Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103011429/ta1411sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103011429/ta1411Isup2.hkl |
CCDC reference: 217132
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.
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.
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. |
[AlBr(C2H3N)5][AlBr4]2·C2H3N | F(000) = 1944 |
Mr = 1046.4 | Dx = 2.153 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: p 2ac 2ab | Cell parameters from 6185 reflections |
a = 10.406 (1) Å | θ = 2.6–26.4° |
b = 14.479 (2) Å | µ = 11.27 mm−1 |
c = 21.421 (3) Å | T = 150 K |
V = 3227.5 (7) Å3 | Block, colourless |
Z = 4 | 0.18 × 0.15 × 0.12 mm |
Bruker SMART CCD diffractometer | 4571 independent reflections |
Radiation source: sealed tube | 3187 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
ω scans | θmax = 29.0°, θmin = 1.7° |
Absorption correction: multi-scan SADABS; Sheldrick, 1996 | h = −14→14 |
Tmin = 0.126, Tmax = 0.252 | k = −19→19 |
32073 measured reflections | l = −29→29 |
Refinement on F | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters not refined |
wR(F2) = 0.027 | w = [1/σ2(F) + 0.0004F2] |
S = 0.97 | (Δ/σ)max = 0.016 |
3187 reflections | Δρmax = 0.67 e Å−3 |
272 parameters | Δρmin = −0.57 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
0 constraints | Absolute structure parameter: 0.04 (1) |
[AlBr(C2H3N)5][AlBr4]2·C2H3N | V = 3227.5 (7) Å3 |
Mr = 1046.4 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 10.406 (1) Å | µ = 11.27 mm−1 |
b = 14.479 (2) Å | T = 150 K |
c = 21.421 (3) Å | 0.18 × 0.15 × 0.12 mm |
Bruker SMART CCD diffractometer | 4571 independent reflections |
Absorption correction: multi-scan SADABS; Sheldrick, 1996 | 3187 reflections with I > 2σ(I) |
Tmin = 0.126, Tmax = 0.252 | Rint = 0.049 |
32073 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters not refined |
wR(F2) = 0.027 | Δρmax = 0.67 e Å−3 |
S = 0.97 | Δρmin = −0.57 e Å−3 |
3187 reflections | Absolute structure: Flack (1983) |
272 parameters | Absolute structure parameter: 0.04 (1) |
0 restraints |
x | y | z | Uiso*/Ueq | ||
Al1 | 0.6376 (2) | 0.37710 (16) | 0.66449 (11) | 0.0171 (12) | |
Br1 | 0.41388 (8) | 0.34433 (6) | 0.65860 (4) | 0.0251 (4) | |
N11 | 0.8268 (6) | 0.4020 (5) | 0.6683 (3) | 0.020 (4) | |
C11 | 0.9349 (8) | 0.4118 (5) | 0.6696 (3) | 0.020 (4) | |
C12 | 1.0742 (8) | 0.4213 (7) | 0.6721 (4) | 0.036 (5) | |
N21 | 0.6189 (6) | 0.4644 (5) | 0.7346 (3) | 0.021 (4) | |
C21 | 0.6103 (8) | 0.5136 (6) | 0.7747 (4) | 0.020 (5) | |
C22 | 0.5980 (8) | 0.5781 (6) | 0.8272 (4) | 0.028 (5) | |
N31 | 0.6248 (6) | 0.4795 (5) | 0.6045 (3) | 0.021 (4) | |
C31 | 0.6133 (8) | 0.5385 (6) | 0.5706 (4) | 0.023 (5) | |
C32 | 0.5979 (9) | 0.6148 (6) | 0.5259 (4) | 0.029 (5) | |
N41 | 0.6729 (6) | 0.2798 (5) | 0.7273 (3) | 0.019 (4) | |
C41 | 0.7003 (8) | 0.2311 (6) | 0.7668 (4) | 0.020 (5) | |
C42 | 0.7388 (8) | 0.1695 (6) | 0.8174 (4) | 0.030 (5) | |
N51 | 0.6818 (6) | 0.2921 (5) | 0.5958 (3) | 0.021 (4) | |
C51 | 0.7148 (8) | 0.2491 (6) | 0.5538 (4) | 0.018 (4) | |
C52 | 0.7583 (8) | 0.1952 (6) | 0.5007 (4) | 0.028 (5) | |
Al2 | 1.0117 (3) | 0.5747 (2) | 0.50464 (13) | 0.0223 (15) | |
Br21 | 0.92713 (10) | 0.64444 (7) | 0.41773 (4) | 0.0358 (5) | |
Br22 | 0.94896 (10) | 0.42208 (7) | 0.50297 (5) | 0.0312 (5) | |
Br23 | 1.23160 (9) | 0.58420 (8) | 0.50739 (5) | 0.0418 (6) | |
Br24 | 0.93251 (10) | 0.64351 (7) | 0.59251 (4) | 0.0397 (6) | |
Al3 | 0.9958 (2) | 0.0566 (2) | 0.65220 (11) | 0.0227 (14) | |
Br31 | 0.77485 (8) | 0.05796 (6) | 0.65693 (4) | 0.0276 (5) | |
Br32 | 1.06756 (11) | 0.11389 (7) | 0.55902 (4) | 0.0415 (6) | |
Br33 | 1.06981 (9) | −0.09163 (7) | 0.66291 (4) | 0.0329 (5) | |
Br34 | 1.07132 (11) | 0.14761 (8) | 0.73147 (4) | 0.0454 (6) | |
N01 | 0.4314 (7) | 0.1727 (5) | 0.8142 (3) | 0.030 (4) | |
C01 | 0.3632 (9) | 0.2325 (6) | 0.8187 (4) | 0.025 (5) | |
C02 | 0.2769 (9) | 0.3124 (6) | 0.8250 (4) | 0.034 (5) | |
H12a | 1.11473 | 0.36163 | 0.67373 | 0.05400* | |
H12b | 1.09964 | 0.45431 | 0.70932 | 0.05400* | |
H12c | 1.10659 | 0.45351 | 0.63655 | 0.05400* | |
H22a | 0.68033 | 0.59966 | 0.84128 | 0.04200* | |
H22b | 0.55448 | 0.55139 | 0.86232 | 0.04200* | |
H22c | 0.55085 | 0.63209 | 0.81491 | 0.04200* | |
H32a | 0.57676 | 0.59247 | 0.48504 | 0.04300* | |
H32b | 0.67509 | 0.65059 | 0.52272 | 0.04300* | |
H32c | 0.52991 | 0.65503 | 0.53849 | 0.04300* | |
H42a | 0.71756 | 0.19338 | 0.85759 | 0.04300* | |
H42b | 0.82766 | 0.15440 | 0.81648 | 0.04300* | |
H42c | 0.69532 | 0.11146 | 0.81263 | 0.04300* | |
H52a | 0.83673 | 0.21991 | 0.48313 | 0.04300* | |
H52b | 0.69613 | 0.19157 | 0.46855 | 0.04300* | |
H52c | 0.77584 | 0.13327 | 0.51331 | 0.04300* | |
H02a | 0.19144 | 0.29847 | 0.80986 | 0.05200* | |
H02b | 0.30768 | 0.36447 | 0.80175 | 0.05200* | |
H02c | 0.27022 | 0.33107 | 0.86708 | 0.05200* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Al1 | 0.0194 (12) | 0.0161 (13) | 0.0157 (12) | −0.0003 (10) | 0.0000 (10) | 0.0009 (10) |
Br1 | 0.0189 (4) | 0.0293 (5) | 0.0271 (4) | −0.0027 (4) | −0.0019 (4) | 0.0032 (4) |
N11 | 0.023 (4) | 0.019 (4) | 0.016 (4) | 0.002 (3) | −0.001 (3) | 0.001 (3) |
C11 | 0.027 (5) | 0.019 (4) | 0.013 (4) | 0.003 (4) | 0.001 (4) | 0.003 (3) |
C12 | 0.015 (4) | 0.052 (7) | 0.040 (5) | −0.005 (5) | 0.002 (4) | 0.002 (5) |
N21 | 0.026 (4) | 0.018 (4) | 0.018 (4) | 0.002 (3) | 0.003 (3) | 0.002 (3) |
C21 | 0.019 (5) | 0.019 (5) | 0.023 (5) | −0.002 (4) | −0.002 (4) | 0.008 (4) |
C22 | 0.036 (5) | 0.026 (5) | 0.023 (5) | −0.003 (4) | 0.006 (4) | −0.008 (4) |
N31 | 0.024 (4) | 0.022 (4) | 0.018 (4) | 0.001 (3) | 0.000 (3) | 0.003 (3) |
C31 | 0.025 (5) | 0.026 (5) | 0.016 (4) | −0.004 (4) | 0.003 (4) | −0.007 (4) |
C32 | 0.036 (6) | 0.019 (5) | 0.031 (5) | −0.003 (4) | −0.002 (4) | 0.010 (4) |
N41 | 0.023 (4) | 0.021 (4) | 0.015 (4) | 0.002 (3) | 0.001 (3) | −0.002 (3) |
C41 | 0.019 (5) | 0.019 (5) | 0.023 (5) | 0.002 (4) | −0.000 (4) | −0.004 (4) |
C42 | 0.029 (5) | 0.034 (6) | 0.027 (5) | 0.014 (4) | 0.006 (4) | 0.015 (4) |
N51 | 0.021 (4) | 0.022 (4) | 0.021 (4) | 0.001 (3) | −0.004 (3) | 0.001 (3) |
C51 | 0.019 (4) | 0.015 (5) | 0.021 (5) | −0.003 (4) | −0.005 (4) | 0.008 (4) |
C52 | 0.034 (5) | 0.032 (5) | 0.020 (4) | 0.003 (4) | −0.000 (4) | −0.012 (4) |
Al2 | 0.0223 (14) | 0.0241 (16) | 0.0204 (14) | −0.0023 (12) | 0.0001 (12) | −0.0008 (14) |
Br21 | 0.0438 (6) | 0.0317 (5) | 0.0319 (5) | −0.0034 (5) | −0.0071 (5) | 0.0113 (4) |
Br22 | 0.0414 (6) | 0.0256 (5) | 0.0267 (5) | −0.0096 (5) | −0.0023 (5) | 0.0041 (5) |
Br23 | 0.0211 (5) | 0.0578 (7) | 0.0464 (6) | −0.0065 (5) | 0.0006 (5) | −0.0142 (6) |
Br24 | 0.0347 (5) | 0.0529 (6) | 0.0316 (5) | 0.0033 (6) | 0.0021 (4) | −0.0180 (5) |
Al3 | 0.0235 (13) | 0.0256 (15) | 0.0191 (13) | −0.0033 (12) | 0.0014 (11) | −0.0002 (12) |
Br31 | 0.0225 (4) | 0.0214 (5) | 0.0388 (5) | 0.0019 (4) | 0.0015 (4) | −0.0005 (4) |
Br32 | 0.0488 (6) | 0.0470 (7) | 0.0287 (5) | −0.0074 (6) | 0.0118 (5) | 0.0109 (4) |
Br33 | 0.0318 (5) | 0.0342 (5) | 0.0328 (5) | 0.0121 (5) | 0.0013 (5) | 0.0041 (4) |
Br34 | 0.0413 (6) | 0.0586 (7) | 0.0362 (5) | −0.0151 (6) | −0.0002 (5) | −0.0223 (5) |
N01 | 0.032 (4) | 0.021 (4) | 0.036 (4) | 0.001 (4) | 0.002 (4) | 0.000 (3) |
C01 | 0.032 (5) | 0.025 (5) | 0.017 (4) | −0.009 (5) | −0.000 (4) | 0.002 (4) |
C02 | 0.033 (5) | 0.030 (6) | 0.041 (6) | 0.007 (5) | −0.002 (5) | −0.006 (5) |
Al1—Br1 | 2.380 (2) | C41—C42 | 1.461 (12) |
Al1—N11 | 2.003 (7) | C42—H42a | 0.953 |
Al1—N21 | 1.972 (7) | C42—H42b | 0.950 |
Al1—N31 | 1.967 (7) | C42—H42c | 0.960 |
Al1—N41 | 1.983 (7) | N51—C51 | 1.147 (11) |
Al1—N51 | 1.972 (7) | C51—C52 | 1.453 (12) |
N11—C11 | 1.134 (11) | C52—H52a | 0.967 |
C11—C12 | 1.458 (12) | C52—H52b | 0.946 |
C12—H12a | 0.961 | C52—H52c | 0.954 |
C12—H12b | 0.966 | Al2—Br21 | 2.293 (3) |
C12—H12c | 0.955 | Al2—Br22 | 2.305 (3) |
N21—C21 | 1.121 (11) | Al2—Br23 | 2.293 (3) |
C21—C22 | 1.468 (12) | Al2—Br24 | 2.283 (3) |
C22—H22a | 0.961 | Al3—Br31 | 2.302 (3) |
C22—H22b | 0.959 | Al3—Br32 | 2.287 (3) |
C22—H22c | 0.960 | Al3—Br33 | 2.292 (3) |
N31—C31 | 1.128 (11) | Al3—Br34 | 2.288 (3) |
C31—C32 | 1.471 (12) | N01—C01 | 1.125 (12) |
C32—H32a | 0.959 | C01—C02 | 1.470 (13) |
C32—H32b | 0.958 | C02—H02a | 0.968 |
C32—H32c | 0.955 | C02—H02b | 0.960 |
N41—C41 | 1.137 (11) | C02—H02c | 0.943 |
Br1—Al1—N11 | 178.7 (2) | H32a—C32—H32c | 107.1 |
Br1—Al1—N21 | 94.1 (2) | H32b—C32—H32c | 108.2 |
Br1—Al1—N31 | 92.8 (2) | Al1—N41—C41 | 172.6 (7) |
Br1—Al1—N41 | 94.3 (2) | N41—C41—C42 | 178.5 (9) |
Br1—Al1—N51 | 93.7 (2) | C41—C42—H42a | 112.7 |
N11—Al1—N21 | 87.2 (3) | C41—C42—H42b | 113.0 |
N11—Al1—N31 | 87.6 (3) | C41—C42—H42c | 109.0 |
N11—Al1—N41 | 85.3 (3) | H42a—C42—H42b | 109.2 |
N11—Al1—N51 | 85.0 (3) | H42a—C42—H42c | 107.8 |
N21—Al1—N31 | 90.5 (3) | H42b—C42—H42c | 104.8 |
N21—Al1—N41 | 87.5 (3) | Al1—N51—C51 | 173.6 (7) |
N21—Al1—N51 | 172.2 (3) | N51—C51—C52 | 179.2 (9) |
N31—Al1—N41 | 172.7 (3) | C51—C52—H52a | 111.7 |
N31—Al1—N51 | 89.9 (3) | C51—C52—H52b | 112.8 |
N41—Al1—N51 | 91.1 (3) | C51—C52—H52c | 110.0 |
Al1—N11—C11 | 176.6 (7) | H52a—C52—H52b | 108.3 |
N11—C11—C12 | 178.1 (9) | H52a—C52—H52c | 107.2 |
C11—C12—H12a | 110.6 | H52b—C52—H52c | 106.5 |
C11—C12—H12b | 110.4 | Br21—Al2—Br22 | 107.50 (12) |
C11—C12—H12c | 111.5 | Br21—Al2—Br23 | 112.17 (12) |
H12a—C12—H12b | 107.2 | Br21—Al2—Br24 | 109.80 (12) |
H12a—C12—H12c | 108.2 | Br22—Al2—Br23 | 109.89 (12) |
H12b—C12—H12c | 108.6 | Br22—Al2—Br24 | 109.20 (12) |
Al1—N21—C21 | 178.8 (7) | Br23—Al2—Br24 | 108.24 (12) |
N21—C21—C22 | 179.6 (9) | Br31—Al3—Br32 | 111.19 (11) |
C21—C22—H22a | 111.7 | Br31—Al3—Br33 | 109.81 (11) |
C21—C22—H22b | 112.7 | Br31—Al3—Br34 | 107.78 (11) |
C21—C22—H22c | 110.6 | Br32—Al3—Br33 | 108.50 (11) |
H22a—C22—H22b | 107.9 | Br32—Al3—Br34 | 109.08 (12) |
H22a—C22—H22c | 106.1 | Br33—Al3—Br34 | 110.47 (11) |
H22b—C22—H22c | 107.6 | N01—C01—C02 | 178.5 (10) |
Al1—N31—C31 | 177.8 (7) | C01—C02—H02a | 111.5 |
N31—C31—C32 | 179.5 (9) | C01—C02—H02b | 111.5 |
C31—C32—H32a | 111.4 | C01—C02—H02c | 111.0 |
C31—C32—H32b | 111.1 | H02a—C02—H02b | 107.2 |
C31—C32—H32c | 110.8 | H02a—C02—H02c | 108.2 |
H32a—C32—H32b | 108.0 | H02b—C02—H02c | 107.2 |
Experimental details
Crystal data | |
Chemical formula | [AlBr(C2H3N)5][AlBr4]2·C2H3N |
Mr | 1046.4 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 150 |
a, b, c (Å) | 10.406 (1), 14.479 (2), 21.421 (3) |
V (Å3) | 3227.5 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 11.27 |
Crystal size (mm) | 0.18 × 0.15 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan SADABS; Sheldrick, 1996 |
Tmin, Tmax | 0.126, 0.252 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32073, 4571, 3187 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.027, 0.97 |
No. of reflections | 3187 |
No. of parameters | 272 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.67, −0.57 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.04 (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.
Al1—Br1 | 2.380 (2) | Al2—Br22 | 2.305 (3) |
Al1—N11 | 2.003 (7) | Al2—Br23 | 2.293 (3) |
Al1—N21 | 1.972 (7) | Al2—Br24 | 2.283 (3) |
Al1—N31 | 1.967 (7) | Al3—Br31 | 2.302 (3) |
Al1—N41 | 1.983 (7) | Al3—Br32 | 2.287 (3) |
Al1—N51 | 1.972 (7) | Al3—Br33 | 2.292 (3) |
Al2—Br21 | 2.293 (3) | Al3—Br34 | 2.288 (3) |
Br1—Al1—N11 | 178.7 (2) | N41—Al1—N51 | 91.1 (3) |
Br1—Al1—N21 | 94.1 (2) | Br21—Al2—Br22 | 107.50 (12) |
Br1—Al1—N31 | 92.8 (2) | Br21—Al2—Br23 | 112.17 (12) |
Br1—Al1—N41 | 94.3 (2) | Br21—Al2—Br24 | 109.80 (12) |
Br1—Al1—N51 | 93.7 (2) | Br22—Al2—Br23 | 109.89 (12) |
N11—Al1—N21 | 87.2 (3) | Br22—Al2—Br24 | 109.20 (12) |
N11—Al1—N31 | 87.6 (3) | Br23—Al2—Br24 | 108.24 (12) |
N11—Al1—N41 | 85.3 (3) | Br31—Al3—Br32 | 111.19 (11) |
N11—Al1—N51 | 85.0 (3) | Br31—Al3—Br33 | 109.81 (11) |
N21—Al1—N31 | 90.5 (3) | Br31—Al3—Br34 | 107.78 (11) |
N21—Al1—N41 | 87.5 (3) | Br32—Al3—Br33 | 108.50 (11) |
N21—Al1—N51 | 172.2 (3) | Br32—Al3—Br34 | 109.08 (12) |
N31—Al1—N41 | 172.7 (3) | Br33—Al3—Br34 | 110.47 (11) |
N31—Al1—N51 | 89.9 (3) |
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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).