5-Bromo-2-(thio­phen-2-yl)-1-(thio­phen-2-ylmeth­yl)-1H-benzimidazole

Geiger, D.K.; Destefano, M.R.

doi:10.1107/S1600536812042146

organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3123

doi:10.1107/S1600536812042146

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5-Bromo-2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzimidazole

David K. Geiger ^a ^* and Matthew R. Destefano ^a

^aDepartment of Chemistry, State University of New York-College at Geneseo, 1 College Circle, Geneseo, NY 14454, USA
^*Correspondence e-mail: geiger@geneseo.edu

(Received 27 September 2012; accepted 8 October 2012; online 13 October 2012)

There are two independent molecules in the asymmetric unit of the title compound, C₁₆H₁₁BrN₂S₂. 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).

Related 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

C₁₆H₁₁BrN₂S₂
M_r = 375.30
Monoclinic, P 2₁ /n
a = 12.6753 (17) Å
b = 10.5413 (11) Å
c = 23.581 (3) Å
β = 100.878 (4)°
V = 3094.1 (6) Å³
Z = 8
Mo Kα radiation
μ = 2.92 mm⁻¹
T = 200 K
0.60 × 0.20 × 0.10 mm

Data collection

Bruker SMART X2S benchtop diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.46, T_max = 0.76
19813 measured reflections
5581 independent reflections
4191 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.091
S = 1.02
5581 reflections
392 parameters
91 restraints
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.80 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: APEX2 (Bruker, 2010 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812042146/lr2085sup1.cif

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

checkCIF report

Comment top

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.

Related literature top

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 benzimdazoles, see: López-Rodríguez et al. (1999); Varala et al. (2007); Horton et al. (2003). For the synthesis of substituted benzimidazoles, see: Grimmett (1997).

Experimental top

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 column chromatography on silica gel using a 1:4 ethylacetate:hexanes eluent. 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).

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: 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).

Figures top

	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.

5-Bromo-2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzimidazole top

Crystal data top

C₁₆H₁₁BrN₂S₂	F(000) = 1504
M_r = 375.30	D_x = 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

Data collection top

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	R_int = 0.059
Detector resolution: 8.3330 pixels mm^-1	θ_max = 25.4°, θ_min = 2.1°
ω scans	h = −15→15
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	k = −12→12
T_min = 0.46, T_max = 0.76	l = −28→24
19813 measured reflections

Refinement top

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(F_o²) + (0.036P)² + 0.884P] where P = (F_o² + 2F_c²)/3
5581 reflections	(Δ/σ)_max = 0.001
392 parameters	Δρ_max = 0.65 e Å⁻³
91 restraints	Δρ_min = −0.80 e Å⁻³

Crystal data top

C₁₆H₁₁BrN₂S₂	V = 3094.1 (6) Å³
M_r = 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)°

Data collection top

Bruker SMART X2S benchtop diffractometer	5581 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	4191 reflections with I > 2σ(I)
T_min = 0.46, T_max = 0.76	R_int = 0.059
19813 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	91 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.02	Δρ_max = 0.65 e Å⁻³
5581 reflections	Δρ_min = −0.80 e Å⁻³
392 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.46, 0.76
No. of measured, independent and observed [I > 2σ(I)] reflections	19813, 5581, 4191
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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.

References

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