2-[2-Benzoyl-3,3-bis-(methyl-sulfan-yl)prop-2-enyl-idene]malononitrile.

The title compound, C(15)H(12)N(2)OS(2), is an example of a push-pull butadiene in which the electron-releasing methyl-sulfanyl groups and electron-withdrawing nitrile groups on either end of the butadiene chain enhance the conjugation in the system. Short intra-molecular C-H⋯S inter-actions are observed. In the crystal structure, an O⋯C short contact of 2.917 (3) Å is observed.

Related literature

The title compound was obtained during the synthesis of pyr­idene derivatives, see: Anabha & Asokan (2006 ▶). In push–pull butadienes, the C=C double bonds usually become more polarized due to π-electron delocalization (Dahne, 1978 ▶; Michalik et al., 2002 ▶). For related structures, see: Dastidar et al. (1993 ▶); Freier et al. (1999 ▶); Homrighausen & Krause Bauer (2004 ▶).

Experimental

Crystal data

C15H12N2OS2

M = 300.39

Monoclinic,

a = 5.6557 (2) Å

b = 8.5153 (3) Å

c = 31.4726 (11) Å

β = 90.106 (2)°

V = 1515.72 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.35 mm−1

T = 298 K

0.40 × 0.35 × 0.30 mm

Data collection

MacScience DIPLabo 32001 diffractometer

Absorption correction: none

9663 measured reflections

2816 independent reflections

2338 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.128

S = 1.13

2816 reflections

183 parameters

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.25 e Å−3

Data collection: XPRESS (MacScience, 2002 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97 and PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809024635/ci2822sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024635/ci2822Isup2.hkl

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

C15H12N2OS2	F(000) = 624
Mr = 300.39	Dx = 1.316 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9663 reflections
a = 5.6557 (2) Å	θ = 1.3–25.5°
b = 8.5153 (3) Å	µ = 0.35 mm−1
c = 31.4726 (11) Å	T = 298 K
β = 90.106 (2)°	Block, pale yellow
V = 1515.72 (9) Å3	0.40 × 0.35 × 0.30 mm
Z = 4

MacScience DIPLabo 32001 diffractometer	2338 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
graphite	θmax = 25.5°, θmin = 1.3°
Detector resolution: 10.0 pixels mm-1	h = −6→6
ω scans	k = −10→8
9663 measured reflections	l = −32→38
2816 independent 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.0656P)2 + 0.4642P] where P = (Fo2 + 2Fc2)/3
2816 reflections	(Δ/σ)max = 0.001
183 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.25 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	0.00111 (11)	0.11114 (7)	0.06548 (2)	0.0548 (2)
S2	−0.42287 (10)	0.19748 (8)	0.11875 (2)	0.0644 (2)
C13	0.1963 (4)	0.6023 (2)	0.06658 (7)	0.0428 (5)
C8	−0.0899 (3)	0.4037 (2)	0.09460 (6)	0.0416 (5)
O1	−0.3112 (3)	0.6304 (2)	0.11057 (6)	0.0612 (5)
C14	0.1880 (4)	0.7065 (3)	0.10221 (8)	0.0476 (5)
C7	−0.2105 (3)	0.5153 (3)	0.12490 (7)	0.0442 (5)
C4	−0.2015 (4)	0.4849 (3)	0.17132 (7)	0.0471 (5)
C9	−0.1611 (4)	0.2504 (3)	0.09308 (6)	0.0433 (5)
N1	0.1825 (4)	0.7886 (3)	0.13089 (8)	0.0688 (6)
N2	0.4570 (5)	0.6939 (3)	0.00423 (8)	0.0775 (7)
C12	0.0782 (4)	0.4644 (3)	0.06452 (7)	0.0436 (5)
H12	0.1091	0.4017	0.0410	0.052*
C15	0.3442 (4)	0.6523 (3)	0.03182 (8)	0.0531 (6)
C3	−0.0286 (5)	0.3946 (3)	0.18964 (8)	0.0632 (7)
H3	0.0884	0.3489	0.1730	0.076*
C11	−0.2165 (5)	−0.0279 (3)	0.04676 (9)	0.0673 (7)
H11A	−0.2667	−0.0931	0.0699	0.101*
H11B	−0.1483	−0.0923	0.0249	0.101*
H11C	−0.3502	0.0277	0.0354	0.101*
C10	−0.3350 (6)	0.0311 (4)	0.15069 (10)	0.0833 (9)
H10A	−0.2272	−0.0333	0.1349	0.125*
H10B	−0.4722	−0.0293	0.1581	0.125*
H10C	−0.2588	0.0675	0.1761	0.125*
C5	−0.3728 (5)	0.5550 (4)	0.19670 (8)	0.0672 (7)
H5	−0.4862	0.6200	0.1845	0.081*
C1	−0.2049 (7)	0.4371 (5)	0.25760 (9)	0.0886 (10)
H1	−0.2081	0.4190	0.2867	0.106*
C6	−0.3743 (6)	0.5282 (5)	0.23948 (10)	0.0907 (10)
H6	−0.4918	0.5726	0.2563	0.109*
C2	−0.0300 (7)	0.3719 (4)	0.23359 (10)	0.0841 (9)
H2	0.0881	0.3124	0.2465	0.101*

	U11	U22	U33	U12	U13	U23
S1	0.0588 (4)	0.0489 (4)	0.0568 (4)	−0.0146 (3)	0.0101 (3)	−0.0086 (3)
S2	0.0452 (3)	0.0742 (5)	0.0739 (5)	−0.0231 (3)	0.0133 (3)	−0.0116 (3)
C13	0.0436 (11)	0.0424 (11)	0.0423 (11)	−0.0046 (9)	−0.0006 (8)	0.0003 (9)
C8	0.0394 (10)	0.0470 (11)	0.0384 (11)	−0.0078 (9)	−0.0043 (8)	−0.0007 (9)
O1	0.0509 (9)	0.0683 (11)	0.0644 (11)	0.0137 (8)	0.0015 (8)	0.0101 (9)
C14	0.0399 (11)	0.0470 (12)	0.0560 (14)	−0.0030 (9)	−0.0046 (9)	−0.0036 (11)
C7	0.0329 (9)	0.0503 (12)	0.0493 (12)	−0.0041 (9)	−0.0017 (8)	−0.0002 (10)
C4	0.0448 (11)	0.0511 (12)	0.0453 (12)	−0.0066 (9)	−0.0003 (9)	−0.0023 (10)
C9	0.0411 (10)	0.0502 (12)	0.0384 (11)	−0.0111 (9)	−0.0021 (8)	−0.0014 (9)
N1	0.0609 (13)	0.0696 (14)	0.0758 (15)	−0.0004 (10)	−0.0015 (11)	−0.0257 (13)
N2	0.0999 (18)	0.0699 (15)	0.0628 (14)	−0.0293 (13)	0.0150 (13)	0.0073 (12)
C12	0.0479 (11)	0.0463 (12)	0.0367 (11)	−0.0061 (9)	0.0003 (8)	−0.0033 (9)
C15	0.0646 (14)	0.0431 (12)	0.0517 (14)	−0.0139 (11)	0.0008 (11)	0.0007 (11)
C3	0.0706 (16)	0.0651 (16)	0.0538 (15)	0.0063 (13)	−0.0092 (12)	−0.0026 (12)
C11	0.0893 (18)	0.0542 (14)	0.0584 (15)	−0.0278 (13)	0.0043 (13)	−0.0119 (12)
C10	0.109 (2)	0.081 (2)	0.0601 (17)	−0.0354 (18)	0.0254 (16)	0.0058 (15)
C5	0.0591 (14)	0.0854 (19)	0.0571 (16)	0.0016 (14)	0.0114 (12)	−0.0041 (14)
C1	0.116 (3)	0.107 (3)	0.0429 (15)	−0.017 (2)	0.0079 (16)	0.0082 (17)
C6	0.088 (2)	0.130 (3)	0.0549 (18)	0.003 (2)	0.0176 (16)	−0.0021 (19)
C2	0.104 (2)	0.084 (2)	0.0641 (19)	0.0032 (18)	−0.0244 (17)	0.0116 (16)

S1—C9	1.734 (2)	C12—H12	0.93
S1—C11	1.806 (2)	C3—C2	1.397 (4)
S2—C9	1.747 (2)	C3—H3	0.93
S2—C10	1.806 (3)	C11—H11A	0.96
C13—C12	1.352 (3)	C11—H11B	0.96
C13—C14	1.431 (3)	C11—H11C	0.96
C13—C15	1.443 (3)	C10—H10A	0.96
C8—C9	1.366 (3)	C10—H10B	0.96
C8—C12	1.439 (3)	C10—H10C	0.96
C8—C7	1.510 (3)	C5—C6	1.365 (4)
O1—C7	1.220 (3)	C5—H5	0.93
C14—N1	1.142 (3)	C1—C6	1.358 (5)
C7—C4	1.485 (3)	C1—C2	1.364 (5)
C4—C3	1.371 (3)	C1—H1	0.93
C4—C5	1.391 (3)	C6—H6	0.93
N2—C15	1.135 (3)	C2—H2	0.93
C9—S1—C11	104.55 (12)	S1—C11—H11A	109.5
C9—S2—C10	103.13 (13)	S1—C11—H11B	109.5
C12—C13—C14	124.00 (19)	H11A—C11—H11B	109.5
C12—C13—C15	120.4 (2)	S1—C11—H11C	109.5
C14—C13—C15	115.56 (19)	H11A—C11—H11C	109.5
C9—C8—C12	121.01 (19)	H11B—C11—H11C	109.5
C9—C8—C7	119.33 (18)	S2—C10—H10A	109.5
C12—C8—C7	119.26 (18)	S2—C10—H10B	109.5
N1—C14—C13	179.3 (2)	H10A—C10—H10B	109.5
O1—C7—C4	121.3 (2)	S2—C10—H10C	109.5
O1—C7—C8	118.9 (2)	H10A—C10—H10C	109.5
C4—C7—C8	119.80 (19)	H10B—C10—H10C	109.5
C3—C4—C5	119.8 (2)	C6—C5—C4	120.0 (3)
C3—C4—C7	122.3 (2)	C6—C5—H5	120.0
C5—C4—C7	117.9 (2)	C4—C5—H5	120.0
C8—C9—S1	120.97 (16)	C6—C1—C2	120.8 (3)
C8—C9—S2	118.70 (17)	C6—C1—H1	119.6
S1—C9—S2	120.31 (12)	C2—C1—H1	119.6
C13—C12—C8	127.4 (2)	C1—C6—C5	120.3 (3)
C13—C12—H12	116.3	C1—C6—H6	119.9
C8—C12—H12	116.3	C5—C6—H6	119.9
N2—C15—C13	178.5 (3)	C1—C2—C3	119.9 (3)
C4—C3—C2	119.3 (3)	C1—C2—H2	120.1
C4—C3—H3	120.4	C3—C2—H2	120.1
C2—C3—H3	120.4
C9—C8—C7—O1	−119.9 (2)	C10—S2—C9—C8	−129.17 (19)
C12—C8—C7—O1	53.0 (3)	C10—S2—C9—S1	51.99 (17)
C9—C8—C7—C4	61.1 (3)	C14—C13—C12—C8	6.1 (4)
C12—C8—C7—C4	−126.1 (2)	C15—C13—C12—C8	−174.6 (2)
O1—C7—C4—C3	−156.3 (2)	C9—C8—C12—C13	−167.0 (2)
C8—C7—C4—C3	22.7 (3)	C7—C8—C12—C13	20.3 (3)
O1—C7—C4—C5	22.0 (3)	C5—C4—C3—C2	1.2 (4)
C8—C7—C4—C5	−159.0 (2)	C7—C4—C3—C2	179.5 (2)
C12—C8—C9—S1	17.8 (3)	C3—C4—C5—C6	−2.8 (4)
C7—C8—C9—S1	−169.48 (15)	C7—C4—C5—C6	178.8 (3)
C12—C8—C9—S2	−161.03 (16)	C2—C1—C6—C5	0.5 (6)
C7—C8—C9—S2	11.7 (3)	C4—C5—C6—C1	2.0 (5)
C11—S1—C9—C8	−148.69 (19)	C6—C1—C2—C3	−2.1 (6)
C11—S1—C9—S2	30.13 (17)	C4—C3—C2—C1	1.2 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···S1	0.96	2.82	3.360 (3)	116
C12—H12···S1	0.93	2.66	3.040 (2)	105

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯S1	0.96	2.82	3.360 (3)	116
C12—H12⋯S1	0.93	2.66	3.040 (2)	105