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.

S1. Comment

Phosphorus-bridged ansa-metallocenes have attracted considerable interest as precursors for olefin polymerization catalysts. Anderson & Lin (1987, 1988) 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; Tamm, 2008; Tamm et al., 2010). 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.

The two Cl ligands and the centroids of the two cyclopentadienyl (Cp) ligands in (I) adopt a distorted tetrahedral arrangement about the Zr atom, arising from 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)]. As the tilt angle increases, the metal atom is displaced further towards the ansa bridge. The Cl1—Zr—Cl2 angle is 101.49 (2)°, and the Zr—Cl bond lengths are 2.4224 (4) and 2.4316 (4) Å. The deviation from a symmetric η⁵-coordination towards an η³-coordination mode, associated with the tilting, is indicated by a range of 0.111 Å for the individual Zr—C_Cp 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 [C11—P1—C6 = 106.40 (8) and C11—P1—C1 = 100.40 (8)°].

Table 3 collates related data for the compounds [PhP(C₅Me₄)₂]ZrCl₂, (II) (Shin et al., 1999), and [MeP(C₅H₄)₂]ZrCl₂, (III) (Häp et al., 1999). The closely related compound [MeP(C₅Me₄)₂]ZrCl₂ (Shin et al., 1999) 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 C_Cp—P—C_Cp 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) of the Cp rings. Some more recent redeterminations at lower temperature can be found in the Cambridge Structural Database (Version?; Allen, 2002), but suffer from various imperfections such as a lack of s.u. values. The complex Cp*₂ZrCl₂, (V) (Böhme & Rittmeister, 1998), is also adduced.

Table 3 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 an η³-coordination mode [the range of Zr—C_Cp for (II) is 0.173 Å]. The Cl1—Zr—Cl2 angle in (I) [101.49 (2)°] 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—C_Cp 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, 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 3.506 (1) Å (symmetry code as in Table 1). The molecules are connected by all these interactions to form thick layers parallel to the bc plane at x ≈ 1/4 and 3/4. However, the general view of such a layer is too complex to be useful. We therefore present two separate packing diagrams. Fig. 2 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. 3) form chains parallel to the c axis.

S2. Experimental

The ansa-zirconocene, (I), first synthesized by Anderson & Lin (1987, 1988), was obtained as a by-product during the attempted synthesis of a P-functionalized zirconocene. In a Schlenk flask were placed (LiC₅H₄)₂PPh (303 mg, 1.2 mmol) and ZrCl₄ (565 mg, 2.4 mmol; 2 equivalents). 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.

S3. Refinement

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).

Computing details

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

Figures

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

Fig. 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 paper, the a axis vertical and the c axis from right to left. (b) The three contacts C—H···P, C—H···π and Cl1···P (thin dashed lines) connect the molecules to form chains parallel to the c axis. The origin is at the bottom left, the b axis out of paper and the c axis from left to right. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. Symmetry codes as in Table 1.

[bis(η⁵-cyclopentadienyl)phenylphosphine]dichloridozirconium(IV)

Crystal data

[ZrCl2(C16H13P)]	F(000) = 1584
Mr = 398.35	Dx = 1.742 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 27.2712 (6) Å	Cell parameters from 12715 reflections
b = 7.3272 (2) Å	θ = 2.8–32.4°
c = 15.4592 (3) Å	µ = 1.17 mm^−1
β = 100.389 (2)°	T = 100 K
V = 3038.44 (12) Å^3	Prism, colourless
Z = 8	0.16 × 0.10 × 0.07 mm

Data collection

Oxford Diffraction Xcalibur E diffractometer	4641 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3627 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
Detector resolution: 16.1057 pixels mm^-1	θmax = 30.5°, θmin = 2.8°
ω scans	h = −38→38
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −10→10
Tmin = 0.970, Tmax = 1.000	l = −22→21
31688 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.053	H-atom parameters constrained
S = 0.91	w = 1/[σ^2(Fo^2) + (0.0277P)^2] where P = (Fo^2 + 2Fc^2)/3
4641 reflections	(Δ/σ)max = 0.002
181 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

25.8611 (0.0075) x + 1.3403 (0.0062) y + 1.3004 (0.0135) z = 12.3858 (0.0059)

* 0.0096 (0.0010) C1 * −0.0135 (0.0010) C2 * 0.0123 (0.0010) C3 * −0.0061 (0.0011) C4 * −0.0023 (0.0011) C5 − 2.1966 (0.0007) Zr1 − 0.4739 (0.0027) P1

Rms deviation of fitted atoms = 0.0097

− 19.0976 (0.0170) x + 2.0586 (0.0060) y + 11.9310 (0.0086) z = 3.5400 (0.0106)

Angle to previous plane (with approximate e.s.d.) = 63.74 (0.06)

* 0.0081 (0.0010) C6 * −0.0115 (0.0011) C7 * 0.0106 (0.0011) C8 * −0.0055 (0.0011) C9 * −0.0017 (0.0010) C10 − 2.1894 (0.0008) Zr1 − 0.4960 (0.0027) P1

Rms deviation of fitted atoms = 0.0083

Distance CONT

3.5063 (0.0006) Cl1 - P1_$3

Operators for generating equivalent atoms:

$3 x, −y + 1, z − 1/2

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 (Ų)

	x	y	z	Uiso*/Ueq
Zr1	0.343302 (6)	0.40253 (2)	0.593256 (11)	0.01089 (4)
Cl1	0.311868 (16)	0.52983 (6)	0.44932 (3)	0.01723 (9)
Cl2	0.331694 (17)	0.07750 (6)	0.56503 (3)	0.02140 (10)
P1	0.394476 (16)	0.49951 (6)	0.80037 (3)	0.01261 (9)
C1	0.41940 (6)	0.4781 (2)	0.69852 (11)	0.0138 (3)
C2	0.41536 (6)	0.6073 (2)	0.62811 (11)	0.0150 (3)
H2	0.4076	0.7332	0.6315	0.018*
C3	0.42492 (6)	0.5150 (2)	0.55278 (12)	0.0173 (4)
H3	0.4259	0.5692	0.4973	0.021*
C4	0.43270 (6)	0.3310 (3)	0.57351 (12)	0.0182 (4)
H4	0.4390	0.2377	0.5343	0.022*
C5	0.42957 (6)	0.3074 (2)	0.66300 (11)	0.0166 (4)
H5	0.4336	0.1952	0.6942	0.020*
C6	0.33057 (6)	0.5059 (2)	0.73923 (11)	0.0130 (3)
C7	0.30706 (6)	0.6376 (2)	0.67723 (11)	0.0147 (3)
H7	0.3180	0.7595	0.6716	0.018*
C8	0.26475 (7)	0.5552 (2)	0.62557 (12)	0.0189 (4)
H8	0.2417	0.6132	0.5805	0.023*
C9	0.26274 (6)	0.3730 (2)	0.65244 (12)	0.0194 (4)
H9	0.2385	0.2853	0.6279	0.023*
C10	0.30280 (6)	0.3429 (2)	0.72208 (11)	0.0157 (3)
H10	0.3100	0.2309	0.7527	0.019*
C11	0.41145 (6)	0.7339 (2)	0.83000 (11)	0.0131 (3)
C12	0.46219 (6)	0.7738 (2)	0.84183 (12)	0.0168 (4)
H12	0.4847	0.6850	0.8271	0.020*
C13	0.48011 (7)	0.9409 (2)	0.87474 (13)	0.0202 (4)
H13	0.5147	0.9669	0.8824	0.024*
C14	0.44741 (7)	1.0706 (2)	0.89662 (13)	0.0196 (4)
H14	0.4596	1.1858	0.9190	0.023*
C15	0.39714 (7)	1.0323 (2)	0.88585 (12)	0.0183 (4)
H15	0.3748	1.1211	0.9013	0.022*
C16	0.37891 (6)	0.8640 (2)	0.85247 (11)	0.0152 (3)
H16	0.3443	0.8382	0.8451	0.018*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zr1	0.01094 (7)	0.01250 (8)	0.00932 (8)	−0.00147 (6)	0.00203 (5)	−0.00046 (6)
Cl1	0.0177 (2)	0.0213 (2)	0.0122 (2)	0.00031 (16)	0.00143 (16)	0.00273 (16)
Cl2	0.0277 (2)	0.0145 (2)	0.0231 (2)	−0.00373 (17)	0.00733 (18)	−0.00210 (17)
P1	0.0142 (2)	0.0132 (2)	0.0102 (2)	−0.00007 (16)	0.00129 (16)	−0.00038 (16)
C1	0.0088 (7)	0.0192 (8)	0.0127 (8)	−0.0015 (6)	0.0004 (6)	−0.0023 (7)
C2	0.0120 (7)	0.0181 (8)	0.0149 (8)	−0.0035 (7)	0.0024 (6)	−0.0011 (7)
C3	0.0121 (8)	0.0279 (10)	0.0128 (8)	−0.0049 (7)	0.0044 (7)	0.0003 (7)
C4	0.0134 (8)	0.0257 (9)	0.0158 (9)	0.0033 (7)	0.0031 (7)	−0.0055 (8)
C5	0.0119 (8)	0.0202 (9)	0.0168 (9)	0.0040 (7)	0.0002 (7)	−0.0025 (7)
C6	0.0125 (8)	0.0163 (8)	0.0111 (8)	−0.0017 (6)	0.0046 (6)	−0.0028 (6)
C7	0.0151 (8)	0.0147 (8)	0.0149 (8)	0.0018 (6)	0.0040 (7)	−0.0022 (6)
C8	0.0129 (8)	0.0270 (10)	0.0166 (9)	0.0045 (7)	0.0018 (7)	−0.0031 (7)
C9	0.0134 (8)	0.0267 (10)	0.0197 (9)	−0.0061 (7)	0.0073 (7)	−0.0077 (7)
C10	0.0182 (8)	0.0172 (8)	0.0137 (8)	−0.0042 (7)	0.0083 (7)	−0.0004 (7)
C11	0.0164 (8)	0.0145 (8)	0.0080 (8)	−0.0011 (6)	0.0016 (6)	−0.0001 (6)
C12	0.0143 (8)	0.0177 (8)	0.0183 (9)	0.0016 (7)	0.0027 (7)	−0.0037 (7)
C13	0.0151 (8)	0.0216 (9)	0.0237 (10)	−0.0042 (7)	0.0027 (7)	−0.0023 (7)
C14	0.0223 (9)	0.0136 (8)	0.0222 (10)	−0.0017 (7)	0.0025 (8)	−0.0012 (7)
C15	0.0213 (9)	0.0139 (8)	0.0207 (10)	0.0027 (7)	0.0063 (7)	0.0007 (7)
C16	0.0140 (8)	0.0169 (8)	0.0151 (9)	0.0003 (6)	0.0034 (7)	0.0005 (7)

Geometric parameters (Å, º)

Zr1—Cl1	2.4224 (4)	C7—C8	1.415 (2)
Zr1—Cl2	2.4316 (4)	C8—C9	1.402 (3)
Zr1—C2	2.4538 (16)	C9—C10	1.406 (3)
Zr1—C1	2.4585 (17)	C11—C16	1.388 (2)
Zr1—C6	2.4635 (16)	C11—C12	1.393 (2)
Zr1—C7	2.4681 (16)	C12—C13	1.381 (2)
Zr1—C10	2.4842 (16)	C13—C14	1.386 (2)
Zr1—C5	2.5037 (16)	C14—C15	1.380 (3)
Zr1—C9	2.5368 (17)	C15—C16	1.393 (2)
Zr1—C8	2.5448 (17)	C2—H2	0.9500
Zr1—C3	2.5550 (16)	C3—H3	0.9500
Zr1—C4	2.5653 (17)	C4—H4	0.9500
P1—C11	1.8161 (17)	C5—H5	0.9500
P1—C6	1.8273 (17)	C7—H7	0.9500
P1—C1	1.8308 (18)	C8—H8	0.9500
C1—C5	1.413 (2)	C9—H9	0.9500
C1—C2	1.432 (2)	C10—H10	0.9500
C2—C3	1.411 (2)	C12—H12	0.9500
C3—C4	1.393 (3)	C13—H13	0.9500
C4—C5	1.412 (2)	C14—H14	0.9500
C6—C10	1.414 (2)	C15—H15	0.9500
C6—C7	1.428 (2)	C16—H16	0.9500
Cl1—Zr1—Cl2	101.490 (16)	P1—C1—Zr1	100.87 (7)
Cl1—Zr1—C2	95.91 (4)	C3—C2—C1	108.08 (15)
Cl2—Zr1—C2	135.36 (4)	C3—C2—Zr1	77.62 (10)
Cl1—Zr1—C1	129.64 (4)	C1—C2—Zr1	73.23 (9)
Cl2—Zr1—C1	113.98 (4)	C4—C3—C2	108.48 (16)
C2—Zr1—C1	33.89 (6)	C4—C3—Zr1	74.61 (10)
Cl1—Zr1—C6	129.65 (4)	C2—C3—Zr1	69.73 (9)
Cl2—Zr1—C6	115.48 (4)	C3—C4—C5	108.07 (16)
C2—Zr1—C6	81.40 (5)	C3—C4—Zr1	73.80 (10)
C1—Zr1—C6	64.28 (5)	C5—C4—Zr1	71.44 (9)
Cl1—Zr1—C7	96.06 (4)	C4—C5—C1	108.85 (16)
Cl2—Zr1—C7	136.59 (4)	C4—C5—Zr1	76.24 (10)
C2—Zr1—C7	80.71 (6)	C1—C5—Zr1	71.70 (9)
C1—Zr1—C7	82.24 (6)	C10—C6—C7	106.54 (15)
C6—Zr1—C7	33.67 (6)	C10—C6—P1	120.28 (13)
Cl1—Zr1—C10	132.01 (4)	C7—C6—P1	129.44 (13)
Cl2—Zr1—C10	84.79 (4)	C10—C6—Zr1	74.20 (9)
C2—Zr1—C10	112.70 (6)	C7—C6—Zr1	73.34 (9)
C1—Zr1—C10	87.33 (6)	P1—C6—Zr1	100.79 (7)
C6—Zr1—C10	33.20 (5)	C8—C7—C6	108.20 (15)
C7—Zr1—C10	54.76 (6)	C8—C7—Zr1	76.62 (10)
Cl1—Zr1—C5	130.70 (4)	C6—C7—Zr1	72.99 (9)
Cl2—Zr1—C5	83.48 (4)	C9—C8—C7	108.08 (16)
C2—Zr1—C5	54.73 (6)	C9—C8—Zr1	73.67 (10)
C1—Zr1—C5	33.08 (5)	C7—C8—Zr1	70.65 (10)
C6—Zr1—C5	88.16 (6)	C8—C9—C10	108.07 (16)
C7—Zr1—C5	113.71 (6)	C8—C9—Zr1	74.30 (10)
C10—Zr1—C5	97.18 (6)	C10—C9—Zr1	71.69 (9)
Cl1—Zr1—C9	100.26 (5)	C9—C10—C6	109.07 (16)
Cl2—Zr1—C9	83.58 (4)	C9—C10—Zr1	75.81 (10)
C2—Zr1—C9	133.17 (6)	C6—C10—Zr1	72.60 (9)
C1—Zr1—C9	117.58 (6)	C16—C11—C12	119.20 (15)
C6—Zr1—C9	54.66 (6)	C16—C11—P1	124.52 (13)
C7—Zr1—C9	54.18 (6)	C12—C11—P1	115.67 (12)
C10—Zr1—C9	32.50 (6)	C13—C12—C11	120.75 (16)
C5—Zr1—C9	128.95 (6)	C12—C13—C14	119.81 (17)
Cl1—Zr1—C8	80.80 (4)	C15—C14—C13	120.01 (16)
Cl2—Zr1—C8	112.26 (4)	C14—C15—C16	120.34 (16)
C2—Zr1—C8	110.93 (6)	C11—C16—C15	119.90 (16)
C1—Zr1—C8	114.27 (6)	C3—C2—H2	126.0
C6—Zr1—C8	54.71 (6)	C1—C2—H2	126.0
C7—Zr1—C8	32.74 (6)	Zr1—C2—H2	115.3
C10—Zr1—C8	53.72 (6)	C4—C3—H3	125.8
C5—Zr1—C8	142.82 (6)	C2—C3—H3	125.8
C9—Zr1—C8	32.03 (6)	Zr1—C3—H3	121.6
Cl1—Zr1—C3	80.23 (4)	C3—C4—H4	126.0
Cl2—Zr1—C3	111.29 (4)	C5—C4—H4	126.0
C2—Zr1—C3	32.65 (5)	Zr1—C4—H4	120.6
C1—Zr1—C3	54.60 (6)	C4—C5—H5	125.6
C6—Zr1—C3	113.46 (6)	C1—C5—H5	125.6
C7—Zr1—C3	110.66 (6)	Zr1—C5—H5	118.3
C10—Zr1—C3	141.83 (6)	C8—C7—H7	125.9
C5—Zr1—C3	53.33 (6)	C6—C7—H7	125.9
C9—Zr1—C3	164.84 (6)	Zr1—C7—H7	116.5
C8—Zr1—C3	135.04 (6)	C9—C8—H8	126.0
Cl1—Zr1—C4	98.97 (4)	C7—C8—H8	126.0
Cl2—Zr1—C4	82.78 (4)	Zr1—C8—H8	121.4
C2—Zr1—C4	53.87 (6)	C8—C9—H9	126.0
C1—Zr1—C4	54.39 (6)	C10—C9—H9	126.0
C6—Zr1—C4	117.76 (6)	Zr1—C9—H9	119.9
C7—Zr1—C4	133.19 (6)	C9—C10—H10	125.5
C10—Zr1—C4	128.98 (6)	C6—C10—H10	125.5
C5—Zr1—C4	32.32 (6)	Zr1—C10—H10	118.0
C9—Zr1—C4	158.28 (6)	C13—C12—H12	119.6
C8—Zr1—C4	164.78 (6)	C11—C12—H12	119.6
C3—Zr1—C4	31.58 (6)	C12—C13—H13	120.1
C11—P1—C6	106.40 (8)	C14—C13—H13	120.1
C11—P1—C1	100.40 (8)	C15—C14—H14	120.0
C6—P1—C1	91.42 (7)	C13—C14—H14	120.0
C5—C1—C2	106.46 (15)	C14—C15—H15	119.8
C5—C1—P1	122.63 (13)	C16—C15—H15	119.8
C2—C1—P1	127.41 (13)	C11—C16—H16	120.1
C5—C1—Zr1	75.22 (10)	C15—C16—H16	120.1
C2—C1—Zr1	72.88 (9)
C11—P1—C1—C5	160.05 (14)	Cl1—Zr1—C6—C10	108.73 (10)
C6—P1—C1—C5	−92.99 (15)	Cl2—Zr1—C6—C10	−24.23 (11)
C11—P1—C1—C2	−43.98 (16)	C2—Zr1—C6—C10	−160.70 (11)
C6—P1—C1—C2	62.98 (16)	C1—Zr1—C6—C10	−129.91 (12)
C11—P1—C1—Zr1	−120.64 (7)	C7—Zr1—C6—C10	113.17 (14)
C6—P1—C1—Zr1	−13.69 (8)	C5—Zr1—C6—C10	−106.11 (11)
Cl1—Zr1—C1—C5	−106.25 (10)	C9—Zr1—C6—C10	36.44 (10)
Cl2—Zr1—C1—C5	24.42 (11)	C8—Zr1—C6—C10	75.97 (11)
C2—Zr1—C1—C5	−112.83 (14)	C3—Zr1—C6—C10	−154.41 (10)
C6—Zr1—C1—C5	132.38 (11)	C4—Zr1—C6—C10	−119.59 (11)
C7—Zr1—C1—C5	162.30 (11)	Cl1—Zr1—C6—C7	−4.44 (11)
C10—Zr1—C1—C5	107.51 (11)	Cl2—Zr1—C6—C7	−137.40 (9)
C9—Zr1—C1—C5	119.83 (10)	C2—Zr1—C6—C7	86.13 (10)
C8—Zr1—C1—C5	155.38 (10)	C1—Zr1—C6—C7	116.92 (11)
C3—Zr1—C1—C5	−75.44 (11)	C10—Zr1—C6—C7	−113.17 (14)
C4—Zr1—C1—C5	−36.39 (10)	C5—Zr1—C6—C7	140.71 (10)
Cl1—Zr1—C1—C2	6.58 (12)	C9—Zr1—C6—C7	−76.74 (11)
Cl2—Zr1—C1—C2	137.25 (9)	C8—Zr1—C6—C7	−37.21 (9)
C6—Zr1—C1—C2	−114.80 (11)	C3—Zr1—C6—C7	92.42 (10)
C7—Zr1—C1—C2	−84.87 (10)	C4—Zr1—C6—C7	127.23 (10)
C10—Zr1—C1—C2	−139.66 (10)	Cl1—Zr1—C6—P1	−132.61 (5)
C5—Zr1—C1—C2	112.83 (14)	Cl2—Zr1—C6—P1	94.43 (6)
C9—Zr1—C1—C2	−127.34 (10)	C2—Zr1—C6—P1	−42.04 (7)
C8—Zr1—C1—C2	−91.80 (10)	C1—Zr1—C6—P1	−11.25 (6)
C3—Zr1—C1—C2	37.38 (9)	C7—Zr1—C6—P1	−128.17 (13)
C4—Zr1—C1—C2	76.44 (11)	C10—Zr1—C6—P1	118.66 (13)
Cl1—Zr1—C1—P1	132.61 (5)	C5—Zr1—C6—P1	12.54 (7)
Cl2—Zr1—C1—P1	−96.72 (7)	C9—Zr1—C6—P1	155.10 (10)
C2—Zr1—C1—P1	126.03 (13)	C8—Zr1—C6—P1	−165.38 (10)
C6—Zr1—C1—P1	11.23 (6)	C3—Zr1—C6—P1	−35.75 (9)
C7—Zr1—C1—P1	41.16 (7)	C4—Zr1—C6—P1	−0.94 (9)
C10—Zr1—C1—P1	−13.63 (7)	C10—C6—C7—C8	1.85 (19)
C5—Zr1—C1—P1	−121.14 (13)	P1—C6—C7—C8	159.58 (14)
C9—Zr1—C1—P1	−1.32 (10)	Zr1—C6—C7—C8	69.19 (12)
C8—Zr1—C1—P1	34.23 (9)	C10—C6—C7—Zr1	−67.34 (11)
C3—Zr1—C1—P1	163.41 (10)	P1—C6—C7—Zr1	90.39 (14)
C4—Zr1—C1—P1	−157.53 (10)	Cl1—Zr1—C7—C8	62.46 (10)
C5—C1—C2—C3	−2.18 (18)	Cl2—Zr1—C7—C8	−51.35 (13)
P1—C1—C2—C3	−161.23 (13)	C2—Zr1—C7—C8	157.48 (11)
Zr1—C1—C2—C3	−70.50 (12)	C1—Zr1—C7—C8	−168.27 (11)
C5—C1—C2—Zr1	68.32 (11)	C6—Zr1—C7—C8	−114.11 (15)
P1—C1—C2—Zr1	−90.73 (13)	C10—Zr1—C7—C8	−76.06 (11)
Cl1—Zr1—C2—C3	−61.46 (10)	C5—Zr1—C7—C8	−157.83 (10)
Cl2—Zr1—C2—C3	51.48 (12)	C9—Zr1—C7—C8	−35.84 (10)
C1—Zr1—C2—C3	113.45 (14)	C3—Zr1—C7—C8	144.28 (10)
C6—Zr1—C2—C3	169.26 (11)	C4—Zr1—C7—C8	170.79 (10)
C7—Zr1—C2—C3	−156.66 (11)	Cl1—Zr1—C7—C6	176.56 (9)
C10—Zr1—C2—C3	157.94 (10)	Cl2—Zr1—C7—C6	62.76 (11)
C5—Zr1—C2—C3	75.41 (11)	C2—Zr1—C7—C6	−88.41 (10)
C9—Zr1—C2—C3	−171.50 (10)	C1—Zr1—C7—C6	−54.17 (10)
C8—Zr1—C2—C3	−143.85 (10)	C10—Zr1—C7—C6	38.05 (9)
C4—Zr1—C2—C3	35.34 (10)	C5—Zr1—C7—C6	−43.73 (11)
Cl1—Zr1—C2—C1	−174.91 (9)	C9—Zr1—C7—C6	78.27 (11)
Cl2—Zr1—C2—C1	−61.97 (11)	C8—Zr1—C7—C6	114.11 (15)
C6—Zr1—C2—C1	55.81 (10)	C3—Zr1—C7—C6	−101.62 (10)
C7—Zr1—C2—C1	89.89 (10)	C4—Zr1—C7—C6	−75.10 (12)
C10—Zr1—C2—C1	44.49 (11)	C6—C7—C8—C9	−2.1 (2)
C5—Zr1—C2—C1	−38.04 (9)	Zr1—C7—C8—C9	64.64 (12)
C9—Zr1—C2—C1	75.05 (12)	C6—C7—C8—Zr1	−66.75 (11)
C8—Zr1—C2—C1	102.71 (10)	Cl1—Zr1—C8—C9	126.81 (11)
C3—Zr1—C2—C1	−113.45 (14)	Cl2—Zr1—C8—C9	28.08 (11)
C4—Zr1—C2—C1	−78.11 (11)	C2—Zr1—C8—C9	−140.34 (10)
C1—C2—C3—C4	2.46 (19)	C1—Zr1—C8—C9	−103.71 (11)
Zr1—C2—C3—C4	−65.06 (12)	C6—Zr1—C8—C9	−78.16 (11)
C1—C2—C3—Zr1	67.52 (11)	C7—Zr1—C8—C9	−116.47 (16)
Cl1—Zr1—C3—C4	−125.59 (10)	C10—Zr1—C8—C9	−36.94 (10)
Cl2—Zr1—C3—C4	−26.97 (11)	C5—Zr1—C8—C9	−81.60 (14)
C2—Zr1—C3—C4	116.87 (15)	C3—Zr1—C8—C9	−167.11 (10)
C1—Zr1—C3—C4	78.00 (11)	C4—Zr1—C8—C9	−142.9 (2)
C6—Zr1—C3—C4	105.28 (11)	Cl1—Zr1—C8—C7	−116.72 (10)
C7—Zr1—C3—C4	141.58 (10)	Cl2—Zr1—C8—C7	144.55 (9)
C10—Zr1—C3—C4	82.78 (13)	C2—Zr1—C8—C7	−23.87 (12)
C5—Zr1—C3—C4	36.80 (10)	C1—Zr1—C8—C7	12.76 (12)
C9—Zr1—C3—C4	141.2 (2)	C6—Zr1—C8—C7	38.31 (10)
C8—Zr1—C3—C4	168.12 (10)	C10—Zr1—C8—C7	79.53 (11)
Cl1—Zr1—C3—C2	117.54 (10)	C5—Zr1—C8—C7	34.87 (15)
Cl2—Zr1—C3—C2	−143.84 (9)	C9—Zr1—C8—C7	116.47 (16)
C1—Zr1—C3—C2	−38.87 (10)	C3—Zr1—C8—C7	−50.64 (14)
C6—Zr1—C3—C2	−11.59 (12)	C4—Zr1—C8—C7	−26.4 (3)
C7—Zr1—C3—C2	24.70 (12)	C7—C8—C9—C10	1.5 (2)
C10—Zr1—C3—C2	−34.09 (15)	Zr1—C8—C9—C10	64.22 (12)
C5—Zr1—C3—C2	−80.07 (11)	C7—C8—C9—Zr1	−62.68 (12)
C9—Zr1—C3—C2	24.3 (3)	Cl1—Zr1—C9—C8	−53.44 (11)
C8—Zr1—C3—C2	51.24 (14)	Cl2—Zr1—C9—C8	−154.00 (11)
C4—Zr1—C3—C2	−116.87 (15)	C2—Zr1—C9—C8	54.82 (14)
C2—C3—C4—C5	−1.76 (19)	C1—Zr1—C9—C8	92.25 (11)
Zr1—C3—C4—C5	−63.68 (12)	C6—Zr1—C9—C8	78.37 (11)
C2—C3—C4—Zr1	61.91 (12)	C7—Zr1—C9—C8	36.66 (10)
Cl1—Zr1—C4—C3	54.23 (10)	C10—Zr1—C9—C8	115.62 (15)
Cl2—Zr1—C4—C3	154.79 (10)	C5—Zr1—C9—C8	129.76 (11)
C2—Zr1—C4—C3	−36.57 (10)	C3—Zr1—C9—C8	37.1 (3)
C1—Zr1—C4—C3	−78.72 (11)	C4—Zr1—C9—C8	154.64 (15)
C6—Zr1—C4—C3	−90.16 (11)	Cl1—Zr1—C9—C10	−169.06 (10)
C7—Zr1—C4—C3	−52.91 (13)	Cl2—Zr1—C9—C10	90.38 (10)
C10—Zr1—C4—C3	−127.93 (11)	C2—Zr1—C9—C10	−60.80 (13)
C5—Zr1—C4—C3	−116.00 (16)	C1—Zr1—C9—C10	−23.37 (12)
C9—Zr1—C4—C3	−153.73 (14)	C6—Zr1—C9—C10	−37.25 (10)
C8—Zr1—C4—C3	−33.7 (3)	C7—Zr1—C9—C10	−78.96 (11)
Cl1—Zr1—C4—C5	170.23 (10)	C5—Zr1—C9—C10	14.14 (13)
Cl2—Zr1—C4—C5	−89.21 (10)	C8—Zr1—C9—C10	−115.62 (15)
C2—Zr1—C4—C5	79.43 (11)	C3—Zr1—C9—C10	−78.5 (3)
C1—Zr1—C4—C5	37.28 (10)	C4—Zr1—C9—C10	39.0 (2)
C6—Zr1—C4—C5	25.83 (13)	C8—C9—C10—C6	−0.4 (2)
C7—Zr1—C4—C5	63.09 (13)	Zr1—C9—C10—C6	65.56 (12)
C10—Zr1—C4—C5	−11.94 (14)	C8—C9—C10—Zr1	−65.93 (12)
C9—Zr1—C4—C5	−37.7 (2)	C7—C6—C10—C9	−0.91 (19)
C8—Zr1—C4—C5	82.3 (3)	P1—C6—C10—C9	−161.10 (12)
C3—Zr1—C4—C5	116.00 (16)	Zr1—C6—C10—C9	−67.66 (12)
C3—C4—C5—C1	0.39 (19)	C7—C6—C10—Zr1	66.74 (11)
Zr1—C4—C5—C1	−64.84 (12)	P1—C6—C10—Zr1	−93.44 (11)
C3—C4—C5—Zr1	65.22 (12)	Cl1—Zr1—C10—C9	14.56 (13)
C2—C1—C5—C4	1.11 (19)	Cl2—Zr1—C10—C9	−86.22 (10)
P1—C1—C5—C4	161.40 (13)	C2—Zr1—C10—C9	136.37 (10)
Zr1—C1—C5—C4	67.81 (12)	C1—Zr1—C10—C9	159.40 (11)
C2—C1—C5—Zr1	−66.70 (11)	C6—Zr1—C10—C9	115.62 (15)
P1—C1—C5—Zr1	93.59 (12)	C7—Zr1—C10—C9	77.01 (11)
Cl1—Zr1—C5—C4	−12.78 (13)	C5—Zr1—C10—C9	−168.96 (10)
Cl2—Zr1—C5—C4	86.79 (10)	C8—Zr1—C10—C9	36.39 (10)
C2—Zr1—C5—C4	−76.54 (11)	C3—Zr1—C10—C9	155.50 (10)
C1—Zr1—C5—C4	−115.56 (15)	C4—Zr1—C10—C9	−162.56 (10)
C6—Zr1—C5—C4	−157.31 (11)	Cl1—Zr1—C10—C6	−101.06 (10)
C7—Zr1—C5—C4	−134.76 (11)	Cl2—Zr1—C10—C6	158.16 (10)
C10—Zr1—C5—C4	170.67 (11)	C2—Zr1—C10—C6	20.75 (12)
C9—Zr1—C5—C4	163.07 (10)	C1—Zr1—C10—C6	43.78 (10)
C8—Zr1—C5—C4	−154.50 (11)	C7—Zr1—C10—C6	−38.60 (10)
C3—Zr1—C5—C4	−35.94 (10)	C5—Zr1—C10—C6	75.42 (11)
Cl1—Zr1—C5—C1	102.78 (10)	C9—Zr1—C10—C6	−115.62 (15)
Cl2—Zr1—C5—C1	−157.66 (10)	C8—Zr1—C10—C6	−79.23 (11)
C2—Zr1—C5—C1	39.01 (10)	C3—Zr1—C10—C6	39.88 (15)
C6—Zr1—C5—C1	−41.75 (10)	C4—Zr1—C10—C6	81.82 (12)
C7—Zr1—C5—C1	−19.21 (12)	C6—P1—C11—C16	35.78 (17)
C10—Zr1—C5—C1	−73.77 (11)	C1—P1—C11—C16	130.38 (15)
C9—Zr1—C5—C1	−81.37 (12)	C6—P1—C11—C12	−153.25 (13)
C8—Zr1—C5—C1	−38.94 (15)	C1—P1—C11—C12	−58.65 (15)
C3—Zr1—C5—C1	79.62 (11)	C16—C11—C12—C13	−0.6 (3)
C4—Zr1—C5—C1	115.56 (15)	P1—C11—C12—C13	−172.07 (14)
C11—P1—C6—C10	−167.17 (13)	C11—C12—C13—C14	0.2 (3)
C1—P1—C6—C10	91.55 (14)	C12—C13—C14—C15	0.3 (3)
C11—P1—C6—C7	37.71 (17)	C13—C14—C15—C16	−0.4 (3)
C1—P1—C6—C7	−63.57 (16)	C12—C11—C16—C15	0.4 (3)
C11—P1—C6—Zr1	114.93 (7)	P1—C11—C16—C15	171.11 (14)
C1—P1—C6—Zr1	13.66 (8)	C14—C15—C16—C11	0.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···Cl1^i	0.95	2.84	3.7649 (18)	165
C8—H8···Cl1^ii	0.95	2.99	3.7520 (18)	138
C3—H3···P1^iii	0.95	3.05	3.8416 (18)	142
C7—H7···Cl2^iv	0.95	2.92	3.7775 (18)	151
C4—H4···Cg^iii	0.95	2.80	3.656	150

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1/2, −y+3/2, −z+1; (iii) x, −y+1, z−1/2; (iv) x, y+1, z.