organic compounds
5-Bromo-2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzimidazole
aDepartment of Chemistry, State University of New York-College at Geneseo, 1 College Circle, Geneseo, NY 14454, USA
*Correspondence e-mail: geiger@geneseo.edu
There are two independent molecules in the 16H11BrN2S2. In the crystal, weak C—H⋯N hydrogen bonds and C—H⋯thiophene ring interactions link the molecules into chains along [100]. The structure exhibits disorder of the 2-thiophen-2-yl substituent of one of the symmetry-unique molecules with a major:minor component ratio of 0.914 (3):0.086 (3).
of the title compound, CRelated literature
For the characterization of 2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzimidazole, see: Geiger et al. (2012). For examples of pharmacological uses of benzimidazoles, see: López-Rodríguez et al. (1999); Varala et al. (2007); Horton et al. (2003). For the synthesis of substituted benzimidazoles, see: Grimmett (1997).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2010); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: XSHELL (Bruker, 2004) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536812042146/lr2085sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812042146/lr2085Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812042146/lr2085Isup3.mol
Supporting information file. DOI: 10.1107/S1600536812042146/lr2085Isup4.cml
An approximately equimolar mixture of the 5-bromo and 6-bromo derivatives of the 1,2-disubstituted benzimidazole was prepared by reaction of 500 mg 1,2-diamino-4-bromobenzenene and 0.50 ml 2-thiophenecarboxaldehyde in refluxing dichloromethane (8 ml) in the presence of a catalytic amount of aluminium trichloride for eight hours. After removal of insoluble inorganic material, the solvent was removed by rotary evaporation leaving a brown, tarry substance. The mixture was subjected to
on silica gel using a 1:4 ethylacetate:hexanes A light yellow fraction was collected. Based on the presence of two CH2 resonances in the 1H NMR spectrum, the 5-Br and 6-Br isomers were present in a 3:2 ratio.Slow evaporation of a 1:4 ethylacetate:hexanes solution at 40°C yielded single crystals of the title compound suitable for X-ray diffraction. A 1H NMR spectrum of a solution of single crystals showed that only the 5-Br isomer was present. 1H NMR spectrum (CDCl3, 400 MHz, p.p.m.): 7.93 (1H, s), 7.54 (1H, m), 7.48 (1H, m), 7.36 (1H, m), 7.23 (2H, m), 7.15 (1H, m), 6.85 (1H, bs), 5.68 (2H, s).
The H atoms were refined using a riding model with a C—H distance of 0.99 Å for the methylene carbon atoms and 0.95 Å for the phenyl and thiophene carbon atoms. The H atom thermal parameters were set using the approximation Uiso = 1.2Ueq(C).
During the later stages of
the thiophene ring containing S3 was found to be rotationally disordered. The disorder was resolved using the metrics of the major component to establish coordinates of the minor component. The major:minor site occupancies refined to 0.914 (3):0.086 (3).Data collection: APEX2 (Bruker, 2010); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: XSHELL (Bruker, 2004) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. Perspective view of the title compound showing both molecules in the asymmetric unit. Displacement ellipsoids of the nonhydrogen atoms are drawn a at the 50% probability level. Only the major component of the disordered thiophene is shown. | |
Fig. 2. The unit cell of the title compound viewed down the a axis. Hydrogen atoms have been omitted for clarity. Only the major component of the disordered thiophene substituent is shown. | |
Fig. 3. Perspective drawing showing the close intermolecular contacts forming chains parallel to the a axis. Only the major component of the disordered thiophene substituent is shown. |
C16H11BrN2S2 | F(000) = 1504 |
Mr = 375.30 | Dx = 1.611 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 12.6753 (17) Å | Cell parameters from 6104 reflections |
b = 10.5413 (11) Å | θ = 2.5–24.4° |
c = 23.581 (3) Å | µ = 2.92 mm−1 |
β = 100.878 (4)° | T = 200 K |
V = 3094.1 (6) Å3 | Plate, colourless |
Z = 8 | 0.60 × 0.20 × 0.10 mm |
Bruker SMART X2S benchtop diffractometer | 5581 independent reflections |
Radiation source: XOS X-beam microfocus source | 4191 reflections with I > 2σ(I) |
Doubly curved silicon crystal monochromator | Rint = 0.059 |
Detector resolution: 8.3330 pixels mm-1 | θmax = 25.4°, θmin = 2.1° |
ω scans | h = −15→15 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a) | k = −12→12 |
Tmin = 0.46, Tmax = 0.76 | l = −28→24 |
19813 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.036P)2 + 0.884P] where P = (Fo2 + 2Fc2)/3 |
5581 reflections | (Δ/σ)max = 0.001 |
392 parameters | Δρmax = 0.65 e Å−3 |
91 restraints | Δρmin = −0.80 e Å−3 |
C16H11BrN2S2 | V = 3094.1 (6) Å3 |
Mr = 375.30 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.6753 (17) Å | µ = 2.92 mm−1 |
b = 10.5413 (11) Å | T = 200 K |
c = 23.581 (3) Å | 0.60 × 0.20 × 0.10 mm |
β = 100.878 (4)° |
Bruker SMART X2S benchtop diffractometer | 5581 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a) | 4191 reflections with I > 2σ(I) |
Tmin = 0.46, Tmax = 0.76 | Rint = 0.059 |
19813 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 91 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.65 e Å−3 |
5581 reflections | Δρmin = −0.80 e Å−3 |
392 parameters |
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) | |
Br1 | 0.75134 (3) | 1.11709 (4) | 0.458735 (16) | 0.05101 (14) | |
Br2 | 0.11272 (3) | 1.13960 (3) | 0.03496 (14) | 0.03685 (12) | |
S1 | 0.41783 (7) | 0.73442 (9) | 0.17228 (4) | 0.0370 (2) | |
S2 | 0.81366 (8) | 1.15655 (8) | 0.16253 (4) | 0.0354 (2) | |
S3 | −0.03440 (10) | 0.73244 (14) | 0.31444 (5) | 0.0301 (3) | 0.914 (3) |
C24 | 0.0711 (5) | 0.8382 (6) | 0.32690 (16) | 0.0225 (9) | 0.914 (3) |
C25 | 0.1030 (6) | 0.8601 (8) | 0.3841 (3) | 0.0350 (16) | 0.914 (3) |
H25 | 0.1597 | 0.9164 | 0.3994 | 0.042* | 0.914 (3) |
C26 | 0.0435 (4) | 0.7907 (4) | 0.41889 (18) | 0.0348 (12) | 0.914 (3) |
H26 | 0.0558 | 0.795 | 0.4598 | 0.042* | 0.914 (3) |
C27 | −0.0325 (4) | 0.7179 (4) | 0.38673 (17) | 0.0331 (11) | 0.914 (3) |
H27 | −0.0798 | 0.6643 | 0.4026 | 0.04* | 0.914 (3) |
S300 | 0.118 (2) | 0.872 (3) | 0.3950 (10) | 0.0301 (3) | 0.086 (3) |
C240 | 0.062 (5) | 0.846 (7) | 0.3243 (10) | 0.0225 (9) | 0.086 (3) |
C250 | −0.013 (4) | 0.753 (6) | 0.3166 (15) | 0.0350 (16) | 0.086 (3) |
H250 | −0.0504 | 0.7253 | 0.2801 | 0.042* | 0.086 (3) |
C260 | −0.028 (4) | 0.702 (5) | 0.3704 (17) | 0.0348 (12) | 0.086 (3) |
H260 | −0.08 | 0.6398 | 0.3741 | 0.042* | 0.086 (3) |
C270 | 0.041 (5) | 0.753 (5) | 0.4156 (15) | 0.0331 (11) | 0.086 (3) |
H270 | 0.0454 | 0.7255 | 0.4544 | 0.04* | 0.086 (3) |
S4 | 0.36606 (8) | 1.15559 (8) | 0.33291 (4) | 0.0359 (2) | |
C29 | 0.3469 (2) | 1.0042 (3) | 0.35642 (13) | 0.0243 (7) | |
C30 | 0.37895 (19) | 0.9943 (2) | 0.41524 (11) | 0.0290 (8) | |
H30 | 0.3759 | 0.9179 | 0.4363 | 0.035* | |
C31 | 0.41740 (19) | 1.1124 (2) | 0.44115 (11) | 0.0372 (9) | |
H31 | 0.4422 | 1.1238 | 0.4814 | 0.045* | |
C32 | 0.4144 (3) | 1.2058 (3) | 0.40164 (15) | 0.0383 (9) | |
H32 | 0.4367 | 1.2905 | 0.4111 | 0.046* | |
N1 | 0.6914 (2) | 0.9247 (2) | 0.21670 (11) | 0.0237 (6) | |
N2 | 0.5457 (2) | 0.9232 (3) | 0.25919 (11) | 0.0259 (6) | |
N3 | 0.2090 (2) | 0.9262 (2) | 0.27375 (11) | 0.0232 (6) | |
N4 | 0.0354 (2) | 0.9291 (2) | 0.22968 (11) | 0.0233 (6) | |
C1 | 0.7240 (2) | 0.9759 (3) | 0.27135 (13) | 0.0222 (7) | |
C2 | 0.6323 (2) | 0.9745 (3) | 0.29708 (13) | 0.0225 (7) | |
C3 | 0.6388 (3) | 1.0186 (3) | 0.35289 (14) | 0.0272 (8) | |
H3 | 0.5777 | 1.0208 | 0.3708 | 0.033* | |
C4 | 0.7381 (3) | 1.0590 (3) | 0.38108 (13) | 0.0279 (8) | |
C5 | 0.8299 (3) | 1.0590 (3) | 0.35640 (14) | 0.0275 (8) | |
H5 | 0.8967 | 1.0864 | 0.3783 | 0.033* | |
C6 | 0.8232 (2) | 1.0189 (3) | 0.30016 (14) | 0.0252 (7) | |
H6 | 0.8839 | 1.0208 | 0.2819 | 0.03* | |
C7 | 0.5840 (3) | 0.8946 (3) | 0.21240 (14) | 0.0241 (7) | |
C8 | 0.5183 (2) | 0.8366 (3) | 0.16143 (14) | 0.0266 (7) | |
C9 | 0.5175 (3) | 0.8543 (3) | 0.10299 (15) | 0.0317 (8) | |
H9 | 0.5664 | 0.9071 | 0.088 | 0.038* | |
C10 | 0.4344 (3) | 0.7835 (4) | 0.06878 (16) | 0.0420 (10) | |
H10 | 0.4213 | 0.7838 | 0.0278 | 0.05* | |
C11 | 0.3754 (3) | 0.7156 (3) | 0.09998 (16) | 0.0399 (9) | |
H11 | 0.3168 | 0.6631 | 0.0834 | 0.048* | |
C12 | 0.7635 (3) | 0.8988 (3) | 0.17647 (13) | 0.0252 (7) | |
H12A | 0.7361 | 0.824 | 0.1528 | 0.03* | |
H12B | 0.8352 | 0.8766 | 0.199 | 0.03* | |
C13 | 0.7760 (2) | 1.0068 (3) | 0.13666 (14) | 0.0260 (8) | |
C14 | 0.7663 (3) | 1.0014 (3) | 0.07791 (14) | 0.0310 (8) | |
H14 | 0.7466 | 0.9271 | 0.0557 | 0.037* | |
C15 | 0.7891 (3) | 1.1198 (3) | 0.05394 (16) | 0.0369 (9) | |
H15 | 0.7866 | 1.1329 | 0.0139 | 0.044* | |
C16 | 0.8147 (3) | 1.2113 (4) | 0.09412 (17) | 0.0408 (10) | |
H16 | 0.8314 | 1.2962 | 0.0855 | 0.049* | |
C17 | 0.2065 (2) | 0.9796 (3) | 0.21996 (13) | 0.0228 (7) | |
C18 | 0.0977 (2) | 0.9815 (3) | 0.19334 (13) | 0.0230 (7) | |
C19 | 0.0678 (3) | 1.0299 (3) | 0.13786 (14) | 0.0251 (7) | |
H19 | −0.0053 | 1.0341 | 0.1191 | 0.03* | |
C20 | 0.1492 (3) | 1.0714 (3) | 0.11131 (13) | 0.0262 (7) | |
C21 | 0.2576 (3) | 1.0675 (3) | 0.13697 (14) | 0.0283 (8) | |
H21 | 0.3104 | 1.0956 | 0.1161 | 0.034* | |
C22 | 0.2882 (3) | 1.0226 (3) | 0.19272 (14) | 0.0273 (8) | |
H22 | 0.3614 | 1.0211 | 0.2115 | 0.033* | |
C23 | 0.1038 (2) | 0.8981 (3) | 0.27693 (14) | 0.0226 (7) | |
C28 | 0.3078 (2) | 0.8977 (3) | 0.31505 (13) | 0.0244 (7) | |
H28A | 0.365 | 0.8763 | 0.2933 | 0.029* | |
H28B | 0.2952 | 0.8218 | 0.3376 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0473 (3) | 0.0758 (3) | 0.0317 (2) | −0.0111 (2) | 0.01178 (18) | −0.0179 (2) |
Br2 | 0.0475 (2) | 0.0365 (2) | 0.02852 (19) | 0.00007 (17) | 0.01243 (17) | 0.00434 (16) |
S1 | 0.0262 (5) | 0.0372 (6) | 0.0474 (6) | −0.0087 (4) | 0.0061 (4) | −0.0036 (4) |
S2 | 0.0361 (5) | 0.0294 (5) | 0.0426 (5) | −0.0005 (4) | 0.0121 (4) | −0.0066 (4) |
S3 | 0.0251 (7) | 0.0301 (8) | 0.0354 (6) | −0.0096 (4) | 0.0067 (4) | 0.0013 (4) |
C24 | 0.016 (2) | 0.021 (2) | 0.0304 (17) | −0.0001 (16) | 0.0044 (14) | 0.0012 (14) |
C25 | 0.027 (4) | 0.044 (4) | 0.035 (3) | −0.012 (2) | 0.008 (3) | 0.000 (3) |
C26 | 0.035 (2) | 0.040 (3) | 0.030 (2) | −0.009 (2) | 0.0067 (17) | 0.0000 (19) |
C27 | 0.027 (2) | 0.039 (3) | 0.035 (2) | −0.0082 (19) | 0.011 (2) | 0.007 (2) |
S300 | 0.0251 (7) | 0.0301 (8) | 0.0354 (6) | −0.0096 (4) | 0.0067 (4) | 0.0013 (4) |
C240 | 0.016 (2) | 0.021 (2) | 0.0304 (17) | −0.0001 (16) | 0.0044 (14) | 0.0012 (14) |
C250 | 0.027 (4) | 0.044 (4) | 0.035 (3) | −0.012 (2) | 0.008 (3) | 0.000 (3) |
C260 | 0.035 (2) | 0.040 (3) | 0.030 (2) | −0.009 (2) | 0.0067 (17) | 0.0000 (19) |
C270 | 0.027 (2) | 0.039 (3) | 0.035 (2) | −0.0082 (19) | 0.011 (2) | 0.007 (2) |
S4 | 0.0356 (5) | 0.0281 (5) | 0.0425 (5) | −0.0021 (4) | 0.0030 (4) | 0.0085 (4) |
C29 | 0.0116 (16) | 0.0272 (19) | 0.0346 (18) | 0.0006 (13) | 0.0053 (14) | 0.0074 (15) |
C30 | 0.0213 (18) | 0.027 (2) | 0.039 (2) | −0.0034 (15) | 0.0060 (15) | 0.0092 (16) |
C31 | 0.031 (2) | 0.039 (2) | 0.038 (2) | 0.0003 (17) | −0.0014 (17) | −0.0018 (18) |
C32 | 0.036 (2) | 0.030 (2) | 0.046 (2) | −0.0029 (17) | 0.0019 (18) | −0.0006 (18) |
N1 | 0.0152 (14) | 0.0286 (15) | 0.0279 (14) | −0.0007 (12) | 0.0058 (11) | −0.0034 (12) |
N2 | 0.0166 (15) | 0.0289 (16) | 0.0322 (15) | 0.0000 (12) | 0.0050 (12) | −0.0014 (12) |
N3 | 0.0155 (14) | 0.0252 (15) | 0.0297 (14) | −0.0007 (11) | 0.0061 (11) | 0.0038 (12) |
N4 | 0.0148 (14) | 0.0265 (15) | 0.0292 (14) | 0.0007 (11) | 0.0061 (12) | 0.0019 (12) |
C1 | 0.0171 (16) | 0.0238 (18) | 0.0266 (17) | 0.0030 (14) | 0.0067 (14) | −0.0006 (14) |
C2 | 0.0165 (17) | 0.0208 (18) | 0.0302 (17) | 0.0008 (14) | 0.0045 (14) | 0.0024 (14) |
C3 | 0.0212 (18) | 0.0292 (19) | 0.0333 (18) | 0.0021 (14) | 0.0107 (15) | 0.0007 (15) |
C4 | 0.030 (2) | 0.029 (2) | 0.0252 (17) | 0.0014 (15) | 0.0072 (15) | −0.0043 (15) |
C5 | 0.0208 (18) | 0.0253 (19) | 0.0352 (19) | −0.0024 (14) | 0.0020 (15) | −0.0021 (15) |
C6 | 0.0151 (16) | 0.0267 (19) | 0.0348 (18) | −0.0023 (14) | 0.0074 (14) | −0.0028 (15) |
C7 | 0.0183 (17) | 0.0214 (18) | 0.0325 (18) | 0.0005 (14) | 0.0044 (14) | 0.0006 (14) |
C8 | 0.0178 (17) | 0.0275 (19) | 0.0335 (18) | 0.0000 (14) | 0.0026 (14) | −0.0014 (15) |
C9 | 0.0187 (18) | 0.034 (2) | 0.040 (2) | −0.0031 (15) | −0.0003 (15) | −0.0033 (16) |
C10 | 0.034 (2) | 0.053 (3) | 0.037 (2) | 0.0028 (19) | −0.0003 (18) | −0.0079 (19) |
C11 | 0.025 (2) | 0.042 (2) | 0.050 (2) | −0.0056 (17) | −0.0014 (17) | −0.0116 (19) |
C12 | 0.0171 (17) | 0.0298 (19) | 0.0306 (18) | 0.0018 (14) | 0.0093 (14) | −0.0056 (15) |
C13 | 0.0165 (17) | 0.0286 (19) | 0.0343 (19) | 0.0028 (14) | 0.0085 (15) | −0.0044 (15) |
C14 | 0.0251 (19) | 0.033 (2) | 0.0362 (19) | −0.0008 (15) | 0.0101 (15) | −0.0055 (16) |
C15 | 0.034 (2) | 0.044 (2) | 0.034 (2) | 0.0089 (17) | 0.0108 (17) | 0.0057 (18) |
C16 | 0.039 (2) | 0.032 (2) | 0.056 (2) | 0.0057 (18) | 0.0203 (19) | 0.007 (2) |
C17 | 0.0191 (17) | 0.0190 (17) | 0.0311 (17) | −0.0001 (13) | 0.0067 (14) | −0.0001 (14) |
C18 | 0.0173 (17) | 0.0217 (18) | 0.0314 (18) | 0.0012 (14) | 0.0081 (14) | −0.0014 (14) |
C19 | 0.0192 (17) | 0.0238 (18) | 0.0338 (18) | 0.0019 (14) | 0.0090 (14) | −0.0020 (15) |
C20 | 0.032 (2) | 0.0222 (18) | 0.0269 (17) | 0.0025 (15) | 0.0111 (15) | −0.0013 (14) |
C21 | 0.0270 (19) | 0.0242 (19) | 0.0378 (19) | −0.0022 (15) | 0.0167 (16) | 0.0000 (16) |
C22 | 0.0184 (17) | 0.0248 (19) | 0.0404 (19) | −0.0018 (14) | 0.0099 (15) | 0.0005 (16) |
C23 | 0.0169 (16) | 0.0198 (18) | 0.0325 (18) | −0.0020 (13) | 0.0085 (14) | −0.0005 (14) |
C28 | 0.0171 (17) | 0.0234 (18) | 0.0327 (18) | 0.0005 (14) | 0.0047 (14) | 0.0066 (14) |
Br1—C4 | 1.908 (3) | N3—C28 | 1.465 (4) |
Br2—C20 | 1.912 (3) | N4—C23 | 1.317 (4) |
S1—C11 | 1.700 (4) | N4—C18 | 1.384 (4) |
S1—C8 | 1.723 (3) | C1—C6 | 1.387 (4) |
S2—C16 | 1.716 (4) | C1—C2 | 1.409 (4) |
S2—C13 | 1.727 (3) | C2—C3 | 1.384 (4) |
S3—C27 | 1.707 (4) | C3—C4 | 1.376 (4) |
S3—C24 | 1.723 (4) | C3—H3 | 0.95 |
C24—C25 | 1.352 (6) | C4—C5 | 1.396 (4) |
C24—C23 | 1.464 (4) | C5—C6 | 1.379 (4) |
C25—C26 | 1.417 (7) | C5—H5 | 0.95 |
C25—H25 | 0.95 | C6—H6 | 0.95 |
C26—C27 | 1.348 (5) | C7—C8 | 1.461 (4) |
C26—H26 | 0.95 | C8—C9 | 1.389 (5) |
C27—H27 | 0.95 | C9—C10 | 1.412 (5) |
S300—C240 | 1.707 (17) | C9—H9 | 0.95 |
S300—C270 | 1.721 (17) | C10—C11 | 1.349 (5) |
C240—C250 | 1.353 (17) | C10—H10 | 0.95 |
C240—C23 | 1.430 (17) | C11—H11 | 0.95 |
C250—C260 | 1.422 (17) | C12—C13 | 1.503 (4) |
C250—H250 | 0.95 | C12—H12A | 0.99 |
C260—C270 | 1.349 (16) | C12—H12B | 0.99 |
C260—H260 | 0.95 | C13—C14 | 1.369 (4) |
C270—H270 | 0.95 | C14—C15 | 1.422 (5) |
S4—C32 | 1.705 (4) | C14—H14 | 0.95 |
S4—C29 | 1.722 (3) | C15—C16 | 1.348 (5) |
C29—C30 | 1.374 (4) | C15—H15 | 0.95 |
C29—C28 | 1.509 (4) | C16—H16 | 0.95 |
C30—C31 | 1.4313 | C17—C22 | 1.393 (4) |
C30—H30 | 0.95 | C17—C18 | 1.404 (4) |
C31—C32 | 1.351 (4) | C18—C19 | 1.388 (4) |
C31—H31 | 0.95 | C19—C20 | 1.375 (4) |
C32—H32 | 0.95 | C19—H19 | 0.95 |
N1—C7 | 1.383 (4) | C20—C21 | 1.393 (4) |
N1—C1 | 1.386 (4) | C21—C22 | 1.382 (4) |
N1—C12 | 1.461 (4) | C21—H21 | 0.95 |
N2—C7 | 1.321 (4) | C22—H22 | 0.95 |
N2—C2 | 1.387 (4) | C28—H28A | 0.99 |
N3—C23 | 1.383 (4) | C28—H28B | 0.99 |
N3—C17 | 1.383 (4) | ||
C11—S1—C8 | 91.52 (17) | C5—C6—H6 | 121.4 |
C16—S2—C13 | 91.50 (17) | C1—C6—H6 | 121.4 |
C27—S3—C24 | 91.35 (18) | N2—C7—N1 | 113.4 (3) |
C25—C24—C23 | 130.8 (5) | N2—C7—C8 | 122.7 (3) |
C25—C24—S3 | 110.9 (4) | N1—C7—C8 | 123.8 (3) |
C23—C24—S3 | 118.0 (3) | C9—C8—C7 | 131.0 (3) |
C24—C25—C26 | 113.5 (5) | C9—C8—S1 | 111.3 (2) |
C24—C25—H25 | 123.3 | C7—C8—S1 | 117.5 (2) |
C26—C25—H25 | 123.3 | C8—C9—C10 | 111.2 (3) |
C27—C26—C25 | 111.7 (4) | C8—C9—H9 | 124.4 |
C27—C26—H26 | 124.2 | C10—C9—H9 | 124.4 |
C25—C26—H26 | 124.2 | C11—C10—C9 | 113.5 (3) |
C26—C27—S3 | 112.6 (3) | C11—C10—H10 | 123.2 |
C26—C27—H27 | 123.7 | C9—C10—H10 | 123.2 |
S3—C27—H27 | 123.7 | C10—C11—S1 | 112.5 (3) |
C240—S300—C270 | 90.3 (11) | C10—C11—H11 | 123.8 |
C250—C240—C23 | 122 (3) | S1—C11—H11 | 123.8 |
C250—C240—S300 | 113.4 (14) | N1—C12—C13 | 114.7 (3) |
C23—C240—S300 | 124 (2) | N1—C12—H12A | 108.6 |
C240—C250—C260 | 111.3 (17) | C13—C12—H12A | 108.6 |
C240—C250—H250 | 124.3 | N1—C12—H12B | 108.6 |
C260—C250—H250 | 124.3 | C13—C12—H12B | 108.6 |
C270—C260—C250 | 112.5 (18) | H12A—C12—H12B | 107.6 |
C270—C260—H260 | 123.8 | C14—C13—C12 | 127.0 (3) |
C250—C260—H260 | 123.8 | C14—C13—S2 | 111.2 (3) |
C260—C270—S300 | 112.3 (16) | C12—C13—S2 | 121.8 (2) |
C260—C270—H270 | 123.8 | C13—C14—C15 | 112.3 (3) |
S300—C270—H270 | 123.8 | C13—C14—H14 | 123.8 |
C32—S4—C29 | 91.66 (16) | C15—C14—H14 | 123.8 |
C30—C29—C28 | 126.5 (3) | C16—C15—C14 | 112.9 (3) |
C30—C29—S4 | 111.3 (2) | C16—C15—H15 | 123.6 |
C28—C29—S4 | 122.1 (2) | C14—C15—H15 | 123.6 |
C29—C30—C31 | 112.13 (16) | C15—C16—S2 | 112.1 (3) |
C29—C30—H30 | 123.9 | C15—C16—H16 | 123.9 |
C31—C30—H30 | 123.9 | S2—C16—H16 | 123.9 |
C32—C31—C30 | 112.13 (19) | N3—C17—C22 | 131.7 (3) |
C32—C31—H31 | 123.9 | N3—C17—C18 | 105.5 (3) |
C30—C31—H31 | 123.9 | C22—C17—C18 | 122.9 (3) |
C31—C32—S4 | 112.8 (3) | N4—C18—C19 | 130.1 (3) |
C31—C32—H32 | 123.6 | N4—C18—C17 | 110.1 (3) |
S4—C32—H32 | 123.6 | C19—C18—C17 | 119.7 (3) |
C7—N1—C1 | 105.9 (2) | C20—C19—C18 | 116.9 (3) |
C7—N1—C12 | 129.5 (3) | C20—C19—H19 | 121.6 |
C1—N1—C12 | 124.3 (3) | C18—C19—H19 | 121.6 |
C7—N2—C2 | 104.9 (3) | C19—C20—C21 | 123.7 (3) |
C23—N3—C17 | 106.4 (2) | C19—C20—Br2 | 118.7 (3) |
C23—N3—C28 | 129.2 (3) | C21—C20—Br2 | 117.6 (2) |
C17—N3—C28 | 124.2 (3) | C22—C21—C20 | 120.0 (3) |
C23—N4—C18 | 105.2 (3) | C22—C21—H21 | 120.0 |
N1—C1—C6 | 131.8 (3) | C20—C21—H21 | 120.0 |
N1—C1—C2 | 105.7 (3) | C21—C22—C17 | 116.7 (3) |
C6—C1—C2 | 122.5 (3) | C21—C22—H22 | 121.6 |
C3—C2—N2 | 129.9 (3) | C17—C22—H22 | 121.6 |
C3—C2—C1 | 120.0 (3) | N4—C23—N3 | 112.8 (3) |
N2—C2—C1 | 110.1 (3) | N4—C23—C240 | 118 (2) |
C4—C3—C2 | 116.6 (3) | N3—C23—C240 | 129 (2) |
C4—C3—H3 | 121.7 | N4—C23—C24 | 123.2 (3) |
C2—C3—H3 | 121.7 | N3—C23—C24 | 124.0 (3) |
C3—C4—C5 | 123.9 (3) | C240—C23—C24 | 6 (3) |
C3—C4—Br1 | 118.0 (2) | N3—C28—C29 | 114.4 (3) |
C5—C4—Br1 | 118.1 (2) | N3—C28—H28A | 108.7 |
C6—C5—C4 | 119.8 (3) | C29—C28—H28A | 108.7 |
C6—C5—H5 | 120.1 | N3—C28—H28B | 108.7 |
C4—C5—H5 | 120.1 | C29—C28—H28B | 108.7 |
C5—C6—C1 | 117.2 (3) | H28A—C28—H28B | 107.6 |
Cg2 and Cg4 are the centroids of the S2,C13–C16 and S4,C29–C32 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12i—H12Bi···N4 | 0.99 | 2.57 | 3.454 (4) | 149 |
C22—H22···N2 | 0.95 | 2.61 | 3.504 (4) | 158 |
C28—H28A···N2 | 0.99 | 2.61 | 3.522 (4) | 152 |
C6i—H6i···N4 | 0.95 | 2.65 | 3.547 (4) | 157 |
C3—H3···Cg4 | 0.95 | 2.68 | 3.578 (4) | 158 |
C19—H19···Cg2i | 0.95 | 2.62 | 3.512 (4) | 157 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C16H11BrN2S2 |
Mr | 375.30 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 200 |
a, b, c (Å) | 12.6753 (17), 10.5413 (11), 23.581 (3) |
β (°) | 100.878 (4) |
V (Å3) | 3094.1 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.92 |
Crystal size (mm) | 0.60 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART X2S benchtop diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2008a) |
Tmin, Tmax | 0.46, 0.76 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19813, 5581, 4191 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.603 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.091, 1.02 |
No. of reflections | 5581 |
No. of parameters | 392 |
No. of restraints | 91 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −0.80 |
Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), XSHELL (Bruker, 2004) and Mercury (Macrae et al., 2008), publCIF (Westrip, 2010).
Cg2 and Cg4 are the centroids of the S2,C13–C16 and S4,C29–C32 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12i—H12Bi···N4 | 0.99 | 2.57 | 3.454 (4) | 149 |
C22—H22···N2 | 0.95 | 2.61 | 3.504 (4) | 158 |
C28—H28A···N2 | 0.99 | 2.61 | 3.522 (4) | 152 |
C6i—H6i···N4 | 0.95 | 2.65 | 3.547 (4) | 157 |
C3—H3···Cg4 | 0.95 | 2.68 | 3.578 (4) | 158 |
C19—H19···Cg2i | 0.95 | 2.62 | 3.512 (4) | 157 |
Symmetry code: (i) x−1, y, z. |
Acknowledgements
This work was supported by a Congressionally directed grant from the US Department of Education (grant No. P116Z100020) for the X-ray diffractometer and a grant from the Geneseo Foundation.
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Benzimidazole derivatives have a myriad of pharmacological uses, including as inhibitors of serotonin activated neurotransmission (López-Rodríguez et al., 1999) and antiviral agents (Varala et al., 2007). They are also in antiarrhythmic, antihistamine, antiulcer, anticancer, fungicidal, and anthelmintical drugs (Horton et al., 2003).
Numerous methods are available for the synthesis of substituted benzimidazoles (Grimmett, 1997). Our efforts have focused on the preparation of benzimidazole analogues which have substituents capable of binding metals. Toward that end, we have prepared the title compound from a reaction of 1,2-diamino-4-bromobenzene with 2-thiophenecarboxaldehyde. The 5-bromo and 6-bromo substituted benzimidazoles are formed in an approximately 3:2 ratio based on 1H NMR spectral data. However, only the 5-bromo isomer forms single crystals under the crystallization conditions employed.
Figure 1 shows a perspective view of the two molecules in the asymmetric unit with the atom-labeling scheme. The molecules exhibit the expected planar benzimidazole moieties with maximum deviations of 0.030 (3) Å (C5) and 0.026 (2) Å (C21) in molecules 1 and 2, respectively. The thiophene rings display maximum deviations from planarity of 0.0004 (23) Å (C10 and C11), 0.005 (2) Å (C16), 0.005 (4) Å (C24), and 0.007 (2) Å (C29).
Figure 2 shows the unit cell as viewed down the a axis. Chains of molecules are held together via weak C—H···N and C—H···thiophene ring interactions. The motif is shown in Figure 3. The H19···Cg2 and H3···Cg4, where Cgn refers to the centroid of the thiophene ring containing the sulfur labeled Sn, are 2.62 Å and 2.68 Å, respectively. H19 is 2.618 (3) Å from the thiophene mean plane and H3 is 2.673 (3) Å from the thiophene mean plane.