The structure of the title compound, C11H12N2S, established by an X-ray crystallographic study, shows that the molecule is composed of three cycles: bicyclic benzimidazole and the thiazepine ring which is bent.
Supporting information
CCDC reference: 162832
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.001 Å
- R factor = 0.052
- wR factor = 0.091
- Data-to-parameter ratio = 11.6
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level B:
REFLT_03
From the CIF: _diffrn_reflns_theta_max 25.16
From the CIF: _reflns_number_total 1573
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 1795
Completeness (_total/calc) 87.63%
Alert B: < 90% complete (theta max?)
Alert Level C:
PLAT_732 Alert C Angle Calc 100.35(10), Rep 100.36(4) .... 2.50 s.u-Ratio
C2 -S1 -C14 1.555 1.555 1.555
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
1 Alert Level C = Please check
A solution of benzimidazole-2-thione (0.007 mol) and 1,4-dibromobutane (0.014 mol) in 50 ml of saturated aqueous solution of sodium bicarbonate and 50 ml of
2-propanol, was heated under reflux for 1 h. After isolation of
1,4-bis(2-mercaptobenzimidazolyl)butane, the reaction product was obtained by
removing the 2-propanol and then extracting the residue with chloroform.
Removal of chloroform gave the title compound, yield: 40%, m.p. 403–407 K.
Crystals were obtained by evaporation of an ethanol solution at room
temperature.
Data collection: KappaCCD Reference Manual (Nonius, 1998); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: maXus (Mackay et al., 1999); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: maXus.
Crystal data top
C11H12N2S | Z = 2 |
Mr = 204.29 | F(000) = 186 |
Triclinic, P1 | Dx = 1.352 Mg m−3 |
a = 6.6159 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.507 (1) Å | Cell parameters from 2941 reflections |
c = 9.468 (1) Å | θ = 1–25.1° |
α = 88.57 (6)° | µ = 0.28 mm−1 |
β = 72.53 (9)° | T = 298 K |
γ = 80.89 (4)° | Prism, colourless |
V = 501.7 (1) Å3 | 0.45 × 0.30 × 0.15 mm |
Data collection top
KappaCCD diffractometer | Rint = 0.037 |
Radiation source: fine-focus sealed tube | θmax = 25.2° |
ϕ scans | h = −7→0 |
1581 measured reflections | k = −10→10 |
1573 independent reflections | l = −11→11 |
1476 reflections with I > 3σ(I) | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: geom, diff |
R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.091 | Weighting scheme based on measured s.u.'s w = 1/[s2(Fo2) + 0.03Fo2] |
S = 1.01 | (Δ/σ)max = 0.028 |
1476 reflections | Δρmax = 0.15 e Å−3 |
127 parameters | Δρmin = −0.17 e Å−3 |
Primary atom site location: structure-invariant direct methods | |
Crystal data top
C11H12N2S | γ = 80.89 (4)° |
Mr = 204.29 | V = 501.7 (1) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.6159 (7) Å | Mo Kα radiation |
b = 8.507 (1) Å | µ = 0.28 mm−1 |
c = 9.468 (1) Å | T = 298 K |
α = 88.57 (6)° | 0.45 × 0.30 × 0.15 mm |
β = 72.53 (9)° | |
Data collection top
KappaCCD diffractometer | 1476 reflections with I > 3σ(I) |
1581 measured reflections | Rint = 0.037 |
1573 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 127 parameters |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.15 e Å−3 |
1476 reflections | Δρmin = −0.17 e Å−3 |
Special details top
Geometry. All standard uncertainties (except dihedral angles between l.s. planes) are
estimated using the full covariance matrix. The standard uncertainties in cell
dimensions are are used in calculating the standard uncertainties of bond
distances, angles and torsion angles. Angles between l.s. planes have standard
uncertainties calculated from atomic positional standard uncertainties; the
errors in cell dimensions are not used in this case. |
Refinement. Refinement on F2. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 1.24260 (3) | 0.22405 (2) | 0.79212 (2) | 0.04973 (9) | |
N3 | 1.14387 (11) | 0.18114 (7) | 1.08865 (7) | 0.0457 (3) | |
N10 | 0.85830 (10) | 0.21690 (6) | 1.00161 (6) | 0.0403 (3) | |
C2 | 1.07490 (13) | 0.20699 (7) | 0.97136 (8) | 0.0415 (3) | |
C4 | 0.95771 (13) | 0.17408 (7) | 1.20354 (8) | 0.0420 (3) | |
C5 | 0.93098 (15) | 0.15167 (9) | 1.35532 (9) | 0.0521 (4) | |
C6 | 0.72519 (17) | 0.15675 (10) | 1.44690 (9) | 0.0569 (4) | |
C7 | 0.54882 (15) | 0.17977 (9) | 1.39352 (9) | 0.0547 (4) | |
C8 | 0.56951 (13) | 0.20047 (8) | 1.24454 (9) | 0.0475 (4) | |
C9 | 0.77886 (12) | 0.19723 (7) | 1.15226 (7) | 0.0396 (3) | |
C11 | 0.73328 (14) | 0.24006 (8) | 0.89663 (8) | 0.0480 (4) | |
C12 | 0.72632 (15) | 0.40543 (9) | 0.83061 (9) | 0.0525 (4) | |
C13 | 0.92451 (16) | 0.43009 (9) | 0.70569 (9) | 0.0567 (4) | |
C14 | 1.12830 (15) | 0.42160 (9) | 0.74748 (9) | 0.0538 (4) | |
H5 | 1.04877 | 0.13307 | 1.39552 | 0.07072* | |
H6 | 0.69849 | 0.14565 | 1.55169 | 0.07505* | |
H7 | 0.40582 | 0.18047 | 1.45991 | 0.07157* | |
H8 | 0.45061 | 0.21586 | 1.20334 | 0.06535* | |
H11A | 0.79497 | 0.16456 | 0.81563 | 0.06715* | |
H11B | 0.58697 | 0.22456 | 0.94573 | 0.06715* | |
H12A | 0.70261 | 0.47913 | 0.91070 | 0.07075* | |
H12B | 0.60001 | 0.42303 | 0.79550 | 0.07075* | |
H13A | 0.88790 | 0.53358 | 0.67129 | 0.07390* | |
H13B | 0.99080 | 0.34858 | 0.61179 | 0.07390* | |
H14A | 1.24482 | 0.44740 | 0.66246 | 0.07142* | |
H14B | 1.10546 | 0.49409 | 0.84231 | 0.07142* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.04547 (14) | 0.04663 (12) | 0.04777 (12) | −0.00441 (8) | −0.00527 (9) | 0.00188 (8) |
N3 | 0.0418 (4) | 0.0401 (3) | 0.0509 (4) | −0.0051 (2) | −0.0195 (3) | 0.0039 (2) |
N10 | 0.0370 (4) | 0.0380 (3) | 0.0422 (3) | −0.0077 (2) | −0.0151 (3) | 0.0069 (2) |
C2 | 0.0398 (4) | 0.0332 (3) | 0.0463 (4) | −0.0064 (3) | −0.0125 (3) | 0.0044 (3) |
C4 | 0.0449 (5) | 0.0313 (3) | 0.0454 (4) | −0.0061 (3) | −0.0173 (3) | 0.0036 (3) |
C5 | 0.0605 (6) | 0.0438 (4) | 0.0487 (4) | −0.0104 (3) | −0.0262 (4) | 0.0063 (3) |
C6 | 0.0699 (7) | 0.0527 (4) | 0.0415 (4) | −0.0124 (4) | −0.0170 (4) | 0.0054 (3) |
C7 | 0.0544 (6) | 0.0527 (4) | 0.0477 (4) | −0.0114 (4) | −0.0060 (4) | 0.0065 (3) |
C8 | 0.0423 (5) | 0.0428 (4) | 0.0512 (4) | −0.0068 (3) | −0.0132 (3) | 0.0077 (3) |
C9 | 0.0420 (4) | 0.0301 (3) | 0.0419 (4) | −0.0061 (3) | −0.0139 (3) | 0.0047 (3) |
C11 | 0.0505 (5) | 0.0446 (4) | 0.0465 (4) | −0.0130 (3) | −0.0234 (3) | 0.0103 (3) |
C12 | 0.0533 (5) | 0.0454 (4) | 0.0535 (4) | −0.0066 (3) | −0.0212 (4) | 0.0120 (3) |
C13 | 0.0671 (6) | 0.0459 (4) | 0.0500 (4) | −0.0113 (4) | −0.0185 (4) | 0.0130 (3) |
C14 | 0.0579 (6) | 0.0438 (4) | 0.0519 (4) | −0.0162 (3) | −0.0104 (4) | 0.0087 (3) |
Geometric parameters (Å, º) top
S1—C2 | 1.7437 (7) | C4—C9 | 1.3932 (11) |
S1—C14 | 1.8245 (8) | C5—C6 | 1.3718 (13) |
N3—C2 | 1.3228 (10) | C6—C7 | 1.3900 (13) |
N3—C4 | 1.3855 (10) | C7—C8 | 1.3851 (11) |
N10—C2 | 1.3635 (11) | C8—C9 | 1.3947 (11) |
N10—C9 | 1.3801 (8) | C11—C12 | 1.5248 (10) |
N10—C11 | 1.4640 (9) | C12—C13 | 1.5185 (12) |
C4—C5 | 1.4062 (10) | C13—C14 | 1.5058 (14) |
| | | |
C2—S1—C14 | 100.36 (4) | C4—C5—C6 | 117.23 (8) |
C2—N3—C4 | 103.52 (7) | C5—C6—C7 | 122.17 (7) |
C2—N10—C9 | 106.09 (6) | C6—C7—C8 | 122.11 (8) |
C2—N10—C11 | 127.57 (6) | C7—C8—C9 | 115.44 (7) |
C9—N10—C11 | 126.32 (6) | N10—C9—C4 | 105.37 (6) |
S1—C2—N3 | 123.93 (6) | N10—C9—C8 | 131.31 (7) |
S1—C2—N10 | 121.98 (6) | C4—C9—C8 | 123.32 (7) |
N3—C2—N10 | 114.08 (6) | N10—C11—C12 | 113.27 (6) |
N3—C4—C5 | 129.34 (8) | C11—C12—C13 | 115.32 (7) |
N3—C4—C9 | 110.93 (6) | C12—C13—C14 | 115.82 (7) |
C5—C4—C9 | 119.72 (8) | S1—C14—C13 | 115.53 (6) |
Experimental details
Crystal data |
Chemical formula | C11H12N2S |
Mr | 204.29 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 6.6159 (7), 8.507 (1), 9.468 (1) |
α, β, γ (°) | 88.57 (6), 72.53 (9), 80.89 (4) |
V (Å3) | 501.7 (1) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.28 |
Crystal size (mm) | 0.45 × 0.30 × 0.15 |
|
Data collection |
Diffractometer | KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 3σ(I)] reflections | 1581, 1573, 1476 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.598 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.091, 1.01 |
No. of reflections | 1476 |
No. of parameters | 127 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.17 |
Selected geometric parameters (Å, º) topS1—C2 | 1.7437 (7) | N10—C2 | 1.3635 (11) |
S1—C14 | 1.8245 (8) | N10—C9 | 1.3801 (8) |
N3—C2 | 1.3228 (10) | N10—C11 | 1.4640 (9) |
N3—C4 | 1.3855 (10) | | |
| | | |
C2—S1—C14 | 100.36 (4) | C2—N10—C11 | 127.57 (6) |
C2—N3—C4 | 103.52 (7) | C9—N10—C11 | 126.32 (6) |
C2—N10—C9 | 106.09 (6) | | |
Thiazepinobenzimidazole derivatives constituted an interesting series of heterocyclic compounds, particularly for their biological activities (Nawrocka & Zimecki, 1998; Taniguchi et al., 1993; Kuehler et al., 1998; Tabata et al., 1995; Pedini et al., 1994; Piras et al., 1993; Nukaya et al., 1991). We report here the preparation and crystal structure determination of the title compound, (I).
Selected bond distances and angles are given in Table 1. The molecule is composed of three cycles, i.e. the benzimidazole system and a thiazepine ring. The benzimidazole system is planar (r.m.s. deviation: 0.0136 Å) and the thiazepine seven-membered ring is composed of three planar fragments: S1/C2/N10/C11, which is coplanar with the benzimidazole and at an angle of 118.9 (5)° to the S1/C11/C12/C14 fragment, which is, in turn, at an angle of 121.1 (4)° to the C12/C13/C14 triangle. According to Cremer & Pople (1975), the seven-membered ring conformation can be described on the basis of the total puckering amplitude QT = 0.872 (1) Å and the asymetry parameters that are indicative of a local pseudo-twofold axis running along C13 and the midpoint of the C2—N10 bond.