Hexa-μ-chlorido-hexa-chlorido(η-hexa-methyl-benzene)trialuminium(III)lanthanum(III) benzene solvate.

In the title compound, [Al(3)LaCl(12)(C(12)H(18))]·C(6)H(6), all mol-ecules are located on a mirror plane. Three chloridoaluminate groups and a hexa-methyl-benzene mol-ecule are bound to the central lanthanum(III) ion, forming a distorted penta-gonal bipyramid with the η(6)-coordinated arene located at the apical position. The hexa-methyl-benzene ligand disordered between two orientations in a 1:1 ratio is also involved in parallel-slipped π-π stacking inter-molecular inter-actions with a benzene solvent mol-ecule [centroid-centroid distance 3.612 (4) Å].

Related literature

For the previously characterized lanthanum chloro­aluminate and chloro­gallate complexes, see: Filatov et al. (2008 ▶). For a recent review of other lanthanide chloro­aluminate complexes, see: Bochkarev (2002 ▶). For complexes of lanthanide chloro­gallates with polycyclic aromatic systems, see: Gorlov et al. (2008 ▶).

Experimental

Crystal data

[Al3LaCl12(C12H18)]·C6H6

M = 885.62

Orthorhombic,

a = 12.2127 (6) Å

b = 16.4205 (8) Å

c = 16.9790 (8) Å

V = 3404.9 (3) Å3

Z = 4

Mo- Kα radiation

μ = 2.28 mm−1

T = 173 K

0.22 × 0.20 × 0.16 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.613, T max = 0.697

28535 measured reflections

4250 independent reflections

3911 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.063

S = 1.05

4250 reflections

189 parameters

H-atom parameters not refined

Δρmax = 0.89 e Å−3

Δρmin = −0.99 e Å−3

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809004899/cv2516sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809004899/cv2516Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Al3LaCl12(C12H18)]·C6H6	F(000) = 1728
Mr = 885.62	Dx = 1.728 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 7019 reflections
a = 12.2127 (6) Å	θ = 2.5–28.2°
b = 16.4205 (8) Å	µ = 2.28 mm−1
c = 16.9790 (8) Å	T = 173 K
V = 3404.9 (3) Å3	Block, yellow
Z = 4	0.22 × 0.20 × 0.16 mm

Bruker SMART APEX CCD area-detector diffractometer	4250 independent reflections
Radiation source: fine-focus sealed tube	3911 reflections with I > 2σ(I)
graphite	Rint = 0.018
0.30° ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −15→16
Tmin = 0.613, Tmax = 0.697	k = −21→21
28535 measured reflections	l = −22→22

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.063	H-atom parameters not refined
S = 1.05	w = 1/[σ2(Fo2) + (0.0304P)2 + 3.1621P] where P = (Fo2 + 2Fc2)/3
4250 reflections	(Δ/σ)max < 0.001
189 parameters	Δρmax = 0.89 e Å−3
0 restraints	Δρmin = −0.98 e Å−3

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	Occ. (<1)
La1	0.106393 (12)	0.2500	0.425620 (9)	0.02758 (6)
Al1	0.09537 (6)	0.04272 (4)	0.32343 (5)	0.04146 (16)
Al2	−0.20200 (8)	0.2500	0.41914 (6)	0.0403 (2)
Cl1	−0.02765 (6)	0.03298 (4)	0.23836 (5)	0.06224 (19)
Cl2	0.18966 (7)	−0.06204 (4)	0.34109 (6)	0.0684 (2)
Cl3	0.19872 (5)	0.14875 (3)	0.30139 (3)	0.04206 (13)
Cl4	0.02586 (5)	0.08226 (4)	0.43571 (3)	0.04489 (14)
Cl5	−0.09121 (6)	0.2500	0.52121 (4)	0.04250 (18)
Cl6	−0.08346 (6)	0.2500	0.32208 (4)	0.03682 (16)
Cl7	−0.29273 (6)	0.14181 (5)	0.41927 (4)	0.05841 (18)
C1	0.3384 (3)	0.2500	0.4729 (2)	0.0515 (10)
C2	0.3003 (3)	0.17691 (17)	0.50333 (19)	0.0609 (8)
C3	0.2212 (3)	0.1777 (3)	0.5621 (2)	0.0823 (13)
C4	0.1820 (3)	0.2500	0.5901 (2)	0.096 (3)
C5	0.4271 (4)	0.2500	0.4107 (3)	0.194 (5)
H5A	0.4789	0.2943	0.4214	0.291*	0.50
H5B	0.3940	0.2580	0.3587	0.291*	0.50
H5C	0.4659	0.1978	0.4118	0.291*	0.50
C6	0.3258 (8)	0.0879 (6)	0.4928 (7)	0.087 (3)	0.50
H6A	0.3781	0.0706	0.5332	0.130*	0.50
H6B	0.3577	0.0791	0.4405	0.130*	0.50
H6C	0.2583	0.0561	0.4977	0.130*	0.50
C7	0.1582 (8)	0.1206 (6)	0.6166 (5)	0.093 (3)	0.50
H7A	0.1812	0.1299	0.6711	0.139*	0.50
H7B	0.1735	0.0640	0.6019	0.139*	0.50
H7C	0.0796	0.1312	0.6117	0.139*	0.50
C6X	0.3773 (8)	0.1077 (7)	0.4617 (6)	0.084 (4)	0.50
H6X1	0.4398	0.0956	0.4959	0.126*	0.50
H6X2	0.4039	0.1281	0.4109	0.126*	0.50
H6X3	0.3344	0.0581	0.4533	0.126*	0.50
C7X	0.2146 (9)	0.0787 (5)	0.5824 (6)	0.092 (3)	0.50
H7X1	0.1425	0.0659	0.6045	0.137*	0.50
H7X2	0.2716	0.0646	0.6206	0.137*	0.50
H7X3	0.2257	0.0473	0.5339	0.137*	0.50
C8	0.1026 (4)	0.2500	0.6586 (3)	0.194 (5)
H8A	0.0691	0.1960	0.6636	0.291*	0.50
H8B	0.0454	0.2907	0.6494	0.291*	0.50
H8C	0.1420	0.2633	0.7072	0.291*	0.50
C9	0.5948 (4)	0.2500	0.6119 (3)	0.088 (2)
H9	0.6600	0.2500	0.5814	0.106*
C10	0.5464 (3)	0.1771 (2)	0.6345 (2)	0.0750 (10)
H10	0.5779	0.1265	0.6193	0.090*
C11	0.4547 (3)	0.1790 (2)	0.6780 (2)	0.0679 (9)
H11	0.4212	0.1293	0.6936	0.082*
C12	0.4094 (3)	0.2500	0.7000 (3)	0.0646 (12)
H12	0.3449	0.2500	0.7312	0.077*

	U11	U22	U33	U12	U13	U23
La1	0.02175 (8)	0.03570 (10)	0.02528 (9)	0.000	0.00028 (5)	0.000
Al1	0.0428 (4)	0.0342 (3)	0.0475 (4)	−0.0003 (3)	−0.0093 (3)	−0.0026 (3)
Al2	0.0247 (4)	0.0577 (6)	0.0384 (5)	0.000	0.0008 (4)	0.000
Cl1	0.0664 (4)	0.0525 (4)	0.0678 (4)	0.0015 (3)	−0.0311 (3)	−0.0082 (3)
Cl2	0.0666 (4)	0.0438 (3)	0.0947 (6)	0.0136 (3)	−0.0232 (4)	−0.0036 (4)
Cl3	0.0434 (3)	0.0424 (3)	0.0404 (3)	−0.0030 (2)	0.0099 (2)	−0.0068 (2)
Cl4	0.0460 (3)	0.0431 (3)	0.0456 (3)	−0.0101 (2)	0.0013 (2)	0.0080 (2)
Cl5	0.0288 (3)	0.0687 (5)	0.0300 (3)	0.000	0.0031 (3)	0.000
Cl6	0.0277 (3)	0.0530 (4)	0.0298 (3)	0.000	−0.0025 (3)	0.000
Cl7	0.0418 (3)	0.0720 (5)	0.0615 (4)	−0.0171 (3)	0.0028 (3)	−0.0021 (3)
C1	0.0227 (14)	0.099 (3)	0.0325 (16)	0.000	−0.0035 (12)	0.000
C2	0.0654 (17)	0.0486 (14)	0.0688 (18)	0.0173 (13)	−0.0438 (16)	−0.0151 (13)
C3	0.071 (2)	0.114 (3)	0.0617 (19)	−0.055 (2)	−0.0416 (18)	0.055 (2)
C4	0.0269 (19)	0.237 (9)	0.0259 (18)	0.000	−0.0009 (14)	0.000
C5	0.0328 (17)	0.507 (15)	0.0414 (19)	0.000	0.0080 (14)	0.000
C6	0.082 (7)	0.060 (5)	0.118 (9)	0.034 (5)	−0.054 (6)	−0.025 (5)
C7	0.099 (7)	0.110 (7)	0.070 (5)	−0.061 (6)	−0.042 (5)	0.058 (5)
C6X	0.075 (6)	0.089 (8)	0.087 (7)	0.044 (6)	−0.037 (5)	−0.040 (6)
C7X	0.111 (8)	0.067 (5)	0.097 (7)	−0.032 (5)	−0.053 (6)	0.048 (5)
C8	0.0328 (17)	0.507 (15)	0.0414 (19)	0.000	0.0080 (14)	0.000
C9	0.052 (3)	0.172 (7)	0.041 (2)	0.000	0.0042 (19)	0.000
C10	0.081 (2)	0.080 (2)	0.0634 (19)	0.029 (2)	−0.0217 (18)	−0.0169 (17)
C11	0.070 (2)	0.069 (2)	0.0653 (19)	−0.0142 (17)	−0.0277 (16)	0.0189 (16)
C12	0.039 (2)	0.105 (4)	0.049 (2)	0.000	−0.0136 (17)	0.000

La1—C1	2.945 (3)	C3—C7X	1.663 (8)
La1—C2	2.965 (2)	C4—C3i	1.366 (5)
La1—C3	2.957 (3)	C4—C8	1.514 (6)
La1—C4	2.941 (4)	C5—H5A	0.9800
La1—Cl3	2.9128 (5)	C5—H5B	0.9800
La1—Cl4	2.9298 (6)	C5—H5C	0.9800
La1—Cl5	2.9083 (7)	C8—H8A	0.9800
La1—Cl6	2.9097 (7)	C8—H8B	0.9800
La1—Cg1	2.613 (3)	C8—H8C	0.9800
Cg1—Cg2	3.612 (4)	C6—H6A	0.9800
La1—Cl3i	2.9128 (5)	C6—H6B	0.9800
La1—Cl4i	2.9298 (6)	C6—H6C	0.9800
La1—C3i	2.957 (3)	C7—H7A	0.9800
La1—C2i	2.965 (2)	C7—H7B	0.9800
Al1—Cl1	2.0902 (10)	C7—H7C	0.9800
Al1—Cl2	2.0918 (10)	C6X—H6X1	0.9800
Al1—Cl3	2.1828 (9)	C6X—H6X2	0.9800
Al1—Cl4	2.1855 (10)	C6X—H6X3	0.9800
Al2—Cl7	2.0937 (9)	C7X—H7X1	0.9800
Al2—Cl7i	2.0937 (9)	C7X—H7X2	0.9800
Al2—Cl6	2.1936 (12)	C7X—H7X3	0.9800
Al2—Cl5	2.1987 (12)	C9—C10	1.389 (5)
C1—C2i	1.387 (4)	C9—C10i	1.389 (5)
C1—C2	1.387 (4)	C9—H9	0.9500
C1—C5	1.513 (6)	C10—C11	1.343 (5)
C2—C3	1.389 (5)	C10—H10	0.9500
C2—C6	1.505 (10)	C11—C12	1.344 (4)
C2—C6X	1.635 (10)	C11—H11	0.9500
C3—C4	1.366 (5)	C12—C11i	1.344 (4)
C3—C7	1.525 (7)	C12—H12	0.9500
Cl5—La1—Cl6	71.09 (2)	Cl7—Al2—Cl5	108.96 (4)
Cl5—La1—Cl3	136.497 (15)	Cl7i—Al2—Cl5	108.96 (4)
Cl6—La1—Cl3	82.586 (17)	Cl6—Al2—Cl5	100.72 (5)
Cl5—La1—Cl3i	136.497 (14)	Al1—Cl3—La1	96.16 (3)
Cl6—La1—Cl3i	82.586 (17)	Al1—Cl4—La1	95.61 (3)
Cl3—La1—Cl3i	69.61 (2)	Al2—Cl5—La1	94.06 (4)
Cl5—La1—Cl4	71.868 (13)	Al2—Cl6—La1	94.13 (4)
Cl6—La1—Cl4	76.576 (13)	C2i—C1—C2	119.9 (4)
Cl3—La1—Cl4	68.636 (17)	C2i—C1—C5	119.99 (18)
Cl3i—La1—Cl4	135.147 (17)	C2—C1—C5	119.99 (18)
Cl5—La1—Cl4i	71.868 (13)	C2i—C1—La1	77.23 (17)
Cl6—La1—Cl4i	76.576 (13)	C2—C1—La1	77.23 (17)
Cl3—La1—Cl4i	135.147 (17)	C5—C1—La1	119.9 (3)
Cl3i—La1—Cl4i	68.636 (17)	C1—C2—C3	119.5 (3)
Cl4—La1—Cl4i	140.15 (3)	C1—C2—C6	136.6 (6)
Cl5—La1—C4	74.37 (8)	C3—C2—C6	103.8 (6)
Cl6—La1—C4	145.46 (8)	C1—C2—La1	75.63 (16)
Cl3—La1—C4	124.47 (6)	C3—C2—La1	76.11 (16)
Cl3i—La1—C4	124.47 (6)	C6—C2—La1	120.4 (4)
Cl4—La1—C4	92.86 (3)	C6X—C2—La1	123.2 (4)
Cl4i—La1—C4	92.86 (3)	C4—C3—C2	120.1 (3)
Cl5—La1—C1	130.25 (7)	C4—C3—C7	98.4 (6)
Cl6—La1—C1	158.66 (7)	C2—C3—C7	141.3 (6)
Cl3—La1—C1	79.93 (6)	C4—C3—La1	76.0 (2)
Cl3i—La1—C1	79.93 (6)	C2—C3—La1	76.76 (15)
Cl4—La1—C1	107.879 (16)	C7—C3—La1	118.9 (3)
Cl4i—La1—C1	107.879 (17)	C3i—C4—C3	120.8 (4)
C4—La1—C1	55.88 (10)	C3i—C4—C8	119.5 (2)
Cl5—La1—C3i	87.49 (8)	C3—C4—C8	119.5 (2)
Cl6—La1—C3i	148.34 (6)	C3i—C4—La1	77.2 (2)
Cl3—La1—C3i	127.81 (6)	C3—C4—La1	77.2 (2)
Cl3i—La1—C3i	98.90 (10)	C8—C4—La1	121.9 (3)
Cl4—La1—C3i	119.39 (10)	C1—C5—H5A	109.5
Cl4i—La1—C3i	74.68 (7)	C1—C5—H5B	109.5
C4—La1—C3i	26.77 (10)	H5A—C5—H5B	109.5
C1—La1—C3i	47.94 (8)	C1—C5—H5C	109.5
Cl5—La1—C3	87.49 (8)	H5A—C5—H5C	109.5
Cl6—La1—C3	148.34 (6)	H5B—C5—H5C	109.5
Cl3—La1—C3	98.90 (10)	C4—C8—H8A	109.5
Cl3i—La1—C3	127.81 (6)	C4—C8—H8B	109.5
Cl4—La1—C3	74.68 (7)	H8A—C8—H8B	109.5
Cl4i—La1—C3	119.39 (10)	C4—C8—H8C	109.5
C4—La1—C3	26.77 (10)	H8A—C8—H8C	109.5
C1—La1—C3	47.94 (8)	H8B—C8—H8C	109.5
C3i—La1—C3	47.35 (17)	C2—C6—H6A	109.5
Cl5—La1—C2i	114.49 (8)	C2—C6—H6B	109.5
Cl6—La1—C2i	154.88 (5)	C2—C6—H6C	109.5
Cl3—La1—C2i	104.12 (8)	C3—C7—H7A	109.5
Cl3i—La1—C2i	77.41 (6)	C3—C7—H7B	109.5
Cl4—La1—C2i	128.51 (5)	C3—C7—H7C	109.5
Cl4i—La1—C2i	82.04 (6)	C2—C6X—H6X1	109.5
C4—La1—C2i	47.68 (9)	C2—C6X—H6X2	109.5
C1—La1—C2i	27.14 (7)	H6X1—C6X—H6X2	109.5
C3i—La1—C2i	27.13 (10)	C2—C6X—H6X3	109.5
C3—La1—C2i	55.61 (8)	H6X1—C6X—H6X3	109.5
Cl5—La1—C2	114.49 (8)	H6X2—C6X—H6X3	109.5
Cl6—La1—C2	154.88 (5)	C3—C7X—H7X1	109.5
Cl3—La1—C2	77.41 (6)	C3—C7X—H7X2	109.5
Cl3i—La1—C2	104.12 (8)	H7X1—C7X—H7X2	109.5
Cl4—La1—C2	82.04 (6)	C3—C7X—H7X3	109.5
Cl4i—La1—C2	128.51 (5)	H7X1—C7X—H7X3	109.5
C4—La1—C2	47.68 (9)	H7X2—C7X—H7X3	109.5
C1—La1—C2	27.14 (7)	C10—C9—C10i	119.1 (5)
C3i—La1—C2	55.61 (8)	C10—C9—H9	120.5
C3—La1—C2	27.13 (10)	C10i—C9—H9	120.5
C2i—La1—C2	47.76 (11)	C11—C10—C9	119.2 (4)
Cl1—Al1—Cl2	115.58 (4)	C11—C10—H10	120.4
Cl1—Al1—Cl3	110.99 (4)	C9—C10—H10	120.4
Cl2—Al1—Cl3	111.24 (4)	C10—C11—C12	121.1 (4)
Cl1—Al1—Cl4	110.26 (4)	C10—C11—H11	119.5
Cl2—Al1—Cl4	109.45 (5)	C12—C11—H11	119.5
Cl3—Al1—Cl4	97.89 (3)	C11i—C12—C11	120.5 (5)
Cl7—Al2—Cl7i	116.10 (6)	C11i—C12—H12	119.8
Cl7—Al2—Cl6	110.49 (4)	C11—C12—H12	119.8
Cl7i—Al2—Cl6	110.49 (4)

Table 1

Selected bond lengths (Å)

La1—C1	2.945 (3)
La1—C2	2.965 (2)
La1—C3	2.957 (3)
La1—C4	2.941 (4)
La1—Cl3	2.9128 (5)
La1—Cl4	2.9298 (6)
La1—Cl5	2.9083 (7)
La1—Cl6	2.9097 (7)
La1—Cg1	2.613 (3)