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The crystal structures of five dibromo­benzene derivatives, namely dibromo­boryl­benzene, C6H5BBr2, (I), 1-dibromo­bor­yl-4-(trimethyl­silyl)­benzene, C9H13BBr2Si, (II), 4-bromo-1-(di­bromo­boryl)­benzene, C6H4BBr3, (III), dibromo(di­methyl­am­ino)­(phenyl)­borane, C8H12BBr2N, (IV), and dibromo­(di­methyl­sulfanyl)­[4-(trimethyl­silyl)­phenyl]­borane, C11H19BBr2SSi, (V), have been determined. Compounds (I)-(IV) crystallize with one mol­ecule in the asymmetric unit, but the mol­ecule of (V) is located on a crystallographic mirror plane, implying twofold disorder of the central aromatic ring, the S atom and one of the methyl groups bonded to the S atom. In (I), (II) and (III), the B atom is three-coordinated, and in (IV) and (V) it is four-coordinated. The geometric parameters of the -BBr2 group in these five structures agree well with those of comparable structures retrieved from the Cambridge Structural Database. The C-B and B-Br bond lengths in the mol­ecules with a three-coordinated B atom are significantly shorter than those in the mol­ecules with a four-coordinated B atom. In the compounds with a three-coordinated B atom, the -BBr2 group tends to be coplanar with the aromatic ring to which it is attached.

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Contains datablocks I, II, III, IV, V, global

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CCDC references: 889378; 889379; 889380; 889381; 889382

Comment top

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).

Related literature top

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).

Experimental top

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).

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A perspective view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A packing diagram for (I), viewed in the ab plane.
[Figure 3] Fig. 3. A perspective view of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 4] Fig. 4. A packing diagram for (II), viewed in the bc plane.
[Figure 5] Fig. 5. A perspective view of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 6] Fig. 6. A packing diagram for (III), viewed in the ab plane. Br···Br contacts are shown as dashed lines.
[Figure 7] Fig. 7. A perspective view of (IV), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 8] Fig. 8. A packing diagram for (IV), viewed in the bc plane. H atoms bonded to C atoms have been omitted for clarity. Hydrogen bonds are shown as dashed lines.
[Figure 9] Fig. 9. A perspective view of (V), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Only one of the two disordered orientations of the central ring is shown. [Symmetry code: (A) x, -y + 1/2, z.]
(I) dibromoborylbenzene top
Crystal data top
C6H5BBr2F(000) = 928
Mr = 247.73Dx = 2.140 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 8202 reflections
a = 11.0841 (16) Åθ = 3.7–26.1°
b = 7.8287 (12) ŵ = 10.45 mm1
c = 17.720 (2) ÅT = 173 K
V = 1537.6 (4) Å3Plate, colourless
Z = 80.29 × 0.17 × 0.09 mm
Data collection top
Stoe IPDS II two-circle
diffractometer
1517 independent reflections
Radiation source: fine-focus sealed tube1089 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.081
ω scansθmax = 26.1°, θmin = 3.7°
Absorption correction: multi-scan
(MULABS; Spek, 2009; Blessing, 1995)
h = 1313
Tmin = 0.152, Tmax = 0.453k = 99
14258 measured reflectionsl = 2021
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H-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 parametersΔρmax = 0.59 e Å3
0 restraintsΔρmin = 1.07 e Å3
Crystal data top
C6H5BBr2V = 1537.6 (4) Å3
Mr = 247.73Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 11.0841 (16) ŵ = 10.45 mm1
b = 7.8287 (12) ÅT = 173 K
c = 17.720 (2) Å0.29 × 0.17 × 0.09 mm
Data collection top
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 = 0.453Rint = 0.081
14258 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.110H-atom parameters constrained
S = 1.02Δρmax = 0.59 e Å3
1517 reflectionsΔρmin = 1.07 e Å3
82 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
xyzUiso*/Ueq
B10.3987 (6)0.3634 (9)0.6298 (4)0.0317 (14)
Br10.27993 (6)0.49129 (9)0.68469 (4)0.0418 (2)
Br20.52293 (5)0.26062 (10)0.68982 (4)0.0456 (2)
C10.3939 (5)0.3424 (7)0.5439 (3)0.0282 (12)
C20.4773 (5)0.2416 (8)0.5056 (4)0.0335 (13)
H20.53980.18650.53300.040*
C30.4706 (6)0.2207 (8)0.4287 (4)0.0409 (15)
H30.52730.14930.40390.049*
C40.3819 (6)0.3025 (9)0.3869 (4)0.0400 (14)
H40.37730.28790.33370.048*
C50.3005 (6)0.4058 (9)0.4244 (4)0.0383 (14)
H50.24020.46400.39640.046*
C60.3050 (5)0.4259 (8)0.5009 (4)0.0330 (13)
H60.24760.49700.52530.040*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
B10.031 (3)0.035 (3)0.030 (4)0.004 (3)0.005 (3)0.005 (3)
Br10.0396 (4)0.0480 (4)0.0377 (4)0.0049 (3)0.0047 (2)0.0098 (3)
Br20.0331 (3)0.0690 (5)0.0348 (4)0.0059 (3)0.0021 (3)0.0118 (3)
C10.023 (3)0.030 (3)0.032 (3)0.003 (2)0.001 (2)0.004 (2)
C20.024 (3)0.041 (4)0.035 (3)0.000 (2)0.001 (2)0.002 (3)
C30.038 (3)0.044 (4)0.041 (4)0.005 (3)0.011 (3)0.010 (3)
C40.043 (3)0.047 (4)0.030 (3)0.008 (3)0.000 (3)0.006 (3)
C50.034 (3)0.045 (4)0.036 (4)0.004 (3)0.003 (3)0.007 (3)
C60.026 (3)0.035 (3)0.037 (4)0.001 (2)0.002 (2)0.002 (3)
Geometric parameters (Å, º) top
B1—C11.533 (9)C3—C41.388 (10)
B1—Br21.917 (7)C3—H30.9500
B1—Br11.919 (7)C4—C51.381 (9)
C1—C21.392 (8)C4—H40.9500
C1—C61.407 (8)C5—C61.365 (9)
C2—C31.373 (9)C5—H50.9500
C2—H20.9500C6—H60.9500
C1—B1—Br2122.1 (5)C4—C3—H3119.6
C1—B1—Br1122.4 (5)C5—C4—C3118.4 (6)
Br2—B1—Br1115.5 (4)C5—C4—H4120.8
C2—C1—C6117.7 (6)C3—C4—H4120.8
C2—C1—B1121.5 (5)C6—C5—C4121.4 (6)
C6—C1—B1120.8 (5)C6—C5—H5119.3
C3—C2—C1121.0 (6)C4—C5—H5119.3
C3—C2—H2119.5C5—C6—C1120.6 (6)
C1—C2—H2119.5C5—C6—H6119.7
C2—C3—C4120.9 (6)C1—C6—H6119.7
C2—C3—H3119.6
Br2—B1—C1—C22.6 (8)C1—C2—C3—C41.4 (9)
Br1—B1—C1—C2176.6 (4)C2—C3—C4—C50.0 (10)
Br2—B1—C1—C6176.9 (4)C3—C4—C5—C61.0 (10)
Br1—B1—C1—C63.9 (8)C4—C5—C6—C10.5 (9)
C6—C1—C2—C31.9 (8)C2—C1—C6—C51.0 (8)
B1—C1—C2—C3178.6 (6)B1—C1—C6—C5179.5 (6)
(II) 1-dibromoboryl-4-(trimethylsilyl)benzene top
Crystal data top
C9H13BBr2SiF(000) = 624
Mr = 319.91Dx = 1.669 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 15049 reflections
a = 6.7452 (5) Åθ = 3.3–26.1°
b = 15.2390 (12) ŵ = 6.42 mm1
c = 12.4123 (10) ÅT = 173 K
β = 93.841 (6)°Block, colourless
V = 1273.00 (17) Å30.29 × 0.25 × 0.25 mm
Z = 4
Data collection top
Stoe IPDS II two-circle
diffractometer
2235 independent reflections
Radiation source: fine-focus sealed tube1942 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.064
ω scansθmax = 25.0°, θmin = 3.3°
Absorption correction: multi-scan
(MULABS; Spek, 2009; Blessing, 1995)
h = 78
Tmin = 0.258, Tmax = 0.297k = 1818
19196 measured reflectionsl = 1414
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-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 reflectionsΔρmax = 0.46 e Å3
119 parametersΔρmin = 0.37 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0112 (10)
Crystal data top
C9H13BBr2SiV = 1273.00 (17) Å3
Mr = 319.91Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.7452 (5) ŵ = 6.42 mm1
b = 15.2390 (12) ÅT = 173 K
c = 12.4123 (10) Å0.29 × 0.25 × 0.25 mm
β = 93.841 (6)°
Data collection top
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 = 0.297Rint = 0.064
19196 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.084H-atom parameters constrained
S = 1.08Δρmax = 0.46 e Å3
2235 reflectionsΔρmin = 0.37 e Å3
119 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
xyzUiso*/Ueq
Si10.84456 (13)0.81255 (7)0.56483 (7)0.0410 (2)
B10.4716 (6)0.4874 (3)0.3170 (3)0.0470 (9)
Br10.61752 (6)0.38165 (3)0.30091 (4)0.06453 (18)
Br20.20678 (6)0.48883 (3)0.25108 (3)0.05994 (17)
C10.7300 (5)0.7162 (2)0.4892 (2)0.0397 (7)
C20.5444 (5)0.7203 (3)0.4322 (3)0.0466 (8)
H20.47330.77420.43040.056*
C30.4613 (5)0.6484 (2)0.3784 (3)0.0465 (8)
H30.33340.65360.34190.056*
C40.5617 (5)0.5678 (2)0.3764 (2)0.0409 (7)
C50.7501 (5)0.5635 (2)0.4323 (3)0.0449 (8)
H50.82320.51020.43230.054*
C60.8302 (5)0.6354 (2)0.4870 (3)0.0459 (8)
H60.95720.63010.52440.055*
C71.0707 (6)0.8454 (3)0.4967 (3)0.0613 (10)
H7A1.03260.86450.42280.092*
H7B1.16150.79530.49480.092*
H7C1.13710.89380.53660.092*
C80.9122 (6)0.7764 (3)0.7058 (3)0.0552 (9)
H8A1.00760.72790.70500.083*
H8B0.79250.75670.73930.083*
H8C0.97200.82550.74720.083*
C90.6651 (6)0.9049 (3)0.5639 (3)0.0576 (9)
H9A0.63190.92350.48930.086*
H9B0.72460.95420.60530.086*
H9C0.54400.88580.59660.086*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Si10.0370 (4)0.0426 (6)0.0433 (5)0.0023 (4)0.0019 (3)0.0027 (4)
B10.050 (2)0.051 (3)0.0395 (19)0.0052 (18)0.0032 (15)0.0007 (16)
Br10.0647 (3)0.0493 (3)0.0789 (3)0.00308 (18)0.00029 (19)0.01577 (19)
Br20.0561 (2)0.0596 (3)0.0615 (3)0.00835 (18)0.01491 (16)0.00134 (17)
C10.0400 (16)0.0421 (19)0.0370 (15)0.0028 (14)0.0022 (12)0.0016 (13)
C20.0417 (17)0.046 (2)0.0512 (18)0.0078 (15)0.0001 (13)0.0030 (15)
C30.0388 (16)0.050 (2)0.0495 (17)0.0041 (15)0.0047 (13)0.0008 (16)
C40.0433 (16)0.043 (2)0.0364 (15)0.0004 (15)0.0034 (12)0.0021 (13)
C50.0447 (17)0.039 (2)0.0496 (18)0.0081 (15)0.0025 (14)0.0027 (14)
C60.0436 (17)0.045 (2)0.0473 (17)0.0080 (15)0.0065 (13)0.0014 (15)
C70.0487 (19)0.070 (3)0.066 (2)0.0100 (19)0.0118 (16)0.008 (2)
C80.059 (2)0.058 (3)0.0483 (19)0.0006 (18)0.0029 (16)0.0059 (17)
C90.056 (2)0.047 (2)0.069 (2)0.0081 (18)0.0004 (17)0.0080 (18)
Geometric parameters (Å, º) top
Si1—C91.856 (4)C4—C51.408 (5)
Si1—C81.861 (4)C5—C61.381 (5)
Si1—C71.862 (4)C5—H50.9500
Si1—C11.881 (4)C6—H60.9500
B1—C41.535 (5)C7—H7A0.9800
B1—Br11.906 (4)C7—H7B0.9800
B1—Br21.915 (4)C7—H7C0.9800
C1—C21.397 (5)C8—H8A0.9800
C1—C61.405 (5)C8—H8B0.9800
C2—C31.383 (5)C8—H8C0.9800
C2—H20.9500C9—H9A0.9800
C3—C41.403 (5)C9—H9B0.9800
C3—H30.9500C9—H9C0.9800
C9—Si1—C8110.44 (19)C4—C5—H5119.5
C9—Si1—C7110.3 (2)C5—C6—C1122.1 (3)
C8—Si1—C7110.49 (19)C5—C6—H6118.9
C9—Si1—C1110.06 (17)C1—C6—H6118.9
C8—Si1—C1107.74 (17)Si1—C7—H7A109.5
C7—Si1—C1107.75 (17)Si1—C7—H7B109.5
C4—B1—Br1122.4 (3)H7A—C7—H7B109.5
C4—B1—Br2121.6 (3)Si1—C7—H7C109.5
Br1—B1—Br2116.0 (2)H7A—C7—H7C109.5
C2—C1—C6116.5 (3)H7B—C7—H7C109.5
C2—C1—Si1122.8 (3)Si1—C8—H8A109.5
C6—C1—Si1120.8 (2)Si1—C8—H8B109.5
C3—C2—C1122.0 (3)H8A—C8—H8B109.5
C3—C2—H2119.0Si1—C8—H8C109.5
C1—C2—H2119.0H8A—C8—H8C109.5
C2—C3—C4121.4 (3)H8B—C8—H8C109.5
C2—C3—H3119.3Si1—C9—H9A109.5
C4—C3—H3119.3Si1—C9—H9B109.5
C3—C4—C5117.0 (3)H9A—C9—H9B109.5
C3—C4—B1122.1 (3)Si1—C9—H9C109.5
C5—C4—B1120.9 (3)H9A—C9—H9C109.5
C6—C5—C4121.0 (3)H9B—C9—H9C109.5
C6—C5—H5119.5
C9—Si1—C1—C26.3 (3)C2—C3—C4—B1180.0 (3)
C8—Si1—C1—C2126.7 (3)Br1—B1—C4—C3173.2 (3)
C7—Si1—C1—C2114.0 (3)Br2—B1—C4—C35.1 (4)
C9—Si1—C1—C6174.1 (3)Br1—B1—C4—C57.2 (4)
C8—Si1—C1—C653.6 (3)Br2—B1—C4—C5174.6 (3)
C7—Si1—C1—C665.6 (3)C3—C4—C5—C60.6 (5)
C6—C1—C2—C31.4 (5)B1—C4—C5—C6179.1 (3)
Si1—C1—C2—C3179.0 (3)C4—C5—C6—C10.6 (5)
C1—C2—C3—C41.4 (5)C2—C1—C6—C50.4 (5)
C2—C3—C4—C50.4 (5)Si1—C1—C6—C5180.0 (3)
(III) 4-bromo-1-(dibromoboryl)benzene top
Crystal data top
C6H4BBr3Dx = 2.488 Mg m3
Mr = 326.63Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 4723 reflections
Hall symbol: -I 4adθ = 2.8–25.6°
a = 29.446 (3) ŵ = 13.80 mm1
c = 4.0228 (4) ÅT = 173 K
V = 3488.0 (8) Å3Needle, colourless
Z = 160.26 × 0.11 × 0.11 mm
F(000) = 2400
Data collection top
Stoe IPDS II two-circle
diffractometer
1544 independent reflections
Radiation source: fine-focus sealed tube1111 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.097
ω scansθmax = 25.0°, θmin = 2.8°
Absorption correction: multi-scan
(MULABS; Spek, 2009; Blessing, 1995)
h = 3535
Tmin = 0.124, Tmax = 0.312k = 3535
12710 measured reflectionsl = 44
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.070Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.149H-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 parametersΔρmax = 0.90 e Å3
0 restraintsΔρmin = 1.08 e Å3
Crystal data top
C6H4BBr3Z = 16
Mr = 326.63Mo Kα radiation
Tetragonal, I41/aµ = 13.80 mm1
a = 29.446 (3) ÅT = 173 K
c = 4.0228 (4) Å0.26 × 0.11 × 0.11 mm
V = 3488.0 (8) Å3
Data collection top
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 = 0.312Rint = 0.097
12710 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0700 restraints
wR(F2) = 0.149H-atom parameters constrained
S = 1.05Δρmax = 0.90 e Å3
1544 reflectionsΔρmin = 1.08 e Å3
91 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
xyzUiso*/Ueq
Br10.28681 (5)0.69376 (5)0.6423 (3)0.0440 (4)
Br20.25646 (5)0.59109 (5)0.8282 (3)0.0442 (4)
Br30.04802 (4)0.68695 (5)0.0725 (3)0.0388 (4)
B10.2401 (5)0.6487 (5)0.635 (3)0.038 (3)
C10.1923 (4)0.6581 (4)0.502 (3)0.029 (3)
C20.1825 (5)0.6991 (4)0.353 (3)0.036 (3)
H20.20570.72140.33490.043*
C30.1394 (4)0.7090 (4)0.227 (3)0.032 (3)
H30.13290.73780.13170.039*
C40.1066 (4)0.6755 (4)0.245 (3)0.032 (3)
C50.1155 (4)0.6337 (4)0.387 (3)0.037 (3)
H50.09270.61090.39890.044*
C60.1588 (5)0.6261 (4)0.512 (3)0.041 (3)
H60.16540.59740.60830.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0338 (7)0.0484 (9)0.0498 (8)0.0035 (6)0.0031 (6)0.0050 (6)
Br20.0422 (8)0.0429 (8)0.0475 (8)0.0092 (6)0.0010 (6)0.0098 (6)
Br30.0334 (7)0.0436 (8)0.0394 (7)0.0018 (5)0.0035 (5)0.0019 (6)
B10.047 (9)0.046 (9)0.020 (7)0.005 (7)0.007 (6)0.007 (6)
C10.032 (7)0.034 (7)0.022 (6)0.005 (5)0.003 (4)0.009 (4)
C20.048 (8)0.017 (6)0.042 (7)0.010 (5)0.007 (6)0.007 (5)
C30.036 (7)0.023 (6)0.038 (7)0.002 (5)0.006 (5)0.001 (5)
C40.033 (7)0.041 (7)0.023 (6)0.009 (6)0.003 (5)0.006 (5)
C50.038 (7)0.027 (7)0.045 (7)0.002 (5)0.005 (6)0.008 (5)
C60.060 (9)0.022 (6)0.041 (7)0.008 (6)0.006 (6)0.003 (5)
Geometric parameters (Å, º) top
Br1—B11.911 (16)C2—H20.9500
Br2—B11.926 (16)C3—C41.381 (18)
Br3—C41.890 (12)C3—H30.9500
B1—C11.53 (2)C4—C51.385 (18)
C1—C61.365 (18)C5—C61.388 (19)
C1—C21.381 (17)C5—H50.9500
C2—C31.396 (18)C6—H60.9500
C1—B1—Br1122.8 (10)C2—C3—H3121.1
C1—B1—Br2121.9 (11)C3—C4—C5121.7 (12)
Br1—B1—Br2115.2 (8)C3—C4—Br3119.5 (9)
C6—C1—C2117.7 (12)C5—C4—Br3118.8 (10)
C6—C1—B1122.0 (12)C4—C5—C6117.7 (12)
C2—C1—B1120.2 (11)C4—C5—H5121.1
C1—C2—C3122.0 (11)C6—C5—H5121.1
C1—C2—H2119.0C1—C6—C5122.9 (12)
C3—C2—H2119.0C1—C6—H6118.5
C4—C3—C2117.9 (11)C5—C6—H6118.5
C4—C3—H3121.1
Br1—B1—C1—C6177.1 (9)C2—C3—C4—C51.0 (18)
Br2—B1—C1—C60.2 (16)C2—C3—C4—Br3179.2 (9)
Br1—B1—C1—C25.9 (16)C3—C4—C5—C60.2 (18)
Br2—B1—C1—C2177.2 (9)Br3—C4—C5—C6180.0 (9)
C6—C1—C2—C32.6 (18)C2—C1—C6—C51.8 (18)
B1—C1—C2—C3179.7 (11)B1—C1—C6—C5178.8 (11)
C1—C2—C3—C42.3 (18)C4—C5—C6—C10.6 (19)
(IV) dibromo(dimethylamino)(phenyl)borane top
Crystal data top
C8H12BBr2NF(000) = 568
Mr = 292.82Dx = 1.819 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4532 reflections
a = 8.9095 (9) Åθ = 3.5–25.8°
b = 9.2874 (13) ŵ = 7.53 mm1
c = 12.9306 (13) ÅT = 173 K
β = 92.249 (8)°Block, colourless
V = 1069.1 (2) Å30.19 × 0.09 × 0.05 mm
Z = 4
Data collection top
Stoe IPDS II two-circle
diffractometer
2004 independent reflections
Radiation source: fine-focus sealed tube1413 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.082
ω scansθmax = 25.6°, θmin = 3.5°
Absorption correction: multi-scan
(MULABS; Spek, 2009; Blessing, 1995)
h = 109
Tmin = 0.329, Tmax = 0.705k = 1011
6363 measured reflectionsl = 1515
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H 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 reflectionsΔρmax = 0.98 e Å3
113 parametersΔρmin = 0.96 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0035 (7)
Crystal data top
C8H12BBr2NV = 1069.1 (2) Å3
Mr = 292.82Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.9095 (9) ŵ = 7.53 mm1
b = 9.2874 (13) ÅT = 173 K
c = 12.9306 (13) Å0.19 × 0.09 × 0.05 mm
β = 92.249 (8)°
Data collection top
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 = 0.705Rint = 0.082
6363 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 0.99Δρmax = 0.98 e Å3
2004 reflectionsΔρmin = 0.96 e Å3
113 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
xyzUiso*/Ueq
B10.1562 (8)0.1816 (7)0.4299 (4)0.0238 (15)
Br10.19350 (9)0.00845 (7)0.35462 (4)0.0406 (2)
Br20.06537 (8)0.23148 (8)0.39628 (5)0.0402 (2)
N10.1676 (6)0.1454 (6)0.5521 (3)0.0257 (11)
H10.102 (8)0.080 (8)0.563 (5)0.031*
C10.3197 (8)0.0914 (8)0.5886 (4)0.0388 (17)
H1A0.34780.00870.54640.058*
H1B0.31640.06210.66120.058*
H1C0.39410.16830.58180.058*
C20.1254 (9)0.2710 (8)0.6194 (4)0.0364 (16)
H2A0.02550.30620.59730.055*
H2B0.19910.34850.61270.055*
H2C0.12420.23980.69170.055*
C110.2681 (7)0.3076 (6)0.3985 (3)0.0236 (13)
C120.4201 (7)0.2776 (7)0.3746 (4)0.0298 (14)
H120.45440.18070.37560.036*
C130.5186 (9)0.3861 (8)0.3500 (5)0.0404 (18)
H130.61940.36370.33460.049*
C140.4701 (9)0.5266 (8)0.3479 (4)0.0408 (19)
H140.53730.60100.32970.049*
C150.3260 (10)0.5606 (8)0.3719 (5)0.0447 (19)
H150.29450.65830.37160.054*
C160.2252 (8)0.4517 (7)0.3967 (4)0.0326 (15)
H160.12530.47660.41280.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
B10.033 (4)0.025 (4)0.014 (3)0.003 (3)0.001 (2)0.002 (2)
Br10.0747 (6)0.0223 (3)0.0258 (3)0.0075 (4)0.0150 (3)0.0051 (2)
Br20.0300 (4)0.0557 (5)0.0345 (3)0.0036 (4)0.0027 (2)0.0187 (3)
N10.030 (3)0.029 (3)0.017 (2)0.002 (3)0.001 (2)0.0004 (19)
C10.040 (4)0.049 (4)0.026 (3)0.008 (4)0.005 (3)0.005 (3)
C20.049 (4)0.039 (4)0.021 (3)0.007 (4)0.002 (2)0.010 (3)
C110.036 (4)0.022 (3)0.012 (2)0.001 (3)0.001 (2)0.001 (2)
C120.028 (3)0.037 (4)0.025 (3)0.004 (3)0.003 (2)0.006 (2)
C130.032 (4)0.056 (5)0.034 (3)0.010 (4)0.006 (3)0.015 (3)
C140.052 (5)0.048 (5)0.023 (3)0.031 (4)0.003 (3)0.003 (3)
C150.070 (6)0.020 (3)0.045 (3)0.011 (4)0.012 (4)0.005 (3)
C160.044 (4)0.021 (3)0.034 (3)0.001 (3)0.006 (3)0.002 (2)
Geometric parameters (Å, º) top
B1—C111.600 (9)C2—H2C0.9800
B1—N11.615 (7)C11—C161.392 (9)
B1—Br12.049 (6)C11—C121.429 (9)
B1—Br22.058 (7)C12—C131.381 (9)
N1—C11.503 (9)C12—H120.9500
N1—C21.512 (8)C13—C141.375 (10)
N1—H10.85 (7)C13—H130.9500
C1—H1A0.9800C14—C151.369 (11)
C1—H1B0.9800C14—H140.9500
C1—H1C0.9800C15—C161.399 (10)
C2—H2A0.9800C15—H150.9500
C2—H2B0.9800C16—H160.9500
C11—B1—N1112.6 (5)N1—C2—H2C109.5
C11—B1—Br1113.3 (4)H2A—C2—H2C109.5
N1—B1—Br1106.3 (4)H2B—C2—H2C109.5
C11—B1—Br2112.6 (4)C16—C11—C12116.5 (6)
N1—B1—Br2106.1 (4)C16—C11—B1122.3 (6)
Br1—B1—Br2105.4 (3)C12—C11—B1121.2 (5)
C1—N1—C2108.6 (5)C13—C12—C11121.6 (6)
C1—N1—B1113.4 (5)C13—C12—H12119.2
C2—N1—B1113.2 (5)C11—C12—H12119.2
C1—N1—H1109 (5)C14—C13—C12119.6 (7)
C2—N1—H1105 (4)C14—C13—H13120.2
B1—N1—H1107 (4)C12—C13—H13120.2
N1—C1—H1A109.5C15—C14—C13120.8 (7)
N1—C1—H1B109.5C15—C14—H14119.6
H1A—C1—H1B109.5C13—C14—H14119.6
N1—C1—H1C109.5C14—C15—C16120.1 (7)
H1A—C1—H1C109.5C14—C15—H15119.9
H1B—C1—H1C109.5C16—C15—H15119.9
N1—C2—H2A109.5C11—C16—C15121.4 (7)
N1—C2—H2B109.5C11—C16—H16119.3
H2A—C2—H2B109.5C15—C16—H16119.3
C11—B1—N1—C162.4 (7)Br1—B1—C11—C1234.4 (6)
Br1—B1—N1—C162.2 (6)Br2—B1—C11—C12153.9 (4)
Br2—B1—N1—C1174.1 (4)C16—C11—C12—C130.7 (8)
C11—B1—N1—C261.9 (7)B1—C11—C12—C13178.3 (5)
Br1—B1—N1—C2173.4 (4)C11—C12—C13—C140.2 (9)
Br2—B1—N1—C261.6 (6)C12—C13—C14—C151.2 (9)
N1—B1—C11—C1691.3 (6)C13—C14—C15—C161.3 (9)
Br1—B1—C11—C16148.1 (5)C12—C11—C16—C150.6 (8)
Br2—B1—C11—C1628.6 (6)B1—C11—C16—C15178.2 (5)
N1—B1—C11—C1286.2 (6)C14—C15—C16—C110.4 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br1i0.85 (7)2.96 (7)3.705 (6)147 (6)
N1—H1···Br2i0.85 (7)2.96 (7)3.684 (5)143 (6)
Symmetry code: (i) x, y, z+1.
(V) dibromo(dimethylsulfanyl)[4-(trimethylsilyl)phenyl]borane top
Crystal data top
C11H19BBr2SSiF(000) = 760
Mr = 382.04Dx = 1.576 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 4391 reflections
a = 6.6950 (5) Åθ = 2.5–26.1°
b = 11.0880 (8) ŵ = 5.21 mm1
c = 21.6870 (16) ÅT = 173 K
V = 1609.9 (2) Å3Needle, colourless
Z = 40.20 × 0.10 × 0.05 mm
Data collection top
Stoe IPDS II two-circle
diffractometer
1705 independent reflections
Radiation source: fine-focus sealed tube1146 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.073
ω scansθmax = 26.3°, θmin = 2.1°
Absorption correction: multi-scan
(MULABS; Spek, 2009; Blessing, 1995)
h = 88
Tmin = 0.422, Tmax = 0.781k = 1313
22983 measured reflectionsl = 2626
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H 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 reflectionsΔρmax = 0.40 e Å3
110 parametersΔρmin = 0.56 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0045 (5)
Crystal data top
C11H19BBr2SSiV = 1609.9 (2) Å3
Mr = 382.04Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 6.6950 (5) ŵ = 5.21 mm1
b = 11.0880 (8) ÅT = 173 K
c = 21.6870 (16) Å0.20 × 0.10 × 0.05 mm
Data collection top
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 = 0.781Rint = 0.073
22983 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.083H atoms treated by a mixture of independent and constrained refinement
S = 0.90Δρmax = 0.40 e Å3
1705 reflectionsΔρmin = 0.56 e Å3
110 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br10.37440 (6)0.39945 (4)0.329307 (19)0.04263 (17)
B10.4191 (9)0.25000.3810 (3)0.0364 (16)
Si10.0014 (2)0.25000.64318 (8)0.0446 (5)
C110.0842 (7)0.1116 (5)0.6848 (2)0.0569 (14)
H11A0.03980.04000.66210.085*
H11B0.02600.11080.72630.085*
H11C0.23020.11120.68790.085*
C120.2773 (8)0.25000.6347 (3)0.0528 (18)
H12A0.31930.17700.61270.079*0.50
H12B0.31880.32140.61130.079*0.50
H12C0.33940.25160.67560.079*
C10.3037 (7)0.25000.4451 (3)0.0336 (13)
C20.1890 (12)0.1637 (7)0.4669 (4)0.0324 (17)0.50
H20.16790.09450.44190.039*0.50
C30.0962 (11)0.1672 (7)0.5247 (4)0.0349 (18)0.50
H30.00990.10240.53520.042*0.50
C2'0.3222 (11)0.1412 (8)0.4839 (4)0.0358 (19)0.50
H2'0.39520.07360.46930.043*0.50
C3'0.2327 (12)0.1373 (8)0.5421 (4)0.0365 (19)0.50
H3'0.24220.06760.56740.044*0.50
C40.1185 (8)0.25000.5637 (3)0.0434 (15)
S10.7046 (2)0.2722 (4)0.40129 (8)0.0332 (12)0.50
C1S0.8347 (7)0.25000.3299 (3)0.0457 (15)
H1S10.78720.17580.31020.068*0.50
H1S20.97830.24340.33790.068*0.50
H1S30.80970.31870.30250.068*0.50
C2S0.7549 (13)0.1347 (8)0.4431 (4)0.044 (2)0.50
H2S10.73090.05620.42370.067*0.50
H2S20.67230.14190.48020.067*0.50
H2S30.89620.14150.45440.067*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0363 (2)0.0504 (3)0.0412 (3)0.0024 (2)0.00076 (19)0.0077 (2)
B10.025 (3)0.048 (4)0.036 (4)0.0000.001 (2)0.000
Si10.0298 (8)0.0701 (13)0.0340 (9)0.0000.0022 (7)0.000
C110.043 (3)0.083 (4)0.044 (3)0.005 (3)0.0031 (19)0.004 (3)
C120.033 (3)0.073 (5)0.053 (4)0.0000.007 (3)0.000
C10.024 (2)0.044 (4)0.033 (3)0.0000.003 (2)0.000
C20.034 (4)0.028 (4)0.035 (4)0.003 (3)0.002 (3)0.007 (4)
C30.031 (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)
C40.023 (2)0.075 (5)0.033 (3)0.0000.002 (3)0.000
S10.0215 (6)0.040 (4)0.0386 (9)0.0008 (9)0.0012 (6)0.0011 (10)
C1S0.025 (3)0.062 (4)0.050 (4)0.0000.006 (3)0.000
C2S0.039 (5)0.045 (6)0.049 (5)0.006 (4)0.002 (4)0.012 (4)
Geometric parameters (Å, º) top
Br1—B12.022 (4)C1—C2'1.476 (9)
B1—C11.592 (8)C2—C31.399 (11)
B1—S11.977 (6)C2—H20.9500
B1—S1i1.977 (6)C3—C41.258 (9)
B1—Br1i2.022 (4)C3—H30.9500
Si1—C11i1.865 (5)C2'—C3'1.398 (11)
Si1—C111.865 (5)C2'—H2'0.9500
Si1—C121.874 (6)C3'—C41.538 (9)
Si1—C41.893 (6)C3'—H3'0.9500
C11—H11A0.9800S1—C2S1.806 (9)
C11—H11B0.9800S1—C1S1.794 (6)
C11—H11C0.9800C1S—H1S10.9800
C12—H12A0.9800C1S—H1S20.9800
C12—H12B0.9800C1S—H1S30.9800
C12—H12C0.9800C2S—H2S10.9800
C1—C21.315 (8)C2S—H2S20.9800
C1—C2i1.315 (8)C2S—H2S30.9800
C1—C2'i1.476 (9)
C1—B1—S1105.9 (4)C4—C3—C2124.8 (7)
C1—B1—S1i105.9 (4)C2—C3—C3i91.6 (5)
C1—B1—Br1i114.3 (2)C4—C3—H3117.6
S1—B1—Br1i111.6 (2)C2—C3—H3117.6
S1i—B1—Br1i99.5 (2)C3i—C3—H3139.2
C1—B1—Br1114.3 (2)C3'—C2'—C1120.3 (7)
S1—B1—Br199.5 (2)C3'—C2'—H2'119.9
S1i—B1—Br1111.6 (2)C1—C2'—H2'119.9
Br1i—B1—Br1110.0 (3)C2'—C3'—C4117.6 (7)
C11i—Si1—C11110.8 (3)C2'—C3'—H3'121.2
C11i—Si1—C12110.08 (18)C4—C3'—H3'121.2
C11—Si1—C12110.08 (18)C3—C4—C3i93.7 (8)
C11i—Si1—C4108.50 (17)C3—C4—C3'i116.5 (6)
C11—Si1—C4108.50 (17)C3i—C4—C3'116.5 (6)
C12—Si1—C4108.8 (3)C3'i—C4—C3'108.7 (7)
Si1—C11—H11A109.5C3—C4—Si1124.3 (4)
Si1—C11—H11B109.5C3i—C4—Si1124.3 (4)
H11A—C11—H11B109.5C3'i—C4—Si1118.9 (4)
Si1—C11—H11C109.5C3'—C4—Si1118.9 (4)
H11A—C11—H11C109.5C2Si—S1—C2S104.5 (7)
H11B—C11—H11C109.5C2Si—S1—C1S122.5 (4)
Si1—C12—H12A109.5C2S—S1—C1S103.1 (4)
Si1—C12—H12B109.5C2Si—S1—B1117.7 (4)
H12A—C12—H12B109.5C2S—S1—B1100.8 (3)
Si1—C12—H12C109.5C1S—S1—B1105.1 (3)
H12A—C12—H12C109.5S1—C1S—H1S1109.5
H12B—C12—H12C109.5S1—C1S—H1S2109.5
C2—C1—C2i93.4 (8)H1S1—C1S—H1S2109.5
C2—C1—C2'i116.0 (6)S1—C1S—H1S3109.5
C2i—C1—C2'116.0 (6)H1S1—C1S—H1S3109.5
C2'i—C1—C2'109.6 (8)H1S2—C1S—H1S3109.5
C2—C1—B1126.7 (4)S1i—C2S—H2S1109.5
C2i—C1—B1126.7 (4)S1—C2S—H2S1120.2
C2'i—C1—B1117.2 (4)S1i—C2S—H2S2109.5
C2'—C1—B1117.2 (4)S1—C2S—H2S2103.8
C1—C2—C3124.1 (7)H2S1—C2S—H2S2109.5
C3—C2—C2i88.4 (5)S1i—C2S—H2S3109.5
C1—C2—H2117.9S1—C2S—H2S3103.9
C3—C2—H2117.9H2S1—C2S—H2S3109.5
C2i—C2—H2143.8H2S2—C2S—H2S3109.5
S1—B1—C1—C2122.2 (6)C2—C3—C4—Si1177.0 (6)
S1i—B1—C1—C2107.3 (6)C3i—C3—C4—Si1136.7 (8)
Br1i—B1—C1—C21.2 (8)C2'—C3'—C4—C371.2 (9)
Br1—B1—C1—C2129.3 (6)C2'—C3'—C4—C3i7.3 (11)
S1—B1—C1—C2i107.3 (6)C2'—C3'—C4—C3'i38.0 (11)
S1i—B1—C1—C2i122.2 (6)C2'—C3'—C4—Si1178.3 (6)
Br1i—B1—C1—C2i129.3 (6)C11i—Si1—C4—C3178.2 (6)
Br1—B1—C1—C2i1.2 (8)C11—Si1—C4—C357.7 (6)
S1—B1—C1—C2'i59.3 (5)C12—Si1—C4—C362.0 (6)
S1i—B1—C1—C2'i74.2 (5)C11i—Si1—C4—C3i57.7 (6)
Br1i—B1—C1—C2'i177.3 (4)C11—Si1—C4—C3i178.2 (6)
Br1—B1—C1—C2'i49.1 (6)C12—Si1—C4—C3i62.0 (6)
S1—B1—C1—C2'74.2 (5)C11i—Si1—C4—C3'i7.9 (5)
S1i—B1—C1—C2'59.3 (5)C11—Si1—C4—C3'i128.3 (5)
Br1i—B1—C1—C2'49.1 (6)C12—Si1—C4—C3'i111.9 (5)
Br1—B1—C1—C2'177.3 (4)C11i—Si1—C4—C3'128.3 (5)
C2i—C1—C2—C339.8 (12)C11—Si1—C4—C3'7.9 (5)
C2'i—C1—C2—C33.6 (12)C12—Si1—C4—C3'111.9 (5)
C2'—C1—C2—C386.9 (10)C1—B1—S1—S1i92.06 (7)
B1—C1—C2—C3177.9 (6)Br1i—B1—S1—S1i33.0 (2)
C2'i—C1—C2—C2i36.1 (4)Br1—B1—S1—S1i149.1 (2)
C2'—C1—C2—C2i126.7 (7)C1—B1—S1—C2Si47.8 (5)
B1—C1—C2—C2i142.4 (9)S1i—B1—S1—C2Si139.9 (5)
C1—C2—C3—C43.6 (14)Br1i—B1—S1—C2Si172.9 (5)
C2i—C2—C3—C429.6 (8)Br1—B1—S1—C2Si71.0 (5)
C1—C2—C3—C3i26.0 (8)C1—B1—S1—C2S65.0 (3)
C2i—C2—C3—C3i0.000 (3)S1i—B1—S1—C2S27.1 (3)
C2—C1—C2'—C3'67.5 (8)Br1i—B1—S1—C2S60.1 (4)
C2i—C1—C2'—C3'4.5 (11)Br1—B1—S1—C2S176.2 (4)
C2'i—C1—C2'—C3'40.0 (11)C1—B1—S1—C1S171.85 (15)
B1—C1—C2'—C3'176.9 (6)S1i—B1—S1—C1S79.79 (18)
C1—C2'—C3'—C40.7 (11)Br1i—B1—S1—C1S46.8 (3)
C2—C3—C4—C3i46.3 (11)Br1—B1—S1—C1S69.3 (3)
C2—C3—C4—C3'i8.9 (12)C2Si—S1—C2S—S1i180.000 (11)
C3i—C3—C4—C3'i37.3 (5)C1S—S1—C2S—S1i50.9 (5)
C2—C3—C4—C3'80.1 (9)B1—S1—C2S—S1i57.5 (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 formulaC6H5BBr2C9H13BBr2SiC6H4BBr3C8H12BBr2N
Mr247.73319.91326.63292.82
Crystal system, space groupOrthorhombic, PbcaMonoclinic, P21/cTetragonal, I41/aMonoclinic, P21/c
Temperature (K)173173173173
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, 9090, 93.841 (6), 9090, 90, 9090, 92.249 (8), 90
V3)1537.6 (4)1273.00 (17)3488.0 (8)1069.1 (2)
Z84164
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)10.456.4213.807.53
Crystal size (mm)0.29 × 0.17 × 0.090.29 × 0.25 × 0.250.26 × 0.11 × 0.110.19 × 0.09 × 0.05
Data collection
DiffractometerStoe IPDS II two-circle
diffractometer
Stoe IPDS II two-circle
diffractometer
Stoe IPDS II two-circle
diffractometer
Stoe IPDS II two-circle
diffractometer
Absorption correctionMulti-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, Tmax0.152, 0.4530.258, 0.2970.124, 0.3120.329, 0.705
No. of measured, independent and
observed [I > 2σ(I)] reflections
14258, 1517, 1089 19196, 2235, 1942 12710, 1544, 1111 6363, 2004, 1413
Rint0.0810.0640.0970.082
(sin θ/λ)max1)0.6190.5950.5950.608
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 reflections1517223515442004
No. of parameters8211991113
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.59, 1.070.46, 0.370.90, 1.080.98, 0.96


(V)
Crystal data
Chemical formulaC11H19BBr2SSi
Mr382.04
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)173
a, b, c (Å)6.6950 (5), 11.0880 (8), 21.6870 (16)
α, β, γ (°)90, 90, 90
V3)1609.9 (2)
Z4
Radiation typeMo Kα
µ (mm1)5.21
Crystal size (mm)0.20 × 0.10 × 0.05
Data collection
DiffractometerStoe IPDS II two-circle
diffractometer
Absorption correctionMulti-scan
(MULABS; Spek, 2009; Blessing, 1995)
Tmin, Tmax0.422, 0.781
No. of measured, independent and
observed [I > 2σ(I)] reflections
22983, 1705, 1146
Rint0.073
(sin θ/λ)max1)0.623
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.083, 0.90
No. of reflections1705
No. of parameters110
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.40, 0.56

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) for (IV) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br1i0.85 (7)2.96 (7)3.705 (6)147 (6)
N1—H1···Br2i0.85 (7)2.96 (7)3.684 (5)143 (6)
Symmetry code: (i) x, y, z+1.
Bond lengths (Å) for (I)–(V) top
Bond(I)(II)(III)(IV)(V)
C—B1.533 (9)1.535 (5)1.53 (2)1.600 (9)1.592 (8)
B—Br1.917 (7)1.906 (4)1.911 (16)2.049 (6)2.022 (4)
B—Br1.919 (7)1.915 (4)1.926 (16)2.058 (7)2.022 (4)
 

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