A three-dimensional heterometallic Cu^I/V^IV 1,2-bis­(1,2,4-triazol-4-yl)ethane framework: a new insight into the structure of vanadium oxyfluoride coordination hybrids

The bitopic ligand 1,2-bis­(1,2,4-triazol-4-yl)ethane (tr₂eth) provides an unprecedented short-distance N¹:N²-triazole bridging of Cu^I and V^IV ions in poly[bis­[[mu]₄-1,2-bis­(1,2,4-triazol-4-yl)ethane]di-[mu]₂-fluorido-tetra­fluoridodi-[mu]₂-oxido-dicopper(I)divanadium(IV)], [Cu₂V₂F₆O₂(C₆H₈N₆)₂]_n. The Cu^I ions and tr₂eth linkers afford a two-dimensional square-grid topology involving centrosymmetric (tr)Cu([mu]-tr)₂Cu(tr) [tr is triazole; Cu-N = 1.9525 (16)-2.0768 (18) Å] binuclear net nodes, which are expanded in a third dimension by centrosymmetric [V₂O₂F₆]^2- pillars. The concerted [mu]-tr and [mu]-O bridging between the Cu^I and V^IV ions allows a multi-centre accommodation of the vanadium oxyfluoride moiety on a cationic Cu/tr₂eth matrix [Cu-O = 2.1979 (15) Å and V-N = 2.1929 (17) Å]. The distorted octa­hedral coordination of [VONF₄] is completed by two terminal and two bridging F^- ions [V-F = 1.8874 (14)-1.8928 (13) and 2.0017 (13)-2.1192 (12) Å, respectively]. The resulting three-dimensional framework has a primitive cubic net topology and adopts a threefold inter­penetration.

S1. Comment

In recent years, the structure-directing properties of vanadium oxyfluoride (VOF) species have found a range of applications in crystal design with a view to preparing magnetic materials (Aldous, Goff et al., 2007) and in the construction of polar optically active arrays (Stephens et al., 2005). In particular, both discrete and oligomeric VOF units have been exploited as bifunctional anionic linkers between complex cations, such as [CuPy₄]²⁺, to generate polymeric chains (Welk et al., 2000; Mahenthirarajah et al., 2008) and complicated three-dimensional frameworks (Mahenthirarajah & Lightfoot, 2008). Even more versatile possibilities may be found with the utilization of VOF anions as polynucleating linkers between polynuclear complex cations, or as pillaring groups between extended metal–organic layers (Noro et al., 2002). Such systems possess a special and as yet completely unexplored potential for sustaining the inorganic/organic integrity of framework solids. Our present strategy considers further modification of the VOF unit by substitution of the fluoride ligands and setting up additional V—N bonds with the metal–amine portion of the structure, which could complement the short inorganic M—O—M links (Lysenko et al., 2006). We have therefore examined a prototypical polydentate ligand, 1,2-bis(1,2,4-triazol-4-yl)ethane (tr₂eth), typically used to support short N¹,N²-triazole bridges between pairs of metal ions (Habib, Hoffmann, Hoppe & Janiak, 2009). Here, we report the structure of a [Cu₂(tr₂eth)₂[V₂O₂F₆]] complex, (I), that features an exceptional concerted organic/inorganic linkage between two types of metal ions, leading to a multi-centre and an extremely tight accommodation of the anionic VOF unit on a cationic metal–organic matrix.

The asymmetric unit of (I) includes one Cu^I cation, one organic ligand and one-half of a [V₂O₂F₆]^2- anion, which resides across an inversion centre (Fig. 1). Selected geometric paramaters are given in Table 1. It is important from synthetic considerations that both metals appear in a reduced form (Cu^I and V^IV). Such behaviour of V₂O₅/HF systems is well known for hydrothermal reactions (Aldous, Goff et al., 2007 or Aldous, Stephens & Lightfoot, 2007 ?), while Cu^II ions under similar conditions are also readily reduced in the presence of triazole ligands (Habib, Hoffmann, Hoppe, Steinfeld & Janiak, 2009).

Atom Cu1 adopts a distorted coordination tetrahedron, [CuN₃O], in which the Cu—N bond lengths [1.9525 (16)–2.0768 (18) Å] are characteristic of tetracoordinate Cu(µ-tr)₂Cu complexes [tr is triazole; Cu—N = 1.991 (3)–2.082 (3) Å; Drabent et al., 2003]. The Cu1—O1 bond is slightly elongated [2.1979 (15) Å] and therefore the metal ion approaches the plane of the three N donor atoms as close as 0.2388 (11) Å. The present complex VOF unit is sustained with two [VNOF₄] octahedra sharing the F···F edge. It may be directly related to a previously reported binuclear anion, [V₂O₂(µ-F)₂F₄(H₂O)₂]^2- (Bukove et al., 1981), as a result of substitution of the weakly bound aqua ligands (which are cis-positioned towards the V═O bond) by triazole groups, with the formation of triazole/oxido double bridges. Notably, the coordination of the oxido ligand to the Cu^I ion results in elongation of the short V═O bond to 1.6275 (15) Å, which may be compared with the same distance in the tetramethylammonium and 4,4'-bipyridinium ionic salts of the above diaqua anion [1.607 (5) and 1.606 (2) Å, respectively; Aldous, Stephens & Lightfoot, 2007). This also produces a shortening of the V1—F3 bond compared with the corresponding trans-fluoride ligand [2.1192 (12) Å in (I) versus 2.173 (3) Å reported by Bukove et al. (1981)]. The distorted coordination octahedron around the V^IV ion is completed by two terminal and two µ-fluorides and a relatively distant triazole-N donor atom [V1—N2 = 2.1929 (17) Å].

The bis(triazole) ligands adopt a µ₄-coordination, with the triazole halves providing a double connection for two Cu^I ions [Cu1···Cu1^iv = 3.6104 (5) Å; symmetry code: (iv) = 2 - x, 1 - y, 1 - z], as well as unprecedented bridging of the heterometallic Cu^I/V^IV pair [Cu1···V1 = 3.4174 (5) Å] (Fig. 1). Thus, the triazole and oxido bridges are complementary and they act in synergy for the incorporation of the VOF fragment into the –(VVCuCu)_n– polymeric chains. The latter run along the c direction and include alternation of the above Cu(µ-tr)₂Cu, Cu(µ-tr)(µ-O)V and V(µ-F)₂V fragments [V1···V1ⁱⁱⁱ = 3.3367 (7) Å; symmetry code: (iii) 2 - x, 1 - y, -z], whereas the double functionality of the bis(triazole) linkers allows propagation of this geometry in two other directions. Recently, we have demonstrated the utility of combining triazole and oxido bridging for the design of metal oxide–organic frameworks (Lysenko et al., 2010).

The entire three-dimensional connectivity in (I) may be best described in terms of a primitive cubic framework (NaCl) composed of organic and oxyfluoride links. Thus, the Cu^I ions and bis(triazole) ligands afford a distinct subtopology of the structure, which exists in the form of a two-dimensional square-grid net parallel to (001) (Fig. 2). The net nodes are sustained by characteristic (tr)Cu(µ-tr)₂Cu(tr) dimers, which themselves typically dominate self-assembly in such systems involving either monofunctional (Drabent et al., 2003) or bitopic triazole ligands (Habib, Hoffmann, Hoppe, Steinfeld & Janiak, 2009). These layers are stacked on top of one another, separated by 11.2220 (16) Å, and are interconnected by inorganic [V₂O₂F₆]^2- units acting as pillars which expand the structure in the third dimension (Fig. 3). For the accommodation of such pillaring with building blocks on the two axial sides of the layer, the available functionality at the Cu₂(tr)₄ nodes includes unsaturated coordination positions at the Cu^I ions in combination with uncoordinated triazole-N donors. This case perfectly complements the bonding preferences of the coordinatively unsaturated [V₂O₂F₆]^2- blocks and enables a double interaction (Cu—O and V—N) between the counterparts.

The resulting three-dimensional array is open since it contains channels of ca 6.0 × 6.5 Å (calculated using PLATON; Spek, 2009) running along the c direction, while the porosity of the structure is eliminated by the interpenetration of three identical frameworks (Fig. 4). This is a relatively rare threefold class Ia interpenetration, where equivalent nets are related by a single translation vector (Blatov et al., 2004). Close interaction between the interpenetrating frameworks occurs by means of weak C—H···F hydrogen bonding, involving the terminal fluoride ligands and the CH groups of the triazole groups, with the shortest C···F separation being only 2.803 (2) Å (Table 2).

In conclusion, our findings suggest a flexible approach for the development of hybrid heterometallic frameworks incorporating metal oxyfluoride units. The utility of triazole ligands for the concerted organic/oxido bridging of Cu^I and V^IV ions provides a new design tool for the integration of organic and inorganic counterparts, which could find wider application in the synthesis of functionalized MOF materials.

Related literature

For related literature, see: Aldous, Goff, Attfield & Lightfoot (2007); Aldous, Stephens & Lightfoot (2007); Blatov et al. (2004); Bukove et al. (1981); Drabent et al. (2003); Habib, Hoffmann, Hoppe & Janiak (2009); Habib, Hoffmann, Hoppe, Steinfeld & Janiak (2009); Lysenko et al. (2006, 2010); Mahenthirarajah & Lightfoot (2008); Mahenthirarajah, Li & Lightfoot (2008); Noro et al. (2002); Spek (2009); Stephens et al. (2005); Welk (2000).

S2. Experimental

1,2-Bis(1,2,4-triazol-4-yl)ethane (tr₂eth) was prepared in a 65% yield by reacting ethylenediamine (1.50 g, 1.67 ml, 25.0 mmol) and dimethylformamide azine (8.87 g, 62.5 mmol) in boiling xylene (12 ml) in the presence of TsOH.H₂O (0.38 g, 2.0 mmol) as a catalyst. Complex (I) was prepared under hydrothermal conditions starting with V₂O₅ and 48% HF solution. In a typical reaction, Cu(OAc)₂.H₂O (19.9 mg, 0.10 mmol), tr₂eth (16.4 mg, 0.10 mmol), V₂O₅ (18.1 mg, 0.10 mmol), aqueous HF (100 µl) and water (5 ml) were added to a Teflon vessel, which was placed in a steel bomb and heated to 448 K for 24 h. The mixture was then slowly cooled to room temperature over a period of 60 h and afforded brownish crystals of (I) (yield 13.4 mg, 38%).

S3. Refinement

All H atoms were located in difference Fourier maps and then refined as riding, with C—H (aromatic) = 0.94 Å and C—H (methylene) = 0.98 Å, and with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: IPDS Software (Stoe & Cie, 2000); cell refinement: IPDS Software (Stoe & Cie, 2000); data reduction: IPDS Software (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Version 1.70.01; Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Note the unprecedented triazole bridge between the Cu^I and V^iv ions. [Symmetry codes: (i) 3/2 + x, 1/2 - y, 1/2 + z; (ii) 1/2 - x, 1/2 + y, 1/2 - z; (iii) 2 - x, 1 - y, -z; (iv) 2 - x, 1 - y, 1 - z.]
	Fig. 2. The copper(I)–bis(triazole) subtopology in the structure of (I), in the form of the planar square-grid net supported by the dinuclear nodes. N atoms are shaded grey and the paler bonds indicate the location of the [V2O2F6]^2- moieties, which reside above and below the layer plane. [Symmetry codes: (iv) 2 - x, 1 - y, 1 - z; (v) 1/2 - x, -1/2 + y, 1/2 - z.]
	Fig. 3. A projection on the ac plane, showing the mode of interconnection of the copper(I)–bis(triazole) layers (which are orthogonal to the drawing plane) by [V2O2F6]^2- pillars, shown as polyhedra. H atoms have been omitted for clarity [Symmetry code: (iv) 2 - x, 1 - y, 1 - z.]
	Fig. 4. The interpenetration of three topologically identical three-dimensional frameworks in the structure of (I), shown in projection on the ab plane. A single framework is shaded grey and marked with black bonds.

poly[bis[µ₄-1,2-bis(1,2,4-triazol-4-yl)ethane]di-µ₂-fluorido-tetrafluoridodi-µ₂-oxido-dicopper(I)divanadium(IV)]

Crystal data

[Cu2V2F6O2(C6H8N6)2]	F(000) = 692
Mr = 703.33	Dx = 2.249 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.1630 (6) Å	Cell parameters from 8000 reflections
b = 13.7698 (10) Å	θ = 2.2–28.0°
c = 12.4856 (11) Å	µ = 2.99 mm^−1
β = 101.370 (8)°	T = 213 K
V = 1038.77 (16) Å^3	Prism, brown
Z = 2	0.15 × 0.12 × 0.12 mm

Data collection

Stoe IPDS diffractometer	2499 independent reflections
Radiation source: fine-focus sealed tube	2157 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ϕ oscillation scans	θmax = 28.0°, θmin = 2.2°
Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]	h = −8→8
Tmin = 0.663, Tmax = 0.716	k = −18→18
8977 measured reflections	l = −16→16

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0472P)^2] where P = (Fo^2 + 2Fc^2)/3
2499 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.66 e Å^−3
0 restraints	Δρmin = −0.47 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	0.96536 (4)	0.438375 (18)	0.370120 (19)	0.01751 (9)
V1	0.97241 (6)	0.54180 (2)	0.12202 (3)	0.01560 (9)
F1	0.7280 (2)	0.61927 (9)	0.13772 (11)	0.0273 (3)
F2	1.1206 (3)	0.65737 (10)	0.09656 (12)	0.0328 (3)
F3	1.1748 (2)	0.46611 (9)	0.04611 (10)	0.0200 (3)
O1	1.0975 (3)	0.52238 (11)	0.24764 (12)	0.0234 (3)
N1	0.7868 (3)	0.37056 (12)	0.24042 (13)	0.0162 (3)
N2	0.7642 (3)	0.41574 (12)	0.13880 (13)	0.0154 (3)
N3	0.5257 (3)	0.29648 (12)	0.12491 (13)	0.0166 (3)
N4	−0.2421 (3)	0.03688 (13)	0.08686 (14)	0.0193 (4)
N5	−0.2818 (3)	0.08723 (13)	−0.01205 (13)	0.0169 (3)
N6	−0.0064 (3)	0.15786 (13)	0.09907 (14)	0.0182 (3)
C1	0.6428 (3)	0.29921 (15)	0.22963 (17)	0.0189 (4)
H1	0.6234	0.2564	0.2857	0.023*
C2	0.6060 (3)	0.37025 (15)	0.07158 (16)	0.0171 (4)
H2	0.5557	0.3863	−0.0023	0.021*
C3	−0.0766 (3)	0.08084 (16)	0.15119 (17)	0.0203 (4)
H3	−0.0155	0.0617	0.2231	0.024*
C4	−0.1380 (4)	0.15891 (15)	−0.00192 (17)	0.0209 (4)
H4	−0.1278	0.2044	−0.0568	0.025*
C5	0.3494 (4)	0.22702 (16)	0.07982 (18)	0.0231 (4)
H5A	0.4113	0.1613	0.0824	0.028*
H5B	0.2895	0.2431	0.0032	0.028*
C6	0.1653 (3)	0.22970 (16)	0.14392 (18)	0.0216 (4)
H6A	0.2252	0.2150	0.2209	0.026*
H6B	0.1001	0.2948	0.1397	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01492 (14)	0.02149 (14)	0.01532 (13)	0.00205 (9)	0.00100 (9)	−0.00204 (9)
V1	0.01753 (18)	0.01434 (16)	0.01496 (16)	−0.00425 (12)	0.00324 (13)	−0.00021 (11)
F1	0.0281 (7)	0.0264 (7)	0.0277 (7)	0.0056 (5)	0.0063 (6)	−0.0067 (5)
F2	0.0429 (9)	0.0205 (6)	0.0374 (7)	−0.0131 (6)	0.0141 (7)	0.0005 (5)
F3	0.0168 (6)	0.0254 (6)	0.0186 (6)	0.0031 (5)	0.0055 (5)	0.0003 (5)
O1	0.0232 (8)	0.0303 (8)	0.0168 (7)	−0.0105 (6)	0.0040 (6)	0.0009 (6)
N1	0.0154 (8)	0.0172 (8)	0.0161 (8)	−0.0018 (6)	0.0035 (6)	0.0011 (6)
N2	0.0125 (8)	0.0186 (8)	0.0157 (7)	−0.0018 (6)	0.0045 (6)	0.0012 (6)
N3	0.0124 (8)	0.0174 (8)	0.0198 (8)	−0.0041 (6)	0.0027 (6)	−0.0010 (6)
N4	0.0135 (8)	0.0255 (9)	0.0188 (8)	−0.0047 (7)	0.0030 (7)	0.0054 (7)
N5	0.0134 (8)	0.0217 (8)	0.0159 (8)	−0.0039 (6)	0.0032 (6)	0.0042 (6)
N6	0.0120 (8)	0.0215 (8)	0.0211 (8)	−0.0048 (6)	0.0033 (6)	0.0014 (6)
C1	0.0174 (10)	0.0198 (9)	0.0192 (9)	−0.0046 (7)	0.0033 (8)	0.0022 (7)
C2	0.0129 (9)	0.0223 (10)	0.0169 (9)	−0.0029 (7)	0.0045 (7)	0.0005 (7)
C3	0.0126 (9)	0.0290 (11)	0.0187 (10)	−0.0058 (8)	0.0016 (8)	0.0054 (8)
C4	0.0175 (10)	0.0242 (10)	0.0207 (9)	−0.0050 (8)	0.0028 (8)	0.0055 (8)
C5	0.0200 (11)	0.0239 (10)	0.0266 (11)	−0.0103 (8)	0.0070 (9)	−0.0081 (8)
C6	0.0134 (9)	0.0217 (10)	0.0301 (11)	−0.0057 (7)	0.0049 (8)	−0.0068 (8)

Geometric parameters (Å, º)

Cu1—N5^i	1.9525 (16)	N4—C3	1.315 (3)
Cu1—N1	2.0007 (16)	N4—N5	1.395 (2)
Cu1—N4^ii	2.0768 (18)	N5—C4	1.316 (3)
Cu1—O1	2.1979 (15)	N6—C4	1.358 (3)
V1—O1	1.6275 (15)	N6—C3	1.359 (3)
V1—F1	1.8874 (14)	N6—C6	1.476 (2)
V1—F2	1.8928 (13)	C1—H1	0.9400
V1—F3	2.0017 (13)	C2—H2	0.9400
V1—F3^iii	2.1192 (12)	C3—H3	0.9400
V1—N2	2.1929 (17)	C4—H4	0.9400
N1—C1	1.313 (3)	C5—C6	1.512 (3)
N1—N2	1.395 (2)	C5—H5A	0.9800
N2—C2	1.314 (2)	C5—H5B	0.9800
N3—C2	1.360 (3)	C6—H6A	0.9800
N3—C1	1.364 (2)	C6—H6B	0.9800
N3—C5	1.474 (2)
N5^i—Cu1—N1	139.07 (7)	C3—N4—Cu1^iv	128.05 (14)
N5^i—Cu1—N4^ii	113.20 (7)	N5—N4—Cu1^iv	122.95 (12)
N1—Cu1—N4^ii	103.15 (7)	C4—N5—N4	106.87 (16)
N5^i—Cu1—O1	105.62 (7)	C4—N5—Cu1^v	129.06 (14)
N1—Cu1—O1	84.41 (6)	N4—N5—Cu1^v	123.50 (13)
N4^ii—Cu1—O1	101.04 (7)	C4—N6—C3	105.34 (16)
O1—V1—F1	103.23 (7)	C4—N6—C6	126.68 (18)
O1—V1—F2	98.48 (7)	C3—N6—C6	127.86 (17)
F1—V1—F2	87.91 (7)	N1—C1—N3	109.77 (18)
O1—V1—F3	98.61 (7)	N1—C1—H1	125.1
F1—V1—F3	158.15 (6)	N3—C1—H1	125.1
F2—V1—F3	89.53 (6)	N2—C2—N3	109.83 (17)
O1—V1—F3^iii	167.19 (7)	N2—C2—H2	125.1
F1—V1—F3^iii	86.41 (5)	N3—C2—H2	125.1
F2—V1—F3^iii	90.19 (6)	N4—C3—N6	110.41 (17)
F3—V1—F3^iii	71.90 (5)	N4—C3—H3	124.8
O1—V1—N2	87.30 (7)	N6—C3—H3	124.8
F1—V1—N2	86.76 (6)	N5—C4—N6	110.42 (18)
F2—V1—N2	172.91 (7)	N5—C4—H4	124.8
F3—V1—N2	93.68 (6)	N6—C4—H4	124.8
F3^iii—V1—N2	84.82 (6)	N3—C5—C6	110.84 (17)
V1—F3—V1^iii	108.10 (5)	N3—C5—H5A	109.5
V1—O1—Cu1	125.94 (8)	C6—C5—H5A	109.5
C1—N1—N2	107.22 (16)	N3—C5—H5B	109.5
C1—N1—Cu1	133.24 (14)	C6—C5—H5B	109.5
N2—N1—Cu1	117.93 (12)	H5A—C5—H5B	108.1
C2—N2—N1	107.27 (16)	N6—C6—C5	109.84 (17)
C2—N2—V1	133.73 (14)	N6—C6—H6A	109.7
N1—N2—V1	118.97 (12)	C5—C6—H6A	109.7
C2—N3—C1	105.91 (16)	N6—C6—H6B	109.7
C2—N3—C5	127.56 (16)	C5—C6—H6B	109.7
C1—N3—C5	126.53 (17)	H6A—C6—H6B	108.2
C3—N4—N5	106.96 (17)
O1—V1—F3—V1^iii	171.14 (7)	F1—V1—N2—N1	−98.14 (14)
F1—V1—F3—V1^iii	−7.14 (18)	F2—V1—N2—N1	−139.4 (5)
F2—V1—F3—V1^iii	−90.36 (7)	F3—V1—N2—N1	103.75 (14)
F3^iii—V1—F3—V1^iii	0.0	F3^iii—V1—N2—N1	175.18 (14)
N2—V1—F3—V1^iii	83.32 (6)	C3—N4—N5—C4	0.0 (2)
F1—V1—O1—Cu1	65.90 (11)	Cu1^iv—N4—N5—C4	164.87 (15)
F2—V1—O1—Cu1	155.74 (10)	C3—N4—N5—Cu1^v	−172.12 (15)
F3—V1—O1—Cu1	−113.45 (10)	Cu1^iv—N4—N5—Cu1^v	−7.2 (2)
F3^iii—V1—O1—Cu1	−72.1 (4)	N2—N1—C1—N3	−0.4 (2)
N2—V1—O1—Cu1	−20.13 (11)	Cu1—N1—C1—N3	164.27 (14)
N5^i—Cu1—O1—V1	165.16 (11)	C2—N3—C1—N1	0.1 (2)
N1—Cu1—O1—V1	25.62 (11)	C5—N3—C1—N1	179.83 (19)
N4^ii—Cu1—O1—V1	−76.72 (12)	N1—N2—C2—N3	−0.6 (2)
N5^i—Cu1—N1—C1	71.4 (2)	V1—N2—C2—N3	−178.40 (14)
N4^ii—Cu1—N1—C1	−81.1 (2)	C1—N3—C2—N2	0.4 (2)
O1—Cu1—N1—C1	178.8 (2)	C5—N3—C2—N2	−179.39 (19)
N5^i—Cu1—N1—N2	−125.20 (14)	N5—N4—C3—N6	0.2 (2)
N4^ii—Cu1—N1—N2	82.32 (15)	Cu1^iv—N4—C3—N6	−163.73 (15)
O1—Cu1—N1—N2	−17.75 (14)	C4—N6—C3—N4	−0.2 (3)
C1—N1—N2—C2	0.7 (2)	C6—N6—C3—N4	175.94 (19)
Cu1—N1—N2—C2	−166.79 (14)	N4—N5—C4—N6	−0.1 (2)
C1—N1—N2—V1	178.83 (14)	Cu1^v—N5—C4—N6	171.40 (14)
Cu1—N1—N2—V1	11.38 (19)	C3—N6—C4—N5	0.2 (3)
O1—V1—N2—C2	−177.1 (2)	C6—N6—C4—N5	−176.02 (19)
F1—V1—N2—C2	79.4 (2)	C2—N3—C5—C6	−123.3 (2)
F2—V1—N2—C2	38.1 (7)	C1—N3—C5—C6	57.0 (3)
F3—V1—N2—C2	−78.7 (2)	C4—N6—C6—C5	−64.8 (3)
F3^iii—V1—N2—C2	−7.24 (19)	C3—N6—C6—C5	119.8 (2)
O1—V1—N2—N1	5.29 (15)	N3—C5—C6—N6	−178.56 (17)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···F1^vi	0.94	2.23	2.999 (2)	138
C2—H2···F1^vii	0.94	2.18	2.994 (2)	144
C4—H4···F2^vii	0.94	1.97	2.803 (2)	147

Symmetry codes: (vi) −x+3/2, y−1/2, −z+1/2; (vii) −x+1, −y+1, −z.