2,2'-Bis(methyl-ene)-3,3'-(2-thioxo-2,3-dihydro-1H-benzimidazole-1,3-di-yl)dipropane-nitrile.

In the title compound, C(15)H(12)N(4)S, the benzimidazole ring is essentially planar, with a mean deviation of 0.0082 (1) Å from the least-squares plane defined by the nine constituent atoms. In the crystal, inversion dimers linked by pairs of C-H⋯N hydrogen bonds occur.

Related literature

Benzimidazole is a potential precursor in heterocyclic chemistry and the benzimidazol-2-thione ring is present in many pharmacologically active substances, see: Hwa et al. (2008 ▶). For ammonium salts from Mannich adducts as precursors for the synthesis of acrylic derivatives carrying functionalized thio­methyl groups, see: M’rabet et al. (2009 ▶). For a related structure, see: Khan et al. (2008 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C15H12N4S

M = 280.35

Triclinic,

a = 8.6274 (3) Å

b = 9.8271 (2) Å

c = 9.8271 (2) Å

α = 70.553 (2)°

β = 89.730 (2)°

γ = 67.853 (3)°

V = 720.67 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.22 mm−1

T = 293 K

0.22 × 0.20 × 0.18 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer

Absorption correction: none

6594 measured reflections

3297 independent reflections

2449 reflections with I > 2σ(I)

R int = 0.018

2 standard reflections frequency: 120 min intensity decay: 3%

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.111

S = 1.02

3297 reflections

181 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.32 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); 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 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809043438/pv2216sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043438/pv2216Isup2.hkl

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

C15H12N4S	Z = 2
Mr = 280.35	F(000) = 292
Triclinic, P1	Dx = 1.292 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6274 (3) Å	Cell parameters from 25 reflections
b = 9.8271 (2) Å	θ = 9.0–11.0°
c = 9.8271 (2) Å	µ = 0.22 mm−1
α = 70.553 (2)°	T = 293 K
β = 89.730 (2)°	Prism, colourless
γ = 67.853 (3)°	0.22 × 0.20 × 0.18 mm
V = 720.67 (3) Å3

Enraf–Nonius TurboCAD-4 diffractometer	Rint = 0.018
Radiation source: fine-focus sealed tube	θmax = 28.0°, θmin = 2.2°
graphite	h = −11→11
Nonprofiled ω scans	k = −12→12
6594 measured reflections	l = −12→12
3297 independent reflections	2 standard reflections every 120 min
2449 reflections with I > 2σ(I)	intensity decay: 3%

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) = 0.111	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0547P)2 + 0.1378P] where P = (Fo2 + 2Fc2)/3
3297 reflections	(Δ/σ)max = 0.002
181 parameters	Δρmax = 0.19 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

Geometry. All e.s.d.'s 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	0.21056 (7)	0.61386 (6)	0.54777 (5)	0.06747 (18)
N1	0.12971 (16)	0.64019 (15)	0.80813 (13)	0.0438 (3)
N2	0.36099 (16)	0.43553 (15)	0.82525 (13)	0.0443 (3)
C2	0.33686 (19)	0.43018 (18)	0.96681 (16)	0.0429 (3)
C1	0.19084 (19)	0.55980 (18)	0.95584 (16)	0.0421 (3)
C7	0.2340 (2)	0.56319 (18)	0.72744 (16)	0.0452 (3)
C9	0.01720 (18)	0.92638 (18)	0.74111 (16)	0.0447 (3)
C10	0.1474 (2)	0.95298 (19)	0.65727 (17)	0.0478 (4)
C14	0.3569 (2)	0.1382 (2)	0.84115 (19)	0.0529 (4)
C13	0.45594 (19)	0.20653 (18)	0.74643 (17)	0.0455 (3)
C12	0.5016 (2)	0.3244 (2)	0.78361 (19)	0.0510 (4)
H12A	0.5942	0.2689	0.8632	0.061*
H12B	0.5405	0.3823	0.7000	0.061*
N3	0.2515 (2)	0.9733 (2)	0.59254 (18)	0.0649 (4)
C6	0.1282 (2)	0.5886 (2)	1.07808 (18)	0.0529 (4)
H6	0.0298	0.6752	1.0707	0.063*
C8	−0.0187 (2)	0.78626 (19)	0.74714 (19)	0.0510 (4)
H8A	−0.1083	0.7813	0.8060	0.061*
H8B	−0.0575	0.7988	0.6495	0.061*
N4	0.2784 (2)	0.0869 (2)	0.9192 (2)	0.0810 (5)
C3	0.4283 (2)	0.3241 (2)	1.10096 (18)	0.0563 (4)
H3	0.5264	0.2372	1.1085	0.068*
C5	0.2197 (3)	0.4820 (2)	1.21154 (19)	0.0638 (5)
H5	0.1814	0.4969	1.2962	0.077*
C15	0.5064 (3)	0.1615 (3)	0.6360 (2)	0.0681 (5)
H15A	0.4778	0.0855	0.6195	0.082*
H15B	0.5706	0.2057	0.5745	0.082*
C11	−0.0631 (2)	1.0256 (2)	0.8061 (2)	0.0638 (5)
H11A	−0.0353	1.1105	0.7973	0.077*
H11B	−0.1475	1.0105	0.8607	0.077*
C4	0.3670 (3)	0.3534 (2)	1.22258 (19)	0.0651 (5)
H4	0.4260	0.2853	1.3143	0.078*

	U11	U22	U33	U12	U13	U23
S1	0.0965 (4)	0.0682 (3)	0.0385 (2)	−0.0351 (3)	0.0141 (2)	−0.0176 (2)
N1	0.0492 (7)	0.0414 (7)	0.0399 (6)	−0.0177 (5)	0.0080 (5)	−0.0138 (5)
N2	0.0505 (7)	0.0423 (7)	0.0441 (7)	−0.0195 (6)	0.0117 (5)	−0.0193 (5)
C2	0.0511 (8)	0.0414 (8)	0.0432 (7)	−0.0239 (7)	0.0072 (6)	−0.0172 (6)
C1	0.0502 (8)	0.0432 (8)	0.0403 (7)	−0.0250 (7)	0.0090 (6)	−0.0166 (6)
C7	0.0570 (9)	0.0446 (8)	0.0419 (8)	−0.0268 (7)	0.0121 (7)	−0.0173 (6)
C9	0.0394 (7)	0.0421 (8)	0.0441 (8)	−0.0114 (6)	0.0058 (6)	−0.0107 (6)
C10	0.0486 (9)	0.0456 (8)	0.0487 (8)	−0.0170 (7)	0.0085 (7)	−0.0181 (7)
C14	0.0571 (10)	0.0575 (10)	0.0575 (9)	−0.0287 (8)	0.0212 (8)	−0.0303 (8)
C13	0.0442 (8)	0.0462 (8)	0.0505 (8)	−0.0196 (7)	0.0147 (6)	−0.0208 (7)
C12	0.0476 (8)	0.0542 (9)	0.0620 (10)	−0.0240 (7)	0.0193 (7)	−0.0295 (8)
N3	0.0637 (9)	0.0732 (11)	0.0700 (10)	−0.0339 (8)	0.0260 (8)	−0.0331 (8)
C6	0.0649 (10)	0.0564 (10)	0.0522 (9)	−0.0317 (8)	0.0190 (8)	−0.0287 (8)
C8	0.0446 (8)	0.0502 (9)	0.0538 (9)	−0.0182 (7)	0.0051 (7)	−0.0142 (7)
N4	0.0919 (13)	0.1025 (14)	0.0810 (12)	−0.0640 (12)	0.0448 (10)	−0.0434 (11)
C3	0.0618 (10)	0.0496 (9)	0.0524 (9)	−0.0208 (8)	−0.0045 (8)	−0.0136 (8)
C5	0.0945 (14)	0.0776 (13)	0.0429 (9)	−0.0515 (12)	0.0189 (9)	−0.0303 (9)
C15	0.0859 (13)	0.0850 (14)	0.0663 (11)	−0.0532 (12)	0.0376 (10)	−0.0450 (11)
C11	0.0618 (11)	0.0577 (11)	0.0732 (12)	−0.0217 (9)	0.0246 (9)	−0.0272 (9)
C4	0.0887 (14)	0.0639 (11)	0.0425 (9)	−0.0355 (11)	−0.0051 (9)	−0.0125 (8)

S1—C7	1.6577 (15)	C9—C11	1.319 (3)
N1—C1	1.3924 (19)	C12—C13	1.503 (3)
N1—C7	1.375 (2)	C13—C14	1.434 (2)
N1—C8	1.452 (2)	C13—C15	1.317 (3)
N2—C2	1.3922 (19)	C3—H3	0.9300
N2—C7	1.367 (2)	C4—H4	0.9300
N2—C12	1.458 (2)	C5—H5	0.9300
N3—C10	1.138 (3)	C6—H6	0.9300
N4—C14	1.139 (3)	C8—H8A	0.9700
C1—C2	1.386 (2)	C8—H8B	0.9700
C1—C6	1.386 (2)	C11—H11A	0.9300
C2—C3	1.386 (2)	C11—H11B	0.9300
C3—C4	1.378 (3)	C12—H12A	0.9700
C4—C5	1.387 (4)	C12—H12B	0.9700
C5—C6	1.383 (3)	C15—H15A	0.9300
C8—C9	1.504 (3)	C15—H15B	0.9300
C9—C10	1.442 (2)
C1—N1—C7	109.85 (14)	C14—C13—C15	119.89 (19)
C1—N1—C8	125.42 (14)	N4—C14—C13	177.6 (2)
C7—N1—C8	124.70 (13)	C2—C3—H3	122.00
C2—N2—C7	110.30 (14)	C4—C3—H3	122.00
C2—N2—C12	126.00 (14)	C3—C4—H4	119.00
C7—N2—C12	123.70 (13)	C5—C4—H4	119.00
N1—C1—C2	106.98 (14)	C4—C5—H5	119.00
N1—C1—C6	131.26 (16)	C6—C5—H5	119.00
C2—C1—C6	121.74 (15)	C1—C6—H6	122.00
N2—C2—C1	106.69 (13)	C5—C6—H6	122.00
N2—C2—C3	131.89 (16)	N1—C8—H8A	109.00
C1—C2—C3	121.42 (15)	N1—C8—H8B	109.00
C2—C3—C4	116.90 (18)	C9—C8—H8A	109.00
C3—C4—C5	121.62 (17)	C9—C8—H8B	109.00
C4—C5—C6	121.78 (19)	H8A—C8—H8B	108.00
C1—C6—C5	116.53 (19)	C9—C11—H11A	120.00
S1—C7—N1	127.09 (13)	C9—C11—H11B	120.00
S1—C7—N2	126.73 (13)	H11A—C11—H11B	120.00
N1—C7—N2	106.18 (12)	N2—C12—H12A	109.00
N1—C8—C9	111.91 (15)	N2—C12—H12B	109.00
C8—C9—C10	117.04 (15)	C13—C12—H12A	109.00
C8—C9—C11	124.34 (16)	C13—C12—H12B	109.00
C10—C9—C11	118.62 (16)	H12A—C12—H12B	108.00
N3—C10—C9	179.21 (18)	C13—C15—H15A	120.00
N2—C12—C13	113.07 (15)	C13—C15—H15B	120.00
C12—C13—C14	116.74 (15)	H15A—C15—H15B	120.00
C12—C13—C15	123.33 (19)
C7—N1—C1—C2	0.2 (2)	C2—N2—C12—C13	101.76 (19)
C7—N1—C1—C6	−178.16 (19)	C7—N2—C12—C13	−79.4 (2)
C8—N1—C1—C2	−177.94 (16)	N1—C1—C2—N2	0.21 (19)
C8—N1—C1—C6	3.7 (3)	N1—C1—C2—C3	−179.34 (16)
C1—N1—C7—S1	179.15 (14)	C6—C1—C2—N2	178.77 (16)
C1—N1—C7—N2	−0.56 (19)	C6—C1—C2—C3	−0.8 (3)
C8—N1—C7—S1	−2.7 (3)	N1—C1—C6—C5	178.7 (2)
C8—N1—C7—N2	177.61 (15)	C2—C1—C6—C5	0.5 (3)
C1—N1—C8—C9	78.8 (2)	N2—C2—C3—C4	−179.3 (2)
C7—N1—C8—C9	−99.06 (19)	C1—C2—C3—C4	0.2 (3)
C7—N2—C2—C1	−0.6 (2)	C2—C3—C4—C5	0.7 (3)
C7—N2—C2—C3	178.92 (19)	C3—C4—C5—C6	−1.0 (4)
C12—N2—C2—C1	178.44 (16)	C4—C5—C6—C1	0.3 (4)
C12—N2—C2—C3	−2.1 (3)	N1—C8—C9—C10	59.16 (19)
C2—N2—C7—S1	−179.02 (14)	N1—C8—C9—C11	−121.4 (2)
C2—N2—C7—N1	0.69 (19)	N2—C12—C13—C14	−43.4 (2)
C12—N2—C7—S1	2.0 (3)	N2—C12—C13—C15	138.7 (2)
C12—N2—C7—N1	−178.34 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···S1	0.97	2.77	3.204 (2)	108
C11—H11B···N4i	0.93	2.51	3.387 (3)	158

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11B⋯N4i	0.93	2.51	3.387 (3)	158

Symmetry code: (i) .