A copper(II)–pyrazole complex cation with imposed symmetry

The reaction of Cu(ClO₄)₂·6H₂O, NaAsF₆ and excess pyrazole yields hexakis­(pyrazole-κN²)copper(II) bis­(hexa­fluoroarsenate), [Cu(C₃H₄N₂)₆](AsF₆)₂ or [Cu(pzH)₆](AsF₆)₂ (pzH is pyrazole), (I). The analogous hexakis­(pyrazole-κN²)copper(II) hexafluorophosphate perchlorate complex, [Cu(C₃H₄N₂)₆](PF₆)_1.29(ClO₄)_0.71 or [Cu(pzH)₆](PF₆)_1.29(ClO₄)_0.71, (II), is obtained in a similar fashion, using KPF₆ in place of NaAsF₆. Both compounds contain the hitherto unknown [Cu(pzH)₆]²⁺ complex cation, in which the copper(II) ion lies at the center of a regular octahedron of coordinated N atoms. The cation has crystallographically imposed symmetry. The X-ray data indicate that the lack of the expected distortion can be accounted for by the presence of either static Jahn–Teller disorder or dynamic Jahn–Teller distortion.

S1. Comment

Pyrazole (pzH) forms a variety of metal complexes (Steel, 1990; Trofimenko, 1986, 1972), the simplest having the formulation [M(pzH)_n]X_p, where M is a metal and X is an anion. Reported complexes with n = 6 include [M(pzH)₆]X₂ (with M = Mg, Mn, Fe, Co, Ni, Zn or Cd, and X = NO₃, BF₄ or ClO₄; Trofimenko, 1972). The structures of [Ni(pzH)₆](BF₄)₂ (Ten-Hoedt et al., 1983), [Ni(pzH)₆](NO₃)₂ (Reimann et al., 1970) and [Mn(pzH)₆](ClO₄)₂ (Lumme et al., 1988) are known. Thus, hexakis(pyrazole) complexes exist for all first-row divalent transition metal ions from Mn to Zn, except for Cu. It has been suggested that a maximum of four pyrazoles can coordinate to Cu^II (Trofimenko, 1972; Nicholls & Warburton, 1971; Daugherty & Swisher, 1968). We attributed this lack of maximal coordination to the tendency of six-coordinate Cu^II complexes to undergo Jahn-Teller distortions (Hathaway & Billing, 1970). Such distorted structures are, presumably, more likely to form with six nonequivalent ligands. Hence, we anticipated that six pyrazoles could coordinate to Cu^II if non-coordinating anions were used and, therefore, undertook to prepare hexakis(pyrazole)copper(II) complexes by using weakly ligating AsF₆^- and PF₆^- as the counterions. We have isolated two isostructural salts containing the [Cu(pzH)₆]²⁺ complex cation, namely [Cu(pzH)₆](AsF₆)₂, (I), and [Cu(pzH)₆](PF₆)₂, (II), and their crystal structures are presented here. \sch

The Cu^II atoms in (I) (Fig. 1, Table 1) and (II) (Fig. 2, Table 2) occupy sites with 3 symmetry, requiring symmetry-equivalent Cu—N bonds. Such equal copper-ligand bond distances are atypical for Cu^II and warrant further discussion. Six-coordinate Cu^II complexes tend to have distorted octahedral geometries, usually with two long axial bonds and four short equatorial bonds, in accordance with the Jahn-Teller theorem (Hathaway & Billing, 1970; Ham, 1962). Few compounds have been reported in which the symmetry of the Cu coordination polyhedron is higher than that allowed by the Jahn-Teller theorem. These include [Cu(H₂O)₆](BrO₃)₂ (Blackburn et al., 1991) and [K₂Pb(Cu(NO₂)₆] (Isaacs & Kennard, 1967), which contain monodentate ligands, [Cu(en)₃](SO₄) (en is ethylenediamine; Cullen & Lingafelter, 1970), which contains three bidentate ligands, and [Cu(ompa)₂](ClO₄)₂ (ompa is octamethylpyrophosphoramide; Joesten et al., 1968, 1970) and [Cu(tach)₂](NO₃)₂ (tach is cis,cis-1,3,5-triaminocylohexane; Ammeter et al., 1979), which contain two tridentate ligands.

One explanation of these apparent violations of the Jahn-Teller theorem is the existence of a dynamic Jahn-Teller distortion, i.e. the complex could oscillate between three possible distortions, giving a regular time average. A second possibility is disordered static Jahn-Teller distortion, in which each molecule is trapped in a single distortion, and these distortions in turn are distributed randomly to produce a spatial average.

Evidence in support of Jahn-Teller effects in (I) and (II) is provided by the direction of the maximum anisotropic displacement parameter of each bonded N atom (Figs. 1 and 2), which is nearly parallel to the metal-N bond (Cullen & Lingafelter, 1970; Blackburn et al., 1991). The angle between the largest principle axis of the displacement ellipsoid and the metal-N1 bond is 23.5° in (I) and 26.2° in (II). In contrast, a much larger angle (49.5°) is observed for the isomorphous Ni^II complex, [Ni(pzH)₆](NO₃)₂, which is not subject to Jahn-Teller effects. These effects are also quantifiable in terms of ΔU values (Chandrasekhar & Bürgi, 1984). For compounds (I) and (II), the ΔU values along the Cu—N1 bonds are 0.0323 and 0.0324 Ų, respectively. These are roughly an order of magnitude larger than the ΔU values for the other bonded pairs of atoms in the pyrazole ring in both (I) and (II). They are also relatively larger than the value of 0.0105 Ų obtained for ΔU along the Ni—N1 bond in [Ni(pzH)₆](NO₃)₂.

Hydrogen bonds in (I) and (II) create an extended network of [Cu(pzH)₆]²⁺ and AsF₆^- or PF₆^- moieties. For example, as illustrated in Fig. 3, the N—H H atom of each pyrazole ring in (I) forms a hydrogen bond to an F atom of the AsF₆^- ion [H2···F1 2.074 (3) Å]. Each AsF₆^- anion forms hydrogen bonds to three different [Cu(pzH)₆]²⁺ moieties, and each [Cu(pzH)₆]²⁺ moiety forms hydrogen bonds to six different AsF₆^- anions.

The magnetic moment and visible spectrum data for (I) and (II) (see Experimental) are characteristic of a magnetically dilute six-coordinate Cu^II ion. The energy of the peak maximum in the visible spectra (15100 cm^-1) is comparable with those observed for other complexes containing the [CuN₆]²⁺ chromophore (McKenzie, 1970). The IR bands for the PF₆^- and AsF₆^- moieties are assigned on the basis of data from previously characterized hexafluorophosphate and hexafluoroarsenate complexes (Morrison & Thompson, 1982). For (I), ν₃ and ν₄ of the AsF₆^- group are observed at 705 and 411 cm^-1, respectively, and show no splitting. The corresponding bands for the PF₆^- group in (II) are observed at 840 and 561 cm^-1, respectively. These data are consistent with criteria for non-coordinating AsF₆^- or PF₆^- moieties (Morrison & Thompson, 1982).

S2. Experimental

To prepare compound (I), a solution of Cu(ClO₄)₂·6H₂O (0.849 g, 2.29 mmol) in ethanol (5 ml) containing 10% v/v 2,2-dimethoxypropane was added to NaAsF₆ (0.961 g, 4.54 mmol) dissolved in the same solvent (30 ml). The mixture was stirred for 15 min and filtered. To the filtrate was added more NaAsF₆ (0.500 g, 2.36 mmol), and the mixture was once again stirred for 15 min and then filtered into a solution of pyrazole (1.00 g, 14.7 mmol) in the above solvent (4 ml). The mixture was stirred for 30 min, after which the solvent was pumped off under vacuum. The blue solid product was recrystallized from methanol. Blue crystals of (I) were obtained in about 2 d. Crystals for X-ray analysis were removed directly from the supernatant liquid. The rest of the product was isolated by decantation, washed with small amounts of methanol and dried in a desiccator containing Drierite. Analysis found: C 25.81, H 2.91, N 19.29%; C₁₈H₂₄As₂CuF₁₂N₁₂ requires: C 25.44, H 2.85, N 19.78%. Spectroscopic data: visible (λ_max, nm, MeOH): 664; ε (dm³ mol^-1 cm^-1): 33; IR (ν, cm^-1, AsF₆^-): 705 (v s), 411 (s); µ_eff/BM (296 K) 1.90.

Compound (II) was prepared following the same procedure as above, using Cu(ClO₄)₂·6H₂O (0.823 g, 2.22 mmol), KPF₆ (0.830 g, 4.51 mmol and 0.485 g, 2.64 mmol) and pyrazole (1.098 g, 16.1 mmol). The KPF₆, however, only partially dissolves in the solvent. Analysis found: C 28.37, H 3.14, N 21.94%; C₁₈H₂₄CuF₁₂N₁₂P₂ requires: C 28.37, H 3.17, N 22.06%. Spectroscopic data: visible (λ_max, nm, MeOH): 663; ε (dm³ mol^-1 cm^-1): 34; IR (ν, cm^-1, PF₆^-): 840 (v s), 561 (s); µ_eff/BM (296 K) 1.91. The crystal of (II) used for X-ray studies contained roughly one third ClO₄^- ions. This was not characteristic of the bulk sample, for which elemental analysis and IR data indicate minimal, if any, ClO₄^-.

Elemental analyses were performed by Midwest Microlab, Indianapolis, Indiana. IR spectra were recorded as KBr pellets on a Bio-Rad Model FTS3000 FT—IR spectrometer. Visible spectra were recorded on a Cary 1 C UV-Visible spectrophotometer. Magnetic measurements were made at room temperature on a Johnson-Matthey Model MKI magnetic susceptibility balance.

S3. Refinement

H atoms were found in difference Fourier maps and refined using a riding model. Upon refinement, the crystal of (II) was found to contain a mixture of anions, the major component being the expected PF₆^-, with a small fraction of ClO₄^-. A disorder model was constructed by including a fractional Cl atom constrained to the same coordinates and anisotropic displacement parameters as the P atom, and fractional O-atom positions obtained from a difference Fourier map.

Computing details

For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXL97 and local procedures.

Figures

	Fig. 1. A view of the structure of the cation of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
	Fig. 2. A view of the structure of the cation of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
	Fig. 3. A packing diagram for (I) projected down the c axis, with the hydrogen-bonding interactions shown as dashed lines. The As atom sits on the threefold axis in P3, resulting in two sets of (three) nonequivalent F atoms, only one set of which is involved in hydrogen bonding.

(I) hexakis(pyrazole-N²)copper(II) bis(hexafluoroarsenate)

Crystal data

[Cu(C3H4N2)6](AsF6)2	Dx = 1.943 Mg m^−3
Mr = 849.87	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3	Cell parameters from 3793 reflections
a = 10.1780 (14) Å	θ = 1.0–27.5°
c = 8.0980 (16) Å	µ = 3.12 mm^−1
V = 726.5 (2) Å^3	T = 173 K
Z = 1	Irregular block, blue
F(000) = 419	0.30 × 0.28 × 0.25 mm

Data collection

Nonius KappaCCD area-detector diffractometer	1107 independent reflections
Radiation source: fine-focus sealed tube	949 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
Detector resolution: 18 pixels mm^-1	θmax = 27.4°, θmin = 2.3°
ω scans at fixed χ = 55°	h = −13→8
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −12→13
Tmin = 0.409, Tmax = 0.458	l = −10→10
4497 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
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) = 0.097	w = 1/[σ^2(Fo^2) + (0.0486P)^2 + 0.9805P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
1107 reflections	Δρmax = 0.97 e Å^−3
70 parameters	Δρmin = −0.77 e Å^−3
16 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (2)

Special details

Experimental. To assess crystal decay, the first area-detector scan was repeated at the end of the data collection. Comparison of the processed intensities from the first and last scans (128° in ω, 3100 reflections) revealed random fluctuations of less than 1%.

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
Cu	0.0000	0.0000	0.0000	0.0203 (2)
N1	0.1098 (3)	−0.0880 (3)	−0.1530 (3)	0.0352 (6)
N2	0.2597 (3)	−0.0385 (3)	−0.1463 (3)	0.0367 (6)
H2	0.3207	0.0230	−0.0697	0.044*
C1	0.0610 (4)	−0.1772 (4)	−0.2872 (4)	0.0387 (8)
H1	−0.0410	−0.2288	−0.3250	0.046*
C2	0.1794 (4)	−0.1839 (4)	−0.3632 (4)	0.0421 (8)
H2A	0.1749	−0.2392	−0.4597	0.050*
C3	0.3045 (4)	−0.0935 (4)	−0.2690 (5)	0.0439 (8)
H3	0.4049	−0.0737	−0.2880	0.053*
As	0.3333	−0.3333	0.13772 (7)	0.0308 (2)
F1	0.4574 (2)	−0.1859 (2)	0.0146 (3)	0.0418 (5)
F2	0.3121 (3)	−0.2072 (3)	0.2582 (3)	0.0570 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0205 (3)	0.0205 (3)	0.0200 (4)	0.01023 (15)	0.000	0.000
N1	0.0308 (14)	0.0333 (14)	0.0251 (13)	0.0039 (12)	−0.0046 (11)	0.0027 (10)
N2	0.0352 (15)	0.0352 (15)	0.0332 (14)	0.0125 (12)	−0.0095 (12)	0.0017 (12)
C1	0.0362 (17)	0.0383 (18)	0.0283 (15)	0.0088 (15)	−0.0050 (14)	0.0007 (13)
C2	0.053 (2)	0.0390 (19)	0.0308 (16)	0.0209 (17)	−0.0041 (15)	0.0044 (14)
C3	0.0411 (19)	0.043 (2)	0.046 (2)	0.0195 (16)	−0.0022 (16)	0.0108 (16)
As	0.0282 (2)	0.0282 (2)	0.0360 (3)	0.01409 (12)	0.000	0.000
F1	0.0345 (10)	0.0319 (10)	0.0525 (11)	0.0118 (8)	−0.0008 (9)	0.0040 (9)
F2	0.0624 (15)	0.0530 (14)	0.0601 (14)	0.0321 (12)	0.0024 (12)	−0.0180 (11)

Geometric parameters (Å, º)

Cu—N1^i	2.142 (3)	C1—H1	0.9500
Cu—N1	2.142 (3)	C2—C3	1.371 (5)
Cu—N1^ii	2.142 (3)	C2—H2A	0.9500
Cu—N1^iii	2.142 (3)	C3—H3	0.9500
Cu—N1^iv	2.142 (3)	As—F2^vi	1.709 (2)
Cu—N1^v	2.142 (3)	As—F2^vii	1.709 (2)
N1—C1	1.342 (4)	As—F2	1.710 (2)
N1—N2	1.347 (4)	As—F1^vi	1.716 (2)
N2—C3	1.328 (5)	As—F1^vii	1.716 (2)
N2—H2	0.8800	As—F1	1.716 (2)
C1—C2	1.385 (5)
N1^i—Cu—N1	90.11 (10)	C2—C1—H1	124.5
N1^i—Cu—N1^ii	89.89 (10)	C3—C2—C1	105.0 (3)
N1—Cu—N1^ii	90.11 (10)	C3—C2—H2A	127.5
N1^i—Cu—N1^iii	90.11 (10)	C1—C2—H2A	127.5
N1—Cu—N1^iii	89.89 (10)	N2—C3—C2	107.5 (3)
N1^ii—Cu—N1^iii	180.0	N2—C3—H3	126.3
N1^i—Cu—N1^iv	89.89 (10)	C2—C3—H3	126.3
N1—Cu—N1^iv	180.00 (11)	F2^vi—As—F2^vii	90.68 (12)
N1^ii—Cu—N1^iv	89.89 (10)	F2^vi—As—F2	90.68 (12)
N1^iii—Cu—N1^iv	90.11 (10)	F2^vii—As—F2	90.68 (12)
N1^i—Cu—N1^v	180.0	F2^vi—As—F1^vi	89.38 (11)
N1—Cu—N1^v	89.89 (10)	F2^vii—As—F1^vi	179.01 (10)
N1^ii—Cu—N1^v	90.11 (10)	F2—As—F1^vi	90.31 (11)
N1^iii—Cu—N1^v	89.89 (10)	F2^vi—As—F1^vii	90.31 (11)
N1^iv—Cu—N1^v	90.11 (10)	F2^vii—As—F1^vii	89.38 (11)
C1—N1—N2	104.6 (3)	F2—As—F1^vii	179.01 (10)
C1—N1—Cu	131.1 (2)	F1^vi—As—F1^vii	89.63 (10)
N2—N1—Cu	123.4 (2)	F2^vi—As—F1	179.01 (10)
C3—N2—N1	112.1 (3)	F2^vii—As—F1	90.31 (11)
C3—N2—H2	124.0	F2—As—F1	89.38 (11)
N1—N2—H2	124.0	F1^vi—As—F1	89.63 (10)
N1—C1—C2	110.9 (3)	F1^vii—As—F1	89.63 (10)
N1—C1—H1	124.5
N1^i—Cu—N1—C1	89.4 (2)	C1—N1—N2—C3	−0.3 (4)
N1^ii—Cu—N1—C1	179.3 (3)	Cu—N1—N2—C3	−170.5 (2)
N1^iii—Cu—N1—C1	−0.7 (3)	N2—N1—C1—C2	0.3 (4)
N1^v—Cu—N1—C1	−90.6 (2)	Cu—N1—C1—C2	169.5 (2)
N1^i—Cu—N1—N2	−103.2 (3)	N1—C1—C2—C3	−0.2 (4)
N1^ii—Cu—N1—N2	−13.3 (2)	N1—N2—C3—C2	0.2 (4)
N1^iii—Cu—N1—N2	166.7 (2)	C1—C2—C3—N2	0.0 (4)
N1^v—Cu—N1—N2	76.8 (3)

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

(II) hexakis(pyrazole-N²)copper(II) hexafluorophosphate perchlorate

Crystal data

[Cu(C3H4N2)6](PF6)1.29(ClO4)0.71	Dx = 1.740 Mg m^−3
Mr = 729.90	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3	Cell parameters from 4084 reflections
a = 9.995 (1) Å	θ = 1.0–27.5°
c = 8.052 (1) Å	µ = 1.03 mm^−1
V = 696.63 (13) Å^3	T = 173 K
Z = 1	Irregular block, blue
F(000) = 369	0.4 × 0.4 × 0.4 mm

Data collection

Nonius KappaCCD area-detector diffractometer	1072 independent reflections
Radiation source: fine-focus sealed tube	967 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 18 pixels mm^-1	θmax = 27.5°, θmin = 2.4°
ω scans at fixed χ = 55°	h = −12→10
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −12→12
Tmin = 0.623, Tmax = 0.685	l = −10→10
4132 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.049P)^2 + 0.3481P] where P = (Fo^2 + 2Fc^2)/3
1072 reflections	(Δ/σ)max = 0.002
82 parameters	Δρmax = 0.27 e Å^−3
93 restraints	Δρmin = −0.60 e Å^−3

Special details

Experimental. To assess crystal decay, the first area-detector scan was repeated at the end of the data collection. Comparison of the processed intensities from the first and last scans (104° in ω, 2594 reflections) revealed random fluctuations of less than 1%. Upon refinement, the crystal of (II) was found to contain a mixture of anions, the major component being the expected PF₆^-, with a small fraction of ClO₄^-. A disorder model was constructed by including including a fractional Cl atom constrained to the same coordinates and anisotropic displacement parameters as the P atom, and fractional O-atom positions obtained from a difference Fourier map.

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	Occ. (<1)
Cu	0.0000	0.0000	0.0000	0.0288 (2)
N1	0.1117 (2)	0.1999 (2)	0.1531 (2)	0.0448 (5)
N2	0.2639 (2)	0.3012 (2)	0.1476 (2)	0.0497 (5)
H2	0.3261	0.3003	0.0708	0.060*
C1	0.0626 (3)	0.2429 (3)	0.2872 (3)	0.0507 (6)
H1	−0.0415	0.1924	0.3244	0.061*
C2	0.1822 (3)	0.3694 (3)	0.3641 (3)	0.0522 (6)
H2A	0.1772	0.4218	0.4602	0.063*
C3	0.3099 (3)	0.4026 (3)	0.2708 (3)	0.0571 (6)
H3	0.4126	0.4835	0.2909	0.068*
P	0.6667	0.3333	0.14457 (13)	0.0431 (3)	0.643 (6)
F1	0.6445 (3)	0.1946 (3)	0.0207 (3)	0.0465 (7)	0.643 (6)
F2	0.5269 (3)	0.2137 (3)	0.2488 (3)	0.0607 (11)	0.643 (6)
Cl	0.6667	0.3333	0.14457 (13)	0.0431 (3)	0.357 (6)
O1A	0.6667	0.3333	0.3225 (15)	0.155 (8)	0.357 (6)
O2A	0.5774 (18)	0.1831 (12)	0.0960 (18)	0.163 (7)	0.357 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0298 (2)	0.0298 (2)	0.0267 (3)	0.01492 (11)	0.000	0.000
N1	0.0418 (10)	0.0669 (13)	0.0323 (9)	0.0321 (10)	0.0023 (7)	0.0066 (8)
N2	0.0516 (11)	0.0537 (12)	0.0432 (11)	0.0259 (10)	0.0129 (9)	0.0099 (9)
C1	0.0500 (13)	0.0775 (17)	0.0349 (11)	0.0395 (13)	0.0036 (10)	0.0036 (11)
C2	0.0694 (16)	0.0581 (14)	0.0421 (13)	0.0417 (13)	0.0029 (11)	0.0073 (11)
C3	0.0578 (15)	0.0486 (14)	0.0606 (15)	0.0235 (12)	0.0050 (12)	0.0125 (12)
P	0.0365 (3)	0.0365 (3)	0.0562 (6)	0.01827 (17)	0.000	0.000
F1	0.0537 (14)	0.0396 (12)	0.0535 (14)	0.0288 (11)	−0.0050 (10)	−0.0035 (10)
F2	0.0558 (16)	0.0590 (16)	0.0611 (18)	0.0242 (12)	0.0230 (12)	0.0222 (12)
Cl	0.0365 (3)	0.0365 (3)	0.0562 (6)	0.01827 (17)	0.000	0.000
O1A	0.200 (13)	0.200 (13)	0.064 (6)	0.100 (7)	0.000	0.000
O2A	0.160 (12)	0.070 (5)	0.167 (13)	−0.011 (7)	−0.085 (12)	−0.016 (7)

Geometric parameters (Å, º)

Cu—N1^i	2.128 (2)	C1—H1	0.9500
Cu—N1	2.128 (2)	C2—C3	1.371 (4)
Cu—N1^ii	2.128 (2)	C2—H2A	0.9500
Cu—N1^iii	2.128 (2)	C3—H3	0.9500
Cu—N1^iv	2.128 (2)	P—F2^vi	1.554 (2)
Cu—N1^v	2.128 (2)	P—F2	1.554 (2)
N1—N2	1.342 (3)	P—F2^vii	1.554 (2)
N1—C1	1.342 (3)	P—F1	1.631 (3)
N2—C3	1.326 (3)	P—F1^vii	1.631 (3)
N2—H2	0.8800	P—F1^vi	1.631 (3)
C1—C2	1.378 (4)
N1—Cu—N1^iv	180.0 (12)	C2—C1—H1	124.2
N1—Cu—N1^ii	90.20 (7)	C3—C2—C1	104.5 (2)
N1^iv—Cu—N1^ii	89.80 (7)	C3—C2—H2A	127.7
N1—Cu—N1^iii	89.80 (7)	C1—C2—H2A	127.7
N1^iv—Cu—N1^iii	90.20 (7)	N2—C3—C2	107.4 (2)
N1^ii—Cu—N1^iii	180.00 (12)	N2—C3—H3	126.3
N1—Cu—N1^v	89.80 (7)	C2—C3—H3	126.3
N1^iv—Cu—N1^v	90.20 (7)	F2^vi—P—F2	93.57 (15)
N1^ii—Cu—N1^v	90.20 (7)	F2^vi—P—F2^vii	93.57 (15)
N1^iii—Cu—N1^v	89.80 (7)	F2—P—F2^vii	93.57 (15)
N1—Cu—N1^i	90.20 (7)	F2^vi—P—F1	174.93 (16)
N1^iv—Cu—N1^i	89.80 (7)	F2—P—F1	89.34 (14)
N1^ii—Cu—N1^i	89.80 (7)	F2^vii—P—F1	90.39 (14)
N1^iii—Cu—N1^i	90.20 (7)	F2^vi—P—F1^vii	90.39 (14)
N1^v—Cu—N1^i	180.00 (12)	F2—P—F1^vii	174.92 (16)
N2—N1—C1	104.1 (2)	F2^vii—P—F1^vii	89.34 (14)
N2—N1—Cu	123.64 (15)	F1—P—F1^vii	86.48 (15)
C1—N1—Cu	131.48 (18)	F2^vi—P—F1^vi	89.34 (14)
C3—N2—N1	112.4 (2)	F2—P—F1^vi	90.39 (14)
C3—N2—H2	123.8	F2^vii—P—F1^vi	174.92 (16)
N1—N2—H2	123.8	F1—P—F1^vi	86.48 (15)
N1—C1—C2	111.5 (2)	F1^vii—P—F1^vi	86.48 (15)
N1—C1—H1	124.2
N1^ii—Cu—N1—N2	−103.5 (2)	C1—N1—N2—C3	0.2 (3)
N1^iii—Cu—N1—N2	76.5 (2)	Cu—N1—N2—C3	−170.45 (16)
N1^v—Cu—N1—N2	166.33 (16)	N2—N1—C1—C2	0.2 (3)
N1^i—Cu—N1—N2	−13.67 (16)	Cu—N1—C1—C2	169.81 (16)
N1^ii—Cu—N1—C1	88.62 (17)	N1—C1—C2—C3	−0.5 (3)
N1^iii—Cu—N1—C1	−91.38 (17)	N1—N2—C3—C2	−0.5 (3)
N1^v—Cu—N1—C1	−1.6 (2)	C1—C2—C3—N2	0.6 (3)
N1^i—Cu—N1—C1	178.4 (2)

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