2,6-Bis(1-benzyl-1H-1,2,3-triazol-4-yl)pyridine and its octa­hedral copper complex

In the tridentate ligand 2,6-bis­(1-benzyl-1H-1,2,3-triazol-4-yl)pyridine, C₂₃H₁₉N₇, both sets of triazole N atoms are anti with respect to the pyridine N atom, while in the copper complex aqua­[2,6-bis­(1-benzyl-1H-1,2,3-triazol-4-yl)pyridine](pyridine)(tetra­fluoro­borato)copper(II) tetra­fluoro­borate, [Cu(BF₄)(C₅H₅N)(C₂₃H₁₉N₇)(H₂O)]BF₄, the triazole N atoms are in the syn–syn conformation. The coordination of the Cu^II atom is distorted octa­hedral. The ligand structure is stabilized through inter­molecular C—H...N inter­actions, while the crystal structure of the Cu complex is stabilized through water- and BF₄-mediated hydrogen bonds. Photoluminiscence studies of the ligand and complex show that the ligand is fluorescent due to triazole–pyridine conjugation, but that the fluorescence is quenched on complexation.

S1. Comment

Huisgen's dipolar cycloaddition of organic azides with alkynes is the most direct route for the synthesis of 1,2,3-triazoles (Huisgen et al., 1967). These are nitrogen heteroarenes which have found numerous applications in organic (Karthikeyan & Sankararaman, 2008), organometallic (Karthikeyan & Sankararaman, 2009) and medicinal chemistry (Shia et al., 2002), as well as in materials chemistry (Crowley & Bandeen, 2010). 1,2,3-Triazole-based materials have advantageous properties for high-performance metal coatings and adhesives (Zhu et al., 2006). However, there are major problems commonly associated with Huisgen's dipolar cycloaddition methodology, including the need for long reaction times and high temperatures, as well as the formation of regioisomeric mixtures of products when using unsymmetrical alkynes. It was found that cycloadditions of terminal alkynes with alkyl azides catalysed by Cu^I can be conducted at room temperature and are highly regioselective (Rostovtsev et al., 2002). The cycloaddition of alkynes with azides under Cu^I-catalysed conditions leads exclusively to 1,4-substituted-1,2,3-triazoles in high yields. This type of copper catalysis, however, does not promote the cycloaddition of internal alkynes. Mechanistic studies have demonstrated that these reactions involve terminal copper acetylides and proceed via a stepwise non-concerted process (Tornoe et al., 2002). We made benzyl triazole from benzyl azide and alkynes using a `click reaction' (Horne et al., 2004), which gave 1,4-disubstituted 1,2,3 triazoles. 1,2,3-Triazoles can be used for the preparation of bi- and tridentate ligands by suitably choosing the alkynes that are used for the cycloaddition reaction. The title tridentate triazole ligand, (I), was prepared from 1,5-diethynylpyridine. The first published work on 2,6-bis(1,2,3-triazol-4-yl)pyridine (BTP) was by Meudtner et al. (2007). The tridentate triazole coordination to a metal ion leads to conformational changes in the ligand. The conformational sensitivity of BTP can be suitably modulated to design nanoswitches (Piot et al., 2009) sensitive to metal ions or pH changes.

A view of the title BTP ligand, (I), with its `horse-shoe' conformation and the atom-numbering scheme, is shown in Fig. 1. The torsion angles N7—C14—C15—N4 [156.1 (3)°, anti-periplanar] and N7—C10—C9—N3 [171.8 (3)°, anti-periplanar] show that the triazole moieties are positioned anti–anti wth respect to the N atom of the pyridine ring. The anti–anti conformation is preferred by BTP, due to electrostatic repulsion between the lone pairs of atoms N5 and N2 and N7. Protonation of these N atoms or coordination with metals can remove this electrostatic interaction and make the conformation between triazole and pyridine syn–syn. Density functional theory calculations (Meudtner et al., 2007) on a model system predict the stabilization energy for the syn–syn phase to be 6.4 kcal mol^-1 (1 kcal mol^-1 = 4.184 kJ mol^-1) more than that for the anti–anti phase. The dihedral angles of the triazole rings N1–N3/C9/C8 and N4–N6/C16/C15 with the pyridine ring are 7.5 (3) and 22.5 (2)°, respectively. The benzyl rings C1–C6 and C18–C23 are inclined to each other at an angle of 14.3 (2)°. Analysis of the shortest intermolecular contacts shows that chains of molecules are developed along the a direction by C—H···N interactions (Table 1, Fig. 2). The inversion-related five-membered rings N1–N3/C8/C9 at (x, y, z) and (1 - x, 1 - y, 1 - z) overlap significantly, with a centroid-to-centroid separation of 3.537 (2) Å, leading to an N2···N3ⁱⁱ separation of 3.576 (5) Å [symmetry code: (ii) 1 - x, 1 - y, 1 - z].

A view of the copper complex with BTP, aqua[2,6-bis(1-benzyl-1H-1,2,3-triazol-4-yl)pyridine](pyridine)(tetrafluoroborato)copper(II) tetrafluoroborate (CUBTP), (II), is shown in Fig. 3. The coordination geometry around the Cu^II ion is distorted octahedral. The two bite angles of the ligand with the metal atom are N4—Cu—N7 = 78.94 (11)° and N7—Cu—N3 = 78.54 (11)°. Atoms N3, N4, N7 and N8 form a near-regular plane, with the metal atom deviating slightly out of the mean plane in the direction of the water molecule [0.0755 (2) Å]. The water molecule is almost normal to the equatorial plane. The axial bond lengths [Cu1—O1 2.271 (3) Å and Cu1—F7 2.464 (4) Å] are considerably elongated compared with the four Cu—N coordination distances [Cu—N 1.948 (3)–2.067 (3)Å]. This is common among octahedrally coordinated copper compounds (Silverside et al., 2007).

As would be expected, there is considerable conformational change between the free BTP ligand, (I), and the coordinated ligand in the CUBTP complex, (II). The pyridine and triazole moieties are nearly in the same plane, the dihedral angle between the two triazole moieties being 7.5 (2)° [the corresponding value in the ligand is 24.7 (2)°]. The triazole rings have almost rotated through 180° about the respective pyridine–triazole bonds, making both triazole N atoms in a syn–syn conformation with respect to the pyridine N atoms. The relevant torsion angles in the complex (with corresponding values in the ligand in parentheses) are N7—C10—C9—N3 = 0.1 (5)° [-171.8 (3)°] and N7—C14—C15—N4 = 2.3 (5) [156.1 (3)°]. Similar conformational changes during complexation were noticed in 4-(2-pyridyl)-1,2,3-triazole (Meudtner et al., 2007).

In the CUBTP crystal structure, the cations and anions are linked by O—H···F hydrogen bonds to generate chains which extend in the a direction; details are in Table 2 and Fig. 4. In addition to the O—H···F hydrogen bonds, geometry calculations show other significant interactions, including C—H···F and C—H···O contacts and a C13—H13···π interaction with the centroid of the C1–C6 phenyl ring at (1 - x, -y, 2 - z); details are in Table 2. There are also π–π interactions, with an almost complete overlap of the coordinated pyridine rings at (x, y, z) and (1 - x, -y, 2 - z), and a centroid-to-centroid separation of 3.815 (2) Å and a slippage of only 0.60 Å (slippage is the distance between the centroid of one ring and the perpendicular projection of the centroid of the second ring on the first ring). The phenyl ring C1–C6 and its equivalent at (-x, -1 - y, 2 - z) have a centroid-to-centroid separation of 3.837 (2) Å but with a slippage of 1.95 Å; the distance between the centroid of one ring and the plane of the inversion-related ring is 3.302 (2) Å.

The BTP ligand is photoluminiscent. Fig. 5 shows the excitation and emission spectra of BTP. There are two excitation bands centred at 237 and 301 nm, and an emission band at 339 nm. The luminiscence is quenched on complexation or protonation of the ligand. Fig. 6 shows the luminiscence being quenched when copper tetrafluoroborate is added to the ligand solution. The conformational change of the pyridine–triazole moiety, from anti–anti in the ligand to syn–syn in the complex, is the cause of the quenching (Choi et al., 2006). The ligand could thus be potentially useful as a pH or metal ion sensor.

S2. Experimental

Sonagashira coupling reaction (Sonogashira et al., 1975) of 2,6-dibromopyridine with 2-methylbut-3-yn-2-ol gave 4,4'-(pyridine-2,6-diyl)bis(2-methylbut-3-yn-2-ol) in good yield. 2,6-Diethynylpyridine was prepared from 4,4'-(pyridine-2,6-diyl)bis(2-methylbut-3-yn-2-ol) by treating it with KOH in toluene at 353 K in 70% yield (Shinohara et al., 2001). 2,6-Diethynylpyridine (0.25g, 2 mmol) was dissolved in ^tBuOH–H₂O (1:1 v/v, 4.0 ml), and benzyl azide (0.53g, 4 mmol), CuSO₄ (20 mg) and sodium ascorbate (40 mg) were added. The resulting mixture was stirred at room temperature overnight, diluted with NaCl and extracted with dichloromethane. The organic layer was dried over Na₂SO₄ and the solvent evaporated under reduced pressure. The crude products were purified by flash chromatography on silica gel eluting with CH₂Cl₂–EtOAc, to yield the corresponding ligand, BTP, (I). The compound was crystallized from chloroform.

Complex (II) was prepared from copper(II) tetrafluoroborate and the BTP ligand. BTP (0.1 g, 0.03 mmol) and copper(II) tetrafluoroborate (0.08 g, 0.03mmol) were dissolved in acetonitrile. A drop of pyridine was added and the mixture warmed to give a clear solution. The clear solution was allowed to stand for crystallization of (II).

S3. Refinement

One of the benzyl moieties (C18–C23) in CUBTP is disordered. The occupancies assigned to the disordered components were refined as least-squares variables with their sum kept as 1. When the refinement converged, the occupancies were almost 0.5 each. In the final refinement the occupancies of the components were set at 0.5. The disordered rings were constrained as idealized hexagons, with C—C = 1.39 Å. The methylene H atoms associated with atom C17 were geometrically fixed with respect to both disordered components of the benzyl moiety. Each of these four H atoms was given 50% occupancy. Their positions were fixed only after the refinement convergence and hence not refined in the last set of cycles. The U_iso(H) values of these H atoms were fixed at 1.2U_eq(C17). Water H atoms were located in a difference map and refined isotropically without restraints. In both compounds, the remaining H atoms bound to C atoms were constrained as riding, with C—H = 0.95 Å for aromatic CH and 0.97 Å for secondary CH₂ groups, with U_iso(H) = 1.2U_eq(C).

Thermal motion analysis of BTP (refined without restraints) showed the difference between the mean square displacements of N7 and C10 in the direction of the N7—C10 bond as 0.0205 Å^{2 and the standard deviation of MSDA as 0.0027 Å}2. To avoid this apparent inconsistency, a rigid-bond restraint was set between N7 and C10. In CUBTP, pseudo-isotropic restraints were applied to the C atoms of the disordered phenyl ring to remove minor inconsistencies among displacement parameters caused by disorder.

Computing details

For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004) and SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004) and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The BTP ligand, (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. The packing of BTP in the unit cell. Intermolecular interactions are shown as dashed lines. [Symmetry codes: (i) x - 1, y, z; (ii) 1 - x, 1 - y, 1 - z.]
	Fig. 3. The molecular structure of CUBTP, (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Only one of the two disordered orientations for the C18–C23 ring is shown.
	Fig. 4. A view of the hydrogen-bonded chain extending along the a direction in CUBTP. For symmetry codes, see Table 2.
	Fig. 5. The fluorescence spectra of BTP in acetonitrile (5 × 10^-5 M). (A) Excitation spectrum of BTP (λemission = 339 nm), (B) emission spectrum of BTP (λexcitation = 237 nm), (C) emission spectrum of BTP (λexcitation = 301 nm).
	Fig. 6. The fluorescence emission spectra of BTP in acetonitrile (5 × 10^-5 M) with (A) 1 × 10^-5 M copper tetrafluoroborate, (B) 2 × 10^-5 M copper tetrafluoroborate and (C) 3 × 10^-5 M copper tetrafluoroborate.

(I) 2,6-bis(1-benzyl-1H-1,2,3-triazol-4-yl)pyridine

Crystal data

C23H19N7	Z = 2
Mr = 393.45	F(000) = 412
Triclinic, P1	Dx = 1.314 Mg m^−3
a = 5.8800 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.460 (2) Å	Cell parameters from 7794 reflections
c = 16.140 (3) Å	θ = 2.8–25.9°
α = 103.53 (3)°	µ = 0.08 mm^−1
β = 99.31 (3)°	T = 298 K
γ = 104.61 (3)°	Needle, colourless
V = 994.6 (3) Å^3	0.25 × 0.22 × 0.20 mm

Data collection

Bruker Kappa APEX2 CCD area-detector diffractometer	3417 independent reflections
Radiation source: fine-focus sealed tube	1811 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
ω and ϕ scans	θmax = 25.0°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −5→6
Tmin = 0.934, Tmax = 0.973	k = −13→13
10767 measured reflections	l = −19→19

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)] = 0.054	H-atom parameters constrained
wR(F^2) = 0.185	w = 1/[σ^2(Fo^2) + (0.0791P)^2 + 0.3737P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
3417 reflections	Δρmax = 0.33 e Å^−3
272 parameters	Δρmin = −0.25 e Å^−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.007 (2)

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
C1	0.3432 (7)	1.0200 (3)	0.3308 (2)	0.0693 (10)
H1	0.3505	1.0847	0.3047	0.083*
C2	0.1824 (8)	0.9972 (4)	0.3818 (3)	0.0791 (11)
H2	0.0777	1.0455	0.3895	0.095*
C3	0.1752 (6)	0.9035 (3)	0.4215 (2)	0.0681 (10)
H3	0.0650	0.8889	0.4560	0.082*
C4	0.3277 (5)	0.8307 (3)	0.41135 (18)	0.0497 (8)
C5	0.4858 (6)	0.8533 (3)	0.3587 (2)	0.0627 (9)
H5	0.5895	0.8046	0.3501	0.075*
C6	0.4924 (7)	0.9473 (3)	0.3184 (2)	0.0701 (10)
H6	0.5995	0.9612	0.2827	0.084*
C7	0.3192 (6)	0.7354 (3)	0.4612 (2)	0.0632 (9)
H7A	0.3800	0.7796	0.5231	0.076*
H7B	0.1517	0.6870	0.4525	0.076*
C9	0.5882 (5)	0.5004 (3)	0.37662 (19)	0.0505 (8)
C8	0.4044 (6)	0.5510 (3)	0.3657 (2)	0.0558 (9)
H8	0.2707	0.5234	0.3186	0.067*
C10	0.6303 (5)	0.3921 (3)	0.3188 (2)	0.0507 (8)
C11	0.8216 (6)	0.3492 (3)	0.3448 (2)	0.0607 (9)
H11	0.9241	0.3870	0.4003	0.073*
C12	0.8590 (6)	0.2495 (3)	0.2875 (2)	0.0655 (10)
H12	0.9855	0.2187	0.3046	0.079*
C13	0.7100 (6)	0.1964 (3)	0.2057 (2)	0.0610 (9)
H13	0.7350	0.1293	0.1669	0.073*
C14	0.5212 (6)	0.2423 (3)	0.1804 (2)	0.0511 (8)
C15	0.3671 (6)	0.1939 (3)	0.0921 (2)	0.0493 (8)
C16	0.1439 (6)	0.1987 (3)	0.0590 (2)	0.0565 (9)
H16	0.0462	0.2347	0.0899	0.068*
C17	−0.1106 (6)	0.1312 (3)	−0.0951 (2)	0.0630 (9)
H17A	−0.2584	0.1132	−0.0746	0.076*
H17B	−0.1267	0.0623	−0.1460	0.076*
C18	−0.0732 (6)	0.2524 (3)	−0.1202 (2)	0.0573 (9)
C19	0.0978 (7)	0.2868 (4)	−0.1645 (2)	0.0797 (11)
H19	0.1874	0.2331	−0.1817	0.096*
C20	0.1412 (8)	0.3988 (4)	−0.1843 (3)	0.0938 (13)
H20	0.2588	0.4203	−0.2149	0.113*
C21	0.0135 (8)	0.4784 (4)	−0.1596 (3)	0.0831 (12)
H21	0.0464	0.5555	−0.1719	0.100*
C22	−0.1617 (8)	0.4461 (4)	−0.1171 (3)	0.0892 (13)
H22	−0.2534	0.4995	−0.1017	0.107*
C23	−0.2041 (7)	0.3319 (3)	−0.0963 (2)	0.0778 (11)
H23	−0.3224	0.3101	−0.0660	0.093*
N1	0.4558 (5)	0.6490 (2)	0.43693 (17)	0.0546 (7)
N2	0.6644 (5)	0.6605 (3)	0.49136 (18)	0.0652 (8)
N3	0.7433 (5)	0.5690 (3)	0.45419 (18)	0.0640 (8)
N4	0.4445 (6)	0.1332 (3)	0.0247 (2)	0.0686 (8)
N5	0.2767 (6)	0.1020 (3)	−0.04726 (19)	0.0706 (9)
N6	0.0928 (5)	0.1417 (2)	−0.02644 (17)	0.0555 (7)
N7	0.4806 (5)	0.3394 (2)	0.23758 (17)	0.0573 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.085 (3)	0.051 (2)	0.071 (2)	0.018 (2)	0.016 (2)	0.0199 (18)
C2	0.090 (3)	0.068 (3)	0.092 (3)	0.040 (2)	0.027 (2)	0.025 (2)
C3	0.063 (2)	0.070 (2)	0.071 (2)	0.020 (2)	0.0247 (18)	0.0140 (19)
C4	0.0437 (19)	0.0471 (19)	0.0504 (18)	0.0079 (16)	0.0078 (14)	0.0078 (15)
C5	0.059 (2)	0.063 (2)	0.074 (2)	0.0228 (18)	0.0222 (18)	0.0256 (19)
C6	0.078 (3)	0.064 (2)	0.075 (2)	0.018 (2)	0.0305 (19)	0.028 (2)
C7	0.058 (2)	0.066 (2)	0.066 (2)	0.0128 (19)	0.0203 (17)	0.0223 (18)
C9	0.0440 (19)	0.0518 (19)	0.0538 (19)	0.0038 (16)	0.0057 (16)	0.0269 (16)
C8	0.053 (2)	0.052 (2)	0.055 (2)	0.0072 (17)	0.0036 (16)	0.0177 (17)
C10	0.0481 (19)	0.0492 (19)	0.0578 (16)	0.0073 (15)	0.0116 (13)	0.0299 (15)
C11	0.052 (2)	0.061 (2)	0.070 (2)	0.0090 (18)	0.0074 (17)	0.0351 (19)
C12	0.066 (2)	0.062 (2)	0.086 (3)	0.0273 (19)	0.023 (2)	0.042 (2)
C13	0.070 (2)	0.053 (2)	0.078 (2)	0.0257 (19)	0.0297 (19)	0.0355 (18)
C14	0.061 (2)	0.0408 (18)	0.063 (2)	0.0160 (16)	0.0259 (17)	0.0265 (16)
C15	0.063 (2)	0.0383 (17)	0.0591 (19)	0.0213 (16)	0.0262 (17)	0.0230 (15)
C16	0.072 (2)	0.051 (2)	0.056 (2)	0.0246 (18)	0.0270 (17)	0.0206 (16)
C17	0.070 (2)	0.049 (2)	0.065 (2)	0.0114 (17)	0.0129 (18)	0.0169 (17)
C18	0.064 (2)	0.0453 (19)	0.059 (2)	0.0106 (17)	0.0082 (17)	0.0192 (16)
C19	0.088 (3)	0.075 (3)	0.096 (3)	0.029 (2)	0.038 (2)	0.046 (2)
C20	0.095 (3)	0.095 (3)	0.112 (3)	0.020 (3)	0.038 (3)	0.067 (3)
C21	0.088 (3)	0.061 (3)	0.097 (3)	0.009 (2)	0.005 (2)	0.044 (2)
C22	0.095 (3)	0.061 (3)	0.117 (3)	0.028 (2)	0.017 (3)	0.036 (2)
C23	0.087 (3)	0.061 (2)	0.088 (3)	0.018 (2)	0.026 (2)	0.027 (2)
N1	0.0514 (18)	0.0525 (17)	0.0568 (16)	0.0074 (14)	0.0091 (14)	0.0210 (14)
N2	0.0566 (19)	0.064 (2)	0.0612 (18)	0.0086 (16)	−0.0005 (15)	0.0126 (15)
N3	0.0566 (19)	0.0630 (19)	0.0639 (18)	0.0130 (16)	−0.0001 (15)	0.0175 (15)
N4	0.087 (2)	0.0635 (19)	0.0694 (19)	0.0437 (17)	0.0256 (18)	0.0184 (15)
N5	0.096 (2)	0.0590 (19)	0.0694 (19)	0.0404 (18)	0.0282 (19)	0.0176 (15)
N6	0.0693 (19)	0.0418 (15)	0.0618 (18)	0.0177 (14)	0.0223 (15)	0.0210 (13)
N7	0.0617 (18)	0.0505 (16)	0.0615 (15)	0.0110 (13)	0.0154 (12)	0.0254 (13)

Geometric parameters (Å, º)

C1—C6	1.361 (5)	C13—H13	0.9300
C1—C2	1.366 (5)	C14—N7	1.369 (4)
C1—H1	0.9300	C14—C15	1.455 (4)
C2—C3	1.369 (5)	C15—C16	1.354 (4)
C2—H2	0.9300	C15—N4	1.356 (4)
C3—C4	1.375 (4)	C16—N6	1.329 (4)
C3—H3	0.9300	C16—H16	0.9300
C4—C5	1.376 (4)	C17—N6	1.452 (4)
C4—C7	1.495 (4)	C17—C18	1.510 (4)
C5—C6	1.377 (4)	C17—H17A	0.9700
C5—H5	0.9300	C17—H17B	0.9700
C6—H6	0.9300	C18—C19	1.358 (5)
C7—N1	1.450 (4)	C18—C23	1.363 (5)
C7—H7A	0.9700	C19—C20	1.367 (5)
C7—H7B	0.9700	C19—H19	0.9300
C9—N3	1.351 (4)	C20—C21	1.352 (6)
C9—C8	1.356 (4)	C20—H20	0.9300
C9—C10	1.470 (4)	C21—C22	1.351 (6)
C8—N1	1.336 (4)	C21—H21	0.9300
C8—H8	0.9300	C22—C23	1.399 (5)
C10—N7	1.359 (4)	C22—H22	0.9300
C10—C11	1.380 (4)	C23—H23	0.9300
C11—C12	1.381 (5)	N1—N2	1.345 (3)
C11—H11	0.9300	N2—N3	1.310 (4)
C12—C13	1.364 (5)	N4—N5	1.307 (4)
C12—H12	0.9300	N5—N6	1.335 (4)
C13—C14	1.388 (4)
C6—C1—C2	119.5 (3)	N7—C14—C15	117.6 (3)
C6—C1—H1	120.2	C13—C14—C15	121.9 (3)
C2—C1—H1	120.2	C16—C15—N4	107.6 (3)
C1—C2—C3	120.1 (4)	C16—C15—C14	132.0 (3)
C1—C2—H2	119.9	N4—C15—C14	120.4 (3)
C3—C2—H2	119.9	N6—C16—C15	106.2 (3)
C2—C3—C4	121.3 (3)	N6—C16—H16	126.9
C2—C3—H3	119.4	C15—C16—H16	126.9
C4—C3—H3	119.4	N6—C17—C18	110.1 (3)
C3—C4—C5	117.9 (3)	N6—C17—H17A	109.6
C3—C4—C7	118.1 (3)	C18—C17—H17A	109.6
C5—C4—C7	124.0 (3)	N6—C17—H17B	109.6
C4—C5—C6	120.8 (3)	C18—C17—H17B	109.6
C4—C5—H5	119.6	H17A—C17—H17B	108.2
C6—C5—H5	119.6	C19—C18—C23	118.4 (3)
C1—C6—C5	120.3 (3)	C19—C18—C17	120.7 (3)
C1—C6—H6	119.8	C23—C18—C17	120.9 (3)
C5—C6—H6	119.8	C18—C19—C20	121.4 (4)
N1—C7—C4	114.9 (3)	C18—C19—H19	119.3
N1—C7—H7A	108.5	C20—C19—H19	119.3
C4—C7—H7A	108.5	C21—C20—C19	120.2 (4)
N1—C7—H7B	108.5	C21—C20—H20	119.9
C4—C7—H7B	108.5	C19—C20—H20	119.9
H7A—C7—H7B	107.5	C22—C21—C20	120.1 (4)
N3—C9—C8	107.8 (3)	C22—C21—H21	120.0
N3—C9—C10	122.2 (3)	C20—C21—H21	120.0
C8—C9—C10	129.9 (3)	C21—C22—C23	119.5 (4)
N1—C8—C9	105.5 (3)	C21—C22—H22	120.2
N1—C8—H8	127.3	C23—C22—H22	120.2
C9—C8—H8	127.3	C18—C23—C22	120.4 (4)
N7—C10—C11	121.3 (3)	C18—C23—H23	119.8
N7—C10—C9	117.5 (3)	C22—C23—H23	119.8
C11—C10—C9	121.1 (3)	C8—N1—N2	110.7 (3)
C10—C11—C12	119.3 (3)	C8—N1—C7	129.5 (3)
C10—C11—H11	120.4	N2—N1—C7	119.8 (3)
C12—C11—H11	120.4	N3—N2—N1	106.5 (2)
C13—C12—C11	119.8 (3)	N2—N3—C9	109.5 (3)
C13—C12—H12	120.1	N5—N4—C15	108.5 (3)
C11—C12—H12	120.1	N4—N5—N6	107.7 (3)
C12—C13—C14	120.0 (3)	C16—N6—N5	110.0 (3)
C12—C13—H13	120.0	C16—N6—C17	129.6 (3)
C14—C13—H13	120.0	N5—N6—C17	120.0 (3)
N7—C14—C13	120.4 (3)	C10—N7—C14	119.2 (3)
C6—C1—C2—C3	1.3 (6)	C23—C18—C19—C20	0.6 (6)
C1—C2—C3—C4	0.0 (6)	C17—C18—C19—C20	−177.1 (3)
C2—C3—C4—C5	−1.1 (5)	C18—C19—C20—C21	0.2 (6)
C2—C3—C4—C7	176.4 (3)	C19—C20—C21—C22	−1.7 (7)
C3—C4—C5—C6	0.8 (5)	C20—C21—C22—C23	2.2 (6)
C7—C4—C5—C6	−176.5 (3)	C19—C18—C23—C22	−0.1 (5)
C2—C1—C6—C5	−1.5 (6)	C17—C18—C23—C22	177.6 (3)
C4—C5—C6—C1	0.4 (5)	C21—C22—C23—C18	−1.3 (6)
C3—C4—C7—N1	170.7 (3)	C9—C8—N1—N2	−0.1 (3)
C5—C4—C7—N1	−12.0 (5)	C9—C8—N1—C7	−178.4 (3)
N3—C9—C8—N1	0.3 (3)	C4—C7—N1—C8	−74.7 (4)
C10—C9—C8—N1	−179.1 (3)	C4—C7—N1—N2	107.1 (3)
N3—C9—C10—N7	−171.8 (3)	C8—N1—N2—N3	−0.3 (3)
C8—C9—C10—N7	7.6 (5)	C7—N1—N2—N3	178.3 (3)
N3—C9—C10—C11	5.4 (4)	N1—N2—N3—C9	0.5 (3)
C8—C9—C10—C11	−175.2 (3)	C8—C9—N3—N2	−0.5 (4)
N7—C10—C11—C12	−1.0 (4)	C10—C9—N3—N2	179.0 (3)
C9—C10—C11—C12	−178.1 (3)	C16—C15—N4—N5	0.2 (4)
C10—C11—C12—C13	1.2 (5)	C14—C15—N4—N5	−178.5 (3)
C11—C12—C13—C14	−0.1 (5)	C15—N4—N5—N6	−0.2 (3)
C12—C13—C14—N7	−1.1 (4)	C15—C16—N6—N5	−0.1 (3)
C12—C13—C14—C15	176.1 (3)	C15—C16—N6—C17	−172.9 (3)
N7—C14—C15—C16	−22.2 (5)	N4—N5—N6—C16	0.2 (3)
C13—C14—C15—C16	160.5 (3)	N4—N5—N6—C17	173.8 (3)
N7—C14—C15—N4	156.2 (3)	C18—C17—N6—C16	78.2 (4)
C13—C14—C15—N4	−21.1 (4)	C18—C17—N6—N5	−94.0 (3)
N4—C15—C16—N6	−0.1 (3)	C11—C10—N7—C14	−0.2 (4)
C14—C15—C16—N6	178.5 (3)	C9—C10—N7—C14	176.9 (2)
N6—C17—C18—C19	70.5 (4)	C13—C14—N7—C10	1.3 (4)
N6—C17—C18—C23	−107.2 (4)	C15—C14—N7—C10	−176.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···N3^i	0.97	2.45	3.411 (5)	171

Symmetry code: (i) x−1, y, z.

(II) aqua[2,6-bis(1-benzyl-1H-1,2,3-triazol-4- yl)pyridine](pyridine)(tetrafluoroborato)copper(II) tetrafluoroborate

Crystal data

[Cu(BF4)(C5H5N)(C23H19N7)(H2O)]BF4	Z = 2
Mr = 727.73	F(000) = 738
Triclinic, P1	Dx = 1.557 Mg m^−3
a = 8.2990 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.956 (3) Å	Cell parameters from 5323 reflections
c = 14.520 (3) Å	θ = 2.8–28.1°
α = 88.56 (3)°	µ = 0.79 mm^−1
β = 84.76 (3)°	T = 173 K
γ = 87.36 (3)°	Rectangle, blue
V = 1552.7 (5) Å^3	0.41 × 0.22 × 0.20 mm

Data collection

Bruker Kappa APEX2 CCD area-detector diffractometer	7222 independent reflections
Radiation source: fine-focus sealed tube	4381 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ω and ϕ scans	θmax = 28.5°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −10→10
Tmin = 0.761, Tmax = 0.903	k = −16→17
20211 measured reflections	l = −19→19

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0585P)^2 + 1.7736P] where P = (Fo^2 + 2Fc^2)/3
7222 reflections	(Δ/σ)max = 0.001
459 parameters	Δρmax = 0.58 e Å^−3
72 restraints	Δρmin = −0.61 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)
C1	0.2125 (6)	−0.4025 (3)	1.0440 (3)	0.0451 (11)
H1	0.2896	−0.4245	1.0857	0.054*
C2	0.0462 (6)	−0.3990 (3)	1.0728 (3)	0.0496 (13)
H2	0.0094	−0.4202	1.1339	0.060*
C3	−0.0622 (6)	−0.3650 (3)	1.0125 (4)	0.0545 (13)
H3	−0.1747	−0.3625	1.0321	0.065*
C4	−0.0113 (6)	−0.3346 (3)	0.9246 (4)	0.0538 (13)
H4	−0.0877	−0.3093	0.8836	0.065*
C5	0.1493 (6)	−0.3406 (3)	0.8956 (3)	0.0456 (11)
H5	0.1839	−0.3217	0.8336	0.055*
C6	0.2623 (5)	−0.3736 (3)	0.9547 (3)	0.0370 (10)
C7	0.4385 (5)	−0.3826 (3)	0.9208 (3)	0.0486 (12)
H7A	0.4982	−0.4218	0.9673	0.058*
H7B	0.4515	−0.4218	0.8628	0.058*
C8	0.5606 (5)	−0.2193 (3)	0.9661 (3)	0.0348 (9)
H8	0.5567	−0.2300	1.0312	0.042*
C9	0.6202 (5)	−0.1377 (3)	0.9154 (2)	0.0287 (8)
C10	0.7024 (5)	−0.0454 (3)	0.9351 (2)	0.0274 (8)
C11	0.7415 (5)	−0.0146 (3)	1.0194 (2)	0.0347 (9)
H11	0.7113	−0.0537	1.0740	0.042*
C12	0.8254 (5)	0.0740 (3)	1.0233 (3)	0.0390 (10)
H12	0.8523	0.0972	1.0813	0.047*
C13	0.8707 (5)	0.1295 (3)	0.9436 (2)	0.0325 (9)
H13	0.9298	0.1904	0.9456	0.039*
C14	0.8279 (4)	0.0942 (2)	0.8607 (2)	0.0265 (8)
C15	0.8597 (5)	0.1407 (3)	0.7699 (2)	0.0281 (8)
C16	0.9374 (5)	0.2249 (3)	0.7344 (3)	0.0339 (9)
H16	0.9951	0.2722	0.7665	0.041*
C17	0.9679 (4)	0.30328 (16)	0.57307 (14)	0.0449 (11)
C18	0.9318 (4)	0.40708 (16)	0.60536 (14)	0.045 (4)	0.50
C19	0.7710 (4)	0.44294 (16)	0.61746 (14)	0.056 (3)	0.50
H19	0.6870	0.3988	0.6060	0.068*	0.50
C20	0.7330 (4)	0.54333 (16)	0.64632 (14)	0.081 (4)	0.50
H20	0.6231	0.5678	0.6546	0.097*	0.50
C21	0.8559 (4)	0.60786 (16)	0.66308 (14)	0.057 (3)	0.50
H21	0.8299	0.6765	0.6828	0.069*	0.50
C22	1.0167 (4)	0.57201 (16)	0.65098 (14)	0.066 (3)	0.50
H22	1.1007	0.6161	0.6624	0.079*	0.50
C23	1.0547 (4)	0.47162 (16)	0.62212 (14)	0.058 (3)	0.50
H23	1.1646	0.4471	0.6139	0.070*	0.50
C18'	0.9013 (4)	0.40917 (16)	0.59899 (14)	0.026 (3)	0.50
C19'	0.7372 (4)	0.43403 (16)	0.59558 (14)	0.073 (4)	0.50
H19'	0.6678	0.3843	0.5759	0.088*	0.50
C20'	0.6747 (4)	0.53162 (16)	0.62105 (14)	0.095 (5)	0.50
H20'	0.5626	0.5486	0.6187	0.114*	0.50
C21'	0.7763 (4)	0.60434 (16)	0.64991 (14)	0.067 (4)	0.50
H21'	0.7336	0.6710	0.6673	0.081*	0.50
C22'	0.9404 (4)	0.57948 (16)	0.65331 (14)	0.040 (2)	0.50
H22'	1.0099	0.6292	0.6730	0.048*	0.50
C23'	1.0029 (4)	0.48190 (16)	0.62785 (14)	0.033 (2)	0.50
H23'	1.1151	0.4649	0.6302	0.040*	0.50
C24	0.5110 (5)	−0.1468 (3)	0.6131 (3)	0.0365 (9)
H24	0.4443	−0.1611	0.6683	0.044*
C25	0.4712 (6)	−0.1857 (3)	0.5320 (3)	0.0473 (11)
H25	0.3785	−0.2259	0.5310	0.057*
C26	0.5659 (6)	−0.1660 (3)	0.4530 (3)	0.0462 (11)
H26	0.5407	−0.1923	0.3958	0.055*
C27	0.6988 (5)	−0.1074 (3)	0.4570 (3)	0.0407 (10)
H27	0.7673	−0.0930	0.4026	0.049*
C28	0.7314 (5)	−0.0702 (3)	0.5404 (2)	0.0334 (9)
H28	0.8228	−0.0291	0.5427	0.040*
B1	0.3973 (7)	0.3176 (4)	0.7870 (3)	0.0420 (12)
B2	1.0833 (6)	−0.1243 (3)	0.6993 (3)	0.0386 (11)
N1	0.5089 (4)	−0.2807 (2)	0.9039 (2)	0.0357 (8)
N2	0.5307 (4)	−0.2428 (2)	0.8176 (2)	0.0359 (8)
N3	0.5984 (4)	−0.1545 (2)	0.8252 (2)	0.0284 (7)
N4	0.7967 (4)	0.0952 (2)	0.69900 (19)	0.0287 (7)
N5	0.8299 (4)	0.1473 (2)	0.6220 (2)	0.0320 (7)
N6	0.9146 (4)	0.2263 (2)	0.6443 (2)	0.0343 (8)
N7	0.7433 (4)	0.0090 (2)	0.85778 (19)	0.0255 (7)
N8	0.6393 (4)	−0.0895 (2)	0.6183 (2)	0.0295 (7)
O1	0.4330 (4)	0.0437 (3)	0.7635 (2)	0.0408 (7)
F1	0.2933 (5)	0.2436 (3)	0.8215 (3)	0.1203 (16)
F2	0.3308 (9)	0.3650 (4)	0.7207 (4)	0.199 (3)
F3	0.4230 (4)	0.38174 (19)	0.85615 (18)	0.0657 (8)
F4	0.5311 (4)	0.2672 (3)	0.7544 (3)	0.1206 (16)
F5	1.1758 (4)	−0.2133 (2)	0.6892 (3)	0.0993 (13)
F6	1.0747 (4)	−0.0803 (3)	0.6143 (2)	0.0928 (11)
F7	0.9336 (3)	−0.14432 (19)	0.74031 (19)	0.0552 (7)
F8	1.1567 (4)	−0.0579 (3)	0.7512 (2)	0.0932 (12)
Cu1	0.68168 (6)	−0.03638 (3)	0.73765 (3)	0.02770 (15)
H17A	1.0849	0.2932	0.5560	0.054*	0.50
H17B	0.9105	0.2938	0.5168	0.054*	0.50
H17C	0.9284	0.2854	0.5131	0.054*	0.50
H17D	1.0868	0.3029	0.5652	0.054*	0.50
H1A	0.346 (6)	0.024 (3)	0.753 (3)	0.042 (14)*
H2A	0.420 (5)	0.104 (4)	0.765 (3)	0.043 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.061 (3)	0.0231 (19)	0.051 (3)	−0.012 (2)	0.002 (2)	0.0006 (17)
C2	0.065 (3)	0.0242 (19)	0.056 (3)	−0.018 (2)	0.022 (3)	−0.0136 (19)
C3	0.038 (3)	0.040 (2)	0.084 (4)	−0.014 (2)	0.012 (3)	−0.024 (2)
C4	0.044 (3)	0.048 (3)	0.072 (4)	−0.006 (2)	−0.008 (3)	−0.020 (2)
C5	0.049 (3)	0.036 (2)	0.051 (3)	−0.006 (2)	−0.001 (2)	−0.0086 (19)
C6	0.038 (3)	0.0210 (17)	0.050 (2)	−0.0068 (17)	0.007 (2)	−0.0028 (16)
C7	0.049 (3)	0.0179 (18)	0.077 (3)	−0.0043 (19)	0.009 (2)	0.0090 (19)
C8	0.038 (3)	0.0266 (18)	0.036 (2)	0.0025 (17)	0.0073 (18)	0.0088 (16)
C9	0.029 (2)	0.0277 (18)	0.0277 (19)	−0.0007 (16)	0.0036 (16)	0.0055 (14)
C10	0.030 (2)	0.0255 (17)	0.0249 (18)	0.0031 (16)	0.0028 (16)	0.0014 (14)
C11	0.042 (3)	0.037 (2)	0.0235 (19)	0.0019 (18)	−0.0002 (17)	0.0078 (16)
C12	0.058 (3)	0.035 (2)	0.0244 (19)	0.000 (2)	−0.0081 (19)	−0.0048 (16)
C13	0.043 (3)	0.0245 (18)	0.031 (2)	−0.0008 (17)	−0.0097 (18)	−0.0035 (15)
C14	0.030 (2)	0.0223 (17)	0.0273 (18)	−0.0002 (15)	−0.0020 (16)	0.0017 (14)
C15	0.033 (2)	0.0254 (17)	0.0269 (18)	−0.0049 (16)	−0.0046 (16)	−0.0005 (14)
C16	0.041 (3)	0.0289 (19)	0.032 (2)	−0.0090 (18)	−0.0023 (18)	−0.0008 (15)
C17	0.061 (3)	0.032 (2)	0.038 (2)	−0.006 (2)	0.013 (2)	0.0098 (17)
C18	0.053 (6)	0.044 (7)	0.038 (6)	−0.008 (5)	−0.005 (5)	0.010 (5)
C19	0.056 (6)	0.051 (6)	0.063 (6)	−0.011 (5)	−0.009 (5)	−0.004 (5)
C20	0.075 (8)	0.078 (7)	0.085 (7)	0.018 (6)	0.002 (6)	−0.005 (6)
C21	0.069 (8)	0.044 (6)	0.056 (6)	0.013 (5)	0.005 (6)	0.001 (5)
C22	0.077 (8)	0.057 (6)	0.066 (6)	−0.027 (5)	−0.009 (5)	0.004 (5)
C23	0.064 (6)	0.058 (6)	0.055 (6)	−0.012 (5)	−0.017 (5)	0.006 (5)
C18'	0.024 (4)	0.024 (5)	0.029 (5)	0.000 (4)	0.002 (4)	0.009 (4)
C19'	0.062 (7)	0.071 (7)	0.087 (7)	0.002 (6)	−0.015 (6)	−0.009 (6)
C20'	0.075 (8)	0.094 (8)	0.114 (8)	0.030 (6)	−0.010 (7)	−0.003 (7)
C21'	0.076 (8)	0.051 (6)	0.072 (7)	0.000 (5)	0.006 (6)	−0.006 (5)
C22'	0.048 (6)	0.028 (4)	0.042 (5)	−0.003 (4)	0.007 (4)	0.003 (4)
C23'	0.036 (5)	0.031 (4)	0.032 (5)	−0.003 (4)	−0.002 (3)	0.009 (4)
C24	0.040 (3)	0.038 (2)	0.030 (2)	−0.0071 (19)	0.0019 (18)	−0.0065 (16)
C25	0.052 (3)	0.055 (3)	0.038 (2)	−0.021 (2)	−0.009 (2)	−0.008 (2)
C26	0.060 (3)	0.046 (2)	0.034 (2)	−0.003 (2)	−0.012 (2)	−0.0085 (19)
C27	0.053 (3)	0.044 (2)	0.024 (2)	−0.003 (2)	0.0008 (19)	−0.0008 (17)
C28	0.036 (2)	0.037 (2)	0.0264 (19)	−0.0043 (18)	−0.0002 (17)	−0.0010 (16)
B1	0.051 (3)	0.042 (3)	0.035 (3)	0.001 (3)	−0.008 (2)	−0.009 (2)
B2	0.032 (3)	0.034 (2)	0.049 (3)	−0.003 (2)	−0.005 (2)	0.002 (2)
N1	0.030 (2)	0.0236 (15)	0.051 (2)	−0.0036 (14)	0.0058 (16)	0.0076 (14)
N2	0.033 (2)	0.0278 (16)	0.046 (2)	−0.0088 (14)	0.0043 (16)	0.0021 (14)
N3	0.0257 (18)	0.0242 (14)	0.0348 (17)	−0.0054 (13)	0.0021 (14)	0.0006 (12)
N4	0.040 (2)	0.0233 (14)	0.0230 (15)	−0.0066 (14)	−0.0001 (14)	0.0019 (12)
N5	0.043 (2)	0.0266 (15)	0.0254 (16)	−0.0076 (14)	0.0012 (14)	0.0040 (12)
N6	0.045 (2)	0.0244 (15)	0.0325 (17)	−0.0092 (15)	0.0034 (15)	0.0014 (13)
N7	0.0299 (18)	0.0228 (14)	0.0232 (15)	−0.0042 (13)	0.0009 (13)	0.0028 (11)
N8	0.0339 (19)	0.0262 (15)	0.0286 (16)	−0.0047 (14)	−0.0014 (14)	−0.0025 (12)
O1	0.042 (2)	0.0348 (18)	0.0448 (18)	−0.0023 (16)	−0.0012 (15)	−0.0022 (13)
F1	0.122 (3)	0.100 (3)	0.138 (3)	−0.058 (3)	0.033 (3)	−0.068 (3)
F2	0.320 (8)	0.156 (4)	0.136 (4)	0.070 (5)	−0.147 (5)	0.000 (3)
F3	0.086 (2)	0.0537 (15)	0.0581 (17)	−0.0272 (15)	0.0086 (15)	−0.0222 (13)
F4	0.066 (2)	0.112 (3)	0.183 (4)	0.011 (2)	0.007 (3)	−0.086 (3)
F5	0.053 (2)	0.0559 (18)	0.178 (4)	0.0029 (16)	0.037 (2)	0.023 (2)
F6	0.072 (2)	0.154 (3)	0.0539 (19)	−0.018 (2)	−0.0130 (16)	0.034 (2)
F7	0.0350 (15)	0.0541 (15)	0.0735 (18)	−0.0039 (12)	0.0101 (13)	0.0048 (13)
F8	0.082 (2)	0.139 (3)	0.064 (2)	−0.060 (2)	0.0057 (17)	−0.037 (2)
Cu1	0.0349 (3)	0.0258 (2)	0.0229 (2)	−0.01012 (19)	−0.00085 (19)	−0.00054 (16)

Geometric parameters (Å, º)

C1—C6	1.373 (6)	C21—C22	1.3900
C1—C2	1.405 (6)	C21—H21	0.9500
C1—H1	0.9500	C22—C23	1.3900
C2—C3	1.363 (7)	C22—H22	0.9500
C2—H2	0.9500	C23—H23	0.9500
C3—C4	1.362 (7)	C18'—C19'	1.3900
C3—H3	0.9500	C18'—C23'	1.3900
C4—C5	1.359 (6)	C19'—C20'	1.3900
C4—H4	0.9500	C19'—H19'	0.9500
C5—C6	1.374 (6)	C20'—C21'	1.3900
C5—H5	0.9500	C20'—H20'	0.9500
C6—C7	1.500 (6)	C21'—C22'	1.3900
C7—N1	1.474 (4)	C21'—H21'	0.9500
C7—H7A	0.9900	C22'—C23'	1.3900
C7—H7B	0.9900	C22'—H22'	0.9500
C8—N1	1.331 (5)	C23'—H23'	0.9500
C8—C9	1.359 (5)	C24—N8	1.335 (5)
C8—H8	0.9500	C24—C25	1.366 (5)
C9—N3	1.363 (5)	C24—H24	0.9500
C9—C10	1.451 (5)	C25—C26	1.356 (6)
C10—N7	1.335 (4)	C25—H25	0.9500
C10—C11	1.368 (5)	C26—C27	1.374 (6)
C11—C12	1.376 (5)	C26—H26	0.9500
C11—H11	0.9500	C27—C28	1.369 (5)
C12—C13	1.379 (5)	C27—H27	0.9500
C12—H12	0.9500	C28—N8	1.331 (5)
C13—C14	1.380 (5)	C28—H28	0.9500
C13—H13	0.9500	B1—F2	1.282 (6)
C14—N7	1.338 (4)	B1—F4	1.317 (6)
C14—C15	1.443 (5)	B1—F3	1.357 (5)
C15—N4	1.355 (4)	B1—F1	1.375 (6)
C15—C16	1.359 (5)	B2—F6	1.353 (6)
C16—N6	1.339 (5)	B2—F8	1.358 (5)
C16—H16	0.9500	B2—F5	1.359 (6)
C17—C18	1.4446	B2—F7	1.361 (5)
C17—N6	1.472 (3)	N1—N2	1.335 (4)
C17—C18'	1.4990	N2—N3	1.309 (4)
C17—H17A	0.983 (3)	N3—Cu1	2.067 (3)
C17—H17B	0.995 (3)	N4—N5	1.305 (4)
C17—H17C	0.994 (3)	N4—Cu1	2.034 (3)
C17—H17D	0.983 (3)	N5—N6	1.330 (4)
C18—C19	1.3900	N7—Cu1	1.973 (3)
C18—C23	1.3900	N8—Cu1	1.948 (3)
C19—C20	1.3900	O1—Cu1	2.271 (3)
C19—H19	0.9500	O1—H1A	0.81 (5)
C20—C21	1.3900	O1—H2A	0.78 (5)
C20—H20	0.9500	F7—CU1	2.464 (4)
C6—C1—C2	119.1 (4)	C23—C22—C21	120.0
C6—C1—H1	120.5	C23—C22—H22	120.0
C2—C1—H1	120.5	C21—C22—H22	120.0
C3—C2—C1	119.6 (4)	C22—C23—C18	120.0
C3—C2—H2	120.2	C22—C23—H23	120.0
C1—C2—H2	120.2	C18—C23—H23	120.0
C4—C3—C2	120.8 (5)	C19'—C18'—C23'	120.0
C4—C3—H3	119.6	C19'—C18'—C17	119.9
C2—C3—H3	119.6	C23'—C18'—C17	120.1
C5—C4—C3	119.7 (5)	C18'—C19'—C20'	120.0
C5—C4—H4	120.1	C18'—C19'—H19'	120.0
C3—C4—H4	120.1	C20'—C19'—H19'	120.0
C4—C5—C6	121.1 (4)	C21'—C20'—C19'	120.0
C4—C5—H5	119.5	C21'—C20'—H20'	120.0
C6—C5—H5	119.5	C19'—C20'—H20'	120.0
C1—C6—C5	119.6 (4)	C20'—C21'—C22'	120.0
C1—C6—C7	119.9 (4)	C20'—C21'—H21'	120.0
C5—C6—C7	120.4 (4)	C22'—C21'—H21'	120.0
N1—C7—C6	112.1 (3)	C21'—C22'—C23'	120.0
N1—C7—H7A	109.2	C21'—C22'—H22'	120.0
C6—C7—H7A	109.2	C23'—C22'—H22'	120.0
N1—C7—H7B	109.2	C22'—C23'—C18'	120.0
C6—C7—H7B	109.2	C22'—C23'—H23'	120.0
H7A—C7—H7B	107.9	C18'—C23'—H23'	120.0
N1—C8—C9	104.4 (3)	N8—C24—C25	122.9 (4)
N1—C8—H8	127.8	N8—C24—H24	118.6
C9—C8—H8	127.8	C25—C24—H24	118.6
C8—C9—N3	107.4 (3)	C26—C25—C24	119.0 (4)
C8—C9—C10	135.4 (4)	C26—C25—H25	120.5
N3—C9—C10	117.2 (3)	C24—C25—H25	120.5
N7—C10—C11	121.4 (3)	C25—C26—C27	118.9 (4)
N7—C10—C9	111.3 (3)	C25—C26—H26	120.5
C11—C10—C9	127.2 (3)	C27—C26—H26	120.5
C10—C11—C12	118.5 (3)	C28—C27—C26	119.2 (4)
C10—C11—H11	120.7	C28—C27—H27	120.4
C12—C11—H11	120.7	C26—C27—H27	120.4
C11—C12—C13	120.4 (3)	N8—C28—C27	122.2 (4)
C11—C12—H12	119.8	N8—C28—H28	118.9
C13—C12—H12	119.8	C27—C28—H28	118.9
C12—C13—C14	118.1 (3)	F2—B1—F4	109.9 (5)
C12—C13—H13	120.9	F2—B1—F3	112.4 (5)
C14—C13—H13	120.9	F4—B1—F3	112.3 (4)
N7—C14—C13	121.0 (3)	F2—B1—F1	106.9 (6)
N7—C14—C15	111.5 (3)	F4—B1—F1	106.1 (4)
C13—C14—C15	127.4 (3)	F3—B1—F1	108.9 (4)
N4—C15—C16	107.4 (3)	F6—B2—F8	107.8 (4)
N4—C15—C14	116.9 (3)	F6—B2—F5	107.7 (4)
C16—C15—C14	135.7 (3)	F8—B2—F5	109.6 (4)
N6—C16—C15	104.6 (3)	F6—B2—F7	111.4 (4)
N6—C16—H16	127.7	F8—B2—F7	110.0 (4)
C15—C16—H16	127.7	F5—B2—F7	110.3 (4)
C18—C17—N6	110.98 (15)	C8—N1—N2	113.0 (3)
C18—C17—C18'	10.6	C8—N1—C7	127.4 (3)
N6—C17—C18'	110.66 (16)	N2—N1—C7	119.6 (3)
C18—C17—H17A	109.78 (13)	N3—N2—N1	104.9 (3)
N6—C17—H17A	109.9 (3)	N2—N3—C9	110.3 (3)
C18'—C17—H17A	118.65 (13)	N2—N3—Cu1	137.1 (2)
C18—C17—H17B	108.71 (14)	C9—N3—Cu1	112.6 (2)
N6—C17—H17B	109.2 (2)	N5—N4—C15	110.2 (3)
C18'—C17—H17B	99.46 (15)	N5—N4—Cu1	136.4 (2)
H17A—C17—H17B	108.2 (2)	C15—N4—Cu1	113.3 (2)
C18—C17—H17C	117.45 (14)	N4—N5—N6	105.7 (3)
N6—C17—H17C	109.3 (2)	N5—N6—C16	112.1 (3)
C18'—C17—H17C	108.78 (15)	N5—N6—C17	119.9 (3)
H17A—C17—H17C	98.6 (2)	C16—N6—C17	127.9 (3)
H17B—C17—H17C	10.67 (3)	C10—N7—C14	120.5 (3)
C18—C17—H17D	100.29 (13)	C10—N7—Cu1	120.3 (2)
N6—C17—H17D	110.0 (3)	C14—N7—Cu1	119.2 (2)
C18'—C17—H17D	109.73 (13)	C28—N8—C24	117.8 (3)
H17A—C17—H17D	10.88 (4)	C28—N8—Cu1	123.1 (3)
H17B—C17—H17D	117.3 (2)	C24—N8—Cu1	119.1 (2)
H17C—C17—H17D	108.3 (2)	Cu1—O1—H1A	129 (3)
C19—C18—C23	120.0	Cu1—O1—H2A	122 (3)
C19—C18—C17	118.8	H1A—O1—H2A	104 (5)
C23—C18—C17	121.2	N8—Cu1—N7	174.61 (13)
C20—C19—C18	120.0	N8—Cu1—N4	101.53 (12)
C20—C19—H19	120.0	N7—Cu1—N4	78.94 (11)
C18—C19—H19	120.0	N8—Cu1—N3	100.68 (12)
C21—C20—C19	120.0	N7—Cu1—N3	78.54 (11)
C21—C20—H20	120.0	N4—Cu1—N3	157.37 (12)
C19—C20—H20	120.0	N8—Cu1—O1	94.26 (13)
C20—C21—C22	120.0	N7—Cu1—O1	91.04 (12)
C20—C21—H21	120.0	N4—Cu1—O1	94.82 (13)
C22—C21—H21	120.0	N3—Cu1—O1	87.75 (12)
C6—C1—C2—C3	−1.4 (5)	N1—N2—N3—Cu1	179.8 (3)
C1—C2—C3—C4	0.2 (6)	C8—C9—N3—N2	−1.0 (4)
C2—C3—C4—C5	1.7 (6)	C10—C9—N3—N2	176.7 (3)
C3—C4—C5—C6	−2.3 (6)	C8—C9—N3—Cu1	179.6 (2)
C2—C1—C6—C5	0.9 (5)	C10—C9—N3—Cu1	−2.7 (4)
C2—C1—C6—C7	−176.4 (3)	C16—C15—N4—N5	−0.7 (4)
C4—C5—C6—C1	1.0 (6)	C14—C15—N4—N5	177.7 (3)
C4—C5—C6—C7	178.3 (4)	C16—C15—N4—Cu1	177.9 (3)
C1—C6—C7—N1	−111.1 (4)	C14—C15—N4—Cu1	−3.7 (4)
C5—C6—C7—N1	71.6 (5)	C15—N4—N5—N6	0.1 (4)
N1—C8—C9—N3	0.9 (4)	Cu1—N4—N5—N6	−178.0 (3)
N1—C8—C9—C10	−176.1 (4)	N4—N5—N6—C16	0.6 (4)
C8—C9—C10—N7	176.9 (4)	N4—N5—N6—C17	−178.1 (3)
N3—C9—C10—N7	0.1 (5)	C15—C16—N6—N5	−1.0 (4)
C8—C9—C10—C11	−1.1 (7)	C15—C16—N6—C17	177.6 (3)
N3—C9—C10—C11	−177.9 (4)	C18—C17—N6—N5	132.4 (3)
N7—C10—C11—C12	−0.3 (6)	C18'—C17—N6—N5	121.0 (3)
C9—C10—C11—C12	177.6 (4)	C18—C17—N6—C16	−46.2 (4)
C10—C11—C12—C13	−0.9 (6)	C18'—C17—N6—C16	−57.5 (4)
C11—C12—C13—C14	0.7 (6)	C11—C10—N7—C14	1.7 (5)
C12—C13—C14—N7	0.6 (6)	C9—C10—N7—C14	−176.5 (3)
C12—C13—C14—C15	178.7 (4)	C11—C10—N7—Cu1	−179.0 (3)
N7—C14—C15—N4	2.2 (5)	C9—C10—N7—Cu1	2.9 (4)
C13—C14—C15—N4	−176.0 (4)	C13—C14—N7—C10	−1.9 (5)
N7—C14—C15—C16	−179.9 (4)	C15—C14—N7—C10	179.8 (3)
C13—C14—C15—C16	1.8 (7)	C13—C14—N7—Cu1	178.8 (3)
N4—C15—C16—N6	1.0 (4)	C15—C14—N7—Cu1	0.4 (4)
C14—C15—C16—N6	−177.0 (4)	C27—C28—N8—C24	−0.5 (6)
N6—C17—C18—C19	−69.4 (2)	C27—C28—N8—Cu1	−179.4 (3)
C18'—C17—C18—C19	20.8	C25—C24—N8—C28	0.0 (6)
N6—C17—C18—C23	112.1 (2)	C25—C24—N8—Cu1	179.0 (3)
C18'—C17—C18—C23	−157.6	C28—N8—Cu1—N7	−66.8 (14)
C23—C18—C19—C20	0.0	C24—N8—Cu1—N7	114.3 (13)
C17—C18—C19—C20	−178.5	C28—N8—Cu1—N4	27.7 (3)
C18—C19—C20—C21	0.0	C24—N8—Cu1—N4	−151.2 (3)
C19—C20—C21—C22	0.0	C28—N8—Cu1—N3	−148.0 (3)
C20—C21—C22—C23	0.0	C24—N8—Cu1—N3	33.1 (3)
C21—C22—C23—C18	0.0	C28—N8—Cu1—O1	123.5 (3)
C19—C18—C23—C22	0.0	C24—N8—Cu1—O1	−55.4 (3)
C17—C18—C23—C22	178.4	C10—N7—Cu1—N8	−85.7 (13)
C18—C17—C18'—C19'	−165.2	C14—N7—Cu1—N8	93.7 (13)
N6—C17—C18'—C19'	−71.4 (2)	C10—N7—Cu1—N4	178.8 (3)
C18—C17—C18'—C23'	13.7	C14—N7—Cu1—N4	−1.9 (3)
N6—C17—C18'—C23'	107.5 (2)	C10—N7—Cu1—N3	−3.4 (3)
C23'—C18'—C19'—C20'	0.0	C14—N7—Cu1—N3	175.9 (3)
C17—C18'—C19'—C20'	178.9	C10—N7—Cu1—O1	84.1 (3)
C18'—C19'—C20'—C21'	0.0	C14—N7—Cu1—O1	−96.6 (3)
C19'—C20'—C21'—C22'	0.0	N5—N4—Cu1—N8	6.5 (4)
C20'—C21'—C22'—C23'	0.0	C15—N4—Cu1—N8	−171.6 (3)
C21'—C22'—C23'—C18'	0.0	N5—N4—Cu1—N7	−179.0 (4)
C19'—C18'—C23'—C22'	0.0	C15—N4—Cu1—N7	3.0 (3)
C17—C18'—C23'—C22'	−178.9	N5—N4—Cu1—N3	175.4 (3)
N8—C24—C25—C26	0.3 (7)	C15—N4—Cu1—N3	−2.7 (5)
C24—C25—C26—C27	−0.1 (7)	N5—N4—Cu1—O1	−88.9 (4)
C25—C26—C27—C28	−0.4 (6)	C15—N4—Cu1—O1	93.1 (3)
C26—C27—C28—N8	0.7 (6)	N2—N3—Cu1—N8	−1.5 (4)
C9—C8—N1—N2	−0.6 (4)	C9—N3—Cu1—N8	177.7 (2)
C9—C8—N1—C7	177.5 (4)	N2—N3—Cu1—N7	−176.0 (4)
C6—C7—N1—C8	81.2 (5)	C9—N3—Cu1—N7	3.1 (2)
C6—C7—N1—N2	−100.9 (4)	N2—N3—Cu1—N4	−170.4 (3)
C8—N1—N2—N3	0.0 (4)	C9—N3—Cu1—N4	8.8 (5)
C7—N1—N2—N3	−178.2 (3)	N2—N3—Cu1—O1	92.4 (4)
N1—N2—N3—C9	0.6 (4)	C9—N3—Cu1—O1	−88.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H2A···F4	0.79 (5)	2.34 (5)	3.040 (5)	150 (4)
O1—H2A···F1	0.79 (5)	2.19 (5)	2.901 (5)	150 (4)
O1—H1A···F8^i	0.81 (5)	1.94 (5)	2.718 (5)	162 (4)
C5—H5···F5^i	0.95	2.50	3.379 (6)	154
C24—H24···F5^i	0.95	2.35	3.051 (5)	130
C22—H22···F5^ii	0.95	2.37	3.213 (4)	147
C11—H11···O1^iii	0.95	2.55	3.366 (4)	144
C13—H13···Cg^iii	0.95	2.55	3.331 (4)	140

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