Tetra-kis(1,1,1-trifluoro-acetyl-acetonato-κO,O')hafnium(IV) toluene disolvate.

In the title compound, [Hf(C(5)H(4)F(3)O(2))(4)]·2C(7)H(8), the Hf(IV) atom, lying on a twofold rotation axis, is coordinated by eight O atoms from four 1,1,1-trifluoro-acetyl-acetonate 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 mol-ecule. 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 = 975.09

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.018

wR(F 2) = 0.042

S = 1.07

4518 reflections

252 parameters

H-atom parameters constrained

Δρmax = 1.12 e Å−3

Δρmin = −0.91 e Å−3

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 ▶).

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

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

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

[Hf(C5H4F3O2)4]·2C7H8	F000 = 1920
Mr = 975.09	Dx = 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 = 2.7–28.3º
b = 8.0642 (5) Å	µ = 2.98 mm−1
c = 22.712 (2) Å	T = 100 (2) K
β = 118.211 (2)º	Block, colourless
V = 3631.2 (5) Å3	0.33 × 0.25 × 0.22 mm
Z = 4

Bruker X8 APEXII 4K KappaCCD diffractometer	4518 independent reflections
Monochromator: graphite	4256 reflections with I > 2σ(I)
Detector resolution: 8.4 pixels mm-1	Rint = 0.023
T = 100(2) K	θmax = 28.4º
φ and ω scans	θmin = 2.0º
Absorption correction: multi-scan(SADABS; Bruker, 2001)	h = −30→26
Tmin = 0.439, Tmax = 0.560	k = −10→10
18332 measured reflections	l = −29→30

Refinement on F2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0173P)2 + 5.3839P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.019	(Δ/σ)max = 0.002
wR(F2) = 0.042	Δρmax = 1.12 e Å−3
S = 1.07	Δρmin = −0.91 e Å−3
4518 reflections	Extinction correction: none
252 parameters

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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

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

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) .

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