(μ-Oxalato-O¹,O²:O^1′,O^2′)bis[aqua(diethyl­enetri­amine)nickel(II)] bis(hexafluorophosphate) dihydrate

The title compound, [Ni₂(C₂O₄)(C₄H₁₃N₃)₂(H₂O)₂](PF₆)₂·-2H₂O, contains a dinuclear oxalato-bridged nickel(II) complex cation. The structure determination reveals the presence of a centrosymmetric binuclear complex where the oxalate ligand is coordinated in a bis­-bidentate mode to the Ni atoms. The distorted octahedral environment of each Ni atom is completed by the three N atoms of the diethyl­enetri­amine ligand in a fac arrangement and by one O atom from a water mol­ecule. PF₆⁻ acts as counter-anion. A two-dimensional network of hydrogen bonds links the cations and anions and stabilizes the structure.

S1. Comment

The design and synthesis of molecular magnetic compounds has attracted increasing attention over the past two decades (Gatteschi et al., 1991; Bruce & O'Hare, 1992). A significant amount of magnetostructural research work during the last twenty five years has been devoted to analysing the remarkable ability of the oxalate bridge to mediate exchange coupling between first-row transition metal ions (Alvarez et al., 1990; Cano et al., 1999). The simple binuclear geometry involving symmetric, in-plane bridging with a single oxalate anion binding through two oxygen atoms to each of two metal centres has been observed in the chemistry of nickel (Alcock et al., 1987; Battaglia et al., 1988; Bencini et al., 1990; Castro et al., 1997; Travnicek et al., 1997), and these O-bridged nickel(II) complexes have attracted much attention due to the strong magneto-structural correlations found in these kind of compounds (Khan, 1993).

Despite these exhaustive studies, dimeric structures are predominant in the solid-state chemistry of µ-oxalato nickel(II) complexes and only in the last years have infinitely extended networks based on transition metal oxalato complexes been reported (Decurtins et al., 1996).

Compounds containing the [{Ni(dien)(H₂O)}₂(µ-ox)]²⁺ cation (dien = diethylenetriamine and ox = oxalate) are known as the dichloride, [{Ni(dien)(H₂O)}₂(µ-ox)]Cl₂ (Román et al., 1996), dibromide, [{Ni(dien)(H₂O)}₂(µ-ox)]Br₂ (Muga, 2001), diperchlorate monohydrate, [{Ni(dien)(H₂O)}₂(µ-ox)](ClO₄)₂·H₂O (Travnicek et al., 1997) and dinitrate, [{Ni(dien)(H₂O)}₂(µ-ox)](NO₃)₂ (Guzmán et al., 2001).

We report here the synthesis and crystal structure of [{Ni(dien)(H₂O)}₂(µ-ox)](PF₆)₂·2H₂O. This compound was obtained starting from [{Ni(dien)(H₂O)}₂(µ-ox)]Cl₂ by exchanging Cl^- for PF₆^-. Analogously to [{Ni(dien)(H₂O)}₂(µ-ox)]Cl₂, the title compound can be used as a precursor in the synthesis of other derivatives owing to the extreme lability of its water molecules (Román et al., 1996; Muga et al., 1997; Muga et al., 2000).

The asymmetric unit of this compound consists of a noncoordinated hexafluorophosphate ion, a water molecule, and half of a [Ni₂(dien)₂(H₂O)₂(µ-ox)]²⁺ dinuclear cation, which has an inversion centre at the midpoint of the C—C bond of the oxalate bridge. The oxalato ligand joins two adjacent Ni coordination polyhedra with its oxygen atoms occupying two cis equatorial positions, and the dien ligand acting as a facially coordinated tridentate ligand.

The coordination geometry around each metal ion is NiN₃O₃ distorted octahedral. The equatorial plane is built by two O atoms from opposite ends of the oxalato ligand, and the terminal N atoms, N1 and N7, from the dien ligand, whereas the axial positions are occupied by a water molecule, O3w, and the central N atom, N4, from the dien ligand.

The values of the Ni—N bond lengths are in the range 2.068 (3)–2.080 (3) Å. The Ni—O(ox) bonds are also very similar (Table 1) and they subtend a quite acute angle at Ni1 of 79.45 (9)°. The Ni—O3w axial bond is almost perpendicular, 87.55 (11)°, to the mean O1—O2—N1—N7 equatorial plane. The metal atom is displaced by 0.043 (1) Å from this plane in the direction of the water ligand.

The bridging oxalate anion is exactly planar, and the nickel(II) ion is 0.066 (1) Å out of this plane. The dihedral angle between the equatorial (N2O2) and oxalato mean planes is 4.23 (11)°. The intramolecular Ni···Ni distance is 5.4579 (11) Å whereas the shortest intermolecular Ni···Ni separation is 5.1542 (6) Å.

One of the carbon atoms (C2) of the dien ligand is disordered over two unequally occupied positions, C2A and C2B. The conformations of the two chelate rings within the dien ligand can be analysed in terms of the positions of the carbon atoms relative to the N—Ni—N planes of each five-membered chelate ring. The two rings show an asymmetric distribution of the carbon atoms. Whereas one C atom is above and one below the N—Ni—N plane in the minor disordered form of the first ring and in the second ring, they are located on the same side of the plane in the major disordered form of the first ring. Considering only the major disordered form of the complex, the two chelate rings adopt the λ configuration, while the chelate ring spanned by the atoms Ni1,N1, C2B, C3 and N4 adopts the δ configuration (Zelewsky, 1996).

The crystal structure consists of corrugated layers of complex cations hydrogen-bonded by the water molecules, which lie parallel to the (1 0 0) plane. Inside the layer, the hydration and coordinated water molecules give rise to hydrogen bonded chains ···O3w···O4w···O3w(1/2 - x, y - 1/2, 1/2 - z)···, in which they act alternatively as donor and acceptor atoms. Besides these, longer hydrogen bonds are formed between the O4w water molecules and both O atoms of an adjacent oxalate moiety [O1ⁱⁱ and O2ⁱⁱⁱ; (ii) x, y - 1, z, (iii) 1/2 - x, -1/2 - y, 1 - z] in a direction perpendicular to the above-mentioned chains.

The PF₆^- anions are located above and below each dinuclear complex, forming two hydrogen bonds that connect N4(1/2 - x, 1/2 - y, 1 - z) and O3w with the F4 atom. They also contribute to the crystal packing by forming three additional N—H···F hydrogen bonds that bridge between neighbouring complex cations [N···F distances in the range 3.106 (6)–3.256 (7) Å] (Fig. 2)

A remarkable aspect of the salts containing this binuclear complex cation is the different degree of hydration which gets higher as the anion becomes larger. All salts present a two-dimensional hydrogen-bonded arrangement, but the details of the hydrogen bonding network inside these layers are strongly dependent on the anion and the number of water molecules. As can be seen in Fig. 3 the interlamellar distance, d_il, is strongly dependent on the anionic radius (Jenkins et al., 1999), with a correlation factor of 0.975 for the five compounds.

S2. Experimental

To an aqueous solution (50 ml) of [{Ni(dien)H₂O}₂(µ-ox)]Cl₂ (Román et al., 1996) (0.5 g, 1.0 mmol), an aqueous solution (20 ml) of AgPF₆ (0.5 g, 2 mmol) was slowly added with continuous stirring. The mixture was stirred for 10 min. A highly insoluble grey residue precipitated during the reaction. After filtration, the resulting blue solution was allowed to stand at room temperature for several days, to give blue prismatic crystals of the complex. The crystals were collected, washed with cool water, and air dried. Suitable single crystals were obtained by recristallization from an aqueous solution, yield >95%.

S3. Refinement

The diethylenetriamine ligand has a disordered arrangement of the C2 atom over two positions. During the refinement, soft restraints were imposed on the N1, C2A, C2B and N3 atoms so that equivalent distances and angles between them, and the components of the anisotropic displacement parameters of C2A and C2B, were similar. Refinement of the site-occupation factors revealed a partial occupation of 0.692 (14) and 0.308 (14) for C2A and C2B, respectively. The H atoms of the water molecules were found from difference Fourier maps and their positions were refined with isotropic displacement parameters fixed at 1.5 times the equivalent isotropic displacement parameters of their parent atoms. The positions of all remaining H atoms were calculated geometrically and were treated as riding, with isotropic displacement parameters fixed at 1.2 (C or N) times the equivalent isotropic displacement parameters of their parent atoms. The maximum peak of residual density (1.34 e Å^-3) is 1.08 Å from F2, while the minimum (-1.40 e Å^-3) is 0.88 Å from Ni1.

Computing details

Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: DIRDIF96 (Beurskens et al., 1996); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); PLATON (Spek, 1990); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Figures

	Fig. 1. ORTEP view of the complex cation, water molecule and hexafluorophosphate anion showing 50% probability displacement ellipsoids. Ethylene H atoms are omitted for clarity. Only the major disordered form is shown.
	Fig. 2. Packing diagram viewed down the b axis, showing the O—H···O hydrogen bonding network. H atoms omitted for clarity.
	Fig. 3. Correlation diagram between the interlamellar distances (Å) and the anionic radii (Å).

(I)

Crystal data

[Ni2(C2O4)(C4H13N2)(H2O)2].2PF6.2H2O	F(000) = 1576
Mr = 773.79	Dx = 1.873 Mg m^−3 Dm = 1.86 (1) Mg m^−3 Dm measured by flotation
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 22.994 (3) Å	θ = 7.8–12.1°
b = 7.185 (1) Å	µ = 1.62 mm^−1
c = 16.806 (3) Å	T = 293 K
β = 98.86 (1)°	Prism, blue
V = 2743.4 (7) Å^3	0.3 × 0.3 × 0.2 mm
Z = 4

Data collection

Enraf Nonius CAD4 diffractometer	Rint = 0.022
Radiation source: x-ray tube	θmax = 30.0°, θmin = 1.8°
ω/2θ scans	h = −32→32
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
Tmin = 0.605, Tmax = 0.799	l = 0→23
4099 measured reflections	2 standard reflections every 98 reflections
3969 independent reflections	intensity decay: none
3370 reflections with I > 2σ(I)

Refinement

Refinement on F^2	38 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.061	w = 1/[σ^2(Fo^2) + (0.1249P)^2 + 5.9096P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.191	(Δ/σ)max = 0.001
S = 1.08	Δρmax = 1.34 e Å^−3
3969 reflections	Δρmin = −1.40 e Å^−3
193 parameters

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 on F^{2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F}2, conventional R-factors R are based on F, with F set to zero for negative F^{2. The observed criterion of F}2 > σ(F^{2) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F}2 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	0.179352 (16)	0.02743 (6)	0.39461 (2)	0.02721 (16)
C1	0.24313 (13)	0.3334 (4)	0.47094 (18)	0.0284 (5)
O1	0.21024 (10)	0.3027 (3)	0.40594 (14)	0.0339 (5)
O2	0.23426 (12)	0.0133 (3)	0.50730 (16)	0.0378 (6)
O3w	0.25067 (13)	−0.0329 (4)	0.3343 (2)	0.0480 (7)
H31w	0.2816 (18)	0.024 (3)	0.3488 (9)	0.072*
H32w	0.2607 (6)	−0.144 (6)	0.3308 (3)	0.072*
N1	0.12576 (14)	0.1058 (5)	0.28923 (17)	0.0406 (7)
H11A	0.1464	0.1675	0.2563	0.049*	0.692 (14)
H12A	0.1086	0.0060	0.2631	0.049*	0.692 (14)
H11B	0.1368	0.2190	0.2741	0.049*	0.308 (14)
H12B	0.1302	0.0246	0.2499	0.049*	0.308 (14)
C3	0.0565 (2)	0.1434 (9)	0.3844 (3)	0.0612 (12)
H31A	0.0304	0.0431	0.3635	0.073*	0.692 (14)
H32A	0.0337	0.2339	0.4094	0.073*	0.692 (14)
H31B	0.0536	0.2764	0.3929	0.073*	0.308 (14)
H32B	0.0195	0.0879	0.3926	0.073*	0.308 (14)
C2A	0.0803 (3)	0.2316 (10)	0.3181 (4)	0.0486 (17)	0.692 (14)
H21A	0.0983	0.3496	0.3359	0.058*	0.692 (14)
H22A	0.0487	0.2560	0.2741	0.058*	0.692 (14)
C2B	0.0647 (5)	0.111 (2)	0.2998 (7)	0.050 (4)	0.308 (14)
H21B	0.0462	−0.0057	0.2816	0.060*	0.308 (14)
H22B	0.0450	0.2095	0.2664	0.060*	0.308 (14)
N4	0.10349 (13)	0.0688 (5)	0.44557 (19)	0.0363 (6)
H4	0.1115	0.1538	0.4859	0.044*
C5	0.0891 (2)	−0.1113 (7)	0.4811 (3)	0.0569 (11)
H51	0.0482	−0.1110	0.4889	0.068*
H52	0.1133	−0.1272	0.5332	0.068*
C6	0.0996 (2)	−0.2703 (7)	0.4270 (3)	0.0542 (10)
H61	0.0973	−0.3873	0.4552	0.065*
H62	0.0697	−0.2707	0.3796	0.065*
N7	0.15821 (13)	−0.2510 (4)	0.40288 (19)	0.0375 (6)
H71	0.1584	−0.3067	0.3550	0.045*
H72	0.1853	−0.3074	0.4394	0.045*
O4w	0.2765 (2)	−0.3876 (5)	0.3242 (2)	0.0708 (12)
H41w	0.2699 (5)	−0.442 (4)	0.288 (3)	0.106*
H42w	0.2675 (7)	−0.439 (4)	0.360 (3)	0.106*
P1	0.41065 (5)	0.12878 (17)	0.35642 (6)	0.0451 (3)
F1	0.3949 (4)	−0.0843 (7)	0.3557 (4)	0.145 (2)
F2	0.4610 (3)	0.1057 (15)	0.3104 (5)	0.212 (5)
F3	0.4523 (2)	0.1217 (10)	0.4397 (3)	0.1198 (19)
F4	0.35914 (17)	0.1510 (9)	0.4085 (3)	0.122 (2)
F5	0.3672 (3)	0.1400 (12)	0.2780 (3)	0.159 (3)
F6	0.4245 (3)	0.3421 (7)	0.3635 (4)	0.148 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0270 (2)	0.0256 (2)	0.0274 (2)	−0.00334 (13)	−0.00091 (15)	−0.00169 (13)
C1	0.0291 (12)	0.0238 (13)	0.0302 (13)	−0.0018 (10)	−0.0027 (10)	0.0039 (10)
O1	0.0398 (11)	0.0273 (10)	0.0301 (10)	−0.0056 (9)	−0.0085 (8)	0.0033 (8)
O2	0.0420 (13)	0.0269 (11)	0.0385 (12)	−0.0073 (9)	−0.0129 (10)	0.0057 (9)
O3w	0.0400 (14)	0.0455 (16)	0.0618 (18)	−0.0048 (11)	0.0182 (13)	−0.0078 (13)
N1	0.0431 (15)	0.0468 (18)	0.0287 (12)	−0.0047 (13)	−0.0044 (11)	0.0007 (12)
C3	0.045 (2)	0.081 (3)	0.057 (2)	0.022 (2)	0.0038 (17)	0.002 (2)
C2A	0.037 (3)	0.051 (4)	0.055 (3)	0.004 (2)	−0.003 (2)	0.011 (3)
C2B	0.035 (5)	0.063 (10)	0.046 (5)	0.001 (6)	−0.014 (4)	0.011 (6)
N4	0.0388 (14)	0.0351 (14)	0.0358 (13)	−0.0009 (11)	0.0079 (11)	−0.0037 (11)
C5	0.064 (3)	0.052 (3)	0.061 (3)	−0.009 (2)	0.029 (2)	0.003 (2)
C6	0.058 (2)	0.045 (2)	0.062 (3)	−0.0160 (18)	0.015 (2)	0.0014 (19)
N7	0.0402 (14)	0.0285 (13)	0.0427 (15)	−0.0037 (11)	0.0025 (11)	−0.0035 (11)
O4w	0.110 (3)	0.054 (2)	0.0584 (19)	0.023 (2)	0.045 (2)	0.0160 (16)
P1	0.0437 (5)	0.0528 (6)	0.0388 (5)	−0.0075 (4)	0.0066 (4)	−0.0010 (4)
F1	0.222 (7)	0.060 (3)	0.160 (5)	−0.029 (4)	0.055 (5)	−0.019 (3)
F2	0.141 (5)	0.338 (11)	0.187 (7)	−0.107 (6)	0.124 (5)	−0.148 (7)
F3	0.082 (3)	0.179 (6)	0.086 (3)	−0.009 (3)	−0.027 (2)	0.007 (3)
F4	0.070 (2)	0.187 (6)	0.117 (3)	−0.038 (3)	0.037 (2)	−0.083 (4)
F5	0.135 (4)	0.262 (9)	0.062 (2)	−0.056 (5)	−0.042 (3)	0.038 (4)
F6	0.210 (6)	0.066 (3)	0.160 (6)	−0.047 (4)	0.001 (5)	0.011 (3)

Geometric parameters (Å, º)

Ni1—N7	2.068 (3)	C3—H32B	0.9700
Ni1—N1	2.074 (3)	C2A—H21A	0.9700
Ni1—N4	2.080 (3)	C2A—H22A	0.9700
Ni1—O1	2.100 (2)	C2B—H21B	0.9700
Ni1—O3w	2.102 (3)	C2B—H22B	0.9700
Ni1—O2	2.111 (2)	N4—C5	1.483 (6)
C1—O1	1.249 (3)	N4—H4	0.9100
C1—O2^i	1.249 (4)	C5—C6	1.502 (7)
C1—C1^i	1.547 (6)	C5—H51	0.9700
O2—C1^i	1.249 (4)	C5—H52	0.9700
O3w—H31w	0.82 (4)	C6—N7	1.472 (5)
O3w—H32w	0.83 (4)	C6—H61	0.9700
N1—C2B	1.442 (11)	C6—H62	0.9700
N1—C2A	1.517 (7)	N7—H71	0.9000
N1—H11A	0.9000	N7—H72	0.9000
N1—H12A	0.9000	O4w—H41w	0.72 (4)
N1—H11B	0.9000	O4w—H42w	0.76 (4)
N1—H12B	0.9000	P1—F2	1.498 (5)
C3—C2A	1.460 (8)	P1—F5	1.528 (4)
C3—N4	1.472 (5)	P1—F6	1.567 (5)
C3—C2B	1.481 (13)	P1—F3	1.570 (4)
C3—H31A	0.9700	P1—F1	1.573 (5)
C3—H32A	0.9700	P1—F4	1.586 (4)
C3—H31B	0.9700
N7—Ni1—N1	101.84 (13)	C3—C2A—H22A	109.7
N7—Ni1—N4	83.67 (13)	N1—C2A—H22A	109.7
N1—Ni1—N4	83.52 (13)	H21A—C2A—H22A	108.2
N7—Ni1—O1	169.86 (11)	N1—C2B—C3	113.1 (8)
N1—Ni1—O1	88.27 (11)	N1—C2B—H21B	109.0
N4—Ni1—O1	96.98 (11)	C3—C2B—H21B	109.0
N7—Ni1—O3w	92.40 (12)	N1—C2B—H22B	109.0
N1—Ni1—O3w	92.81 (14)	C3—C2B—H22B	109.0
N4—Ni1—O3w	173.94 (12)	H21B—C2B—H22B	107.8
O1—Ni1—O3w	87.70 (11)	C3—N4—C5	114.4 (4)
N7—Ni1—O2	90.42 (11)	C3—N4—Ni1	109.6 (3)
N1—Ni1—O2	166.94 (12)	C5—N4—Ni1	107.1 (3)
N4—Ni1—O2	93.51 (12)	C3—N4—H4	108.5
O1—Ni1—O2	79.45 (9)	C5—N4—H4	108.5
O3w—Ni1—O2	91.13 (13)	Ni1—N4—H4	108.5
O1—C1—O2^i	125.5 (3)	N4—C5—C6	110.7 (3)
O1—C1—C1^i	116.9 (3)	N4—C5—H51	109.5
O2^i—C1—C1^i	117.6 (3)	C6—C5—H51	109.5
C1—O1—Ni1	113.35 (19)	N4—C5—H52	109.5
C1^i—O2—Ni1	112.63 (19)	C6—C5—H52	109.5
Ni1—O3w—H31w	117.2 (18)	H51—C5—H52	108.1
Ni1—O3w—H32w	118.5 (12)	N7—C6—C5	109.5 (3)
H31w—O3w—H32w	105 (2)	N7—C6—H61	109.8
C2B—N1—Ni1	111.3 (5)	C5—C6—H61	109.8
C2A—N1—Ni1	103.7 (3)	N7—C6—H62	109.8
C2A—N1—H11A	111.0	C5—C6—H62	109.8
Ni1—N1—H11A	111.0	H61—C6—H62	108.2
C2A—N1—H12A	111.0	C6—N7—Ni1	110.1 (3)
Ni1—N1—H12A	111.0	C6—N7—H71	109.6
H11A—N1—H12A	109.0	Ni1—N7—H71	109.6
C2B—N1—H11B	109.4	C6—N7—H72	109.6
Ni1—N1—H11B	109.4	Ni1—N7—H72	109.6
C2B—N1—H12B	109.4	H71—N7—H72	108.1
Ni1—N1—H12B	109.4	H41w—O4w—H42w	111 (4)
H11B—N1—H12B	108.0	F2—P1—F5	90.9 (4)
C2A—C3—N4	111.8 (4)	F2—P1—F6	89.0 (5)
N4—C3—C2B	115.2 (6)	F5—P1—F6	96.5 (4)
C2A—C3—H31A	109.3	F2—P1—F3	92.5 (4)
N4—C3—H31A	109.3	F5—P1—F3	176.6 (4)
C2A—C3—H32A	109.3	F6—P1—F3	82.8 (3)
N4—C3—H32A	109.3	F2—P1—F1	94.7 (5)
H31A—C3—H32A	107.9	F5—P1—F1	85.7 (4)
N4—C3—H31B	108.5	F6—P1—F1	175.6 (4)
C2B—C3—H31B	108.5	F3—P1—F1	94.8 (4)
N4—C3—H32B	108.5	F2—P1—F4	177.6 (5)
C2B—C3—H32B	108.5	F5—P1—F4	91.5 (3)
H31B—C3—H32B	107.5	F6—P1—F4	91.2 (4)
C3—C2A—N1	110.0 (5)	F3—P1—F4	85.2 (3)
C3—C2A—H21A	109.7	F1—P1—F4	85.0 (3)
N1—C2A—H21A	109.7
O2^i—C1—O1—Ni1	−178.0 (3)	C2A—N1—C2B—C3	−59.6 (9)
C1^i—C1—O1—Ni1	2.0 (4)	Ni1—N1—C2B—C3	25.4 (13)
N7—Ni1—O1—C1	−3.1 (8)	C2A—C3—C2B—N1	62.9 (9)
N1—Ni1—O1—C1	173.2 (2)	N4—C3—C2B—N1	−31.0 (14)
N4—Ni1—O1—C1	90.0 (2)	C2A—C3—N4—C5	−141.9 (5)
O3w—Ni1—O1—C1	−93.9 (2)	C2B—C3—N4—C5	−100.0 (9)
O2—Ni1—O1—C1	−2.3 (2)	C2A—C3—N4—Ni1	−21.6 (6)
N7—Ni1—O2—C1^i	−177.9 (3)	C2B—C3—N4—Ni1	20.3 (9)
N1—Ni1—O2—C1^i	−17.9 (7)	N7—Ni1—N4—C3	−107.5 (3)
N4—Ni1—O2—C1^i	−94.2 (3)	N1—Ni1—N4—C3	−4.8 (3)
O1—Ni1—O2—C1^i	2.2 (2)	O1—Ni1—N4—C3	82.7 (3)
O3w—Ni1—O2—C1^i	89.7 (3)	O2—Ni1—N4—C3	162.5 (3)
N7—Ni1—N1—C2B	70.8 (8)	N7—Ni1—N4—C5	17.2 (3)
N4—Ni1—N1—C2B	−11.3 (8)	N1—Ni1—N4—C5	119.9 (3)
O1—Ni1—N1—C2B	−108.6 (8)	O1—Ni1—N4—C5	−152.6 (3)
O3w—Ni1—N1—C2B	163.8 (8)	O2—Ni1—N4—C5	−72.8 (3)
O2—Ni1—N1—C2B	−88.8 (9)	C3—N4—C5—C6	81.8 (5)
N7—Ni1—N1—C2A	110.0 (3)	Ni1—N4—C5—C6	−40.0 (4)
N4—Ni1—N1—C2A	27.9 (3)	N4—C5—C6—N7	48.7 (5)
O1—Ni1—N1—C2A	−69.3 (3)	C5—C6—N7—Ni1	−32.2 (4)
O3w—Ni1—N1—C2A	−156.9 (3)	N1—Ni1—N7—C6	−73.7 (3)
O2—Ni1—N1—C2A	−49.5 (7)	N4—Ni1—N7—C6	8.3 (3)
N4—C3—C2A—N1	47.6 (7)	O1—Ni1—N7—C6	102.6 (7)
C2B—C3—C2A—N1	−55.9 (8)	O3w—Ni1—N7—C6	−167.1 (3)
C2B—N1—C2A—C3	59.0 (8)	O2—Ni1—N7—C6	101.8 (3)
Ni1—N1—C2A—C3	−48.2 (5)

Symmetry code: (i) −x+1/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3w—H32w···O4w	0.84 (4)	1.79 (4)	2.628 (5)	175.5 (18)
O4w—H41w···O3w^ii	0.72 (4)	2.14 (5)	2.840 (5)	165 (4)
O3w—H31w···F4	0.82 (4)	2.11 (3)	2.926 (6)	168.9 (17)
O4w—H42w···O1^iii	0.76 (4)	2.47 (3)	3.131 (5)	147 (4)
O4w—H42w···O2^iv	0.76 (4)	2.30 (5)	3.019 (4)	158 (3)
N1—H11A···O4w^v	0.90	2.42	3.163 (5)	140
N1—H12A···F6^ii	0.90	2.45	3.256 (7)	150
N1—H12B···F6^ii	0.90	2.49	3.256 (7)	143
N4—H4···F4^i	0.91	2.28	3.187 (7)	174
N7—H71···F5^ii	0.90	2.25	3.106 (6)	158
N7—H72···O2^iv	0.90	2.43	3.285 (4)	159

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