5,8-Dibromo-15,18-dimeth-oxy-2,11-dithia-[3.3]paracyclo-phane.

IN THE TITLE COMPOUND [SYSTEMATIC NAME: 1(2),1(5)-dibromo-5(2),5(5)-dimethoxy-2,7-dithia-1,5(1,4)-dibenzenaoctaphane], C(18)H(18)Br(2)O(2)S(2), the dihedral angle between the aromatic rings is 0.6 (2)° and their centroid separation is 3.251 (2) Å, indicating that a trans-annular π-π interaction occurs. The dimeth-oxy and dibromo substituents are located at crossed positions because of the electronic and the steric nature of the substituents.

Related literature

For the preparation of the title compound, see: Kay & Baek (1997 ▶); Xu et al. (2008 ▶). For paracyclo­phane and its derivatives, see: Clément et al. (2009 ▶); Wang et al. (2006 ▶); Yamamoto et al. (1997 ▶). For studies on the benzene dimer of [2.2]paracyclo­phane, see: Ball et al. (2004 ▶); Dahmen & Bräse (2002 ▶); Rowlands (2008 ▶); Valentini et al. (2008 ▶). For studies of [3.3]paracyclo­phane, see: Wang et al. (2004 ▶).

Experimental

Crystal data

C18H18Br2O2S2

M = 490.26

Monoclinic,

a = 8.9576 (8) Å

b = 16.2291 (14) Å

c = 13.0251 (11) Å

β = 103.240 (1)°

V = 1843.2 (3) Å3

Z = 4

Mo Kα radiation

μ = 4.63 mm−1

T = 298 K

0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer

12800 measured reflections

4475 independent reflections

2812 reflections with I > 2σ(I)

R int = 0.126

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.151

S = 0.95

4475 reflections

219 parameters

H-atom parameters constrained

Δρmax = 1.00 e Å−3

Δρmin = −1.27 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536810029053/si2274sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029053/si2274Isup2.hkl

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

C18H18Br2O2S2	F(000) = 976
Mr = 490.26	Dx = 1.767 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3885 reflections
a = 8.9576 (8) Å	θ = 2.5–26.9°
b = 16.2291 (14) Å	µ = 4.63 mm−1
c = 13.0251 (11) Å	T = 298 K
β = 103.240 (1)°	Block, colorless
V = 1843.2 (3) Å3	0.16 × 0.12 × 0.10 mm
Z = 4

Bruker SMART CCD area detector diffractometer	2812 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.126
graphite	θmax = 28.3°, θmin = 2.0°
phi and ω scans	h = −11→11
12800 measured reflections	k = −19→21
4475 independent reflections	l = −15→17

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151	H-atom parameters constrained
S = 0.95	w = 1/[σ2(Fo2) + (0.0753P)2] where P = (Fo2 + 2Fc2)/3
4475 reflections	(Δ/σ)max = 0.001
219 parameters	Δρmax = 1.00 e Å−3
0 restraints	Δρmin = −1.27 e Å−3

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	0.56512 (6)	0.00221 (3)	0.68306 (4)	0.0672 (2)
Br2	1.04343 (6)	0.17844 (3)	0.44267 (4)	0.05796 (19)
C1	0.9651 (5)	0.0721 (2)	0.6001 (3)	0.0383 (9)
C2	0.8556 (5)	0.0352 (2)	0.6428 (3)	0.0414 (9)
H2	0.8858	−0.0067	0.6919	0.050*
C3	0.7037 (5)	0.0569 (2)	0.6166 (3)	0.0421 (9)
C4	0.6510 (5)	0.1210 (2)	0.5448 (3)	0.0426 (9)
C5	0.7568 (5)	0.1535 (2)	0.4937 (3)	0.0419 (9)
H5	0.7248	0.1924	0.4408	0.050*
C6	0.9099 (5)	0.1296 (2)	0.5193 (3)	0.0386 (9)
C7	1.1351 (5)	0.0552 (3)	0.6408 (3)	0.0478 (10)
H7A	1.1921	0.1026	0.6250	0.057*
H7B	1.1630	0.0085	0.6027	0.057*
C8	1.2053 (5)	0.1368 (3)	0.8357 (3)	0.0603 (13)
H8A	1.2330	0.1323	0.9120	0.072*
H8B	1.2865	0.1669	0.8140	0.072*
C9	1.0584 (5)	0.1853 (3)	0.8039 (3)	0.0483 (11)
C10	0.9312 (5)	0.1636 (3)	0.8413 (3)	0.0466 (10)
C11	0.7901 (5)	0.1997 (3)	0.7979 (3)	0.0461 (10)
H11	0.7041	0.1842	0.8220	0.055*
C12	0.7759 (5)	0.2590 (3)	0.7186 (3)	0.0423 (9)
C13	0.9054 (5)	0.2850 (3)	0.6891 (3)	0.0447 (10)
C14	1.0460 (5)	0.2476 (3)	0.7292 (3)	0.0480 (10)
H14	1.1321	0.2642	0.7061	0.058*
C15	0.6193 (5)	0.2917 (3)	0.6623 (4)	0.0519 (11)
H15A	0.6279	0.3141	0.5948	0.062*
H15B	0.5928	0.3368	0.7035	0.062*
C16	0.4926 (5)	0.1575 (3)	0.5276 (4)	0.0531 (11)
H16A	0.4179	0.1132	0.5143	0.064*
H16B	0.4745	0.1922	0.4654	0.064*
C17	0.8336 (7)	0.0803 (4)	0.9594 (4)	0.0767 (16)
H17A	0.7924	0.1276	0.9874	0.115*
H17B	0.8688	0.0411	1.0149	0.115*
H17C	0.7553	0.0555	0.9054	0.115*
C18	1.0126 (6)	0.3817 (3)	0.5888 (4)	0.0703 (14)
H18A	1.0703	0.4095	0.6503	0.106*
H18B	0.9807	0.4208	0.5328	0.106*
H18C	1.0756	0.3402	0.5673	0.106*
O1	0.9536 (4)	0.1039 (2)	0.9173 (2)	0.0666 (9)
O2	0.8860 (4)	0.34533 (19)	0.6119 (2)	0.0584 (8)
S1	1.19297 (14)	0.03433 (8)	0.77929 (9)	0.0601 (3)
S2	0.46307 (13)	0.21831 (8)	0.63885 (10)	0.0559 (3)

	U11	U22	U33	U12	U13	U23
Br1	0.0566 (3)	0.0782 (4)	0.0670 (4)	−0.0235 (2)	0.0142 (3)	0.0087 (2)
Br2	0.0558 (3)	0.0679 (3)	0.0542 (3)	−0.0029 (2)	0.0209 (2)	0.0073 (2)
C1	0.038 (2)	0.041 (2)	0.0332 (19)	0.0023 (16)	0.0015 (15)	−0.0064 (16)
C2	0.046 (2)	0.039 (2)	0.036 (2)	−0.0006 (18)	0.0028 (17)	0.0016 (17)
C3	0.043 (2)	0.046 (2)	0.036 (2)	−0.0103 (18)	0.0058 (17)	−0.0035 (17)
C4	0.039 (2)	0.048 (2)	0.035 (2)	−0.0046 (18)	−0.0025 (16)	−0.0061 (17)
C5	0.045 (2)	0.050 (2)	0.0287 (19)	−0.0017 (18)	0.0036 (16)	0.0002 (17)
C6	0.041 (2)	0.045 (2)	0.0292 (18)	−0.0044 (17)	0.0055 (16)	−0.0023 (16)
C7	0.043 (2)	0.059 (3)	0.040 (2)	0.005 (2)	0.0048 (18)	−0.0066 (19)
C8	0.041 (3)	0.097 (4)	0.036 (2)	0.002 (2)	−0.0063 (18)	−0.010 (2)
C9	0.036 (2)	0.072 (3)	0.032 (2)	−0.005 (2)	−0.0033 (17)	−0.018 (2)
C10	0.049 (3)	0.064 (3)	0.0253 (19)	0.000 (2)	0.0041 (17)	−0.0072 (18)
C11	0.037 (2)	0.064 (3)	0.039 (2)	−0.0033 (19)	0.0114 (17)	−0.0076 (19)
C12	0.036 (2)	0.051 (2)	0.038 (2)	−0.0044 (18)	0.0059 (16)	−0.0099 (18)
C13	0.043 (2)	0.054 (2)	0.034 (2)	−0.0112 (19)	0.0024 (17)	−0.0136 (18)
C14	0.037 (2)	0.068 (3)	0.037 (2)	−0.011 (2)	0.0034 (16)	−0.018 (2)
C15	0.040 (2)	0.059 (3)	0.056 (3)	−0.003 (2)	0.010 (2)	0.002 (2)
C16	0.032 (2)	0.072 (3)	0.050 (2)	−0.003 (2)	−0.0010 (18)	−0.001 (2)
C17	0.077 (4)	0.100 (4)	0.054 (3)	0.002 (3)	0.017 (3)	0.027 (3)
C18	0.068 (3)	0.069 (3)	0.072 (3)	−0.023 (3)	0.014 (3)	−0.004 (3)
O1	0.055 (2)	0.102 (3)	0.0419 (17)	0.0117 (19)	0.0104 (15)	0.0129 (17)
O2	0.056 (2)	0.0589 (18)	0.058 (2)	−0.0108 (16)	0.0077 (15)	0.0047 (15)
S1	0.0459 (7)	0.0797 (8)	0.0499 (7)	0.0193 (6)	0.0010 (5)	0.0161 (6)
S2	0.0312 (6)	0.0714 (8)	0.0654 (8)	−0.0008 (5)	0.0113 (5)	−0.0028 (6)

Br1—C3	1.889 (4)	C10—C11	1.390 (6)
Br2—C6	1.898 (4)	C11—C12	1.397 (6)
C1—C2	1.372 (6)	C11—H11	0.9300
C1—C6	1.408 (5)	C12—C13	1.369 (6)
C1—C7	1.518 (6)	C12—C15	1.521 (6)
C2—C3	1.371 (6)	C13—O2	1.386 (5)
C2—H2	0.9300	C13—C14	1.388 (6)
C3—C4	1.407 (5)	C14—H14	0.9300
C4—C5	1.382 (6)	C15—S2	1.809 (4)
C4—C16	1.506 (6)	C15—H15A	0.9700
C5—C6	1.390 (6)	C15—H15B	0.9700
C5—H5	0.9300	C16—S2	1.822 (5)
C7—S1	1.792 (4)	C16—H16A	0.9700
C7—H7A	0.9700	C16—H16B	0.9700
C7—H7B	0.9700	C17—O1	1.369 (6)
C8—C9	1.508 (6)	C17—H17A	0.9600
C8—S1	1.812 (5)	C17—H17B	0.9600
C8—H8A	0.9700	C17—H17C	0.9600
C8—H8B	0.9700	C18—O2	1.372 (6)
C9—C10	1.384 (6)	C18—H18A	0.9600
C9—C14	1.389 (6)	C18—H18B	0.9600
C10—O1	1.368 (5)	C18—H18C	0.9600
C2—C1—C6	115.5 (4)	C12—C11—H11	119.6
C2—C1—C7	122.2 (4)	C13—C12—C11	118.7 (4)
C6—C1—C7	122.2 (4)	C13—C12—C15	120.3 (4)
C3—C2—C1	123.3 (4)	C11—C12—C15	120.9 (4)
C3—C2—H2	118.4	C12—C13—O2	116.6 (4)
C1—C2—H2	118.4	C12—C13—C14	120.9 (4)
C2—C3—C4	121.2 (4)	O2—C13—C14	122.3 (4)
C2—C3—Br1	119.0 (3)	C13—C14—C9	120.1 (4)
C4—C3—Br1	119.8 (3)	C13—C14—H14	119.9
C5—C4—C3	116.1 (4)	C9—C14—H14	119.9
C5—C4—C16	120.4 (4)	C12—C15—S2	116.4 (3)
C3—C4—C16	123.4 (4)	C12—C15—H15A	108.2
C4—C5—C6	121.7 (4)	S2—C15—H15A	108.2
C4—C5—H5	119.1	C12—C15—H15B	108.2
C6—C5—H5	119.1	S2—C15—H15B	108.2
C5—C6—C1	121.5 (4)	H15A—C15—H15B	107.3
C5—C6—Br2	117.6 (3)	C4—C16—S2	113.5 (3)
C1—C6—Br2	120.9 (3)	C4—C16—H16A	108.9
C1—C7—S1	114.9 (3)	S2—C16—H16A	108.9
C1—C7—H7A	108.5	C4—C16—H16B	108.9
S1—C7—H7A	108.5	S2—C16—H16B	108.9
C1—C7—H7B	108.5	H16A—C16—H16B	107.7
S1—C7—H7B	108.5	O1—C17—H17A	109.5
H7A—C7—H7B	107.5	O1—C17—H17B	109.5
C9—C8—S1	113.5 (3)	H17A—C17—H17B	109.5
C9—C8—H8A	108.9	O1—C17—H17C	109.5
S1—C8—H8A	108.9	H17A—C17—H17C	109.5
C9—C8—H8B	108.9	H17B—C17—H17C	109.5
S1—C8—H8B	108.9	O2—C18—H18A	109.5
H8A—C8—H8B	107.7	O2—C18—H18B	109.5
C10—C9—C14	119.4 (4)	H18A—C18—H18B	109.5
C10—C9—C8	120.5 (4)	O2—C18—H18C	109.5
C14—C9—C8	119.8 (4)	H18A—C18—H18C	109.5
O1—C10—C9	116.0 (4)	H18B—C18—H18C	109.5
O1—C10—C11	124.2 (4)	C10—O1—C17	119.3 (4)
C9—C10—C11	119.7 (4)	C18—O2—C13	119.4 (4)
C10—C11—C12	120.7 (4)	C7—S1—C8	102.2 (2)
C10—C11—H11	119.6	C15—S2—C16	104.1 (2)
C6—C1—C2—C3	−5.6 (6)	O1—C10—C11—C12	−178.4 (4)
C7—C1—C2—C3	171.5 (4)	C9—C10—C11—C12	−1.5 (6)
C1—C2—C3—C4	−1.6 (6)	C10—C11—C12—C13	−4.2 (6)
C1—C2—C3—Br1	−179.0 (3)	C10—C11—C12—C15	173.1 (4)
C2—C3—C4—C5	7.4 (6)	C11—C12—C13—O2	−178.4 (4)
Br1—C3—C4—C5	−175.2 (3)	C15—C12—C13—O2	4.2 (5)
C2—C3—C4—C16	−168.8 (4)	C11—C12—C13—C14	6.4 (6)
Br1—C3—C4—C16	8.6 (5)	C15—C12—C13—C14	−171.0 (4)
C3—C4—C5—C6	−6.0 (6)	C12—C13—C14—C9	−2.8 (6)
C16—C4—C5—C6	170.4 (4)	O2—C13—C14—C9	−177.7 (3)
C4—C5—C6—C1	−1.2 (6)	C10—C9—C14—C13	−3.0 (6)
C4—C5—C6—Br2	179.7 (3)	C8—C9—C14—C13	171.4 (4)
C2—C1—C6—C5	7.0 (5)	C13—C12—C15—S2	141.2 (3)
C7—C1—C6—C5	−170.2 (4)	C11—C12—C15—S2	−36.0 (5)
C2—C1—C6—Br2	−174.0 (3)	C5—C4—C16—S2	−105.9 (4)
C7—C1—C6—Br2	8.8 (5)	C3—C4—C16—S2	70.2 (5)
C2—C1—C7—S1	−32.5 (5)	C9—C10—O1—C17	178.9 (4)
C6—C1—C7—S1	144.4 (3)	C11—C10—O1—C17	−4.1 (7)
S1—C8—C9—C10	69.9 (5)	C12—C13—O2—C18	171.4 (4)
S1—C8—C9—C14	−104.4 (4)	C14—C13—O2—C18	−13.5 (6)
C14—C9—C10—O1	−177.8 (4)	C1—C7—S1—C8	−80.3 (4)
C8—C9—C10—O1	7.9 (6)	C9—C8—S1—C7	56.6 (4)
C14—C9—C10—C11	5.1 (6)	C12—C15—S2—C16	−76.7 (4)
C8—C9—C10—C11	−169.2 (4)	C4—C16—S2—C15	53.5 (4)