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Colourless crystals of the title compound, bis(2-bromophenyl) disulfide, C
12H
8Br
2S
2, are obtained from the reaction of 2-bromophenylmercaptan with metallic sodium and either zinc chloride or cadmium chloride in methanol. In the presence of Zn
II ions, the crystals are orthorhombic (space group
Pbca, with
Z′ = 1); with Cd
II ions present, the product is triclinic (space group
, with
Z′ = 4). Both polymorphs exhibit significant intramolecular C—H
S hydrogen bonds. In the orthorhombic form, molecules are linked by intermolecular C—H
Br hydrogen bonds, while in the triclinic form, molecules exhibit Br
Br contacts.
Supporting information
CCDC references: 214182; 214183
The title compound was prepared by refluxing a methanolic solution (15 ml) of 2-bromophenylmercaptan (2 mmol) in the presence of metallic sodium (1 g) and either ZnCl2 or CdCl2 (1 mmol). After refluxing for 4 h at 338 K, the volume of the solution was concentrated to 5 ml and maintained at 278 K for a week, leading to the formation of colourless columns (ZnCl2) or plates (CdCl2). IR and NMR spectra for both crystals correspond to the title compound. Analysis; found for the orthorhomic form: C 38.15, H 2.38, S 17.22%; found for the triclinic form: C 38.15, H 2.30, S 16.98%; calculated for C12H8Br2S2: C 38.30, H 2.13, S 17.02%.
All H atoms were initially located from difference Fourier maps and thereafter placed at idealized positions and refined using a riding model with a C—H distance of 0.93 Å and Uiso(H) equal to 1.2Uiso(C).
For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT. Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for (I); SHELXS97 (Sheldrick, 1997a) for (II). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for (I); SHELXL97 (Sheldrick, 1997b) for (II). Molecular graphics: SHELXTL (Sheldrick, 1994) for (I); SHELXTL version 5.03 (Sheldrick, 1994) for (II). For both compounds, software used to prepare material for publication: SHELXL97.
(I) Bis(2-bromophenyl) disulfide
top
Crystal data top
C12H8Br2S2 | F(000) = 1456 |
Mr = 376.12 | Dx = 2.014 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 2137 reflections |
a = 7.6844 (10) Å | θ = 1.8–26.4° |
b = 14.4240 (18) Å | µ = 6.84 mm−1 |
c = 22.378 (3) Å | T = 150 K |
V = 2480.4 (6) Å3 | Column, colourless |
Z = 8 | 0.38 × 0.20 × 0.16 mm |
Data collection top
Bruker SMART APEX CCD with an Oxford Cryosystems low-temperature device diffractometer | 2537 independent reflections |
Radiation source: normal-focus sealed tube | 2224 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ϕ and ω scans | θmax = 26.4°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.211, Tmax = 0.335 | k = −18→18 |
18462 measured reflections | l = −27→27 |
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)] = 0.019 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.049 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0317P)2] where P = (Fo2 + 2Fc2)/3 |
2537 reflections | (Δ/σ)max = 0.003 |
145 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Crystal data top
C12H8Br2S2 | V = 2480.4 (6) Å3 |
Mr = 376.12 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.6844 (10) Å | µ = 6.84 mm−1 |
b = 14.4240 (18) Å | T = 150 K |
c = 22.378 (3) Å | 0.38 × 0.20 × 0.16 mm |
Data collection top
Bruker SMART APEX CCD with an Oxford Cryosystems low-temperature device diffractometer | 2537 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2224 reflections with I > 2σ(I) |
Tmin = 0.211, Tmax = 0.335 | Rint = 0.028 |
18462 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.019 | 0 restraints |
wR(F2) = 0.049 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.42 e Å−3 |
2537 reflections | Δρmin = −0.22 e Å−3 |
145 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 | Uiso*/Ueq | |
Br11 | 0.05417 (3) | 0.23178 (15) | 0.77159 (9) | 0.02855 (7) | |
Br21 | 0.16418 (3) | 0.08851 (16) | 0.41499 (9) | 0.02884 (7) | |
S11 | 0.08670 (7) | 0.19803 (4) | 0.63232 (2) | 0.02425 (12) | |
S21 | 0.08815 (6) | 0.14544 (4) | 0.54832 (2) | 0.02407 (12) | |
C11 | 0.1261 (2) | 0.10068 (13) | 0.67967 (8) | 0.0205 (4) | |
C12 | 0.1127 (3) | 0.11313 (14) | 0.74100 (9) | 0.0216 (4) | |
C13 | 0.1414 (3) | 0.04130 (15) | 0.78041 (9) | 0.0267 (5) | |
H13 | 0.1325 | 0.0511 | 0.8214 | 0.032* | |
C14 | 0.1837 (3) | −0.04574 (16) | 0.75844 (9) | 0.0298 (5) | |
H14 | 0.2015 | −0.0949 | 0.7846 | 0.036* | |
C15 | 0.1993 (3) | −0.05908 (15) | 0.69761 (9) | 0.0270 (5) | |
H15 | 0.2283 | −0.1173 | 0.6829 | 0.032* | |
C16 | 0.1722 (3) | 0.01333 (14) | 0.65864 (9) | 0.0235 (4) | |
H16 | 0.1848 | 0.0037 | 0.6178 | 0.028* | |
C21 | 0.3112 (3) | 0.14005 (13) | 0.52705 (8) | 0.0204 (4) | |
C22 | 0.3488 (3) | 0.11346 (14) | 0.46889 (8) | 0.0217 (4) | |
C23 | 0.5177 (3) | 0.10200 (14) | 0.44959 (9) | 0.0254 (4) | |
H23 | 0.5400 | 0.0829 | 0.4106 | 0.030* | |
C24 | 0.6535 (3) | 0.11899 (15) | 0.48833 (9) | 0.0282 (5) | |
H24 | 0.7678 | 0.1115 | 0.4756 | 0.034* | |
C25 | 0.6188 (3) | 0.14731 (14) | 0.54629 (9) | 0.0270 (5) | |
H25 | 0.7103 | 0.1593 | 0.5724 | 0.032* | |
C26 | 0.4494 (3) | 0.15788 (14) | 0.56553 (9) | 0.0245 (4) | |
H26 | 0.4274 | 0.1771 | 0.6045 | 0.029* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br11 | 0.03719 (14) | 0.02434 (12) | 0.02411 (12) | 0.00021 (9) | 0.00742 (9) | −0.00358 (8) |
Br21 | 0.02800 (12) | 0.03817 (14) | 0.02035 (11) | −0.00169 (10) | −0.00360 (8) | −0.00441 (9) |
S11 | 0.0287 (3) | 0.0247 (3) | 0.0193 (2) | 0.0037 (2) | 0.0021 (2) | 0.0014 (2) |
S21 | 0.0205 (2) | 0.0338 (3) | 0.0179 (2) | −0.0007 (2) | −0.00069 (19) | 0.0005 (2) |
C11 | 0.0171 (9) | 0.0230 (11) | 0.0213 (10) | −0.0022 (8) | −0.0004 (8) | 0.0024 (8) |
C12 | 0.0210 (10) | 0.0199 (10) | 0.0240 (10) | −0.0005 (8) | 0.0031 (8) | −0.0037 (8) |
C13 | 0.0326 (12) | 0.0286 (12) | 0.0189 (10) | −0.0011 (10) | 0.0012 (9) | 0.0013 (8) |
C14 | 0.0361 (13) | 0.0263 (11) | 0.0272 (11) | 0.0007 (9) | −0.0006 (9) | 0.0067 (9) |
C15 | 0.0282 (11) | 0.0227 (11) | 0.0300 (11) | 0.0001 (9) | 0.0009 (9) | −0.0028 (9) |
C16 | 0.0239 (11) | 0.0266 (11) | 0.0201 (10) | −0.0008 (8) | 0.0013 (8) | −0.0018 (8) |
C21 | 0.0227 (10) | 0.0189 (10) | 0.0196 (9) | 0.0002 (8) | 0.0007 (8) | 0.0031 (8) |
C22 | 0.0233 (10) | 0.0213 (10) | 0.0204 (9) | −0.0026 (8) | −0.0032 (8) | 0.0018 (8) |
C23 | 0.0290 (11) | 0.0250 (11) | 0.0222 (10) | 0.0009 (9) | 0.0048 (9) | −0.0022 (8) |
C24 | 0.0199 (10) | 0.0308 (11) | 0.0340 (12) | 0.0010 (9) | 0.0037 (9) | 0.0028 (10) |
C25 | 0.0212 (10) | 0.0320 (12) | 0.0278 (11) | −0.0026 (9) | −0.0044 (9) | 0.0012 (9) |
C26 | 0.0263 (11) | 0.0270 (11) | 0.0202 (10) | −0.0026 (9) | −0.0017 (8) | −0.0007 (9) |
Geometric parameters (Å, º) top
Br11—C12 | 1.897 (2) | C15—H15 | 0.9300 |
Br21—C22 | 1.897 (2) | C16—H16 | 0.9300 |
S11—C11 | 1.785 (2) | C21—C22 | 1.387 (3) |
S11—S21 | 2.0270 (7) | C21—C26 | 1.391 (3) |
S21—C21 | 1.780 (2) | C22—C23 | 1.378 (3) |
C11—C12 | 1.388 (3) | C23—C24 | 1.378 (3) |
C11—C16 | 1.391 (3) | C23—H23 | 0.9300 |
C12—C13 | 1.378 (3) | C24—C25 | 1.386 (3) |
C13—C14 | 1.387 (3) | C24—H24 | 0.9300 |
C13—H13 | 0.9300 | C25—C26 | 1.380 (3) |
C14—C15 | 1.380 (3) | C25—H25 | 0.9300 |
C14—H14 | 0.9300 | C26—H26 | 0.9300 |
C15—C16 | 1.377 (3) | | |
| | | |
C11—S11—S21 | 104.78 (7) | C11—C16—H16 | 119.6 |
C21—S21—S11 | 105.64 (7) | C22—C21—C26 | 118.21 (18) |
C12—C11—C16 | 118.08 (17) | C22—C21—S21 | 117.61 (15) |
C12—C11—S11 | 118.20 (15) | C26—C21—S21 | 124.15 (15) |
C16—C11—S11 | 123.71 (15) | C23—C22—C21 | 121.55 (19) |
C13—C12—C11 | 121.57 (19) | C23—C22—Br21 | 118.86 (15) |
C13—C12—Br11 | 119.02 (15) | C21—C22—Br21 | 119.56 (15) |
C11—C12—Br11 | 119.41 (15) | C24—C23—C22 | 119.64 (18) |
C12—C13—C14 | 119.41 (18) | C24—C23—H23 | 120.2 |
C12—C13—H13 | 120.3 | C22—C23—H23 | 120.2 |
C14—C13—H13 | 120.3 | C23—C24—C25 | 119.73 (19) |
C15—C14—C13 | 119.75 (19) | C23—C24—H24 | 120.1 |
C15—C14—H14 | 120.1 | C25—C24—H24 | 120.1 |
C13—C14—H14 | 120.1 | C26—C25—C24 | 120.4 (2) |
C16—C15—C14 | 120.4 (2) | C26—C25—H25 | 119.8 |
C16—C15—H15 | 119.8 | C24—C25—H25 | 119.8 |
C14—C15—H15 | 119.8 | C25—C26—C21 | 120.46 (19) |
C15—C16—C11 | 120.77 (18) | C25—C26—H26 | 119.8 |
C15—C16—H16 | 119.6 | C21—C26—H26 | 119.8 |
| | | |
C11—S11—S21—C21 | −83.34 (9) | S11—S21—C21—C22 | −174.69 (14) |
S21—S11—C11—C12 | −172.68 (14) | S11—S21—C21—C26 | 7.46 (19) |
S21—S11—C11—C16 | 8.33 (18) | C26—C21—C22—C23 | 1.9 (3) |
C16—C11—C12—C13 | −0.9 (3) | S21—C21—C22—C23 | −176.04 (16) |
S11—C11—C12—C13 | −179.94 (17) | C26—C21—C22—Br21 | −179.99 (15) |
C16—C11—C12—Br11 | 178.90 (15) | S21—C21—C22—Br21 | 2.0 (2) |
S11—C11—C12—Br11 | −0.1 (2) | C21—C22—C23—C24 | −1.3 (3) |
C11—C12—C13—C14 | −0.4 (3) | Br21—C22—C23—C24 | −179.40 (16) |
Br11—C12—C13—C14 | 179.80 (16) | C22—C23—C24—C25 | 0.1 (3) |
C12—C13—C14—C15 | 1.0 (3) | C23—C24—C25—C26 | 0.5 (3) |
C13—C14—C15—C16 | −0.4 (3) | C24—C25—C26—C21 | 0.2 (3) |
C14—C15—C16—C11 | −1.0 (3) | C22—C21—C26—C25 | −1.3 (3) |
C12—C11—C16—C15 | 1.6 (3) | S21—C21—C26—C25 | 176.50 (16) |
S11—C11—C16—C15 | −179.43 (16) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···S21 | 0.93 | 2.67 | 3.185 (2) | 115 |
C26—H26···S11 | 0.93 | 2.71 | 3.215 (2) | 115 |
C25—H25···S21i | 0.93 | 2.96 | 3.607 (2) | 128 |
C24—H24···S21i | 0.93 | 2.99 | 3.620 (2) | 126 |
C26—H26···Br11ii | 0.93 | 3.04 | 3.882 (2) | 151 |
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, y, −z+3/2. |
(II) Bis(2-bromophenyl) disulfide
top
Crystal data top
C12H8Br2S2 | Z = 8 |
Mr = 376.12 | F(000) = 1456 |
Triclinic, P1 | Dx = 1.974 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.8186 (19) Å | Cell parameters from 3180 reflections |
b = 15.489 (3) Å | θ = 1.4–28.8° |
c = 15.653 (3) Å | µ = 6.70 mm−1 |
α = 102.122 (5)° | T = 150 K |
β = 100.393 (5)° | Plate, colourless |
γ = 110.001 (5)° | 0.13 × 0.11 × 0.06 mm |
V = 2531.4 (8) Å3 | |
Data collection top
Bruker SMART APEX CCD with an Oxford Cryosystems low-temperature device diffractometer | 13188 independent reflections |
Radiation source: normal-focus sealed tube | 8387 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 28.8°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→16 |
Tmin = 0.408, Tmax = 0.669 | k = −20→20 |
22934 measured reflections | l = −21→21 |
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)] = 0.035 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.060 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0121P)2] where P = (Fo2 + 2Fc2)/3 |
11915 reflections | (Δ/σ)max = 0.002 |
577 parameters | Δρmax = 0.98 e Å−3 |
0 restraints | Δρmin = −1.03 e Å−3 |
Crystal data top
C12H8Br2S2 | γ = 110.001 (5)° |
Mr = 376.12 | V = 2531.4 (8) Å3 |
Triclinic, P1 | Z = 8 |
a = 11.8186 (19) Å | Mo Kα radiation |
b = 15.489 (3) Å | µ = 6.70 mm−1 |
c = 15.653 (3) Å | T = 150 K |
α = 102.122 (5)° | 0.13 × 0.11 × 0.06 mm |
β = 100.393 (5)° | |
Data collection top
Bruker SMART APEX CCD with an Oxford Cryosystems low-temperature device diffractometer | 13188 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 8387 reflections with I > 2σ(I) |
Tmin = 0.408, Tmax = 0.669 | Rint = 0.031 |
22934 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.060 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.98 e Å−3 |
11915 reflections | Δρmin = −1.03 e Å−3 |
577 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 | Uiso*/Ueq | |
Br11 | 0.48434 (3) | 0.14082 (2) | 0.16448 (3) | 0.03224 (9) | |
Br21 | 0.96195 (3) | −0.12266 (3) | 0.03784 (3) | 0.03552 (10) | |
S11 | 0.68930 (8) | 0.05653 (6) | 0.13605 (7) | 0.0309 (2) | |
S21 | 0.78582 (8) | −0.01581 (7) | 0.08068 (6) | 0.0317 (2) | |
C11 | 0.5307 (3) | −0.0289 (2) | 0.1035 (2) | 0.0227 (8) | |
C12 | 0.4404 (3) | 0.0067 (2) | 0.1184 (2) | 0.0221 (7) | |
C13 | 0.3166 (3) | −0.0544 (2) | 0.1015 (2) | 0.0282 (8) | |
H13 | 0.2577 | −0.0295 | 0.1132 | 0.034* | |
C14 | 0.2808 (3) | −0.1522 (2) | 0.0675 (2) | 0.0313 (9) | |
H14 | 0.1977 | −0.1936 | 0.0557 | 0.038* | |
C15 | 0.3699 (3) | −0.1884 (2) | 0.0509 (2) | 0.0304 (9) | |
H15 | 0.3461 | −0.2544 | 0.0281 | 0.036* | |
C16 | 0.4941 (3) | −0.1270 (2) | 0.0682 (2) | 0.0268 (8) | |
H16 | 0.5528 | −0.1518 | 0.0560 | 0.032* | |
C21 | 0.8256 (3) | −0.0752 (2) | 0.1600 (2) | 0.0224 (8) | |
C22 | 0.9021 (3) | −0.1232 (2) | 0.1423 (2) | 0.0252 (8) | |
C23 | 0.9352 (3) | −0.1730 (2) | 0.1995 (3) | 0.0350 (9) | |
H23 | 0.9863 | −0.2053 | 0.1866 | 0.042* | |
C24 | 0.8921 (3) | −0.1746 (3) | 0.2750 (3) | 0.0394 (10) | |
H24 | 0.9147 | −0.2077 | 0.3136 | 0.047* | |
C25 | 0.8153 (3) | −0.1273 (3) | 0.2941 (2) | 0.0363 (9) | |
H25 | 0.7857 | −0.1290 | 0.3452 | 0.044* | |
C26 | 0.7826 (3) | −0.0774 (2) | 0.2373 (2) | 0.0293 (8) | |
H26 | 0.7317 | −0.0450 | 0.2506 | 0.035* | |
Br31 | 0.50331 (3) | 0.30046 (3) | 0.38136 (3) | 0.03634 (10) | |
Br41 | 0.98069 (3) | 0.66116 (3) | 0.88201 (2) | 0.03702 (10) | |
S31 | 0.69929 (8) | 0.42892 (6) | 0.57070 (6) | 0.0282 (2) | |
S41 | 0.78617 (8) | 0.52974 (7) | 0.69348 (6) | 0.0313 (2) | |
C31 | 0.6561 (3) | 0.4911 (2) | 0.4953 (2) | 0.0228 (8) | |
C32 | 0.5738 (3) | 0.4367 (2) | 0.4108 (2) | 0.0256 (8) | |
C33 | 0.5392 (3) | 0.4780 (3) | 0.3468 (2) | 0.0337 (9) | |
H33 | 0.4822 | 0.4399 | 0.2910 | 0.040* | |
C34 | 0.5904 (3) | 0.5774 (3) | 0.3665 (3) | 0.0386 (10) | |
H34 | 0.5695 | 0.6063 | 0.3231 | 0.046* | |
C35 | 0.6724 (3) | 0.6336 (3) | 0.4508 (3) | 0.0358 (9) | |
H35 | 0.7051 | 0.7002 | 0.4644 | 0.043* | |
C36 | 0.7057 (3) | 0.5911 (2) | 0.5144 (2) | 0.0277 (8) | |
H36 | 0.7617 | 0.6292 | 0.5706 | 0.033* | |
C41 | 0.9454 (3) | 0.5836 (2) | 0.6920 (2) | 0.0230 (8) | |
C42 | 1.0326 (3) | 0.6403 (2) | 0.7746 (2) | 0.0242 (8) | |
C43 | 1.1584 (3) | 0.6869 (2) | 0.7793 (2) | 0.0277 (8) | |
H43 | 1.2160 | 0.7253 | 0.8348 | 0.033* | |
C44 | 1.1968 (3) | 0.6757 (2) | 0.7011 (3) | 0.0303 (9) | |
H44 | 1.2809 | 0.7054 | 0.7040 | 0.036* | |
C45 | 1.1107 (3) | 0.6205 (2) | 0.6185 (2) | 0.0302 (9) | |
H45 | 1.1367 | 0.6146 | 0.5657 | 0.036* | |
C46 | 0.9853 (3) | 0.5739 (2) | 0.6140 (2) | 0.0268 (8) | |
H46 | 0.9279 | 0.5359 | 0.5583 | 0.032* | |
Br51 | 0.16503 (4) | 0.13950 (3) | 0.20227 (3) | 0.04086 (11) | |
Br61 | 0.36130 (3) | −0.12415 (3) | 0.58307 (3) | 0.04290 (11) | |
S51 | 0.25242 (8) | 0.03597 (7) | 0.33919 (6) | 0.0329 (2) | |
S61 | 0.26338 (8) | −0.04125 (7) | 0.42816 (6) | 0.0316 (2) | |
C51 | 0.1415 (3) | 0.0850 (2) | 0.3643 (2) | 0.0246 (8) | |
C52 | 0.1022 (3) | 0.1319 (2) | 0.3047 (2) | 0.0272 (8) | |
C53 | 0.0171 (3) | 0.1720 (2) | 0.3192 (3) | 0.0342 (9) | |
H53 | −0.0094 | 0.2019 | 0.2787 | 0.041* | |
C54 | −0.0286 (3) | 0.1676 (2) | 0.3941 (3) | 0.0374 (10) | |
H54 | −0.0866 | 0.1942 | 0.4037 | 0.045* | |
C55 | 0.0114 (3) | 0.1240 (2) | 0.4547 (3) | 0.0357 (9) | |
H55 | −0.0179 | 0.1228 | 0.5059 | 0.043* | |
C56 | 0.0948 (3) | 0.0823 (2) | 0.4391 (2) | 0.0301 (8) | |
H56 | 0.1201 | 0.0519 | 0.4795 | 0.036* | |
C61 | 0.3719 (3) | 0.0441 (2) | 0.5309 (2) | 0.0241 (8) | |
C62 | 0.4148 (3) | 0.0102 (2) | 0.5995 (3) | 0.0275 (8) | |
C63 | 0.4983 (3) | 0.0716 (3) | 0.6810 (3) | 0.0352 (9) | |
H63 | 0.5257 | 0.0471 | 0.7263 | 0.042* | |
C64 | 0.5407 (3) | 0.1692 (3) | 0.6951 (3) | 0.0371 (10) | |
H64 | 0.5971 | 0.2109 | 0.7499 | 0.045* | |
C65 | 0.4996 (3) | 0.2055 (3) | 0.6276 (3) | 0.0364 (9) | |
H65 | 0.5282 | 0.2715 | 0.6370 | 0.044* | |
C66 | 0.4161 (3) | 0.1432 (2) | 0.5462 (2) | 0.0299 (9) | |
H66 | 0.3889 | 0.1679 | 0.5010 | 0.036* | |
Br71 | 0.35381 (3) | 0.31781 (3) | 0.08740 (3) | 0.04085 (11) | |
Br81 | 1.09271 (4) | 0.61651 (3) | 0.11356 (3) | 0.04224 (11) | |
S71 | 0.64557 (8) | 0.41596 (6) | 0.11577 (6) | 0.0310 (2) | |
S81 | 0.81287 (8) | 0.49280 (7) | 0.09867 (6) | 0.0335 (2) | |
C71 | 0.5633 (3) | 0.4934 (2) | 0.1174 (2) | 0.0223 (8) | |
C72 | 0.4356 (3) | 0.4530 (2) | 0.1089 (2) | 0.0253 (8) | |
C73 | 0.3659 (3) | 0.5080 (3) | 0.1143 (2) | 0.0297 (9) | |
H73 | 0.2806 | 0.4795 | 0.1086 | 0.036* | |
C74 | 0.4229 (3) | 0.6051 (3) | 0.1283 (2) | 0.0362 (9) | |
H74 | 0.3761 | 0.6427 | 0.1322 | 0.043* | |
C75 | 0.5496 (3) | 0.6473 (2) | 0.1368 (2) | 0.0322 (9) | |
H75 | 0.5881 | 0.7131 | 0.1461 | 0.039* | |
C76 | 0.6195 (3) | 0.5912 (2) | 0.1313 (2) | 0.0271 (8) | |
H76 | 0.7048 | 0.6198 | 0.1369 | 0.033* | |
C81 | 0.9092 (3) | 0.5642 (2) | 0.2106 (2) | 0.0244 (8) | |
C82 | 1.0333 (3) | 0.6206 (2) | 0.2186 (2) | 0.0262 (8) | |
C83 | 1.1141 (3) | 0.6801 (2) | 0.3021 (3) | 0.0334 (9) | |
H83 | 1.1969 | 0.7170 | 0.3064 | 0.040* | |
C84 | 1.0718 (3) | 0.6846 (2) | 0.3792 (3) | 0.0341 (9) | |
H84 | 1.1256 | 0.7246 | 0.4355 | 0.041* | |
C85 | 0.9478 (3) | 0.6285 (2) | 0.3712 (2) | 0.0318 (9) | |
H85 | 0.9188 | 0.6308 | 0.4227 | 0.038* | |
C86 | 0.8677 (3) | 0.5696 (2) | 0.2879 (2) | 0.0279 (8) | |
H86 | 0.7848 | 0.5330 | 0.2835 | 0.033* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br11 | 0.02924 (19) | 0.02342 (19) | 0.0378 (2) | 0.01103 (16) | 0.00326 (17) | 0.00035 (17) |
Br21 | 0.02816 (19) | 0.0395 (2) | 0.0349 (2) | 0.01291 (18) | 0.00990 (18) | 0.00261 (19) |
S11 | 0.0233 (5) | 0.0255 (5) | 0.0432 (6) | 0.0099 (4) | 0.0069 (4) | 0.0101 (5) |
S21 | 0.0303 (5) | 0.0414 (6) | 0.0357 (6) | 0.0206 (5) | 0.0137 (5) | 0.0210 (5) |
C11 | 0.0222 (18) | 0.0232 (19) | 0.020 (2) | 0.0073 (15) | 0.0016 (15) | 0.0065 (16) |
C12 | 0.0271 (18) | 0.0206 (18) | 0.0169 (19) | 0.0085 (15) | 0.0035 (15) | 0.0061 (15) |
C13 | 0.0249 (19) | 0.034 (2) | 0.027 (2) | 0.0144 (17) | 0.0031 (16) | 0.0095 (18) |
C14 | 0.0272 (19) | 0.026 (2) | 0.033 (2) | 0.0033 (17) | 0.0024 (17) | 0.0097 (18) |
C15 | 0.037 (2) | 0.022 (2) | 0.025 (2) | 0.0078 (17) | 0.0025 (18) | 0.0060 (17) |
C16 | 0.032 (2) | 0.025 (2) | 0.025 (2) | 0.0132 (17) | 0.0068 (17) | 0.0069 (17) |
C21 | 0.0170 (16) | 0.0222 (18) | 0.022 (2) | 0.0043 (15) | −0.0001 (15) | 0.0054 (16) |
C22 | 0.0215 (18) | 0.0233 (19) | 0.022 (2) | 0.0054 (15) | −0.0001 (15) | −0.0010 (16) |
C23 | 0.035 (2) | 0.026 (2) | 0.040 (3) | 0.0150 (18) | 0.0002 (19) | 0.0060 (19) |
C24 | 0.044 (2) | 0.030 (2) | 0.037 (3) | 0.0112 (19) | −0.004 (2) | 0.015 (2) |
C25 | 0.036 (2) | 0.038 (2) | 0.026 (2) | 0.0049 (19) | 0.0047 (18) | 0.0112 (19) |
C26 | 0.0253 (19) | 0.031 (2) | 0.028 (2) | 0.0097 (17) | 0.0050 (17) | 0.0073 (18) |
Br31 | 0.0327 (2) | 0.0279 (2) | 0.0352 (2) | 0.00597 (17) | 0.00460 (18) | −0.00316 (18) |
Br41 | 0.0352 (2) | 0.0427 (2) | 0.0236 (2) | 0.01079 (19) | 0.00437 (18) | 0.00151 (19) |
S31 | 0.0245 (5) | 0.0263 (5) | 0.0272 (5) | 0.0052 (4) | 0.0011 (4) | 0.0078 (4) |
S41 | 0.0222 (5) | 0.0405 (6) | 0.0240 (5) | 0.0071 (4) | 0.0039 (4) | 0.0064 (5) |
C31 | 0.0197 (17) | 0.0253 (19) | 0.023 (2) | 0.0091 (15) | 0.0052 (16) | 0.0068 (17) |
C32 | 0.0224 (18) | 0.026 (2) | 0.025 (2) | 0.0082 (16) | 0.0053 (16) | 0.0041 (17) |
C33 | 0.031 (2) | 0.046 (3) | 0.023 (2) | 0.0168 (19) | 0.0043 (17) | 0.0073 (19) |
C34 | 0.046 (2) | 0.051 (3) | 0.040 (3) | 0.033 (2) | 0.020 (2) | 0.025 (2) |
C35 | 0.034 (2) | 0.029 (2) | 0.050 (3) | 0.0157 (19) | 0.018 (2) | 0.014 (2) |
C36 | 0.0217 (18) | 0.027 (2) | 0.031 (2) | 0.0085 (16) | 0.0056 (17) | 0.0059 (18) |
C41 | 0.0194 (17) | 0.0207 (18) | 0.028 (2) | 0.0076 (15) | 0.0037 (16) | 0.0070 (16) |
C42 | 0.0260 (18) | 0.0224 (19) | 0.022 (2) | 0.0113 (16) | 0.0011 (16) | 0.0034 (16) |
C43 | 0.0252 (19) | 0.0211 (19) | 0.028 (2) | 0.0049 (16) | −0.0032 (17) | 0.0052 (17) |
C44 | 0.0210 (18) | 0.023 (2) | 0.040 (3) | 0.0031 (16) | 0.0070 (18) | 0.0070 (18) |
C45 | 0.031 (2) | 0.031 (2) | 0.030 (2) | 0.0114 (18) | 0.0110 (18) | 0.0099 (18) |
C46 | 0.0251 (19) | 0.0236 (19) | 0.024 (2) | 0.0057 (16) | 0.0016 (16) | 0.0031 (16) |
Br51 | 0.0408 (2) | 0.0511 (3) | 0.0304 (2) | 0.0127 (2) | 0.00922 (19) | 0.0210 (2) |
Br61 | 0.0367 (2) | 0.0384 (2) | 0.0625 (3) | 0.01736 (19) | 0.0124 (2) | 0.0296 (2) |
S51 | 0.0331 (5) | 0.0470 (6) | 0.0271 (6) | 0.0221 (5) | 0.0114 (4) | 0.0148 (5) |
S61 | 0.0323 (5) | 0.0305 (5) | 0.0322 (6) | 0.0142 (4) | 0.0054 (4) | 0.0093 (5) |
C51 | 0.0205 (17) | 0.0242 (19) | 0.023 (2) | 0.0039 (15) | 0.0025 (16) | 0.0055 (16) |
C52 | 0.0236 (18) | 0.026 (2) | 0.022 (2) | 0.0015 (16) | 0.0019 (16) | 0.0051 (17) |
C53 | 0.030 (2) | 0.028 (2) | 0.040 (3) | 0.0076 (17) | 0.0010 (19) | 0.0152 (19) |
C54 | 0.032 (2) | 0.027 (2) | 0.052 (3) | 0.0133 (18) | 0.013 (2) | 0.008 (2) |
C55 | 0.038 (2) | 0.031 (2) | 0.036 (2) | 0.0100 (19) | 0.0149 (19) | 0.0070 (19) |
C56 | 0.033 (2) | 0.029 (2) | 0.028 (2) | 0.0122 (17) | 0.0068 (18) | 0.0100 (18) |
C61 | 0.0234 (18) | 0.030 (2) | 0.021 (2) | 0.0121 (16) | 0.0075 (16) | 0.0089 (17) |
C62 | 0.0256 (18) | 0.030 (2) | 0.036 (2) | 0.0142 (17) | 0.0146 (18) | 0.0173 (19) |
C63 | 0.029 (2) | 0.053 (3) | 0.029 (2) | 0.017 (2) | 0.0116 (18) | 0.019 (2) |
C64 | 0.029 (2) | 0.047 (3) | 0.026 (2) | 0.0105 (19) | 0.0060 (18) | 0.000 (2) |
C65 | 0.038 (2) | 0.031 (2) | 0.042 (3) | 0.0118 (19) | 0.017 (2) | 0.012 (2) |
C66 | 0.033 (2) | 0.029 (2) | 0.030 (2) | 0.0122 (18) | 0.0106 (18) | 0.0137 (19) |
Br71 | 0.0335 (2) | 0.0278 (2) | 0.0477 (3) | −0.00217 (17) | 0.00650 (19) | 0.0117 (2) |
Br81 | 0.0369 (2) | 0.0491 (3) | 0.0468 (3) | 0.0146 (2) | 0.0220 (2) | 0.0215 (2) |
S71 | 0.0255 (5) | 0.0243 (5) | 0.0378 (6) | 0.0084 (4) | 0.0028 (4) | 0.0056 (4) |
S81 | 0.0272 (5) | 0.0410 (6) | 0.0286 (6) | 0.0129 (4) | 0.0058 (4) | 0.0056 (5) |
C71 | 0.0215 (17) | 0.0244 (19) | 0.0186 (19) | 0.0084 (15) | 0.0005 (15) | 0.0067 (16) |
C72 | 0.0261 (19) | 0.0213 (19) | 0.020 (2) | 0.0016 (16) | 0.0015 (16) | 0.0053 (16) |
C73 | 0.0195 (18) | 0.040 (2) | 0.025 (2) | 0.0083 (17) | 0.0036 (16) | 0.0080 (18) |
C74 | 0.039 (2) | 0.041 (2) | 0.033 (2) | 0.025 (2) | 0.0030 (19) | 0.010 (2) |
C75 | 0.035 (2) | 0.024 (2) | 0.031 (2) | 0.0084 (17) | 0.0017 (18) | 0.0088 (18) |
C76 | 0.0221 (18) | 0.025 (2) | 0.027 (2) | 0.0038 (16) | 0.0003 (16) | 0.0078 (17) |
C81 | 0.0237 (18) | 0.027 (2) | 0.023 (2) | 0.0126 (16) | 0.0023 (16) | 0.0090 (17) |
C82 | 0.0291 (19) | 0.026 (2) | 0.027 (2) | 0.0130 (17) | 0.0095 (17) | 0.0101 (17) |
C83 | 0.0236 (19) | 0.027 (2) | 0.045 (3) | 0.0068 (17) | 0.0038 (19) | 0.012 (2) |
C84 | 0.033 (2) | 0.029 (2) | 0.033 (2) | 0.0100 (18) | −0.0029 (18) | 0.0060 (18) |
C85 | 0.036 (2) | 0.034 (2) | 0.027 (2) | 0.0149 (18) | 0.0073 (18) | 0.0116 (19) |
C86 | 0.0219 (18) | 0.029 (2) | 0.033 (2) | 0.0102 (16) | 0.0048 (17) | 0.0111 (18) |
Geometric parameters (Å, º) top
Br11—C12 | 1.898 (3) | Br51—C52 | 1.894 (3) |
Br21—C22 | 1.896 (3) | Br61—C62 | 1.901 (3) |
S11—C11 | 1.789 (3) | S51—C51 | 1.787 (3) |
S11—S21 | 2.0326 (12) | S51—S61 | 2.0317 (13) |
S21—C21 | 1.782 (3) | S61—C61 | 1.783 (3) |
C11—C16 | 1.384 (4) | C51—C56 | 1.383 (4) |
C11—C12 | 1.391 (4) | C51—C52 | 1.405 (4) |
C12—C13 | 1.384 (4) | C52—C53 | 1.377 (4) |
C13—C14 | 1.378 (4) | C53—C54 | 1.381 (5) |
C13—H13 | 0.9300 | C53—H53 | 0.9300 |
C14—C15 | 1.391 (4) | C54—C55 | 1.380 (5) |
C14—H14 | 0.9300 | C54—H54 | 0.9300 |
C15—C16 | 1.388 (4) | C55—C56 | 1.381 (4) |
C15—H15 | 0.9300 | C55—H55 | 0.9300 |
C16—H16 | 0.9300 | C56—H56 | 0.9300 |
C21—C22 | 1.382 (4) | C61—C62 | 1.381 (4) |
C21—C26 | 1.396 (4) | C61—C66 | 1.393 (4) |
C22—C23 | 1.385 (4) | C62—C63 | 1.379 (5) |
C23—C24 | 1.371 (5) | C63—C64 | 1.373 (5) |
C23—H23 | 0.9300 | C63—H63 | 0.9300 |
C24—C25 | 1.383 (5) | C64—C65 | 1.385 (5) |
C24—H24 | 0.9300 | C64—H64 | 0.9300 |
C25—C26 | 1.381 (4) | C65—C66 | 1.380 (5) |
C25—H25 | 0.9300 | C65—H65 | 0.9300 |
C26—H26 | 0.9300 | C66—H66 | 0.9300 |
Br31—C32 | 1.900 (3) | Br71—C72 | 1.906 (3) |
Br41—C42 | 1.895 (3) | Br81—C82 | 1.898 (3) |
S31—C31 | 1.782 (3) | S71—C71 | 1.783 (3) |
S31—S41 | 2.0291 (14) | S71—S81 | 2.0279 (13) |
S41—C41 | 1.785 (3) | S81—C81 | 1.787 (3) |
C31—C32 | 1.383 (4) | C71—C76 | 1.381 (4) |
C31—C36 | 1.398 (4) | C71—C72 | 1.391 (4) |
C32—C33 | 1.371 (4) | C72—C73 | 1.373 (4) |
C33—C34 | 1.389 (5) | C73—C74 | 1.371 (5) |
C33—H33 | 0.9300 | C73—H73 | 0.9300 |
C34—C35 | 1.385 (5) | C74—C75 | 1.383 (4) |
C34—H34 | 0.9300 | C74—H74 | 0.9300 |
C35—C36 | 1.375 (4) | C75—C76 | 1.388 (4) |
C35—H35 | 0.9300 | C75—H75 | 0.9300 |
C36—H36 | 0.9300 | C76—H76 | 0.9300 |
C41—C46 | 1.384 (4) | C81—C86 | 1.382 (4) |
C41—C42 | 1.389 (4) | C81—C82 | 1.393 (4) |
C42—C43 | 1.392 (4) | C82—C83 | 1.382 (5) |
C43—C44 | 1.378 (4) | C83—C84 | 1.384 (5) |
C43—H43 | 0.9300 | C83—H83 | 0.9300 |
C44—C45 | 1.379 (4) | C84—C85 | 1.392 (5) |
C44—H44 | 0.9300 | C84—H84 | 0.9300 |
C45—C46 | 1.390 (4) | C85—C86 | 1.376 (4) |
C45—H45 | 0.9300 | C85—H85 | 0.9300 |
C46—H46 | 0.9300 | C86—H86 | 0.9300 |
| | | |
Br11···Br71 | 3.8681 (9) | Br21···Br51i | 3.7056 (10) |
Br11···Br31 | 3.6755 (9) | Br31···Br61iii | 3.6926 (9) |
Br21···Br71i | 3.7499 (9) | Br51···Br71 | 3.8931 (10) |
Br21···Br41ii | 3.8056 (9) | | |
| | | |
C11—S11—S21 | 105.42 (11) | C51—S51—S61 | 104.42 (12) |
C21—S21—S11 | 105.55 (12) | C61—S61—S51 | 105.17 (12) |
C16—C11—C12 | 118.9 (3) | C56—C51—C52 | 118.2 (3) |
C16—C11—S11 | 124.2 (2) | C56—C51—S51 | 124.7 (3) |
C12—C11—S11 | 117.0 (2) | C52—C51—S51 | 117.0 (2) |
C13—C12—C11 | 121.2 (3) | C53—C52—C51 | 120.8 (3) |
C13—C12—Br11 | 118.1 (2) | C53—C52—Br51 | 119.2 (3) |
C11—C12—Br11 | 120.8 (2) | C51—C52—Br51 | 120.0 (2) |
C14—C13—C12 | 119.8 (3) | C52—C53—C54 | 119.8 (3) |
C14—C13—H13 | 120.1 | C52—C53—H53 | 120.1 |
C12—C13—H13 | 120.1 | C54—C53—H53 | 120.1 |
C13—C14—C15 | 119.5 (3) | C53—C54—C55 | 120.3 (3) |
C13—C14—H14 | 120.2 | C53—C54—H54 | 119.9 |
C15—C14—H14 | 120.2 | C55—C54—H54 | 119.9 |
C16—C15—C14 | 120.6 (3) | C54—C55—C56 | 119.8 (3) |
C16—C15—H15 | 119.7 | C54—C55—H55 | 120.1 |
C14—C15—H15 | 119.7 | C56—C55—H55 | 120.1 |
C11—C16—C15 | 120.1 (3) | C55—C56—C51 | 121.1 (3) |
C11—C16—H16 | 120.0 | C55—C56—H56 | 119.5 |
C15—C16—H16 | 120.0 | C51—C56—H56 | 119.5 |
C22—C21—C26 | 118.6 (3) | C62—C61—C66 | 117.9 (3) |
C22—C21—S21 | 117.3 (3) | C62—C61—S61 | 118.3 (3) |
C26—C21—S21 | 124.1 (2) | C66—C61—S61 | 123.8 (3) |
C21—C22—C23 | 121.0 (3) | C63—C62—C61 | 121.7 (3) |
C21—C22—Br21 | 120.0 (3) | C63—C62—Br61 | 117.8 (3) |
C23—C22—Br21 | 119.0 (3) | C61—C62—Br61 | 120.4 (3) |
C24—C23—C22 | 119.7 (3) | C64—C63—C62 | 119.6 (3) |
C24—C23—H23 | 120.2 | C64—C63—H63 | 120.2 |
C22—C23—H23 | 120.2 | C62—C63—H63 | 120.2 |
C23—C24—C25 | 120.4 (3) | C63—C64—C65 | 120.1 (4) |
C23—C24—H24 | 119.8 | C63—C64—H64 | 120.0 |
C25—C24—H24 | 119.8 | C65—C64—H64 | 120.0 |
C26—C25—C24 | 119.9 (3) | C66—C65—C64 | 119.8 (4) |
C26—C25—H25 | 120.1 | C66—C65—H65 | 120.1 |
C24—C25—H25 | 120.1 | C64—C65—H65 | 120.1 |
C25—C26—C21 | 120.4 (3) | C65—C66—C61 | 120.9 (3) |
C25—C26—H26 | 119.8 | C65—C66—H66 | 119.5 |
C21—C26—H26 | 119.8 | C61—C66—H66 | 119.5 |
C31—S31—S41 | 105.39 (12) | C71—S71—S81 | 104.62 (11) |
C41—S41—S31 | 104.64 (12) | C81—S81—S71 | 105.05 (12) |
C32—C31—C36 | 118.1 (3) | C76—C71—C72 | 118.3 (3) |
C32—C31—S31 | 117.8 (2) | C76—C71—S71 | 124.1 (2) |
C36—C31—S31 | 124.0 (3) | C72—C71—S71 | 117.5 (2) |
C33—C32—C31 | 122.0 (3) | C73—C72—C71 | 121.6 (3) |
C33—C32—Br31 | 118.1 (3) | C73—C72—Br71 | 118.8 (3) |
C31—C32—Br31 | 119.9 (3) | C71—C72—Br71 | 119.6 (2) |
C32—C33—C34 | 119.1 (4) | C74—C73—C72 | 119.6 (3) |
C32—C33—H33 | 120.4 | C74—C73—H73 | 120.2 |
C34—C33—H33 | 120.4 | C72—C73—H73 | 120.2 |
C35—C34—C33 | 120.0 (4) | C73—C74—C75 | 120.2 (3) |
C35—C34—H34 | 120.0 | C73—C74—H74 | 119.9 |
C33—C34—H34 | 120.0 | C75—C74—H74 | 119.9 |
C36—C35—C34 | 120.2 (3) | C74—C75—C76 | 119.9 (3) |
C36—C35—H35 | 119.9 | C74—C75—H75 | 120.0 |
C34—C35—H35 | 119.9 | C76—C75—H75 | 120.0 |
C35—C36—C31 | 120.5 (3) | C71—C76—C75 | 120.4 (3) |
C35—C36—H36 | 119.7 | C71—C76—H76 | 119.8 |
C31—C36—H36 | 119.7 | C75—C76—H76 | 119.8 |
C46—C41—C42 | 118.9 (3) | C86—C81—C82 | 118.7 (3) |
C46—C41—S41 | 124.0 (3) | C86—C81—S81 | 124.6 (3) |
C42—C41—S41 | 117.1 (3) | C82—C81—S81 | 116.7 (3) |
C41—C42—C43 | 120.8 (3) | C83—C82—C81 | 120.9 (3) |
C41—C42—Br41 | 120.3 (2) | C83—C82—Br81 | 119.3 (3) |
C43—C42—Br41 | 118.8 (3) | C81—C82—Br81 | 119.8 (3) |
C44—C43—C42 | 119.5 (3) | C82—C83—C84 | 120.0 (3) |
C44—C43—H43 | 120.2 | C82—C83—H83 | 120.0 |
C42—C43—H43 | 120.2 | C84—C83—H83 | 120.0 |
C43—C44—C45 | 120.2 (3) | C83—C84—C85 | 119.1 (4) |
C43—C44—H44 | 119.9 | C83—C84—H84 | 120.4 |
C45—C44—H44 | 119.9 | C85—C84—H84 | 120.4 |
C44—C45—C46 | 120.2 (3) | C86—C85—C84 | 120.6 (3) |
C44—C45—H45 | 119.9 | C86—C85—H85 | 119.7 |
C46—C45—H45 | 119.9 | C84—C85—H85 | 119.7 |
C41—C46—C45 | 120.4 (3) | C85—C86—C81 | 120.7 (3) |
C41—C46—H46 | 119.8 | C85—C86—H86 | 119.7 |
C45—C46—H46 | 119.8 | C81—C86—H86 | 119.7 |
| | | |
C11—S11—S21—C21 | −84.88 (16) | C51—S51—S61—C61 | −83.35 (16) |
S21—S11—C11—C16 | 14.1 (3) | S61—S51—C51—C56 | 10.2 (3) |
S21—S11—C11—C12 | −168.4 (2) | S61—S51—C51—C52 | −171.7 (2) |
C16—C11—C12—C13 | 2.4 (5) | C56—C51—C52—C53 | −1.6 (5) |
S11—C11—C12—C13 | −175.3 (3) | S51—C51—C52—C53 | −179.8 (3) |
C16—C11—C12—Br11 | −178.7 (2) | C56—C51—C52—Br51 | 179.0 (2) |
S11—C11—C12—Br11 | 3.5 (4) | S51—C51—C52—Br51 | 0.8 (4) |
C11—C12—C13—C14 | −1.5 (5) | C51—C52—C53—C54 | 1.2 (5) |
Br11—C12—C13—C14 | 179.6 (3) | Br51—C52—C53—C54 | −179.5 (3) |
C12—C13—C14—C15 | 0.4 (5) | C52—C53—C54—C55 | 0.5 (5) |
C13—C14—C15—C16 | −0.1 (5) | C53—C54—C55—C56 | −1.8 (5) |
C12—C11—C16—C15 | −2.1 (5) | C54—C55—C56—C51 | 1.3 (5) |
S11—C11—C16—C15 | 175.4 (3) | C52—C51—C56—C55 | 0.4 (5) |
C14—C15—C16—C11 | 1.0 (5) | S51—C51—C56—C55 | 178.4 (3) |
S11—S21—C21—C22 | −174.3 (2) | S51—S61—C61—C62 | −169.2 (2) |
S11—S21—C21—C26 | 6.8 (3) | S51—S61—C61—C66 | 10.9 (3) |
C26—C21—C22—C23 | 0.4 (5) | C66—C61—C62—C63 | 0.2 (5) |
S21—C21—C22—C23 | −178.5 (3) | S61—C61—C62—C63 | −179.7 (2) |
C26—C21—C22—Br21 | 179.7 (2) | C66—C61—C62—Br61 | −178.9 (2) |
S21—C21—C22—Br21 | 0.7 (4) | S61—C61—C62—Br61 | 1.2 (4) |
C21—C22—C23—C24 | −0.4 (5) | C61—C62—C63—C64 | −0.1 (5) |
Br21—C22—C23—C24 | −179.6 (3) | Br61—C62—C63—C64 | 179.0 (2) |
C22—C23—C24—C25 | 0.4 (5) | C62—C63—C64—C65 | 0.1 (5) |
C23—C24—C25—C26 | −0.6 (5) | C63—C64—C65—C66 | −0.1 (5) |
C24—C25—C26—C21 | 0.7 (5) | C64—C65—C66—C61 | 0.2 (5) |
C22—C21—C26—C25 | −0.6 (5) | C62—C61—C66—C65 | −0.2 (5) |
S21—C21—C26—C25 | 178.3 (3) | S61—C61—C66—C65 | 179.6 (3) |
C31—S31—S41—C41 | −85.78 (15) | C71—S71—S81—C81 | 85.61 (15) |
S41—S31—C31—C32 | −167.6 (2) | S81—S71—C71—C76 | −16.9 (3) |
S41—S31—C31—C36 | 16.2 (3) | S81—S71—C71—C72 | 166.6 (2) |
C36—C31—C32—C33 | −0.8 (5) | C76—C71—C72—C73 | −0.3 (5) |
S31—C31—C32—C33 | −177.2 (2) | S71—C71—C72—C73 | 176.4 (3) |
C36—C31—C32—Br31 | −179.9 (2) | C76—C71—C72—Br71 | 178.8 (2) |
S31—C31—C32—Br31 | 3.7 (3) | S71—C71—C72—Br71 | −4.4 (4) |
C31—C32—C33—C34 | 1.4 (5) | C71—C72—C73—C74 | 0.2 (5) |
Br31—C32—C33—C34 | −179.4 (2) | Br71—C72—C73—C74 | −179.0 (3) |
C32—C33—C34—C35 | −1.8 (5) | C72—C73—C74—C75 | 0.1 (5) |
C33—C34—C35—C36 | 1.5 (5) | C73—C74—C75—C76 | −0.2 (5) |
C34—C35—C36—C31 | −0.8 (5) | C72—C71—C76—C75 | 0.3 (5) |
C32—C31—C36—C35 | 0.4 (4) | S71—C71—C76—C75 | −176.2 (3) |
S31—C31—C36—C35 | 176.6 (2) | C74—C75—C76—C71 | 0.0 (5) |
S31—S41—C41—C46 | 15.6 (3) | S71—S81—C81—C86 | −6.1 (3) |
S31—S41—C41—C42 | −166.1 (2) | S71—S81—C81—C82 | 176.5 (2) |
C46—C41—C42—C43 | 0.0 (5) | C86—C81—C82—C83 | 0.8 (5) |
S41—C41—C42—C43 | −178.4 (2) | S81—C81—C82—C83 | 178.4 (2) |
C46—C41—C42—Br41 | 176.6 (2) | C86—C81—C82—Br81 | −179.0 (2) |
S41—C41—C42—Br41 | −1.8 (4) | S81—C81—C82—Br81 | −1.5 (4) |
C41—C42—C43—C44 | −0.6 (5) | C81—C82—C83—C84 | −0.5 (5) |
Br41—C42—C43—C44 | −177.3 (2) | Br81—C82—C83—C84 | 179.3 (2) |
C42—C43—C44—C45 | 1.5 (5) | C82—C83—C84—C85 | 0.3 (5) |
C43—C44—C45—C46 | −1.7 (5) | C83—C84—C85—C86 | −0.4 (5) |
C42—C41—C46—C45 | −0.2 (5) | C84—C85—C86—C81 | 0.7 (5) |
S41—C41—C46—C45 | 178.1 (2) | C82—C81—C86—C85 | −0.9 (5) |
C44—C45—C46—C41 | 1.1 (5) | S81—C81—C86—C85 | −178.3 (2) |
Symmetry codes: (i) −x+1, −y, −z; (ii) x, y−1, z−1; (iii) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···S21 | 0.93 | 2.73 | 3.232 (3) | 114 |
C26—H26···S11 | 0.93 | 2.71 | 3.216 (4) | 115 |
C36—H36···S41 | 0.93 | 2.74 | 3.230 (4) | 114 |
C46—H46···S31 | 0.93 | 2.71 | 3.205 (3) | 114 |
C56—H56···S61 | 0.93 | 2.70 | 3.202 (3) | 115 |
C66—H66···S51 | 0.93 | 2.70 | 3.206 (4) | 115 |
C76—H76···S81 | 0.93 | 2.71 | 3.207 (3) | 114 |
C86—H86···S71 | 0.93 | 2.70 | 3.208 (4) | 115 |
C44—H44···Br11iv | 0.93 | 2.99 | 3.743 (3) | 139 |
Symmetry code: (iv) −x+2, −y+1, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C12H8Br2S2 | C12H8Br2S2 |
Mr | 376.12 | 376.12 |
Crystal system, space group | Orthorhombic, Pbca | Triclinic, P1 |
Temperature (K) | 150 | 150 |
a, b, c (Å) | 7.6844 (10), 14.4240 (18), 22.378 (3) | 11.8186 (19), 15.489 (3), 15.653 (3) |
α, β, γ (°) | 90, 90, 90 | 102.122 (5), 100.393 (5), 110.001 (5) |
V (Å3) | 2480.4 (6) | 2531.4 (8) |
Z | 8 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 6.84 | 6.70 |
Crystal size (mm) | 0.38 × 0.20 × 0.16 | 0.13 × 0.11 × 0.06 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD with an Oxford Cryosystems low-temperature device diffractometer | Bruker SMART APEX CCD with an Oxford Cryosystems low-temperature device diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.211, 0.335 | 0.408, 0.669 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18462, 2537, 2224 | 22934, 13188, 8387 |
Rint | 0.028 | 0.031 |
(sin θ/λ)max (Å−1) | 0.626 | 0.678 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.019, 0.049, 1.02 | 0.035, 0.060, 1.00 |
No. of reflections | 2537 | 11915 |
No. of parameters | 145 | 577 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.22 | 0.98, −1.03 |
Selected geometric parameters (Å, º) for (I) topBr11—C12 | 1.897 (2) | S11—S21 | 2.0270 (7) |
Br21—C22 | 1.897 (2) | S21—C21 | 1.780 (2) |
S11—C11 | 1.785 (2) | | |
| | | |
C11—S11—S21 | 104.78 (7) | C11—C12—Br11 | 119.41 (15) |
C21—S21—S11 | 105.64 (7) | C22—C21—S21 | 117.61 (15) |
C12—C11—S11 | 118.20 (15) | C26—C21—S21 | 124.15 (15) |
C16—C11—S11 | 123.71 (15) | C23—C22—Br21 | 118.86 (15) |
C13—C12—Br11 | 119.02 (15) | C21—C22—Br21 | 119.56 (15) |
| | | |
C11—S11—S21—C21 | −83.34 (9) | S11—S21—C21—C22 | −174.69 (14) |
S21—S11—C11—C12 | −172.68 (14) | S11—S21—C21—C26 | 7.46 (19) |
S21—S11—C11—C16 | 8.33 (18) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···S21 | 0.93 | 2.67 | 3.185 (2) | 115 |
C26—H26···S11 | 0.93 | 2.71 | 3.215 (2) | 115 |
C25—H25···S21i | 0.93 | 2.96 | 3.607 (2) | 128 |
C24—H24···S21i | 0.93 | 2.99 | 3.620 (2) | 126 |
C26—H26···Br11ii | 0.93 | 3.04 | 3.882 (2) | 151 |
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, y, −z+3/2. |
Selected geometric parameters (Å, º) for (II) topBr11—C12 | 1.898 (3) | Br51—C52 | 1.894 (3) |
Br21—C22 | 1.896 (3) | Br61—C62 | 1.901 (3) |
S11—C11 | 1.789 (3) | S51—C51 | 1.787 (3) |
S11—S21 | 2.0326 (12) | S51—S61 | 2.0317 (13) |
S21—C21 | 1.782 (3) | S61—C61 | 1.783 (3) |
Br31—C32 | 1.900 (3) | Br71—C72 | 1.906 (3) |
Br41—C42 | 1.895 (3) | Br81—C82 | 1.898 (3) |
S31—C31 | 1.782 (3) | S71—C71 | 1.783 (3) |
S31—S41 | 2.0291 (14) | S71—S81 | 2.0279 (13) |
S41—C41 | 1.785 (3) | S81—C81 | 1.787 (3) |
| | | |
Br11···Br71 | 3.8681 (9) | Br21···Br51i | 3.7056 (10) |
Br11···Br31 | 3.6755 (9) | Br31···Br61iii | 3.6926 (9) |
Br21···Br71i | 3.7499 (9) | Br51···Br71 | 3.8931 (10) |
Br21···Br41ii | 3.8056 (9) | | |
| | | |
C11—S11—S21 | 105.42 (11) | C42—C41—S41 | 117.1 (3) |
C21—S21—S11 | 105.55 (12) | C51—S51—S61 | 104.42 (12) |
C16—C11—S11 | 124.2 (2) | C61—S61—S51 | 105.17 (12) |
C12—C11—S11 | 117.0 (2) | C56—C51—S51 | 124.7 (3) |
C22—C21—S21 | 117.3 (3) | C52—C51—S51 | 117.0 (2) |
C26—C21—S21 | 124.1 (2) | C62—C61—S61 | 118.3 (3) |
C31—S31—S41 | 105.39 (12) | C66—C61—S61 | 123.8 (3) |
C41—S41—S31 | 104.64 (12) | C71—S71—S81 | 104.62 (11) |
C32—C31—S31 | 117.8 (2) | C81—S81—S71 | 105.05 (12) |
C36—C31—S31 | 124.0 (3) | C76—C71—S71 | 124.1 (2) |
C32—C33—C34 | 119.1 (4) | C72—C71—S71 | 117.5 (2) |
C32—C33—H33 | 120.4 | C86—C81—S81 | 124.6 (3) |
C34—C33—H33 | 120.4 | C82—C81—S81 | 116.7 (3) |
C46—C41—S41 | 124.0 (3) | | |
| | | |
C11—S11—S21—C21 | −84.88 (16) | C51—S51—S61—C61 | −83.35 (16) |
S21—S11—C11—C16 | 14.1 (3) | S61—S51—C51—C56 | 10.2 (3) |
S21—S11—C11—C12 | −168.4 (2) | S61—S51—C51—C52 | −171.7 (2) |
S11—S21—C21—C22 | −174.3 (2) | S51—S61—C61—C62 | −169.2 (2) |
S11—S21—C21—C26 | 6.8 (3) | S51—S61—C61—C66 | 10.9 (3) |
C31—S31—S41—C41 | −85.78 (15) | C71—S71—S81—C81 | 85.61 (15) |
S41—S31—C31—C32 | −167.6 (2) | S81—S71—C71—C76 | −16.9 (3) |
S41—S31—C31—C36 | 16.2 (3) | S81—S71—C71—C72 | 166.6 (2) |
S31—S41—C41—C46 | 15.6 (3) | S71—S81—C81—C86 | −6.1 (3) |
S31—S41—C41—C42 | −166.1 (2) | S71—S81—C81—C82 | 176.5 (2) |
Symmetry codes: (i) −x+1, −y, −z; (ii) x, y−1, z−1; (iii) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···S21 | 0.93 | 2.73 | 3.232 (3) | 114 |
C26—H26···S11 | 0.93 | 2.71 | 3.216 (4) | 115 |
C36—H36···S41 | 0.93 | 2.74 | 3.230 (4) | 114 |
C46—H46···S31 | 0.93 | 2.71 | 3.205 (3) | 114 |
C56—H56···S61 | 0.93 | 2.70 | 3.202 (3) | 115 |
C66—H66···S51 | 0.93 | 2.70 | 3.206 (4) | 115 |
C76—H76···S81 | 0.93 | 2.71 | 3.207 (3) | 114 |
C86—H86···S71 | 0.93 | 2.70 | 3.208 (4) | 115 |
C44—H44···Br11iv | 0.93 | 2.99 | 3.743 (3) | 139 |
Symmetry code: (iv) −x+2, −y+1, −z+1. |
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The electronic and structural properties of transition and main group metal complexes coordinated by S-donor atoms have attracted intense research interest over the past 30 years (Kasper et al., 1976; Kobayashi et al., 1982; Pullen et al., 1998; Kie-Moon et al. 2001). Although some works have appeared describing the behaviour of the disulfide group as a donor (Valde et al., 1983; Matsubayashi et al., 1990; Ohio, 1993; Kobayashi et al., 1990), it has not been subjected to such detailed study as a number of other donor groups (Balch et al., 1968; Gray, 1966; Schrauzer & Mayweg, 1966). This neglect is in part because the disulfide group tends to give bridged or polymeric metal complexes, which are extremely insoluble and are accordingly difficult to characterize or study. We report here the structures of two polymorphs of bis(2-bromophenyl)disulfide isolated during attempts to synthesize zinc(II) or cadmium(II) complexes of the ligand. There are no significant differences in the bond lengths observed for the two polymorphs (Figs. 1 and 2 and Tables 1 and 2). The substituents are essentially coplanar with their respective ring, giving molecules in which all the atoms lie in two planes. The dihedral angle between the two phenyl rings in the orthorhombic form is 83.34 (9)°, while an average value of 84.90 (2)° is observed for the triclinic form. The values of the S11—S21—C21—C22, S11—S21—C21—C26, S21—S11—C11—C12 and S21—S11—C11—C16 torsion angles in the orthorhombic form [−174.7 (2), 7.5 (2), −172.7 (2) and 8.3 (2)°, respectively] are slightly different from the corresponding mean angles in the triclinic system [−169.9 (2), 11.1 (2), −169.2 (2) and 13.5 (2)°, respectively]. The orthorhombic form crystallizes with one independent molecule in each asymmetric unit (Fig. 1), while in the triclinic form there are four (Fig. 2). In both polymorphs, phenyl rings participate in significant intramolecular C—H···S interactions, with average H···S distances of 2.69 and 2.72 Å (for the orthorhombic and triclinic forms, respectively). The crystal packing for the orthorhombic form shows repulsion between Br atoms, leading to a staggered arrangement of Br atoms in adjacent molecules. The staggered conformation in the orthorhombic form involves intermolecular C—H···S and C—H···Br hydrogen bonds, which are not present in the triclinic form (Fig. 3 and Table 2). The orthorhombic form exhibits mean H···S and H···Br distances of 2.98 and 3.04 Å, respectively. In contrast, the triclinic form shows eclipsed dispositions for the br atoms in different molecules (Fig. 4), which minimizes the intermolecular hydrogen bonding predominant in the orthorhombic form (Table 5). As a result of this eclipsed conformation between adjacent Br atoms and the large covalent radius of the Br atoms (1.14 Å), an accumulation of charge exists around each Br atom. The higher electron density around the Br atoms produces closer [3.770 (9) Å] repulsive contacts between them (Table 4), giving rise to less efficient packing, which can be seen by comparing the cell volumes [2480.4 (6) Å3 and 2531.4 (8) Å3] and crystal densities (2.014 and 1.974 g cm−3) for the orthorhombic and triclinic forms.