Bis{2,6-bis­[1-(4-fluoro­phenyl­imino)­eth­yl]pyridine}-1κ³N,N′,N′′;3κ³N,N′,N′′-di-μ-chlorido-1:2κ²Cl:Cl;2:3κ²Cl:Cl-trichlorido-1κCl,2κCl,3κCl-2-copper(I)-1,3-dicopper(II)

The title complex, [Cu₃Cl₅(C₂₁H₁₇N₃F₂)₂], is the first reported copper trimer including both Cu^I and Cu^II ions. The two Cu^II ions are five-coordinate in a significantly distorted square-pyramidal arrangement, with the bridging Cl atom located in the apical position, and the pyridine (py) N atom, the two imine N atoms and the other Cl atom located in the basal plane. The Cu^I ion is in a trigonal planar configuration surrounded by three Cl atoms. The structure is stabilized by intra- and inter­molecular C—H...Cl and C—H...π(py) hydrogen bonds.

S1. Comment

Multidentate ligands play an important role in transition metal chemistry, enhancing stability of complexes and allowing the manipulation of steric and electronic parameters which control reactivity at the metal center (Togni & Venanzi, 1994). An attractive multidentate ligand is the neutral N,N',N''-tridentate pyridine-2,6-diimine (pydim) ligand, in which the central pyridine-based ring donor contains keto–imine substituents in the ortho positions. Upon coordination to transition metals, the bis-chelate framework may confer on such complexes interesting stoichiometries and catalytic activities (Gibson & Spitzmesser, 2003; Çetinkaya et al., 1999; Dayan & Çetinkaya, 2007).

While their catalytic properties have been examined extensively, reports of the structural properties of these compounds are rare in the literature. We have therefore prepared pyridinediimine complexes of various transition metals (Özdemir et al., 2006a,b). We were attempting to obtain a monomer complex between (I) (Scheme 1) and CuCl₂. However, CHN analysis showed that the desired product did not form, but rather a new trimer, (II), between pydim and CuCl₂ in a 2:3 ratio. Understanding the shape of the coordination polyhedra in the case of five-coordination is one of the current problems in coordination chemistry. This study of (II) establishes the structural parameters and the coordination geometries about the metal atoms.

The molecular structure of complex (II), together with the atom-labelling scheme, is shown in Fig. 1. Selected geometric parameters are listed in Table 1. The structure of the title trimer is composed of two Cu^II metal centres bound to one (N,N'Z,N,N'E)-N,N'-[1,1'-(pyridine-2,6-diyl)bis(ethan-1-yl-1-ylidene)] bis(4-fluoroaniline) ligand, (I), and one Cl atom, and a tricholorocopper(I) unit which links the two Cu^II metal centres. The ligand (I), with its two imino groups in ortho positions with respect to the pyridine N atom, behaves as a symmetrical N,N',N-tridentate chelate. The two Cu^II ions are therefore five-coordinated by two imine N atoms, one pyridine N atom and two Cl atoms, while the Cu^I ion is coordinated by three Cl atoms (Fig. 1) in a trigonal–planar configuration. The Cu1/N1/C1/C14/N3, Cu1/N1/C5/C6/N2, Cu3/N4/C22/C35/N6 and Cu3/N4/C26/C27/N5 chelate rings are approximately planar, and the maximum deviations from their planes are 0.024 (3), 0.020 (2), 0.031 (2) and 0.010 (2) Å for atoms C14, N1, N6 and N5, respectively. The Cu1- and Cu3-containing pairs of chelate rings make dihedral angles of, respectively, 3.00 (12) and 1.74 (12)° with one another, indicating that they are nearly coplanar.

Five-coordinate copper(II) complexes have geometries ranging from trigonal–bipyramidal to square–pyramidal. Energetically, these limiting forms are often almost equally favourable, with a low activation barrier to interconversion. Further information can be obtained by determining the structural index, τ, which represents the relative amount of trigonality [for a square pyramid, τ = 0, and for a trigonal bipyramid, τ = 1; τ = (β - α)/60°, α and β being the two largest angles around the central atom (Addison et al., 1984)]. The values of τ for atoms Cu1 and Cu3 in (II) are 0.23 and 0.03, respectively, indicating that the coordination geometry of the Cu^II ions is closer to a regular square pyramid than to a regular trigonal bipyramid. For both Cu^II ions, the axial positions are occupied by the Cl atoms coordinated to a Cu^I ion, while the four basal positions consist of the other chloride ligand and the three N-atom donors of the tridentate ligand (I). The Cu1 and Cu3 atoms lie 0.4210 (4) and 0.2659 (3) Å, respectively, out of the least-squares planes of the pyramid bases. As can be seen in Table 1, the bond lengths and angles at the Cu^II ions show that the coordination geometries are distorted significantly (from equal lengths and 90° angles). Axial Cu—Cl distances are longer than equatorial Cu—Cl distances, confirming the weaker interactions between the bridging Cl atoms and the Cu atoms. When the Cu—Cl distances in polymeric Cu^I– or Cu^II–Cl compounds are surveyed, it is observed that elongation of the bridging Cu—Cl distances in the axial position is common for these types of complexes (Schuitema et al., 2003; Johansson et al., 2004; Rybak-Akimova et al., 1997; Vasilevsky et al., 1989).

A comparison of the appropriate bond distances and angles in (II) indicates that the two Cu^II ions possess approximate noncrystallographic C_s symmetry about a plane bisecting the central pyridine ring and containing the metal atom and the two halogen atoms. The planes of the benzene rings substituted on the bis(imino)pyridine ligand backbone make dihedral angles of 52.94 (16), 71.88 (15), 56.48 (15) and 81.95 (16)° with the plane of the central pyridine ring for the C8–C13, C16–C21, C29–C34 and C37–C42 rings, respectively. The dihedral angle between the C8–C13 and C16–C21 rings is 86.38 (15)°, while the dihedral angle between the C29–C34 and C37–C42 rings is 84.05 (15)°. The geometries at the N_imino-atom centers are all trigonal–planar, the sums of the three bond angles around these centers being 359.9 (2), 360.0 (2), 359.9 (2) and 359.8 (2)°, and none is more than ca 0.03 Å out of its associated CuC₂ plane.

There are several reported structures containing various transition metal complexes of pydim-based ligands (Britovsek et al., 1999; Dias et al., 2000; Nakayama et al., 2005; Humphries et al., 2005). The M—N bond distances in (II) and in these examples indicate that the two M—N_imino bonds are ca 0.1–0.2 Å longer than the corresponding M—N_pyridine bond within each metal–tridentate-chelate unit. Furthermore, it is observed that the N_imino—M—N_pyridine bond angle for the five-membered chelate rings of pydim complexes is inversely related to the magnitude of the M—N_pyridine bond; as the M—N_pyridine distance increases, the corresponding inner `bite' angle decreases, as shown in Table 3.

The intra- and intermolecular interactions in (II) are given in Table 2. An intramolecular C9—H9···Cl2 interaction leads to the formation of a six-membered ring. In addition, there is also an intramolecular C—H···π contact between atom H7B and the centroid of the N4/C22–C26 ring (entry 2 in Table 2, and Fig. 1). Molecules of the title compound are packed in columns running along the b axis and three C—H···Cl intermolecular interactions are observed (Fig. 2); these type of interaction have been observed previously (Vasilevsky et al., 1989; Özdemir et al., 2006a,b).

Related literature

For related literature, see: Addison et al. (1984); Britovsek et al. (1999); Dayan & Çetinkaya (2007); Dias et al. (2000); Gibson & Spitzmesser (2003); Humphries et al. (2005); Johansson et al. (2004); Nakayama et al. (2005); Rybak-Akimova, Busch, Kahol, Pinto, Alcock & Clase (1997); Schuitema et al. (2003); Sheldrick (1997); Togni & Venanzi (1994); Vasilevsky et al. (1989); Özdemir et al. (2006a, 2006b); Çetinkaya et al. (1999).

S2. Experimental

The ligand (I) was prepared by a modification of the method described by Çetinkaya et al. (1999). A solution of CuCl₂.2H₂0 (510 mg, 3 mmol) in EtOH (10 ml) was added dropwise to a solution of (I) (350 mg, 1 mmol) in ethanol (10 ml). The resulting brown solution was refluxed for 4 h and was concentrated (5 ml). Water was added dropwise with stirring to a final volume of 10 ml, causing a brown powder to precipitate. The brown precipitate was filtered off, washed with cold EtOH and Et₂O, respectively, and dried. X-ray quality crystals were grown from CH₂Cl₂–Et₂O (30 ml, 1:2 v/v) (yield 420 mg, 39%; m.p. 460–462 K). Analysis calculated for C₄₂H₃₄Cl₅Cu₃F₄N₆: C 47.29, H 3.21, N 7.88%; found: C 47.98, H 3.12, N 7.31%. Other experimental data are given in the _exptl_special _details section of the deposited CIF.

S3. Refinement

H atoms were positioned geometrically and treated using a riding model, fixing the bond lengths at 0.96 and 0.93 Å for CH₃ and aromatic CH groups, respectively. The displacement parameters of the H atoms were constrained [U_iso(H) = 1.2U_eq(C) for non-methyl and U_iso(H) = 1.5U_eq(C) for methyl H atoms]. Riding methyl H atoms were allowed to rotate freely during refinement using the AFIX 137 command of SHELXL97 (Sheldrick, 2008).

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures

	Fig. 1. : A view of (II), with 30% probability displacement ellipsoids and the atom-numbering scheme. For clarity, only H atoms involved in hydrogen bonding (shown by dashed lines) have been included.
	Fig. 2. : A partial cell packing diagram for complex (II), showing the C—H···Cl interactions (dashed lines). For clarity, only H atoms involved in hydrogen bonding have been included. [Symmetry codes: (i) -x + 1, y - 1/2, -z + 1/2; (ii) -x + 1, y + 1/2, -z + 1/2.]

Bis{2,6-bis[1-(4-fluorophenylimino)ethyl]pyridine}- 1κ³N,N',N'';3κ³N,N',N''-di-µ-chlorido-trichlorido-1λCl,2κCl,3κCl- copper(I)dicopper(II)

Crystal data

[Cu3Cl5(C21H17N3F2)2]	F(000) = 2144
Mr = 1066.62	Dx = 1.629 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 43031 reflections
a = 18.4646 (9) Å	θ = 1.6–26.1°
b = 9.0930 (3) Å	µ = 1.82 mm^−1
c = 28.0986 (14) Å	T = 296 K
β = 112.774 (4)°	Prismatic stick, dark red
V = 4349.9 (4) Å^3	0.62 × 0.31 × 0.10 mm
Z = 4

Data collection

Stoe IPDS-II diffractometer	8530 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	6353 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.057
Detector resolution: 6.67 pixels mm^-1	θmax = 26.1°, θmin = 1.6°
ω scans	h = −22→22
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −11→11
Tmin = 0.595, Tmax = 0.883	l = −34→34
39069 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0361P)^2] where P = (Fo^2 + 2Fc^2)/3
8530 reflections	(Δ/σ)max = 0.001
545 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.60 e Å^−3

Special details

Experimental. Melting points were determined in open capillary tubes on a digital Electrothermal 9100 melting point apparatus. IR spectra (KBr pellets) were recorded in the range 400–4000 cm^-1 on an ATI UNICAM 2000 spectrophotometer. Elemental analyses were carried out by the analytical service of TÜBİTAK (the Scientific and Technical Research Council of Turkey) using a Carlo Erba 1106 apparatus. CuCl₂.2H₂0 (Merck), diacetylpyridine (Fluka), 4-flouroaniline (Acros) were used as received. Solvents were of analytical grade. IR (KBr): 1614 (ν_C═N) cm^-1.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.454008 (18)	0.04742 (4)	0.124655 (12)	0.03725 (8)
Cu2	0.66881 (2)	0.24990 (4)	0.140867 (14)	0.05292 (10)
Cu3	0.874668 (18)	−0.01527 (3)	0.247785 (12)	0.03684 (8)
Cl1	0.36684 (4)	0.10107 (8)	0.15922 (3)	0.04491 (16)
Cl2	0.53127 (4)	0.26183 (8)	0.11538 (3)	0.04861 (17)
Cl3	0.70269 (4)	0.40568 (9)	0.09265 (3)	0.05511 (18)
Cl4	0.73171 (4)	0.08096 (9)	0.19944 (3)	0.0576 (2)
Cl5	0.94597 (5)	0.18490 (8)	0.26228 (3)	0.05492 (19)
F1	0.62302 (12)	0.1957 (2)	0.38307 (7)	0.0723 (5)
F2	0.13067 (14)	0.4540 (3)	−0.00803 (10)	0.0991 (8)
F3	0.97175 (13)	0.2763 (2)	0.05611 (8)	0.0757 (6)
F4	0.88227 (14)	0.4128 (2)	0.45593 (9)	0.0877 (7)
N1	0.49090 (12)	−0.1095 (2)	0.09283 (8)	0.0387 (5)
N2	0.54149 (12)	−0.0425 (2)	0.18838 (8)	0.0368 (5)
N3	0.37827 (12)	0.0651 (2)	0.04839 (8)	0.0392 (5)
N4	0.85086 (12)	−0.2221 (2)	0.24975 (8)	0.0356 (5)
N5	0.88536 (12)	−0.0907 (2)	0.18149 (8)	0.0376 (5)
N6	0.85987 (12)	−0.0315 (2)	0.31773 (8)	0.0382 (5)
C1	0.45585 (16)	−0.1304 (3)	0.04205 (10)	0.0425 (6)
C2	0.47901 (19)	−0.2453 (3)	0.01874 (12)	0.0576 (8)
H2	0.4557	−0.2599	−0.0167	0.069*
C3	0.5375 (2)	−0.3367 (4)	0.04964 (14)	0.0670 (9)
H3	0.5543	−0.4140	0.0348	0.080*
C4	0.57178 (19)	−0.3161 (3)	0.10245 (13)	0.0569 (8)
H4	0.6105	−0.3796	0.1233	0.068*
C5	0.54686 (15)	−0.1979 (3)	0.12344 (11)	0.0411 (6)
C6	0.57556 (15)	−0.1557 (3)	0.17872 (10)	0.0399 (6)
C7	0.63983 (18)	−0.2438 (4)	0.21706 (12)	0.0558 (8)
H7A	0.6641	−0.1877	0.2482	0.084*
H7B	0.6783	−0.2675	0.2031	0.084*
H7C	0.6185	−0.3328	0.2247	0.084*
C8	0.56327 (14)	0.0157 (3)	0.23947 (9)	0.0370 (6)
C9	0.58153 (16)	0.1628 (3)	0.24735 (11)	0.0449 (6)
H9	0.5804	0.2214	0.2199	0.054*
C10	0.60145 (17)	0.2238 (3)	0.29567 (11)	0.0497 (7)
H10	0.6141	0.3230	0.3013	0.060*
C11	0.60226 (17)	0.1351 (4)	0.33512 (11)	0.0503 (7)
C12	0.58305 (19)	−0.0093 (4)	0.32853 (11)	0.0580 (8)
H12	0.5830	−0.0660	0.3561	0.070*
C13	0.56341 (17)	−0.0712 (3)	0.28003 (11)	0.0507 (7)
H13	0.5504	−0.1704	0.2747	0.061*
C14	0.39145 (16)	−0.0227 (3)	0.01699 (10)	0.0415 (6)
C15	0.34862 (19)	−0.0256 (4)	−0.04010 (11)	0.0583 (8)
H15A	0.3174	0.0618	−0.0511	0.087*
H15B	0.3151	−0.1105	−0.0497	0.087*
H15C	0.3858	−0.0301	−0.0563	0.087*
C16	0.31398 (15)	0.1671 (3)	0.03098 (9)	0.0412 (6)
C17	0.32809 (19)	0.3149 (4)	0.03133 (12)	0.0554 (8)
H17	0.3791	0.3495	0.0406	0.066*
C18	0.2652 (2)	0.4132 (4)	0.01760 (13)	0.0652 (9)
H18	0.2734	0.5139	0.0170	0.078*
C19	0.1916 (2)	0.3579 (5)	0.00510 (12)	0.0636 (9)
C20	0.17698 (18)	0.2125 (5)	0.00554 (12)	0.0638 (9)
H20	0.1261	0.1786	−0.0025	0.077*
C21	0.23855 (17)	0.1159 (4)	0.01801 (12)	0.0544 (7)
H21	0.2293	0.0153	0.0177	0.065*
C22	0.83411 (15)	−0.2745 (3)	0.28869 (10)	0.0384 (6)
C23	0.81603 (17)	−0.4203 (3)	0.29051 (11)	0.0484 (7)
H23	0.8032	−0.4560	0.3173	0.058*
C24	0.81714 (19)	−0.5129 (3)	0.25190 (12)	0.0533 (7)
H24	0.8057	−0.6123	0.2527	0.064*
C25	0.83526 (17)	−0.4577 (3)	0.21198 (12)	0.0501 (7)
H25	0.8366	−0.5192	0.1859	0.060*
C26	0.85139 (15)	−0.3087 (3)	0.21155 (10)	0.0390 (6)
C27	0.87070 (15)	−0.2285 (3)	0.17218 (10)	0.0409 (6)
C28	0.8681 (2)	−0.3106 (4)	0.12565 (12)	0.0631 (9)
H28A	0.8710	−0.2424	0.1004	0.095*
H28B	0.8199	−0.3651	0.1114	0.095*
H28C	0.9118	−0.3773	0.1352	0.095*
C29	0.90714 (15)	0.0017 (3)	0.14770 (9)	0.0375 (6)
C30	0.86428 (17)	0.1262 (3)	0.12785 (11)	0.0501 (7)
H30	0.8209	0.1481	0.1356	0.060*
C31	0.88493 (19)	0.2195 (4)	0.09642 (12)	0.0559 (8)
H31	0.8557	0.3035	0.0825	0.067*
C32	0.94935 (18)	0.1848 (3)	0.08645 (11)	0.0513 (7)
C33	0.99451 (18)	0.0630 (4)	0.10636 (12)	0.0540 (7)
H33	1.0385	0.0433	0.0990	0.065*
C34	0.97315 (17)	−0.0301 (3)	0.13758 (11)	0.0481 (7)
H34	1.0029	−0.1134	0.1517	0.058*
C35	0.83813 (15)	−0.1586 (3)	0.32710 (10)	0.0394 (6)
C36	0.81738 (19)	−0.1960 (4)	0.37175 (11)	0.0545 (8)
H36A	0.8173	−0.1081	0.3907	0.082*
H36B	0.8553	−0.2639	0.3939	0.082*
H36C	0.7662	−0.2401	0.3595	0.082*
C37	0.86643 (15)	0.0868 (3)	0.35315 (10)	0.0387 (6)
C38	0.80436 (17)	0.1819 (3)	0.34349 (12)	0.0510 (7)
H38	0.7594	0.1725	0.3135	0.061*
C39	0.8093 (2)	0.2919 (4)	0.37887 (13)	0.0577 (8)
H39	0.7676	0.3560	0.3734	0.069*
C40	0.8765 (2)	0.3034 (4)	0.42149 (13)	0.0566 (8)
C41	0.93883 (19)	0.2123 (4)	0.43157 (12)	0.0586 (8)
H41	0.9839	0.2240	0.4613	0.070*
C42	0.93393 (17)	0.1018 (4)	0.39671 (11)	0.0510 (7)
H42	0.9759	0.0381	0.4027	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03682 (16)	0.04031 (18)	0.03284 (16)	0.00851 (13)	0.01154 (13)	−0.00051 (13)
Cu2	0.0620 (2)	0.0475 (2)	0.0485 (2)	0.00086 (18)	0.02058 (18)	−0.00043 (17)
Cu3	0.04182 (17)	0.03449 (17)	0.03585 (16)	−0.00376 (13)	0.01683 (14)	−0.00150 (13)
Cl1	0.0445 (4)	0.0472 (4)	0.0470 (4)	0.0091 (3)	0.0221 (3)	0.0006 (3)
Cl2	0.0401 (3)	0.0534 (4)	0.0515 (4)	−0.0014 (3)	0.0168 (3)	0.0093 (3)
Cl3	0.0510 (4)	0.0498 (4)	0.0663 (5)	0.0001 (3)	0.0246 (4)	0.0089 (4)
Cl4	0.0405 (4)	0.0693 (5)	0.0630 (5)	0.0116 (3)	0.0199 (3)	0.0226 (4)
Cl5	0.0602 (4)	0.0485 (4)	0.0595 (4)	−0.0197 (3)	0.0269 (4)	−0.0124 (3)
F1	0.0872 (14)	0.0847 (14)	0.0428 (10)	0.0020 (11)	0.0229 (10)	−0.0168 (9)
F2	0.0801 (15)	0.1068 (19)	0.1000 (17)	0.0570 (14)	0.0235 (13)	0.0195 (14)
F3	0.0946 (14)	0.0693 (13)	0.0774 (13)	−0.0027 (11)	0.0490 (12)	0.0249 (11)
F4	0.1060 (17)	0.0773 (15)	0.0915 (16)	−0.0025 (13)	0.0510 (14)	−0.0407 (12)
N1	0.0372 (11)	0.0384 (12)	0.0396 (12)	0.0047 (10)	0.0137 (10)	−0.0025 (10)
N2	0.0336 (10)	0.0382 (12)	0.0363 (11)	0.0015 (9)	0.0110 (9)	0.0008 (9)
N3	0.0373 (11)	0.0436 (13)	0.0333 (11)	0.0038 (10)	0.0098 (9)	−0.0002 (10)
N4	0.0350 (11)	0.0365 (12)	0.0333 (11)	−0.0012 (9)	0.0109 (9)	−0.0009 (9)
N5	0.0396 (11)	0.0378 (13)	0.0355 (11)	0.0000 (9)	0.0146 (9)	0.0014 (9)
N6	0.0407 (11)	0.0403 (13)	0.0345 (11)	−0.0008 (10)	0.0155 (9)	−0.0002 (9)
C1	0.0430 (14)	0.0440 (16)	0.0402 (15)	0.0007 (12)	0.0159 (12)	−0.0047 (12)
C2	0.066 (2)	0.0548 (19)	0.0482 (17)	0.0094 (16)	0.0179 (15)	−0.0171 (15)
C3	0.075 (2)	0.055 (2)	0.068 (2)	0.0180 (18)	0.0250 (18)	−0.0192 (17)
C4	0.0580 (18)	0.0441 (17)	0.065 (2)	0.0172 (15)	0.0202 (16)	−0.0029 (15)
C5	0.0380 (14)	0.0381 (14)	0.0465 (15)	0.0044 (11)	0.0155 (12)	−0.0012 (12)
C6	0.0334 (13)	0.0398 (15)	0.0451 (15)	0.0019 (11)	0.0136 (11)	0.0029 (12)
C7	0.0528 (17)	0.0554 (19)	0.0545 (18)	0.0194 (15)	0.0155 (14)	0.0096 (15)
C8	0.0318 (12)	0.0417 (15)	0.0337 (13)	0.0039 (11)	0.0087 (10)	0.0013 (11)
C9	0.0494 (16)	0.0435 (16)	0.0427 (15)	0.0040 (13)	0.0190 (13)	0.0042 (12)
C10	0.0528 (17)	0.0433 (16)	0.0514 (17)	0.0035 (13)	0.0184 (14)	−0.0039 (13)
C11	0.0454 (15)	0.064 (2)	0.0398 (16)	0.0036 (14)	0.0152 (13)	−0.0092 (14)
C12	0.064 (2)	0.070 (2)	0.0393 (16)	−0.0073 (17)	0.0194 (15)	0.0053 (15)
C13	0.0531 (17)	0.0502 (18)	0.0428 (16)	−0.0109 (14)	0.0118 (13)	0.0012 (13)
C14	0.0430 (14)	0.0438 (16)	0.0355 (14)	−0.0019 (12)	0.0127 (11)	−0.0034 (12)
C15	0.066 (2)	0.064 (2)	0.0379 (15)	0.0075 (16)	0.0121 (14)	−0.0072 (14)
C16	0.0415 (14)	0.0504 (17)	0.0287 (13)	0.0095 (12)	0.0104 (11)	0.0022 (12)
C17	0.0548 (18)	0.0514 (19)	0.0546 (18)	0.0082 (15)	0.0154 (15)	0.0035 (15)
C18	0.080 (2)	0.0497 (19)	0.058 (2)	0.0189 (18)	0.0186 (18)	0.0077 (15)
C19	0.057 (2)	0.086 (3)	0.0440 (17)	0.0338 (19)	0.0146 (15)	0.0117 (17)
C20	0.0421 (16)	0.092 (3)	0.0536 (19)	0.0168 (17)	0.0146 (14)	0.0160 (18)
C21	0.0487 (17)	0.062 (2)	0.0493 (17)	0.0058 (15)	0.0158 (14)	0.0081 (15)
C22	0.0365 (13)	0.0412 (15)	0.0345 (13)	−0.0008 (11)	0.0105 (11)	0.0036 (11)
C23	0.0555 (17)	0.0427 (17)	0.0446 (16)	−0.0086 (13)	0.0166 (14)	0.0063 (13)
C24	0.0647 (19)	0.0338 (15)	0.0567 (18)	−0.0068 (14)	0.0183 (15)	0.0032 (13)
C25	0.0580 (17)	0.0391 (16)	0.0516 (17)	−0.0048 (13)	0.0195 (14)	−0.0088 (13)
C26	0.0382 (13)	0.0364 (14)	0.0394 (14)	−0.0020 (11)	0.0117 (11)	−0.0022 (11)
C27	0.0382 (14)	0.0468 (17)	0.0351 (13)	−0.0013 (12)	0.0115 (11)	−0.0018 (12)
C28	0.086 (2)	0.064 (2)	0.0481 (18)	−0.0190 (18)	0.0357 (17)	−0.0182 (16)
C29	0.0397 (13)	0.0406 (15)	0.0314 (13)	−0.0011 (11)	0.0129 (11)	0.0007 (11)
C30	0.0487 (16)	0.0550 (18)	0.0502 (17)	0.0077 (14)	0.0230 (14)	0.0083 (14)
C31	0.0610 (19)	0.0506 (18)	0.0579 (19)	0.0108 (15)	0.0249 (16)	0.0159 (15)
C32	0.0616 (18)	0.0499 (18)	0.0470 (16)	−0.0018 (15)	0.0260 (15)	0.0095 (14)
C33	0.0544 (17)	0.0577 (19)	0.0597 (19)	0.0002 (15)	0.0331 (15)	0.0055 (15)
C34	0.0483 (16)	0.0495 (17)	0.0510 (16)	0.0095 (13)	0.0241 (13)	0.0113 (13)
C35	0.0358 (13)	0.0461 (16)	0.0344 (13)	−0.0034 (12)	0.0113 (11)	0.0017 (12)
C36	0.067 (2)	0.0589 (19)	0.0473 (17)	−0.0127 (16)	0.0330 (15)	−0.0019 (14)
C37	0.0451 (14)	0.0398 (15)	0.0361 (14)	−0.0031 (12)	0.0213 (12)	0.0011 (11)
C38	0.0483 (16)	0.0551 (19)	0.0484 (16)	0.0072 (14)	0.0172 (13)	0.0009 (14)
C39	0.067 (2)	0.0528 (19)	0.062 (2)	0.0141 (16)	0.0345 (17)	0.0030 (15)
C40	0.073 (2)	0.0507 (18)	0.0585 (19)	−0.0048 (16)	0.0394 (18)	−0.0125 (15)
C41	0.0527 (18)	0.071 (2)	0.0503 (18)	−0.0085 (16)	0.0184 (15)	−0.0183 (16)
C42	0.0460 (16)	0.0569 (19)	0.0505 (17)	0.0023 (14)	0.0192 (14)	−0.0080 (14)

Geometric parameters (Å, º)

Cu1—N1	1.942 (2)	C14—C15	1.489 (4)
Cu1—N2	2.060 (2)	C15—H15A	0.9600
Cu1—N3	2.063 (2)	C15—H15B	0.9600
Cu1—Cl1	2.2320 (7)	C15—H15C	0.9600
Cu1—Cl2	2.4884 (8)	C16—C17	1.368 (4)
Cu2—Cl3	2.2111 (8)	C16—C21	1.377 (4)
Cu2—Cl4	2.2221 (8)	C17—C18	1.396 (4)
Cu2—Cl2	2.3594 (8)	C17—H17	0.9300
Cu3—N4	1.937 (2)	C18—C19	1.361 (5)
Cu3—N5	2.065 (2)	C18—H18	0.9300
Cu3—N6	2.092 (2)	C19—C20	1.351 (5)
Cu3—Cl5	2.1903 (8)	C20—C21	1.371 (4)
Cu3—Cl4	2.6082 (8)	C20—H20	0.9300
F1—C11	1.366 (3)	C21—H21	0.9300
F2—C19	1.358 (4)	C22—C23	1.373 (4)
F3—C32	1.365 (3)	C22—C35	1.490 (4)
F4—C40	1.363 (4)	C23—C24	1.380 (4)
N1—C5	1.329 (3)	C23—H23	0.9300
N1—C1	1.333 (3)	C24—C25	1.383 (4)
N2—C6	1.289 (3)	C24—H24	0.9300
N2—C8	1.434 (3)	C25—C26	1.387 (4)
N3—C14	1.281 (3)	C25—H25	0.9300
N3—C16	1.435 (3)	C26—C27	1.479 (4)
N4—C26	1.335 (3)	C27—C28	1.491 (4)
N4—C22	1.335 (3)	C28—H28A	0.9600
N5—C27	1.287 (3)	C28—H28B	0.9600
N5—C29	1.437 (3)	C28—H28C	0.9600
N6—C35	1.283 (3)	C29—C30	1.370 (4)
N6—C37	1.439 (3)	C29—C34	1.385 (4)
C1—C2	1.385 (4)	C30—C31	1.380 (4)
C1—C14	1.490 (4)	C30—H30	0.9300
C2—C3	1.373 (5)	C31—C32	1.360 (4)
C2—H2	0.9300	C31—H31	0.9300
C3—C4	1.382 (5)	C32—C33	1.369 (4)
C3—H3	0.9300	C33—C34	1.381 (4)
C4—C5	1.387 (4)	C33—H33	0.9300
C4—H4	0.9300	C34—H34	0.9300
C5—C6	1.484 (4)	C35—C36	1.486 (4)
C6—C7	1.490 (4)	C36—H36A	0.9600
C7—H7A	0.9600	C36—H36B	0.9600
C7—H7B	0.9600	C36—H36C	0.9600
C7—H7C	0.9600	C37—C42	1.374 (4)
C8—C9	1.376 (4)	C37—C38	1.376 (4)
C8—C13	1.386 (4)	C38—C39	1.388 (4)
C9—C10	1.378 (4)	C38—H38	0.9300
C9—H9	0.9300	C39—C40	1.354 (5)
C10—C11	1.366 (4)	C39—H39	0.9300
C10—H10	0.9300	C40—C41	1.357 (5)
C11—C12	1.354 (5)	C41—C42	1.382 (4)
C12—C13	1.387 (4)	C41—H41	0.9300
C12—H12	0.9300	C42—H42	0.9300
C13—H13	0.9300
N1—Cu1—N2	79.16 (9)	C14—C15—H15C	109.5
N1—Cu1—N3	78.25 (9)	H15A—C15—H15C	109.5
N2—Cu1—N3	157.24 (8)	H15B—C15—H15C	109.5
N1—Cu1—Cl1	143.28 (7)	C17—C16—C21	120.3 (3)
N2—Cu1—Cl1	99.40 (6)	C17—C16—N3	120.2 (3)
N3—Cu1—Cl1	97.00 (6)	C21—C16—N3	119.4 (3)
N1—Cu1—Cl2	102.11 (7)	C16—C17—C18	119.4 (3)
N2—Cu1—Cl2	96.52 (6)	C16—C17—H17	120.3
N3—Cu1—Cl2	90.90 (7)	C18—C17—H17	120.3
Cl1—Cu1—Cl2	114.43 (3)	C19—C18—C17	118.4 (3)
Cl3—Cu2—Cl4	134.91 (3)	C19—C18—H18	120.8
Cl3—Cu2—Cl2	108.13 (3)	C17—C18—H18	120.8
Cl4—Cu2—Cl2	116.69 (3)	C20—C19—F2	119.0 (3)
N4—Cu3—N5	78.77 (9)	C20—C19—C18	122.8 (3)
N4—Cu3—N6	77.93 (9)	F2—C19—C18	118.2 (4)
N5—Cu3—N6	156.49 (9)	C19—C20—C21	118.7 (3)
N4—Cu3—Cl5	158.17 (7)	C19—C20—H20	120.6
N5—Cu3—Cl5	100.56 (6)	C21—C20—H20	120.6
N6—Cu3—Cl5	99.90 (6)	C20—C21—C16	120.3 (3)
N4—Cu3—Cl4	98.36 (6)	C20—C21—H21	119.8
N5—Cu3—Cl4	94.16 (6)	C16—C21—H21	119.8
N6—Cu3—Cl4	92.24 (6)	N4—C22—C23	120.8 (3)
Cl5—Cu3—Cl4	103.44 (3)	N4—C22—C35	112.3 (2)
Cu2—Cl2—Cu1	121.71 (3)	C23—C22—C35	126.9 (2)
Cu2—Cl4—Cu3	138.68 (4)	C22—C23—C24	118.8 (3)
C5—N1—C1	122.7 (2)	C22—C23—H23	120.6
C5—N1—Cu1	118.02 (18)	C24—C23—H23	120.6
C1—N1—Cu1	119.13 (18)	C23—C24—C25	119.8 (3)
C6—N2—C8	122.3 (2)	C23—C24—H24	120.1
C6—N2—Cu1	114.60 (17)	C25—C24—H24	120.1
C8—N2—Cu1	123.05 (16)	C24—C25—C26	118.8 (3)
C14—N3—C16	121.4 (2)	C24—C25—H25	120.6
C14—N3—Cu1	115.71 (18)	C26—C25—H25	120.6
C16—N3—Cu1	122.91 (16)	N4—C26—C25	120.0 (2)
C26—N4—C22	121.6 (2)	N4—C26—C27	112.9 (2)
C26—N4—Cu3	118.54 (17)	C25—C26—C27	127.1 (3)
C22—N4—Cu3	119.81 (17)	N5—C27—C26	114.9 (2)
C27—N5—C29	121.7 (2)	N5—C27—C28	126.8 (3)
C27—N5—Cu3	114.88 (17)	C26—C27—C28	118.3 (3)
C29—N5—Cu3	123.41 (17)	C27—C28—H28A	109.5
C35—N6—C37	118.7 (2)	C27—C28—H28B	109.5
C35—N6—Cu3	114.93 (17)	H28A—C28—H28B	109.5
C37—N6—Cu3	126.19 (16)	C27—C28—H28C	109.5
N1—C1—C2	120.2 (3)	H28A—C28—H28C	109.5
N1—C1—C14	112.3 (2)	H28B—C28—H28C	109.5
C2—C1—C14	127.4 (3)	C30—C29—C34	120.3 (3)
C3—C2—C1	117.9 (3)	C30—C29—N5	119.1 (2)
C3—C2—H2	121.0	C34—C29—N5	120.5 (2)
C1—C2—H2	121.0	C29—C30—C31	120.6 (3)
C2—C3—C4	121.2 (3)	C29—C30—H30	119.7
C2—C3—H3	119.4	C31—C30—H30	119.7
C4—C3—H3	119.4	C32—C31—C30	118.0 (3)
C3—C4—C5	118.2 (3)	C32—C31—H31	121.0
C3—C4—H4	120.9	C30—C31—H31	121.0
C5—C4—H4	120.9	C31—C32—F3	119.2 (3)
N1—C5—C4	119.7 (3)	C31—C32—C33	123.1 (3)
N1—C5—C6	113.2 (2)	F3—C32—C33	117.7 (3)
C4—C5—C6	127.0 (3)	C32—C33—C34	118.5 (3)
N2—C6—C5	114.9 (2)	C32—C33—H33	120.8
N2—C6—C7	126.4 (3)	C34—C33—H33	120.8
C5—C6—C7	118.6 (2)	C33—C34—C29	119.5 (3)
C6—C7—H7A	109.5	C33—C34—H34	120.2
C6—C7—H7B	109.5	C29—C34—H34	120.2
H7A—C7—H7B	109.5	N6—C35—C36	125.6 (3)
C6—C7—H7C	109.5	N6—C35—C22	114.8 (2)
H7A—C7—H7C	109.5	C36—C35—C22	119.5 (2)
H7B—C7—H7C	109.5	C35—C36—H36A	109.5
C9—C8—C13	120.0 (3)	C35—C36—H36B	109.5
C9—C8—N2	118.4 (2)	H36A—C36—H36B	109.5
C13—C8—N2	121.5 (2)	C35—C36—H36C	109.5
C8—C9—C10	120.3 (3)	H36A—C36—H36C	109.5
C8—C9—H9	119.8	H36B—C36—H36C	109.5
C10—C9—H9	119.8	C42—C37—C38	120.8 (3)
C11—C10—C9	118.5 (3)	C42—C37—N6	119.7 (2)
C11—C10—H10	120.8	C38—C37—N6	119.5 (2)
C9—C10—H10	120.8	C37—C38—C39	119.5 (3)
C12—C11—F1	119.0 (3)	C37—C38—H38	120.2
C12—C11—C10	122.8 (3)	C39—C38—H38	120.2
F1—C11—C10	118.2 (3)	C40—C39—C38	118.2 (3)
C11—C12—C13	118.9 (3)	C40—C39—H39	120.9
C11—C12—H12	120.5	C38—C39—H39	120.9
C13—C12—H12	120.5	C39—C40—C41	123.4 (3)
C8—C13—C12	119.5 (3)	C39—C40—F4	118.5 (3)
C8—C13—H13	120.2	C41—C40—F4	118.1 (3)
C12—C13—H13	120.2	C40—C41—C42	118.6 (3)
N3—C14—C15	126.1 (3)	C40—C41—H41	120.7
N3—C14—C1	114.4 (2)	C42—C41—H41	120.7
C15—C14—C1	119.4 (2)	C37—C42—C41	119.4 (3)
C14—C15—H15A	109.5	C37—C42—H42	120.3
C14—C15—H15B	109.5	C41—C42—H42	120.3
H15A—C15—H15B	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···Cl2	0.93	2.74	3.572 (3)	149
C7—H7B···Cg1	0.96	2.81	3.518 (3)	131
C36—H36C···Cl1^i	0.96	2.72	3.666 (3)	169
C10—H10···Cl1^ii	0.93	2.73	3.626 (3)	162
C13—H13···Cl1^i	0.93	2.81	3.428 (3)	125

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