supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

ng2389 scheme

Acta Cryst. (2008). E64, m361    [ doi:10.1107/S1600536807061417 ]

Dichlorido-1[kappa]Cl,3[kappa]Cl-hexakis[1,1,2,2,3,3([eta]5)-methylcyclopentadienyl]di-[mu]2-oxido-1:2[kappa]2O:O;2:3[kappa]2O:O-trihafnium(IV)

A. Wisniewska, K. Baranowska and J. Pikies

Abstract top

The title compound, [Hf3(C6H7)6Cl2O2], is a trinuclear molecule having two (MeCp)2HfCl units (MeCp is methylcyclopentadienyl) each connected to an (MeCp)2Hf unit by an oxide bridge. The two Hf-O-Hf bridges are nearly linear. The geometry of the three Hf atoms is tetrahedral (assuming the MeCp group occupies one coordination site); the O-Hf-O angle is 99.8 (5)°. One of the Cl atoms is disordered, with site occupancies of 0.61 (7) and 0.39 (7).

Comment top

The molecular structure of (1) is shown in Fig.1. The crystal structure of (1) is build up of discrete molecules. The geometry of the central Hf atom in (1) is distorted pseudotetrahedral (O1—Hf2—O2 angle is 99.99 °) similar to the geometry of Cl—Hf—Cl in [(η5-C5H4Me)2HfCl2] (Wisniewska et al., 2007). The Hf—Cl distances are in the typical range for hafnocene dichlorides. The Hf1—O1—Hf2 and Hf3—O2—Hf2 angles are large (172.91 and 178.82°.). It is typical for Hf—O—Hf moieties (Fronczek et al., 1976; Parkanyi et al., 1993). The related angles in cyclic tris(µ2-Oxo)-tris(hafnocene) are smaller (142.61°.) (Rogers et al., 1982). The Hf—O distances 1.852Å - 2.024 Å are in typical range for hafnocene - oxygen moieties.

Related literature top

For another dichloridobis(η5-methylcyclopentadienyl)hafnium(IV) compound, see Wisniewska et al. (2007). For tris(µ2-oxo)-tris(hafnocene) toluene solvate, see Rogers et al. (1982). For (µ2-oxo)-bis(methylohafnocene), see Fronczek et al. (1976). For (µ2-oxo)-bis(chlorohafnocene) see Parkanyi et al. (1993).

Experimental top

The title compound [(η5-CH3C5H4)2HfCl-O-(η5-CH3C5H4)2Hf—O-(η5-CH3C5H4)2HfCl] (1) has been isolated as a colourless crystals in a reaction of (CpMe)2HfCl2 with (iPr2N)2P—P(SiMe3)Li 2,5 THF in Toluene. After standing for 1 day at room temperature, the mixture was dried under vacuum at 1 mTorr (1 Torr = 133.322 Pa) for 1 h, and the residue dissolved in pentane (4 ml) and filtered. After 2 days at 243 K, the solution yielded small colorless crystals of (1).

Explanation. [(η5-CH3C5H4)2HfCl-O-(η5-CH3C5H4)2Hf—O-(η5-CH3C5H4)2HfCl] (1) is a byproduct in the reaction of (CH3C5H4)Li with HfCl4 in mol ratio 2:1. The commercially available hafnium tetrachloride contains probably Cl3Hf—O-HfCl2—O-HfCl3, which reacts with (CH3C5H4)Li yielding small amounts of (1).

Refinement top

All H atoms were refined as riding on C atoms with aromatic C—H = 0.95 Å, methyl C—H = 0.98 Å, and Uiso(H) = 1.2Ueq(C) for CH groups, 1.5Ueq(C) for CH3 groups. Atom Cl2 is disordered (0.61 (7)/0.39 (7)). Two methylcyclopentadienyl molecules (C13–C18 and C19–C24) were constrained to be flat.

The largest peak/deepest hole in the final difference Fourier map was in the vicinity of the hafnium atoms.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (1), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
Dichlorido-1κCl,3κCl-hexakis[1,1,2,2,3,3(η5)-methylcyclopentadienyl]di- µ2-oxido-1:2κ2O:O;2:3κ2O:O-trihafnium(IV) top
Crystal data top
[Hf3(C6H7)6Cl2O2]F000 = 2096
Mr = 1113.07Dx = 2.168 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6065 reflections
a = 18.9598 (10) Åθ = 1.9–32.4º
b = 12.9710 (5) ŵ = 9.30 mm−1
c = 14.6178 (6) ÅT = 120 (2) K
β = 108.466 (4)ºPrism, colourless
V = 3409.8 (3) Å30.1 × 0.08 × 0.04 mm
Z = 4
Data collection top
Oxford Diffraction KM4 CCD
diffractometer		5801 independent reflections
Monochromator: graphite4052 reflections with I > 2σ(I)
Detector resolution: 8.1883 pixels mm-1Rint = 0.057
T = 120(2) Kθmax = 25.1º
ω scans, 0.75 deg widthθmin = 1.9º
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2006)		h = −21→22
Tmin = 0.283, Tmax = 0.434k = −7→15
11353 measured reflectionsl = −16→17
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.061H-atom parameters constrained
wR(F2) = 0.185  w = 1/[σ2(Fo2) + (0.1162P)2 + 4.6904P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.002
5801 reflectionsΔρmax = 2.41 e Å−3
284 parametersΔρmin = −2.70 e Å−3
6 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Hf3(C6H7)6Cl2O2]V = 3409.8 (3) Å3
Mr = 1113.07Z = 4
Monoclinic, P21/cMo Kα
a = 18.9598 (10) ŵ = 9.30 mm−1
b = 12.9710 (5) ÅT = 120 (2) K
c = 14.6178 (6) Å0.1 × 0.08 × 0.04 mm
β = 108.466 (4)º
Data collection top
Oxford Diffraction KM4 CCD
diffractometer		5801 independent reflections
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2006)		4052 reflections with I > 2σ(I)
Tmin = 0.283, Tmax = 0.434Rint = 0.057
11353 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0616 restraints
wR(F2) = 0.185H-atom parameters constrained
S = 1.06Δρmax = 2.41 e Å−3
5801 reflectionsΔρmin = −2.70 e Å−3
284 parameters
Special details top

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.

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 > σ(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
xyzUiso*/UeqOcc. (<1)
Hf10.11659 (4)0.32908 (5)0.39912 (5)0.0309 (2)
Hf20.31749 (4)0.38207 (5)0.56434 (5)0.0279 (2)
Hf30.30910 (4)0.67984 (5)0.58248 (5)0.0331 (2)
O10.2183 (6)0.3553 (8)0.4746 (9)0.037 (3)
O20.3134 (7)0.5372 (8)0.5725 (10)0.049 (4)
Cl10.0620 (3)0.3676 (3)0.5261 (4)0.0450 (11)
Cl20.2938 (12)0.741 (3)0.4165 (7)0.056 (7)0.61 (7)
Cl2A0.319 (2)0.693 (3)0.4198 (12)0.051 (8)0.39 (7)
C10.0637 (13)0.3899 (16)0.2276 (16)0.059 (6)
H10.04840.33990.17760.07*
C20.1362 (13)0.4306 (14)0.2644 (15)0.052 (5)
H20.17770.4110.24520.062*
C30.1366 (13)0.5039 (13)0.3334 (15)0.049 (5)
H30.17740.54610.36760.059*
C40.0661 (11)0.5041 (13)0.3434 (15)0.046 (5)
H40.05140.54460.38840.056*
C50.0181 (11)0.4330 (14)0.2745 (16)0.050 (5)
C6−0.0606 (12)0.4165 (17)0.261 (2)0.070 (7)
H6A−0.07770.35490.22110.105*
H6B−0.08910.47650.22850.105*
H6C−0.06790.40690.32370.105*
C70.1181 (10)0.1447 (13)0.4586 (17)0.051 (5)
H70.13310.13320.52620.061*
C80.1654 (14)0.1518 (14)0.398 (3)0.075 (9)
H80.21790.14370.41810.09*
C90.1227 (14)0.1712 (15)0.3092 (19)0.059 (6)
H90.140.18120.25550.07*
C100.0499 (14)0.1749 (12)0.3057 (16)0.051 (5)
H100.00840.18680.24980.062*
C110.0472 (13)0.1584 (14)0.3974 (19)0.057 (6)
C12−0.0240 (13)0.1464 (17)0.426 (2)0.068 (7)
H12A−0.0380.07350.42280.102*
H12B−0.06430.1860.38090.102*
H12C−0.01490.17220.49150.102*
C130.3497 (13)0.3140 (18)0.4161 (18)0.066 (3)
H130.3110.28750.36270.079*
C140.3922 (12)0.2589 (19)0.4995 (17)0.066 (3)
H140.38620.18790.51120.079*
C150.4404 (13)0.3201 (17)0.5573 (19)0.066 (3)
H150.47490.30.61740.079*
C160.4349 (13)0.4140 (19)0.5209 (17)0.066 (3)
H160.46440.47170.55020.079*
C170.3762 (12)0.4144 (18)0.4285 (17)0.066 (3)
C180.3580 (13)0.5119 (17)0.3697 (18)0.066 (3)
H18A0.39020.51730.3290.08*
H18B0.36620.57150.4130.08*
H18C0.30590.51030.32890.08*
C190.2593 (18)0.283 (2)0.6744 (16)0.081 (3)
H190.21370.24780.64480.097*
C200.2703 (18)0.381 (2)0.7065 (15)0.081 (3)
H200.23090.42850.7020.097*
C210.3378 (18)0.404 (2)0.7429 (15)0.081 (3)
H210.35420.47070.76850.097*
C220.3828 (19)0.330 (2)0.7422 (16)0.081 (3)
H220.43550.33310.76670.097*
C230.3394 (17)0.242 (2)0.6982 (13)0.081 (3)
C240.3580 (17)0.1362 (19)0.6783 (17)0.081 (3)
H24A0.31990.11030.62050.08*
H24B0.360.0920.73340.08*
H24C0.40650.13580.66760.08*
C250.3903 (12)0.8149 (18)0.6894 (18)0.064 (3)
H250.3660.87460.70230.076*
C260.3995 (12)0.7254 (17)0.7377 (18)0.064 (3)
H260.38310.71270.79180.076*
C270.4380 (12)0.6501 (18)0.6960 (18)0.064 (3)
H270.45190.58160.71720.076*
C280.4500 (12)0.7013 (17)0.6182 (18)0.064 (3)
H280.47210.67170.57450.076*
C290.4241 (12)0.8036 (18)0.6143 (18)0.064 (3)
C300.4338 (12)0.8816 (17)0.5436 (17)0.064 (3)
H30A0.38890.9240.52040.08*
H30B0.44240.84610.48890.08*
H30C0.47650.92580.57520.08*
C310.2248 (13)0.7771 (18)0.658 (2)0.071 (3)
H310.2440.82310.71090.086*
C320.2150 (13)0.6754 (18)0.665 (2)0.071 (3)
H320.23120.63630.72290.086*
C330.1776 (13)0.6357 (19)0.574 (2)0.071 (3)
H330.15890.56750.56080.086*
C340.1724 (13)0.7119 (17)0.508 (2)0.071 (3)
H340.15260.70460.44030.086*
C350.2015 (14)0.8040 (18)0.559 (2)0.071 (3)
C360.2008 (13)0.9084 (16)0.520 (2)0.071 (3)
H36A0.15040.93680.50240.08*
H36B0.21660.90570.4620.08*
H36C0.23490.95250.56830.08*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hf10.0263 (4)0.0324 (4)0.0300 (4)−0.0008 (3)0.0031 (3)−0.0028 (3)
Hf20.0227 (4)0.0375 (4)0.0232 (4)−0.0005 (3)0.0069 (3)0.0003 (3)
Hf30.0318 (4)0.0381 (4)0.0296 (4)−0.0057 (3)0.0101 (3)−0.0056 (3)
O10.032 (7)0.036 (6)0.041 (7)0.001 (5)0.009 (6)0.003 (5)
O20.039 (8)0.031 (6)0.078 (11)−0.008 (5)0.019 (8)−0.003 (6)
Cl10.039 (3)0.046 (2)0.054 (3)0.0013 (19)0.021 (2)−0.009 (2)
Cl20.068 (9)0.058 (15)0.042 (5)−0.007 (9)0.019 (5)0.010 (5)
Cl2A0.086 (15)0.028 (13)0.043 (8)0.005 (12)0.026 (8)0.011 (6)
C10.058 (15)0.058 (12)0.044 (13)−0.004 (11)−0.005 (11)−0.001 (10)
C20.068 (15)0.048 (10)0.042 (12)0.000 (10)0.021 (12)0.012 (9)
C30.066 (15)0.030 (8)0.050 (13)0.003 (9)0.018 (11)0.004 (9)
C40.045 (12)0.035 (8)0.050 (13)−0.001 (8)0.003 (10)0.002 (9)
C50.043 (12)0.043 (10)0.059 (14)0.004 (9)0.009 (11)0.020 (10)
C60.043 (13)0.060 (12)0.10 (2)0.016 (10)0.013 (14)0.026 (13)
C70.021 (10)0.041 (9)0.067 (15)0.001 (7)−0.018 (10)−0.013 (10)
C80.047 (14)0.032 (10)0.15 (3)−0.003 (9)0.035 (18)−0.024 (14)
C90.061 (16)0.057 (12)0.066 (16)0.023 (11)0.031 (14)0.002 (11)
C100.076 (16)0.030 (9)0.043 (13)−0.004 (9)0.010 (12)−0.007 (8)
C110.056 (14)0.038 (10)0.080 (17)−0.018 (9)0.024 (13)−0.009 (10)
C120.051 (15)0.064 (13)0.10 (2)−0.008 (11)0.035 (14)−0.006 (13)
C130.070 (7)0.081 (6)0.059 (6)0.005 (5)0.035 (6)−0.003 (5)
C140.070 (7)0.081 (6)0.059 (6)0.005 (5)0.035 (6)−0.003 (5)
C150.070 (7)0.081 (6)0.059 (6)0.005 (5)0.035 (6)−0.003 (5)
C160.070 (7)0.081 (6)0.059 (6)0.005 (5)0.035 (6)−0.003 (5)
C170.070 (7)0.081 (6)0.059 (6)0.005 (5)0.035 (6)−0.003 (5)
C180.070 (7)0.081 (6)0.059 (6)0.005 (5)0.035 (6)−0.003 (5)
C190.106 (10)0.087 (7)0.057 (7)0.004 (7)0.038 (7)0.015 (6)
C200.106 (10)0.087 (7)0.057 (7)0.004 (7)0.038 (7)0.015 (6)
C210.106 (10)0.087 (7)0.057 (7)0.004 (7)0.038 (7)0.015 (6)
C220.106 (10)0.087 (7)0.057 (7)0.004 (7)0.038 (7)0.015 (6)
C230.106 (10)0.087 (7)0.057 (7)0.004 (7)0.038 (7)0.015 (6)
C240.106 (10)0.087 (7)0.057 (7)0.004 (7)0.038 (7)0.015 (6)
C250.038 (5)0.078 (6)0.069 (7)−0.027 (5)0.007 (5)−0.018 (5)
C260.038 (5)0.078 (6)0.069 (7)−0.027 (5)0.007 (5)−0.018 (5)
C270.038 (5)0.078 (6)0.069 (7)−0.027 (5)0.007 (5)−0.018 (5)
C280.038 (5)0.078 (6)0.069 (7)−0.027 (5)0.007 (5)−0.018 (5)
C290.038 (5)0.078 (6)0.069 (7)−0.027 (5)0.007 (5)−0.018 (5)
C300.038 (5)0.078 (6)0.069 (7)−0.027 (5)0.007 (5)−0.018 (5)
C310.047 (6)0.066 (5)0.091 (8)0.010 (5)0.009 (6)−0.015 (6)
C320.047 (6)0.066 (5)0.091 (8)0.010 (5)0.009 (6)−0.015 (6)
C330.047 (6)0.066 (5)0.091 (8)0.010 (5)0.009 (6)−0.015 (6)
C340.047 (6)0.066 (5)0.091 (8)0.010 (5)0.009 (6)−0.015 (6)
C350.047 (6)0.066 (5)0.091 (8)0.010 (5)0.009 (6)−0.015 (6)
C360.047 (6)0.066 (5)0.091 (8)0.010 (5)0.009 (6)−0.015 (6)
Geometric parameters (Å, °) top
Hf1—O11.925 (12)C10—H100.95
Hf1—Cl12.446 (4)C11—C121.54 (3)
Hf1—C92.46 (2)C12—H12A0.98
Hf1—C82.482 (19)C12—H12B0.98
Hf1—C22.493 (18)C12—H12C0.98
Hf1—C42.498 (18)C13—C171.39 (3)
Hf1—C12.51 (2)C13—C141.42 (3)
Hf1—C102.524 (18)C13—H130.95
Hf1—C32.538 (18)C14—C151.30 (3)
Hf1—C72.541 (19)C14—H140.95
Hf1—C52.543 (19)C15—C161.32 (3)
Hf1—C112.571 (18)C15—H150.95
Hf2—O11.953 (12)C16—C171.45 (4)
Hf2—O22.019 (11)C16—H160.95
Hf2—C152.498 (18)C17—C181.51 (3)
Hf2—C202.510 (19)C18—H18A0.98
Hf2—C142.511 (17)C18—H18B0.98
Hf2—C212.53 (2)C18—H18C0.98
Hf2—C162.536 (18)C19—C201.36 (4)
Hf2—C192.57 (2)C19—C231.54 (4)
Hf2—C132.586 (19)C19—H190.95
Hf2—C222.59 (2)C20—C211.26 (4)
Hf2—C172.599 (15)C20—H200.95
Hf2—C232.606 (17)C21—C221.29 (4)
Hf3—O21.859 (11)C21—H210.95
Hf3—C262.44 (2)C22—C231.44 (4)
Hf3—Cl2A2.447 (17)C22—H220.95
Hf3—C322.45 (3)C23—C241.47 (3)
Hf3—Cl22.479 (13)C24—H24A0.98
Hf3—C342.51 (2)C24—H24B0.98
Hf3—C272.51 (2)C24—H24C0.98
Hf3—C252.52 (2)C25—C261.34 (3)
Hf3—C332.52 (2)C25—C291.44 (3)
Hf3—C352.54 (2)C25—H250.95
Hf3—C312.55 (2)C26—C271.46 (3)
Hf3—C282.57 (2)C26—H260.95
C1—C51.38 (3)C27—C281.40 (3)
C1—C21.41 (3)C27—H270.95
C1—H10.95C28—C291.41 (3)
C2—C31.39 (3)C28—H280.95
C2—H20.95C29—C301.50 (3)
C3—C41.39 (3)C30—H30A0.98
C3—H30.95C30—H30B0.98
C4—C51.45 (3)C30—H30C0.98
C4—H40.95C31—C321.34 (3)
C5—C61.46 (3)C31—C351.43 (4)
C6—H6A0.98C31—H310.95
C6—H6B0.98C32—C331.39 (4)
C6—H6C0.98C32—H320.95
C7—C111.37 (3)C33—C341.36 (4)
C7—C81.45 (3)C33—H330.95
C7—H70.95C34—C351.42 (3)
C8—C91.31 (4)C34—H340.95
C8—H80.95C35—C361.47 (3)
C9—C101.37 (3)C36—H36A0.98
C9—H90.95C36—H36B0.98
C10—C111.37 (3)C36—H36C0.98
O1—Hf1—Cl196.7 (4)C1—C2—Hf174.5 (12)
O1—Hf1—C9104.2 (7)C3—C2—H2125.8
Cl1—Hf1—C9132.8 (6)C1—C2—H2125.8
O1—Hf1—C881.9 (7)Hf1—C2—H2116
Cl1—Hf1—C8116.4 (7)C2—C3—C4107.1 (19)
C9—Hf1—C830.9 (8)C2—C3—Hf172.2 (10)
O1—Hf1—C289.2 (6)C4—C3—Hf172.4 (10)
Cl1—Hf1—C2134.2 (5)C2—C3—H3126.5
C9—Hf1—C288.5 (7)C4—C3—H3126.5
C8—Hf1—C2109.5 (9)Hf1—C3—H3120.7
O1—Hf1—C4103.7 (5)C3—C4—C5109.8 (19)
Cl1—Hf1—C481.5 (5)C3—C4—Hf175.6 (11)
C9—Hf1—C4131.4 (8)C5—C4—Hf175.0 (10)
C8—Hf1—C4160.9 (9)C3—C4—H4125.1
C2—Hf1—C453.1 (7)C5—C4—H4125.1
O1—Hf1—C1121.8 (6)Hf1—C4—H4116.2
Cl1—Hf1—C1124.2 (6)C1—C5—C4104.4 (19)
C9—Hf1—C178.4 (8)C1—C5—C6130 (2)
C8—Hf1—C1108.3 (10)C4—C5—C6125 (2)
C2—Hf1—C132.7 (7)C1—C5—Hf173.0 (12)
C4—Hf1—C153.1 (7)C4—C5—Hf171.6 (11)
O1—Hf1—C10133.6 (6)C6—C5—Hf1120.5 (13)
Cl1—Hf1—C10108.2 (5)C5—C6—H6A109.5
C9—Hf1—C1031.8 (7)C5—C6—H6B109.5
C8—Hf1—C1052.1 (8)H6A—C6—H6B109.5
C2—Hf1—C1099.5 (7)C5—C6—H6C109.5
C4—Hf1—C10118.0 (7)H6A—C6—H6C109.5
C1—Hf1—C1074.7 (7)H6B—C6—H6C109.5
O1—Hf1—C379.4 (6)C11—C7—C8105 (2)
Cl1—Hf1—C3104.7 (5)C11—C7—Hf175.7 (11)
C9—Hf1—C3120.3 (7)C8—C7—Hf171.0 (12)
C8—Hf1—C3136.4 (8)C11—C7—H7127.5
C2—Hf1—C332.0 (6)C8—C7—H7127.5
C4—Hf1—C332.0 (6)Hf1—C7—H7118.1
C1—Hf1—C353.3 (7)C9—C8—C7108 (2)
C10—Hf1—C3127.8 (7)C9—C8—Hf173.5 (13)
O1—Hf1—C794.0 (5)C7—C8—Hf175.4 (11)
Cl1—Hf1—C783.9 (5)C9—C8—H8126.1
C9—Hf1—C753.2 (8)C7—C8—H8126.1
C8—Hf1—C733.6 (8)Hf1—C8—H8117.1
C2—Hf1—C7141.2 (7)C8—C9—C10110 (2)
C4—Hf1—C7158.2 (6)C8—C9—Hf175.7 (14)
C1—Hf1—C7126.4 (7)C10—C9—Hf176.8 (11)
C10—Hf1—C752.3 (7)C8—C9—H9124.9
C3—Hf1—C7169.6 (7)C10—C9—H9124.9
O1—Hf1—C5133.8 (5)Hf1—C9—H9114.5
Cl1—Hf1—C592.6 (5)C9—C10—C11108 (2)
C9—Hf1—C5102.0 (8)C9—C10—Hf171.4 (12)
C8—Hf1—C5132.6 (9)C11—C10—Hf176.3 (11)
C2—Hf1—C554.1 (7)C9—C10—H10126.1
C4—Hf1—C533.5 (6)C11—C10—H10126.1
C1—Hf1—C531.7 (7)Hf1—C10—H10118.2
C10—Hf1—C584.5 (7)C7—C11—C10109 (2)
C3—Hf1—C554.5 (7)C7—C11—C12125 (2)
C7—Hf1—C5132.1 (6)C10—C11—C12126 (2)
O1—Hf1—C11125.0 (6)C7—C11—Hf173.3 (11)
Cl1—Hf1—C1181.1 (5)C10—C11—Hf172.5 (11)
C9—Hf1—C1152.2 (7)C12—C11—Hf1125.0 (14)
C8—Hf1—C1152.6 (7)C11—C12—H12A109.5
C2—Hf1—C11130.6 (7)C11—C12—H12B109.5
C4—Hf1—C11129.6 (7)H12A—C12—H12B109.5
C1—Hf1—C11102.7 (8)C11—C12—H12C109.5
C10—Hf1—C1131.3 (7)H12A—C12—H12C109.5
C3—Hf1—C11154.6 (8)H12B—C12—H12C109.5
C7—Hf1—C1131.1 (7)C17—C13—C14106 (2)
C5—Hf1—C11101.1 (7)C17—C13—Hf275.0 (10)
O1—Hf2—O299.8 (5)C14—C13—Hf270.9 (9)
O1—Hf2—C15128.9 (7)C17—C13—H13127
O2—Hf2—C15112.2 (6)C14—C13—H13127
O1—Hf2—C2092.0 (8)Hf2—C13—H13119.1
O2—Hf2—C2085.6 (7)C15—C14—C13110 (2)
C15—Hf2—C20128.0 (9)C15—C14—Hf274.4 (10)
O1—Hf2—C1499.8 (7)C13—C14—Hf276.7 (9)
O2—Hf2—C14133.9 (7)C15—C14—H14125
C15—Hf2—C1430.1 (7)C13—C14—H14125
C20—Hf2—C14134.6 (8)Hf2—C14—H14115.8
O1—Hf2—C21120.8 (8)C14—C15—C16111 (3)
O2—Hf2—C2179.7 (7)C14—C15—Hf275.5 (10)
C15—Hf2—C21103.9 (9)C16—C15—Hf276.3 (9)
C20—Hf2—C2128.9 (8)C14—C15—H15124.7
C14—Hf2—C21122.9 (9)C16—C15—H15124.7
O1—Hf2—C16126.6 (7)Hf2—C15—H15115.3
O2—Hf2—C1684.6 (6)C15—C16—C17108 (2)
C15—Hf2—C1630.4 (7)C15—C16—Hf273.2 (9)
C20—Hf2—C16141.2 (9)C17—C16—Hf276.0 (10)
C14—Hf2—C1650.6 (8)C15—C16—H16125.8
C21—Hf2—C16112.4 (9)C17—C16—H16125.8
O1—Hf2—C1979.5 (8)Hf2—C16—H16117
O2—Hf2—C19115.5 (7)C13—C17—C16105 (2)
C15—Hf2—C19117.1 (8)C13—C17—C18135 (2)
C20—Hf2—C1931.0 (8)C16—C17—C18120 (2)
C14—Hf2—C19108.9 (8)C13—C17—Hf274.0 (9)
C21—Hf2—C1950.7 (9)C16—C17—Hf271.2 (9)
C16—Hf2—C19145.6 (9)C18—C17—Hf2119.7 (7)
O1—Hf2—C1379.0 (6)C17—C18—H18A109.5
O2—Hf2—C13114.4 (6)C17—C18—H18B109.5
C15—Hf2—C1352.0 (8)H18A—C18—H18B109.5
C20—Hf2—C13159.0 (8)C17—C18—H18C109.5
C14—Hf2—C1332.4 (7)H18A—C18—H18C109.5
C21—Hf2—C13154.7 (9)H18B—C18—H18C109.5
C16—Hf2—C1352.2 (8)C20—C19—C23102 (3)
C19—Hf2—C13128.1 (8)C20—C19—Hf272.2 (10)
O1—Hf2—C22132.9 (7)C23—C19—Hf274.1 (10)
O2—Hf2—C22102.4 (7)C20—C19—H19128.8
C15—Hf2—C2278.6 (9)C23—C19—H19128.8
C20—Hf2—C2249.5 (10)Hf2—C19—H19117.6
C14—Hf2—C2293.8 (8)C21—C20—C19113 (3)
C21—Hf2—C2229.1 (8)C21—C20—Hf276.5 (12)
C16—Hf2—C2296.6 (9)C19—C20—Hf276.8 (10)
C19—Hf2—C2253.4 (9)C21—C20—H20123.4
C13—Hf2—C22126.0 (8)C19—C20—H20123.4
O1—Hf2—C1794.0 (7)Hf2—C20—H20114.8
O2—Hf2—C1785.3 (6)C20—C21—C22114 (3)
C15—Hf2—C1752.4 (8)C20—C21—Hf274.6 (12)
C20—Hf2—C17169.8 (8)C22—C21—Hf278.0 (11)
C14—Hf2—C1752.1 (7)C20—C21—H21123
C21—Hf2—C17143.8 (9)C22—C21—H21123
C16—Hf2—C1732.9 (8)Hf2—C21—H21115.7
C19—Hf2—C17158.9 (8)C21—C22—C23108 (3)
C13—Hf2—C1731.0 (7)C21—C22—Hf272.9 (12)
C22—Hf2—C17128.7 (9)C23—C22—Hf274.5 (11)
O1—Hf2—C23105.7 (8)C21—C22—H22125.9
O2—Hf2—C23130.6 (7)C23—C22—H22125.9
C15—Hf2—C2383.0 (8)Hf2—C22—H22118.6
C20—Hf2—C2352.4 (8)C22—C23—C24134 (3)
C14—Hf2—C2382.2 (8)C22—C23—C19102 (2)
C21—Hf2—C2350.9 (8)C24—C23—C19124 (3)
C16—Hf2—C23111.0 (9)C22—C23—Hf273.3 (11)
C19—Hf2—C2334.7 (8)C24—C23—Hf2119.6 (8)
C13—Hf2—C23111.5 (8)C19—C23—Hf271.3 (10)
C22—Hf2—C2332.1 (8)C23—C24—H24A109.5
C17—Hf2—C23132.9 (8)C23—C24—H24B109.5
O2—Hf3—C26106.2 (7)H24A—C24—H24B109.5
O2—Hf3—Cl2A88.4 (10)C23—C24—H24C109.5
C26—Hf3—Cl2A129.8 (8)H24A—C24—H24C109.5
O2—Hf3—C3294.1 (7)H24B—C24—H24C109.5
C26—Hf3—C3287.4 (8)C26—C25—C29107 (2)
Cl2A—Hf3—C32140.3 (12)C26—C25—Hf371.2 (12)
O2—Hf3—Cl2103.5 (10)C29—C25—Hf377.8 (12)
C26—Hf3—Cl2131.5 (6)C26—C25—H25126.3
Cl2A—Hf3—Cl218.0 (4)C29—C25—H25126.3
C32—Hf3—Cl2127.7 (9)Hf3—C25—H25116.8
O2—Hf3—C34101.3 (7)C25—C26—C27111 (2)
C26—Hf3—C34133.3 (8)C25—C26—Hf377.6 (14)
Cl2A—Hf3—C3487.3 (13)C27—C26—Hf375.4 (13)
C32—Hf3—C3453.3 (9)C25—C26—H26124.5
Cl2—Hf3—C3474.9 (9)C27—C26—H26124.5
O2—Hf3—C2780.9 (7)Hf3—C26—H26114.4
C26—Hf3—C2734.3 (7)C28—C27—C26105 (2)
Cl2A—Hf3—C27107.3 (12)C28—C27—Hf376.3 (14)
C32—Hf3—C27112.3 (9)C26—C27—Hf370.3 (13)
Cl2—Hf3—C27118.9 (8)C28—C27—H27127.7
C34—Hf3—C27165.4 (9)C26—C27—H27127.7
O2—Hf3—C25135.0 (7)Hf3—C27—H27118
C26—Hf3—C2531.3 (7)C27—C28—C29110 (2)
Cl2A—Hf3—C25109.7 (7)C27—C28—Hf371.8 (13)
C32—Hf3—C2596.2 (8)C29—C28—Hf376.6 (13)
Cl2—Hf3—C25104.2 (8)C27—C28—H28125.2
C34—Hf3—C25119.8 (8)C29—C28—H28125.2
C27—Hf3—C2554.7 (8)Hf3—C28—H28118.2
O2—Hf3—C3380.7 (6)C28—C29—C25107 (2)
C26—Hf3—C33119.3 (8)C28—C29—C30123 (2)
Cl2A—Hf3—C33110.2 (10)C25—C29—C30130 (2)
C32—Hf3—C3332.4 (8)C28—C29—Hf372.0 (11)
Cl2—Hf3—C33102.6 (8)C25—C29—Hf369.7 (11)
C34—Hf3—C3331.4 (8)C30—C29—Hf3124.5 (15)
C27—Hf3—C33137.4 (8)C29—C30—H30A109.5
C25—Hf3—C33125.9 (8)C29—C30—H30B109.5
O2—Hf3—C35132.4 (7)H30A—C30—H30B109.5
C26—Hf3—C35105.7 (8)C29—C30—H30C109.5
Cl2A—Hf3—C3597.3 (14)H30A—C30—H30C109.5
C32—Hf3—C3553.3 (9)H30B—C30—H30C109.5
Cl2—Hf3—C3579.9 (11)C32—C31—C35108 (2)
C34—Hf3—C3532.7 (7)C32—C31—Hf370.4 (14)
C27—Hf3—C35139.5 (8)C35—C31—Hf373.2 (14)
C25—Hf3—C3587.2 (8)C32—C31—H31126
C33—Hf3—C3553.0 (8)C35—C31—H31126
O2—Hf3—C31125.1 (7)Hf3—C31—H31122
C26—Hf3—C3180.1 (8)C31—C32—C33110 (3)
Cl2A—Hf3—C31129.7 (14)C31—C32—Hf378.6 (16)
C32—Hf3—C3131.0 (7)C33—C32—Hf376.8 (16)
Cl2—Hf3—C31111.9 (11)C31—C32—H32125.1
C34—Hf3—C3153.2 (9)C33—C32—H32125.1
C27—Hf3—C31113.7 (8)Hf3—C32—H32111.8
C25—Hf3—C3174.3 (8)C34—C33—C32108 (2)
C33—Hf3—C3152.2 (8)C34—C33—Hf373.6 (14)
C35—Hf3—C3132.6 (8)C32—C33—Hf370.9 (14)
O2—Hf3—C2893.2 (6)C34—C33—H33126
C26—Hf3—C2853.6 (8)C32—C33—H33126
Cl2A—Hf3—C2878.4 (10)Hf3—C33—H33121.2
C32—Hf3—C28140.8 (9)C33—C34—C35108 (3)
Cl2—Hf3—C2887.5 (7)C33—C34—Hf374.9 (14)
C34—Hf3—C28159.4 (8)C35—C34—Hf374.7 (14)
C27—Hf3—C2831.9 (8)C33—C34—H34125.9
C25—Hf3—C2853.7 (8)C35—C34—H34125.9
C33—Hf3—C28169.1 (8)Hf3—C34—H34116.5
C35—Hf3—C28134.3 (8)C34—C35—C31106 (2)
C31—Hf3—C28127.8 (8)C34—C35—C36128 (3)
Hf1—O1—Hf2173.3 (7)C31—C35—C36126 (2)
Hf3—O2—Hf2178.7 (8)C34—C35—Hf372.6 (13)
C5—C1—C2110.2 (19)C31—C35—Hf374.2 (13)
C5—C1—Hf175.3 (12)C36—C35—Hf3123.1 (17)
C2—C1—Hf172.8 (11)C35—C36—H36A109.5
C5—C1—H1124.9C35—C36—H36B109.5
C2—C1—H1124.9H36A—C36—H36B109.5
Hf1—C1—H1118.7C35—C36—H36C109.5
C3—C2—C1108 (2)H36A—C36—H36C109.5
C3—C2—Hf175.8 (11)H36B—C36—H36C109.5
Table 1
Selected geometric parameters (Å, °) top
Hf1—O11.925 (12)Hf2—O22.019 (11)
Hf1—Cl12.446 (4)Hf3—O21.859 (11)
Hf2—O11.953 (12)Hf3—Cl22.479 (13)
O1—Hf1—Cl196.7 (4)Hf1—O1—Hf2173.3 (7)
O1—Hf2—O299.8 (5)Hf3—O2—Hf2178.7 (8)
O2—Hf3—Cl2103.5 (10)
Acknowledgements top

The authors thank Dr Jarosław Chojnacki for helpful comments.

references
References top

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Fronczek, F. R., Baker, E. C., Raymond, K. N., Alt, H. G. & Rausch, M. D. (1976). Inorg. Chem. 15, 2284–2289.

Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Versions 1.171.29.9. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.

Parkanyi, L., Sharma, S., Cervantes-Lee, F. & Pannell, K. H. (1993). Z. Kristallogr. 208, 335–337.

Rogers, R. D., Bynum, R. V. & Atwood, J. L. (1982). J. Crystallogr. Spectrosc. Res. 12, 239–244.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Wisniewska, A., Baranowska, K. & Pikies, J. (2007). Acta Cryst. E63, m2174–?.