Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802013909/bt6177sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802013909/bt6177Isup2.hkl |
CCDC reference: 197451
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.007 Å
- R factor = 0.022
- wR factor = 0.052
- Data-to-parameter ratio = 17.1
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Crystals of the title compound were obtained from a reaction between BiCl2Ph and [NMe4]Cl in tetrahydrofuran overlaid with hexane.
Methyl H atoms were positioned using a rotating-group refinement, with isotropic displacement parameters 1.5 times that of their adjacent C atom. The phenyl H atoms were constrained to ideal geometries and assigned isotropic displacement parameters 1.2 times that of their adjacent C atom. The two highest residual electron-density peaks (1.59 and 1.50 e Å−3) are found 0.97 and 0.98 Å from the Bi atom. All other residual electron-density peaks with have values less than 1 e Å−3.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SHELXTL (Bruker 1998); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids. |
(C4H12N)[BiCl2(C6H5)2] | F(000) = 968 |
Mr = 508.23 | Dx = 1.865 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 181 reflections |
a = 12.162 (3) Å | θ = 2–20° |
b = 11.1693 (15) Å | µ = 10.03 mm−1 |
c = 14.241 (3) Å | T = 173 K |
β = 110.642 (14)° | Block, colourless |
V = 1810.3 (7) Å3 | 0.30 × 0.10 × 0.05 mm |
Z = 4 |
Bruker CCD area-detector diffractometer | 3185 independent reflections |
Radiation source: fine-focus sealed tube | 2787 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
0.3° ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→14 |
Tmin = 0.305, Tmax = 0.605 | k = −13→13 |
9238 measured reflections | l = −16→16 |
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)] = 0.022 | H-atom parameters constrained |
wR(F2) = 0.052 | w = 1/[σ2(Fo2) + (0.0278P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
3185 reflections | Δρmax = 1.59 e Å−3 |
186 parameters | Δρmin = −1.28 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00272 (13) |
(C4H12N)[BiCl2(C6H5)2] | V = 1810.3 (7) Å3 |
Mr = 508.23 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.162 (3) Å | µ = 10.03 mm−1 |
b = 11.1693 (15) Å | T = 173 K |
c = 14.241 (3) Å | 0.30 × 0.10 × 0.05 mm |
β = 110.642 (14)° |
Bruker CCD area-detector diffractometer | 3185 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2787 reflections with I > 2σ(I) |
Tmin = 0.305, Tmax = 0.605 | Rint = 0.026 |
9238 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.052 | H-atom parameters constrained |
S = 1.02 | Δρmax = 1.59 e Å−3 |
3185 reflections | Δρmin = −1.28 e Å−3 |
186 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 | ||
Bi1 | 0.415160 (15) | 0.078860 (13) | 0.160384 (11) | 0.02378 (8) | |
Cl1 | 0.40223 (11) | 0.28055 (9) | 0.04809 (8) | 0.0321 (3) | |
Cl2 | 0.45006 (12) | −0.11612 (10) | 0.28320 (9) | 0.0360 (3) | |
C1 | 0.4514 (4) | 0.2000 (4) | 0.2944 (3) | 0.0249 (10) | |
C2 | 0.3835 (4) | 0.3023 (4) | 0.2881 (4) | 0.0316 (11) | |
H2A | 0.3241 | 0.3230 | 0.2262 | 0.038* | |
C3 | 0.4023 (5) | 0.3737 (4) | 0.3714 (4) | 0.0382 (12) | |
H3A | 0.3558 | 0.4433 | 0.3667 | 0.046* | |
C4 | 0.4880 (5) | 0.3443 (4) | 0.4614 (4) | 0.0355 (12) | |
H4A | 0.5002 | 0.3937 | 0.5185 | 0.043* | |
C5 | 0.5564 (4) | 0.2439 (4) | 0.4691 (3) | 0.0347 (11) | |
H5A | 0.6156 | 0.2238 | 0.5313 | 0.042* | |
C6 | 0.5377 (4) | 0.1720 (4) | 0.3847 (3) | 0.0280 (10) | |
H6A | 0.5850 | 0.1030 | 0.3895 | 0.034* | |
C7 | 0.6037 (4) | 0.0627 (3) | 0.1748 (3) | 0.0240 (10) | |
C8 | 0.6875 (4) | 0.1500 (4) | 0.2222 (3) | 0.0269 (10) | |
H8A | 0.6647 | 0.2183 | 0.2508 | 0.032* | |
C9 | 0.8026 (4) | 0.1382 (4) | 0.2280 (3) | 0.0319 (11) | |
H9A | 0.8585 | 0.1983 | 0.2601 | 0.038* | |
C10 | 0.8368 (5) | 0.0378 (4) | 0.1867 (3) | 0.0332 (11) | |
H10A | 0.9164 | 0.0281 | 0.1923 | 0.040* | |
C11 | 0.7544 (5) | −0.0472 (4) | 0.1378 (3) | 0.0339 (12) | |
H11A | 0.7767 | −0.1141 | 0.1074 | 0.041* | |
C12 | 0.6393 (4) | −0.0355 (4) | 0.1327 (3) | 0.0286 (10) | |
H12A | 0.5837 | −0.0955 | 0.1000 | 0.034* | |
N1 | 0.3057 (3) | 0.6255 (3) | 0.0236 (2) | 0.0245 (8) | |
C13 | 0.2892 (5) | 0.7578 (4) | 0.0116 (4) | 0.0383 (12) | |
H13A | 0.2101 | 0.7751 | −0.0358 | 0.057* | |
H13B | 0.3476 | 0.7912 | −0.0141 | 0.057* | |
H13C | 0.2990 | 0.7941 | 0.0767 | 0.057* | |
C14 | 0.2131 (5) | 0.5717 (4) | 0.0568 (4) | 0.0380 (12) | |
H14A | 0.1355 | 0.5883 | 0.0067 | 0.057* | |
H14B | 0.2180 | 0.6066 | 0.1213 | 0.057* | |
H14C | 0.2250 | 0.4850 | 0.0643 | 0.057* | |
C15 | 0.4222 (4) | 0.6017 (4) | 0.1007 (3) | 0.0343 (11) | |
H15A | 0.4837 | 0.6326 | 0.0777 | 0.051* | |
H15B | 0.4326 | 0.5152 | 0.1120 | 0.051* | |
H15C | 0.4276 | 0.6413 | 0.1635 | 0.051* | |
C16 | 0.2989 (4) | 0.5720 (4) | −0.0746 (3) | 0.0298 (11) | |
H16A | 0.2231 | 0.5921 | −0.1260 | 0.045* | |
H16B | 0.3066 | 0.4848 | −0.0679 | 0.045* | |
H16C | 0.3626 | 0.6040 | −0.0943 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Bi1 | 0.02518 (11) | 0.02316 (11) | 0.02378 (11) | −0.00265 (7) | 0.00958 (8) | 0.00010 (7) |
Cl1 | 0.0390 (7) | 0.0267 (5) | 0.0322 (6) | 0.0024 (5) | 0.0146 (5) | 0.0055 (5) |
Cl2 | 0.0441 (8) | 0.0294 (6) | 0.0350 (6) | −0.0065 (5) | 0.0144 (6) | 0.0053 (5) |
C1 | 0.028 (3) | 0.026 (2) | 0.029 (2) | −0.0056 (19) | 0.019 (2) | −0.0009 (18) |
C2 | 0.032 (3) | 0.029 (2) | 0.038 (3) | 0.003 (2) | 0.018 (2) | 0.003 (2) |
C3 | 0.045 (3) | 0.027 (2) | 0.052 (3) | 0.004 (2) | 0.028 (3) | −0.004 (2) |
C4 | 0.040 (3) | 0.034 (3) | 0.038 (3) | −0.008 (2) | 0.021 (3) | −0.011 (2) |
C5 | 0.034 (3) | 0.041 (3) | 0.030 (2) | −0.006 (2) | 0.013 (2) | −0.006 (2) |
C6 | 0.031 (3) | 0.029 (2) | 0.027 (2) | 0.002 (2) | 0.014 (2) | 0.0007 (19) |
C7 | 0.031 (3) | 0.024 (2) | 0.018 (2) | 0.0033 (19) | 0.010 (2) | 0.0053 (17) |
C8 | 0.033 (3) | 0.024 (2) | 0.025 (2) | 0.003 (2) | 0.012 (2) | −0.0008 (18) |
C9 | 0.029 (3) | 0.040 (3) | 0.026 (2) | 0.001 (2) | 0.009 (2) | 0.002 (2) |
C10 | 0.027 (3) | 0.048 (3) | 0.026 (2) | 0.011 (2) | 0.010 (2) | 0.008 (2) |
C11 | 0.042 (3) | 0.033 (2) | 0.031 (3) | 0.016 (2) | 0.018 (2) | 0.006 (2) |
C12 | 0.038 (3) | 0.025 (2) | 0.027 (2) | 0.004 (2) | 0.016 (2) | 0.0014 (18) |
N1 | 0.026 (2) | 0.0243 (18) | 0.0239 (19) | 0.0017 (16) | 0.0095 (17) | −0.0033 (15) |
C13 | 0.058 (4) | 0.023 (2) | 0.039 (3) | 0.002 (2) | 0.022 (3) | −0.002 (2) |
C14 | 0.036 (3) | 0.044 (3) | 0.041 (3) | −0.005 (2) | 0.023 (3) | −0.001 (2) |
C15 | 0.032 (3) | 0.037 (3) | 0.028 (3) | 0.000 (2) | 0.003 (2) | −0.005 (2) |
C16 | 0.035 (3) | 0.035 (3) | 0.020 (2) | 0.003 (2) | 0.010 (2) | −0.0052 (19) |
Bi1—C7 | 2.236 (5) | C10—C11 | 1.378 (7) |
Bi1—C1 | 2.252 (4) | C10—H10A | 0.9500 |
Bi1—Cl2 | 2.7310 (11) | C11—C12 | 1.382 (7) |
Bi1—Cl1 | 2.7348 (11) | C11—H11A | 0.9500 |
C1—C6 | 1.379 (6) | C12—H12A | 0.9500 |
C1—C2 | 1.394 (6) | N1—C15 | 1.479 (6) |
C2—C3 | 1.381 (6) | N1—C14 | 1.492 (6) |
C2—H2A | 0.9500 | N1—C13 | 1.494 (5) |
C3—C4 | 1.376 (7) | N1—C16 | 1.497 (5) |
C3—H3A | 0.9500 | C13—H13A | 0.9800 |
C4—C5 | 1.377 (7) | C13—H13B | 0.9800 |
C4—H4A | 0.9500 | C13—H13C | 0.9800 |
C5—C6 | 1.397 (6) | C14—H14A | 0.9800 |
C5—H5A | 0.9500 | C14—H14B | 0.9800 |
C6—H6A | 0.9500 | C14—H14C | 0.9800 |
C7—C12 | 1.390 (6) | C15—H15A | 0.9800 |
C7—C8 | 1.400 (6) | C15—H15B | 0.9800 |
C8—C9 | 1.379 (7) | C15—H15C | 0.9800 |
C8—H8A | 0.9500 | C16—H16A | 0.9800 |
C9—C10 | 1.396 (7) | C16—H16B | 0.9800 |
C9—H9A | 0.9500 | C16—H16C | 0.9800 |
C7—Bi1—C1 | 94.74 (16) | C10—C11—C12 | 120.2 (4) |
C7—Bi1—Cl2 | 87.37 (10) | C10—C11—H11A | 119.9 |
C1—Bi1—Cl2 | 89.82 (11) | C12—C11—H11A | 119.9 |
C7—Bi1—Cl1 | 88.04 (10) | C11—C12—C7 | 121.1 (5) |
C1—Bi1—Cl1 | 87.37 (10) | C11—C12—H12A | 119.5 |
Cl2—Bi1—Cl1 | 174.40 (4) | C7—C12—H12A | 119.5 |
C6—C1—C2 | 119.0 (4) | C15—N1—C14 | 109.0 (4) |
C6—C1—Bi1 | 120.7 (3) | C15—N1—C13 | 108.5 (4) |
C2—C1—Bi1 | 120.2 (3) | C14—N1—C13 | 110.4 (4) |
C3—C2—C1 | 120.2 (5) | C15—N1—C16 | 110.1 (3) |
C3—C2—H2A | 119.9 | C14—N1—C16 | 109.7 (3) |
C1—C2—H2A | 119.9 | C13—N1—C16 | 109.1 (3) |
C4—C3—C2 | 120.3 (5) | N1—C13—H13A | 109.5 |
C4—C3—H3A | 119.9 | N1—C13—H13B | 109.5 |
C2—C3—H3A | 119.9 | H13A—C13—H13B | 109.5 |
C3—C4—C5 | 120.5 (4) | N1—C13—H13C | 109.5 |
C3—C4—H4A | 119.8 | H13A—C13—H13C | 109.5 |
C5—C4—H4A | 119.8 | H13B—C13—H13C | 109.5 |
C4—C5—C6 | 119.3 (4) | N1—C14—H14A | 109.5 |
C4—C5—H5A | 120.4 | N1—C14—H14B | 109.5 |
C6—C5—H5A | 120.4 | H14A—C14—H14B | 109.5 |
C1—C6—C5 | 120.8 (4) | N1—C14—H14C | 109.5 |
C1—C6—H6A | 119.6 | H14A—C14—H14C | 109.5 |
C5—C6—H6A | 119.6 | H14B—C14—H14C | 109.5 |
C12—C7—C8 | 118.2 (4) | N1—C15—H15A | 109.5 |
C12—C7—Bi1 | 119.3 (3) | N1—C15—H15B | 109.5 |
C8—C7—Bi1 | 122.5 (3) | H15A—C15—H15B | 109.5 |
C9—C8—C7 | 120.9 (4) | N1—C15—H15C | 109.5 |
C9—C8—H8A | 119.6 | H15A—C15—H15C | 109.5 |
C7—C8—H8A | 119.6 | H15B—C15—H15C | 109.5 |
C8—C9—C10 | 119.9 (4) | N1—C16—H16A | 109.5 |
C8—C9—H9A | 120.1 | N1—C16—H16B | 109.5 |
C10—C9—H9A | 120.1 | H16A—C16—H16B | 109.5 |
C11—C10—C9 | 119.7 (5) | N1—C16—H16C | 109.5 |
C11—C10—H10A | 120.2 | H16A—C16—H16C | 109.5 |
C9—C10—H10A | 120.2 | H16B—C16—H16C | 109.5 |
C7—Bi1—C1—C6 | −48.7 (4) | C1—Bi1—C7—C12 | 157.2 (3) |
Cl2—Bi1—C1—C6 | 38.6 (3) | Cl2—Bi1—C7—C12 | 67.6 (3) |
Cl1—Bi1—C1—C6 | −136.6 (3) | Cl1—Bi1—C7—C12 | −115.6 (3) |
C7—Bi1—C1—C2 | 133.7 (3) | C1—Bi1—C7—C8 | −24.8 (3) |
Cl2—Bi1—C1—C2 | −138.9 (3) | Cl2—Bi1—C7—C8 | −114.4 (3) |
Cl1—Bi1—C1—C2 | 45.9 (3) | Cl1—Bi1—C7—C8 | 62.4 (3) |
C6—C1—C2—C3 | −0.5 (7) | C12—C7—C8—C9 | −0.7 (6) |
Bi1—C1—C2—C3 | 177.1 (3) | Bi1—C7—C8—C9 | −178.7 (3) |
C1—C2—C3—C4 | 0.0 (7) | C7—C8—C9—C10 | −0.4 (7) |
C2—C3—C4—C5 | 0.3 (7) | C8—C9—C10—C11 | 1.9 (7) |
C3—C4—C5—C6 | 0.0 (7) | C9—C10—C11—C12 | −2.4 (7) |
C2—C1—C6—C5 | 0.7 (7) | C10—C11—C12—C7 | 1.3 (7) |
Bi1—C1—C6—C5 | −176.8 (3) | C8—C7—C12—C11 | 0.3 (6) |
C4—C5—C6—C1 | −0.5 (7) | Bi1—C7—C12—C11 | 178.3 (3) |
Experimental details
Crystal data | |
Chemical formula | (C4H12N)[BiCl2(C6H5)2] |
Mr | 508.23 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 12.162 (3), 11.1693 (15), 14.241 (3) |
β (°) | 110.642 (14) |
V (Å3) | 1810.3 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 10.03 |
Crystal size (mm) | 0.30 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.305, 0.605 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9238, 3185, 2787 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.052, 1.02 |
No. of reflections | 3185 |
No. of parameters | 186 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.59, −1.28 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Bruker 1998), SHELXTL.
Bi1—C7 | 2.236 (5) | Bi1—Cl2 | 2.7310 (11) |
Bi1—C1 | 2.252 (4) | Bi1—Cl1 | 2.7348 (11) |
C7—Bi1—C1 | 94.74 (16) | C7—Bi1—Cl1 | 88.04 (10) |
C7—Bi1—Cl2 | 87.37 (10) | C1—Bi1—Cl1 | 87.37 (10) |
C1—Bi1—Cl2 | 89.82 (11) | Cl2—Bi1—Cl1 | 174.40 (4) |
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A variety of anions of formula [ECl2Ph2]− are known for arsenic (Grewe et al., 1998) and antimony (Sheldrick & Martin, 1992; Hall & Sowerby, 1988; Calderazzo et al., 1991; Stark et al., 1999). For bismuth, the [BiBr2Ph2]− (Stark et al., 1999; Clegg et al., 1992) and [BiI2Ph2]− (Clegg et al., 1993) ions have been structurally characterized. This paper reports the structure of the [BiCl2Ph2]− anion as the tetramethylammonium salt, (I).
The structure of the anion in (I) is similar to that found for other diaryldihalobismuthate(III) anions. The geometry is based on a trigonal bipyramid in which the formal lone pair and phenyl groups occupy equatorial positions and the halides reside in axial sites. For bismuth, the C—Bi—C angle between the equatorial phenyl groups approaches 90°, which is typical of inter-bond angles in BiIII structures (Clegg et al. 1992, 1993).