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An­hydro­us aluminium(III) tribromide crystallizes from aceto­nitrile as a disolvate, AlBr3·2MeCN, in the form [AlBr(C2H3N)5][AlBr4]2·C2H3N, which is isomorphous with its orthorhombic chloride counterpart.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103011429/ta1411sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103011429/ta1411Isup2.hkl
Contains datablock I

CCDC reference: 217132

Comment top

Aluminium trichloride, which crystallizes from acetonitrile as the acetonitrile disolvate AlCl3·2MeCN, is orthorhombic (space group P212121) and is shown to be of the form [ClAl(NCMe)5][AlCl4]2·MeCN (Z = 4) by a single-crystal X-ray study (Beattie et al., 1979). By contrast, FeCl3·2MeCN (orthorhombic, Pna21) is of the form cis-[Cl2Fe(NCMe)4][FeCl4] (Z = 4), while a stoichiometric mixed metal adduct, AlCl3·2FeCl3·6MeCN, can be crystallized in the P212121 form (Z = 4) as [ClAl(NCMe)5][FeCl4]2·MeCN (Gao et al., 1993). While the form of the cation differs between the pure aluminium and the iron complexes, it may be that the difference in form is influenced by increased metal–halide distances throughout the transition, and in this context it is of interest to consider the nature of crystalline material deposited from solutions of aluminium bromide in acetonitrile.

The present material was found to be isostructural with AlCl3·2MeCN, the present coordinate setting being a connected set based on that of the latter. The volumes of the respective MCl3·2MeCN units for AlCl3·2MeCN, FeCl3·2MeCN and AlBr3·2MeCN are 258.6, 253.3 (both at 295 K) and 269.0 Å3 (153 K), while for AlCl3·2FeCl3·6MeCN (295 K), the counterpart value is 257.0 Å3. The present value, even at low temperature, thus exceeds that of all counterpart room-temperature structures by a considerable margin, suggesting that packing volume is not a prime determinant of the structural type. The structure of the anion has numerous precedents with which it is harmonious; in the cation, the Al—N distance trans to the halide [2.003 (7) Å] is comparable to the counterpart value in the chloride analogue [2.021 (8) Å] and is longer than the other Al—N distances in both cases. The present determination appears to be the first that defines bromine coordinated to 'octahedral' aluminium(III).

Refinement top

H atoms were located from difference Fourier maps, and were placed at idealized positions [C—H = 0.95 Å and Uiso(H) = 1.5Ueq(C)] and not refined.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: Xtal (Hall, King, and Stewart, 1995); program(s) used to solve structure: Xtal3.5 (Hall et al., 1995); program(s) used to refine structure: CRYLSQ in Xtal3.5; molecular graphics: Xtal3.5; software used to prepare material for publication: BONDLA CIFIO in Xtal3.5.

Figures top
[Figure 1] Fig. 1. A projection of the cation, showing displacement ellipsoids at the 50% probablilty level for non-H atoms. H atoms are shown with arbitrary radii of 0.1 Å.
(I) top
Crystal data top
[AlBr(C2H3N)5][AlBr4]2·C2H3NF(000) = 1944
Mr = 1046.4Dx = 2.153 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: p 2ac 2abCell parameters from 6185 reflections
a = 10.406 (1) Åθ = 2.6–26.4°
b = 14.479 (2) ŵ = 11.27 mm1
c = 21.421 (3) ÅT = 150 K
V = 3227.5 (7) Å3Block, colourless
Z = 40.18 × 0.15 × 0.12 mm
Data collection top
Bruker SMART CCD
diffractometer
4571 independent reflections
Radiation source: sealed tube3187 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
ω scansθmax = 29.0°, θmin = 1.7°
Absorption correction: multi-scan
SADABS; Sheldrick, 1996
h = 1414
Tmin = 0.126, Tmax = 0.252k = 1919
32073 measured reflectionsl = 2929
Refinement top
Refinement on FPrimary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029H-atom parameters not refined
wR(F2) = 0.027 w = [1/σ2(F) + 0.0004F2]
S = 0.97(Δ/σ)max = 0.016
3187 reflectionsΔρmax = 0.67 e Å3
272 parametersΔρmin = 0.57 e Å3
0 restraintsAbsolute structure: Flack (1983)
0 constraintsAbsolute structure parameter: 0.04 (1)
Crystal data top
[AlBr(C2H3N)5][AlBr4]2·C2H3NV = 3227.5 (7) Å3
Mr = 1046.4Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 10.406 (1) ŵ = 11.27 mm1
b = 14.479 (2) ÅT = 150 K
c = 21.421 (3) Å0.18 × 0.15 × 0.12 mm
Data collection top
Bruker SMART CCD
diffractometer
4571 independent reflections
Absorption correction: multi-scan
SADABS; Sheldrick, 1996
3187 reflections with I > 2σ(I)
Tmin = 0.126, Tmax = 0.252Rint = 0.049
32073 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters not refined
wR(F2) = 0.027Δρmax = 0.67 e Å3
S = 0.97Δρmin = 0.57 e Å3
3187 reflectionsAbsolute structure: Flack (1983)
272 parametersAbsolute structure parameter: 0.04 (1)
0 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Al10.6376 (2)0.37710 (16)0.66449 (11)0.0171 (12)
Br10.41388 (8)0.34433 (6)0.65860 (4)0.0251 (4)
N110.8268 (6)0.4020 (5)0.6683 (3)0.020 (4)
C110.9349 (8)0.4118 (5)0.6696 (3)0.020 (4)
C121.0742 (8)0.4213 (7)0.6721 (4)0.036 (5)
N210.6189 (6)0.4644 (5)0.7346 (3)0.021 (4)
C210.6103 (8)0.5136 (6)0.7747 (4)0.020 (5)
C220.5980 (8)0.5781 (6)0.8272 (4)0.028 (5)
N310.6248 (6)0.4795 (5)0.6045 (3)0.021 (4)
C310.6133 (8)0.5385 (6)0.5706 (4)0.023 (5)
C320.5979 (9)0.6148 (6)0.5259 (4)0.029 (5)
N410.6729 (6)0.2798 (5)0.7273 (3)0.019 (4)
C410.7003 (8)0.2311 (6)0.7668 (4)0.020 (5)
C420.7388 (8)0.1695 (6)0.8174 (4)0.030 (5)
N510.6818 (6)0.2921 (5)0.5958 (3)0.021 (4)
C510.7148 (8)0.2491 (6)0.5538 (4)0.018 (4)
C520.7583 (8)0.1952 (6)0.5007 (4)0.028 (5)
Al21.0117 (3)0.5747 (2)0.50464 (13)0.0223 (15)
Br210.92713 (10)0.64444 (7)0.41773 (4)0.0358 (5)
Br220.94896 (10)0.42208 (7)0.50297 (5)0.0312 (5)
Br231.23160 (9)0.58420 (8)0.50739 (5)0.0418 (6)
Br240.93251 (10)0.64351 (7)0.59251 (4)0.0397 (6)
Al30.9958 (2)0.0566 (2)0.65220 (11)0.0227 (14)
Br310.77485 (8)0.05796 (6)0.65693 (4)0.0276 (5)
Br321.06756 (11)0.11389 (7)0.55902 (4)0.0415 (6)
Br331.06981 (9)0.09163 (7)0.66291 (4)0.0329 (5)
Br341.07132 (11)0.14761 (8)0.73147 (4)0.0454 (6)
N010.4314 (7)0.1727 (5)0.8142 (3)0.030 (4)
C010.3632 (9)0.2325 (6)0.8187 (4)0.025 (5)
C020.2769 (9)0.3124 (6)0.8250 (4)0.034 (5)
H12a1.114730.361630.673730.05400*
H12b1.099640.454310.709320.05400*
H12c1.106590.453510.636550.05400*
H22a0.680330.599660.841280.04200*
H22b0.554480.551390.862320.04200*
H22c0.550850.632090.814910.04200*
H32a0.576760.592470.485040.04300*
H32b0.675090.650590.522720.04300*
H32c0.529910.655030.538490.04300*
H42a0.717560.193380.857590.04300*
H42b0.827660.154400.816480.04300*
H42c0.695320.111460.812630.04300*
H52a0.836730.219910.483130.04300*
H52b0.696130.191570.468550.04300*
H52c0.775840.133270.513310.04300*
H02a0.191440.298470.809860.05200*
H02b0.307680.364470.801750.05200*
H02c0.270220.331070.867080.05200*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Al10.0194 (12)0.0161 (13)0.0157 (12)0.0003 (10)0.0000 (10)0.0009 (10)
Br10.0189 (4)0.0293 (5)0.0271 (4)0.0027 (4)0.0019 (4)0.0032 (4)
N110.023 (4)0.019 (4)0.016 (4)0.002 (3)0.001 (3)0.001 (3)
C110.027 (5)0.019 (4)0.013 (4)0.003 (4)0.001 (4)0.003 (3)
C120.015 (4)0.052 (7)0.040 (5)0.005 (5)0.002 (4)0.002 (5)
N210.026 (4)0.018 (4)0.018 (4)0.002 (3)0.003 (3)0.002 (3)
C210.019 (5)0.019 (5)0.023 (5)0.002 (4)0.002 (4)0.008 (4)
C220.036 (5)0.026 (5)0.023 (5)0.003 (4)0.006 (4)0.008 (4)
N310.024 (4)0.022 (4)0.018 (4)0.001 (3)0.000 (3)0.003 (3)
C310.025 (5)0.026 (5)0.016 (4)0.004 (4)0.003 (4)0.007 (4)
C320.036 (6)0.019 (5)0.031 (5)0.003 (4)0.002 (4)0.010 (4)
N410.023 (4)0.021 (4)0.015 (4)0.002 (3)0.001 (3)0.002 (3)
C410.019 (5)0.019 (5)0.023 (5)0.002 (4)0.000 (4)0.004 (4)
C420.029 (5)0.034 (6)0.027 (5)0.014 (4)0.006 (4)0.015 (4)
N510.021 (4)0.022 (4)0.021 (4)0.001 (3)0.004 (3)0.001 (3)
C510.019 (4)0.015 (5)0.021 (5)0.003 (4)0.005 (4)0.008 (4)
C520.034 (5)0.032 (5)0.020 (4)0.003 (4)0.000 (4)0.012 (4)
Al20.0223 (14)0.0241 (16)0.0204 (14)0.0023 (12)0.0001 (12)0.0008 (14)
Br210.0438 (6)0.0317 (5)0.0319 (5)0.0034 (5)0.0071 (5)0.0113 (4)
Br220.0414 (6)0.0256 (5)0.0267 (5)0.0096 (5)0.0023 (5)0.0041 (5)
Br230.0211 (5)0.0578 (7)0.0464 (6)0.0065 (5)0.0006 (5)0.0142 (6)
Br240.0347 (5)0.0529 (6)0.0316 (5)0.0033 (6)0.0021 (4)0.0180 (5)
Al30.0235 (13)0.0256 (15)0.0191 (13)0.0033 (12)0.0014 (11)0.0002 (12)
Br310.0225 (4)0.0214 (5)0.0388 (5)0.0019 (4)0.0015 (4)0.0005 (4)
Br320.0488 (6)0.0470 (7)0.0287 (5)0.0074 (6)0.0118 (5)0.0109 (4)
Br330.0318 (5)0.0342 (5)0.0328 (5)0.0121 (5)0.0013 (5)0.0041 (4)
Br340.0413 (6)0.0586 (7)0.0362 (5)0.0151 (6)0.0002 (5)0.0223 (5)
N010.032 (4)0.021 (4)0.036 (4)0.001 (4)0.002 (4)0.000 (3)
C010.032 (5)0.025 (5)0.017 (4)0.009 (5)0.000 (4)0.002 (4)
C020.033 (5)0.030 (6)0.041 (6)0.007 (5)0.002 (5)0.006 (5)
Geometric parameters (Å, º) top
Al1—Br12.380 (2)C41—C421.461 (12)
Al1—N112.003 (7)C42—H42a0.953
Al1—N211.972 (7)C42—H42b0.950
Al1—N311.967 (7)C42—H42c0.960
Al1—N411.983 (7)N51—C511.147 (11)
Al1—N511.972 (7)C51—C521.453 (12)
N11—C111.134 (11)C52—H52a0.967
C11—C121.458 (12)C52—H52b0.946
C12—H12a0.961C52—H52c0.954
C12—H12b0.966Al2—Br212.293 (3)
C12—H12c0.955Al2—Br222.305 (3)
N21—C211.121 (11)Al2—Br232.293 (3)
C21—C221.468 (12)Al2—Br242.283 (3)
C22—H22a0.961Al3—Br312.302 (3)
C22—H22b0.959Al3—Br322.287 (3)
C22—H22c0.960Al3—Br332.292 (3)
N31—C311.128 (11)Al3—Br342.288 (3)
C31—C321.471 (12)N01—C011.125 (12)
C32—H32a0.959C01—C021.470 (13)
C32—H32b0.958C02—H02a0.968
C32—H32c0.955C02—H02b0.960
N41—C411.137 (11)C02—H02c0.943
Br1—Al1—N11178.7 (2)H32a—C32—H32c107.1
Br1—Al1—N2194.1 (2)H32b—C32—H32c108.2
Br1—Al1—N3192.8 (2)Al1—N41—C41172.6 (7)
Br1—Al1—N4194.3 (2)N41—C41—C42178.5 (9)
Br1—Al1—N5193.7 (2)C41—C42—H42a112.7
N11—Al1—N2187.2 (3)C41—C42—H42b113.0
N11—Al1—N3187.6 (3)C41—C42—H42c109.0
N11—Al1—N4185.3 (3)H42a—C42—H42b109.2
N11—Al1—N5185.0 (3)H42a—C42—H42c107.8
N21—Al1—N3190.5 (3)H42b—C42—H42c104.8
N21—Al1—N4187.5 (3)Al1—N51—C51173.6 (7)
N21—Al1—N51172.2 (3)N51—C51—C52179.2 (9)
N31—Al1—N41172.7 (3)C51—C52—H52a111.7
N31—Al1—N5189.9 (3)C51—C52—H52b112.8
N41—Al1—N5191.1 (3)C51—C52—H52c110.0
Al1—N11—C11176.6 (7)H52a—C52—H52b108.3
N11—C11—C12178.1 (9)H52a—C52—H52c107.2
C11—C12—H12a110.6H52b—C52—H52c106.5
C11—C12—H12b110.4Br21—Al2—Br22107.50 (12)
C11—C12—H12c111.5Br21—Al2—Br23112.17 (12)
H12a—C12—H12b107.2Br21—Al2—Br24109.80 (12)
H12a—C12—H12c108.2Br22—Al2—Br23109.89 (12)
H12b—C12—H12c108.6Br22—Al2—Br24109.20 (12)
Al1—N21—C21178.8 (7)Br23—Al2—Br24108.24 (12)
N21—C21—C22179.6 (9)Br31—Al3—Br32111.19 (11)
C21—C22—H22a111.7Br31—Al3—Br33109.81 (11)
C21—C22—H22b112.7Br31—Al3—Br34107.78 (11)
C21—C22—H22c110.6Br32—Al3—Br33108.50 (11)
H22a—C22—H22b107.9Br32—Al3—Br34109.08 (12)
H22a—C22—H22c106.1Br33—Al3—Br34110.47 (11)
H22b—C22—H22c107.6N01—C01—C02178.5 (10)
Al1—N31—C31177.8 (7)C01—C02—H02a111.5
N31—C31—C32179.5 (9)C01—C02—H02b111.5
C31—C32—H32a111.4C01—C02—H02c111.0
C31—C32—H32b111.1H02a—C02—H02b107.2
C31—C32—H32c110.8H02a—C02—H02c108.2
H32a—C32—H32b108.0H02b—C02—H02c107.2

Experimental details

Crystal data
Chemical formula[AlBr(C2H3N)5][AlBr4]2·C2H3N
Mr1046.4
Crystal system, space groupOrthorhombic, P212121
Temperature (K)150
a, b, c (Å)10.406 (1), 14.479 (2), 21.421 (3)
V3)3227.5 (7)
Z4
Radiation typeMo Kα
µ (mm1)11.27
Crystal size (mm)0.18 × 0.15 × 0.12
Data collection
DiffractometerBruker SMART CCD
diffractometer
Absorption correctionMulti-scan
SADABS; Sheldrick, 1996
Tmin, Tmax0.126, 0.252
No. of measured, independent and
observed [I > 2σ(I)] reflections
32073, 4571, 3187
Rint0.049
(sin θ/λ)max1)0.682
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.027, 0.97
No. of reflections3187
No. of parameters272
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.67, 0.57
Absolute structureFlack (1983)
Absolute structure parameter0.04 (1)

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), Xtal (Hall, King, and Stewart, 1995), Xtal3.5 (Hall et al., 1995), CRYLSQ in Xtal3.5, BONDLA CIFIO in Xtal3.5.

Selected geometric parameters (Å, º) top
Al1—Br12.380 (2)Al2—Br222.305 (3)
Al1—N112.003 (7)Al2—Br232.293 (3)
Al1—N211.972 (7)Al2—Br242.283 (3)
Al1—N311.967 (7)Al3—Br312.302 (3)
Al1—N411.983 (7)Al3—Br322.287 (3)
Al1—N511.972 (7)Al3—Br332.292 (3)
Al2—Br212.293 (3)Al3—Br342.288 (3)
Br1—Al1—N11178.7 (2)N41—Al1—N5191.1 (3)
Br1—Al1—N2194.1 (2)Br21—Al2—Br22107.50 (12)
Br1—Al1—N3192.8 (2)Br21—Al2—Br23112.17 (12)
Br1—Al1—N4194.3 (2)Br21—Al2—Br24109.80 (12)
Br1—Al1—N5193.7 (2)Br22—Al2—Br23109.89 (12)
N11—Al1—N2187.2 (3)Br22—Al2—Br24109.20 (12)
N11—Al1—N3187.6 (3)Br23—Al2—Br24108.24 (12)
N11—Al1—N4185.3 (3)Br31—Al3—Br32111.19 (11)
N11—Al1—N5185.0 (3)Br31—Al3—Br33109.81 (11)
N21—Al1—N3190.5 (3)Br31—Al3—Br34107.78 (11)
N21—Al1—N4187.5 (3)Br32—Al3—Br33108.50 (11)
N21—Al1—N51172.2 (3)Br32—Al3—Br34109.08 (12)
N31—Al1—N41172.7 (3)Br33—Al3—Br34110.47 (11)
N31—Al1—N5189.9 (3)
 

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