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Acta Crystallogr C. 2010 March 15; 66(Pt 3): m86–m88.
Published online 2010 February 24. doi:  10.1107/S0108270110004531
PMCID: PMC2855579

The ansa-zirconocene [bis­(η5-cyclo­penta­dien­yl)phenyl­phosphine]­dichloridozirconium(IV)


In the title compound, [Zr(C16H13P)Cl2], the geometry at the metal atom is distorted tetra­hedral; the Cl—Zr—Cl angle is 101.490 (16)° and the cyclo­penta­dienyl (Cp) centroids subtend an angle of 122.63 (3)° at the Zr atom. The P atom lies 0.474 (3) and 0.496 (3) Å out of the planes of the Cp rings. The C—P—C angle of 91.42 (7)° reflects the pincer effect of the two Cp rings. Three C—H(...)Cl, one C—H(...)P, one C—H(...)π and one Cl(...)P inter­action link the mol­ecules to form thick layers parallel to the bc plane.


Phospho­rus-bridged ansa-metallocenes have attracted con­siderable inter­est as precursors for olefin polymerization catalysts. Anderson & Lin (1987 [triangle], 1988 [triangle]) reported the synthesis of the title ansa-compound [PhP(η5-C5H4)2]ZrCl2, (I). We are inter­ested in novel donor-functionalized cyclo­hepta­trien­yl–cyclo­penta­dienyl zirconium sandwich compounds, using zirconocenes as starting materials (Büschel et al., 2009 [triangle]; Tamm, 2008 [triangle]; Tamm et al., 2010 [triangle]). During these studies, we accidentally obtained single crystals of (I) that were suitable for X-ray diffraction studies. The mol­ecular structure of (I) in the solid state is shown in Fig. 1 [triangle].

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Figure 1
The mol­ecule of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

The two Cl ligands and the centroids of the two cyclo­penta­dienyl (Cp) ligands in (I) adopt a distorted tetra­hedral arrangement about the Zr atom due to the presence of a PhP moiety as the bridging unit between the two carbocyclic fragments. The angle α subtended by the Cp centroids at the metal atom is 122.63 (3)°. The angle β between the Cp ring normals is 116.3 (1)°, resulting in a value of 3.2° for the tilt angle γ [γ = (α − β)/2; the angles α, β and γ, which describe the bending of the ansa-zirconocene compound in more detail, are defined graphically in the second scheme, taken from Shin et al. (1999 [triangle])]. As the tilt angle increases, the metal atom is displaced further towards the ansa bridge. The Cl1—Zr—Cl2 angle is 101.490 (16)°, and the Zr—Cl bond lengths are 2.4224 (4) and 2.4316 (4) Å. The deviation from a symmetric η5-coordination towards a η3-coordination mode, associated with the tilting, is indicated by a range of 0.111 Å for the individual Zr—CCp bond lengths [2.454 (1)–2.565 (1) Å]. Distortion involving the P atom is also observed; it lies 0.474 (3) Å out of the plane of the ring C1–C5 and 0.496 (3) Å out of the plane of the ring C6–C10. The C6—P1—C1 angle, at 91.42 (7)°, is considerably narrowed by the pincer effect of the two Cp rings [cf. C11—P1—C6 = 106.40 (8)° and C11—P1—C1 = 100.40 (8)°].

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Table 2 [triangle] collates related data for the compounds [PhP(C5Me4)2]ZrCl2, (II) (Shin et al., 1999 [triangle]), and [MeP(C5H4)2]ZrCl2, (III) (Häp et al., 1999 [triangle]). The closely related compound [MeP(C5Me4)2]ZrCl2 (Shin et al., 1999 [triangle]) must be omitted from a detailed comparison because it suffers from disorder. Inspection of the supplementary material reveals that the reported space group is C2/c, with the Zr and P atoms lying on a twofold axis, and the methyl C atom is therefore disordered over two sites; the CCp—P—CCp angle seems improbably large at 107.8°. For comparison with systems lacking the bridging atom, the compound Cp2ZrCl2, (IV), may be used, but the structure suffers somewhat from high U values (Corey et al., 1995 [triangle]) of the Cp rings. Some more recent redeterminations at lower temperature can be found in the Cambridge Structural Database (Version 1.11; Allen, 2002 [triangle]), but suffer from various imperfections such as a lack of s.u. values. The complex Cp*2ZrCl2, (V) (Böhme & Rittmeister, 1998 [triangle]), is also adduced.

Table 2
Selected dimensions (Å, °) of (I) and related structures

Table 2 [triangle] indicates that the β angles are almost identical for all three compounds (I)–(III), so that the relative disposition of the Cp rings is also closely similar. Indeed, all three bending angles are very similar in (I) and (III). However, the α angle is significantly smaller in (I) than in (II), necessarily leading to a more pronounced tilting. The γ angle is largest for (II), also reflected in a larger deviation of (II) from a symmetric η5-coordination towards a η3-coordination mode [the range of Zr—CCp distances for (II) is 0.173 Å]. The Cl1—Zr—Cl2 angle in (I) [101.490 (19)°] is appreciably larger than that in (III), perhaps reflecting the differing spatial demands of methyl and phenyl groups at P, but the Zr—Cl bond lengths of both compounds are similar.

The unbridged complexes (IV) and (V), as expected, display larger values of α and (especially) β, somewhat lower Cl—Zr—Cl bond angles and a smaller range of Zr—CCp bond lengths, corresponding to more symmetric coordination of the Cp rings.

As would be expected, there are no unusually short inter­molecular contacts in (I). Four weak hydrogen bonds are given in Table 1 [triangle], of which we regard the H3(...)P1 inter­action as borderline. There is also a C—H(...)π contact to the centroid of the phenyl ring, and finally a short Cl1(...)P1iii contact of 3.5064 (7) Å (symmetry code as in Table 1 [triangle]). The mol­ecules are connected by all these inter­actions to form thick layers parallel to the bc plane at x [similar, equals] An external file that holds a picture, illustration, etc.
Object name is c-66-00m86-efi1.jpg and An external file that holds a picture, illustration, etc.
Object name is c-66-00m86-efi2.jpg. However, the general view of such a layer is too complex to be useful. We therefore present two separate packing diagrams. Fig. 2 [triangle](a) shows that the three H(...)Cl contacts link the mol­ecules to form double chains parallel to the b axis, whereas the other three contacts (Fig. 2 [triangle] b) form chains parallel to the c axis.

Figure 2
Packing diagrams for (I). (a) The three C—H(...)Cl contacts (thin dashed lines) connect the mol­ecules to form double chains parallel to the b axis. The origin is at the bottom right, the c axis out of the paper, the a axis vertical ...
Table 1
Hydrogen-bond geometry (Å, °)


The title ansa-zirconocene, (I), first synthesized by Anderson & Lin (1987 [triangle], 1988 [triangle]), was obtained as a by-product during the attempted synthesis of a P-functionalized zirconocene. (LiC5H4)2PPh (303 mg, 1.2 mmol) and ZrCl4 (565 mg, 2.4 mmol; 2 equivalents) were placed in a Schlenk flask. Toluene (60 ml) was added and the mixture was cooled to 213 K, followed by the addition of tetra­hydro­furan (1 ml). After warming to room temperature overnight, the yellow suspension was filtered through a plug of Celite. The solvent was removed in vacuo until approximately 3 ml remained. A yellow solid precipitated and was filtered off. The filtrate was cooled to 248 K. After 2 d, yellow crystals of (I) suitable for X-ray diffraction analysis were obtained.

Crystal data

  • [Zr(C16H13P)Cl2]
  • M r = 398.35
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is c-66-00m86-efi3.jpg
  • a = 27.2712 (6) Å
  • b = 7.3272 (2) Å
  • c = 15.4592 (3) Å
  • β = 100.389 (2)°
  • V = 3038.44 (12) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 1.17 mm−1
  • T = 100 K
  • 0.16 × 0.10 × 0.07 mm

Data collection

  • Oxford Diffraction Xcalibur E diffractometer
  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 [triangle]) T min = 0.970, T max = 1.000
  • 31688 measured reflections
  • 4641 independent reflections
  • 3627 reflections with I > 2σ(I)
  • R int = 0.050


  • R[F 2 > 2σ(F 2)] = 0.025
  • wR(F 2) = 0.053
  • S = 0.91
  • 4641 reflections
  • 181 parameters
  • H-atom parameters constrained
  • Δρmax = 0.50 e Å−3
  • Δρmin = −0.31 e Å−3

H atoms were introduced at calculated positions and refined using a riding model, with C—H = 0.95 Å and U iso(H) = 1.2U eq(C).

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP (Siemens, 1994 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S0108270110004531/gd3332sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S0108270110004531/gd3332Isup2.hkl


Supplementary data for this paper are available from the IUCr electronic archives (Reference: GD3332). Services for accessing these data are described at the back of the journal.


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  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
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