Poly[(μ-penta­fluoro­benzoato-κ²O:O′)(penta­fluoro­benzoato-κO)(μ-pyrazine-κ²N:N′)copper(II)]: a coordination polymer linked into a three-dimensional network by inter­molecular C—H...F—C inter­actions

In the title compound, [Cu(C₆F₅COO)₂(C₄H₄N₂)]_n, (I), the asymmetric unit contains one Cu^II cation, two anionic penta­fluoro­benzoate ligands and one pyrazine ligand. Each Cu^II centre is five-coordinated by three O atoms from three independent penta­fluoro­benzoate anions, as well as by two N atoms from two pyrazine ligands, giving rise to an approximately square-pyramidal coordination geometry. Adjacent Cu^II cations are bridged by a pyrazine ligand and two penta­fluoro­benzoate anions to give a two-dimensional layer. The layers are stacked to generate a three-dimensional supra­molecular architecture via strong inter­molecular C—H...F—C inter­actions, as indicated by the F...H distance of 2.38 Å.

S1. Introduction

Studies of coordination polymers have witnessed an upsurge in recent years due to their novel architectures, as well as their potential applications as functional materials (Hou et al., 2014; Freslon et al., 2014; Rybak et al., 2010; Deng et al., 2010). To date, a large number of coordination polymers have already been obtained through the assembly of various organic ligands and metal ions. However, the rational design and controllable prediction of prospective networks is still a great challenge, due to complicated factors such as the organic ligands, metal ions, solvent, temperature and counter-ions that could influence the ultimate structures (Manna et al., 2014; Lee et al., 2004). Recently, the utilization of mixed-ligand systems based on carboxyl­ates and N-donor ligands has proved to be an effective strategy to construct more intricate coordination polymers (Zhang et al., 2013; Wang et al., 2013). In dual-ligand systems, metal–carboxyl­ate architectures can be finely tuned by incorporating the different secondary N-donor linkers.

Taking all the above into account, we have successfully synthesized two new coordination polymers having the same coordination modes and structures, based on reactions of copper acetate, penta­fluoro­benzoic acid and pyrazine under different reaction conditions. Poly[[tris­(µ-penta­fluoro­benzoato-κ²O:O')bis­(µ-pyrazine-κ²N:N')copper(II)], (I), has been synthesized by a one-pot method with tri­ethyl­amine in ethanol. The same compound, denoted (II), has been obtained under hydro­thermal conditions without tri­ethyl­amine. In this paper, we report mainly the structural characterization of (I), and compare the two reaction pathways.

S2. Experimental

S2.1. Synthesis and crystallization

For the preparation of the (I), Cu(CH₃COO)₂·H₂O (0.040 g, 0.20 mmol), penta­fluoro­benzoic acid (0.083 g, 0.40 mmol) and pyrazine (0.016 g, 0.20 mmol) were mixed in ethanol (10 ml) and tri­ethyl­amine (0.06 ml) in a flask equipped with a condenser, and the mixture was heated at 353 K for 3 h. During this period, a blue precipitate formed. The reaction mixture was cooled to room temperature, the precipitate removed by filtration, and the blue solid washed with ethanol (6 ml) and then dried under vacuum. The crude product was dissolved in di­methyl­formamide (12 ml) and the solution was layered with ethanol. Blue block-shaped crystals formed after 7 d (yield 0.067 g, 60% based on Cu²⁺). Analysis, calculated for C₁₈H₄CuF₁₀N₂O₄: C 38.21, H 0.71, N 4.95%; found: C 38.14, H 0.80, N 5.03%.

For the preparation of (II), a mixture containing Cu(CH₃COO)₂·H₂O (0.040 g, 0.20 mmol), penta­fluoro­benzoic acid (0.083 g, 0.40 mmol) and pyrazine (0.016 g, 0.30 mmol) in water (10 ml) was sealed in a Teflon-lined autoclave and heated under autogenic pressure to 358 K for 3 d and then allowed to cool to room temperature at a rate of 1 K h^-1. Blue block-shaped crystals were obtained and these were collected by filtration, washed several times with distilled water and dried in air (yield 0.061 g, 55% based on Cu²⁺). Analysis, calculated for C₁₈H₄CuF₁₀N₂O₄: C 38.21, H 0.71, N 4.95%; found: C,38.38, H 0.75, N 4.89%.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in geometrically idealized positions and refined using a riding model, with C—H = 0.93 Å and with U_iso(H) = 1.2U_eq(C). [Please check added text]

S3. Results and discussion

X-ray crystallographic analysis revealed that (I) crystallizes in the triclinic space group P1 with the molecule residing on a general position (Fig. 1). The relevant asymmetric unit consists of one crystallographically independent Cu^II centre, three penta­fluoro­benzoate anions (C₆F₅COO^-) and two pyrazine ligands. The Cu^II cation is in an approximately square-pyramidal coordination environment, in which the equatorial plane is composed of two N atoms from two pyrazine ligands and two O atoms from two independent penta­fluoro­benzoate anions, while one O atom from a different penta­fluoro­benzoate anion occupies the apical position. Each Cu^II centre is five coordinated by three O atoms (O1 and O3, with O2 in the apical position) from three different penta­fluoro­benzoate anions (Table 2). Of the three independent Cu—O distances (Table 2), the apical Cu1—O2 distance is longer than the others, and it is especially longer than the two Cu—N distances. The angles among the two O atoms (O1 and O3) and two N atoms (N1 and N2) with Cu1 indicate that these five atoms are approximately located in an equatorial plane. The angles involving atom O2 (located at the apical position) and the equatorial plane (Table 2) indicate an approximately square-pyramidal coordination geometry. This coordination geometry of the five-coordinated Cu^II cation has been reported previously in recent years (Kennedy et al., 2014; Tjioe et al., 2011; Boonmak et al., 2009; Cui et al., 2008).

The penta­fluoro­benzoate anion coordination mode of µ₃-η¹:η² is found in the crystal structure. The C₆F₅COO^- group bridges two Cu^II cations; the carboxyl­ate group at C17 is monondentate, while that at C18 is bidentate-chelating to the Cu^II cations. The two carboxyl­ate groups of the penta­fluoro­benzoate anions coordinate two Cu^II cations to form a Cu–C₆F₅COO^- chain, with a Cu1···Cu2 distance of 4.8046 (9) Å. Consequently, a one-dimensional linear chain is formed (Fig. 2). The Cu···Cu distance is longer than twice the sum of the van der Waals radius of copper (2.8 Å; Bondi, 1964), suggesting that there are no significant metal–metal inter­actions.

The pyrazine ligands connect adjacent Cu^II cations to form a one-dimensional linear chain, with a Cu1···Cu2 distance of 6.9047 (9) Å (Fig. 3). Obviously, the two kinds of one-dimensional chain cross each other by sharing Cu^II cations, generating a two-dimensional sheet. A schematic diagram of the two-dimensional polymeric layer is shown in Fig. 4. Adjacent two-dimensional layers are linked by inter­molecular C—H···F—C inter­actions between pyrazine H atoms and the F atoms of the penta­fluoro­benzoate anions, constructing a three-dimensional supra­molecular framework (Fig. 5).

From a thermodynamic point of view, the C—F bond is exceptionally strong, which is one of the reasons for the unique nature of fluorinated compounds. Incorporation of F atoms can lead to high stability, but also to a distinctly altered reactivity of fluorinated compounds compared with their nonfluorinated counterparts. For fluoro­aromatic compounds, C—H···F—C inter­actions, although weak, contribute significantly to regulating the arrangement of organic molecules in the crystalline state and to stabilizing the secondary structure of biomolecules such as DNA. The sum of the van der Waals radii of fluorine and hydrogen is about 2.67 Å. Consequently, an F···H distance up to 2.9 Å is considered as a C—H···F—C inter­action. The C—H···F angles [In (I)?] range from 70 to 180°, and such a wide range suggests weak inter­actions (Reichenbächer et al., 2005). In (I), the shortest F···H distance is 2.38 Å and the corresponding C—H···F angle is 144°. These results indicate the existence of strong C—H···F—C inter­actions in (I). Compared with (I), compound (II) has a shorter H···F distance of 2.37 Å and the C—H···F angle is 141°.

In order to investigate the function of tri­ethyl­amine, two different experiments were carried out in ethanol under one-pot conditions, the first including the addition of tri­ethyl­amine and the second with no tri­ethyl­amine. After 10 d, blue-block crystals formed in the former, but no crystals appeared in the latter. So tri­ethyl­amine, as a weak organic base, deprotonates C₆F₅COOH to C₆F₅COO^-, and plays an important role in assisting crystal formation and controlling crystal size (Nordin et al., 2014; Tanaka & Ajiki, 2005; Klein et al., 2004).

It has been demonstrated previously that Cu^II can be easily hydro­thermally converted into Cu^I in the presence of different types of aromatic species (Chen & Tong, 2007; Lu, 2003). We expected that a Cu^I compound could be obtained under hydro­thermal conditions in our experiment. Nevertheless, the result demonstrated that Cu^II had not been reduced to Cu^I. Further studies of the effects of solvent and temperature on the formation of diverse Cu^I compounds under hydro­thermal conditions are in progress in our laboratory. Comparing the two reaction pathways, we think the hydro­thermal method has more advantages than the one-pot reflux method, firstly because the use of water as solvent is environmentally sound and a low-cost method, and secondly because, by virtue of high temperature and pressure, novel crystal structures and topologies can appear.

In summary, two similar structures have been obtained under different reaction conditions, indicating that the title compound is a stable structure with a five-coordinated Cu^II cation. Moreover, the results show that C—H···F—C inter­actions may play an important role in the formation of new supra­molecular structures, and can be utilized in crystal design and engineering.

Related literature

For related literature, see: Bondi (1964); Boonmak et al. (2009); Chen & Tong (2007); Cui et al. (2008); Deng et al. (2010); Freslon et al. (2014); Hou et al. (2014); Kennedy et al. (2014); Klein et al. (2004); Lee et al. (2004); Lu (2003); Manna et al. (2014); Nordin et al. (2014); Reichenbächer et al. (2005); Rybak et al. (2010); Tanaka & Ajiki (2005); Tjioe et al. (2011); Wang et al. (2013); Zhang et al. (2013).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. All H atoms have been omitted for clarity.
	Fig. 2. Part of the one-dimensional linear chain formed by the Cu—O coordination linkage.
	Fig. 3. Part of the one-dimensional linear chain formed by the Cu—N coordination bonds. All pentafluorobenzene rings have been omitted for clarity.
	Fig. 4. The two-dimensional sheet formed by Cu—O and Cu—N coordination bonds. All pentafluorobenzene rings have been omitted for clarity.
	Fig. 5. A molecular packing diagram of (I), showing the intermolecular H···F contacts (dashed lines).

(I) Poly[[(µ-pentafluorobenzoato-κ²O:O')(pentafluorobenzoato-κO)(µ-pyrazine-κ²N:N')copper(II)]:

Crystal data

[Cu(C7F5O2)2(C4H4N2)]	Z = 2
Mr = 565.77	F(000) = 554
Triclinic, P1	Dx = 1.951 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.8046 (9) Å	Cell parameters from 2974 reflections
b = 13.072 (2) Å	θ = 2.7–24.7°
c = 15.357 (3) Å	µ = 1.26 mm^−1
α = 89.785 (2)°	T = 293 K
β = 89.660 (2)°	Block, blue
γ = 86.666 (2)°	0.10 × 0.10 × 0.08 mm
V = 962.9 (3) Å^3

Data collection

Bruker SMART 1000 diffractometer	3385 independent reflections
Radiation source: fine-focus sealed tube	2753 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω scans	θmax = 25.0°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −5→5
Tmin = 0.881, Tmax = 0.904	k = −15→15
9285 measured reflections	l = −18→18

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.059P)^2] where P = (Fo^2 + 2Fc^2)/3
3385 reflections	(Δ/σ)max < 0.001
316 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Cu1	0.26122 (7)	0.74938 (3)	0.48090 (2)	0.02369 (14)
N1	0.1068 (5)	0.89955 (18)	0.49009 (17)	0.0267 (6)
N2	0.4137 (5)	0.60168 (18)	0.48714 (17)	0.0255 (6)
O1	0.4520 (4)	0.78130 (16)	0.37229 (14)	0.0320 (5)
O2	0.8640 (4)	0.71430 (17)	0.41473 (14)	0.0329 (5)
O3	0.1077 (5)	0.72142 (15)	0.59561 (14)	0.0311 (5)
O4	0.4588 (6)	0.7989 (3)	0.65249 (19)	0.0661 (9)
F1	−0.0892 (6)	0.8952 (2)	0.75694 (17)	0.0758 (8)
F2	−0.3298 (8)	0.8494 (3)	0.9105 (2)	0.1320 (15)
F3	−0.2351 (10)	0.6620 (4)	0.9812 (2)	0.1562 (18)
F4	0.1025 (13)	0.5183 (3)	0.8986 (3)	0.181 (2)
F5	0.3344 (9)	0.5638 (2)	0.7437 (2)	0.1187 (14)
F6	0.5716 (6)	0.94161 (18)	0.26382 (16)	0.0767 (9)
F7	0.7947 (7)	0.9858 (2)	0.11008 (18)	0.0954 (10)
F8	1.1780 (7)	0.8540 (3)	0.03530 (17)	0.0980 (10)
F9	1.3248 (7)	0.6741 (3)	0.11389 (18)	0.1082 (12)
F10	1.0936 (6)	0.62475 (19)	0.26519 (15)	0.0746 (8)
C1	0.6123 (6)	0.5749 (2)	0.5441 (2)	0.0295 (7)
H1	0.6945	0.6253	0.5759	0.035*
C2	0.3009 (6)	0.5272 (2)	0.4432 (2)	0.0277 (7)
H2	0.1610	0.5438	0.4032	0.033*
C3	0.2094 (6)	0.9763 (2)	0.4454 (2)	0.0292 (7)
H3	0.3554	0.9623	0.4064	0.035*
C4	−0.1049 (6)	0.9237 (2)	0.5448 (2)	0.0307 (7)
H4	−0.1832	0.8720	0.5768	0.037*
C5	−0.0415 (8)	0.8019 (3)	0.7916 (3)	0.0528 (10)
C6	−0.1641 (10)	0.7788 (5)	0.8696 (3)	0.0783 (16)
C7	−0.1147 (14)	0.6836 (6)	0.9048 (3)	0.096 (2)
C8	0.0531 (16)	0.6115 (5)	0.8637 (4)	0.103 (2)
C9	0.1708 (12)	0.6354 (4)	0.7847 (3)	0.0714 (14)
C10	0.1260 (8)	0.7306 (3)	0.7470 (2)	0.0427 (9)
C11	0.7539 (8)	0.8721 (3)	0.2282 (2)	0.0436 (9)
C12	0.8687 (9)	0.8974 (3)	0.1489 (3)	0.0557 (11)
C13	1.0615 (9)	0.8305 (4)	0.1112 (3)	0.0608 (12)
C14	1.1369 (9)	0.7396 (4)	0.1511 (3)	0.0619 (12)
C15	1.0175 (8)	0.7159 (3)	0.2297 (2)	0.0451 (9)
C16	0.8233 (6)	0.7810 (3)	0.2715 (2)	0.0310 (7)
C17	0.2476 (7)	0.7541 (3)	0.6589 (2)	0.0349 (8)
C18	0.7091 (6)	0.7564 (2)	0.3602 (2)	0.0261 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0249 (2)	0.0157 (2)	0.0298 (2)	0.00401 (14)	0.00551 (15)	0.00319 (14)
N1	0.0282 (14)	0.0201 (13)	0.0312 (15)	0.0038 (10)	0.0051 (11)	0.0020 (11)
N2	0.0248 (13)	0.0193 (13)	0.0318 (15)	0.0021 (10)	0.0064 (11)	0.0021 (11)
O1	0.0279 (12)	0.0294 (12)	0.0371 (13)	0.0098 (9)	0.0088 (10)	0.0067 (10)
O2	0.0259 (11)	0.0418 (13)	0.0309 (13)	−0.0033 (10)	−0.0021 (10)	0.0101 (10)
O3	0.0382 (13)	0.0243 (11)	0.0302 (13)	0.0009 (10)	0.0058 (10)	0.0028 (10)
O4	0.0505 (17)	0.100 (2)	0.0520 (18)	−0.0365 (17)	0.0059 (14)	−0.0016 (16)
F1	0.0881 (19)	0.0735 (18)	0.0621 (17)	0.0263 (15)	0.0060 (14)	−0.0094 (14)
F2	0.114 (3)	0.201 (4)	0.074 (2)	0.046 (3)	0.044 (2)	−0.027 (2)
F3	0.198 (4)	0.215 (5)	0.058 (2)	−0.042 (4)	0.064 (3)	0.026 (2)
F4	0.335 (7)	0.114 (3)	0.091 (3)	−0.004 (4)	0.052 (4)	0.061 (2)
F5	0.203 (4)	0.067 (2)	0.080 (2)	0.042 (2)	0.047 (2)	0.0221 (16)
F6	0.107 (2)	0.0524 (15)	0.0651 (16)	0.0358 (14)	0.0394 (15)	0.0252 (12)
F7	0.143 (3)	0.078 (2)	0.0625 (18)	0.0115 (19)	0.0236 (18)	0.0428 (15)
F8	0.111 (2)	0.136 (3)	0.0462 (16)	−0.007 (2)	0.0399 (16)	0.0233 (17)
F9	0.112 (2)	0.139 (3)	0.0653 (18)	0.056 (2)	0.0522 (18)	0.0014 (19)
F10	0.100 (2)	0.0663 (16)	0.0510 (14)	0.0484 (15)	0.0232 (14)	0.0074 (12)
C1	0.0315 (17)	0.0212 (16)	0.0357 (19)	0.0007 (13)	−0.0012 (14)	−0.0010 (14)
C2	0.0274 (16)	0.0229 (16)	0.0323 (18)	0.0032 (13)	−0.0011 (14)	0.0018 (14)
C3	0.0276 (16)	0.0231 (16)	0.0361 (18)	0.0048 (13)	0.0105 (14)	0.0035 (13)
C4	0.0309 (17)	0.0214 (16)	0.039 (2)	0.0012 (13)	0.0124 (15)	0.0065 (14)
C5	0.047 (2)	0.072 (3)	0.038 (2)	0.001 (2)	0.0022 (18)	−0.007 (2)
C6	0.064 (3)	0.123 (5)	0.046 (3)	0.009 (3)	0.019 (2)	−0.014 (3)
C7	0.108 (5)	0.138 (6)	0.043 (3)	−0.022 (4)	0.029 (3)	0.011 (3)
C8	0.165 (6)	0.090 (4)	0.055 (3)	−0.013 (4)	0.027 (4)	0.030 (3)
C9	0.105 (4)	0.061 (3)	0.047 (3)	0.002 (3)	0.019 (3)	0.011 (2)
C10	0.042 (2)	0.054 (2)	0.032 (2)	−0.0054 (17)	0.0025 (16)	−0.0018 (17)
C11	0.050 (2)	0.045 (2)	0.035 (2)	0.0057 (17)	0.0106 (17)	0.0074 (17)
C12	0.068 (3)	0.055 (3)	0.043 (2)	0.000 (2)	0.008 (2)	0.019 (2)
C13	0.062 (3)	0.088 (3)	0.032 (2)	−0.003 (2)	0.017 (2)	0.011 (2)
C14	0.056 (3)	0.086 (3)	0.041 (2)	0.019 (2)	0.019 (2)	0.000 (2)
C15	0.045 (2)	0.055 (2)	0.032 (2)	0.0147 (18)	0.0104 (17)	0.0030 (17)
C16	0.0256 (16)	0.0388 (19)	0.0282 (18)	0.0008 (14)	0.0029 (13)	0.0034 (15)
C17	0.0365 (19)	0.0360 (19)	0.0314 (19)	0.0034 (15)	0.0055 (16)	0.0013 (15)
C18	0.0281 (17)	0.0231 (16)	0.0270 (17)	−0.0014 (13)	0.0058 (14)	−0.0026 (13)

Geometric parameters (Å, º)

Cu1—O3	1.947 (2)	F10—C15	1.341 (4)
Cu1—O1	1.954 (2)	C1—C2^iii	1.388 (4)
Cu1—N2	2.027 (2)	C1—H1	0.9300
Cu1—N1	2.063 (2)	C2—C1^iii	1.388 (4)
Cu1—O2^i	2.239 (2)	C2—H2	0.9300
N1—C3	1.331 (4)	C3—C4^iv	1.381 (4)
N1—C4	1.339 (4)	C3—H3	0.9300
N2—C1	1.329 (4)	C4—C3^iv	1.381 (4)
N2—C2	1.329 (4)	C4—H4	0.9300
O1—C18	1.272 (4)	C5—C6	1.373 (6)
O2—C18	1.230 (4)	C5—C10	1.377 (5)
O2—Cu1^ii	2.239 (2)	C6—C7	1.363 (8)
O3—C17	1.274 (4)	C7—C8	1.358 (8)
O4—C17	1.204 (4)	C8—C9	1.379 (7)
F1—C5	1.337 (5)	C9—C10	1.376 (6)
F2—C6	1.338 (6)	C10—C17	1.508 (5)
F3—C7	1.341 (6)	C11—C12	1.381 (5)
F4—C8	1.339 (6)	C11—C16	1.385 (5)
F5—C9	1.343 (5)	C12—C13	1.364 (6)
F6—C11	1.341 (4)	C13—C14	1.366 (6)
F7—C12	1.329 (5)	C14—C15	1.375 (5)
F8—C13	1.332 (4)	C15—C16	1.383 (5)
F9—C14	1.335 (4)	C16—C18	1.507 (4)
O3—Cu1—O1	173.78 (10)	F3—C7—C8	120.2 (6)
O3—Cu1—N2	84.24 (9)	F3—C7—C6	118.7 (6)
O1—Cu1—N2	95.41 (9)	C8—C7—C6	121.1 (5)
O3—Cu1—N1	89.80 (9)	F4—C8—C7	121.0 (5)
O1—Cu1—N1	90.19 (9)	F4—C8—C9	120.1 (6)
N2—Cu1—N1	173.36 (10)	C7—C8—C9	118.9 (5)
O3—Cu1—O2^i	92.26 (9)	F5—C9—C10	119.3 (4)
O1—Cu1—O2^i	93.96 (9)	F5—C9—C8	118.9 (5)
N2—Cu1—O2^i	95.23 (9)	C10—C9—C8	121.8 (5)
N1—Cu1—O2^i	87.90 (9)	C9—C10—C5	117.3 (4)
C3—N1—C4	116.7 (2)	C9—C10—C17	121.1 (3)
C3—N1—Cu1	123.6 (2)	C5—C10—C17	121.6 (3)
C4—N1—Cu1	119.6 (2)	F6—C11—C12	116.7 (3)
C1—N2—C2	117.5 (3)	F6—C11—C16	120.2 (3)
C1—N2—Cu1	119.7 (2)	C12—C11—C16	123.1 (3)
C2—N2—Cu1	122.3 (2)	F7—C12—C13	120.4 (4)
C18—O1—Cu1	121.7 (2)	F7—C12—C11	120.7 (4)
C18—O2—Cu1^ii	136.3 (2)	C13—C12—C11	118.9 (4)
C17—O3—Cu1	114.6 (2)	F8—C13—C12	119.9 (4)
N2—C1—C2^iii	121.1 (3)	F8—C13—C14	119.8 (4)
N2—C1—H1	119.5	C12—C13—C14	120.3 (4)
C2^iii—C1—H1	119.5	F9—C14—C13	120.2 (4)
N2—C2—C1^iii	121.4 (3)	F9—C14—C15	120.3 (4)
N2—C2—H2	119.3	C13—C14—C15	119.6 (4)
C1^iii—C2—H2	119.3	F10—C15—C14	117.3 (3)
N1—C3—C4^iv	121.8 (3)	F10—C15—C16	119.9 (3)
N1—C3—H3	119.1	C14—C15—C16	122.8 (4)
C4^iv—C3—H3	119.1	C15—C16—C11	115.3 (3)
N1—C4—C3^iv	121.5 (3)	C15—C16—C18	121.7 (3)
N1—C4—H4	119.3	C11—C16—C18	122.8 (3)
C3^iv—C4—H4	119.3	O4—C17—O3	125.6 (3)
F1—C5—C6	119.5 (4)	O4—C17—C10	120.9 (3)
F1—C5—C10	118.9 (4)	O3—C17—C10	113.5 (3)
C6—C5—C10	121.6 (4)	O2—C18—O1	124.9 (3)
F2—C6—C7	120.7 (5)	O2—C18—C16	119.5 (3)
F2—C6—C5	120.1 (5)	O1—C18—C16	115.6 (3)
C7—C6—C5	119.3 (5)
O3—Cu1—N1—C3	156.8 (3)	F5—C9—C10—C17	2.6 (7)
O1—Cu1—N1—C3	−17.0 (3)	C8—C9—C10—C17	−177.7 (5)
O2^i—Cu1—N1—C3	−110.9 (3)	F1—C5—C10—C9	179.9 (4)
O3—Cu1—N1—C4	−21.9 (2)	C6—C5—C10—C9	−1.3 (6)
O1—Cu1—N1—C4	164.3 (2)	F1—C5—C10—C17	−2.2 (6)
O2^i—Cu1—N1—C4	70.4 (2)	C6—C5—C10—C17	176.5 (4)
O3—Cu1—N2—C1	−68.1 (2)	F6—C11—C12—F7	−1.4 (6)
O1—Cu1—N2—C1	105.6 (2)	C16—C11—C12—F7	179.9 (4)
O2^i—Cu1—N2—C1	−159.9 (2)	F6—C11—C12—C13	178.1 (4)
O3—Cu1—N2—C2	104.0 (2)	C16—C11—C12—C13	−0.6 (7)
O1—Cu1—N2—C2	−82.3 (2)	F7—C12—C13—F8	0.5 (7)
O2^i—Cu1—N2—C2	12.2 (2)	C11—C12—C13—F8	−179.0 (4)
N2—Cu1—O1—C18	−46.8 (2)	F7—C12—C13—C14	−179.9 (5)
N1—Cu1—O1—C18	129.6 (2)	C11—C12—C13—C14	0.7 (7)
O2^i—Cu1—O1—C18	−142.5 (2)	F8—C13—C14—F9	−0.6 (7)
N2—Cu1—O3—C17	100.1 (2)	C12—C13—C14—F9	179.8 (4)
N1—Cu1—O3—C17	−77.0 (2)	F8—C13—C14—C15	179.6 (4)
O2^i—Cu1—O3—C17	−164.9 (2)	C12—C13—C14—C15	−0.1 (8)
C2—N2—C1—C2^iii	0.3 (5)	F9—C14—C15—F10	−1.4 (7)
Cu1—N2—C1—C2^iii	172.7 (2)	C13—C14—C15—F10	178.5 (4)
C1—N2—C2—C1^iii	−0.3 (5)	F9—C14—C15—C16	179.6 (4)
Cu1—N2—C2—C1^iii	−172.5 (2)	C13—C14—C15—C16	−0.6 (7)
C4—N1—C3—C4^iv	0.6 (5)	F10—C15—C16—C11	−178.4 (4)
Cu1—N1—C3—C4^iv	−178.2 (2)	C14—C15—C16—C11	0.7 (6)
C3—N1—C4—C3^iv	−0.6 (5)	F10—C15—C16—C18	4.9 (6)
Cu1—N1—C4—C3^iv	178.2 (3)	C14—C15—C16—C18	−176.0 (4)
F1—C5—C6—F2	0.0 (7)	F6—C11—C16—C15	−178.7 (4)
C10—C5—C6—F2	−178.8 (4)	C12—C11—C16—C15	−0.1 (6)
F1—C5—C6—C7	−180.0 (5)	F6—C11—C16—C18	−2.0 (6)
C10—C5—C6—C7	1.3 (8)	C12—C11—C16—C18	176.6 (4)
F2—C6—C7—F3	−0.1 (9)	Cu1—O3—C17—O4	−0.2 (5)
C5—C6—C7—F3	179.8 (5)	Cu1—O3—C17—C10	−179.4 (2)
F2—C6—C7—C8	180.0 (6)	C9—C10—C17—O4	−98.9 (5)
C5—C6—C7—C8	−0.1 (10)	C5—C10—C17—O4	83.3 (5)
F3—C7—C8—F4	−0.3 (11)	C9—C10—C17—O3	80.4 (5)
C6—C7—C8—F4	179.6 (7)	C5—C10—C17—O3	−97.4 (4)
F3—C7—C8—C9	179.1 (6)	Cu1^ii—O2—C18—O1	−121.5 (3)
C6—C7—C8—C9	−1.0 (11)	Cu1^ii—O2—C18—C16	58.9 (4)
F4—C8—C9—F5	0.1 (10)	Cu1—O1—C18—O2	−2.8 (4)
C7—C8—C9—F5	−179.4 (6)	Cu1—O1—C18—C16	176.8 (2)
F4—C8—C9—C10	−179.7 (6)	C15—C16—C18—O2	37.4 (5)
C7—C8—C9—C10	0.9 (10)	C11—C16—C18—O2	−139.0 (3)
F5—C9—C10—C5	−179.5 (5)	C15—C16—C18—O1	−142.2 (3)
C8—C9—C10—C5	0.2 (8)	C11—C16—C18—O1	41.3 (5)

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

(II) Poly[[(µ-pentafluorobenzoato-κ²O:O')(pentafluorobenzoato-κO)(µ-pyrazine-κ²N:N')copper(II)]:

Crystal data

[Cu(C7F5O2)2(C4H4N2)]	Z = 2
Mr = 565.77	F(000) = 554
Triclinic, P1	Dx = 1.945 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.8100 (12) Å	Cell parameters from 5716 reflections
b = 13.095 (3) Å	θ = 2.7–27.3°
c = 15.366 (4) Å	µ = 1.26 mm^−1
α = 89.784 (3)°	T = 293 K
β = 89.654 (3)°	Block, blue
γ = 86.678 (3)°	0.16 × 0.15 × 0.10 mm
V = 966.2 (4) Å^3

Data collection

Bruker SMART 1000 diffractometer	3380 independent reflections
Radiation source: fine-focus sealed tube	3041 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −5→5
Tmin = 0.818, Tmax = 0.882	k = −15→15
9152 measured reflections	l = −18→18

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) = 0.102	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0703P)^2 + 0.4449P] where P = (Fo^2 + 2Fc^2)/3
3380 reflections	(Δ/σ)max < 0.001
316 parameters	Δρmax = 0.93 e Å^−3
0 restraints	Δρmin = −0.52 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
Cu1	0.76146 (6)	0.24937 (2)	0.480927 (19)	0.02640 (13)
N1	0.9135 (4)	0.10153 (15)	0.48708 (14)	0.0280 (4)
N3	0.6064 (4)	0.39922 (16)	0.48980 (14)	0.0294 (5)
O1	0.9517 (4)	0.28140 (14)	0.37218 (12)	0.0343 (4)
O2	0.6067 (4)	0.22117 (13)	0.59549 (12)	0.0328 (4)
O3	1.3648 (4)	0.21413 (15)	0.41465 (12)	0.0362 (4)
O4	0.9592 (5)	0.2988 (2)	0.65229 (16)	0.0690 (7)
F12	1.5949 (5)	0.12473 (17)	0.26502 (14)	0.0769 (7)
F13	1.8272 (6)	0.1743 (2)	0.11415 (17)	0.1100 (11)
F15	1.6783 (6)	0.3533 (2)	0.03520 (15)	0.1006 (9)
F16	1.0714 (5)	0.44149 (16)	0.26396 (15)	0.0789 (7)
F22	0.8340 (8)	0.0635 (2)	0.7433 (2)	0.1198 (12)
F23	0.6016 (13)	0.0180 (3)	0.8982 (2)	0.181 (2)
F24	0.2660 (10)	0.1624 (4)	0.9812 (2)	0.1598 (17)
F25	0.1706 (7)	0.3494 (3)	0.9108 (2)	0.1348 (14)
F26	0.4102 (5)	0.39505 (19)	0.75688 (16)	0.0785 (7)
F33	1.2945 (7)	0.4860 (2)	0.11012 (16)	0.0964 (9)
C1	1.2096 (5)	0.25614 (18)	0.36011 (16)	0.0281 (5)
C2	0.7466 (6)	0.2538 (2)	0.65890 (18)	0.0367 (6)
C11	1.3232 (5)	0.2810 (2)	0.27162 (17)	0.0347 (6)
C12	1.5185 (7)	0.2159 (3)	0.2296 (2)	0.0481 (8)
C13	1.6365 (8)	0.2393 (3)	0.1515 (2)	0.0662 (11)
C14	1.5622 (8)	0.3299 (3)	0.1109 (2)	0.0656 (10)
C15	1.3685 (8)	0.3973 (3)	0.1493 (2)	0.0600 (9)
C16	1.2537 (7)	0.3718 (2)	0.2281 (2)	0.0480 (7)
C21	0.6259 (6)	0.2307 (3)	0.74670 (19)	0.0455 (7)
C22	0.6701 (11)	0.1356 (3)	0.7846 (3)	0.0763 (12)
C23	0.5503 (15)	0.1117 (4)	0.8634 (3)	0.1042 (19)
C24	0.3843 (13)	0.1847 (5)	0.9050 (3)	0.0980 (17)
C25	0.3356 (9)	0.2789 (5)	0.8694 (3)	0.0838 (14)
C26	0.4581 (7)	0.3023 (3)	0.7914 (2)	0.0562 (9)
C31	1.1143 (5)	0.07479 (19)	0.54401 (18)	0.0319 (6)
H31	1.1980	0.1253	0.5753	0.038*
C32	0.8006 (5)	0.02693 (18)	0.44288 (17)	0.0309 (5)
H32	0.6620	0.0436	0.4025	0.037*
C33	0.7103 (5)	0.47648 (19)	0.44555 (18)	0.0330 (6)
H33	0.8570	0.4626	0.4069	0.040*
C34	0.3939 (5)	0.42339 (19)	0.54442 (18)	0.0337 (6)
H34	0.3150	0.3718	0.5762	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02404 (19)	0.02072 (18)	0.0339 (2)	0.00282 (11)	0.00640 (12)	0.00369 (12)
N1	0.0248 (10)	0.0215 (10)	0.0372 (11)	0.0013 (8)	0.0071 (8)	0.0033 (8)
N3	0.0267 (11)	0.0233 (10)	0.0375 (12)	0.0031 (8)	0.0061 (9)	0.0031 (9)
O1	0.0282 (9)	0.0327 (10)	0.0407 (10)	0.0082 (7)	0.0102 (8)	0.0081 (8)
O2	0.0349 (10)	0.0282 (9)	0.0349 (10)	0.0010 (7)	0.0056 (8)	0.0039 (7)
O3	0.0259 (9)	0.0476 (11)	0.0354 (10)	−0.0043 (8)	0.0000 (8)	0.0087 (8)
O4	0.0495 (14)	0.106 (2)	0.0551 (14)	−0.0358 (14)	0.0057 (11)	0.0006 (14)
F12	0.0993 (17)	0.0712 (14)	0.0538 (12)	0.0467 (13)	0.0241 (11)	0.0082 (10)
F13	0.110 (2)	0.142 (2)	0.0706 (16)	0.0531 (19)	0.0538 (16)	0.0043 (16)
F15	0.110 (2)	0.141 (2)	0.0493 (13)	−0.0054 (18)	0.0414 (13)	0.0246 (14)
F16	0.1061 (18)	0.0561 (13)	0.0695 (14)	0.0340 (12)	0.0404 (13)	0.0255 (11)
F22	0.197 (4)	0.0720 (17)	0.0840 (18)	0.040 (2)	0.046 (2)	0.0231 (14)
F23	0.323 (7)	0.120 (3)	0.098 (2)	−0.003 (3)	0.052 (3)	0.062 (2)
F24	0.193 (4)	0.227 (5)	0.0626 (18)	−0.040 (3)	0.064 (2)	0.024 (2)
F25	0.115 (3)	0.205 (4)	0.0781 (19)	0.045 (2)	0.0480 (18)	−0.024 (2)
F26	0.0847 (16)	0.0793 (16)	0.0682 (14)	0.0238 (13)	0.0054 (12)	−0.0094 (12)
F33	0.140 (2)	0.0804 (16)	0.0666 (15)	0.0073 (16)	0.0217 (15)	0.0412 (13)
C1	0.0252 (12)	0.0261 (12)	0.0329 (13)	−0.0009 (9)	0.0041 (10)	−0.0010 (10)
C2	0.0335 (14)	0.0401 (15)	0.0359 (14)	0.0010 (11)	0.0040 (12)	0.0011 (12)
C11	0.0278 (13)	0.0449 (15)	0.0311 (13)	0.0000 (11)	0.0064 (11)	0.0031 (11)
C12	0.0447 (17)	0.060 (2)	0.0377 (16)	0.0139 (14)	0.0086 (13)	0.0039 (14)
C13	0.056 (2)	0.095 (3)	0.0446 (19)	0.020 (2)	0.0213 (16)	−0.0012 (19)
C14	0.064 (2)	0.096 (3)	0.0366 (17)	−0.008 (2)	0.0185 (16)	0.0100 (18)
C15	0.069 (2)	0.066 (2)	0.0450 (18)	−0.0034 (18)	0.0100 (17)	0.0196 (16)
C16	0.0496 (18)	0.0508 (18)	0.0425 (17)	0.0041 (14)	0.0122 (14)	0.0076 (14)
C21	0.0424 (16)	0.0602 (19)	0.0345 (15)	−0.0089 (14)	0.0040 (12)	0.0008 (14)
C22	0.109 (4)	0.070 (3)	0.048 (2)	0.002 (2)	0.020 (2)	0.0088 (19)
C23	0.161 (6)	0.092 (4)	0.061 (3)	−0.017 (4)	0.025 (3)	0.027 (3)
C24	0.111 (4)	0.139 (5)	0.046 (2)	−0.025 (4)	0.028 (2)	0.007 (3)
C25	0.066 (3)	0.135 (4)	0.049 (2)	0.007 (3)	0.0191 (19)	−0.018 (3)
C26	0.0479 (19)	0.078 (2)	0.0424 (17)	0.0019 (17)	0.0028 (14)	−0.0050 (17)
C31	0.0287 (13)	0.0267 (13)	0.0403 (14)	−0.0003 (10)	−0.0010 (11)	0.0006 (11)
C32	0.0275 (13)	0.0289 (13)	0.0358 (14)	0.0019 (10)	0.0004 (10)	0.0032 (10)
C33	0.0285 (13)	0.0301 (13)	0.0398 (14)	0.0028 (10)	0.0129 (11)	0.0050 (11)
C34	0.0314 (13)	0.0266 (13)	0.0424 (15)	0.0015 (10)	0.0126 (11)	0.0068 (11)

Geometric parameters (Å, º)

Cu1—O2	1.9495 (18)	F33—C15	1.337 (4)
Cu1—O1	1.9561 (18)	C1—C11	1.504 (4)
Cu1—N1	2.032 (2)	C2—C21	1.502 (4)
Cu1—N3	2.063 (2)	C11—C16	1.387 (4)
Cu1—O3^i	2.2406 (18)	C11—C12	1.389 (4)
N1—C32	1.335 (3)	C12—C13	1.366 (5)
N1—C31	1.338 (3)	C13—C14	1.368 (6)
N3—C33	1.336 (3)	C14—C15	1.377 (5)
N3—C34	1.343 (3)	C15—C16	1.376 (5)
O1—C1	1.278 (3)	C21—C22	1.379 (5)
O2—C2	1.276 (3)	C21—C26	1.383 (5)
O3—C1	1.232 (3)	C22—C23	1.381 (6)
O3—Cu1^ii	2.2405 (18)	C23—C24	1.368 (8)
O4—C2	1.213 (4)	C24—C25	1.355 (7)
F12—C12	1.343 (4)	C25—C26	1.374 (6)
F13—C13	1.342 (4)	C31—C32^iii	1.385 (3)
F15—C14	1.330 (4)	C31—H31	0.9300
F16—C16	1.346 (4)	C32—C31^iii	1.385 (3)
F22—C22	1.351 (5)	C32—H32	0.9300
F23—C23	1.347 (6)	C33—C34^iv	1.385 (4)
F24—C24	1.338 (5)	C33—H33	0.9300
F25—C25	1.342 (5)	C34—C33^iv	1.385 (4)
F26—C26	1.332 (4)	C34—H34	0.9300
O2—Cu1—O1	174.06 (7)	F33—C15—C16	120.9 (3)
O2—Cu1—N1	84.22 (8)	F33—C15—C14	120.1 (3)
O1—Cu1—N1	95.49 (8)	C16—C15—C14	119.0 (3)
O2—Cu1—N3	89.91 (8)	F16—C16—C15	116.6 (3)
O1—Cu1—N3	90.08 (8)	F16—C16—C11	120.0 (3)
N1—Cu1—N3	173.54 (8)	C15—C16—C11	123.3 (3)
O2—Cu1—O3^i	92.09 (7)	C22—C21—C26	117.3 (3)
O1—Cu1—O3^i	93.85 (8)	C22—C21—C2	121.1 (3)
N1—Cu1—O3^i	95.07 (8)	C26—C21—C2	121.6 (3)
N3—Cu1—O3^i	87.80 (8)	F22—C22—C21	119.2 (3)
C32—N1—C31	117.7 (2)	F22—C22—C23	119.0 (4)
C32—N1—Cu1	122.34 (17)	C21—C22—C23	121.8 (4)
C31—N1—Cu1	119.58 (17)	F23—C23—C24	121.4 (5)
C33—N3—C34	116.6 (2)	F23—C23—C22	119.6 (5)
C33—N3—Cu1	123.75 (17)	C24—C23—C22	118.9 (5)
C34—N3—Cu1	119.63 (17)	F24—C24—C25	119.7 (5)
C1—O1—Cu1	121.54 (16)	F24—C24—C23	119.5 (5)
C2—O2—Cu1	114.41 (17)	C25—C24—C23	120.8 (4)
C1—O3—Cu1^ii	136.31 (17)	F25—C25—C24	120.1 (4)
O3—C1—O1	125.0 (2)	F25—C25—C26	120.1 (5)
O3—C1—C11	119.5 (2)	C24—C25—C26	119.9 (4)
O1—C1—C11	115.4 (2)	F26—C26—C25	119.6 (4)
O4—C2—O2	125.4 (3)	F26—C26—C21	119.0 (3)
O4—C2—C21	120.9 (3)	C25—C26—C21	121.3 (4)
O2—C2—C21	113.7 (2)	N1—C31—C32^iii	121.0 (2)
C16—C11—C12	115.1 (3)	N1—C31—H31	119.5
C16—C11—C1	123.1 (2)	C32^iii—C31—H31	119.5
C12—C11—C1	121.7 (2)	N1—C32—C31^iii	121.3 (2)
F12—C12—C13	117.2 (3)	N1—C32—H32	119.3
F12—C12—C11	119.9 (3)	C31^iii—C32—H32	119.3
C13—C12—C11	122.9 (3)	N3—C33—C34^iv	122.0 (2)
F13—C13—C12	120.5 (4)	N3—C33—H33	119.0
F13—C13—C14	119.5 (3)	C34^iv—C33—H33	119.0
C12—C13—C14	120.0 (3)	N3—C34—C33^iv	121.5 (2)
F15—C14—C13	120.2 (4)	N3—C34—H34	119.3
F15—C14—C15	120.1 (4)	C33^iv—C34—H34	119.3
C13—C14—C15	119.7 (3)
O2—Cu1—N1—C32	103.9 (2)	F33—C15—C16—F16	−1.7 (6)
O1—Cu1—N1—C32	−82.1 (2)	C14—C15—C16—F16	178.2 (4)
O3^i—Cu1—N1—C32	12.3 (2)	F33—C15—C16—C11	−179.9 (3)
O2—Cu1—N1—C31	−68.7 (2)	C14—C15—C16—C11	0.0 (6)
O1—Cu1—N1—C31	105.3 (2)	C12—C11—C16—F16	−178.4 (3)
O3^i—Cu1—N1—C31	−160.33 (19)	C1—C11—C16—F16	−1.7 (5)
O2—Cu1—N3—C33	156.3 (2)	C12—C11—C16—C15	−0.3 (5)
O1—Cu1—N3—C33	−17.7 (2)	C1—C11—C16—C15	176.4 (3)
O3^i—Cu1—N3—C33	−111.6 (2)	O4—C2—C21—C22	−99.1 (4)
O2—Cu1—N3—C34	−21.7 (2)	O2—C2—C21—C22	80.4 (4)
O1—Cu1—N3—C34	164.2 (2)	O4—C2—C21—C26	83.3 (4)
O3^i—Cu1—N3—C34	70.4 (2)	O2—C2—C21—C26	−97.3 (3)
N1—Cu1—O1—C1	−46.8 (2)	C26—C21—C22—F22	−179.6 (4)
N3—Cu1—O1—C1	129.9 (2)	C2—C21—C22—F22	2.6 (6)
O3^i—Cu1—O1—C1	−142.26 (19)	C26—C21—C22—C23	0.7 (7)
N1—Cu1—O2—C2	100.05 (19)	C2—C21—C22—C23	−177.0 (5)
N3—Cu1—O2—C2	−77.26 (18)	F22—C22—C23—F23	0.9 (9)
O3^i—Cu1—O2—C2	−165.06 (18)	C21—C22—C23—F23	−179.4 (5)
Cu1^ii—O3—C1—O1	−121.2 (2)	F22—C22—C23—C24	−179.9 (5)
Cu1^ii—O3—C1—C11	58.9 (3)	C21—C22—C23—C24	−0.3 (9)
Cu1—O1—C1—O3	−3.0 (3)	F23—C23—C24—F24	−1.1 (10)
Cu1—O1—C1—C11	176.94 (16)	C22—C23—C24—F24	179.7 (6)
Cu1—O2—C2—O4	−0.1 (4)	F23—C23—C24—C25	179.7 (6)
Cu1—O2—C2—C21	−179.54 (19)	C22—C23—C24—C25	0.5 (9)
O3—C1—C11—C16	−139.1 (3)	F24—C24—C25—F25	0.3 (8)
O1—C1—C11—C16	40.9 (4)	C23—C24—C25—F25	179.5 (5)
O3—C1—C11—C12	37.4 (4)	F24—C24—C25—C26	179.6 (5)
O1—C1—C11—C12	−142.5 (3)	C23—C24—C25—C26	−1.2 (8)
C16—C11—C12—F12	−178.2 (3)	F25—C25—C26—F26	−0.6 (6)
C1—C11—C12—F12	5.0 (5)	C24—C25—C26—F26	−179.8 (4)
C16—C11—C12—C13	0.5 (5)	F25—C25—C26—C21	−179.0 (4)
C1—C11—C12—C13	−176.2 (3)	C24—C25—C26—C21	1.7 (7)
F12—C12—C13—F13	−2.1 (6)	C22—C21—C26—F26	−179.9 (3)
C11—C12—C13—F13	179.1 (4)	C2—C21—C26—F26	−2.2 (5)
F12—C12—C13—C14	178.4 (4)	C22—C21—C26—C25	−1.5 (5)
C11—C12—C13—C14	−0.4 (6)	C2—C21—C26—C25	176.3 (3)
F13—C13—C14—F15	−0.1 (7)	C32—N1—C31—C32^iii	−0.7 (4)
C12—C13—C14—F15	179.5 (4)	Cu1—N1—C31—C32^iii	172.31 (19)
F13—C13—C14—C15	−179.4 (4)	C31—N1—C32—C31^iii	0.7 (4)
C12—C13—C14—C15	0.1 (6)	Cu1—N1—C32—C31^iii	−172.11 (19)
F15—C14—C15—F33	0.6 (6)	C34—N3—C33—C34^iv	0.3 (4)
C13—C14—C15—F33	−180.0 (4)	Cu1—N3—C33—C34^iv	−177.8 (2)
F15—C14—C15—C16	−179.3 (4)	C33—N3—C34—C33^iv	−0.3 (4)
C13—C14—C15—C16	0.1 (6)	Cu1—N3—C34—C33^iv	177.8 (2)

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