(2,2-Dimethyl-α,α,α′,α′-tetra­phenyl-1,3-dioxolane-4,5-dimethano­lato-κ²O⁴,O⁵)eth­yl(tetra­hydro­furan-κO)aluminium(III)

The title compound, [Al(C₂H₅)(C₃₁H₂₈O₄)(C₄H₈O)], has a slightly distorted tetra­hedral geometry around the Al^III metal centre. The bidentate TADDOLate ligand and the Al^III metal atom form a seven-membered ring, with an O—Al—O angle of 111.19 (10)°, which is close to the ideal tetra­hedral angle. The Al—O—C(alkoxide) angles of 139.17 (17) and 137.95 (17)° are larger than the sp³ bond angle, suggesting substantial π-donation of the alkoxide O atom to the Al^III metal centre.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.042
• wR factor = 0.122
• Data-to-parameter ratio = 9.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.84 Ratio
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.83 Ratio
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C32    -   C33     ..      11.44 su
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         C5
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        C32

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.748     1.000
            Tmin(prime) and Tmax expected:      0.920     0.980
            RR(prime) =      0.797
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.80
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.80 mm
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C35
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C37
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.980
            Tmax scaled      0.980 Tmin scaled      0.733
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.03
           From the CIF: _reflns_number_total               3591
           Count of symmetry unique reflns         3609
           Completeness (_total/calc)             99.50%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3     = .          R

   0 ALERT level A = In general: serious problem
   5 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   6 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

The asymmetric C—C bond formation reaction catalyzed by Lewis acidic metals is one of the most important reactions studied in the past decade (Pu & Yu, 2001; Ramón & Yus, 2006). Among the chiral diol ligands developed, α,α,α',α'-tetraaryl-1,3-dioxolane-4,5-dimethanols (TADDOLs) and 1,1'-bi(2-naphthol) (BINOL) are the two ligand types having the most diversified applications. Titanium and aluminium BINOLate complexes have been applied to a variety of asymmetric reactions and crystal structures of complexes of both metals were documented (Balsells et al., 2002; Arai et al., 1996; Nöth et al., 2001). In contrast, applications of TADDOLate ligands mainly focus on titanium catalytic systems and only a few molecular structures of titanium complexes were reported (Seebach et al., 1992; Hafner et al., 1992; Gothelf et al., 1995; Hintermann & Togni, 2000; Sheen & Gau, 2004). Yet, to our knowledge, there is no report of crystal structure of aluminium complex of the TADDOLate ligand. We report here the synthesis and crystal structure of the title compound,(I), an aluminium complex of the TADDOLate ligand.

The molecular structure of (I) has a slightly distorted tetrahedral geometry around the aluminium metal center with short Al—O(TADDOLate) bond lengths of 1.712 (2) and 1.719 (2) Å which are shorter by 0.05 Å than the Al—O(BINOLate) bond distances of 1.762 (1) and 1.754 (1) Å in the tetrahedral Al(BINOLate)py(Et) complex (Son et al., 2003) having a similar seven-membered chelate ring system. The seven-membered chelate TADDOLate O—Al—O angle of 111.19 (10)° is close to the ideal tetrahedral angle comparing to 106.65 (6)° for the Al(BINOLate)py(Et) structure. However, considerable deviations from the tetrahedral geometry are observed for the C—Al—O(TADDOLate) angles of 113.97 (11) and 118.74 (12)°. In comparison with the tetrahedral Ti(TADDOLate)₂ (Seebach et al., 1992) and the six-coordinate octahedral TiCl₂(TADDOLate)(dppe) (Shao & Gau, 1998) structures, the Al—O(TADDOLate) bond lengths are shorter by 0.07 Å and the TADDOLate O—Al—O bond angle is much larger than the averaged angle of the tetrahedral Ti(TADDOLate)₂ complex of 102.5° and the angle of the six-coordinate complex of 98.7 (1)°. The Al—O—C(TADDOLate) angles are observed to be 139.17 (17)° and 137.95 (17)°, indicating considerable π-donation (Gau et al., 1996)) from the alkoxide oxygen donor atom to empty 3 d orbitals of the aluminium(III) metal center. These angles are smaller than the averaged angles of the tetrahedral Ti(IV) complex of 145.3° and the octahedral Ti(IV) complex of 149.5°. However, these angles are larger than the angles of 124.2 (1) and 114.2 (1)° for the Al(BINOLate)py(Et) complex, suggesting a better π-donation ability of the TADDOLate ligand than the BINOLate ligand.

Related literature

For related literature, see: Arai et al. (1996, 1998); Balsells et al. (2002); Gau et al. (1996); Gothelf et al. (1995); Hafner et al. (1992); Hintermann & Togni (2000); Nöth et al. (2001); Pu & Yu (2001); Ramón & Yus (2006); Seebach et al. (1992); Shao & Gau (1998); Sheen & Gau (2004); Son et al. (2003).

S2. Experimental

To an ice cold solution of α,α,α',α'-tetraphenyl-2,2-dimethyl- 1,3-dioxolane-4,5-dimethanol (4.67 g, 10.0 mmol) in THF (70 ml) at 273 K, AlEt₃ (12.0 ml, 15 wt% in hexane, 10.0 mmol) was added slowly in 30 min. After stirring for 1 h at 273 K, the solution was warmed to room temperature and was allowed to react for another 3.5 h. The volatile material was removed under reduced pressure to give a white residue. The residue was recrystallized from THF (100 ml) at 277 K to afford the first crop of compound (I) (2.07 g, 35.0%). The filtrate was cooled to 248 K to furnish the second crop of the product (2.00 g, 33.8%). The second filtrate was dried and the residue was dissolved in CH₂Cl₂. The solution was cooled to 248 K to afford colorless crystals (0.54 g, 9.0%) for molecular structure determination. ¹H NMR (400 MHz, CDCl₃): δ 7.66–7.12 (m, 20H, Ph), 5.02 (d, J = 6.4 Hz, 1H, CH), 4.91 (d, J = 6.4 Hz, 1H, CH), 4.10–3.90 (m, 4H, OCH₂), 1.81 (m, 4H, CH₂), 0.75 (t, J = 8.0 Hz, 3H, CH₃), 0.48 (s, 3H, OCCH₃), 0.43 (s, 3H, OCCH₃),-0.16 - -0.35 (m, 2H, AlCH₂) p.p.m..

S3. Refinement

All H atoms were treated as riding, with C—H = 0.93–0.98 Å, and with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C). In this investigation, the U_eq of C32 was low compared to its neighbors, suggesting a possiblitiy of a heavier atom at this site. However, the ¹H NMR spectrum of the crystalline material used for the X-ray diffraction study gives exclusive signals of an ethyl group with the C32 bonded to the Al metal center. In the absence of significant anomalous scattering, Friedel pairs were merged prior to the final refinement.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures

Fig. 1. The molecular structure of (I), with atom-numbering scheme. Displacement ellipsoids are drawn at the 20% probability level. H atoms (except tertiary) have been omitted for clarity.

(2,2-Dimethyl-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanolato- κ²O⁴,O⁵)ethyl(tetrahydrofuran-κO)aluminium(III)

Crystal data

[Al(C2H5)(C31H28O4)(C4H8O)]	F(000) = 1264
Mr = 592.68	Dx = 1.210 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6990 reflections
a = 9.6123 (8) Å	θ = 2.3–25.6°
b = 15.7991 (13) Å	µ = 0.10 mm^−1
c = 21.4207 (18) Å	T = 293 K
V = 3253.1 (5) Å^3	Block, colourless
Z = 4	0.80 × 0.23 × 0.19 mm

Data collection

Bruker SMART 1000 CCD diffractometer	3591 independent reflections
Radiation source: fine-focus sealed tube	2940 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
φ and ω scans	θmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.748, Tmax = 1.000	k = −19→18
18371 measured reflections	l = −20→26

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.122	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0821P)^2] where P = (Fo^2 + 2Fc^2)/3
3591 reflections	(Δ/σ)max = 0.001
388 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.14 e Å^−3
0 constraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Al	0.78827 (9)	0.09324 (5)	0.85554 (4)	0.0411 (2)
O1	0.7584 (3)	0.09540 (12)	0.93466 (9)	0.0542 (5)
O2	0.7893 (2)	−0.10724 (12)	1.01477 (9)	0.0509 (5)
O3	0.9896 (2)	−0.13100 (13)	0.96129 (9)	0.0515 (5)
O4	0.8597 (2)	−0.00121 (12)	0.83308 (9)	0.0471 (5)
O5	0.9322 (2)	0.17413 (12)	0.84797 (11)	0.0543 (5)
C1	0.7350 (3)	0.03898 (17)	0.98380 (11)	0.0411 (6)
C2	0.7832 (3)	−0.05201 (16)	0.96227 (12)	0.0401 (6)
H2A	0.7151	−0.0743	0.9324	0.048*
C3	0.9291 (3)	−0.05808 (17)	0.93323 (12)	0.0413 (6)
H3A	0.9830	−0.0081	0.9455	0.050*
C4	0.9352 (3)	−0.06764 (16)	0.86033 (13)	0.0414 (6)
C5	0.9102 (4)	−0.1571 (2)	1.01377 (15)	0.0570 (8)
C6	0.8713 (8)	−0.2479 (3)	1.0058 (4)	0.154 (3)
H6A	0.8170	−0.2543	0.9685	0.232*
H6B	0.8178	−0.2662	1.0411	0.232*
H6C	0.9541	−0.2815	1.0026	0.232*
C7	0.9958 (6)	−0.1355 (5)	1.07144 (18)	0.139 (3)
H7A	1.0136	−0.0757	1.0724	0.208*
H7B	1.0825	−0.1656	1.0701	0.208*
H7C	0.9453	−0.1516	1.1082	0.208*
C8	0.8179 (3)	0.07032 (17)	1.04086 (14)	0.0443 (6)
C9	0.9188 (3)	0.1324 (2)	1.03385 (16)	0.0551 (7)
H9A	0.9364	0.1541	0.9943	0.066*
C10	0.9936 (4)	0.1627 (2)	1.0840 (2)	0.0694 (10)
H10A	1.0616	0.2038	1.0779	0.083*
C11	0.9680 (4)	0.1325 (2)	1.1427 (2)	0.0743 (11)
H11A	1.0190	0.1527	1.1765	0.089*
C12	0.8663 (5)	0.0720 (2)	1.15179 (17)	0.0717 (10)
H12A	0.8472	0.0521	1.1917	0.086*
C13	0.7926 (4)	0.0409 (2)	1.10072 (14)	0.0572 (8)
H13A	0.7250	−0.0004	1.1069	0.069*
C14	0.5786 (3)	0.03763 (18)	0.99948 (13)	0.0444 (6)
C15	0.4991 (4)	0.1091 (2)	0.98485 (17)	0.0665 (9)
H15A	0.5407	0.1551	0.9653	0.080*
C16	0.3583 (4)	0.1116 (3)	0.9993 (2)	0.0814 (12)
H16A	0.3067	0.1595	0.9891	0.098*
C17	0.2938 (4)	0.0449 (3)	1.0283 (2)	0.0812 (12)
H17A	0.1996	0.0473	1.0381	0.097*
C18	0.3709 (4)	−0.0257 (3)	1.0425 (2)	0.0777 (11)
H18A	0.3286	−0.0716	1.0621	0.093*
C19	0.5116 (4)	−0.0291 (2)	1.02802 (18)	0.0634 (9)
H19A	0.5619	−0.0776	1.0378	0.076*
C20	0.8713 (3)	−0.15198 (18)	0.83976 (13)	0.0453 (6)
C21	0.7343 (3)	−0.1554 (2)	0.81897 (14)	0.0556 (8)
H21A	0.6820	−0.1060	0.8173	0.067*
C22	0.6744 (5)	−0.2314 (3)	0.80058 (19)	0.0759 (11)
H22A	0.5826	−0.2323	0.7869	0.091*
C23	0.7490 (5)	−0.3045 (3)	0.80237 (19)	0.0827 (13)
H23A	0.7080	−0.3554	0.7905	0.099*
C24	0.8855 (6)	−0.3028 (2)	0.8218 (2)	0.0804 (13)
H24A	0.9374	−0.3525	0.8220	0.097*
C25	0.9464 (4)	−0.2273 (2)	0.84102 (16)	0.0632 (9)
H25A	1.0381	−0.2272	0.8549	0.076*
C26	1.0860 (3)	−0.06168 (18)	0.83610 (14)	0.0471 (7)
C27	1.2033 (4)	−0.0667 (2)	0.87345 (17)	0.0663 (9)
H27A	1.1935	−0.0754	0.9162	0.080*
C28	1.3356 (4)	−0.0589 (3)	0.8478 (2)	0.0858 (13)
H28A	1.4136	−0.0615	0.8734	0.103*
C29	1.3516 (5)	−0.0472 (3)	0.7845 (2)	0.0850 (13)
H29A	1.4401	−0.0427	0.7673	0.102*
C30	1.2366 (5)	−0.0424 (3)	0.74697 (19)	0.0756 (11)
H30A	1.2472	−0.0344	0.7042	0.091*
C31	1.1037 (4)	−0.0495 (2)	0.77246 (16)	0.0604 (8)
H31A	1.0262	−0.0460	0.7466	0.072*
C32	0.6370 (3)	0.13669 (18)	0.79692 (14)	0.0493 (7)
H32A	0.5617	0.0959	0.7951	0.059*
H32B	0.5997	0.1894	0.8131	0.059*
C33	0.6929 (7)	0.1510 (5)	0.7327 (2)	0.136 (2)
H33A	0.6196	0.1711	0.7061	0.203*
H33B	0.7288	0.0987	0.7164	0.203*
H33C	0.7661	0.1923	0.7343	0.203*
C34	1.0796 (4)	0.1596 (2)	0.85889 (19)	0.0656 (9)
H34A	1.1252	0.1406	0.8210	0.079*
H34B	1.0932	0.1174	0.8912	0.079*
C35	1.1364 (5)	0.2442 (3)	0.8793 (3)	0.0909 (14)
H35A	1.1299	0.2508	0.9243	0.109*
H35B	1.2327	0.2509	0.8667	0.109*
C36	1.0441 (5)	0.3061 (2)	0.8461 (2)	0.0835 (12)
H36A	1.0418	0.3599	0.8678	0.100*
H36B	1.0755	0.3153	0.8036	0.100*
C37	0.9060 (5)	0.2650 (2)	0.8471 (3)	0.0864 (13)
H37A	0.8542	0.2820	0.8839	0.104*
H37B	0.8529	0.2805	0.8103	0.104*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Al	0.0473 (4)	0.0348 (4)	0.0413 (4)	0.0003 (4)	−0.0033 (3)	0.0023 (3)
O1	0.0811 (15)	0.0354 (9)	0.0462 (10)	0.0090 (10)	0.0087 (10)	0.0044 (8)
O2	0.0554 (12)	0.0430 (10)	0.0543 (11)	0.0116 (10)	0.0114 (10)	0.0110 (9)
O3	0.0554 (11)	0.0510 (11)	0.0480 (10)	0.0184 (10)	0.0080 (10)	0.0067 (10)
O4	0.0583 (12)	0.0414 (10)	0.0416 (10)	0.0076 (9)	0.0008 (9)	0.0010 (8)
O5	0.0563 (12)	0.0367 (10)	0.0698 (13)	−0.0069 (9)	−0.0054 (11)	0.0041 (9)
C1	0.0521 (16)	0.0353 (13)	0.0361 (13)	0.0073 (12)	0.0022 (11)	−0.0012 (10)
C2	0.0451 (14)	0.0328 (12)	0.0423 (13)	0.0055 (12)	0.0049 (12)	0.0010 (11)
C3	0.0476 (15)	0.0336 (12)	0.0427 (14)	0.0051 (12)	−0.0006 (12)	−0.0023 (11)
C4	0.0466 (14)	0.0356 (13)	0.0421 (14)	0.0037 (11)	0.0032 (12)	−0.0016 (11)
C5	0.0595 (18)	0.0489 (17)	0.0627 (19)	0.0190 (15)	0.0135 (15)	0.0187 (14)
C6	0.149 (6)	0.043 (2)	0.271 (8)	0.013 (3)	0.117 (6)	0.015 (3)
C7	0.096 (3)	0.269 (8)	0.050 (2)	0.076 (5)	0.002 (2)	0.031 (4)
C8	0.0471 (16)	0.0377 (14)	0.0480 (14)	0.0095 (11)	0.0006 (12)	−0.0055 (12)
C9	0.0529 (17)	0.0457 (16)	0.0668 (19)	0.0038 (14)	0.0051 (15)	−0.0062 (15)
C10	0.061 (2)	0.0506 (18)	0.096 (3)	0.0026 (17)	−0.014 (2)	−0.0168 (19)
C11	0.083 (3)	0.0559 (19)	0.084 (3)	0.0126 (19)	−0.032 (2)	−0.020 (2)
C12	0.100 (3)	0.060 (2)	0.0546 (19)	0.010 (2)	−0.0201 (19)	−0.0032 (16)
C13	0.071 (2)	0.0497 (16)	0.0516 (16)	0.0009 (16)	−0.0049 (16)	−0.0024 (14)
C14	0.0484 (15)	0.0438 (14)	0.0409 (14)	0.0111 (12)	−0.0029 (12)	−0.0063 (12)
C15	0.071 (2)	0.060 (2)	0.069 (2)	0.0287 (18)	−0.0049 (17)	0.0004 (17)
C16	0.066 (2)	0.077 (3)	0.101 (3)	0.036 (2)	−0.012 (2)	−0.005 (2)
C17	0.048 (2)	0.091 (3)	0.104 (3)	0.019 (2)	−0.001 (2)	−0.021 (2)
C18	0.053 (2)	0.067 (2)	0.113 (3)	0.0044 (18)	0.016 (2)	−0.004 (2)
C19	0.0538 (19)	0.0514 (18)	0.085 (2)	0.0082 (15)	0.0096 (17)	0.0002 (17)
C20	0.0573 (17)	0.0387 (14)	0.0399 (14)	−0.0013 (13)	0.0076 (12)	−0.0029 (11)
C21	0.0597 (19)	0.0545 (18)	0.0526 (16)	−0.0065 (15)	0.0007 (15)	−0.0047 (14)
C22	0.077 (3)	0.076 (3)	0.075 (2)	−0.026 (2)	0.001 (2)	−0.012 (2)
C23	0.109 (4)	0.062 (2)	0.077 (2)	−0.034 (2)	0.016 (2)	−0.0141 (19)
C24	0.120 (4)	0.0363 (17)	0.085 (3)	0.001 (2)	0.017 (3)	−0.0081 (17)
C25	0.079 (2)	0.0444 (16)	0.066 (2)	0.0063 (16)	0.0037 (18)	−0.0063 (15)
C26	0.0507 (16)	0.0388 (14)	0.0518 (16)	−0.0006 (12)	0.0094 (13)	−0.0075 (12)
C27	0.0534 (19)	0.078 (2)	0.0673 (19)	0.0008 (18)	0.0087 (16)	−0.0037 (18)
C28	0.0483 (19)	0.113 (3)	0.096 (3)	−0.004 (2)	0.013 (2)	−0.009 (3)
C29	0.060 (2)	0.094 (3)	0.101 (3)	−0.016 (2)	0.033 (2)	−0.022 (3)
C30	0.090 (3)	0.068 (2)	0.069 (2)	−0.014 (2)	0.038 (2)	−0.0127 (18)
C31	0.068 (2)	0.0567 (18)	0.0565 (19)	−0.0046 (16)	0.0150 (16)	−0.0091 (15)
C32	0.0559 (17)	0.0358 (14)	0.0564 (16)	0.0104 (13)	−0.0090 (13)	0.0005 (13)
C33	0.174 (6)	0.166 (5)	0.066 (3)	0.067 (5)	−0.043 (3)	−0.003 (3)
C34	0.0554 (18)	0.0527 (18)	0.089 (2)	−0.0069 (16)	0.0023 (19)	0.0076 (18)
C35	0.085 (3)	0.071 (3)	0.117 (4)	−0.023 (2)	−0.024 (3)	0.010 (2)
C36	0.103 (3)	0.051 (2)	0.097 (3)	−0.019 (2)	−0.018 (3)	0.010 (2)
C37	0.082 (3)	0.0402 (17)	0.137 (4)	−0.0054 (18)	−0.016 (3)	−0.002 (2)

Geometric parameters (Å, º)

Al—O4	1.712 (2)	C16—H16A	0.93
Al—O1	1.719 (2)	C17—C18	1.374 (6)
Al—O5	1.891 (2)	C17—H17A	0.93
Al—C32	2.040 (3)	C18—C19	1.388 (5)
O1—C1	1.397 (3)	C18—H18A	0.93
O2—C5	1.404 (4)	C19—H19A	0.93
O2—C2	1.425 (3)	C20—C21	1.391 (4)
O3—C5	1.420 (4)	C20—C25	1.393 (5)
O3—C3	1.423 (3)	C21—C22	1.388 (5)
O4—C4	1.403 (3)	C21—H21A	0.93
O5—C34	1.454 (4)	C22—C23	1.361 (6)
O5—C37	1.458 (4)	C22—H22A	0.93
C1—C14	1.541 (4)	C23—C24	1.377 (7)
C1—C8	1.541 (4)	C23—H23A	0.93
C1—C2	1.579 (3)	C24—C25	1.391 (5)
C2—C3	1.537 (4)	C24—H24A	0.93
C2—H2A	0.98	C25—H25A	0.93
C3—C4	1.570 (4)	C26—C31	1.387 (5)
C3—H3A	0.98	C26—C27	1.385 (5)
C4—C20	1.532 (4)	C27—C28	1.392 (5)
C4—C26	1.543 (4)	C27—H27A	0.93
C5—C6	1.492 (6)	C28—C29	1.376 (7)
C5—C7	1.523 (6)	C28—H28A	0.93
C6—H6A	0.96	C29—C30	1.369 (6)
C6—H6B	0.96	C29—H29A	0.93
C6—H6C	0.96	C30—C31	1.393 (5)
C7—H7A	0.96	C30—H30A	0.93
C7—H7B	0.96	C31—H31A	0.93
C7—H7C	0.96	C32—C33	1.494 (6)
C8—C9	1.388 (4)	C32—H32A	0.97
C8—C13	1.385 (4)	C32—H32B	0.97
C9—C10	1.379 (5)	C33—H33A	0.96
C9—H9A	0.93	C33—H33B	0.96
C10—C11	1.368 (6)	C33—H33C	0.96
C10—H10A	0.93	C34—C35	1.508 (5)
C11—C12	1.382 (6)	C34—H34A	0.97
C11—H11A	0.93	C34—H34B	0.97
C12—C13	1.393 (5)	C35—C36	1.500 (6)
C12—H12A	0.93	C35—H35A	0.97
C13—H13A	0.93	C35—H35B	0.97
C14—C19	1.378 (5)	C36—C37	1.478 (6)
C14—C15	1.398 (4)	C36—H36A	0.97
C15—C16	1.389 (6)	C36—H36B	0.97
C15—H15A	0.93	C37—H37A	0.97
C16—C17	1.372 (6)	C37—H37B	0.97
O4—Al—O1	111.19 (10)	C18—C17—C16	118.7 (4)
O4—Al—O5	105.76 (11)	C18—C17—H17A	120.6
O1—Al—O5	101.15 (11)	C16—C17—H17A	120.6
O4—Al—C32	113.97 (11)	C17—C18—C19	120.5 (4)
O1—Al—C32	118.74 (12)	C17—C18—H18A	119.8
O5—Al—C32	103.97 (11)	C19—C18—H18A	119.8
C1—O1—Al	139.17 (17)	C14—C19—C18	121.7 (3)
C5—O2—C2	111.5 (2)	C14—C19—H19A	119.2
C5—O3—C3	110.5 (2)	C18—C19—H19A	119.2
C4—O4—Al	137.95 (17)	C21—C20—C25	117.6 (3)
C34—O5—C37	109.0 (3)	C21—C20—C4	120.4 (3)
C34—O5—Al	126.35 (19)	C25—C20—C4	122.0 (3)
C37—O5—Al	122.7 (2)	C20—C21—C22	121.2 (3)
O1—C1—C14	109.3 (2)	C20—C21—H21A	119.4
O1—C1—C8	108.0 (2)	C22—C21—H21A	119.4
C14—C1—C8	109.6 (2)	C23—C22—C21	120.5 (4)
O1—C1—C2	108.3 (2)	C23—C22—H22A	119.7
C14—C1—C2	109.7 (2)	C21—C22—H22A	119.7
C8—C1—C2	111.9 (2)	C22—C23—C24	119.6 (4)
O2—C2—C3	104.1 (2)	C22—C23—H23A	120.2
O2—C2—C1	109.8 (2)	C24—C23—H23A	120.2
C3—C2—C1	116.3 (2)	C23—C24—C25	120.5 (4)
O2—C2—H2A	108.8	C23—C24—H24A	119.7
C3—C2—H2A	108.8	C25—C24—H24A	119.7
C1—C2—H2A	108.8	C24—C25—C20	120.6 (4)
O3—C3—C2	104.6 (2)	C24—C25—H25A	119.7
O3—C3—C4	109.1 (2)	C20—C25—H25A	119.7
C2—C3—C4	116.3 (2)	C31—C26—C27	118.4 (3)
O3—C3—H3A	108.9	C31—C26—C4	117.0 (3)
C2—C3—H3A	108.9	C27—C26—C4	124.6 (3)
C4—C3—H3A	108.9	C26—C27—C28	120.7 (3)
O4—C4—C20	108.9 (2)	C26—C27—H27A	119.7
O4—C4—C26	107.5 (2)	C28—C27—H27A	119.7
C20—C4—C26	109.5 (2)	C29—C28—C27	120.2 (4)
O4—C4—C3	108.8 (2)	C29—C28—H28A	119.9
C20—C4—C3	110.8 (2)	C27—C28—H28A	119.9
C26—C4—C3	111.3 (2)	C30—C29—C28	119.7 (4)
O2—C5—O3	107.1 (2)	C30—C29—H29A	120.1
O2—C5—C6	109.5 (4)	C28—C29—H29A	120.1
O3—C5—C6	108.8 (4)	C29—C30—C31	120.4 (3)
O2—C5—C7	108.0 (3)	C29—C30—H30A	119.8
O3—C5—C7	106.7 (3)	C31—C30—H30A	119.8
C6—C5—C7	116.3 (6)	C26—C31—C30	120.6 (4)
C5—C6—H6A	109.5	C26—C31—H31A	119.7
C5—C6—H6B	109.5	C30—C31—H31A	119.7
H6A—C6—H6B	109.5	C33—C32—Al	111.2 (3)
C5—C6—H6C	109.5	C33—C32—H32A	109.4
H6A—C6—H6C	109.5	Al—C32—H32A	109.4
H6B—C6—H6C	109.5	C33—C32—H32B	109.4
C5—C7—H7A	109.5	Al—C32—H32B	109.4
C5—C7—H7B	109.5	H32A—C32—H32B	108.0
H7A—C7—H7B	109.5	C32—C33—H33A	109.5
C5—C7—H7C	109.5	C32—C33—H33B	109.5
H7A—C7—H7C	109.5	H33A—C33—H33B	109.5
H7B—C7—H7C	109.5	C32—C33—H33C	109.5
C9—C8—C13	117.4 (3)	H33A—C33—H33C	109.5
C9—C8—C1	120.2 (3)	H33B—C33—H33C	109.5
C13—C8—C1	122.4 (3)	O5—C34—C35	105.1 (3)
C10—C9—C8	121.7 (3)	O5—C34—H34A	110.7
C10—C9—H9A	119.1	C35—C34—H34A	110.7
C8—C9—H9A	119.1	O5—C34—H34B	110.7
C11—C10—C9	120.1 (4)	C35—C34—H34B	110.7
C11—C10—H10A	119.9	H34A—C34—H34B	108.8
C9—C10—H10A	119.9	C36—C35—C34	103.0 (3)
C10—C11—C12	119.9 (3)	C36—C35—H35A	111.2
C10—C11—H11A	120.1	C34—C35—H35A	111.2
C12—C11—H11A	120.1	C36—C35—H35B	111.2
C11—C12—C13	119.6 (4)	C34—C35—H35B	111.2
C11—C12—H12A	120.2	H35A—C35—H35B	109.1
C13—C12—H12A	120.2	C37—C36—C35	103.8 (3)
C8—C13—C12	121.3 (3)	C37—C36—H36A	111.0
C8—C13—H13A	119.4	C35—C36—H36A	111.0
C12—C13—H13A	119.4	C37—C36—H36B	111.0
C19—C14—C15	117.5 (3)	C35—C36—H36B	111.0
C19—C14—C1	124.3 (3)	H36A—C36—H36B	109.0
C15—C14—C1	118.2 (3)	O5—C37—C36	106.1 (3)
C16—C15—C14	120.4 (4)	O5—C37—H37A	110.5
C16—C15—H15A	119.8	C36—C37—H37A	110.5
C14—C15—H15A	119.8	O5—C37—H37B	110.5
C17—C16—C15	121.2 (4)	C36—C37—H37B	110.5
C17—C16—H16A	119.4	H37A—C37—H37B	108.7
C15—C16—H16A	119.4