Acta Cryst. (2009). E65, o774 [ doi:10.1107/S1600536809008769 ]
In the title compound, C14H12S, the central seven-membered C6S ring has a twist-boat conformation. The dihedral angle between the two benzene rings is 52.4 (1)°.
The reaction of 2,2'-bis(bromomethyl)-1,1'-biphenyl with 2-aminoethanethiol in ethanol gave a colorless solution. To the resulting solution was added diethylether, followed by allowing to stand in a refrigerator, which produced colorless stick crystals of (I) as a byproduct.
H atoms bonded to C atoms were placed at calculated positions (C—H = 0.95 or 0.99 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2009).
![[Figure 1]](./is2397fig1thm.gif)
| Fig. 1. Perspective view of the title compound, (I), with the atom numbering scheme. Displacement ellipsoids are at the 70% probability level. H atoms are drawn as spheres of arbitrary radii. |
![[Figure 2]](./is2397fig2thm.gif)
| Fig. 2. The crystal packing of title compound, (I). Displacement ellipsoids are at the 70% probability level. H atoms are drawn as spheres of arbitrary radii. |
| C14H12S | F(000) = 448 |
| Mr = 212.30 | Dx = 1.267 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71075 Å |
| Hall symbol: -P 2yn | Cell parameters from 4537 reflections |
| a = 5.645 (3) Å | θ = 3.6–27.5° |
| b = 17.316 (9) Å | µ = 0.25 mm−1 |
| c = 11.398 (5) Å | T = 200 K |
| β = 92.444 (19)° | Prismatic, colourless |
| V = 1113.1 (10) Å3 | 0.15 × 0.15 × 0.10 mm |
| Z = 4 |
| Rigaku R-AXIS RAPID diffractometer | 2464 independent reflections |
| Radiation source: fine-focus sealed tube | 1324 reflections with I > 2σ(I) |
| graphite | Rint = 0.114 |
| Detector resolution: 10.00 pixels mm-1 | θmax = 27.5°, θmin = 3.6° |
| ω scans | h = −4→7 |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −22→22 |
| Tmin = 0.962, Tmax = 0.975 | l = −14→14 |
| 7548 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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.165 | H-atom parameters constrained |
| S = 1.06 | w = 1/[σ2(Fo2) + (0.0655P)2] where P = (Fo2 + 2Fc2)/3 |
| 2464 reflections | (Δ/σ)max < 0.001 |
| 136 parameters | Δρmax = 0.31 e Å−3 |
| 0 restraints | Δρmin = −0.30 e Å−3 |
| 0 constraints |
| C14H12S | V = 1113.1 (10) Å3 |
| Mr = 212.30 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 5.645 (3) Å | µ = 0.25 mm−1 |
| b = 17.316 (9) Å | T = 200 K |
| c = 11.398 (5) Å | 0.15 × 0.15 × 0.10 mm |
| β = 92.444 (19)° |
| Rigaku R-AXIS RAPID diffractometer | 2464 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1324 reflections with I > 2σ(I) |
| Tmin = 0.962, Tmax = 0.975 | Rint = 0.114 |
| 7548 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.063 | H-atom parameters constrained |
| wR(F2) = 0.165 | Δρmax = 0.31 e Å−3 |
| S = 1.06 | Δρmin = −0.30 e Å−3 |
| 2464 reflections | Absolute structure: ? |
| 136 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| S1 | 1.27862 (17) | 0.41043 (5) | −0.05701 (6) | 0.0391 (3) | |
| C1 | 1.3831 (7) | 0.39078 (19) | 0.0932 (2) | 0.0357 (8) | |
| H1 | 1.4103 | 0.3346 | 0.1023 | 0.043* | |
| H2 | 1.5369 | 0.4172 | 0.1083 | 0.043* | |
| C2 | 1.2131 (6) | 0.41676 (17) | 0.1826 (2) | 0.0281 (7) | |
| C3 | 1.2565 (7) | 0.48526 (17) | 0.2447 (2) | 0.0330 (8) | |
| H3 | 1.3926 | 0.5153 | 0.2294 | 0.040* | |
| C4 | 1.1020 (7) | 0.50965 (19) | 0.3284 (2) | 0.0363 (9) | |
| H4 | 1.1289 | 0.5572 | 0.3684 | 0.044* | |
| C5 | 0.9098 (6) | 0.4648 (2) | 0.3532 (2) | 0.0363 (9) | |
| H5 | 0.8061 | 0.4810 | 0.4120 | 0.044* | |
| C6 | 0.8660 (6) | 0.39652 (19) | 0.2937 (2) | 0.0332 (8) | |
| H6 | 0.7331 | 0.3659 | 0.3123 | 0.040* | |
| C7 | 1.0160 (6) | 0.37196 (17) | 0.2059 (2) | 0.0276 (8) | |
| C8 | 0.9612 (6) | 0.30059 (17) | 0.1387 (2) | 0.0293 (7) | |
| C9 | 0.9182 (7) | 0.23099 (19) | 0.1957 (3) | 0.0369 (8) | |
| H7 | 0.9236 | 0.2295 | 0.2790 | 0.044* | |
| C10 | 0.8682 (7) | 0.1646 (2) | 0.1335 (3) | 0.0420 (9) | |
| H8 | 0.8406 | 0.1176 | 0.1738 | 0.050* | |
| C11 | 0.8582 (8) | 0.1662 (2) | 0.0120 (3) | 0.0483 (10) | |
| H9 | 0.8242 | 0.1204 | −0.0313 | 0.058* | |
| C12 | 0.8979 (7) | 0.23477 (19) | −0.0461 (3) | 0.0395 (9) | |
| H10 | 0.8892 | 0.2357 | −0.1295 | 0.047* | |
| C13 | 0.9499 (6) | 0.30201 (17) | 0.0150 (2) | 0.0270 (7) | |
| C14 | 0.9761 (6) | 0.37741 (18) | −0.0492 (2) | 0.0320 (8) | |
| H11 | 0.8833 | 0.4175 | −0.0095 | 0.038* | |
| H12 | 0.9073 | 0.3716 | −0.1300 | 0.038* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0500 (6) | 0.0390 (5) | 0.0295 (4) | −0.0065 (5) | 0.0140 (4) | 0.0003 (4) |
| C1 | 0.038 (2) | 0.0342 (19) | 0.0360 (16) | −0.0057 (17) | 0.0081 (14) | −0.0011 (14) |
| C2 | 0.041 (2) | 0.0229 (16) | 0.0206 (13) | 0.0035 (15) | 0.0040 (12) | 0.0033 (12) |
| C3 | 0.046 (2) | 0.0246 (17) | 0.0286 (15) | −0.0038 (16) | 0.0003 (14) | 0.0045 (13) |
| C4 | 0.057 (3) | 0.0234 (17) | 0.0289 (16) | 0.0046 (17) | 0.0016 (15) | −0.0023 (13) |
| C5 | 0.044 (2) | 0.041 (2) | 0.0239 (15) | 0.0118 (18) | 0.0062 (14) | −0.0004 (14) |
| C6 | 0.039 (2) | 0.039 (2) | 0.0226 (14) | −0.0031 (16) | 0.0078 (13) | 0.0036 (13) |
| C7 | 0.038 (2) | 0.0242 (17) | 0.0213 (14) | 0.0017 (15) | 0.0039 (13) | 0.0045 (12) |
| C8 | 0.033 (2) | 0.0237 (17) | 0.0312 (15) | −0.0039 (15) | 0.0029 (13) | 0.0009 (12) |
| C9 | 0.045 (2) | 0.0331 (19) | 0.0326 (16) | −0.0082 (17) | −0.0004 (14) | 0.0038 (14) |
| C10 | 0.048 (3) | 0.0267 (19) | 0.051 (2) | −0.0082 (18) | −0.0012 (17) | 0.0045 (15) |
| C11 | 0.069 (3) | 0.027 (2) | 0.048 (2) | −0.009 (2) | −0.0008 (18) | −0.0093 (15) |
| C12 | 0.056 (3) | 0.0317 (19) | 0.0310 (16) | −0.0033 (18) | 0.0023 (15) | −0.0054 (14) |
| C13 | 0.0226 (18) | 0.0290 (18) | 0.0296 (15) | −0.0006 (15) | 0.0033 (12) | 0.0012 (12) |
| C14 | 0.043 (2) | 0.0316 (18) | 0.0216 (14) | 0.0011 (17) | 0.0045 (13) | 0.0035 (12) |
| S1—C14 | 1.807 (4) | C7—C8 | 1.480 (4) |
| S1—C1 | 1.819 (3) | C8—C9 | 1.395 (4) |
| C1—C2 | 1.499 (4) | C8—C13 | 1.409 (4) |
| C1—H1 | 0.9900 | C9—C10 | 1.374 (5) |
| C1—H2 | 0.9900 | C9—H7 | 0.9500 |
| C2—C7 | 1.391 (4) | C10—C11 | 1.384 (4) |
| C2—C3 | 1.397 (4) | C10—H8 | 0.9500 |
| C3—C4 | 1.386 (5) | C11—C12 | 1.382 (5) |
| C3—H3 | 0.9500 | C11—H9 | 0.9500 |
| C4—C5 | 1.373 (5) | C12—C13 | 1.382 (4) |
| C4—H4 | 0.9500 | C12—H10 | 0.9500 |
| C5—C6 | 1.381 (4) | C13—C14 | 1.507 (4) |
| C5—H5 | 0.9500 | C14—H11 | 0.9900 |
| C6—C7 | 1.404 (4) | C14—H12 | 0.9900 |
| C6—H6 | 0.9500 | ||
| C14—S1—C1 | 99.41 (15) | C9—C8—C13 | 118.6 (3) |
| C2—C1—S1 | 113.1 (3) | C9—C8—C7 | 121.2 (2) |
| C2—C1—H1 | 109.0 | C13—C8—C7 | 120.2 (2) |
| S1—C1—H1 | 109.0 | C10—C9—C8 | 121.3 (3) |
| C2—C1—H2 | 109.0 | C10—C9—H7 | 119.3 |
| S1—C1—H2 | 109.0 | C8—C9—H7 | 119.3 |
| H1—C1—H2 | 107.8 | C9—C10—C11 | 119.8 (3) |
| C7—C2—C3 | 120.1 (3) | C9—C10—H8 | 120.1 |
| C7—C2—C1 | 120.2 (3) | C11—C10—H8 | 120.1 |
| C3—C2—C1 | 119.7 (3) | C12—C11—C10 | 119.8 (3) |
| C4—C3—C2 | 120.3 (3) | C12—C11—H9 | 120.1 |
| C4—C3—H3 | 119.8 | C10—C11—H9 | 120.1 |
| C2—C3—H3 | 119.8 | C13—C12—C11 | 121.2 (3) |
| C5—C4—C3 | 119.7 (3) | C13—C12—H10 | 119.4 |
| C5—C4—H4 | 120.1 | C11—C12—H10 | 119.4 |
| C3—C4—H4 | 120.1 | C12—C13—C8 | 119.3 (3) |
| C4—C5—C6 | 120.6 (3) | C12—C13—C14 | 120.6 (3) |
| C4—C5—H5 | 119.7 | C8—C13—C14 | 120.0 (3) |
| C6—C5—H5 | 119.7 | C13—C14—S1 | 114.2 (2) |
| C5—C6—C7 | 120.6 (3) | C13—C14—H11 | 108.7 |
| C5—C6—H6 | 119.7 | S1—C14—H11 | 108.7 |
| C7—C6—H6 | 119.7 | C13—C14—H12 | 108.7 |
| C2—C7—C6 | 118.6 (3) | S1—C14—H12 | 108.7 |
| C2—C7—C8 | 121.2 (3) | H11—C14—H12 | 107.6 |
| C6—C7—C8 | 120.2 (3) | ||
| C14—S1—C1—C2 | −45.4 (3) | C2—C7—C8—C13 | −51.6 (5) |
| S1—C1—C2—C7 | 79.6 (3) | C6—C7—C8—C13 | 127.2 (3) |
| S1—C1—C2—C3 | −102.0 (3) | C13—C8—C9—C10 | 0.7 (5) |
| C7—C2—C3—C4 | −1.0 (5) | C7—C8—C9—C10 | −179.7 (4) |
| C1—C2—C3—C4 | −179.4 (3) | C8—C9—C10—C11 | −0.5 (5) |
| C2—C3—C4—C5 | 2.2 (5) | C9—C10—C11—C12 | −0.2 (6) |
| C3—C4—C5—C6 | −1.5 (5) | C10—C11—C12—C13 | 0.6 (6) |
| C4—C5—C6—C7 | −0.5 (5) | C11—C12—C13—C8 | −0.4 (6) |
| C3—C2—C7—C6 | −1.0 (4) | C11—C12—C13—C14 | −175.8 (4) |
| C1—C2—C7—C6 | 177.4 (3) | C9—C8—C13—C12 | −0.3 (5) |
| C3—C2—C7—C8 | 177.8 (3) | C7—C8—C13—C12 | −179.8 (3) |
| C1—C2—C7—C8 | −3.7 (4) | C9—C8—C13—C14 | 175.1 (3) |
| C5—C6—C7—C2 | 1.8 (4) | C7—C8—C13—C14 | −4.4 (5) |
| C5—C6—C7—C8 | −177.1 (3) | C12—C13—C14—S1 | −105.8 (3) |
| C2—C7—C8—C9 | 128.8 (3) | C8—C13—C14—S1 | 78.8 (3) |
| C6—C7—C8—C9 | −52.3 (5) | C1—S1—C14—C13 | −43.6 (2) |
This work was supported by a Grant-in-Aid for JSPS Fellows from the Japan Society for the Promotion of Science (JSPS).
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119.
Foubelo, F., Moreno, B., Soler, T. & Yus, M. (2005). Tetrahedron, 61, 9082–9096.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Westrip, S. P. (2009). publCIF. In preparation.
Yoshinari, N. & Konno, T. (2008). Inorg. Chem. 47, 7450–7452. Check name of 2nd author – was Kanno in Comment
As a part of our ongoing studies on the synthesis and structures of the transition metal complexes with thioether donor groups, we prepared a pair of atrop diastereomeric RhIII complexes having a 2,2'-bis(2-aminoethylthiomethyl)-1,1'-biphenyl ligand (Yoshinari & Konno, 2008). We report herein the structure of the title compound, 5,7-dihydrodibenzo[c,e]thiepine, (I), which was accidentally obtained in the course of a direct synthesis of 2,2'-bis(2-aminoethylthiomethyl)-1,1'-biphenyl from 2,2'-bis(bromomethyl)-1,1'-biphenyl and 2-aminoethanethiol.
In the crystal structure of (I), two aromatic rings (C2—C7 and C8—C13) are inclined around the C7—C8 bond with a dihedral angle of 52.4 (1)°.
This compound (I) has been synthesized by treatment of 2,2'-bis(bromomethyl)-1,1'-biphenyl with sulfide anion, but has not been structurally characterized (Foubelo et al. 2005).