3,9-Dibromo-6,7-dihydro-5H-dibenzo[c,e]thiepine.

In the title mol-ecule, C(14)H(10)Br(2)S, the two benzene rings form a dihedral angle of 48.35 (14)°. The seven-membered ring adopts a boat conformation. In the crystal structure, mol-ecules are related by translation along the b axis and exhibit C-H⋯π inter-actions.

Related literature

For the synthesis of dibenzo[c,e]thiepine derivatives, see: Truce et al. (1956 ▶). For the chiroptical properties of dibenzo[c,e]thiepine derivatives, see: Tomascovic et al. (2000 ▶), respectively.

Experimental

Crystal data

C14H10Br2S

M = 370.10

Monoclinic,

a = 8.6629 (12) Å

b = 4.7219 (5) Å

c = 30.867 (3) Å

β = 93.720 (5)°

V = 1260.0 (3) Å3

Z = 4

Mo Kα radiation

μ = 6.57 mm−1

T = 291 (2) K

0.16 × 0.14 × 0.13 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.419, T max = 0.482 (expected range = 0.370–0.426)

4858 measured reflections

2850 independent reflections

1840 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.078

S = 1.01

2850 reflections

154 parameters

H-atom parameters constrained

Δρmax = 0.79 e Å−3

Δρmin = −0.54 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808013226/cv2397sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808013226/cv2397Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H10Br2S	F000 = 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 = 5.0–54.9º
b = 4.7219 (5) Å	µ = 6.57 mm−1
c = 30.867 (3) Å	T = 291 (2) K
β = 93.720 (5)º	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)
Monochromator: graphite	Rint = 0.045
T = 291(2) K	θmax = 27.5º
ω scans	θmin = 2.6º
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	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038	H-atom parameters constrained
wR(F2) = 0.078	w = 1/[σ2(Fo2) + (0.0319P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
2850 reflections	Δρmax = 0.79 e Å−3
154 parameters	Δρmin = −0.54 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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

Table 1

Hydrogen-bond geometry (Å, °)

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) . Cg is the centroid of the benzene ring.