In situ synthesis of mononuclear copper(II) complexes of the new tridentate ligand bis­[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]­amine

Two mononuclear copper complexes, {bis­[(3,5-dimethyl-1H-pyrazol-1-yl-[kappa]N²)meth­yl]amine-[kappa]N}(3,5-dimethyl-1H-pyrazole-[kappa]N²)(perchlorato-[kappa]O)copper(II) perchlorate, [Cu(ClO₄)(C₅H₈N₂)(C₁₂H₁₉N₅)]ClO₄, (I), and {bis­[(3,5-dimethyl-1H-pyrazol-1-yl-[kappa]N²)meth­yl]amine-[kappa]N}­bis­(3,5-dimethyl-1H-pyrazole-[kappa]N²)copper(II) bis­(hexa­fluoridophosphate), [Cu(C₅H₈N₂)₂(C₁₂H₁₉N₅)](PF₆)₂, (II), have been synthesized by the reactions of different copper salts with the tripodal ligand tris­[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]­amine (TDPA) in acetone-water solutions at room temperature. Single-crystal X-ray diffraction analysis revealed that they contain the new tridentate ligand bis­[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]­amine (BDPA), which cannot be obtained by normal organic reactions and has thus been captured in the solid state by in situ synthesis. The coordination of the Cu^II ion is distorted square pyramidal in (I) and distorted trigonal bipyramidal in (II). The new in situ generated tridentate BDPA ligand can act as a meridional or facial ligand during the process of coordination. The crystal structures of these two compounds are stabilized by classical hydrogen bonding as well as intricate nonclassical hydrogen-bond interactions.

S1. Comment

Polydentate pyrazole ligands, which could act as terminal chelate ligands coordinated to metal ions, have been shown to be efficient in the construction of metalloenzymes (Melnik, 1982). These compounds, built of copper ions and polydentate pyrazole ligands, can also be seen as models for bioinorganic systems, as well as for the discovery of new catalyst precursors. In order to expand the range of metalloenzymes and obtain a deeper insight into the biologically interesting effects of complexes of polydentate pyrazole ligands with metal ions, it is important to design and synthesize new terminal polydentate ligands for the construction of metalloenzymes. In situ metal–ligand reactions, which have been investigated for many decades, are a very important method for the generation of novel coordination compounds with ligands that are inaccessible in normal organic reactions (Chen & Tong, 2007). To date, many kinds of functional compounds built out of in situ generated ligands and metal ions have been documented (Chen & Tong, 2007). Recently, our attempts to synthesize new types of mononuclear precursor compounds by the reaction of the Cu^II ion and the tripodal ligand tris[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]amine (TDPA) yielded two mononuclear Cu^II compounds with a new in situ generated tridentate ligand, bis[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]amine (BDPA). To the best of our knowledge, a successful synthetic route to the tridentate BDPA ligand has not been documented and synthetic attempts to obtain BDPA have failed due to the uncontrollable reaction of (pyrazol-1-yl)methanol and primary amines (Daoudi et al., 2006). Here, with the help of in situ synthesis, the BDPA ligand has been captured in the solid state and characterized by single-crystal X-ray crystallography. The crystal structures of these mononuclear copper compounds, namely {bis[(3,5-dimethyl-1H-pyrazol-1-yl-κN²)methyl]amine}(3,5-dimethyl-1H-pyrazole-κN²)(perchlorato-κO)copper(II) perchlorate, (I), and {bis[(3,5-dimethyl-1H-pyrazol-1-yl-κN²)methyl]amine}bis(3,5-dimethyl-1H-pyrazole-κN²)copper(II) bis(hexafluoridophosphate), (II), the characteristics of the new BDPA ligand and the possible mechanism of the in situ reaction are described herein.

In the process of the coordination reaction between Cu^II salts and the tripodal TDPA ligand in a molar ratio of 1:1 in the open air, the tripodal ligand decomposed to the tridentate BDPA ligand (L1), 3,5-dimethyl-1H-pyrazole (L2) and HCHO, as a result of C—N bond cleavage catalysed by the Cu^II ions in the reaction liquid (see Scheme 2; Barszcz et al., 2004). The new BDPA ligand is then stabilized via coordination with the Cu^II ion and is captured in the solid state. Thus, the new tridentate BDPA ligand, which could not be obtained by normal organic synthesis, has been generated in situ.

Complex (I) crystallizes in the monoclinic space group C2/c. A perspective view of its asymmetric unit is depicted in Fig. 1. The complex contains two different coordinated ligands obtained during the reaction process, viz. BDPA and L2, without the original tripodal TDPA ligand. The central Cu^II ion is five-coordinated by one tridentate chelate ligand (atoms N4, N6 and N7), one neutral in pyrazole ligand (N2) and one coordinated perchlorate anion (O4). The coordination geometry around the Cu^II ion is presented in Table 1. The bond angles indicate that the coordination geometry can be best described as distorted square pyramidal. The equatorial sites are occupied by the three N atoms from L1 and and one N atom from L2, while the apical position is occupied by an O atom from one of the two independent perchlorate anions. The other perchlorate anion is noncoordinating. The tridentate BDPA ligand acts as a meridional ligand, with a dihedral angle between the two BDPA pyrazole rings of 12.39 (3)°. The in situ-generated L2 ligand coordinates to the central Cu^II ion trans to the central N atom, N7, of the BDPA ligand. The Cu—N bond lengths in (I) are similar to those observed for related Cu^II complexes with pyrazole and pyridine donor ligands (Watson et al., 1987). There is an intramolecular hydrogen bond between the noncoordinating amine group of L2 and an O atom of the the coordinated perchlorate anion. The central amine group of the BDPA ligand also forms a hydrogen bond with the free perchlorate anion (Table 2) to form a hydrogen-bonded ion pair, but there is no extension of the classical hydrogen bonding network beyond this. Two weak C—H···.O interactions may be present (Table 2). One, involving C12—H12B is just a further interaction between the cation and free perchlorate anion involved in the described ion pair, while that involving C8—H8A links complex cations through the coordinated perchlorate ligand into extended chains which run parallel to the [010] direction.

In contrast with the crystal structure of (I), the central Cu^II ion in (II) is coordinated by five N atoms, three from the tridentate L1 ligand (N6, N8 and N9) and the others from two independent L2 ligands (N2 and N4) (Fig. 2). The tridentate L1 ligand coordinates in a facial mode, with a dihedral angle between the two BDPA pyrazole rings of 58.95 (2)°. The coordination geometry around the Cu^II ion is presented in Table 3, which indicates that the Cu^II ion has a slightly distorted trigonal bipyramidal geometry. The three equatorial positions are occupied by atoms N6, N8 and N2, and the axial positions are occupied by atoms N4 and N9. The two independent hexafluorophosphate anions occupy approximate columns between the cations. Several weak N—H···F interactions involving all N—H donors of the L1 and L2 ligands serve to link the ions into extended chains which run parallel to the [010] direction (Table 4). N3—H of one L2 ligand has a bifurcated interaction with two F atoms of the same anion, while N9—H of the other L2 ligand also has bifurcated interactions with two F atoms of the other independent cation. This latter anion also accepts the N1—H interaction and a very weak C4—H interaction from the central amine group of the BDPA ligand of a different cation, thereby forming the link that leads to the extended chain.

Related literature

For related literature, see: Barszcz et al. (2004); Chen & Tong (2007); Daoudi et al. (2006); Melnik (1982); Watson et al. (1987).

S2. Experimental

An acetone solution (5 ml) of the tripodal ligand TDPA (0.1 mmol) was added to aqueous solutions (10 ml) of different copper salts [0.1 mmol Cu(ClO₄)₂ for (I) and (II)], and after stirring the mixture at room temperature for 30 min the counterions were added [0.5 mmol NaClO₄ for (I) and 0.5 mmol KPF₆ for (II)]. The resulting solutions were filtered and allowed to stand at room temperature, and two similar mononuclear single-crystal samples were obtained after one week (yields 40–45%).

S3. Refinement

All H atoms were placed geometrically, with C—H = 0.93 (aromatic) or 0.96 Å (CH₂) and N—H = 0.86–0.91 Å, and refined using a riding-atom model, with U_iso(H) = 1.2U_eq(C). The remaining H atoms were located in difference Fourier maps. For (II), disordered atoms F5 and F6 were set as two sites with the respective occupancies summing to one [final refined occupancies 0.53 (3):0.47 (3) for F5 and 0.546 (16):0.454 (16) for F6]. [Please check added text]

Computing details

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The asymmetric unit of (I), showing the atomic-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
	Fig. 2. The asymmetric unit of (II), showing the atomic-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms and hexafluoridophosphate counterions have been omitted for clarity.

(I) {bis[(3,5-dimethyl-1H-pyrazol-1-yl-κN²)methyl]amine}(3,5- dimethyl-1H-pyrazole-κN²)(perchlorato-κO)copper(II) perchlorate

Crystal data

[Cu(ClO4)(C5H8N2)(C12H19N5)]ClO4	F(000) = 2440
Mr = 591.91	Dx = 1.620 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3113 reflections
a = 37.574 (3) Å	θ = 2.3–28.9°
b = 8.5769 (4) Å	µ = 1.18 mm^−1
c = 15.661 (1) Å	T = 293 K
β = 105.938 (8)°	Block-like, blue
V = 4853.0 (5) Å^3	0.30 × 0.20 × 0.20 mm
Z = 8

Data collection

Oxford Gemini S Ultra diffractometer	4701 independent reflections
Radiation source: fine-focus sealed tube	2699 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
Detector resolution: 0 pixels mm^-1	θmax = 26.0°, θmin = 2.4°
ω scans	h = −46→43
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −7→10
Tmin = 0.719, Tmax = 0.799	l = −19→19
11887 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H-atom parameters constrained
S = 0.88	w = 1/[σ^2(Fo^2) + (0.0319P)^2] where P = (Fo^2 + 2Fc^2)/3
4701 reflections	(Δ/σ)max = 0.001
322 parameters	Δρmax = 1.07 e Å^−3
0 restraints	Δρmin = −0.50 e Å^−3

Special details

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.4 (release 27-04-2006 CrysAlis171 .NET) (compiled Apr 27 2007,17:53:11) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	0.381241 (15)	0.62688 (5)	0.74971 (3)	0.02052 (14)
Cl2	0.45687 (3)	0.37363 (13)	0.59411 (7)	0.0338 (3)
N7	0.42188 (10)	0.5478 (3)	0.8541 (2)	0.0264 (9)
H7A	0.4164	0.5814	0.9041	0.032*
O4	0.35312 (9)	0.7270 (3)	0.8566 (2)	0.0387 (8)
O8	0.44379 (12)	0.3828 (4)	0.6705 (2)	0.0608 (11)
C12	0.42169 (11)	0.3778 (4)	0.8565 (3)	0.0230 (9)
H12A	0.4365	0.3360	0.8201	0.028*
H12B	0.4318	0.3411	0.9169	0.028*
N6	0.41760 (10)	0.7998 (3)	0.7556 (2)	0.0209 (8)
O7	0.45817 (9)	0.5258 (3)	0.5589 (2)	0.0343 (8)
N5	0.44949 (10)	0.7745 (3)	0.8220 (2)	0.0201 (8)
C1	0.42064 (12)	0.9464 (4)	0.7267 (3)	0.0206 (10)
C6	0.45695 (12)	0.6162 (4)	0.8546 (3)	0.0299 (10)
H6A	0.4685	0.5573	0.8165	0.036*
H6B	0.4734	0.6164	0.9143	0.036*
C2	0.45443 (12)	1.0073 (4)	0.7752 (3)	0.0236 (10)
H2A	0.4633	1.1065	0.7684	0.028*
O6	0.49283 (11)	0.3060 (3)	0.6153 (3)	0.0639 (12)
N3	0.38399 (10)	0.3290 (3)	0.8230 (2)	0.0212 (8)
N4	0.36107 (10)	0.4142 (3)	0.7574 (2)	0.0215 (8)
C3	0.47256 (11)	0.8973 (4)	0.8347 (3)	0.0201 (9)
N2	0.34318 (10)	0.7034 (3)	0.6478 (2)	0.0218 (8)
O5	0.43179 (10)	0.2788 (3)	0.5275 (2)	0.0472 (9)
C4	0.39161 (13)	1.0220 (4)	0.6561 (3)	0.0283 (11)
H4A	0.3808	0.9469	0.6111	0.042*
H4B	0.4023	1.1052	0.6304	0.042*
H4C	0.3729	1.0633	0.6808	0.042*
Cl1	0.31775 (3)	0.74134 (12)	0.87480 (8)	0.0339 (3)
O3	0.29686 (10)	0.8551 (4)	0.8143 (2)	0.0564 (10)
C13	0.29814 (12)	0.8574 (5)	0.5706 (3)	0.0285 (10)
N1	0.31712 (10)	0.8120 (3)	0.6516 (2)	0.0259 (9)
H1A	0.3134	0.8466	0.7000	0.031*
C8	0.33191 (13)	0.2052 (4)	0.7879 (3)	0.0273 (11)
H8A	0.3134	0.1321	0.7856	0.033*
C9	0.36677 (13)	0.2006 (4)	0.8427 (3)	0.0242 (11)
C5	0.50922 (12)	0.8959 (4)	0.9014 (3)	0.0308 (11)
H5A	0.5063	0.8643	0.9579	0.046*
H5B	0.5198	0.9984	0.9064	0.046*
H5C	0.5253	0.8238	0.8831	0.046*
C15	0.33962 (12)	0.6833 (4)	0.5613 (3)	0.0230 (10)
O2	0.30002 (11)	0.5962 (3)	0.8612 (3)	0.0647 (12)
C11	0.38637 (14)	0.0878 (4)	0.9119 (3)	0.0344 (12)
H11A	0.4005	0.1438	0.9631	0.052*
H11B	0.4027	0.0246	0.8889	0.052*
H11C	0.3686	0.0224	0.9283	0.052*
C14	0.31226 (13)	0.7780 (4)	0.5125 (3)	0.0301 (11)
H14A	0.3047	0.7863	0.4510	0.036*
C7	0.32868 (13)	0.3388 (4)	0.7356 (3)	0.0267 (11)
O1	0.32281 (12)	0.7927 (4)	0.9626 (2)	0.0616 (12)
C10	0.29569 (13)	0.3961 (5)	0.6666 (3)	0.0368 (12)
H10A	0.2898	0.4997	0.6813	0.055*
H10B	0.2751	0.3283	0.6639	0.055*
H10C	0.3009	0.3972	0.6099	0.055*
C16	0.26878 (14)	0.9803 (5)	0.5581 (3)	0.0448 (13)
H16A	0.2611	0.9900	0.6115	0.067*
H16B	0.2479	0.9513	0.5099	0.067*
H16C	0.2785	1.0782	0.5450	0.067*
C17	0.36449 (14)	0.5706 (4)	0.5325 (3)	0.0361 (12)
H17A	0.3633	0.4710	0.5595	0.054*
H17B	0.3895	0.6086	0.5506	0.054*
H17C	0.3567	0.5600	0.4691	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0197 (3)	0.0177 (3)	0.0227 (3)	−0.0024 (2)	0.0036 (2)	0.0020 (2)
Cl2	0.0325 (7)	0.0327 (6)	0.0328 (7)	−0.0001 (6)	0.0035 (6)	0.0083 (6)
N7	0.023 (2)	0.0207 (18)	0.033 (2)	−0.0036 (16)	0.0037 (19)	0.0040 (16)
O4	0.037 (2)	0.0416 (17)	0.043 (2)	−0.0017 (15)	0.0205 (19)	−0.0115 (15)
O8	0.092 (3)	0.065 (2)	0.032 (2)	−0.010 (2)	0.028 (2)	0.0026 (19)
C12	0.027 (2)	0.014 (2)	0.025 (2)	−0.006 (2)	0.003 (2)	0.0000 (19)
N6	0.025 (2)	0.0176 (18)	0.021 (2)	−0.0038 (15)	0.0081 (19)	−0.0015 (15)
O7	0.033 (2)	0.0219 (15)	0.044 (2)	−0.0056 (14)	0.0041 (18)	0.0094 (14)
N5	0.022 (2)	0.0146 (18)	0.024 (2)	0.0008 (16)	0.0067 (18)	0.0031 (15)
C1	0.026 (3)	0.018 (2)	0.023 (2)	0.0003 (19)	0.015 (2)	−0.0038 (19)
C6	0.033 (3)	0.025 (2)	0.031 (3)	−0.005 (2)	0.008 (2)	0.009 (2)
C2	0.026 (3)	0.014 (2)	0.035 (3)	−0.0047 (19)	0.015 (2)	0.0000 (19)
O6	0.040 (3)	0.0357 (18)	0.103 (3)	0.0117 (17)	−0.001 (2)	0.007 (2)
N3	0.027 (2)	0.0143 (18)	0.023 (2)	−0.0029 (15)	0.0084 (19)	0.0000 (15)
N4	0.023 (2)	0.0155 (18)	0.025 (2)	−0.0021 (15)	0.0057 (18)	0.0009 (15)
C3	0.023 (2)	0.013 (2)	0.026 (2)	−0.0054 (18)	0.009 (2)	−0.0049 (19)
N2	0.024 (2)	0.0178 (17)	0.023 (2)	−0.0010 (15)	0.0057 (18)	0.0017 (15)
O5	0.054 (3)	0.0420 (18)	0.038 (2)	−0.0196 (17)	0.000 (2)	−0.0032 (16)
C4	0.036 (3)	0.018 (2)	0.033 (3)	0.001 (2)	0.013 (3)	0.006 (2)
Cl1	0.0376 (7)	0.0316 (6)	0.0395 (7)	−0.0007 (5)	0.0227 (7)	0.0026 (5)
O3	0.061 (3)	0.055 (2)	0.062 (2)	0.027 (2)	0.031 (2)	0.026 (2)
C13	0.018 (2)	0.030 (2)	0.037 (3)	0.000 (2)	0.007 (2)	0.004 (2)
N1	0.023 (2)	0.0238 (18)	0.031 (2)	0.0019 (16)	0.006 (2)	−0.0002 (16)
C8	0.030 (3)	0.022 (2)	0.034 (3)	−0.012 (2)	0.016 (3)	−0.008 (2)
C9	0.035 (3)	0.016 (2)	0.027 (3)	−0.009 (2)	0.018 (3)	−0.0087 (19)
C5	0.029 (3)	0.024 (2)	0.038 (3)	−0.007 (2)	0.008 (2)	−0.001 (2)
C15	0.022 (3)	0.021 (2)	0.026 (3)	−0.0026 (18)	0.006 (2)	0.0028 (19)
O2	0.057 (3)	0.045 (2)	0.100 (3)	−0.0247 (18)	0.034 (3)	0.003 (2)
C11	0.046 (3)	0.023 (2)	0.037 (3)	−0.006 (2)	0.016 (3)	0.007 (2)
C14	0.029 (3)	0.040 (3)	0.020 (2)	−0.004 (2)	0.004 (2)	0.003 (2)
C7	0.028 (3)	0.026 (2)	0.029 (3)	−0.006 (2)	0.013 (2)	−0.006 (2)
O1	0.080 (3)	0.075 (2)	0.041 (2)	0.014 (2)	0.036 (2)	−0.0064 (19)
C10	0.023 (3)	0.035 (3)	0.046 (3)	−0.011 (2)	−0.001 (2)	−0.001 (2)
C16	0.031 (3)	0.044 (3)	0.057 (4)	0.012 (2)	0.008 (3)	0.008 (3)
C17	0.041 (3)	0.034 (3)	0.037 (3)	0.003 (2)	0.016 (3)	0.000 (2)

Geometric parameters (Å, º)

Cu1—N2	1.941 (4)	C4—H4B	0.9600
Cu1—N4	1.991 (3)	C4—H4C	0.9600
Cu1—N6	2.001 (3)	Cl1—O2	1.400 (3)
Cu1—N7	2.023 (4)	Cl1—O1	1.406 (3)
Cu1—O4	2.373 (3)	Cl1—O3	1.434 (3)
Cl2—O8	1.415 (3)	C13—N1	1.332 (5)
Cl2—O7	1.423 (3)	C13—C14	1.356 (5)
Cl2—O6	1.423 (4)	C13—C16	1.499 (6)
Cl2—O5	1.448 (3)	N1—H1A	0.8600
N7—C6	1.440 (5)	C8—C9	1.355 (6)
N7—C12	1.459 (4)	C8—C7	1.394 (5)
N7—H7A	0.9100	C8—H8A	0.9300
O4—Cl1	1.439 (3)	C9—C11	1.488 (6)
C12—N3	1.432 (5)	C5—H5A	0.9600
C12—H12A	0.9700	C5—H5B	0.9600
C12—H12B	0.9700	C5—H5C	0.9600
N6—C1	1.352 (4)	C15—C14	1.367 (6)
N6—N5	1.371 (5)	C15—C17	1.497 (5)
N5—C3	1.344 (4)	C11—H11A	0.9600
N5—C6	1.451 (4)	C11—H11B	0.9600
C1—C2	1.390 (6)	C11—H11C	0.9600
C1—C4	1.473 (6)	C14—H14A	0.9300
C6—H6A	0.9700	C7—C10	1.487 (6)
C6—H6B	0.9700	C10—H10A	0.9600
C2—C3	1.368 (5)	C10—H10B	0.9600
C2—H2A	0.9300	C10—H10C	0.9600
N3—C9	1.355 (4)	C16—H16A	0.9600
N3—N4	1.359 (5)	C16—H16B	0.9600
N4—C7	1.337 (5)	C16—H16C	0.9600
C3—C5	1.483 (6)	C17—H17A	0.9600
N2—C15	1.335 (5)	C17—H17B	0.9600
N2—N1	1.365 (4)	C17—H17C	0.9600
C4—H4A	0.9600
N2—Cu1—N4	98.76 (14)	H4A—C4—H4B	109.5
N2—Cu1—N6	97.31 (14)	C1—C4—H4C	109.5
N4—Cu1—N6	160.43 (14)	H4A—C4—H4C	109.5
N2—Cu1—N7	178.50 (14)	H4B—C4—H4C	109.5
N4—Cu1—N7	81.93 (14)	O2—Cl1—O1	111.0 (2)
N6—Cu1—N7	81.75 (14)	O2—Cl1—O3	110.7 (3)
N2—Cu1—O4	95.03 (13)	O1—Cl1—O3	109.6 (2)
N4—Cu1—O4	92.21 (11)	O2—Cl1—O4	108.71 (19)
N6—Cu1—O4	97.44 (11)	O1—Cl1—O4	109.6 (2)
N7—Cu1—O4	86.27 (13)	O3—Cl1—O4	107.14 (19)
O8—Cl2—O7	109.48 (19)	N1—C13—C14	106.6 (4)
O8—Cl2—O6	110.7 (3)	N1—C13—C16	120.8 (4)
O7—Cl2—O6	109.45 (19)	C14—C13—C16	132.5 (5)
O8—Cl2—O5	109.4 (2)	C13—N1—N2	111.1 (3)
O7—Cl2—O5	108.74 (19)	C13—N1—H1A	124.4
O6—Cl2—O5	109.1 (2)	N2—N1—H1A	124.4
C6—N7—C12	114.7 (3)	C9—C8—C7	108.0 (4)
C6—N7—Cu1	110.7 (2)	C9—C8—H8A	126.0
C12—N7—Cu1	110.4 (3)	C7—C8—H8A	126.0
C6—N7—H7A	106.9	N3—C9—C8	105.8 (4)
C12—N7—H7A	106.9	N3—C9—C11	121.5 (4)
Cu1—N7—H7A	106.9	C8—C9—C11	132.7 (4)
Cl1—O4—Cu1	141.7 (2)	C3—C5—H5A	109.5
N3—C12—N7	107.1 (3)	C3—C5—H5B	109.5
N3—C12—H12A	110.3	H5A—C5—H5B	109.5
N7—C12—H12A	110.3	C3—C5—H5C	109.5
N3—C12—H12B	110.3	H5A—C5—H5C	109.5
N7—C12—H12B	110.3	H5B—C5—H5C	109.5
H12A—C12—H12B	108.5	N2—C15—C14	110.0 (4)
C1—N6—N5	105.3 (3)	N2—C15—C17	119.4 (4)
C1—N6—Cu1	142.5 (3)	C14—C15—C17	130.6 (4)
N5—N6—Cu1	111.2 (2)	C9—C11—H11A	109.5
C3—N5—N6	112.5 (3)	C9—C11—H11B	109.5
C3—N5—C6	128.9 (4)	H11A—C11—H11B	109.5
N6—N5—C6	117.3 (3)	C9—C11—H11C	109.5
N6—C1—C2	108.3 (4)	H11A—C11—H11C	109.5
N6—C1—C4	123.2 (4)	H11B—C11—H11C	109.5
C2—C1—C4	128.4 (4)	C13—C14—C15	107.2 (4)
N7—C6—N5	106.9 (3)	C13—C14—H14A	126.4
N7—C6—H6A	110.3	C15—C14—H14A	126.4
N5—C6—H6A	110.3	N4—C7—C8	108.8 (4)
N7—C6—H6B	110.3	N4—C7—C10	123.0 (4)
N5—C6—H6B	110.3	C8—C7—C10	128.3 (4)
H6A—C6—H6B	108.6	C7—C10—H10A	109.5
C3—C2—C1	108.8 (3)	C7—C10—H10B	109.5
C3—C2—H2A	125.6	H10A—C10—H10B	109.5
C1—C2—H2A	125.6	C7—C10—H10C	109.5
C9—N3—N4	111.5 (4)	H10A—C10—H10C	109.5
C9—N3—C12	129.9 (4)	H10B—C10—H10C	109.5
N4—N3—C12	118.5 (3)	C13—C16—H16A	109.5
C7—N4—N3	106.0 (3)	C13—C16—H16B	109.5
C7—N4—Cu1	139.7 (3)	H16A—C16—H16B	109.5
N3—N4—Cu1	111.5 (3)	C13—C16—H16C	109.5
N5—C3—C2	105.0 (4)	H16A—C16—H16C	109.5
N5—C3—C5	122.3 (3)	H16B—C16—H16C	109.5
C2—C3—C5	132.7 (4)	C15—C17—H17A	109.5
C15—N2—N1	105.0 (3)	C15—C17—H17B	109.5
C15—N2—Cu1	129.5 (3)	H17A—C17—H17B	109.5
N1—N2—Cu1	124.7 (3)	C15—C17—H17C	109.5
C1—C4—H4A	109.5	H17A—C17—H17C	109.5
C1—C4—H4B	109.5	H17B—C17—H17C	109.5
N2—Cu1—N7—C6	30 (5)	N2—Cu1—N4—N3	177.1 (2)
N4—Cu1—N7—C6	148.0 (3)	N6—Cu1—N4—N3	32.2 (5)
N6—Cu1—N7—C6	−21.2 (3)	N7—Cu1—N4—N3	−1.6 (2)
O4—Cu1—N7—C6	−119.2 (3)	O4—Cu1—N4—N3	−87.5 (2)
N2—Cu1—N7—C12	−98 (5)	N6—N5—C3—C2	1.2 (4)
N4—Cu1—N7—C12	19.9 (2)	C6—N5—C3—C2	167.4 (3)
N6—Cu1—N7—C12	−149.3 (3)	N6—N5—C3—C5	−178.5 (3)
O4—Cu1—N7—C12	112.6 (2)	C6—N5—C3—C5	−12.3 (6)
N2—Cu1—O4—Cl1	43.6 (3)	C1—C2—C3—N5	−0.8 (4)
N4—Cu1—O4—Cl1	−55.4 (3)	C1—C2—C3—C5	178.8 (4)
N6—Cu1—O4—Cl1	141.7 (3)	N4—Cu1—N2—C15	−83.4 (3)
N7—Cu1—O4—Cl1	−137.1 (3)	N6—Cu1—N2—C15	85.4 (3)
C6—N7—C12—N3	−158.8 (3)	N7—Cu1—N2—C15	34 (5)
Cu1—N7—C12—N3	−32.9 (4)	O4—Cu1—N2—C15	−176.4 (3)
N2—Cu1—N6—C1	16.4 (4)	N4—Cu1—N2—N1	107.6 (3)
N4—Cu1—N6—C1	161.4 (4)	N6—Cu1—N2—N1	−83.6 (3)
N7—Cu1—N6—C1	−164.8 (4)	N7—Cu1—N2—N1	−135 (5)
O4—Cu1—N6—C1	−79.7 (4)	O4—Cu1—N2—N1	14.6 (3)
N2—Cu1—N6—N5	−177.6 (2)	Cu1—O4—Cl1—O2	47.6 (4)
N4—Cu1—N6—N5	−32.6 (5)	Cu1—O4—Cl1—O1	169.1 (3)
N7—Cu1—N6—N5	1.3 (2)	Cu1—O4—Cl1—O3	−72.1 (3)
O4—Cu1—N6—N5	86.4 (2)	C14—C13—N1—N2	−0.5 (5)
C1—N6—N5—C3	−1.2 (4)	C16—C13—N1—N2	−178.0 (3)
Cu1—N6—N5—C3	−172.4 (2)	C15—N2—N1—C13	0.0 (4)
C1—N6—N5—C6	−169.0 (3)	Cu1—N2—N1—C13	171.2 (3)
Cu1—N6—N5—C6	19.7 (4)	N4—N3—C9—C8	−0.1 (4)
N5—N6—C1—C2	0.6 (4)	C12—N3—C9—C8	−175.8 (4)
Cu1—N6—C1—C2	167.1 (3)	N4—N3—C9—C11	179.3 (3)
N5—N6—C1—C4	−178.7 (3)	C12—N3—C9—C11	3.6 (6)
Cu1—N6—C1—C4	−12.1 (6)	C7—C8—C9—N3	−0.2 (4)
C12—N7—C6—N5	160.9 (3)	C7—C8—C9—C11	−179.5 (4)
Cu1—N7—C6—N5	35.2 (4)	N1—N2—C15—C14	0.5 (4)
C3—N5—C6—N7	157.7 (4)	Cu1—N2—C15—C14	−170.1 (3)
N6—N5—C6—N7	−36.7 (4)	N1—N2—C15—C17	179.7 (3)
N6—C1—C2—C3	0.2 (4)	Cu1—N2—C15—C17	9.1 (5)
C4—C1—C2—C3	179.3 (4)	N1—C13—C14—C15	0.8 (5)
N7—C12—N3—C9	−150.0 (3)	C16—C13—C14—C15	177.9 (4)
N7—C12—N3—N4	34.5 (4)	N2—C15—C14—C13	−0.8 (5)
C9—N3—N4—C7	0.4 (4)	C17—C15—C14—C13	−179.9 (4)
C12—N3—N4—C7	176.6 (3)	N3—N4—C7—C8	−0.5 (4)
C9—N3—N4—Cu1	165.2 (2)	Cu1—N4—C7—C8	−158.4 (3)
C12—N3—N4—Cu1	−18.5 (4)	N3—N4—C7—C10	179.0 (3)
N2—Cu1—N4—C7	−25.8 (4)	Cu1—N4—C7—C10	21.1 (7)
N6—Cu1—N4—C7	−170.6 (4)	C9—C8—C7—N4	0.5 (4)
N7—Cu1—N4—C7	155.6 (4)	C9—C8—C7—C10	−179.0 (4)
O4—Cu1—N4—C7	69.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.86	2.05	2.876 (5)	161
N1—H1A···Cl1	0.86	2.84	3.541 (4)	139
N7—H7A···O5^i	0.91	2.21	3.029 (5)	149
N7—H7A···Cl2^i	0.91	2.97	3.688 (4)	137
C8—H8A···O3^ii	0.93	2.53	3.350 (5)	148
C12—H12B···O7^i	0.97	2.45	3.198 (5)	133
C16—H16C···O1^iii	0.96	2.62	3.438 (6)	144
C4—H4B···O5^iv	0.96	2.65	3.585 (5)	165
C12—H12A···O6^v	0.97	2.58	3.180 (5)	120

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

(II) {bis[(3,5-dimethyl-1H-pyrazol-1-yl-κN²)methyl]amine}bis(3,5- dimethyl-1H-pyrazole-κN²)copper(II) bis(hexafluoridophosphate)

Crystal data

[Cu(C5H8N2)2(C12H19N5)](PF6)2	F(000) = 3176
Mr = 779.07	Dx = 1.575 Mg m^−3 Dm = 1.575 Mg m^−3 Dm measured by not measured
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 44134 reflections
a = 16.498 (3) Å	θ = 6.0–55.0°
b = 16.912 (3) Å	µ = 0.86 mm^−1
c = 23.552 (5) Å	T = 293 K
V = 6571 (2) Å^3	Block, blue
Z = 8	0.35 × 0.20 × 0.20 mm

Data collection

Oxford Gemini S Ultra diffractometer	6441 independent reflections
Radiation source: fine-focus sealed tube	5187 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 0 pixels mm^-1	θmax = 26.0°, θmin = 3.0°
ω scans	h = −19→20
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −20→20
Tmin = 0.753, Tmax = 0.847	l = −29→29
54743 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.169	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.1026P)^2 + 3.353P] where P = (Fo^2 + 2Fc^2)/3
6441 reflections	(Δ/σ)max = 0.038
443 parameters	Δρmax = 0.68 e Å^−3
0 restraints	Δρmin = −0.47 e Å^−3

Special details

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.4 (release 27-04-2006 CrysAlis171 .NET) (compiled Apr 27 2007,17:53:11) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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 > 2sigma(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	0.88192 (2)	0.23401 (2)	0.373961 (14)	0.04191 (15)
N6	0.85786 (16)	0.29499 (16)	0.44978 (11)	0.0476 (6)
N4	0.87871 (15)	0.32368 (17)	0.31952 (11)	0.0489 (6)
N9	0.90837 (15)	0.14711 (15)	0.43292 (10)	0.0459 (6)
H9D	0.8941	0.0992	0.4185	0.055*
N8	0.98932 (15)	0.19338 (15)	0.34320 (10)	0.0467 (6)
N5	0.86289 (16)	0.24591 (16)	0.49586 (11)	0.0495 (6)
N7	1.03085 (15)	0.15281 (16)	0.38407 (11)	0.0476 (6)
N1	0.70384 (15)	0.19856 (16)	0.39186 (12)	0.0511 (6)
H1A	0.7023	0.2366	0.4161	0.061*
N3	0.94704 (17)	0.36853 (15)	0.31760 (11)	0.0522 (6)
H3A	0.9870	0.3637	0.3408	0.063*
C15	0.8624 (3)	0.2483 (3)	0.60248 (18)	0.0799 (12)
H15A	0.9103	0.2165	0.6059	0.120*
H15B	0.8153	0.2155	0.6068	0.120*
H15C	0.8625	0.2883	0.6314	0.120*
C22	0.99674 (19)	0.1496 (2)	0.44028 (13)	0.0524 (7)
H22A	1.0124	0.1958	0.4620	0.063*
H22B	1.0155	0.1027	0.4601	0.063*
N2	0.76912 (15)	0.18173 (16)	0.35929 (11)	0.0488 (6)
C16	0.8627 (2)	0.1612 (2)	0.48559 (14)	0.0530 (7)
H16A	0.8076	0.1421	0.4817	0.064*
H16B	0.8881	0.1336	0.5171	0.064*
C19	1.1011 (2)	0.1240 (2)	0.36347 (17)	0.0581 (8)
C1	0.6418 (2)	0.1490 (2)	0.38208 (14)	0.0524 (8)
C11	0.8548 (2)	0.3682 (2)	0.47113 (15)	0.0540 (8)
C13	0.8607 (2)	0.2870 (2)	0.54487 (14)	0.0583 (9)
C3	0.74810 (18)	0.11922 (18)	0.32819 (13)	0.0478 (7)
C7	0.8724 (2)	0.4105 (2)	0.24882 (16)	0.0670 (10)
H7A	0.8530	0.4386	0.2177	0.080*
C8	0.8325 (2)	0.3500 (2)	0.27674 (14)	0.0583 (8)
C12	0.8559 (2)	0.3648 (2)	0.53003 (16)	0.0622 (9)
H12A	0.8537	0.4077	0.5547	0.075*
C17	1.0346 (2)	0.18763 (19)	0.29597 (14)	0.0527 (7)
C5	0.8050 (2)	0.0839 (2)	0.28605 (16)	0.0656 (9)
H5A	0.8597	0.0970	0.2962	0.098*
H5B	0.7932	0.1045	0.2490	0.098*
H5C	0.7986	0.0275	0.2858	0.098*
C18	1.1042 (2)	0.1452 (2)	0.30798 (16)	0.0604 (9)
H18A	1.1456	0.1334	0.2826	0.072*
C6	0.9446 (2)	0.4214 (2)	0.27495 (15)	0.0618 (9)
C21	1.1582 (3)	0.0778 (3)	0.4006 (2)	0.0874 (14)
H21A	1.1742	0.1097	0.4324	0.131*
H21B	1.2054	0.0633	0.3791	0.131*
H21C	1.1316	0.0309	0.4140	0.131*
C2	0.6687 (2)	0.0973 (2)	0.34124 (15)	0.0568 (8)
H2A	0.6396	0.0557	0.3254	0.068*
C20	1.0075 (3)	0.2218 (3)	0.24066 (16)	0.0751 (11)
H20A	0.9507	0.2338	0.2426	0.113*
H20B	1.0169	0.1842	0.2108	0.113*
H20C	1.0374	0.2693	0.2330	0.113*
C14	0.8513 (3)	0.4389 (2)	0.43388 (18)	0.0743 (11)
H14A	0.8244	0.4255	0.3990	0.112*
H14B	0.9054	0.4566	0.4258	0.112*
H14C	0.8219	0.4802	0.4527	0.112*
C10	0.7511 (3)	0.3158 (3)	0.26306 (18)	0.0808 (12)
H10A	0.7230	0.3037	0.2977	0.121*
H10B	0.7580	0.2684	0.2412	0.121*
H10C	0.7203	0.3534	0.2415	0.121*
C9	1.0134 (3)	0.4769 (3)	0.2644 (2)	0.0880 (13)
H9A	1.0239	0.5072	0.2981	0.132*
H9B	0.9997	0.5120	0.2338	0.132*
H9C	1.0610	0.4473	0.2544	0.132*
C4	0.5633 (2)	0.1552 (3)	0.41285 (19)	0.0799 (12)
H4A	0.5720	0.1454	0.4525	0.120*
H4B	0.5260	0.1168	0.3980	0.120*
H4C	0.5413	0.2072	0.4078	0.120*
P1	1.08942 (7)	0.08319 (6)	0.59198 (4)	0.0667 (3)
P2	1.14233 (7)	0.37825 (8)	0.41456 (5)	0.0768 (3)
F3	1.0535 (4)	0.0110 (2)	0.62689 (14)	0.162 (2)
F2	1.1299 (4)	0.1486 (2)	0.55730 (19)	0.176 (2)
F8	1.05370 (19)	0.3484 (3)	0.42685 (18)	0.1534 (16)
F7	1.1264 (3)	0.3459 (3)	0.3534 (2)	0.180 (2)
F1	1.1060 (4)	0.0299 (2)	0.54009 (17)	0.188 (2)
F4	1.0723 (4)	0.1354 (2)	0.64386 (18)	0.176 (2)
F12	1.1095 (3)	0.4598 (3)	0.3918 (3)	0.190 (2)
F11	1.2292 (2)	0.4033 (3)	0.3976 (3)	0.189 (2)
F10	1.1722 (3)	0.3000 (3)	0.4390 (3)	0.201 (3)
F9	1.1543 (5)	0.4167 (3)	0.4718 (2)	0.228 (3)
F6	1.1723 (4)	0.0916 (10)	0.6228 (4)	0.163 (6)	0.551 (16)
F6A	1.1565 (6)	0.0239 (7)	0.6078 (5)	0.138 (5)	0.449 (16)
F5	1.0091 (7)	0.0715 (13)	0.5612 (5)	0.124 (6)	0.48 (3)
F5A	1.0201 (10)	0.1329 (14)	0.5707 (4)	0.166 (8)	0.52 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0408 (2)	0.0434 (2)	0.0416 (2)	0.00138 (14)	−0.00008 (13)	0.00370 (14)
N6	0.0531 (14)	0.0469 (14)	0.0430 (13)	0.0015 (11)	0.0023 (11)	−0.0018 (11)
N4	0.0513 (14)	0.0501 (15)	0.0454 (14)	0.0052 (11)	0.0006 (10)	0.0051 (11)
N9	0.0502 (13)	0.0418 (13)	0.0456 (13)	−0.0004 (11)	0.0012 (10)	0.0033 (10)
N8	0.0489 (13)	0.0472 (14)	0.0440 (13)	0.0067 (11)	0.0032 (10)	0.0027 (11)
N5	0.0508 (14)	0.0561 (15)	0.0415 (14)	−0.0025 (12)	0.0040 (11)	0.0001 (11)
N7	0.0424 (13)	0.0491 (14)	0.0513 (14)	0.0056 (11)	0.0006 (10)	0.0006 (11)
N1	0.0452 (14)	0.0535 (15)	0.0545 (14)	0.0014 (11)	0.0004 (11)	−0.0070 (12)
N3	0.0560 (15)	0.0460 (14)	0.0545 (15)	0.0016 (12)	0.0051 (12)	0.0074 (12)
C15	0.078 (3)	0.114 (4)	0.047 (2)	−0.017 (2)	0.0022 (19)	0.002 (2)
C22	0.0528 (17)	0.0585 (19)	0.0460 (17)	0.0063 (14)	−0.0050 (13)	0.0045 (14)
N2	0.0425 (13)	0.0506 (15)	0.0533 (14)	0.0006 (11)	−0.0016 (11)	−0.0067 (12)
C16	0.0561 (18)	0.0540 (18)	0.0489 (17)	−0.0042 (15)	0.0060 (14)	0.0089 (14)
C19	0.0437 (16)	0.060 (2)	0.071 (2)	0.0079 (15)	−0.0026 (15)	−0.0064 (17)
C1	0.0451 (16)	0.0572 (19)	0.0549 (18)	−0.0018 (14)	−0.0044 (13)	0.0111 (15)
C11	0.0501 (16)	0.0529 (18)	0.0590 (19)	−0.0003 (14)	0.0056 (14)	−0.0098 (15)
C13	0.0469 (16)	0.085 (3)	0.0432 (17)	−0.0091 (17)	0.0047 (13)	−0.0099 (16)
C3	0.0514 (17)	0.0420 (15)	0.0501 (16)	0.0052 (13)	−0.0114 (13)	0.0008 (13)
C7	0.090 (3)	0.059 (2)	0.052 (2)	0.0182 (19)	0.0010 (18)	0.0143 (17)
C8	0.069 (2)	0.059 (2)	0.0469 (17)	0.0191 (17)	−0.0028 (15)	0.0034 (15)
C12	0.0565 (19)	0.071 (2)	0.059 (2)	−0.0046 (17)	0.0052 (15)	−0.0212 (18)
C17	0.0564 (18)	0.0504 (18)	0.0514 (17)	0.0026 (14)	0.0111 (14)	−0.0043 (14)
C5	0.064 (2)	0.070 (2)	0.063 (2)	0.0115 (18)	−0.0060 (16)	−0.0145 (18)
C18	0.0527 (18)	0.064 (2)	0.065 (2)	0.0037 (16)	0.0129 (15)	−0.0088 (17)
C6	0.079 (2)	0.0486 (18)	0.0581 (19)	0.0108 (17)	0.0167 (17)	0.0096 (15)
C21	0.060 (2)	0.113 (4)	0.089 (3)	0.035 (2)	−0.010 (2)	0.002 (3)
C2	0.0573 (18)	0.0487 (18)	0.064 (2)	−0.0088 (15)	−0.0119 (16)	0.0020 (15)
C20	0.094 (3)	0.082 (3)	0.049 (2)	0.021 (2)	0.0168 (19)	0.0053 (18)
C14	0.094 (3)	0.0442 (19)	0.084 (3)	0.0069 (19)	0.004 (2)	−0.0092 (18)
C10	0.075 (3)	0.092 (3)	0.075 (3)	0.006 (2)	−0.026 (2)	0.016 (2)
C9	0.100 (3)	0.069 (3)	0.096 (3)	−0.009 (2)	0.021 (2)	0.027 (2)
C4	0.054 (2)	0.102 (3)	0.084 (3)	−0.001 (2)	0.0115 (19)	0.016 (2)
P1	0.0848 (7)	0.0531 (5)	0.0622 (6)	−0.0020 (5)	−0.0180 (5)	−0.0011 (4)
P2	0.0635 (6)	0.0837 (8)	0.0832 (8)	−0.0021 (5)	−0.0095 (5)	−0.0219 (6)
F3	0.284 (6)	0.101 (3)	0.100 (3)	−0.052 (3)	0.040 (3)	−0.0060 (18)
F2	0.295 (6)	0.100 (3)	0.133 (3)	−0.091 (3)	0.044 (3)	−0.007 (2)
F8	0.0728 (19)	0.224 (4)	0.163 (3)	−0.007 (2)	0.010 (2)	0.015 (3)
F7	0.203 (5)	0.199 (5)	0.138 (3)	−0.050 (4)	0.046 (3)	−0.090 (4)
F1	0.368 (7)	0.084 (2)	0.113 (3)	−0.019 (3)	0.081 (4)	−0.023 (2)
F4	0.323 (7)	0.106 (3)	0.100 (2)	−0.024 (4)	0.041 (4)	−0.035 (2)
F12	0.225 (6)	0.115 (3)	0.230 (5)	0.051 (3)	−0.073 (4)	−0.027 (4)
F11	0.103 (3)	0.169 (4)	0.295 (6)	−0.051 (3)	0.013 (3)	0.039 (4)
F10	0.108 (3)	0.128 (3)	0.368 (8)	−0.002 (2)	−0.031 (4)	0.089 (4)
F9	0.364 (8)	0.191 (5)	0.128 (3)	−0.048 (5)	−0.037 (4)	−0.071 (4)
F6	0.096 (5)	0.222 (15)	0.172 (8)	−0.023 (6)	−0.049 (4)	−0.048 (7)
F6A	0.134 (8)	0.103 (8)	0.176 (10)	0.021 (6)	−0.052 (7)	0.048 (7)
F5	0.114 (6)	0.164 (13)	0.094 (6)	−0.029 (6)	−0.053 (5)	0.014 (6)
F5A	0.130 (9)	0.212 (17)	0.155 (7)	0.103 (11)	−0.059 (6)	−0.048 (8)

Geometric parameters (Å, º)

Cu1—N4	1.987 (3)	C8—C10	1.497 (5)
Cu1—N8	2.034 (2)	C12—H12A	0.9300
Cu1—N9	2.068 (2)	C17—C18	1.383 (5)
Cu1—N2	2.089 (3)	C17—C20	1.494 (5)
Cu1—N6	2.100 (3)	C5—H5A	0.9600
N6—C11	1.337 (4)	C5—H5B	0.9600
N6—N5	1.369 (4)	C5—H5C	0.9600
N4—C8	1.340 (4)	C18—H18A	0.9300
N4—N3	1.360 (4)	C6—C9	1.494 (6)
N9—C22	1.469 (4)	C21—H21A	0.9600
N9—C16	1.471 (4)	C21—H21B	0.9600
N9—H9D	0.9100	C21—H21C	0.9600
N8—C17	1.344 (4)	C2—H2A	0.9300
N8—N7	1.366 (3)	C20—H20A	0.9600
N5—C13	1.348 (4)	C20—H20B	0.9600
N5—C16	1.453 (4)	C20—H20C	0.9600
N7—C19	1.347 (4)	C14—H14A	0.9600
N7—C22	1.440 (4)	C14—H14B	0.9600
N1—C1	1.343 (4)	C14—H14C	0.9600
N1—N2	1.352 (4)	C10—H10A	0.9600
N1—H1A	0.8600	C10—H10B	0.9600
N3—C6	1.345 (4)	C10—H10C	0.9600
N3—H3A	0.8600	C9—H9A	0.9600
C15—C13	1.507 (5)	C9—H9B	0.9600
C15—H15A	0.9600	C9—H9C	0.9600
C15—H15B	0.9600	C4—H4A	0.9600
C15—H15C	0.9600	C4—H4B	0.9600
C22—H22A	0.9700	C4—H4C	0.9600
C22—H22B	0.9700	P1—F5A	1.506 (7)
N2—C3	1.332 (4)	P1—F5	1.522 (7)
C16—H16A	0.9700	P1—F2	1.529 (4)
C16—H16B	0.9700	P1—F4	1.534 (4)
C19—C18	1.356 (5)	P1—F6A	1.540 (7)
C19—C21	1.505 (5)	P1—F1	1.543 (4)
C1—C2	1.374 (5)	P1—F6	1.555 (6)
C1—C4	1.487 (5)	P1—F3	1.586 (4)
C11—C12	1.388 (5)	P2—F9	1.510 (4)
C11—C14	1.484 (5)	P2—F10	1.524 (4)
C13—C12	1.364 (5)	P2—F11	1.546 (4)
C3—C2	1.396 (5)	P2—F7	1.563 (5)
C3—C5	1.490 (5)	P2—F8	1.574 (4)
C7—C6	1.354 (5)	P2—F12	1.576 (5)
C7—C8	1.382 (5)	F3—F6A	1.772 (12)
C7—H7A	0.9300
N4—Cu1—N8	92.93 (10)	C19—C18—C17	107.6 (3)
N4—Cu1—N9	168.90 (10)	C19—C18—H18A	126.2
N8—Cu1—N9	79.36 (10)	C17—C18—H18A	126.2
N4—Cu1—N2	101.10 (11)	N3—C6—C7	106.0 (3)
N8—Cu1—N2	125.04 (11)	N3—C6—C9	121.3 (4)
N9—Cu1—N2	89.90 (10)	C7—C6—C9	132.7 (4)
N4—Cu1—N6	99.73 (11)	C19—C21—H21A	109.5
N8—Cu1—N6	129.31 (10)	C19—C21—H21B	109.5
N9—Cu1—N6	79.51 (10)	H21A—C21—H21B	109.5
N2—Cu1—N6	100.37 (10)	C19—C21—H21C	109.5
C11—N6—N5	105.4 (3)	H21A—C21—H21C	109.5
C11—N6—Cu1	141.4 (2)	H21B—C21—H21C	109.5
N5—N6—Cu1	111.40 (19)	C1—C2—C3	106.8 (3)
C8—N4—N3	105.1 (3)	C1—C2—H2A	126.6
C8—N4—Cu1	139.0 (3)	C3—C2—H2A	126.6
N3—N4—Cu1	115.16 (19)	C17—C20—H20A	109.5
C22—N9—C16	113.8 (2)	C17—C20—H20B	109.5
C22—N9—Cu1	105.58 (18)	H20A—C20—H20B	109.5
C16—N9—Cu1	110.08 (19)	C17—C20—H20C	109.5
C22—N9—H9D	109.1	H20A—C20—H20C	109.5
C16—N9—H9D	109.1	H20B—C20—H20C	109.5
Cu1—N9—H9D	109.1	C11—C14—H14A	109.5
C17—N8—N7	105.6 (2)	C11—C14—H14B	109.5
C17—N8—Cu1	143.5 (2)	H14A—C14—H14B	109.5
N7—N8—Cu1	110.83 (18)	C11—C14—H14C	109.5
C13—N5—N6	111.4 (3)	H14A—C14—H14C	109.5
C13—N5—C16	130.6 (3)	H14B—C14—H14C	109.5
N6—N5—C16	117.8 (2)	C8—C10—H10A	109.5
C19—N7—N8	111.0 (3)	C8—C10—H10B	109.5
C19—N7—C22	130.8 (3)	H10A—C10—H10B	109.5
N8—N7—C22	118.1 (2)	C8—C10—H10C	109.5
C1—N1—N2	112.3 (3)	H10A—C10—H10C	109.5
C1—N1—H1A	123.9	H10B—C10—H10C	109.5
N2—N1—H1A	123.9	C6—C9—H9A	109.5
C6—N3—N4	111.8 (3)	C6—C9—H9B	109.5
C6—N3—H3A	124.1	H9A—C9—H9B	109.5
N4—N3—H3A	124.1	C6—C9—H9C	109.5
C13—C15—H15A	109.5	H9A—C9—H9C	109.5
C13—C15—H15B	109.5	H9B—C9—H9C	109.5
H15A—C15—H15B	109.5	C1—C4—H4A	109.5
C13—C15—H15C	109.5	C1—C4—H4B	109.5
H15A—C15—H15C	109.5	H4A—C4—H4B	109.5
H15B—C15—H15C	109.5	C1—C4—H4C	109.5
N7—C22—N9	106.3 (2)	H4A—C4—H4C	109.5
N7—C22—H22A	110.5	H4B—C4—H4C	109.5
N9—C22—H22A	110.5	F5A—P1—F5	41.7 (5)
N7—C22—H22B	110.5	F5A—P1—F2	75.5 (10)
N9—C22—H22B	110.5	F5—P1—F2	102.7 (5)
H22A—C22—H22B	108.7	F5A—P1—F4	78.7 (6)
C3—N2—N1	105.8 (3)	F5—P1—F4	107.1 (9)
C3—N2—Cu1	131.2 (2)	F2—P1—F4	95.1 (2)
N1—N2—Cu1	121.8 (2)	F5A—P1—F6A	172.2 (10)
N5—C16—N9	107.4 (2)	F5—P1—F6A	131.0 (10)
N5—C16—H16A	110.2	F2—P1—F6A	106.7 (5)
N9—C16—H16A	110.2	F4—P1—F6A	108.3 (6)
N5—C16—H16B	110.2	F5A—P1—F1	101.4 (6)
N9—C16—H16B	110.2	F5—P1—F1	72.6 (9)
H16A—C16—H16B	108.5	F2—P1—F1	85.6 (2)
N7—C19—C18	106.5 (3)	F4—P1—F1	179.3 (3)
N7—C19—C21	121.2 (4)	F6A—P1—F1	71.6 (6)
C18—C19—C21	132.3 (4)	F5A—P1—F6	140.5 (12)
N1—C1—C2	105.7 (3)	F5—P1—F6	177.7 (11)
N1—C1—C4	122.5 (3)	F2—P1—F6	78.4 (6)
C2—C1—C4	131.8 (4)	F4—P1—F6	74.7 (5)
N6—C11—C12	109.7 (3)	F6A—P1—F6	46.7 (5)
N6—C11—C14	121.7 (3)	F1—P1—F6	105.5 (5)
C12—C11—C14	128.6 (3)	F5A—P1—F3	108.6 (10)
N5—C13—C12	106.2 (3)	F5—P1—F3	79.7 (5)
N5—C13—C15	123.1 (4)	F2—P1—F3	175.5 (3)
C12—C13—C15	130.6 (4)	F4—P1—F3	87.8 (2)
N2—C3—C2	109.5 (3)	F6A—P1—F3	69.0 (5)
N2—C3—C5	121.3 (3)	F1—P1—F3	91.6 (2)
C2—C3—C5	129.1 (3)	F6—P1—F3	99.0 (6)
C6—C7—C8	107.7 (3)	F9—P2—F10	89.7 (4)
C6—C7—H7A	126.2	F9—P2—F11	89.6 (4)
C8—C7—H7A	126.2	F10—P2—F11	92.1 (3)
N4—C8—C7	109.5 (3)	F9—P2—F7	174.7 (4)
N4—C8—C10	122.9 (3)	F10—P2—F7	95.6 (4)
C7—C8—C10	127.6 (3)	F11—P2—F7	90.8 (3)
C13—C12—C11	107.2 (3)	F9—P2—F8	95.5 (3)
C13—C12—H12A	126.4	F10—P2—F8	87.3 (2)
C11—C12—H12A	126.4	F11—P2—F8	175.0 (3)
N8—C17—C18	109.2 (3)	F7—P2—F8	84.3 (2)
N8—C17—C20	121.8 (3)	F9—P2—F12	88.4 (3)
C18—C17—C20	128.9 (3)	F10—P2—F12	177.6 (4)
C3—C5—H5A	109.5	F11—P2—F12	89.5 (3)
C3—C5—H5B	109.5	F7—P2—F12	86.3 (3)
H5A—C5—H5B	109.5	F8—P2—F12	91.4 (3)
C3—C5—H5C	109.5	P1—F3—F6A	54.2 (3)
H5A—C5—H5C	109.5	P1—F6A—F3	56.7 (4)
H5B—C5—H5C	109.5
N4—Cu1—N6—C11	−13.8 (4)	C22—N9—C16—N5	78.8 (3)
N8—Cu1—N6—C11	88.2 (4)	Cu1—N9—C16—N5	−39.5 (3)
N9—Cu1—N6—C11	154.9 (4)	N8—N7—C19—C18	−1.1 (4)
N2—Cu1—N6—C11	−117.1 (4)	C22—N7—C19—C18	−178.6 (3)
N4—Cu1—N6—N5	−175.32 (19)	N8—N7—C19—C21	179.3 (3)
N8—Cu1—N6—N5	−73.3 (2)	C22—N7—C19—C21	1.7 (6)
N9—Cu1—N6—N5	−6.57 (19)	N2—N1—C1—C2	0.3 (4)
N2—Cu1—N6—N5	81.4 (2)	N2—N1—C1—C4	179.7 (3)
N8—Cu1—N4—C8	117.4 (3)	N5—N6—C11—C12	−1.5 (4)
N9—Cu1—N4—C8	163.0 (5)	Cu1—N6—C11—C12	−163.6 (3)
N2—Cu1—N4—C8	−9.2 (4)	N5—N6—C11—C14	178.3 (3)
N6—Cu1—N4—C8	−111.9 (3)	Cu1—N6—C11—C14	16.1 (6)
N8—Cu1—N4—N3	−51.1 (2)	N6—N5—C13—C12	−1.2 (4)
N9—Cu1—N4—N3	−5.5 (7)	C16—N5—C13—C12	−175.5 (3)
N2—Cu1—N4—N3	−177.7 (2)	N6—N5—C13—C15	177.9 (3)
N6—Cu1—N4—N3	79.6 (2)	C16—N5—C13—C15	3.6 (5)
N4—Cu1—N9—C22	−10.3 (6)	N1—N2—C3—C2	0.5 (3)
N8—Cu1—N9—C22	36.24 (19)	Cu1—N2—C3—C2	167.4 (2)
N2—Cu1—N9—C22	162.0 (2)	N1—N2—C3—C5	179.1 (3)
N6—Cu1—N9—C22	−97.4 (2)	Cu1—N2—C3—C5	−13.9 (5)
N4—Cu1—N9—C16	112.9 (6)	N3—N4—C8—C7	0.1 (4)
N8—Cu1—N9—C16	159.5 (2)	Cu1—N4—C8—C7	−169.1 (3)
N2—Cu1—N9—C16	−74.7 (2)	N3—N4—C8—C10	179.3 (3)
N6—Cu1—N9—C16	25.9 (2)	Cu1—N4—C8—C10	10.1 (6)
N4—Cu1—N8—C17	−31.7 (4)	C6—C7—C8—N4	0.1 (4)
N9—Cu1—N8—C17	156.4 (4)	C6—C7—C8—C10	−179.1 (4)
N2—Cu1—N8—C17	74.1 (4)	N5—C13—C12—C11	0.3 (4)
N6—Cu1—N8—C17	−136.8 (4)	C15—C13—C12—C11	−178.7 (4)
N4—Cu1—N8—N7	153.2 (2)	N6—C11—C12—C13	0.8 (4)
N9—Cu1—N8—N7	−18.74 (19)	C14—C11—C12—C13	−178.9 (4)
N2—Cu1—N8—N7	−101.0 (2)	N7—N8—C17—C18	−1.2 (4)
N6—Cu1—N8—N7	48.1 (2)	Cu1—N8—C17—C18	−176.4 (3)
C11—N6—N5—C13	1.7 (3)	N7—N8—C17—C20	177.2 (3)
Cu1—N6—N5—C13	169.8 (2)	Cu1—N8—C17—C20	2.0 (6)
C11—N6—N5—C16	176.7 (3)	N7—C19—C18—C17	0.3 (4)
Cu1—N6—N5—C16	−15.1 (3)	C21—C19—C18—C17	179.9 (4)
C17—N8—N7—C19	1.4 (4)	N8—C17—C18—C19	0.6 (4)
Cu1—N8—N7—C19	178.4 (2)	C20—C17—C18—C19	−177.7 (4)
C17—N8—N7—C22	179.3 (3)	N4—N3—C6—C7	0.3 (4)
Cu1—N8—N7—C22	−3.7 (3)	N4—N3—C6—C9	−179.7 (3)
C8—N4—N3—C6	−0.3 (3)	C8—C7—C6—N3	−0.2 (4)
Cu1—N4—N3—C6	172.0 (2)	C8—C7—C6—C9	179.7 (4)
C19—N7—C22—N9	−148.2 (3)	N1—C1—C2—C3	0.0 (4)
N8—N7—C22—N9	34.4 (4)	C4—C1—C2—C3	−179.3 (4)
C16—N9—C22—N7	−167.3 (3)	N2—C3—C2—C1	−0.3 (4)
Cu1—N9—C22—N7	−46.4 (3)	C5—C3—C2—C1	−178.8 (3)
C1—N1—N2—C3	−0.5 (4)	F5A—P1—F3—F6A	172.1 (9)
C1—N1—N2—Cu1	−169.0 (2)	F5—P1—F3—F6A	141.6 (11)
N4—Cu1—N2—C3	99.1 (3)	F2—P1—F3—F6A	19 (3)
N8—Cu1—N2—C3	−2.5 (3)	F4—P1—F3—F6A	−110.6 (7)
N9—Cu1—N2—C3	−79.4 (3)	F1—P1—F3—F6A	69.6 (7)
N6—Cu1—N2—C3	−158.7 (3)	F6—P1—F3—F6A	−36.4 (6)
N4—Cu1—N2—N1	−95.7 (2)	F5A—P1—F6A—F3	−74 (7)
N8—Cu1—N2—N1	162.7 (2)	F5—P1—F6A—F3	−54.1 (8)
N9—Cu1—N2—N1	85.8 (2)	F2—P1—F6A—F3	−178.5 (2)
N6—Cu1—N2—N1	6.5 (3)	F4—P1—F6A—F3	80.2 (4)
C13—N5—C16—N9	−149.6 (3)	F1—P1—F6A—F3	−99.1 (4)
N6—N5—C16—N9	36.5 (4)	F6—P1—F6A—F3	126.3 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···F8	0.86	2.32	3.136 (5)	158
N3—H3A···F7	0.86	2.34	3.101 (6)	148
C22—H22A···F8	0.97	2.79	3.506 (6)	131
C9—H9A···F12	0.96	2.74	3.407 (7)	127
N9—H9D···F3^i	0.91	2.32	3.088 (5)	142
N9—H9D···F1^i	0.91	2.39	3.069 (5)	131
N1—H1A···F2^ii	0.86	2.36	3.099 (5)	144
C9—H9B···F3^iii	0.96	2.70	3.311 (6)	122
C20—H20C···F4^iii	0.96	2.71	3.489 (6)	139
C10—H10C···F7^iv	0.96	2.72	3.466 (6)	135
C10—H10A···F6^ii	0.96	2.71	3.371 (10)	127
C4—H4A···F9^ii	0.96	2.47	3.333 (8)	149

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