A nitronyl nitro­xide complex of ­nickel(II) with nitrate as a ligand

The complex cation in [4,5-di­hydro-4,4,5,5-tetra­methyl-2-(2-pyridyl-κN)­imidazol-1-oxyl 3-oxide-κO³](nitrato-κ²O,O′)(N,N,N′,N′-tetra­methyl-1,2-ethanedi­am­ine-κ²N,N′)­nickel(II) hexafluorophosphate dichloromethane solvate, [Ni(NO₃)(C₆H₁₆N₂)(C₁₂H₁₆N₃O₂)]PF₆·CH₂Cl₂, is the first example of a nitro­nyl nitro­xide complex of a transition metal ion having d electrons in which nitrate is coordinated as a bidentate ligand. Owing to the smaller steric requirement of NO₃⁻, the Ni—­O(nitro­xide) bond length [2.014 (2) Å] is remarkably shorter than that in the corresponding ­β-­diketonate complexes [2.052 (4)–2.056 (2) Å].

S1. Comment

During the last two decades, there have been a large number of investigations of the magneto/structural chemistry of transition metal complexes bearing nitronyl nitroxide radicals. Initially, most of the complexes contained 1,1,1,5,5,5-hexafluoropentane-2,4-dionate (hfac) or a halide as a ligand because of the weak Lewis basicity of the nitroxide-O donor (Caneschi et al., 1991). However, other types of nitronyl nitroxide complexes have recently been reported, such as those in which nitroxides are bound to carboxylate-bridged dinuclear metal centres (Handa et al., 1998; Conge et al., 1994) and those having oxalate (Oshio et al., 2000) or cis-1,2-dicyano-1,2-ethylenedithiolate (Sutter et al., 1996) as a ligand. The N-heteroaromatic derivatives of nitronyl nitroxides have also been used advantageously to construct various types of transition metal–nitroxide complexes, because the auxiliary N-heteroaromatic donor group can make the nitroxide-O atom bind to a poorly electrophilic metal centre through the chelate effect (Luneau et al., 1993). Such nitronyl nitroxides also opened up the syntheses of transition metal complexes having various kinds of co-ligands. In fact, using the 2-pyridyl derivative 4,5-dihydro-4,4,5,5-tetramethyl-2-(2-pyridyl)imidazol-1-oxyl 3-oxide (NIT2py), we have recently succeeded in preparing and characterizing novel Ni^II–nitronyl nitroxide complexes containing both N,N,N',N'-tetramethyl-1,2-ethanediamine (tmen) and various kinds of β-diketonate ligands (Yoshida et al., 1999). We report here another intriguing Ni^II–nitronyl nitroxide complex containing nitrate instead of β-diketonate, i.e. [Ni(NO₃)(tmen)(NIT2py)]PF₆.CH₂Cl₂, (I). This is the first nitronyl nitroxide complex of the late transition metal ions containing nitrate as a ligand, although there has been a recent report concerning lanthanide(III)–nitronyl nitroxide complexes having three nitrate ligands, [Ln(NO₃)₃(NITtrz)₂] (Ln = Y, La or Gd; NITtrz = 4,5-dihydro-4,4,5,5-tetramethyl-2-(4,5-dimethyl-1,2,4-triazol-3-yl)imidazol-1- oxyl 3-oxide) (Sutter et al., 1998). [Please check that dihydroimidazol is appropriate in this case]

Compound (I) was prepared from [Ni(NO₃)₂(tmen)], NIT2py and KPF₆, and was recrystallized from CH₂Cl₂/Et₂O, affording dark-green crystals. The X-ray analysis confirmed that the nitrate acts as a bidentate ligand in the complex cation of (I) (Fig. 1). The nitronyl nitroxide, NIT2py, coordinates to the Ni^II ion via the pyridyl-N and nitroxide-O atoms to form a six-membered chelate ring. As in the other Ni^II–NIT2py complexes (Luneau et al., 1993; Yoshida et al., 1999), the coordinated N—O bond [N1—O1 = 1.296 (3)Å] is longer by ca 0.02Å than the uncoordinated N—O bond [N2—O2 = 1.276 (4)Å]. The diamine, tmen, also chelates to Ni^II forming a five-membered chelate ring, with a typical gauche conformation, and the coordination geometry around the Ni^II atom is a distorted octahedron. The geometrical structure of the complex cation is assigned as a mer (cis, trans) N₃O₃ configuration, similar to the corresponding pentane-2,4-dionate (acac), 1-phenylbutane-1,3-dionate (bzac) and 1,1,1-trifluoro-4-phenylbutane-2,4-dionate (tfbzac) complexes, i.e. [Ni(acac, bzac or tfbzac)(tmen)(NIT2py)]PF₆ (Yoshida et al., 1999). Also, the conformations of the NIT2py and tmen chelate rings in (I) are similar to those in the above-mentioned β-diketonate complexes; for the complex cation having a Λ absolute configuration around the Ni^II centre, δ(lel) and λ(ob) conformations are observed for NIT2py and tmen, respectively.

The structure of the coordinated nitrate moiety is not anomalous, although the Ni—O3 and Ni—O4 bond lengths [2.129 (2) and 2.125 (3)Å, respectively] are slightly shorter than those in the related Ni^II–NO₃ complexes; for example, in [Ni(NO₃)(acac)(1,2-dipiperidinoethane)] [2.168 (3) and 2.161 (3)Å; Fukuda et al., 1989] and [Ni(NO₃)(N,N'-dipropyl-1,2-ethanediamine)₂]NO₃ [2.149 (2) and 2.152 (3)Å; Laskar et al., 1998]. As indicated by the small O3—Ni—O4 bite angle of 61.0 (1)°, nitrate is sterically more compact than the β-diketonates, which have bite angles in the range 90.54 (8)–92.0 (2)° (Yoshida et al., 1999). Such a compactness of the NO₃^- ligand results in noticeable deviations in the structural parameters of the nitrate complex from those of the β-diketonate complexes (Yoshida et al., 1999), as mentioned below.

While the Ni—N4 bond length in (I) [2.154 (3)Å] is comparable to that of the corresponding β-diketonate complexes [2.144 (6)–2.170 (6)Å], the Ni—N5 bond [2.100 (3)Å] is much shorter than that of the β-diketonate complexes [2.168 (6)–2.171 (6)Å]. This seems to result from a reduction of the steric congestion around the Ni^II centre by coordination of NO₃^- instead of β-diketonate. The wider N5—Ni—O3 bond angle of 105.2 (1)° in (I) compared with similar angles in the β-diketonate complexes [91.6 (2)–93.5 (2)°] is indicative of such a reduction. The O1—Ni—O4 and O1—Ni—N5 angles of 99.3 (1) and 94.8 (1)° in (I) are also wider compared with those of the β-diketonate complexes [87.7 (2)–88.5 (1) and 87.0 (2)–88.8 (2)°, respectively]. Therefore, the reduction of steric congestion would also result in the shortening of the Ni—O1 bond of the NIT2py coordination. In fact, while the Ni—N3 bond length of 2.134 (4)Å is almost the same as that of the β-diketonate complexes [2.123 (5)–2.144 (5)Å], the Ni—O1 bond length of 2.014 (2)Å is shorter than that of the β-diketonate complexes [2.052 (4)–2.056 (2)Å]. The Ni—O1—N1 angle in (I) [119.2 (2)°] is almost the same as that in the β-diketonate complexes [117.8 (2)–118.9 (3)°], but the dihedral angle between the nitronyl nitroxide mean plane and the plane of the pyridyl ring of (I) [32.7 (1)°] is a little larger than the corresponding angle of the β-diketonate complexes (23.2–28.7°).

There are no remarkable intermolecular contacts between the nitronyl nitroxide moieties, the shortest intermolecular distance between them being 4.267 (5)Å for O2···N2ⁱ [symmetry code: (i) 1-x, 1-y, 2-z].

The temperature dependence of the magnetic susceptibility of compound (I) was analysed by a similar method to that used for the analysis of the β-diketonate complexes, and the best-fit parameters obtained are g = 2.24, J = -111.1 cm^-1 and θ = -0.649 K. Although the Ni—O(nitroxide) bond is shorter, as mentioned above, the magnetic interaction parameter is nearly equal to the those found in the β-diketonate complexes, viz. -149.0 cm^{-1 _{for the acac, -110.1 cm}}-1 ^{for the bzac and -99.8 cm}-1 ^{for the tfbzac complexes (Yoshida et al., 1999).}

Related literature

For related literature, see: Caneschi et al. (1991); Conge et al. (1994); Fukuda et al. (1989); Handa et al. (1998); Laskar et al. (1998); Luneau et al. (1993); Oshio et al. (2000); Sutter et al. (1996, 1998); Yoshida et al. (1999).

S2. Experimental

A mixture of [Ni(NO₃)₂(tmen)] (0.47 mmol) and NIT2py (0.51 mmol) in CH₂Cl₂ (30 ml) was stirred at room temperature for 30 min, and then evaporated to dryness under reduced pressure. The residue was dissolved in CH₃OH (50 ml) and solid KPF₆ (0.49 mmol) was added to the solution, giving dark-green precipitate. The precipitate was filtered off and extracted with CH₂Cl₂. The extract was evaporated, again, to dryness, and the residue was recrystallized from CH₂Cl₂/Et₂O giving dark-green crystals of compound (I) (yield: 64%). Analysis found: C 32.62, H 4.80, N 12.04%; calculated for C₁₉H₃₄Cl₂F₆N₆NiO₅P: C 32.55, H 4.89, N 11.99%.

S3. Refinement

H-atom parameters were constrained; C—H = 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Rigaku, 1985); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation and Rigaku, 2000); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1970); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A perspective view of the complex cation in (I). H atoms have been omitted for clarity and displacement ellipsoids are drawn at the 40% probability level.

[4,5-Dihydro-4,4,5,5-tetramethyl-2-(2-pyridyl-κN)imidazol-1-oxyl 3-oxide-κO³](nitrato-κ²O,O')(N,N,N',N'-tetramethyl-1,2-ethanediamine- κ²N,N')nickel(II) hexafluorophophate dichloromethane solvate

Crystal data

[Ni(NO3)(C6H16N2)(C12H16N3O2)]PF6·CH2Cl2	F(000) = 1444
Mr = 701.08	Dx = 1.577 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
a = 8.6307 (18) Å	Cell parameters from 25 reflections
b = 26.690 (6) Å	θ = 14.7–15.0°
c = 13.119 (2) Å	µ = 0.97 mm^−1
β = 102.305 (15)°	T = 296 K
V = 2952.6 (10) Å^3	Prism, dark green
Z = 4	0.26 × 0.22 × 0.10 mm

Data collection

Rigaku AFC-7R diffractometer	3922 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.039
Graphite monochromator	θmax = 30.0°, θmin = 2.5°
ω–2θ scans	h = 0→12
Absorption correction: integration (Coppens et al., 1965)	k = −37→0
Tmin = 0.802, Tmax = 0.881	l = −18→18
9114 measured reflections	3 standard reflections every 150 reflections
8605 independent reflections	intensity decay: 0.4%

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.154	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0634P)^2] where P = (Fo^2 + 2Fc^2)/3
8605 reflections	(Δ/σ)max = 0.017
369 parameters	Δρmax = 0.75 e Å^−3
0 restraints	Δρmin = −0.62 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Ni	0.41129 (5)	0.410130 (15)	0.66249 (3)	0.03195 (11)
Cl1	0.6878 (2)	0.70824 (5)	0.74479 (10)	0.0886 (4)
Cl2	0.89180 (19)	0.62099 (6)	0.77924 (13)	0.0982 (5)
P	0.14341 (16)	0.73457 (5)	0.09915 (10)	0.0674 (4)
F1	0.1098 (4)	0.79279 (12)	0.1031 (3)	0.1081 (11)
F2	0.3162 (5)	0.74151 (18)	0.1505 (4)	0.174 (2)
F3	0.0941 (6)	0.72666 (16)	0.2033 (3)	0.160 (2)
F4	0.1807 (6)	0.74055 (15)	−0.0121 (3)	0.1473 (17)
F5	−0.0333 (5)	0.72698 (16)	0.0408 (4)	0.1541 (18)
F6	0.1799 (5)	0.67706 (12)	0.0953 (3)	0.1212 (13)
O1	0.4495 (3)	0.36687 (8)	0.79122 (16)	0.0394 (5)
O2	0.7405 (4)	0.46434 (12)	1.0546 (2)	0.0701 (9)
O3	0.3417 (3)	0.47299 (9)	0.56337 (19)	0.0471 (6)
O4	0.2691 (3)	0.46675 (9)	0.71039 (19)	0.0457 (6)
O5	0.1911 (4)	0.53047 (11)	0.6093 (3)	0.0810 (10)
N1	0.5019 (3)	0.38735 (10)	0.88158 (19)	0.0327 (6)
N2	0.6435 (4)	0.43159 (12)	1.0072 (2)	0.0457 (7)
N3	0.6205 (3)	0.45047 (10)	0.7323 (2)	0.0352 (6)
N4	0.2051 (3)	0.36722 (11)	0.5914 (2)	0.0399 (7)
N5	0.5331 (3)	0.36274 (10)	0.5786 (2)	0.0391 (6)
N6	0.2643 (4)	0.49164 (11)	0.6277 (3)	0.0491 (8)
C1	0.6182 (4)	0.42088 (12)	0.9043 (2)	0.0358 (7)
C2	0.4257 (4)	0.37535 (13)	0.9721 (3)	0.0388 (7)
C3	0.5479 (4)	0.39892 (14)	1.0646 (3)	0.0444 (8)
C4	0.2654 (5)	0.40188 (17)	0.9493 (3)	0.0610 (11)
H4A	0.2814	0.4374	0.9455	0.075*
H4B	0.2104	0.3948	1.0040	0.075*
H4C	0.2034	0.3902	0.8840	0.075*
C5	0.4050 (6)	0.31903 (14)	0.9780 (3)	0.0589 (11)
H5A	0.3688	0.3108	1.0403	0.073*
H5B	0.5046	0.3028	0.9793	0.073*
H5C	0.3284	0.3079	0.9181	0.073*
C6	0.4795 (6)	0.43214 (19)	1.1380 (4)	0.0762 (14)
H6A	0.5643	0.4459	1.1899	0.095*
H6B	0.4111	0.4126	1.1714	0.095*
H6C	0.4200	0.4589	1.0991	0.095*
C7	0.6658 (6)	0.36214 (19)	1.1267 (4)	0.0728 (14)
H7A	0.6104	0.3382	1.1603	0.089*
H7B	0.7411	0.3800	1.1784	0.089*
H7C	0.7205	0.3450	1.0805	0.089*
C8	0.7016 (4)	0.44415 (12)	0.8315 (2)	0.0350 (7)
C9	0.8576 (4)	0.46030 (15)	0.8645 (3)	0.0481 (9)
H9	0.9125	0.4542	0.9324	0.059*
C10	0.9295 (5)	0.48525 (15)	0.7958 (3)	0.0534 (10)
H10	1.0337	0.4963	0.8167	0.063*
C11	0.8467 (4)	0.49380 (14)	0.6966 (3)	0.0488 (9)
H11	0.8927	0.5112	0.6492	0.060*
C12	0.6926 (4)	0.47600 (13)	0.6680 (3)	0.0426 (8)
H12	0.6365	0.4821	0.6004	0.052*
C13	0.2621 (5)	0.33203 (16)	0.5203 (4)	0.0640 (12)
H13A	0.2523	0.3476	0.4524	0.077*
H13B	0.1965	0.3022	0.5116	0.077*
C14	0.4305 (5)	0.31769 (14)	0.5617 (4)	0.0606 (11)
H14A	0.4393	0.2999	0.6271	0.074*
H14B	0.4657	0.2955	0.5127	0.074*
C15	0.0731 (5)	0.39703 (16)	0.5283 (3)	0.0615 (11)
H15A	0.0304	0.4190	0.5733	0.075*
H15B	−0.0085	0.3748	0.4932	0.075*
H15C	0.1124	0.4165	0.4776	0.075*
C16	0.1372 (5)	0.33916 (17)	0.6686 (3)	0.0598 (11)
H16A	0.0971	0.3623	0.7127	0.075*
H16B	0.2180	0.3187	0.7104	0.075*
H16C	0.0523	0.3182	0.6329	0.075*
C17	0.5530 (6)	0.38405 (17)	0.4787 (3)	0.0645 (12)
H17A	0.6287	0.4109	0.4917	0.077*
H17B	0.4530	0.3966	0.4408	0.077*
H17C	0.5903	0.3585	0.4383	0.077*
C18	0.6906 (5)	0.34657 (17)	0.6376 (4)	0.0646 (12)
H18A	0.6827	0.3365	0.7066	0.082*
H18B	0.7642	0.3739	0.6422	0.082*
H18C	0.7273	0.3189	0.6025	0.082*
C19	0.8837 (7)	0.6864 (2)	0.7862 (4)	0.0911 (17)
H19A	0.9497	0.7009	0.7426	0.108*
H19B	0.9251	0.6971	0.8574	0.108*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0309 (2)	0.03157 (19)	0.03237 (19)	−0.00208 (19)	0.00456 (14)	0.00162 (18)
Cl1	0.1133 (12)	0.0825 (9)	0.0734 (8)	−0.0056 (8)	0.0277 (8)	−0.0089 (7)
Cl2	0.0929 (11)	0.0907 (10)	0.1147 (12)	−0.0056 (8)	0.0306 (9)	0.0051 (9)
P	0.0641 (8)	0.0749 (8)	0.0668 (7)	0.0291 (6)	0.0214 (6)	0.0230 (6)
F1	0.124 (3)	0.078 (2)	0.120 (3)	0.033 (2)	0.023 (2)	0.0144 (19)
F2	0.073 (3)	0.164 (4)	0.258 (6)	0.014 (3)	−0.022 (3)	−0.003 (4)
F3	0.235 (5)	0.157 (4)	0.124 (3)	0.113 (4)	0.120 (3)	0.064 (3)
F4	0.242 (5)	0.120 (3)	0.102 (3)	0.045 (3)	0.085 (3)	0.042 (2)
F5	0.097 (3)	0.129 (3)	0.211 (5)	0.012 (3)	−0.023 (3)	0.035 (3)
F6	0.165 (4)	0.081 (2)	0.129 (3)	0.056 (2)	0.056 (3)	0.033 (2)
O1	0.0483 (14)	0.0348 (12)	0.0321 (11)	−0.0095 (11)	0.0022 (10)	0.0012 (9)
O2	0.080 (2)	0.080 (2)	0.0486 (16)	−0.0380 (17)	0.0088 (15)	−0.0193 (15)
O3	0.0457 (15)	0.0488 (15)	0.0465 (14)	0.0007 (12)	0.0093 (12)	0.0142 (12)
O4	0.0493 (15)	0.0428 (13)	0.0476 (14)	0.0029 (11)	0.0164 (12)	0.0018 (11)
O5	0.069 (2)	0.0481 (17)	0.127 (3)	0.0233 (16)	0.024 (2)	0.0252 (18)
N1	0.0332 (14)	0.0317 (13)	0.0320 (13)	−0.0013 (11)	0.0043 (11)	0.0011 (11)
N2	0.0452 (17)	0.0511 (17)	0.0384 (15)	−0.0122 (15)	0.0035 (13)	−0.0060 (13)
N3	0.0332 (14)	0.0340 (14)	0.0388 (15)	−0.0046 (11)	0.0085 (12)	0.0028 (12)
N4	0.0306 (14)	0.0433 (16)	0.0434 (16)	−0.0055 (12)	0.0028 (12)	−0.0031 (13)
N5	0.0398 (16)	0.0391 (15)	0.0394 (15)	0.0017 (13)	0.0106 (12)	−0.0015 (12)
N6	0.0380 (17)	0.0390 (17)	0.067 (2)	−0.0002 (14)	0.0043 (16)	0.0057 (15)
C1	0.0345 (17)	0.0346 (17)	0.0379 (16)	−0.0038 (13)	0.0072 (14)	−0.0010 (13)
C2	0.0424 (19)	0.0405 (18)	0.0363 (17)	−0.0024 (15)	0.0146 (15)	0.0011 (14)
C3	0.049 (2)	0.051 (2)	0.0344 (17)	−0.0002 (16)	0.0103 (15)	−0.0004 (15)
C4	0.047 (2)	0.081 (3)	0.058 (2)	0.002 (2)	0.0170 (19)	−0.007 (2)
C5	0.088 (3)	0.044 (2)	0.048 (2)	−0.018 (2)	0.023 (2)	0.0007 (17)
C6	0.073 (3)	0.094 (4)	0.065 (3)	−0.010 (3)	0.024 (2)	−0.036 (3)
C7	0.064 (3)	0.085 (3)	0.060 (3)	−0.005 (3)	−0.007 (2)	0.022 (2)
C8	0.0342 (17)	0.0338 (16)	0.0366 (17)	−0.0017 (14)	0.0063 (13)	−0.0018 (13)
C9	0.0366 (19)	0.056 (2)	0.050 (2)	−0.0051 (17)	0.0053 (16)	0.0013 (18)
C10	0.034 (2)	0.058 (2)	0.067 (3)	−0.0100 (18)	0.0097 (18)	−0.006 (2)
C11	0.044 (2)	0.047 (2)	0.058 (2)	−0.0149 (17)	0.0153 (18)	0.0060 (18)
C12	0.041 (2)	0.044 (2)	0.0427 (19)	−0.0058 (16)	0.0087 (15)	0.0066 (16)
C13	0.055 (3)	0.063 (3)	0.072 (3)	−0.018 (2)	0.011 (2)	−0.030 (2)
C14	0.061 (3)	0.040 (2)	0.086 (3)	−0.0011 (19)	0.025 (2)	−0.016 (2)
C15	0.042 (2)	0.060 (3)	0.071 (3)	−0.0073 (19)	−0.0140 (19)	0.008 (2)
C16	0.045 (2)	0.070 (3)	0.062 (3)	−0.021 (2)	0.0075 (19)	0.009 (2)
C17	0.083 (3)	0.062 (3)	0.054 (2)	−0.008 (2)	0.028 (2)	−0.002 (2)
C18	0.052 (3)	0.066 (3)	0.073 (3)	0.024 (2)	0.006 (2)	−0.008 (2)
C19	0.091 (4)	0.093 (4)	0.088 (4)	−0.037 (3)	0.016 (3)	−0.010 (3)

Geometric parameters (Å, º)

Ni—O1	2.014 (2)	C4—H4B	0.9600
Ni—O3	2.129 (2)	C4—H4C	0.9600
Ni—O4	2.125 (2)	C5—H5A	0.9600
Ni—N3	2.134 (3)	C5—H5B	0.9600
Ni—N4	2.154 (3)	C5—H5C	0.9600
Ni—N5	2.100 (3)	C6—H6A	0.9600
Cl1—C19	1.761 (6)	C6—H6B	0.9600
Cl2—C19	1.750 (6)	C6—H6C	0.9600
P—F2	1.512 (4)	C7—H7A	0.9600
P—F3	1.530 (3)	C7—H7B	0.9600
P—F5	1.567 (4)	C7—H7C	0.9600
P—F4	1.569 (4)	C8—C9	1.392 (5)
P—F6	1.570 (3)	C9—C10	1.370 (5)
P—F1	1.584 (3)	C9—H9	0.9300
O1—N1	1.296 (3)	C10—C11	1.364 (5)
O2—N2	1.276 (4)	C10—H10	0.9300
O3—N6	1.283 (4)	C11—C12	1.387 (5)
O4—N6	1.265 (4)	C11—H11	0.9300
O5—N6	1.211 (4)	C12—H12	0.9300
N1—C1	1.330 (4)	C13—C14	1.490 (6)
N1—C2	1.509 (4)	C13—H13A	0.9700
N2—C1	1.351 (4)	C13—H13B	0.9700
N2—C3	1.508 (5)	C14—H14A	0.9700
N3—C12	1.337 (4)	C14—H14B	0.9700
N3—C8	1.351 (4)	C15—H15A	0.9600
N4—C16	1.478 (5)	C15—H15B	0.9600
N4—C13	1.480 (5)	C15—H15C	0.9600
N4—C15	1.488 (5)	C16—H16A	0.9600
N5—C17	1.472 (5)	C16—H16B	0.9600
N5—C18	1.479 (5)	C16—H16C	0.9600
N5—C14	1.481 (5)	C17—H17A	0.9600
C1—C8	1.452 (4)	C17—H17B	0.9600
C2—C5	1.518 (5)	C17—H17C	0.9600
C2—C4	1.526 (5)	C18—H18A	0.9600
C2—C3	1.561 (5)	C18—H18B	0.9600
C3—C6	1.518 (5)	C18—H18C	0.9600
C3—C7	1.520 (6)	C19—H19A	0.9700
C4—H4A	0.9600	C19—H19B	0.9700
O2···N2^i	4.267 (5)	N2···N2^i	4.394 (6)
O2···O2^i	4.513 (6)
O1—Ni—O3	159.76 (10)	H4B—C4—H4C	109.5
O1—Ni—O4	99.29 (10)	C2—C5—H5A	109.5
O1—Ni—N3	87.55 (9)	C2—C5—H5B	109.5
O1—Ni—N4	91.76 (10)	H5A—C5—H5B	109.5
O1—Ni—N5	94.79 (10)	C2—C5—H5C	109.5
O3—Ni—O4	60.96 (10)	H5A—C5—H5C	109.5
O3—Ni—N3	88.11 (10)	H5B—C5—H5C	109.5
O3—Ni—N4	93.16 (10)	C3—C6—H6A	109.5
O4—Ni—N3	90.19 (11)	C3—C6—H6B	109.5
O4—Ni—N4	91.74 (11)	H6A—C6—H6B	109.5
N3—Ni—N4	178.03 (11)	C3—C6—H6C	109.5
N5—Ni—O3	105.19 (11)	H6A—C6—H6C	109.5
N5—Ni—O4	165.63 (10)	H6B—C6—H6C	109.5
N5—Ni—N3	93.25 (11)	C3—C7—H7A	109.5
N5—Ni—N4	84.97 (11)	C3—C7—H7B	109.5
F2—P—F3	93.1 (3)	H7A—C7—H7B	109.5
F2—P—F5	177.3 (3)	C3—C7—H7C	109.5
F3—P—F5	89.5 (3)	H7A—C7—H7C	109.5
F2—P—F4	91.4 (3)	H7B—C7—H7C	109.5
F3—P—F4	175.3 (3)	N3—C8—C9	122.0 (3)
F5—P—F4	86.0 (3)	N3—C8—C1	117.3 (3)
F2—P—F6	87.0 (2)	C9—C8—C1	120.7 (3)
F3—P—F6	89.4 (2)	C10—C9—C8	119.3 (3)
F5—P—F6	92.2 (2)	C10—C9—H9	120.4
F4—P—F6	89.3 (2)	C8—C9—H9	120.4
F2—P—F1	92.0 (2)	C11—C10—C9	119.4 (4)
F3—P—F1	91.0 (2)	C11—C10—H10	120.3
F5—P—F1	88.7 (2)	C9—C10—H10	120.3
F4—P—F1	90.3 (2)	C10—C11—C12	118.6 (3)
F6—P—F1	179.0 (2)	C10—C11—H11	120.7
N1—O1—Ni	119.20 (18)	C12—C11—H11	120.7
N6—O3—Ni	91.28 (19)	N3—C12—C11	123.6 (3)
N6—O4—Ni	92.0 (2)	N3—C12—H12	118.2
O1—N1—C1	126.0 (3)	C11—C12—H12	118.2
O1—N1—C2	120.3 (2)	N4—C13—C14	111.3 (3)
C1—N1—C2	113.7 (3)	N4—C13—H13A	109.4
O2—N2—C1	125.5 (3)	C14—C13—H13A	109.4
O2—N2—C3	121.6 (3)	N4—C13—H13B	109.4
C1—N2—C3	112.8 (3)	C14—C13—H13B	109.4
C12—N3—C8	117.1 (3)	H13A—C13—H13B	108.0
C12—N3—Ni	116.9 (2)	N5—C14—C13	110.6 (3)
C8—N3—Ni	124.6 (2)	N5—C14—H14A	109.5
C16—N4—C13	110.1 (3)	C13—C14—H14A	109.5
C16—N4—C15	106.5 (3)	N5—C14—H14B	109.5
C13—N4—C15	107.8 (3)	C13—C14—H14B	109.5
C16—N4—Ni	112.6 (2)	H14A—C14—H14B	108.1
C13—N4—Ni	104.8 (2)	N4—C15—H15A	109.5
C15—N4—Ni	114.8 (2)	N4—C15—H15B	109.5
C17—N5—C18	108.1 (3)	H15A—C15—H15B	109.5
C17—N5—C14	111.1 (3)	N4—C15—H15C	109.5
C18—N5—C14	107.1 (3)	H15A—C15—H15C	109.5
C17—N5—Ni	113.6 (2)	H15B—C15—H15C	109.5
C18—N5—Ni	114.1 (2)	N4—C16—H16A	109.5
C14—N5—Ni	102.6 (2)	N4—C16—H16B	109.5
O5—N6—O4	122.8 (4)	H16A—C16—H16B	109.5
O5—N6—O3	121.5 (3)	N4—C16—H16C	109.5
O4—N6—O3	115.7 (3)	H16A—C16—H16C	109.5
N1—C1—N2	108.6 (3)	H16B—C16—H16C	109.5
N1—C1—C8	126.6 (3)	N5—C17—H17A	109.5
N2—C1—C8	124.7 (3)	N5—C17—H17B	109.5
N1—C2—C5	109.0 (3)	H17A—C17—H17B	109.5
N1—C2—C4	106.1 (3)	N5—C17—H17C	109.5
C5—C2—C4	111.0 (3)	H17A—C17—H17C	109.5
N1—C2—C3	101.0 (3)	H17B—C17—H17C	109.5
C5—C2—C3	115.3 (3)	N5—C18—H18A	109.5
C4—C2—C3	113.6 (3)	N5—C18—H18B	109.5
N2—C3—C6	107.9 (3)	H18A—C18—H18B	109.5
N2—C3—C7	105.4 (3)	N5—C18—H18C	109.5
C6—C3—C7	110.1 (4)	H18A—C18—H18C	109.5
N2—C3—C2	101.3 (3)	H18B—C18—H18C	109.5
C6—C3—C2	116.0 (3)	Cl2—C19—Cl1	111.2 (3)
C7—C3—C2	114.9 (3)	Cl2—C19—H19A	109.4
C2—C4—H4A	109.5	Cl1—C19—H19A	109.4
C2—C4—H4B	109.5	Cl2—C19—H19B	109.4
H4A—C4—H4B	109.5	Cl1—C19—H19B	109.4
C2—C4—H4C	109.5	H19A—C19—H19B	108.0
H4A—C4—H4C	109.5
N5—Ni—O1—N1	131.5 (2)	Ni—O3—N6—O5	−178.4 (3)
O4—Ni—O1—N1	−51.3 (2)	Ni—O3—N6—O4	1.1 (3)
O3—Ni—O1—N1	−39.3 (4)	O1—N1—C1—N2	−177.2 (3)
N3—Ni—O1—N1	38.5 (2)	C2—N1—C1—N2	5.2 (4)
N4—Ni—O1—N1	−143.4 (2)	O1—N1—C1—C8	5.0 (5)
O1—Ni—O3—N6	−14.3 (4)	C2—N1—C1—C8	−172.6 (3)
N5—Ni—O3—N6	175.19 (19)	O2—N2—C1—N1	−175.9 (3)
O4—Ni—O3—N6	−0.69 (18)	C3—N2—C1—N1	6.3 (4)
N3—Ni—O3—N6	−91.96 (19)	O2—N2—C1—C8	1.9 (6)
N4—Ni—O3—N6	89.5 (2)	C3—N2—C1—C8	−175.9 (3)
O1—Ni—O4—N6	175.98 (19)	O1—N1—C2—C5	47.0 (4)
N5—Ni—O4—N6	−15.5 (5)	C1—N1—C2—C5	−135.3 (3)
O3—Ni—O4—N6	0.70 (18)	O1—N1—C2—C4	−72.6 (4)
N3—Ni—O4—N6	88.43 (19)	C1—N1—C2—C4	105.1 (3)
N4—Ni—O4—N6	−91.9 (2)	O1—N1—C2—C3	168.7 (3)
Ni—O1—N1—C1	−44.4 (4)	C1—N1—C2—C3	−13.5 (4)
Ni—O1—N1—C2	133.0 (2)	O2—N2—C3—C6	45.6 (5)
O1—Ni—N3—C12	157.8 (3)	C1—N2—C3—C6	−136.5 (3)
N5—Ni—N3—C12	63.2 (3)	O2—N2—C3—C7	−72.0 (4)
O4—Ni—N3—C12	−102.9 (2)	C1—N2—C3—C7	105.9 (4)
O3—Ni—N3—C12	−41.9 (3)	O2—N2—C3—C2	167.9 (3)
O1—Ni—N3—C8	−8.2 (3)	C1—N2—C3—C2	−14.2 (4)
N5—Ni—N3—C8	−102.9 (3)	N1—C2—C3—N2	15.1 (3)
O4—Ni—N3—C8	91.1 (3)	C5—C2—C3—N2	132.4 (3)
O3—Ni—N3—C8	152.0 (3)	C4—C2—C3—N2	−98.0 (3)
O1—Ni—N4—C16	21.4 (3)	N1—C2—C3—C6	131.6 (4)
N5—Ni—N4—C16	116.0 (3)	C5—C2—C3—C6	−111.1 (4)
O4—Ni—N4—C16	−78.0 (3)	C4—C2—C3—C6	18.5 (5)
O3—Ni—N4—C16	−139.0 (3)	N1—C2—C3—C7	−98.0 (4)
O1—Ni—N4—C13	−98.3 (3)	C5—C2—C3—C7	19.3 (5)
N5—Ni—N4—C13	−3.7 (3)	C4—C2—C3—C7	148.9 (4)
O4—Ni—N4—C13	162.3 (3)	C12—N3—C8—C9	−4.3 (5)
O3—Ni—N4—C13	101.3 (3)	Ni—N3—C8—C9	161.7 (3)
O1—Ni—N4—C15	143.5 (3)	C12—N3—C8—C1	174.0 (3)
N5—Ni—N4—C15	−121.8 (3)	Ni—N3—C8—C1	−20.0 (4)
O4—Ni—N4—C15	44.2 (3)	N1—C1—C8—N3	30.1 (5)
O3—Ni—N4—C15	−16.8 (3)	N2—C1—C8—N3	−147.4 (3)
O1—Ni—N5—C17	−172.5 (3)	N1—C1—C8—C9	−151.6 (4)
O4—Ni—N5—C17	18.9 (6)	N2—C1—C8—C9	31.0 (5)
O3—Ni—N5—C17	4.2 (3)	N3—C8—C9—C10	2.8 (6)
N3—Ni—N5—C17	−84.7 (3)	C1—C8—C9—C10	−175.5 (3)
N4—Ni—N5—C17	96.1 (3)	C8—C9—C10—C11	0.1 (6)
O1—Ni—N5—C18	−48.0 (3)	C9—C10—C11—C12	−1.2 (6)
O4—Ni—N5—C18	143.4 (4)	C8—N3—C12—C11	3.2 (5)
O3—Ni—N5—C18	128.7 (3)	Ni—N3—C12—C11	−163.9 (3)
N3—Ni—N5—C18	39.8 (3)	C10—C11—C12—N3	−0.5 (6)
N4—Ni—N5—C18	−139.3 (3)	C16—N4—C13—C14	−89.6 (4)
O1—Ni—N5—C14	67.5 (2)	C15—N4—C13—C14	154.6 (4)
O4—Ni—N5—C14	−101.1 (5)	Ni—N4—C13—C14	31.8 (4)
O3—Ni—N5—C14	−115.8 (2)	C17—N5—C14—C13	−72.7 (4)
N3—Ni—N5—C14	155.3 (2)	C18—N5—C14—C13	169.5 (4)
N4—Ni—N5—C14	−23.9 (2)	Ni—N5—C14—C13	49.1 (4)
Ni—O4—N6—O5	178.4 (3)	N4—C13—C14—N5	−57.5 (5)
Ni—O4—N6—O3	−1.1 (3)

Symmetry code: (i) −x+1, −y+1, −z+2.