Di-μ-hydroxido-bis­[tris­(4,4,4-trifluoro-1-phenyl­acetyl­acetonato-κ² O,O′)hafnium(IV)] dimethyl­formamide disolvate

Abstract

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 ų, 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,

• a = 12.4143 (3) Å

• b = 19.244 (5) Å

• c = 17.503 (5) Å

• β = 122.937 (5)°

• V = 3509 (2) ų

• 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[F ² > 2σ(F ²)] = 0.030

• wR(F ²) = 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

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

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

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The aromatic, methine, and methyl H atoms were placed in geometrically idealized positions (C—H = 0.93–0.98) and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C) for aromatic and methine, and U_iso(H) = 1.5U_eq(C) for methyl H-atoms. The highest residual electron density was located 1.05 Å from H1A and was essentially meaningless.

Figures

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.

Crystal data

[Hf2(C10H6F3O2)6(OH)2]·2C3H7NO	F(000) = 1792
Mr = 1828.08	Dx = 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

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

Refinement

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(Fo2) + (0.0285P)2 + 4.244P] where P = (Fo2 + 2Fc2)/3
8726 reflections	(Δ/σ)max = 0.004
475 parameters	Δρmax = 1.33 e Å−3
1 restraint	Δρmin = −0.97 e Å−3
1 constraint

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, −y+1, −z+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)