6,14-Dibromo-2,11-dithia­[3.3]paracyclo­phane

Zhu, X.; Hu, M.

doi:10.1107/S1600536810028874

organic compounds

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Volume 66| Part 8| August 2010| Page o2123

https://doi.org/10.1107/S1600536810028874

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6,14-Dibromo-2,11-dithia[3.3]paracyclophane

Xingxun Zhu ^a and Ming Hu ^a ^*

^aKey Laboratory of Pesticides and Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China
^*Correspondence e-mail: zhuxingxun1986@sina.com

(Received 30 June 2010; accepted 20 July 2010; online 24 July 2010)

In the title compound, C₁₆H₁₄Br₂S₂ [systematic name: 1²,5²-dibromo-2,7-dithia-1,5(1,4)-dibenzenaoctaphane], the centroids of the two benzene rings are separated by 3.313 (5) Å. The crystal packing exhibits weak intermolecular S⋯S contacts of 3.538 (2) Å.

Related literature

For the preparation of the title compound, see: Wang et al. (2003 , 2006 ). For a related structure, see: Huang et al. (2010 ).

Experimental

Crystal data

C₁₆H₁₄Br₂S₂
M_r = 430.21
Orthorhombic, P b c a
a = 9.0563 (11) Å
b = 13.8931 (17) Å
c = 24.641 (3) Å
V = 3100.4 (7) Å³
Z = 8
Mo Kα radiation
μ = 5.49 mm⁻¹
T = 298 K
0.26 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.330, T_max = 0.610
21950 measured reflections
3372 independent reflections
2150 reflections with I > 2σ(I)
R_int = 0.12

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.115
S = 0.99
3372 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.93 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810028874/cv2739sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810028874/cv2739Isup2.hkl

checkCIF report

Comment top

As a contribution to a structural study of dithia[3.3]paracyclophane derivatives with the bromine sustituents (Huang et al., 2010), herewith we present the crystal structure of the title compound (Fig. 1).

The short distance of 3.313 (5) Å between the centroids of two benzene rings is less than the normal packing distance (3.4 Å) between the aromatic rings in organic compounds, thus supporting potential transannular π-π interaction between the rings in the cyclophane unit.

Related literature top

For the preparation of the title compound, see: Wang et al. (2003, 2006). For a related structure, see: Huang et al. (2010).

Experimental top

The dithiaparacyclophanes were prepared by coupling the corresponding pair of dithiol and dibromide under high dilution conditions (Wang et al., 2003, 2006). A solution with equimolar amounts of the dithiol and the dibromide in degassed THF (500 ml) was added dropwise under N₂ over 12 h to a refluxing solution of K₂CO₃ (5 equiv) in EtOH (1.2 L). After an additional 2 h at the reflux temperature, the mixture was cooled and the solvent were removed. The resulting residue was treated with CH₂Cl₂(300 ml) and water (300 ml).The organic phase was separated, the aqueous extracted with CH₂Cl₂ three times. The combined organic layers were dried over Na₂SO₄, then solvent was removed, and the resulting solid was chromatographed on silica gel using CH₂Cl₂ petroleum ether (1:1, v/v) as eluent.

Structure description top

For the preparation of the title compound, see: Wang et al. (2003, 2006). For a related structure, see: Huang et al. (2010).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of (I), showing the atom-labelling scheme, with displacement ellipsoids drawn at the 50% probability level.

1²,5²-dibromo-2,7-dithia-1,5(1,4)-dibenzenaoctaphane top

Crystal data top

C₁₆H₁₄Br₂S₂	F(000) = 1696
M_r = 430.21	D_x = 1.839 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5026 reflections
a = 9.0563 (11) Å	θ = 2.8–25.5°
b = 13.8931 (17) Å	µ = 5.49 mm⁻¹
c = 24.641 (3) Å	T = 298 K
V = 3100.4 (7) Å³	Block, colourless
Z = 8	0.26 × 0.20 × 0.10 mm

Data collection top

Bruker SMART APEX diffractometer	3372 independent reflections
Radiation source: fine-focus sealed tube	2150 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.12
phi and ω scans	θ_max = 27.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→11
T_min = 0.330, T_max = 0.610	k = −17→17
21950 measured reflections	l = −31→31

Refinement top

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0521P)²] where P = (F_o² + 2F_c²)/3
3372 reflections	(Δ/σ)_max = 0.001
181 parameters	Δρ_max = 0.93 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₆H₁₄Br₂S₂	V = 3100.4 (7) Å³
M_r = 430.21	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.0563 (11) Å	µ = 5.49 mm⁻¹
b = 13.8931 (17) Å	T = 298 K
c = 24.641 (3) Å	0.26 × 0.20 × 0.10 mm

Data collection top

Bruker SMART APEX diffractometer	3372 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2150 reflections with I > 2σ(I)
T_min = 0.330, T_max = 0.610	R_int = 0.12
21950 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 0.99	Δρ_max = 0.93 e Å⁻³
3372 reflections	Δρ_min = −0.38 e Å⁻³
181 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	−0.01106 (5)	0.31316 (4)	0.233829 (17)	0.05380 (18)
Br2	−0.18330 (6)	0.72155 (4)	0.04515 (2)	0.0638 (2)
C1	−0.0858 (4)	0.4030 (3)	0.13260 (15)	0.0325 (9)
C2	0.0281 (4)	0.3739 (3)	0.16606 (15)	0.0324 (9)
C3	0.1766 (4)	0.3880 (3)	0.15182 (16)	0.0364 (9)
H3	0.2509	0.3694	0.1757	0.044*
C4	0.2127 (4)	0.4289 (3)	0.10301 (17)	0.0364 (9)
C5	0.0981 (4)	0.4501 (3)	0.06696 (15)	0.0397 (10)
H5	0.1197	0.4726	0.0323	0.048*
C6	−0.0453 (4)	0.4379 (3)	0.08239 (15)	0.0366 (9)
H6	−0.1194	0.4540	0.0579	0.044*
C7	0.3717 (4)	0.4516 (3)	0.0900 (2)	0.0507 (11)
H7A	0.4112	0.3984	0.0690	0.061*
H7B	0.4260	0.4536	0.1239	0.061*
C8	0.3707 (5)	0.6542 (3)	0.1030 (2)	0.0527 (12)
H8A	0.4314	0.6433	0.1348	0.063*
H8B	0.3986	0.7160	0.0878	0.063*
C9	0.2122 (4)	0.6589 (3)	0.12027 (16)	0.0380 (10)
C10	0.1679 (4)	0.6251 (3)	0.16986 (17)	0.0420 (10)
H10	0.2385	0.6104	0.1960	0.050*
C11	0.0198 (4)	0.6126 (3)	0.18176 (16)	0.0353 (9)
H11	−0.0071	0.5876	0.2153	0.042*
C12	−0.0886 (4)	0.6365 (3)	0.14498 (15)	0.0342 (9)
C13	−0.0416 (5)	0.6791 (3)	0.09759 (17)	0.0379 (10)
C14	0.1044 (5)	0.6900 (3)	0.08435 (17)	0.0432 (10)
H14	0.1310	0.7181	0.0515	0.052*
C15	−0.2488 (4)	0.6110 (3)	0.15519 (18)	0.0492 (11)
H15A	−0.2963	0.6022	0.1203	0.059*
H15B	−0.2955	0.6659	0.1725	0.059*
C16	−0.2467 (4)	0.4062 (3)	0.15006 (17)	0.0435 (10)
H16A	−0.2715	0.3461	0.1679	0.052*
H16B	−0.3084	0.4120	0.1181	0.052*
S1	0.41002 (13)	0.56115 (8)	0.05360 (5)	0.0539 (3)
S2	−0.28742 (12)	0.50583 (8)	0.19606 (5)	0.0497 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0655 (3)	0.0599 (3)	0.0360 (3)	−0.0119 (2)	−0.0004 (2)	0.0092 (2)
Br2	0.0722 (4)	0.0703 (4)	0.0490 (3)	0.0220 (3)	−0.0132 (2)	0.0041 (3)
C1	0.034 (2)	0.030 (2)	0.033 (2)	−0.0036 (17)	0.0022 (16)	−0.0072 (17)
C2	0.037 (2)	0.033 (2)	0.0276 (19)	−0.0034 (17)	0.0013 (16)	0.0008 (16)
C3	0.039 (2)	0.032 (2)	0.038 (2)	0.0051 (18)	−0.0051 (18)	−0.0020 (18)
C4	0.035 (2)	0.028 (2)	0.046 (2)	0.0032 (18)	0.0047 (17)	−0.0039 (18)
C5	0.050 (3)	0.039 (2)	0.030 (2)	0.006 (2)	0.0070 (18)	−0.0010 (18)
C6	0.032 (2)	0.043 (2)	0.035 (2)	0.0051 (19)	−0.0032 (17)	−0.0034 (19)
C7	0.034 (2)	0.046 (3)	0.072 (3)	0.004 (2)	0.014 (2)	0.002 (2)
C8	0.040 (3)	0.051 (3)	0.067 (3)	−0.006 (2)	0.016 (2)	−0.010 (2)
C9	0.039 (2)	0.027 (2)	0.047 (2)	−0.0050 (18)	0.0051 (19)	−0.0080 (18)
C10	0.042 (3)	0.041 (2)	0.042 (2)	0.003 (2)	−0.0049 (19)	−0.009 (2)
C11	0.039 (2)	0.036 (2)	0.031 (2)	−0.0020 (18)	0.0074 (17)	−0.0042 (17)
C12	0.036 (2)	0.033 (2)	0.034 (2)	0.0043 (18)	0.0072 (17)	−0.0033 (17)
C13	0.045 (2)	0.031 (2)	0.038 (2)	0.0117 (19)	−0.0023 (18)	−0.0021 (18)
C14	0.055 (3)	0.034 (2)	0.040 (2)	0.002 (2)	0.011 (2)	−0.0012 (19)
C15	0.038 (2)	0.054 (3)	0.056 (3)	0.010 (2)	0.007 (2)	−0.004 (2)
C16	0.033 (2)	0.048 (3)	0.049 (2)	−0.005 (2)	0.002 (2)	−0.006 (2)
S1	0.0477 (7)	0.0482 (7)	0.0658 (8)	−0.0043 (6)	0.0279 (6)	−0.0069 (6)
S2	0.0453 (7)	0.0557 (7)	0.0481 (6)	−0.0039 (6)	0.0205 (5)	−0.0097 (6)

Geometric parameters (Å, º) top

Br1—C2	1.905 (4)	C8—H8A	0.9700
Br2—C13	1.914 (4)	C8—H8B	0.9700
C1—C6	1.379 (5)	C9—C10	1.369 (6)
C1—C2	1.381 (5)	C9—C14	1.387 (6)
C1—C16	1.519 (5)	C10—C11	1.384 (5)
C2—C3	1.403 (5)	C10—H10	0.9300
C3—C4	1.370 (5)	C11—C12	1.377 (5)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.398 (5)	C12—C13	1.377 (5)
C4—C7	1.508 (5)	C12—C15	1.514 (6)
C5—C6	1.364 (5)	C13—C14	1.370 (6)
C5—H5	0.9300	C14—H14	0.9300
C6—H6	0.9300	C15—S2	1.809 (5)
C7—S1	1.800 (4)	C15—H15A	0.9700
C7—H7A	0.9700	C15—H15B	0.9700
C7—H7B	0.9700	C16—S2	1.827 (4)
C8—C9	1.498 (6)	C16—H16A	0.9700
C8—S1	1.811 (4)	C16—H16B	0.9700

C6—C1—C2	116.1 (3)	C10—C9—C8	121.3 (4)
C6—C1—C16	119.9 (4)	C14—C9—C8	120.5 (4)
C2—C1—C16	123.8 (3)	C9—C10—C11	121.1 (4)
C1—C2—C3	121.7 (3)	C9—C10—H10	119.5
C1—C2—Br1	120.9 (3)	C11—C10—H10	119.5
C3—C2—Br1	117.4 (3)	C12—C11—C10	121.4 (4)
C4—C3—C2	120.4 (4)	C12—C11—H11	119.3
C4—C3—H3	119.8	C10—C11—H11	119.3
C2—C3—H3	119.8	C11—C12—C13	116.2 (3)
C3—C4—C5	117.9 (4)	C11—C12—C15	121.2 (4)
C3—C4—C7	120.1 (4)	C13—C12—C15	122.5 (4)
C5—C4—C7	122.0 (4)	C14—C13—C12	123.2 (4)
C6—C5—C4	120.3 (4)	C14—C13—Br2	116.9 (3)
C6—C5—H5	119.9	C12—C13—Br2	119.8 (3)
C4—C5—H5	119.9	C13—C14—C9	119.5 (4)
C5—C6—C1	123.2 (4)	C13—C14—H14	120.2
C5—C6—H6	118.4	C9—C14—H14	120.2
C1—C6—H6	118.4	C12—C15—S2	117.8 (3)
C4—C7—S1	117.8 (3)	C12—C15—H15A	107.9
C4—C7—H7A	107.9	S2—C15—H15A	107.9
S1—C7—H7A	107.9	C12—C15—H15B	107.9
C4—C7—H7B	107.9	S2—C15—H15B	107.9
S1—C7—H7B	107.9	H15A—C15—H15B	107.2
H7A—C7—H7B	107.2	C1—C16—S2	113.0 (3)
C9—C8—S1	114.2 (3)	C1—C16—H16A	109.0
C9—C8—H8A	108.7	S2—C16—H16A	109.0
S1—C8—H8A	108.7	C1—C16—H16B	109.0
C9—C8—H8B	108.7	S2—C16—H16B	109.0
S1—C8—H8B	108.7	H16A—C16—H16B	107.8
H8A—C8—H8B	107.6	C7—S1—C8	103.3 (2)
C10—C9—C14	118.0 (4)	C15—S2—C16	103.2 (2)

C6—C1—C2—C3	6.1 (5)	C9—C10—C11—C12	−2.1 (6)
C16—C1—C2—C3	−168.6 (4)	C10—C11—C12—C13	−4.2 (6)
C6—C1—C2—Br1	−174.1 (3)	C10—C11—C12—C15	172.1 (4)
C16—C1—C2—Br1	11.2 (5)	C11—C12—C13—C14	6.0 (6)
C1—C2—C3—C4	−1.9 (6)	C15—C12—C13—C14	−170.3 (4)
Br1—C2—C3—C4	178.3 (3)	C11—C12—C13—Br2	−176.7 (3)
C2—C3—C4—C5	−4.0 (6)	C15—C12—C13—Br2	7.0 (5)
C2—C3—C4—C7	174.8 (4)	C12—C13—C14—C9	−1.4 (6)
C3—C4—C5—C6	5.7 (6)	Br2—C13—C14—C9	−178.8 (3)
C7—C4—C5—C6	−173.1 (4)	C10—C9—C14—C13	−5.1 (6)
C4—C5—C6—C1	−1.4 (6)	C8—C9—C14—C13	169.4 (4)
C2—C1—C6—C5	−4.4 (5)	C11—C12—C15—S2	−28.6 (5)
C16—C1—C6—C5	170.4 (4)	C13—C12—C15—S2	147.5 (3)
C3—C4—C7—S1	−141.7 (3)	C6—C1—C16—S2	−100.7 (4)
C5—C4—C7—S1	37.1 (5)	C2—C1—C16—S2	73.7 (5)
S1—C8—C9—C10	104.9 (4)	C4—C7—S1—C8	70.3 (4)
S1—C8—C9—C14	−69.4 (5)	C9—C8—S1—C7	−64.4 (4)
C14—C9—C10—C11	6.8 (6)	C12—C15—S2—C16	−74.8 (3)
C8—C9—C10—C11	−167.6 (4)	C1—C16—S2—C15	62.9 (3)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄Br₂S₂
M_r	430.21
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	9.0563 (11), 13.8931 (17), 24.641 (3)
V (Å³)	3100.4 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	5.49
Crystal size (mm)	0.26 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART APEX
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.330, 0.610
No. of measured, independent and observed [I > 2σ(I)] reflections	21950, 3372, 2150
R_int	0.12
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.115, 0.99
No. of reflections	3372
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.93, −0.38

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors are grateful to Xiang Gao Meng for the data collection.

References

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