Bis­(tri­chloro­phosphine)­iminium salts, [Cl₃P=N=PCl₃]⁺, with transition metal halide counter-ions

The structures of four bis­(tri­chloro­phosphine)­iminium {[Cl₃P=N=PCl₃]⁺; systematic name: tri­chloro­[(tri­chloro­phos­phor­an­yl­idene)im­in­io]phos­phor­us(V)} salts, namely bis(tri­chloro­phosphine)­iminium hexa­chloro­niobate, (Cl₆NP₂)[NbCl₆], (I), bis­(tri­chloro­phosphine)­iminium hexa­chloro­tantalate, (Cl₆NP₂)[TaCl₆], (II), bis­(tri­chloro­phosphine)­iminium tri-[mu]-chloro-bis­[tri­chloro­titanium(IV)], (Cl₆NP₂)[Ti₂Cl₉], (III), and bis­[bis­(tri­chloro­phosphine)­iminium] di-[mu]-chloro-bis­[tetrachloro­zirconium(IV)], (Cl₆NP₂)₂[Zr₂Cl₁₀], (IV), have been determined. The P=N distances in the discrete [Cl₃P=N=PCl₃]⁺ moieties in structures (I), (II) and (IV) range from 1.5460 (14) to 1.5554 (16) Å, and the P=N=P angles range from 136.8 (3) to 143.4 (4)°. The [Cl₃P=N=PCl₃]⁺ cation in (III) is disordered and the calculated geometries for the cation are therefore less reliable. Compounds (I) and (II) are isostructural and the metal anions have slightly distorted octahedral geometries. The anion in compound (III) consists of two distorted octahedral Ti centres linked by three [mu]₂-Cl atoms, while in compound (IV), the dianion is derived from two distorted edge-shared ZrCl₆ octahedra.

S1. Comment

Bis(trichlorophosphino)iminium salts are commonly used precursors for the synthesis of inorganic heterocycles (Becke-Goehring & Muller, 1968; Dodge et al., 1990). In addition, [Cl₃P═N ═PCl₃][PCl₆] is proposed as an intermediate in the formation of poly(dichlorophosphazene) via the living cationic polymerization of Cl₃P═NSiMe₃ with PCl₅ (Honeyman et al., 1995). As part of our studies involving the chemistry of boron-containing heterophosphazene ring systems (Gates et al., 1998; McWilliams et al., 2002), we discovered that the tetrachloroborate salt [Cl₃P═N ═PCl₃][BCl₄] reacted quickly with early metal halides in chlorinated solvents to produce BCl₃ gas and a series of new bis(trichlorophosphino)iminium salts with transition-metal-containing counter-ions, (I)–(IV).

Analysis of the resulting products was consistent with the absence of the [BCl₄]^- anion, as no signal was detected in the ¹¹B NMR spectra. In addition, a signal at 22.2 p.p.m. was observed in the ³¹P NMR spectra of salts (I)–(IV), indicative of the [Cl₃P═N ═PCl₃] cation. (Faggiani et al., 1980).

Salts (I)–(IV) crystallize as discrete cations and metal anions. The cation in (III) is disordered over two sites (see Experimental) and therefore its intramolecular geometry is not dicussed in detail. In the crystal structures of (I), (II) and (IV), the [Cl₃P═N ═PCl₃]⁺ moieties lie on crystallographic twofold axes. The twofold axes pass through the central N atom and bisect the P═N ═P angle. In (I), (II) and (IV), the [Cl₃P═N ═PCl₃] cations have P—N distances in the range 1.5460 (14)–1.5554 (16) Å. These values compare well with the P—N distances in the recently redetermined structure of [Cl₃P═N ═PCl₃][PCl₆] (Belaj, 1998), which vary from 1.556 (3) to 1.562 (3) Å. The P—N—P bond angles within the cations of (I), (II) and (IV) are in the range 136.8 (3)–143.4 (4)° and are slightly larger than the angles observed in [Cl₃P═N ═PCl₃][PCl₆] [133.3 (2) and 135.8 (2)°]. The size of the P—N—P angle appears to depend on the nature of the anion and reflects the low energy required to deform the PNP unit (Faggiani et al., 1980). Using the `W' form of the Cl—P—N—P—Cl groupings for [Cl<sub>3</sub>P═N ═ PCl<sub>3</sub>]<sup>+</sup> [previously described by Belaj (1998)], the Cl—P—N—P torsion angles Cl—P—N1—P for (I) and (II) are -145.96 (6) and -146.05 (8)°, respectively. This is in contrast with the equivalent Cl—P—N—P torsion angles in [Cl<sub>3</sub>P═N ═PCl<sub>3</sub>][PCl<sub>6</sub>], which are closer to 180°. The values in [Cl<sub>3</sub>P═N ═PCl<sub>3</sub>][PCl<sub>6</sub>], however, are close to those found in (IV), which has a `W'-form Cl—P—N—P torsion angle of -178.31 (6)°. In 1980, Belaj also found that the Cl—P—N angles in the cation were significantly smaller for the angle containing a Cl atom from the `W' fragment [Cl6 for (I), (II) and (IV)] than the other Cl—P—N angles. This feature is also observed in each of (I), (II) and (IV) (see Tables 1, 2 and 4), despite the variation of the Cl—P—N—P torsion angle in (IV) from both (I) and (II).

Compounds (I) and (II) are isostructural in space group C2/c with Z = 4. A Ta atom in (II) replaces the Nb atom in (I). In these two structures, the NbCl₆^- or TaCl₆^- ion has a slightly distorted octahedral geometry, with the metal atom located on a crystallographic inversion center. Due to the similar size of the Nb and Ta atoms, the M—Cl (M = Nb or Ta) distances within these anions are also similar [2.3457 (7)–2.3613 (7) Å in NbCl₆^- and 2.3428 (11)–2.3559 (9) Å in TaCl₆^-]. The inversion symmetry in the anions of (I) and (II) restricts the trans Cl—M—Cl angles to exactly 180°, while the cis angles are in the range 89.36 (3)–90.64 (3)° for (I) and 89.37 (4)–90.63 (4)° for (II). Fig. 5 shows a polyhedral representation of the crystal packing in structures (I) and (II), viewed perpendicular to the xy plane. The figure shows alternate layers (superimposed in the xy plane) of anion octahedra and cations packing in the z direction.

In compound (III), both the cation and the anion are on gerneral positions, but the cation is disordered over two sites (see Experimental). The Ti₂Cl₉^- anion within (III) consists of two psuedo-distorted octahedral Ti centres linked by three µ₂-Cl atoms. The Ti—Cl(bridging)—Ti angles range from 86.39 (3) to 87.45 (3)° and consequently the bridging Ti—Cl bond lengths [2.4548 (9)–2.5127 (8) Å] are longer than the terminal Ti—Cl bond lengths [2.2036 (10)–2.2319 (10) Å]. The trans Cl—Ti—Cl angles in (III) vary from 164.15 (4) to 166.69 (4)°, while the cis angles have values in the range 76.94 (3)–99.91 (4)°. The crystal structue of (III) as viewed in Fig. 6 shows layers of anions (face-shared octahedra) alternating with cations in the x direction.

The remaining compound, (IV), crystallized as the 2:1 salt [Cl₃P═N ═ PCl₃]₂[Zr₂Cl₁₀], containing the unusual decachlorodizirconiate dianion (derived from two edge-shared ZrCl₆ octahedra). The Cl₁₀Zr₂ dianion has crystallographic 2/m symmetry, with a mirror plane running through the two Zr atoms and the six equatorial Cl atoms, while a twofold axis (perpendicular to the mirror plane) is located at the centre of the four-membered ring formed by the two Zr atoms and the two bridging Cl atoms. Again, a distorted octahedral geometry is observed about the transition metal with a symmetry-unique bridging Zr—Cl—Zr angle of 101.92 (4)° and two elongated bridging Zr—Cl bonds of 2.6106 (11) and 2.6354 (12) Å. The shortened terminal Zr—Cl bonds are in the range 2.3640 (12)–2.4266 (9) Å. The trans Cl—Zr—Cl angles range from 167.20 (4) to 174.74 (5)°, while the cis angles have values ranging from 78.08 (4) to 100.04 (5)°. Fig. 7 illustrates the packing in the crystal structure of (IV), which consists of alternating layers of Zr₂Cl₁₀^- anions (edge-shared octahedra) and cations in the x direction.

In the structures of (I)–(IV), there are intermolecular Cl···Cl distances which are shorter than the sum of the van der Waals radii of 3.50 Å (Bondi, 1964). The shortest Cl···Cl distance, for each compound, ranges from 3.184 (6) Å for Cl17···Cl1A(x, -1 + y, z) in (III) to 3.3908 (13) Å for Cl7···Cl3(-x + 1/2, -y + 1/2, -z + 1) in (I). In all four title structures, the closest intermolecular Cl···Cl distances are between a Cl atom of a cation and a Cl atom of an anion. In the structure of [Cl₃P═N ═PCl₃][PCl₆], the shortest intermolecluar Cl···Cl distances [3.182 (2) and 3.194 (2) Å] are between two Cl atoms each of which are bonded to anions and these close contacts have been explained (Belaj, 1998). This anion–anion close contact is not present, however, in structure (I)–(IV).

S2. Experimental

All manipulations of reagents and products were conducted under strictly anhydrous and anaerobic conditions. The metal-containing salts were prepared by the reaction of [Cl₃P═N═PCl₃][BCl₄] (Binder & Fluck, 1971) with one or two equivalents of metal halide at room temperature for 12 h in dichloromethane. Gas evolution (BCl₃) was observed during the reaction, and removal of the volatiles in vacuo afforded white solids (80–95% yields). Recrystallization from dichloromethane (243 K, 12 h) gave yellow (I) or colourless (II)–(IV) crystals suitable for single-crystal X-ray diffraction studies. Data for (I)–(IV), ³¹P NMR (CDCl₃): 22.1 (s) p.p.m.. ¹¹B NMR (CDCl₃): no signal detected. IR (ν, cm^-1): 1378 (s), 1267 (w), 835 (m), 665 (m) and 632 (s). Analysis calculated for (II) (Cl₁₂NP₂Ta, M_r = 682.3): N 2.05%; found: N 2.19%.

S3. Refinement

During the refinement of (III), the anisotropic displacement parameter of the central N atom of the [Cl₃P═N═PCl₃]⁺ cation refined to an unusually large value, compared to the values for the atoms in the anion. In addition to this feature, difference Fourier maps showed several residual electron-density peaks, of approximately 1 e %A^-3, close to the anisotropic Cl atoms in the cation. This suggested that the [Cl₃P═N═PCl₃]⁺ moiety was disordered over two sites. In the final cycles of refinement, the cation was refined with two disorder components of equal geometry [using the SAME command in SHELXL97 (Sheldrick, 1997)], with all atoms occupying two independent sites. The minor-occupany disorder component is an equivalent [Cl₃P═N═PCl₃]⁺ moiety in which the central N atom is shifted by about 0.7 Å and the rest of the molecule is, in turn, displaced by this shift. The final value for the occupancy was 0.852 (6) for the major component and 0.148 (2) for the minor component. The N, P and Cl atoms with major occupancy and the Cl atoms with minor occupancy were refined with anistropic displacement parameters, while the minor-occupany P and N atoms were refined with isotropic displacement parameters. The final R[I > 2σ(I)] value improved from 0.0422 for the ordered anisotropic model to 0.0363 for the refinement using a disordered model. The final model of the cation gave values for the P—N distances and P—N—P angles that were unusual (see Table 3) compared to compounds (I), (II) and (IV), and the values in other previously determined salts containing Cl₃P═N═PCl₃ cations (Belaj, 1998; Muller et al., 1998). Although the values in (III) appear unusual, least-squares refinements performed using geometric restraints (using previously determined geometries for [Cl₃P═N═PCl₃] cations) caused the refinement to become unstable.

Computing details

For all compounds, data collection: COLLECT (Nonius BV, 2001); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXTL (Sheldrick, 1999); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of (I), with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) 1 - x, y, 3/2 - z; (ii) 1 - x, 1 - y, 1 - z.]
	Fig. 2. View of (II), with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) 1 - x, y, 3/2 - z; (ii) 1 - x, 1 - y, 1 - z.]
	Fig. 3. View of (III), with displacement ellipsoids drawn at the 50% probability level. The disorder component has been omitted for clarity.
	Fig. 4. View of (IV), with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) -x, -y, 1 - z; (ii) -x, y, z; (iii) 1/2 - x, y, 3/2 - z.]
	Fig. 5. Polyhedral representation of the crystal packing of structures (I) and (II).
	Fig. 6. Polyhedral representation of the crystal packing of structure (III).
	Fig. 7. Polyhedral representation of the crystal packing of structure (IV).

(I) Bis(trichlorophosphino)iminium hexachloroniobate

Crystal data

(Cl6NP2)[NbCl6]	F(000) = 1128
Mr = 594.26	Dx = 2.364 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 17033 reflections
a = 13.4095 (7) Å	θ = 2.5–27.5°
b = 8.5268 (6) Å	µ = 2.81 mm^−1
c = 15.0432 (9) Å	T = 150 K
β = 103.928 (4)°	Block, yellow
V = 1669.47 (18) Å^3	0.23 × 0.20 × 0.20 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	1908 independent reflections
Radiation source: fine-focus sealed tube	1676 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
ϕ scans and ω scans with κ offsets	h = −17→17
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	k = −11→11
Tmin = 0.531, Tmax = 0.568	l = −19→18
6672 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)] = 0.031	w = 1/[σ^2(Fo^2) + (0.0358P)^2 + 2.7251P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.082	(Δ/σ)max = 0.003
S = 1.08	Δρmax = 0.95 e Å^−3
1908 reflections	Δρmin = −0.78 e Å^−3
76 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0010 (2)

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.

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
Nb1	0.5000	0.5000	0.5000	0.01987 (14)
Cl1	0.43029 (6)	0.52104 (10)	0.34174 (5)	0.03082 (19)
Cl2	0.33755 (5)	0.55809 (10)	0.52679 (5)	0.0305 (2)
Cl3	0.46019 (6)	0.23098 (9)	0.49137 (5)	0.02995 (19)
Cl4	0.36747 (6)	−0.13810 (10)	0.67486 (7)	0.0428 (2)
Cl5	0.33281 (6)	0.06664 (10)	0.83832 (5)	0.0349 (2)
Cl6	0.29883 (6)	0.21551 (10)	0.64448 (5)	0.0327 (2)
P1	0.38737 (5)	0.07236 (9)	0.72896 (5)	0.02275 (19)
N1	0.5000	0.1297 (5)	0.7500	0.0342 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Nb1	0.0221 (2)	0.0193 (2)	0.0186 (2)	−0.00044 (12)	0.00564 (14)	−0.00037 (12)
Cl1	0.0373 (4)	0.0343 (4)	0.0195 (3)	−0.0025 (3)	0.0042 (3)	0.0018 (3)
Cl2	0.0254 (4)	0.0340 (4)	0.0343 (4)	0.0006 (3)	0.0113 (3)	−0.0056 (3)
Cl3	0.0349 (4)	0.0202 (4)	0.0339 (4)	−0.0027 (3)	0.0067 (3)	−0.0010 (3)
Cl4	0.0375 (4)	0.0274 (5)	0.0617 (6)	−0.0019 (3)	0.0087 (4)	−0.0169 (4)
Cl5	0.0379 (4)	0.0387 (5)	0.0306 (4)	−0.0030 (3)	0.0128 (3)	0.0059 (3)
Cl6	0.0306 (4)	0.0351 (5)	0.0307 (4)	0.0041 (3)	0.0039 (3)	0.0072 (3)
P1	0.0183 (3)	0.0197 (4)	0.0305 (4)	0.0002 (3)	0.0065 (3)	−0.0008 (3)
N1	0.0221 (17)	0.025 (2)	0.056 (2)	0.000	0.0105 (16)	0.000

Geometric parameters (Å, º)

Nb1—Cl1	2.3457 (7)	Cl5—P1	1.9554 (11)
Nb1—Cl3	2.3517 (7)	Cl6—P1	1.9464 (10)
Nb1—Cl2	2.3613 (7)	P1—N1	1.5460 (14)
Cl4—P1	1.9620 (11)
Cl1—Nb1—Cl1^i	180.000 (1)	Cl1^i—Nb1—Cl2^i	89.92 (3)
Cl1—Nb1—Cl3^i	90.64 (3)	Cl3^i—Nb1—Cl2^i	90.43 (3)
Cl1^i—Nb1—Cl3^i	89.36 (3)	Cl3—Nb1—Cl2^i	89.57 (3)
Cl1—Nb1—Cl3	89.36 (3)	Cl2—Nb1—Cl2^i	180.0
Cl1^i—Nb1—Cl3	90.64 (3)	N1—P1—Cl6	110.34 (12)
Cl3^i—Nb1—Cl3	180.0	N1—P1—Cl5	112.37 (5)
Cl1—Nb1—Cl2	89.92 (3)	Cl6—P1—Cl5	105.78 (5)
Cl1^i—Nb1—Cl2	90.08 (3)	N1—P1—Cl4	113.76 (13)
Cl3^i—Nb1—Cl2	89.57 (3)	Cl6—P1—Cl4	107.58 (5)
Cl3—Nb1—Cl2	90.43 (3)	Cl5—P1—Cl4	106.57 (5)
Cl1—Nb1—Cl2^i	90.08 (3)	P1—N1—P1^ii	143.1 (3)
Cl6—P1—N1—P1^ii	−145.96 (6)	Cl4—P1—N1—P1^ii	−24.95 (5)
Cl5—P1—N1—P1^ii	96.25 (7)

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

(II) Bis(trichlorophosphino)iminium hexachlorotantalate

Crystal data

(Cl6NP2)[TaCl6]	F(000) = 1256
Mr = 682.30	Dx = 2.711 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 10506 reflections
a = 13.3957 (5) Å	θ = 2.5–27.5°
b = 8.5165 (4) Å	µ = 8.66 mm^−1
c = 15.0937 (5) Å	T = 150 K
β = 103.855 (3)°	Needle, colourless
V = 1671.86 (11) Å^3	0.21 × 0.17 × 0.15 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	1917 independent reflections
Radiation source: fine-focus sealed tube	1675 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
ϕ scans and ω scans with κ offsets	h = −17→17
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	k = −11→11
Tmin = 0.200, Tmax = 0.271	l = −19→19
6759 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)] = 0.027	w = 1/[σ^2(Fo^2) + (0.0322P)^2 + 1.5713P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.069	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 1.29 e Å^−3
1917 reflections	Δρmin = −1.35 e Å^−3
76 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00092 (12)

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.

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
Ta1	0.5000	0.5000	0.5000	0.01880 (11)
Cl1	0.43104 (9)	0.52079 (12)	0.34243 (7)	0.0296 (2)
Cl2	0.33754 (7)	0.55757 (14)	0.52638 (7)	0.0298 (2)
Cl3	0.46034 (8)	0.23099 (12)	0.49147 (7)	0.0295 (2)
Cl4	0.36758 (8)	−0.13868 (14)	0.67504 (9)	0.0427 (3)
Cl5	0.33272 (8)	0.06577 (15)	0.83807 (7)	0.0348 (3)
Cl6	0.29916 (8)	0.21558 (13)	0.64515 (7)	0.0321 (2)
P1	0.38721 (7)	0.07149 (12)	0.72910 (7)	0.0225 (2)
N1	0.5000	0.1287 (6)	0.7500	0.0370 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ta1	0.02090 (15)	0.01762 (16)	0.01829 (16)	−0.00047 (7)	0.00553 (10)	−0.00070 (7)
Cl1	0.0359 (6)	0.0331 (6)	0.0183 (5)	−0.0020 (4)	0.0038 (4)	0.0012 (4)
Cl2	0.0248 (5)	0.0325 (6)	0.0340 (5)	0.0014 (4)	0.0111 (4)	−0.0050 (5)
Cl3	0.0342 (5)	0.0196 (5)	0.0342 (5)	−0.0025 (4)	0.0070 (4)	−0.0014 (4)
Cl4	0.0365 (6)	0.0271 (6)	0.0625 (8)	−0.0012 (5)	0.0079 (5)	−0.0178 (5)
Cl5	0.0380 (6)	0.0379 (7)	0.0311 (5)	−0.0031 (5)	0.0134 (4)	0.0057 (5)
Cl6	0.0295 (5)	0.0343 (6)	0.0312 (5)	0.0045 (4)	0.0044 (4)	0.0079 (4)
P1	0.0185 (4)	0.0185 (6)	0.0311 (5)	−0.0004 (4)	0.0070 (4)	0.0000 (4)
N1	0.020 (2)	0.026 (3)	0.064 (4)	0.000	0.009 (2)	0.000

Geometric parameters (Å, º)

Ta1—Cl1	2.3428 (11)	Cl5—P1	1.9532 (14)
Ta1—Cl3	2.3484 (10)	Cl6—P1	1.9460 (14)
Ta1—Cl2	2.3559 (9)	P1—N1	1.546 (2)
Cl4—P1	1.9586 (15)
Cl1—Ta1—Cl1^i	180.0	Cl1^i—Ta1—Cl2^i	90.01 (4)
Cl1—Ta1—Cl3	89.37 (4)	Cl3—Ta1—Cl2^i	89.64 (4)
Cl1^i—Ta1—Cl3	90.63 (4)	Cl3^i—Ta1—Cl2^i	90.36 (4)
Cl1—Ta1—Cl3^i	90.63 (4)	Cl2—Ta1—Cl2^i	180.0
Cl1^i—Ta1—Cl3^i	89.37 (4)	N1—P1—Cl6	110.14 (17)
Cl3—Ta1—Cl3^i	180.0	N1—P1—Cl5	112.33 (7)
Cl1—Ta1—Cl2	90.01 (4)	Cl6—P1—Cl5	105.88 (6)
Cl1^i—Ta1—Cl2	89.99 (4)	N1—P1—Cl4	113.59 (18)
Cl3—Ta1—Cl2	90.36 (4)	Cl6—P1—Cl4	107.76 (7)
Cl3^i—Ta1—Cl2	89.64 (4)	Cl5—P1—Cl4	106.74 (7)
Cl1—Ta1—Cl2^i	89.99 (4)	P1—N1—P1^ii	143.3 (4)
Cl6—P1—N1—P1^ii	−146.05 (8)	Cl4—P1—N1—P1^ii	−25.08 (7)
Cl5—P1—N1—P1^ii	96.20 (10)

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

(III) Bis(trichlorophosphino)iminium tri-µ-chloro-bis[trichlorotitanium(IV)]

Crystal data

(Cl6NP2)[Ti2Cl9]	Z = 2
Mr = 703.50	F(000) = 672
Triclinic, P1	Dx = 2.213 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9436 (4) Å	Cell parameters from 12979 reflections
b = 9.0892 (4) Å	θ = 4.3–26.3°
c = 14.2963 (6) Å	µ = 2.79 mm^−1
α = 91.770 (2)°	T = 250 K
β = 105.714 (3)°	Needle, colourless
γ = 107.973 (2)°	0.25 × 0.15 × 0.15 mm
V = 1055.78 (8) Å^3

Data collection

Nonius KappaCCD diffractometer	4258 independent reflections
Radiation source: fine-focus sealed tube	3346 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 9 pixels mm^-1	θmax = 26.3°, θmin = 4.3°
ϕ scans and ω scans with κ offsets	h = 0→11
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	k = −11→10
Tmin = 0.526, Tmax = 0.660	l = −17→17
12979 measured reflections

Refinement

Refinement on F^2	57 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.036	Secondary atom site location: difference Fourier map
wR(F^2) = 0.099	w = 1/[σ^2(Fo^2) + (0.0575P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
4258 reflections	Δρmax = 0.51 e Å^−3
248 parameters	Δρmin = −0.54 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.

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	Occ. (<1)
Ti1	0.35977 (6)	0.20032 (6)	0.07903 (4)	0.03053 (15)
Ti2	0.54436 (7)	0.18594 (6)	0.32013 (4)	0.03525 (16)
Cl10	0.81739 (11)	0.27859 (12)	0.37889 (7)	0.0575 (3)
Cl11	0.50611 (12)	−0.04308 (10)	0.37568 (6)	0.0486 (2)
Cl12	0.48944 (12)	0.30989 (11)	0.43719 (6)	0.0507 (2)
Cl13	0.51682 (10)	0.29241 (10)	−0.01527 (6)	0.0430 (2)
Cl14	0.19919 (10)	−0.02184 (9)	−0.01198 (6)	0.0435 (2)
Cl15	0.19202 (10)	0.33726 (10)	0.03959 (6)	0.0469 (2)
Cl16	0.25198 (9)	0.11061 (9)	0.21983 (5)	0.03626 (19)
Cl17	0.55712 (10)	0.07112 (9)	0.16598 (6)	0.03882 (19)
Cl18	0.54615 (9)	0.40449 (8)	0.21881 (5)	0.03630 (18)
N1	1.0190 (5)	0.6578 (5)	0.3119 (3)	0.0703 (13)	0.852 (6)
P1	0.9470 (2)	0.77731 (19)	0.34034 (16)	0.0394 (10)	0.852 (6)
P2	1.0800 (2)	0.57493 (19)	0.24280 (18)	0.0396 (8)	0.852 (6)
Cl1	0.8195 (2)	0.8451 (3)	0.22815 (15)	0.0813 (6)	0.852 (6)
Cl2	1.1151 (3)	0.9636 (3)	0.41932 (16)	0.0594 (6)	0.852 (6)
Cl3	0.8014 (3)	0.6936 (3)	0.4199 (2)	0.0558 (5)	0.852 (6)
Cl4	1.2374 (2)	0.4844 (3)	0.31688 (14)	0.0664 (5)	0.852 (6)
Cl5	1.1869 (4)	0.7110 (3)	0.16047 (19)	0.0633 (6)	0.852 (6)
Cl6	0.9013 (3)	0.4073 (3)	0.15365 (16)	0.0582 (5)	0.852 (6)
N1A	0.9703 (14)	0.6649 (14)	0.2651 (9)	0.072 (9)*	0.148 (6)
P1A	0.9404 (9)	0.7795 (8)	0.3313 (6)	0.032 (5)*	0.148 (6)
P2A	1.0706 (10)	0.5770 (9)	0.2309 (6)	0.029 (4)*	0.148 (6)
Cl1A	0.8152 (12)	0.9016 (13)	0.2593 (8)	0.0716 (18)	0.148 (6)
Cl2A	1.1438 (12)	0.9262 (14)	0.4175 (8)	0.051 (2)	0.148 (6)
Cl3A	0.8185 (18)	0.6721 (19)	0.4178 (11)	0.058 (2)	0.148 (6)
Cl4A	1.2195 (11)	0.5296 (14)	0.3422 (7)	0.0622 (19)	0.148 (6)
Cl5A	1.203 (2)	0.691 (2)	0.1519 (10)	0.059 (2)	0.148 (6)
Cl6A	0.9304 (13)	0.3808 (14)	0.1511 (9)	0.0488 (19)	0.148 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0302 (3)	0.0306 (3)	0.0295 (3)	0.0084 (2)	0.0087 (2)	0.0032 (2)
Ti2	0.0362 (3)	0.0358 (3)	0.0313 (3)	0.0102 (3)	0.0080 (2)	0.0047 (2)
Cl10	0.0377 (5)	0.0667 (6)	0.0557 (6)	0.0091 (4)	0.0021 (4)	0.0170 (5)
Cl11	0.0585 (5)	0.0413 (5)	0.0448 (5)	0.0162 (4)	0.0127 (4)	0.0138 (4)
Cl12	0.0669 (6)	0.0525 (5)	0.0342 (4)	0.0229 (5)	0.0143 (4)	0.0007 (4)
Cl13	0.0401 (4)	0.0469 (5)	0.0395 (4)	0.0061 (4)	0.0171 (4)	0.0068 (3)
Cl14	0.0446 (5)	0.0372 (4)	0.0391 (4)	0.0025 (4)	0.0107 (4)	−0.0035 (3)
Cl15	0.0422 (5)	0.0474 (5)	0.0541 (5)	0.0213 (4)	0.0112 (4)	0.0100 (4)
Cl16	0.0333 (4)	0.0391 (4)	0.0356 (4)	0.0073 (3)	0.0141 (3)	0.0051 (3)
Cl17	0.0438 (4)	0.0426 (4)	0.0378 (4)	0.0235 (4)	0.0137 (3)	0.0055 (3)
Cl18	0.0379 (4)	0.0295 (4)	0.0353 (4)	0.0057 (3)	0.0074 (3)	0.0020 (3)
N1	0.104 (4)	0.073 (3)	0.065 (3)	0.057 (3)	0.041 (3)	0.007 (2)
P1	0.0444 (13)	0.0440 (13)	0.0328 (9)	0.0211 (7)	0.0096 (5)	−0.0018 (4)
P2	0.0429 (10)	0.0391 (10)	0.0404 (9)	0.0188 (6)	0.0124 (6)	0.0005 (5)
Cl1	0.0887 (10)	0.1117 (16)	0.0548 (10)	0.0615 (10)	0.0052 (8)	0.0223 (10)
Cl2	0.0570 (9)	0.0571 (11)	0.0530 (7)	−0.0029 (7)	0.0253 (7)	−0.0092 (7)
Cl3	0.0517 (8)	0.0523 (10)	0.0591 (8)	0.0039 (6)	0.0262 (6)	−0.0057 (7)
Cl4	0.0672 (8)	0.0838 (12)	0.0605 (9)	0.0504 (8)	0.0089 (7)	0.0105 (8)
Cl5	0.0782 (11)	0.0428 (10)	0.0620 (9)	0.0034 (7)	0.0291 (7)	0.0056 (8)
Cl6	0.0384 (9)	0.0654 (11)	0.0591 (7)	−0.0003 (7)	0.0178 (7)	−0.0099 (7)
Cl1A	0.086 (3)	0.104 (4)	0.052 (3)	0.075 (3)	0.013 (3)	0.013 (3)
Cl2A	0.044 (3)	0.055 (4)	0.048 (3)	0.004 (3)	0.021 (3)	−0.005 (3)
Cl3A	0.058 (4)	0.051 (4)	0.052 (3)	−0.002 (3)	0.020 (3)	−0.005 (3)
Cl4A	0.059 (3)	0.080 (4)	0.058 (3)	0.043 (3)	0.009 (3)	0.014 (3)
Cl5A	0.073 (3)	0.041 (3)	0.064 (3)	0.005 (3)	0.040 (3)	0.002 (3)
Cl6A	0.034 (3)	0.045 (3)	0.069 (3)	0.010 (2)	0.025 (3)	−0.025 (2)

Geometric parameters (Å, º)

Ti1—Cl15	2.2036 (10)	P1—Cl1	1.938 (2)
Ti1—Cl13	2.2047 (9)	P1—Cl2	1.9477 (16)
Ti1—Cl14	2.2065 (9)	P1—Cl3	1.9531 (16)
Ti1—Cl17	2.4941 (9)	P2—Cl4	1.934 (2)
Ti1—Cl18	2.5047 (9)	P2—Cl6	1.9426 (16)
Ti1—Cl16	2.5127 (8)	P2—Cl5	1.9488 (18)
Ti2—Cl11	2.2115 (10)	N1A—P1A	1.517 (3)
Ti2—Cl10	2.2256 (11)	N1A—P2A	1.528 (3)
Ti2—Cl12	2.2319 (10)	P1A—Cl1A	1.938 (2)
Ti2—Cl17	2.4548 (9)	P1A—Cl2A	1.9477 (18)
Ti2—Cl16	2.4832 (9)	P1A—Cl3A	1.9532 (18)
Ti2—Cl18	2.4930 (9)	P2A—Cl4A	1.934 (2)
N1—P1	1.519 (3)	P2A—Cl6A	1.9429 (18)
N1—P2	1.530 (3)	P2A—Cl5A	1.949 (2)
Cl15—Ti1—Cl13	98.57 (4)	Ti2—Cl16—Ti1	86.43 (3)
Cl15—Ti1—Cl14	98.77 (4)	Ti2—Cl17—Ti1	87.45 (3)
Cl13—Ti1—Cl14	99.31 (4)	Ti2—Cl18—Ti1	86.39 (3)
Cl15—Ti1—Cl17	165.71 (4)	P1—N1—P2	154.3 (3)
Cl13—Ti1—Cl17	90.38 (3)	N1—P1—Cl1	113.0 (2)
Cl14—Ti1—Cl17	90.69 (4)	N1—P1—Cl2	112.55 (19)
Cl15—Ti1—Cl18	90.80 (3)	Cl1—P1—Cl2	107.08 (10)
Cl13—Ti1—Cl18	91.66 (3)	N1—P1—Cl3	111.23 (19)
Cl14—Ti1—Cl18	164.15 (4)	Cl1—P1—Cl3	106.92 (9)
Cl17—Ti1—Cl18	77.75 (3)	Cl2—P1—Cl3	105.66 (9)
Cl15—Ti1—Cl16	91.36 (3)	N1—P2—Cl4	110.3 (2)
Cl13—Ti1—Cl16	165.03 (4)	N1—P2—Cl6	111.82 (18)
Cl14—Ti1—Cl16	90.15 (3)	Cl4—P2—Cl6	107.47 (8)
Cl17—Ti1—Cl16	77.84 (3)	N1—P2—Cl5	113.88 (18)
Cl18—Ti1—Cl16	76.94 (3)	Cl4—P2—Cl5	107.10 (8)
Cl11—Ti2—Cl10	97.92 (4)	Cl6—P2—Cl5	105.92 (10)
Cl11—Ti2—Cl12	98.20 (4)	P1A—N1A—P2A	155.8 (4)
Cl10—Ti2—Cl12	97.33 (4)	N1A—P1A—Cl1A	112.9 (2)
Cl11—Ti2—Cl17	89.98 (3)	N1A—P1A—Cl2A	112.7 (2)
Cl10—Ti2—Cl17	91.88 (4)	Cl1A—P1A—Cl2A	107.03 (14)
Cl12—Ti2—Cl17	166.69 (4)	N1A—P1A—Cl3A	111.2 (2)
Cl11—Ti2—Cl16	92.26 (4)	Cl1A—P1A—Cl3A	106.91 (13)
Cl10—Ti2—Cl16	166.44 (4)	Cl2A—P1A—Cl3A	105.62 (12)
Cl12—Ti2—Cl16	90.02 (4)	N1A—P2A—Cl4A	110.4 (2)
Cl17—Ti2—Cl16	79.14 (3)	N1A—P2A—Cl6A	111.7 (2)
Cl11—Ti2—Cl18	166.04 (4)	Cl4A—P2A—Cl6A	107.45 (13)
Cl10—Ti2—Cl18	90.67 (4)	N1A—P2A—Cl5A	113.9 (2)
Cl12—Ti2—Cl18	91.55 (3)	Cl4A—P2A—Cl5A	107.09 (12)
Cl17—Ti2—Cl18	78.70 (3)	Cl6A—P2A—Cl5A	105.92 (13)
Cl16—Ti2—Cl18	77.70 (3)
Cl11—Ti2—Cl16—Ti1	−128.87 (3)	Cl10—Ti2—Cl18—Ti1	131.46 (4)
Cl10—Ti2—Cl16—Ti1	9.87 (18)	Cl12—Ti2—Cl18—Ti1	−131.18 (4)
Cl12—Ti2—Cl16—Ti1	132.93 (3)	Cl17—Ti2—Cl18—Ti1	39.68 (3)
Cl17—Ti2—Cl16—Ti1	−39.32 (3)	Cl16—Ti2—Cl18—Ti1	−41.51 (3)
Cl18—Ti2—Cl16—Ti1	41.34 (3)	Cl15—Ti1—Cl18—Ti2	132.27 (3)
Cl15—Ti1—Cl16—Ti2	−131.76 (3)	Cl13—Ti1—Cl18—Ti2	−129.13 (3)
Cl13—Ti1—Cl16—Ti2	−0.01 (15)	Cl14—Ti1—Cl18—Ti2	4.88 (14)
Cl14—Ti1—Cl16—Ti2	129.47 (3)	Cl17—Ti1—Cl18—Ti2	−39.10 (3)
Cl17—Ti1—Cl16—Ti2	38.79 (3)	Cl16—Ti1—Cl18—Ti2	41.06 (3)
Cl18—Ti1—Cl16—Ti2	−41.26 (3)	P2—N1—P1—Cl1	23.6 (8)
Cl11—Ti2—Cl17—Ti1	131.93 (4)	P2—N1—P1—Cl2	−97.9 (7)
Cl10—Ti2—Cl17—Ti1	−130.15 (4)	P2—N1—P1—Cl3	143.8 (7)
Cl12—Ti2—Cl17—Ti1	3.73 (18)	P1—N1—P2—Cl4	155.0 (7)
Cl16—Ti2—Cl17—Ti1	39.62 (3)	P1—N1—P2—Cl6	−85.5 (7)
Cl18—Ti2—Cl17—Ti1	−39.84 (3)	P1—N1—P2—Cl5	34.5 (8)
Cl15—Ti1—Cl17—Ti2	2.38 (16)	P2A—N1A—P1A—Cl1A	138 (2)
Cl13—Ti1—Cl17—Ti2	131.40 (3)	P2A—N1A—P1A—Cl2A	16 (2)
Cl14—Ti1—Cl17—Ti2	−129.28 (3)	P2A—N1A—P1A—Cl3A	−102 (2)
Cl18—Ti1—Cl17—Ti2	39.78 (3)	P1A—N1A—P2A—Cl4A	36 (2)
Cl16—Ti1—Cl17—Ti2	−39.28 (3)	P1A—N1A—P2A—Cl6A	156 (2)
Cl11—Ti2—Cl18—Ti1	3.27 (17)	P1A—N1A—P2A—Cl5A	−84 (2)

(IV) Bis[bis(trichlorophosphino)iminium] di-µ-chloro-bis[tetrachlorozirconium(IV)]

Crystal data

(Cl6NP2)2[Zr2Cl10]	F(000) = 2112
Mr = 1114.24	Dx = 2.285 Mg m^−3
Orthorhombic, Cmca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2	Cell parameters from 7047 reflections
a = 18.0456 (4) Å	θ = 3.3–26.5°
b = 11.4295 (6) Å	µ = 2.66 mm^−1
c = 15.7039 (5) Å	T = 250 K
V = 3239.0 (2) Å^3	Needle, colourless
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer	1725 independent reflections
Radiation source: fine-focus sealed tube	1386 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 9 pixels mm^-1	θmax = 26.5°, θmin = 3.3°
ϕ scans and ω scans with κ offsets	h = −22→22
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	k = −14→14
Tmin = 0.498, Tmax = 0.769	l = −19→0
7407 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)] = 0.030	w = 1/[σ^2(Fo^2) + (0.0297P)^2 + 3.226P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.074	(Δ/σ)max = 0.001
S = 1.06	Δρmax = 0.40 e Å^−3
1725 reflections	Δρmin = −0.40 e Å^−3
76 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00067 (9)

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.

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	0.0000	0.15039 (3)	0.56964 (2)	0.03063 (15)
Cl1	0.0000	0.07877 (9)	0.41179 (7)	0.0422 (3)
Cl2	0.0000	0.17037 (11)	0.72136 (7)	0.0470 (3)
Cl3	0.13433 (5)	0.14417 (8)	0.56419 (6)	0.0552 (3)
Cl4	0.0000	0.34968 (10)	0.52937 (9)	0.0537 (3)
Cl5	0.11584 (6)	0.40936 (9)	0.73073 (7)	0.0635 (3)
Cl6	0.14964 (6)	0.63068 (9)	0.61942 (6)	0.0614 (3)
Cl7	0.24468 (6)	0.40472 (8)	0.59714 (6)	0.0588 (3)
P1	0.19578 (5)	0.50311 (8)	0.68220 (5)	0.0385 (2)
N1	0.2500	0.5532 (3)	0.7500	0.0401 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zr1	0.0313 (3)	0.0286 (2)	0.0319 (2)	0.000	0.000	−0.00253 (16)
Cl1	0.0650 (8)	0.0310 (5)	0.0306 (5)	0.000	0.000	−0.0006 (4)
Cl2	0.0627 (8)	0.0454 (7)	0.0329 (6)	0.000	0.000	−0.0031 (5)
Cl3	0.0321 (5)	0.0592 (6)	0.0743 (6)	0.0003 (4)	0.0017 (4)	−0.0189 (5)
Cl4	0.0711 (9)	0.0328 (6)	0.0570 (7)	0.000	0.000	0.0092 (5)
Cl5	0.0547 (6)	0.0701 (7)	0.0656 (6)	−0.0202 (5)	0.0057 (5)	0.0059 (5)
Cl6	0.0643 (6)	0.0631 (6)	0.0567 (5)	0.0129 (5)	−0.0102 (5)	0.0139 (5)
Cl7	0.0741 (7)	0.0578 (6)	0.0446 (5)	0.0040 (5)	0.0047 (4)	−0.0150 (4)
P1	0.0428 (5)	0.0395 (5)	0.0332 (4)	−0.0012 (4)	0.0001 (3)	0.0004 (3)
N1	0.047 (2)	0.040 (2)	0.0335 (19)	0.000	−0.0014 (16)	0.000

Geometric parameters (Å, º)

Zr1—Cl4	2.3640 (12)	Cl5—P1	1.9520 (12)
Zr1—Cl2	2.3935 (11)	Cl6—P1	1.9471 (12)
Zr1—Cl3	2.4266 (9)	Cl7—P1	1.9565 (12)
Zr1—Cl1	2.6106 (11)	P1—N1	1.5554 (16)
Zr1—Cl1^i	2.6354 (12)
Cl4—Zr1—Cl2	100.04 (5)	Cl3—Zr1—Cl1^i	88.55 (2)
Cl4—Zr1—Cl3	91.08 (3)	Cl3^ii—Zr1—Cl1^i	88.55 (2)
Cl2—Zr1—Cl3	92.17 (2)	Cl1—Zr1—Cl1^i	78.08 (4)
Cl4—Zr1—Cl3^ii	91.08 (3)	Zr1—Cl1—Zr1^i	101.92 (4)
Cl2—Zr1—Cl3^ii	92.17 (2)	N1—P1—Cl6	109.86 (14)
Cl3—Zr1—Cl3^ii	174.74 (5)	N1—P1—Cl5	113.57 (8)
Cl4—Zr1—Cl1	92.76 (4)	Cl6—P1—Cl5	107.02 (6)
Cl2—Zr1—Cl1	167.20 (4)	N1—P1—Cl7	113.29 (9)
Cl3—Zr1—Cl1	87.55 (2)	Cl6—P1—Cl7	106.12 (6)
Cl3^ii—Zr1—Cl1	87.55 (2)	Cl5—P1—Cl7	106.52 (6)
Cl4—Zr1—Cl1^i	170.84 (4)	P1—N1—P1^iii	136.8 (3)
Cl2—Zr1—Cl1^i	89.12 (4)
Cl4—Zr1—Cl1—Zr1^i	180.0	Cl1^i—Zr1—Cl1—Zr1^i	0.0
Cl2—Zr1—Cl1—Zr1^i	0.0	Cl6—P1—N1—P1^iii	−178.31 (6)
Cl3—Zr1—Cl1—Zr1^i	89.04 (3)	Cl5—P1—N1—P1^iii	61.88 (7)
Cl3^ii—Zr1—Cl1—Zr1^i	−89.04 (3)	Cl7—P1—N1—P1^iii	−59.83 (7)

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