Tris(methyl 3-oxobutanoato-κ²O,O′)aluminium(III)

In the title compound, [Al(C₅H₇O₃)₃], three acac-type ligands (methyl 3-oxobutanoate anions) chelate to the aluminium(III) cation in a slightly distorted AlO₆ octa­hedral coordination geometry. Electron delocalization occurs within the chelating rings.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.068
• wR factor = 0.189
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT094_ALERT_2_B Ratio of Maximum / Minimum Residual Density ....       4.53
PLAT230_ALERT_2_B Hirshfeld Test Diff for    O7     --  C12     ..       8.34 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C12    --  C13     ..       7.93 su

Alert level C
DIFMX01_ALERT_2_C  The maximum difference density is > 0.1*ZMAX*0.75
            _refine_diff_density_max given =      1.260
            Test value =      0.975
DIFMX02_ALERT_1_C  The maximum difference density is > 0.1*ZMAX*0.75
            The relevant atom site should be identified.
PLAT097_ALERT_2_C Large Reported Max.  (Positive) Residual Density       1.26 eA-3
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          6
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595          9

Alert level G
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K

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

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

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Related literature

For the crystal structure of tris(acetylacetonato)aluminium, see: von Chrzanowski et al. (2007).

S1. Experimental

Aluminium isopropoxide (10 mmol, 2.04 g) was dissolved in toluene (25 ml) under a nitrogen atmosphere. Methyl acetoacetate (30 mmol, 3.2 ml) was added. The mixture turned yellow. The solution was stirred for 6 h. The solvent was removed by fractional distillation under vacuum to yield the product, which was purified by repeated recrystallization from cyclohexane.

S2. Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.96 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C). The final difference Fourier map had a peak in the vicinity of the C13 and C14 atoms.

Computing details

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of Al(C5H7O3)3 at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Tris(methyl 3-oxobutanoato-κ²O,O')aluminium(III)

Crystal data

[Al(C5H7O3)3]	Z = 2
Mr = 372.30	F(000) = 392
Triclinic, P1	Dx = 1.350 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.476 (1) Å	Cell parameters from 712 reflections
b = 9.986 (2) Å	θ = 2.5–25.9°
c = 14.368 (2) Å	µ = 0.15 mm^−1
α = 90.478 (2)°	T = 293 K
β = 92.229 (2)°	Block, yellow
γ = 99.337 (2)°	0.5 × 0.4 × 0.2 mm
V = 916.1 (2) Å^3

Data collection

Bruker SMART APEX diffractometer	3207 independent reflections
Radiation source: fine-focus sealed tube	2304 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ω scans	θmax = 25.0°, θmin = 1.4°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −7→7
Tmin = 0.927, Tmax = 0.970	k = −11→11
8801 measured reflections	l = −17→17

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.189	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0907P)^2 + 1.477P] where P = (Fo^2 + 2Fc^2)/3
3207 reflections	(Δ/σ)max = 0.001
232 parameters	Δρmax = 1.26 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Al1	0.61876 (18)	0.34609 (11)	0.25756 (8)	0.0287 (3)
O1	0.8373 (4)	0.4902 (2)	0.29494 (17)	0.0298 (6)
O2	1.0420 (4)	0.6906 (3)	0.2872 (2)	0.0407 (7)
O3	0.4846 (4)	0.4644 (3)	0.18716 (19)	0.0348 (7)
O4	0.7671 (4)	0.2253 (2)	0.32512 (17)	0.0279 (6)
O5	0.8034 (4)	0.0612 (3)	0.42532 (19)	0.0388 (7)
O6	0.4689 (4)	0.3726 (2)	0.36122 (18)	0.0317 (6)
O7	0.7870 (4)	0.3167 (3)	0.15592 (17)	0.0342 (7)
O8	0.9151 (5)	0.1916 (3)	0.0516 (2)	0.0472 (8)
O9	0.4156 (4)	0.1989 (3)	0.21949 (19)	0.0375 (7)
C1	1.1890 (6)	0.6352 (5)	0.3464 (3)	0.0419 (10)
H1A	1.3137	0.7011	0.3560	0.063*
H1B	1.2235	0.5551	0.3176	0.063*
H1C	1.1283	0.6125	0.4052	0.063*
C2	0.8676 (6)	0.6084 (4)	0.2614 (3)	0.0302 (9)
C3	0.7318 (7)	0.6615 (4)	0.1987 (3)	0.0364 (10)
H3	0.7674	0.7509	0.1799	0.044*
C4	0.5509 (6)	0.5875 (4)	0.1646 (3)	0.0324 (9)
C5	0.4062 (7)	0.6453 (4)	0.0957 (3)	0.0418 (11)
H5A	0.2692	0.6377	0.1203	0.063*
H5B	0.3978	0.5957	0.0378	0.063*
H5C	0.4602	0.7391	0.0854	0.063*
C6	0.9613 (7)	0.0242 (5)	0.3656 (3)	0.0423 (10)
H6A	1.0342	−0.0400	0.3968	0.063*
H6B	1.0590	0.1039	0.3518	0.063*
H6C	0.8953	−0.0157	0.3088	0.063*
C7	0.7055 (6)	0.1615 (4)	0.3967 (3)	0.0280 (8)
C9	0.4357 (6)	0.2936 (4)	0.4312 (3)	0.0317 (9)
C8	0.5413 (6)	0.1888 (4)	0.4513 (3)	0.0336 (9)
H8	0.5038	0.1345	0.5021	0.040*
C10	0.2692 (7)	0.3274 (4)	0.4948 (3)	0.0433 (11)
H10A	0.1454	0.3372	0.4583	0.065*
H10B	0.3205	0.4109	0.5279	0.065*
H10C	0.2364	0.2557	0.5385	0.065*
C11	1.0873 (7)	0.2966 (5)	0.0492 (3)	0.0464 (11)
H11A	1.1911	0.2695	0.0104	0.070*
H11B	1.1462	0.3157	0.1112	0.070*
H11C	1.0424	0.3766	0.0244	0.070*
C12	0.7677 (7)	0.2051 (5)	0.1104 (3)	0.0380 (10)
C13	0.5996 (7)	0.0964 (4)	0.1146 (3)	0.0403 (10)
H13	0.6048	0.0183	0.0796	0.048*
C14	0.4322 (7)	0.1000 (4)	0.1665 (3)	0.0379 (10)
C15	0.2460 (7)	−0.0173 (4)	0.1643 (3)	0.0434 (11)
H15A	0.1178	0.0182	0.1545	0.065*
H15B	0.2434	−0.0639	0.2225	0.065*
H15C	0.2605	−0.0795	0.1145	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Al1	0.0348 (7)	0.0243 (6)	0.0268 (6)	0.0046 (5)	0.0003 (5)	0.0002 (4)
O1	0.0298 (14)	0.0295 (14)	0.0295 (14)	0.0021 (11)	0.0035 (11)	−0.0032 (11)
O2	0.0372 (17)	0.0351 (15)	0.0484 (18)	0.0012 (13)	0.0016 (14)	0.0019 (13)
O3	0.0390 (16)	0.0275 (14)	0.0395 (16)	0.0099 (12)	0.0002 (13)	0.0030 (12)
O4	0.0289 (14)	0.0320 (14)	0.0233 (13)	0.0055 (11)	0.0028 (11)	0.0030 (11)
O5	0.0450 (17)	0.0441 (17)	0.0313 (15)	0.0179 (14)	0.0079 (13)	0.0078 (12)
O6	0.0277 (14)	0.0289 (14)	0.0385 (16)	0.0035 (11)	0.0059 (12)	0.0016 (12)
O7	0.0491 (17)	0.0345 (15)	0.0217 (14)	0.0136 (13)	0.0050 (12)	−0.0011 (11)
O8	0.0407 (18)	0.058 (2)	0.0421 (18)	0.0050 (15)	0.0080 (14)	−0.0004 (15)
O9	0.0457 (17)	0.0283 (14)	0.0366 (16)	0.0027 (12)	−0.0069 (13)	−0.0013 (12)
C1	0.030 (2)	0.051 (3)	0.044 (3)	0.0045 (19)	0.0002 (19)	−0.001 (2)
C2	0.030 (2)	0.027 (2)	0.032 (2)	−0.0037 (16)	0.0129 (17)	−0.0102 (16)
C3	0.047 (3)	0.027 (2)	0.037 (2)	0.0094 (18)	0.0084 (19)	0.0068 (17)
C4	0.040 (2)	0.033 (2)	0.028 (2)	0.0124 (18)	0.0097 (17)	−0.0013 (16)
C5	0.055 (3)	0.037 (2)	0.038 (2)	0.022 (2)	0.004 (2)	0.0085 (18)
C6	0.044 (3)	0.047 (3)	0.041 (2)	0.023 (2)	0.006 (2)	0.007 (2)
C7	0.030 (2)	0.0283 (19)	0.0240 (19)	0.0028 (16)	−0.0050 (16)	0.0005 (15)
C9	0.029 (2)	0.029 (2)	0.034 (2)	−0.0040 (16)	0.0020 (17)	−0.0061 (17)
C8	0.038 (2)	0.035 (2)	0.026 (2)	−0.0002 (18)	0.0076 (17)	0.0030 (16)
C10	0.039 (2)	0.044 (2)	0.047 (3)	0.002 (2)	0.021 (2)	−0.006 (2)
C11	0.030 (2)	0.074 (3)	0.036 (2)	0.008 (2)	0.0128 (19)	0.003 (2)
C12	0.044 (2)	0.058 (3)	0.0174 (19)	0.026 (2)	0.0062 (17)	0.0084 (18)
C13	0.058 (3)	0.022 (2)	0.039 (2)	0.0031 (19)	−0.007 (2)	−0.0040 (17)
C14	0.049 (3)	0.036 (2)	0.030 (2)	0.0126 (19)	−0.0016 (19)	0.0033 (18)
C15	0.051 (3)	0.033 (2)	0.044 (3)	−0.001 (2)	0.009 (2)	−0.0113 (19)

Geometric parameters (Å, º)

Al1—O1	1.905 (3)	C4—C5	1.518 (6)
Al1—O3	1.859 (3)	C5—H5A	0.9600
Al1—O4	1.909 (3)	C5—H5B	0.9600
Al1—O6	1.849 (3)	C5—H5C	0.9600
Al1—O7	1.904 (3)	C6—H6A	0.9600
Al1—O9	1.869 (3)	C6—H6B	0.9600
O1—C2	1.267 (5)	C6—H6C	0.9600
O2—C2	1.322 (4)	C7—C8	1.406 (5)
O2—C1	1.432 (5)	C9—C8	1.367 (6)
O3—C4	1.284 (5)	C9—C10	1.517 (5)
O4—C7	1.258 (4)	C8—H8	0.9300
O5—C7	1.329 (4)	C10—H10A	0.9600
O5—C6	1.450 (5)	C10—H10B	0.9600
O6—C9	1.286 (5)	C10—H10C	0.9600
O7—C12	1.273 (5)	C11—H11A	0.9600
O8—C12	1.322 (5)	C11—H11B	0.9600
O8—C11	1.403 (5)	C11—H11C	0.9600
O9—C14	1.263 (5)	C12—C13	1.411 (6)
C1—H1A	0.9600	C13—C14	1.345 (6)
C1—H1B	0.9600	C13—H13	0.9300
C1—H1C	0.9600	C14—C15	1.538 (6)
C2—C3	1.401 (6)	C15—H15A	0.9600
C3—C4	1.352 (6)	C15—H15B	0.9600
C3—H3	0.9300	C15—H15C	0.9600
O6—Al1—O3	92.13 (12)	H5B—C5—H5C	109.5
O6—Al1—O9	90.45 (13)	O5—C6—H6A	109.5
O3—Al1—O9	91.19 (13)	O5—C6—H6B	109.5
O6—Al1—O1	91.76 (12)	H6A—C6—H6B	109.5
O3—Al1—O1	90.98 (12)	O5—C6—H6C	109.5
O9—Al1—O1	176.85 (13)	H6A—C6—H6C	109.5
O6—Al1—O7	176.44 (13)	H6B—C6—H6C	109.5
O3—Al1—O7	90.98 (12)	O4—C7—O5	118.6 (3)
O9—Al1—O7	91.22 (13)	O4—C7—C8	125.3 (3)
O1—Al1—O7	86.45 (12)	O5—C7—C8	116.1 (3)
O6—Al1—O4	90.71 (12)	O6—C9—C8	124.9 (4)
O3—Al1—O4	177.05 (13)	O6—C9—C10	114.6 (3)
O9—Al1—O4	89.59 (12)	C8—C9—C10	120.5 (4)
O1—Al1—O4	88.13 (12)	C9—C8—C7	121.4 (3)
O7—Al1—O4	86.16 (12)	C9—C8—H8	119.3
C2—O1—Al1	126.1 (3)	C7—C8—H8	119.3
C2—O2—C1	116.9 (3)	C9—C10—H10A	109.5
C4—O3—Al1	129.5 (3)	C9—C10—H10B	109.5
C7—O4—Al1	125.6 (2)	H10A—C10—H10B	109.5
C7—O5—C6	116.8 (3)	C9—C10—H10C	109.5
C9—O6—Al1	127.3 (2)	H10A—C10—H10C	109.5
C12—O7—Al1	123.6 (3)	H10B—C10—H10C	109.5
C12—O8—C11	117.6 (4)	O8—C11—H11A	109.5
C14—O9—Al1	129.2 (3)	O8—C11—H11B	109.5
O2—C1—H1A	109.5	H11A—C11—H11B	109.5
O2—C1—H1B	109.5	O8—C11—H11C	109.5
H1A—C1—H1B	109.5	H11A—C11—H11C	109.5
O2—C1—H1C	109.5	H11B—C11—H11C	109.5
H1A—C1—H1C	109.5	O7—C12—O8	117.0 (4)
H1B—C1—H1C	109.5	O7—C12—C13	126.0 (4)
O1—C2—O2	118.0 (4)	O8—C12—C13	116.9 (4)
O1—C2—C3	125.9 (3)	C14—C13—C12	123.3 (4)
O2—C2—C3	116.1 (3)	C14—C13—H13	118.4
C4—C3—C2	122.4 (4)	C12—C13—H13	118.4
C4—C3—H3	118.8	O9—C14—C13	122.9 (4)
C2—C3—H3	118.8	O9—C14—C15	115.5 (4)
O3—C4—C3	124.0 (4)	C13—C14—C15	121.6 (4)
O3—C4—C5	114.0 (4)	C14—C15—H15A	109.5
C3—C4—C5	122.0 (4)	C14—C15—H15B	109.5
C4—C5—H5A	109.5	H15A—C15—H15B	109.5
C4—C5—H5B	109.5	C14—C15—H15C	109.5
H5A—C5—H5B	109.5	H15A—C15—H15C	109.5
C4—C5—H5C	109.5	H15B—C15—H15C	109.5
H5A—C5—H5C	109.5
O6—Al1—O1—C2	−102.8 (3)	C1—O2—C2—C3	−176.1 (3)
O3—Al1—O1—C2	−10.6 (3)	O1—C2—C3—C4	−2.0 (6)
O7—Al1—O1—C2	80.3 (3)	O2—C2—C3—C4	178.1 (4)
O4—Al1—O1—C2	166.6 (3)	Al1—O3—C4—C3	−8.0 (6)
O6—Al1—O3—C4	102.4 (3)	Al1—O3—C4—C5	172.5 (3)
O9—Al1—O3—C4	−167.1 (3)	C2—C3—C4—O3	1.4 (6)
O1—Al1—O3—C4	10.6 (3)	C2—C3—C4—C5	−179.1 (4)
O7—Al1—O3—C4	−75.8 (3)	Al1—O4—C7—O5	166.7 (2)
O6—Al1—O4—C7	22.3 (3)	Al1—O4—C7—C8	−14.6 (5)
O9—Al1—O4—C7	−68.1 (3)	C6—O5—C7—O4	−6.2 (5)
O1—Al1—O4—C7	114.0 (3)	C6—O5—C7—C8	175.0 (3)
O7—Al1—O4—C7	−159.4 (3)	Al1—O6—C9—C8	14.4 (5)
O3—Al1—O6—C9	158.5 (3)	Al1—O6—C9—C10	−167.3 (3)
O9—Al1—O6—C9	67.3 (3)	O6—C9—C8—C7	2.3 (6)
O1—Al1—O6—C9	−110.5 (3)	C10—C9—C8—C7	−175.8 (4)
O4—Al1—O6—C9	−22.3 (3)	O4—C7—C8—C9	−1.8 (6)
O3—Al1—O7—C12	−110.4 (3)	O5—C7—C8—C9	176.9 (3)
O9—Al1—O7—C12	−19.2 (3)	Al1—O7—C12—O8	−169.6 (2)
O1—Al1—O7—C12	158.7 (3)	Al1—O7—C12—C13	12.8 (5)
O4—Al1—O7—C12	70.3 (3)	C11—O8—C12—O7	4.5 (5)
O6—Al1—O9—C14	−157.2 (3)	C11—O8—C12—C13	−177.6 (4)
O3—Al1—O9—C14	110.6 (3)	O7—C12—C13—C14	2.2 (7)
O7—Al1—O9—C14	19.6 (3)	O8—C12—C13—C14	−175.4 (4)
O4—Al1—O9—C14	−66.5 (3)	Al1—O9—C14—C13	−11.6 (6)
Al1—O1—C2—O2	−171.6 (2)	Al1—O9—C14—C15	168.8 (3)
Al1—O1—C2—C3	8.6 (5)	C12—C13—C14—O9	−3.4 (7)
C1—O2—C2—O1	4.1 (5)	C12—C13—C14—C15	176.2 (4)