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Acta Cryst. (2008). E64, m667    [ doi:10.1107/S1600536808009574 ]

Bis([eta]5-cyclopentadienyl)bis(2,4,6-trimethylphenyltellurolato)zirconium(IV)

A. L. Hector, W. Levason, G. Reid, S. D. Reid and M. Webster

Abstract top

The structure of the title compound, [Zr(C5H5)2(C9H11Te)2], consists of a zirconium(IV) centre bonded to two [eta]5-coordinated cyclopentadienyl groups and two mesityltellurolate ligands; the discrete molecule has crystallographic twofold rotation symmetry. The structural parameters compared with those in [([eta]5-Me5Cp)2Zr(TePh)2] [Howard, Trnka & Parkin (1995). Inorg. Chem. 34, 5900-5909] show that the greater steric demands of the bulky mesityl substituents are accommodated by widening Te-Zr-Te (~8°) and by more acute Zr-Te-C (~5°) angles, although the Zr-Te distances are essentially the same. The crystal studied exhibited some inversion twinning.

Comment top

Thiolate ligands (RS-) form complexes with most metals and metalloids in the Periodic Table. In contrast, much less is known about corresponding selenolates (RSe-), and few tellurolate (RTe-) complexes have been characterized in detail (Arnold, 1995). The latter include [(η5-Me5Cp)2Zr(TePh)2] prepared from [(η5-Me5Cp)2Zr(CO)2], PhOH and Ph2Te2, (Howard et al., 1995) and [(η5-Cp)2Zr(TePh)2] prepared from [(η5-Cp)2ZrCl2] and PhTeLi, (Sato & Yoshida, 1974). We have recently characterized a range of complexes of Ti, Zr and Hf (M) of type [(η5-Cp)2M(SetBu)2] and shown that these complexes serve as single-source precursors for LPCVD (low pressure chemical vapour deposition) of MSe2 films (Hector et al., 2008), but that the corresponding t-butyltellurolates decompose to deposit elemental tellurium. During attempts to improve the stability of the tellurato-complexes, we obtained crystals of the title complex which we now report.

Red crystals of the title compound (I) were obtained in poor yield by reaction of [(η5-Cp)2ZrCl2] with (Me3C6H2)TeMgBr in anhydrous THF solution. The discrete molecule has 2-fold crystallographic symmetry, and shows the typical metallocene geometry with η5-coordinated Cp rings (Zr—C 2.455 (7)–2.519 (8) Å, 2.49 (3) Å (av)) rather shorter than those in [(η5-Me5Cp)2Zr(TePh)2] (2.56 (5) Å (av)) (Howard et al., 1995), but similar to those in the silyltellurolate [(η5-Cp)2Zr{TeSi(SiMe3)3}2] (2.50 (1) Å (av)) (Christou et al., 1993). The Zr—Te distances in [(η5-Cp)2Zr{TeSi(SiMe3)3}2] (2.866 (1) Å), [(η5-Cp)2Zr(TeC6H2Me3)2] (2.869 (1) Å), and [(η5-Me5Cp)2Zr(TePh)2] (2.87 (2) Å) are very similar as are the Te—C distances in the last two compounds (2.150 (7) and 2.12 (2) Å respectively). A more notable difference is in the Te—Zr—Te and Zr—Te—C angles between [(η5-Cp)2Zr(TeC6H2Me3)2] and [(η5-Me5Cp)2Zr(TePh)2] with Te—Zr—Te 105.34 (5) ° versus 97.2 (1) °, and Zr—Te—C 108.06 (16) ° versus 113.1 (7) °, consistent with the greater steric effects of the mesityl groups.

Related literature top

For a review, see: Arnold (1995). For related structures, see: Christou et al. (1993); Hector et al. (2008); Howard et al. (1995); Sato & Yoshida (1974).

Experimental top

To a stirred suspension of Mg turnings (66 mg, 2.72 mmol) in THF (30 ml) was added MesBr (56 mg, 2.82 mmol). The resulting mixture was stirred for 2 h, after which the Grignard was transferred by cannula to a suspension of freshly ground Te powder (300 mg, 2.35 mmol) in THF (10 ml). The mixture turned orange and was stirred for 1 h. Cp2ZrCl2 (345 mg, 1.18 mmol) was dissolved in THF (10 ml) and the Grignard solution added dropwise by cannula, during which time the solution turned red. The reaction was allowed to proceed overnight. The volatiles were removed in vacuo, the residue extracted with CH2Cl2 (20 ml) and filtered through celite. The solvent was removed under reduced pressure, the residue crystallized from Et2O to produce a small number of red crystals. 125Te{1H} NMR (CH2Cl2/CDCl3, 300 K): δTe = 887 p.p.m.

Refinement top

H atoms were placed in calculated positions [C—H = 0.95 (aromatic and Cp) and 0.98 Å (methyl)]. Uiso(H) values for methyl H atoms were set at 1.5Ueq(C) of the bonded C, and the rest at 1.2Ueq(C). Racemic twinning was allowed in the final refinement. The number of Friedel pairs measured is 1405.

Computing details top

Data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); data reduction: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The discrete molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are omitted for clarity. Symmetry operation: a = 1 - x, 1 - y, z.
Bis(η5-cyclopentadienyl)bis(2,4,6-trimethylphenyltellurolato)zirconium(IV) top
Crystal data top
[Zr(C5H5)2(C9H11Te)2]F000 = 1376
Mr = 714.96Dx = 1.737 Mg m−3
Orthorhombic, Aba2Mo Kα radiation
λ = 0.71073 Å
Hall symbol: A 2 -2acCell parameters from 7078 reflections
a = 9.0483 (15) Åθ = 2.9–27.5º
b = 21.881 (6) ŵ = 2.51 mm−1
c = 13.806 (4) ÅT = 120 (2) K
V = 2733.3 (12) Å3Plate, red
Z = 40.20 × 0.10 × 0.02 mm
Data collection top
Bruker Nonius KappaCCD
diffractometer		3046 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode2444 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.059
T = 120(2) Kθmax = 27.5º
φ and ω scansθmin = 3.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)		h = −9→11
Tmin = 0.758, Tmax = 0.951k = −28→26
9201 measured reflectionsl = −17→16
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.040  w = 1/[σ2(Fo2) + (0.0276P)2 + 1.8865P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.087(Δ/σ)max = 0.001
S = 1.05Δρmax = 1.50 e Å−3
3046 reflectionsΔρmin = −1.16 e Å−3
145 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), 1405 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.14 (5)
Secondary atom site location: difference Fourier map
Crystal data top
[Zr(C5H5)2(C9H11Te)2]V = 2733.3 (12) Å3
Mr = 714.96Z = 4
Orthorhombic, Aba2Mo Kα
a = 9.0483 (15) ŵ = 2.51 mm−1
b = 21.881 (6) ÅT = 120 (2) K
c = 13.806 (4) Å0.20 × 0.10 × 0.02 mm
Data collection top
Bruker Nonius KappaCCD
diffractometer		3046 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)		2444 reflections with I > 2σ(I)
Tmin = 0.758, Tmax = 0.951Rint = 0.059
9201 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.087Δρmax = 1.50 e Å−3
S = 1.05Δρmin = −1.16 e Å−3
3046 reflectionsAbsolute structure: Flack (1983), 1405 Friedel pairs
145 parametersFlack parameter: 0.14 (5)
1 restraint
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*/Ueq
Zr10.50000.5000−0.06403 (8)0.01613 (16)
Te10.74620 (4)0.522546 (15)0.06201 (7)0.02158 (12)
C10.4387 (14)0.6120 (4)−0.0508 (8)0.066 (3)
H10.43890.63550.00700.079*
C20.3184 (8)0.5854 (4)−0.0922 (6)0.043 (2)
H20.22080.5869−0.06700.052*
C30.3574 (7)0.5607 (3)−0.1807 (6)0.0324 (16)
H30.29150.5453−0.22840.039*
C40.5054 (9)0.5768 (3)−0.1952 (7)0.051 (2)
H40.55780.5726−0.25440.062*
C50.5545 (11)0.6072 (4)−0.1164 (10)0.067 (4)
H50.64750.6271−0.11100.081*
C60.7316 (6)0.6154 (3)0.1121 (5)0.0222 (14)
C70.6309 (7)0.6307 (3)0.1845 (4)0.0221 (16)
C80.6241 (7)0.6926 (3)0.2140 (6)0.0278 (15)
H80.55450.70390.26240.033*
C90.7141 (8)0.7370 (4)0.1756 (6)0.0293 (19)
C100.8146 (8)0.7201 (3)0.1041 (6)0.0312 (17)
H100.87730.75020.07640.037*
C110.8248 (6)0.6597 (3)0.0723 (6)0.0261 (14)
C120.5339 (7)0.5842 (3)0.2340 (5)0.0296 (17)
H12A0.47870.56110.18520.044*
H12B0.46440.60520.27710.044*
H12C0.59550.55620.27190.044*
C130.6987 (9)0.8020 (4)0.2084 (7)0.041 (2)
H13A0.59760.81610.19610.062*
H13B0.76850.82780.17270.062*
H13C0.71980.80460.27790.062*
C140.9425 (8)0.6443 (4)−0.0014 (6)0.0388 (19)
H14A0.89580.6352−0.06380.058*
H14B0.99840.60850.02070.058*
H14C1.00970.6791−0.00880.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zr10.0179 (3)0.0137 (3)0.0168 (3)0.0028 (3)0.0000.000
Te10.02085 (18)0.01997 (19)0.0239 (2)0.00485 (15)−0.00464 (18)−0.0039 (2)
C10.139 (10)0.024 (4)0.035 (7)0.037 (5)−0.038 (7)−0.002 (4)
C20.033 (4)0.041 (5)0.055 (7)0.022 (3)0.023 (4)0.028 (4)
C30.049 (4)0.014 (3)0.035 (4)−0.002 (3)−0.028 (4)0.003 (3)
C40.065 (5)0.039 (4)0.050 (6)0.032 (4)0.032 (6)0.034 (4)
C50.060 (6)0.016 (5)0.126 (11)−0.014 (4)−0.053 (7)0.028 (6)
C60.022 (3)0.022 (3)0.022 (4)0.006 (2)−0.004 (3)−0.006 (3)
C70.023 (3)0.026 (4)0.017 (4)0.002 (3)−0.003 (2)−0.008 (3)
C80.024 (3)0.023 (4)0.036 (4)0.003 (3)−0.002 (3)−0.009 (3)
C90.025 (4)0.031 (5)0.032 (5)−0.002 (3)−0.002 (3)−0.013 (4)
C100.032 (4)0.028 (4)0.033 (5)−0.007 (3)0.003 (3)−0.007 (3)
C110.019 (3)0.027 (3)0.032 (4)−0.003 (2)0.002 (3)0.002 (3)
C120.037 (4)0.028 (4)0.023 (4)−0.002 (3)0.002 (3)−0.004 (3)
C130.039 (4)0.030 (5)0.055 (6)0.003 (4)0.001 (4)−0.013 (4)
C140.033 (4)0.044 (5)0.040 (5)−0.010 (3)0.016 (3)−0.015 (4)
Geometric parameters (Å, °) top
Zr1—C12.519 (8)C5—H50.9500
Zr1—C22.519 (7)C6—C71.393 (9)
Zr1—C32.455 (7)C6—C111.398 (9)
Zr1—C42.470 (7)C7—C81.415 (9)
Zr1—C52.504 (8)C7—C121.507 (9)
Zr1—C3i2.455 (7)C8—C91.375 (11)
Zr1—C4i2.470 (7)C8—H80.9500
Zr1—C5i2.504 (8)C9—C101.393 (11)
Zr1—C2i2.519 (7)C9—C131.499 (12)
Zr1—C1i2.519 (8)C10—C111.395 (9)
Zr1—Te12.8694 (10)C10—H100.9500
Zr1—Te1i2.8694 (10)C11—C141.512 (9)
Te1—C62.150 (7)C12—H12A0.9800
C1—C21.360 (13)C12—H12B0.9800
C1—C51.390 (15)C12—H12C0.9800
C1—H10.9500C13—H13A0.9800
C2—C31.382 (12)C13—H13B0.9800
C2—H20.9500C13—H13C0.9800
C3—C41.399 (10)C14—H14A0.9800
C3—H30.9500C14—H14B0.9800
C4—C51.350 (13)C14—H14C0.9800
C4—H40.9500
C3—Zr1—C3i98.0 (4)C2—C1—C5107.3 (9)
C3—Zr1—C4i82.9 (3)C2—C1—Zr174.3 (5)
C3i—Zr1—C4i33.0 (2)C5—C1—Zr173.3 (6)
C3—Zr1—C433.0 (2)C2—C1—H1125.9
C3i—Zr1—C482.9 (3)C5—C1—H1125.9
C4i—Zr1—C485.7 (5)Zr1—C1—H1125.9
C3—Zr1—C5i102.3 (4)C1—C2—C3109.6 (7)
C3i—Zr1—C5i53.6 (2)C1—C2—Zr174.3 (4)
C4i—Zr1—C5i31.5 (3)C3—C2—Zr171.3 (4)
C4—Zr1—C5i115.4 (5)C1—C2—H2125.1
C3—Zr1—C553.6 (2)C3—C2—H2125.1
C3i—Zr1—C5102.3 (4)Zr1—C2—H2125.1
C4i—Zr1—C5115.4 (5)C2—C3—C4105.8 (7)
C4—Zr1—C531.5 (3)C2—C3—Zr176.4 (4)
C5i—Zr1—C5146.4 (6)C4—C3—Zr174.1 (4)
C3—Zr1—C2i130.0 (3)C2—C3—H3126.3
C3i—Zr1—C2i32.2 (3)C4—C3—H3126.3
C4i—Zr1—C2i52.8 (2)Zr1—C3—H3126.3
C4—Zr1—C2i112.2 (3)C5—C4—C3108.9 (8)
C5i—Zr1—C2i52.3 (3)C5—C4—Zr175.6 (5)
C5—Zr1—C2i121.5 (3)C3—C4—Zr172.9 (4)
C3—Zr1—C232.2 (3)C5—C4—H4125.2
C3i—Zr1—C2130.0 (3)C3—C4—H4125.2
C4i—Zr1—C2112.2 (3)Zr1—C4—H4125.2
C4—Zr1—C252.8 (2)C4—C5—C1108.3 (8)
C5i—Zr1—C2121.5 (3)C4—C5—Zr172.9 (5)
C5—Zr1—C252.3 (3)C1—C5—Zr174.5 (6)
C2i—Zr1—C2162.2 (4)C4—C5—H5125.6
C3—Zr1—C1i133.6 (3)C1—C5—H5125.6
C3i—Zr1—C1i53.5 (3)Zr1—C5—H5125.6
C4i—Zr1—C1i52.8 (3)C7—C6—C11120.6 (6)
C4—Zr1—C1i135.3 (3)C7—C6—Te1119.9 (5)
C5i—Zr1—C1i32.1 (3)C11—C6—Te1119.5 (5)
C5—Zr1—C1i152.7 (3)C6—C7—C8117.7 (6)
C2i—Zr1—C1i31.3 (3)C6—C7—C12123.0 (6)
C2—Zr1—C1i151.2 (3)C8—C7—C12119.3 (6)
C3—Zr1—C153.5 (3)C9—C8—C7122.6 (7)
C3i—Zr1—C1133.6 (3)C9—C8—H8118.7
C4i—Zr1—C1135.3 (3)C7—C8—H8118.7
C4—Zr1—C152.8 (3)C8—C9—C10118.2 (7)
C5i—Zr1—C1152.7 (3)C8—C9—C13119.9 (7)
C5—Zr1—C132.1 (3)C10—C9—C13121.8 (8)
C2i—Zr1—C1151.2 (3)C9—C10—C11121.2 (7)
C2—Zr1—C131.3 (3)C9—C10—H10119.4
C1i—Zr1—C1171.7 (5)C11—C10—H10119.4
C3—Zr1—Te1135.49 (14)C10—C11—C6119.6 (6)
C3i—Zr1—Te194.75 (19)C10—C11—C14118.1 (6)
C4i—Zr1—Te1125.22 (16)C6—C11—C14122.3 (6)
C4—Zr1—Te1108.2 (2)C7—C12—H12A109.5
C5i—Zr1—Te1119.3 (3)C7—C12—H12B109.5
C5—Zr1—Te182.0 (2)H12A—C12—H12B109.5
C2i—Zr1—Te173.43 (16)C7—C12—H12C109.5
C2—Zr1—Te1118.2 (2)H12A—C12—H12C109.5
C1i—Zr1—Te187.3 (3)H12B—C12—H12C109.5
C1—Zr1—Te187.7 (3)C9—C13—H13A109.5
C3—Zr1—Te1i94.75 (19)C9—C13—H13B109.5
C3i—Zr1—Te1i135.49 (14)H13A—C13—H13B109.5
C4i—Zr1—Te1i108.2 (2)C9—C13—H13C109.5
C4—Zr1—Te1i125.22 (16)H13A—C13—H13C109.5
C5i—Zr1—Te1i82.0 (2)H13B—C13—H13C109.5
C5—Zr1—Te1i119.3 (3)C11—C14—H14A109.5
C2i—Zr1—Te1i118.2 (2)C11—C14—H14B109.5
C2—Zr1—Te1i73.43 (16)H14A—C14—H14B109.5
C1i—Zr1—Te1i87.7 (3)C11—C14—H14C109.5
C1—Zr1—Te1i87.3 (3)H14A—C14—H14C109.5
Te1—Zr1—Te1i105.34 (5)H14B—C14—H14C109.5
C6—Te1—Zr1108.06 (16)
Zr1—Te1—C6—C777.0 (5)Te1i—Zr1—Te1—C6−79.80 (19)
Zr1—Te1—C6—C11−103.8 (5)
Symmetry codes: (i) −x+1, −y+1, z.
Table 1
Selected geometric parameters (Å, °) top
Zr1—C12.519 (8)Zr1—C52.504 (8)
Zr1—C22.519 (7)Zr1—Te12.8694 (10)
Zr1—C32.455 (7)Te1—C62.150 (7)
Zr1—C42.470 (7)
Te1—Zr1—Te1i105.34 (5)C7—C6—C11120.6 (6)
C6—Te1—Zr1108.06 (16)
Zr1—Te1—C6—C777.0 (5)Te1i—Zr1—Te1—C6−79.80 (19)
Zr1—Te1—C6—C11−103.8 (5)
Symmetry codes: (i) −x+1, −y+1, z.
Acknowledgements top

The authors thank the EPSRC for support (grant EP/C001176/1), and for access to the Chemical Database Service at Daresbury.

references
References top

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