6-Chloro-2-(thio-phen-2-yl)-1-[(thio-phen-2-yl)meth-yl]-1H-benzimidazole.

The title compound, C16H11ClN2S2, co-crystallizes with a small amount of the 5-chloro- isomer. The ratio of 6-chloro- to 5-chloro- isomers is 0.969 (2):0.031 (2). One thio-phen-2-yl substitutent displays rotational disorder with 80.6 (4)% of the mol-ecules exhibiting the major orientation. In the crystal, weak C-H⋯N and C-H⋯S hydrogen-bonding inter-actions result in chains of mol-ecules parallel to [001].

Related literature

For the structure of 2-(thio­phen-2-yl)-1-(thio­phen-2-ylmeth­yl)-1H-benzimidazole, see: Geiger et al. (2012 ▶). For the structure of the 5-bromo analogue, see: Geiger & Destefano (2012 ▶).

Experimental

Crystal data

C16H11ClN2S2

M = 330.84

Monoclinic,

a = 15.465 (3) Å

b = 6.3578 (10) Å

c = 15.634 (3) Å

β = 103.687 (5)°

V = 1493.5 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.53 mm−1

T = 200 K

0.80 × 0.60 × 0.20 mm

Data collection

Bruker SMART X2S CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2010 ▶) T min = 0.62, T max = 0.90

23773 measured reflections

2665 independent reflections

2184 reflections with I > 2σ(I)

R int = 0.088

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.148

S = 1.11

2665 reflections

210 parameters

38 restraints

H-atom parameters constrained

Δρmax = 0.49 e Å−3

Δρmin = −0.46 e Å−3

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813011124/pv2630sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813011124/pv2630Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813011124/pv2630Isup3.mol

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813011124/pv2630Isup4.cml

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

C16H11ClN2S2	F(000) = 680
Mr = 330.84	Dx = 1.471 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.465 (3) Å	Cell parameters from 7129 reflections
b = 6.3578 (10) Å	θ = 2.7–25.0°
c = 15.634 (3) Å	µ = 0.53 mm−1
β = 103.687 (5)°	T = 200 K
V = 1493.5 (4) Å3	Plate, colourless
Z = 4	0.80 × 0.60 × 0.20 mm

Bruker SMART X2S CCD diffractometer	2665 independent reflections
Radiation source: XOS X-beam microfocus source	2184 reflections with I > 2σ(I)
Doubly curved silicon crystal monochromator	Rint = 0.088
Detector resolution: 8.3330 pixels mm-1	θmax = 25.4°, θmin = 2.7°
ω scans	h = −18→18
Absorption correction: multi-scan (SADABS; Bruker, 2010)	k = −7→7
Tmin = 0.62, Tmax = 0.90	l = −18→18
23773 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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148	H-atom parameters constrained
S = 1.11	w = 1/[σ2(Fo2) + (0.0645P)2 + 1.4022P] where P = (Fo2 + 2Fc2)/3
2665 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.49 e Å−3
38 restraints	Δρmin = −0.46 e Å−3

Experimental. 1H NMR spectrum (CDCl3, 400 MHz, p.p.m.): 7.71 (1 H, d), 7.53 (1 H, d), 7.48 (1 H, d), 7.34 (1 H, s), 7.28 (2 H, m), 7.17 (1 H, t), 6.96 (1 H, t), 6.91 (1 H, d), 5.60 (2 H, s).

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	Occ. (<1)
Cl1	0.55843 (7)	1.26049 (17)	0.40613 (7)	0.0561 (3)	0.969 (2)
Cl01	0.5861 (12)	0.817 (5)	0.327 (2)	0.0561 (3)	0.031 (2)
S1	0.06013 (11)	0.5424 (3)	0.29173 (10)	0.0530 (5)	0.806 (4)
C8	0.1134 (4)	0.7175 (17)	0.3728 (6)	0.0402 (8)	0.806 (4)
C9	0.0602 (5)	0.7532 (12)	0.4316 (6)	0.054 (2)	0.806 (4)
H9	0.0787	0.8349	0.4836	0.065*	0.806 (4)
C10	−0.0230 (4)	0.6567 (13)	0.4065 (5)	0.0593 (16)	0.806 (4)
H10	−0.0684	0.6749	0.4375	0.071*	0.806 (4)
C11	−0.0327 (4)	0.5363 (12)	0.3347 (5)	0.0610 (18)	0.806 (4)
H11	−0.0847	0.4567	0.3103	0.073*	0.806 (4)
S101	0.0553 (7)	0.8069 (15)	0.4406 (7)	0.0530 (5)	0.194 (4)
C108	0.1165 (15)	0.718 (7)	0.370 (3)	0.0402 (8)	0.194 (4)
C109	0.0711 (18)	0.573 (5)	0.3138 (19)	0.054 (2)	0.194 (4)
H109	0.0943	0.5069	0.2697	0.065*	0.194 (4)
C110	−0.0137 (18)	0.531 (6)	0.327 (2)	0.0593 (16)	0.194 (4)
H110	−0.0536	0.4314	0.2936	0.071*	0.194 (4)
C111	−0.0324 (15)	0.647 (5)	0.393 (2)	0.0610 (18)	0.194 (4)
H111	−0.0871	0.6415	0.4104	0.073*	0.194 (4)
S2	0.22671 (7)	1.02453 (14)	0.60821 (6)	0.0445 (3)
C13	0.2293 (2)	1.2089 (5)	0.52711 (19)	0.0334 (7)
C14	0.2588 (2)	1.3996 (5)	0.5637 (2)	0.0412 (8)
H14	0.2646	1.5215	0.5304	0.049*
C15	0.2795 (3)	1.3940 (6)	0.6571 (2)	0.0473 (9)
H15	0.3014	1.5117	0.6932	0.057*
C16	0.2647 (2)	1.2027 (6)	0.6895 (2)	0.0464 (9)
H16	0.2745	1.172	0.7505	0.056*
N1	0.24103 (19)	0.9760 (4)	0.40255 (16)	0.0352 (6)
N2	0.2615 (2)	0.6596 (4)	0.34595 (18)	0.0414 (7)
C1	0.3275 (2)	0.9754 (5)	0.39196 (19)	0.0357 (8)
C2	0.3389 (2)	0.7765 (5)	0.3565 (2)	0.0397 (8)
C3	0.4206 (3)	0.7300 (6)	0.3371 (2)	0.0485 (10)
H3	0.4304	0.597	0.3133	0.058*
C4	0.4859 (3)	0.8794 (6)	0.3528 (2)	0.0482 (9)
H4	0.5416	0.8495	0.3398	0.058*	0.969 (2)
C5	0.4722 (2)	1.0756 (6)	0.3878 (2)	0.0438 (9)
H5'	0.5192	1.1755	0.3979	0.053*	0.031 (2)
C6	0.3929 (2)	1.1299 (6)	0.4083 (2)	0.0397 (8)
H6	0.3838	1.2635	0.4319	0.048*
C7	0.2048 (2)	0.7813 (5)	0.3739 (2)	0.0381 (8)
C12	0.1983 (2)	1.1614 (5)	0.4306 (2)	0.0368 (8)
H12A	0.1332	1.139	0.4162	0.044*
H12B	0.2104	1.285	0.3967	0.044*

	U11	U22	U33	U12	U13	U23
Cl1	0.0502 (6)	0.0575 (7)	0.0627 (7)	0.0008 (5)	0.0178 (5)	0.0148 (5)
Cl01	0.0502 (6)	0.0575 (7)	0.0627 (7)	0.0008 (5)	0.0178 (5)	0.0148 (5)
S1	0.0640 (9)	0.0371 (9)	0.0530 (9)	0.0065 (6)	0.0038 (7)	−0.0067 (6)
C8	0.055 (2)	0.0272 (18)	0.0366 (19)	0.0077 (16)	0.0083 (16)	0.0024 (14)
C9	0.052 (3)	0.031 (4)	0.084 (5)	−0.002 (3)	0.024 (3)	−0.008 (3)
C10	0.049 (3)	0.058 (4)	0.071 (4)	0.002 (3)	0.016 (3)	−0.002 (3)
C11	0.056 (4)	0.044 (3)	0.078 (4)	0.007 (3)	0.005 (3)	−0.005 (3)
S101	0.0640 (9)	0.0371 (9)	0.0530 (9)	0.0065 (6)	0.0038 (7)	−0.0067 (6)
C108	0.055 (2)	0.0272 (18)	0.0366 (19)	0.0077 (16)	0.0083 (16)	0.0024 (14)
C109	0.052 (3)	0.031 (4)	0.084 (5)	−0.002 (3)	0.024 (3)	−0.008 (3)
C110	0.049 (3)	0.058 (4)	0.071 (4)	0.002 (3)	0.016 (3)	−0.002 (3)
C111	0.056 (4)	0.044 (3)	0.078 (4)	0.007 (3)	0.005 (3)	−0.005 (3)
S2	0.0658 (6)	0.0309 (5)	0.0383 (5)	0.0023 (4)	0.0152 (4)	0.0043 (4)
C13	0.0431 (18)	0.0285 (18)	0.0311 (16)	0.0049 (14)	0.0140 (14)	0.0016 (13)
C14	0.055 (2)	0.035 (2)	0.0352 (18)	−0.0048 (16)	0.0134 (16)	0.0021 (15)
C15	0.066 (2)	0.038 (2)	0.0389 (19)	−0.0094 (18)	0.0140 (17)	−0.0089 (16)
C16	0.056 (2)	0.052 (2)	0.0334 (18)	−0.0029 (18)	0.0134 (16)	0.0007 (16)
N1	0.0522 (17)	0.0255 (15)	0.0290 (14)	0.0074 (12)	0.0120 (12)	0.0007 (11)
N2	0.0614 (19)	0.0277 (15)	0.0383 (15)	0.0089 (14)	0.0182 (14)	−0.0002 (12)
C1	0.051 (2)	0.0329 (19)	0.0247 (16)	0.0087 (15)	0.0121 (14)	0.0065 (13)
C2	0.060 (2)	0.0323 (19)	0.0287 (17)	0.0121 (16)	0.0151 (16)	0.0060 (14)
C3	0.069 (3)	0.040 (2)	0.042 (2)	0.0144 (19)	0.0252 (19)	0.0075 (16)
C4	0.055 (2)	0.051 (2)	0.044 (2)	0.0177 (19)	0.0223 (17)	0.0109 (17)
C5	0.051 (2)	0.046 (2)	0.0360 (18)	0.0053 (17)	0.0137 (16)	0.0125 (16)
C6	0.056 (2)	0.0347 (19)	0.0305 (17)	0.0082 (17)	0.0137 (15)	0.0050 (14)
C7	0.057 (2)	0.0284 (19)	0.0284 (16)	0.0057 (16)	0.0098 (15)	0.0040 (13)
C12	0.0502 (19)	0.0261 (17)	0.0349 (17)	0.0099 (15)	0.0118 (15)	0.0019 (14)

Cl1—C5	1.750 (4)	C13—C12	1.502 (4)
Cl01—C4	1.740 (5)	C14—C15	1.419 (5)
S1—C11	1.724 (6)	C14—H14	0.95
S1—C8	1.740 (7)	C15—C16	1.357 (5)
C8—C9	1.389 (9)	C15—H15	0.95
C8—C7	1.468 (6)	C16—H16	0.95
C9—C10	1.396 (9)	N1—C1	1.386 (4)
C9—H9	0.95	N1—C7	1.388 (4)
C10—C11	1.337 (7)	N1—C12	1.468 (4)
C10—H10	0.95	N2—C7	1.319 (4)
C11—H11	0.95	N2—C2	1.385 (5)
S101—C108	1.707 (18)	C1—C6	1.389 (5)
S101—C111	1.717 (17)	C1—C2	1.408 (5)
C108—C109	1.351 (17)	C2—C3	1.399 (5)
C108—C7	1.411 (15)	C3—C4	1.366 (5)
C109—C110	1.401 (17)	C3—H3	0.95
C109—H109	0.95	C4—C5	1.398 (5)
C110—C111	1.352 (16)	C4—H4	0.95
C110—H110	0.95	C5—C6	1.383 (5)
C111—H111	0.95	C5—H5'	0.95
S2—C16	1.700 (4)	C6—H6	0.95
S2—C13	1.734 (3)	C12—H12A	0.99
C13—C14	1.372 (5)	C12—H12B	0.99
C11—S1—C8	91.4 (3)	S2—C16—H16	123.9
C9—C8—C7	131.8 (6)	C1—N1—C7	106.6 (3)
C9—C8—S1	109.5 (4)	C1—N1—C12	123.5 (3)
C7—C8—S1	118.3 (4)	C7—N1—C12	129.6 (3)
C8—C9—C10	113.1 (7)	C7—N2—C2	105.6 (3)
C8—C9—H9	123.4	N1—C1—C6	131.1 (3)
C10—C9—H9	123.4	N1—C1—C2	105.2 (3)
C11—C10—C9	113.6 (6)	C6—C1—C2	123.7 (3)
C11—C10—H10	123.2	N2—C2—C3	131.3 (3)
C9—C10—H10	123.2	N2—C2—C1	110.1 (3)
C10—C11—S1	112.0 (5)	C3—C2—C1	118.6 (3)
C10—C11—H11	124.0	C4—C3—C2	118.8 (3)
S1—C11—H11	124.0	C4—C3—H3	120.6
C108—S101—C111	91.5 (11)	C2—C3—H3	120.6
C109—C108—C7	124.7 (18)	C3—C4—C5	121.2 (3)
C109—C108—S101	111.3 (12)	C3—C4—Cl01	117.4 (12)
C7—C108—S101	123.9 (16)	C5—C4—Cl01	121.4 (12)
C108—C109—C110	113.3 (16)	C3—C4—H4	119.4
C108—C109—H109	123.4	C5—C4—H4	119.4
C110—C109—H109	123.4	C6—C5—C4	122.5 (3)
C111—C110—C109	112.5 (19)	C6—C5—Cl1	118.5 (3)
C111—C110—H110	123.7	C4—C5—Cl1	118.9 (3)
C109—C110—H110	123.7	C6—C5—H5'	118.7
C110—C111—S101	111.4 (17)	C4—C5—H5'	118.7
C110—C111—H111	124.3	C5—C6—C1	115.3 (3)
S101—C111—H111	124.3	C5—C6—H6	122.3
C16—S2—C13	91.85 (17)	C1—C6—H6	122.3
C14—C13—C12	126.3 (3)	N2—C7—N1	112.4 (3)
C14—C13—S2	110.8 (2)	N2—C7—C108	122.2 (13)
C12—C13—S2	122.8 (2)	N1—C7—C108	125.3 (14)
C13—C14—C15	112.3 (3)	N2—C7—C8	123.3 (4)
C13—C14—H14	123.9	N1—C7—C8	124.3 (4)
C15—C14—H14	123.9	N1—C12—C13	113.7 (3)
C16—C15—C14	112.9 (3)	N1—C12—H12A	108.8
C16—C15—H15	123.6	C13—C12—H12A	108.8
C14—C15—H15	123.6	N1—C12—H12B	108.8
C15—C16—S2	112.2 (3)	C13—C12—H12B	108.8
C15—C16—H16	123.9	H12A—C12—H12B	107.7
C11—S1—C8—C9	3.5 (8)	C2—C3—C4—Cl01	−179.3 (12)
C11—S1—C8—C7	177.2 (8)	C3—C4—C5—C6	0.0 (5)
C7—C8—C9—C10	−177.9 (10)	Cl01—C4—C5—C6	179.4 (13)
S1—C8—C9—C10	−5.3 (11)	C3—C4—C5—Cl1	−179.8 (3)
C8—C9—C10—C11	4.8 (9)	Cl01—C4—C5—Cl1	−0.4 (13)
C9—C10—C11—S1	−2.0 (6)	C4—C5—C6—C1	0.2 (5)
C8—S1—C11—C10	−0.9 (6)	Cl1—C5—C6—C1	180.0 (2)
C111—S101—C108—C109	0 (3)	N1—C1—C6—C5	−178.5 (3)
C111—S101—C108—C7	−177 (4)	C2—C1—C6—C5	−0.4 (5)
C7—C108—C109—C110	177 (4)	C2—N2—C7—N1	0.2 (4)
S101—C108—C109—C110	0 (4)	C2—N2—C7—C108	177 (2)
C108—C109—C110—C111	1 (4)	C2—N2—C7—C8	179.1 (6)
C109—C110—C111—S101	−1.2 (17)	C1—N1—C7—N2	−0.2 (3)
C108—S101—C111—C110	0.9 (16)	C12—N1—C7—N2	173.8 (3)
C16—S2—C13—C14	0.0 (3)	C1—N1—C7—C108	−177 (2)
C16—S2—C13—C12	−177.1 (3)	C12—N1—C7—C108	−3 (2)
C12—C13—C14—C15	177.4 (3)	C1—N1—C7—C8	−179.1 (6)
S2—C13—C14—C15	0.4 (4)	C12—N1—C7—C8	−5.1 (7)
C13—C14—C15—C16	−0.7 (5)	C109—C108—C7—N2	−24 (5)
C14—C15—C16—S2	0.7 (4)	S101—C108—C7—N2	152 (2)
C13—S2—C16—C15	−0.4 (3)	C109—C108—C7—N1	153 (3)
C7—N1—C1—C6	178.5 (3)	S101—C108—C7—N1	−31 (5)
C12—N1—C1—C6	4.1 (5)	C109—C108—C7—C8	−150..90
C7—N1—C1—C2	0.2 (3)	S101—C108—C7—C8	20..80
C12—N1—C1—C2	−174.3 (3)	C9—C8—C7—N2	142.3 (10)
C7—N2—C2—C3	−179.0 (3)	S1—C8—C7—N2	−29.7 (11)
C7—N2—C2—C1	−0.1 (4)	C9—C8—C7—N1	−39.0 (15)
N1—C1—C2—N2	−0.1 (3)	S1—C8—C7—N1	149.0 (5)
C6—C1—C2—N2	−178.6 (3)	C9—C8—C7—C108	−170..80
N1—C1—C2—C3	179.0 (3)	S1—C8—C7—C108	20..80
C6—C1—C2—C3	0.5 (5)	C1—N1—C12—C13	−75.6 (4)
N2—C2—C3—C4	178.5 (3)	C7—N1—C12—C13	111.3 (4)
C1—C2—C3—C4	−0.3 (5)	C14—C13—C12—N1	129.4 (3)
C2—C3—C4—C5	0.0 (5)	S2—C13—C12—N1	−54.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···N2i	0.95	2.62	3.369 (4)	136
C12—H12B···N2ii	0.99	2.69	3.654 (4)	165
C12—H12B···S1ii	0.99	2.99	3.599 (4)	120

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16⋯N2i	0.95	2.62	3.369 (4)	136
C12—H12B⋯N2ii	0.99	2.69	3.654 (4)	165
C12—H12B⋯S1ii	0.99	2.99	3.599 (4)	120

Symmetry codes: (i) ; (ii) .