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The crystal structure of the title compound, (C4H12N)[BiCl2(C6H5)2], contains a [BiCl2Ph2]- anion with an equatorially vacant trigonal-bipyramidal geometry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802013909/bt6177sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802013909/bt6177Isup2.hkl
Contains datablock I

CCDC reference: 197451

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](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








Comment top

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).

Experimental top

Crystals of the title compound were obtained from a reaction between BiCl2Ph and [NMe4]Cl in tetrahydrofuran overlaid with hexane.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids.
(I) top
Crystal data top
(C4H12N)[BiCl2(C6H5)2]F(000) = 968
Mr = 508.23Dx = 1.865 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 181 reflections
a = 12.162 (3) Åθ = 2–20°
b = 11.1693 (15) ŵ = 10.03 mm1
c = 14.241 (3) ÅT = 173 K
β = 110.642 (14)°Block, colourless
V = 1810.3 (7) Å30.30 × 0.10 × 0.05 mm
Z = 4
Data collection top
Bruker CCD area-detector
diffractometer
3185 independent reflections
Radiation source: fine-focus sealed tube2787 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
0.3° ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1114
Tmin = 0.305, Tmax = 0.605k = 1313
9238 measured reflectionsl = 1616
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)] = 0.022H-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 reflectionsΔρmax = 1.59 e Å3
186 parametersΔρmin = 1.28 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00272 (13)
Crystal data top
(C4H12N)[BiCl2(C6H5)2]V = 1810.3 (7) Å3
Mr = 508.23Z = 4
Monoclinic, P21/nMo Kα radiation
a = 12.162 (3) ŵ = 10.03 mm1
b = 11.1693 (15) ÅT = 173 K
c = 14.241 (3) Å0.30 × 0.10 × 0.05 mm
β = 110.642 (14)°
Data collection top
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 = 0.605Rint = 0.026
9238 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.052H-atom parameters constrained
S = 1.02Δρmax = 1.59 e Å3
3185 reflectionsΔρmin = 1.28 e Å3
186 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
Bi10.415160 (15)0.078860 (13)0.160384 (11)0.02378 (8)
Cl10.40223 (11)0.28055 (9)0.04809 (8)0.0321 (3)
Cl20.45006 (12)0.11612 (10)0.28320 (9)0.0360 (3)
C10.4514 (4)0.2000 (4)0.2944 (3)0.0249 (10)
C20.3835 (4)0.3023 (4)0.2881 (4)0.0316 (11)
H2A0.32410.32300.22620.038*
C30.4023 (5)0.3737 (4)0.3714 (4)0.0382 (12)
H3A0.35580.44330.36670.046*
C40.4880 (5)0.3443 (4)0.4614 (4)0.0355 (12)
H4A0.50020.39370.51850.043*
C50.5564 (4)0.2439 (4)0.4691 (3)0.0347 (11)
H5A0.61560.22380.53130.042*
C60.5377 (4)0.1720 (4)0.3847 (3)0.0280 (10)
H6A0.58500.10300.38950.034*
C70.6037 (4)0.0627 (3)0.1748 (3)0.0240 (10)
C80.6875 (4)0.1500 (4)0.2222 (3)0.0269 (10)
H8A0.66470.21830.25080.032*
C90.8026 (4)0.1382 (4)0.2280 (3)0.0319 (11)
H9A0.85850.19830.26010.038*
C100.8368 (5)0.0378 (4)0.1867 (3)0.0332 (11)
H10A0.91640.02810.19230.040*
C110.7544 (5)0.0472 (4)0.1378 (3)0.0339 (12)
H11A0.77670.11410.10740.041*
C120.6393 (4)0.0355 (4)0.1327 (3)0.0286 (10)
H12A0.58370.09550.10000.034*
N10.3057 (3)0.6255 (3)0.0236 (2)0.0245 (8)
C130.2892 (5)0.7578 (4)0.0116 (4)0.0383 (12)
H13A0.21010.77510.03580.057*
H13B0.34760.79120.01410.057*
H13C0.29900.79410.07670.057*
C140.2131 (5)0.5717 (4)0.0568 (4)0.0380 (12)
H14A0.13550.58830.00670.057*
H14B0.21800.60660.12130.057*
H14C0.22500.48500.06430.057*
C150.4222 (4)0.6017 (4)0.1007 (3)0.0343 (11)
H15A0.48370.63260.07770.051*
H15B0.43260.51520.11200.051*
H15C0.42760.64130.16350.051*
C160.2989 (4)0.5720 (4)0.0746 (3)0.0298 (11)
H16A0.22310.59210.12600.045*
H16B0.30660.48480.06790.045*
H16C0.36260.60400.09430.045*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Bi10.02518 (11)0.02316 (11)0.02378 (11)0.00265 (7)0.00958 (8)0.00010 (7)
Cl10.0390 (7)0.0267 (5)0.0322 (6)0.0024 (5)0.0146 (5)0.0055 (5)
Cl20.0441 (8)0.0294 (6)0.0350 (6)0.0065 (5)0.0144 (6)0.0053 (5)
C10.028 (3)0.026 (2)0.029 (2)0.0056 (19)0.019 (2)0.0009 (18)
C20.032 (3)0.029 (2)0.038 (3)0.003 (2)0.018 (2)0.003 (2)
C30.045 (3)0.027 (2)0.052 (3)0.004 (2)0.028 (3)0.004 (2)
C40.040 (3)0.034 (3)0.038 (3)0.008 (2)0.021 (3)0.011 (2)
C50.034 (3)0.041 (3)0.030 (2)0.006 (2)0.013 (2)0.006 (2)
C60.031 (3)0.029 (2)0.027 (2)0.002 (2)0.014 (2)0.0007 (19)
C70.031 (3)0.024 (2)0.018 (2)0.0033 (19)0.010 (2)0.0053 (17)
C80.033 (3)0.024 (2)0.025 (2)0.003 (2)0.012 (2)0.0008 (18)
C90.029 (3)0.040 (3)0.026 (2)0.001 (2)0.009 (2)0.002 (2)
C100.027 (3)0.048 (3)0.026 (2)0.011 (2)0.010 (2)0.008 (2)
C110.042 (3)0.033 (2)0.031 (3)0.016 (2)0.018 (2)0.006 (2)
C120.038 (3)0.025 (2)0.027 (2)0.004 (2)0.016 (2)0.0014 (18)
N10.026 (2)0.0243 (18)0.0239 (19)0.0017 (16)0.0095 (17)0.0033 (15)
C130.058 (4)0.023 (2)0.039 (3)0.002 (2)0.022 (3)0.002 (2)
C140.036 (3)0.044 (3)0.041 (3)0.005 (2)0.023 (3)0.001 (2)
C150.032 (3)0.037 (3)0.028 (3)0.000 (2)0.003 (2)0.005 (2)
C160.035 (3)0.035 (3)0.020 (2)0.003 (2)0.010 (2)0.0052 (19)
Geometric parameters (Å, º) top
Bi1—C72.236 (5)C10—C111.378 (7)
Bi1—C12.252 (4)C10—H10A0.9500
Bi1—Cl22.7310 (11)C11—C121.382 (7)
Bi1—Cl12.7348 (11)C11—H11A0.9500
C1—C61.379 (6)C12—H12A0.9500
C1—C21.394 (6)N1—C151.479 (6)
C2—C31.381 (6)N1—C141.492 (6)
C2—H2A0.9500N1—C131.494 (5)
C3—C41.376 (7)N1—C161.497 (5)
C3—H3A0.9500C13—H13A0.9800
C4—C51.377 (7)C13—H13B0.9800
C4—H4A0.9500C13—H13C0.9800
C5—C61.397 (6)C14—H14A0.9800
C5—H5A0.9500C14—H14B0.9800
C6—H6A0.9500C14—H14C0.9800
C7—C121.390 (6)C15—H15A0.9800
C7—C81.400 (6)C15—H15B0.9800
C8—C91.379 (7)C15—H15C0.9800
C8—H8A0.9500C16—H16A0.9800
C9—C101.396 (7)C16—H16B0.9800
C9—H9A0.9500C16—H16C0.9800
C7—Bi1—C194.74 (16)C10—C11—C12120.2 (4)
C7—Bi1—Cl287.37 (10)C10—C11—H11A119.9
C1—Bi1—Cl289.82 (11)C12—C11—H11A119.9
C7—Bi1—Cl188.04 (10)C11—C12—C7121.1 (5)
C1—Bi1—Cl187.37 (10)C11—C12—H12A119.5
Cl2—Bi1—Cl1174.40 (4)C7—C12—H12A119.5
C6—C1—C2119.0 (4)C15—N1—C14109.0 (4)
C6—C1—Bi1120.7 (3)C15—N1—C13108.5 (4)
C2—C1—Bi1120.2 (3)C14—N1—C13110.4 (4)
C3—C2—C1120.2 (5)C15—N1—C16110.1 (3)
C3—C2—H2A119.9C14—N1—C16109.7 (3)
C1—C2—H2A119.9C13—N1—C16109.1 (3)
C4—C3—C2120.3 (5)N1—C13—H13A109.5
C4—C3—H3A119.9N1—C13—H13B109.5
C2—C3—H3A119.9H13A—C13—H13B109.5
C3—C4—C5120.5 (4)N1—C13—H13C109.5
C3—C4—H4A119.8H13A—C13—H13C109.5
C5—C4—H4A119.8H13B—C13—H13C109.5
C4—C5—C6119.3 (4)N1—C14—H14A109.5
C4—C5—H5A120.4N1—C14—H14B109.5
C6—C5—H5A120.4H14A—C14—H14B109.5
C1—C6—C5120.8 (4)N1—C14—H14C109.5
C1—C6—H6A119.6H14A—C14—H14C109.5
C5—C6—H6A119.6H14B—C14—H14C109.5
C12—C7—C8118.2 (4)N1—C15—H15A109.5
C12—C7—Bi1119.3 (3)N1—C15—H15B109.5
C8—C7—Bi1122.5 (3)H15A—C15—H15B109.5
C9—C8—C7120.9 (4)N1—C15—H15C109.5
C9—C8—H8A119.6H15A—C15—H15C109.5
C7—C8—H8A119.6H15B—C15—H15C109.5
C8—C9—C10119.9 (4)N1—C16—H16A109.5
C8—C9—H9A120.1N1—C16—H16B109.5
C10—C9—H9A120.1H16A—C16—H16B109.5
C11—C10—C9119.7 (5)N1—C16—H16C109.5
C11—C10—H10A120.2H16A—C16—H16C109.5
C9—C10—H10A120.2H16B—C16—H16C109.5
C7—Bi1—C1—C648.7 (4)C1—Bi1—C7—C12157.2 (3)
Cl2—Bi1—C1—C638.6 (3)Cl2—Bi1—C7—C1267.6 (3)
Cl1—Bi1—C1—C6136.6 (3)Cl1—Bi1—C7—C12115.6 (3)
C7—Bi1—C1—C2133.7 (3)C1—Bi1—C7—C824.8 (3)
Cl2—Bi1—C1—C2138.9 (3)Cl2—Bi1—C7—C8114.4 (3)
Cl1—Bi1—C1—C245.9 (3)Cl1—Bi1—C7—C862.4 (3)
C6—C1—C2—C30.5 (7)C12—C7—C8—C90.7 (6)
Bi1—C1—C2—C3177.1 (3)Bi1—C7—C8—C9178.7 (3)
C1—C2—C3—C40.0 (7)C7—C8—C9—C100.4 (7)
C2—C3—C4—C50.3 (7)C8—C9—C10—C111.9 (7)
C3—C4—C5—C60.0 (7)C9—C10—C11—C122.4 (7)
C2—C1—C6—C50.7 (7)C10—C11—C12—C71.3 (7)
Bi1—C1—C6—C5176.8 (3)C8—C7—C12—C110.3 (6)
C4—C5—C6—C10.5 (7)Bi1—C7—C12—C11178.3 (3)

Experimental details

Crystal data
Chemical formula(C4H12N)[BiCl2(C6H5)2]
Mr508.23
Crystal system, space groupMonoclinic, P21/n
Temperature (K)173
a, b, c (Å)12.162 (3), 11.1693 (15), 14.241 (3)
β (°) 110.642 (14)
V3)1810.3 (7)
Z4
Radiation typeMo Kα
µ (mm1)10.03
Crystal size (mm)0.30 × 0.10 × 0.05
Data collection
DiffractometerBruker CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.305, 0.605
No. of measured, independent and
observed [I > 2σ(I)] reflections
9238, 3185, 2787
Rint0.026
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.052, 1.02
No. of reflections3185
No. of parameters186
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.59, 1.28

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Bruker 1998), SHELXTL.

Selected geometric parameters (Å, º) top
Bi1—C72.236 (5)Bi1—Cl22.7310 (11)
Bi1—C12.252 (4)Bi1—Cl12.7348 (11)
C7—Bi1—C194.74 (16)C7—Bi1—Cl188.04 (10)
C7—Bi1—Cl287.37 (10)C1—Bi1—Cl187.37 (10)
C1—Bi1—Cl289.82 (11)Cl2—Bi1—Cl1174.40 (4)
 

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