Crystal structure of an unknown solvate of bis-(tetra-n-butyl-ammonium) [N,N'-(4-tri-fluoro-methyl-1,2-phenyl-ene)bis-(oxamato)-κ(4) O,N,N',O']nickelate(II).

In the title compound, [N(C4H9)4]2[Ni(C11H3F3N2O6)] or [N(n-Bu)4]2[Ni(topbo)] [n-Bu = n-butyl and topbo = 4-tri-fluoro-methyl-1,2-phenyl-enebis(oxamate)], the Ni(2+) cation is coordinated by two deprotonated amido N atoms and two carboxyl-ate O atoms, setting up a slightly distorted square-planar coordination environment. The [Ni(topbo](2-) anion lies on a twofold rotation axis. Due to an incompatibility with the point-group symmetry of the complete mol-ecule, orientational disorder of the CF3 group is observed. The tetra-hedral ammonium cations and the anion are linked by weak inter-molecular C-H⋯O and C-H⋯F hydrogen-bonding inter-actions into a three-dimensional network. A region of electron density was treated with the SQUEEZE procedure in PLATON [Spek (2015). Acta Cryst. C71, 9-18] following unsuccessful attempts to model it as plausible solvent mol-ecule(s). The given chemical formula and other crystal data do not take into account the unknown solvent mol-ecule.

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)-κ4 O,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.

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 ▸).

Figure 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 + .]

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. A packing diagram is shown in Fig. 2 ▸.

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C11H11AO1	0.97	2.42	3.347(2)	160
C11H11BO1i	0.97	2.40	3.368(2)	172
C15H15AO2ii	0.97	2.56	3.529(2)	174
C17H17AO2iii	0.97	2.41	3.333(3)	159
C19H19AO3i	0.97	2.55	3.441(2)	152
C21H21BF1	0.97	2.29	3.208(4)	156

Symmetry codes: (i) ; (ii) ; (iii) .

Figure 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).

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 ▸.

Figure 3

Scheme representing the synthesis of compound (I).

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.

Table 2

Experimental details

Crystal data
Chemical formula	(C16H36N)2[Ni(C11H3F3N2O6)]
M r	859.78
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	110
a, b, c ()	19.5285(3), 17.3370(3), 14.1484(3)
()	92.136(2)
V (3)	4786.83(15)
Z	4
Radiation type	Cu K
(mm1)	1.06
Crystal size (mm)	0.10 0.08 0.06
Data collection
Diffractometer	Oxford Gemini S
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2006 ▸)
T min, T max	0.807, 1.000
No. of measured, independent and observed [I > 2(I)] reflections	15600, 3545, 3142
R int	0.023
max ()	60.5
(sin /)max (1)	0.564
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.036, 0.102, 1.09
No. of reflections	3545
No. of parameters	277
H-atom treatment	H-atom parameters constrained
max, min (e 3)	0.32, 0.20

Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2006 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2013 (Sheldrick, 2015b ▸), SHELXTL (Sheldrick, 2008 ▸), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ▸), PLATON (Spek, 2009 ▸), publCIF (Westrip, 2010 ▸) and SQUEEZE (Spek, 2015 ▸).

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 Å3 occupied by 24 electrons per unit cell. Fig. 2 ▸ shows the positions of the voids within the unit cell.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S205698901500835X/wm5144sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500835X/wm5144Isup2.hkl

CCDC reference: 1062184

Additional supporting information: crystallographic information; 3D view; checkCIF report

(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) Å3	Block, orange
Z = 4	0.1 × 0.08 × 0.06 mm

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 on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036	H-atom parameters constrained
wR(F2) = 0.102	w = 1/[σ2(Fo2) + (0.0577P)2 + 2.8029P] where P = (Fo2 + 2Fc2)/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

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.

	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)

	U11	U22	U33	U12	U13	U23
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

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—C3i	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—C5i	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—F3i	1.308 (5)
C13—H13B	0.9700	Ni1—N1i	1.9047 (16)
C14—H14A	0.9600	Ni1—O2i	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—C3i	119.50 (12)	C17—C16—H16B	109.7
N1—C3—C3i	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
C5i—C5—C4	120.69 (13)	C18—C17—H17B	109.0
C5i—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	F3i—F3—C6	124.5 (2)
H14A—C14—H14B	109.5	N1i—Ni1—N1	83.96 (9)
C13—C14—H14C	109.5	N1i—Ni1—O2	168.49 (6)
H14A—C14—H14C	109.5	N1—Ni1—O2	84.71 (6)
H14B—C14—H14C	109.5	N1i—Ni1—O2i	84.72 (6)
C16—C15—N2	116.49 (15)	N1—Ni1—O2i	168.49 (6)
C16—C15—H15A	108.2	O2—Ni1—O2i	106.67 (8)
N2—C15—H15A	108.2
O1—C1—C2—O3	−1.0 (3)	C3i—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)	C3i—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)
C3i—C3—C4—C5	2.9 (4)	C16—C15—N2—C11	59.3 (2)
C3—C4—C5—C5i	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—F3i	−131.6 (5)
C2—C1—N1—Ni1	0.4 (2)	F2—C6—F3—F3i	116.8 (5)
C4—C3—N1—C1	3.6 (3)

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···O1ii	0.97	2.40	3.368 (2)	172
C15—H15A···O2iii	0.97	2.56	3.529 (2)	174
C17—H17A···O2iv	0.97	2.41	3.333 (3)	159
C19—H19A···O3ii	0.97	2.55	3.441 (2)	152
C21—H21B···F1	0.97	2.29	3.208 (4)	156