Hexa-μ-chlorido-hexa­chlorido(η6-hexa­methyl­benzene)trialuminium(III)lanthanum(III) benzene solvate

Filatov, A.S.; Gifford, S.N.; Kumar, D.K.; Petrukhina, M.A.

doi:10.1107/S1600536809004899

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Pages m286-m287

doi:10.1107/S1600536809004899

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Hexa-μ-chlorido-hexachlorido(η⁶-hexamethylbenzene)trialuminium(III)lanthanum(III) benzene solvate

Alexander S. Filatov,^a Sarah N. Gifford,^a D. Krishna Kumar ^a and Marina A. Petrukhina ^a ^*

^aDepartment of Chemistry, University at Albany, 1400 Washington Avenue, Albany, NY 12222, USA
^*Correspondence e-mail: marina@albany.edu

(Received 2 February 2009; accepted 10 February 2009; online 18 February 2009)

In the title compound, [Al₃LaCl₁₂(C₁₂H₁₈)]·C₆H₆, all molecules are located on a mirror plane. Three chloridoaluminate groups and a hexamethylbenzene molecule are bound to the central lanthanum(III) ion, forming a distorted pentagonal bipyramid with the η⁶-coordinated arene located at the apical position. The hexamethylbenzene ligand disordered between two orientations in a 1:1 ratio is also involved in parallel-slipped π–π stacking intermolecular interactions with a benzene solvent molecule [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_r = 885.62
Orthorhombic, P n m a
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[F² > 2σ(F²)] = 0.025
wR(F²) = 0.063
S = 1.05
4250 reflections
189 parameters
H-atom parameters not refined
Δρ_max = 0.89 e Å⁻³
Δρ_min = −0.99 e Å⁻³

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)

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 ).

Supporting information

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

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

checkCIF report

Comment top

We have recently reported X-ray structural characterization of the first two lanthanum(III) chloroaluminate complexes with neutral arenes, [La(η⁶-C₆H₅Me)(AlCl₄)₃] and [La(η⁶-C₆Me₆)(AlCl₄)₃], as well as of the first lanthanum(III) chlorogallate complex, [La(η⁶-C₆Me₆)(GaCl₄)₃] (Filatov et al., 2008). The [La(η⁶-C₆Me₆)(AlCl₄)₃]^.0.5C₆H₆ complex crystallizes in the monoclinic P2₁/c space group with the β angle being close to 90° (β = 90.27°). We later found that under slightly different experimental conditions, namely at a higher temperature (285 versus 273 K), the lanthanum complex with hexamethylbenzene, [La(η⁶-C₆Me₆)(AlCl₄)₃]^.C₆H₆ (I), is crystallized.

The molecular structure of (I) is comprised of the three chloroaluminate groups and a hexamethylbenzene molecule bound to the central lanthanum(III) ion (Fig.1). The coordination polyhedron is a distorted pentagonal bipyramid with the η⁶-arene located at the apical position. The La–C bond distances span from 2.941 (4) to 2.965 (2) Å with a La–centroid distance being 2.613 (3) Å. These distances are comparable to those found in the previously reported complex [La(η⁶-C₆Me₆)(AlCl₄)₃]^.0.5C₆H₆ (II) [La—C 2.927 (7)–3.035 (7)Å; La–centroid 2.633 (7)Å].

In (I), coordinated hexamethylbenzene is engaged into π-π stacking interactions with a solvent benzene molecule. The intercentroid distance between their 6-membered rings is 3.612 (4) Å. The two ring planes are not parallel and the dihedral angle is 12.7° (Fig.2). In the above hemisolvate (II), on the contrary, both benzene faces are involved in π-π stacking interactions as benzene is sandwiched between two hexamethylbenzene molecules. The distance between the centroids of the hexamethylbenzene and benzene rings (3.688 (4) Å) is noticeably longer than that found in (I).

Related literature top

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 top

LaCl₃ (100 mg, 0.41 mmol), AlCl₃ (163 mg, 1.22 mmol), hexamethylbenzene (66 mg, 0.41 mmol) and an excess of aluminium foil were placed into a Schlenk flask inside the glove box. Benzene (10 ml) was added to the flask and the mixture was refluxed for two hours. The LaCl₃, AlCl₃, and hexamethylbenzene dissolved completely to give a yellow solution. The solution was filtered while hot through a pad of Celite and then kept at 12°C under argon for 2 days to afford a yellow crystalline material. Yield: 240 mg (65%). IR data (cm^-1): 3091 (w), 3071 (w), 3036 (w), 1598 (m), 1531 (w), 1478 (m), 1423 (s), 1382 (m), 1332 (m), 1272 (m), 1180 (w), 1076 (w), 983 (w), 824 (w), 677 (s).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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 (Sheldrick, 2008) and publCIF (Westrip, 2009).

Figures top

	Fig. 1. A view of the molecular structure of (I), along with the atom numbering scheme [symmetry code: (i) x, -y + 1/2, z]. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms and disordered parts are omitted for clarity.
	Fig. 2. A view of the molecular structure of (I) showing π-π stacking interactions between coordinated C₆Me₆ and benzene rings.

Hexa-µ-chlorido-hexachlorido(η⁶- hexamethylbenzene)trialuminium(III)lanthanum(III) benzene solvate top

Crystal data top

[Al₃LaCl₁₂(C₁₂H₁₈)]·C₆H₆	F(000) = 1728
M_r = 885.62	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0304P)² + 3.1621P] where P = (F_o² + 2F_c²)/3
4250 reflections	(Δ/σ)_max < 0.001
189 parameters	Δρ_max = 0.89 e Å⁻³
0 restraints	Δρ_min = −0.99 e Å⁻³

Crystal data top

[Al₃LaCl₁₂(C₁₂H₁₈)]·C₆H₆	V = 3404.9 (3) Å³
M_r = 885.62	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 12.2127 (6) Å	µ = 2.28 mm⁻¹
b = 16.4205 (8) Å	T = 173 K
c = 16.9790 (8) Å	0.22 × 0.20 × 0.16 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4250 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	3911 reflections with I > 2σ(I)
T_min = 0.613, T_max = 0.697	R_int = 0.018
28535 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.063	H-atom parameters not refined
S = 1.05	Δρ_max = 0.89 e Å⁻³
4250 reflections	Δρ_min = −0.99 e Å⁻³
189 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

	x	y	z	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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

Geometric parameters (Å, º) top

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)

Symmetry code: (i) x, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	[Al₃LaCl₁₂(C₁₂H₁₈)]·C₆H₆
M_r	885.62
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	173
a, b, c (Å)	12.2127 (6), 16.4205 (8), 16.9790 (8)
V (Å³)	3404.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.28
Crystal size (mm)	0.22 × 0.20 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.613, 0.697
No. of measured, independent and observed [I > 2σ(I)] reflections	28535, 4250, 3911
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.063, 1.05
No. of reflections	4250
No. of parameters	189
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.89, −0.99

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2009).

Selected bond lengths (Å) top

La1—C1	2.945 (3)	La1—Cl4	2.9298 (6)
La1—C2	2.965 (2)	La1—Cl5	2.9083 (7)
La1—C3	2.957 (3)	La1—Cl6	2.9097 (7)
La1—C4	2.941 (4)	La1—Cg1	2.613 (3)
La1—Cl3	2.9128 (5)	Cg1—Cg2	3.612 (4)

Acknowledgements

We thank the National Science Foundation for financial support (CHE-0546945). We are also very grateful to the University at Albany for supporting the X-ray center at the Department of Chemistry.

References

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