A benzene-rich pseudopolymorph of bis­[μ-1,3-bis­(penta­fluoro­phen­yl)­prop­ane-1,3-dionato]-κ³O,O′:O′;κ³O:O,O′-bis­{aqua­[1,3-bis­(penta­fluoro­phen­yl)propane-1,3-dionato-κ²O,O′]nickel(II)} benzene tetra­solvate

The title complex comprises two Ni²⁺ ions, four fluorinated ligands and two water mol­ecules in a centrosymmetric dinuclear complex. This compound was crystallized from benzene–CH₂Cl₂, and two types of crystals, viz. the title benzene tetra­solvate, [Ni₂(C₁₅HF₁₀O₂)₄(H₂O)₂]·4C₆H₆, (I), and the previously reported benzene disolvate, [Ni₂(C₁₅HF₁₀O₂)₄(H₂O)₂]·2C₆H₆, (II) [Hori et al. (2009). Bull. Chem. Soc. Jpn, 82, 96–98], were obtained as pseudopolymorphs. In the crystal structure of (I), the four benzene solvent mol­ecules inter­act closely with all the penta­fluoro­phenyl groups of the complex through arene–perfluoro­arene inter­actions. The mol­ecular structures of the two compounds show essentially the same conformation, although the benzene mol­ecules are accommodated in a columnar packing in (I), while they are isolated from each other in (II).

S1. Comment

Coordination complexes with dibenzoylmethane (dbm) and transition metals (M = Co^II, Ni^II, Cu^II or Pd^II) form isomorphs of the flat mononuclear complex M(dbm)₂ (Vigato et al., 2009; Soldatov et al., 2001). While single crystals of M(dbm)₂ have no crystallization solvent molecules, coordination complexes of bis(pentafluorophenyl)propane-1,3-dione (L), which is fully fluorinated dbm, produce unique crystals which take in benzene molecules abundantly when crystallized from a benzene–CH₂Cl₂ solvent mixture (Hori & Arii, 2007, Hori et al., 2009). For example, single crystals of [Cu(L)₂] were obtained as [Cu(L)₂].3C₆H₆ with 21 wt% benzene molecules. Complexation of L and Ni^II ions gave a dinuclear nickel(II) complex, and single crystals were obtained as [Ni₂(L)₄(H₂O)₂].2C₆H₆, (II), with 8 wt% benzene molecules. These high capacities for solvent occlusion are explained by the arene–perfluoroarene interaction, which is currently well known as an electrostatic interaction (Patrick & Prosser, 1960; Williams, 1993), between the pentafluorophenyl groups of the complex and the benzene molecules. In the crystal structure of (II) (Hori et al., 2009), however, the pentafluorophenyl groups are in close contact not only with benzene molecules, but also with other pentafluorophenyl groups by π–π stacking.

During detailed analysis of a series of complexes showing arene–perfluoroarene interactions, we accidentally found the title unique pseudopolymorph example of [Ni₂(L)₄(H₂O)₂].4C₆H₆, (I), with 15 wt% benzene molecules. Four benzene molecules are included in one complex unit. In this study, the two crystal forms, (I) and (II), are compared and discussed in relation to the arene–perfluoroarene interaction.

Two types of green crystals were obtained from a benzene–CH₂Cl₂ mixture. The shapes of the crystals were mainly blocks, but a few crystals showed prismatic forms. Most crystals were monoclinic, P2₁/n, a = 11.5848 (5) Å, b = 16.1079 (6) Å, c = 18.0508 (7) Å, β = 99.0500 (10)°, V = 3326.5 (2) ų and Z = 2, which are the cell parameters of [Ni₂(L)₄(H₂O)₂].2C₆H₆, (II). However, we found a crystal with different parameters, namely triclinic, P1, a = 12.0236 (13) Å, b = 12.4384 (14) Å, c = 14.0058 (15) Å, α = 82.9800 (10)°, β = 73.4110 (10)°, γ = 74.5360 (10)°, V = 1932.4 (4) ų, and Z = 1. This is a benzene-rich pseudopolymorph of [Ni₂(L)₄(H₂O)₂].4C₆H₆, (I). Unfortunately, we could not control the ratio of the products to isolate (I).

The structure of the entire complex and the surrounding benzene molecules of (I) is shown in Fig. 1. The asymmetric unit contains one-half of the complex, one whole benzene molecule (C31–C36, benzene-1), and two half-benzene molecules (C37–C39, benzene-2; C40–C42, benzene-3). The complex is centrosymmetric and comprises two Ni^II ions, four L ligands and two water molecules to give a dinuclear nickel(II) complex. The compositions of the complexes in (I) and (II) are exactly the same. The same coordination mode exhibited by these complexes is also known for Ni^II ions and acetylacetonate ligands (Tahir et al., 2007). The geometries around the metal centres are pseudo-octahedral. The metal–metal separations are 3.115 Å in (I) and 3.139 Å in (II). The Ni1—O1, Ni1—O2, Ni1—O3, Ni1—O4 and Ni1—O4ⁱ [symmetry code: (i) -x, -y + 1, -z in (I) and -x + 1, -y, -z in (II)] distances are 1.9804 (13), 1.9974 (13), 2.0003 (13), 2.0401 (13) and 2.0922 (13) Å for (I), and 1.9842 (11), 2.0138 (12), 2.0087 (12), 2.0231 (11) and 2.1224 (12) Å for (II), respectively. The Ni1—O5_water distances in (I) and (II) are 2.0854 (14) and 2.0829 (13) Å, respectively. The O═C bond distances of (I) and (II) are very close to each other: O1—C7 = 1.267 (2), O2—C9 = 1.278 (2), O3—C22 = 1.251 (2) and O4—C24 = 1.288 (2) Å for (I); O1—C7 = 1.266 (2), O2—C9 = 1.271 (2), O3—C22 = 1.252 (2) and O4—C24 = 1.293 (2) Å for (II).

The pentafluorophenyl groups of (I) and (II) are highly twisted with respect to the coordination plane. The torsion angles C5—C6—C7—C8, C8—C9—C10—C15, C20—C21—C22—C23 and C23—C24—C25—C30 are 34.0 (3), 31.2 (3), 51.3 (3) and 67.1 (3)°, respectively, in (I), and 37.9 (2), 64.5 (2), 36.0 (2) and 67.2 (2)°, respectively, in (II); the two torsion angles C5—C6—C7—C8 and C23—C24—C25—C30 are almost the same. Thus, it is clearly shown that the direction and angles of the intramolecular π–π stacking between the two corresponding pentafluorophenyl rings, C1–C6 and C25–C30, are essentially the same. In the structure of (II), the C10–C15 ring is surrounded by four pentafluorophenyl groups of other molecules and no significant plane-to-plane stacking is observed. In contrast, all the pentafluorophenyl rings have intermolecular stacking with benzene molecules in the structure of (I). In particular, six pentafluorophenyl rings of the complex and three benzene molecules (two benzene-1 and one benzene-3) are columnar stacked along the c axis. The remaining two pentafluorophenyl rings (C16–C21) and benzene-2 are perpendicularly aligned with respect to the other rings.

The packing structures of (I) and (II) are shown in Figs. 2 and 3, respectively. In the crystal structure of (I), cavities exist along the b axis, and benzene-2 and benzene-3 are packed alternately in these cavities with the benzene planes twisted. No strong intermolecular interactions are observed between the benzene molecules in the cavities; the closest intermolecular H···H distances of the benzene molecules are around 2.78–2.93 Å. The cavity is surrounded by pentafluorophenyl rings from four directions to stabilize the benzene positions. The benzene-2 and benzene-3 molecules are sandwiched between the C16–C21 and C1–C6 pentafluorophenyl rings, respectively. Both of the average intermolecular plane-to-plane distances are around 3.5 Å, and the shortest F15···C38 distance is 3.07 Å and that of C1···C42 is 3.31 Å, indicating arene–perfluoroarene interaction. Benzene-1 is also stabilized between the two pentafluorophenyl rings, C10–C15 and C25–C30, and the average distance of the intermolecular stacking is around 3.5 Å. C—H···F interactions (Thalladi et al., 1998) are also observed as intermolecular interactions between the benzene and pentafluorophenyl rings, e.g. the F20···H31 and F20···H36 distances are 2.61 and 2.55 Å, respectively. Additionally, C—F···π interactions are observed between the pentafluorophenyl rings; the intermolecular distances of F14···C15, F13···C12 and F13···C13 are 3.16, 2.95 and 2.98 Å, respectively.

The crystal structure of (I) contains two types of benzene molecule; benzene-2 and benzene-3 are packed alternately in the cavity, and benzene-1 is adjacently packed in the same direction as benzene-3. In the crystal structure of (II), on the other hand, the benzene molecules are three-dimensionally isolated by pentafluorophenyl rings of the complex, as shown in Fig. 3. The benzene molecule is sandwiched by two pentafluorophenyl rings, C16–C21 and C25–C30, and the intermolecular plane-to-plane distances are around 3.4 Å. In both (I) and (II), the benzene molecules are stabilized by the arene–perfluoroarene interaction through a strong host–guest interaction.

S2. Experimental

The dinuclear nickel(II) complex was prepared as reported by Hori et al. (2009). The result of the elemental analysis showed the formation of the complex (calculated for C₆₀H₈F₄₀Ni₂O₁₀: C 40.81, H 0.46%; found: C 40.98, H 0.47%]. The complex was crystallized from CH₂Cl₂ by the gas-phase diffusion of benzene to give green crystals of (I) and (II), in principle optically indistinguishable from each other, and suitable for X-ray structural work.

S3. Refinement

H atoms attached to C atoms were refined as riding on their idealized positions, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) [Please check added text]. Water atoms H5A and H5B were located in a difference Fourier density map and refined freely [O—H5A = 0.88 (3) Å and O5—H5B = 0.99 (4) Å].

Computing details

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The entire dinuclear nickel(II) complex, (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the ??% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A crystal packing view of (I), projected along the c axis, showing the columnar arrangement of the benzene molecules linked by arene–perfluoroarene interactions between the pentafluorophenyl groups and the benzene solvent molecules.
	Fig. 3. A crystal packing view of (II) (Hori et al., 2009), projected along the c axis.

bis[µ-1,3-bis(pentafluorophenyl)propane-1,3-dionato]- κ³O,O':O';κ³O:O,O'- bis{aqua[1,3-bis(pentafluorophenyl)propane-1,3-dionato- κ²O,O']nickel(II)} benzene tetrasolvate

Crystal data

[Ni2(C15HF10O2)4(H2O)2]·4C6H6	Z = 1
Mr = 2078.48	F(000) = 1032
Triclinic, P1	Dx = 1.786 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.0236 (13) Å	Cell parameters from 7845 reflections
b = 12.4384 (14) Å	θ = 2.2–27.6°
c = 14.0058 (15) Å	µ = 0.65 mm^−1
α = 82.980 (1)°	T = 100 K
β = 73.411 (1)°	Prism, green
γ = 74.536 (1)°	0.25 × 0.20 × 0.15 mm
V = 1932.4 (4) Å^3

Data collection

Bruker APEXII CCD area-detector diffractometer	8387 independent reflections
Radiation source: fine-focus sealed tube	6817 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 8.333 pixels mm^-1	θmax = 27.1°, θmin = 2.0°
ϕ and ω scans	h = −15→15
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick 1996)	k = −15→15
Tmin = 0.855, Tmax = 0.909	l = −17→17
21369 measured reflections

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0419P)^2 + 0.918P] where P = (Fo^2 + 2Fc^2)/3
8387 reflections	(Δ/σ)max = 0.001
621 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.29 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
Ni1	−0.00116 (2)	0.410022 (19)	0.087777 (17)	0.01701 (7)
O1	−0.06914 (11)	0.27984 (10)	0.14248 (9)	0.0181 (3)
O2	−0.15215 (11)	0.51274 (11)	0.16044 (9)	0.0200 (3)
O3	0.08529 (11)	0.37625 (11)	0.19468 (10)	0.0212 (3)
O4	0.06909 (11)	0.54509 (11)	0.03721 (9)	0.0186 (3)
O5	0.14767 (12)	0.31271 (13)	−0.00840 (11)	0.0251 (3)
C1	−0.05628 (17)	0.07334 (16)	0.25328 (14)	0.0216 (4)
C2	−0.06490 (17)	−0.03333 (16)	0.29060 (15)	0.0231 (4)
C3	−0.17241 (18)	−0.05077 (15)	0.34902 (15)	0.0232 (4)
C4	−0.27162 (17)	0.03806 (16)	0.36960 (15)	0.0229 (4)
C5	−0.26185 (17)	0.14316 (16)	0.33049 (14)	0.0212 (4)
C6	−0.15453 (16)	0.16564 (15)	0.27212 (14)	0.0188 (4)
C7	−0.14225 (16)	0.27988 (15)	0.22797 (14)	0.0177 (4)
C8	−0.21252 (16)	0.37416 (15)	0.28141 (14)	0.0190 (4)
H8	−0.2561	0.3629	0.3485	0.023*
C9	−0.22165 (16)	0.48339 (15)	0.24116 (13)	0.0174 (4)
C10	−0.32179 (17)	0.57730 (16)	0.29007 (14)	0.0197 (4)
C11	−0.30947 (17)	0.68702 (17)	0.27761 (14)	0.0228 (4)
C12	−0.40326 (19)	0.77692 (16)	0.31306 (15)	0.0252 (4)
C13	−0.51227 (18)	0.75891 (16)	0.36614 (15)	0.0252 (4)
C14	−0.52769 (17)	0.65183 (18)	0.38150 (15)	0.0265 (4)
C15	−0.43503 (18)	0.56379 (16)	0.34259 (15)	0.0235 (4)
C16	0.27702 (17)	0.23856 (17)	0.27436 (15)	0.0231 (4)
C17	0.33567 (18)	0.18178 (17)	0.34349 (16)	0.0268 (4)
C18	0.35604 (17)	0.24058 (17)	0.41139 (15)	0.0245 (4)
C19	0.32161 (17)	0.35547 (17)	0.40775 (14)	0.0232 (4)
C20	0.26868 (17)	0.41129 (16)	0.33414 (14)	0.0215 (4)
C21	0.24184 (16)	0.35471 (16)	0.26780 (14)	0.0206 (4)
C22	0.17306 (17)	0.41247 (16)	0.19419 (14)	0.0202 (4)
C23	0.21164 (17)	0.50139 (17)	0.13233 (14)	0.0231 (4)
H23	0.2798	0.5205	0.1403	0.028*
C24	0.15817 (16)	0.56236 (16)	0.06154 (14)	0.0190 (4)
C25	0.20685 (17)	0.66029 (16)	0.00974 (14)	0.0212 (4)
C26	0.14104 (18)	0.76875 (17)	0.02604 (15)	0.0264 (4)
C27	0.1862 (2)	0.85962 (18)	−0.01646 (19)	0.0367 (5)
C28	0.3000 (2)	0.8419 (2)	−0.07911 (19)	0.0400 (6)
C29	0.3672 (2)	0.7356 (2)	−0.09809 (17)	0.0379 (6)
C30	0.32053 (19)	0.64587 (18)	−0.05342 (16)	0.0293 (5)
C31	0.5354 (2)	0.7238 (2)	0.08381 (18)	0.0380 (5)
H31	0.6042	0.6697	0.0520	0.046*
C32	0.5359 (2)	0.8354 (2)	0.07292 (19)	0.0432 (6)
H32	0.6054	0.8581	0.0342	0.052*
C33	0.4349 (2)	0.9144 (2)	0.1184 (2)	0.0454 (6)
H33	0.4356	0.9912	0.1110	0.055*
C34	0.3330 (2)	0.8822 (2)	0.17455 (17)	0.0370 (5)
H34	0.2636	0.9367	0.2048	0.044*
C35	0.3329 (2)	0.7696 (2)	0.18638 (17)	0.0361 (5)
H35	0.2633	0.7471	0.2253	0.043*
C36	0.4334 (2)	0.6903 (2)	0.14175 (18)	0.0350 (5)
H36	0.4332	0.6134	0.1503	0.042*
C37	0.9668 (2)	0.4303 (2)	0.44925 (18)	0.0396 (6)
H37	0.9441	0.3825	0.4142	0.048*
C38	1.0097 (2)	0.3888 (2)	0.53128 (19)	0.0403 (6)
H38	1.0164	0.3125	0.5530	0.048*
C39	0.9569 (2)	0.5413 (2)	0.41813 (18)	0.0402 (6)
H39	0.9271	0.5699	0.3618	0.048*
C40	0.0792 (2)	0.8956 (2)	0.48733 (17)	0.0355 (5)
H40	0.1332	0.8240	0.4786	0.043*
C41	0.1142 (2)	0.9893 (2)	0.43793 (17)	0.0357 (5)
H41	0.1927	0.9821	0.3954	0.043*
C42	0.0354 (2)	1.0930 (2)	0.45026 (17)	0.0358 (5)
H42	0.0598	1.1570	0.4158	0.043*
F1	0.05228 (10)	0.08518 (9)	0.20182 (9)	0.0286 (3)
F2	0.03185 (11)	−0.11903 (9)	0.27132 (9)	0.0311 (3)
F3	−0.18009 (11)	−0.15337 (9)	0.38715 (9)	0.0313 (3)
F4	−0.37591 (10)	0.02181 (9)	0.42704 (9)	0.0309 (3)
F5	−0.36339 (10)	0.22482 (9)	0.34957 (9)	0.0283 (3)
F6	−0.20381 (10)	0.71082 (9)	0.23051 (9)	0.0300 (3)
F7	−0.38674 (12)	0.88024 (10)	0.29644 (10)	0.0361 (3)
F8	−0.60317 (11)	0.84391 (10)	0.40384 (10)	0.0340 (3)
F9	−0.63544 (10)	0.63517 (10)	0.43230 (10)	0.0384 (3)
F10	−0.45929 (10)	0.46316 (10)	0.35450 (10)	0.0357 (3)
F11	0.25902 (11)	0.17869 (10)	0.20925 (10)	0.0345 (3)
F12	0.37338 (12)	0.07036 (10)	0.34506 (11)	0.0398 (3)
F13	0.40947 (11)	0.18648 (10)	0.48103 (9)	0.0329 (3)
F14	0.33847 (11)	0.41106 (10)	0.47627 (9)	0.0306 (3)
F15	0.24082 (11)	0.52320 (9)	0.33078 (9)	0.0286 (3)
F16	0.02907 (11)	0.78803 (11)	0.08585 (10)	0.0378 (3)
F17	0.12123 (15)	0.96378 (12)	0.00224 (14)	0.0592 (4)
F18	0.34468 (15)	0.92954 (13)	−0.12210 (13)	0.0629 (5)
F19	0.47805 (13)	0.71798 (15)	−0.15911 (12)	0.0601 (5)
F20	0.38947 (11)	0.54283 (12)	−0.07312 (11)	0.0451 (4)
H5A	0.161 (2)	0.348 (2)	−0.067 (2)	0.055 (9)*
H5B	0.164 (3)	0.231 (3)	−0.014 (2)	0.081 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01482 (12)	0.01921 (13)	0.01695 (13)	−0.00518 (9)	−0.00446 (9)	0.00217 (9)
O1	0.0166 (6)	0.0200 (7)	0.0172 (6)	−0.0047 (5)	−0.0041 (5)	0.0008 (5)
O2	0.0195 (7)	0.0198 (7)	0.0189 (7)	−0.0055 (5)	−0.0030 (5)	0.0015 (5)
O3	0.0191 (7)	0.0247 (7)	0.0216 (7)	−0.0072 (6)	−0.0082 (5)	0.0028 (5)
O4	0.0159 (6)	0.0225 (7)	0.0186 (6)	−0.0062 (5)	−0.0061 (5)	0.0019 (5)
O5	0.0207 (7)	0.0278 (8)	0.0223 (8)	−0.0019 (6)	−0.0036 (6)	0.0013 (6)
C1	0.0173 (9)	0.0240 (10)	0.0221 (10)	−0.0050 (8)	−0.0039 (7)	0.0004 (8)
C2	0.0230 (10)	0.0175 (9)	0.0273 (10)	0.0006 (8)	−0.0089 (8)	−0.0026 (8)
C3	0.0306 (11)	0.0144 (9)	0.0265 (10)	−0.0069 (8)	−0.0103 (8)	0.0022 (8)
C4	0.0216 (10)	0.0229 (10)	0.0245 (10)	−0.0087 (8)	−0.0041 (8)	0.0007 (8)
C5	0.0189 (9)	0.0205 (10)	0.0227 (10)	−0.0023 (8)	−0.0060 (8)	0.0000 (8)
C6	0.0181 (9)	0.0194 (9)	0.0195 (9)	−0.0046 (7)	−0.0066 (7)	0.0011 (7)
C7	0.0143 (9)	0.0205 (9)	0.0194 (9)	−0.0049 (7)	−0.0075 (7)	0.0035 (7)
C8	0.0173 (9)	0.0210 (9)	0.0174 (9)	−0.0048 (7)	−0.0034 (7)	0.0010 (7)
C9	0.0156 (9)	0.0208 (9)	0.0180 (9)	−0.0060 (7)	−0.0063 (7)	−0.0011 (7)
C10	0.0196 (9)	0.0195 (9)	0.0197 (9)	−0.0037 (7)	−0.0062 (7)	−0.0004 (7)
C11	0.0224 (10)	0.0260 (10)	0.0215 (10)	−0.0083 (8)	−0.0059 (8)	−0.0012 (8)
C12	0.0312 (11)	0.0181 (10)	0.0286 (11)	−0.0063 (8)	−0.0106 (9)	−0.0030 (8)
C13	0.0255 (10)	0.0202 (10)	0.0291 (11)	0.0038 (8)	−0.0115 (8)	−0.0080 (8)
C14	0.0180 (10)	0.0299 (11)	0.0290 (11)	−0.0035 (8)	−0.0030 (8)	−0.0043 (9)
C15	0.0235 (10)	0.0190 (10)	0.0277 (10)	−0.0047 (8)	−0.0065 (8)	−0.0012 (8)
C16	0.0198 (10)	0.0262 (10)	0.0265 (10)	−0.0100 (8)	−0.0083 (8)	0.0011 (8)
C17	0.0230 (10)	0.0224 (10)	0.0348 (12)	−0.0074 (8)	−0.0096 (9)	0.0082 (9)
C18	0.0171 (9)	0.0334 (11)	0.0239 (10)	−0.0099 (8)	−0.0086 (8)	0.0117 (8)
C19	0.0189 (9)	0.0322 (11)	0.0210 (10)	−0.0114 (8)	−0.0062 (8)	0.0029 (8)
C20	0.0191 (9)	0.0214 (10)	0.0240 (10)	−0.0065 (8)	−0.0058 (8)	0.0031 (8)
C21	0.0153 (9)	0.0254 (10)	0.0215 (10)	−0.0067 (8)	−0.0053 (7)	0.0028 (8)
C22	0.0192 (9)	0.0220 (10)	0.0194 (9)	−0.0029 (8)	−0.0066 (7)	−0.0026 (7)
C23	0.0196 (10)	0.0289 (11)	0.0244 (10)	−0.0095 (8)	−0.0104 (8)	0.0041 (8)
C24	0.0164 (9)	0.0214 (10)	0.0181 (9)	−0.0047 (7)	−0.0027 (7)	−0.0013 (7)
C25	0.0218 (10)	0.0274 (10)	0.0192 (9)	−0.0111 (8)	−0.0108 (8)	0.0047 (8)
C26	0.0260 (11)	0.0287 (11)	0.0280 (11)	−0.0097 (9)	−0.0113 (9)	0.0024 (9)
C27	0.0454 (14)	0.0249 (12)	0.0482 (14)	−0.0114 (10)	−0.0255 (12)	0.0045 (10)
C28	0.0461 (14)	0.0436 (14)	0.0422 (14)	−0.0296 (12)	−0.0227 (12)	0.0218 (11)
C29	0.0274 (12)	0.0571 (16)	0.0321 (12)	−0.0232 (11)	−0.0074 (10)	0.0146 (11)
C30	0.0239 (11)	0.0329 (12)	0.0296 (11)	−0.0085 (9)	−0.0061 (9)	0.0054 (9)
C31	0.0299 (12)	0.0404 (14)	0.0417 (14)	−0.0015 (10)	−0.0107 (10)	−0.0081 (11)
C32	0.0350 (13)	0.0465 (15)	0.0442 (15)	−0.0094 (11)	−0.0085 (11)	0.0057 (12)
C33	0.0522 (16)	0.0320 (13)	0.0490 (15)	−0.0051 (12)	−0.0165 (13)	0.0051 (11)
C34	0.0325 (12)	0.0412 (14)	0.0339 (13)	0.0021 (10)	−0.0123 (10)	−0.0056 (10)
C35	0.0258 (11)	0.0479 (14)	0.0366 (13)	−0.0073 (10)	−0.0121 (10)	−0.0045 (11)
C36	0.0318 (12)	0.0361 (13)	0.0430 (13)	−0.0062 (10)	−0.0181 (10)	−0.0082 (10)
C37	0.0297 (12)	0.0504 (16)	0.0401 (14)	−0.0069 (11)	−0.0098 (10)	−0.0120 (11)
C38	0.0302 (12)	0.0412 (14)	0.0443 (14)	−0.0017 (10)	−0.0075 (11)	−0.0044 (11)
C39	0.0271 (12)	0.0563 (16)	0.0332 (13)	0.0007 (11)	−0.0109 (10)	−0.0048 (11)
C40	0.0289 (12)	0.0409 (13)	0.0363 (13)	0.0009 (10)	−0.0135 (10)	−0.0100 (10)
C41	0.0225 (11)	0.0549 (15)	0.0310 (12)	−0.0086 (10)	−0.0067 (9)	−0.0092 (11)
C42	0.0341 (12)	0.0433 (14)	0.0331 (12)	−0.0133 (11)	−0.0103 (10)	−0.0018 (10)
F1	0.0177 (6)	0.0254 (6)	0.0352 (7)	−0.0019 (5)	−0.0003 (5)	0.0025 (5)
F2	0.0280 (6)	0.0186 (6)	0.0407 (7)	0.0039 (5)	−0.0083 (5)	−0.0022 (5)
F3	0.0362 (7)	0.0170 (6)	0.0398 (7)	−0.0077 (5)	−0.0103 (6)	0.0051 (5)
F4	0.0266 (6)	0.0234 (6)	0.0384 (7)	−0.0110 (5)	0.0010 (5)	0.0023 (5)
F5	0.0165 (6)	0.0194 (6)	0.0419 (7)	−0.0022 (4)	−0.0004 (5)	0.0024 (5)
F6	0.0275 (6)	0.0241 (6)	0.0369 (7)	−0.0118 (5)	−0.0004 (5)	−0.0036 (5)
F7	0.0411 (8)	0.0188 (6)	0.0482 (8)	−0.0070 (5)	−0.0107 (6)	−0.0044 (5)
F8	0.0286 (7)	0.0249 (6)	0.0426 (7)	0.0058 (5)	−0.0074 (6)	−0.0123 (5)
F9	0.0202 (6)	0.0326 (7)	0.0536 (8)	−0.0036 (5)	0.0041 (6)	−0.0096 (6)
F10	0.0219 (6)	0.0213 (6)	0.0562 (8)	−0.0075 (5)	0.0052 (6)	−0.0050 (6)
F11	0.0400 (7)	0.0262 (6)	0.0448 (8)	−0.0063 (5)	−0.0233 (6)	−0.0044 (6)
F12	0.0443 (8)	0.0207 (6)	0.0588 (9)	−0.0062 (6)	−0.0267 (7)	0.0082 (6)
F13	0.0311 (7)	0.0378 (7)	0.0329 (7)	−0.0114 (6)	−0.0185 (5)	0.0171 (6)
F14	0.0325 (7)	0.0402 (7)	0.0249 (6)	−0.0128 (6)	−0.0134 (5)	−0.0006 (5)
F15	0.0356 (7)	0.0217 (6)	0.0324 (7)	−0.0062 (5)	−0.0164 (5)	0.0003 (5)
F16	0.0294 (7)	0.0325 (7)	0.0467 (8)	−0.0044 (6)	−0.0026 (6)	−0.0085 (6)
F17	0.0676 (11)	0.0249 (7)	0.0897 (13)	−0.0127 (7)	−0.0301 (10)	0.0047 (8)
F18	0.0716 (11)	0.0562 (10)	0.0764 (12)	−0.0462 (9)	−0.0316 (9)	0.0358 (9)
F19	0.0342 (8)	0.0802 (12)	0.0579 (10)	−0.0287 (8)	0.0049 (7)	0.0183 (9)
F20	0.0268 (7)	0.0425 (8)	0.0522 (9)	−0.0036 (6)	0.0048 (6)	0.0020 (7)

Geometric parameters (Å, º)

Ni1—O1	1.9804 (13)	C19—F14	1.337 (2)
Ni1—O2	1.9974 (13)	C19—C20	1.384 (3)
Ni1—O3	2.0003 (13)	C20—F15	1.340 (2)
Ni1—O4	2.0401 (13)	C20—C21	1.384 (3)
Ni1—O5	2.0854 (14)	C21—C22	1.501 (3)
Ni1—O4^i	2.0922 (13)	C22—C23	1.414 (3)
O1—C7	1.267 (2)	C23—C24	1.375 (3)
O2—C9	1.278 (2)	C23—H23	0.9500
O3—C22	1.251 (2)	C24—C25	1.508 (3)
O4—C24	1.288 (2)	C25—C30	1.379 (3)
O4—Ni1^i	2.0922 (13)	C25—C26	1.379 (3)
O5—H5A	0.88 (3)	C26—F16	1.343 (2)
O5—H5B	0.99 (4)	C26—C27	1.380 (3)
C1—F1	1.336 (2)	C27—F17	1.336 (3)
C1—C2	1.385 (3)	C27—C28	1.375 (4)
C1—C6	1.399 (3)	C28—F18	1.344 (2)
C2—F2	1.339 (2)	C28—C29	1.365 (4)
C2—C3	1.375 (3)	C29—F19	1.340 (3)
C3—F3	1.338 (2)	C29—C30	1.384 (3)
C3—C4	1.380 (3)	C30—F20	1.340 (3)
C4—F4	1.334 (2)	C31—C32	1.379 (3)
C4—C5	1.376 (3)	C31—C36	1.399 (3)
C5—F5	1.346 (2)	C31—H31	0.9500
C5—C6	1.395 (3)	C32—C33	1.386 (4)
C6—C7	1.506 (3)	C32—H32	0.9500
C7—C8	1.405 (3)	C33—C34	1.383 (4)
C8—C9	1.394 (3)	C33—H33	0.9500
C8—H8	0.9500	C34—C35	1.391 (3)
C9—C10	1.503 (3)	C34—H34	0.9500
C10—C15	1.394 (3)	C35—C36	1.381 (3)
C10—C11	1.396 (3)	C35—H35	0.9500
C11—F6	1.346 (2)	C36—H36	0.9500
C11—C12	1.383 (3)	C37—C38	1.380 (3)
C12—F7	1.335 (2)	C37—C39	1.380 (4)
C12—C13	1.371 (3)	C37—H37	0.9500
C13—F8	1.335 (2)	C38—C39^ii	1.384 (3)
C13—C14	1.376 (3)	C38—H38	0.9500
C14—F9	1.345 (2)	C39—C38^ii	1.384 (3)
C14—C15	1.373 (3)	C39—H39	0.9500
C15—F10	1.340 (2)	C40—C41	1.382 (3)
C16—F11	1.341 (2)	C40—C42^iii	1.386 (3)
C16—C17	1.375 (3)	C40—H40	0.9500
C16—C21	1.392 (3)	C41—C42	1.379 (3)
C17—F12	1.338 (2)	C41—H41	0.9500
C17—C18	1.378 (3)	C42—C40^iii	1.386 (3)
C18—F13	1.336 (2)	C42—H42	0.9500
C18—C19	1.377 (3)
O1—Ni1—O2	90.24 (5)	F13—C18—C19	119.60 (19)
O1—Ni1—O3	87.64 (5)	F13—C18—C17	120.21 (18)
O2—Ni1—O3	99.14 (5)	C19—C18—C17	120.19 (18)
O1—Ni1—O4	177.63 (5)	F14—C19—C18	119.38 (17)
O2—Ni1—O4	88.91 (5)	F14—C19—C20	121.18 (18)
O3—Ni1—O4	90.31 (5)	C18—C19—C20	119.43 (19)
O1—Ni1—O5	92.56 (6)	F15—C20—C19	117.55 (17)
O2—Ni1—O5	170.92 (6)	F15—C20—C21	120.66 (17)
O3—Ni1—O5	89.60 (6)	C19—C20—C21	121.77 (18)
O4—Ni1—O5	88.62 (6)	C20—C21—C16	117.02 (17)
O1—Ni1—O4^i	99.98 (5)	C20—C21—C22	123.10 (17)
O2—Ni1—O4^i	85.44 (5)	C16—C21—C22	119.82 (17)
O3—Ni1—O4^i	171.13 (5)	O3—C22—C23	126.41 (17)
O4—Ni1—O4^i	82.15 (5)	O3—C22—C21	115.41 (16)
O5—Ni1—O4^i	85.57 (5)	C23—C22—C21	118.18 (16)
C7—O1—Ni1	121.36 (12)	C24—C23—C22	125.07 (18)
C9—O2—Ni1	123.15 (12)	C24—C23—H23	117.5
C22—O3—Ni1	125.02 (12)	C22—C23—H23	117.5
C24—O4—Ni1	124.01 (12)	O4—C24—C23	126.12 (17)
C24—O4—Ni1^i	134.13 (12)	O4—C24—C25	117.26 (16)
Ni1—O4—Ni1^i	97.85 (5)	C23—C24—C25	116.60 (17)
Ni1—O5—H5A	108.8 (18)	C30—C25—C26	116.83 (18)
Ni1—O5—H5B	125.4 (19)	C30—C25—C24	121.70 (18)
H5A—O5—H5B	112 (3)	C26—C25—C24	121.44 (17)
F1—C1—C2	116.69 (17)	F16—C26—C25	119.53 (18)
F1—C1—C6	121.10 (17)	F16—C26—C27	118.08 (19)
C2—C1—C6	122.14 (17)	C25—C26—C27	122.4 (2)
F2—C2—C3	120.04 (17)	F17—C27—C28	119.8 (2)
F2—C2—C1	120.04 (17)	F17—C27—C26	121.1 (2)
C3—C2—C1	119.91 (17)	C28—C27—C26	119.1 (2)
F3—C3—C2	119.94 (17)	F18—C28—C29	120.1 (2)
F3—C3—C4	120.22 (18)	F18—C28—C27	119.8 (2)
C2—C3—C4	119.84 (17)	C29—C28—C27	120.1 (2)
F4—C4—C5	120.46 (17)	F19—C29—C28	120.3 (2)
F4—C4—C3	120.10 (17)	F19—C29—C30	120.0 (2)
C5—C4—C3	119.44 (18)	C28—C29—C30	119.7 (2)
F5—C5—C4	116.24 (16)	F20—C30—C25	120.15 (18)
F5—C5—C6	120.75 (16)	F20—C30—C29	118.00 (19)
C4—C5—C6	122.99 (17)	C25—C30—C29	121.9 (2)
C5—C6—C1	115.66 (17)	C32—C31—C36	120.0 (2)
C5—C6—C7	123.78 (16)	C32—C31—H31	120.0
C1—C6—C7	120.53 (16)	C36—C31—H31	120.0
O1—C7—C8	126.52 (17)	C31—C32—C33	120.0 (2)
O1—C7—C6	114.43 (16)	C31—C32—H32	120.0
C8—C7—C6	119.02 (16)	C33—C32—H32	120.0
C9—C8—C7	123.44 (17)	C34—C33—C32	120.4 (2)
C9—C8—H8	118.3	C34—C33—H33	119.8
C7—C8—H8	118.3	C32—C33—H33	119.8
O2—C9—C8	125.00 (17)	C33—C34—C35	119.6 (2)
O2—C9—C10	114.30 (16)	C33—C34—H34	120.2
C8—C9—C10	120.65 (16)	C35—C34—H34	120.2
C15—C10—C11	115.44 (17)	C36—C35—C34	120.3 (2)
C15—C10—C9	123.26 (17)	C36—C35—H35	119.8
C11—C10—C9	121.05 (17)	C34—C35—H35	119.8
F6—C11—C12	116.11 (17)	C35—C36—C31	119.7 (2)
F6—C11—C10	121.22 (17)	C35—C36—H36	120.2
C12—C11—C10	122.67 (18)	C31—C36—H36	120.2
F7—C12—C13	120.54 (18)	C38—C37—C39	119.9 (2)
F7—C12—C11	119.88 (18)	C38—C37—H37	120.0
C13—C12—C11	119.58 (18)	C39—C37—H37	120.0
F8—C13—C12	120.75 (18)	C37—C38—C39^ii	119.8 (2)
F8—C13—C14	119.67 (19)	C37—C38—H38	120.1
C12—C13—C14	119.57 (18)	C39^ii—C38—H38	120.1
F9—C14—C15	120.63 (18)	C37—C39—C38^ii	120.2 (2)
F9—C14—C13	119.14 (18)	C37—C39—H39	119.9
C15—C14—C13	120.19 (19)	C38^ii—C39—H39	119.9
F10—C15—C14	116.73 (17)	C41—C40—C42^iii	119.5 (2)
F10—C15—C10	120.77 (17)	C41—C40—H40	120.3
C14—C15—C10	122.47 (18)	C42^iii—C40—H40	120.3
F11—C16—C17	117.86 (18)	C42—C41—C40	120.2 (2)
F11—C16—C21	120.12 (17)	C42—C41—H41	119.9
C17—C16—C21	121.94 (19)	C40—C41—H41	119.9
F12—C17—C16	120.64 (19)	C41—C42—C40^iii	120.3 (2)
F12—C17—C18	119.89 (18)	C41—C42—H42	119.8
C16—C17—C18	119.47 (18)	C40^iii—C42—H42	119.8
O2—Ni1—O1—C7	−32.04 (13)	C9—C10—C15—F10	1.9 (3)
O3—Ni1—O1—C7	67.10 (13)	C11—C10—C15—C14	−1.4 (3)
O5—Ni1—O1—C7	156.60 (13)	C9—C10—C15—C14	−175.83 (18)
O1—Ni1—O2—C9	27.32 (14)	F11—C16—C17—F12	0.1 (3)
O3—Ni1—O2—C9	−60.33 (14)	C21—C16—C17—F12	−176.85 (18)
O4—Ni1—O2—C9	−150.47 (14)	F11—C16—C17—C18	179.82 (17)
O4^i—Ni1—O2—C9	127.31 (14)	C21—C16—C17—C18	2.9 (3)
O1—Ni1—O3—C22	162.49 (15)	F12—C17—C18—F13	−2.4 (3)
O2—Ni1—O3—C22	−107.65 (15)	C16—C17—C18—F13	177.86 (17)
O4—Ni1—O3—C22	−18.71 (15)	F12—C17—C18—C19	177.48 (18)
O5—Ni1—O3—C22	69.91 (15)	C16—C17—C18—C19	−2.3 (3)
O2—Ni1—O4—C24	114.24 (14)	F13—C18—C19—F14	−2.3 (3)
O3—Ni1—O4—C24	15.10 (14)	C17—C18—C19—F14	177.79 (17)
O5—Ni1—O4—C24	−74.50 (14)	F13—C18—C19—C20	178.58 (17)
O4^i—Ni1—O4—C24	−160.21 (17)	C17—C18—C19—C20	−1.3 (3)
O2—Ni1—O4—Ni1^i	−85.55 (6)	F14—C19—C20—F15	3.5 (3)
O3—Ni1—O4—Ni1^i	175.31 (5)	C18—C19—C20—F15	−177.41 (17)
O5—Ni1—O4—Ni1^i	85.71 (6)	F14—C19—C20—C21	−174.65 (17)
O4^i—Ni1—O4—Ni1^i	0.0	C18—C19—C20—C21	4.4 (3)
F1—C1—C2—F2	−2.4 (3)	F15—C20—C21—C16	178.12 (17)
C6—C1—C2—F2	−179.41 (18)	C19—C20—C21—C16	−3.8 (3)
F1—C1—C2—C3	176.34 (17)	F15—C20—C21—C22	−4.7 (3)
C6—C1—C2—C3	−0.6 (3)	C19—C20—C21—C22	173.40 (18)
F2—C2—C3—F3	0.4 (3)	F11—C16—C21—C20	−176.78 (17)
C1—C2—C3—F3	−178.34 (17)	C17—C16—C21—C20	0.1 (3)
F2—C2—C3—C4	179.29 (18)	F11—C16—C21—C22	6.0 (3)
C1—C2—C3—C4	0.5 (3)	C17—C16—C21—C22	−177.17 (18)
F3—C3—C4—F4	−0.5 (3)	Ni1—O3—C22—C23	15.0 (3)
C2—C3—C4—F4	−179.35 (18)	Ni1—O3—C22—C21	−165.46 (12)
F3—C3—C4—C5	179.43 (18)	C20—C21—C22—O3	−128.3 (2)
C2—C3—C4—C5	0.6 (3)	C16—C21—C22—O3	48.8 (2)
F4—C4—C5—F5	−3.2 (3)	C20—C21—C22—C23	51.3 (3)
C3—C4—C5—F5	176.87 (17)	C16—C21—C22—C23	−131.6 (2)
F4—C4—C5—C6	178.31 (18)	O3—C22—C23—C24	−0.4 (3)
C3—C4—C5—C6	−1.6 (3)	C21—C22—C23—C24	−179.97 (18)
F5—C5—C6—C1	−176.96 (17)	Ni1—O4—C24—C23	−7.6 (3)
C4—C5—C6—C1	1.5 (3)	Ni1^i—O4—C24—C23	−159.70 (15)
F5—C5—C6—C7	1.0 (3)	Ni1—O4—C24—C25	174.14 (12)
C4—C5—C6—C7	179.48 (18)	Ni1^i—O4—C24—C25	22.0 (3)
F1—C1—C6—C5	−177.17 (17)	C22—C23—C24—O4	−3.5 (3)
C2—C1—C6—C5	−0.3 (3)	C22—C23—C24—C25	174.81 (18)
F1—C1—C6—C7	4.8 (3)	O4—C24—C25—C30	−114.4 (2)
C2—C1—C6—C7	−178.41 (18)	C23—C24—C25—C30	67.1 (3)
Ni1—O1—C7—C8	20.8 (2)	O4—C24—C25—C26	67.8 (2)
Ni1—O1—C7—C6	−161.17 (11)	C23—C24—C25—C26	−110.7 (2)
C5—C6—C7—O1	−144.21 (18)	C30—C25—C26—F16	179.13 (18)
C1—C6—C7—O1	33.7 (2)	C24—C25—C26—F16	−3.0 (3)
C5—C6—C7—C8	34.0 (3)	C30—C25—C26—C27	−1.4 (3)
C1—C6—C7—C8	−148.08 (18)	C24—C25—C26—C27	176.50 (19)
O1—C7—C8—C9	8.1 (3)	F16—C26—C27—F17	0.8 (3)
C6—C7—C8—C9	−169.85 (17)	C25—C26—C27—F17	−178.7 (2)
Ni1—O2—C9—C8	−10.0 (2)	F16—C26—C27—C28	−179.0 (2)
Ni1—O2—C9—C10	172.71 (11)	C25—C26—C27—C28	1.5 (3)
C7—C8—C9—O2	−14.2 (3)	F17—C27—C28—F18	−0.8 (3)
C7—C8—C9—C10	162.99 (17)	C26—C27—C28—F18	179.1 (2)
O2—C9—C10—C15	146.20 (18)	F17—C27—C28—C29	179.6 (2)
C8—C9—C10—C15	−31.2 (3)	C26—C27—C28—C29	−0.5 (4)
O2—C9—C10—C11	−27.9 (2)	F18—C28—C29—F19	0.4 (4)
C8—C9—C10—C11	154.63 (18)	C27—C28—C29—F19	180.0 (2)
C15—C10—C11—F6	178.25 (17)	F18—C28—C29—C30	179.9 (2)
C9—C10—C11—F6	−7.2 (3)	C27—C28—C29—C30	−0.5 (4)
C15—C10—C11—C12	−1.2 (3)	C26—C25—C30—F20	−179.68 (18)
C9—C10—C11—C12	173.40 (18)	C24—C25—C30—F20	2.4 (3)
F6—C11—C12—F7	2.4 (3)	C26—C25—C30—C29	0.4 (3)
C10—C11—C12—F7	−178.17 (18)	C24—C25—C30—C29	−177.49 (19)
F6—C11—C12—C13	−176.82 (17)	F19—C29—C30—F20	0.2 (3)
C10—C11—C12—C13	2.6 (3)	C28—C29—C30—F20	−179.4 (2)
F7—C12—C13—F8	−1.3 (3)	F19—C29—C30—C25	−179.9 (2)
C11—C12—C13—F8	177.90 (18)	C28—C29—C30—C25	0.5 (3)
F7—C12—C13—C14	179.32 (18)	C36—C31—C32—C33	−0.8 (4)
C11—C12—C13—C14	−1.5 (3)	C31—C32—C33—C34	−0.3 (4)
F8—C13—C14—F9	1.7 (3)	C32—C33—C34—C35	0.9 (4)
C12—C13—C14—F9	−178.97 (18)	C33—C34—C35—C36	−0.5 (3)
F8—C13—C14—C15	179.62 (18)	C34—C35—C36—C31	−0.5 (3)
C12—C13—C14—C15	−1.0 (3)	C32—C31—C36—C35	1.1 (3)
F9—C14—C15—F10	2.6 (3)	C39—C37—C38—C39^ii	−0.2 (4)
C13—C14—C15—F10	−175.33 (19)	C38—C37—C39—C38^ii	0.2 (4)
F9—C14—C15—C10	−179.55 (18)	C42^iii—C40—C41—C42	−0.4 (4)
C13—C14—C15—C10	2.5 (3)	C40—C41—C42—C40^iii	0.4 (4)
C11—C10—C15—F10	176.35 (17)

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