Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112020604/sk3438sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112020604/sk3438Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112020604/sk3438IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112020604/sk3438IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112020604/sk3438IVsup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112020604/sk3438Vsup6.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112020604/sk3438Isup7.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112020604/sk3438IIsup8.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112020604/sk3438IIIsup9.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112020604/sk3438IVsup10.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112020604/sk3438Vsup11.cml |
CCDC references: 889378; 889379; 889380; 889381; 889382
For related literature, see: Allen (2002); Braunschweig et al. (2008); Brown et al. (1998); Grisby & Power (1996); Haberecht et al. (2004); Heilmann-Brohl, Schödel, Bolte, Wagner & Lerner (2011); Lorbach et al. (2012); Olmstead et al. (2003).
All experiments were carried out under dry nitrogen or argon with strict exclusion of air and moisture using standard Schlenk techniques. The starting materials were purchased from commercial sources and used without further purification. The solvents were distilled from sodium/benzophenone prior to use. C6D6 was dried over molecular sieves and stored under dry nitrogen. The NMR spectra were recorded on Bruker AM 250, DPX 250, Avance 300 and Avance 400 spectrometers. Abbreviations: s = singlet, d = doublet, t = triplet, q = quartet, quin = quintet, mult = multiplet and br = broad [pt = ?].
For the synthesis of (I), trimethylphenylsilane (8.5 ml, 49.2 mmol, 1 equivalent) was dissolved in hexane (10 ml) and cooled down to 273 K. BBr3 (5 ml, 52.9 mmol, 1.1 equivalents) was added rapidly via a syringe. The mixture was allowed to warm slowly to room temperature and was then heated under reflux for 2 h. During removal of all volatile components in vacuo, dibromoborylbenzene was obtained as colourless crystals (yield 11.46 g, 94%). 1H NMR (250.1 MHz, C6D6, δ, p.p.m.): 6.95 (pt, 3JHH = 7.5 Hz, 2H, Ph—Hmeta), 7.11 (t, 3JHH = 7.4 Hz, 1H, Ph—Hpara), 8.04 (d, 3JHH = 7.6 Hz, 2H, Ph—Hortho). 11B NMR (128.4 MHz, C6D6, δ, p.p.m.): 57.4 (h1/2 = 90 Hz). 13C NMR (62.9 MHz, C6D6, δ, p.p.m.): 128.3 (Ph—Cmeta), 135.3 (Ph—Cpara), 138.0 (Ph—Cortho), n.b. (Ph—Cipso). When a benzene (0.6 ml) solution of (I) (0.1 mmol) in the presence of an excess of HNMe2 was left to stand for one week, single crystals of the composition PhBBr2.HNMe2, (IV), could be isolated.
For the synthesis of (II), 1,4-bis(trimethylsilyl)benzene (4.95 g, 21.8 mmol, 1 equivalent) and BBr3 (2.3 ml, 23.9 mmol, 1.1 equivalents) were dissolved in hexane (15 ml) and stirred for 24 h at room temperature. The solution was evaporated to dryness in vacuo to give (II) as colourless crystals (yield 6.13 g, 86%). 1H NMR (400.1 MHz, C6D6, δ, p.p.m.): 0.13 (s, 9H, SiMe3), 7.34 (d, 3JHH = 8.1 Hz, 2H, Ph—H2/6), 8.08 (d, 3JHH = 8.1 Hz, 2H, Ph—H3/5). 11B NMR (128.4 MHz, C6D6, δ, p.p.m.): 57.0 (h1/2 = 280 Hz). 13C NMR (100.6 MHz, C6D6, δ, p.p.m.): -1.5 (SiMe3), 133.3 (CAr), 136.8 (CAr), 150.1 (SiCAr), n.b. (BCAr). When a benzene (0.6 ml) solution of (II) (0.1 mmol) in the presence of an excess of SMe2 was left to stand for one week, single crystals of the composition Me3SiC6H4BBr2.SMe2, (V), could be isolated.
For the synthesis of (III), 4-bromo-1-(trimethylsilyl)benzene (4.3 ml, 21.8 mmol, 1 equivalent) was added in a solution of BBr3 (2.3 ml, 23.9 mmol, 1.1 equivalents) and hexane (15 ml). After the mixture had been heated under reflux for 4 h, the solvent was removed in vacuo to give single crystals of (III) (yield 5.87 g, 82%). 1H NMR (400.1 MHz, C6D6, δ, p.p.m.): 7.12 (d, 3JHH = 8.3 Hz, 2H, Ph—H2/6), 7.66 (d, 3JHH = 8.3 Hz, 2H, Ph—H3/5). 11B NMR (128.4 MHz, C6D6, δ, p.p.m.): 57.4 (h1/2 = 180 Hz). 13C NMR (100.6 MHz, C6D6, δ, p.p.m.): 131.6 (CAr), 131.7 (BrCAr), 139.0 (CAr), n.b. (BCAr).
The H atoms were initially located by difference Fourier synthesis. Subsequently, H atoms bonded to C atoms were refined using a riding model, with methyl C—H = 0.98 Å, aromatic C—H = 0.95 Å and Uiso(H) = 1.5Ueq(C) for methyl or 1.2Ueq(C) for aromatic H atoms. The coordinates of the H atom bonded to the N atom in (IV) were refined with Uiso(H) = 1.2Ueq(N). Due to imposed crystallographic mirror symmetry, the central ring of (V), the S atom and one of the methyl groups bonded to the S atom are disordered over two equally occupied positions.
For all compounds, data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C6H5BBr2 | F(000) = 928 |
Mr = 247.73 | Dx = 2.140 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 8202 reflections |
a = 11.0841 (16) Å | θ = 3.7–26.1° |
b = 7.8287 (12) Å | µ = 10.45 mm−1 |
c = 17.720 (2) Å | T = 173 K |
V = 1537.6 (4) Å3 | Plate, colourless |
Z = 8 | 0.29 × 0.17 × 0.09 mm |
Stoe IPDS II two-circle diffractometer | 1517 independent reflections |
Radiation source: fine-focus sealed tube | 1089 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.081 |
ω scans | θmax = 26.1°, θmin = 3.7° |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | h = −13→13 |
Tmin = 0.152, Tmax = 0.453 | k = −9→9 |
14258 measured reflections | l = −20→21 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0417P)2] where P = (Fo2 + 2Fc2)/3 |
1517 reflections | (Δ/σ)max < 0.001 |
82 parameters | Δρmax = 0.59 e Å−3 |
0 restraints | Δρmin = −1.07 e Å−3 |
C6H5BBr2 | V = 1537.6 (4) Å3 |
Mr = 247.73 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 11.0841 (16) Å | µ = 10.45 mm−1 |
b = 7.8287 (12) Å | T = 173 K |
c = 17.720 (2) Å | 0.29 × 0.17 × 0.09 mm |
Stoe IPDS II two-circle diffractometer | 1517 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | 1089 reflections with I > 2σ(I) |
Tmin = 0.152, Tmax = 0.453 | Rint = 0.081 |
14258 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.59 e Å−3 |
1517 reflections | Δρmin = −1.07 e Å−3 |
82 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 | ||
B1 | 0.3987 (6) | 0.3634 (9) | 0.6298 (4) | 0.0317 (14) | |
Br1 | 0.27993 (6) | 0.49129 (9) | 0.68469 (4) | 0.0418 (2) | |
Br2 | 0.52293 (5) | 0.26062 (10) | 0.68982 (4) | 0.0456 (2) | |
C1 | 0.3939 (5) | 0.3424 (7) | 0.5439 (3) | 0.0282 (12) | |
C2 | 0.4773 (5) | 0.2416 (8) | 0.5056 (4) | 0.0335 (13) | |
H2 | 0.5398 | 0.1865 | 0.5330 | 0.040* | |
C3 | 0.4706 (6) | 0.2207 (8) | 0.4287 (4) | 0.0409 (15) | |
H3 | 0.5273 | 0.1493 | 0.4039 | 0.049* | |
C4 | 0.3819 (6) | 0.3025 (9) | 0.3869 (4) | 0.0400 (14) | |
H4 | 0.3773 | 0.2879 | 0.3337 | 0.048* | |
C5 | 0.3005 (6) | 0.4058 (9) | 0.4244 (4) | 0.0383 (14) | |
H5 | 0.2402 | 0.4640 | 0.3964 | 0.046* | |
C6 | 0.3050 (5) | 0.4259 (8) | 0.5009 (4) | 0.0330 (13) | |
H6 | 0.2476 | 0.4970 | 0.5253 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
B1 | 0.031 (3) | 0.035 (3) | 0.030 (4) | −0.004 (3) | 0.005 (3) | 0.005 (3) |
Br1 | 0.0396 (4) | 0.0480 (4) | 0.0377 (4) | 0.0049 (3) | 0.0047 (2) | −0.0098 (3) |
Br2 | 0.0331 (3) | 0.0690 (5) | 0.0348 (4) | 0.0059 (3) | −0.0021 (3) | 0.0118 (3) |
C1 | 0.023 (3) | 0.030 (3) | 0.032 (3) | −0.003 (2) | 0.001 (2) | 0.004 (2) |
C2 | 0.024 (3) | 0.041 (4) | 0.035 (3) | 0.000 (2) | 0.001 (2) | −0.002 (3) |
C3 | 0.038 (3) | 0.044 (4) | 0.041 (4) | −0.005 (3) | 0.011 (3) | −0.010 (3) |
C4 | 0.043 (3) | 0.047 (4) | 0.030 (3) | −0.008 (3) | 0.000 (3) | −0.006 (3) |
C5 | 0.034 (3) | 0.045 (4) | 0.036 (4) | −0.004 (3) | −0.003 (3) | 0.007 (3) |
C6 | 0.026 (3) | 0.035 (3) | 0.037 (4) | −0.001 (2) | 0.002 (2) | −0.002 (3) |
B1—C1 | 1.533 (9) | C3—C4 | 1.388 (10) |
B1—Br2 | 1.917 (7) | C3—H3 | 0.9500 |
B1—Br1 | 1.919 (7) | C4—C5 | 1.381 (9) |
C1—C2 | 1.392 (8) | C4—H4 | 0.9500 |
C1—C6 | 1.407 (8) | C5—C6 | 1.365 (9) |
C2—C3 | 1.373 (9) | C5—H5 | 0.9500 |
C2—H2 | 0.9500 | C6—H6 | 0.9500 |
C1—B1—Br2 | 122.1 (5) | C4—C3—H3 | 119.6 |
C1—B1—Br1 | 122.4 (5) | C5—C4—C3 | 118.4 (6) |
Br2—B1—Br1 | 115.5 (4) | C5—C4—H4 | 120.8 |
C2—C1—C6 | 117.7 (6) | C3—C4—H4 | 120.8 |
C2—C1—B1 | 121.5 (5) | C6—C5—C4 | 121.4 (6) |
C6—C1—B1 | 120.8 (5) | C6—C5—H5 | 119.3 |
C3—C2—C1 | 121.0 (6) | C4—C5—H5 | 119.3 |
C3—C2—H2 | 119.5 | C5—C6—C1 | 120.6 (6) |
C1—C2—H2 | 119.5 | C5—C6—H6 | 119.7 |
C2—C3—C4 | 120.9 (6) | C1—C6—H6 | 119.7 |
C2—C3—H3 | 119.6 | ||
Br2—B1—C1—C2 | 2.6 (8) | C1—C2—C3—C4 | 1.4 (9) |
Br1—B1—C1—C2 | −176.6 (4) | C2—C3—C4—C5 | 0.0 (10) |
Br2—B1—C1—C6 | −176.9 (4) | C3—C4—C5—C6 | −1.0 (10) |
Br1—B1—C1—C6 | 3.9 (8) | C4—C5—C6—C1 | 0.5 (9) |
C6—C1—C2—C3 | −1.9 (8) | C2—C1—C6—C5 | 1.0 (8) |
B1—C1—C2—C3 | 178.6 (6) | B1—C1—C6—C5 | −179.5 (6) |
C9H13BBr2Si | F(000) = 624 |
Mr = 319.91 | Dx = 1.669 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 15049 reflections |
a = 6.7452 (5) Å | θ = 3.3–26.1° |
b = 15.2390 (12) Å | µ = 6.42 mm−1 |
c = 12.4123 (10) Å | T = 173 K |
β = 93.841 (6)° | Block, colourless |
V = 1273.00 (17) Å3 | 0.29 × 0.25 × 0.25 mm |
Z = 4 |
Stoe IPDS II two-circle diffractometer | 2235 independent reflections |
Radiation source: fine-focus sealed tube | 1942 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
ω scans | θmax = 25.0°, θmin = 3.3° |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | h = −7→8 |
Tmin = 0.258, Tmax = 0.297 | k = −18→18 |
19196 measured reflections | l = −14→14 |
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)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.084 | w = 1/[σ2(Fo2) + (0.0311P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
2235 reflections | Δρmax = 0.46 e Å−3 |
119 parameters | Δρmin = −0.37 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0112 (10) |
C9H13BBr2Si | V = 1273.00 (17) Å3 |
Mr = 319.91 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.7452 (5) Å | µ = 6.42 mm−1 |
b = 15.2390 (12) Å | T = 173 K |
c = 12.4123 (10) Å | 0.29 × 0.25 × 0.25 mm |
β = 93.841 (6)° |
Stoe IPDS II two-circle diffractometer | 2235 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | 1942 reflections with I > 2σ(I) |
Tmin = 0.258, Tmax = 0.297 | Rint = 0.064 |
19196 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.46 e Å−3 |
2235 reflections | Δρmin = −0.37 e Å−3 |
119 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 | ||
Si1 | 0.84456 (13) | 0.81255 (7) | 0.56483 (7) | 0.0410 (2) | |
B1 | 0.4716 (6) | 0.4874 (3) | 0.3170 (3) | 0.0470 (9) | |
Br1 | 0.61752 (6) | 0.38165 (3) | 0.30091 (4) | 0.06453 (18) | |
Br2 | 0.20678 (6) | 0.48883 (3) | 0.25108 (3) | 0.05994 (17) | |
C1 | 0.7300 (5) | 0.7162 (2) | 0.4892 (2) | 0.0397 (7) | |
C2 | 0.5444 (5) | 0.7203 (3) | 0.4322 (3) | 0.0466 (8) | |
H2 | 0.4733 | 0.7742 | 0.4304 | 0.056* | |
C3 | 0.4613 (5) | 0.6484 (2) | 0.3784 (3) | 0.0465 (8) | |
H3 | 0.3334 | 0.6536 | 0.3419 | 0.056* | |
C4 | 0.5617 (5) | 0.5678 (2) | 0.3764 (2) | 0.0409 (7) | |
C5 | 0.7501 (5) | 0.5635 (2) | 0.4323 (3) | 0.0449 (8) | |
H5 | 0.8232 | 0.5102 | 0.4323 | 0.054* | |
C6 | 0.8302 (5) | 0.6354 (2) | 0.4870 (3) | 0.0459 (8) | |
H6 | 0.9572 | 0.6301 | 0.5244 | 0.055* | |
C7 | 1.0707 (6) | 0.8454 (3) | 0.4967 (3) | 0.0613 (10) | |
H7A | 1.0326 | 0.8645 | 0.4228 | 0.092* | |
H7B | 1.1615 | 0.7953 | 0.4948 | 0.092* | |
H7C | 1.1371 | 0.8938 | 0.5366 | 0.092* | |
C8 | 0.9122 (6) | 0.7764 (3) | 0.7058 (3) | 0.0552 (9) | |
H8A | 1.0076 | 0.7279 | 0.7050 | 0.083* | |
H8B | 0.7925 | 0.7567 | 0.7393 | 0.083* | |
H8C | 0.9720 | 0.8255 | 0.7472 | 0.083* | |
C9 | 0.6651 (6) | 0.9049 (3) | 0.5639 (3) | 0.0576 (9) | |
H9A | 0.6319 | 0.9235 | 0.4893 | 0.086* | |
H9B | 0.7246 | 0.9542 | 0.6053 | 0.086* | |
H9C | 0.5440 | 0.8858 | 0.5966 | 0.086* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1 | 0.0370 (4) | 0.0426 (6) | 0.0433 (5) | 0.0023 (4) | 0.0019 (3) | −0.0027 (4) |
B1 | 0.050 (2) | 0.051 (3) | 0.0395 (19) | −0.0052 (18) | 0.0032 (15) | 0.0007 (16) |
Br1 | 0.0647 (3) | 0.0493 (3) | 0.0789 (3) | 0.00308 (18) | −0.00029 (19) | −0.01577 (19) |
Br2 | 0.0561 (2) | 0.0596 (3) | 0.0615 (3) | −0.00835 (18) | −0.01491 (16) | 0.00134 (17) |
C1 | 0.0400 (16) | 0.0421 (19) | 0.0370 (15) | 0.0028 (14) | 0.0022 (12) | 0.0016 (13) |
C2 | 0.0417 (17) | 0.046 (2) | 0.0512 (18) | 0.0078 (15) | 0.0001 (13) | −0.0030 (15) |
C3 | 0.0388 (16) | 0.050 (2) | 0.0495 (17) | 0.0041 (15) | −0.0047 (13) | 0.0008 (16) |
C4 | 0.0433 (16) | 0.043 (2) | 0.0364 (15) | 0.0004 (15) | 0.0034 (12) | 0.0021 (13) |
C5 | 0.0447 (17) | 0.039 (2) | 0.0496 (18) | 0.0081 (15) | −0.0025 (14) | 0.0027 (14) |
C6 | 0.0436 (17) | 0.045 (2) | 0.0473 (17) | 0.0080 (15) | −0.0065 (13) | −0.0014 (15) |
C7 | 0.0487 (19) | 0.070 (3) | 0.066 (2) | −0.0100 (19) | 0.0118 (16) | −0.008 (2) |
C8 | 0.059 (2) | 0.058 (3) | 0.0483 (19) | 0.0006 (18) | −0.0029 (16) | −0.0059 (17) |
C9 | 0.056 (2) | 0.047 (2) | 0.069 (2) | 0.0081 (18) | 0.0004 (17) | −0.0080 (18) |
Si1—C9 | 1.856 (4) | C4—C5 | 1.408 (5) |
Si1—C8 | 1.861 (4) | C5—C6 | 1.381 (5) |
Si1—C7 | 1.862 (4) | C5—H5 | 0.9500 |
Si1—C1 | 1.881 (4) | C6—H6 | 0.9500 |
B1—C4 | 1.535 (5) | C7—H7A | 0.9800 |
B1—Br1 | 1.906 (4) | C7—H7B | 0.9800 |
B1—Br2 | 1.915 (4) | C7—H7C | 0.9800 |
C1—C2 | 1.397 (5) | C8—H8A | 0.9800 |
C1—C6 | 1.405 (5) | C8—H8B | 0.9800 |
C2—C3 | 1.383 (5) | C8—H8C | 0.9800 |
C2—H2 | 0.9500 | C9—H9A | 0.9800 |
C3—C4 | 1.403 (5) | C9—H9B | 0.9800 |
C3—H3 | 0.9500 | C9—H9C | 0.9800 |
C9—Si1—C8 | 110.44 (19) | C4—C5—H5 | 119.5 |
C9—Si1—C7 | 110.3 (2) | C5—C6—C1 | 122.1 (3) |
C8—Si1—C7 | 110.49 (19) | C5—C6—H6 | 118.9 |
C9—Si1—C1 | 110.06 (17) | C1—C6—H6 | 118.9 |
C8—Si1—C1 | 107.74 (17) | Si1—C7—H7A | 109.5 |
C7—Si1—C1 | 107.75 (17) | Si1—C7—H7B | 109.5 |
C4—B1—Br1 | 122.4 (3) | H7A—C7—H7B | 109.5 |
C4—B1—Br2 | 121.6 (3) | Si1—C7—H7C | 109.5 |
Br1—B1—Br2 | 116.0 (2) | H7A—C7—H7C | 109.5 |
C2—C1—C6 | 116.5 (3) | H7B—C7—H7C | 109.5 |
C2—C1—Si1 | 122.8 (3) | Si1—C8—H8A | 109.5 |
C6—C1—Si1 | 120.8 (2) | Si1—C8—H8B | 109.5 |
C3—C2—C1 | 122.0 (3) | H8A—C8—H8B | 109.5 |
C3—C2—H2 | 119.0 | Si1—C8—H8C | 109.5 |
C1—C2—H2 | 119.0 | H8A—C8—H8C | 109.5 |
C2—C3—C4 | 121.4 (3) | H8B—C8—H8C | 109.5 |
C2—C3—H3 | 119.3 | Si1—C9—H9A | 109.5 |
C4—C3—H3 | 119.3 | Si1—C9—H9B | 109.5 |
C3—C4—C5 | 117.0 (3) | H9A—C9—H9B | 109.5 |
C3—C4—B1 | 122.1 (3) | Si1—C9—H9C | 109.5 |
C5—C4—B1 | 120.9 (3) | H9A—C9—H9C | 109.5 |
C6—C5—C4 | 121.0 (3) | H9B—C9—H9C | 109.5 |
C6—C5—H5 | 119.5 | ||
C9—Si1—C1—C2 | 6.3 (3) | C2—C3—C4—B1 | −180.0 (3) |
C8—Si1—C1—C2 | 126.7 (3) | Br1—B1—C4—C3 | 173.2 (3) |
C7—Si1—C1—C2 | −114.0 (3) | Br2—B1—C4—C3 | −5.1 (4) |
C9—Si1—C1—C6 | −174.1 (3) | Br1—B1—C4—C5 | −7.2 (4) |
C8—Si1—C1—C6 | −53.6 (3) | Br2—B1—C4—C5 | 174.6 (3) |
C7—Si1—C1—C6 | 65.6 (3) | C3—C4—C5—C6 | 0.6 (5) |
C6—C1—C2—C3 | 1.4 (5) | B1—C4—C5—C6 | −179.1 (3) |
Si1—C1—C2—C3 | −179.0 (3) | C4—C5—C6—C1 | −0.6 (5) |
C1—C2—C3—C4 | −1.4 (5) | C2—C1—C6—C5 | −0.4 (5) |
C2—C3—C4—C5 | 0.4 (5) | Si1—C1—C6—C5 | 180.0 (3) |
C6H4BBr3 | Dx = 2.488 Mg m−3 |
Mr = 326.63 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 4723 reflections |
Hall symbol: -I 4ad | θ = 2.8–25.6° |
a = 29.446 (3) Å | µ = 13.80 mm−1 |
c = 4.0228 (4) Å | T = 173 K |
V = 3488.0 (8) Å3 | Needle, colourless |
Z = 16 | 0.26 × 0.11 × 0.11 mm |
F(000) = 2400 |
Stoe IPDS II two-circle diffractometer | 1544 independent reflections |
Radiation source: fine-focus sealed tube | 1111 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.097 |
ω scans | θmax = 25.0°, θmin = 2.8° |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | h = −35→35 |
Tmin = 0.124, Tmax = 0.312 | k = −35→35 |
12710 measured reflections | l = −4→4 |
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)] = 0.070 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0652P)2] where P = (Fo2 + 2Fc2)/3 |
1544 reflections | (Δ/σ)max < 0.001 |
91 parameters | Δρmax = 0.90 e Å−3 |
0 restraints | Δρmin = −1.08 e Å−3 |
C6H4BBr3 | Z = 16 |
Mr = 326.63 | Mo Kα radiation |
Tetragonal, I41/a | µ = 13.80 mm−1 |
a = 29.446 (3) Å | T = 173 K |
c = 4.0228 (4) Å | 0.26 × 0.11 × 0.11 mm |
V = 3488.0 (8) Å3 |
Stoe IPDS II two-circle diffractometer | 1544 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | 1111 reflections with I > 2σ(I) |
Tmin = 0.124, Tmax = 0.312 | Rint = 0.097 |
12710 measured reflections |
R[F2 > 2σ(F2)] = 0.070 | 0 restraints |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.90 e Å−3 |
1544 reflections | Δρmin = −1.08 e Å−3 |
91 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 | 0.28681 (5) | 0.69376 (5) | 0.6423 (3) | 0.0440 (4) | |
Br2 | 0.25646 (5) | 0.59109 (5) | 0.8282 (3) | 0.0442 (4) | |
Br3 | 0.04802 (4) | 0.68695 (5) | 0.0725 (3) | 0.0388 (4) | |
B1 | 0.2401 (5) | 0.6487 (5) | 0.635 (3) | 0.038 (3) | |
C1 | 0.1923 (4) | 0.6581 (4) | 0.502 (3) | 0.029 (3) | |
C2 | 0.1825 (5) | 0.6991 (4) | 0.353 (3) | 0.036 (3) | |
H2 | 0.2057 | 0.7214 | 0.3349 | 0.043* | |
C3 | 0.1394 (4) | 0.7090 (4) | 0.227 (3) | 0.032 (3) | |
H3 | 0.1329 | 0.7378 | 0.1317 | 0.039* | |
C4 | 0.1066 (4) | 0.6755 (4) | 0.245 (3) | 0.032 (3) | |
C5 | 0.1155 (4) | 0.6337 (4) | 0.387 (3) | 0.037 (3) | |
H5 | 0.0927 | 0.6109 | 0.3989 | 0.044* | |
C6 | 0.1588 (5) | 0.6261 (4) | 0.512 (3) | 0.041 (3) | |
H6 | 0.1654 | 0.5974 | 0.6083 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0338 (7) | 0.0484 (9) | 0.0498 (8) | −0.0035 (6) | −0.0031 (6) | 0.0050 (6) |
Br2 | 0.0422 (8) | 0.0429 (8) | 0.0475 (8) | 0.0092 (6) | 0.0010 (6) | 0.0098 (6) |
Br3 | 0.0334 (7) | 0.0436 (8) | 0.0394 (7) | −0.0018 (5) | −0.0035 (5) | 0.0019 (6) |
B1 | 0.047 (9) | 0.046 (9) | 0.020 (7) | 0.005 (7) | 0.007 (6) | −0.007 (6) |
C1 | 0.032 (7) | 0.034 (7) | 0.022 (6) | −0.005 (5) | 0.003 (4) | −0.009 (4) |
C2 | 0.048 (8) | 0.017 (6) | 0.042 (7) | −0.010 (5) | 0.007 (6) | 0.007 (5) |
C3 | 0.036 (7) | 0.023 (6) | 0.038 (7) | 0.002 (5) | 0.006 (5) | −0.001 (5) |
C4 | 0.033 (7) | 0.041 (7) | 0.023 (6) | 0.009 (6) | −0.003 (5) | −0.006 (5) |
C5 | 0.038 (7) | 0.027 (7) | 0.045 (7) | −0.002 (5) | −0.005 (6) | −0.008 (5) |
C6 | 0.060 (9) | 0.022 (6) | 0.041 (7) | 0.008 (6) | 0.006 (6) | −0.003 (5) |
Br1—B1 | 1.911 (16) | C2—H2 | 0.9500 |
Br2—B1 | 1.926 (16) | C3—C4 | 1.381 (18) |
Br3—C4 | 1.890 (12) | C3—H3 | 0.9500 |
B1—C1 | 1.53 (2) | C4—C5 | 1.385 (18) |
C1—C6 | 1.365 (18) | C5—C6 | 1.388 (19) |
C1—C2 | 1.381 (17) | C5—H5 | 0.9500 |
C2—C3 | 1.396 (18) | C6—H6 | 0.9500 |
C1—B1—Br1 | 122.8 (10) | C2—C3—H3 | 121.1 |
C1—B1—Br2 | 121.9 (11) | C3—C4—C5 | 121.7 (12) |
Br1—B1—Br2 | 115.2 (8) | C3—C4—Br3 | 119.5 (9) |
C6—C1—C2 | 117.7 (12) | C5—C4—Br3 | 118.8 (10) |
C6—C1—B1 | 122.0 (12) | C4—C5—C6 | 117.7 (12) |
C2—C1—B1 | 120.2 (11) | C4—C5—H5 | 121.1 |
C1—C2—C3 | 122.0 (11) | C6—C5—H5 | 121.1 |
C1—C2—H2 | 119.0 | C1—C6—C5 | 122.9 (12) |
C3—C2—H2 | 119.0 | C1—C6—H6 | 118.5 |
C4—C3—C2 | 117.9 (11) | C5—C6—H6 | 118.5 |
C4—C3—H3 | 121.1 | ||
Br1—B1—C1—C6 | −177.1 (9) | C2—C3—C4—C5 | 1.0 (18) |
Br2—B1—C1—C6 | −0.2 (16) | C2—C3—C4—Br3 | −179.2 (9) |
Br1—B1—C1—C2 | 5.9 (16) | C3—C4—C5—C6 | −0.2 (18) |
Br2—B1—C1—C2 | −177.2 (9) | Br3—C4—C5—C6 | −180.0 (9) |
C6—C1—C2—C3 | 2.6 (18) | C2—C1—C6—C5 | −1.8 (18) |
B1—C1—C2—C3 | 179.7 (11) | B1—C1—C6—C5 | −178.8 (11) |
C1—C2—C3—C4 | −2.3 (18) | C4—C5—C6—C1 | 0.6 (19) |
C8H12BBr2N | F(000) = 568 |
Mr = 292.82 | Dx = 1.819 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4532 reflections |
a = 8.9095 (9) Å | θ = 3.5–25.8° |
b = 9.2874 (13) Å | µ = 7.53 mm−1 |
c = 12.9306 (13) Å | T = 173 K |
β = 92.249 (8)° | Block, colourless |
V = 1069.1 (2) Å3 | 0.19 × 0.09 × 0.05 mm |
Z = 4 |
Stoe IPDS II two-circle diffractometer | 2004 independent reflections |
Radiation source: fine-focus sealed tube | 1413 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.082 |
ω scans | θmax = 25.6°, θmin = 3.5° |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | h = −10→9 |
Tmin = 0.329, Tmax = 0.705 | k = −10→11 |
6363 measured reflections | l = −15→15 |
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)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0472P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max < 0.001 |
2004 reflections | Δρmax = 0.98 e Å−3 |
113 parameters | Δρmin = −0.96 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0035 (7) |
C8H12BBr2N | V = 1069.1 (2) Å3 |
Mr = 292.82 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.9095 (9) Å | µ = 7.53 mm−1 |
b = 9.2874 (13) Å | T = 173 K |
c = 12.9306 (13) Å | 0.19 × 0.09 × 0.05 mm |
β = 92.249 (8)° |
Stoe IPDS II two-circle diffractometer | 2004 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | 1413 reflections with I > 2σ(I) |
Tmin = 0.329, Tmax = 0.705 | Rint = 0.082 |
6363 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.98 e Å−3 |
2004 reflections | Δρmin = −0.96 e Å−3 |
113 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 | ||
B1 | 0.1562 (8) | 0.1816 (7) | 0.4299 (4) | 0.0238 (15) | |
Br1 | 0.19350 (9) | −0.00845 (7) | 0.35462 (4) | 0.0406 (2) | |
Br2 | −0.06537 (8) | 0.23148 (8) | 0.39628 (5) | 0.0402 (2) | |
N1 | 0.1676 (6) | 0.1454 (6) | 0.5521 (3) | 0.0257 (11) | |
H1 | 0.102 (8) | 0.080 (8) | 0.563 (5) | 0.031* | |
C1 | 0.3197 (8) | 0.0914 (8) | 0.5886 (4) | 0.0388 (17) | |
H1A | 0.3478 | 0.0087 | 0.5464 | 0.058* | |
H1B | 0.3164 | 0.0621 | 0.6612 | 0.058* | |
H1C | 0.3941 | 0.1683 | 0.5818 | 0.058* | |
C2 | 0.1254 (9) | 0.2710 (8) | 0.6194 (4) | 0.0364 (16) | |
H2A | 0.0255 | 0.3062 | 0.5973 | 0.055* | |
H2B | 0.1991 | 0.3485 | 0.6127 | 0.055* | |
H2C | 0.1242 | 0.2398 | 0.6917 | 0.055* | |
C11 | 0.2681 (7) | 0.3076 (6) | 0.3985 (3) | 0.0236 (13) | |
C12 | 0.4201 (7) | 0.2776 (7) | 0.3746 (4) | 0.0298 (14) | |
H12 | 0.4544 | 0.1807 | 0.3756 | 0.036* | |
C13 | 0.5186 (9) | 0.3861 (8) | 0.3500 (5) | 0.0404 (18) | |
H13 | 0.6194 | 0.3637 | 0.3346 | 0.049* | |
C14 | 0.4701 (9) | 0.5266 (8) | 0.3479 (4) | 0.0408 (19) | |
H14 | 0.5373 | 0.6010 | 0.3297 | 0.049* | |
C15 | 0.3260 (10) | 0.5606 (8) | 0.3719 (5) | 0.0447 (19) | |
H15 | 0.2945 | 0.6583 | 0.3716 | 0.054* | |
C16 | 0.2252 (8) | 0.4517 (7) | 0.3967 (4) | 0.0326 (15) | |
H16 | 0.1253 | 0.4766 | 0.4128 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
B1 | 0.033 (4) | 0.025 (4) | 0.014 (3) | 0.003 (3) | 0.001 (2) | 0.002 (2) |
Br1 | 0.0747 (6) | 0.0223 (3) | 0.0258 (3) | −0.0075 (4) | 0.0150 (3) | −0.0051 (2) |
Br2 | 0.0300 (4) | 0.0557 (5) | 0.0345 (3) | −0.0036 (4) | −0.0027 (2) | 0.0187 (3) |
N1 | 0.030 (3) | 0.029 (3) | 0.017 (2) | −0.002 (3) | 0.001 (2) | −0.0004 (19) |
C1 | 0.040 (4) | 0.049 (4) | 0.026 (3) | 0.008 (4) | −0.005 (3) | 0.005 (3) |
C2 | 0.049 (4) | 0.039 (4) | 0.021 (3) | −0.007 (4) | 0.002 (2) | −0.010 (3) |
C11 | 0.036 (4) | 0.022 (3) | 0.012 (2) | −0.001 (3) | 0.001 (2) | −0.001 (2) |
C12 | 0.028 (3) | 0.037 (4) | 0.025 (3) | 0.004 (3) | 0.003 (2) | 0.006 (2) |
C13 | 0.032 (4) | 0.056 (5) | 0.034 (3) | −0.010 (4) | 0.006 (3) | 0.015 (3) |
C14 | 0.052 (5) | 0.048 (5) | 0.023 (3) | −0.031 (4) | −0.003 (3) | 0.003 (3) |
C15 | 0.070 (6) | 0.020 (3) | 0.045 (3) | −0.011 (4) | 0.012 (4) | −0.005 (3) |
C16 | 0.044 (4) | 0.021 (3) | 0.034 (3) | −0.001 (3) | 0.006 (3) | −0.002 (2) |
B1—C11 | 1.600 (9) | C2—H2C | 0.9800 |
B1—N1 | 1.615 (7) | C11—C16 | 1.392 (9) |
B1—Br1 | 2.049 (6) | C11—C12 | 1.429 (9) |
B1—Br2 | 2.058 (7) | C12—C13 | 1.381 (9) |
N1—C1 | 1.503 (9) | C12—H12 | 0.9500 |
N1—C2 | 1.512 (8) | C13—C14 | 1.375 (10) |
N1—H1 | 0.85 (7) | C13—H13 | 0.9500 |
C1—H1A | 0.9800 | C14—C15 | 1.369 (11) |
C1—H1B | 0.9800 | C14—H14 | 0.9500 |
C1—H1C | 0.9800 | C15—C16 | 1.399 (10) |
C2—H2A | 0.9800 | C15—H15 | 0.9500 |
C2—H2B | 0.9800 | C16—H16 | 0.9500 |
C11—B1—N1 | 112.6 (5) | N1—C2—H2C | 109.5 |
C11—B1—Br1 | 113.3 (4) | H2A—C2—H2C | 109.5 |
N1—B1—Br1 | 106.3 (4) | H2B—C2—H2C | 109.5 |
C11—B1—Br2 | 112.6 (4) | C16—C11—C12 | 116.5 (6) |
N1—B1—Br2 | 106.1 (4) | C16—C11—B1 | 122.3 (6) |
Br1—B1—Br2 | 105.4 (3) | C12—C11—B1 | 121.2 (5) |
C1—N1—C2 | 108.6 (5) | C13—C12—C11 | 121.6 (6) |
C1—N1—B1 | 113.4 (5) | C13—C12—H12 | 119.2 |
C2—N1—B1 | 113.2 (5) | C11—C12—H12 | 119.2 |
C1—N1—H1 | 109 (5) | C14—C13—C12 | 119.6 (7) |
C2—N1—H1 | 105 (4) | C14—C13—H13 | 120.2 |
B1—N1—H1 | 107 (4) | C12—C13—H13 | 120.2 |
N1—C1—H1A | 109.5 | C15—C14—C13 | 120.8 (7) |
N1—C1—H1B | 109.5 | C15—C14—H14 | 119.6 |
H1A—C1—H1B | 109.5 | C13—C14—H14 | 119.6 |
N1—C1—H1C | 109.5 | C14—C15—C16 | 120.1 (7) |
H1A—C1—H1C | 109.5 | C14—C15—H15 | 119.9 |
H1B—C1—H1C | 109.5 | C16—C15—H15 | 119.9 |
N1—C2—H2A | 109.5 | C11—C16—C15 | 121.4 (7) |
N1—C2—H2B | 109.5 | C11—C16—H16 | 119.3 |
H2A—C2—H2B | 109.5 | C15—C16—H16 | 119.3 |
C11—B1—N1—C1 | −62.4 (7) | Br1—B1—C11—C12 | −34.4 (6) |
Br1—B1—N1—C1 | 62.2 (6) | Br2—B1—C11—C12 | −153.9 (4) |
Br2—B1—N1—C1 | 174.1 (4) | C16—C11—C12—C13 | −0.7 (8) |
C11—B1—N1—C2 | 61.9 (7) | B1—C11—C12—C13 | −178.3 (5) |
Br1—B1—N1—C2 | −173.4 (4) | C11—C12—C13—C14 | −0.2 (9) |
Br2—B1—N1—C2 | −61.6 (6) | C12—C13—C14—C15 | 1.2 (9) |
N1—B1—C11—C16 | −91.3 (6) | C13—C14—C15—C16 | −1.3 (9) |
Br1—B1—C11—C16 | 148.1 (5) | C12—C11—C16—C15 | 0.6 (8) |
Br2—B1—C11—C16 | 28.6 (6) | B1—C11—C16—C15 | 178.2 (5) |
N1—B1—C11—C12 | 86.2 (6) | C14—C15—C16—C11 | 0.4 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Br1i | 0.85 (7) | 2.96 (7) | 3.705 (6) | 147 (6) |
N1—H1···Br2i | 0.85 (7) | 2.96 (7) | 3.684 (5) | 143 (6) |
Symmetry code: (i) −x, −y, −z+1. |
C11H19BBr2SSi | F(000) = 760 |
Mr = 382.04 | Dx = 1.576 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 4391 reflections |
a = 6.6950 (5) Å | θ = 2.5–26.1° |
b = 11.0880 (8) Å | µ = 5.21 mm−1 |
c = 21.6870 (16) Å | T = 173 K |
V = 1609.9 (2) Å3 | Needle, colourless |
Z = 4 | 0.20 × 0.10 × 0.05 mm |
Stoe IPDS II two-circle diffractometer | 1705 independent reflections |
Radiation source: fine-focus sealed tube | 1146 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
ω scans | θmax = 26.3°, θmin = 2.1° |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | h = −8→8 |
Tmin = 0.422, Tmax = 0.781 | k = −13→13 |
22983 measured reflections | l = −26→26 |
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)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.083 | w = 1/[σ2(Fo2) + (0.0454P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.90 | (Δ/σ)max < 0.001 |
1705 reflections | Δρmax = 0.40 e Å−3 |
110 parameters | Δρmin = −0.56 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0045 (5) |
C11H19BBr2SSi | V = 1609.9 (2) Å3 |
Mr = 382.04 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 6.6950 (5) Å | µ = 5.21 mm−1 |
b = 11.0880 (8) Å | T = 173 K |
c = 21.6870 (16) Å | 0.20 × 0.10 × 0.05 mm |
Stoe IPDS II two-circle diffractometer | 1705 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | 1146 reflections with I > 2σ(I) |
Tmin = 0.422, Tmax = 0.781 | Rint = 0.073 |
22983 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.90 | Δρmax = 0.40 e Å−3 |
1705 reflections | Δρmin = −0.56 e Å−3 |
110 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | Occ. (<1) | |
Br1 | 0.37440 (6) | 0.39945 (4) | 0.329307 (19) | 0.04263 (17) | |
B1 | 0.4191 (9) | 0.2500 | 0.3810 (3) | 0.0364 (16) | |
Si1 | 0.0014 (2) | 0.2500 | 0.64318 (8) | 0.0446 (5) | |
C11 | 0.0842 (7) | 0.1116 (5) | 0.6848 (2) | 0.0569 (14) | |
H11A | 0.0398 | 0.0400 | 0.6621 | 0.085* | |
H11B | 0.0260 | 0.1108 | 0.7263 | 0.085* | |
H11C | 0.2302 | 0.1112 | 0.6879 | 0.085* | |
C12 | −0.2773 (8) | 0.2500 | 0.6347 (3) | 0.0528 (18) | |
H12A | −0.3193 | 0.1770 | 0.6127 | 0.079* | 0.50 |
H12B | −0.3188 | 0.3214 | 0.6113 | 0.079* | 0.50 |
H12C | −0.3394 | 0.2516 | 0.6756 | 0.079* | |
C1 | 0.3037 (7) | 0.2500 | 0.4451 (3) | 0.0336 (13) | |
C2 | 0.1890 (12) | 0.1637 (7) | 0.4669 (4) | 0.0324 (17) | 0.50 |
H2 | 0.1679 | 0.0945 | 0.4419 | 0.039* | 0.50 |
C3 | 0.0962 (11) | 0.1672 (7) | 0.5247 (4) | 0.0349 (18) | 0.50 |
H3 | 0.0099 | 0.1024 | 0.5352 | 0.042* | 0.50 |
C2' | 0.3222 (11) | 0.1412 (8) | 0.4839 (4) | 0.0358 (19) | 0.50 |
H2' | 0.3952 | 0.0736 | 0.4693 | 0.043* | 0.50 |
C3' | 0.2327 (12) | 0.1373 (8) | 0.5421 (4) | 0.0365 (19) | 0.50 |
H3' | 0.2422 | 0.0676 | 0.5674 | 0.044* | 0.50 |
C4 | 0.1185 (8) | 0.2500 | 0.5637 (3) | 0.0434 (15) | |
S1 | 0.7046 (2) | 0.2722 (4) | 0.40129 (8) | 0.0332 (12) | 0.50 |
C1S | 0.8347 (7) | 0.2500 | 0.3299 (3) | 0.0457 (15) | |
H1S1 | 0.7872 | 0.1758 | 0.3102 | 0.068* | 0.50 |
H1S2 | 0.9783 | 0.2434 | 0.3379 | 0.068* | 0.50 |
H1S3 | 0.8097 | 0.3187 | 0.3025 | 0.068* | 0.50 |
C2S | 0.7549 (13) | 0.1347 (8) | 0.4431 (4) | 0.044 (2) | 0.50 |
H2S1 | 0.7309 | 0.0562 | 0.4237 | 0.067* | 0.50 |
H2S2 | 0.6723 | 0.1419 | 0.4802 | 0.067* | 0.50 |
H2S3 | 0.8962 | 0.1415 | 0.4544 | 0.067* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0363 (2) | 0.0504 (3) | 0.0412 (3) | 0.0024 (2) | −0.00076 (19) | 0.0077 (2) |
B1 | 0.025 (3) | 0.048 (4) | 0.036 (4) | 0.000 | 0.001 (2) | 0.000 |
Si1 | 0.0298 (8) | 0.0701 (13) | 0.0340 (9) | 0.000 | 0.0022 (7) | 0.000 |
C11 | 0.043 (3) | 0.083 (4) | 0.044 (3) | 0.005 (3) | 0.0031 (19) | 0.004 (3) |
C12 | 0.033 (3) | 0.073 (5) | 0.053 (4) | 0.000 | 0.007 (3) | 0.000 |
C1 | 0.024 (2) | 0.044 (4) | 0.033 (3) | 0.000 | −0.003 (2) | 0.000 |
C2 | 0.034 (4) | 0.028 (4) | 0.035 (4) | −0.003 (3) | 0.002 (3) | −0.007 (4) |
C3 | 0.031 (4) | 0.035 (5) | 0.039 (5) | −0.001 (4) | 0.001 (3) | 0.004 (4) |
C2' | 0.022 (4) | 0.043 (5) | 0.042 (5) | 0.009 (3) | 0.000 (3) | −0.001 (4) |
C3' | 0.032 (4) | 0.037 (5) | 0.040 (5) | 0.005 (4) | 0.009 (4) | 0.010 (4) |
C4 | 0.023 (2) | 0.075 (5) | 0.033 (3) | 0.000 | −0.002 (3) | 0.000 |
S1 | 0.0215 (6) | 0.040 (4) | 0.0386 (9) | −0.0008 (9) | −0.0012 (6) | 0.0011 (10) |
C1S | 0.025 (3) | 0.062 (4) | 0.050 (4) | 0.000 | 0.006 (3) | 0.000 |
C2S | 0.039 (5) | 0.045 (6) | 0.049 (5) | 0.006 (4) | −0.002 (4) | 0.012 (4) |
Br1—B1 | 2.022 (4) | C1—C2' | 1.476 (9) |
B1—C1 | 1.592 (8) | C2—C3 | 1.399 (11) |
B1—S1 | 1.977 (6) | C2—H2 | 0.9500 |
B1—S1i | 1.977 (6) | C3—C4 | 1.258 (9) |
B1—Br1i | 2.022 (4) | C3—H3 | 0.9500 |
Si1—C11i | 1.865 (5) | C2'—C3' | 1.398 (11) |
Si1—C11 | 1.865 (5) | C2'—H2' | 0.9500 |
Si1—C12 | 1.874 (6) | C3'—C4 | 1.538 (9) |
Si1—C4 | 1.893 (6) | C3'—H3' | 0.9500 |
C11—H11A | 0.9800 | S1—C2S | 1.806 (9) |
C11—H11B | 0.9800 | S1—C1S | 1.794 (6) |
C11—H11C | 0.9800 | C1S—H1S1 | 0.9800 |
C12—H12A | 0.9800 | C1S—H1S2 | 0.9800 |
C12—H12B | 0.9800 | C1S—H1S3 | 0.9800 |
C12—H12C | 0.9800 | C2S—H2S1 | 0.9800 |
C1—C2 | 1.315 (8) | C2S—H2S2 | 0.9800 |
C1—C2i | 1.315 (8) | C2S—H2S3 | 0.9800 |
C1—C2'i | 1.476 (9) | ||
C1—B1—S1 | 105.9 (4) | C4—C3—C2 | 124.8 (7) |
C1—B1—S1i | 105.9 (4) | C2—C3—C3i | 91.6 (5) |
C1—B1—Br1i | 114.3 (2) | C4—C3—H3 | 117.6 |
S1—B1—Br1i | 111.6 (2) | C2—C3—H3 | 117.6 |
S1i—B1—Br1i | 99.5 (2) | C3i—C3—H3 | 139.2 |
C1—B1—Br1 | 114.3 (2) | C3'—C2'—C1 | 120.3 (7) |
S1—B1—Br1 | 99.5 (2) | C3'—C2'—H2' | 119.9 |
S1i—B1—Br1 | 111.6 (2) | C1—C2'—H2' | 119.9 |
Br1i—B1—Br1 | 110.0 (3) | C2'—C3'—C4 | 117.6 (7) |
C11i—Si1—C11 | 110.8 (3) | C2'—C3'—H3' | 121.2 |
C11i—Si1—C12 | 110.08 (18) | C4—C3'—H3' | 121.2 |
C11—Si1—C12 | 110.08 (18) | C3—C4—C3i | 93.7 (8) |
C11i—Si1—C4 | 108.50 (17) | C3—C4—C3'i | 116.5 (6) |
C11—Si1—C4 | 108.50 (17) | C3i—C4—C3' | 116.5 (6) |
C12—Si1—C4 | 108.8 (3) | C3'i—C4—C3' | 108.7 (7) |
Si1—C11—H11A | 109.5 | C3—C4—Si1 | 124.3 (4) |
Si1—C11—H11B | 109.5 | C3i—C4—Si1 | 124.3 (4) |
H11A—C11—H11B | 109.5 | C3'i—C4—Si1 | 118.9 (4) |
Si1—C11—H11C | 109.5 | C3'—C4—Si1 | 118.9 (4) |
H11A—C11—H11C | 109.5 | C2Si—S1—C2S | 104.5 (7) |
H11B—C11—H11C | 109.5 | C2Si—S1—C1S | 122.5 (4) |
Si1—C12—H12A | 109.5 | C2S—S1—C1S | 103.1 (4) |
Si1—C12—H12B | 109.5 | C2Si—S1—B1 | 117.7 (4) |
H12A—C12—H12B | 109.5 | C2S—S1—B1 | 100.8 (3) |
Si1—C12—H12C | 109.5 | C1S—S1—B1 | 105.1 (3) |
H12A—C12—H12C | 109.5 | S1—C1S—H1S1 | 109.5 |
H12B—C12—H12C | 109.5 | S1—C1S—H1S2 | 109.5 |
C2—C1—C2i | 93.4 (8) | H1S1—C1S—H1S2 | 109.5 |
C2—C1—C2'i | 116.0 (6) | S1—C1S—H1S3 | 109.5 |
C2i—C1—C2' | 116.0 (6) | H1S1—C1S—H1S3 | 109.5 |
C2'i—C1—C2' | 109.6 (8) | H1S2—C1S—H1S3 | 109.5 |
C2—C1—B1 | 126.7 (4) | S1i—C2S—H2S1 | 109.5 |
C2i—C1—B1 | 126.7 (4) | S1—C2S—H2S1 | 120.2 |
C2'i—C1—B1 | 117.2 (4) | S1i—C2S—H2S2 | 109.5 |
C2'—C1—B1 | 117.2 (4) | S1—C2S—H2S2 | 103.8 |
C1—C2—C3 | 124.1 (7) | H2S1—C2S—H2S2 | 109.5 |
C3—C2—C2i | 88.4 (5) | S1i—C2S—H2S3 | 109.5 |
C1—C2—H2 | 117.9 | S1—C2S—H2S3 | 103.9 |
C3—C2—H2 | 117.9 | H2S1—C2S—H2S3 | 109.5 |
C2i—C2—H2 | 143.8 | H2S2—C2S—H2S3 | 109.5 |
S1—B1—C1—C2 | −122.2 (6) | C2—C3—C4—Si1 | −177.0 (6) |
S1i—B1—C1—C2 | −107.3 (6) | C3i—C3—C4—Si1 | 136.7 (8) |
Br1i—B1—C1—C2 | 1.2 (8) | C2'—C3'—C4—C3 | 71.2 (9) |
Br1—B1—C1—C2 | 129.3 (6) | C2'—C3'—C4—C3i | 7.3 (11) |
S1—B1—C1—C2i | 107.3 (6) | C2'—C3'—C4—C3'i | −38.0 (11) |
S1i—B1—C1—C2i | 122.2 (6) | C2'—C3'—C4—Si1 | −178.3 (6) |
Br1i—B1—C1—C2i | −129.3 (6) | C11i—Si1—C4—C3 | 178.2 (6) |
Br1—B1—C1—C2i | −1.2 (8) | C11—Si1—C4—C3 | 57.7 (6) |
S1—B1—C1—C2'i | 59.3 (5) | C12—Si1—C4—C3 | −62.0 (6) |
S1i—B1—C1—C2'i | 74.2 (5) | C11i—Si1—C4—C3i | −57.7 (6) |
Br1i—B1—C1—C2'i | −177.3 (4) | C11—Si1—C4—C3i | −178.2 (6) |
Br1—B1—C1—C2'i | −49.1 (6) | C12—Si1—C4—C3i | 62.0 (6) |
S1—B1—C1—C2' | −74.2 (5) | C11i—Si1—C4—C3'i | −7.9 (5) |
S1i—B1—C1—C2' | −59.3 (5) | C11—Si1—C4—C3'i | −128.3 (5) |
Br1i—B1—C1—C2' | 49.1 (6) | C12—Si1—C4—C3'i | 111.9 (5) |
Br1—B1—C1—C2' | 177.3 (4) | C11i—Si1—C4—C3' | 128.3 (5) |
C2i—C1—C2—C3 | −39.8 (12) | C11—Si1—C4—C3' | 7.9 (5) |
C2'i—C1—C2—C3 | −3.6 (12) | C12—Si1—C4—C3' | −111.9 (5) |
C2'—C1—C2—C3 | 86.9 (10) | C1—B1—S1—S1i | 92.06 (7) |
B1—C1—C2—C3 | 177.9 (6) | Br1i—B1—S1—S1i | −33.0 (2) |
C2'i—C1—C2—C2i | 36.1 (4) | Br1—B1—S1—S1i | −149.1 (2) |
C2'—C1—C2—C2i | 126.7 (7) | C1—B1—S1—C2Si | −47.8 (5) |
B1—C1—C2—C2i | −142.4 (9) | S1i—B1—S1—C2Si | −139.9 (5) |
C1—C2—C3—C4 | −3.6 (14) | Br1i—B1—S1—C2Si | −172.9 (5) |
C2i—C2—C3—C4 | −29.6 (8) | Br1—B1—S1—C2Si | 71.0 (5) |
C1—C2—C3—C3i | 26.0 (8) | C1—B1—S1—C2S | 65.0 (3) |
C2i—C2—C3—C3i | 0.000 (3) | S1i—B1—S1—C2S | −27.1 (3) |
C2—C1—C2'—C3' | −67.5 (8) | Br1i—B1—S1—C2S | −60.1 (4) |
C2i—C1—C2'—C3' | −4.5 (11) | Br1—B1—S1—C2S | −176.2 (4) |
C2'i—C1—C2'—C3' | 40.0 (11) | C1—B1—S1—C1S | 171.85 (15) |
B1—C1—C2'—C3' | 176.9 (6) | S1i—B1—S1—C1S | 79.79 (18) |
C1—C2'—C3'—C4 | −0.7 (11) | Br1i—B1—S1—C1S | 46.8 (3) |
C2—C3—C4—C3i | 46.3 (11) | Br1—B1—S1—C1S | −69.3 (3) |
C2—C3—C4—C3'i | 8.9 (12) | C2Si—S1—C2S—S1i | 180.000 (11) |
C3i—C3—C4—C3'i | −37.3 (5) | C1S—S1—C2S—S1i | −50.9 (5) |
C2—C3—C4—C3' | −80.1 (9) | B1—S1—C2S—S1i | 57.5 (5) |
C3i—C3—C4—C3' | −126.4 (6) |
Symmetry code: (i) x, −y+1/2, z. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C6H5BBr2 | C9H13BBr2Si | C6H4BBr3 | C8H12BBr2N |
Mr | 247.73 | 319.91 | 326.63 | 292.82 |
Crystal system, space group | Orthorhombic, Pbca | Monoclinic, P21/c | Tetragonal, I41/a | Monoclinic, P21/c |
Temperature (K) | 173 | 173 | 173 | 173 |
a, b, c (Å) | 11.0841 (16), 7.8287 (12), 17.720 (2) | 6.7452 (5), 15.2390 (12), 12.4123 (10) | 29.446 (3), 29.446 (3), 4.0228 (4) | 8.9095 (9), 9.2874 (13), 12.9306 (13) |
α, β, γ (°) | 90, 90, 90 | 90, 93.841 (6), 90 | 90, 90, 90 | 90, 92.249 (8), 90 |
V (Å3) | 1537.6 (4) | 1273.00 (17) | 3488.0 (8) | 1069.1 (2) |
Z | 8 | 4 | 16 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 10.45 | 6.42 | 13.80 | 7.53 |
Crystal size (mm) | 0.29 × 0.17 × 0.09 | 0.29 × 0.25 × 0.25 | 0.26 × 0.11 × 0.11 | 0.19 × 0.09 × 0.05 |
Data collection | ||||
Diffractometer | Stoe IPDS II two-circle diffractometer | Stoe IPDS II two-circle diffractometer | Stoe IPDS II two-circle diffractometer | Stoe IPDS II two-circle diffractometer |
Absorption correction | Multi-scan (MULABS; Spek, 2009; Blessing, 1995) | Multi-scan (MULABS; Spek, 2009; Blessing, 1995) | Multi-scan (MULABS; Spek, 2009; Blessing, 1995) | Multi-scan (MULABS; Spek, 2009; Blessing, 1995) |
Tmin, Tmax | 0.152, 0.453 | 0.258, 0.297 | 0.124, 0.312 | 0.329, 0.705 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14258, 1517, 1089 | 19196, 2235, 1942 | 12710, 1544, 1111 | 6363, 2004, 1413 |
Rint | 0.081 | 0.064 | 0.097 | 0.082 |
(sin θ/λ)max (Å−1) | 0.619 | 0.595 | 0.595 | 0.608 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.110, 1.02 | 0.036, 0.084, 1.08 | 0.070, 0.149, 1.05 | 0.046, 0.104, 0.99 |
No. of reflections | 1517 | 2235 | 1544 | 2004 |
No. of parameters | 82 | 119 | 91 | 113 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.59, −1.07 | 0.46, −0.37 | 0.90, −1.08 | 0.98, −0.96 |
(V) | |
Crystal data | |
Chemical formula | C11H19BBr2SSi |
Mr | 382.04 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 173 |
a, b, c (Å) | 6.6950 (5), 11.0880 (8), 21.6870 (16) |
α, β, γ (°) | 90, 90, 90 |
V (Å3) | 1609.9 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.21 |
Crystal size (mm) | 0.20 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Stoe IPDS II two-circle diffractometer |
Absorption correction | Multi-scan (MULABS; Spek, 2009; Blessing, 1995) |
Tmin, Tmax | 0.422, 0.781 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22983, 1705, 1146 |
Rint | 0.073 |
(sin θ/λ)max (Å−1) | 0.623 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.083, 0.90 |
No. of reflections | 1705 |
No. of parameters | 110 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.56 |
Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Br1i | 0.85 (7) | 2.96 (7) | 3.705 (6) | 147 (6) |
N1—H1···Br2i | 0.85 (7) | 2.96 (7) | 3.684 (5) | 143 (6) |
Symmetry code: (i) −x, −y, −z+1. |
Bond | (I) | (II) | (III) | (IV) | (V) |
C—B | 1.533 (9) | 1.535 (5) | 1.53 (2) | 1.600 (9) | 1.592 (8) |
B—Br | 1.917 (7) | 1.906 (4) | 1.911 (16) | 2.049 (6) | 2.022 (4) |
B—Br | 1.919 (7) | 1.915 (4) | 1.926 (16) | 2.058 (7) | 2.022 (4) |
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In the past few decades, dihaloboryl-substituted arenes have gained significant importance as starting materials for e.g. aryl(hydro)boranes (Lorbach et al., 2012) and BN addition compounds (Heilmann-Brohl et al., 2011). Both classes of substance feature intriguing optoelectronic behaviour. We present here the crystal structures of a series of dibromoborylated benzene derivatives and a comparison of their molecular structures.
Dibromoborylbenzene, (I) (Fig. 1), features an essentially planar molecule (r.m.s. deviation for all non-H atoms = 0.007 Å) and a dihedral angle of 3.7 (3)° between the –BBr2 group and the aromatic ring. The packing (Fig. 2) shows pairs of centrosymmetrically related molecules, with the B atom located almost directly over the C atom in the para position of the ring [B1—C4i = 3.584 (9) Å; symmetry code: (i) -x + 1, -y + 1, -z + 1].
In 1-dibromoboryl-4-(trimethylsilyl)benzene, (II), the para position of the dibromobenzene ring is substituted with a trimethylsilyl residue (Fig. 3). The dihedral angle between the aromatic ring and the –BBr2 group is 6.4 (3)°. As for (I), the packing (Fig. 4) shows pairs of centrosymmetrically related molecules, which are slightly displaced from one another. The B atom is located over (but with a slight displacement from) the C atom in the ortho position of the ring [B1—C5i =3.626 (5) Å; symmetry code: (i) -x + 1, -y + 1, -z + 1].
In 4-bromo-1-(dibromoboryl)benzene, (III), a bromine residue is located in the the para position of the dibromobenzene ring (Fig. 5), decreasing the electron density of the C atom to which it is bonded. The dihedral angle between the aromatic ring and the –BBr2 group is 6.4 (3)°. The packing (Fig. 6) shows intermolecular contacts between the Br atoms in the para position of the ring [Br3···Br3i = 3.663 Å and Br3···Br3ii = 3.663 (2) Å; symmetry codes: (i) y - 3/4, -x + 3/4, -z - 1/4; (ii) -y + 3/4, x + 3/4, -z - 1/4].
Dibromo(dimethylamino)(phenyl)borane, (IV) (Fig. 7), is the reaction product of (I) with dimethylamine. Whereas the B atom is still located in the plane of the aromatic ring [it deviates by just 0.034 (9) Å from the ring plane], the two Br atoms deviate by -0.976 (9) (Br1) and -0.819 (10) Å (Br2) from the ring plane. The N atom is displaced even further [1.538 (9) Å] from the ring plane in the opposite direction to the Br residues. The crystal packing (Fig. 8) shows that the molecules are connected by N—H···Br hydrogen bonds to form centrosymmetric dimers. It is remarkable that the amino H atom forms two almost equal hydrogen bonds to the two Br atoms of another molecule (Table 1).
Dibromo(dimethylsulfanyl)[4-(trimethylsilyl)phenyl]borane, (V) (Fig. 9), is the reaction product of (II) with dimethyl sulfide. The molecule is located on a crystallographic mirror plane. As a result, the central ring, the S atom and one of the methyl groups bonded to the S atom are disordered over two equally occupied orientations. Due to this disorder, the deviation of the B, Br and S atoms from the ring plane(s) is not discussed.
In order to compare these five structures with similar compounds, a search of the Cambridge Structural Database (CSD, Version 5.33 of November 2011 plus one update; Allen, 2002) was performed for an aromatic ring carrying a –BBr2 residue. Eight entries were found, namely 4-(dibromoboryl)toluene (AYUHIL), 1,3-bis(dibromoboryl)benzene (AYUHOR), 1,4-bis(dibromoboryl)benzene (AYUHUX), 1,3,5-tris(dibromoboryl)benzene (AYUJAF) and 4,4'-bis(dibromoboryl)biphenyl (AYUJEJ) (Haberecht et al., 2004), dibromo(2,4,6-triisopropylphenyl)borane (EHUBEO) (Olmstead et al., 2003), and dibromo(2,6-dimesitylphenyl)borane (TIZXAB) and dibromo[2,6-bis(2,4,6-triisopropylphenyl)phenyl]borane (TIZXEF) (Grisby & Power, 1996), with a mean C—B bond length of 1.55 (3) Å and a mean B—Br bond length of 1.91 (1) Å. These values agree well with those in (I), (II) and (III) (Table 2).
If the substitutents of the ring in the ortho position with respect to the –BBr2 group are H atoms, the –BBr2 group is coplanar with the ring. The dihedral angle between the ring and the –BBr2 group ranges from 1.8 (AYUJEJ) to 8.8° (AYUJAF). In three of the structures, the ortho substituents are very bulky and force the –BBr2 group into an almost perpendicular position with respect to the aromatic ring (dihedral angles BBr2/ring: 87.3° in EHUBEO, 77.5° in TIZXAB and 90.0° in TIZXEF).
A search of the CSD for an aromatic ring carrying a –BBr2 residue with a four-coordinated B atom revealed only two structures, dibromo(2-dimethylaminomethylphenyl)borane (CEJWUJ; Brown et al., 1998) and bromo(bromo{4-[dibromo(tricyclohexylphosphino)boranyl]phenyl}boranyl-B)- bis(tricyclohexylphosphino)platinum benzene n-hexane solvate (QOMLEK; Braunschweig et al., 2008). The C—B bond lengths of 1.559 (CEJWUJ) and 1.609 Å (QOMLEK), and the B—Br bond lengths (2.019 and 2.020 Å in CEJWUJ, and 2.046 and 2.056 Å in QOMLEK) are in good agreement with those of (IV) and (V) (Table 2). Apart from these distances, the two database structures differ too much from (IV) and (V) for further comparison.
In conclusion, it can be said that the C—B and B—Br bonds are significantly elongated if the number of substituents at the B atom is increased from three to four. Molecules containing a three-coordinated B atom carrying two Br atoms tend to have the –BBr2 group coplanar with the aromatic ring, as long as no bulky substituents in the ortho position of the aromatic ring prevent coplanarity. The crystal packing of these structures depends on the substitution pattern. Compounds (I) and (II), with electron-rich residues in the position para to the –BBr2 group, feature a B–π interaction in their crystal structures, whereas no such interaction is observed in the structures of (III), (IV) and (V).