Crystal structure of an unknown solvate of bis­(tetra-n-butyl­ammonium) [N,N′-(4-tri­fluoro­methyl-1,2-phenyl­ene)bis­(oxamato)-κ⁴O,N,N′,O′]nickelate(II)

In the title compound, the Ni²⁺ cation is coordinated by two deprotonated amido N atoms and two carboxyl­ate O atoms, setting up a square-planar coordination environment. The cations and the anion are linked by weak intra- and inter­molecular C—H...O and C—H...F hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 110 K
• Mean [sigma](Wav) = 0.000 Å
• R factor = 0.036
• wR factor = 0.102
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level B
THETM01_ALERT_3_B  The value of sine(theta_max)/wavelength is less than 0.575
            Calculated sin(theta_max)/wavelength =    0.5643

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   0 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   0 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Chemical context

\ Oxamate-bridged polymetallic complexes are of inter­est in the discipline of supra­molecular magnetism as they exhibit diverse supra­molecular architectures and magnetic properties (Pardo et al., 2008; Kahn, 1987, 2000) and have been synthesized by, for example, Ruiz et al. (1997a,b), Berg et al. (2002), Martín et al. (2002) and Ottenwaelder et al. (2005). Over the last decade, we have been inter­ested in the synthesis of bis­(oxamates) and bis­(oxamate) complexes (Rüffer et al., 2007a,b, 2008, 2009; Eya'ane Meva et al., 2012), as well as their deposition as thin films (Bräuer et al., 2006, 2008, 2009). In order to optimize the deposition conditions and to increase the thin-film quality, the monometallic title compound, bis­(tetra-n-butyl­ammonium) [N,N'-(4-tri­fluoro­methyl-1,2-phenyl­ene)bis­(oxamato)-\ κ⁴O,N,N',O']nickelate(II), (I), was prepared. The complex includes four sites of coordination and a CF₃ group which provides a good solubility in organic solvents.

S2. Structural commentary

The asymmetric unit of compound (I) contains one [N(n-Bu)₄]⁺ cation and half of the complex anion [Ni(topbo)]^2– (Fig. 1). The anion possesses point-group symmetry 2. This imposes orientational disorder of the CF₃ group, which lies on both sides of the twofold rotation axis with 0.5 occupancy. The anion is essentially planar (root-mean-square deviation 0.145 Å), the highest deviation from planarity being observed for C6 [0.440 (5) Å]. The Ni²⁺ cation is coordinated by two deprotonated amido N atoms and two carboxyl­ate O atoms, resulting in a slightly distorted square-planar coordination geometry. In agreement with related nickel compounds, the Ni—N bonds are significantly shorter than the Ni—O bonds, which is due to the stronger donicity of the amido nitro­gens (Fettouhi et al., 1996; Rüffer et al., 2007a,b, 2008; Abdulmalic et al., 2013; Milek et al., 2013). Compared to the respective nickel complex without the CF₃ group (Abdulmalic et al., 2013), compound (I) exhibits longer Ni—N and Ni—O bonds. It is instructive to note that for other complexes, the presence of electron-withdrawing substituents at the benzene moiety, e.g. Cl, NO₂, causes a shortening of the Ni—N and Ni—O bonds (Fettouhi et al., 1996; Rüffer et al., 2008).

S3. Supra­molecular features

Five weak C—H···O and one weak C—H···F hydrogen bonds (Steiner, 2002) are observed in the crystal structure of (I) (Table 1), which connect the [N(n-Bu)₄]⁺ cations and the [Ni(topbo)]^2– anion, forming a three-dimensional network (Fig. 2).

S4. Synthesis and crystallization

4-Tri­fluoro­methyl-1,2-phenyl­enebis(ethyl oxamate) was prepared from ethyl oxalyl chloride and 4-tri­fluoro­methyl-1,2-phenyl­enedi­amine in analogy to Cervera et al. (1998). To a solution of 4-tri­fluoro­methyl-1,2-phenyl­enedi­amine (0.4 g, 2.22 mmol) dissolved in tetra­hydro­furan (50 ml) was added dropwise via a dropping funnel a solution of ethyl oxalyl chloride (5.05 g, 4.45 mmol) in tetra­hydro­furan (25 ml) within 20 min. The resulting mixture was refluxed for 30 min at 343 K, filtrated and concentrated to about one third on a rotary evaporator. The careful addition of water resulted in the precipitation of a brown solid which was filtered off and dried in air.

To a solution of 4-tri­fluoro­methyl-1,2-phenyl­enebis(ethyl oxamate) (0.4 g, 1.06 mmol) in ethanol (40 ml) was added dropwise under stirring [N(n-Bu)₄]OH (2.76 g, 4.25 mmol, 40 wt-% aqueous solution) in water (20 ml); the resulting mixture was refluxed for 30 min. After cooling to room temperature, an aqueous solution (20 ml) of NiCl₂·6H₂O (0.25 g, 1.05 mmol) was added dropwise under stirring. The yellow solution was filtered, concentrated to a volume of 20 ml on a rotatory evaporator, and extracted with di­chloro­methane (100 ml). The organic layer was separated, washed with water (3 x 25 ml) dried over Na₂SO₄ and concentrated to a volume of 10 ml. The title compound was precipitated by adding Et₂O (100 ml). The yellow solid was filtered off, washed with Et₂O and dried in air. Single crystals were obtained by the slow diffusion of Et₂O into a saturated solution of the title compound in CH₂Cl₂/thf (1:1).

The overall synthetic procedure is schematically shown in Fig. 3.

S5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. C-bonded H atoms were placed in calculated positions and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C) and a C—H distance of 0.93 Å for aromatic and 0.97 Å for methyl­ene protons as well as U_iso(H) = 1.5U_eq(C) and a C—H distance of 0.96 Å for methyl protons.

A small region of electron density at a distance of 1.6–3.7 Å from the tri­fluoro­methyl group indicates the presence of a disordered solvent molecule. All attempts to model a disordered tetra­hydro­furan, di­chloro­methane or di­ethyl ether molecule (solvents used for crystallization) failed. Therefore, the solvent contributions have been removed using the SQUEEZE procedure in PLATON (Spek, 2015). SQUEEZE calculated a void volume of approximately 310 ų occupied by 24 electrons per unit cell. Fig. 2 shows the positions of the voids within the unit cell.

Related literature

For related literature, see: Abdulmalic et al. (2013pp); Berg et al. (2002pp); Bräuer et al. (2006pp, 2008p, 2009p); Cervera et al. (1998pp); Eya'ane Meva, Schaarschmidt, Abdulmalic & Rüffer (2012); Fettouhi et al. (1996pp); Kahn (1987pxpx, 2000p); Martín et al. (2002); Milek et al. (2013pp); Ottenwaelder et al. (2005pp); Pardo et al. (2008pp); Rüffer et al. (2008pp, 2009p); Rüffer, Bräuer, Eya'ane Meva, Walfort, Salvan, Powell, Hewitt, Sorace & Caneschi (2007); Rüffer, Bräuer, Powell, Hewitt & Salvan (2007); Ruiz, Surville-Barland, Aukauloo, Anxolabehere-Mallart, Journaux, Cano & Muñoz (1997); Ruiz, Triannidis, Aukauloo, Journaux, Fernández, Pedro, Cervera, Castro & Muñoz (1997); Spek (2009); Steiner (2002pp).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012), publCIF (Westrip, 2010) and SQUEEZE (Spek, 2015).

Figures

	Fig. 1. The molecular components of (I) drawn with displacement ellipsoids at the 50% probability level. H atoms were omitted for clarity. Only one disordered part of the –CF3 group is shown. [Symmetry code: (A) -x + 2, y, -z + 3/2.]
	Fig. 2. Packing diagram of compound (I), with voids in the structure represented by yellow spheres [drawn using the CAVITYPLOT routine in PLATON (Spek, 2009)]. H atoms are omitted for clarity. Color code: black (C), blue (N), red (O), green (F), purple (Ni).
	Fig. 3. Scheme representing the synthesis of compound (I).

Bis(tetra-n-butylammonium) [N,N'-(4-trifluoromethyl-1,2-phenylene)bis(oxamato)-κ⁴O,N,N',O']nickelate(II)

Crystal data

(C16H36N)2[Ni(C11H3F3N2O6)]	F(000) = 1856
Mr = 859.78	Dx = 1.193 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
a = 19.5285 (3) Å	Cell parameters from 5954 reflections
b = 17.3370 (3) Å	θ = 4.5–60.4°
c = 14.1484 (3) Å	µ = 1.06 mm^−1
β = 92.136 (2)°	T = 110 K
V = 4786.83 (15) Å^3	Block, orange
Z = 4	0.1 × 0.08 × 0.06 mm

Data collection

Oxford Gemini S diffractometer	Rint = 0.023
ω scans	θmax = 60.5°, θmin = 3.4°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	h = −21→21
Tmin = 0.807, Tmax = 1.000	k = −19→19
15600 measured reflections	l = −15→15
3545 independent reflections	2 standard reflections every 25 reflections
3142 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.0577P)^2 + 2.8029P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
3545 reflections	Δρmax = 0.32 e Å^−3
277 parameters	Δρmin = −0.20 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.88594 (10)	0.35368 (11)	0.65544 (14)	0.0356 (5)
C2	0.88021 (10)	0.44362 (12)	0.65187 (14)	0.0370 (5)
C3	0.96883 (10)	0.25942 (11)	0.72161 (15)	0.0371 (4)
C4	0.94040 (11)	0.18979 (12)	0.69174 (16)	0.0454 (5)
H4	0.9011	0.1893	0.6525	0.055*
C5	0.97086 (14)	0.12088 (13)	0.72067 (18)	0.0566 (6)
H5	0.9519	0.0743	0.7004	0.068*	0.5
C7	0.68930 (10)	0.16654 (11)	0.76809 (14)	0.0363 (4)
H7A	0.6668	0.2105	0.7958	0.044*
H7B	0.6729	0.1207	0.7993	0.044*
C8	0.76537 (10)	0.17349 (11)	0.79037 (14)	0.0386 (5)
H8A	0.7821	0.2220	0.7661	0.046*
H8B	0.7895	0.1319	0.7600	0.046*
C9	0.77901 (12)	0.16984 (13)	0.89696 (15)	0.0466 (5)
H9A	0.7528	0.2100	0.9267	0.056*
H9B	0.7631	0.1206	0.9201	0.056*
C10	0.85411 (13)	0.17956 (14)	0.92587 (17)	0.0567 (6)
H10A	0.8596	0.1768	0.9935	0.085*
H10B	0.8699	0.2288	0.9045	0.085*
H10C	0.8803	0.1393	0.8979	0.085*
C11	0.68357 (10)	0.23650 (11)	0.61193 (14)	0.0356 (4)
H11A	0.7321	0.2469	0.6224	0.043*
H11B	0.6756	0.2277	0.5447	0.043*
C12	0.64405 (11)	0.30812 (11)	0.63902 (16)	0.0412 (5)
H12A	0.6507	0.3180	0.7062	0.049*
H12B	0.5955	0.3006	0.6252	0.049*
C13	0.67014 (11)	0.37655 (12)	0.58245 (17)	0.0466 (5)
H13A	0.7196	0.3798	0.5912	0.056*
H13B	0.6596	0.3679	0.5157	0.056*
C14	0.63858 (16)	0.45253 (15)	0.6120 (2)	0.0789 (9)
H14A	0.6558	0.4935	0.5739	0.118*
H14B	0.6503	0.4623	0.6774	0.118*
H14C	0.5897	0.4498	0.6032	0.118*
C15	0.59008 (10)	0.14707 (11)	0.66235 (14)	0.0358 (4)
H15A	0.5822	0.1001	0.6975	0.043*
H15B	0.5684	0.1889	0.6956	0.043*
C16	0.55475 (10)	0.13920 (11)	0.56594 (14)	0.0378 (5)
H16A	0.5698	0.0922	0.5358	0.045*
H16B	0.5668	0.1825	0.5265	0.045*
C17	0.47760 (10)	0.13688 (13)	0.57613 (16)	0.0445 (5)
H17A	0.4669	0.0999	0.6248	0.053*
H17B	0.4622	0.1872	0.5966	0.053*
C18	0.43874 (11)	0.11520 (15)	0.48520 (17)	0.0532 (6)
H18A	0.3905	0.1147	0.4958	0.080*
H18B	0.4529	0.0649	0.4653	0.080*
H18C	0.4483	0.1522	0.4370	0.080*
C19	0.70443 (10)	0.09850 (10)	0.61375 (14)	0.0348 (4)
H19A	0.6871	0.0961	0.5487	0.042*
H19B	0.7526	0.1121	0.6128	0.042*
C20	0.69831 (11)	0.01936 (11)	0.65738 (15)	0.0390 (5)
H20A	0.6509	0.0027	0.6530	0.047*
H20B	0.7124	0.0217	0.7238	0.047*
C21	0.74277 (12)	−0.03850 (12)	0.60717 (17)	0.0497 (6)
H21A	0.7284	−0.0410	0.5409	0.060*
H21B	0.7901	−0.0214	0.6111	0.060*
C22	0.73766 (14)	−0.11826 (13)	0.65073 (17)	0.0544 (6)
H22A	0.7661	−0.1535	0.6176	0.082*
H22B	0.6909	−0.1356	0.6461	0.082*
H22C	0.7527	−0.1161	0.7161	0.082*
N1	0.94347 (8)	0.33319 (9)	0.70205 (12)	0.0356 (4)
N2	0.66664 (8)	0.16218 (9)	0.66403 (11)	0.0338 (4)
O1	0.84134 (7)	0.31211 (8)	0.61726 (10)	0.0410 (3)
O2	0.92921 (7)	0.48170 (7)	0.69564 (10)	0.0391 (3)
O3	0.83119 (7)	0.47330 (8)	0.60942 (10)	0.0445 (4)
C6	0.9520 (2)	0.0478 (2)	0.6727 (4)	0.0499 (11)	0.5
F1	0.88379 (14)	0.04371 (15)	0.6729 (3)	0.0760 (9)	0.5
F2	0.96828 (17)	0.03869 (15)	0.5806 (2)	0.0698 (8)	0.5
F3	0.97597 (13)	−0.01539 (13)	0.7165 (2)	0.0581 (7)	0.5
Ni1	1.0000	0.41486 (2)	0.7500	0.02432 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0395 (11)	0.0420 (11)	0.0257 (11)	0.0005 (9)	0.0080 (8)	0.0002 (8)
C2	0.0439 (11)	0.0423 (11)	0.0253 (11)	0.0022 (9)	0.0080 (9)	0.0001 (9)
C3	0.0452 (10)	0.0352 (10)	0.0312 (11)	0.0002 (8)	0.0084 (8)	0.0005 (8)
C4	0.0555 (13)	0.0409 (12)	0.0397 (13)	−0.0012 (9)	−0.0016 (10)	−0.0032 (9)
C5	0.0773 (16)	0.0352 (11)	0.0563 (15)	−0.0023 (11)	−0.0124 (12)	−0.0044 (11)
C7	0.0501 (11)	0.0329 (10)	0.0264 (11)	−0.0015 (8)	0.0098 (9)	−0.0003 (8)
C8	0.0516 (12)	0.0328 (10)	0.0318 (12)	−0.0029 (8)	0.0068 (9)	−0.0016 (8)
C9	0.0641 (14)	0.0428 (12)	0.0328 (13)	−0.0020 (10)	0.0028 (10)	0.0022 (9)
C10	0.0729 (16)	0.0570 (14)	0.0396 (14)	−0.0056 (12)	−0.0062 (11)	0.0000 (11)
C11	0.0407 (10)	0.0342 (10)	0.0322 (12)	−0.0057 (8)	0.0073 (8)	0.0031 (8)
C12	0.0496 (12)	0.0362 (11)	0.0384 (13)	−0.0024 (9)	0.0106 (9)	0.0017 (9)
C13	0.0521 (12)	0.0381 (11)	0.0505 (14)	−0.0008 (9)	0.0113 (10)	0.0080 (10)
C14	0.097 (2)	0.0411 (14)	0.101 (3)	0.0092 (14)	0.0333 (18)	0.0174 (14)
C15	0.0406 (11)	0.0334 (10)	0.0342 (12)	−0.0024 (8)	0.0120 (8)	−0.0008 (8)
C16	0.0434 (11)	0.0360 (10)	0.0348 (12)	−0.0025 (8)	0.0108 (9)	−0.0011 (8)
C17	0.0429 (11)	0.0479 (12)	0.0435 (13)	−0.0054 (9)	0.0114 (9)	0.0027 (10)
C18	0.0421 (12)	0.0666 (15)	0.0510 (15)	−0.0062 (10)	0.0040 (10)	0.0046 (11)
C19	0.0404 (10)	0.0342 (10)	0.0303 (11)	−0.0004 (8)	0.0087 (8)	−0.0038 (8)
C20	0.0500 (12)	0.0366 (10)	0.0309 (12)	−0.0019 (9)	0.0079 (9)	−0.0030 (8)
C21	0.0631 (14)	0.0442 (12)	0.0427 (14)	0.0123 (10)	0.0124 (11)	0.0008 (10)
C22	0.0783 (16)	0.0412 (12)	0.0437 (14)	0.0138 (11)	0.0028 (12)	−0.0010 (10)
N1	0.0391 (9)	0.0356 (9)	0.0324 (10)	−0.0001 (7)	0.0047 (7)	−0.0002 (7)
N2	0.0427 (9)	0.0326 (8)	0.0266 (9)	−0.0030 (7)	0.0096 (7)	−0.0009 (6)
O1	0.0432 (8)	0.0456 (8)	0.0344 (8)	−0.0040 (6)	0.0030 (6)	−0.0010 (6)
O2	0.0435 (7)	0.0365 (7)	0.0376 (8)	0.0027 (6)	0.0048 (6)	−0.0005 (6)
O3	0.0485 (8)	0.0476 (8)	0.0373 (9)	0.0078 (7)	0.0012 (7)	0.0029 (6)
C6	0.050 (3)	0.037 (2)	0.062 (3)	0.0017 (19)	0.004 (2)	−0.004 (2)
F1	0.0477 (16)	0.0465 (15)	0.134 (3)	−0.0011 (12)	0.0005 (16)	−0.0231 (17)
F2	0.100 (2)	0.0521 (16)	0.0572 (19)	0.0026 (15)	−0.0005 (16)	−0.0133 (14)
F3	0.0630 (17)	0.0351 (13)	0.076 (2)	0.0013 (11)	0.0042 (12)	0.0005 (12)
Ni1	0.0293 (2)	0.0226 (2)	0.0215 (3)	0.000	0.00539 (16)	0.000

Geometric parameters (Å, º)

C1—O1	1.239 (2)	C14—H14B	0.9600
C1—N1	1.330 (3)	C14—H14C	0.9600
C1—C2	1.564 (3)	C15—C16	1.512 (3)
C2—O3	1.224 (2)	C15—N2	1.517 (2)
C2—O2	1.300 (2)	C15—H15A	0.9700
C3—C4	1.388 (3)	C15—H15B	0.9700
C3—N1	1.396 (2)	C16—C17	1.519 (3)
C3—C3^i	1.433 (4)	C16—H16A	0.9700
C4—C5	1.389 (3)	C16—H16B	0.9700
C4—H4	0.9300	C17—C18	1.516 (3)
C5—C5^i	1.383 (5)	C17—H17A	0.9700
C5—H5	0.9300	C17—H17B	0.9700
C7—C8	1.512 (3)	C18—H18A	0.9600
C7—N2	1.523 (2)	C18—H18B	0.9600
C7—H7A	0.9700	C18—H18C	0.9600
C7—H7B	0.9700	C19—C20	1.511 (3)
C8—C9	1.523 (3)	C19—N2	1.519 (2)
C8—H8A	0.9700	C19—H19A	0.9700
C8—H8B	0.9700	C19—H19B	0.9700
C9—C10	1.517 (3)	C20—C21	1.520 (3)
C9—H9A	0.9700	C20—H20A	0.9700
C9—H9B	0.9700	C20—H20B	0.9700
C10—H10A	0.9600	C21—C22	1.519 (3)
C10—H10B	0.9600	C21—H21A	0.9700
C10—H10C	0.9600	C21—H21B	0.9700
C11—C12	1.519 (3)	C22—H22A	0.9600
C11—N2	1.527 (2)	C22—H22B	0.9600
C11—H11A	0.9700	C22—H22C	0.9600
C11—H11B	0.9700	N1—Ni1	1.9047 (16)
C12—C13	1.529 (3)	O2—Ni1	1.9407 (13)
C12—H12A	0.9700	C6—F1	1.333 (5)
C12—H12B	0.9700	C6—F3	1.335 (5)
C13—C14	1.519 (3)	C6—F2	1.361 (6)
C13—H13A	0.9700	F3—F3^i	1.308 (5)
C13—H13B	0.9700	Ni1—N1^i	1.9047 (16)
C14—H14A	0.9600	Ni1—O2^i	1.9408 (13)
O1—C1—N1	128.92 (18)	C16—C15—H15B	108.2
O1—C1—C2	121.17 (17)	N2—C15—H15B	108.2
N1—C1—C2	109.91 (16)	H15A—C15—H15B	107.3
O3—C2—O2	124.63 (18)	C15—C16—C17	109.73 (16)
O3—C2—C1	119.25 (18)	C15—C16—H16A	109.7
O2—C2—C1	116.12 (16)	C17—C16—H16A	109.7
C4—C3—N1	127.00 (19)	C15—C16—H16B	109.7
C4—C3—C3^i	119.50 (12)	C17—C16—H16B	109.7
N1—C3—C3^i	113.51 (11)	H16A—C16—H16B	108.2
C3—C4—C5	119.7 (2)	C18—C17—C16	113.12 (18)
C3—C4—H4	120.1	C18—C17—H17A	109.0
C5—C4—H4	120.1	C16—C17—H17A	109.0
C5^i—C5—C4	120.69 (13)	C18—C17—H17B	109.0
C5^i—C5—H5	119.7	C16—C17—H17B	109.0
C4—C5—H5	119.7	H17A—C17—H17B	107.8
C8—C7—N2	116.96 (15)	C17—C18—H18A	109.5
C8—C7—H7A	108.1	C17—C18—H18B	109.5
N2—C7—H7A	108.1	H18A—C18—H18B	109.5
C8—C7—H7B	108.1	C17—C18—H18C	109.5
N2—C7—H7B	108.1	H18A—C18—H18C	109.5
H7A—C7—H7B	107.3	H18B—C18—H18C	109.5
C7—C8—C9	109.72 (16)	C20—C19—N2	114.92 (16)
C7—C8—H8A	109.7	C20—C19—H19A	108.5
C9—C8—H8A	109.7	N2—C19—H19A	108.5
C7—C8—H8B	109.7	C20—C19—H19B	108.5
C9—C8—H8B	109.7	N2—C19—H19B	108.5
H8A—C8—H8B	108.2	H19A—C19—H19B	107.5
C10—C9—C8	113.21 (18)	C19—C20—C21	110.68 (17)
C10—C9—H9A	108.9	C19—C20—H20A	109.5
C8—C9—H9A	108.9	C21—C20—H20A	109.5
C10—C9—H9B	108.9	C19—C20—H20B	109.5
C8—C9—H9B	108.9	C21—C20—H20B	109.5
H9A—C9—H9B	107.8	H20A—C20—H20B	108.1
C9—C10—H10A	109.5	C22—C21—C20	111.33 (18)
C9—C10—H10B	109.5	C22—C21—H21A	109.4
H10A—C10—H10B	109.5	C20—C21—H21A	109.4
C9—C10—H10C	109.5	C22—C21—H21B	109.4
H10A—C10—H10C	109.5	C20—C21—H21B	109.4
H10B—C10—H10C	109.5	H21A—C21—H21B	108.0
C12—C11—N2	116.55 (16)	C21—C22—H22A	109.5
C12—C11—H11A	108.2	C21—C22—H22B	109.5
N2—C11—H11A	108.2	H22A—C22—H22B	109.5
C12—C11—H11B	108.2	C21—C22—H22C	109.5
N2—C11—H11B	108.2	H22A—C22—H22C	109.5
H11A—C11—H11B	107.3	H22B—C22—H22C	109.5
C11—C12—C13	108.66 (17)	C1—N1—C3	129.06 (17)
C11—C12—H12A	110.0	C1—N1—Ni1	116.48 (13)
C13—C12—H12A	110.0	C3—N1—Ni1	114.46 (13)
C11—C12—H12B	110.0	C15—N2—C19	111.27 (14)
C13—C12—H12B	110.0	C15—N2—C7	105.92 (14)
H12A—C12—H12B	108.3	C19—N2—C7	111.10 (14)
C14—C13—C12	112.47 (19)	C15—N2—C11	111.66 (14)
C14—C13—H13A	109.1	C19—N2—C11	105.63 (14)
C12—C13—H13A	109.1	C7—N2—C11	111.37 (14)
C14—C13—H13B	109.1	C2—O2—Ni1	112.72 (12)
C12—C13—H13B	109.1	F1—C6—F3	106.8 (4)
H13A—C13—H13B	107.8	F1—C6—F2	105.4 (4)
C13—C14—H14A	109.5	F3—C6—F2	105.0 (4)
C13—C14—H14B	109.5	F3^i—F3—C6	124.5 (2)
H14A—C14—H14B	109.5	N1^i—Ni1—N1	83.96 (9)
C13—C14—H14C	109.5	N1^i—Ni1—O2	168.49 (6)
H14A—C14—H14C	109.5	N1—Ni1—O2	84.71 (6)
H14B—C14—H14C	109.5	N1^i—Ni1—O2^i	84.72 (6)
C16—C15—N2	116.49 (15)	N1—Ni1—O2^i	168.49 (6)
C16—C15—H15A	108.2	O2—Ni1—O2^i	106.67 (8)
N2—C15—H15A	108.2
O1—C1—C2—O3	−1.0 (3)	C3^i—C3—N1—C1	−176.8 (2)
N1—C1—C2—O3	178.08 (18)	C4—C3—N1—Ni1	−176.64 (18)
O1—C1—C2—O2	178.84 (17)	C3^i—C3—N1—Ni1	3.0 (3)
N1—C1—C2—O2	−2.0 (2)	C16—C15—N2—C19	−58.4 (2)
N1—C3—C4—C5	−177.5 (2)	C16—C15—N2—C7	−179.28 (16)
C3^i—C3—C4—C5	2.9 (4)	C16—C15—N2—C11	59.3 (2)
C3—C4—C5—C5^i	0.3 (5)	C20—C19—N2—C15	−62.1 (2)
N2—C7—C8—C9	−174.95 (15)	C20—C19—N2—C7	55.7 (2)
C7—C8—C9—C10	−177.74 (18)	C20—C19—N2—C11	176.60 (16)
N2—C11—C12—C13	177.74 (17)	C8—C7—N2—C15	174.15 (16)
C11—C12—C13—C14	−174.2 (2)	C8—C7—N2—C19	53.2 (2)
N2—C15—C16—C17	−171.21 (16)	C8—C7—N2—C11	−64.3 (2)
C15—C16—C17—C18	−169.98 (18)	C12—C11—N2—C15	50.4 (2)
N2—C19—C20—C21	−175.07 (17)	C12—C11—N2—C19	171.52 (17)
C19—C20—C21—C22	179.53 (19)	C12—C11—N2—C7	−67.8 (2)
O1—C1—N1—C3	−0.8 (3)	O3—C2—O2—Ni1	−177.48 (16)
C2—C1—N1—C3	−179.87 (18)	C1—C2—O2—Ni1	2.7 (2)
O1—C1—N1—Ni1	179.39 (16)	F1—C6—F3—F3^i	−131.6 (5)
C2—C1—N1—Ni1	0.4 (2)	F2—C6—F3—F3^i	116.8 (5)
C4—C3—N1—C1	3.6 (3)

Symmetry code: (i) −x+2, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O1	0.97	2.42	3.347 (2)	160
C11—H11B···O1^ii	0.97	2.40	3.368 (2)	172
C15—H15A···O2^iii	0.97	2.56	3.529 (2)	174
C17—H17A···O2^iv	0.97	2.41	3.333 (3)	159
C19—H19A···O3^ii	0.97	2.55	3.441 (2)	152
C21—H21B···F1	0.97	2.29	3.208 (4)	156

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