Tetra­kis(1,3-diphenyl­propane-1,3-dionato)hafnium(IV)

J Augustinus Viljoen; Hendrik G Visser; Andreas Roodt

doi:10.1107/S1600536810030400

. 2010 Aug 4;66(Pt 9):m1053–m1054. doi: 10.1107/S1600536810030400

Tetrakis(1,3-diphenylpropane-1,3-dionato)hafnium(IV)

J Augustinus Viljoen ^a,^*, Hendrik G Visser ^a, Andreas Roodt ^a

PMCID: PMC3008122 PMID: 21588480

Abstract

In the title compound, [Hf(C₁₅H₁₁O₂)₄], the Hf^IV atom is coordinated by four 1,3-diphenylpropane-1,3-dionato ligands with an average Hf—O distance of 2.17 (3) Å and O—Hf—O bite angles varying from 74.5 (1) to 75.02 (9)°. The coordination polyhedron shows a slightly distorted Archimedean square-antiprismatic geometry. The crystal packing is stabilized by weak C—H⋯O interactions.

Related literature

For a monoclinic isomorph of the title compound, see: Fay et al. (1979 ▶). For related literature on hafnium and zirconium diketonato complexes, see: Viljoen et al. (2008 ▶, 2009a ▶,b ▶, 2010 ▶); Steyn et al. (2008 ▶); Lewis & Fay (1974 ▶); Demakopoulos et al. (1995 ▶). For the use of acetylacetone in separation chemistry and homogenous catalysis, see: Van Aswegen et al. (1991 ▶); Steyn et al. (1992 ▶, 1997 ▶); Otto et al. (1998 ▶); Roodt & Steyn (2000 ▶); Brink et al. (2010 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

[Hf(C₁₅H₁₁O₂)₄]
M _r = 1071.44
Monoclinic,
a = 24.846 (2) Å
b = 10.2236 (8) Å
c = 19.3155 (13) Å
β = 101.618 (4)°
V = 4805.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.23 mm⁻¹
T = 100 K
0.20 × 0.19 × 0.11 mm

Data collection

Bruker X8 APEXII 4K KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.661, T _max = 0.783
39626 measured reflections
11555 independent reflections
9232 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.122
S = 1.16
11555 reflections
623 parameters
H-atom parameters constrained
Δρ_max = 1.17 e Å⁻³
Δρ_min = −1.29 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SIR92 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810030400/bg2349sup1.cif

e-66-m1053-sup1.cif^{(37.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030400/bg2349Isup2.hkl

e-66-m1053-Isup2.hkl^{(553.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C43—H43⋯O6ⁱ	0.95	2.6	3.538 (5)	170

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial assistance from the Advanced Metals Initiative (AMI) and the Department of Science and Technology (DST) of South Africa, as well as the New Metals Development Network (NMDN) and the South African Nuclear Energy Corporation Limited (Necsa) is gratefully acknowledged. Financial assistance from the University of the Free State is gratefully acknowledged.

supplementary crystallographic information

Comment

Acetylacetone find applications as a ligand in the extraction and separation industry world-wide. However, it is also utilized in homogenous catalysis applications as a model precursor (Van Aswegen et al. (1991); Steyn et al. (1992, 1997); Otto et al. (1998); Roodt & Steyn, (2000); Brink et al. (2010)). This study forms part of ongoing research to investigate the reactions of O,O'- and N,O-bidentate ligands with hafnium(IV) and zirconium(IV) with possible applications in the mentioned industries (Steyn et al., (2008); Viljoen et al. (2008, 2009a, 2009b, 2010); Demakopoulos et al. (1995) and Lewis & Fay (1974)).

Colourless cubic-like crystals of the title compound crystallize in the monoclinic crystal system (P2₁/c, Z=4) (Figure 1). The Hf(IV) atom is eight coordinated and surrounded by four β-diketonate ligands, dibenzoylmethane (dbm^-), adopting an Archimedean antiprismatic coordination geometry. The Hf—O bond lengths vary from 2.133 (2) Å to 2.200 (2) Å, with the average Hf—O distance being 2.169 (3) Å. This average Hf—O bond distance is somewhat larger than the average of 2.159 (5) Å obtained from the Cambridge Structural Database (Allen (2002)) (data extracted from 22 hits, yielding 60 observations ranging from 2.079 to 2.262 Å). The O—Hf—O bite angles vary between 74.5 (1) and 75.02 (9)°. The molecules of the title compound pack in horizontal layers along the bc-plane and are stabilized by weak C—H···O interactions (Table 1, Figure 2).

Experimental

Chemicals were purchased from Sigma-Aldrich and used as received. HfCl₄ (203 mg, 0.63 mmol) was dissolved in a minimal amount of DMF. While stirring this solution at room temperature, another solution of [C₁₅H₁₂O₂] (568 mg, 2.5 mmol) was dissolved in a minimal amount of DMF and slowly added to the HfCl₄ solution, resulting in the formation of a yellow solution, which was left to stand at 252 K for a few days after which colourless crystals, suitable for X-ray diffraction were obtained (Yield: 891 mg, 83%).