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access3,9-Dibromo-6,7-dihydro-5H-dibenzo[c,e]thiepine
aState Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, People's Republic of China, and bState Key Laboratory of Supramolecular Structures and Materials, Jilin University, Changchun 130012, People's Republic of China
*Correspondence e-mail: hqzhang@ysu.edu.cn
In the title molecule, C14H10Br2S, the two benzene rings form a dihedral angle of 48.35 (14)°. The seven-membered ring adopts a boat conformation. In the molecules are related by translation along the b axis and exhibit C—H⋯π interactions.
Related literature
For the synthesis of dibenzo[c,e]thiepine derivatives, see: Truce et al. (1956![[Truce, W. E. & Emrick, D. D. (1956). J. Am. Chem. Soc. 78, 6130-6137. ]](../../../../../../logos/arrows/e_arr.gif "Truce, W. E. & Emrick, D. D. (1956). J. Am. Chem. Soc. 78, 6130-6137.")
). For the chiroptical properties of dibenzo[c,e]thiepine derivatives, see: Tomascovic et al. (2000), respectively.
![[Scheme 1]](cv2397scheme1.gif)
Experimental
Crystal data
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Refinement
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Data collection: RAPID-AUTO (Rigaku, 1998); cell RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC and Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536808013226/cv2397sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536808013226/cv2397Isup2.hkl
The title compound has been prepared in a four-step reaction. Step 1: the 2,7-dibromophenanthrenequinone was obtained by direct bromination of phenanthrenequinone in the presence of n-bromosuccinimide in H2SO4. Step 2: the oxidation of 2,7-dibromophenanthrenequinone in the presence of pure oxygen and Cu(I)Cl gave 4,4-dibromodiphenic acid. Step 3: the reduction of 4,4-dibromodiphenic acid using NaBH4 gave 4,4'-dibromo-2,2'-bis-(hydroxymethyl)-bipheny. Step 4: the reacton of 4,4'-dibromo-2,2'-bis-(hydroxymethyl)-biphenyl and sodium sulfate nonahydrate gave the title compound. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a ethanol solution.
H atoms were geometrically positioned (C—H = 0.93–0.97 Å) and refined as riding, with Uiso(H) = 1.2–1.5Ueq(C).
Data collection: RAPID-AUTO (Rigaku, 1998); cell RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC and Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./cv2397fig1thm.gif) | Fig. 1. The molecular structure of (I) showing the atomic numbering and 40% probability displacement ellipsoids. |
| C14H10Br2S | F(000) = 720 |
| Mr = 370.10 | Dx = 1.951 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 3351 reflections |
| a = 8.6629 (12) Å | θ = 5.0–54.9° |
| b = 4.7219 (5) Å | µ = 6.57 mm−1 |
| c = 30.867 (3) Å | T = 291 K |
| β = 93.720 (5)° | Block, colourless |
| V = 1260.0 (3) Å3 | 0.16 × 0.14 × 0.13 mm |
| Z = 4 |
| Rigaku R-AXIS RAPID diffractometer | 2850 independent reflections |
| Radiation source: fine-focus sealed tube | 1840 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.045 |
| ω scans | θmax = 27.5°, θmin = 2.6° |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −11→11 |
| Tmin = 0.420, Tmax = 0.482 | k = −6→6 |
| 4858 measured reflections | l = −40→40 |
| 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) = 0.078 | H-atom parameters constrained |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.0319P)2] where P = (Fo2 + 2Fc2)/3 |
| 2850 reflections | (Δ/σ)max < 0.001 |
| 154 parameters | Δρmax = 0.79 e Å−3 |
| 0 restraints | Δρmin = −0.54 e Å−3 |
| C14H10Br2S | V = 1260.0 (3) Å3 |
| Mr = 370.10 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 8.6629 (12) Å | µ = 6.57 mm−1 |
| b = 4.7219 (5) Å | T = 291 K |
| c = 30.867 (3) Å | 0.16 × 0.14 × 0.13 mm |
| β = 93.720 (5)° |
| Rigaku R-AXIS RAPID diffractometer | 2850 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1840 reflections with I > 2σ(I) |
| Tmin = 0.420, Tmax = 0.482 | Rint = 0.045 |
| 4858 measured reflections |
| R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
| wR(F2) = 0.078 | H-atom parameters constrained |
| S = 1.01 | Δρmax = 0.79 e Å−3 |
| 2850 reflections | Δρmin = −0.54 e Å−3 |
| 154 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 | ||
| Br1 | 0.41895 (5) | 0.61945 (10) | 0.055440 (15) | 0.03375 (14) | |
| Br2 | 1.35085 (6) | 1.76323 (11) | 0.226693 (14) | 0.03785 (14) | |
| S3 | 1.09057 (13) | 1.1401 (3) | 0.04915 (4) | 0.0327 (3) | |
| C12 | 1.2114 (5) | 1.4013 (9) | 0.16192 (12) | 0.0249 (9) | |
| H12A | 1.3131 | 1.3583 | 0.1564 | 0.030* | |
| C1 | 0.5734 (5) | 0.8581 (9) | 0.08152 (14) | 0.0275 (10) | |
| C5 | 0.6896 (5) | 1.0665 (9) | 0.14581 (13) | 0.0276 (10) | |
| H5A | 0.6905 | 1.0957 | 0.1756 | 0.033* | |
| C11 | 1.0890 (4) | 1.2718 (9) | 0.13757 (12) | 0.0229 (9) | |
| C9 | 0.9122 (5) | 1.5295 (9) | 0.17965 (12) | 0.0264 (10) | |
| H9A | 0.8115 | 1.5724 | 0.1861 | 0.032* | |
| C2 | 0.6805 (4) | 0.9909 (9) | 0.05755 (13) | 0.0267 (9) | |
| H2A | 0.6759 | 0.9670 | 0.0276 | 0.032* | |
| C3 | 0.7955 (5) | 1.1598 (9) | 0.07744 (13) | 0.0258 (10) | |
| C7 | 1.1815 (5) | 1.5920 (9) | 0.19398 (13) | 0.0278 (10) | |
| C10 | 0.9356 (4) | 1.3383 (9) | 0.14641 (12) | 0.0217 (9) | |
| C8 | 1.0326 (5) | 1.6569 (9) | 0.20317 (13) | 0.0318 (11) | |
| H8A | 1.0137 | 1.7854 | 0.2250 | 0.038* | |
| C6 | 0.5753 (5) | 0.9018 (9) | 0.12604 (13) | 0.0284 (10) | |
| H6A | 0.5000 | 0.8204 | 0.1422 | 0.034* | |
| C14 | 1.1210 (5) | 1.0451 (9) | 0.10551 (12) | 0.0270 (10) | |
| H14A | 1.0559 | 0.8835 | 0.1110 | 0.032* | |
| H14B | 1.2277 | 0.9850 | 0.1108 | 0.032* | |
| C4 | 0.8037 (5) | 1.1905 (9) | 0.12287 (13) | 0.0267 (10) | |
| C13 | 0.9066 (4) | 1.3159 (9) | 0.05066 (12) | 0.0264 (10) | |
| H13A | 0.9229 | 1.5046 | 0.0625 | 0.032* | |
| H13B | 0.8611 | 1.3355 | 0.0213 | 0.032* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0284 (2) | 0.0346 (3) | 0.0382 (3) | 0.0011 (2) | 0.00183 (18) | −0.0060 (2) |
| Br2 | 0.0429 (3) | 0.0450 (3) | 0.0250 (2) | −0.0075 (2) | −0.00297 (19) | −0.0022 (2) |
| S3 | 0.0311 (6) | 0.0410 (7) | 0.0266 (5) | 0.0019 (5) | 0.0057 (5) | −0.0010 (5) |
| C12 | 0.027 (2) | 0.023 (2) | 0.024 (2) | 0.001 (2) | 0.0027 (17) | 0.006 (2) |
| C1 | 0.025 (2) | 0.025 (2) | 0.032 (2) | 0.009 (2) | 0.0002 (18) | −0.004 (2) |
| C5 | 0.030 (2) | 0.033 (3) | 0.021 (2) | 0.005 (2) | 0.0075 (17) | −0.0017 (19) |
| C11 | 0.027 (2) | 0.021 (2) | 0.0209 (19) | 0.0035 (19) | 0.0031 (17) | 0.0046 (19) |
| C9 | 0.029 (2) | 0.026 (2) | 0.025 (2) | 0.0064 (19) | 0.0061 (18) | 0.0033 (19) |
| C2 | 0.026 (2) | 0.030 (2) | 0.024 (2) | 0.006 (2) | 0.0037 (18) | 0.002 (2) |
| C3 | 0.028 (2) | 0.024 (2) | 0.026 (2) | 0.0075 (19) | 0.0071 (18) | 0.0032 (19) |
| C7 | 0.033 (2) | 0.028 (2) | 0.022 (2) | −0.004 (2) | −0.0004 (18) | 0.005 (2) |
| C10 | 0.023 (2) | 0.022 (2) | 0.020 (2) | 0.0029 (18) | 0.0016 (16) | 0.0039 (17) |
| C8 | 0.048 (3) | 0.025 (3) | 0.023 (2) | 0.000 (2) | 0.009 (2) | 0.0008 (19) |
| C6 | 0.027 (2) | 0.030 (2) | 0.029 (2) | −0.001 (2) | 0.0065 (18) | 0.005 (2) |
| C14 | 0.024 (2) | 0.025 (3) | 0.032 (2) | 0.0041 (18) | 0.0034 (18) | −0.0042 (19) |
| C4 | 0.026 (2) | 0.029 (3) | 0.025 (2) | 0.0058 (19) | 0.0044 (17) | 0.0021 (19) |
| C13 | 0.031 (2) | 0.030 (3) | 0.0186 (19) | 0.0030 (19) | 0.0047 (17) | 0.0019 (18) |
| Br1—C1 | 1.889 (4) | C9—C10 | 1.392 (5) |
| Br2—C7 | 1.906 (4) | C9—H9A | 0.9300 |
| S3—C14 | 1.800 (4) | C2—C3 | 1.388 (6) |
| S3—C13 | 1.800 (4) | C2—H2A | 0.9300 |
| C12—C7 | 1.375 (6) | C3—C4 | 1.407 (5) |
| C12—C11 | 1.400 (5) | C3—C13 | 1.502 (5) |
| C12—H12A | 0.9300 | C7—C8 | 1.373 (6) |
| C1—C2 | 1.375 (6) | C10—C4 | 1.488 (6) |
| C1—C6 | 1.389 (6) | C8—H8A | 0.9300 |
| C5—C6 | 1.371 (6) | C6—H6A | 0.9300 |
| C5—C4 | 1.382 (6) | C14—H14A | 0.9700 |
| C5—H5A | 0.9300 | C14—H14B | 0.9700 |
| C11—C10 | 1.409 (5) | C13—H13A | 0.9700 |
| C11—C14 | 1.496 (6) | C13—H13B | 0.9700 |
| C9—C8 | 1.370 (6) | ||
| C14—S3—C13 | 99.46 (18) | C9—C10—C11 | 118.1 (4) |
| C7—C12—C11 | 120.1 (4) | C9—C10—C4 | 121.4 (4) |
| C7—C12—H12A | 120.0 | C11—C10—C4 | 120.4 (4) |
| C11—C12—H12A | 120.0 | C9—C8—C7 | 119.0 (4) |
| C2—C1—C6 | 120.0 (4) | C9—C8—H8A | 120.5 |
| C2—C1—Br1 | 121.8 (3) | C7—C8—H8A | 120.5 |
| C6—C1—Br1 | 118.2 (3) | C5—C6—C1 | 119.1 (4) |
| C6—C5—C4 | 122.2 (4) | C5—C6—H6A | 120.4 |
| C6—C5—H5A | 118.9 | C1—C6—H6A | 120.4 |
| C4—C5—H5A | 118.9 | C11—C14—S3 | 116.1 (3) |
| C12—C11—C10 | 119.3 (4) | C11—C14—H14A | 108.3 |
| C12—C11—C14 | 120.1 (4) | S3—C14—H14A | 108.3 |
| C10—C11—C14 | 120.3 (4) | C11—C14—H14B | 108.3 |
| C8—C9—C10 | 122.2 (4) | S3—C14—H14B | 108.3 |
| C8—C9—H9A | 118.9 | H14A—C14—H14B | 107.4 |
| C10—C9—H9A | 118.9 | C5—C4—C3 | 118.4 (4) |
| C1—C2—C3 | 120.9 (4) | C5—C4—C10 | 120.0 (4) |
| C1—C2—H2A | 119.5 | C3—C4—C10 | 121.5 (4) |
| C3—C2—H2A | 119.5 | C3—C13—S3 | 112.8 (3) |
| C2—C3—C4 | 119.2 (4) | C3—C13—H13A | 109.0 |
| C2—C3—C13 | 120.4 (4) | S3—C13—H13A | 109.0 |
| C4—C3—C13 | 120.4 (4) | C3—C13—H13B | 109.0 |
| C8—C7—C12 | 121.2 (4) | S3—C13—H13B | 109.0 |
| C8—C7—Br2 | 119.8 (3) | H13A—C13—H13B | 107.8 |
| C12—C7—Br2 | 119.0 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C14—H14a···Cgi | 0.97 | 2.69 | 3.446 (9) | 136 |
| Symmetry code: (i) x, y−1, z. |
Experimental details
| Crystal data | |
| Chemical formula | C14H10Br2S |
| Mr | 370.10 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 291 |
| a, b, c (Å) | 8.6629 (12), 4.7219 (5), 30.867 (3) |
| β (°) | 93.720 (5) |
| V (Å3) | 1260.0 (3) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 6.57 |
| Crystal size (mm) | 0.16 × 0.14 × 0.13 |
| Data collection | |
| Diffractometer | Rigaku R-AXIS RAPID diffractometer |
| Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
| Tmin, Tmax | 0.420, 0.482 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 4858, 2850, 1840 |
| Rint | 0.045 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.078, 1.01 |
| No. of reflections | 2850 |
| No. of parameters | 154 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.79, −0.54 |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC and Rigaku, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).
| D—H···A | D—H | H···A | D···A | D—H···A |
| C14—H14a···Cgi | 0.97 | 2.69 | 3.446 (9) | 136 |
| Symmetry code: (i) x, y−1, z. |
Acknowledgements
The authors acknowledge the financial support from the National Science Foundation of China (grant Nos. 20125421, 90101026, 50303007 and 60207003) and the Ministry of Science and Technology of China (grant Nos. 2002cb6134003 and 2003cb3147032).
References
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC and Rigaku (2002). CrystalStructure. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tomascovic, L. L., Arneri, R. S., Brundic, A. H., Nagl, A., Mintas, M. & Sandtrom, J. (2000). Helv. Chim. Acta, 83, 479–493. Google Scholar
Truce, W. E. & Emrick, D. D. (1956). J. Am. Chem. Soc. 78, 6130–6137. CrossRef CAS Web of Science Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
The dibenzo[c,e]thiepine derivatives (Truce et al. 1956) exhibit remarkable chiroptical properties (Tomascovic et al. 2000). Introducing Br on benzene ring of dibenzo[c,e]thiepine can expand the field of their application, such as photoluminescence, electro-luminescence devices and nonlinear potics etc. Herein we present the crysal structure of the title compound, (I).
The molecular structure of (I) is shown in Fig. 1. The molecule exhibits twisted conformation with a dihedral angle of 48.35 (14)° between two benzene rings, while central 7-member ring has a boat conformation. The crystal structure of (I) is stabilized by C—H···π interactions (Table 1).