metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

aMaterials Research Centre, Indian Institute of Science, Bangalore 560 012, India, and bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my

(Received 19 November 2009; accepted 20 November 2009; online 25 November 2009)

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.

Related literature

For the crystal structure of tris­(acetyl­acetonato)aluminium, see: von Chrzanowski et al. (2007[Chrzanowski, L. S. von, Lutz, M. & Spek, A. L. (2007). Acta Cryst. C63, m129-m134.]).

[Scheme 1]

Experimental

Crystal data
  • [Al(C5H7O3)3]

  • Mr = 372.30

  • Triclinic, [P \overline 1]

  • a = 6.476 (1) Å

  • b = 9.986 (2) Å

  • c = 14.368 (2) Å

  • α = 90.478 (2)°

  • β = 92.229 (2)°

  • γ = 99.337 (2)°

  • V = 916.1 (2) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.15 mm−1

  • T = 293 K

  • 0.5 × 0.4 × 0.2 mm

Data collection
  • Bruker SMART APEX diffractometer

  • Absorption correction: multi-scan SADABS (Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.927, Tmax = 0.970

  • 8801 measured reflections

  • 3207 independent reflections

  • 2304 reflections with I > 2σ(I)

  • Rint = 0.041

Refinement
  • R[F2 > 2σ(F2)] = 0.068

  • wR(F2) = 0.189

  • S = 1.02

  • 3207 reflections

  • 232 parameters

  • H-atom parameters constrained

  • Δρmax = 1.26 e Å−3

  • Δρmin = −0.28 e Å−3

Table 1
Selected bond lengths (Å)

Al1—O1 1.905 (3)
Al1—O3 1.859 (3)
Al1—O4 1.909 (3)
Al1—O6 1.849 (3)
Al1—O7 1.904 (3)
Al1—O9 1.869 (3)

Data collection: SMART (Bruker, 2004[Bruker (2004). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2009[Westrip, S. P. (2009). publCIF. In preparation.]).

Supporting information


Related literature top

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

Experimental top

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.

Refinement top

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 top

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 top
[Figure 1] 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) top
Crystal data top
[Al(C5H7O3)3]Z = 2
Mr = 372.30F(000) = 392
Triclinic, P1Dx = 1.350 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.476 (1) ÅCell parameters from 712 reflections
b = 9.986 (2) Åθ = 2.5–25.9°
c = 14.368 (2) ŵ = 0.15 mm1
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) Å3
Data collection top
Bruker SMART APEX
diffractometer
3207 independent reflections
Radiation source: fine-focus sealed tube2304 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
ω scansθmax = 25.0°, θmin = 1.4°
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)
h = 77
Tmin = 0.927, Tmax = 0.970k = 1111
8801 measured reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.068Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.189H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0907P)2 + 1.477P]
where P = (Fo2 + 2Fc2)/3
3207 reflections(Δ/σ)max = 0.001
232 parametersΔρmax = 1.26 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
[Al(C5H7O3)3]γ = 99.337 (2)°
Mr = 372.30V = 916.1 (2) Å3
Triclinic, P1Z = 2
a = 6.476 (1) ÅMo Kα radiation
b = 9.986 (2) ŵ = 0.15 mm1
c = 14.368 (2) ÅT = 293 K
α = 90.478 (2)°0.5 × 0.4 × 0.2 mm
β = 92.229 (2)°
Data collection top
Bruker SMART APEX
diffractometer
3207 independent reflections
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)
2304 reflections with I > 2σ(I)
Tmin = 0.927, Tmax = 0.970Rint = 0.041
8801 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0680 restraints
wR(F2) = 0.189H-atom parameters constrained
S = 1.02Δρmax = 1.26 e Å3
3207 reflectionsΔρmin = 0.28 e Å3
232 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Al10.61876 (18)0.34609 (11)0.25756 (8)0.0287 (3)
O10.8373 (4)0.4902 (2)0.29494 (17)0.0298 (6)
O21.0420 (4)0.6906 (3)0.2872 (2)0.0407 (7)
O30.4846 (4)0.4644 (3)0.18716 (19)0.0348 (7)
O40.7671 (4)0.2253 (2)0.32512 (17)0.0279 (6)
O50.8034 (4)0.0612 (3)0.42532 (19)0.0388 (7)
O60.4689 (4)0.3726 (2)0.36122 (18)0.0317 (6)
O70.7870 (4)0.3167 (3)0.15592 (17)0.0342 (7)
O80.9151 (5)0.1916 (3)0.0516 (2)0.0472 (8)
O90.4156 (4)0.1989 (3)0.21949 (19)0.0375 (7)
C11.1890 (6)0.6352 (5)0.3464 (3)0.0419 (10)
H1A1.31370.70110.35600.063*
H1B1.22350.55510.31760.063*
H1C1.12830.61250.40520.063*
C20.8676 (6)0.6084 (4)0.2614 (3)0.0302 (9)
C30.7318 (7)0.6615 (4)0.1987 (3)0.0364 (10)
H30.76740.75090.17990.044*
C40.5509 (6)0.5875 (4)0.1646 (3)0.0324 (9)
C50.4062 (7)0.6453 (4)0.0957 (3)0.0418 (11)
H5A0.26920.63770.12030.063*
H5B0.39780.59570.03780.063*
H5C0.46020.73910.08540.063*
C60.9613 (7)0.0242 (5)0.3656 (3)0.0423 (10)
H6A1.03420.04000.39680.063*
H6B1.05900.10390.35180.063*
H6C0.89530.01570.30880.063*
C70.7055 (6)0.1615 (4)0.3967 (3)0.0280 (8)
C90.4357 (6)0.2936 (4)0.4312 (3)0.0317 (9)
C80.5413 (6)0.1888 (4)0.4513 (3)0.0336 (9)
H80.50380.13450.50210.040*
C100.2692 (7)0.3274 (4)0.4948 (3)0.0433 (11)
H10A0.14540.33720.45830.065*
H10B0.32050.41090.52790.065*
H10C0.23640.25570.53850.065*
C111.0873 (7)0.2966 (5)0.0492 (3)0.0464 (11)
H11A1.19110.26950.01040.070*
H11B1.14620.31570.11120.070*
H11C1.04240.37660.02440.070*
C120.7677 (7)0.2051 (5)0.1104 (3)0.0380 (10)
C130.5996 (7)0.0964 (4)0.1146 (3)0.0403 (10)
H130.60480.01830.07960.048*
C140.4322 (7)0.1000 (4)0.1665 (3)0.0379 (10)
C150.2460 (7)0.0173 (4)0.1643 (3)0.0434 (11)
H15A0.11780.01820.15450.065*
H15B0.24340.06390.22250.065*
H15C0.26050.07950.11450.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Al10.0348 (7)0.0243 (6)0.0268 (6)0.0046 (5)0.0003 (5)0.0002 (4)
O10.0298 (14)0.0295 (14)0.0295 (14)0.0021 (11)0.0035 (11)0.0032 (11)
O20.0372 (17)0.0351 (15)0.0484 (18)0.0012 (13)0.0016 (14)0.0019 (13)
O30.0390 (16)0.0275 (14)0.0395 (16)0.0099 (12)0.0002 (13)0.0030 (12)
O40.0289 (14)0.0320 (14)0.0233 (13)0.0055 (11)0.0028 (11)0.0030 (11)
O50.0450 (17)0.0441 (17)0.0313 (15)0.0179 (14)0.0079 (13)0.0078 (12)
O60.0277 (14)0.0289 (14)0.0385 (16)0.0035 (11)0.0059 (12)0.0016 (12)
O70.0491 (17)0.0345 (15)0.0217 (14)0.0136 (13)0.0050 (12)0.0011 (11)
O80.0407 (18)0.058 (2)0.0421 (18)0.0050 (15)0.0080 (14)0.0004 (15)
O90.0457 (17)0.0283 (14)0.0366 (16)0.0027 (12)0.0069 (13)0.0013 (12)
C10.030 (2)0.051 (3)0.044 (3)0.0045 (19)0.0002 (19)0.001 (2)
C20.030 (2)0.027 (2)0.032 (2)0.0037 (16)0.0129 (17)0.0102 (16)
C30.047 (3)0.027 (2)0.037 (2)0.0094 (18)0.0084 (19)0.0068 (17)
C40.040 (2)0.033 (2)0.028 (2)0.0124 (18)0.0097 (17)0.0013 (16)
C50.055 (3)0.037 (2)0.038 (2)0.022 (2)0.004 (2)0.0085 (18)
C60.044 (3)0.047 (3)0.041 (2)0.023 (2)0.006 (2)0.007 (2)
C70.030 (2)0.0283 (19)0.0240 (19)0.0028 (16)0.0050 (16)0.0005 (15)
C90.029 (2)0.029 (2)0.034 (2)0.0040 (16)0.0020 (17)0.0061 (17)
C80.038 (2)0.035 (2)0.026 (2)0.0002 (18)0.0076 (17)0.0030 (16)
C100.039 (2)0.044 (2)0.047 (3)0.002 (2)0.021 (2)0.006 (2)
C110.030 (2)0.074 (3)0.036 (2)0.008 (2)0.0128 (19)0.003 (2)
C120.044 (2)0.058 (3)0.0174 (19)0.026 (2)0.0062 (17)0.0084 (18)
C130.058 (3)0.022 (2)0.039 (2)0.0031 (19)0.007 (2)0.0040 (17)
C140.049 (3)0.036 (2)0.030 (2)0.0126 (19)0.0016 (19)0.0033 (18)
C150.051 (3)0.033 (2)0.044 (3)0.001 (2)0.009 (2)0.0113 (19)
Geometric parameters (Å, º) top
Al1—O11.905 (3)C4—C51.518 (6)
Al1—O31.859 (3)C5—H5A0.9600
Al1—O41.909 (3)C5—H5B0.9600
Al1—O61.849 (3)C5—H5C0.9600
Al1—O71.904 (3)C6—H6A0.9600
Al1—O91.869 (3)C6—H6B0.9600
O1—C21.267 (5)C6—H6C0.9600
O2—C21.322 (4)C7—C81.406 (5)
O2—C11.432 (5)C9—C81.367 (6)
O3—C41.284 (5)C9—C101.517 (5)
O4—C71.258 (4)C8—H80.9300
O5—C71.329 (4)C10—H10A0.9600
O5—C61.450 (5)C10—H10B0.9600
O6—C91.286 (5)C10—H10C0.9600
O7—C121.273 (5)C11—H11A0.9600
O8—C121.322 (5)C11—H11B0.9600
O8—C111.403 (5)C11—H11C0.9600
O9—C141.263 (5)C12—C131.411 (6)
C1—H1A0.9600C13—C141.345 (6)
C1—H1B0.9600C13—H130.9300
C1—H1C0.9600C14—C151.538 (6)
C2—C31.401 (6)C15—H15A0.9600
C3—C41.352 (6)C15—H15B0.9600
C3—H30.9300C15—H15C0.9600
O6—Al1—O392.13 (12)H5B—C5—H5C109.5
O6—Al1—O990.45 (13)O5—C6—H6A109.5
O3—Al1—O991.19 (13)O5—C6—H6B109.5
O6—Al1—O191.76 (12)H6A—C6—H6B109.5
O3—Al1—O190.98 (12)O5—C6—H6C109.5
O9—Al1—O1176.85 (13)H6A—C6—H6C109.5
O6—Al1—O7176.44 (13)H6B—C6—H6C109.5
O3—Al1—O790.98 (12)O4—C7—O5118.6 (3)
O9—Al1—O791.22 (13)O4—C7—C8125.3 (3)
O1—Al1—O786.45 (12)O5—C7—C8116.1 (3)
O6—Al1—O490.71 (12)O6—C9—C8124.9 (4)
O3—Al1—O4177.05 (13)O6—C9—C10114.6 (3)
O9—Al1—O489.59 (12)C8—C9—C10120.5 (4)
O1—Al1—O488.13 (12)C9—C8—C7121.4 (3)
O7—Al1—O486.16 (12)C9—C8—H8119.3
C2—O1—Al1126.1 (3)C7—C8—H8119.3
C2—O2—C1116.9 (3)C9—C10—H10A109.5
C4—O3—Al1129.5 (3)C9—C10—H10B109.5
C7—O4—Al1125.6 (2)H10A—C10—H10B109.5
C7—O5—C6116.8 (3)C9—C10—H10C109.5
C9—O6—Al1127.3 (2)H10A—C10—H10C109.5
C12—O7—Al1123.6 (3)H10B—C10—H10C109.5
C12—O8—C11117.6 (4)O8—C11—H11A109.5
C14—O9—Al1129.2 (3)O8—C11—H11B109.5
O2—C1—H1A109.5H11A—C11—H11B109.5
O2—C1—H1B109.5O8—C11—H11C109.5
H1A—C1—H1B109.5H11A—C11—H11C109.5
O2—C1—H1C109.5H11B—C11—H11C109.5
H1A—C1—H1C109.5O7—C12—O8117.0 (4)
H1B—C1—H1C109.5O7—C12—C13126.0 (4)
O1—C2—O2118.0 (4)O8—C12—C13116.9 (4)
O1—C2—C3125.9 (3)C14—C13—C12123.3 (4)
O2—C2—C3116.1 (3)C14—C13—H13118.4
C4—C3—C2122.4 (4)C12—C13—H13118.4
C4—C3—H3118.8O9—C14—C13122.9 (4)
C2—C3—H3118.8O9—C14—C15115.5 (4)
O3—C4—C3124.0 (4)C13—C14—C15121.6 (4)
O3—C4—C5114.0 (4)C14—C15—H15A109.5
C3—C4—C5122.0 (4)C14—C15—H15B109.5
C4—C5—H5A109.5H15A—C15—H15B109.5
C4—C5—H5B109.5C14—C15—H15C109.5
H5A—C5—H5B109.5H15A—C15—H15C109.5
C4—C5—H5C109.5H15B—C15—H15C109.5
H5A—C5—H5C109.5
O6—Al1—O1—C2102.8 (3)C1—O2—C2—C3176.1 (3)
O3—Al1—O1—C210.6 (3)O1—C2—C3—C42.0 (6)
O7—Al1—O1—C280.3 (3)O2—C2—C3—C4178.1 (4)
O4—Al1—O1—C2166.6 (3)Al1—O3—C4—C38.0 (6)
O6—Al1—O3—C4102.4 (3)Al1—O3—C4—C5172.5 (3)
O9—Al1—O3—C4167.1 (3)C2—C3—C4—O31.4 (6)
O1—Al1—O3—C410.6 (3)C2—C3—C4—C5179.1 (4)
O7—Al1—O3—C475.8 (3)Al1—O4—C7—O5166.7 (2)
O6—Al1—O4—C722.3 (3)Al1—O4—C7—C814.6 (5)
O9—Al1—O4—C768.1 (3)C6—O5—C7—O46.2 (5)
O1—Al1—O4—C7114.0 (3)C6—O5—C7—C8175.0 (3)
O7—Al1—O4—C7159.4 (3)Al1—O6—C9—C814.4 (5)
O3—Al1—O6—C9158.5 (3)Al1—O6—C9—C10167.3 (3)
O9—Al1—O6—C967.3 (3)O6—C9—C8—C72.3 (6)
O1—Al1—O6—C9110.5 (3)C10—C9—C8—C7175.8 (4)
O4—Al1—O6—C922.3 (3)O4—C7—C8—C91.8 (6)
O3—Al1—O7—C12110.4 (3)O5—C7—C8—C9176.9 (3)
O9—Al1—O7—C1219.2 (3)Al1—O7—C12—O8169.6 (2)
O1—Al1—O7—C12158.7 (3)Al1—O7—C12—C1312.8 (5)
O4—Al1—O7—C1270.3 (3)C11—O8—C12—O74.5 (5)
O6—Al1—O9—C14157.2 (3)C11—O8—C12—C13177.6 (4)
O3—Al1—O9—C14110.6 (3)O7—C12—C13—C142.2 (7)
O7—Al1—O9—C1419.6 (3)O8—C12—C13—C14175.4 (4)
O4—Al1—O9—C1466.5 (3)Al1—O9—C14—C1311.6 (6)
Al1—O1—C2—O2171.6 (2)Al1—O9—C14—C15168.8 (3)
Al1—O1—C2—C38.6 (5)C12—C13—C14—O93.4 (7)
C1—O2—C2—O14.1 (5)C12—C13—C14—C15176.2 (4)

Experimental details

Crystal data
Chemical formula[Al(C5H7O3)3]
Mr372.30
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)6.476 (1), 9.986 (2), 14.368 (2)
α, β, γ (°)90.478 (2), 92.229 (2), 99.337 (2)
V3)916.1 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.15
Crystal size (mm)0.5 × 0.4 × 0.2
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correctionMulti-scan
SADABS (Sheldrick, 1996)
Tmin, Tmax0.927, 0.970
No. of measured, independent and
observed [I > 2σ(I)] reflections
8801, 3207, 2304
Rint0.041
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.068, 0.189, 1.02
No. of reflections3207
No. of parameters232
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.26, 0.28

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Selected bond lengths (Å) top
Al1—O11.905 (3)Al1—O61.849 (3)
Al1—O31.859 (3)Al1—O71.904 (3)
Al1—O41.909 (3)Al1—O91.869 (3)
 

Acknowledgements

We acknowledge the use of the X-ray CCD facility at the Indian Institute of Science, Bangalore under the IRHPA/DST program, and we thank the University of Malaya for supporting this study.

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (2004). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChrzanowski, L. S. von, Lutz, M. & Spek, A. L. (2007). Acta Cryst. C63, m129–m134.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2009). publCIF. In preparation.  Google Scholar

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