Dichloro­[(1E,1'E)-1,1'-(pyridine-2,6-diyl)diethanone bis­(O-methyl­oxime)-[kappa]³N¹,N²,N⁶]copper(II)

In the title compound, [CuCl₂(C₁₁H₁₅N₃O₂)], the Cu^II ion is five-coordinated in a strongly distorted trigonal-bipyramidal arrangement, with the two methyl­oxime N atoms located in the apical positions, and the pyridine N and the Cl atoms located in the basal plane. The two axial Cu-N distances are almost equal (mean 2.098 Å) and are substantially longer than the equatorial Cu-N bond [1.9757 (15) Å]. It is observed that the N(oxime)-M-N(pyridine) bond angle for five-membered chelate rings of 2,6-diacetyl­pyridine dioxime complexes is inversely related to the magnitude of the M-N(pyridine) bond. The structure is stabilized by intra- and inter­molecular C-H...Cl hydrogen bonds which involve the methyl H atoms, except for one of the two acetyl­methyl groups.

S1. Comment

Remarkable advances in homogeneous catalyst technology have recently been achieved with systems comprising late transition metals and 2,6-bis(imino)pyridiyl ligands (Small & Brookhart, 1998, 1999; Britovsek et al., 1999). Upon coordination to a transition metal, the bis(chelate) framework may confer on such complexes interesting stoichiometric and catalytic reactivities (Çetinkaya et al., 1999; Dayan & Çetinkaya; 2005; Gibson & Spitzmesser, 2003). This family of catalysts has attracted great interest, both in academia and in industry (Gibson & Was, 1999; Bennett, 1999). Although a number of 2,6-diacetylpyridine dioxime-based Cu^II complexes have been reported (Glynn & Turnbull, 2002; Baugh et al., 2003; Chandra & Gupta, 2001, 2002; Singh et al., 1997; Abboud et al., 1994; Nicholson et al., 1980, 1982), the chemistry of the related 2,6-diacetylpyridine bis(O-methyloxime) complexes has been studied insufficiently. In addition, copper is an oligo-element with an essential role in a number of enzymes (Price, 1987). It has been demonstrated that Cu chelates are good anticonvulsant agents for the treatment of epileptic seizures. Moreover, many classes of Cu chelates, including amino acids, salicylates and Schiff bases, as well as Cu chelates of well known anti-epileptic drugs, are more effective anticonvulsants than the parent ligand (Viossat et al., 2003).

In the present study, the title new five-coordinate compound, (II), was synthesized in good yield (81%) by the reaction sequence depicted in the scheme. The composition of this complex has been confirmed by CHN analyses and IR spectroscopy. Understanding the shape of coordination polyhedra in the case of five-coordination is one of the current problems in coordination chemistry. In order to establish the coordination geometry about the metal and to examine the structural parameters in this case, we present here the synthesis and crystal structure of this mononuclear copper 2,6-diacetylpyridine bis(O-methyloxime) compound with two chloride ligands.

The molecular structure of complex (II), together with the atom-labelling scheme and the intramolecular hydrogen bonding, are shown in Fig. 1. Selected geometric parameters are listed in Table 1. The structure of the title complex is composed of a 2,6-diacetylpyridine bis(O-methyloxime) ligand with a Cu^II metal centre and two Cl ligands. As expected, complex (II) does not crystallize with solvent molecules and the ligand, (I), with its two imino groups in ortho positions with respect to the pyridine N atom, behaves as a symmetrical tridentate N,N',N-chelate. The Cu^II ion is pentacoordinated by two methyloxime N atoms, one pyridine N atom and two Cl atoms (Fig. 1). The five-membered chelate rings formed by atoms Cu1/N1/C1/C8/N3 and Cu1/N1/C5/C6/N2 are essentially planar and the maximum deviations from their planes are 0.0221 (9) and −0.0368 (11) Å, respectively, [for which atoms?]. These two chelate rings make a small dihedral angle of 2.37 (10)° with each other, 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. The question arises as to whether the coordination polyhedron around the Cu^II ion in complex (II) can be best described as a distorted square pyramid or a distorted trigonal bipyramid. Further information can be obtained by determining the structural index τ, which represents the relative amount of trigonality [square pyramid τ = 0 and 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 value of τ for the Cu^II ion in (II) is 0.53, indicating that the coordination geometry lies almost midway between a regular square pyramid (SQP) and a regular trigonal bipyramid (TBP), but can be accepted as a strongly distorted trigonal bipyramid, since the value of τ is a little closer to TBP than SQP, as can also be seen from the distances and angles around the metal (Table 1). Atoms Cl1, Cl2 and N1 act as the basal plane of the trigonal bipyramid, while the apical positions are occupied by atoms N2 and N3. In the axial direction, the N2—Cu1—N3 angle of the bipyramid deviates greatly from linearity. However, the bond angles within the basal plane have nearly the ideal value of 120° for a perfect TBP, and the apical N atoms are symmetrically disposed above and below the plane. This ligand disposition in (II) is consistent with approximate C_2v point group symmetry for the molecule. Atoms N1, Cl1 and Cl2 are coplanar, and the Cu^II ion is located in the middle of the base of the TBP, 0.0148 (5) Å out of the mean plane (toward N2) formed by the equatorial ligand atoms. The axial(ax)–equatorial(eq) angles fall into two groups, with N_ax—Cu—N_eq values in the range 76.66 (6)–76.85 (6)° and N_ax—Cu—Cl_eq in the range 93.72 (5)–99.73 (4)°, which also reflects the fact that the Cu atom is displaced out of the plane of the three equatorial atoms. In the molecular structure, the bond lengths of C6═N2 and C8═N3 conform to the value for a double bond, while those of N2—O1 and N3—O2 conform to the value for a single bond.

The Cu1—N2 and Cu1—N3 bond distances in the axial direction are longer than the Cu1—N1 bond in the equatorial plane. In addition, the basal Cu1—Cl2 distance is 0.02 Å longer than the other basal Cu1—Cl1 distance. Since the electronic ground state in this Cu^II complex is not likely to be degenerate, the observed variations in these bond distances are probably due to a second-order Jahn–Teller effect of the d⁹ metal atom. Pearson (1969) has examined this problem of molecular distortions with the aid of second-order perturbation theory and group theory. His analysis has shown that, for molecules with a nondegenerate ground state and low-lying excited states (within about 4 eV), only totally symmetric motions will occur until the energy of the molecule is minimized. Thus, the bond lengths and angles change to produce the lowest energy configuration that still retains the original point group symmetry of the molecule. The Jahn–Teller effect is also observed in the UV spectrum, in which complex (II) exhibits a weak transition at 565 nm corresponding to ²B_1g→²B_2g, which indicates the presence of fivefold coordination around Cu (Lever, 1984). A less intense band at 364 nm is due to the Jahn–Teller effect in the complex. The absorption band below 330 nm results from the overlap of a low-energy π–π^* transition mainly localized within the imine choromophore and the ligand-to-metal charge-transfer bands (LCMT).

There are several structures reported in the literature containing various metal complexes of 2,6-diacetylpyridine dioxime ligands (Sproul & Stucky, 1973; Nicholson et al., 1982; Abboud et al., 1994; Glynn & Turnbull, 2002). An examination of the M—N bond distances in (II) and in these examples indicates that the two M—N(oxime) bonds are ca 0.1–0.2 Å longer than the corresponding M—N(pyridine) bond within each metal–tridentate chelate unit. This structural feature contrasts with that observed for α-amine oxime (Liss & Schlemper, 1975; Gavel & Schlemper; 1979; Curtis et al., 2004) and trinuclear Cu^II oxime complexes (Ross et al., 1974). In these particular systems, the trend is reversed, with the Cu—N(oxime) distances consistently 0.03–0.07 Å shorter than the interior Cu—N(amine) distances. Finally, it is observed that the N(oxime)—M—N(pyridine) bond angle for the five-membered chelate rings of 2,6-diacetylpyridine dioxime complexes is inversely related to the magnitude of the M—N(pyridine) bond. As the M—N(pyridine) distance increases from 1.837 (4) Å for Ni(DAPD)₂ (DAPD is 2,6-diacetylpyridine dioximate; Sproul & Stucky, 1973) to 1.9757 (15) Å for (II) to 2.063 (2) Å for Zn(DAPDH₂)Cl₂ (DAPDH₂ is 2,6-diacetylpyridine dioxime; Nicholson et al., 1982) to 2.180 (5) Å (average) for [Mn(DAPDH₂)₂](ClO₄)₂ (Glynn & Turnbull, 2002), the corresponding inner `bite' angle decreases continually from 82.4 (average) to 76.76 (average) to 73.7 (average) to 70.65° (average), respectively.

In the molecular structure of (II), three intramolecular interactions are observed between the methyl H and Cl atoms, forming six-membered rings. In the construction of the intermolecular connections, 2₁ screw symmetry-related molecules, which form pairs of neighbouring molecules translated linearly along the b axis of the unit cell, play an active bridging role. Atom C7 acts as a hydrogen-bond donor, via atom H7B, to atom Cl1 at (1 − x, −1/2 + y, −1/2 − z). Extension of this hydrogen-bonding interaction along b in a zigzag arrangement results in the formation of molecular chains along the [010] direction (Fig. 2). There are no intermolecular interactions in the a or c directions. The full geometry of the intra- and intermolecular interactions is given in Table 2.

S2. 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) and methoxylaminehydrochloride (Acros) were used as received. Compound (I) was prepared by a modification of the method of Çetinkaya (Çetinkaya et al., 1999; Dayan & Çetinkaya; 2005; Gibson & Spitzmesser, 2003). Solvents were of analytical grade and were distilled after drying. A solution of CuCl₂·2H₂0 (77 mg, 0.45 mmol) in ethanol (10 ml) was added dropwise to a solution of (I) (100 mg, 0.45 mmol) in ethanol (10 m). The resulting brown solution was refluxed for 4 h and then concentrated (5 ml). Et₂O was added dropwise with stirring to a final volume of 20 ml, causing a brown powder to precipitate. The brown precipitate was filtered off, washed with Et₂O and dried. X-ray quality crystals of (II) were grown from a solution in CH₂Cl₂–Et₂O (Ratio?) (yield 130 mg, 81%; m.p. 483–485 K). Analysis, calculated for C₁₁H₁₅Cl₂CuN₃O₂: C 37.14, H 4.25, N 11.81%; found: C 36.92, H 4.1, N 11.56. IR (KBr): 1621 (ν_C═N) cm⁻¹.

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 CH(aromatic), respectively. The displacement parameters of the H atoms were constrained as U_iso(H) = 1.2U_eq (1.5U_eq for methyl) of the parent atom.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); 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 40% probability displacement ellipsoids and the atom-numbering scheme. Intramolecular C—H···Cl contacts are represented by dashed lines.
	Fig. 2. The molecular packing of (II), viewed along the a axis. Dashed lines show the C—H···Cl interactions. For clarity, only H atoms involved in hydrogen bonding have been included.

Dichloro[(1E,1'E)-1,1'-(pyridine-2,6-diyl)diethanone bis(O-methyloxime)-κ²N²,N⁶]copper(II)

Crystal data

[CuCl2(C11H15N3O2)]	F(000) = 724
Mr = 355.70	Dx = 1.639 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 19775 reflections
a = 11.1308 (6) Å	θ = 2.0–28.0°
b = 10.4656 (5) Å	µ = 1.89 mm^−1
c = 13.6747 (7) Å	T = 296 K
β = 115.152 (4)°	Prism, brown
V = 1441.93 (13) Å^3	0.54 × 0.51 × 0.48 mm
Z = 4

Data collection

Stoe IPDS-2 diffractometer	3441 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	3005 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.070
Detector resolution: 6.67 pixels mm^-1	θmax = 28.0°, θmin = 2.0°
ω scans	h = −14→14
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −13→13
Tmin = 0.309, Tmax = 0.574	l = −17→17
19881 measured reflections

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)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.087	w = 1/[σ^2(Fo^2) + (0.0466P)^2 + 0.2674P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
3441 reflections	Δρmax = 0.35 e Å^−3
177 parameters	Δρmin = −0.35 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0389 (19)

Special details

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

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

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

	x	y	z	Uiso*/Ueq
Cu1	0.77272 (2)	0.74169 (2)	0.007730 (19)	0.04304 (11)
Cl1	0.70923 (6)	0.94929 (5)	−0.03353 (5)	0.06060 (16)
Cl2	0.85236 (5)	0.67678 (5)	0.18535 (4)	0.04995 (14)
O1	0.47555 (17)	0.7102 (2)	−0.01732 (17)	0.0712 (5)
O2	1.06819 (14)	0.82100 (15)	0.06380 (14)	0.0592 (4)
N1	0.75633 (15)	0.61571 (14)	−0.10487 (12)	0.0401 (3)
N2	0.57576 (16)	0.67441 (16)	−0.04581 (14)	0.0490 (4)
N3	0.95809 (17)	0.74838 (14)	0.00503 (14)	0.0430 (4)
C1	0.86158 (18)	0.59136 (17)	−0.12398 (14)	0.0406 (4)
C2	0.8548 (2)	0.50059 (19)	−0.20008 (17)	0.0508 (4)
H2	0.9286	0.4816	−0.2126	0.061*
C3	0.7353 (2)	0.4393 (2)	−0.25663 (18)	0.0584 (5)
H3	0.7285	0.3783	−0.3082	0.070*
C4	0.6255 (2)	0.4671 (2)	−0.23789 (16)	0.0524 (5)
H4	0.5445	0.4270	−0.2771	0.063*
C5	0.63961 (18)	0.55652 (17)	−0.15900 (14)	0.0429 (4)
C6	0.53517 (18)	0.59693 (18)	−0.12595 (16)	0.0463 (4)
C7	0.3949 (2)	0.5534 (3)	−0.1836 (2)	0.0658 (6)
H7A	0.3718	0.5025	−0.1357	0.099*
H7B	0.3852	0.5032	−0.2453	0.099*
H7C	0.3374	0.6264	−0.2069	0.099*
C8	0.97867 (18)	0.66997 (17)	−0.05916 (15)	0.0420 (4)
C9	1.1057 (2)	0.6609 (2)	−0.06907 (18)	0.0548 (5)
H9A	1.1107	0.7285	−0.1146	0.082*
H9B	1.1105	0.5799	−0.1003	0.082*
H9C	1.1782	0.6682	0.0012	0.082*
C10	0.5196 (3)	0.7919 (3)	0.0747 (2)	0.0651 (6)
H10A	0.5890	0.7503	0.1348	0.098*
H10B	0.4467	0.8102	0.0925	0.098*
H10C	0.5527	0.8701	0.0589	0.098*
C11	1.0446 (2)	0.9154 (2)	0.12911 (18)	0.0562 (5)
H11A	0.9638	0.9601	0.0867	0.084*
H11B	1.1172	0.9749	0.1554	0.084*
H11C	1.0371	0.8747	0.1892	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03261 (15)	0.04739 (15)	0.04619 (16)	−0.00063 (8)	0.01392 (11)	−0.00733 (8)
Cl1	0.0504 (3)	0.0532 (3)	0.0718 (3)	0.0132 (2)	0.0198 (2)	0.0166 (2)
Cl2	0.0469 (3)	0.0533 (3)	0.0466 (3)	0.00199 (18)	0.0170 (2)	0.00630 (18)
O1	0.0409 (8)	0.0915 (11)	0.0839 (12)	−0.0058 (8)	0.0294 (9)	−0.0309 (10)
O2	0.0359 (7)	0.0648 (9)	0.0730 (10)	−0.0113 (6)	0.0194 (7)	−0.0206 (7)
N1	0.0347 (7)	0.0442 (7)	0.0382 (7)	0.0006 (5)	0.0123 (6)	−0.0012 (6)
N2	0.0317 (7)	0.0572 (9)	0.0565 (9)	0.0002 (6)	0.0172 (7)	−0.0087 (7)
N3	0.0331 (8)	0.0482 (8)	0.0446 (9)	−0.0032 (5)	0.0134 (7)	−0.0026 (6)
C1	0.0388 (9)	0.0442 (8)	0.0382 (8)	0.0035 (7)	0.0157 (7)	0.0036 (6)
C2	0.0534 (11)	0.0520 (10)	0.0512 (11)	0.0041 (8)	0.0262 (9)	−0.0022 (8)
C3	0.0664 (14)	0.0548 (12)	0.0536 (12)	−0.0023 (9)	0.0251 (11)	−0.0135 (9)
C4	0.0495 (11)	0.0524 (10)	0.0477 (11)	−0.0067 (8)	0.0134 (9)	−0.0086 (8)
C5	0.0362 (8)	0.0454 (9)	0.0391 (9)	−0.0018 (7)	0.0083 (7)	−0.0009 (7)
C6	0.0339 (9)	0.0507 (10)	0.0484 (10)	−0.0036 (7)	0.0120 (8)	−0.0016 (7)
C7	0.0387 (10)	0.0805 (15)	0.0714 (15)	−0.0154 (10)	0.0167 (10)	−0.0175 (12)
C8	0.0356 (8)	0.0483 (9)	0.0412 (9)	0.0036 (7)	0.0154 (7)	0.0049 (7)
C9	0.0408 (10)	0.0681 (13)	0.0595 (12)	0.0011 (9)	0.0253 (9)	−0.0002 (9)
C10	0.0584 (14)	0.0702 (14)	0.0742 (16)	0.0055 (11)	0.0354 (12)	−0.0147 (12)
C11	0.0489 (11)	0.0616 (12)	0.0521 (11)	−0.0101 (9)	0.0158 (9)	−0.0128 (9)

Geometric parameters (Å, º)

Cu1—N1	1.9757 (15)	C3—H3	0.9300
Cu1—N3	2.0805 (18)	C4—C5	1.385 (3)
Cu1—N2	2.1151 (16)	C4—H4	0.9300
Cu1—Cl1	2.2802 (6)	C5—C6	1.477 (3)
Cu1—Cl2	2.3057 (5)	C6—C7	1.490 (3)
O1—N2	1.380 (2)	C7—H7A	0.9600
O1—C10	1.425 (3)	C7—H7B	0.9600
O2—N3	1.374 (2)	C7—H7C	0.9600
O2—C11	1.429 (3)	C8—C9	1.480 (3)
N1—C1	1.329 (2)	C9—H9A	0.9600
N1—C5	1.342 (2)	C9—H9B	0.9600
N2—C6	1.281 (3)	C9—H9C	0.9600
N3—C8	1.291 (2)	C10—H10A	0.9600
C1—C2	1.387 (3)	C10—H10B	0.9600
C1—C8	1.476 (3)	C10—H10C	0.9600
C2—C3	1.380 (3)	C11—H11A	0.9600
C2—H2	0.9300	C11—H11B	0.9600
C3—C4	1.383 (3)	C11—H11C	0.9600
N1—Cu1—N3	76.85 (6)	N1—C5—C4	120.28 (18)
N1—Cu1—N2	76.66 (6)	N1—C5—C6	113.72 (16)
N3—Cu1—N2	153.50 (6)	C4—C5—C6	126.01 (17)
N1—Cu1—Cl1	121.79 (5)	N2—C6—C5	113.94 (16)
N3—Cu1—Cl1	99.73 (4)	N2—C6—C7	123.7 (2)
N2—Cu1—Cl1	93.72 (5)	C5—C6—C7	122.33 (18)
N1—Cu1—Cl2	119.42 (5)	C6—C7—H7A	109.5
N3—Cu1—Cl2	95.08 (5)	C6—C7—H7B	109.5
N2—Cu1—Cl2	98.31 (5)	H7A—C7—H7B	109.5
Cl1—Cu1—Cl2	118.77 (2)	C6—C7—H7C	109.5
N2—O1—C10	113.34 (16)	H7A—C7—H7C	109.5
N3—O2—C11	113.15 (15)	H7B—C7—H7C	109.5
C1—N1—C5	122.04 (16)	N3—C8—C1	113.33 (16)
C1—N1—Cu1	118.95 (12)	N3—C8—C9	123.75 (18)
C5—N1—Cu1	119.01 (13)	C1—C8—C9	122.90 (17)
C6—N2—O1	112.30 (16)	C8—C9—H9A	109.5
C6—N2—Cu1	116.33 (13)	C8—C9—H9B	109.5
O1—N2—Cu1	130.92 (13)	H9A—C9—H9B	109.5
C8—N3—O2	112.17 (16)	C8—C9—H9C	109.5
C8—N3—Cu1	117.03 (13)	H9A—C9—H9C	109.5
O2—N3—Cu1	130.76 (12)	H9B—C9—H9C	109.5
N1—C1—C2	120.48 (18)	O1—C10—H10A	109.5
N1—C1—C8	113.71 (15)	O1—C10—H10B	109.5
C2—C1—C8	125.80 (18)	H10A—C10—H10B	109.5
C3—C2—C1	118.10 (19)	O1—C10—H10C	109.5
C3—C2—H2	121.0	H10A—C10—H10C	109.5
C1—C2—H2	121.0	H10B—C10—H10C	109.5
C2—C3—C4	121.05 (19)	O2—C11—H11A	109.5
C2—C3—H3	119.5	O2—C11—H11B	109.5
C4—C3—H3	119.5	H11A—C11—H11B	109.5
C3—C4—C5	118.02 (19)	O2—C11—H11C	109.5
C3—C4—H4	121.0	H11A—C11—H11C	109.5
C5—C4—H4	121.0	H11B—C11—H11C	109.5
N3—Cu1—N1—C1	3.20 (13)	Cu1—N1—C1—C2	177.98 (14)
N2—Cu1—N1—C1	−177.33 (14)	C5—N1—C1—C8	177.69 (16)
Cl1—Cu1—N1—C1	96.60 (13)	Cu1—N1—C1—C8	−2.9 (2)
Cl2—Cu1—N1—C1	−85.22 (13)	N1—C1—C2—C3	1.6 (3)
N3—Cu1—N1—C5	−177.40 (15)	C8—C1—C2—C3	−177.40 (19)
N2—Cu1—N1—C5	2.07 (13)	C1—C2—C3—C4	−0.2 (3)
Cl1—Cu1—N1—C5	−84.00 (14)	C2—C3—C4—C5	−1.3 (3)
Cl2—Cu1—N1—C5	94.18 (13)	C1—N1—C5—C4	−0.2 (3)
C10—O1—N2—C6	177.3 (2)	Cu1—N1—C5—C4	−179.58 (14)
C10—O1—N2—Cu1	−10.7 (3)	C1—N1—C5—C6	−179.96 (16)
N1—Cu1—N2—C6	−5.02 (15)	Cu1—N1—C5—C6	0.7 (2)
N3—Cu1—N2—C6	−3.9 (3)	C3—C4—C5—N1	1.5 (3)
Cl1—Cu1—N2—C6	116.79 (15)	C3—C4—C5—C6	−178.7 (2)
Cl2—Cu1—N2—C6	−123.41 (15)	O1—N2—C6—C5	179.92 (18)
N1—Cu1—N2—O1	−176.7 (2)	Cu1—N2—C6—C5	6.7 (2)
N3—Cu1—N2—O1	−175.55 (17)	O1—N2—C6—C7	1.6 (3)
Cl1—Cu1—N2—O1	−54.9 (2)	Cu1—N2—C6—C7	−171.63 (18)
Cl2—Cu1—N2—O1	64.9 (2)	N1—C5—C6—N2	−4.9 (3)
C11—O2—N3—C8	175.35 (18)	C4—C5—C6—N2	175.31 (19)
C11—O2—N3—Cu1	−7.0 (3)	N1—C5—C6—C7	173.4 (2)
N1—Cu1—N3—C8	−3.07 (14)	C4—C5—C6—C7	−6.3 (3)
N2—Cu1—N3—C8	−4.2 (2)	O2—N3—C8—C1	−179.55 (15)
Cl1—Cu1—N3—C8	−123.65 (13)	Cu1—N3—C8—C1	2.4 (2)
Cl2—Cu1—N3—C8	115.99 (14)	O2—N3—C8—C9	−0.8 (3)
N1—Cu1—N3—O2	179.35 (18)	Cu1—N3—C8—C9	−178.77 (15)
N2—Cu1—N3—O2	178.20 (16)	N1—C1—C8—N3	0.2 (2)
Cl1—Cu1—N3—O2	58.77 (17)	C2—C1—C8—N3	179.23 (18)
Cl2—Cu1—N3—O2	−61.59 (17)	N1—C1—C8—C9	−178.61 (17)
C5—N1—C1—C2	−1.4 (3)	C2—C1—C8—C9	0.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···Cl1	0.96	2.60	3.457 (2)	148
C10—H10C···Cl1	0.96	2.68	3.467 (3)	139
C10—H10A···Cl2	0.96	2.82	3.563 (3)	135
C7—H7B···Cl1^i	0.96	2.81	3.700 (3)	155

Symmetry code: (i) −x+1, y−1/2, −z−1/2.