Tetra­kis(1,1,1-trifluoro­acetyl­acetonato-κ2O,O′)hafnium(IV) toluene disolvate

Viljoen, J.A.; Muller, A.; Roodt, A.

doi:10.1107/S1600536808015237

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Pages m838-m839

doi:10.1107/S1600536808015237

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Tetrakis(1,1,1-trifluoroacetylacetonato-κ²O,O′)hafnium(IV) toluene disolvate

J. Augustinus Viljoen,^a Alfred Muller ^a ^* and Andreas Roodt ^a

^aDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein 9300, South Africa
^*Correspondence e-mail: mulleraj.sci@ufs.ac.za

(Received 7 May 2008; accepted 20 May 2008; online 24 May 2008)

In the title compound, [Hf(C₅H₄F₃O₂)₄]·2C₇H₈, the Hf^IV atom, lying on a twofold rotation axis, is coordinated by eight O atoms from four 1,1,1-trifluoroacetylacetonate ligands with an average Hf—O distance of 2.173 (1) Å and O—Hf—O bite angles of 75.69 (5) and 75.54 (5)°. The coordination polyhedron shows a slightly distorted Archimedean square antiprismatic geometry. The asymmetric unit contains a toluene solvent molecule. The crystal structure involves C—H⋯.F hydrogen bonds.

Related literature

For the triclinic polymorph of the title compound, see: Zherikova et al. (2005 ). For related literature on hafnium β-diketone complexes, see: Chattoraj et al. (1968 ). For the isomorphous zirconium complex, see: Steyn et al. (2008 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

[Hf(C₅H₄F₃O₂)₄]·2C₇H₈
M_r = 975.09
Monoclinic, C 2/c
a = 22.4983 (15) Å
b = 8.0642 (5) Å
c = 22.712 (2) Å
β = 118.211 (2)°
V = 3631.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.98 mm⁻¹
T = 100 (2) K
0.33 × 0.25 × 0.22 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.439, T_max = 0.560 (expected range = 0.407–0.519)
18332 measured reflections
4518 independent reflections
4256 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.018
wR(F²) = 0.042
S = 1.07
4518 reflections
252 parameters
H-atom parameters constrained
Δρ_max = 1.12 e Å⁻³
Δρ_min = −0.91 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Hf—O2	2.1527 (13)
Hf—O4	2.1571 (13)
Hf—O1	2.1861 (13)
Hf—O3	2.1933 (13)

O2—Hf—O2ⁱ	141.66 (7)
O2—Hf—O4	80.96 (5)
O2ⁱ—Hf—O4	111.77 (5)
O4—Hf—O4ⁱ	142.02 (7)
O2—Hf—O1ⁱ	141.35 (5)
O4—Hf—O1ⁱ	72.52 (5)
O2—Hf—O1	75.69 (5)
O4—Hf—O1	76.79 (5)
O1ⁱ—Hf—O1	71.28 (7)
O2—Hf—O3ⁱ	72.21 (5)
O4—Hf—O3ⁱ	141.11 (5)
O1—Hf—O3ⁱ	121.11 (5)
O2—Hf—O3	76.82 (5)
O4—Hf—O3	75.54 (5)
O1—Hf—O3	143.48 (5)
O3ⁱ—Hf—O3	71.35 (7)
Symmetry code: (i) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯F2	0.93	2.37	2.712 (2)	102
C8—H8⋯F5	0.93	2.37	2.721 (2)	102

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg & Putz, 1999 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808015237/hy2134sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015237/hy2134Isup2.hkl

checkCIF report

Comment top

This study was done as part of ongoing research in our group to investigate reactions of O,O'- and O,N-bidentate ligands with hafnium(IV) and zirconium(IV). The total separation of zircon ore (ZrSiO₄) is important to have materials viable for nuclear applications. Previous work on hafnium(IV) complexes with β-diketone was done to determine their thermal decomposition to yield metal oxides (Chattoraj et al., 1968). Hafnium β-diketonates are also promising precursor materials for producing metal oxide films, providing the possibility to manufacture technologically important coatings (Zherikova et al., 2005).

The title compound crystallizes as the monoclinic polymorph (C2/c, Z = 4) (Fig. 1) with two toluene solvent molecules. The triclinic polymorph earlier reported by Zherikova et al. (2005) contains no solvent molecules and cannot be superimposed with the title compound due to differences in metal coordination modes. An isomorphous zirconium complex has been reported by Steyn et al. (2008). The Hf^IV atom in the title compound is situated on a twofold rotation axis, with four β-diketonate ligands, 1,1,1-trifluoroacetylacetonate (tfaa), coordinating to the Hf^IV atom adopting an Archimedean antiprism coordination geometry (Fig. 2). The Hf—O bond lengths vary from 2.1527 (13) Å to 2.1933 (13) Å, with the average Hf—O distance being 2.173 (1) Å. The O—Hf—O bite angles are 75.69 (5)° and 75.54 (5)° (Table 1). This average bond distance is somewhat larger than the average of 2.156 Å obtained from the Cambridge Structural Database (Allen, 2002) (data extracted from 19 hits, yielding 45 observations ranging from 2.039 to 2.248 Å). Pairs of toluene molecules are π-stacked (interplanar distance = 3.65 (1) Å, centroid–centroid distance = 4.92 (1) Å) in channels formed by the metal complex moieties parallel to the b-axis (Fig. 3). The preferred CF₃-group conformation is probably due to weak C—H···F interactions (Table 2).

Related literature top

For the triclinic polymorph of the title compound, see: Zherikova et al. (2005). For related literature on hafnium β-diketone complexes, see: Chattoraj et al. (1968). For the isomorphous zirconium complex, see: Steyn et al. (2008). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Chemicals were purchased from Sigma and Aldrich and used as received except for toluene, which was dried by passage over alumina. Syntheses were performed using modified Schlenk conditions. The ligand salt (Natfaa) was prepared by adding Htfaa (6.05 ml, 50 mmol) dropwise to NaOH (2.02 g, 50 mmol) over a period of 3 minutes. The resulting solids were washed with toluene and dried in vacuo. Natfaa (0.459 g, 2.6 mmol) was added to a suspension of HfCl₄ (0.207 g, 0.65 mmol) in toluene (10 ml). Dissolution gave a slightly yellow solution after 10 min. After refluxing for ca 20 h the crude product was filtered and washed with toluene. The filtrate was slowly recrystallized at 253 K at near quantitative yield. Spectroscopy data: ¹⁹F {H} NMR (C₆D₆; 564.77 MHz): -75.49 p.p.m.; IR (ATR): ν(CO) 1533 cm^-1.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Structure of the title compound. Displacement ellipsoids are drawn at the 30 % probability level. H atoms have been omitted for clarity.
	Fig. 2. Slightly distorted Archimedean antiprism coordination polyhedron surrounding Hf atom.
	Fig. 3. Packing diagram of the title compound along the b-axis showing π-stacking of toluene molecule pairs. H atoms have been omitted for clarity.

Tetrakis(1,1,1-trifluoroacetylacetonato-κ²O,O')hafnium(IV) toluene disolvate top

Crystal data top

[Hf(C₅H₄F₃O₂)₄]·2C₇H₈	F(000) = 1920
M_r = 975.09	D_x = 1.784 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6211 reflections
a = 22.4983 (15) Å	θ = 2.7–28.3°
b = 8.0642 (5) Å	µ = 2.98 mm⁻¹
c = 22.712 (2) Å	T = 100 K
β = 118.211 (2)°	Block, colourless
V = 3631.2 (5) Å³	0.33 × 0.25 × 0.22 mm
Z = 4

Data collection top

Bruker X8 APEXII 4K KappaCCD diffractometer	4518 independent reflections
Radiation source: fine-focus sealed tube	4256 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 8.4 pixels mm^-1	θ_max = 28.4°, θ_min = 2.0°
ϕ and ω scans	h = −30→26
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −10→10
T_min = 0.439, T_max = 0.560	l = −29→30
18332 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.019	w = 1/[σ²(F_o²) + (0.0173P)² + 5.3839P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.042	(Δ/σ)_max = 0.002
S = 1.07	Δρ_max = 1.12 e Å⁻³
4518 reflections	Δρ_min = −0.91 e Å⁻³
252 parameters

Crystal data top

[Hf(C₅H₄F₃O₂)₄]·2C₇H₈	V = 3631.2 (5) Å³
M_r = 975.09	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 22.4983 (15) Å	µ = 2.98 mm⁻¹
b = 8.0642 (5) Å	T = 100 K
c = 22.712 (2) Å	0.33 × 0.25 × 0.22 mm
β = 118.211 (2)°

Data collection top

Bruker X8 APEXII 4K KappaCCD diffractometer	4518 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	4256 reflections with I > 2σ(I)
T_min = 0.439, T_max = 0.560	R_int = 0.023
18332 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	0 restraints
wR(F²) = 0.042	H-atom parameters constrained
S = 1.07	Δρ_max = 1.12 e Å⁻³
4518 reflections	Δρ_min = −0.91 e Å⁻³
252 parameters

Special details top

Experimental. The intensity data was collected on a Bruker X8 Apex II 4 K Kappa CCD diffractometer using an exposure time of 20 s/frame. A total of 1897 frames were collected with a frame width of 0.5° covering up to θ = 28.35° with 99.8% completeness accomplished.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Hf	0.5	0.165295 (14)	0.75	0.01071 (4)
O1	0.51936 (7)	−0.05501 (17)	0.81255 (6)	0.0145 (3)
O2	0.49393 (7)	0.25296 (17)	0.83653 (6)	0.0150 (3)
C1	0.50749 (11)	−0.2808 (3)	0.87229 (11)	0.0220 (4)
H1A	0.508	−0.3448	0.8369	0.033*
H1B	0.4696	−0.3133	0.8783	0.033*
H1C	0.5485	−0.2998	0.9129	0.033*
C2	0.50184 (10)	−0.1008 (3)	0.85482 (9)	0.0156 (4)
C3	0.47953 (10)	0.0117 (3)	0.88823 (10)	0.0184 (4)
H3	0.4644	−0.0284	0.9172	0.022*
C4	0.48009 (10)	0.1778 (3)	0.87820 (9)	0.0154 (4)
C5	0.46372 (11)	0.2975 (3)	0.92078 (10)	0.0207 (4)
F1	0.40902 (8)	0.3862 (2)	0.88355 (7)	0.0409 (4)
F2	0.45382 (8)	0.21987 (18)	0.96725 (7)	0.0343 (3)
F3	0.51363 (7)	0.40485 (17)	0.95280 (7)	0.0316 (3)
O3	0.43603 (7)	0.38624 (17)	0.71276 (7)	0.0146 (3)
O4	0.40009 (6)	0.07826 (17)	0.72464 (6)	0.0136 (3)
C6	0.36205 (11)	0.6104 (3)	0.69597 (12)	0.0229 (4)
H6A	0.4012	0.6754	0.7049	0.034*
H6B	0.3434	0.6475	0.724	0.034*
H6C	0.329	0.6231	0.6499	0.034*
C7	0.38151 (10)	0.4318 (2)	0.71005 (9)	0.0158 (4)
C8	0.33652 (10)	0.3194 (2)	0.71708 (10)	0.0175 (4)
H8	0.2986	0.3595	0.7188	0.021*
C9	0.34868 (10)	0.1536 (2)	0.72125 (9)	0.0148 (4)
C10	0.29459 (10)	0.0341 (3)	0.71829 (11)	0.0197 (4)
F4	0.31970 (6)	−0.07336 (16)	0.76889 (6)	0.0261 (3)
F5	0.24293 (7)	0.11096 (17)	0.72015 (8)	0.0338 (3)
F6	0.26890 (6)	−0.05534 (17)	0.66195 (6)	0.0274 (3)
C11	0.65622 (14)	0.3966 (4)	0.96674 (17)	0.0550 (9)
H11A	0.6943	0.427	0.9608	0.082*
H11B	0.6541	0.4676	0.9996	0.082*
H11C	0.6156	0.4084	0.9251	0.082*
C12	0.66358 (11)	0.2194 (3)	0.98981 (12)	0.0313 (5)
C13	0.66964 (12)	0.1760 (3)	1.05128 (12)	0.0336 (6)
H13	0.6681	0.258	1.0793	0.04*
C14	0.67800 (13)	0.0117 (4)	1.07158 (12)	0.0376 (6)
H14	0.682	−0.0156	1.1131	0.045*
C15	0.68046 (13)	−0.1112 (4)	1.03081 (14)	0.0384 (6)
H15	0.6867	−0.2213	1.0446	0.046*
C16	0.67360 (12)	−0.0688 (4)	0.96942 (14)	0.0406 (7)
H16	0.6747	−0.1509	0.9412	0.049*
C17	0.66513 (12)	0.0941 (4)	0.94935 (12)	0.0372 (6)
H17	0.6603	0.1204	0.9075	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hf	0.01298 (6)	0.00766 (6)	0.01517 (6)	0	0.00966 (4)	0
O1	0.0157 (6)	0.0118 (7)	0.0192 (6)	0.0011 (5)	0.0108 (5)	0.0027 (5)
O2	0.0207 (7)	0.0117 (7)	0.0170 (6)	−0.0013 (6)	0.0126 (6)	0.0003 (5)
C1	0.0315 (12)	0.0136 (10)	0.0271 (11)	0.0000 (9)	0.0190 (9)	0.0039 (8)
C2	0.0145 (9)	0.0143 (10)	0.0175 (9)	−0.0012 (8)	0.0071 (7)	0.0020 (8)
C3	0.0239 (10)	0.0171 (10)	0.0195 (9)	−0.0018 (8)	0.0148 (8)	0.0026 (8)
C4	0.0160 (9)	0.0166 (10)	0.0161 (8)	−0.0014 (8)	0.0097 (7)	−0.0013 (8)
C5	0.0300 (11)	0.0179 (11)	0.0211 (10)	0.0006 (8)	0.0179 (9)	0.0009 (8)
F1	0.0431 (9)	0.0495 (10)	0.0335 (8)	0.0248 (8)	0.0209 (7)	−0.0008 (7)
F2	0.0647 (10)	0.0234 (7)	0.0379 (8)	−0.0053 (7)	0.0433 (8)	−0.0026 (6)
F3	0.0485 (9)	0.0217 (7)	0.0361 (7)	−0.0106 (6)	0.0294 (7)	−0.0127 (6)
O3	0.0160 (7)	0.0110 (7)	0.0210 (7)	0.0019 (5)	0.0122 (6)	0.0026 (5)
O4	0.0136 (6)	0.0109 (7)	0.0194 (7)	0.0020 (5)	0.0104 (5)	0.0003 (5)
C6	0.0229 (11)	0.0131 (10)	0.0375 (12)	0.0034 (8)	0.0183 (10)	0.0040 (9)
C7	0.0187 (9)	0.0124 (10)	0.0183 (9)	0.0012 (8)	0.0104 (8)	0.0008 (7)
C8	0.0164 (9)	0.0131 (10)	0.0288 (10)	0.0017 (8)	0.0155 (8)	0.0005 (8)
C9	0.0147 (9)	0.0147 (10)	0.0186 (9)	0.0005 (8)	0.0109 (7)	0.0002 (8)
C10	0.0185 (10)	0.0143 (10)	0.0312 (11)	0.0008 (8)	0.0158 (9)	0.0002 (8)
F4	0.0291 (7)	0.0205 (7)	0.0348 (7)	−0.0030 (5)	0.0201 (6)	0.0060 (6)
F5	0.0273 (7)	0.0185 (7)	0.0731 (10)	0.0012 (6)	0.0382 (7)	−0.0005 (7)
F6	0.0228 (6)	0.0246 (7)	0.0335 (7)	−0.0089 (5)	0.0122 (6)	−0.0067 (6)
C11	0.0259 (14)	0.0496 (19)	0.067 (2)	−0.0055 (13)	0.0033 (13)	0.0194 (16)
C12	0.0156 (10)	0.0374 (14)	0.0306 (12)	−0.0050 (10)	0.0024 (9)	0.0040 (11)
C13	0.0294 (12)	0.0384 (15)	0.0324 (12)	−0.0058 (11)	0.0141 (10)	−0.0126 (11)
C14	0.0352 (13)	0.0514 (18)	0.0272 (12)	−0.0092 (13)	0.0154 (10)	0.0039 (12)
C15	0.0270 (13)	0.0302 (14)	0.0523 (16)	−0.0051 (11)	0.0141 (12)	−0.0008 (12)
C16	0.0235 (12)	0.0549 (19)	0.0425 (15)	−0.0074 (12)	0.0150 (11)	−0.0250 (14)
C17	0.0229 (12)	0.065 (2)	0.0222 (11)	−0.0077 (12)	0.0094 (10)	−0.0013 (12)

Geometric parameters (Å, º) top

Hf—O2	2.1527 (13)	C6—H6B	0.96
Hf—O2ⁱ	2.1527 (13)	C6—H6C	0.96
Hf—O4	2.1571 (13)	C7—C8	1.423 (3)
Hf—O4ⁱ	2.1571 (13)	C8—C9	1.359 (3)
Hf—O1ⁱ	2.1861 (13)	C8—H8	0.93
Hf—O1	2.1861 (13)	C9—C10	1.529 (3)
Hf—O3ⁱ	2.1933 (14)	C10—F4	1.333 (2)
Hf—O3	2.1933 (13)	C10—F5	1.335 (2)
O1—C2	1.253 (2)	C10—F6	1.339 (2)
O2—C4	1.280 (2)	C11—C12	1.504 (4)
C1—C2	1.494 (3)	C11—H11A	0.96
C1—H1A	0.96	C11—H11B	0.96
C1—H1B	0.96	C11—H11C	0.96
C1—H1C	0.96	C12—C17	1.377 (4)
C2—C3	1.418 (3)	C12—C13	1.382 (4)
C3—C4	1.359 (3)	C13—C14	1.386 (4)
C3—H3	0.93	C13—H13	0.93
C4—C5	1.530 (3)	C14—C15	1.375 (4)
C5—F1	1.325 (3)	C14—H14	0.93
C5—F3	1.329 (3)	C15—C16	1.372 (4)
C5—F2	1.333 (2)	C15—H15	0.93
O3—C7	1.254 (2)	C16—C17	1.374 (4)
O4—C9	1.276 (2)	C16—H16	0.93
C6—C7	1.496 (3)	C17—H17	0.93
C6—H6A	0.96

O2—Hf—O2ⁱ	141.66 (7)	F3—C5—C4	111.30 (17)
O2—Hf—O4	80.96 (5)	F2—C5—C4	112.58 (17)
O2ⁱ—Hf—O4	111.77 (5)	C7—O3—Hf	134.87 (13)
O2—Hf—O4ⁱ	111.77 (5)	C9—O4—Hf	131.43 (13)
O2ⁱ—Hf—O4ⁱ	80.96 (5)	C7—C6—H6A	109.5
O4—Hf—O4ⁱ	142.02 (7)	C7—C6—H6B	109.5
O2—Hf—O1ⁱ	141.35 (5)	H6A—C6—H6B	109.5
O2ⁱ—Hf—O1ⁱ	75.69 (5)	C7—C6—H6C	109.5
O4—Hf—O1ⁱ	72.52 (5)	H6A—C6—H6C	109.5
O4ⁱ—Hf—O1ⁱ	76.79 (5)	H6B—C6—H6C	109.5
O2—Hf—O1	75.69 (5)	O3—C7—C8	122.62 (18)
O2ⁱ—Hf—O1	141.35 (5)	O3—C7—C6	118.27 (18)
O4—Hf—O1	76.79 (5)	C8—C7—C6	119.06 (18)
O4ⁱ—Hf—O1	72.52 (5)	C9—C8—C7	120.28 (18)
O1ⁱ—Hf—O1	71.28 (7)	C9—C8—H8	119.9
O2—Hf—O3ⁱ	72.21 (5)	C7—C8—H8	119.9
O2ⁱ—Hf—O3ⁱ	76.82 (5)	O4—C9—C8	128.26 (18)
O4—Hf—O3ⁱ	141.11 (5)	O4—C9—C10	112.50 (17)
O4ⁱ—Hf—O3ⁱ	75.54 (5)	C8—C9—C10	119.16 (17)
O1ⁱ—Hf—O3ⁱ	143.48 (5)	F4—C10—F5	107.15 (16)
O1—Hf—O3ⁱ	121.11 (5)	F4—C10—F6	106.83 (17)
O2—Hf—O3	76.82 (5)	F5—C10—F6	106.94 (17)
O2ⁱ—Hf—O3	72.21 (5)	F4—C10—C9	111.58 (16)
O4—Hf—O3	75.54 (5)	F5—C10—C9	113.11 (17)
O4ⁱ—Hf—O3	141.11 (5)	F6—C10—C9	110.90 (16)
O1ⁱ—Hf—O3	121.11 (5)	C12—C11—H11A	109.5
O1—Hf—O3	143.48 (5)	C12—C11—H11B	109.5
O3ⁱ—Hf—O3	71.35 (7)	H11A—C11—H11B	109.5
C2—O1—Hf	134.34 (13)	C12—C11—H11C	109.5
C4—O2—Hf	131.45 (13)	H11A—C11—H11C	109.5
C2—C1—H1A	109.5	H11B—C11—H11C	109.5
C2—C1—H1B	109.5	C17—C12—C13	117.8 (3)
H1A—C1—H1B	109.5	C17—C12—C11	119.9 (3)
C2—C1—H1C	109.5	C13—C12—C11	122.3 (3)
H1A—C1—H1C	109.5	C12—C13—C14	120.7 (2)
H1B—C1—H1C	109.5	C12—C13—H13	119.6
O1—C2—C3	122.69 (19)	C14—C13—H13	119.6
O1—C2—C1	118.14 (18)	C15—C14—C13	120.5 (2)
C3—C2—C1	119.12 (18)	C15—C14—H14	119.8
C4—C3—C2	120.47 (18)	C13—C14—H14	119.8
C4—C3—H3	119.8	C16—C15—C14	118.9 (3)
C2—C3—H3	119.8	C16—C15—H15	120.5
O2—C4—C3	127.96 (18)	C14—C15—H15	120.5
O2—C4—C5	112.58 (17)	C15—C16—C17	120.5 (3)
C3—C4—C5	119.46 (17)	C15—C16—H16	119.8
F1—C5—F3	106.71 (18)	C17—C16—H16	119.8
F1—C5—F2	107.83 (17)	C16—C17—C12	121.6 (2)
F3—C5—F2	106.67 (17)	C16—C17—H17	119.2
F1—C5—C4	111.44 (17)	C12—C17—H17	119.2

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···F2	0.93	2.37	2.712 (2)	102
C8—H8···F5	0.93	2.37	2.721 (2)	102

Experimental details

Crystal data
Chemical formula	[Hf(C₅H₄F₃O₂)₄]·2C₇H₈
M_r	975.09
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	22.4983 (15), 8.0642 (5), 22.712 (2)
β (°)	118.211 (2)
V (Å³)	3631.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.98
Crystal size (mm)	0.33 × 0.25 × 0.22

Data collection
Diffractometer	Bruker X8 APEXII 4K KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.439, 0.560
No. of measured, independent and observed [I > 2σ(I)] reflections	18332, 4518, 4256
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.042, 1.07
No. of reflections	4518
No. of parameters	252
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.12, −0.91

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 1999), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Hf—O2	2.1527 (13)	Hf—O1	2.1861 (13)
Hf—O4	2.1571 (13)	Hf—O3	2.1933 (13)

O2—Hf—O2ⁱ	141.66 (7)	O1ⁱ—Hf—O1	71.28 (7)
O2—Hf—O4	80.96 (5)	O2—Hf—O3ⁱ	72.21 (5)
O2ⁱ—Hf—O4	111.77 (5)	O4—Hf—O3ⁱ	141.11 (5)
O4—Hf—O4ⁱ	142.02 (7)	O1—Hf—O3ⁱ	121.11 (5)
O2—Hf—O1ⁱ	141.35 (5)	O2—Hf—O3	76.82 (5)
O4—Hf—O1ⁱ	72.52 (5)	O4—Hf—O3	75.54 (5)
O2—Hf—O1	75.69 (5)	O1—Hf—O3	143.48 (5)
O4—Hf—O1	76.79 (5)	O3ⁱ—Hf—O3	71.35 (7)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···F2	0.93	2.37	2.712 (2)	102
C8—H8···F5	0.93	2.37	2.721 (2)	102

Acknowledgements

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. Dr R. Meijboom is aknowledged for his kind assistance in the use of modified Schlenk techniques.

References

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