Di-μ-chlorido-bis­({2-[1-(2-pyridyl­ethyl­imino)eth­yl]pyrrolato-κ³N,N′,N′′}­copper(II))

The title compound, [Cu₂(C₁₃H₁₄N₃)₂Cl₂], is a neutral dimeric copper(II) complex. The two Cu^II atoms are asymmetrically bridged by two chloride ions. Each Cu^II atom is also bound to the three N atoms of a deprotonated tridentate Schiff base ligand, giving a distorted square-pyramidal N₃Cl₂ coordination environment overall. The dinuclear complex lies across an inversion centre in the space group P. This work demonstrates the effect of ligand flexibility and steric constraints on the structures of copper(II) complexes.

S1. Comment

In recent years, much attention has been paid to the complexes of a wide range of acyclic Schiff base ligands, in particular pyridine-containing systems. However, much less is known about complexes of the pyrrole analogues of such ligands, despite their potentially interesting similarities to porphyrins. Recently, our focus has been on the copper(II) chemistry of N₃ tridentate Schiff base ligands, in particular mixed pyrrole–imine–pyridine ligands. Ligands L₁^-, L₂^- and L₃^-, the deprotonated forms of HL₁, HL₂ and HL₃ {where HL₁ is N-(1H-pyrrol-2-ylmethylene)-2-pyridineethanamine, HL₂ is N-(1-(1H-pyrrol-2-yl)ethylidene)(pyridin-2-yl)methanamine and HL₃ is N-[1-(1H-pyrrol-2-yl)ethylidene]-2-(pyridine-2-yl)ethanamine}, are of this type.

These ligands are closely related to pyridine–imine–pyridine ligands, which have been well studied (Arriortua et al., 1991; Cortés et al., 1992, 1995; Garland et al., 1996; Larramendi et al., 1991; Larramendi et al., 1992; Rojo et al., 1990). In our previous work using ligands L₁^- and L₂^-, monomeric, dimeric and one-dimensional chain polymeric copper(II) complexes have been synthesized (Li, Moubaraki et al., 2008; Li, Zhao et al., 2008), depending on the nature of the ligand and the choice of halide or pseudohalide coligand. Among these complexes, the dimeric and one-dimensional chain polymeric complexes exhibit weak antiferromagnetic exchange.

These examples, together with those obtained with the pyridine–imine–pyridine ligands mentioned above, indicate that the use of less flexible tridentate ligands tends to result in the formation of monomeric and dimeric complexes, while the use of more flexible tridentate ligands tends to give rise to dimeric or polymeric complexes. Ligand L₃^- is very closely related to L₁^- and L₂^-, with its flexibility being similar to that of L₁^- but greater than that of L₂^-. In addition, attachment of a methyl substituent to the C atom of the imino C═N bond of L₁^-, which results in L₃^-, imposes some steric constraints on L₃^-. These differences in ligand flexibility and steric constraints are expected to influence the structural properties of the complexes of this ligand. The title compound, [Cu₂(µ-Cl)₂(L₃)₂], (I), has been prepared using L₃^- as the next example within the framework of our ongoing studies. We report here the crystal structure of (I) and compare it with those of the copper(II) complexes of ligands L₁^-, L₂^- and some other reported closely related tridentate ligands.

The asymmetric unit of (I) (Fig. 1) contains one-half of the neutral dimeric molecule; the other half is generated by a centre of inversion. The two Cu^II ions are asymmetrically bridged by two Cl^- ions. Each Cu atom is also bound to the three N atoms (one deprotonated pyrrole N donor, one pyridine N donor and one imine N donor) of the tridentate ligand, L₃^-, giving an N₃Cl₂ coordination environment overall. The coordination geometry about each Cu^II ion can be described as a distorted square pyramid according to the τ value of 0.14 (Addison et al., 1984). The basal coordination sites are occupied by the three N atoms of L₃^- and one bridging Cl^- ion, Cl1. The apical position is occupied by the second bridging Cl^- ion, Cl1ⁱ [symmetry code: (i) -x + 1, -y, -z]. The apical Cu—Cl bond is significantly longer than the basal Cu—Cl bond (Table 1), a feature which appears frequently in square-pyramidal copper(II) complexes (Urtiaga et al., 1996; Rojo et al., 1987). The coordination mode and geometry about the Cu^II ions in (I) are very similar to those observed for the Cu^II ions in the analogous doubly halide-bridged dimers of ligand L₁^-, [Cu₂(L₁)₂(µ-X)₂] [X = Cl^-, (II); X = Br^-, (III)] (Li, Moubaraki et al., 2008). However, the low completeness of the dataset for complex (II) prevents detailed comparison of the geometric parameters between structures (I) and (II). On the other hand, the chloridocopper(II) complex of ligand L₂^- is a monomer, [Cu(L₂)Cl], (IV), and the central Cu^II ion is bound to the three N atoms of L₂^- and to one Cl^- ion in a square-planar N₃Cl coordination (Li, Zhao et al., 2008). So the coordination mode and arrangement of donor atoms around the Cu^II centre in (IV) are different from those observed for the copper(II) dimers of L₁^- and L₃^-, (I)–(III).

Of the three basal Cu—N bond distances in (I), the shortest (Cu1—N1) occurs between the Cu atom and the deprotonated negatively charged pyrrole N atom and the longest (Cu1—N3) between the Cu atom and the pyridine N donor which is trans to the pyrrole N atom. This phenomenon was also seen in (II)–(IV). In the coordination polyhedron, the average value of the Cl(apical)—Cu1—atom(basal) angles is 96.0°, while the average value of the cis basal angles is 89.5°. The three Cu—N basal bond distances and one cis basal angle (N1—Cu1—N2) in (I) are very close to those in (III) and (IV). The other three cis basal angles in (I) are quite different from those in (IV), although they are very similar to the corresponding ones in (III). As expected, the cis basal angle N2—Cu1—N3 in (I) [90.17 (11)°] is much larger than that in (IV) [80.55 (9)°], since in (I) it forms in the six-membered pyridine–imine chelate, while in (IV) it forms in the five-membered pyridine–imine chelate. On the other hand, the two cis N—Cu—Cl basal angles in (I) are smaller than those in (IV). These bond distances and angles also compare well with the values reported for related copper(II) complexes (Bertrand & Kirkwood, 1972; Brooker & Carter, 1995; Colacio et al., 2000; Larramendi et al., 1991; Matsumoto et al., 1999). It is worth noting that the Cu—N3 distance lies at the high end of the literature values. This is probably because of the strong bond between the deprotonated negatively charged pyrrole N atom and the Cu^II atom.

The two basal planes, N1/N2/N3/Cl1 and N1ⁱ/N2ⁱ/N3ⁱ/Cl1ⁱ, are exactly parallel to each other, by symmetry, and the average distance between them is just 2.922 Å. The four basal atoms are closely coplanar, with a maximum deviation from the mean basal plane of only 0.0773 (14) Å observed for the imine atom N2. The Cu atom is located 0.2063 (13) Å out of the basal plane towards the apical ligand.

The bridging Cu₂Cl₂ core is exactly planar, due to the presence of the crystallographic inversion centre in the middle of the dimer, and is approximately rectangular with angles Cu1—Cl1—Cu1ⁱ = 90.85 (4)° and Cl1—Cu1—Cl1ⁱ = 89.15 (4)°. The same type of bridging Cu₂X₂ core was also found in (II) (X = Cl^-) and (III) (X = Br^-), as well as in [Cu₂(apyhist)₂(µ-Cl)₂](ClO₄)₂ [apyhist = (4-imidazolyl)ethylene-2-amino-1-ethylpyridine], (V) (Alves et al., 2003), and [Cu₂(terpy)₂(µ-Cl)₂](PF₆)₂ (terpy = 2,2':6',2''-terpyridine), (VI) (Rojo et al., 1987). These angles are close to the corresponding angles in (III) [Cu—Br—Cuⁱ = 88.23 (5)° and Br—Cu—Brⁱ = 91.77 (5)°]. The Cu₂Cl₂ plane is nearly perpendicular to the basal N₃Cl planes, with a dihedral angle of 87.40 (5)°, which is smaller than the corresponding angle in (III) [97.75 (6)°]. The intramolecular Cu···Cu separation is 3.5573 (14) Å, which is, as expected, shorter than in (III) [3.7721 (27) Å]. However, (I) has a slightly longer Cu···Cu separation compared with that in (V) [3.478 (1) Å] and (VI) [3.510 (14) Å]. This is presumably because (I) has a longer Cu—Cl(basal) bond distance and a larger Cu—Cl—Cuⁱ bond angle in comparison with the corresponding values in (V) [2.271 (1) Å and 87.46 (4)°] and (VI) [2.218 (19) Å and 89.9 (2)°].

Ligands L₁^-, L₂^- and L₃^- are very closely related to each other. However, complexation of them with CuCl₂ gives two different structural types, monomer and dimer. Examination of these ligands shows that L₁^- and L₃^- have similar flexibility but both ligands are more flexible than L₂^-. Correspondingly, copper(II) dimers (I) and (II) formed with L₃^- and L₁^-, respectively, while the copper(II) monomer, (IV), was obtained with L₂^-. It is probably the reduced flexibility and greater steric constraint of L₂^- that results in the formation of such a monomer. In addition, comparison of (I) and (II) indicates that attachment of a bulky methyl substituent to the imino C atom of L₁^-, which gives L₃^- and imposes some steric constraints on L₃^-, makes (I) more distorted towards trigonal–bipyramidal than (II) [τ = 0.14 for (I) and nearly zero for (II)], although the imposed steric constrains have no influence on the dimerization of the [Cu(L₃)Cl] unit to form the dimer (I), [Cu₂(L₃)₂(µ-Cl)₂]. However, the introduction of a bulky Br substituent at the β position on the pyrrole ring of L₁^- results in the formation of a singly bromide-bridged one-dimensional chain polymeric copper(II) complex (Li, Moubaraki et al., 2008).

Related literature

For related literature, see: Addison et al. (1984); Alves et al. (2003); Arriortua et al. (1991); Bertrand & Kirkwood (1972); Brooker & Carter (1995); Colacio et al. (2000); Cortés et al. (1992, 1995); Garland et al. (1996); Larramendi et al. (1991, 1992); Li, Moubaraki, Murray & Brooker (2008); Li, Zhao, Tang & Tao (2008); Matsumoto et al. (1999); Rojo et al. (1987, 1990); Urtiaga et al. (1996).

S2. Experimental

Ligand HL₃ was synthesized from the condensation of 2-acetylpyrrole with 2-(2-aminoethyl)pyridine. To a solution of HL₃ (0.340 mmol) in methanol (5 ml) was added triethylamine (0.347 mmol) in methanol (5 ml). To the resulting solution was added a green solution of copper(II) chloride dihydrate (0.338 mmol) in methanol (5 ml), and a precipitate formed. The resulting mixture was stirred for 3.5 h, after which the solid was collected by filtration, washed with methanol and dried in vacuo (yield 0.083 g, 79% based on copper(II) chloride used). Single crystals of complex (I) suitable for X-ray determination were obtained by vapour diffusion of diethyl ether into a dichloromethane solution. Analysis, found: C 50.15, H 4.65, N 13.44%; calculated for C₂₆H₂₈N₆Cu₂Cl₂: C 50.16, H 4.53, N, 13.50%.

S3. Refinement

H atoms were positioned geometrically and refined using a riding model, with C—H bonds = 0.93–0.98 Å, and with U_iso (H) = 1.2U_eq(C), or 1.5U_eq(C) for the methyl group.

Computing details

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); data reduction: CrystalStructure (Molecular Structure Corporation & Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

Fig. 1. A view of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (i) -x + 1,-y,-z.]

Bis(µ₂-chlorido)-bis{2-[1-(2-pyridylethylimino)ethyl]pyrrolato- κ³N,N',N''}dicopper(II)

Crystal data

[Cu2Cl2(C13H14N3)2]	Z = 1
Mr = 622.54	F(000) = 318
Triclinic, P1	Dx = 1.643 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 8.122 (2) Å	Cell parameters from 2087 reflections
b = 8.412 (3) Å	θ = 3.2–25.3°
c = 9.240 (3) Å	µ = 1.93 mm^−1
α = 91.973 (8)°	T = 213 K
β = 93.386 (9)°	Block, green-blue
γ = 92.464 (8)°	0.42 × 0.20 × 0.05 mm
V = 629.2 (3) Å^3

Data collection

Rigaku Mercury CCD diffractometer	2286 independent reflections
Radiation source: fine-focus sealed tube	1939 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Detector resolution: 7.31 pixels mm^-1	θmax = 25.3°, θmin = 3.2°
ω scans	h = −9→9
Absorption correction: multi-scan (Jacobson, 1998)	k = −9→10
Tmin = 0.531, Tmax = 0.908	l = −11→11
6145 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0281P)^2 + 0.5114P] where P = (Fo^2 + 2Fc^2)/3
2286 reflections	(Δ/σ)max < 0.001
165 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.35 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
Cu1	0.47083 (5)	0.02517 (5)	0.18855 (4)	0.02431 (15)
Cl1	0.67831 (10)	0.11924 (10)	0.04848 (9)	0.0263 (2)
N1	0.6040 (3)	−0.1449 (3)	0.2636 (3)	0.0252 (7)
N2	0.3179 (3)	−0.0567 (3)	0.3349 (3)	0.0228 (6)
N3	0.3426 (3)	0.2280 (3)	0.1740 (3)	0.0242 (6)
C1	0.7456 (4)	−0.2176 (4)	0.2406 (4)	0.0296 (8)
H1	0.8160	−0.1930	0.1665	0.036*
C2	0.7729 (5)	−0.3335 (4)	0.3409 (4)	0.0334 (9)
H2	0.8629	−0.4001	0.3470	0.040*
C3	0.6419 (5)	−0.3322 (4)	0.4309 (4)	0.0309 (9)
H3	0.6257	−0.3977	0.5097	0.037*
C4	0.5394 (4)	−0.2152 (4)	0.3813 (4)	0.0232 (8)
C5	0.3788 (4)	−0.1650 (4)	0.4159 (4)	0.0251 (8)
C6	0.1539 (4)	−0.0004 (4)	0.3542 (4)	0.0319 (9)
H6A	0.1583	0.0793	0.4343	0.038*
H6B	0.0798	−0.0893	0.3782	0.038*
C7	0.0886 (4)	0.0727 (4)	0.2152 (4)	0.0294 (8)
H7A	0.0999	−0.0026	0.1335	0.035*
H7B	−0.0293	0.0906	0.2218	0.035*
C8	0.1770 (4)	0.2272 (4)	0.1861 (4)	0.0275 (8)
C9	0.0917 (5)	0.3663 (5)	0.1745 (4)	0.0383 (10)
H9	−0.0234	0.3631	0.1811	0.046*
C10	0.1749 (5)	0.5083 (5)	0.1534 (4)	0.0415 (10)
H10	0.1174	0.6025	0.1451	0.050*
C11	0.3434 (5)	0.5108 (4)	0.1447 (4)	0.0336 (9)
H11	0.4040	0.6066	0.1326	0.040*
C12	0.4205 (5)	0.3698 (4)	0.1542 (4)	0.0283 (8)
H12	0.5354	0.3718	0.1464	0.034*
C13	0.2892 (5)	−0.2385 (5)	0.5360 (4)	0.0347 (9)
H13A	0.2585	−0.1554	0.6034	0.052*
H13B	0.3605	−0.3106	0.5867	0.052*
H13C	0.1905	−0.2970	0.4957	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0218 (2)	0.0254 (3)	0.0263 (3)	0.00143 (17)	0.00315 (18)	0.00524 (18)
Cl1	0.0213 (4)	0.0301 (5)	0.0277 (5)	−0.0012 (4)	0.0033 (4)	0.0043 (4)
N1	0.0226 (16)	0.0242 (16)	0.0293 (17)	0.0005 (12)	0.0037 (13)	0.0046 (12)
N2	0.0251 (15)	0.0206 (15)	0.0230 (16)	0.0020 (12)	0.0038 (13)	0.0012 (12)
N3	0.0252 (16)	0.0260 (16)	0.0214 (15)	−0.0014 (13)	0.0004 (13)	0.0039 (12)
C1	0.026 (2)	0.027 (2)	0.036 (2)	−0.0001 (16)	0.0038 (17)	−0.0008 (16)
C2	0.028 (2)	0.029 (2)	0.044 (2)	0.0067 (16)	0.0006 (18)	0.0033 (17)
C3	0.038 (2)	0.026 (2)	0.029 (2)	0.0011 (16)	−0.0016 (17)	0.0046 (15)
C4	0.0278 (19)	0.0218 (18)	0.0196 (18)	−0.0015 (15)	−0.0003 (15)	−0.0021 (14)
C5	0.030 (2)	0.0237 (18)	0.0208 (18)	−0.0061 (15)	0.0019 (16)	−0.0018 (14)
C6	0.025 (2)	0.033 (2)	0.039 (2)	0.0004 (16)	0.0056 (17)	0.0033 (17)
C7	0.0206 (19)	0.035 (2)	0.032 (2)	0.0020 (16)	0.0021 (16)	−0.0001 (16)
C8	0.0247 (19)	0.035 (2)	0.0232 (19)	0.0032 (16)	0.0012 (16)	−0.0003 (15)
C9	0.029 (2)	0.043 (3)	0.044 (2)	0.0130 (19)	0.0019 (19)	0.0046 (19)
C10	0.052 (3)	0.030 (2)	0.043 (2)	0.015 (2)	0.001 (2)	0.0021 (18)
C11	0.052 (3)	0.025 (2)	0.025 (2)	0.0031 (18)	0.0066 (19)	0.0057 (15)
C12	0.033 (2)	0.029 (2)	0.0227 (19)	−0.0005 (17)	0.0020 (16)	0.0018 (15)
C13	0.040 (2)	0.038 (2)	0.027 (2)	0.0008 (18)	0.0084 (18)	0.0097 (17)

Geometric parameters (Å, º)

Cu1—N1	1.952 (3)	C5—C13	1.499 (5)
Cu1—N2	2.009 (3)	C6—C7	1.520 (5)
Cu1—N3	2.041 (3)	C6—H6A	0.9800
Cu1—Cl1	2.3139 (10)	C6—H6B	0.9800
Cu1—Cl1^i	2.6676 (11)	C7—C8	1.498 (5)
Cl1—Cu1^i	2.6676 (11)	C7—H7A	0.9800
N1—C1	1.350 (4)	C7—H7B	0.9800
N1—C4	1.375 (4)	C8—C9	1.389 (5)
N2—C5	1.295 (4)	C9—C10	1.372 (6)
N2—C6	1.451 (4)	C9—H9	0.9400
N3—C12	1.349 (4)	C10—C11	1.376 (6)
N3—C8	1.356 (4)	C10—H10	0.9400
C1—C2	1.384 (5)	C11—C12	1.368 (5)
C1—H1	0.9400	C11—H11	0.9400
C2—C3	1.389 (5)	C12—H12	0.9400
C2—H2	0.9400	C13—H13A	0.9700
C3—C4	1.388 (5)	C13—H13B	0.9700
C3—H3	0.9400	C13—H13C	0.9700
C4—C5	1.439 (5)
N1—Cu1—N2	81.45 (11)	C4—C5—C13	121.0 (3)
N1—Cu1—N3	162.52 (11)	N2—C6—C7	109.5 (3)
N2—Cu1—N3	90.17 (11)	N2—C6—H6A	109.8
N1—Cu1—Cl1	92.66 (9)	C7—C6—H6A	109.8
N2—Cu1—Cl1	171.19 (8)	N2—C6—H6B	109.8
N3—Cu1—Cl1	93.70 (8)	C7—C6—H6B	109.8
N1—Cu1—Cl1^i	101.06 (9)	H6A—C6—H6B	108.2
N2—Cu1—Cl1^i	98.38 (8)	C8—C7—C6	112.8 (3)
N3—Cu1—Cl1^i	95.30 (8)	C8—C7—H7A	109.0
Cl1—Cu1—Cl1^i	89.15 (4)	C6—C7—H7A	109.0
Cu1—Cl1—Cu1^i	90.85 (4)	C8—C7—H7B	109.0
C1—N1—C4	106.2 (3)	C6—C7—H7B	109.0
C1—N1—Cu1	140.7 (2)	H7A—C7—H7B	107.8
C4—N1—Cu1	113.0 (2)	N3—C8—C9	121.0 (3)
C5—N2—C6	121.2 (3)	N3—C8—C7	118.2 (3)
C5—N2—Cu1	114.2 (2)	C9—C8—C7	120.8 (3)
C6—N2—Cu1	124.6 (2)	C10—C9—C8	120.3 (4)
C12—N3—C8	117.1 (3)	C10—C9—H9	119.9
C12—N3—Cu1	121.0 (2)	C8—C9—H9	119.9
C8—N3—Cu1	121.9 (2)	C9—C10—C11	119.0 (3)
N1—C1—C2	110.7 (3)	C9—C10—H10	120.5
N1—C1—H1	124.7	C11—C10—H10	120.5
C2—C1—H1	124.7	C12—C11—C10	118.1 (4)
C1—C2—C3	106.8 (3)	C12—C11—H11	120.9
C1—C2—H2	126.6	C10—C11—H11	120.9
C3—C2—H2	126.6	N3—C12—C11	124.4 (3)
C4—C3—C2	106.4 (3)	N3—C12—H12	117.8
C4—C3—H3	126.8	C11—C12—H12	117.8
C2—C3—H3	126.8	C5—C13—H13A	109.5
N1—C4—C3	109.9 (3)	C5—C13—H13B	109.5
N1—C4—C5	115.2 (3)	H13A—C13—H13B	109.5
C3—C4—C5	134.6 (3)	C5—C13—H13C	109.5
N2—C5—C4	115.6 (3)	H13A—C13—H13C	109.5
N2—C5—C13	123.4 (3)	H13B—C13—H13C	109.5
N1—Cu1—Cl1—Cu1^i	101.03 (9)	Cu1—N1—C4—C3	−178.7 (2)
N3—Cu1—Cl1—Cu1^i	−95.26 (8)	C1—N1—C4—C5	−174.3 (3)
Cl1^i—Cu1—Cl1—Cu1^i	0.0	Cu1—N1—C4—C5	7.1 (4)
N2—Cu1—N1—C1	175.1 (4)	C2—C3—C4—N1	0.0 (4)
N3—Cu1—N1—C1	−122.7 (4)	C2—C3—C4—C5	172.7 (4)
Cl1—Cu1—N1—C1	−11.5 (4)	C6—N2—C5—C4	177.3 (3)
Cl1^i—Cu1—N1—C1	78.2 (4)	Cu1—N2—C5—C4	−3.9 (4)
N2—Cu1—N1—C4	−7.0 (2)	C6—N2—C5—C13	−1.2 (5)
N3—Cu1—N1—C4	55.1 (5)	Cu1—N2—C5—C13	177.6 (3)
Cl1—Cu1—N1—C4	166.4 (2)	N1—C4—C5—N2	−2.0 (4)
Cl1^i—Cu1—N1—C4	−104.0 (2)	C3—C4—C5—N2	−174.4 (4)
N1—Cu1—N2—C5	6.1 (2)	N1—C4—C5—C13	176.4 (3)
N3—Cu1—N2—C5	−158.5 (2)	C3—C4—C5—C13	4.1 (6)
Cl1^i—Cu1—N2—C5	106.1 (2)	C5—N2—C6—C7	−158.0 (3)
N1—Cu1—N2—C6	−175.2 (3)	Cu1—N2—C6—C7	23.3 (4)
N3—Cu1—N2—C6	20.2 (3)	N2—C6—C7—C8	−70.1 (4)
Cl1^i—Cu1—N2—C6	−75.1 (3)	C12—N3—C8—C9	1.7 (5)
N1—Cu1—N3—C12	83.5 (5)	Cu1—N3—C8—C9	−179.4 (3)
N2—Cu1—N3—C12	144.5 (3)	C12—N3—C8—C7	−177.1 (3)
Cl1—Cu1—N3—C12	−27.6 (2)	Cu1—N3—C8—C7	1.7 (4)
Cl1^i—Cu1—N3—C12	−117.1 (2)	C6—C7—C8—N3	58.4 (4)
N1—Cu1—N3—C8	−95.3 (4)	C6—C7—C8—C9	−120.5 (4)
N2—Cu1—N3—C8	−34.3 (3)	N3—C8—C9—C10	−1.4 (6)
Cl1—Cu1—N3—C8	153.6 (2)	C7—C8—C9—C10	177.5 (4)
Cl1^i—Cu1—N3—C8	64.1 (3)	C8—C9—C10—C11	−0.3 (6)
C4—N1—C1—C2	0.2 (4)	C9—C10—C11—C12	1.5 (6)
Cu1—N1—C1—C2	178.1 (3)	C8—N3—C12—C11	−0.5 (5)
N1—C1—C2—C3	−0.1 (4)	Cu1—N3—C12—C11	−179.4 (3)
C1—C2—C3—C4	0.1 (4)	C10—C11—C12—N3	−1.1 (6)
C1—N1—C4—C3	−0.1 (4)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···Cl1^i	0.98	2.73	3.559 (4)	143
C7—H7B···Cl1^ii	0.98	2.81	3.630 (4)	142

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