Di-μ-hydroxido-bis­[tris­(4,4,4-trifluoro-1-phenyl­acetyl­acetonato-κ2O,O′)hafnium(IV)] dimethyl­formamide disolvate

Viljoen, J.A.; Visser, H.G.; Roodt, A.

doi:10.1107/S1600536811049543

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1822-m1823

https://doi.org/10.1107/S1600536811049543

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Di-μ-hydroxido-bis[tris(4,4,4-trifluoro-1-phenylacetylacetonato-κ²O,O′)hafnium(IV)] dimethylformamide disolvate

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

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

(Received 10 November 2011; accepted 20 November 2011; online 25 November 2011)

The binuclear molecule of the title compound, [Hf₂(C₁₀H₆F₃O₂)₆(OH)₂]·2C₃H₇NO, lies across an inversion centre and contains a Hf^IV atom which is eight-coordinated and surrounded by three chelating β-diketonato tris(4,4,4-trifluoro-1-phenylacetylacetonate (tfba⁻) ligands and two bridging OH⁻ groups in a distorted square-antiprismatic geometry. The Hf—O bond lengths vary from 2.073 (2) to 2.244 (2) Å and the O—Hf—O bite angles vary from 73.49 (9) to 75.60 (9)°. Weak O—H⋯O hydrogen-bonding interactions are observed between the bridging hydroxy groups and the dimethylformamide solvent molecules. The unit cell contains solvent-accessible voids of 131 Å³, but the residual electron density in the difference Fourier map suggests no solvent molecule occupies this void.

Related literature

For our ongoing research investigating the reactions of various O,O′-and N,O-bidentate ligands with hafnium(IV) and zirconium(IV) to exploit possible separation techniques and for the crystal structures of hafnium(IV) and zirconium(IV) complexes, see: Viljoen et al. (2010 ); Steyn et al. (2011 ).

Experimental

Crystal data

[Hf₂(C₁₀H₆F₃O₂)₆(OH)₂]·2C₃H₇NO
M_r = 1828.08
Monoclinic, P 2₁ /c
a = 12.4143 (3) Å
b = 19.244 (5) Å
c = 17.503 (5) Å
β = 122.937 (5)°
V = 3509 (2) Å³
Z = 2
Mo Kα radiation
μ = 3.07 mm⁻¹
T = 100 K
0.28 × 0.23 × 0.21 mm

Data collection

Bruker X8 APEXII 4K KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.431, T_max = 0.526
41903 measured reflections
8726 independent reflections
6864 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.072
S = 1.03
8726 reflections
475 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.33 e Å⁻³
Δρ_min = −0.97 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H1A⋯O8	0.78 (2)	1.94 (2)	2.712 (3)	171 (5)

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811049543/pv2484sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811049543/pv2484Isup2.hkl

checkCIF report

Comment top

This study forms part of ongoing research to investigate the reactions of various O,O'-and N,O-bidentate ligands with hafnium(IV) and zirconium(IV) to exploit possible separation techniques (Steyn et al. 2011; Viljoen et al. (2010).

The metal complex of the title compound (Figure 1) consists of a Hf^IV atom which is eight-coordinated and surrounded by three tfba^- ligands and two bridging OH-groups thereby adopting a slightly distorted anti-prismatic coordination geometry. The Hf—O bond lengths vary from 2.073 (2) Å to 2.244 (2) Å and the O—Hf—O bite angles vary from 73.49 (9) ° to 75.60 (9) °. The dimer skeleton exhibits a flat diamond-like structure and lies across an inversion centre with Hf—O7, Hf—O7ⁱ and Hf—Hfⁱ distances of 2.135 (2), 2.073 (2) and 3.4958 (8) Å, respectively, and a bite angle of 67.66 (11) °. Lastly, weak hydrogen bonding interactions are observed between one of the bridging hydroxy groups (O7—H1A) and the solvent molecule (Table 1).

Related literature top

For our ongoing research investigating the reactions of various O,O'-and N,O-bidentate ligands with hafnium(IV) and zirconium(IV) to exploit possible separation techniques and for the crystal structures of hafnium(IV) and zirconium(IV) complexes, see: Viljoen et al. (2010); Steyn et al. (2011).

Experimental top

Chemicals were purchased from Sigma and Aldrich and used as received. 4,4,4-Trifluoro-1-phenyl-1,3-butanedione,tfbaH, (540 mg, 2.5 mmol) was added slowly to HfCl₄ (200 mg, 0.624 mmol) in N,N-dimethylformamide (25 ml). After refluxing for ca 12 h, the crude product was filtered and left to stand at room temperature for colorless crystals to form.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); 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).

Figures top

Fig. 1. Representation of the title compound, showing the numbering scheme and displacement ellipsoids (50% probability). Primed atoms are related to the unprimed atoms by symmetry operation: -x+1, -y+1, -z+1.

Di-µ-hydroxido-bis[tris(4,4,4-trifluoro-1-phenylacetylacetonato- κ²O,O')hafnium(IV)] dimethylformamide disolvate top

Crystal data top

[Hf₂(C₁₀H₆F₃O₂)₆(OH)₂]·2C₃H₇NO	F(000) = 1792
M_r = 1828.08	D_x = 1.73 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 9995 reflections
a = 12.4143 (3) Å	θ = 2.9–28.1°
b = 19.244 (5) Å	µ = 3.07 mm⁻¹
c = 17.503 (5) Å	T = 100 K
β = 122.937 (5)°	Cuboid, colourless
V = 3509 (2) Å³	0.28 × 0.23 × 0.21 mm
Z = 2

Data collection top

Bruker X8 APEXII 4K KappaCCD diffractometer	8726 independent reflections
Radiation source: fine-focus sealed tube	6864 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ω and φ scans	θ_max = 28.3°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −16→16
T_min = 0.431, T_max = 0.526	k = −25→25
41903 measured reflections	l = −23→22

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0285P)² + 4.244P] where P = (F_o² + 2F_c²)/3
8726 reflections	(Δ/σ)_max = 0.004
475 parameters	Δρ_max = 1.33 e Å⁻³
1 restraint	Δρ_min = −0.97 e Å⁻³
1 constraint

Crystal data top

[Hf₂(C₁₀H₆F₃O₂)₆(OH)₂]·2C₃H₇NO	V = 3509 (2) Å³
M_r = 1828.08	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.4143 (3) Å	µ = 3.07 mm⁻¹
b = 19.244 (5) Å	T = 100 K
c = 17.503 (5) Å	0.28 × 0.23 × 0.21 mm
β = 122.937 (5)°

Data collection top

Bruker X8 APEXII 4K KappaCCD diffractometer	8726 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	6864 reflections with I > 2σ(I)
T_min = 0.431, T_max = 0.526	R_int = 0.050
41903 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	1 restraint
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 1.33 e Å⁻³
8726 reflections	Δρ_min = −0.97 e Å⁻³
475 parameters

Special details top

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
C1	0.5472 (4)	0.7683 (2)	0.4852 (3)	0.0300 (9)
C2	0.5889 (4)	0.69251 (18)	0.5092 (2)	0.0229 (8)
C3	0.6788 (3)	0.67550 (19)	0.5996 (2)	0.0234 (8)
H3	0.6964	0.7074	0.6465	0.028*
C4	0.7430 (3)	0.6123 (2)	0.6218 (2)	0.0235 (8)
C5	0.8546 (3)	0.5979 (2)	0.7159 (2)	0.0261 (8)
C6	0.9359 (4)	0.5421 (2)	0.7303 (3)	0.0332 (9)
H6	0.9175	0.5136	0.6803	0.04*
C7	1.0431 (4)	0.5276 (2)	0.8162 (3)	0.0403 (11)
H7	1.0991	0.4906	0.8246	0.048*
C8	1.0673 (5)	0.5682 (3)	0.8900 (3)	0.0488 (12)
H8	1.1394	0.5583	0.9492	0.059*
C9	0.9859 (5)	0.6229 (3)	0.8769 (3)	0.0447 (12)
H9	1.0019	0.6498	0.9276	0.054*
C10	0.8804 (4)	0.6388 (2)	0.7898 (3)	0.0344 (10)
H10	0.8268	0.6772	0.781	0.041*
C11	0.3785 (4)	0.4208 (2)	0.1663 (3)	0.0335 (10)
C12	0.3762 (4)	0.47465 (18)	0.2301 (2)	0.0225 (8)
C13	0.2820 (3)	0.52375 (18)	0.1939 (2)	0.0233 (8)
H13	0.2233	0.5263	0.1298	0.028*
C14	0.2716 (3)	0.57057 (17)	0.2511 (2)	0.0174 (7)
C15	0.1616 (3)	0.61903 (18)	0.2168 (2)	0.0197 (7)
C16	0.1675 (4)	0.66931 (19)	0.2764 (3)	0.0267 (8)
H16	0.2405	0.6717	0.337	0.032*
C17	0.0675 (4)	0.7157 (2)	0.2477 (3)	0.0377 (10)
H17	0.0722	0.7505	0.2879	0.045*
C18	−0.0389 (4)	0.7110 (2)	0.1603 (3)	0.0449 (12)
H18	−0.109	0.7417	0.1412	0.054*
C19	−0.0453 (4)	0.6628 (2)	0.1004 (3)	0.0420 (11)
H19	−0.1182	0.6612	0.0397	0.05*
C20	0.0543 (3)	0.6165 (2)	0.1283 (2)	0.0279 (8)
H20	0.0496	0.5829	0.0869	0.033*
C21	0.6419 (4)	0.6077 (2)	0.2317 (3)	0.0332 (9)
C22	0.6666 (4)	0.56527 (19)	0.3136 (2)	0.0242 (8)
C23	0.7556 (4)	0.5129 (2)	0.3462 (3)	0.0279 (8)
H23	0.8017	0.504	0.3182	0.033*
C24	0.7798 (3)	0.47168 (18)	0.4211 (2)	0.0204 (7)
C25	0.8870 (3)	0.42024 (18)	0.4640 (2)	0.0210 (7)
C26	0.9601 (4)	0.4044 (2)	0.4279 (3)	0.0337 (9)
H26	0.9425	0.4266	0.3738	0.04*
C27	1.0581 (4)	0.3563 (2)	0.4706 (3)	0.0401 (11)
H27	1.1081	0.3462	0.4459	0.048*
C28	1.0843 (4)	0.3230 (2)	0.5477 (3)	0.0366 (10)
H28	1.151	0.2894	0.5757	0.044*
C29	1.0127 (4)	0.3387 (2)	0.5849 (3)	0.0318 (9)
H29	1.031	0.3163	0.639	0.038*
C30	0.9153 (4)	0.3868 (2)	0.5430 (3)	0.0259 (8)
H30	0.8666	0.3973	0.5687	0.031*
C31	0.6169 (4)	0.31446 (19)	0.4081 (3)	0.0264 (8)
H31	0.5679	0.3489	0.3634	0.032*
C32	0.7378 (5)	0.2081 (2)	0.4479 (3)	0.0432 (11)
H32A	0.7447	0.2167	0.5056	0.065*
H32B	0.8236	0.209	0.4581	0.065*
H32C	0.6986	0.1625	0.4241	0.065*
C33	0.6361 (5)	0.2557 (3)	0.2929 (3)	0.0524 (14)
H33A	0.578	0.293	0.2544	0.079*
H33B	0.597	0.2106	0.2664	0.079*
H33C	0.7176	0.2599	0.2967	0.079*
N1	0.6595 (3)	0.26113 (16)	0.3833 (2)	0.0285 (7)
O1	0.5438 (2)	0.65377 (12)	0.44087 (15)	0.0214 (5)
O2	0.7170 (2)	0.56513 (13)	0.56345 (16)	0.0221 (5)
O3	0.4665 (2)	0.46540 (12)	0.31343 (15)	0.0206 (5)
O4	0.3564 (2)	0.57330 (12)	0.33550 (15)	0.0195 (5)
O5	0.5958 (2)	0.58469 (12)	0.34167 (16)	0.0221 (5)
O6	0.7133 (2)	0.47712 (12)	0.45494 (16)	0.0191 (5)
O7	0.5352 (2)	0.44652 (12)	0.48937 (16)	0.0171 (5)
O8	0.6357 (2)	0.32287 (13)	0.48407 (17)	0.0253 (6)
F1	0.5519 (3)	0.80248 (12)	0.55312 (15)	0.0458 (7)
F2	0.6313 (3)	0.80097 (12)	0.47024 (18)	0.0461 (7)
F3	0.4326 (2)	0.77581 (11)	0.41168 (15)	0.0343 (5)
F4	0.3554 (3)	0.35768 (12)	0.18342 (19)	0.0472 (7)
F5	0.4918 (2)	0.41859 (13)	0.17586 (17)	0.0420 (6)
F6	0.2911 (3)	0.43385 (16)	0.07841 (16)	0.0641 (9)
F7	0.5246 (3)	0.59463 (14)	0.15994 (16)	0.0494 (7)
F8	0.6486 (3)	0.67553 (13)	0.24721 (17)	0.0448 (6)
F9	0.7245 (3)	0.59400 (14)	0.20724 (18)	0.0505 (7)
Hf1	0.547988 (13)	0.538181 (7)	0.432516 (9)	0.01636 (5)
H1A	0.572 (4)	0.4128 (15)	0.492 (3)	0.039 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.042 (2)	0.027 (2)	0.0213 (18)	−0.0132 (18)	0.0173 (18)	−0.0075 (16)
C2	0.026 (2)	0.0212 (18)	0.0303 (19)	−0.0097 (15)	0.0213 (17)	−0.0065 (15)
C3	0.0222 (19)	0.032 (2)	0.0174 (16)	−0.0139 (16)	0.0114 (15)	−0.0107 (15)
C4	0.0195 (18)	0.031 (2)	0.0223 (17)	−0.0119 (16)	0.0130 (15)	−0.0047 (16)
C5	0.0178 (18)	0.040 (2)	0.0160 (17)	−0.0118 (16)	0.0062 (15)	−0.0041 (15)
C6	0.029 (2)	0.039 (2)	0.029 (2)	−0.0104 (19)	0.0140 (18)	−0.0004 (18)
C7	0.029 (2)	0.044 (3)	0.036 (2)	−0.0053 (19)	0.0093 (19)	0.010 (2)
C8	0.039 (3)	0.054 (3)	0.033 (2)	−0.015 (2)	0.006 (2)	0.004 (2)
C9	0.046 (3)	0.050 (3)	0.023 (2)	−0.018 (2)	0.009 (2)	−0.006 (2)
C10	0.030 (2)	0.044 (2)	0.0231 (19)	−0.0135 (19)	0.0105 (18)	−0.0076 (18)
C11	0.031 (2)	0.038 (2)	0.0208 (19)	0.0041 (19)	0.0073 (17)	−0.0106 (17)
C12	0.025 (2)	0.0217 (19)	0.0210 (17)	−0.0046 (15)	0.0130 (16)	−0.0087 (14)
C13	0.0211 (19)	0.028 (2)	0.0150 (16)	0.0020 (15)	0.0061 (14)	−0.0025 (14)
C14	0.0150 (17)	0.0162 (16)	0.0195 (16)	−0.0015 (13)	0.0084 (14)	0.0015 (13)
C15	0.0176 (17)	0.0212 (18)	0.0208 (16)	0.0015 (14)	0.0107 (15)	0.0038 (14)
C16	0.028 (2)	0.031 (2)	0.0246 (18)	0.0110 (17)	0.0165 (17)	0.0087 (16)
C17	0.044 (3)	0.041 (2)	0.039 (2)	0.020 (2)	0.029 (2)	0.012 (2)
C18	0.034 (3)	0.053 (3)	0.050 (3)	0.025 (2)	0.024 (2)	0.018 (2)
C19	0.020 (2)	0.052 (3)	0.037 (2)	0.010 (2)	0.0046 (19)	0.012 (2)
C20	0.0206 (19)	0.031 (2)	0.0250 (18)	−0.0009 (16)	0.0075 (16)	0.0002 (17)
C21	0.032 (2)	0.043 (3)	0.030 (2)	0.0046 (19)	0.0197 (19)	0.0102 (19)
C22	0.030 (2)	0.0272 (19)	0.0199 (17)	−0.0069 (16)	0.0164 (17)	0.0021 (15)
C23	0.030 (2)	0.035 (2)	0.028 (2)	0.0038 (17)	0.0213 (18)	0.0071 (17)
C24	0.0179 (17)	0.0237 (19)	0.0191 (16)	−0.0057 (14)	0.0097 (14)	−0.0035 (14)
C25	0.0179 (18)	0.0194 (18)	0.0278 (18)	−0.0038 (14)	0.0139 (16)	−0.0030 (15)
C26	0.037 (2)	0.031 (2)	0.049 (3)	0.0023 (18)	0.033 (2)	0.0047 (19)
C27	0.042 (3)	0.030 (2)	0.069 (3)	0.0055 (19)	0.043 (3)	0.004 (2)
C28	0.026 (2)	0.026 (2)	0.059 (3)	0.0033 (17)	0.024 (2)	0.004 (2)
C29	0.025 (2)	0.032 (2)	0.037 (2)	0.0018 (17)	0.0169 (19)	0.0030 (18)
C30	0.0201 (19)	0.028 (2)	0.0292 (19)	−0.0006 (16)	0.0131 (16)	−0.0016 (17)
C31	0.028 (2)	0.0212 (19)	0.033 (2)	0.0055 (16)	0.0193 (18)	0.0017 (16)
C32	0.050 (3)	0.032 (2)	0.042 (3)	0.017 (2)	0.021 (2)	−0.001 (2)
C33	0.083 (4)	0.047 (3)	0.048 (3)	0.025 (3)	0.049 (3)	0.008 (2)
N1	0.0352 (19)	0.0240 (17)	0.0325 (17)	0.0077 (14)	0.0223 (16)	0.0009 (14)
O1	0.0303 (14)	0.0155 (12)	0.0202 (12)	−0.0092 (10)	0.0149 (11)	−0.0039 (10)
O2	0.0161 (13)	0.0287 (13)	0.0181 (12)	−0.0070 (10)	0.0072 (10)	−0.0047 (10)
O3	0.0205 (13)	0.0201 (12)	0.0169 (11)	0.0018 (10)	0.0073 (10)	−0.0016 (10)
O4	0.0180 (13)	0.0199 (12)	0.0192 (12)	0.0006 (10)	0.0092 (10)	−0.0031 (10)
O5	0.0250 (14)	0.0234 (13)	0.0221 (12)	−0.0002 (11)	0.0155 (11)	0.0030 (10)
O6	0.0188 (13)	0.0224 (13)	0.0199 (12)	0.0008 (10)	0.0130 (10)	0.0025 (10)
O7	0.0170 (13)	0.0179 (13)	0.0189 (12)	0.0002 (10)	0.0113 (10)	0.0013 (10)
O8	0.0284 (15)	0.0238 (13)	0.0259 (13)	−0.0015 (11)	0.0162 (12)	−0.0021 (11)
F1	0.075 (2)	0.0270 (13)	0.0293 (13)	0.0005 (12)	0.0248 (14)	−0.0080 (10)
F2	0.0503 (17)	0.0319 (13)	0.0557 (16)	−0.0103 (12)	0.0285 (14)	0.0114 (12)
F3	0.0451 (15)	0.0229 (12)	0.0314 (12)	−0.0004 (10)	0.0186 (12)	−0.0015 (10)
F4	0.0547 (17)	0.0318 (13)	0.0639 (18)	−0.0097 (12)	0.0380 (15)	−0.0225 (13)
F5	0.0423 (15)	0.0498 (16)	0.0424 (14)	−0.0010 (12)	0.0285 (13)	−0.0169 (12)
F6	0.066 (2)	0.072 (2)	0.0230 (13)	0.0296 (16)	0.0041 (13)	−0.0179 (13)
F7	0.0449 (16)	0.0691 (19)	0.0260 (13)	−0.0045 (14)	0.0138 (12)	0.0138 (12)
F8	0.0593 (18)	0.0378 (15)	0.0450 (15)	0.0059 (12)	0.0334 (14)	0.0191 (12)
F9	0.0599 (18)	0.0659 (18)	0.0527 (16)	0.0217 (14)	0.0480 (15)	0.0306 (14)
Hf1	0.01553 (8)	0.01823 (8)	0.01458 (7)	−0.00176 (6)	0.00772 (6)	−0.00041 (6)

Geometric parameters (Å, º) top

C1—F3	1.307 (5)	C21—F7	1.331 (5)
C1—F1	1.331 (4)	C21—F9	1.335 (4)
C1—F2	1.360 (4)	C21—C22	1.529 (5)
C1—C2	1.529 (5)	C22—O5	1.274 (4)
C2—O1	1.253 (4)	C22—C23	1.370 (5)
C2—C3	1.392 (5)	C23—C24	1.418 (5)
C3—C4	1.389 (5)	C23—H23	0.95
C3—H3	0.95	C24—O6	1.255 (4)
C4—O2	1.269 (4)	C24—C25	1.492 (5)
C4—C5	1.493 (5)	C25—C30	1.386 (5)
C5—C10	1.394 (5)	C25—C26	1.393 (5)
C5—C6	1.398 (6)	C26—C27	1.381 (6)
C6—C7	1.391 (6)	C26—H26	0.95
C6—H6	0.95	C27—C28	1.362 (6)
C7—C8	1.394 (7)	C27—H27	0.95
C7—H7	0.95	C28—C29	1.392 (6)
C8—C9	1.390 (7)	C28—H28	0.95
C8—H8	0.95	C29—C30	1.376 (5)
C9—C10	1.401 (6)	C29—H29	0.95
C9—H9	0.95	C30—H30	0.95
C10—H10	0.95	C31—O8	1.229 (4)
C11—F4	1.320 (5)	C31—N1	1.330 (4)
C11—F5	1.323 (5)	C31—H31	0.95
C11—F6	1.339 (4)	C32—N1	1.439 (5)
C11—C12	1.535 (5)	C32—H32A	0.98
C12—O3	1.279 (4)	C32—H32B	0.98
C12—C13	1.362 (5)	C32—H32C	0.98
C13—C14	1.404 (5)	C33—N1	1.451 (5)
C13—H13	0.95	C33—H33A	0.98
C14—O4	1.266 (4)	C33—H33B	0.98
C14—C15	1.484 (5)	C33—H33C	0.98
C15—C20	1.390 (5)	O1—Hf1	2.232 (2)
C15—C16	1.396 (5)	O2—Hf1	2.167 (2)
C16—C17	1.383 (5)	O3—Hf1	2.244 (2)
C16—H16	0.95	O4—Hf1	2.146 (2)
C17—C18	1.377 (6)	O5—Hf1	2.170 (2)
C17—H17	0.95	O6—Hf1	2.207 (2)
C18—C19	1.370 (6)	O7—Hf1	2.073 (2)
C18—H18	0.95	O7—Hf1ⁱ	2.135 (2)
C19—C20	1.379 (5)	O7—H1A	0.780 (19)
C19—H19	0.95	Hf1—O7ⁱ	2.135 (2)
C20—H20	0.95	Hf1—Hf1ⁱ	3.4958 (8)
C21—F8	1.327 (5)

F3—C1—F1	108.7 (3)	C30—C25—C26	118.5 (3)
F3—C1—F2	107.3 (3)	C30—C25—C24	118.8 (3)
F1—C1—F2	106.2 (3)	C26—C25—C24	122.7 (3)
F3—C1—C2	113.6 (3)	C27—C26—C25	120.0 (4)
F1—C1—C2	112.5 (3)	C27—C26—H26	120
F2—C1—C2	108.2 (3)	C25—C26—H26	120
O1—C2—C3	127.7 (3)	C28—C27—C26	121.2 (4)
O1—C2—C1	113.4 (3)	C28—C27—H27	119.4
C3—C2—C1	118.6 (3)	C26—C27—H27	119.4
C4—C3—C2	120.5 (3)	C27—C28—C29	119.4 (4)
C4—C3—H3	119.8	C27—C28—H28	120.3
C2—C3—H3	119.8	C29—C28—H28	120.3
O2—C4—C3	123.0 (3)	C30—C29—C28	119.8 (4)
O2—C4—C5	115.6 (3)	C30—C29—H29	120.1
C3—C4—C5	121.2 (3)	C28—C29—H29	120.1
C10—C5—C6	119.2 (4)	C29—C30—C25	121.1 (4)
C10—C5—C4	121.7 (4)	C29—C30—H30	119.5
C6—C5—C4	119.1 (3)	C25—C30—H30	119.5
C7—C6—C5	121.3 (4)	O8—C31—N1	125.4 (4)
C7—C6—H6	119.3	O8—C31—H31	117.3
C5—C6—H6	119.3	N1—C31—H31	117.3
C6—C7—C8	119.2 (5)	N1—C32—H32A	109.5
C6—C7—H7	120.4	N1—C32—H32B	109.5
C8—C7—H7	120.4	H32A—C32—H32B	109.5
C9—C8—C7	120.0 (4)	N1—C32—H32C	109.5
C9—C8—H8	120	H32A—C32—H32C	109.5
C7—C8—H8	120	H32B—C32—H32C	109.5
C8—C9—C10	120.7 (4)	N1—C33—H33A	109.5
C8—C9—H9	119.6	N1—C33—H33B	109.5
C10—C9—H9	119.6	H33A—C33—H33B	109.5
C5—C10—C9	119.5 (4)	N1—C33—H33C	109.5
C5—C10—H10	120.2	H33A—C33—H33C	109.5
C9—C10—H10	120.2	H33B—C33—H33C	109.5
F4—C11—F5	106.8 (3)	C31—N1—C32	120.6 (3)
F4—C11—F6	107.0 (3)	C31—N1—C33	122.2 (3)
F5—C11—F6	107.0 (3)	C32—N1—C33	117.1 (3)
F4—C11—C12	111.3 (3)	C2—O1—Hf1	129.9 (2)
F5—C11—C12	111.7 (3)	C4—O2—Hf1	134.3 (2)
F6—C11—C12	112.7 (3)	C12—O3—Hf1	130.1 (2)
O3—C12—C13	128.8 (3)	C14—O4—Hf1	140.4 (2)
O3—C12—C11	112.5 (3)	C22—O5—Hf1	133.1 (2)
C13—C12—C11	118.7 (3)	C24—O6—Hf1	138.4 (2)
C12—C13—C14	120.1 (3)	Hf1—O7—Hf1ⁱ	112.34 (11)
C12—C13—H13	120	Hf1—O7—H1A	123 (3)
C14—C13—H13	120	Hf1ⁱ—O7—H1A	124 (3)
O4—C14—C13	121.2 (3)	O7—Hf1—O7ⁱ	67.66 (11)
O4—C14—C15	116.4 (3)	O7—Hf1—O4	107.84 (9)
C13—C14—C15	122.4 (3)	O7ⁱ—Hf1—O4	75.48 (9)
C20—C15—C16	119.1 (3)	O7—Hf1—O2	88.79 (9)
C20—C15—C14	122.9 (3)	O7ⁱ—Hf1—O2	79.46 (10)
C16—C15—C14	118.0 (3)	O4—Hf1—O2	141.33 (9)
C17—C16—C15	120.2 (4)	O7—Hf1—O5	145.64 (9)
C17—C16—H16	119.9	O7ⁱ—Hf1—O5	146.39 (9)
C15—C16—H16	119.9	O4—Hf1—O5	85.28 (9)
C18—C17—C16	119.4 (4)	O2—Hf1—O5	100.53 (9)
C18—C17—H17	120.3	O7—Hf1—O6	76.60 (9)
C16—C17—H17	120.3	O7ⁱ—Hf1—O6	133.34 (9)
C19—C18—C17	121.1 (4)	O4—Hf1—O6	146.29 (9)
C19—C18—H18	119.5	O2—Hf1—O6	70.56 (9)
C17—C18—H18	119.5	O5—Hf1—O6	75.60 (9)
C18—C19—C20	119.9 (4)	O7—Hf1—O1	143.71 (9)
C18—C19—H19	120.1	O7ⁱ—Hf1—O1	77.53 (9)
C20—C19—H19	120.1	O4—Hf1—O1	71.51 (9)
C19—C20—C15	120.2 (4)	O2—Hf1—O1	74.67 (9)
C19—C20—H20	119.9	O5—Hf1—O1	70.26 (9)
C15—C20—H20	119.9	O6—Hf1—O1	124.85 (9)
F8—C21—F7	107.1 (3)	O7—Hf1—O3	78.55 (9)
F8—C21—F9	106.7 (3)	O7ⁱ—Hf1—O3	123.38 (9)
F7—C21—F9	107.3 (3)	O4—Hf1—O3	73.49 (9)
F8—C21—C22	112.0 (3)	O2—Hf1—O3	145.08 (9)
F7—C21—C22	110.0 (3)	O5—Hf1—O3	75.02 (9)
F9—C21—C22	113.4 (3)	O6—Hf1—O3	74.86 (9)
O5—C22—C23	128.6 (3)	O1—Hf1—O3	131.92 (8)
O5—C22—C21	112.1 (3)	O7—Hf1—Hf1ⁱ	34.39 (7)
C23—C22—C21	119.3 (3)	O7ⁱ—Hf1—Hf1ⁱ	33.27 (6)
C22—C23—C24	120.9 (3)	O4—Hf1—Hf1ⁱ	91.64 (7)
C22—C23—H23	119.5	O2—Hf1—Hf1ⁱ	82.86 (7)
C24—C23—H23	119.5	O5—Hf1—Hf1ⁱ	176.54 (7)
O6—C24—C23	121.8 (3)	O6—Hf1—Hf1ⁱ	106.36 (6)
O6—C24—C25	117.0 (3)	O1—Hf1—Hf1ⁱ	110.26 (6)
C23—C24—C25	121.2 (3)	O3—Hf1—Hf1ⁱ	102.61 (6)

F3—C1—C2—O1	31.8 (4)	O8—C31—N1—C33	−178.3 (4)
F1—C1—C2—O1	155.8 (3)	C3—C2—O1—Hf1	15.9 (5)
F2—C1—C2—O1	−87.2 (4)	C1—C2—O1—Hf1	−170.8 (2)
F3—C1—C2—C3	−154.2 (3)	C3—C4—O2—Hf1	−24.7 (5)
F1—C1—C2—C3	−30.2 (5)	C5—C4—O2—Hf1	159.6 (2)
F2—C1—C2—C3	86.8 (4)	C13—C12—O3—Hf1	−18.8 (6)
O1—C2—C3—C4	9.1 (6)	C11—C12—O3—Hf1	162.2 (2)
C1—C2—C3—C4	−163.9 (3)	C13—C14—O4—Hf1	13.5 (6)
C2—C3—C4—O2	−5.8 (5)	C15—C14—O4—Hf1	−166.8 (2)
C2—C3—C4—C5	169.7 (3)	C23—C22—O5—Hf1	−13.5 (6)
O2—C4—C5—C10	−168.6 (3)	C21—C22—O5—Hf1	165.4 (2)
C3—C4—C5—C10	15.6 (5)	C23—C24—O6—Hf1	0.2 (5)
O2—C4—C5—C6	11.8 (5)	C25—C24—O6—Hf1	179.5 (2)
C3—C4—C5—C6	−164.0 (3)	Hf1ⁱ—O7—Hf1—O7ⁱ	0
C10—C5—C6—C7	−1.3 (6)	Hf1ⁱ—O7—Hf1—O4	−65.36 (13)
C4—C5—C6—C7	178.3 (3)	Hf1ⁱ—O7—Hf1—O2	79.09 (12)
C5—C6—C7—C8	2.2 (6)	Hf1ⁱ—O7—Hf1—O5	−173.87 (12)
C6—C7—C8—C9	−1.0 (7)	Hf1ⁱ—O7—Hf1—O6	149.39 (13)
C7—C8—C9—C10	−1.1 (7)	Hf1ⁱ—O7—Hf1—O1	17.5 (2)
C6—C5—C10—C9	−0.8 (6)	Hf1ⁱ—O7—Hf1—O3	−133.65 (12)
C4—C5—C10—C9	179.6 (4)	C14—O4—Hf1—O7	−95.4 (4)
C8—C9—C10—C5	2.0 (6)	C14—O4—Hf1—O7ⁱ	−155.6 (4)
F4—C11—C12—O3	65.1 (4)	C14—O4—Hf1—O2	153.1 (3)
F5—C11—C12—O3	−54.1 (5)	C14—O4—Hf1—O5	52.2 (3)
F6—C11—C12—O3	−174.6 (3)	C14—O4—Hf1—O6	−2.8 (4)
F4—C11—C12—C13	−114.0 (4)	C14—O4—Hf1—O1	122.9 (4)
F5—C11—C12—C13	126.8 (4)	C14—O4—Hf1—O3	−23.6 (3)
F6—C11—C12—C13	6.2 (6)	C14—O4—Hf1—Hf1ⁱ	−126.3 (3)
O3—C12—C13—C14	−3.6 (6)	C4—O2—Hf1—O7	−113.9 (3)
C11—C12—C13—C14	175.4 (3)	C4—O2—Hf1—O7ⁱ	−46.4 (3)
C12—C13—C14—O4	7.8 (5)	C4—O2—Hf1—O4	3.8 (4)
C12—C13—C14—C15	−172.0 (3)	C4—O2—Hf1—O5	99.4 (3)
O4—C14—C15—C20	−172.3 (3)	C4—O2—Hf1—O6	169.9 (3)
C13—C14—C15—C20	7.4 (5)	C4—O2—Hf1—O1	33.5 (3)
O4—C14—C15—C16	8.0 (5)	C4—O2—Hf1—O3	178.3 (3)
C13—C14—C15—C16	−172.3 (3)	C4—O2—Hf1—Hf1ⁱ	−79.9 (3)
C20—C15—C16—C17	0.3 (5)	C22—O5—Hf1—O7	−23.2 (4)
C14—C15—C16—C17	180.0 (3)	C22—O5—Hf1—O7ⁱ	167.1 (3)
C15—C16—C17—C18	1.2 (6)	C22—O5—Hf1—O4	−138.3 (3)
C16—C17—C18—C19	−2.4 (7)	C22—O5—Hf1—O2	80.3 (3)
C17—C18—C19—C20	2.0 (7)	C22—O5—Hf1—O6	13.7 (3)
C18—C19—C20—C15	−0.5 (7)	C22—O5—Hf1—O1	149.7 (3)
C16—C15—C20—C19	−0.7 (6)	C22—O5—Hf1—O3	−64.1 (3)
C14—C15—C20—C19	179.7 (4)	C24—O6—Hf1—O7	151.9 (3)
F8—C21—C22—O5	52.0 (4)	C24—O6—Hf1—O7ⁱ	−167.7 (3)
F7—C21—C22—O5	−67.0 (4)	C24—O6—Hf1—O4	49.8 (4)
F9—C21—C22—O5	172.8 (3)	C24—O6—Hf1—O2	−114.6 (3)
F8—C21—C22—C23	−129.0 (4)	C24—O6—Hf1—O5	−7.7 (3)
F7—C21—C22—C23	112.0 (4)	C24—O6—Hf1—O1	−60.5 (3)
F9—C21—C22—C23	−8.2 (5)	C24—O6—Hf1—O3	70.4 (3)
O5—C22—C23—C24	−0.2 (7)	C24—O6—Hf1—Hf1ⁱ	169.4 (3)
C21—C22—C23—C24	−179.0 (3)	C2—O1—Hf1—O7	38.1 (4)
C22—C23—C24—O6	6.7 (6)	C2—O1—Hf1—O7ⁱ	54.6 (3)
C22—C23—C24—C25	−172.7 (3)	C2—O1—Hf1—O4	133.2 (3)
O6—C24—C25—C30	−6.3 (5)	C2—O1—Hf1—O2	−27.7 (3)
C23—C24—C25—C30	173.0 (3)	C2—O1—Hf1—O5	−135.2 (3)
O6—C24—C25—C26	173.7 (3)	C2—O1—Hf1—O6	−80.1 (3)
C23—C24—C25—C26	−6.9 (5)	C2—O1—Hf1—O3	178.6 (3)
C30—C25—C26—C27	0.0 (6)	C2—O1—Hf1—Hf1ⁱ	48.5 (3)
C24—C25—C26—C27	−180.0 (4)	C12—O3—Hf1—O7	136.6 (3)
C25—C26—C27—C28	0.8 (7)	C12—O3—Hf1—O7ⁱ	83.4 (3)
C26—C27—C28—C29	−1.2 (7)	C12—O3—Hf1—O4	23.9 (3)
C27—C28—C29—C30	0.9 (6)	C12—O3—Hf1—O2	−152.5 (3)
C28—C29—C30—C25	−0.1 (6)	C12—O3—Hf1—O5	−65.5 (3)
C26—C25—C30—C29	−0.4 (6)	C12—O3—Hf1—O6	−144.3 (3)
C24—C25—C30—C29	179.7 (3)	C12—O3—Hf1—O1	−20.8 (3)
O8—C31—N1—C32	−2.1 (6)	C12—O3—Hf1—Hf1ⁱ	111.9 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H1A···O8	0.78 (2)	1.94 (2)	2.712 (3)	171 (5)

Experimental details

Crystal data
Chemical formula	[Hf₂(C₁₀H₆F₃O₂)₆(OH)₂]·2C₃H₇NO
M_r	1828.08
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.4143 (3), 19.244 (5), 17.503 (5)
β (°)	122.937 (5)
V (Å³)	3509 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.07
Crystal size (mm)	0.28 × 0.23 × 0.21

Data collection
Diffractometer	Bruker X8 APEXII 4K KappaCCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.431, 0.526
No. of measured, independent and observed [I > 2σ(I)] reflections	41903, 8726, 6864
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.072, 1.03
No. of reflections	8726
No. of parameters	475
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.33, −0.97

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SIR92 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H1A···O8	0.780 (19)	1.94 (2)	2.712 (3)	171 (5)

Acknowledgements

Financial assistance from the Department of Science and Technology (DST) of South Africa and the Advanced Metals Initiative (AMI) as well as the New Metals Development Network (NMDN) and the South African Nuclear Energy Corporation Limited (Necsa) is acknowledged. The authors also thank SASOL, the South African NRF and THRIP and the University of the Free State Research Fund for financial support. The views expressed do not necessarily represent those of the NRF.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2004). SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
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Viljoen, J. A., Visser, H. G. & Roodt, A. (2010). Acta Cryst. E66, m1053–m1054. Web of Science CSD CrossRef IUCr Journals Google Scholar

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