Tris(3-chloro­pentane-2,4-dionato-κ2O,O′)aluminium

Perdih, F.

doi:10.1107/S1600536812023203

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page m806

doi:10.1107/S1600536812023203

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Tris(3-chloropentane-2,4-dionato-κ²O,O′)aluminium

Franc Perdih ^a,^b ^*

^aFaculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, PO Box 537, SI-1000 Ljubljana, Slovenia, and ^bCO EN–FIST, Dunajska 156, SI-1000 Ljubljana, Slovenia
^*Correspondence e-mail: franc.perdih@fkkt.uni-lj.si

(Received 30 April 2012; accepted 21 May 2012; online 26 May 2012)

In the title compound, [Al(C₅H₆ClO₂)₃], the Al^III cation is situated on a twofold rotation axis and is coordinated by six O atoms from three 3-chloropentane-2,4-dionate ligands in an octahedral environment. Al—O bond lengths are in the range 1.8741 (14)–1.8772 (14) Å. In the crystal, molecules are linked via C—H⋯Cl contacts.

Related literature

For applications of metal complexes with β-diketonate ligands, see: Bray et al. (2007 ); Garibay et al. (2009 ); Lichtenberger et al. (2010 ); Perdih (2011 ); Vreshch et al. (2004 ); Wu & Wang (2009 ). For related structures, see: Hon & Pfluger (1973 ); Perdih (2012 ).

Experimental

Crystal data

[Al(C₅H₆ClO₂)₃]
M_r = 427.62
Monoclinic, C 2/c
a = 12.8790 (3) Å
b = 9.9086 (2) Å
c = 15.5311 (4) Å
β = 106.368 (2)°
V = 1901.64 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.56 mm⁻¹
T = 293 K
0.33 × 0.25 × 0.08 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.838, T_max = 0.957
3916 measured reflections
2156 independent reflections
1759 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.125
S = 1.05
2156 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯Cl1ⁱ	0.96	2.94	3.796 (2)	149
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812023203/im2374sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812023203/im2374Isup2.hkl

checkCIF report

Comment top

β-Diketonates have been proven to be versatile ligands for various metal ions. They can be easily derivatized, thus modifying the electronic and steric nature of these ligands to design suitable structure/function relationships (Bray et al., 2007; Garibay et al., 2009; Perdih, 2011). β-Diketonate compounds of aluminium have received great attention due to the promise of the construction of cages (Vreshch et al., 2004; Wu & Wang, 2009). Besides that, aluminium β-diketonates and malonates can be good precursors in metal-organic chemical vapour deposition (MOCVD) (Bray et al., 2007; Garibay et al., 2009; Lichtenberger et al., 2010).

In the title molecule (Fig. 1), the aluminium(III) cation is situated on a twofold axis, and is surrounded by six O atoms from three 3-chloropentane-2,4-dionate ligands in a octahedral environment. The geometry around aluminium is close to the orthogonallity as can be seen from the angles. The Al—O bond lengths are in the range 1.8741 (14)–1.8772 (14) Å and are similar as for example in Al(acac)₃ (Hon & Pfluger, 1973). The displacement of the metal atom is best described by a bending of a chelate ligand about the "bite" atoms. The angles between the O—Al—O and the ligand chelate mean planes are 0.38° and 1.72°. For comparison these values are 0.78° and 12.68° in the isostructural iron(III) compound (Perdih, 2012). A 1-D framework is achieved due to intermolecular C6–H6A···Cl1 (–x + 1/2, –y + 1/2, –z) contacts (Fig. 2).

Related literature top

For applications of metal complexes with β-diketonate ligands, see: Bray et al. (2007); Garibay et al. (2009); Lichtenberger et al. (2010; Perdih (2011); Vreshch et al. (2004); Wu & Wang (2009). For related structures, see: Hon & Pfluger (1973); Perdih (2012).

Experimental top

To a clear solution of Al₂(SO₄)₃^.18H₂O (1 mmol, 0.67 g) in water (15 ml) a solution of 3-chloropentane-2,4-dione (6 mmol, 0.81 g) in methanol (5 ml) was added while stirring. Afterwards 1 M NaOH (6 ml) was slowly added and the resulting solution was stirred at 70°C for 15 minutes. After cooling to room temperature the light pink product was filtrated, washed with water (20 ml), and subsequently air-dried. Yield: 0.60 g, 70%. Crystals suitable for X-ray analysis were obtained by recrystallization from ethanol.

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the title complex showing displacement ellipsoids at the 30% probability level. Symmetry code: i = –x + 1, y, –z + 1/2.
	Fig. 2. 1D infinte chain with dashed lines indicating intermolecular C6—H6A···Cl1 hydrogen bonding. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Symmetry code: ii = –x + 1/2, –y + 1/2, –z.

Tris(3-chloropentane-2,4-dionato-κ²O,O')aluminium top

Crystal data top

[Al(C₅H₆ClO₂)₃]	F(000) = 880
M_r = 427.62	D_x = 1.494 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2269 reflections
a = 12.8790 (3) Å	θ = 2.6–27.5°
b = 9.9086 (2) Å	µ = 0.56 mm⁻¹
c = 15.5311 (4) Å	T = 293 K
β = 106.368 (2)°	Plate, pink
V = 1901.64 (8) Å³	0.33 × 0.25 × 0.08 mm
Z = 4

Data collection top

Nonius KappaCCD area-detector diffractometer	2156 independent reflections
Graphite monochromator	1759 reflections with I > 2σ(I)
Detector resolution: 0.055 pixels mm^-1	R_int = 0.014
ω scans	θ_max = 27.5°, θ_min = 5.6°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −16→16
T_min = 0.838, T_max = 0.957	k = −10→12
3916 measured reflections	l = −20→20

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0632P)² + 1.1678P] where P = (F_o² + 2F_c²)/3
2156 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Al(C₅H₆ClO₂)₃]	V = 1901.64 (8) Å³
M_r = 427.62	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.8790 (3) Å	µ = 0.56 mm⁻¹
b = 9.9086 (2) Å	T = 293 K
c = 15.5311 (4) Å	0.33 × 0.25 × 0.08 mm
β = 106.368 (2)°

Data collection top

Nonius KappaCCD area-detector diffractometer	2156 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	1759 reflections with I > 2σ(I)
T_min = 0.838, T_max = 0.957	R_int = 0.014
3916 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 1.05	Δρ_max = 0.33 e Å⁻³
2156 reflections	Δρ_min = −0.34 e Å⁻³
118 parameters

Special details top

Experimental. 211 frames in 5 sets of ω scans. Rotation/frame = 2.0 °. Crystal-detector distance = 25.00 mm. Measuring time = 55 s/°.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Al1	0.5	0.15245 (8)	0.25	0.0454 (2)
Cl1	0.36200 (7)	0.39260 (8)	−0.04272 (5)	0.0995 (3)
Cl2	0.5	−0.35153 (8)	0.25	0.0799 (3)
O1	0.39394 (11)	0.28432 (14)	0.20496 (10)	0.0575 (4)
O2	0.53620 (11)	0.15368 (15)	0.14118 (9)	0.0565 (4)
O3	0.39461 (10)	0.01885 (13)	0.20911 (9)	0.0527 (3)
C1	0.2712 (2)	0.4373 (3)	0.1141 (2)	0.0824 (8)
H1A	0.2095	0.4025	0.0694	0.124*
H1B	0.292	0.5223	0.0945	0.124*
H1C	0.2532	0.4496	0.1695	0.124*
C2	0.36336 (15)	0.33939 (18)	0.12819 (15)	0.0558 (5)
C3	0.41130 (17)	0.3110 (2)	0.06059 (14)	0.0587 (5)
C4	0.49653 (15)	0.2202 (2)	0.06969 (12)	0.0529 (4)
C5	0.5460 (2)	0.1956 (3)	−0.00518 (15)	0.0756 (7)
H5A	0.6094	0.1406	0.016	0.113*
H5B	0.5656	0.2803	−0.0262	0.113*
H5C	0.4947	0.1502	−0.0534	0.113*
C6	0.29806 (17)	−0.1843 (2)	0.17442 (17)	0.0671 (6)
H6A	0.2393	−0.1214	0.156	0.101*
H6B	0.2852	−0.2439	0.2191	0.101*
H6C	0.3034	−0.2359	0.1235	0.101*
C7	0.40167 (15)	−0.10871 (18)	0.21301 (11)	0.0468 (4)
C8	0.5	−0.1744 (3)	0.25	0.0493 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Al1	0.0412 (4)	0.0466 (4)	0.0457 (4)	0	0.0078 (3)	0
Cl1	0.1147 (6)	0.0930 (5)	0.0719 (4)	0.0188 (4)	−0.0043 (4)	0.0304 (3)
Cl2	0.0779 (6)	0.0479 (4)	0.0966 (6)	0	−0.0039 (4)	0
O1	0.0517 (7)	0.0531 (8)	0.0671 (8)	0.0097 (6)	0.0155 (6)	0.0005 (6)
O2	0.0512 (7)	0.0686 (8)	0.0482 (7)	0.0139 (6)	0.0116 (5)	0.0076 (6)
O3	0.0422 (6)	0.0522 (7)	0.0565 (7)	0.0005 (5)	0.0021 (5)	−0.0059 (6)
C1	0.0621 (13)	0.0577 (12)	0.114 (2)	0.0167 (11)	0.0029 (13)	−0.0025 (13)
C2	0.0430 (9)	0.0406 (9)	0.0739 (13)	−0.0008 (7)	0.0002 (8)	−0.0001 (8)
C3	0.0546 (11)	0.0536 (10)	0.0573 (11)	−0.0005 (9)	−0.0015 (8)	0.0105 (9)
C4	0.0461 (9)	0.0589 (10)	0.0483 (9)	−0.0071 (8)	0.0043 (7)	0.0034 (8)
C5	0.0700 (14)	0.1046 (19)	0.0528 (11)	0.0003 (14)	0.0182 (10)	0.0051 (12)
C6	0.0496 (11)	0.0674 (13)	0.0775 (14)	−0.0105 (10)	0.0066 (10)	−0.0102 (11)
C7	0.0457 (9)	0.0526 (10)	0.0400 (8)	−0.0046 (7)	0.0088 (7)	−0.0045 (7)
C8	0.0512 (14)	0.0484 (13)	0.0443 (12)	0	0.0072 (10)	0

Geometric parameters (Å, º) top

Al1—O3	1.8741 (14)	C1—H1C	0.96
Al1—O3ⁱ	1.8741 (14)	C2—C3	1.389 (3)
Al1—O2ⁱ	1.8756 (13)	C3—C4	1.395 (3)
Al1—O2	1.8756 (13)	C4—C5	1.495 (3)
Al1—O1ⁱ	1.8772 (14)	C5—H5A	0.96
Al1—O1	1.8772 (14)	C5—H5B	0.96
Cl1—C3	1.748 (2)	C5—H5C	0.96
Cl2—C8	1.755 (3)	C6—C7	1.500 (3)
O1—C2	1.269 (3)	C6—H6A	0.96
O2—C4	1.268 (2)	C6—H6B	0.96
O3—C7	1.267 (2)	C6—H6C	0.96
C1—C2	1.500 (3)	C7—C8	1.396 (2)
C1—H1A	0.96	C8—C7ⁱ	1.396 (2)
C1—H1B	0.96

O3—Al1—O3ⁱ	90.12 (8)	C3—C2—C1	121.5 (2)
O3—Al1—O2ⁱ	88.26 (6)	C2—C3—C4	123.97 (18)
O3ⁱ—Al1—O2ⁱ	92.26 (6)	C2—C3—Cl1	118.44 (16)
O3—Al1—O2	92.26 (6)	C4—C3—Cl1	117.59 (17)
O3ⁱ—Al1—O2	88.26 (6)	O2—C4—C3	122.35 (18)
O2ⁱ—Al1—O2	179.26 (10)	O2—C4—C5	116.20 (19)
O3—Al1—O1ⁱ	178.02 (6)	C3—C4—C5	121.44 (19)
O3ⁱ—Al1—O1ⁱ	89.08 (6)	C4—C5—H5A	109.5
O2ⁱ—Al1—O1ⁱ	89.96 (6)	C4—C5—H5B	109.5
O2—Al1—O1ⁱ	89.53 (7)	H5A—C5—H5B	109.5
O3—Al1—O1	89.08 (6)	C4—C5—H5C	109.5
O3ⁱ—Al1—O1	178.02 (6)	H5A—C5—H5C	109.5
O2ⁱ—Al1—O1	89.53 (7)	H5B—C5—H5C	109.5
O2—Al1—O1	89.96 (6)	C7—C6—H6A	109.5
O1ⁱ—Al1—O1	91.78 (9)	C7—C6—H6B	109.5
C2—O1—Al1	130.55 (13)	H6A—C6—H6B	109.5
C4—O2—Al1	130.63 (13)	C7—C6—H6C	109.5
C7—O3—Al1	130.76 (12)	H6A—C6—H6C	109.5
C2—C1—H1A	109.5	H6B—C6—H6C	109.5
C2—C1—H1B	109.5	O3—C7—C8	121.98 (17)
H1A—C1—H1B	109.5	O3—C7—C6	115.78 (17)
C2—C1—H1C	109.5	C8—C7—C6	122.24 (19)
H1A—C1—H1C	109.5	C7ⁱ—C8—C7	124.4 (2)
H1B—C1—H1C	109.5	C7ⁱ—C8—Cl2	117.82 (12)
O1—C2—C3	122.47 (17)	C7—C8—Cl2	117.82 (12)
O1—C2—C1	116.0 (2)

O3—Al1—O1—C2	−89.43 (17)	C1—C2—C3—C4	−179.5 (2)
O2ⁱ—Al1—O1—C2	−177.70 (17)	O1—C2—C3—Cl1	179.76 (15)
O2—Al1—O1—C2	2.83 (18)	C1—C2—C3—Cl1	0.1 (3)
O1ⁱ—Al1—O1—C2	92.36 (17)	Al1—O2—C4—C3	−0.2 (3)
O3—Al1—O2—C4	87.74 (18)	Al1—O2—C4—C5	179.99 (15)
O3ⁱ—Al1—O2—C4	177.79 (18)	C2—C3—C4—O2	1.3 (3)
O1ⁱ—Al1—O2—C4	−93.12 (18)	Cl1—C3—C4—O2	−178.31 (15)
O1—Al1—O2—C4	−1.34 (18)	C2—C3—C4—C5	−179.0 (2)
O3ⁱ—Al1—O3—C7	1.05 (13)	Cl1—C3—C4—C5	1.4 (3)
O2ⁱ—Al1—O3—C7	−91.21 (17)	Al1—O3—C7—C8	−2.0 (3)
O2—Al1—O3—C7	89.32 (16)	Al1—O3—C7—C6	178.65 (13)
O1—Al1—O3—C7	179.24 (16)	O3—C7—C8—C7ⁱ	1.01 (12)
Al1—O1—C2—C3	−2.7 (3)	C6—C7—C8—C7ⁱ	−179.72 (19)
Al1—O1—C2—C1	176.98 (15)	O3—C7—C8—Cl2	−178.99 (12)
O1—C2—C3—C4	0.2 (3)	C6—C7—C8—Cl2	0.28 (19)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···Cl1ⁱⁱ	0.96	2.94	3.796 (2)	149

Symmetry code: (ii) −x+1/2, −y+1/2, −z.

Experimental details

Crystal data
Chemical formula	[Al(C₅H₆ClO₂)₃]
M_r	427.62
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	12.8790 (3), 9.9086 (2), 15.5311 (4)
β (°)	106.368 (2)
V (Å³)	1901.64 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.56
Crystal size (mm)	0.33 × 0.25 × 0.08

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.838, 0.957
No. of measured, independent and observed [I > 2σ(I)] reflections	3916, 2156, 1759
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.125, 1.05
No. of reflections	2156
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.34

Computer programs: COLLECT (Hooft, 1998), DENZO-SMN (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···Cl1ⁱ	0.96	2.94	3.796 (2)	149.2

Symmetry code: (i) −x+1/2, −y+1/2, −z.

Acknowledgements

The author thanks the Ministry of Higher Education, Science and Technology of the Republic of Slovenia and the Slovenian Research Agency for financial support through grants P1–0230–0175 and X–2000.

References

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