Structure, magnetism and colour in simple bis­(phosphine)nickel(II) dihalide complexes: an experimental and theoretical investigation

The complex [1,2-bis­(di-tert-butyl­phosphan­yl)ethane-κ²P,P′]di­iodido­nickel(II), [NiI₂(C₁₈H₄₀P₂] or (dtbpe-κ²P)NiI₂, [dtbpe is 1,2-bis­(di-tert-butyl­phosphan­yl)ethane], is bright blue–green in the solid state and in solution, but, contrary to the structure predicted for a blue or green nickel(II) bis­(phos­phine) complex, it is found to be close to square planar in the solid state. The solution structure is deduced to be similar, because the optical spectra measured in solution and in the solid state contain similar absorptions. In solution at room temperature, no ³¹P{¹H} NMR resonance is observed, but the very small solid-state magnetic moment at temperatures down to 4 K indicates that the weak paramagnetism of this nickel(II) complex can be ascribed to temperature independent paramagnetism, and that the complex has no unpaired electrons. The red [1,2-bis­(di-tert-butyl­phosphan­yl)ethane-κ²P,P′]di­chlorido­nickel(II), [NiCl₂(C₁₈H₄₀P₂] or (dtbpe-κ²P)NiCl₂, is very close to square planar and very weakly paramagnetic in the solid state and in solution, while the maroon [1,2-bis­(di-tert-butyl­phosphan­yl)ethane-κ²P,P′]di­bromido­nickel(II), [NiBr₂(C₁₈H₄₀P₂] or (dtbpe-κ²P)NiBr₂, is isostructural with the diiodide in the solid state, and displays paramagnetism inter­mediate between that of the dichloride and the diiodide in the solid state and in solution. Density functional calculations demonstrate that distortion from an ideal square plane for these complexes occurs on a flat potential energy surface. The calculations reproduce the observed structures and colours, and explain the trends observed for these and similar complexes. Although theoretical investigation identified magnetic-dipole-allowed excitations that are characteristic for temperature-independent paramagnetism (TIP), theory predicts the mol­ecules to be diamagnetic.

S1. Introduction

It is axiomatic in the chemistry of nickel(II) complexes with four ligands that orange and red examples are square planar and diamagnetic, while green and blue examples are tetra­hedral and paramagnetic (Cotton et al., 1999; Hayter & Humiec, 1965). The magnetism can be explained by a simple crystal field model as resulting from the eight valence electrons occupying the d orbitals, split by the different crystal fields of the two geometries as shown in Fig. 1. For a square-planar geometry, the d_x2-y2 orbital lies at much higher energy than the other d orbitals and so the ground state is expected to be diamagnetic. For a tetra­hedral geometry, paramagnetism results from single occupation of two of the degenerate d_xy, d_xz and d_yz orbitals, leading to a triplet ground state.

A few exceptions to the `square planar equals diamagnetic' rule for Ni^II have been reported, involving N—P—O chelating ligands (Brück et al., 1996; Frömmel et al., 1992); these square-planar paramagnetic complexes are green or blue. The origin of their paramagnetism has been deduced through theoretical investigations to lie in the strong π bonding of the amide group, which leads to a smaller gap between the two highest energy orbitals. In combination with the relatively large pairing energy of Ni^II this can lead to a high-spin ground state, depending on the ligands (Bridgeman, 2008).

The colours of transition metal complexes result largely from electronic transitions within the d orbitals. In the vast majority of four-coordinate Ni^II complexes, square planar, diamagnetic examples are observed to be red or orange, while tetra­hedral, paramagnetic complexes are green or blue (Hayter & Humiec, 1965). For the C_2v symmetric square-planar complexes, the colour has been ascribed to the ¹A₁ → ¹B₂ transition (Jarrett & Sadler, 1991; van Hecke & Horrocks, 1966).

A solution square-planar (diamagnetic)–tetra­hedral (paramagnetic) equilibrium for complexes of the type Ni(PR₃)₂X₂ was first proposed 50 years ago (Hayter & Humiec, 1962). In that work, Ni(PEtPh₂)₂Br₂ is found to crystallize either in a green tetra­hedral paramagnetic form or in a red square-planar diamagnetic form, depending on the solvent used. The dichloride forms such red crystals while the diiodide forms a brown–red tetra­hedral paramagnetic structure. For the simplest member of this series, Ni(PPh₃)₂Cl₂, first reported 55 years ago (Venanzi, 1958), crystals can be grown of either the blue–green tetra­hedral or the red square-planar isomer, depending on the solvent used (Corain et al., 1985).

In this work, we focus on neutral complexes of the type P₂NiX₂, with P₂ being a bidentate phosphine ligand and X a halide. With the bidentate ligand bis­(di­phenyl­phosphanyl)propane (dppp), the three dihalides, (dppp-κ²P)NiX₂ (X = Cl, Br, I), are found to be diamagnetic and red (Cl and Br) or purple (I) in the solid state, but show paramagnetism in solution, increasing in the order Cl < Br < I, which can be attributed to an equilibrium between structures with singlet and triplet ground states (van Hecke & Horrocks, 1966). Only the crystal structure of the dichloride has been reported, and it is square planar in the sold state (Bomfim et al., 2003). The analogous complexes of bis­(di­phenyl­phosphanyl)ethane, (dppe-κ²P)NiX₂ (X = Cl, Br, I), with an ethyl­ene, rather than a propyl­ene, bridge between the P atoms are reported to be red (Cl and Br) and deep purple (I), and diamagnetic in the solid state and in solution at all temperatures (van Hecke & Horrocks, 1966), although the initial report of (dppe-κ²P)NiCl₂ indicated that it showed variable amounts of paramagnetism (Booth & Chatt, 1965). The structures of the dichloride and dibromide have been reported multiple times and the compounds are always square planar (Beaudoin et al., 2001; Bomfim et al., 2003; Busby et al., 1993; Rahn et al., 1989; Spek et al., 1987). However, the same complexes (dppe-κ²P)NiX₂ (X = Cl, Br, I) have also been reported to exhibit temperature-independent paramagnetism in the solid state (Hudson et al., 1968; Jarrett & Sadler, 1991) while being diamagnetic in solution (Jarrett & Sadler, 1991).

A search of the Cambridge Structural Database (CSD; Version 5.34; Allen, 2002) shows that all 25 reported Ni(P–P)X₂ complexes that have been crystallographically characterized involving bidentate ligands of this type are cis-oriented and square planar, including some with heteroatoms in the ligand (Lavanant et al., 2008), and with very long chelate rings (up to eight members) (Pandarus et al., 2008). All dichloride and dibromide complexes that have been crystallographically characterised are described as red or orange. To date, only one Ni^II bis­(phosphine) diiodide has been characterized crystallographically; this square-planar complex is described as purple (Angulo, Bouwman, Lutz et al., 2001).

In published reports of distorted square-planar complexes, the distortion has usually been measured by defining two planes based on the metal and the ligand pairs (in these cases, P–P—Ni and X–X—Ni) and measuring the dihedral angle between these planes (Martin et al., 1991; Miedaner et al., 1991). This method is easy to define and calculate but has the major disadvantage that the planes may be tilted as well as rotated with respect to each other. That is, this method measures a mixture of pyramidalization and tetra­hedral distortion. In complexes with unsymmetrical ligands, the pyramidalization frequently makes a larger contribution to the observed angle than the tetra­hedral distortion. In this work, we use the mean of the two torsion angles P···P···X···X to describe deviations from ideal square-planar geometry.

Bidentate bis­(phosphines) with alkyl substituents such as methyl (dmpe), ethyl (depe) and cyclo­hexyl (dcpe) have long been used in nickel chemistry. In recent years, inter­est has moved to the more bulky tert-butyl substituent on the ligand bis­(di-tert-butyl­phosphanyl)ethane (dtbpe). The compound (dtbpe-κ²P)NiCl₂ has been used as a starting material for nickel complexes with inter­esting properties by Pörschke (Bach et al., 1999) and Hillhouse (Anderson et al., 2010; Kitiachvili et al., 2004; Mindiola & Hillhouse, 2001; Waterman & Hillhouse, 2008). In Pörschke's reported synthesis, it is described as red and paramagnetic, based on the lack of observation of a ³¹P{¹H} NMR resonance. This observation seemed to contradict the general rule of red Ni^II complexes being square planar and diamagnetic, and so warranted further investigation. The related nickel(I) dimer, [(dtbpe-κ²P)NiCl]₂, has been reported by Hillhouse, and is found to be tetra­hedral; inter­estingly, oxidation of a single nickel centre leads to a structure in which both nickel centres are almost square planar (Mindiola et al., 2003).

It was therefore of inter­est to resolve the issue of structure and magnetism for the rather simple complex (dtbpe-κ²P)NiCl₂ and its homologues (dtbpe-κ²P)NiBr₂ and (dtbpe-κ²P)NiI₂. Experimental techniques including spectroscopy and X-ray crystallography have been supplemented by the use of density functional theory to probe the molecular structure, the predicted electronic ground state and the expected electronic absorptions. To validate our theoretical methods we also prepared and characterised (dppe-κ²P)NiI₂. During the course of our investigations we became inter­ested in the theoretical study of temperature independent paramagnetism of these molecules and the results of this study are also reported.

S2. Results and discussion

S2.1. Synthesis

The synthesis of the dichloride and diiodide complexes, (dtbpe-κ²P)NiX₂ (X = Cl, I) and (dppe-κ²P)NiI₂ proceeded in high yield from the corresponding anhydrous nickel halides and bis­(phosphine) ligands in refluxing ethanol, while the bromide was prepared from NiBr₂(PPh₃)₂ in toluene. The compounds are quite air stable as solids [although (dtbpe-κ²P)NiI₂ decomposes in the solid state over years] but they decompose in solution in air over a few hours. Scheme 1 shows the connectivity of the complexes studied in this work.

S2.2. Characterization

S2.2.1. Crystal and Molecular Structures

Crystal data, data collection and structure refinement details are summarized in Table 1. The solid-state structures of the four compounds were determined by X-ray crystallography at 200 K. A structure of the dichloride has previously been provided as a personal communication to the CSD with two molecules of chloro­form in the asymmetric unit, with a mean of the torsion angles P···P···Cl···Cl of 11° (Batsanov et al., 2009). We were able to obtain X-ray quality crystals of the dichloride with and without chloro­form, both with different space groups and unit cell parameters from those of the structure in the CSD.

Table 2 contains important bond distances and angles for the five crystal structures, while data collection and structure solution parameters are included in the Experimental section. Fig. 2 shows the two chemically equivalent but crystallographically unique molecules in the asymmetric unit for solvent-free (dtbpe-κ²P)NiCl₂. A view of (dtbpe-κ²P)NiI₂ is shown in Fig. 3. The dibromide is isostructural to the diiodide.

It can be seen from Figs. 2 and 3 that the halide atoms are not in the plane formed by the Ni^II and two P atoms; the means of the two torsion angles P···P···X···X for each structure are provided in Table 2. The distortion from square planarity for the dibromide and diiodide, over 19°, is greater than in any analogous complex in the CSD; the only other values above 15° are found for complexes with a propyl­ene rather than ethyl­ene tether in the bis­(phosphine) ligand (Angulo, Bouwman, Lok et al., 2001).

Examples of crystallographically characterised nickel(II) bis­(phosphine) dihalide complexes are relatively common; nearly 60 structures can be found in the CSD although several complexes have been reported in multiple modifications. Compared with the typical distances and angles for those reported structures, the bond distances and angles are slightly unusual in the four dtbpe structures. In particular, with an ethyl­ene bridge between the two P atoms (23 structures in the CSD), P—Ni—P angles of around 87° are more common than the 90° observed in these dtbpe structures, and the Ni—P bond distances of 2.2 Å observed here are somewhat longer than is found for complexes with other substituents on the phosphine, where Ni—P distances of around 2.15 Å are more usual. The bond distances and angles in the structure of (dppe-κ²P)NiI₂ reported here fall exactly in the normal ranges. Thus, the steric bulk of the tert-butyl groups appears to be putting pressure on the coordination environment. However, the Ni—X distances are not changed in the dtbpe structures from those observed in structures with less bulky ligands.

A steric explanation for the non-zero torsion angles, which is consistent with the changes to bond distances and angles just described, can be found in the orientation of the tert-butyl groups of the dtbpe ligand. As can be seen from the structures in Figs. 2 and 3, the four tert-butyl groups are not equivalent in the crystals. The (dtbpe-κ²P)Ni fragment possesses pseudo-C₂ symmetry, so that the pairs of tert-butyl groups that are transformed into one another by rotation are nearly symmetry equivalent. Two of the tert-butyl groups are in a perfectly staggered conformation with respect to the other substituents on the phospho­rus atom (C_A and C_A'), each of which has one methyl group pointing towards the halide ligands (C_A1 and C_A'1). The other two tert-butyl groups are slightly rotated with respect to a staggered conformation, and none of their methyl groups point at the halide ligands (C_B and C_B' in Figs. 2 and 3). This results in openings in the coordination environment across one, but not the other, diagonal looking along the axis from Ni to the midpoint of P1 and P2 (the view in Figs. 2 and 3). In all but one of the dtbpe structures, the two halide ligands are notably distorted into these openings, as can be seen in Figures 2 and 3. We define a positive dihedral distortion (mean of the torsion angles P···P···X···X) as one in which the halide ligands are moved towards the opening as described. A negative dihedral distortion is then rotation of the halide ligands towards the nearest methyl groups. Such a negative distortion has been observed once in these structures, in the second unique molecule in the asymmetric unit of the solvent free dichloride, a view of which is shown in Fig. 4.

The fact that in most cases the direction of distortion is apparently determined by the tert-butyl groups implies that it is of steric origin. Because the Ni—I and Ni—Br distances are longer than the Ni—Cl distance, the larger halide ligands are closer to the region where the methyl protons are found, and so more sensitive to this steric effect. This explains the lower distortion in the dichloride and the existence of the sterically unfavourable conformation shown in Fig. 4.

In the absence of the steric pressure caused by the tert-butyl groups, such as in (dppe-κ²P)NiI₂, no distortion from square-planar geometry is observed. This is consistent with the square-planar structures previously reported for compounds of this type, which have significantly less bulky substituents on phospho­rus.

The ethyl­ene backbone of the dtbpe ligand can be oriented parallel to the diagonal opening in which the halide ligands fit from C_B to C_B', which we call the P conformation and which is the conformation observed in the structures in Figs. 2 and 3, or in the opposite direction, the O conformation. Alternatively, the halide ligands can be oriented towards the closest methyl groups as seen in Fig. 4, which we call the K conformation. These structural possibilities and their inter­conversions are summarized in Fig. 5.

Only the P and K conformations have been observed crystallographically. However, in the calculations discussed below, minima were located for the P and O conformations.

S2.2.2. Optical spectroscopy

The colours of the three compounds are very different; the dichloride is deep red, the dibromide, maroon, and the diiodide is deep blue–green. The optical spectra were measured in di­chloro­methane solution and in the solid state using diffuse refle­cta­nce on a powdered sample and transmittance on thin films. Fig. 6 contains the solution spectra, while Table 2 provides the observed λ_max values for both solution and solid-state measurements.

It can be seen from Table 3 that the positions of the absorptions are almost unchanged on going from the solution to the solid state spectra, and the characteristic double absorption of the dibromide appears in both spectra. This indicates that the structures are very likely the same in solution as those determined in the solid state. For this reason, a solution equilibrium between the square-planar and tetra­hedral forms is considered unlikely although we cannot rule it out.

No band is observed in any of the spectra in the range 800–1000 nm for freshly prepared and recrystallized complexes. A band in this region is reported to result from the ³T₁ → ³A₂ transition of the tetra­hedral isomer (van Hecke & Horrocks, 1966), and its absence speaks against the existence of a solution equilibrium between the two geometries. A band was observed in solution at 913 nm and in the solid state at 937 nm for samples of the diiodide that had partially decomposed. It is worth noting that freshly prepared samples of the diiodide appear blue–green, and as the samples stand in air in solution they become visibly more green within minutes. The dibromide and dichloride decompose more slowly in air in solution over hours, and lose colour as they do so.

S2.2.3. Magnetism

The magnetism of the three complexes was measured in the solid state at room temperature using a Gouy balance, and then at temperatures from 4–300 K using a SQUID magnetometer. Only extremely small values that did not vary with temperature were recorded for freshly recrystallised samples of the dibromide (0.2 BM at room temperature) and diiodide (0.4 BM at room temperature), while the dichloride appeared diamagnetic, with a small negative value recorded at room temperature. Low magnetic moments between 0.1–0.4 BM recorded for complexes of the type (dppe-κ²P)NiX₂ (X = Cl, Br, I) were originally ascribed to some oxidation of the complexes (Hudson et al., 1968); however, they may derive from the temperature-independent paramagnetism in pure samples, as has subsequently been reported (Jarrett & Sadler, 1991).

The ¹H NMR spectra of the three complexes at room temperature in CD₂Cl₂ solution indicate that they vary from very slightly (dichloride: ν_1/2 = 100 Hz at room temperature) to somewhat paramagnetic; in a solution of the diiodide complex, no ³¹P signal is observed. The temperature dependence of the ¹H NMR and ³¹P{¹H} spectra for the dichloride and dibromide were measured; all become sharper at lower temperatures and broader at higher temperatures, as well as moving to lower field with increasing temperature. Fig. 7 contains a chemical shift versus 1/T plot for the ³¹P{¹H} resonance of the dibromide; similar data were obtained for the dichloride. Table 3 presents the variable temperature NMR data.

Non-linear plots of chemical shift versus 1/T indicate that the behaviour is non-Curie–Weiss. Multiple attempts to qu­antify the solution magnetism using the Evans method were unsuccessful (Evans, 1959); due to the low magnetic moments only extremely small changes in chemical shift were observed and no qu­anti­tative data could be obtained. Sophisticated NMR methods are now available for the inter­pretation of paramagnetic complexes (Cremer & Burger, 2003; Köhler, 2011). However, to date the NMR data could not be fitted with these methods to an equilibrium between a paramagnetic (tetra­hedral) and a diamagnetic (square planar) complex, as has been done for related systems (Pignolet & Horrocks, 1969).

S2.2.4. Density functional theory

Structure optimizations were carried out for singlet closed-shell and triplet (unrestricted Kohn–Sham) ground states using TURBOMOLE (Bauernschmitt & Ahlrichs, 1996; Bauernschmitt et al., 1997; Deglmann et al., 2004; Eichkorn et al., 1995; Eichkorn et al., 1997; Furche & Ahlrichs, 2002; Furche & Rappoport, 2005; Häser & Ahlrichs, 1989; Hättig & Köhn, 2002; Hättig & Weigend, 2000; Schäfer et al., 1992; Treutler & Ahlrichs, 1995; TURBOMOLE, 2012; Weigend, 2006; Weigend & Ahlrichs, 2005; Weigend et al., 1998, 2003). Although the wavefunctions with S_z = 1n at UHF/UKS level are not eigenfunctions of S², we will refer to them as triplet wavefunctions because they show only moderate spin-contamination, typically the deviation from <S²> = 2n² is about 0.01 n². The triplet-optimized structures show a pseudo-tetra­hedral coordination on the nickel atom, which is significantly different from that observed in the crystal structures. In terms of energy, triplet and singlet ground state energies for the corresponding optimized structures are similar. The singlet–triplet splitting varies systematically with the amount of Hartree–Fock (HF) exchange used in the exchange–correlation functional, where more HF exchange favours the triplet ground state. The triplet UHF wavefunction itself is lower in energy than the singlet RHF wave function even for (DFT) singlet optimized structures. Based on the calculations it can therefore not be excluded that the pseudo-tetra­hedral structure with a triplet ground state is significantly populated in an equilibrium in solution. Unless otherwise noted, energies are discussed at the B3LYP/def2-TZVPP//BP86/def2-TZVP level of theory (Becke, 1988, 1993; Dirac, 1929; Lee et al., 1988; Perdew, 1986; Slater, 1951; Vosko et al., 1980).

Since the crystal structure as well as the magnetic properties in solution indicate that the singlet structure dominates, only singlet states will be discussed in the following. The structural possibilities discussed above lead to two distinctive minima for conformations of the (dtbpe-κ²P)NiX₂ complexes depicted in Fig. 5. The ethyl­ene backbone is found to be oriented parallel with (P) or opposite (O) the opening in the coordination environment created by the tert-butyl groups; no minimum was found for the K conformation. The energy barrier required for inversion of the ethyl­ene backbone is very low (< 25 kJ mol^-1) in all cases. The energy of O relative to P is 7 (Cl), 1 (Br) and -3 (I). Figs. 8–10 show a relaxed potential surface for the distortion of the complexes out of planarity in each conformation. It can be seen that the minimum found for the O isomer is in all cases the more distorted one, and the distortion angles increase in the order Cl < Br < I. The planar structures have the shortest Ni—X distances and the distorted structures exhibit miniscule changes in the Ni—X distances with distances elongated around 0.004, 0.006 and 0.015 Å for the dichloride, dibromide and diiodide, respectively. The diiodide complex is the only one for which P and O have a minimum structure at similar distortion angles at around 23°, slightly greater than the crystallographically observed angle of 19.7°.

As explained above, all but one of the crystal structures correspond to the P isomers, and the bond distances and angles for the calculated minimum energy P structures are given in Table 2. It can be seen from that table that the calculations reproduce the bond distances and angles of the observed structures well, in particular the elongation of the Ni—P bond compared with less bulky phosphines described above. The distortion from planarity is also found for the minimum-energy structures. The calculations indicate that this is a very soft potential surface and also that flipping the backbone conformation (P to O) is a low-energy process. The existence of at least three different crystalline modifications of the dichloride with four different distortion angles supports the notion that the distortion is on a flat energy surface, and that packing effects will significantly affect the observed structure.

Using the calculated minimum structures, the vertical excitation spectra (showing the energy differences between ground and excited states at ground state geometry) were calculated at the B3LYP/def2-TZVPP//BP86/def2-TZVP level of linear response-time-dependent density functional theory (TDDFT) within the adiabatic approximation. Other choices of functionals for excitation or geometry optimization did not significantly change the relative positions of the excitations under consideration, but moved their absolute positions. The chosen methodology showed the best agreement with the absolute positions of excitations observed experimentally. The colour was attributed to the most intense absorption in the region with highest spectral sensitivity to human visual perception, between 650–450 nm. The computed excitation energies are in good agreement with experiment (Table 5).

The location of the main absorption differs between P and O isomers by less than 5 nm. For the dibromide and dichloride, the distortion of the minimum structures with respect to planarity changes the excitation energy only very slightly. In the case of the diiodide, the restriction to planarity leads to a blue shift of 20 nm. The change of the total electron density associated with this excitation is metal-centred and implies a d_xy to d_x2-y2 transition in all studied complexes of P-type. Fig. 11 shows the calculated energies of the excited states of the P isomers for the different dihalide complexes.

Based on these TDDFT calculations, the excitation cannot be attributed to a simple transition from one occupied to one virtual orbital. Instead, there are several occupied to LUMO (lowest unoccupied molecular orbital) contributions. The LUMO is the anti­bonding combination of metal d_x2-y2 and halide p-orbitals. The most important contributing occupied orbitals are bonding or non-bonding combinations of the d_xy-metal and p-halide orbitals. In all cases the HOMO-2 (highest occupied molecular orbital) has the largest contribution, for the less distorted complexes about 60%.

The red shift of the main absorption on going from the dichloride complex to the dibromide complex and from a planar diiodide complex to the actual distorted diiodide complex (see Table 5 and Fig. 11) is reflected in the increasing orbital energies of contributing occupied orbitals and decreasing LUMO orbital energy. This can be rationalized in terms of higher p-orbital energies of the heavier halogen atoms and less overlap of halogen p-orbitals with metal orbitals, which results in weaker bonding and anti­bonding character. The influence of distortion can be understood in terms of further reduced overlap in bonding and anti­bonding orbitals. This dependence on the halide ligand is also predicted by the spectrochemical series. To verify this methodology, calculations were used to predict the positions of the corresponding absorptions of analogous complexes with phenyl-substituted bis­(phosphine) ligands, which have colours, structures and magnetism as described in the introduction and above. Table 6 summarizes the results.

As can be seen from Tables 5 and 6, the computed wavelengths are systematically red-shifted by around 10–20 nm so that the observed trends both in terms of bis­(phosphine) ligand dtbpe > dppp > dppe and halide ligand I > Br > Cl are correctly predicted. This is illustrated in Fig. 12.

In general, the agreement of calculated absorptions with experiment is somewhat worse for phenyl-substituted ligands compared with dtbpe. A reason for this could be dispersion inter­action between the phenyl rings, which influences the structures of the complexes. Indeed, if the geometry is optimized with Grimme's dispersion correction (Grimme et al., 2010) and the excitation energy then recomputed [B3LYP/def2-TZVPP//BP86—D3/def2-SV(P)], the values for dtbpe change less than those for phenyl-containing bis­(phosphines). Although the results obtained are somewhat improved, this should not be overinter­preted. Effects of dispersion inter­actions on the structures with phenyl-substituted ligands probably influence the excitation energies to a degree comparable to the deviations between experiment and theory.

The calculations also show that as compared to dtbpe, dppe complexes have a more stable singlet ground state, while dppp complexes have a more stable triplet ground state. This is in agreement with the fact that an equilibrium between molecules with singlet and triplet ground states has been observed for the complexes (dppp-κ²P)NiX₂ (van Hecke & Horrocks, 1966). As above, the calculated singlet-triplet splitting varies with the amount of HF-exchange used, while the ligand dependence is the same for all functionals.

S2.2.5. Temperature independent paramagnetism

Small magnetic moments are difficult to measure experimentally and are sensitive to impurities from compounds with higher magnetic moments (Walter et al., 2006). In particular, temperature independent paramagnetism (TIP) is difficult to measure accurately, particularly for compounds that can decompose to products with temperature dependent paramagnetism, such as the nickel complexes in this study. We have investigated TIP in detail for the complexes introduced above using DFT/TDDFT and for model complexes also using coupled cluster calculations; an extensive discussion is given in the Supplementary Information. We conclude that planar d⁸ nickel complexes can, based on simple crystal-field arguments and based on our DFT and ab initio calculations, be expected to have paramagnetic contributions to the magnetisability comparable to those of the molecules for which TIP is well-established (such as BH and isoelectronic molecules) (Fowler & Steiner, 1992, 1993; Pelloni et al., 2009; Ruud et al., 1995; Sauer et al., 1993; Stevens & Lipscomb, 1965). The magnitude of the individual contributions is similar and the corresponding excitations can be understood in terms of simple orbital considerations. However, the nickel bis­(phosphine) complexes have a much higher number of atoms and electrons and therefore a much larger diamagnetic contribution, which overcompensates this paramagnetic part by far, so no TIP is expected according to these calculations. The calculations therefore suggest that the small paramagnetism observed in experiments is due to conventional, temperature-dependent paramagnetism of species that are present only in very small concentrations. These are likely pseudo-tetra­hedral nickel bis­(phosphine) complexes with triplet ground states that either result from decomposition, or exist in equilibrium with the near planar complexes, at concentrations too low to be observed by optical spectroscopy.

S3. Conclusions

The crystal structures and spectroscopic and magnetic properties of the compounds (dtbpe-κ²P)NiX₂ are not as straightforward as their rather simple chemical structures would suggest. Density functional theory indicates that the distortions from square planarity observed in the solid state lie on a very flat energy surface. Good agreement between theory and experiment was observed for the geometries and colours of the complexes. The colour of the diiodide, while somewhat unexpected, does not indicate a tetra­hedral structure and is the result of the reduced excitation energy for this combination of sterically hindered ligand and heavy halide.

Experiments showed weak paramagnetism similar to that previously found in dppe complexes and attributed in those reports to temperature independent paramagnetism (TIP). Theory does not predict TIP for these complexes because the calculated paramagnetic contribution is outweighed by the diamagnetic component. Traces of paramagnetic impurities, or an equilibrium between planar (singlet) and pseudo-tetra­hedral (triplet) complexes, are more likely responsible for the observed magnetism according to our calculations, and cannot be ruled out on the basis of the experiments.

S4. Experimental

S4.1. Synthetic details

For the preparation of (dtbpe-κ²P)NiCl₂, anhydrous nickel dichloride (0.20 g, 1.5 mmol) was suspended in ethanol (20 ml) and a solution of dtbpe (0.50 g, 1.6 mmol) in ethanol (30 ml) was added. The resulting mixture was heated under reflux for 4 h, during which time the colour changed from orange to deep red. Upon cooling, a red solid product was obtained (yield 0.50 g, 1.1 mmol, 74%). Recrystallisation from CH₂Cl₂ led to the formation of solvent-free X-ray-quality crystals. Recrystallization from CHCl₃ led to the formation of X-ray quality crystals of (dtbpe-κ²P)NiCl₂.2CHCl₃, which lose solvent readily. Both sets of crystals are air-stable when dry but decompose over hours in solution. When heated to 523 K the compound loses colour irreversibly but it does not melt to 573 K Analysis calculated for C₁₈H₄₀NiCl₂P₂: C 48.25, H 9.00, P 13.83%; found: C 48.14, H 8.96, P 13.83%. UV–Vis: solution: 351 (1800), 495 (790) nm; solid: 323, 491 nm. MS(FAB): 448 (M⁺), 411 (M - Cl)⁺ (with correct isotope patterns). ¹H NMR (500 MHz, CDCl₃, 298 K): δ 1.71 (br d, 4H, CH₂CH₂), 1.58 (br d, 36H, t-Bu). ³¹P{¹H} NMR (202 MHz, CDCl₃, 298 K): δ 89.5 (ν_1/2 = 300 Hz).

For the preparation of (dtbpe-κ²P)NiBr₂, NiBr₂(PPh₃)₂ (0.70 g, 0.94 mmol) and dtbpe (0.30 g, 0.94 mmol) were weighed into separate Schlenk flasks. Toluene (20 ml) was added to both flasks which were warmed slightly. The dtbpe solution was added to the green nickel suspension via cannula, and the resulting deep-red mixture was heated to reflux. The toluene was removed in vacuo and the product was extracted to CH₂Cl₂ and filtered through Celite, then the CH₂Cl₂ was also removed under dynamic vacuum. The PPh₃ was washed out with hexane and deep maroon microcrystals were collected (yield 0.35 g, 0.65 mmol, 69%). The compound decomposes without melting at 543 K. Analysis calculated for C₁₈H₄₀NiBr₂P₂: C 40.26, H 7.51, P 11.54%; found: C 40.03, H 7.37, P 11.41%. UV–Vis: solution: 417 (340), 523 (420) nm; solid: 550, 425 nm. MS(FAB): 457 (M - Br)⁺ (correct isotope pattern). ¹H NMR (500 MHz, CDCl₃, 298 K): δ 1.7 (br, 4H, CH₂CH₂), 1.5 (br, 36H, t-Bu). ³¹P{¹H} NMR (202 MHz, CDCl₃, 298 K): δ 100 (ν_1/2 = 240 Hz).

(dtbpe-κ²P)NiI₂ was prepared as deep-blue–green crystals in exactly the same manner as the dichloride analogue, starting from NiI₂ (yield 60%). It turns black and melts at 544–545 K. The ¹H NMR spectrum contains very broad peaks and no ³¹P resonance is observed at room temperature. Analysis calculated for C₁₈H₄₀NiI₂P₂: C 34.26, H 6.39, P 9.82%; found: C 34.22, H 6.49, P 9.80%. UV–Vis: solution: 391 (3050), 606 (817) nm; solid: 396, 602 nm. MS(FAB): 630 (M⁺), 503 (M - I)⁺ (correct isotope pattern).

(dppe-κ²P)NiI₂.CH₂Cl₂, was prepared according to the published procedure of Hudson et al. (1968) and crystallized from di­chloro­methane to provide the solvated crystals.

S4.2. X-ray crystallography

For (dtbpe-κ²P)NiCl₂.2CHCl₃, H atoms were placed at calculated positions and refined as riding atoms, with U_iso values set at 1.5U_eq of the respective parent for CH₃ groups (refined with free rotation) and at 1.2U_eq in all other groups. Both chloro­form solvent molecules were disordered and were refined as the superposition of two orientations. The solvent molecules were restrained to have threefold local symmetry and to have similar bond lengths and angles within and across both molecules.

For (dtbpe-κ²P)NiCl₂, most H atoms were located in a difference map; they were placed at calculated positions and were refined as riding atoms, with U_iso values set at 1.2 U_eq of the respective parent atoms for CH₂ groups and at 1.5U_eq with free rotation for CH₃ groups. One tert-butyl group in one of the two independent molecules was refined with a disorder model of two different conformations. These two superimposed orientations were restrained to have a local threefold rotational symmetry and similar bond lengths and angles. The occupations refined to about 40:60%.

For (dtbpe-κ²P)NiBr₂, H atoms were placed at calculated positions and refined as riding atoms, with U_iso values set at 1.2U_eq of the respective parent atoms for CH₂ groups and at 1.5U_eq (with free rotation) for CH₃ groups.

For (dtbpe-κ²<P)NiI₂, all H atoms were located in a difference map but then placed at calculated positions and refined as riding atoms, with U_iso values set at 1.2U_eq of the respective parent atoms for CH₂ groups and at1.5U_eq (with free rotation) for CH₃ groups.

For (dppe-κ²P)NiI₂.CH₂Cl₂, H atoms could not be located in a difference map; they were placed at calculated positions and were refined as riding atoms, with U_iso values set at 1.2U_eq of their respective parent atoms.

Related literature

For related literature, see: Allen (2002); Anderson et al. (2010); Angulo, Bouwman, Lok, Lutz, Mul & Spek (2001); Angulo, Bouwman, Lutz, Mul & Spek (2001); Bach et al. (1999); Batsanov et al. (2009); Bauernschmitt & Ahlrichs (1996); Bauernschmitt et al. (1997); Beaudoin et al. (2001); Becke (1988, 1993); Bomfim et al. (2003); Booth & Chatt (1965); Brück et al. (1996); Bridgeman (2008); Busby et al. (1993); Corain et al. (1985); Cotton et al. (1999); Cremer & Burger (2003); Deglmann et al. (2004); Dirac (1929); Eichkorn et al. (1995, 1997); Evans (1959); Fowler & Steiner (1992, 1993); Frömmel et al. (1992); Furche & Ahlrichs (2002); Furche & Rappoport (2005); Grimme et al. (2010); Häser & Ahlrichs (1989); Hättig & Köhn (2002); Hättig & Weigend (2000); Hayter & Humiec (1962, 1965); Hecke & Horrocks (1966); Hudson et al. (1968); Jarrett & Sadler (1991); Köhler (2011); Kitiachvili et al. (2004); Lavanant et al. (2008); Lee et al. (1988); Martin et al. (1991); Miedaner et al. (1991); Mindiola & Hillhouse (2001); Mindiola et al. (2003); Pandarus et al. (2008); Pelloni et al. (2009); Perdew (1986); Pignolet & Horrocks (1969); Rahn et al. (1989); Ruud et al. (1995); Sauer et al. (1993); Schäfer et al. (1992); Slater (1951); Spek et al. (1987); Stevens & Lipscomb (1965); TURBOMOLE (2012); Treutler & Ahlrichs (1995); Venanzi (1958); Vosko et al. (1980); Walter et al. (2006); Waterman & Hillhouse (2008); Weigend (2006); Weigend & Ahlrichs (2005); Weigend et al. (1998, 2003).

Computing details

Data collection: SMART (Bruker, 2001) for msc6, msc11; APEX2 (Bruker, 2005) for lw27, lw23, lw29. Cell refinement: SMART (Bruker, 2001) for msc6, msc11; SAINT (Bruker, 2005) for lw27, lw23, lw29. Data reduction: SAINT (Bruker, 2001) for msc6, msc11; SAINT (Bruker, 2005) for lw27, lw23, lw29. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures

	Fig. 1. Crystal field splitting diagrams for square planar (left) and tetrahedral (right) geometries with d^8 occupation.
	Fig. 2. The molecular structure of (dtbpe-κ^2P)NiCl2 (one of two unique molecules in asymmetric unit), with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.
	Fig. 3. The molecular structure of (dtbpe-κ^2P)NiI2, with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.
	Fig. 4. The molecular structure of (dtbpe-κ^2P)NiCl2 (second of two unique molecules in the asymmetric unit), with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.
	Fig. 5. Schematic representation of principal conformations of (dtbpe-κ^2P)NiX2 and their relation by backbone-inversion without tert-butyl substituent rotation, or rotation of halide ligands.
	Fig. 6. Optical spectra of (dtbpe-κ^2P)NiX2 (X = Cl, Br, I) in solution.
	Fig. 7. Temperature dependence of ^31P{^1H} chemical shift of a CD2Cl2 solution of (dtbpe-κ^2P)NiBr2.
	Fig. 8. Relative energies in kJ mol^-1 of (dtbpe-κ^2P)NiCl2 P and O structures. The angle is the mean of the two P···P···X···X torsion angles. BP86/def2-TZVP.
	Fig. 9. Relative energies in kJ mol^-1 of (dtbpe-κ^2P)NiBr2 P and O structures. The angle is the mean of the two P···P···X···X torsion angles. BP86/def2-TZVP.
	Fig. 10. Relative energies in kJ mol^-1 of (dtbpe-κ^2P)NiI2 P and O structures. The angle is the mean of the two P···P···X···X torsion angles. BP86/def2-TZVP.
	Fig. 11. Energy of the excited state of the P isomer (top line) for the different halide complexes including the planarized diiodide complex; difference between density of excited and ground state of dichloride and diiodide (left and right diagrams at top; red: negative; blue: positive). Energies of orbitals that contribute most to the excitation are also depicted, along with plots of the orbitals for dichloride and diiodide. All energies are given in eV.
	Fig. 12. Comparison of the experimentally observed and calculated wavelengths of the main absorption of complexes P2NiX2 as a function of bis(phosphine) and halide ligand (nm).

(msc6) [1,2-Bis(di-tert-butylphosphanyl)ethane-κ²P,P']dichloridonickel(II) chloroform disolvate

Crystal data

[NiCl2(C18H40P2)]·2CHCl3	F(000) = 2848
Mr = 686.78	Dx = 1.438 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.2040 (3) Å	Cell parameters from 7319 reflections
b = 18.2618 (3) Å	µ = 1.40 mm^−1
c = 20.2538 (4) Å	T = 200 K
β = 94.572 (1)°	Polyhedron, red
V = 6343.0 (2) Å^3	0.42 × 0.40 × 0.15 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer	7308 independent reflections
Radiation source: fine-focus sealed tube	5638 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ω scans	θmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −22→22
Tmin = 0.61, Tmax = 0.83	k = −23→23
32371 measured reflections	l = −26→26

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.129	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0417P)^2 + 25.352P] where P = (Fo^2 + 2Fc^2)/3
7308 reflections	(Δ/σ)max = 0.001
326 parameters	Δρmax = 1.20 e Å^−3
132 restraints	Δρmin = −0.64 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)
Ni1	0.73904 (2)	0.00993 (2)	0.30173 (2)	0.02831 (11)
P1	0.74269 (5)	0.12608 (5)	0.33156 (4)	0.03154 (19)
P2	0.73218 (5)	0.04086 (5)	0.19651 (4)	0.03277 (19)
Cl1	0.73926 (6)	−0.10701 (5)	0.27272 (5)	0.0479 (2)
Cl2	0.74224 (7)	−0.02311 (5)	0.40635 (4)	0.0509 (3)
C9	0.7545 (2)	0.17882 (19)	0.25551 (18)	0.0435 (9)
H9A	0.7309	0.2279	0.2596	0.052*
H9B	0.8108	0.1856	0.2502	0.052*
C10	0.7166 (3)	0.14080 (19)	0.19459 (17)	0.0438 (9)
H10A	0.7382	0.1612	0.1546	0.053*
H10B	0.6599	0.1509	0.1913	0.053*
C11	0.8307 (2)	0.1536 (2)	0.38836 (19)	0.0440 (8)
C12	0.8494 (3)	0.2353 (3)	0.3825 (3)	0.0677 (13)
H12A	0.8061	0.2643	0.3973	0.101*
H12B	0.8567	0.2471	0.3362	0.101*
H12C	0.8972	0.2466	0.4102	0.101*
C13	0.8212 (3)	0.1370 (3)	0.4613 (2)	0.0647 (13)
H13A	0.8697	0.1492	0.4878	0.097*
H13B	0.8096	0.0849	0.4664	0.097*
H13C	0.7784	0.1664	0.4763	0.097*
C14	0.9002 (3)	0.1089 (3)	0.3671 (3)	0.0666 (13)
H14A	0.9460	0.1183	0.3978	0.100*
H14B	0.9114	0.1232	0.3222	0.100*
H14C	0.8874	0.0566	0.3677	0.100*
C15	0.6504 (2)	0.1637 (2)	0.36434 (18)	0.0430 (8)
C16	0.6572 (3)	0.2434 (3)	0.3830 (3)	0.0810 (17)
H16A	0.6738	0.2715	0.3453	0.121*
H16B	0.6958	0.2491	0.4209	0.121*
H16C	0.6065	0.2615	0.3948	0.121*
C17	0.6235 (3)	0.1177 (4)	0.4211 (3)	0.0820 (17)
H17A	0.5722	0.1349	0.4324	0.123*
H17B	0.6611	0.1225	0.4598	0.123*
H17C	0.6198	0.0663	0.4075	0.123*
C18	0.5847 (3)	0.1572 (3)	0.3090 (2)	0.0691 (14)
H18A	0.5361	0.1760	0.3247	0.104*
H18B	0.5778	0.1056	0.2963	0.104*
H18C	0.5982	0.1857	0.2705	0.104*
C21	0.6433 (2)	0.0040 (2)	0.14552 (19)	0.0477 (9)
C22	0.6579 (3)	−0.0710 (3)	0.1150 (2)	0.0636 (12)
H22A	0.6090	−0.0898	0.0932	0.095*
H22B	0.6773	−0.1050	0.1499	0.095*
H22C	0.6966	−0.0661	0.0823	0.095*
C23	0.6151 (4)	0.0559 (3)	0.0891 (2)	0.0815 (17)
H23A	0.6580	0.0657	0.0612	0.122*
H23B	0.5975	0.1020	0.1076	0.122*
H23C	0.5717	0.0331	0.0622	0.122*
C24	0.5776 (2)	−0.0048 (3)	0.1923 (2)	0.0602 (12)
H24A	0.5645	0.0431	0.2101	0.090*
H24B	0.5950	−0.0376	0.2288	0.090*
H24C	0.5314	−0.0256	0.1677	0.090*
C25	0.8232 (2)	0.0249 (2)	0.15201 (19)	0.0483 (9)
C26	0.8137 (4)	0.0535 (3)	0.0805 (2)	0.0790 (17)
H26A	0.7988	0.1052	0.0807	0.119*
H26B	0.7732	0.0252	0.0551	0.119*
H26C	0.8632	0.0482	0.0602	0.119*
C27	0.8893 (3)	0.0655 (3)	0.1901 (3)	0.0824 (18)
H27A	0.9381	0.0558	0.1699	0.124*
H27B	0.8940	0.0488	0.2362	0.124*
H27C	0.8784	0.1182	0.1888	0.124*
C28	0.8463 (3)	−0.0561 (2)	0.1506 (2)	0.0579 (11)
H28A	0.8958	−0.0611	0.1302	0.087*
H28B	0.8057	−0.0838	0.1248	0.087*
H28C	0.8523	−0.0751	0.1960	0.087*
C30	0.9062 (5)	−0.1434 (4)	0.3899 (3)	0.051 (2)	0.831 (9)
H30	0.8517	−0.1247	0.3816	0.061*	0.831 (9)
Cl3	0.90719 (17)	−0.22804 (18)	0.4290 (3)	0.1346 (16)	0.831 (9)
Cl4	0.95081 (12)	−0.1507 (3)	0.31618 (9)	0.1053 (15)	0.831 (9)
Cl5	0.9602 (2)	−0.0875 (2)	0.44481 (19)	0.1185 (15)	0.831 (9)
C31	0.6183 (5)	−0.1721 (3)	0.3849 (3)	0.049 (2)	0.852 (7)
H31	0.6439	−0.1300	0.3637	0.059*	0.852 (7)
Cl6	0.56786 (16)	−0.2223 (2)	0.32269 (16)	0.1090 (12)	0.852 (7)
Cl7	0.69096 (16)	−0.22418 (14)	0.42682 (12)	0.0890 (9)	0.852 (7)
Cl8	0.5546 (2)	−0.1367 (2)	0.4395 (2)	0.0835 (14)	0.852 (7)
C30B	0.914 (2)	−0.1335 (11)	0.3951 (8)	0.042 (12)*	0.169 (9)
H30B	0.8594	−0.1144	0.3938	0.051*	0.169 (9)
Cl3B	0.9030 (6)	−0.2284 (6)	0.3924 (6)	0.068 (3)*	0.169 (9)
Cl4B	0.9465 (5)	−0.1071 (6)	0.3192 (4)	0.055 (3)*	0.169 (9)
Cl5B	0.9672 (8)	−0.0747 (7)	0.4491 (6)	0.050 (3)*	0.169 (9)
C31B	0.6040 (16)	−0.1707 (14)	0.3817 (9)	0.058 (18)*	0.148 (7)
H31B	0.6439	−0.1334	0.3713	0.070*	0.148 (7)
Cl6B	0.5434 (7)	−0.1883 (6)	0.3107 (5)	0.059 (3)*	0.148 (7)
Cl7B	0.6514 (10)	−0.2490 (8)	0.4128 (6)	0.089 (4)*	0.148 (7)
Cl8B	0.5474 (12)	−0.1353 (9)	0.4416 (9)	0.051 (4)*	0.148 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0336 (2)	0.0252 (2)	0.0262 (2)	−0.00114 (16)	0.00302 (15)	0.00032 (15)
P1	0.0383 (4)	0.0286 (4)	0.0279 (4)	−0.0020 (3)	0.0036 (3)	−0.0034 (3)
P2	0.0439 (5)	0.0300 (4)	0.0250 (4)	0.0012 (4)	0.0068 (3)	−0.0010 (3)
Cl1	0.0709 (6)	0.0288 (4)	0.0453 (5)	0.0002 (4)	0.0135 (4)	−0.0019 (4)
Cl2	0.0812 (7)	0.0419 (5)	0.0286 (4)	−0.0103 (5)	−0.0023 (4)	0.0041 (4)
C9	0.065 (2)	0.0284 (18)	0.0381 (18)	−0.0036 (16)	0.0104 (17)	0.0009 (14)
C10	0.067 (2)	0.0312 (19)	0.0335 (18)	0.0033 (17)	0.0062 (17)	0.0034 (14)
C11	0.045 (2)	0.043 (2)	0.044 (2)	−0.0056 (16)	−0.0010 (16)	−0.0118 (16)
C12	0.069 (3)	0.051 (3)	0.081 (3)	−0.026 (2)	−0.006 (3)	−0.011 (2)
C13	0.076 (3)	0.072 (3)	0.043 (2)	−0.017 (2)	−0.014 (2)	−0.011 (2)
C14	0.044 (2)	0.081 (3)	0.072 (3)	0.005 (2)	−0.011 (2)	−0.024 (3)
C15	0.046 (2)	0.045 (2)	0.0388 (19)	0.0075 (16)	0.0051 (15)	−0.0085 (16)
C16	0.072 (3)	0.062 (3)	0.109 (4)	0.012 (3)	0.009 (3)	−0.043 (3)
C17	0.068 (3)	0.115 (5)	0.067 (3)	0.027 (3)	0.033 (3)	0.016 (3)
C18	0.048 (2)	0.091 (4)	0.068 (3)	0.010 (2)	0.000 (2)	−0.031 (3)
C21	0.052 (2)	0.051 (2)	0.0381 (19)	0.0057 (18)	−0.0075 (16)	−0.0095 (17)
C22	0.064 (3)	0.064 (3)	0.061 (3)	0.002 (2)	−0.006 (2)	−0.028 (2)
C23	0.105 (4)	0.080 (4)	0.053 (3)	0.016 (3)	−0.032 (3)	−0.005 (3)
C24	0.044 (2)	0.067 (3)	0.068 (3)	0.000 (2)	−0.002 (2)	−0.024 (2)
C25	0.057 (2)	0.048 (2)	0.043 (2)	−0.0047 (18)	0.0246 (18)	−0.0068 (17)
C26	0.120 (5)	0.075 (3)	0.048 (3)	0.010 (3)	0.046 (3)	0.008 (2)
C27	0.057 (3)	0.101 (4)	0.095 (4)	−0.025 (3)	0.037 (3)	−0.038 (3)
C28	0.054 (2)	0.060 (3)	0.063 (3)	0.008 (2)	0.027 (2)	−0.004 (2)
C30	0.041 (3)	0.062 (4)	0.050 (4)	0.004 (3)	0.007 (2)	0.005 (3)
Cl3	0.1143 (18)	0.1015 (18)	0.189 (4)	−0.0034 (14)	0.016 (2)	0.081 (2)
Cl4	0.0756 (12)	0.187 (5)	0.0551 (10)	0.0318 (15)	0.0134 (8)	−0.0076 (13)
Cl5	0.0695 (15)	0.163 (3)	0.124 (2)	−0.0137 (16)	0.0119 (12)	−0.078 (2)
C31	0.048 (3)	0.045 (4)	0.054 (4)	−0.001 (2)	0.011 (2)	−0.007 (2)
Cl6	0.0792 (14)	0.130 (3)	0.1185 (18)	−0.0246 (15)	0.0117 (13)	−0.0751 (18)
Cl7	0.0768 (15)	0.0759 (14)	0.1161 (15)	0.0347 (11)	0.0188 (12)	0.0194 (11)
Cl8	0.0702 (17)	0.113 (2)	0.0671 (13)	0.0392 (13)	0.0075 (9)	−0.0213 (10)

Geometric parameters (Å, º)

Ni1—P2	2.1986 (9)	C21—C23	1.533 (6)
Ni1—Cl2	2.1997 (9)	C21—C24	1.541 (6)
Ni1—P1	2.2049 (9)	C22—H22A	0.9800
Ni1—Cl1	2.2150 (10)	C22—H22B	0.9800
P1—C9	1.841 (4)	C22—H22C	0.9800
P1—C11	1.895 (4)	C23—H23A	0.9800
P1—C15	1.897 (4)	C23—H23B	0.9800
P2—C10	1.845 (4)	C23—H23C	0.9800
P2—C25	1.890 (4)	C24—H24A	0.9800
P2—C21	1.899 (4)	C24—H24B	0.9800
C9—C10	1.517 (5)	C24—H24C	0.9800
C9—H9A	0.9900	C25—C27	1.516 (6)
C9—H9B	0.9900	C25—C28	1.531 (6)
C10—H10A	0.9900	C25—C26	1.536 (6)
C10—H10B	0.9900	C26—H26A	0.9800
C11—C13	1.528 (6)	C26—H26B	0.9800
C11—C12	1.533 (6)	C26—H26C	0.9800
C11—C14	1.537 (6)	C27—H27A	0.9800
C12—H12A	0.9800	C27—H27B	0.9800
C12—H12B	0.9800	C27—H27C	0.9800
C12—H12C	0.9800	C28—H28A	0.9800
C13—H13A	0.9800	C28—H28B	0.9800
C13—H13B	0.9800	C28—H28C	0.9800
C13—H13C	0.9800	C30—Cl5	1.725 (8)
C14—H14A	0.9800	C30—Cl4	1.737 (6)
C14—H14B	0.9800	C30—Cl3	1.737 (7)
C14—H14C	0.9800	C30—H30	1.0000
C15—C16	1.507 (6)	C31—Cl6	1.734 (6)
C15—C17	1.524 (6)	C31—Cl7	1.738 (7)
C15—C18	1.532 (6)	C31—Cl8	1.742 (6)
C16—H16A	0.9800	C31—H31	1.0000
C16—H16B	0.9800	C30B—Cl5B	1.740 (14)
C16—H16C	0.9800	C30B—Cl4B	1.744 (15)
C17—H17A	0.9800	C30B—Cl3B	1.745 (14)
C17—H17B	0.9800	C30B—H30B	1.0000
C17—H17C	0.9800	C31B—Cl6B	1.738 (15)
C18—H18A	0.9800	C31B—Cl7B	1.739 (15)
C18—H18B	0.9800	C31B—Cl8B	1.740 (15)
C18—H18C	0.9800	C31B—H31B	1.0000
C21—C22	1.531 (6)
P2—Ni1—Cl2	178.08 (4)	C15—C18—H18C	109.5
P2—Ni1—P1	90.96 (3)	H18A—C18—H18C	109.5
Cl2—Ni1—P1	90.11 (4)	H18B—C18—H18C	109.5
P2—Ni1—Cl1	89.52 (4)	C22—C21—C23	107.7 (4)
Cl2—Ni1—Cl1	89.46 (4)	C22—C21—C24	107.8 (4)
P1—Ni1—Cl1	178.23 (4)	C23—C21—C24	108.6 (4)
C9—P1—C11	103.48 (18)	C22—C21—P2	112.7 (3)
C9—P1—C15	104.75 (18)	C23—C21—P2	112.4 (3)
C11—P1—C15	110.02 (17)	C24—C21—P2	107.5 (3)
C9—P1—Ni1	106.05 (12)	C21—C22—H22A	109.5
C11—P1—Ni1	115.15 (13)	C21—C22—H22B	109.5
C15—P1—Ni1	115.94 (13)	H22A—C22—H22B	109.5
C10—P2—C25	105.52 (18)	C21—C22—H22C	109.5
C10—P2—C21	103.26 (18)	H22A—C22—H22C	109.5
C25—P2—C21	110.32 (18)	H22B—C22—H22C	109.5
C10—P2—Ni1	105.73 (12)	C21—C23—H23A	109.5
C25—P2—Ni1	116.11 (14)	C21—C23—H23B	109.5
C21—P2—Ni1	114.52 (13)	H23A—C23—H23B	109.5
C10—C9—P1	111.8 (2)	C21—C23—H23C	109.5
C10—C9—H9A	109.2	H23A—C23—H23C	109.5
P1—C9—H9A	109.2	H23B—C23—H23C	109.5
C10—C9—H9B	109.2	C21—C24—H24A	109.5
P1—C9—H9B	109.2	C21—C24—H24B	109.5
H9A—C9—H9B	107.9	H24A—C24—H24B	109.5
C9—C10—P2	112.5 (3)	C21—C24—H24C	109.5
C9—C10—H10A	109.1	H24A—C24—H24C	109.5
P2—C10—H10A	109.1	H24B—C24—H24C	109.5
C9—C10—H10B	109.1	C27—C25—C28	107.2 (4)
P2—C10—H10B	109.1	C27—C25—C26	109.3 (4)
H10A—C10—H10B	107.8	C28—C25—C26	108.6 (3)
C13—C11—C12	107.9 (4)	C27—C25—P2	107.3 (3)
C13—C11—C14	108.1 (4)	C28—C25—P2	112.6 (3)
C12—C11—C14	108.9 (4)	C26—C25—P2	111.6 (3)
C13—C11—P1	113.1 (3)	C25—C26—H26A	109.5
C12—C11—P1	111.9 (3)	C25—C26—H26B	109.5
C14—C11—P1	106.9 (3)	H26A—C26—H26B	109.5
C11—C12—H12A	109.5	C25—C26—H26C	109.5
C11—C12—H12B	109.5	H26A—C26—H26C	109.5
H12A—C12—H12B	109.5	H26B—C26—H26C	109.5
C11—C12—H12C	109.5	C25—C27—H27A	109.5
H12A—C12—H12C	109.5	C25—C27—H27B	109.5
H12B—C12—H12C	109.5	H27A—C27—H27B	109.5
C11—C13—H13A	109.5	C25—C27—H27C	109.5
C11—C13—H13B	109.5	H27A—C27—H27C	109.5
H13A—C13—H13B	109.5	H27B—C27—H27C	109.5
C11—C13—H13C	109.5	C25—C28—H28A	109.5
H13A—C13—H13C	109.5	C25—C28—H28B	109.5
H13B—C13—H13C	109.5	H28A—C28—H28B	109.5
C11—C14—H14A	109.5	C25—C28—H28C	109.5
C11—C14—H14B	109.5	H28A—C28—H28C	109.5
H14A—C14—H14B	109.5	H28B—C28—H28C	109.5
C11—C14—H14C	109.5	Cl5—C30—Cl4	110.4 (5)
H14A—C14—H14C	109.5	Cl5—C30—Cl3	104.3 (5)
H14B—C14—H14C	109.5	Cl4—C30—Cl3	109.6 (4)
C16—C15—C17	111.4 (4)	Cl5—C30—H30	110.8
C16—C15—C18	107.2 (4)	Cl4—C30—H30	110.8
C17—C15—C18	105.0 (4)	Cl3—C30—H30	110.8
C16—C15—P1	112.7 (3)	Cl6—C31—Cl7	111.4 (3)
C17—C15—P1	112.2 (3)	Cl6—C31—Cl8	110.7 (5)
C18—C15—P1	107.7 (3)	Cl7—C31—Cl8	110.9 (3)
C15—C16—H16A	109.5	Cl6—C31—H31	107.9
C15—C16—H16B	109.5	Cl7—C31—H31	107.9
H16A—C16—H16B	109.5	Cl8—C31—H31	107.9
C15—C16—H16C	109.5	Cl5B—C30B—Cl4B	101.2 (11)
H16A—C16—H16C	109.5	Cl5B—C30B—Cl3B	133.1 (19)
H16B—C16—H16C	109.5	Cl4B—C30B—Cl3B	106.8 (11)
C15—C17—H17A	109.5	Cl5B—C30B—H30B	104.3
C15—C17—H17B	109.5	Cl4B—C30B—H30B	104.3
H17A—C17—H17B	109.5	Cl3B—C30B—H30B	104.3
C15—C17—H17C	109.5	Cl6B—C31B—Cl7B	112.4 (13)
H17A—C17—H17C	109.5	Cl6B—C31B—Cl8B	108.3 (14)
H17B—C17—H17C	109.5	Cl7B—C31B—Cl8B	109.0 (15)
C15—C18—H18A	109.5	Cl6B—C31B—H31B	109.0
C15—C18—H18B	109.5	Cl7B—C31B—H31B	109.0
H18A—C18—H18B	109.5	Cl8B—C31B—H31B	109.0
C11—P1—C9—C10	152.3 (3)	C9—P1—C15—C18	55.2 (3)
C15—P1—C9—C10	−92.4 (3)	C11—P1—C15—C18	165.9 (3)
Ni1—P1—C9—C10	30.7 (3)	Ni1—P1—C15—C18	−61.3 (3)
P1—C9—C10—P2	−40.5 (4)	C10—P2—C21—C22	155.3 (3)
C25—P2—C10—C9	−92.4 (3)	C25—P2—C21—C22	43.0 (4)
C21—P2—C10—C9	151.8 (3)	Ni1—P2—C21—C22	−90.2 (3)
Ni1—P2—C10—C9	31.1 (3)	C10—P2—C21—C23	33.5 (4)
C9—P1—C11—C13	161.3 (3)	C25—P2—C21—C23	−78.9 (4)
C15—P1—C11—C13	49.8 (4)	Ni1—P2—C21—C23	147.9 (3)
Ni1—P1—C11—C13	−83.4 (3)	C10—P2—C21—C24	−86.0 (3)
C9—P1—C11—C12	39.3 (3)	C25—P2—C21—C24	161.6 (3)
C15—P1—C11—C12	−72.2 (3)	Ni1—P2—C21—C24	28.4 (3)
Ni1—P1—C11—C12	154.5 (3)	C10—P2—C25—C27	60.6 (4)
C9—P1—C11—C14	−79.8 (3)	C21—P2—C25—C27	171.5 (4)
C15—P1—C11—C14	168.7 (3)	Ni1—P2—C25—C27	−56.1 (4)
Ni1—P1—C11—C14	35.4 (3)	C10—P2—C25—C28	178.4 (3)
C9—P1—C15—C16	−62.9 (4)	C21—P2—C25—C28	−70.7 (4)
C11—P1—C15—C16	47.7 (4)	Ni1—P2—C25—C28	61.7 (3)
Ni1—P1—C15—C16	−179.4 (3)	C10—P2—C25—C26	−59.2 (4)
C9—P1—C15—C17	170.3 (4)	C21—P2—C25—C26	51.7 (4)
C11—P1—C15—C17	−79.1 (4)	Ni1—P2—C25—C26	−175.9 (3)
Ni1—P1—C15—C17	53.8 (4)

(lw27) [1,2-Bis(di-tert-butylphosphanyl)ethane-κ²P,P']dichloridonickel(II)

Crystal data

[NiCl2(C18H40P2)]	F(000) = 960
Mr = 448.05	Dx = 1.298 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 11.1034 (7) Å	Cell parameters from 9977 reflections
b = 15.1216 (9) Å	θ = 2.4–29.0°
c = 14.5301 (9) Å	µ = 1.22 mm^−1
β = 109.965 (1)°	T = 200 K
V = 2293.0 (2) Å^3	Needle, red
Z = 4	0.20 × 0.08 × 0.07 mm

Data collection

Bruker APEXII Quazar diffractometer	11668 independent reflections
Radiation source: ImuS microsource	9616 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.037
ϕ and ω scans	θmax = 28.7°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −15→15
Tmin = 0.793, Tmax = 0.920	k = −19→20
30373 measured reflections	l = −19→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0328P)^2 + 1.7022P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
11668 reflections	Δρmax = 0.51 e Å^−3
479 parameters	Δρmin = −0.43 e Å^−3
67 restraints	Absolute structure: Flack (1983), ???? Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.497 (11)

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)
Ni1_1	0.46480 (4)	1.04090 (3)	0.47529 (3)	0.02289 (10)
Cl1_1	0.56346 (9)	0.94644 (7)	0.41005 (7)	0.0386 (2)
Cl2_1	0.29424 (10)	0.95426 (7)	0.43790 (8)	0.0424 (2)
P1_1	0.37696 (9)	1.12973 (6)	0.55408 (7)	0.0253 (2)
P2_1	0.63105 (9)	1.12983 (6)	0.50540 (6)	0.02363 (19)
C9_1	0.5015 (4)	1.2119 (3)	0.6146 (3)	0.0348 (9)
H9A_1	0.4597	1.2676	0.6231	0.042*
H9B_1	0.5528	1.1898	0.6805	0.042*
C10_1	0.5891 (4)	1.2309 (3)	0.5588 (3)	0.0354 (9)
H10A_1	0.6684	1.2587	0.6031	0.042*
H10B_1	0.5472	1.2734	0.5057	0.042*
C11_1	0.3417 (4)	1.0762 (3)	0.6604 (3)	0.0366 (9)
C12_1	0.4413 (5)	1.0029 (3)	0.7020 (4)	0.0552 (13)
H12A_1	0.4380	0.9607	0.6499	0.083*
H12B_1	0.4224	0.9720	0.7548	0.083*
H12C_1	0.5271	1.0290	0.7278	0.083*
C13_1	0.3523 (6)	1.1414 (4)	0.7437 (4)	0.0700 (17)
H13A_1	0.4411	1.1616	0.7726	0.105*
H13B_1	0.3261	1.1120	0.7939	0.105*
H13C_1	0.2963	1.1923	0.7177	0.105*
C14_1	0.2106 (4)	1.0326 (3)	0.6299 (3)	0.0501 (11)
H14A_1	0.2032	0.9894	0.5780	0.075*
H14B_1	0.1439	1.0778	0.6057	0.075*
H14C_1	0.2001	1.0025	0.6865	0.075*
C15_1	0.2332 (4)	1.1964 (3)	0.4768 (3)	0.0399 (10)
C16_1	0.1812 (5)	1.2568 (3)	0.5390 (5)	0.0630 (15)
H16A_1	0.2522	1.2898	0.5854	0.094*
H16B_1	0.1388	1.2210	0.5752	0.094*
H16C_1	0.1194	1.2984	0.4963	0.094*
C17_1	0.1260 (4)	1.1389 (4)	0.4139 (4)	0.0651 (15)
H17A_1	0.0979	1.0989	0.4556	0.098*
H17B_1	0.1562	1.1042	0.3691	0.098*
H17C_1	0.0540	1.1763	0.3759	0.098*
C18_1	0.2798 (5)	1.2571 (3)	0.4114 (4)	0.0575 (13)
H18A_1	0.3511	1.2934	0.4523	0.086*
H18B_1	0.2094	1.2956	0.3733	0.086*
H18C_1	0.3085	1.2211	0.3667	0.086*
C21_1	0.7893 (18)	1.0986 (11)	0.6028 (13)	0.026 (3)	0.395 (13)
C22_1	0.8978 (12)	1.1676 (9)	0.6190 (11)	0.045 (3)	0.395 (13)
H22A_1	0.9233	1.1701	0.5607	0.068*	0.395 (13)
H22B_1	0.9717	1.1504	0.6759	0.068*	0.395 (13)
H22C_1	0.8671	1.2258	0.6306	0.068*	0.395 (13)
C23_1	0.7624 (11)	1.0885 (12)	0.6990 (8)	0.053 (5)	0.395 (13)
H23A_1	0.6873	1.0505	0.6882	0.080*	0.395 (13)
H23B_1	0.7459	1.1468	0.7216	0.080*	0.395 (13)
H23C_1	0.8369	1.0616	0.7486	0.080*	0.395 (13)
C24_1	0.8380 (17)	1.0097 (10)	0.5773 (14)	0.045 (4)	0.395 (13)
H24A_1	0.7802	0.9621	0.5818	0.067*	0.395 (13)
H24B_1	0.9244	0.9981	0.6234	0.067*	0.395 (13)
H24C_1	0.8402	1.0122	0.5106	0.067*	0.395 (13)
C21B_1	0.7810 (14)	1.0794 (8)	0.5965 (10)	0.034 (3)	0.605 (13)
C22B_1	0.8652 (10)	1.1531 (6)	0.6599 (8)	0.057 (3)	0.605 (13)
H22D_1	0.8896	1.1949	0.6178	0.085*	0.605 (13)
H22E_1	0.9425	1.1270	0.7070	0.085*	0.605 (13)
H22F_1	0.8170	1.1844	0.6953	0.085*	0.605 (13)
C23B_1	0.7408 (7)	1.0182 (7)	0.6648 (6)	0.047 (3)	0.605 (13)
H23D_1	0.6852	0.9714	0.6263	0.070*	0.605 (13)
H23E_1	0.6942	1.0524	0.6991	0.070*	0.605 (13)
H23F_1	0.8172	0.9918	0.7126	0.070*	0.605 (13)
C24B_1	0.8627 (12)	1.0264 (7)	0.5486 (9)	0.047 (3)	0.605 (13)
H24D_1	0.8092	0.9816	0.5047	0.070*	0.605 (13)
H24E_1	0.9333	0.9974	0.5996	0.070*	0.605 (13)
H24F_1	0.8976	1.0667	0.5111	0.070*	0.605 (13)
C25_1	0.6639 (4)	1.1747 (3)	0.3943 (3)	0.0357 (9)
C26_1	0.5365 (5)	1.2001 (5)	0.3179 (4)	0.092 (2)
H26A_1	0.4781	1.1494	0.3048	0.138*
H26B_1	0.5503	1.2177	0.2573	0.138*
H26C_1	0.4991	1.2496	0.3424	0.138*
C27_1	0.7195 (8)	1.1068 (4)	0.3423 (5)	0.098 (3)
H27A_1	0.6621	1.0556	0.3237	0.148*
H27B_1	0.8038	1.0877	0.3863	0.148*
H27C_1	0.7282	1.1334	0.2834	0.148*
C28_1	0.7511 (6)	1.2544 (4)	0.4192 (4)	0.0750 (19)
H28A_1	0.7125	1.3007	0.4473	0.113*
H28B_1	0.7632	1.2768	0.3597	0.113*
H28C_1	0.8343	1.2375	0.4668	0.113*
Ni1_2	0.01605 (4)	0.95328 (3)	−0.03278 (3)	0.02298 (10)
Cl1_2	−0.13978 (11)	1.05016 (7)	−0.06309 (9)	0.0478 (3)
Cl2_2	0.09688 (10)	1.02515 (8)	−0.13063 (8)	0.0514 (3)
P1_2	0.18540 (9)	0.86700 (6)	0.01397 (7)	0.02372 (19)
P2_2	−0.07680 (9)	0.87348 (6)	0.05081 (7)	0.0265 (2)
C9_2	0.1453 (4)	0.7732 (3)	0.0783 (3)	0.0363 (10)
H9A_2	0.1137	0.7239	0.0314	0.044*
H9B_2	0.2242	0.7529	0.1302	0.044*
C10_2	0.0439 (4)	0.7948 (3)	0.1248 (3)	0.0358 (10)
H10A_2	0.0866	0.8201	0.1908	0.043*
H10B_2	0.0006	0.7395	0.1326	0.043*
C11_2	0.3253 (3)	0.9243 (3)	0.1068 (3)	0.0338 (9)
C12_2	0.3661 (4)	1.0085 (3)	0.0671 (4)	0.0488 (12)
H12A_2	0.2916	1.0472	0.0395	0.073*
H12B_2	0.4014	0.9930	0.0159	0.073*
H12C_2	0.4315	1.0394	0.1204	0.073*
C13_2	0.4419 (4)	0.8638 (3)	0.1491 (3)	0.0478 (11)
H13A_2	0.4164	0.8102	0.1756	0.072*
H13B_2	0.5083	0.8949	0.2015	0.072*
H13C_2	0.4757	0.8476	0.0973	0.072*
C14_2	0.2779 (4)	0.9529 (5)	0.1906 (3)	0.0625 (15)
H14A_2	0.2523	0.9005	0.2191	0.094*
H14B_2	0.2043	0.9927	0.1648	0.094*
H14C_2	0.3470	0.9837	0.2412	0.094*
C15_2	0.2390 (4)	0.8099 (3)	−0.0817 (3)	0.0398 (10)
C16_2	0.3112 (5)	0.7231 (3)	−0.0427 (4)	0.0591 (15)
H16A_2	0.3848	0.7355	0.0164	0.089*
H16B_2	0.3412	0.6972	−0.0928	0.089*
H16C_2	0.2534	0.6816	−0.0268	0.089*
C17_2	0.3276 (4)	0.8689 (3)	−0.1165 (3)	0.0439 (10)
H17A_2	0.2887	0.9275	−0.1338	0.066*
H17B_2	0.3401	0.8421	−0.1741	0.066*
H17C_2	0.4107	0.8747	−0.0640	0.066*
C18_2	0.1197 (5)	0.7892 (4)	−0.1693 (4)	0.0690 (17)
H18A_2	0.0711	0.8437	−0.1924	0.104*
H18B_2	0.0662	0.7467	−0.1499	0.104*
H18C_2	0.1451	0.7638	−0.2221	0.104*
C21_2	−0.1326 (4)	0.9303 (3)	0.1465 (3)	0.0378 (10)
C22_2	−0.1341 (5)	0.8656 (4)	0.2277 (4)	0.0650 (15)
H22A_2	−0.0461	0.8484	0.2659	0.098*
H22B_2	−0.1835	0.8129	0.1982	0.098*
H22C_2	−0.1736	0.8943	0.2708	0.098*
C23_2	−0.0376 (4)	1.0052 (3)	0.1929 (3)	0.0496 (12)
H23A_2	0.0466	0.9798	0.2290	0.074*
H23B_2	−0.0684	1.0390	0.2379	0.074*
H23C_2	−0.0304	1.0444	0.1413	0.074*
C24_2	−0.2660 (4)	0.9709 (3)	0.1024 (3)	0.0420 (10)
H24A_2	−0.3292	0.9238	0.0771	0.063*
H24B_2	−0.2677	1.0108	0.0489	0.063*
H24C_2	−0.2867	1.0042	0.1530	0.063*
C25_2	−0.2112 (4)	0.8033 (3)	−0.0326 (4)	0.0431 (11)
C26_2	−0.1518 (5)	0.7383 (3)	−0.0858 (4)	0.0553 (13)
H26A_2	−0.0962	0.6967	−0.0384	0.083*
H26B_2	−0.1012	0.7710	−0.1181	0.083*
H26C_2	−0.2200	0.7055	−0.1350	0.083*
C27_2	−0.3069 (4)	0.8609 (3)	−0.1111 (4)	0.0558 (13)
H27A_2	−0.3419	0.9065	−0.0793	0.084*
H27B_2	−0.3768	0.8239	−0.1525	0.084*
H27C_2	−0.2630	0.8893	−0.1514	0.084*
C28_2	−0.2822 (5)	0.7497 (3)	0.0224 (5)	0.0606 (15)
H28A_2	−0.3283	0.7899	0.0515	0.091*
H28B_2	−0.2203	0.7150	0.0742	0.091*
H28C_2	−0.3433	0.7097	−0.0234	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1_1	0.0322 (2)	0.0164 (2)	0.0192 (2)	0.00034 (18)	0.00768 (17)	−0.00137 (18)
Cl1_1	0.0351 (5)	0.0319 (5)	0.0428 (5)	0.0071 (4)	0.0055 (4)	−0.0160 (5)
Cl2_1	0.0544 (6)	0.0308 (5)	0.0502 (6)	−0.0165 (5)	0.0285 (5)	−0.0127 (5)
P1_1	0.0284 (5)	0.0219 (5)	0.0274 (5)	−0.0029 (4)	0.0119 (4)	−0.0046 (4)
P2_1	0.0281 (5)	0.0227 (5)	0.0208 (4)	0.0006 (4)	0.0093 (4)	−0.0015 (4)
C9_1	0.040 (2)	0.034 (2)	0.034 (2)	−0.0105 (17)	0.0170 (17)	−0.0159 (18)
C10_1	0.045 (2)	0.025 (2)	0.042 (2)	−0.0061 (17)	0.0232 (19)	−0.0102 (17)
C11_1	0.038 (2)	0.044 (3)	0.032 (2)	−0.0052 (18)	0.0171 (18)	0.0002 (18)
C12_1	0.060 (3)	0.065 (3)	0.047 (3)	−0.001 (2)	0.026 (2)	0.023 (2)
C13_1	0.097 (4)	0.080 (4)	0.054 (3)	−0.033 (3)	0.053 (3)	−0.025 (3)
C14_1	0.058 (3)	0.049 (3)	0.053 (3)	−0.012 (2)	0.032 (2)	0.001 (2)
C15_1	0.033 (2)	0.031 (2)	0.052 (3)	0.0027 (18)	0.0101 (19)	0.001 (2)
C16_1	0.045 (3)	0.046 (3)	0.101 (5)	0.010 (2)	0.028 (3)	−0.003 (3)
C17_1	0.044 (3)	0.054 (3)	0.073 (4)	0.000 (2)	−0.013 (2)	−0.002 (3)
C18_1	0.054 (3)	0.050 (3)	0.060 (3)	0.012 (2)	0.009 (2)	0.018 (3)
C21_1	0.013 (6)	0.038 (8)	0.024 (7)	−0.001 (5)	0.003 (5)	0.004 (6)
C22_1	0.026 (6)	0.063 (8)	0.043 (8)	−0.015 (5)	0.005 (5)	−0.018 (6)
C23_1	0.041 (6)	0.090 (12)	0.022 (5)	0.011 (7)	0.003 (4)	0.019 (6)
C24_1	0.022 (8)	0.050 (7)	0.055 (10)	0.005 (5)	0.004 (6)	0.001 (7)
C21B_1	0.034 (5)	0.026 (5)	0.033 (5)	−0.007 (4)	0.001 (4)	0.000 (3)
C22B_1	0.047 (6)	0.057 (6)	0.047 (6)	−0.015 (4)	−0.007 (4)	−0.006 (4)
C23B_1	0.037 (4)	0.065 (6)	0.033 (4)	−0.001 (3)	0.005 (3)	0.016 (4)
C24B_1	0.024 (5)	0.054 (6)	0.060 (7)	0.002 (4)	0.012 (4)	0.005 (5)
C25_1	0.049 (2)	0.031 (2)	0.032 (2)	0.0029 (18)	0.0200 (18)	0.0081 (17)
C26_1	0.066 (4)	0.156 (7)	0.053 (3)	0.010 (4)	0.017 (3)	0.059 (4)
C27_1	0.202 (8)	0.058 (4)	0.084 (4)	0.019 (4)	0.113 (5)	0.012 (3)
C28_1	0.109 (5)	0.075 (4)	0.069 (4)	−0.048 (4)	0.068 (4)	−0.022 (3)
Ni1_2	0.0286 (2)	0.0180 (2)	0.0205 (2)	−0.00148 (18)	0.00606 (17)	0.00289 (18)
Cl1_2	0.0595 (7)	0.0284 (6)	0.0607 (7)	0.0175 (5)	0.0273 (6)	0.0140 (5)
Cl2_2	0.0376 (5)	0.0632 (8)	0.0520 (6)	0.0012 (5)	0.0136 (5)	0.0368 (6)
P1_2	0.0310 (5)	0.0213 (5)	0.0215 (4)	0.0010 (4)	0.0124 (4)	0.0015 (4)
P2_2	0.0343 (5)	0.0192 (5)	0.0308 (5)	0.0032 (4)	0.0173 (4)	0.0033 (4)
C9_2	0.044 (2)	0.025 (2)	0.051 (3)	0.0119 (17)	0.029 (2)	0.0128 (18)
C10_2	0.041 (2)	0.030 (2)	0.047 (2)	0.0152 (17)	0.0286 (19)	0.0197 (18)
C11_2	0.0239 (18)	0.048 (3)	0.0252 (19)	0.0080 (16)	0.0024 (14)	−0.0032 (17)
C12_2	0.035 (2)	0.034 (2)	0.061 (3)	−0.0091 (18)	−0.004 (2)	−0.006 (2)
C13_2	0.036 (2)	0.064 (3)	0.043 (2)	0.017 (2)	0.0129 (19)	0.016 (2)
C14_2	0.035 (2)	0.108 (4)	0.039 (2)	−0.002 (3)	0.0069 (19)	−0.035 (3)
C15_2	0.050 (2)	0.042 (3)	0.038 (2)	−0.013 (2)	0.029 (2)	−0.017 (2)
C16_2	0.082 (4)	0.030 (2)	0.092 (4)	0.001 (2)	0.066 (3)	−0.013 (3)
C17_2	0.052 (2)	0.050 (3)	0.043 (2)	−0.010 (2)	0.034 (2)	−0.004 (2)
C18_2	0.071 (3)	0.096 (4)	0.054 (3)	−0.036 (3)	0.039 (3)	−0.047 (3)
C21_2	0.042 (2)	0.043 (3)	0.037 (2)	0.0087 (18)	0.0254 (18)	0.0026 (18)
C22_2	0.089 (4)	0.075 (4)	0.055 (3)	0.028 (3)	0.055 (3)	0.023 (3)
C23_2	0.050 (3)	0.063 (3)	0.040 (2)	0.010 (2)	0.022 (2)	−0.017 (2)
C24_2	0.041 (2)	0.035 (2)	0.058 (3)	0.0068 (18)	0.026 (2)	−0.005 (2)
C25_2	0.044 (2)	0.025 (2)	0.065 (3)	−0.0056 (18)	0.024 (2)	−0.009 (2)
C26_2	0.056 (3)	0.039 (3)	0.077 (4)	−0.009 (2)	0.031 (3)	−0.023 (3)
C27_2	0.043 (2)	0.043 (3)	0.068 (3)	−0.001 (2)	0.002 (2)	−0.013 (3)
C28_2	0.059 (3)	0.030 (3)	0.111 (5)	−0.007 (2)	0.053 (3)	−0.003 (3)

Geometric parameters (Å, º)

Ni1_1—P1_1	2.1975 (10)	C27_1—H27A_1	0.9800
Ni1_1—Cl1_1	2.2018 (10)	C27_1—H27B_1	0.9800
Ni1_1—P2_1	2.2037 (10)	C27_1—H27C_1	0.9800
Ni1_1—Cl2_1	2.2125 (11)	C28_1—H28A_1	0.9800
P1_1—C9_1	1.844 (4)	C28_1—H28B_1	0.9800
P1_1—C15_1	1.898 (4)	C28_1—H28C_1	0.9800
P1_1—C11_1	1.900 (4)	Ni1_2—Cl1_2	2.1941 (11)
P2_1—C10_1	1.844 (4)	Ni1_2—P1_2	2.1971 (10)
P2_1—C21B_1	1.898 (17)	Ni1_2—P2_2	2.2021 (10)
P2_1—C25_1	1.898 (4)	Ni1_2—Cl2_2	2.2090 (11)
P2_1—C21_1	1.90 (2)	P1_2—C9_2	1.835 (4)
C9_1—C10_1	1.492 (5)	P1_2—C11_2	1.884 (4)
C9_1—H9A_1	0.9900	P1_2—C15_2	1.897 (4)
C9_1—H9B_1	0.9900	P2_2—C10_2	1.840 (4)
C10_1—H10A_1	0.9900	P2_2—C25_2	1.894 (4)
C10_1—H10B_1	0.9900	P2_2—C21_2	1.910 (4)
C11_1—C14_1	1.520 (6)	C9_2—C10_2	1.534 (5)
C11_1—C13_1	1.534 (6)	C9_2—H9A_2	0.9900
C11_1—C12_1	1.537 (6)	C9_2—H9B_2	0.9900
C12_1—H12A_1	0.9800	C10_2—H10A_2	0.9900
C12_1—H12B_1	0.9800	C10_2—H10B_2	0.9900
C12_1—H12C_1	0.9800	C11_2—C12_2	1.529 (6)
C13_1—H13A_1	0.9800	C11_2—C13_2	1.533 (5)
C13_1—H13B_1	0.9800	C11_2—C14_2	1.545 (5)
C13_1—H13C_1	0.9800	C12_2—H12A_2	0.9800
C14_1—H14A_1	0.9800	C12_2—H12B_2	0.9800
C14_1—H14B_1	0.9800	C12_2—H12C_2	0.9800
C14_1—H14C_1	0.9800	C13_2—H13A_2	0.9800
C15_1—C17_1	1.505 (6)	C13_2—H13B_2	0.9800
C15_1—C16_1	1.531 (7)	C13_2—H13C_2	0.9800
C15_1—C18_1	1.532 (7)	C14_2—H14A_2	0.9800
C16_1—H16A_1	0.9800	C14_2—H14B_2	0.9800
C16_1—H16B_1	0.9800	C14_2—H14C_2	0.9800
C16_1—H16C_1	0.9800	C15_2—C18_2	1.524 (6)
C17_1—H17A_1	0.9800	C15_2—C17_2	1.537 (5)
C17_1—H17B_1	0.9800	C15_2—C16_2	1.540 (7)
C17_1—H17C_1	0.9800	C16_2—H16A_2	0.9800
C18_1—H18A_1	0.9800	C16_2—H16B_2	0.9800
C18_1—H18B_1	0.9800	C16_2—H16C_2	0.9800
C18_1—H18C_1	0.9800	C17_2—H17A_2	0.9800
C21_1—C23_1	1.533 (12)	C17_2—H17B_2	0.9800
C21_1—C24_1	1.540 (12)	C17_2—H17C_2	0.9800
C21_1—C22_1	1.550 (12)	C18_2—H18A_2	0.9800
C22_1—H22A_1	0.9800	C18_2—H18B_2	0.9800
C22_1—H22B_1	0.9800	C18_2—H18C_2	0.9800
C22_1—H22C_1	0.9800	C21_2—C24_2	1.527 (5)
C23_1—H23A_1	0.9800	C21_2—C23_2	1.537 (6)
C23_1—H23B_1	0.9800	C21_2—C22_2	1.537 (6)
C23_1—H23C_1	0.9800	C22_2—H22A_2	0.9800
C24_1—H24A_1	0.9800	C22_2—H22B_2	0.9800
C24_1—H24B_1	0.9800	C22_2—H22C_2	0.9800
C24_1—H24C_1	0.9800	C23_2—H23A_2	0.9800
C21B_1—C23B_1	1.530 (11)	C23_2—H23B_2	0.9800
C21B_1—C22B_1	1.542 (10)	C23_2—H23C_2	0.9800
C21B_1—C24B_1	1.543 (11)	C24_2—H24A_2	0.9800
C22B_1—H22D_1	0.9800	C24_2—H24B_2	0.9800
C22B_1—H22E_1	0.9800	C24_2—H24C_2	0.9800
C22B_1—H22F_1	0.9800	C25_2—C28_2	1.532 (6)
C23B_1—H23D_1	0.9800	C25_2—C26_2	1.533 (6)
C23B_1—H23E_1	0.9800	C25_2—C27_2	1.537 (7)
C23B_1—H23F_1	0.9800	C26_2—H26A_2	0.9800
C24B_1—H24D_1	0.9800	C26_2—H26B_2	0.9800
C24B_1—H24E_1	0.9800	C26_2—H26C_2	0.9800
C24B_1—H24F_1	0.9800	C27_2—H27A_2	0.9800
C25_1—C28_1	1.511 (6)	C27_2—H27B_2	0.9800
C25_1—C26_1	1.519 (7)	C27_2—H27C_2	0.9800
C25_1—C27_1	1.525 (6)	C28_2—H28A_2	0.9800
C26_1—H26A_1	0.9800	C28_2—H28B_2	0.9800
C26_1—H26B_1	0.9800	C28_2—H28C_2	0.9800
C26_1—H26C_1	0.9800
P1_1—Ni1_1—Cl1_1	174.52 (4)	C25_1—C28_1—H28B_1	109.5
P1_1—Ni1_1—P2_1	90.82 (4)	H28A_1—C28_1—H28B_1	109.5
Cl1_1—Ni1_1—P2_1	88.57 (4)	C25_1—C28_1—H28C_1	109.5
P1_1—Ni1_1—Cl2_1	89.71 (4)	H28A_1—C28_1—H28C_1	109.5
Cl1_1—Ni1_1—Cl2_1	91.16 (4)	H28B_1—C28_1—H28C_1	109.5
P2_1—Ni1_1—Cl2_1	177.26 (4)	Cl1_2—Ni1_2—P1_2	172.57 (5)
C9_1—P1_1—C15_1	105.48 (19)	Cl1_2—Ni1_2—P2_2	89.48 (4)
C9_1—P1_1—C11_1	103.19 (18)	P1_2—Ni1_2—P2_2	90.95 (4)
C15_1—P1_1—C11_1	110.04 (19)	Cl1_2—Ni1_2—Cl2_2	90.47 (4)
C9_1—P1_1—Ni1_1	105.44 (13)	P1_2—Ni1_2—Cl2_2	89.90 (4)
C15_1—P1_1—Ni1_1	116.71 (15)	P2_2—Ni1_2—Cl2_2	173.84 (5)
C11_1—P1_1—Ni1_1	114.50 (14)	C9_2—P1_2—C11_2	106.0 (2)
C10_1—P2_1—C21B_1	109.1 (4)	C9_2—P1_2—C15_2	102.27 (19)
C10_1—P2_1—C25_1	102.19 (19)	C11_2—P1_2—C15_2	110.23 (17)
C21B_1—P2_1—C25_1	111.1 (3)	C9_2—P1_2—Ni1_2	106.60 (13)
C10_1—P2_1—C21_1	101.2 (5)	C11_2—P1_2—Ni1_2	110.94 (13)
C21B_1—P2_1—C21_1	9.3 (7)	C15_2—P1_2—Ni1_2	119.56 (15)
C25_1—P2_1—C21_1	108.9 (4)	C10_2—P2_2—C25_2	105.6 (2)
C10_1—P2_1—Ni1_1	105.91 (13)	C10_2—P2_2—C21_2	102.61 (18)
C21B_1—P2_1—Ni1_1	111.7 (3)	C25_2—P2_2—C21_2	109.71 (18)
C25_1—P2_1—Ni1_1	116.15 (14)	C10_2—P2_2—Ni1_2	106.98 (12)
C21_1—P2_1—Ni1_1	119.7 (4)	C25_2—P2_2—Ni1_2	111.67 (15)
C10_1—C9_1—P1_1	113.1 (3)	C21_2—P2_2—Ni1_2	118.98 (14)
C10_1—C9_1—H9A_1	109.0	C10_2—C9_2—P1_2	113.7 (3)
P1_1—C9_1—H9A_1	109.0	C10_2—C9_2—H9A_2	108.8
C10_1—C9_1—H9B_1	109.0	P1_2—C9_2—H9A_2	108.8
P1_1—C9_1—H9B_1	109.0	C10_2—C9_2—H9B_2	108.8
H9A_1—C9_1—H9B_1	107.8	P1_2—C9_2—H9B_2	108.8
C9_1—C10_1—P2_1	112.0 (3)	H9A_2—C9_2—H9B_2	107.7
C9_1—C10_1—H10A_1	109.2	C9_2—C10_2—P2_2	112.2 (3)
P2_1—C10_1—H10A_1	109.2	C9_2—C10_2—H10A_2	109.2
C9_1—C10_1—H10B_1	109.2	P2_2—C10_2—H10A_2	109.2
P2_1—C10_1—H10B_1	109.2	C9_2—C10_2—H10B_2	109.2
H10A_1—C10_1—H10B_1	107.9	P2_2—C10_2—H10B_2	109.2
C14_1—C11_1—C13_1	108.4 (4)	H10A_2—C10_2—H10B_2	107.9
C14_1—C11_1—C12_1	106.9 (4)	C12_2—C11_2—C13_2	109.3 (3)
C13_1—C11_1—C12_1	107.7 (4)	C12_2—C11_2—C14_2	106.8 (4)
C14_1—C11_1—P1_1	113.0 (3)	C13_2—C11_2—C14_2	108.6 (3)
C13_1—C11_1—P1_1	112.7 (3)	C12_2—C11_2—P1_2	113.0 (3)
C12_1—C11_1—P1_1	107.9 (3)	C13_2—C11_2—P1_2	112.9 (3)
C11_1—C12_1—H12A_1	109.5	C14_2—C11_2—P1_2	105.9 (3)
C11_1—C12_1—H12B_1	109.5	C11_2—C12_2—H12A_2	109.5
H12A_1—C12_1—H12B_1	109.5	C11_2—C12_2—H12B_2	109.5
C11_1—C12_1—H12C_1	109.5	H12A_2—C12_2—H12B_2	109.5
H12A_1—C12_1—H12C_1	109.5	C11_2—C12_2—H12C_2	109.5
H12B_1—C12_1—H12C_1	109.5	H12A_2—C12_2—H12C_2	109.5
C11_1—C13_1—H13A_1	109.5	H12B_2—C12_2—H12C_2	109.5
C11_1—C13_1—H13B_1	109.5	C11_2—C13_2—H13A_2	109.5
H13A_1—C13_1—H13B_1	109.5	C11_2—C13_2—H13B_2	109.5
C11_1—C13_1—H13C_1	109.5	H13A_2—C13_2—H13B_2	109.5
H13A_1—C13_1—H13C_1	109.5	C11_2—C13_2—H13C_2	109.5
H13B_1—C13_1—H13C_1	109.5	H13A_2—C13_2—H13C_2	109.5
C11_1—C14_1—H14A_1	109.5	H13B_2—C13_2—H13C_2	109.5
C11_1—C14_1—H14B_1	109.5	C11_2—C14_2—H14A_2	109.5
H14A_1—C14_1—H14B_1	109.5	C11_2—C14_2—H14B_2	109.5
C11_1—C14_1—H14C_1	109.5	H14A_2—C14_2—H14B_2	109.5
H14A_1—C14_1—H14C_1	109.5	C11_2—C14_2—H14C_2	109.5
H14B_1—C14_1—H14C_1	109.5	H14A_2—C14_2—H14C_2	109.5
C17_1—C15_1—C16_1	108.9 (4)	H14B_2—C14_2—H14C_2	109.5
C17_1—C15_1—C18_1	109.5 (4)	C18_2—C15_2—C17_2	108.4 (4)
C16_1—C15_1—C18_1	106.5 (4)	C18_2—C15_2—C16_2	109.1 (4)
C17_1—C15_1—P1_1	112.6 (3)	C17_2—C15_2—C16_2	107.8 (4)
C16_1—C15_1—P1_1	112.2 (3)	C18_2—C15_2—P1_2	107.8 (3)
C18_1—C15_1—P1_1	107.0 (3)	C17_2—C15_2—P1_2	111.9 (3)
C15_1—C16_1—H16A_1	109.5	C16_2—C15_2—P1_2	111.8 (3)
C15_1—C16_1—H16B_1	109.5	C15_2—C16_2—H16A_2	109.5
H16A_1—C16_1—H16B_1	109.5	C15_2—C16_2—H16B_2	109.5
C15_1—C16_1—H16C_1	109.5	H16A_2—C16_2—H16B_2	109.5
H16A_1—C16_1—H16C_1	109.5	C15_2—C16_2—H16C_2	109.5
H16B_1—C16_1—H16C_1	109.5	H16A_2—C16_2—H16C_2	109.5
C15_1—C17_1—H17A_1	109.5	H16B_2—C16_2—H16C_2	109.5
C15_1—C17_1—H17B_1	109.5	C15_2—C17_2—H17A_2	109.5
H17A_1—C17_1—H17B_1	109.5	C15_2—C17_2—H17B_2	109.5
C15_1—C17_1—H17C_1	109.5	H17A_2—C17_2—H17B_2	109.5
H17A_1—C17_1—H17C_1	109.5	C15_2—C17_2—H17C_2	109.5
H17B_1—C17_1—H17C_1	109.5	H17A_2—C17_2—H17C_2	109.5
C15_1—C18_1—H18A_1	109.5	H17B_2—C17_2—H17C_2	109.5
C15_1—C18_1—H18B_1	109.5	C15_2—C18_2—H18A_2	109.5
H18A_1—C18_1—H18B_1	109.5	C15_2—C18_2—H18B_2	109.5
C15_1—C18_1—H18C_1	109.5	H18A_2—C18_2—H18B_2	109.5
H18A_1—C18_1—H18C_1	109.5	C15_2—C18_2—H18C_2	109.5
H18B_1—C18_1—H18C_1	109.5	H18A_2—C18_2—H18C_2	109.5
C23_1—C21_1—C24_1	109.0 (12)	H18B_2—C18_2—H18C_2	109.5
C23_1—C21_1—C22_1	108.2 (11)	C24_2—C21_2—C23_2	108.1 (3)
C24_1—C21_1—C22_1	107.8 (12)	C24_2—C21_2—C22_2	108.4 (3)
C23_1—C21_1—P2_1	106.6 (10)	C23_2—C21_2—C22_2	108.5 (4)
C24_1—C21_1—P2_1	110.4 (11)	C24_2—C21_2—P2_2	112.6 (3)
C22_1—C21_1—P2_1	114.7 (11)	C23_2—C21_2—P2_2	107.8 (3)
C23B_1—C21B_1—C22B_1	107.5 (9)	C22_2—C21_2—P2_2	111.3 (3)
C23B_1—C21B_1—C24B_1	109.0 (9)	C21_2—C22_2—H22A_2	109.5
C22B_1—C21B_1—C24B_1	108.3 (10)	C21_2—C22_2—H22B_2	109.5
C23B_1—C21B_1—P2_1	108.3 (8)	H22A_2—C22_2—H22B_2	109.5
C22B_1—C21B_1—P2_1	109.6 (8)	C21_2—C22_2—H22C_2	109.5
C24B_1—C21B_1—P2_1	113.9 (9)	H22A_2—C22_2—H22C_2	109.5
C21B_1—C22B_1—H22D_1	109.5	H22B_2—C22_2—H22C_2	109.5
C21B_1—C22B_1—H22E_1	109.5	C21_2—C23_2—H23A_2	109.5
H22D_1—C22B_1—H22E_1	109.5	C21_2—C23_2—H23B_2	109.5
C21B_1—C22B_1—H22F_1	109.5	H23A_2—C23_2—H23B_2	109.5
H22D_1—C22B_1—H22F_1	109.5	C21_2—C23_2—H23C_2	109.5
H22E_1—C22B_1—H22F_1	109.5	H23A_2—C23_2—H23C_2	109.5
C21B_1—C23B_1—H23D_1	109.5	H23B_2—C23_2—H23C_2	109.5
C21B_1—C23B_1—H23E_1	109.5	C21_2—C24_2—H24A_2	109.5
H23D_1—C23B_1—H23E_1	109.5	C21_2—C24_2—H24B_2	109.5
C21B_1—C23B_1—H23F_1	109.5	H24A_2—C24_2—H24B_2	109.5
H23D_1—C23B_1—H23F_1	109.5	C21_2—C24_2—H24C_2	109.5
H23E_1—C23B_1—H23F_1	109.5	H24A_2—C24_2—H24C_2	109.5
C21B_1—C24B_1—H24D_1	109.5	H24B_2—C24_2—H24C_2	109.5
C21B_1—C24B_1—H24E_1	109.5	C28_2—C25_2—C26_2	108.0 (4)
H24D_1—C24B_1—H24E_1	109.5	C28_2—C25_2—C27_2	109.8 (4)
C21B_1—C24B_1—H24F_1	109.5	C26_2—C25_2—C27_2	107.3 (4)
H24D_1—C24B_1—H24F_1	109.5	C28_2—C25_2—P2_2	113.4 (4)
H24E_1—C24B_1—H24F_1	109.5	C26_2—C25_2—P2_2	107.5 (3)
C28_1—C25_1—C26_1	109.5 (5)	C27_2—C25_2—P2_2	110.6 (3)
C28_1—C25_1—C27_1	108.8 (4)	C25_2—C26_2—H26A_2	109.5
C26_1—C25_1—C27_1	104.0 (5)	C25_2—C26_2—H26B_2	109.5
C28_1—C25_1—P2_1	112.0 (3)	H26A_2—C26_2—H26B_2	109.5
C26_1—C25_1—P2_1	108.1 (3)	C25_2—C26_2—H26C_2	109.5
C27_1—C25_1—P2_1	114.1 (3)	H26A_2—C26_2—H26C_2	109.5
C25_1—C26_1—H26A_1	109.5	H26B_2—C26_2—H26C_2	109.5
C25_1—C26_1—H26B_1	109.5	C25_2—C27_2—H27A_2	109.5
H26A_1—C26_1—H26B_1	109.5	C25_2—C27_2—H27B_2	109.5
C25_1—C26_1—H26C_1	109.5	H27A_2—C27_2—H27B_2	109.5
H26A_1—C26_1—H26C_1	109.5	C25_2—C27_2—H27C_2	109.5
H26B_1—C26_1—H26C_1	109.5	H27A_2—C27_2—H27C_2	109.5
C25_1—C27_1—H27A_1	109.5	H27B_2—C27_2—H27C_2	109.5
C25_1—C27_1—H27B_1	109.5	C25_2—C28_2—H28A_2	109.5
H27A_1—C27_1—H27B_1	109.5	C25_2—C28_2—H28B_2	109.5
C25_1—C27_1—H27C_1	109.5	H28A_2—C28_2—H28B_2	109.5
H27A_1—C27_1—H27C_1	109.5	C25_2—C28_2—H28C_2	109.5
H27B_1—C27_1—H27C_1	109.5	H28A_2—C28_2—H28C_2	109.5
C25_1—C28_1—H28A_1	109.5	H28B_2—C28_2—H28C_2	109.5
Cl1_1—Ni1_1—P1_1—C9_1	74.2 (5)	C21B_1—P2_1—C25_1—C28_1	−68.3 (5)
P2_1—Ni1_1—P1_1—C9_1	−9.42 (15)	C21_1—P2_1—C25_1—C28_1	−58.7 (6)
Cl2_1—Ni1_1—P1_1—C9_1	173.27 (15)	Ni1_1—P2_1—C25_1—C28_1	162.6 (3)
Cl1_1—Ni1_1—P1_1—C15_1	−169.1 (5)	C10_1—P2_1—C25_1—C26_1	−72.9 (4)
P2_1—Ni1_1—P1_1—C15_1	107.27 (15)	C21B_1—P2_1—C25_1—C26_1	170.9 (5)
Cl2_1—Ni1_1—P1_1—C15_1	−70.05 (16)	C21_1—P2_1—C25_1—C26_1	−179.4 (6)
Cl1_1—Ni1_1—P1_1—C11_1	−38.5 (5)	Ni1_1—P2_1—C25_1—C26_1	41.9 (4)
P2_1—Ni1_1—P1_1—C11_1	−122.12 (14)	C10_1—P2_1—C25_1—C27_1	172.0 (4)
Cl2_1—Ni1_1—P1_1—C11_1	60.56 (15)	C21B_1—P2_1—C25_1—C27_1	55.8 (6)
P1_1—Ni1_1—P2_1—C10_1	−8.71 (15)	C21_1—P2_1—C25_1—C27_1	65.5 (7)
Cl1_1—Ni1_1—P2_1—C10_1	176.74 (15)	Ni1_1—P2_1—C25_1—C27_1	−73.2 (4)
Cl2_1—Ni1_1—P2_1—C10_1	92.4 (9)	Cl1_2—Ni1_2—P1_2—C9_2	100.8 (4)
P1_1—Ni1_1—P2_1—C21B_1	109.9 (4)	P2_2—Ni1_2—P1_2—C9_2	7.60 (16)
Cl1_1—Ni1_1—P2_1—C21B_1	−64.6 (4)	Cl2_2—Ni1_2—P1_2—C9_2	−166.30 (16)
Cl2_1—Ni1_1—P2_1—C21B_1	−149.0 (10)	Cl1_2—Ni1_2—P1_2—C11_2	−14.1 (4)
P1_1—Ni1_1—P2_1—C25_1	−121.33 (15)	P2_2—Ni1_2—P1_2—C11_2	−107.33 (14)
Cl1_1—Ni1_1—P2_1—C25_1	64.12 (15)	Cl2_2—Ni1_2—P1_2—C11_2	78.77 (14)
Cl2_1—Ni1_1—P2_1—C25_1	−20.3 (10)	Cl1_2—Ni1_2—P1_2—C15_2	−144.1 (3)
P1_1—Ni1_1—P2_1—C21_1	104.6 (5)	P2_2—Ni1_2—P1_2—C15_2	122.69 (15)
Cl1_1—Ni1_1—P2_1—C21_1	−70.0 (5)	Cl2_2—Ni1_2—P1_2—C15_2	−51.21 (15)
Cl2_1—Ni1_1—P2_1—C21_1	−154.3 (10)	Cl1_2—Ni1_2—P2_2—C10_2	−163.95 (16)
C15_1—P1_1—C9_1—C10_1	−92.8 (3)	P1_2—Ni1_2—P2_2—C10_2	8.64 (16)
C11_1—P1_1—C9_1—C10_1	151.7 (3)	Cl2_2—Ni1_2—P2_2—C10_2	106.5 (4)
Ni1_1—P1_1—C9_1—C10_1	31.3 (3)	Cl1_2—Ni1_2—P2_2—C25_2	80.95 (15)
P1_1—C9_1—C10_1—P2_1	−40.4 (4)	P1_2—Ni1_2—P2_2—C25_2	−106.47 (15)
C21B_1—P2_1—C10_1—C9_1	−90.0 (4)	Cl2_2—Ni1_2—P2_2—C25_2	−8.6 (5)
C25_1—P2_1—C10_1—C9_1	152.4 (3)	Cl1_2—Ni1_2—P2_2—C21_2	−48.47 (15)
C21_1—P2_1—C10_1—C9_1	−95.2 (5)	P1_2—Ni1_2—P2_2—C21_2	124.11 (15)
Ni1_1—P2_1—C10_1—C9_1	30.3 (3)	Cl2_2—Ni1_2—P2_2—C21_2	−138.0 (4)
C9_1—P1_1—C11_1—C14_1	157.8 (3)	C11_2—P1_2—C9_2—C10_2	91.7 (3)
C15_1—P1_1—C11_1—C14_1	45.7 (4)	C15_2—P1_2—C9_2—C10_2	−152.8 (3)
Ni1_1—P1_1—C11_1—C14_1	−88.1 (3)	Ni1_2—P1_2—C9_2—C10_2	−26.6 (4)
C9_1—P1_1—C11_1—C13_1	34.5 (4)	P1_2—C9_2—C10_2—P2_2	34.9 (4)
C15_1—P1_1—C11_1—C13_1	−77.7 (4)	C25_2—P2_2—C10_2—C9_2	92.2 (3)
Ni1_1—P1_1—C11_1—C13_1	148.5 (3)	C21_2—P2_2—C10_2—C9_2	−152.9 (3)
C9_1—P1_1—C11_1—C12_1	−84.2 (3)	Ni1_2—P2_2—C10_2—C9_2	−26.9 (4)
C15_1—P1_1—C11_1—C12_1	163.6 (3)	C9_2—P1_2—C11_2—C12_2	−176.2 (3)
Ni1_1—P1_1—C11_1—C12_1	29.8 (3)	C15_2—P1_2—C11_2—C12_2	73.9 (3)
C9_1—P1_1—C15_1—C17_1	174.3 (4)	Ni1_2—P1_2—C11_2—C12_2	−60.9 (3)
C11_1—P1_1—C15_1—C17_1	−75.1 (4)	C9_2—P1_2—C11_2—C13_2	59.1 (3)
Ni1_1—P1_1—C15_1—C17_1	57.6 (4)	C15_2—P1_2—C11_2—C13_2	−50.8 (3)
C9_1—P1_1—C15_1—C16_1	−62.5 (4)	Ni1_2—P1_2—C11_2—C13_2	174.4 (2)
C11_1—P1_1—C15_1—C16_1	48.2 (4)	C9_2—P1_2—C11_2—C14_2	−59.6 (4)
Ni1_1—P1_1—C15_1—C16_1	−179.1 (3)	C15_2—P1_2—C11_2—C14_2	−169.6 (3)
C9_1—P1_1—C15_1—C18_1	54.0 (4)	Ni1_2—P1_2—C11_2—C14_2	55.7 (4)
C11_1—P1_1—C15_1—C18_1	164.6 (3)	C9_2—P1_2—C15_2—C18_2	84.4 (4)
Ni1_1—P1_1—C15_1—C18_1	−62.7 (3)	C11_2—P1_2—C15_2—C18_2	−163.3 (3)
C10_1—P2_1—C21_1—C23_1	57.0 (9)	Ni1_2—P1_2—C15_2—C18_2	−33.0 (4)
C21B_1—P2_1—C21_1—C23_1	−91 (4)	C9_2—P1_2—C15_2—C17_2	−156.5 (3)
C25_1—P2_1—C21_1—C23_1	164.2 (8)	C11_2—P1_2—C15_2—C17_2	−44.2 (4)
Ni1_1—P2_1—C21_1—C23_1	−58.8 (10)	Ni1_2—P1_2—C15_2—C17_2	86.2 (3)
C10_1—P2_1—C21_1—C24_1	175.2 (9)	C9_2—P1_2—C15_2—C16_2	−35.5 (4)
C21B_1—P2_1—C21_1—C24_1	27 (3)	C11_2—P1_2—C15_2—C16_2	76.8 (3)
C25_1—P2_1—C21_1—C24_1	−77.6 (10)	Ni1_2—P1_2—C15_2—C16_2	−152.9 (3)
Ni1_1—P2_1—C21_1—C24_1	59.4 (10)	C10_2—P2_2—C21_2—C24_2	−157.1 (3)
C10_1—P2_1—C21_1—C22_1	−62.7 (10)	C25_2—P2_2—C21_2—C24_2	−45.2 (4)
C21B_1—P2_1—C21_1—C22_1	149 (5)	Ni1_2—P2_2—C21_2—C24_2	85.1 (3)
C25_1—P2_1—C21_1—C22_1	44.5 (11)	C10_2—P2_2—C21_2—C23_2	83.8 (3)
Ni1_1—P2_1—C21_1—C22_1	−178.5 (8)	C25_2—P2_2—C21_2—C23_2	−164.3 (3)
C10_1—P2_1—C21B_1—C23B_1	87.0 (7)	Ni1_2—P2_2—C21_2—C23_2	−34.0 (3)
C25_1—P2_1—C21B_1—C23B_1	−161.1 (6)	C10_2—P2_2—C21_2—C22_2	−35.2 (4)
C21_1—P2_1—C21B_1—C23B_1	120 (4)	C25_2—P2_2—C21_2—C22_2	76.8 (4)
Ni1_1—P2_1—C21B_1—C23B_1	−29.7 (7)	Ni1_2—P2_2—C21_2—C22_2	−152.9 (3)
C10_1—P2_1—C21B_1—C22B_1	−30.0 (8)	C10_2—P2_2—C25_2—C28_2	66.5 (3)
C25_1—P2_1—C21B_1—C22B_1	81.9 (8)	C21_2—P2_2—C25_2—C28_2	−43.4 (4)
C21_1—P2_1—C21B_1—C22B_1	3 (3)	Ni1_2—P2_2—C25_2—C28_2	−177.6 (3)
Ni1_1—P2_1—C21B_1—C22B_1	−146.7 (7)	C10_2—P2_2—C25_2—C26_2	−52.9 (4)
C10_1—P2_1—C21B_1—C24B_1	−151.5 (7)	C21_2—P2_2—C25_2—C26_2	−162.8 (3)
C25_1—P2_1—C21B_1—C24B_1	−39.6 (8)	Ni1_2—P2_2—C25_2—C26_2	63.1 (3)
C21_1—P2_1—C21B_1—C24B_1	−118 (4)	C10_2—P2_2—C25_2—C27_2	−169.7 (3)
Ni1_1—P2_1—C21B_1—C24B_1	91.8 (7)	C21_2—P2_2—C25_2—C27_2	80.4 (4)
C10_1—P2_1—C25_1—C28_1	47.9 (4)	Ni1_2—P2_2—C25_2—C27_2	−53.7 (3)

(msc11) [1,2-Bis(di-tert-butylphosphanyl)ethane-κ²P,P']dibromidonickel(II)

Crystal data

[NiBr2(C18H40P2)]	F(000) = 1104
Mr = 536.97	Dx = 1.569 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 20.3765 (14) Å	Cell parameters from 2012 reflections
b = 8.1817 (6) Å	µ = 4.51 mm^−1
c = 14.7392 (10) Å	T = 200 K
β = 112.272 (1)°	Polyhedron, dark red
V = 2273.9 (3) Å^3	0.22 × 0.16 × 0.12 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3024 independent reflections
Radiation source: fine-focus sealed tube	2676 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω scans	θmax = 27.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −26→13
Tmin = 0.42, Tmax = 0.67	k = −4→10
3740 measured reflections	l = −17→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	H-atom parameters constrained
wR(F^2) = 0.079	w = 1/[σ^2(Fo^2) + (0.0502P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.004
3024 reflections	Δρmax = 0.58 e Å^−3
220 parameters	Δρmin = −0.50 e Å^−3
2 restraints	Absolute structure: Flack (1983), ???? Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.033 (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
Br1	0.86806 (3)	0.23380 (6)	0.56885 (4)	0.02888 (16)
Br2	0.69196 (4)	0.23502 (9)	0.49396 (5)	0.0412 (2)
Ni3	0.78552 (4)	0.34430 (7)	0.62955 (5)	0.01845 (17)
P4	0.86805 (8)	0.50060 (16)	0.73702 (10)	0.0179 (3)
P5	0.71332 (8)	0.39128 (17)	0.70768 (11)	0.0198 (3)
C1	0.8370 (3)	0.5523 (7)	0.8353 (4)	0.0228 (13)
H1A	0.8575	0.4740	0.8900	0.027*
H1B	0.8541	0.6629	0.8605	0.027*
C3	0.9609 (3)	0.4275 (7)	0.8114 (4)	0.0242 (13)
C2	0.7561 (3)	0.5483 (7)	0.8008 (4)	0.0242 (13)
H2A	0.7372	0.6568	0.7735	0.029*
H2B	0.7432	0.5289	0.8582	0.029*
C11	0.7094 (3)	0.1981 (7)	0.7758 (4)	0.0251 (13)
C14	0.6740 (4)	0.0552 (7)	0.7080 (5)	0.0314 (15)
H14A	0.6235	0.0787	0.6733	0.047*
H14B	0.6795	−0.0446	0.7470	0.047*
H14C	0.6964	0.0399	0.6604	0.047*
C13	0.6728 (5)	0.2236 (8)	0.8494 (6)	0.0419 (19)
H13A	0.6924	0.3210	0.8891	0.063*
H13B	0.6811	0.1279	0.8923	0.063*
H13C	0.6217	0.2381	0.8135	0.063*
C12	0.7858 (4)	0.1450 (8)	0.8339 (5)	0.0363 (16)
H12A	0.7858	0.0441	0.8697	0.054*
H12B	0.8106	0.2312	0.8805	0.054*
H12C	0.8100	0.1258	0.7887	0.054*
C10	0.7998 (4)	0.7792 (7)	0.6417 (6)	0.0356 (16)
H10A	0.7638	0.6997	0.6041	0.053*
H10B	0.7983	0.8739	0.6003	0.053*
H10C	0.7903	0.8147	0.6990	0.053*
C9	0.9260 (4)	0.8221 (7)	0.7428 (5)	0.0313 (14)
H9A	0.9231	0.9255	0.7079	0.047*
H9B	0.9740	0.7774	0.7625	0.047*
H9C	0.9151	0.8414	0.8012	0.047*
C8	0.8889 (4)	0.6687 (7)	0.5835 (5)	0.0318 (15)
H8A	0.9363	0.6207	0.6026	0.048*
H8B	0.8872	0.7721	0.5491	0.048*
H8C	0.8537	0.5931	0.5401	0.048*
C7	0.8727 (3)	0.7005 (7)	0.6753 (5)	0.0248 (14)
C15	0.6208 (3)	0.4818 (7)	0.6466 (5)	0.0312 (14)
C6	0.9953 (3)	0.5201 (7)	0.9083 (4)	0.0317 (15)
H6A	0.9992	0.6362	0.8947	0.048*
H6B	1.0427	0.4755	0.9447	0.048*
H6C	0.9660	0.5078	0.9474	0.048*
C18	0.5971 (4)	0.5732 (8)	0.7209 (6)	0.0433 (19)
H18A	0.5480	0.6100	0.6880	0.065*
H18B	0.6280	0.6680	0.7468	0.065*
H18C	0.6005	0.4995	0.7749	0.065*
C17	0.6229 (4)	0.6035 (9)	0.5693 (6)	0.0433 (18)
H17A	0.5758	0.6519	0.5364	0.065*
H17B	0.6369	0.5469	0.5209	0.065*
H17C	0.6573	0.6899	0.6008	0.065*
C16	0.5645 (3)	0.3520 (8)	0.5971 (5)	0.0351 (15)
H16A	0.5791	0.2872	0.5520	0.053*
H16B	0.5191	0.4054	0.5605	0.053*
H16C	0.5593	0.2801	0.6472	0.053*
C5	1.0111 (3)	0.4395 (7)	0.7539 (5)	0.0315 (14)
H5A	1.0578	0.3949	0.7941	0.047*
H5B	1.0162	0.5542	0.7386	0.047*
H5C	0.9910	0.3768	0.6929	0.047*
C4	0.9571 (4)	0.2448 (7)	0.8375 (5)	0.0327 (15)
H4A	0.9296	0.2345	0.8792	0.049*
H4B	1.0052	0.2030	0.8728	0.049*
H4C	0.9342	0.1817	0.7772	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0324 (4)	0.0317 (3)	0.0267 (3)	0.0010 (3)	0.0159 (3)	−0.0055 (3)
Br2	0.0304 (4)	0.0645 (5)	0.0278 (4)	−0.0184 (4)	0.0100 (3)	−0.0205 (3)
Ni3	0.0198 (4)	0.0197 (3)	0.0166 (3)	−0.0038 (3)	0.0076 (3)	−0.0040 (3)
P4	0.0185 (8)	0.0179 (6)	0.0177 (7)	−0.0012 (6)	0.0075 (6)	−0.0016 (6)
P5	0.0188 (8)	0.0195 (7)	0.0214 (7)	−0.0025 (6)	0.0082 (6)	−0.0030 (6)
C1	0.020 (3)	0.026 (3)	0.028 (3)	−0.008 (3)	0.016 (3)	−0.009 (3)
C3	0.020 (3)	0.024 (3)	0.027 (3)	0.000 (3)	0.007 (3)	−0.002 (3)
C2	0.022 (3)	0.022 (3)	0.032 (3)	−0.005 (3)	0.014 (3)	−0.007 (3)
C11	0.027 (3)	0.024 (3)	0.024 (3)	−0.009 (3)	0.009 (3)	0.001 (2)
C14	0.031 (4)	0.023 (3)	0.039 (4)	−0.008 (3)	0.013 (3)	−0.007 (3)
C13	0.048 (5)	0.045 (4)	0.040 (4)	−0.013 (4)	0.026 (4)	−0.002 (3)
C12	0.032 (4)	0.035 (3)	0.036 (4)	−0.007 (3)	0.006 (3)	0.008 (3)
C10	0.032 (4)	0.028 (3)	0.047 (4)	0.008 (3)	0.015 (4)	0.013 (3)
C9	0.030 (4)	0.021 (3)	0.036 (4)	0.000 (3)	0.005 (3)	−0.004 (3)
C8	0.038 (4)	0.033 (3)	0.024 (3)	0.000 (3)	0.011 (3)	0.009 (3)
C7	0.022 (4)	0.023 (3)	0.034 (4)	−0.001 (2)	0.016 (3)	0.001 (2)
C15	0.018 (3)	0.032 (3)	0.039 (4)	0.006 (3)	0.005 (3)	0.002 (3)
C6	0.022 (4)	0.032 (3)	0.031 (4)	−0.007 (3)	−0.002 (3)	−0.004 (3)
C18	0.025 (4)	0.038 (4)	0.070 (5)	−0.003 (3)	0.022 (4)	−0.016 (4)
C17	0.021 (4)	0.044 (4)	0.056 (5)	0.004 (3)	0.005 (3)	0.019 (4)
C16	0.019 (3)	0.043 (4)	0.039 (4)	−0.006 (3)	0.006 (3)	−0.004 (3)
C5	0.017 (3)	0.033 (3)	0.046 (4)	0.003 (3)	0.014 (3)	0.003 (3)
C4	0.037 (4)	0.029 (3)	0.027 (4)	0.003 (3)	0.007 (3)	0.001 (3)

Geometric parameters (Å, º)

Br1—Ni3	2.3638 (9)	C10—H10B	0.9800
Br2—Ni3	2.3537 (10)	C10—H10C	0.9800
Ni3—P5	2.2186 (16)	C9—C7	1.530 (9)
Ni3—P4	2.2256 (16)	C9—H9A	0.9800
P4—C1	1.837 (5)	C9—H9B	0.9800
P4—C3	1.889 (6)	C9—H9C	0.9800
P4—C7	1.891 (6)	C8—C7	1.533 (8)
P5—C2	1.841 (6)	C8—H8A	0.9800
P5—C11	1.890 (6)	C8—H8B	0.9800
P5—C15	1.904 (6)	C8—H8C	0.9800
C1—C2	1.529 (8)	C15—C17	1.526 (9)
C1—H1A	0.9900	C15—C16	1.530 (9)
C1—H1B	0.9900	C15—C18	1.546 (9)
C3—C6	1.532 (8)	C6—H6A	0.9800
C3—C4	1.553 (7)	C6—H6B	0.9800
C3—C5	1.559 (8)	C6—H6C	0.9800
C2—H2A	0.9900	C18—H18A	0.9800
C2—H2B	0.9900	C18—H18B	0.9800
C11—C12	1.529 (10)	C18—H18C	0.9800
C11—C14	1.529 (8)	C17—H17A	0.9800
C11—C13	1.546 (9)	C17—H17B	0.9800
C14—H14A	0.9800	C17—H17C	0.9800
C14—H14B	0.9800	C16—H16A	0.9800
C14—H14C	0.9800	C16—H16B	0.9800
C13—H13A	0.9800	C16—H16C	0.9800
C13—H13B	0.9800	C5—H5A	0.9800
C13—H13C	0.9800	C5—H5B	0.9800
C12—H12A	0.9800	C5—H5C	0.9800
C12—H12B	0.9800	C4—H4A	0.9800
C12—H12C	0.9800	C4—H4B	0.9800
C10—C7	1.519 (9)	C4—H4C	0.9800
C10—H10A	0.9800
P5—Ni3—P4	90.10 (6)	C7—C10—H10C	109.5
P5—Ni3—Br2	91.35 (5)	H10A—C10—H10C	109.5
P4—Ni3—Br2	166.65 (5)	H10B—C10—H10C	109.5
P5—Ni3—Br1	165.85 (5)	C7—C9—H9A	109.5
P4—Ni3—Br1	92.01 (5)	C7—C9—H9B	109.5
Br2—Ni3—Br1	89.82 (3)	H9A—C9—H9B	109.5
C1—P4—C3	100.6 (3)	C7—C9—H9C	109.5
C1—P4—C7	106.0 (3)	H9A—C9—H9C	109.5
C3—P4—C7	109.4 (3)	H9B—C9—H9C	109.5
C1—P4—Ni3	107.48 (19)	C7—C8—H8A	109.5
C3—P4—Ni3	123.47 (18)	C7—C8—H8B	109.5
C7—P4—Ni3	108.4 (2)	H8A—C8—H8B	109.5
C2—P5—C11	106.9 (3)	C7—C8—H8C	109.5
C2—P5—C15	100.7 (3)	H8A—C8—H8C	109.5
C11—P5—C15	110.0 (3)	H8B—C8—H8C	109.5
C2—P5—Ni3	106.72 (19)	C10—C7—C9	107.6 (5)
C11—P5—Ni3	107.51 (19)	C10—C7—C8	107.2 (5)
C15—P5—Ni3	123.7 (2)	C9—C7—C8	110.2 (5)
C2—C1—P4	112.5 (4)	C10—C7—P4	107.6 (4)
C2—C1—H1A	109.1	C9—C7—P4	113.7 (5)
P4—C1—H1A	109.1	C8—C7—P4	110.2 (4)
C2—C1—H1B	109.1	C17—C15—C16	109.0 (6)
P4—C1—H1B	109.1	C17—C15—C18	108.5 (6)
H1A—C1—H1B	107.8	C16—C15—C18	107.1 (5)
C6—C3—C4	107.0 (5)	C17—C15—P5	107.7 (4)
C6—C3—C5	108.3 (5)	C16—C15—P5	112.6 (4)
C4—C3—C5	107.5 (5)	C18—C15—P5	111.8 (5)
C6—C3—P4	112.8 (4)	C3—C6—H6A	109.5
C4—C3—P4	108.4 (4)	C3—C6—H6B	109.5
C5—C3—P4	112.6 (4)	H6A—C6—H6B	109.5
C1—C2—P5	114.2 (4)	C3—C6—H6C	109.5
C1—C2—H2A	108.7	H6A—C6—H6C	109.5
P5—C2—H2A	108.7	H6B—C6—H6C	109.5
C1—C2—H2B	108.7	C15—C18—H18A	109.5
P5—C2—H2B	108.7	C15—C18—H18B	109.5
H2A—C2—H2B	107.6	H18A—C18—H18B	109.5
C12—C11—C14	106.1 (5)	C15—C18—H18C	109.5
C12—C11—C13	107.8 (6)	H18A—C18—H18C	109.5
C14—C11—C13	109.2 (5)	H18B—C18—H18C	109.5
C12—C11—P5	107.2 (4)	C15—C17—H17A	109.5
C14—C11—P5	113.4 (4)	C15—C17—H17B	109.5
C13—C11—P5	112.9 (4)	H17A—C17—H17B	109.5
C11—C14—H14A	109.5	C15—C17—H17C	109.5
C11—C14—H14B	109.5	H17A—C17—H17C	109.5
H14A—C14—H14B	109.5	H17B—C17—H17C	109.5
C11—C14—H14C	109.5	C15—C16—H16A	109.5
H14A—C14—H14C	109.5	C15—C16—H16B	109.5
H14B—C14—H14C	109.5	H16A—C16—H16B	109.5
C11—C13—H13A	109.5	C15—C16—H16C	109.5
C11—C13—H13B	109.5	H16A—C16—H16C	109.5
H13A—C13—H13B	109.5	H16B—C16—H16C	109.5
C11—C13—H13C	109.5	C3—C5—H5A	109.5
H13A—C13—H13C	109.5	C3—C5—H5B	109.5
H13B—C13—H13C	109.5	H5A—C5—H5B	109.5
C11—C12—H12A	109.5	C3—C5—H5C	109.5
C11—C12—H12B	109.5	H5A—C5—H5C	109.5
H12A—C12—H12B	109.5	H5B—C5—H5C	109.5
C11—C12—H12C	109.5	C3—C4—H4A	109.5
H12A—C12—H12C	109.5	C3—C4—H4B	109.5
H12B—C12—H12C	109.5	H4A—C4—H4B	109.5
C7—C10—H10A	109.5	C3—C4—H4C	109.5
C7—C10—H10B	109.5	H4A—C4—H4C	109.5
H10A—C10—H10B	109.5	H4B—C4—H4C	109.5
P5—Ni3—P4—C1	8.1 (2)	C11—P5—C2—C1	88.6 (5)
Br2—Ni3—P4—C1	104.3 (3)	C15—P5—C2—C1	−156.4 (4)
Br1—Ni3—P4—C1	−157.9 (2)	Ni3—P5—C2—C1	−26.2 (5)
P5—Ni3—P4—C3	124.2 (2)	C2—P5—C11—C12	−64.1 (5)
Br2—Ni3—P4—C3	−139.5 (3)	C15—P5—C11—C12	−172.6 (4)
Br1—Ni3—P4—C3	−41.8 (2)	Ni3—P5—C11—C12	50.2 (5)
P5—Ni3—P4—C7	−106.09 (19)	C2—P5—C11—C14	179.3 (4)
Br2—Ni3—P4—C7	−9.8 (3)	C15—P5—C11—C14	70.7 (5)
Br1—Ni3—P4—C7	87.90 (19)	Ni3—P5—C11—C14	−66.5 (5)
P4—Ni3—P5—C2	7.7 (2)	C2—P5—C11—C13	54.5 (6)
Br2—Ni3—P5—C2	−159.0 (2)	C15—P5—C11—C13	−54.0 (6)
Br1—Ni3—P5—C2	106.3 (3)	Ni3—P5—C11—C13	168.8 (5)
P4—Ni3—P5—C11	−106.7 (2)	C1—P4—C7—C10	−56.1 (5)
Br2—Ni3—P5—C11	86.5 (2)	C3—P4—C7—C10	−163.8 (4)
Br1—Ni3—P5—C11	−8.1 (3)	Ni3—P4—C7—C10	59.0 (5)
P4—Ni3—P5—C15	123.4 (2)	C1—P4—C7—C9	62.9 (5)
Br2—Ni3—P5—C15	−43.4 (2)	C3—P4—C7—C9	−44.8 (5)
Br1—Ni3—P5—C15	−138.0 (3)	Ni3—P4—C7—C9	178.0 (4)
C3—P4—C1—C2	−156.4 (4)	C1—P4—C7—C8	−172.7 (4)
C7—P4—C1—C2	89.8 (4)	C3—P4—C7—C8	79.6 (5)
Ni3—P4—C1—C2	−26.0 (5)	Ni3—P4—C7—C8	−57.6 (5)
C1—P4—C3—C6	−34.3 (5)	C2—P5—C15—C17	84.2 (5)
C7—P4—C3—C6	77.0 (5)	C11—P5—C15—C17	−163.2 (5)
Ni3—P4—C3—C6	−153.7 (3)	Ni3—P5—C15—C17	−34.3 (6)
C1—P4—C3—C4	84.0 (4)	C2—P5—C15—C16	−155.6 (5)
C7—P4—C3—C4	−164.7 (4)	C11—P5—C15—C16	−43.0 (5)
Ni3—P4—C3—C4	−35.4 (5)	Ni3—P5—C15—C16	85.8 (5)
C1—P4—C3—C5	−157.2 (4)	C2—P5—C15—C18	−34.9 (5)
C7—P4—C3—C5	−45.9 (5)	C11—P5—C15—C18	77.7 (5)
Ni3—P4—C3—C5	83.4 (4)	Ni3—P5—C15—C18	−153.5 (4)
P4—C1—C2—P5	34.1 (6)

(lw23) [1,2-Bis(di-tert-butylphosphanyl)ethane-κ²P,P']diiodidonickel(II)

Crystal data

[NiI2(C18H40P2)]	F(000) = 1248
Mr = 630.95	Dx = 1.766 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 20.4783 (9) Å	Cell parameters from 8357 reflections
b = 8.3037 (4) Å	θ = 2.7–27.1°
c = 14.9472 (7) Å	µ = 3.55 mm^−1
β = 110.999 (1)°	T = 200 K
V = 2372.90 (19) Å^3	Plate, green
Z = 4	0.12 × 0.08 × 0.05 mm

Data collection

Bruker APEXII Quazar diffractometer	4689 independent reflections
Radiation source: ImuS microsource	4404 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.024
ϕ and ω scans	θmax = 27.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −26→25
Tmin = 0.675, Tmax = 0.842	k = −10→10
12902 measured reflections	l = −19→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.024	H-atom parameters constrained
wR(F^2) = 0.048	w = 1/[σ^2(Fo^2) + (0.0211P)^2 + 0.1993P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.002
4689 reflections	Δρmax = 0.51 e Å^−3
221 parameters	Δρmin = −0.48 e Å^−3
2 restraints	Absolute structure: Flack (1983), ???? Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.115 (14)

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
Ni1	0.26145 (3)	0.33973 (5)	0.47078 (3)	0.01521 (11)
I1	0.172476 (12)	0.21579 (3)	0.535269 (14)	0.02594 (7)
I2	0.358381 (14)	0.22306 (4)	0.614557 (17)	0.03692 (9)
P1	0.33593 (5)	0.38903 (12)	0.39516 (7)	0.0174 (2)
P2	0.18075 (5)	0.49559 (11)	0.36569 (7)	0.0145 (2)
C9	0.2951 (2)	0.5450 (5)	0.3053 (3)	0.0231 (9)
H9A	0.3131	0.6517	0.3328	0.028*
H9B	0.3090	0.5277	0.2491	0.028*
C10	0.21552 (19)	0.5465 (5)	0.2721 (3)	0.0204 (9)
H10A	0.1967	0.4689	0.2187	0.024*
H10B	0.1985	0.6549	0.2469	0.024*
C11	0.3405 (2)	0.2015 (5)	0.3244 (3)	0.0250 (9)
C12	0.3784 (3)	0.2315 (5)	0.2547 (4)	0.0349 (12)
H12A	0.4278	0.2546	0.2907	0.052*
H12B	0.3570	0.3235	0.2136	0.052*
H12C	0.3747	0.1356	0.2149	0.052*
C13	0.2653 (2)	0.1525 (5)	0.2663 (3)	0.0361 (11)
H13A	0.2429	0.2369	0.2195	0.054*
H13B	0.2393	0.1378	0.3095	0.054*
H13C	0.2653	0.0513	0.2325	0.054*
C14	0.3741 (2)	0.0580 (5)	0.3893 (3)	0.0300 (10)
H14A	0.3716	−0.0376	0.3497	0.045*
H14B	0.3490	0.0374	0.4329	0.045*
H14C	0.4232	0.0826	0.4265	0.045*
C15	0.4278 (2)	0.4799 (5)	0.4544 (3)	0.0273 (9)
C16	0.4505 (2)	0.5723 (6)	0.3813 (4)	0.0441 (14)
H16A	0.4208	0.6674	0.3591	0.066*
H16B	0.4459	0.5022	0.3266	0.066*
H16C	0.4994	0.6061	0.4116	0.066*
C17	0.4840 (2)	0.3523 (5)	0.5000 (3)	0.0297 (10)
H17A	0.5279	0.4054	0.5380	0.045*
H17B	0.4912	0.2876	0.4495	0.045*
H17C	0.4687	0.2822	0.5416	0.045*
C18	0.4263 (2)	0.5994 (6)	0.5310 (4)	0.0402 (12)
H18A	0.4106	0.5445	0.5778	0.060*
H18B	0.3940	0.6874	0.5010	0.060*
H18C	0.4733	0.6430	0.5635	0.060*
C21	0.0885 (2)	0.4260 (5)	0.2892 (3)	0.0202 (9)
C22	0.03674 (19)	0.4410 (5)	0.3412 (3)	0.0263 (9)
H22A	−0.0079	0.3916	0.3022	0.039*
H22B	0.0293	0.5551	0.3514	0.039*
H22C	0.0556	0.3860	0.4032	0.039*
C23	0.0589 (2)	0.5204 (5)	0.1948 (3)	0.0286 (10)
H23A	0.0877	0.4996	0.1559	0.043*
H23B	0.0596	0.6358	0.2088	0.043*
H23C	0.0107	0.4860	0.1596	0.043*
C24	0.0926 (2)	0.2490 (4)	0.2635 (3)	0.0267 (10)
H24A	0.1148	0.1865	0.3223	0.040*
H24B	0.1203	0.2393	0.2222	0.040*
H24C	0.0453	0.2077	0.2296	0.040*
C25	0.1756 (2)	0.6925 (4)	0.4262 (3)	0.0202 (9)
C26	0.1255 (2)	0.8147 (4)	0.3598 (3)	0.0302 (11)
H26A	0.1264	0.9146	0.3952	0.045*
H26B	0.0780	0.7706	0.3364	0.045*
H26C	0.1400	0.8374	0.3054	0.045*
C27	0.2482 (2)	0.7656 (5)	0.4632 (4)	0.0354 (11)
H27A	0.2610	0.7998	0.4089	0.053*
H27B	0.2818	0.6853	0.5010	0.053*
H27C	0.2486	0.8589	0.5035	0.053*
C28	0.1551 (2)	0.6634 (5)	0.5137 (3)	0.0267 (10)
H28A	0.1890	0.5904	0.5582	0.040*
H28B	0.1084	0.6150	0.4932	0.040*
H28C	0.1548	0.7661	0.5458	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0166 (2)	0.0164 (2)	0.0130 (2)	0.0028 (2)	0.00576 (19)	0.0025 (2)
I1	0.02948 (17)	0.02720 (13)	0.02349 (16)	−0.00220 (13)	0.01234 (13)	0.00151 (13)
I2	0.02744 (18)	0.0586 (2)	0.02348 (17)	0.01514 (16)	0.00762 (14)	0.01616 (15)
P1	0.0153 (5)	0.0195 (5)	0.0184 (5)	0.0025 (4)	0.0072 (4)	0.0026 (4)
P2	0.0143 (5)	0.0150 (5)	0.0142 (5)	0.0008 (4)	0.0052 (4)	0.0002 (4)
C9	0.020 (2)	0.027 (2)	0.024 (2)	0.0013 (18)	0.0095 (18)	0.0042 (17)
C10	0.025 (2)	0.022 (2)	0.013 (2)	0.0081 (17)	0.0059 (18)	0.0080 (16)
C11	0.027 (2)	0.024 (2)	0.025 (2)	0.0058 (18)	0.0109 (19)	−0.0010 (17)
C12	0.039 (3)	0.039 (3)	0.037 (3)	0.012 (2)	0.027 (2)	0.006 (2)
C13	0.035 (3)	0.030 (2)	0.037 (3)	0.008 (2)	0.005 (2)	−0.012 (2)
C14	0.031 (3)	0.026 (2)	0.036 (3)	0.0072 (19)	0.016 (2)	0.0007 (19)
C15	0.016 (2)	0.033 (2)	0.032 (2)	0.0011 (18)	0.0072 (18)	0.0027 (19)
C16	0.023 (3)	0.041 (3)	0.066 (4)	−0.006 (2)	0.012 (3)	0.014 (3)
C17	0.014 (2)	0.044 (3)	0.030 (2)	0.0023 (19)	0.0067 (18)	0.005 (2)
C18	0.020 (2)	0.039 (3)	0.054 (3)	−0.007 (2)	0.005 (2)	−0.018 (2)
C21	0.015 (2)	0.028 (2)	0.016 (2)	0.0013 (17)	0.0026 (17)	0.0009 (17)
C22	0.014 (2)	0.031 (2)	0.031 (2)	0.0003 (17)	0.0050 (18)	0.0021 (18)
C23	0.020 (2)	0.034 (2)	0.027 (2)	0.0017 (18)	0.0020 (19)	0.0002 (19)
C24	0.027 (2)	0.029 (2)	0.020 (2)	−0.0053 (18)	0.0028 (19)	−0.0076 (17)
C25	0.023 (2)	0.014 (2)	0.025 (2)	0.0019 (16)	0.0113 (19)	−0.0056 (15)
C26	0.034 (3)	0.015 (2)	0.038 (3)	0.0093 (19)	0.008 (2)	0.0033 (18)
C27	0.030 (3)	0.025 (2)	0.050 (3)	−0.0039 (19)	0.012 (2)	−0.009 (2)
C28	0.041 (3)	0.0180 (19)	0.023 (2)	0.0030 (18)	0.013 (2)	−0.0046 (17)

Geometric parameters (Å, º)

Ni1—P1	2.2377 (11)	C16—H16C	0.9800
Ni1—P2	2.2389 (10)	C17—H17A	0.9800
Ni1—I2	2.5377 (5)	C17—H17B	0.9800
Ni1—I1	2.5626 (5)	C17—H17C	0.9800
P1—C9	1.837 (4)	C18—H18A	0.9800
P1—C11	1.904 (4)	C18—H18B	0.9800
P1—C15	1.923 (4)	C18—H18C	0.9800
P2—C10	1.832 (4)	C21—C22	1.526 (5)
P2—C25	1.889 (4)	C21—C24	1.529 (5)
P2—C21	1.914 (4)	C21—C23	1.536 (5)
C9—C10	1.524 (5)	C22—H22A	0.9800
C9—H9A	0.9900	C22—H22B	0.9800
C9—H9B	0.9900	C22—H22C	0.9800
C10—H10A	0.9900	C23—H23A	0.9800
C10—H10B	0.9900	C23—H23B	0.9800
C11—C12	1.526 (6)	C23—H23C	0.9800
C11—C13	1.529 (6)	C24—H24A	0.9800
C11—C14	1.535 (5)	C24—H24B	0.9800
C12—H12A	0.9800	C24—H24C	0.9800
C12—H12B	0.9800	C25—C27	1.514 (6)
C12—H12C	0.9800	C25—C26	1.529 (6)
C13—H13A	0.9800	C25—C28	1.530 (6)
C13—H13B	0.9800	C26—H26A	0.9800
C13—H13C	0.9800	C26—H26B	0.9800
C14—H14A	0.9800	C26—H26C	0.9800
C14—H14B	0.9800	C27—H27A	0.9800
C14—H14C	0.9800	C27—H27B	0.9800
C15—C18	1.524 (6)	C27—H27C	0.9800
C15—C17	1.533 (6)	C28—H28A	0.9800
C15—C16	1.538 (6)	C28—H28B	0.9800
C16—H16A	0.9800	C28—H28C	0.9800
C16—H16B	0.9800
P1—Ni1—P2	90.30 (4)	C15—C16—H16C	109.5
P1—Ni1—I2	91.70 (3)	H16A—C16—H16C	109.5
P2—Ni1—I2	166.29 (3)	H16B—C16—H16C	109.5
P1—Ni1—I1	165.63 (3)	C15—C17—H17A	109.5
P2—Ni1—I1	92.90 (3)	C15—C17—H17B	109.5
I2—Ni1—I1	88.507 (16)	H17A—C17—H17B	109.5
C9—P1—C11	105.72 (19)	C15—C17—H17C	109.5
C9—P1—C15	100.02 (18)	H17A—C17—H17C	109.5
C11—P1—C15	109.99 (18)	H17B—C17—H17C	109.5
C9—P1—Ni1	106.49 (13)	C15—C18—H18A	109.5
C11—P1—Ni1	108.02 (13)	C15—C18—H18B	109.5
C15—P1—Ni1	124.78 (14)	H18A—C18—H18B	109.5
C10—P2—C25	105.62 (18)	C15—C18—H18C	109.5
C10—P2—C21	100.64 (17)	H18A—C18—H18C	109.5
C25—P2—C21	109.55 (18)	H18B—C18—H18C	109.5
C10—P2—Ni1	106.13 (12)	C22—C21—C24	108.5 (3)
C25—P2—Ni1	108.55 (13)	C22—C21—C23	108.0 (3)
C21—P2—Ni1	124.53 (13)	C24—C21—C23	107.4 (3)
C10—C9—P1	113.4 (3)	C22—C21—P2	112.9 (3)
C10—C9—H9A	108.9	C24—C21—P2	108.0 (3)
P1—C9—H9A	108.9	C23—C21—P2	111.9 (3)
C10—C9—H9B	108.9	C21—C22—H22A	109.5
P1—C9—H9B	108.9	C21—C22—H22B	109.5
H9A—C9—H9B	107.7	H22A—C22—H22B	109.5
C9—C10—P2	114.3 (2)	C21—C22—H22C	109.5
C9—C10—H10A	108.7	H22A—C22—H22C	109.5
P2—C10—H10A	108.7	H22B—C22—H22C	109.5
C9—C10—H10B	108.7	C21—C23—H23A	109.5
P2—C10—H10B	108.7	C21—C23—H23B	109.5
H10A—C10—H10B	107.6	H23A—C23—H23B	109.5
C12—C11—C13	108.1 (4)	C21—C23—H23C	109.5
C12—C11—C14	109.6 (3)	H23A—C23—H23C	109.5
C13—C11—C14	106.5 (3)	H23B—C23—H23C	109.5
C12—C11—P1	112.6 (3)	C21—C24—H24A	109.5
C13—C11—P1	107.0 (3)	C21—C24—H24B	109.5
C14—C11—P1	112.6 (3)	H24A—C24—H24B	109.5
C11—C12—H12A	109.5	C21—C24—H24C	109.5
C11—C12—H12B	109.5	H24A—C24—H24C	109.5
H12A—C12—H12B	109.5	H24B—C24—H24C	109.5
C11—C12—H12C	109.5	C27—C25—C26	108.3 (3)
H12A—C12—H12C	109.5	C27—C25—C28	106.6 (3)
H12B—C12—H12C	109.5	C26—C25—C28	109.5 (3)
C11—C13—H13A	109.5	C27—C25—P2	107.8 (3)
C11—C13—H13B	109.5	C26—C25—P2	113.8 (3)
H13A—C13—H13B	109.5	C28—C25—P2	110.6 (3)
C11—C13—H13C	109.5	C25—C26—H26A	109.5
H13A—C13—H13C	109.5	C25—C26—H26B	109.5
H13B—C13—H13C	109.5	H26A—C26—H26B	109.5
C11—C14—H14A	109.5	C25—C26—H26C	109.5
C11—C14—H14B	109.5	H26A—C26—H26C	109.5
H14A—C14—H14B	109.5	H26B—C26—H26C	109.5
C11—C14—H14C	109.5	C25—C27—H27A	109.5
H14A—C14—H14C	109.5	C25—C27—H27B	109.5
H14B—C14—H14C	109.5	H27A—C27—H27B	109.5
C18—C15—C17	109.3 (4)	C25—C27—H27C	109.5
C18—C15—C16	107.6 (4)	H27A—C27—H27C	109.5
C17—C15—C16	106.9 (3)	H27B—C27—H27C	109.5
C18—C15—P1	108.8 (3)	C25—C28—H28A	109.5
C17—C15—P1	112.8 (3)	C25—C28—H28B	109.5
C16—C15—P1	111.3 (3)	H28A—C28—H28B	109.5
C15—C16—H16A	109.5	C25—C28—H28C	109.5
C15—C16—H16B	109.5	H28A—C28—H28C	109.5
H16A—C16—H16B	109.5	H28B—C28—H28C	109.5
P2—Ni1—P1—C9	7.78 (14)	C9—P1—C11—C14	179.7 (3)
I2—Ni1—P1—C9	−158.66 (14)	C15—P1—C11—C14	72.5 (3)
I1—Ni1—P1—C9	110.72 (18)	Ni1—P1—C11—C14	−66.6 (3)
P2—Ni1—P1—C11	−105.39 (14)	C9—P1—C15—C18	84.3 (3)
I2—Ni1—P1—C11	88.17 (14)	C11—P1—C15—C18	−164.8 (3)
I1—Ni1—P1—C11	−2.4 (2)	Ni1—P1—C15—C18	−34.0 (4)
P2—Ni1—P1—C15	123.03 (16)	C9—P1—C15—C17	−154.2 (3)
I2—Ni1—P1—C15	−43.41 (16)	C11—P1—C15—C17	−43.3 (3)
I1—Ni1—P1—C15	−134.03 (18)	Ni1—P1—C15—C17	87.5 (3)
P1—Ni1—P2—C10	8.05 (14)	C9—P1—C15—C16	−34.1 (3)
I2—Ni1—P2—C10	106.49 (18)	C11—P1—C15—C16	76.9 (3)
I1—Ni1—P2—C10	−157.93 (14)	Ni1—P1—C15—C16	−152.3 (3)
P1—Ni1—P2—C25	−105.07 (14)	C10—P2—C21—C22	−156.1 (3)
I2—Ni1—P2—C25	−6.6 (2)	C25—P2—C21—C22	−45.2 (3)
I1—Ni1—P2—C25	88.94 (14)	Ni1—P2—C21—C22	85.7 (3)
P1—Ni1—P2—C21	123.67 (16)	C10—P2—C21—C24	83.9 (3)
I2—Ni1—P2—C21	−137.90 (18)	C25—P2—C21—C24	−165.1 (3)
I1—Ni1—P2—C21	−42.32 (16)	Ni1—P2—C21—C24	−34.3 (3)
C11—P1—C9—C10	88.5 (3)	C10—P2—C21—C23	−34.1 (3)
C15—P1—C9—C10	−157.2 (3)	C25—P2—C21—C23	76.9 (3)
Ni1—P1—C9—C10	−26.2 (3)	Ni1—P2—C21—C23	−152.2 (2)
P1—C9—C10—P2	35.0 (4)	C10—P2—C25—C27	−57.3 (3)
C25—P2—C10—C9	88.4 (3)	C21—P2—C25—C27	−164.9 (3)
C21—P2—C10—C9	−157.6 (3)	Ni1—P2—C25—C27	56.1 (3)
Ni1—P2—C10—C9	−26.7 (3)	C10—P2—C25—C26	62.8 (3)
C9—P1—C11—C12	55.1 (4)	C21—P2—C25—C26	−44.8 (4)
C15—P1—C11—C12	−52.0 (4)	Ni1—P2—C25—C26	176.3 (3)
Ni1—P1—C11—C12	168.8 (3)	C10—P2—C25—C28	−173.5 (3)
C9—P1—C11—C13	−63.6 (3)	C21—P2—C25—C28	78.9 (3)
C15—P1—C11—C13	−170.7 (3)	Ni1—P2—C25—C28	−60.0 (3)
Ni1—P1—C11—C13	50.1 (3)

(lw29) [1,2-Bis(diphenylphosphanyl)ethane-κ²P,P']diiodidonickel(II) dichloromethane monosolvate

Crystal data

[NiI2(C26H24P2)]·CH2Cl2	Dx = 1.811 Mg m^−3
Mr = 795.83	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41cd	Cell parameters from 9238 reflections
a = 26.3705 (17) Å	θ = 2.4–27.8°
c = 16.7900 (11) Å	µ = 3.09 mm^−1
V = 11675.8 (17) Å^3	T = 200 K
Z = 16	Needle, violet
F(000) = 6176	0.33 × 0.07 × 0.05 mm

Data collection

Bruker APEX diffractometer	7131 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.063
ϕ and ω scans	θmax = 29.1°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −36→36
Tmin = 0.652, Tmax = 0.850	k = −36→36
109821 measured reflections	l = −22→22
7839 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.035	w = 1/[σ^2(Fo^2) + (0.0204P)^2 + 71.4066P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.075	(Δ/σ)max = 0.002
S = 1.04	Δρmax = 1.32 e Å^−3
7839 reflections	Δρmin = −1.26 e Å^−3
307 parameters	Absolute structure: Flack x determined using 3206 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
5 restraints	Absolute structure parameter: −0.004 (7)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.28453 (3)	1.00312 (3)	0.32327 (5)	0.02110 (15)
I1	0.23025 (2)	1.05229 (2)	0.42006 (3)	0.03191 (10)
I2	0.34232 (2)	0.96692 (2)	0.42855 (3)	0.03574 (11)
P1	0.33005 (6)	0.96805 (6)	0.23176 (10)	0.0209 (3)
P2	0.23797 (6)	1.03270 (6)	0.22710 (10)	0.0222 (3)
C9	0.2906 (3)	0.9621 (3)	0.1424 (4)	0.0273 (14)
H9A	0.3120	0.9539	0.0956	0.033*
H9B	0.2655	0.9346	0.1495	0.033*
C10	0.2640 (3)	1.0122 (3)	0.1299 (4)	0.0275 (14)
H10A	0.2363	1.0083	0.0906	0.033*
H10B	0.2883	1.0378	0.1096	0.033*
C11	0.3575 (3)	0.9055 (2)	0.2422 (4)	0.0257 (13)
C12	0.4077 (3)	0.8949 (3)	0.2251 (4)	0.0330 (15)
H12	0.4303	0.9217	0.2121	0.040*
C13	0.4251 (3)	0.8453 (3)	0.2269 (5)	0.0416 (19)
H13	0.4594	0.8381	0.2136	0.050*
C14	0.3932 (4)	0.8066 (3)	0.2478 (5)	0.046 (2)
H14	0.4054	0.7727	0.2490	0.055*
C15	0.3430 (4)	0.8166 (3)	0.2671 (6)	0.052 (2)
H15	0.3208	0.7899	0.2819	0.062*
C16	0.3259 (3)	0.8658 (3)	0.2645 (5)	0.0411 (18)
H16	0.2917	0.8729	0.2782	0.049*
C21	0.3806 (2)	1.0109 (2)	0.2024 (4)	0.0246 (13)
C22	0.3958 (3)	1.0497 (3)	0.2528 (4)	0.0345 (16)
H22	0.3814	1.0526	0.3044	0.041*
C23	0.4322 (3)	1.0845 (3)	0.2280 (5)	0.044 (2)
H23	0.4423	1.1113	0.2623	0.053*
C24	0.4539 (3)	1.0798 (3)	0.1525 (5)	0.045 (2)
H24	0.4791	1.1032	0.1355	0.053*
C25	0.4389 (3)	1.0419 (3)	0.1034 (5)	0.0423 (19)
H25	0.4536	1.0391	0.0519	0.051*
C26	0.4023 (3)	1.0069 (3)	0.1275 (4)	0.0331 (16)
H26	0.3923	0.9804	0.0926	0.040*
C31	0.1743 (3)	1.0062 (3)	0.2245 (4)	0.0269 (13)
C32	0.1382 (3)	1.0263 (3)	0.1712 (5)	0.0359 (15)
H32	0.1459	1.0556	0.1406	0.043*
C33	0.0915 (3)	1.0027 (4)	0.1641 (5)	0.0436 (18)
H33	0.0668	1.0164	0.1289	0.052*
C34	0.0803 (3)	0.9597 (3)	0.2074 (5)	0.045 (2)
H34	0.0485	0.9433	0.2012	0.054*
C35	0.1161 (3)	0.9407 (3)	0.2600 (5)	0.0414 (19)
H35	0.1084	0.9116	0.2910	0.050*
C36	0.1624 (3)	0.9638 (3)	0.2676 (5)	0.0323 (15)
H36	0.1867	0.9501	0.3034	0.039*
C41	0.2344 (3)	1.1014 (3)	0.2191 (4)	0.0274 (14)
C42	0.1910 (3)	1.1283 (3)	0.2384 (5)	0.0339 (16)
H42	0.1614	1.1116	0.2569	0.041*
C43	0.1923 (4)	1.1809 (3)	0.2297 (6)	0.051 (2)
H43	0.1626	1.2000	0.2408	0.061*
C44	0.2351 (4)	1.2059 (3)	0.2057 (6)	0.053 (2)
H44	0.2349	1.2418	0.2010	0.064*
C45	0.2784 (4)	1.1790 (3)	0.1885 (6)	0.048 (2)
H45	0.3082	1.1962	0.1717	0.058*
C46	0.2782 (3)	1.1266 (3)	0.1957 (5)	0.0362 (17)
H46	0.3081	1.1078	0.1846	0.043*
C51	0.1612 (7)	0.8227 (5)	0.1681 (10)	0.154 (7)
H51A	0.1651	0.7885	0.1445	0.184*
H51B	0.1246	0.8309	0.1680	0.184*
Cl1	0.1907 (2)	0.8642 (2)	0.1089 (3)	0.167 (3)
Cl2	0.18145 (19)	0.81989 (16)	0.2668 (4)	0.144 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0225 (4)	0.0240 (4)	0.0168 (3)	−0.0008 (3)	0.0018 (3)	−0.0008 (3)
I1	0.0372 (2)	0.0334 (2)	0.0251 (2)	0.00113 (18)	0.00645 (19)	−0.00370 (19)
I2	0.0360 (2)	0.0478 (3)	0.0234 (2)	0.0068 (2)	−0.00453 (19)	0.0015 (2)
P1	0.0208 (7)	0.0214 (7)	0.0204 (7)	−0.0004 (6)	0.0019 (6)	−0.0012 (6)
P2	0.0230 (8)	0.0241 (8)	0.0194 (7)	0.0016 (6)	0.0007 (6)	−0.0006 (6)
C9	0.030 (3)	0.029 (3)	0.022 (3)	0.000 (3)	0.004 (3)	−0.007 (3)
C10	0.030 (3)	0.037 (4)	0.016 (3)	0.002 (3)	0.002 (3)	−0.002 (3)
C11	0.032 (3)	0.021 (3)	0.023 (3)	−0.001 (3)	0.001 (3)	−0.001 (2)
C12	0.032 (4)	0.031 (4)	0.035 (4)	0.008 (3)	0.003 (3)	0.004 (3)
C13	0.036 (4)	0.044 (5)	0.045 (4)	0.015 (3)	0.001 (3)	0.001 (4)
C14	0.069 (6)	0.026 (4)	0.042 (4)	0.006 (4)	−0.012 (4)	0.000 (3)
C15	0.059 (6)	0.029 (4)	0.067 (6)	−0.001 (4)	−0.009 (5)	0.001 (4)
C16	0.038 (4)	0.027 (4)	0.059 (5)	−0.007 (3)	0.005 (4)	0.001 (4)
C21	0.023 (3)	0.024 (3)	0.026 (3)	0.001 (2)	−0.002 (2)	0.002 (2)
C22	0.040 (4)	0.036 (4)	0.027 (3)	−0.012 (3)	0.002 (3)	−0.001 (3)
C23	0.047 (5)	0.043 (5)	0.042 (4)	−0.023 (4)	0.001 (4)	−0.003 (4)
C24	0.040 (4)	0.048 (5)	0.045 (5)	−0.013 (4)	0.000 (3)	0.015 (4)
C25	0.039 (4)	0.052 (5)	0.037 (4)	−0.011 (4)	0.006 (3)	0.010 (4)
C26	0.034 (4)	0.038 (4)	0.027 (3)	−0.008 (3)	0.009 (3)	−0.003 (3)
C31	0.028 (3)	0.029 (3)	0.024 (3)	−0.001 (3)	0.005 (3)	−0.004 (3)
C32	0.030 (3)	0.044 (4)	0.034 (4)	−0.002 (3)	−0.004 (3)	−0.004 (4)
C33	0.029 (3)	0.064 (5)	0.038 (4)	0.000 (4)	−0.006 (3)	−0.009 (4)
C34	0.036 (4)	0.051 (5)	0.048 (5)	−0.013 (4)	0.009 (4)	−0.022 (4)
C35	0.044 (5)	0.039 (4)	0.041 (4)	−0.016 (4)	0.009 (4)	−0.006 (3)
C36	0.029 (4)	0.033 (4)	0.035 (4)	−0.002 (3)	0.004 (3)	−0.001 (3)
C41	0.034 (4)	0.026 (3)	0.022 (3)	0.000 (3)	−0.005 (3)	−0.002 (3)
C42	0.038 (4)	0.026 (3)	0.038 (4)	0.003 (3)	0.002 (3)	−0.001 (3)
C43	0.057 (6)	0.031 (4)	0.065 (6)	0.006 (4)	0.007 (5)	−0.004 (4)
C44	0.066 (6)	0.027 (4)	0.067 (6)	−0.003 (4)	0.009 (5)	−0.002 (4)
C45	0.055 (5)	0.034 (4)	0.056 (6)	−0.010 (4)	−0.004 (4)	−0.001 (4)
C46	0.035 (4)	0.028 (4)	0.046 (5)	−0.001 (3)	−0.003 (3)	0.003 (3)
C51	0.142 (15)	0.051 (8)	0.268 (16)	−0.020 (8)	−0.074 (16)	0.017 (12)
Cl1	0.154 (4)	0.197 (5)	0.151 (4)	−0.114 (4)	0.066 (3)	−0.106 (4)
Cl2	0.106 (3)	0.076 (3)	0.250 (6)	0.015 (2)	−0.009 (4)	0.053 (3)

Geometric parameters (Å, º)

Ni1—P1	2.1582 (18)	C24—C25	1.353 (12)
Ni1—P2	2.1733 (18)	C24—H24	0.9500
Ni1—I2	2.5216 (9)	C25—C26	1.395 (10)
Ni1—I1	2.5240 (9)	C25—H25	0.9500
P1—C11	1.811 (7)	C26—H26	0.9500
P1—C21	1.816 (7)	C31—C36	1.368 (10)
P1—C9	1.832 (7)	C31—C32	1.408 (10)
P2—C41	1.818 (7)	C32—C33	1.385 (10)
P2—C31	1.820 (7)	C32—H32	0.9500
P2—C10	1.851 (6)	C33—C34	1.379 (13)
C9—C10	1.512 (9)	C33—H33	0.9500
C9—H9A	0.9900	C34—C35	1.385 (13)
C9—H9B	0.9900	C34—H34	0.9500
C10—H10A	0.9900	C35—C36	1.372 (10)
C10—H10B	0.9900	C35—H35	0.9500
C11—C12	1.383 (10)	C36—H36	0.9500
C11—C16	1.387 (10)	C41—C42	1.385 (10)
C12—C13	1.388 (10)	C41—C46	1.389 (10)
C12—H12	0.9500	C42—C43	1.394 (11)
C13—C14	1.370 (12)	C42—H42	0.9500
C13—H13	0.9500	C43—C44	1.365 (13)
C14—C15	1.387 (13)	C43—H43	0.9500
C14—H14	0.9500	C44—C45	1.375 (13)
C15—C16	1.375 (11)	C44—H44	0.9500
C15—H15	0.9500	C45—C46	1.387 (11)
C16—H16	0.9500	C45—H45	0.9500
C21—C26	1.385 (9)	C46—H46	0.9500
C21—C22	1.388 (10)	C51—Cl1	1.670 (14)
C22—C23	1.390 (10)	C51—Cl2	1.743 (15)
C22—H22	0.9500	C51—H51A	0.9900
C23—C24	1.397 (12)	C51—H51B	0.9900
C23—H23	0.9500
P1—Ni1—P2	86.51 (7)	C22—C23—C24	119.7 (8)
P1—Ni1—I2	90.04 (5)	C22—C23—H23	120.1
P2—Ni1—I2	176.51 (6)	C24—C23—H23	120.1
P1—Ni1—I1	173.72 (6)	C25—C24—C23	119.9 (8)
P2—Ni1—I1	88.49 (5)	C25—C24—H24	120.0
I2—Ni1—I1	94.93 (3)	C23—C24—H24	120.0
C11—P1—C21	107.5 (3)	C24—C25—C26	120.9 (8)
C11—P1—C9	103.1 (3)	C24—C25—H25	119.6
C21—P1—C9	104.3 (3)	C26—C25—H25	119.6
C11—P1—Ni1	123.0 (2)	C21—C26—C25	120.0 (7)
C21—P1—Ni1	109.6 (2)	C21—C26—H26	120.0
C9—P1—Ni1	107.7 (2)	C25—C26—H26	120.0
C41—P2—C31	109.4 (3)	C36—C31—C32	119.3 (7)
C41—P2—C10	104.2 (3)	C36—C31—P2	120.8 (6)
C31—P2—C10	102.1 (3)	C32—C31—P2	119.6 (5)
C41—P2—Ni1	116.2 (2)	C33—C32—C31	119.1 (8)
C31—P2—Ni1	113.7 (2)	C33—C32—H32	120.4
C10—P2—Ni1	109.9 (2)	C31—C32—H32	120.4
C10—C9—P1	107.5 (4)	C34—C33—C32	120.9 (8)
C10—C9—H9A	110.2	C34—C33—H33	119.5
P1—C9—H9A	110.2	C32—C33—H33	119.5
C10—C9—H9B	110.2	C33—C34—C35	119.1 (7)
P1—C9—H9B	110.2	C33—C34—H34	120.4
H9A—C9—H9B	108.5	C35—C34—H34	120.4
C9—C10—P2	107.8 (4)	C36—C35—C34	120.4 (8)
C9—C10—H10A	110.1	C36—C35—H35	119.8
P2—C10—H10A	110.1	C34—C35—H35	119.8
C9—C10—H10B	110.1	C31—C36—C35	121.1 (7)
P2—C10—H10B	110.1	C31—C36—H36	119.4
H10A—C10—H10B	108.5	C35—C36—H36	119.4
C12—C11—C16	118.6 (7)	C42—C41—C46	120.4 (7)
C12—C11—P1	123.1 (5)	C42—C41—P2	122.5 (6)
C16—C11—P1	118.2 (6)	C46—C41—P2	117.0 (5)
C11—C12—C13	120.1 (7)	C41—C42—C43	117.8 (8)
C11—C12—H12	119.9	C41—C42—H42	121.1
C13—C12—H12	119.9	C43—C42—H42	121.1
C14—C13—C12	120.3 (8)	C44—C43—C42	122.0 (9)
C14—C13—H13	119.8	C44—C43—H43	119.0
C12—C13—H13	119.8	C42—C43—H43	119.0
C13—C14—C15	120.3 (8)	C43—C44—C45	119.9 (8)
C13—C14—H14	119.9	C43—C44—H44	120.0
C15—C14—H14	119.9	C45—C44—H44	120.0
C16—C15—C14	119.1 (8)	C44—C45—C46	119.4 (8)
C16—C15—H15	120.5	C44—C45—H45	120.3
C14—C15—H15	120.5	C46—C45—H45	120.3
C15—C16—C11	121.5 (8)	C45—C46—C41	120.3 (8)
C15—C16—H16	119.2	C45—C46—H46	119.8
C11—C16—H16	119.2	C41—C46—H46	119.8
C26—C21—C22	119.3 (7)	Cl1—C51—Cl2	116.9 (9)
C26—C21—P1	120.2 (5)	Cl1—C51—H51A	108.1
C22—C21—P1	120.4 (5)	Cl2—C51—H51A	108.1
C21—C22—C23	120.3 (7)	Cl1—C51—H51B	108.1
C21—C22—H22	119.9	Cl2—C51—H51B	108.1
C23—C22—H22	119.9	H51A—C51—H51B	107.3
C11—P1—C9—C10	177.8 (5)	C22—C21—C26—C25	−0.2 (11)
C21—P1—C9—C10	−70.0 (5)	P1—C21—C26—C25	176.0 (6)
Ni1—P1—C9—C10	46.4 (5)	C24—C25—C26—C21	0.3 (13)
P1—C9—C10—P2	−46.2 (5)	C41—P2—C31—C36	−146.0 (6)
C41—P2—C10—C9	154.2 (5)	C10—P2—C31—C36	104.1 (6)
C31—P2—C10—C9	−92.0 (5)	Ni1—P2—C31—C36	−14.2 (6)
Ni1—P2—C10—C9	29.0 (5)	C41—P2—C31—C32	40.9 (7)
C21—P1—C11—C12	−3.4 (7)	C10—P2—C31—C32	−69.1 (6)
C9—P1—C11—C12	106.5 (6)	Ni1—P2—C31—C32	172.6 (5)
Ni1—P1—C11—C12	−131.9 (5)	C36—C31—C32—C33	0.4 (11)
C21—P1—C11—C16	−180.0 (6)	P2—C31—C32—C33	173.7 (6)
C9—P1—C11—C16	−70.1 (6)	C31—C32—C33—C34	−1.0 (12)
Ni1—P1—C11—C16	51.5 (7)	C32—C33—C34—C35	1.5 (13)
C16—C11—C12—C13	2.9 (11)	C33—C34—C35—C36	−1.4 (12)
P1—C11—C12—C13	−173.7 (6)	C32—C31—C36—C35	−0.3 (11)
C11—C12—C13—C14	−1.8 (13)	P2—C31—C36—C35	−173.5 (6)
C12—C13—C14—C15	0.2 (13)	C34—C35—C36—C31	0.8 (12)
C13—C14—C15—C16	0.4 (14)	C31—P2—C41—C42	22.0 (7)
C14—C15—C16—C11	0.7 (14)	C10—P2—C41—C42	130.5 (6)
C12—C11—C16—C15	−2.3 (13)	Ni1—P2—C41—C42	−108.4 (6)
P1—C11—C16—C15	174.4 (7)	C31—P2—C41—C46	−160.8 (5)
C11—P1—C21—C26	68.9 (6)	C10—P2—C41—C46	−52.3 (6)
C9—P1—C21—C26	−40.2 (6)	Ni1—P2—C41—C46	68.8 (6)
Ni1—P1—C21—C26	−155.3 (5)	C46—C41—C42—C43	3.1 (11)
C11—P1—C21—C22	−114.9 (6)	P2—C41—C42—C43	−179.7 (6)
C9—P1—C21—C22	136.0 (6)	C41—C42—C43—C44	−2.3 (14)
Ni1—P1—C21—C22	20.9 (6)	C42—C43—C44—C45	0.8 (16)
C26—C21—C22—C23	0.5 (12)	C43—C44—C45—C46	−0.1 (15)
P1—C21—C22—C23	−175.8 (6)	C44—C45—C46—C41	0.9 (13)
C21—C22—C23—C24	−0.8 (13)	C42—C41—C46—C45	−2.5 (11)
C22—C23—C24—C25	0.8 (14)	P2—C41—C46—C45	−179.8 (6)
C23—C24—C25—C26	−0.6 (14)