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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 2| February 2012| Page o420
doi:10.1107/S1600536811055103

2-(Thio­phen-2-yl)-1-(thio­phen-2-ylmeth­yl)-1H-benzimidazole

David K. Geiger,a* H. Cristina Geiger,a Leo Williamsa and Bruce C. Nollb

aDepartment of Chemistry, State University of New York-College at Geneseo, 1 College Circle, Geneseo, NY 14454, USA, and bChemical Crystallography, Bruker AXS Inc., 5465 East Cheryl Parkway, Madison, Wisconsin, 53711, USA, and 7517 East Pass, Madison, Wisconsin, 53719, USA
*Correspondence e-mail: geiger@geneseo.edu

(Received 18 October 2011; accepted 21 December 2011; online 18 January 2012)

In the title compound, C16H12N2S2, the thio­phene groups are rotationally disordered over two sets of sites, by approximately 180°, with occupancy ratios of 0.916 (2):0.084 (2) and 0.903 (2):0.097 (2). The major components of the thio­phene and methyl­ene substituted thio­phene rings are canted by 24.06 (12) and 85.07 (10)°, respectively, from the benzimidazole ring system plane and the dihedral angle between the major component thio­phene ring planes is 84.90 (14)°. In the crystal, there is a weak C—H⋯N hydrogen bond which links mol­ecules into chains.

Related literature

For a discussion of the rearrangement of 1,2-diimino­benzene species to form benzimidazoles, see: Smith & Ho (1971[Smith, J. G. & Ho, I. (1971). Tetrahedron Lett. 38, 3541-3544.]). See Varala et al. (2007[Varala, R., Nasreen, A., Enugala, R. & Adapa, S. R. (2007). Tetrahedron Lett. 48, 69-72.]) for examples of proline-catalysed 1,2-disubstituted benzimidazole syntheses. Reich et al. (2004[Reich, B. J. E., Justice, A. K., Beckstead, B. T., Reibenspies, J. H. & Miller, S. A. (2004). J. Org. Chem. 69, 1357-1359.]) provide examples of inter­molecular aldimine coupling. For other syntheses of substituted benzimidazoles, see: Grimmett (1997[Grimmett, M. R. (1997). In Imidazole and Benzidmidazole Synthesis. San Diego: Academic Press.]); Bahrami et al. (2007[Bahrami, K., Khodaei, M. M. & Naali, F. (2007). J. Org. Chem. 73, 6835-6837.]); Du & Wang (2007[Du, L.-H. & Wang, Y.-G. (2007). Synthesis, pp. 675-678.]). For the biological activity of benzimidazole derivatives, see: López-Rodríguez et al. (1999[López-Rodríguez, M. L., Benhamú, B., Morcillo, M. J., Tejeda, I. D., Orensanz, L., Alfaro, M. J. & Martín, M. I. (1999). J. Med. Chem. 42, 5020-5028.]); Horton et al. (2003[Horton, D. A., Bourne, G. T. & Smythe, M. L. (2003). Chem. Rev. 103, 893-930.]).

[Scheme 1]

Experimental

Crystal data

  • C16H12N2S2

  • Mr = 296.40

  • Monoclinic, P 21 /n

  • a = 8.9859 (13) Å

  • b = 9.1601 (11) Å

  • c = 17.476 (3) Å

  • β = 93.629 (5)°

  • V = 1435.6 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.36 mm−1

  • T = 300 K

  • 0.80 × 0.30 × 0.10 mm
Data collection

  • Bruker SMART X2S benchtop diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2008[Bruker (2008). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.761, Tmax = 0.965

  • 8857 measured reflections

  • 2527 independent reflections

  • 1942 reflections with I > 2σ(I)

  • Rint = 0.033
Refinement

  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 0.103

  • S = 1.05

  • 2527 reflections

  • 210 parameters

  • 26 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.18 e Å−3

  • Δρmin = −0.25 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C16—H16⋯N2i 0.93 2.54 3.445 (4) 166
Symmetry code: (i) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2010[Bruker (2010). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XSHELL (Bruker, 2004[Bruker (2004). XSHELL. Bruker AXS Inc., Madison, Wisconsin, USA.]); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811055103/lh5359sup1.cif

Supporting information file. DOI: 10.1107/S1600536811055103/lh5359Isup2.mol

Supporting information file. DOI: 10.1107/S1600536811055103/lh5359Isup4.mol

Structure factors: contains datablock I. DOI: 10.1107/S1600536811055103/lh5359Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536811055103/lh5359Isup5.cml

checkCIF report


Comment top

Benzimidazole derivatives are of interest because of their pharmacological uses. Examples include inhibitors of serotonin activated neurotransmission (López-Rodríguez et al., 1999) and antiviral agents (Varala et al., 2007). They have also found use as antiarrhythmic, antihistamine, antiulcer, anticancer, fungicidal, anthelmintical drugs (Horton et al., 2003).

Numerous methods are available for the synthesis of substituted benzimidazoles (Grimmett, 1997). One pot procedures for the synthesis of 2-aryl substituted benzimidazoles involving the condensation of 1,2-diaminobenzene with aldehydes employing hydrogen peroxide and ceric ammonium nitrate (Bahrami et al., 2007) or hypervalent iodine (Du & Wang, 2007) as oxidizing agents have been reported. Syntheses of 1-arylmethyl-2-aryl substituted benzimidazoles via the proline catalyzed condensation of 1,2-diaminobenzene derivatives with aryl aldehydes have also been reported (Varala et al., 2007). Attempts to prepare N,N'-dibenzal-o-phenylenediamine via the condensation of 1,2-diaminobenzene and benzaldehyde lead to presumed rearrangement of the initially formed Schiff base yielding 1-benzyl-2-phenylbenzimidazole (Smith & Ho, 1971).

Our efforts have focused on the preparation of benzimidazole analogues which have substituents capable of binding metals. Toward that end, we have prepared 1-(thiophene-2-methyl)-2-(2-thiophene)benzimidazole, TMTB, from a reaction of 1,2-diaminobenzene with 2-thiophenecarboxaldehyde.

Figure 1 shows a perspective view of TMTB with the atom-labeling scheme. Only the major components of the disordered thiophene groups are displayed. Close C—H16···N2 intermolecular interactions (2.535 Å, 165.8°) result in chains of TMTB as shown in Figure 2. Bifurcated C—H11···C14 and C15 intermolecular contacts (2.843 Å and 2.848 Å) join the chains to form a layer network (see Figure 3). Figure 4 is a perspective view of the compound showing both major and minor components of the disordered thiophene groups.

The structure exhibits the expected planar benzimidazole moiety (maximum deviation 0.0076(0.0014) Å, N1). The major components of the disordered thiophene and methylthiophene rings are canted 24.06 (12) ° and 85.07 (10) °, respectively, from the benzimidazole plane, with a thiophene-methylthiophene dihedral angle of 84.90 (14) °. Together, the thiophene groups provide a structure with the potential to behave as a bidentate ligand employing the sulfur atoms. We are exploring the coordination chemistry of TMTB.

Related literature top

For a discussion of the rearrangement of 1,2-diiminobenzene species to form benzimidazoles, see: Smith & Ho (1971). See Varala et al. (2007) for examples of proline-catalysed 1,2-disubstituted benzimidazole syntheses. Reich et al. (2004) provide examples of intermolecular aldimine coupling. For other synthesis of substituted benzimidazoles, see: Grimmett (1997); Bahrami et al. (2007); Du & Wang (2007). For the biological activity of benzimidazole derivatives, see: López-Rodríguez et al. (1999); Horton et al. (2003).

Experimental top

The title compound was prepared by the reaction of two equivalents of 2-thiophene with 1,2-diaminobenzene in the presence of a catalytic amount of aluminium trichloride under nitrogen in dichloromethane. The reaction mixture was refluxed for 8 h,filtered and the solvent removed by rotary evaporation. The crude product was purified by column chromatography (silica gel)using 20%(v/v) ethylacetate in hexanes.

The purified product was characterized via 1H and 13C NMR spectroscopies. 1H NMR spectrum (DMSO-d6, 400 MHz, p.p.m.): 8.14 (2H, m), 7.98 (1 H, m), 7.50 (2 H, m), 7.44 (1 H, m), 7.39 (1 H, m), 7.10 (1 H, m), 6.94 (1 H, m), 6.05 (2 H, s). 13C NMR spectrum (DMSO-d6, 100 MHz p.p.m.): 177.15, 150.63, 143.52,138.59, 135.33, 133.05, 130.91, 129.49, 128.70, 128.01, 188.14, 117.51, 117.13, 115.37, 22.58.

Single crystals were grown via vapor diffusion of cyclohexane into a concentrated methanolic solution.

Refinement top

During the course of the refinement, alternate positions for the thiophene sulfur atoms were apparent in the residual electron density maps. Refinement of the site occupancy factors led to values of about 8% for the minor components. Based on these values, a model was constructed for the minor component of each of the thiophene rings using the metrics of the major components as a guide. The pivot atoms (C8 and C13) were assumed to have full occupancy and so were not included in the disorder model. The minor four-atom components (S1', C11', C10' and C9; S2', C16', C15', and C14') were constrained to planarity using FLAT. Using DFIX, the S—C bond distances were set to 1.70 Å. Corresponding bond distances of the minor component and major component were set equal using SADI and corresponding thermal parameters were held the same using EADP. All atoms were refined anisotropically with hydrogen atoms in calculated positions using a riding model. With these constraints, the site occupancies of the major components of the methylthiophene and the thiophene refined to 91.6% and 90.3%, respectively. Based on this model, the angles between the mean planes of the major and minor components of the methylthiophene and thiophene are 5.7(1.9)° and 6.6 (9)°.

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, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XSHELL (Bruker, 2004); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Perspective view of the title compound with displacement ellipsoids of non-hydrogen atoms drawn at the 50% probability level. The disorder is not shown.
[Figure 2] Fig. 2. View of the C—H···N intermolecular interactions leading to chain formation.
[Figure 3] Fig. 3. View of layer formed by joining of chains by bifurcated C—H···C intermolecular contacts.
[Figure 4] Fig. 4. The title molecule with displacement ellipsoids of non-hydrogen atoms drawn at the 50% probability level. Major and minor components of the disordered thiophene groups are shown. Hydrogen atoms have been ommitted for clarity.
2-(Thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzimidazole top
Crystal data top
C16H12N2S2F(000) = 616
Mr = 296.40Dx = 1.371 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2556 reflections
a = 8.9859 (13) Åθ = 2.3–24.0°
b = 9.1601 (11) ŵ = 0.36 mm−1
c = 17.476 (3) ÅT = 300 K
β = 93.629 (5)°Plate, clear yellow
V = 1435.6 (3) Å30.80 × 0.30 × 0.10 mm
Z = 4
Data collection top
Bruker SMART X2S benchtop
diffractometer		2527 independent reflections
Radiation source: fine-focus sealed tube1942 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
ω scansθmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		h = −10→10
Tmin = 0.761, Tmax = 0.965k = −10→10
8857 measured reflectionsl = −20→20
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0518P)2 + 0.2347P]
where P = (Fo2 + 2Fc2)/3
2527 reflections(Δ/σ)max < 0.001
210 parametersΔρmax = 0.18 e Å−3
26 restraintsΔρmin = −0.25 e Å−3
Crystal data top
C16H12N2S2V = 1435.6 (3) Å3
Mr = 296.40Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.9859 (13) ŵ = 0.36 mm−1
b = 9.1601 (11) ÅT = 300 K
c = 17.476 (3) Å0.80 × 0.30 × 0.10 mm
β = 93.629 (5)°
Data collection top
Bruker SMART X2S benchtop
diffractometer		2527 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		1942 reflections with I > 2σ(I)
Tmin = 0.761, Tmax = 0.965Rint = 0.033
8857 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04026 restraints
wR(F2) = 0.103H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.18 e Å−3
2527 reflectionsΔρmin = −0.25 e Å−3
210 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
xyzUiso*/UeqOcc. (<1)
S10.21859 (8)0.28769 (8)0.08330 (3)0.0467 (2)0.916 (2)
C90.0913 (5)0.3386 (5)0.2054 (2)0.0620 (12)0.916 (2)
H90.07240.34880.25680.074*0.916 (2)
C10−0.0188 (4)0.3558 (5)0.1464 (2)0.0648 (10)0.916 (2)
H10−0.11680.38190.15400.078*0.916 (2)
C110.0332 (3)0.3301 (5)0.07718 (18)0.0585 (9)0.916 (2)
H11−0.02510.33490.03130.070*0.916 (2)
S1'0.0789 (14)0.3656 (15)0.2202 (7)0.0467 (2)0.084 (2)
C9'0.208 (3)0.300 (4)0.1075 (11)0.0620 (12)0.084 (2)
H9'0.28350.26770.07730.074*0.084 (2)
C11'−0.017 (3)0.384 (6)0.1320 (15)0.0585 (9)0.084 (2)
H11'−0.11500.41590.12460.070*0.084 (2)
C10'0.071 (3)0.344 (6)0.0747 (16)0.0648 (10)0.084 (2)
H10'0.04340.34570.02250.078*0.084 (2)
S20.18792 (12)0.42615 (9)0.47929 (5)0.0647 (3)0.903 (2)
C140.2441 (4)0.1896 (4)0.41297 (19)0.0411 (8)0.903 (2)
H140.27670.12110.37850.049*0.903 (2)
C150.1692 (5)0.1519 (4)0.4778 (3)0.0510 (8)0.903 (2)
H150.14690.05630.49070.061*0.903 (2)
C160.1329 (4)0.2674 (5)0.51922 (17)0.0549 (10)0.903 (2)
H160.08350.26180.56430.066*0.903 (2)
S2'0.2508 (19)0.1572 (12)0.3994 (8)0.0647 (3)0.097 (2)
C14'0.187 (3)0.394 (3)0.4642 (13)0.0411 (8)0.097 (2)
H14'0.18100.49230.47620.049*0.097 (2)
C16'0.146 (5)0.146 (3)0.478 (2)0.0549 (10)0.097 (2)
H16'0.11400.05900.49890.066*0.097 (2)
C15'0.117 (5)0.280 (4)0.5038 (19)0.0510 (8)0.097 (2)
H15'0.05640.29690.54420.061*0.097 (2)
N10.41824 (18)0.32345 (17)0.29374 (9)0.0385 (4)
N20.47184 (19)0.18925 (19)0.19147 (9)0.0453 (4)
C10.5604 (2)0.2661 (2)0.31017 (12)0.0405 (5)
C20.5918 (2)0.1839 (2)0.24593 (12)0.0450 (5)
C30.7282 (3)0.1124 (3)0.24430 (15)0.0606 (7)
H30.749 (3)0.062 (3)0.2051 (14)0.073*
C40.8285 (3)0.1262 (3)0.30724 (16)0.0731 (8)
H40.92030.07930.30710.088*
C50.7950 (3)0.2087 (3)0.37082 (16)0.0671 (7)
H50.86500.21610.41220.081*
C60.6600 (2)0.2799 (3)0.37371 (13)0.0536 (6)
H60.63690.33450.41620.064*
C70.3719 (2)0.2722 (2)0.22212 (11)0.0380 (5)
C80.2290 (2)0.3058 (2)0.18189 (11)0.0398 (5)
C120.3420 (2)0.4205 (2)0.34473 (11)0.0422 (5)
H12A0.26900.47820.31480.051*
H12B0.41390.48700.36950.051*
C130.2649 (2)0.3368 (2)0.40501 (10)0.0374 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0584 (4)0.0489 (4)0.0324 (4)0.0037 (3)0.0007 (3)−0.0022 (3)
C90.0552 (18)0.079 (3)0.053 (2)0.0069 (17)0.0129 (16)−0.0182 (18)
C100.0447 (14)0.078 (3)0.071 (2)0.0102 (15)−0.0007 (15)−0.0031 (18)
C110.0576 (19)0.0612 (18)0.0542 (16)0.0000 (18)−0.0167 (15)−0.0041 (14)
S1'0.0584 (4)0.0489 (4)0.0324 (4)0.0037 (3)0.0007 (3)−0.0022 (3)
C9'0.0552 (18)0.079 (3)0.053 (2)0.0069 (17)0.0129 (16)−0.0182 (18)
C11'0.0576 (19)0.0612 (18)0.0542 (16)0.0000 (18)−0.0167 (15)−0.0041 (14)
C10'0.0447 (14)0.078 (3)0.071 (2)0.0102 (15)−0.0007 (15)−0.0031 (18)
S20.0900 (6)0.0564 (6)0.0515 (5)−0.0007 (4)0.0340 (4)−0.0160 (3)
C140.0445 (14)0.044 (2)0.0355 (19)0.0040 (14)0.0106 (13)−0.0070 (13)
C150.045 (2)0.0523 (16)0.0560 (16)−0.0033 (12)0.0097 (14)0.0101 (13)
C160.0478 (17)0.083 (2)0.0345 (17)0.0014 (15)0.0113 (15)0.0023 (15)
S2'0.0900 (6)0.0564 (6)0.0515 (5)−0.0007 (4)0.0340 (4)−0.0160 (3)
C14'0.0445 (14)0.044 (2)0.0355 (19)0.0040 (14)0.0106 (13)−0.0070 (13)
C16'0.0478 (17)0.083 (2)0.0345 (17)0.0014 (15)0.0113 (15)0.0023 (15)
C15'0.045 (2)0.0523 (16)0.0560 (16)−0.0033 (12)0.0097 (14)0.0101 (13)
N10.0465 (9)0.0396 (9)0.0300 (9)−0.0002 (8)0.0080 (7)−0.0035 (7)
N20.0478 (10)0.0536 (11)0.0354 (10)0.0049 (8)0.0092 (8)−0.0070 (8)
C10.0421 (11)0.0424 (12)0.0375 (12)−0.0069 (9)0.0068 (9)0.0027 (9)
C20.0428 (11)0.0526 (13)0.0405 (12)0.0011 (10)0.0106 (10)0.0035 (10)
C30.0491 (14)0.0785 (18)0.0558 (16)0.0117 (13)0.0157 (12)−0.0021 (13)
C40.0437 (13)0.100 (2)0.076 (2)0.0125 (14)0.0076 (14)0.0171 (17)
C50.0483 (14)0.090 (2)0.0617 (17)−0.0087 (13)−0.0084 (12)0.0143 (15)
C60.0548 (14)0.0645 (15)0.0411 (13)−0.0096 (11)−0.0009 (11)0.0010 (11)
C70.0458 (11)0.0380 (11)0.0309 (11)−0.0025 (9)0.0088 (9)0.0011 (9)
C80.0463 (11)0.0373 (11)0.0360 (11)−0.0022 (9)0.0036 (9)0.0019 (9)
C120.0575 (12)0.0360 (11)0.0341 (11)0.0022 (9)0.0108 (10)−0.0061 (9)
C130.0398 (10)0.0423 (12)0.0303 (10)0.0048 (9)0.0046 (9)−0.0055 (9)
Geometric parameters (Å, º) top
S1—C111.708 (3)C14'—C131.388 (17)
S1—C81.728 (2)C14'—C15'1.42 (2)
C9—C81.362 (4)C14'—H14'0.9300
C9—C101.392 (5)C16'—C15'1.345 (19)
C9—H90.9300C16'—H16'0.9300
C10—C111.345 (4)C15'—H15'0.9300
C10—H100.9300N1—C71.377 (2)
C11—H110.9300N1—C11.394 (3)
S1'—C81.638 (10)N1—C121.460 (2)
S1'—C11'1.726 (14)N2—C71.316 (2)
C9'—C81.303 (19)N2—C21.393 (3)
C9'—C10'1.39 (2)C1—C61.387 (3)
C9'—H9'0.9300C1—C21.395 (3)
C11'—C10'1.366 (19)C2—C31.392 (3)
C11'—H11'0.9300C3—C41.383 (4)
C10'—H10'0.9300C3—H30.86 (2)
S2—C161.700 (4)C4—C51.393 (4)
S2—C131.7166 (18)C4—H40.9300
C14—C131.370 (4)C5—C61.381 (3)
C14—C151.397 (4)C5—H50.9300
C14—H140.9300C6—H60.9300
C15—C161.334 (4)C7—C81.457 (3)
C15—H150.9300C12—C131.507 (3)
C16—H160.9300C12—H12A0.9700
S2'—C131.653 (10)C12—H12B0.9700
S2'—C16'1.711 (15)
C11—S1—C891.82 (13)N1—C1—C2105.49 (18)
C8—C9—C10114.7 (3)C3—C2—N2130.3 (2)
C8—C9—H9122.6C3—C2—C1119.6 (2)
C10—C9—H9122.6N2—C2—C1110.09 (17)
C11—C10—C9112.0 (3)C4—C3—C2118.1 (2)
C11—C10—H10124.0C4—C3—H3121.3 (18)
C9—C10—H10124.0C2—C3—H3120.6 (18)
C10—C11—S1112.1 (2)C3—C4—C5121.4 (2)
C10—C11—H11123.9C3—C4—H4119.3
S1—C11—H11123.9C5—C4—H4119.3
C8—S1'—C11'92.6 (11)C6—C5—C4121.3 (2)
C8—C9'—C10'118 (2)C6—C5—H5119.3
C8—C9'—H9'121.1C4—C5—H5119.3
C10'—C9'—H9'121.1C5—C6—C1116.8 (2)
C10'—C11'—S1'110.5 (16)C5—C6—H6121.6
C10'—C11'—H11'124.7C1—C6—H6121.6
S1'—C11'—H11'124.7N2—C7—N1113.07 (18)
C11'—C10'—C9'108 (2)N2—C7—C8121.92 (18)
C11'—C10'—H10'125.8N1—C7—C8125.00 (17)
C9'—C10'—H10'125.8C9'—C8—C9103.6 (14)
C16—S2—C1392.54 (14)C9'—C8—C7122.6 (13)
C13—C14—C15113.6 (3)C9—C8—C7133.7 (2)
C13—C14—H14123.2C9'—C8—S1'110.7 (13)
C15—C14—H14123.2C9—C8—S1'10.0 (6)
C16—C15—C14113.1 (3)C7—C8—S1'126.6 (5)
C16—C15—H15123.5C9'—C8—S16.0 (13)
C14—C15—H15123.5C9—C8—S1109.2 (2)
C15—C16—S2111.6 (2)C7—C8—S1116.84 (14)
C15—C16—H16124.2S1'—C8—S1116.5 (5)
S2—C16—H16124.2N1—C12—C13111.81 (16)
C13—S2'—C16'93.3 (11)N1—C12—H12A109.3
C13—C14'—C15'110.4 (19)C13—C12—H12A109.3
C13—C14'—H14'124.8N1—C12—H12B109.3
C15'—C14'—H14'124.8C13—C12—H12B109.3
C15'—C16'—S2'110.1 (16)H12A—C12—H12B107.9
C15'—C16'—H16'124.9C14—C13—C14'102.4 (12)
S2'—C16'—H16'124.9C14—C13—C12130.06 (19)
C16'—C15'—C14'114 (2)C14'—C13—C12127.4 (11)
C16'—C15'—H15'123.1C14—C13—S2'10.1 (5)
C14'—C15'—H15'123.1C14'—C13—S2'112.2 (12)
C7—N1—C1106.23 (16)C12—C13—S2'120.1 (4)
C7—N1—C12129.49 (17)C14—C13—S2109.18 (17)
C1—N1—C12124.27 (17)C14'—C13—S28.3 (11)
C7—N2—C2105.12 (16)C12—C13—S2120.76 (15)
C6—C1—N1131.82 (19)S2'—C13—S2119.1 (4)
C6—C1—C2122.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C16—H16···N2i0.932.543.445 (4)166
Symmetry code: (i) x−1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC16H12N2S2
Mr296.40
Crystal system, space groupMonoclinic, P21/n
Temperature (K)300
a, b, c (Å)8.9859 (13), 9.1601 (11), 17.476 (3)
β (°) 93.629 (5)
V (Å3)1435.6 (3)
Z4
Radiation typeMo Kα
µ (mm−1)0.36
Crystal size (mm)0.80 × 0.30 × 0.10
Data collection
DiffractometerBruker SMART X2S benchtop
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.761, 0.965
No. of measured, independent and
observed [I > 2σ(I)] reflections		8857, 2527, 1942
Rint0.033
(sin θ/λ)max (Å−1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.103, 1.05
No. of reflections2527
No. of parameters210
No. of restraints26
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.18, −0.25

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XSHELL (Bruker, 2004).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C16—H16···N2i0.932.543.445 (4)166
Symmetry code: (i) x−1/2, −y+1/2, z+1/2.
 

Acknowledgements

This work was supported by a Congresssionally directed grant from the US Department of Education for the X-ray diffractometer and a grant from the Geneseo Foundation.

References

First citationBahrami, K., Khodaei, M. M. & Naali, F. (2007). J. Org. Chem. 73, 6835–6837.  Web of Science CrossRef Google Scholar
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ISSN: 2056-9890
Volume 68| Part 2| February 2012| Page o420
doi:10.1107/S1600536811055103
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