(Aceto­nitrile)­[2,6-bis­(pyrazol-1-yl)­pyridine](isonicotin­amide)copper(II)–tetra­fluoro­borate–aceto­nitrile (1/2/2)

Molecules of the title compound, [Cu(C₂H₃N)(C₁₁H₉N₅)(C₆H₆N₂O)](BF₄)₂·2C₂H₃N, comprise (aceto­nitrile)[2,6-bis(pyrazol-1-yl)­pyridine](isonicotin­amide)copper(II) cations, tetra­fluoro­borate anions and lattice aceto­nitrile mol­ecules. The cations have distorted square-pyramidal geometries in which the N₃-donor, viz. 2,6-bis­(pyrazol-1-yl)­pyridine, and the N-donor, viz. the isonicotin­amide ligand, occupy the four basal positions, with the coordinated aceto­nitrile N-donor atom occupying the apical position. Pairs of cations are linked by N—H...F hydrogen bonds through tetra­fluoro­borate anions, forming centrosymmetric dimers, which are further linked by C—H...O hydrogen bonds into two-dimensional undulating sheets, three of which interpenetrate to generate a two-dimensional network.

S1. Comment

The title compound, (I), comprises an acetonitrile[2,6-bis(pyrazol-1-yl)pyridine](isonicotinamide)copper(II) cation (Fig. 1), two tetrafluoroborate anions and two lattice acetonitrile molecules. All four F atoms of both tetrafluoroborate anions are disordered over two sites. The tridentate 2,6-bis(pyrazol-1-yl)pyridine ligand occupies three of the four basal positions of a distorted square-pyramidal CuN₅ coordination sphere. The isonicotinamide ligand occupies the fourth basal position and the coordinated acetonitrile molecule the apical position. Of the three ligating N atoms of the tridentate ligand, the pyrazole N-donors atoms form much longer Cu···N contacts [2.024 (3) and 2.026 (3) Å] than the pyridine N-donor atom [1.946 (2) Å], which forms a similar Cu···N contact to the isonicotinamide N-donor atom [1.964 (2) Å]. Typical of square-pyramidal Cu^II centres, the apical acetonitrile N atom is somewhat more distant [2.316 (3) Å]. The magnitude of the distortion of the Cu^II coordination sphere (Fig. 1) can be quantified by the geometric parameter τ [i.e. (171.3 - 156.98)/60] of 0.24 (τ = 0.0 for C_4v symmetry and τ = 1.0 for D_{3 h} symmetry; Addison et al., 1984). The conformation of the pyridine ring of the isonicotinamide ligand is such that it makes a dihedral angle of 47.8(?)° with the pyridine ring of the tridentate ligand, which is effectively planar, with dihedral angles between the pyrazole and pyridine rings of 1.3 and 6.3°.

The cations form centrosymmetrically related pairs (Fig. 2) linked through two tetrafluoroborate anions by a R₄⁴(12) hydrogen-bonding motif (Etter, 1990; Bernstein et al., 1995). Pertinent structural parameters of the hydrogen-bonded contacts are collated in Table 2. The formation of this motif [Scheme 1(a)] was unexpected, the simpler R₂²(8) motif [Scheme 1(b)] based on the amide functionalities being anticipated by analogy with the well known carboxylic acid-based R₂²(8) supramolecular synthon [Scheme 1(c)] (Desiraju, 1995, 2000). Presumably, despite the greater strength of the N—H···O═C hydrogen bond compared with the N—H···F—BF₃ hydrogen bond, the energy release associated with the formation of four of the latter is greater than that associated with the formation of two of the former. Two C—H···O hydrogen bonds, in the form of a R₂¹(7) motif, link the dimers through the amide O atom, generating an undulating sheet structure parallel to the (001) plane (Table 2 and Fig. 3). The periodicity of the undulation (24.5 Å) is such that the two-dimensional network comprises three interpenetrating sheets analogous to those observed in {[Co₂(µ-4,4'-azopyridine)₃(NO₃)₄]}_n (Withersby et al., 1999, 2000).

S2. Experimental

The ligand 2,6-bis(pyrazol-1-yl)pyridine was synthesized by heating to reflux for 72 h the mixture formed by adding 2,6-dichloropyridine (4.12 g, 27.8 mmol) to a solution of sodium pyrazolate previously prepared in tetrahydrofuran (100 ml) by reaction of pyrazole (3.80 g, 55.8 mmol) with excess NaH (60% dispersion in mineral oil (2.80 g, 70 mmol). After cooling, the mixture was poured into iced water and the resultant precipitate recovered by filtration (yield: 5.10 g, 23.7 mmol, 85%). For the preapration of the title compound, (I), isonicotinamide (0.040 g, 0.33 mmol) was added to a mixture of 2,6-bis(pyrazol-1-yl)pyridine (0.068 g, 0.32 mmol) and hydrated {Cu^II(BF₄)}^- (0.100 g, 0.32 mmol) in acetonitrile (25 ml). After stirring at ambient temperature for 24 h, the resulting green solution afforded a small crop of green plate-like crystals.

S3. Refinement

The anions are affected by disorder which was modelled by allowing alternative positions for each F atom, with extensive restraints applied to B—F distances and F—B—F angles. Around B1, the major and minor orientations refined to 0.57 (2) and 0.43 (2), respectively, while the corresponding occupancies around B2 converged to 0.60 (1) and 0.40 (1). Aromatic and amide H atoms, after location from ΔF syntheses, were placed geometrically and refined with a riding model, for which the C—H and N—H distances were constrained to be 0.95 and 0.88 Å, respectively, and U_iso(H) = 1.2U_eq(C, N). Methyl H atoms were located and treated similarly, with C—H distances constrained to be 0.98 Å and U_iso(H) = 1.5U_eq(C)

Computing details

Data collection: IPDS (Stoe & Cie, 1995); cell refinement: IPDS; data reduction: IPDS; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2002).

Figures

	Fig. 1. A view of the cation in (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of arbitrary radii.
	Fig. 2. A view of the centrosymmetric hydrogen-bonded dinuclear construction generated by the N—H···F contacts of the hydrogen-bonded R4^4(12) motif. Only one set of F atoms (F11A, F12A, F13A and F14A) is shown for each tetrafluoroborate anion. (Key: Cu atoms are large pale-grey spheres, C are intermediate black spheres, N are intermediate dark-grey spheres, O are intermediate pale-grey spheres, B are small pale-grey spheres and F are intermediate black spheres.)
	Fig. 3. A projection of the structure of (I) on to the (001) plane, showing the two-dimensional sheet structure generated by the C—H···O contacts of the hydrogen-bonded R2^1(7) motif. The lattice acetonitrile molecules and tetrafluoroborate anions ahve been omitted for clarity. Only one set of F atoms (F11A, F12A, F13A and F14A) is shown for each tetrafluoroborate anion (atom types are as depicted in Fig. 2).

Acetonitrile[2,6-bis(pyrazol-1-yl)pyridine](isonicotinamide)copper(II)– tetrafluoroborate–acetonitrile (1/2/2)

Crystal data

[Cu(C2H3N)(C11H9N5)(C6H6N2O)](BF4)2·2C2H3N	F(000) = 2808
Mr = 693.68	Dx = 1.560 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac2ab	Cell parameters from 12955 reflections
a = 8.1790 (16) Å	θ = 2.5–25.5°
b = 22.747 (5) Å	µ = 0.83 mm^−1
c = 31.752 (6) Å	T = 193 K
V = 5907 (2) Å^3	Plate, green
Z = 8	0.32 × 0.08 × 0.02 mm

Data collection

Stoe IPDS diffractometer	6613 independent reflections
Radiation source: fine-focus sealed tube	4385 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
area detector scans	θmax = 28.1°, θmin = 3.1°
Absorption correction: multi-scan (IPDS; Stoe & Cie, 1995)	h = −9→9
Tmin = 0.84, Tmax = 0.95	k = −30→25
19461 measured reflections	l = −42→29

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.175	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.115P)^2] where P = (Fo^2 + 2Fc^2)/3
6613 reflections	(Δ/σ)max = 0.002
401 parameters	Δρmax = 0.88 e Å^−3
40 restraints	Δρmin = −0.74 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	Occ. (<1)
Cu1	0.52637 (6)	0.308975 (16)	0.103332 (14)	0.02755 (15)
N1	0.4945 (4)	0.39363 (12)	0.10617 (9)	0.0261 (6)
C2	0.6115 (5)	0.42767 (14)	0.12180 (11)	0.0285 (7)
C3	0.5956 (5)	0.48748 (15)	0.12475 (12)	0.0351 (8)
H3	0.6795	0.5113	0.1364	0.042*
C4	0.4513 (5)	0.51138 (15)	0.10985 (14)	0.0383 (9)
H4	0.4363	0.5527	0.1113	0.046*
C5	0.3278 (5)	0.47697 (15)	0.09290 (13)	0.0370 (9)
H5	0.2285	0.4934	0.0828	0.044*
C6	0.3583 (5)	0.41722 (13)	0.09158 (11)	0.0261 (7)
N61	0.2532 (4)	0.37461 (11)	0.07436 (9)	0.0270 (6)
N62	0.3070 (4)	0.31766 (11)	0.07441 (10)	0.0304 (7)
C63	0.1926 (5)	0.28783 (15)	0.05390 (13)	0.0345 (8)
H63	0.1958	0.2467	0.0489	0.041*
C64	0.0666 (5)	0.32513 (16)	0.04063 (13)	0.0358 (8)
H64	−0.0287	0.3144	0.0254	0.043*
C65	0.1085 (5)	0.37984 (15)	0.05404 (12)	0.0316 (7)
H65	0.0479	0.4150	0.0499	0.038*
N21	0.7485 (4)	0.39461 (11)	0.13394 (9)	0.0294 (6)
N22	0.7431 (4)	0.33528 (12)	0.12769 (9)	0.0299 (6)
C23	0.8842 (5)	0.31541 (15)	0.14199 (12)	0.0353 (8)
H23	0.9161	0.2753	0.1417	0.042*
C24	0.9804 (6)	0.36112 (18)	0.15765 (14)	0.0406 (9)
H24	1.0862	0.3580	0.1698	0.049*
C25	0.8912 (6)	0.41119 (16)	0.15190 (13)	0.0380 (9)
H25	0.9231	0.4501	0.1591	0.046*
N11	0.5693 (4)	0.22559 (11)	0.09176 (10)	0.0285 (6)
C12	0.7079 (5)	0.20804 (13)	0.07385 (12)	0.0311 (8)
H12	0.7908	0.2365	0.0688	0.037*
C13	0.7373 (5)	0.15040 (14)	0.06217 (12)	0.0329 (8)
H13	0.8380	0.1394	0.0495	0.040*
C14	0.6156 (5)	0.10920 (13)	0.06944 (11)	0.0276 (7)
C15	0.4735 (5)	0.12711 (14)	0.08878 (12)	0.0312 (7)
H15	0.3896	0.0994	0.0947	0.037*
C16	0.4535 (5)	0.18550 (14)	0.09951 (12)	0.0308 (7)
H16	0.3549	0.1975	0.1127	0.037*
C17	0.6301 (5)	0.04512 (13)	0.05692 (12)	0.0311 (8)
O17	0.5367 (4)	0.00906 (11)	0.07204 (10)	0.0437 (7)
N17	0.7451 (5)	0.03136 (12)	0.02906 (11)	0.0390 (8)
H17A	0.7566	−0.0053	0.0207	0.047*
H17B	0.8098	0.0589	0.0190	0.047*
B1	0.1475 (5)	0.12611 (15)	−0.00064 (12)	0.0314 (8)
F11A	0.0250 (6)	0.0869 (2)	−0.01047 (14)	0.0361 (12)*	0.57
F12A	0.2924 (5)	0.09134 (17)	0.00153 (16)	0.0362 (10)*	0.57
F13A	0.1517 (7)	0.1775 (2)	−0.02314 (18)	0.0438 (14)*	0.57
F14A	0.1375 (7)	0.1399 (2)	0.04272 (15)	0.0439 (14)*	0.57
F11B	−0.0059 (7)	0.1004 (3)	−0.01074 (18)	0.0333 (15)*	0.43
F12B	0.2772 (9)	0.0931 (3)	−0.0126 (3)	0.055 (2)*	0.43
F13B	0.1690 (9)	0.1678 (3)	−0.0328 (2)	0.0413 (18)*	0.43
F14B	0.1282 (9)	0.1545 (3)	0.03640 (18)	0.0418 (17)*	0.43
B2	1.0488 (6)	0.16208 (18)	0.17207 (15)	0.0475 (12)
F21A	0.9755 (8)	0.2040 (2)	0.19773 (15)	0.0488 (13)*	0.60
F22A	1.0674 (8)	0.1894 (2)	0.13152 (15)	0.0616 (13)*	0.60
F23A	1.2059 (7)	0.1514 (3)	0.1869 (2)	0.0726 (16)*	0.60
F24A	0.9480 (8)	0.1165 (3)	0.1674 (2)	0.0853 (19)*	0.60
F21B	1.0372 (13)	0.2085 (3)	0.1977 (2)	0.059 (2)*	0.40
F22B	0.9892 (17)	0.1684 (6)	0.1329 (3)	0.118 (4)*	0.40
F23B	1.1988 (10)	0.1355 (4)	0.1695 (3)	0.080 (3)*	0.40
F24B	0.9687 (11)	0.1112 (3)	0.1900 (3)	0.069 (2)*	0.40
N2	0.4097 (5)	0.29291 (14)	0.16880 (11)	0.0400 (8)
C21	0.3516 (5)	0.29218 (15)	0.20130 (13)	0.0369 (8)
C22	0.2758 (7)	0.2915 (2)	0.24242 (13)	0.0510 (11)
H22A	0.2420	0.3314	0.2500	0.076*
H22B	0.3542	0.2768	0.2633	0.076*
H22C	0.1798	0.2657	0.2418	0.076*
N3	0.5626 (8)	0.0452 (2)	0.18208 (18)	0.0770 (16)
C31	0.5720 (7)	0.0925 (2)	0.19272 (15)	0.0504 (11)
C32	0.5849 (8)	0.1528 (2)	0.20617 (19)	0.0633 (14)
H32A	0.7005	0.1639	0.2080	0.095*
H32B	0.5337	0.1572	0.2339	0.095*
H32C	0.5293	0.1783	0.1858	0.095*
N4	0.5251 (9)	0.4160 (3)	0.2284 (2)	0.0872 (18)
C41	0.4310 (9)	0.4523 (3)	0.22369 (18)	0.0673 (17)
C42	0.3117 (10)	0.4987 (3)	0.2179 (2)	0.083 (2)
H42A	0.2559	0.5063	0.2447	0.125*
H42B	0.2313	0.4866	0.1968	0.125*
H42C	0.3671	0.5345	0.2085	0.125*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0260 (3)	0.0204 (2)	0.0363 (2)	0.00328 (14)	−0.00215 (17)	−0.00143 (14)
N1	0.0221 (18)	0.0233 (12)	0.0328 (14)	0.0018 (10)	−0.0026 (11)	−0.0020 (10)
C2	0.026 (2)	0.0270 (14)	0.0321 (17)	−0.0006 (12)	−0.0015 (14)	−0.0005 (12)
C3	0.033 (2)	0.0277 (15)	0.044 (2)	0.0008 (14)	−0.0046 (16)	−0.0042 (14)
C4	0.038 (3)	0.0236 (15)	0.054 (2)	0.0038 (14)	−0.0081 (17)	−0.0062 (14)
C5	0.030 (3)	0.0287 (16)	0.052 (2)	0.0051 (14)	−0.0053 (16)	−0.0030 (15)
C6	0.021 (2)	0.0254 (14)	0.0317 (16)	0.0040 (12)	−0.0001 (12)	−0.0022 (11)
N61	0.0245 (18)	0.0229 (12)	0.0337 (14)	0.0038 (10)	−0.0028 (12)	−0.0024 (10)
N62	0.0293 (19)	0.0210 (12)	0.0411 (16)	0.0036 (10)	−0.0014 (12)	−0.0028 (11)
C63	0.030 (2)	0.0284 (15)	0.045 (2)	0.0012 (13)	−0.0029 (16)	−0.0023 (14)
C64	0.028 (2)	0.0351 (17)	0.044 (2)	−0.0018 (14)	−0.0077 (15)	−0.0016 (14)
C65	0.024 (2)	0.0316 (15)	0.0390 (19)	0.0051 (13)	−0.0010 (14)	0.0016 (13)
N21	0.0271 (19)	0.0262 (13)	0.0348 (15)	0.0011 (11)	−0.0052 (12)	−0.0009 (11)
N22	0.0303 (19)	0.0251 (12)	0.0343 (15)	0.0037 (11)	−0.0033 (12)	0.0017 (10)
C23	0.035 (3)	0.0344 (16)	0.0366 (18)	0.0082 (14)	−0.0044 (15)	0.0035 (14)
C24	0.031 (3)	0.044 (2)	0.047 (2)	0.0036 (16)	−0.0115 (17)	0.0000 (16)
C25	0.032 (3)	0.0395 (18)	0.042 (2)	−0.0011 (15)	−0.0093 (16)	−0.0010 (15)
N11	0.028 (2)	0.0207 (12)	0.0365 (15)	0.0011 (10)	0.0006 (12)	0.0008 (10)
C12	0.026 (2)	0.0202 (13)	0.047 (2)	−0.0010 (12)	0.0063 (15)	−0.0007 (13)
C13	0.027 (2)	0.0242 (14)	0.048 (2)	−0.0001 (13)	0.0068 (15)	−0.0011 (13)
C14	0.029 (2)	0.0217 (13)	0.0318 (17)	0.0018 (12)	0.0017 (13)	0.0010 (11)
C15	0.027 (2)	0.0261 (15)	0.0403 (18)	−0.0033 (13)	0.0044 (15)	−0.0012 (13)
C16	0.027 (2)	0.0250 (15)	0.0400 (18)	0.0005 (12)	0.0056 (14)	−0.0012 (13)
C17	0.029 (2)	0.0218 (14)	0.043 (2)	−0.0007 (12)	0.0022 (15)	−0.0024 (12)
O17	0.0410 (19)	0.0244 (11)	0.0657 (19)	−0.0079 (11)	0.0194 (14)	−0.0041 (11)
N17	0.047 (2)	0.0202 (12)	0.0501 (19)	−0.0025 (12)	0.0166 (16)	−0.0041 (12)
B1	0.028 (2)	0.0288 (16)	0.038 (2)	−0.0047 (14)	0.0027 (16)	−0.0054 (14)
B2	0.044 (4)	0.042 (2)	0.057 (3)	0.009 (2)	−0.001 (2)	−0.007 (2)
N2	0.044 (2)	0.0364 (15)	0.0399 (18)	0.0021 (14)	0.0070 (15)	−0.0002 (13)
C21	0.034 (2)	0.0343 (17)	0.042 (2)	0.0042 (14)	−0.0036 (17)	0.0027 (15)
C22	0.055 (3)	0.064 (3)	0.034 (2)	0.003 (2)	0.0069 (19)	0.0048 (18)
N3	0.100 (5)	0.050 (2)	0.081 (4)	0.005 (2)	0.022 (3)	−0.012 (2)
C31	0.052 (3)	0.049 (2)	0.050 (3)	0.011 (2)	0.008 (2)	−0.0031 (19)
C32	0.070 (4)	0.054 (3)	0.065 (3)	0.008 (2)	−0.003 (3)	−0.016 (2)
N4	0.100 (5)	0.065 (3)	0.097 (4)	−0.002 (3)	−0.002 (4)	0.000 (3)
C41	0.089 (5)	0.056 (3)	0.058 (3)	−0.023 (3)	0.002 (3)	0.004 (2)
C42	0.091 (6)	0.083 (4)	0.074 (4)	0.001 (4)	0.003 (4)	0.015 (3)

Geometric parameters (Å, º)

Cu1—N1	1.945 (3)	C14—C17	1.516 (4)
Cu1—N2	2.316 (3)	C15—C16	1.381 (5)
Cu1—N11	1.964 (3)	C15—H15	0.9500
Cu1—N22	2.024 (3)	C16—H16	0.9500
Cu1—N62	2.026 (3)	C17—O17	1.220 (4)
N1—C6	1.320 (5)	C17—N17	1.328 (5)
N1—C2	1.327 (4)	N17—H17A	0.8800
C2—C3	1.370 (5)	N17—H17B	0.8800
C2—N21	1.404 (5)	B1—F11A	1.378 (5)
C3—C4	1.383 (6)	B1—F12A	1.426 (5)
C3—H3	0.9500	B1—F13A	1.371 (5)
C4—C5	1.387 (6)	B1—F14A	1.414 (6)
C4—H4	0.9500	B1—F11B	1.421 (6)
C5—C6	1.382 (4)	B1—F12B	1.354 (7)
C5—H5	0.9500	B1—F13B	1.405 (6)
C6—N61	1.406 (4)	B1—F14B	1.351 (6)
N61—C65	1.353 (5)	B2—F21A	1.391 (6)
N61—N62	1.368 (3)	B2—F22A	1.437 (6)
N62—C63	1.326 (5)	B2—F23A	1.390 (7)
C63—C64	1.400 (5)	B2—F24A	1.333 (7)
C63—H63	0.9500	B2—F21B	1.337 (7)
C64—C65	1.359 (5)	B2—F22B	1.345 (8)
C64—H64	0.9500	B2—F23B	1.371 (7)
C65—H65	0.9500	B2—F24B	1.447 (7)
N21—C25	1.353 (5)	N2—C21	1.136 (5)
N21—N22	1.365 (4)	C21—C22	1.446 (6)
N22—C23	1.320 (5)	C22—H22A	0.9800
C23—C24	1.396 (6)	C22—H22B	0.9800
C23—H23	0.9500	C22—H22C	0.9800
C24—C25	1.365 (6)	N3—C31	1.129 (6)
C24—H24	0.9500	C31—C32	1.440 (6)
C25—H25	0.9500	C32—H32A	0.9800
N11—C12	1.329 (5)	C32—H32B	0.9800
N11—C16	1.338 (5)	C32—H32C	0.9800
C12—C13	1.384 (4)	N4—C41	1.139 (9)
C12—H12	0.9500	C41—C42	1.449 (10)
C13—C14	1.387 (5)	C42—H42A	0.9800
C13—H13	0.9500	C42—H42B	0.9800
C14—C15	1.376 (5)	C42—H42C	0.9800
N1—Cu1—N2	93.41 (12)	N11—C12—H12	118.4
N1—Cu1—N11	171.42 (13)	C13—C12—H12	118.4
N1—Cu1—N22	78.87 (12)	C12—C13—C14	118.1 (3)
N1—Cu1—N62	78.80 (11)	C12—C13—H13	120.9
N2—Cu1—N11	95.12 (12)	C14—C13—H13	120.9
N2—Cu1—N22	93.70 (14)	C15—C14—C13	118.7 (3)
N2—Cu1—N62	93.29 (14)	C15—C14—C17	117.9 (3)
N11—Cu1—N22	101.55 (12)	C13—C14—C17	123.4 (3)
N11—Cu1—N62	99.67 (12)	C14—C15—C16	119.6 (3)
N22—Cu1—N62	156.94 (11)	C14—C15—H15	120.2
C6—N1—C2	120.1 (3)	C16—C15—H15	120.2
C6—N1—Cu1	119.9 (2)	N11—C16—C15	121.8 (3)
C2—N1—Cu1	119.9 (2)	N11—C16—H16	119.1
C21—N2—Cu1	171.8 (3)	C15—C16—H16	119.1
N2—C21—C22	179.3 (5)	O17—C17—N17	123.2 (3)
N1—C2—C3	122.5 (3)	O17—C17—C14	119.6 (3)
N1—C2—N21	111.5 (3)	N17—C17—C14	117.2 (3)
C3—C2—N21	126.1 (3)	C17—N17—H17A	120.0
C2—C3—C4	116.6 (3)	C17—N17—H17B	120.0
C2—C3—H3	121.7	H17A—N17—H17B	120.0
C4—C3—H3	121.7	F11A—B1—F12A	104.8 (4)
C3—C4—C5	122.2 (3)	F11A—B1—F13A	116.9 (4)
C3—C4—H4	118.9	F11A—B1—F14A	108.8 (4)
C5—C4—H4	118.9	F12A—B1—F13A	118.5 (4)
C6—C5—C4	115.8 (4)	F12A—B1—F14A	97.1 (4)
C6—C5—H5	122.1	F13A—B1—F14A	108.6 (4)
C4—C5—H5	122.1	F11B—B1—F12B	113.6 (5)
N1—C6—C5	122.8 (3)	F11B—B1—F13B	103.0 (5)
N1—C6—N61	111.8 (3)	F11B—B1—F14B	106.8 (5)
C5—C6—N61	125.4 (3)	F12B—B1—F13B	94.1 (5)
C65—N61—N62	111.4 (3)	F12B—B1—F14B	127.0 (5)
C65—N61—C6	131.3 (3)	F13B—B1—F14B	108.9 (5)
N62—N61—C6	117.1 (3)	F21A—B2—F22A	105.9 (4)
C63—N62—N61	104.9 (3)	F21A—B2—F23A	108.6 (5)
C63—N62—Cu1	142.9 (2)	F21A—B2—F24A	109.4 (5)
N61—N62—Cu1	112.2 (2)	F22A—B2—F23A	106.3 (5)
N62—C63—C64	110.9 (3)	F22A—B2—F24A	107.5 (5)
N62—C63—H63	124.5	F23A—B2—F24A	118.3 (5)
C64—C63—H63	124.5	F21B—B2—F22B	117.0 (7)
C65—C64—C63	106.0 (3)	F21B—B2—F23B	116.7 (7)
C65—C64—H64	127.0	F21B—B2—F24B	111.1 (6)
C63—C64—H64	127.0	F22B—B2—F23B	108.4 (8)
N61—C65—C64	106.8 (3)	F22B—B2—F24B	106.6 (8)
N61—C65—H65	126.6	F23B—B2—F24B	94.3 (6)
C64—C65—H65	126.6	C21—C22—H22A	109.5
C25—N21—N22	111.4 (3)	C21—C22—H22B	109.5
C25—N21—C2	131.0 (3)	H22A—C22—H22B	109.5
N22—N21—C2	117.6 (3)	C21—C22—H22C	109.5
C23—N22—N21	105.1 (3)	H22A—C22—H22C	109.5
C23—N22—Cu1	142.7 (2)	H22B—C22—H22C	109.5
N21—N22—Cu1	112.1 (2)	N3—C31—C32	179.6 (7)
N22—C23—C24	111.1 (3)	C31—C32—H32A	109.5
N22—C23—H23	124.4	C31—C32—H32B	109.5
C24—C23—H23	124.4	H32A—C32—H32B	109.5
C25—C24—C23	105.8 (4)	C31—C32—H32C	109.5
C25—C24—H24	127.1	H32A—C32—H32C	109.5
C23—C24—H24	127.1	H32B—C32—H32C	109.5
N21—C25—C24	106.6 (3)	N4—C41—C42	179.6 (8)
N21—C25—H25	126.7	C41—C42—H42A	109.5
C24—C25—H25	126.7	C41—C42—H42B	109.5
C12—N11—C16	118.5 (3)	H42A—C42—H42B	109.5
C12—N11—Cu1	121.5 (2)	C41—C42—H42C	109.5
C16—N11—Cu1	119.8 (3)	H42A—C42—H42C	109.5
N11—C12—C13	123.2 (3)	H42B—C42—H42C	109.5
C6—N1—C2—C3	2.0 (5)	C3—C2—N21—C25	2.2 (6)
C6—N1—C2—N21	−177.5 (3)	N1—C2—N21—N22	0.9 (4)
N1—C2—C3—C4	−1.1 (6)	C3—C2—N21—N22	−178.5 (4)
N21—C2—C3—C4	178.3 (4)	C25—N21—N22—C23	0.0 (4)
C2—C3—C4—C5	0.3 (6)	C2—N21—N22—C23	−179.4 (3)
C3—C4—C5—C6	−0.4 (6)	N21—N22—C23—C24	0.4 (4)
C2—N1—C6—C5	−2.1 (5)	N22—C23—C24—C25	−0.6 (5)
C2—N1—C6—N61	176.8 (3)	N22—N21—C25—C24	−0.3 (5)
C4—C5—C6—N1	1.3 (6)	C2—N21—C25—C24	179.0 (4)
C4—C5—C6—N61	−177.5 (4)	C23—C24—C25—N21	0.5 (5)
N1—C6—N61—C65	−175.4 (4)	C16—N11—C12—C13	1.1 (6)
C5—C6—N61—C65	3.5 (6)	N11—C12—C13—C14	0.3 (6)
N1—C6—N61—N62	−1.4 (4)	C12—C13—C14—C15	−1.6 (5)
C5—C6—N61—N62	177.5 (4)	C12—C13—C14—C17	178.0 (3)
C65—N61—N62—C63	−0.2 (4)	C13—C14—C15—C16	1.6 (5)
C6—N61—N62—C63	−175.4 (3)	C17—C14—C15—C16	−178.0 (3)
N61—N62—C63—C64	0.2 (4)	C12—N11—C16—C15	−1.1 (6)
N62—C63—C64—C65	−0.1 (5)	C14—C15—C16—N11	−0.3 (6)
N62—N61—C65—C64	0.2 (4)	C15—C14—C17—O17	−16.3 (6)
C6—N61—C65—C64	174.4 (4)	C13—C14—C17—O17	164.1 (4)
C63—C64—C65—N61	0.0 (4)	C15—C14—C17—N17	162.8 (4)
N1—C2—N21—C25	−178.4 (4)	C13—C14—C17—N17	−16.8 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N17—H17A···F11A^i	0.88	2.60	3.334 (6)	142
N17—H17B···F11A^ii	0.88	2.09	2.900 (6)	152
N17—H17B···F11B^ii	0.88	2.01	2.866 (7)	163
N17—H17A···F12A^i	0.88	2.12	2.971 (5)	163
N17—H17A···F12B^i	0.88	2.03	2.885 (7)	163
C5—H5···O17^iii	0.95	2.22	3.140 (5)	162
C65—H65···O17^iii	0.95	2.36	3.221 (4)	151

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