supplementary materials


pk2450 scheme

Acta Cryst. (2012). E68, m1425    [ doi:10.1107/S1600536812044121 ]

Di-[mu]-sulfido-bis{[rac-1,2-bis([eta]5-4,5,6,7-tetrahydroinden-1-yl)ethane]zirconium(IV)} toluene monosolvate

M. Haehnel, K. Altenburger, A. Spannenberg, P. Arndt and U. Rosenthal

Abstract top

The title dimeric zirconium complex, [Zr2(C20H24)2S2]·C7H8, was obtained from the reaction of (ebthi)Zr([eta]2-Me3Si-C2-SiMe3) [ebthi is rac-1,2-bis([eta]5-4,5,6,7-tetrahydroinden-1-yl)ethane] and S=C=N-ada (ada = adamantan-1-yl) along with the formation of the isonitrile C[triple bond]N-ada. Each ZrIV atom is coordinated by the sterically hindered ebthi ligand and two [mu]-sulfide ligands in a strongly distorted tetrahedral geometry. The [ZrS]2 unit is almost planar (mean deviation from the best plane of the four atoms = 0.025 Å). A -CH2-CH2- group in one ebthi ligand was disordered over two sites, with refined occupancy factors of 0.551 (6) and 0.449 (6). The asymmetric unit also contains a toluene solvent molecule.

Comment top

The reaction of isothiocyanates with metallocene precursors L2M(η2-Me3Si—C2—SiMe3) (L 2 = ebthi, Cp2, Cp*2, M = Ti, Zr) was investigated with the aim of synthesizing new 4-membered hetero-metallacycles. In this reaction, a C—S bond cleavage occurred leading to two different products. In addition to a dimeric bis(µ-sulfido) bridged zirconium complex, the formation of the organic N-adamantyl-isocyanide was observed.

In the title compound each zirconium atom is coordinated by two sulfido and the chelating ebthi ligand (Fig. 1). The geometry at the zirconium centers is strongly distorted tetrahedral. The largest deviation from the ideal tetrahedral angle is observed for S1—Zr2—S2 angle with 89.27 (2)°. The [ZrS]2 unit is almost planar (mean deviation from the best plane: 0.025 Å); bond lengths and angles of the [ZrS]2 unit are comparable with those of [Cp2Zr(µ-S)]2 (Bottomley et al., 1986 and Hey et al., 1987). Angles between the planes defined by Zr1, S1, Zr2, S2 and each of the five-membered rings of the ebthi ligands are 31.67 (8)° and 28.28 (5)° (for the ligand coordinated to Zr2), 30.74 (5)° and 28.86 (9)° (for the ligand coordinated to Zr1), respectively. The asymmetric unit of the title compound also contains a toluene solvent molecule.

Related literature top

For µ-sulfide-bridged [Cp2M(µ-S)]2 metallocenes (Cp = C5H5), see: for M = Zr, Bottomley et al. (1986); Hey et al. (1987); for M = Nb, Skripkin et al. (1984). Furthermore, for [Cp'2Th(µ-S)]2 (Cp' = 1,2,4-tri-tert-butylcyclopentadienyl), see: Ren et al. (2011); for [Cp'2Ta(µ-S)]2 (Cp' = C5H4Me), see: Winkler et al. (1998). The starting alkyne complex (ebthi)Zr(η2-Me3Si–C2–SiMe3) was described by Lefeber et al. (1996). For µ-sulfide complexes with a further bridged ligand Cp'M(µ-S)2LMCp', L = µ2-η10-fulvalene, Cp' = Cp, M = Zr, see: Wielstra et al. (1990), L = µ2-bis(η5-cyclopentadienyl)dimethylsilane, Cp' = Cp (cyclopentadienyl), M = Zr, see: Cacciola et al. (1992), L = µ2-bis(η5-cyclopentadienyl)dimethylsilane, Cp' = Cp* (pentamethylcyclopentadienyl), M = Zr, see: Burstynowicz et al. (1995).

Experimental top

To a solution of 469 mg (0,892 mmol) of (ebthi)Zr(η2-Me3Si—C2—SiMe3) in 15 ml of n-hexane was added dropwise a solution of 172 mg (0,892 mmol) N-adamantylisothiocyanate in 10 ml of n-hexane. Instantly, the reaction mixture turned from green to dark red and a colourless solid precipitated. The reaction mixture was allowed to stand for 12 h. After filtration, the dark red solution was evaporated in vacuo. The precipitate was dissolved in 8 ml of toluene, filtered and stored at -40°C. After 7 days, the dark red crystalline product was filtered, washed with cold toluene and dried in vacuo. Yield: 79% (273 mg, 0.212 mmol). Crystals suitable for X-ray analysis were obtained from a saturated solution in toluene at -40°C.

Refinement top

H atoms were placed in idealized positions with d(C—H) = 0.95 Å (CH), 0.99 Å (CH2) and 0.98 Å (CH3) and refined using a riding model with Uiso(H) fixed at 1.2 Ueq(C) for CH, CH2 and 1.5 Ueq(C) for CH3. Atoms C25A, C26A and C25B, C26B are disordered over two sites with occupancies of 0.551 (6):0.449 (6). The SADI instruction was used to improve the geometry of this disordered part of the complex molecule. The largest diff. peak/hole (1.30/-0.89 e Å-3) were 0.58 Å from C26B and 0.36 Å from C25B, respectively. Additional difference map peaks of 0.97 and 0.89 e Å-3 were consistent with disorder of atoms C17 and C18, but was not modelled owing to the low occupancy and comparatively poor definition of the minor component.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with 30% displacement ellipsoids. Hydrogen atoms are omitted for clarity. Minor disorder is indicated by open bonds.
Di-µ-sulfido-bis{[rac-1,2-bis(η5-4,5,6,7-tetrahydroinden-1- yl)ethane]zirconium(IV)} toluene monosolvate top
Crystal data top
[Zr2(C20H24)2S2]·C7H8F(000) = 1800
Mr = 867.48Dx = 1.512 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 12.6436 (3) ÅCell parameters from 15221 reflections
b = 20.9735 (4) Åθ = 1.7–28.4°
c = 14.8855 (3) ŵ = 0.69 mm1
β = 105.092 (2)°T = 150 K
V = 3811.20 (14) Å3Prism, red
Z = 40.60 × 0.30 × 0.25 mm
Data collection top
Stoe IPDS II
diffractometer
9109 independent reflections
Radiation source: fine-focus sealed tube7869 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
ω scansθmax = 27.9°, θmin = 1.7°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2005)
h = 1616
Tmin = 0.777, Tmax = 0.854k = 2727
65438 measured reflectionsl = 1919
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.045P)2 + 1.0943P]
where P = (Fo2 + 2Fc2)/3
9109 reflections(Δ/σ)max = 0.001
460 parametersΔρmax = 1.30 e Å3
15 restraintsΔρmin = 0.89 e Å3
Crystal data top
[Zr2(C20H24)2S2]·C7H8V = 3811.20 (14) Å3
Mr = 867.48Z = 4
Monoclinic, P21/nMo Kα radiation
a = 12.6436 (3) ŵ = 0.69 mm1
b = 20.9735 (4) ÅT = 150 K
c = 14.8855 (3) Å0.60 × 0.30 × 0.25 mm
β = 105.092 (2)°
Data collection top
Stoe IPDS II
diffractometer
9109 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2005)
7869 reflections with I > 2σ(I)
Tmin = 0.777, Tmax = 0.854Rint = 0.036
65438 measured reflectionsθmax = 27.9°
Refinement top
R[F2 > 2σ(F2)] = 0.027H-atom parameters constrained
wR(F2) = 0.072Δρmax = 1.30 e Å3
S = 1.05Δρmin = 0.89 e Å3
9109 reflectionsAbsolute structure: ?
460 parametersFlack parameter: ?
15 restraintsRogers parameter: ?
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)
C25A0.2121 (3)0.1623 (2)0.4520 (3)0.0404 (12)*0.551 (6)
H25A0.22800.20370.48480.049*0.551 (6)
H25B0.17320.17170.38660.049*0.551 (6)
C26A0.1337 (4)0.12520 (15)0.4955 (3)0.0382 (12)*0.551 (6)
H26A0.16990.11370.56080.046*0.551 (6)
H26B0.06760.15080.49430.046*0.551 (6)
C25B0.2419 (3)0.1579 (3)0.5029 (3)0.0382 (14)*0.449 (6)
H25C0.24740.20490.50750.046*0.449 (6)
H25D0.25460.13970.56610.046*0.449 (6)
C26B0.1309 (4)0.13715 (14)0.4406 (4)0.0396 (15)*0.449 (6)
H26C0.12640.15200.37660.048*0.449 (6)
H26D0.07310.15980.46180.048*0.449 (6)
C10.50936 (16)0.19785 (9)0.22541 (14)0.0230 (4)
H10.46870.23640.21990.028*
C20.52098 (16)0.15239 (9)0.29785 (13)0.0225 (4)
H20.49000.15540.34940.027*
C30.58632 (15)0.10219 (9)0.28007 (12)0.0202 (4)
C40.63471 (16)0.04717 (10)0.34053 (13)0.0250 (4)
H4A0.58270.01100.32880.030*
H4B0.64860.05950.40680.030*
C50.74167 (18)0.02721 (11)0.31970 (15)0.0310 (4)
H5A0.77000.01190.35510.037*
H5B0.79690.06130.33950.037*
C60.72301 (18)0.01473 (10)0.21574 (15)0.0286 (4)
H6A0.66480.01780.19580.034*
H6B0.79110.00260.20410.034*
C70.68978 (16)0.07526 (9)0.15759 (13)0.0224 (4)
H7A0.75620.10040.15790.027*
H7B0.65430.06320.09240.027*
C80.61232 (15)0.11573 (9)0.19452 (13)0.0190 (3)
C90.56845 (15)0.17622 (9)0.16281 (13)0.0207 (4)
C100.58321 (16)0.21113 (9)0.07888 (13)0.0237 (4)
H10A0.66240.21650.08440.028*
H10B0.55030.25410.07670.028*
C110.53012 (16)0.17568 (9)0.01194 (13)0.0238 (4)
H11A0.51840.20580.06490.029*
H11B0.58000.14160.02200.029*
C120.42250 (15)0.14693 (9)0.00862 (12)0.0198 (3)
C130.39478 (16)0.08163 (9)0.01703 (12)0.0199 (3)
H130.44210.04790.02410.024*
C140.28447 (16)0.07491 (9)0.01315 (12)0.0204 (3)
H140.24510.03600.01730.025*
C150.24360 (15)0.13585 (9)0.00212 (12)0.0202 (3)
C160.12816 (16)0.15500 (10)0.00663 (14)0.0245 (4)
H16A0.11310.14720.05450.029*
H16B0.07690.12860.05360.029*
C170.10925 (19)0.22487 (10)0.03208 (18)0.0351 (5)
H17A0.10570.23070.09880.042*
H17B0.03820.23850.02210.042*
C180.19963 (19)0.26570 (11)0.02570 (18)0.0361 (5)
H18A0.20480.25840.09240.043*
H18B0.18130.31120.01200.043*
C190.31256 (18)0.25125 (9)0.00682 (15)0.0267 (4)
H19A0.31550.27050.05320.032*
H19B0.37170.27040.05650.032*
C200.32987 (16)0.18022 (9)0.00388 (12)0.0198 (3)
C210.32446 (17)0.04410 (10)0.40258 (13)0.0247 (4)
H210.35610.08380.39310.030*
C220.37861 (17)0.01546 (10)0.41415 (13)0.0257 (4)
H220.45260.02270.41370.031*
C230.30386 (17)0.06192 (10)0.42636 (13)0.0243 (4)
C240.3222 (2)0.13084 (11)0.45239 (15)0.0367 (5)
H24A0.35520.15280.40750.044*0.551 (6)
H24B0.37330.13450.51510.044*0.551 (6)
H24C0.31680.15600.39510.044*0.449 (6)
H24D0.39750.13600.49260.044*0.449 (6)
C270.10359 (19)0.06559 (10)0.43584 (15)0.0321 (5)
H27A0.06300.03610.46660.038*0.551 (6)
H27B0.05420.07770.37500.038*0.551 (6)
H27C0.08910.05120.49490.038*0.449 (6)
H27D0.03780.05690.38440.038*0.449 (6)
C280.20182 (16)0.03123 (9)0.41942 (13)0.0222 (4)
C290.21537 (16)0.03484 (9)0.40748 (13)0.0221 (4)
C300.12928 (18)0.08483 (10)0.40185 (15)0.0291 (4)
H30A0.10590.08490.46040.035*
H30B0.16060.12730.39490.035*
C310.02935 (17)0.07298 (10)0.31952 (15)0.0287 (4)
H31A0.01390.11270.30490.034*
H31B0.01780.04000.33680.034*
C320.06350 (16)0.05142 (9)0.23489 (13)0.0224 (4)
C330.03826 (15)0.00736 (9)0.18818 (14)0.0225 (4)
H330.00150.04130.20610.027*
C340.08243 (15)0.00712 (9)0.10987 (13)0.0208 (4)
H340.07730.04080.06640.025*
C350.13508 (15)0.05170 (9)0.10778 (13)0.0195 (3)
C360.18216 (16)0.07917 (9)0.03361 (13)0.0226 (4)
H36A0.25890.06480.04350.027*
H36B0.13980.06380.02810.027*
C370.17838 (18)0.15160 (10)0.03607 (15)0.0284 (4)
H37A0.10140.16620.01560.034*
H37B0.21830.16930.00730.034*
C380.2300 (2)0.17573 (10)0.13383 (16)0.0327 (5)
H38A0.30540.15880.15550.039*
H38B0.23460.22280.13280.039*
C390.16376 (18)0.15550 (9)0.20201 (15)0.0279 (4)
H39A0.09890.18350.19380.033*
H39B0.20940.16080.26660.033*
C400.12679 (15)0.08734 (9)0.18699 (13)0.0207 (3)
C410.33335 (17)0.19999 (10)0.74341 (14)0.0279 (4)
C420.4157 (2)0.16460 (13)0.72132 (17)0.0386 (5)
H420.41000.11950.71810.046*
C430.5059 (2)0.19406 (17)0.7039 (2)0.0524 (7)
H430.56110.16910.68790.063*
C440.5164 (2)0.25879 (17)0.7095 (2)0.0562 (8)
H440.57850.27890.69740.067*
C450.4366 (3)0.29465 (14)0.7328 (2)0.0530 (7)
H450.44410.33970.73740.064*
C460.3448 (2)0.26551 (11)0.74982 (17)0.0373 (5)
H460.29000.29070.76580.045*
C470.23410 (19)0.16771 (12)0.75869 (16)0.0353 (5)
H47A0.25540.14050.81400.053*
H47B0.20010.14150.70430.053*
H47C0.18170.19990.76780.053*
S10.39577 (4)0.00729 (2)0.19018 (3)0.01783 (9)
S20.24917 (4)0.12761 (2)0.22003 (3)0.01908 (9)
Zr10.239232 (13)0.013567 (8)0.256989 (11)0.01540 (5)
Zr20.400064 (14)0.106505 (8)0.147091 (11)0.01518 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0213 (9)0.0203 (8)0.0276 (9)0.0034 (7)0.0067 (7)0.0073 (7)
C20.0213 (9)0.0272 (9)0.0198 (8)0.0051 (7)0.0067 (7)0.0069 (7)
C30.0182 (9)0.0257 (9)0.0160 (8)0.0038 (7)0.0035 (7)0.0030 (7)
C40.0221 (9)0.0334 (10)0.0176 (8)0.0009 (8)0.0017 (7)0.0032 (8)
C50.0238 (10)0.0404 (12)0.0263 (10)0.0041 (9)0.0021 (8)0.0046 (9)
C60.0273 (10)0.0309 (10)0.0279 (10)0.0062 (8)0.0077 (8)0.0009 (8)
C70.0205 (9)0.0255 (9)0.0226 (9)0.0003 (7)0.0080 (7)0.0007 (7)
C80.0164 (8)0.0218 (8)0.0186 (8)0.0037 (6)0.0045 (7)0.0026 (7)
C90.0194 (9)0.0199 (8)0.0225 (9)0.0041 (7)0.0052 (7)0.0033 (7)
C100.0223 (9)0.0231 (9)0.0268 (9)0.0047 (7)0.0082 (8)0.0019 (7)
C110.0245 (10)0.0261 (9)0.0227 (9)0.0017 (7)0.0096 (7)0.0034 (7)
C120.0234 (9)0.0206 (8)0.0155 (8)0.0001 (7)0.0051 (7)0.0018 (6)
C130.0245 (9)0.0190 (8)0.0161 (8)0.0020 (7)0.0050 (7)0.0007 (7)
C140.0246 (9)0.0191 (8)0.0169 (8)0.0022 (7)0.0042 (7)0.0003 (7)
C150.0212 (9)0.0224 (9)0.0161 (8)0.0007 (7)0.0030 (7)0.0027 (7)
C160.0196 (9)0.0282 (9)0.0245 (9)0.0020 (7)0.0034 (7)0.0041 (8)
C170.0293 (11)0.0288 (10)0.0476 (13)0.0062 (9)0.0107 (10)0.0095 (10)
C180.0331 (12)0.0261 (10)0.0484 (14)0.0049 (9)0.0092 (10)0.0019 (9)
C190.0316 (11)0.0174 (8)0.0293 (10)0.0015 (8)0.0050 (8)0.0008 (7)
C200.0229 (9)0.0196 (8)0.0164 (8)0.0005 (7)0.0042 (7)0.0012 (6)
C210.0264 (10)0.0300 (10)0.0181 (8)0.0077 (8)0.0065 (7)0.0063 (7)
C220.0198 (9)0.0392 (11)0.0167 (8)0.0012 (8)0.0023 (7)0.0029 (8)
C230.0301 (10)0.0283 (10)0.0141 (8)0.0036 (8)0.0050 (7)0.0008 (7)
C240.0554 (15)0.0327 (11)0.0228 (10)0.0155 (10)0.0119 (10)0.0081 (9)
C270.0333 (11)0.0382 (11)0.0277 (10)0.0095 (9)0.0134 (9)0.0009 (9)
C280.0247 (9)0.0264 (9)0.0165 (8)0.0025 (7)0.0071 (7)0.0016 (7)
C290.0250 (10)0.0249 (9)0.0171 (8)0.0010 (7)0.0067 (7)0.0043 (7)
C300.0352 (11)0.0286 (10)0.0269 (10)0.0061 (9)0.0142 (9)0.0051 (8)
C310.0256 (10)0.0333 (11)0.0312 (10)0.0083 (8)0.0145 (8)0.0016 (8)
C320.0174 (9)0.0254 (9)0.0248 (9)0.0037 (7)0.0059 (7)0.0018 (7)
C330.0172 (9)0.0248 (9)0.0243 (9)0.0005 (7)0.0035 (7)0.0034 (7)
C340.0182 (9)0.0207 (8)0.0206 (8)0.0000 (7)0.0000 (7)0.0002 (7)
C350.0160 (8)0.0207 (8)0.0200 (8)0.0031 (6)0.0017 (7)0.0016 (7)
C360.0209 (9)0.0267 (9)0.0196 (8)0.0022 (7)0.0040 (7)0.0034 (7)
C370.0307 (11)0.0247 (9)0.0326 (10)0.0046 (8)0.0134 (9)0.0089 (8)
C380.0362 (12)0.0222 (9)0.0417 (12)0.0058 (8)0.0134 (10)0.0003 (9)
C390.0335 (11)0.0201 (9)0.0304 (10)0.0007 (8)0.0087 (9)0.0022 (8)
C400.0178 (8)0.0209 (8)0.0230 (9)0.0040 (7)0.0044 (7)0.0008 (7)
C410.0255 (10)0.0341 (11)0.0212 (9)0.0011 (8)0.0009 (7)0.0035 (8)
C420.0326 (12)0.0429 (13)0.0388 (12)0.0003 (10)0.0068 (10)0.0076 (10)
C430.0313 (13)0.079 (2)0.0486 (15)0.0056 (13)0.0139 (12)0.0165 (15)
C440.0338 (14)0.083 (2)0.0502 (16)0.0235 (14)0.0073 (12)0.0054 (15)
C450.0510 (17)0.0402 (14)0.0564 (17)0.0174 (12)0.0062 (13)0.0109 (12)
C460.0334 (12)0.0328 (11)0.0392 (12)0.0031 (9)0.0021 (10)0.0032 (9)
C470.0323 (12)0.0446 (13)0.0289 (11)0.0055 (10)0.0080 (9)0.0020 (9)
S10.0170 (2)0.01675 (19)0.0200 (2)0.00062 (15)0.00529 (16)0.00071 (15)
S20.0206 (2)0.0177 (2)0.0203 (2)0.00193 (16)0.00786 (17)0.00083 (16)
Zr10.01483 (9)0.01683 (8)0.01446 (8)0.00059 (6)0.00366 (6)0.00105 (6)
Zr20.01572 (9)0.01542 (8)0.01456 (8)0.00112 (6)0.00423 (6)0.00050 (6)
Geometric parameters (Å, º) top
C25A—C26A1.531 (2)C21—C291.413 (3)
C25A—C241.539 (2)C21—Zr12.4707 (19)
C25A—H25A0.9900C21—H210.9500
C25A—H25B0.9900C22—C231.402 (3)
C26A—C271.523 (2)C22—Zr12.5363 (19)
C26A—H26A0.9900C22—H220.9500
C26A—H26B0.9900C23—C281.421 (3)
C25B—C241.522 (2)C23—C241.499 (3)
C25B—C26B1.531 (2)C23—Zr12.6419 (18)
C25B—H25C0.9900C24—H24A0.9900
C25B—H25D0.9900C24—H24B0.9900
C26B—C271.537 (2)C24—H24C0.9900
C26B—H26C0.9900C24—H24D0.9900
C26B—H26D0.9900C27—C281.510 (3)
C1—C91.412 (3)C27—H27A0.9900
C1—C21.418 (3)C27—H27B0.9900
C1—Zr22.4699 (18)C27—H27C0.9900
C1—H10.9500C27—H27D0.9900
C2—C31.405 (3)C28—C291.413 (3)
C2—Zr22.5521 (18)C28—Zr12.6081 (18)
C2—H20.9500C29—C301.498 (3)
C3—C81.424 (2)C29—Zr12.5479 (18)
C3—C41.493 (3)C30—C311.534 (3)
C3—Zr22.6542 (18)C30—H30A0.9900
C4—C51.523 (3)C30—H30B0.9900
C4—H4A0.9900C31—C321.504 (3)
C4—H4B0.9900C31—H31A0.9900
C5—C61.526 (3)C31—H31B0.9900
C5—H5A0.9900C32—C331.411 (3)
C5—H5B0.9900C32—C401.419 (3)
C6—C71.532 (3)C32—Zr12.5539 (19)
C6—H6A0.9900C33—C341.417 (3)
C6—H6B0.9900C33—Zr12.4834 (19)
C7—C81.504 (2)C33—H330.9500
C7—H7A0.9900C34—C351.406 (3)
C7—H7B0.9900C34—Zr12.5463 (19)
C8—C91.416 (3)C34—H340.9500
C8—Zr22.5984 (18)C35—C401.423 (3)
C9—C101.501 (3)C35—C361.499 (3)
C9—Zr22.5428 (18)C35—Zr12.6491 (18)
C10—C111.536 (3)C36—C371.520 (3)
C10—H10A0.9900C36—H36A0.9900
C10—H10B0.9900C36—H36B0.9900
C11—C121.501 (3)C37—C381.518 (3)
C11—H11A0.9900C37—H37A0.9900
C11—H11B0.9900C37—H37B0.9900
C12—C131.411 (3)C38—C391.534 (3)
C12—C201.417 (3)C38—H38A0.9900
C12—Zr22.5522 (17)C38—H38B0.9900
C13—C141.418 (3)C39—C401.503 (3)
C13—Zr22.4820 (17)C39—H39A0.9900
C13—H130.9500C39—H39B0.9900
C14—C151.404 (3)C40—Zr12.6105 (18)
C14—Zr22.5396 (18)C41—C461.382 (3)
C14—H140.9500C41—C421.386 (3)
C15—C201.419 (3)C41—C471.494 (3)
C15—C161.498 (3)C42—C431.380 (4)
C15—Zr22.6339 (18)C42—H420.9500
C16—C171.517 (3)C43—C441.365 (5)
C16—H16A0.9900C43—H430.9500
C16—H16B0.9900C44—C451.373 (5)
C17—C181.506 (3)C44—H440.9500
C17—H17A0.9900C45—C461.392 (4)
C17—H17B0.9900C45—H450.9500
C18—C191.555 (3)C46—H460.9500
C18—H18A0.9900C47—H47A0.9800
C18—H18B0.9900C47—H47B0.9800
C19—C201.508 (3)C47—H47C0.9800
C19—H19A0.9900S1—Zr12.4744 (5)
C19—H19B0.9900S1—Zr22.4757 (5)
C20—Zr22.5956 (18)S2—Zr12.4648 (5)
C21—C221.413 (3)S2—Zr22.4684 (5)
C26A—C25A—C24117.7 (3)C32—C31—H31A109.4
C26A—C25A—H25A107.9C30—C31—H31A109.4
C24—C25A—H25A107.9C32—C31—H31B109.4
C26A—C25A—H25B107.9C30—C31—H31B109.4
C24—C25A—H25B107.9H31A—C31—H31B108.0
H25A—C25A—H25B107.2C33—C32—C40107.52 (17)
C27—C26A—C25A105.2 (3)C33—C32—C31126.76 (18)
C27—C26A—H26A110.7C40—C32—C31125.72 (18)
C25A—C26A—H26A110.7C33—C32—Zr171.01 (11)
C27—C26A—H26B110.7C40—C32—Zr176.26 (11)
C25A—C26A—H26B110.7C31—C32—Zr1118.85 (13)
H26A—C26A—H26B108.8C32—C33—C34108.38 (17)
C24—C25B—C26B102.7 (3)C32—C33—Zr176.51 (11)
C24—C25B—H25C111.2C34—C33—Zr176.09 (11)
C26B—C25B—H25C111.2C32—C33—H33125.8
C24—C25B—H25D111.2C34—C33—H33125.8
C26B—C25B—H25D111.2Zr1—C33—H33113.9
H25C—C25B—H25D109.1C35—C34—C33108.15 (16)
C25B—C26B—C27117.7 (4)C35—C34—Zr178.37 (11)
C25B—C26B—H26C107.9C33—C34—Zr171.20 (11)
C27—C26B—H26C107.9C35—C34—H34125.9
C25B—C26B—H26D107.9C33—C34—H34125.9
C27—C26B—H26D107.9Zr1—C34—H34116.5
H26C—C26B—H26D107.2C34—C35—C40107.77 (16)
C9—C1—C2108.54 (17)C34—C35—C36129.39 (17)
C9—C1—Zr276.50 (11)C40—C35—C36122.50 (17)
C2—C1—Zr276.81 (11)C34—C35—Zr170.30 (10)
C9—C1—H1125.7C40—C35—Zr172.81 (10)
C2—C1—H1125.7C36—C35—Zr1127.59 (12)
Zr2—C1—H1113.3C35—C36—C37110.20 (16)
C3—C2—C1108.07 (16)C35—C36—H36A109.6
C3—C2—Zr278.39 (11)C37—C36—H36A109.6
C1—C2—Zr270.44 (10)C35—C36—H36B109.6
C3—C2—H2126.0C37—C36—H36B109.6
C1—C2—H2126.0H36A—C36—H36B108.1
Zr2—C2—H2117.2C38—C37—C36110.35 (17)
C2—C3—C8107.62 (16)C38—C37—H37A109.6
C2—C3—C4129.37 (17)C36—C37—H37A109.6
C8—C3—C4122.64 (17)C38—C37—H37B109.6
C2—C3—Zr270.36 (11)C36—C37—H37B109.6
C8—C3—Zr272.11 (10)H37A—C37—H37B108.1
C4—C3—Zr2128.37 (13)C37—C38—C39111.68 (18)
C3—C4—C5109.63 (16)C37—C38—H38A109.3
C3—C4—H4A109.7C39—C38—H38A109.3
C5—C4—H4A109.7C37—C38—H38B109.3
C3—C4—H4B109.7C39—C38—H38B109.3
C5—C4—H4B109.7H38A—C38—H38B107.9
H4A—C4—H4B108.2C40—C39—C38111.53 (16)
C4—C5—C6110.04 (17)C40—C39—H39A109.3
C4—C5—H5A109.7C38—C39—H39A109.3
C6—C5—H5A109.7C40—C39—H39B109.3
C4—C5—H5B109.7C38—C39—H39B109.3
C6—C5—H5B109.7H39A—C39—H39B108.0
H5A—C5—H5B108.2C32—C40—C35108.08 (16)
C5—C6—C7112.21 (17)C32—C40—C39128.66 (17)
C5—C6—H6A109.2C35—C40—C39122.41 (17)
C7—C6—H6A109.2C32—C40—Zr171.87 (10)
C5—C6—H6B109.2C35—C40—Zr175.81 (10)
C7—C6—H6B109.2C39—C40—Zr1126.58 (13)
H6A—C6—H6B107.9C46—C41—C42118.5 (2)
C8—C7—C6111.71 (16)C46—C41—C47121.1 (2)
C8—C7—H7A109.3C42—C41—C47120.4 (2)
C6—C7—H7A109.3C43—C42—C41120.9 (3)
C8—C7—H7B109.3C43—C42—H42119.5
C6—C7—H7B109.3C41—C42—H42119.5
H7A—C7—H7B107.9C44—C43—C42120.4 (3)
C9—C8—C3108.38 (16)C44—C43—H43119.8
C9—C8—C7128.31 (16)C42—C43—H43119.8
C3—C8—C7122.55 (17)C43—C44—C45119.7 (3)
C9—C8—Zr271.87 (10)C43—C44—H44120.2
C3—C8—Zr276.44 (10)C45—C44—H44120.2
C7—C8—Zr2125.69 (12)C44—C45—C46120.5 (3)
C1—C9—C8107.25 (16)C44—C45—H45119.8
C1—C9—C10126.46 (17)C46—C45—H45119.8
C8—C9—C10126.29 (17)C41—C46—C45120.1 (2)
C1—C9—Zr270.82 (10)C41—C46—H46120.0
C8—C9—Zr276.19 (10)C45—C46—H46120.0
C10—C9—Zr2119.11 (12)C41—C47—H47A109.5
C9—C10—C11112.09 (15)C41—C47—H47B109.5
C9—C10—H10A109.2H47A—C47—H47B109.5
C11—C10—H10A109.2C41—C47—H47C109.5
C9—C10—H10B109.2H47A—C47—H47C109.5
C11—C10—H10B109.2H47B—C47—H47C109.5
H10A—C10—H10B107.9Zr1—S1—Zr290.427 (15)
C12—C11—C10110.96 (15)Zr1—S2—Zr290.824 (15)
C12—C11—H11A109.4S2—Zr1—C21129.41 (5)
C10—C11—H11A109.4S2—Zr1—S189.383 (15)
C12—C11—H11B109.4C21—Zr1—S193.11 (5)
C10—C11—H11B109.4S2—Zr1—C3393.72 (5)
H11A—C11—H11B108.0C21—Zr1—C33120.12 (7)
C13—C12—C20107.18 (16)S1—Zr1—C33131.65 (5)
C13—C12—C11126.39 (17)S2—Zr1—C2297.31 (5)
C20—C12—C11126.43 (17)C21—Zr1—C2232.76 (7)
C13—C12—Zr271.00 (10)S1—Zr1—C2286.40 (5)
C20—C12—Zr275.72 (10)C33—Zr1—C22140.52 (6)
C11—C12—Zr2118.65 (12)S2—Zr1—C3486.16 (4)
C12—C13—C14108.48 (16)C21—Zr1—C34142.41 (7)
C12—C13—Zr276.48 (10)S1—Zr1—C3499.79 (4)
C14—C13—Zr275.84 (10)C33—Zr1—C3432.71 (6)
C12—C13—H13125.8C22—Zr1—C34172.97 (6)
C14—C13—H13125.8S2—Zr1—C29127.41 (5)
Zr2—C13—H13114.2C21—Zr1—C2932.67 (6)
C15—C14—C13108.06 (16)S1—Zr1—C29124.97 (5)
C15—C14—Zr277.99 (11)C33—Zr1—C2989.95 (6)
C13—C14—Zr271.38 (10)C22—Zr1—C2953.71 (6)
C15—C14—H14126.0C34—Zr1—C29119.41 (6)
C13—C14—H14126.0S2—Zr1—C32125.62 (5)
Zr2—C14—H14116.7C21—Zr1—C3291.02 (7)
C14—C15—C20107.71 (16)S1—Zr1—C32127.88 (4)
C14—C15—C16128.51 (17)C33—Zr1—C3232.49 (6)
C20—C15—C16123.43 (17)C22—Zr1—C32119.96 (6)
C14—C15—Zr270.58 (10)C34—Zr1—C3253.45 (6)
C20—C15—Zr272.77 (10)C29—Zr1—C3266.57 (6)
C16—C15—Zr2127.54 (12)S2—Zr1—C2895.81 (4)
C15—C16—C17111.01 (17)C21—Zr1—C2853.08 (6)
C15—C16—H16A109.4S1—Zr1—C28139.01 (5)
C17—C16—H16A109.4C33—Zr1—C2888.67 (6)
C15—C16—H16B109.4C22—Zr1—C2852.62 (6)
C17—C16—H16B109.4C34—Zr1—C28121.08 (6)
H16A—C16—H16B108.0C29—Zr1—C2831.78 (6)
C18—C17—C16111.10 (19)C32—Zr1—C2880.41 (6)
C18—C17—H17A109.4S2—Zr1—C40138.74 (4)
C16—C17—H17A109.4C21—Zr1—C4091.20 (7)
C18—C17—H17B109.4S1—Zr1—C4096.07 (4)
C16—C17—H17B109.4C33—Zr1—C4053.16 (6)
H17A—C17—H17B108.0C22—Zr1—C40123.79 (6)
C17—C18—C19112.46 (19)C34—Zr1—C4052.59 (6)
C17—C18—H18A109.1C29—Zr1—C4081.43 (6)
C19—C18—H18A109.1C32—Zr1—C4031.87 (6)
C17—C18—H18B109.1C28—Zr1—C40105.89 (6)
C19—C18—H18B109.1S2—Zr1—C2379.60 (4)
H18A—C18—H18B107.8C21—Zr1—C2352.77 (6)
C20—C19—C18110.16 (17)S1—Zr1—C23111.74 (5)
C20—C19—H19A109.6C33—Zr1—C23116.28 (6)
C18—C19—H19A109.6C22—Zr1—C2331.33 (6)
C20—C19—H19B109.6C34—Zr1—C23145.01 (6)
C18—C19—H19B109.6C29—Zr1—C2352.55 (6)
H19A—C19—H19B108.1C32—Zr1—C23111.73 (6)
C12—C20—C15108.46 (16)C28—Zr1—C2331.41 (6)
C12—C20—C19128.45 (17)C40—Zr1—C23133.87 (6)
C15—C20—C19122.33 (17)S2—Zr1—C35110.94 (4)
C12—C20—Zr272.35 (10)C21—Zr1—C35119.37 (6)
C15—C20—Zr275.75 (10)S1—Zr1—C3581.18 (4)
C19—C20—Zr2125.86 (13)C33—Zr1—C3552.79 (6)
C22—C21—C29108.69 (18)C22—Zr1—C35148.84 (6)
C22—C21—Zr176.17 (11)C34—Zr1—C3531.32 (6)
C29—C21—Zr176.67 (11)C29—Zr1—C35112.61 (6)
C22—C21—H21125.7C32—Zr1—C3552.44 (6)
C29—C21—H21125.7C28—Zr1—C35132.85 (6)
Zr1—C21—H21113.8C40—Zr1—C3531.38 (6)
C23—C22—C21107.98 (18)C23—Zr1—C35163.98 (6)
C23—C22—Zr178.49 (11)S2—Zr2—C193.14 (5)
C21—C22—Zr171.07 (11)S2—Zr2—S189.273 (15)
C23—C22—H22126.0C1—Zr2—S1132.29 (5)
C21—C22—H22126.0S2—Zr2—C13130.15 (5)
Zr1—C22—H22116.5C1—Zr2—C13119.74 (6)
C22—C23—C28107.79 (18)S1—Zr2—C1393.18 (4)
C22—C23—C24129.78 (19)S2—Zr2—C1497.95 (4)
C28—C23—C24122.13 (19)C1—Zr2—C14139.48 (6)
C22—C23—Zr170.18 (11)S1—Zr2—C1486.88 (4)
C28—C23—Zr172.99 (11)C13—Zr2—C1432.78 (6)
C24—C23—Zr1127.26 (13)S2—Zr2—C9125.51 (4)
C23—C24—C25B114.2 (3)C1—Zr2—C932.69 (6)
C23—C24—C25A109.5 (2)S1—Zr2—C9127.22 (4)
C23—C24—H24A109.8C13—Zr2—C991.07 (6)
C25B—C24—H24A127.8C14—Zr2—C9119.98 (6)
C25A—C24—H24A109.8S2—Zr2—C284.28 (4)
C23—C24—H24B109.8C1—Zr2—C232.75 (6)
C25B—C24—H24B82.0S1—Zr2—C2100.62 (5)
C25A—C24—H24B109.8C13—Zr2—C2143.25 (6)
H24A—C24—H24B108.2C14—Zr2—C2172.23 (6)
C23—C24—H24C108.7C9—Zr2—C253.61 (6)
C25B—C24—H24C108.7S2—Zr2—C12128.41 (4)
C25A—C24—H24C84.7C1—Zr2—C1289.44 (6)
H24B—C24—H24C130.6S1—Zr2—C12124.79 (4)
C23—C24—H24D108.7C13—Zr2—C1232.52 (6)
C25B—C24—H24D108.7C14—Zr2—C1253.60 (6)
C25A—C24—H24D133.0C9—Zr2—C1266.68 (6)
H24A—C24—H24D81.3C2—Zr2—C12119.37 (6)
H24C—C24—H24D107.6S2—Zr2—C2096.68 (4)
C28—C27—C26A113.3 (2)C1—Zr2—C2087.44 (6)
C28—C27—C26B106.8 (3)S1—Zr2—C20139.56 (4)
C28—C27—H27A108.9C13—Zr2—C2053.20 (6)
C26A—C27—H27A108.9C14—Zr2—C2052.70 (6)
C26B—C27—H27A136.6C9—Zr2—C2080.33 (6)
C28—C27—H27B108.9C2—Zr2—C20119.74 (6)
C26A—C27—H27B108.9C12—Zr2—C2031.94 (6)
C26B—C27—H27B82.6S2—Zr2—C8136.81 (4)
H27A—C27—H27B107.7C1—Zr2—C853.32 (6)
C28—C27—H27C110.4S1—Zr2—C895.29 (4)
C26A—C27—H27C79.0C13—Zr2—C892.54 (6)
C26B—C27—H27C110.4C14—Zr2—C8125.15 (6)
H27B—C27—H27C132.2C9—Zr2—C831.94 (6)
C28—C27—H27D110.4C2—Zr2—C852.64 (6)
C26A—C27—H27D129.3C12—Zr2—C882.58 (6)
C26B—C27—H27D110.4C20—Zr2—C8106.67 (6)
H27A—C27—H27D79.1S2—Zr2—C1580.34 (4)
H27C—C27—H27D108.6C1—Zr2—C15114.95 (6)
C29—C28—C23108.41 (17)S1—Zr2—C15112.42 (4)
C29—C28—C27128.33 (18)C13—Zr2—C1552.93 (6)
C23—C28—C27122.78 (18)C14—Zr2—C1531.43 (6)
C29—C28—Zr171.76 (10)C9—Zr2—C15111.73 (6)
C23—C28—Zr175.61 (10)C2—Zr2—C15143.12 (6)
C27—C28—Zr1124.98 (13)C12—Zr2—C1552.64 (6)
C28—C29—C21107.05 (17)C20—Zr2—C1531.47 (6)
C28—C29—C30125.68 (18)C8—Zr2—C15135.04 (6)
C21—C29—C30127.27 (19)S2—Zr2—C3108.38 (4)
C28—C29—Zr176.46 (10)C1—Zr2—C352.82 (6)
C21—C29—Zr170.66 (10)S1—Zr2—C381.31 (4)
C30—C29—Zr1118.71 (13)C13—Zr2—C3121.21 (6)
C29—C30—C31111.51 (16)C14—Zr2—C3150.86 (6)
C29—C30—H30A109.3C9—Zr2—C352.56 (6)
C31—C30—H30A109.3C2—Zr2—C331.24 (6)
C29—C30—H30B109.3C12—Zr2—C3113.69 (6)
C31—C30—H30B109.3C20—Zr2—C3132.85 (6)
H30A—C30—H30B108.0C8—Zr2—C331.45 (5)
C32—C31—C30111.19 (16)C15—Zr2—C3164.28 (6)
references
References top

Bottomley, F., Drummond, D. F., Egharevba, G. O. & White, P. S. (1986). Organometallics, 5, 1620–1625.

Burstynowicz, L. M. & Petersen, J. L. (1995). J. Cluster Sci. 6, 93–106.

Cacciola, J., Reddy, K. P. & Petersen, J. L. (1992). Organometallics, 11, 665–672.

Hey, E., Lappert, M. F., Atwood, J. L. & Bott, S. G. (1987). Chem. Commun. pp. 421–422.

Lefeber, C., Baumann, W., Tillack, A., Kempe, R., Görls, H. & Rosenthal, U. (1996). Organometallics, 15, 3486–3490.

Ren, W., Zi, G., Fang, D. & Walter, M. D. (2011). J. Am. Chem. Soc. 133, 13183–13196.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Skripkin, Y. V., Eremenko, I. L., Pasynskii, A. A., Struchkov, Y. T. & Shklover, V. E. (1984). J. Organomet. Chem. 267, 285–292.

Stoe & Cie (2005). X-SHAPE, X-RED32 and X-AREA. Stoe & Cie, Darmstadt, Germany.

Wielstra, Y., Gambarotta, S., Spek, A. L. & Smeets, W. J. J. (1990). Organometallics, 9, 2142–2148.

Winkler, U., Khan, M. A. & Nicholas, K. M. (1998). Inorg. Chem. Commun. 1, 317–319.