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

Neelgund, G.M.; Shivashankar, S.A.; Narasimhamurthy, T.; Ng, S.W.

doi:10.1107/S1600536809049812

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1681

doi:10.1107/S1600536809049812

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

Gururaj M. Neelgund,^a S. A. Shivashankar,^a T. Narasimhamurthy ^a and Seik Weng Ng ^b ^*

^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 ).

Experimental

Crystal data

[Al(C₅H₇O₃)₃]
M_r = 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 ) T_min = 0.927, T_max = 0.970
8801 measured reflections
3207 independent reflections
2304 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.189
S = 1.02
3207 reflections
232 parameters
H-atom parameters constrained
Δρ_max = 1.26 e Å⁻³
Δρ_min = −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 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809049812/xu2684sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809049812/xu2684Isup2.hkl

checkCIF report

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.

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

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
M_r = 372.30	F(000) = 392
Triclinic, P1	D_x = 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) Å³

Data collection top

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

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.189	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0907P)² + 1.477P] where P = (F_o² + 2F_c²)/3
3207 reflections	(Δ/σ)_max = 0.001
232 parameters	Δρ_max = 1.26 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Al(C₅H₇O₃)₃]	γ = 99.337 (2)°
M_r = 372.30	V = 916.1 (2) Å³
Triclinic, P1	Z = 2
a = 6.476 (1) Å	Mo Kα radiation
b = 9.986 (2) Å	µ = 0.15 mm⁻¹
c = 14.368 (2) Å	T = 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)
T_min = 0.927, T_max = 0.970	R_int = 0.041
8801 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.189	H-atom parameters constrained
S = 1.02	Δρ_max = 1.26 e Å⁻³
3207 reflections	Δρ_min = −0.28 e Å⁻³
232 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

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)

Experimental details

Crystal data
Chemical formula	[Al(C₅H₇O₃)₃]
M_r	372.30
Crystal system, space group	Triclinic, 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)
V (Å³)	916.1 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.5 × 0.4 × 0.2

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan SADABS (Sheldrick, 1996)
T_min, T_max	0.927, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	8801, 3207, 2304
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.189, 1.02
No. of reflections	3207
No. of parameters	232
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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—O1	1.905 (3)	Al1—O6	1.849 (3)
Al1—O3	1.859 (3)	Al1—O7	1.904 (3)
Al1—O4	1.909 (3)	Al1—O9	1.869 (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

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
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Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar