57225 (7)	0.0277 (4)
H3	0.9444	1.1086	0.5472	0.033*
C4	0.7947 (3)	1.23226 (16)	0.59816 (8)	0.0314 (4)
H4	0.8989	1.2967	0.5908	0.038*
C5	0.6166 (3)	1.25144 (15)	0.63490 (7)	0.0285 (4)
H5	0.5978	1.3288	0.6524	0.034*
C6	0.4669 (3)	1.15700 (15)	0.64578 (8)	0.0279 (4)
H6	0.3445	1.1693	0.6709	0.033*
C7	0.4950 (3)	1.04384 (15)	0.62004 (7)	0.0252 (3)
H7	0.3931	0.9789	0.6282	0.030*
C8	0.9545 (3)	0.69201 (14)	0.54650 (6)	0.0206 (3)
C9	1.3110 (3)	0.57463 (14)	0.65724 (7)	0.0211 (3)
C10	1.4934 (3)	0.59097 (14)	0.70252 (7)	0.0231 (3)
C11	1.4978 (3)	0.51509 (15)	0.75165 (7)	0.0272 (3)
H11	1.6205	0.5243	0.7825	0.033*
C12	1.3278 (3)	0.42639 (16)	0.75675 (7)	0.0294 (4)
H12	1.3361	0.3745	0.7902	0.035*
C13	1.1459 (3)	0.41438 (16)	0.71253 (7)	0.0288 (4)
H13	1.0267	0.3553	0.7161	0.035*
C14	1.1371 (3)	0.48843 (15)	0.66296 (7)	0.0250 (3)
H14	1.0114	0.4800	0.6328	0.030*
C15	1.6766 (3)	0.68749 (16)	0.69763 (7)	0.0288 (4)
H15A	1.7773	0.6925	0.7348	0.043*
H15B	1.5991	0.7659	0.6894	0.043*
H15C	1.7730	0.6670	0.6655	0.043*

	U11	U22	U33	U12	U13	U23
S1	0.0220 (2)	0.0224 (2)	0.0195 (2)	0.00052 (13)	−0.00217 (14)	−0.00249 (13)
S2	0.0232 (2)	0.0274 (2)	0.0232 (2)	−0.00015 (14)	−0.00370 (15)	−0.00584 (14)
N1	0.0266 (7)	0.0216 (6)	0.0210 (6)	0.0004 (5)	−0.0032 (5)	−0.0029 (5)
N2	0.0217 (7)	0.0245 (7)	0.0207 (7)	−0.0005 (5)	−0.0028 (5)	0.0004 (5)
C1	0.0217 (8)	0.0261 (8)	0.0253 (8)	0.0019 (6)	−0.0035 (6)	−0.0019 (6)
C2	0.0209 (7)	0.0242 (8)	0.0188 (7)	0.0017 (6)	−0.0030 (5)	0.0008 (6)
C3	0.0288 (8)	0.0312 (8)	0.0241 (8)	−0.0025 (7)	0.0065 (6)	−0.0002 (6)
C4	0.0372 (10)	0.0252 (8)	0.0323 (9)	−0.0060 (7)	0.0055 (7)	0.0007 (7)
C5	0.0320 (9)	0.0256 (8)	0.0268 (8)	0.0048 (6)	−0.0037 (6)	−0.0036 (6)
C6	0.0214 (8)	0.0359 (9)	0.0263 (8)	0.0047 (6)	0.0019 (6)	−0.0026 (7)
C7	0.0207 (7)	0.0287 (8)	0.0260 (8)	−0.0021 (6)	0.0003 (6)	0.0016 (6)
C8	0.0230 (7)	0.0233 (7)	0.0157 (7)	−0.0025 (6)	0.0026 (5)	0.0008 (6)
C9	0.0217 (7)	0.0214 (7)	0.0203 (7)	0.0037 (6)	0.0030 (6)	−0.0018 (6)
C10	0.0218 (8)	0.0269 (8)	0.0208 (7)	0.0033 (6)	0.0024 (6)	−0.0049 (6)
C11	0.0255 (8)	0.0366 (9)	0.0192 (7)	0.0045 (7)	0.0000 (6)	−0.0025 (6)
C12	0.0343 (9)	0.0339 (9)	0.0205 (8)	0.0048 (7)	0.0062 (6)	0.0034 (6)
C13	0.0283 (8)	0.0298 (8)	0.0289 (8)	−0.0017 (7)	0.0067 (6)	0.0010 (7)
C14	0.0234 (8)	0.0263 (8)	0.0247 (8)	0.0004 (6)	−0.0004 (6)	−0.0019 (6)
C15	0.0249 (8)	0.0355 (9)	0.0254 (8)	−0.0024 (7)	−0.0016 (6)	−0.0024 (7)

S1—C8	1.7571 (15)	C5—H5	0.9500
S1—C1	1.8247 (16)	C6—C7	1.392 (2)
S2—C8	1.6729 (15)	C6—H6	0.9500
N1—C8	1.331 (2)	C7—H7	0.9500
N1—N2	1.4020 (17)	C9—C14	1.387 (2)
N1—H1n	0.877 (9)	C9—C10	1.407 (2)
N2—C9	1.432 (2)	C10—C11	1.394 (2)
N2—H2n	0.878 (9)	C10—C15	1.501 (2)
C1—C2	1.506 (2)	C11—C12	1.388 (2)
C1—H1A	0.9900	C11—H11	0.9500
C1—H1B	0.9900	C12—C13	1.384 (2)
C2—C3	1.389 (2)	C12—H12	0.9500
C2—C7	1.394 (2)	C13—C14	1.389 (2)
C3—C4	1.381 (2)	C13—H13	0.9500
C3—H3	0.9500	C14—H14	0.9500
C4—C5	1.389 (3)	C15—H15A	0.9800
C4—H4	0.9500	C15—H15B	0.9800
C5—C6	1.382 (2)	C15—H15C	0.9800
C8—S1—C1	101.79 (7)	C2—C7—H7	119.7
C8—N1—N2	120.74 (13)	C6—C7—H7	119.7
C8—N1—H1n	120.8 (13)	N1—C8—S2	121.91 (12)
N2—N1—H1n	118.2 (13)	N1—C8—S1	114.11 (11)
N1—N2—C9	114.19 (12)	S2—C8—S1	123.98 (9)
N1—N2—H2n	108.0 (13)	C14—C9—C10	120.37 (14)
C9—N2—H2n	112.9 (13)	C14—C9—N2	122.02 (14)
C2—C1—S1	108.06 (10)	C10—C9—N2	117.57 (14)
C2—C1—H1A	110.1	C11—C10—C9	117.97 (15)
S1—C1—H1A	110.1	C11—C10—C15	121.44 (14)
C2—C1—H1B	110.1	C9—C10—C15	120.59 (14)
S1—C1—H1B	110.1	C12—C11—C10	121.78 (15)
H1A—C1—H1B	108.4	C12—C11—H11	119.1
C3—C2—C7	118.62 (15)	C10—C11—H11	119.1
C3—C2—C1	121.22 (14)	C13—C12—C11	119.28 (15)
C7—C2—C1	120.15 (14)	C13—C12—H12	120.4
C4—C3—C2	120.69 (15)	C11—C12—H12	120.4
C4—C3—H3	119.7	C12—C13—C14	120.25 (16)
C2—C3—H3	119.7	C12—C13—H13	119.9
C3—C4—C5	120.58 (16)	C14—C13—H13	119.9
C3—C4—H4	119.7	C9—C14—C13	120.29 (15)
C5—C4—H4	119.7	C9—C14—H14	119.9
C6—C5—C4	119.37 (15)	C13—C14—H14	119.9
C6—C5—H5	120.3	C10—C15—H15A	109.5
C4—C5—H5	120.3	C10—C15—H15B	109.5
C5—C6—C7	120.12 (16)	H15A—C15—H15B	109.5
C5—C6—H6	119.9	C10—C15—H15C	109.5
C7—C6—H6	119.9	H15A—C15—H15C	109.5
C2—C7—C6	120.61 (15)	H15B—C15—H15C	109.5
C8—N1—N2—C9	111.24 (16)	C1—S1—C8—S2	−1.24 (12)
C8—S1—C1—C2	176.89 (11)	N1—N2—C9—C14	−9.7 (2)
S1—C1—C2—C3	68.74 (16)	N1—N2—C9—C10	172.43 (13)
S1—C1—C2—C7	−112.65 (14)	C14—C9—C10—C11	2.4 (2)
C7—C2—C3—C4	−1.1 (2)	N2—C9—C10—C11	−179.66 (14)
C1—C2—C3—C4	177.55 (15)	C14—C9—C10—C15	−177.54 (14)
C2—C3—C4—C5	0.0 (3)	N2—C9—C10—C15	0.4 (2)
C3—C4—C5—C6	0.5 (3)	C9—C10—C11—C12	−0.6 (2)
C4—C5—C6—C7	0.0 (2)	C15—C10—C11—C12	179.38 (15)
C3—C2—C7—C6	1.6 (2)	C10—C11—C12—C13	−1.4 (2)
C1—C2—C7—C6	−177.07 (14)	C11—C12—C13—C14	1.5 (2)
C5—C6—C7—C2	−1.0 (2)	C10—C9—C14—C13	−2.3 (2)
N2—N1—C8—S2	−170.63 (11)	N2—C9—C14—C13	179.88 (14)
N2—N1—C8—S1	8.92 (19)	C12—C13—C14—C9	0.3 (2)
C1—S1—C8—N1	179.22 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···S2i	0.88 (1)	2.50 (1)	3.3625 (14)	169 (2)
N2—H2n···S2ii	0.88 (1)	2.79 (2)	3.5919 (13)	152 (1)
C11—H11···Cg1iii	0.95	2.98	3.8594 (18)	155
C5—H5···Cg2iv	0.95	2.84	3.7005 (18)	151

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C2–C7 and C9–C14 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯S2i	0.88 (1)	2.50 (1)	3.3625 (14)	169 (2)
N2—H2n⋯S2ii	0.88 (1)	2.79 (2)	3.5919 (13)	152 (1)
C11—H11⋯Cg1iii	0.95	2.98	3.8594 (18)	155
C5—H5⋯Cg2iv	0.95	2.84	3.7005 (18)	151

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .