3-[(1H-Benzimidazol-2-yl)sulfanyl­methyl]benzonitrile

Abstract

In the title compound, C₁₅H₁₁N₃S, the dihedral angle between the benzimidazole ring system and the benzene ring is 51.8 (2)°. The crystal structure exhibits inter­molecular N—H⋯N hydrogen bonds which lead to the formation of C(4) chains along the [001] direction.

Related literature

For pharmacological activities of benzimidazole and its derivatives, see: Negwer & Scharnow (2001 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

• C₁₅H₁₁N₃S

• M _r = 265.33

• Monoclinic,

• a = 15.384 (4) Å

• b = 9.280 (4) Å

• c = 9.887 (4) Å

• β = 101.63 (3)°

• V = 1382.5 (8) ų

• Z = 4

• Mo Kα radiation

• μ = 0.22 mm⁻¹

• T = 292 K

• 0.35 × 0.30 × 0.25 mm

Data collection

• Rigaku SCXmini diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.927, T _max = 0.947

• 12254 measured reflections

• 2711 independent reflections

• 1926 reflections with I > 2σ(I)

• R _int = 0.052

Refinement

• R[F ² > 2σ(F ²)] = 0.070

• wR(F ²) = 0.184

• S = 1.13

• 2711 reflections

• 172 parameters

• H-atom parameters constrained

• Δρ_max = 0.23 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1i	0.86	1.98	2.838 (3)	174

Symmetry code: (i) .

supplementary crystallographic information

Comment

It is well known that Benzimidazole and its derivatives have received much attention due to their versatile pharmacological activities (Negwer & Scharnow, 2001). To further investigate the influence of the bridging ligand on the formation of supramolecular complexes, we designed and prepared a Benzimidazole-containing ligand, and used the ligand to generate some coordination polymers with interesting topologies. Here, we reported the crystal structure of the title compound. The molecular structure of the title compound, C₁₅H₁₁N₃S, and the atomic labeling scheme are shown in Fig. 1. In this Structure, the nine-membered benzimidazole ring system C1/N1/C2/C3/C4/C5/C6/C7/N2 is essentially planar. The phenyl ring C9/C10–C14 is connected to the benzimidazole ring system by the SCH₂ group. The bond lengths and angles have normal values, the dihedral angle between the benzimidazole ring system and the phenyl substituent is 51.77 (22)°, and the molecules are linked by intermolecular N—H···N hydrogen bonds which leads to the formation chains C(4) along the [001] direction (Bernstein et al., 1995).

Experimental

3-(bromomethyl)benzonitrile (11 mmol) was added to 2-mercaptobenzimidazole (10 mmol) in dry ethanol (25 ml). The mixture was refluxed for 24 h. The reaction mixture was diluted with ethyl acetate (100 ml), and the resulting solid was collected and dissolved in 20 ml of water. 40 ml of a solution of sodium hydrogen carbonate (35 g in 100 ml of water) was added. A white powder was isolated by filtration and dried to give the title compound. Colourless crystals of the title compound suitble for X-ray diffraction were from a solution of 50 mg in 20 ml methanol after 7 d.

Refinement

All H atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic), 0.97 Å (methylene) or 0.96 Å (methyl) with U_iso(H) = 1.2U_eq(Caromatic, Cmethylene)

Figures

Fig. 1.

The molecular structure of the title compound, showing the atomic numbering scheme. The displacement ellipsoids are drawn at the 30% probability level.

Fig. 2.

Packing diagram of the title compound, showing the structure along the a axis.

Crystal data

C15H11N3S	F(000) = 552
Mr = 265.33	Dx = 1.275 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2386 reflections
a = 15.384 (4) Å	θ = 2.6–27.5°
b = 9.280 (4) Å	µ = 0.22 mm−1
c = 9.887 (4) Å	T = 292 K
β = 101.63 (3)°	Prism, colourless
V = 1382.5 (8) Å3	0.35 × 0.30 × 0.25 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer	2711 independent reflections
Radiation source: fine-focus sealed tube	1926 reflections with I > 2σ(I)
graphite	Rint = 0.052
Detector resolution: 13.6612 pixels mm-1	θmax = 26.0°, θmin = 2.6°
ω scans	h = −18→18
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
Tmin = 0.927, Tmax = 0.947	l = −12→12
12254 measured reflections

Refinement

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)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.184	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.0802P)2 + 0.4001P] where P = (Fo2 + 2Fc2)/3
2711 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.16 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3269 (2)	0.2203 (3)	0.2414 (3)	0.0566 (8)
C2	0.3718 (2)	0.4296 (3)	0.3180 (3)	0.0541 (8)
C3	0.3983 (3)	0.5528 (3)	0.3966 (3)	0.0666 (9)
H3	0.3940	0.5575	0.4890	0.080*
C4	0.4308 (3)	0.6672 (3)	0.3330 (3)	0.0710 (10)
H4	0.4484	0.7505	0.3834	0.085*
C5	0.4379 (3)	0.6608 (3)	0.1944 (3)	0.0684 (9)
H5	0.4602	0.7398	0.1546	0.082*
C6	0.4125 (2)	0.5406 (3)	0.1158 (3)	0.0639 (9)
H6	0.4175	0.5362	0.0237	0.077*
C7	0.3791 (2)	0.4256 (3)	0.1795 (3)	0.0517 (7)
C8	0.2071 (3)	0.0318 (4)	0.3261 (4)	0.0835 (11)
H8A	0.2330	0.0408	0.4236	0.100*
H8B	0.1646	0.1092	0.3001	0.100*
C9	0.1622 (3)	−0.1128 (4)	0.2964 (4)	0.0772 (10)
C10	0.1924 (3)	−0.2344 (5)	0.3728 (5)	0.0999 (14)
H10	0.2388	−0.2259	0.4489	0.120*
C11	0.1549 (4)	−0.3684 (5)	0.3378 (6)	0.1166 (17)
H11	0.1762	−0.4493	0.3897	0.140*
C12	0.0852 (4)	−0.3812 (5)	0.2247 (6)	0.1106 (16)
H12	0.0605	−0.4711	0.1993	0.133*
C13	0.0527 (3)	−0.2595 (4)	0.1495 (5)	0.0899 (12)
C14	0.0911 (3)	−0.1256 (4)	0.1844 (4)	0.0814 (11)
H14	0.0694	−0.0446	0.1332	0.098*
C15	−0.0208 (4)	−0.2675 (6)	0.0345 (6)	0.1185 (18)
N1	0.33875 (19)	0.2979 (3)	0.3553 (2)	0.0602 (7)
N2	0.34898 (18)	0.2904 (2)	0.1329 (2)	0.0572 (7)
H2A	0.3450	0.2572	0.0507	0.069*
N3	−0.0786 (4)	−0.2759 (6)	−0.0567 (6)	0.161 (2)
S1	0.29335 (7)	0.03901 (9)	0.22331 (9)	0.0739 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.090 (2)	0.0474 (16)	0.0342 (14)	−0.0029 (15)	0.0174 (15)	0.0013 (12)
C2	0.087 (2)	0.0441 (14)	0.0328 (14)	0.0006 (14)	0.0159 (14)	0.0015 (11)
C3	0.109 (3)	0.0535 (17)	0.0404 (16)	−0.0015 (17)	0.0226 (17)	−0.0079 (13)
C4	0.112 (3)	0.0462 (17)	0.0565 (19)	−0.0052 (18)	0.0212 (19)	−0.0082 (14)
C5	0.103 (3)	0.0458 (16)	0.0602 (19)	−0.0037 (17)	0.0247 (19)	0.0059 (15)
C6	0.101 (3)	0.0558 (18)	0.0389 (15)	−0.0017 (17)	0.0245 (16)	0.0057 (13)
C7	0.083 (2)	0.0421 (14)	0.0311 (13)	0.0052 (14)	0.0148 (13)	0.0009 (11)
C8	0.108 (3)	0.081 (3)	0.067 (2)	−0.022 (2)	0.031 (2)	−0.0129 (19)
C9	0.095 (3)	0.068 (2)	0.073 (2)	−0.016 (2)	0.027 (2)	0.0022 (19)
C10	0.104 (3)	0.094 (3)	0.100 (3)	−0.017 (3)	0.018 (3)	0.016 (3)
C11	0.119 (4)	0.081 (3)	0.146 (5)	−0.016 (3)	0.017 (4)	0.031 (3)
C12	0.123 (4)	0.065 (3)	0.149 (5)	−0.023 (3)	0.040 (4)	0.002 (3)
C13	0.101 (3)	0.074 (3)	0.095 (3)	−0.024 (2)	0.021 (3)	−0.008 (2)
C14	0.096 (3)	0.066 (2)	0.083 (3)	−0.010 (2)	0.023 (2)	−0.0007 (19)
C15	0.139 (5)	0.100 (4)	0.112 (4)	−0.041 (3)	0.018 (4)	−0.014 (3)
N1	0.104 (2)	0.0477 (13)	0.0330 (12)	−0.0047 (13)	0.0241 (13)	−0.0015 (10)
N2	0.0971 (19)	0.0497 (13)	0.0276 (11)	−0.0005 (13)	0.0189 (12)	−0.0020 (10)
N3	0.159 (5)	0.158 (5)	0.149 (5)	−0.053 (4)	−0.010 (4)	−0.015 (4)
S1	0.1199 (8)	0.0501 (5)	0.0600 (6)	−0.0158 (5)	0.0378 (5)	−0.0082 (4)

Geometric parameters (Å, °)

C1—N1	1.319 (3)	C8—S1	1.829 (4)
C1—N2	1.355 (3)	C8—H8A	0.9700
C1—S1	1.758 (3)	C8—H8B	0.9700
C2—C3	1.396 (4)	C9—C10	1.385 (6)
C2—C7	1.397 (4)	C9—C14	1.396 (6)
C2—N1	1.401 (4)	C10—C11	1.386 (6)
C3—C4	1.379 (4)	C10—H10	0.9300
C3—H3	0.9300	C11—C12	1.390 (7)
C4—C5	1.398 (4)	C11—H11	0.9300
C4—H4	0.9300	C12—C13	1.389 (6)
C5—C6	1.370 (4)	C12—H12	0.9300
C5—H5	0.9300	C13—C14	1.389 (5)
C6—C7	1.390 (4)	C13—C15	1.435 (8)
C6—H6	0.9300	C14—H14	0.9300
C7—N2	1.384 (4)	C15—N3	1.135 (7)
C8—C9	1.510 (5)	N2—H2A	0.8600
N1—C1—N2	113.6 (3)	H8A—C8—H8B	108.7
N1—C1—S1	126.6 (2)	C10—C9—C14	119.1 (4)
N2—C1—S1	119.6 (2)	C10—C9—C8	121.8 (4)
C3—C2—C7	119.7 (3)	C14—C9—C8	119.0 (4)
C3—C2—N1	130.4 (3)	C9—C10—C11	121.2 (5)
C7—C2—N1	109.9 (2)	C9—C10—H10	119.4
C4—C3—C2	118.0 (3)	C11—C10—H10	119.4
C4—C3—H3	121.0	C10—C11—C12	119.5 (5)
C2—C3—H3	121.0	C10—C11—H11	120.2
C3—C4—C5	121.4 (3)	C12—C11—H11	120.2
C3—C4—H4	119.3	C13—C12—C11	119.8 (4)
C5—C4—H4	119.3	C13—C12—H12	120.1
C6—C5—C4	121.4 (3)	C11—C12—H12	120.1
C6—C5—H5	119.3	C12—C13—C14	120.4 (4)
C4—C5—H5	119.3	C12—C13—C15	121.6 (4)
C5—C6—C7	117.2 (3)	C14—C13—C15	118.0 (4)
C5—C6—H6	121.4	C13—C14—C9	119.9 (4)
C7—C6—H6	121.4	C13—C14—H14	120.0
N2—C7—C6	132.4 (3)	C9—C14—H14	120.0
N2—C7—C2	105.3 (2)	N3—C15—C13	179.0 (7)
C6—C7—C2	122.3 (3)	C1—N1—C2	104.3 (2)
C9—C8—S1	106.2 (3)	C1—N2—C7	107.0 (2)
C9—C8—H8A	110.5	C1—N2—H2A	126.5
S1—C8—H8A	110.5	C7—N2—H2A	126.5
C9—C8—H8B	110.5	C1—S1—C8	102.13 (15)
S1—C8—H8B	110.5
C7—C2—C3—C4	0.0 (5)	C11—C12—C13—C15	−178.2 (5)
N1—C2—C3—C4	178.4 (3)	C12—C13—C14—C9	−0.6 (7)
C2—C3—C4—C5	−0.4 (6)	C15—C13—C14—C9	179.4 (4)
C3—C4—C5—C6	0.2 (6)	C10—C9—C14—C13	−1.1 (6)
C4—C5—C6—C7	0.3 (5)	C8—C9—C14—C13	175.6 (4)
C5—C6—C7—N2	−179.1 (3)	C12—C13—C15—N3	−23 (38)
C5—C6—C7—C2	−0.6 (5)	C14—C13—C15—N3	157 (37)
C3—C2—C7—N2	179.3 (3)	N2—C1—N1—C2	−0.4 (4)
N1—C2—C7—N2	0.6 (4)	S1—C1—N1—C2	175.5 (3)
C3—C2—C7—C6	0.5 (5)	C3—C2—N1—C1	−178.6 (4)
N1—C2—C7—C6	−178.2 (3)	C7—C2—N1—C1	−0.2 (4)
S1—C8—C9—C10	88.9 (4)	N1—C1—N2—C7	0.8 (4)
S1—C8—C9—C14	−87.8 (4)	S1—C1—N2—C7	−175.4 (2)
C14—C9—C10—C11	1.6 (7)	C6—C7—N2—C1	177.8 (4)
C8—C9—C10—C11	−175.0 (4)	C2—C7—N2—C1	−0.8 (3)
C9—C10—C11—C12	−0.4 (8)	N1—C1—S1—C8	41.3 (4)
C10—C11—C12—C13	−1.3 (8)	N2—C1—S1—C8	−143.1 (3)
C11—C12—C13—C14	1.9 (8)	C9—C8—S1—C1	170.0 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1i	0.86	1.98	2.838 (3)	174

Symmetry codes: (i) x, −y+1/2, z−1/2.