Di­chloro­[(6R,7S,8S,14S)-(-)-sparteine-[kappa]²N,N']­nickel(II)

In the title compound, [NiCl₂(C₁₅H₂₆N₂)], the chiral alkaloid (6R,7S,8S,14S)-(-)-L-sparteine acts as a bidentate ligand, with two chloride ligands occupying the remaining coordination sites, producing a slightly distorted tetrahedron. The N-Ni-N plane in the title complex is twisted by 81.31 (11)° from the Cl-Ni-Cl plane. Other distortions of the tetrahedron are discussed.

S1. Comment

The majority of four-coordinate Ni^II complexes prefer to adopt a square-planar structure as a consequence of the d⁸ configuration. In tetrahedral coordination, the occupation of the unique high-energy antibonding d_x²_-y² orbital is unavoidable and so relatively few tetrahedral Ni^II complexes are known (Cotton et al., 1999). The tetrahedral Ni^II complexes are mainly of the stoichiometric types NiX₄²⁻, NiX₂L₂ and Ni(L–L)₂, where X usually represents a halogen ion, L is a neutral monodentate ligand and L–L is one of several types of bulky bidentate anion (Ban et al., 1973; Koester & Dunn, 1975; Cruse & Gerloch, 1977).

The (-)-sparteine C₁₅H₂₆N₂, a naturally occurring tertiary diamine, has attracted research attention; it has been intensively utilized in medicinal chemistry (Cady et al.,1977), in the asymmetric synthesis of chiral compounds (Kretchmer, 1972; Mason & Peacock, 1973; Beak et al., 1996) and in the preparation of a model compound for the type I copper(II) site in metalloproteins (Kim et al., 2001). The structures of several metal(II) sparteine complexes of type [MX₂(C₁₅H₂₆N₂)] (M = C^II, Cu^II and Zn^II; X = Cl⁻, Br⁻ and N₃⁻) have been reported, and the metal moieties in these compounds are known, without exception, to have a slightly distorted tetrahedral geometry (Kim et al., 2001, 2003; Kuroda & Mason, 1979; Lee et al., 2000; Lee et al., 2002a, 2003a; Lee et al., 2003b; Lopez et al., 1998). This bidentate ligand contains sufficiently bulky substituents on, and adjacent to, the two nitrogen donor atoms to render the planarity of the MX₂(L—L) molecule sterically impossible, and generates a distorted tetrahedron around the metal centers.

Synthesis of the title compound, (I), was prompted by our interest in the preparation of a new paramagnetic and tetrahedral Ni^II compound of the type [Ni^IIX₂(L—L)], and our attempt to compare the stability, coordination geometry and bonding parameters of (I) with analogous Co^II, Cu^II and Zn^II (-)-sparteine dichlorides for which the structures are already known (Kuroda & Mason, 1979; Lopez et al., 1998; Lee et al., 2003b).

As expected from previous studies (Choi et al., 1995; Kim et al., 2001, 2003; Kuroda & Mason, 1979; Lee et al., 2000; Lee et al., 2002a, 2003a; Lee et al., 2003b; Lopez et al., 1998), the conformation of the coordinated (-)-sparteine ligand consists of one terminal ring folded down over the metal (endo) and a second terminal ring folded back away from the metal (exo), identical to the conformation of the free ligand (Boschmann et al., 1974; Wrobleski & Long, 1977) or monoprotonated sparteinium salt (Lee et al., 2002b).

In CuCl₂(C₁₅H₂₆N₂), one consequence of the endo–exo configuration is the slight asymmetry in the Cu—N bond lengths; the endo ring has a shorter Cu—N1 bond length [2.003 (3) Å, compared with 2.021 (3) Å for Cu—N9 (Lopez et al., 1998)]. However, in (I), the two Ni—N bond distances are similar to a more symmetric configuration. The Ni—N bond distances are slightly longer than those in CuCl₂(C₁₅H₂₆N₂) but are shorter than those in CoCl₂(C₁₅H₂₆N₂) [2.040 (7) and 2.068 (8) Å] and ZnCl₂(C₁₅H₂₆N₂) [2.085 (7) and 2.087 (7) Å]. The stability of complexes of the 3 d metal ions with a given ligand almost invariably follows the order Co²⁺ < Ni²⁺ < Cu²⁺ > Zn²⁺ (Irving & Williams, 1953). A similar trend is observable in this series of metal(II) sparteine compounds if it is assumed that the stability of the complexes is inversely related to the metal(II)–nitrogen bond distances.

The dihedral angle between the N1/Ni/N9 and Cl1/Ni/Cl2 planes in (I) is 81.31 (11) ° and is only about 8.7° less than the perfect tetrahedral angle of 90°. The dihedral angles between the N/M/N and Cl/M/Cl (M = Cu^II or Zn^II) planes in CuCl₂(C₁₅H₂₆N₂) and ZnCl₂(C₁₅H₂₆N₂) are reported to be 67.0 and 82.2°, respectively (Lee et al., 2003a; Lopez et al., 1998). The dihedral angle in (I) is very close to that of zinc(II) sparteine dichloride but is much larger than that of copper(II) sparteine dichloride. The Zn^II atom has a closed-shell electronic structure of d¹⁰, and as a result the molecular structure of ZnCl₂(C₁₅H₂₆N₂) has to be determined solely by the steric effect. The very similar values in the dihedral angles of the Ni^II and Zn^II compounds suggest that the electronic effect in the molecular structure of (I) is not as important as in the analogous Cu^II compound, and that the molecular structure is determined by intramolecular steric interactions between the (-)-sparteine ligand and the chloride ions coordinated with Ni^II. The smaller dihedral angle of 67.0° reported for CuCl₂(C₁₅H₂₆N₂) is definitely a result of the balance of the electronic effect of the d⁹ system and the steric effect imposed by a bulky (-)-sparteine ligand (Figgis, 1966).

Another way of looking at the distortion of the tetrahedron is to compare the 'bite angle' and the 'tilt' of the bidentate (-)-sparteine ligand with respect to the Cl/Ni/Cl plane (Lee et al., 2002a, 2003a). The mid-point of the N1···N9 line does not lie on the Cl1/Ni/Cl2 plane but is tilted towards N1 by 0.193 Å (13.5% of half of the N1···N9 distance). Similarly, the mid-point of the Cl1···Cl2 line is tilted toward atom Cl2 by 0.144 Å (7.4% of half of the Cl1···Cl2 distance). The N1—Ni—Cl1 and N9—Ni—Cl2 angles are similar; however, the N1—Ni—Cl2 and N9—Ni—Cl1 angles differ by more than 10°.

In Ni^II complexes, even slight distortion from the perfect tetrahedron reduces the magnetic moment markedly by splitting the orbital degeneracy (Cotton et al., 1999). The room-temperature magnetic moment of (I), estimated from the relation µ_eff = 2.828(χ_M × T)^1/2, is 3.3 BM. This value is much smaller than the vaule of around 4.2 BM that is usually exhibited by truly tetrahedral Ni^II complexes.

S2. Experimental

Complex (I) was prepared by the direct reaction of nickel(II) chloride with a stoichiometric amount of (-)-l-sparteine in an ethanol-triethylorthoformate (5:1 v/v) solution. The resulting violet precipitate was filtered, washed with cold absolute ethanol and dried in a vacuum. Single crystals were obtained by recrystallization at room temperature in a dichloromethane–triethylorthoformate (5:1 v/v) solution. Analysis calculated for C₁₅H₂₆N₂NiCl₂: C 49.49, H 7.20, N 7.70%; found: C 49.50, H 7.14, N 7.74%.

S3. Refinement

H atoms on the sparteine ligand were positioned geometrically and constrained to ride on their attached atoms at distances of 0.97–0.98 Å. The U_iso(H) values were fixed at 1.2U_eq of the parent atoms.

Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. ORTEP-3 (Farrugia, 1997) diagram of (I), showing the atom-numbering scheme and 30% probability ellipsoids. H atoms have been omitted for clarity.

dichloro[(-)-sparteine-N,N']nickel(II)

Crystal data

[NiCl2(C15H26N2)]	F(000) = 768
Mr = 363.99	Dx = 1.484 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 24 reflections
a = 11.1357 (17) Å	θ = 11.5–12.6°
b = 11.8679 (14) Å	µ = 1.51 mm^−1
c = 12.3278 (19) Å	T = 293 K
V = 1629.2 (4) Å^3	Block, dark violet
Z = 4	0.3 × 0.3 × 0.26 mm

Data collection

Enraf Nonius CAD4 diffractometer	2855 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
Graphite monochromator	θmax = 27.5°, θmin = 2.4°
Non–profiled ω/2θ scans	h = −14→14
Absorption correction: ψ scan (North et al., 1968)	k = 0→15
Tmin = 0.612, Tmax = 0.672	l = 0→16
4063 measured reflections	3 standard reflections every 400 reflections
3730 independent reflections	intensity decay: 4%

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)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.0655P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3730 reflections	Δρmax = 0.64 e Å^−3
181 parameters	Δρmin = −0.50 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1597 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (3)

Special details

Experimental. The magnetic susceptibility measurements were made on a powdered sample of (I) with a Quantum Design MPMS7-SQUID susceptometer. The data was corrected for the diamagnetism of the constituent atoms with Pascal's constant.

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
Ni	0.19791 (6)	0.26426 (5)	0.12988 (5)	0.02943 (17)
Cl1	0.18039 (17)	0.43613 (12)	0.05722 (11)	0.0546 (4)
Cl2	0.21219 (16)	0.11399 (12)	0.02154 (11)	0.0485 (4)
N1	0.3053 (4)	0.2910 (3)	0.2606 (3)	0.0284 (8)
C2	0.4278 (5)	0.3240 (5)	0.2233 (5)	0.0394 (13)
H2A	0.4763	0.3441	0.2857	0.047*
H2B	0.4217	0.3899	0.1770	0.047*
C3	0.4886 (5)	0.2306 (5)	0.1619 (4)	0.0423 (13)
H3A	0.5683	0.2549	0.1402	0.051*
H3B	0.4432	0.2139	0.0968	0.051*
C4	0.4986 (5)	0.1255 (5)	0.2303 (5)	0.0466 (15)
H4A	0.5535	0.1389	0.2901	0.056*
H4B	0.5308	0.0645	0.1868	0.056*
C5	0.3756 (5)	0.0919 (5)	0.2749 (5)	0.0422 (14)
H5A	0.3252	0.0664	0.2156	0.051*
H5B	0.3852	0.0298	0.3252	0.051*
C6	0.3145 (5)	0.1894 (4)	0.3323 (4)	0.0342 (11)
H6	0.3671	0.2106	0.3927	0.041*
C7	0.1920 (5)	0.1625 (4)	0.3820 (4)	0.0369 (11)
H7	0.2021	0.0968	0.4293	0.044*
C8	0.1344 (5)	0.3603 (4)	0.3768 (5)	0.0350 (12)
H8	0.1115	0.4252	0.4213	0.042*
N9	0.0584 (3)	0.2328 (3)	0.2311 (3)	0.0259 (8)
C10	−0.0454 (5)	0.2062 (5)	0.1577 (4)	0.0374 (13)
H10A	−0.0296	0.1350	0.1217	0.045*
H10B	−0.0501	0.2638	0.1020	0.045*
C11	−0.1655 (5)	0.1987 (5)	0.2140 (5)	0.0438 (14)
H11A	−0.1644	0.1373	0.2659	0.053*
H11B	−0.2279	0.1835	0.1612	0.053*
C12	−0.1920 (5)	0.3087 (5)	0.2721 (4)	0.0423 (13)
H12A	−0.2681	0.3032	0.3100	0.051*
H12B	−0.1976	0.3696	0.2199	0.051*
C13	−0.0919 (5)	0.3329 (5)	0.3525 (4)	0.0391 (13)
H13A	−0.0915	0.2750	0.4080	0.047*
H13B	−0.1071	0.4047	0.3876	0.047*
C14	0.0313 (5)	0.3366 (4)	0.2970 (4)	0.0304 (11)
H14	0.0293	0.3999	0.2460	0.037*
C15	0.2538 (5)	0.3868 (5)	0.3236 (4)	0.0381 (13)
H15A	0.2434	0.4506	0.2753	0.046*
H15B	0.3107	0.4087	0.3793	0.046*
C16	0.0913 (5)	0.1345 (4)	0.2999 (5)	0.0345 (12)
H16A	0.1176	0.0732	0.2537	0.041*
H16B	0.0208	0.1093	0.3392	0.041*
C17	0.1512 (5)	0.2596 (5)	0.4519 (4)	0.0448 (14)
H17A	0.2110	0.2763	0.5068	0.054*
H17B	0.0762	0.2413	0.4878	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0364 (3)	0.0332 (3)	0.0186 (3)	−0.0020 (3)	0.0027 (3)	−0.0004 (3)
Cl1	0.0840 (13)	0.0449 (8)	0.0351 (7)	0.0023 (8)	0.0051 (8)	0.0147 (6)
Cl2	0.0677 (11)	0.0446 (7)	0.0332 (6)	0.0047 (8)	0.0037 (7)	−0.0119 (6)
N1	0.030 (2)	0.028 (2)	0.0268 (19)	−0.0001 (19)	0.0025 (19)	0.0004 (15)
C2	0.037 (3)	0.042 (3)	0.039 (3)	−0.010 (2)	0.001 (3)	0.004 (3)
C3	0.034 (3)	0.050 (3)	0.044 (3)	0.000 (3)	0.004 (2)	0.004 (3)
C4	0.037 (3)	0.051 (4)	0.052 (4)	0.012 (3)	0.003 (3)	0.007 (3)
C5	0.040 (3)	0.039 (3)	0.048 (3)	0.010 (3)	0.004 (3)	0.014 (3)
C6	0.034 (3)	0.041 (3)	0.027 (2)	0.001 (3)	0.000 (2)	0.007 (2)
C7	0.036 (3)	0.047 (3)	0.028 (2)	0.007 (3)	0.003 (3)	0.014 (2)
C8	0.039 (3)	0.039 (3)	0.027 (3)	0.003 (2)	−0.001 (3)	−0.016 (3)
N9	0.026 (2)	0.029 (2)	0.0221 (18)	0.0000 (18)	−0.0013 (15)	0.0050 (18)
C10	0.035 (3)	0.041 (3)	0.036 (3)	−0.005 (2)	−0.006 (2)	−0.008 (2)
C11	0.034 (3)	0.054 (3)	0.043 (3)	−0.006 (2)	−0.008 (2)	0.007 (3)
C12	0.032 (3)	0.054 (3)	0.041 (3)	0.006 (3)	0.001 (3)	0.011 (3)
C13	0.043 (3)	0.049 (3)	0.025 (3)	0.007 (3)	0.009 (2)	−0.002 (2)
C14	0.037 (3)	0.031 (3)	0.024 (2)	0.002 (2)	0.000 (2)	0.002 (2)
C15	0.041 (3)	0.040 (3)	0.034 (3)	−0.001 (2)	−0.005 (2)	−0.013 (3)
C16	0.036 (3)	0.029 (3)	0.039 (3)	0.001 (2)	0.006 (2)	0.011 (2)
C17	0.044 (3)	0.069 (4)	0.021 (2)	0.006 (3)	0.001 (2)	0.003 (3)

Geometric parameters (Å, º)

Ni—N1	2.032 (4)	C8—C17	1.524 (8)
Ni—N9	2.027 (4)	C8—C14	1.538 (7)
Ni—Cl1	2.2363 (15)	C8—H8	0.9800
Ni—Cl2	2.2337 (14)	N9—C10	1.502 (6)
N1—C2	1.492 (7)	N9—C14	1.506 (6)
N1—C6	1.498 (6)	N9—C16	1.488 (6)
N1—C15	1.491 (6)	C10—C11	1.510 (8)
C2—C3	1.503 (7)	C10—H10A	0.9700
C2—H2A	0.9700	C10—H10B	0.9700
C2—H2B	0.9700	C11—C12	1.518 (8)
C3—C4	1.510 (8)	C11—H11A	0.9700
C3—H3A	0.9700	C11—H11B	0.9700
C3—H3B	0.9700	C12—C13	1.518 (8)
C4—C5	1.528 (8)	C12—H12A	0.9700
C4—H4A	0.9700	C12—H12B	0.9700
C4—H4B	0.9700	C13—C14	1.534 (7)
C5—C6	1.517 (7)	C13—H13A	0.9700
C5—H5A	0.9700	C13—H13B	0.9700
C5—H5B	0.9700	C14—H14	0.9800
C6—C7	1.529 (8)	C15—H15A	0.9700
C6—H6	0.9800	C15—H15B	0.9700
C7—C17	1.510 (8)	C16—H16A	0.9700
C7—C16	1.546 (7)	C16—H16B	0.9700
C7—H7	0.9800	C17—H17A	0.9700
C8—C15	1.516 (8)	C17—H17B	0.9700
N1—Ni—N9	89.51 (16)	C16—N9—C10	111.6 (4)
N1—Ni—Cl1	103.10 (11)	C16—N9—C14	112.5 (4)
N1—Ni—Cl2	123.85 (12)	C10—N9—C14	110.1 (4)
N9—Ni—Cl1	110.35 (12)	C16—N9—Ni	107.9 (3)
N9—Ni—Cl2	105.99 (12)	C10—N9—Ni	104.9 (3)
Cl1—Ni—Cl2	119.67 (6)	C14—N9—Ni	109.6 (3)
C15—N1—C2	108.1 (4)	N9—C10—C11	114.6 (4)
C15—N1—C6	109.4 (4)	N9—C10—H10A	108.6
C2—N1—C6	109.3 (4)	C11—C10—H10A	108.6
C15—N1—Ni	107.8 (3)	N9—C10—H10B	108.6
C2—N1—Ni	109.5 (3)	C11—C10—H10B	108.6
C6—N1—Ni	112.5 (3)	H10A—C10—H10B	107.6
N1—C2—C3	111.9 (4)	C10—C11—C12	109.8 (5)
N1—C2—H2A	109.2	C10—C11—H11A	109.7
C3—C2—H2A	109.2	C12—C11—H11A	109.7
N1—C2—H2B	109.2	C10—C11—H11B	109.7
C3—C2—H2B	109.2	C12—C11—H11B	109.7
H2A—C2—H2B	107.9	H11A—C11—H11B	108.2
C2—C3—C4	111.2 (4)	C11—C12—C13	109.2 (5)
C2—C3—H3A	109.4	C11—C12—H12A	109.8
C4—C3—H3A	109.4	C13—C12—H12A	109.8
C2—C3—H3B	109.4	C11—C12—H12B	109.8
C4—C3—H3B	109.4	C13—C12—H12B	109.8
H3A—C3—H3B	108.0	H12A—C12—H12B	108.3
C3—C4—C5	110.5 (5)	C12—C13—C14	111.7 (4)
C3—C4—H4A	109.6	C12—C13—H13A	109.3
C5—C4—H4A	109.6	C14—C13—H13A	109.3
C3—C4—H4B	109.6	C12—C13—H13B	109.3
C5—C4—H4B	109.6	C14—C13—H13B	109.3
H4A—C4—H4B	108.1	H13A—C13—H13B	107.9
C6—C5—C4	111.8 (5)	N9—C14—C13	113.4 (4)
C6—C5—H5A	109.3	N9—C14—C8	110.2 (4)
C4—C5—H5A	109.3	C13—C14—C8	112.8 (4)
C6—C5—H5B	109.3	N9—C14—H14	106.7
C4—C5—H5B	109.3	C13—C14—H14	106.7
H5A—C5—H5B	107.9	C8—C14—H14	106.7
N1—C6—C5	111.6 (4)	N1—C15—C8	113.8 (4)
N1—C6—C7	110.1 (4)	N1—C15—H15A	108.8
C5—C6—C7	115.3 (4)	C8—C15—H15A	108.8
N1—C6—H6	106.4	N1—C15—H15B	108.8
C5—C6—H6	106.4	C8—C15—H15B	108.8
C7—C6—H6	106.4	H15A—C15—H15B	107.7
C17—C7—C6	109.7 (4)	N9—C16—C7	112.5 (4)
C17—C7—C16	108.6 (4)	N9—C16—H16A	109.1
C6—C7—C16	115.4 (4)	C7—C16—H16A	109.1
C17—C7—H7	107.6	N9—C16—H16B	109.1
C6—C7—H7	107.6	C7—C16—H16B	109.1
C16—C7—H7	107.6	H16A—C16—H16B	107.8
C15—C8—C17	108.6 (4)	C7—C17—C8	106.8 (4)
C15—C8—C14	114.6 (4)	C7—C17—H17A	110.4
C17—C8—C14	109.7 (4)	C8—C17—H17A	110.4
C15—C8—H8	107.9	C7—C17—H17B	110.4
C17—C8—H8	107.9	C8—C17—H17B	110.4
C14—C8—H8	107.9	H17A—C17—H17B	108.6
N9—Ni—N1—C15	−60.3 (3)	Cl2—Ni—N9—C14	−172.2 (3)
Cl2—Ni—N1—C15	−169.3 (3)	Cl1—Ni—N9—C14	−41.3 (3)
Cl1—Ni—N1—C15	50.5 (3)	C16—N9—C10—C11	73.2 (6)
N9—Ni—N1—C2	−177.7 (3)	C14—N9—C10—C11	−52.5 (6)
Cl2—Ni—N1—C2	73.2 (3)	Ni—N9—C10—C11	−170.2 (4)
Cl1—Ni—N1—C2	−66.9 (3)	N9—C10—C11—C12	57.7 (6)
N9—Ni—N1—C6	60.5 (3)	C10—C11—C12—C13	−57.9 (6)
Cl2—Ni—N1—C6	−48.6 (4)	C11—C12—C13—C14	56.7 (6)
Cl1—Ni—N1—C6	171.3 (3)	C16—N9—C14—C13	−75.8 (5)
C15—N1—C2—C3	178.1 (4)	C10—N9—C14—C13	49.4 (5)
C6—N1—C2—C3	59.0 (5)	Ni—N9—C14—C13	164.2 (3)
Ni—N1—C2—C3	−64.7 (5)	C16—N9—C14—C8	51.7 (5)
N1—C2—C3—C4	−58.1 (6)	C10—N9—C14—C8	176.9 (4)
C2—C3—C4—C5	53.6 (7)	Ni—N9—C14—C8	−68.3 (4)
C3—C4—C5—C6	−52.3 (7)	C12—C13—C14—N9	−53.5 (6)
C15—N1—C6—C5	−175.4 (4)	C12—C13—C14—C8	−179.6 (4)
C2—N1—C6—C5	−57.2 (6)	C15—C8—C14—N9	63.3 (5)
Ni—N1—C6—C5	64.8 (5)	C17—C8—C14—N9	−59.0 (5)
C15—N1—C6—C7	55.1 (5)	C15—C8—C14—C13	−168.8 (4)
C2—N1—C6—C7	173.4 (4)	C17—C8—C14—C13	68.8 (5)
Ni—N1—C6—C7	−64.7 (4)	C2—N1—C15—C8	−173.8 (4)
C4—C5—C6—N1	54.9 (6)	C6—N1—C15—C8	−54.8 (6)
C4—C5—C6—C7	−178.5 (4)	Ni—N1—C15—C8	67.8 (5)
N1—C6—C7—C17	−62.1 (5)	C17—C8—C15—N1	58.2 (6)
C5—C6—C7—C17	170.5 (4)	C14—C8—C15—N1	−64.8 (6)
N1—C6—C7—C16	61.1 (6)	C10—N9—C16—C7	−175.9 (4)
C5—C6—C7—C16	−66.3 (6)	C14—N9—C16—C7	−51.6 (5)
N1—Ni—N9—C16	−60.3 (3)	Ni—N9—C16—C7	69.4 (4)
Cl2—Ni—N9—C16	65.0 (3)	C17—C7—C16—N9	57.6 (5)
Cl1—Ni—N9—C16	−164.1 (3)	C6—C7—C16—N9	−66.2 (6)
N1—Ni—N9—C10	−179.4 (3)	C6—C7—C17—C8	64.0 (5)
Cl2—Ni—N9—C10	−54.1 (3)	C16—C7—C17—C8	−63.1 (6)
Cl1—Ni—N9—C10	76.8 (3)	C15—C8—C17—C7	−60.7 (6)
N1—Ni—N9—C14	62.5 (3)	C14—C8—C17—C7	65.2 (6)