The dinuclear copper(II) complexes di-μ-chlorido-bis­{[N,N′-bis­(4-chloro­benz­yl)propane-1,2-diamine]chloridocopper(II)} and di-μ-chlorido-bis­{[N,N′-bis­(3,4-methyl­enedioxy­benz­yl)­prop­ane-1,2-diamine]chloridocopper(II)}

The two title dinuclear copper(II) complexes, [Cu₂Cl₄(C₁₇H₂₀Cl₂N₂)₂], (I), and [Cu₂Cl₄(C₁₉H₂₂N₂O₄)₂], (II), have similar coordination environments. In each complex, the asymmetric unit consists of one half-mol­ecule and the two copper centres are bridged by a pair of Cl atoms, resulting in complexes with centrosymmetric structures containing Cu(μ-Cl)₂Cu paral­lelogram cores; the Cu...Cu separations and Cu—Cl—Cu angles are 3.4285 (8) Å and 83.36 (3)°, respectively, for (I), and 3.565 (2) Å and 84.39 (7)° for (II). Each Cu atom is five-coordinated and the coordination geometry around the Cu atom is best described as a distorted square-pyramid with a τ value of 0.155 (3) for (I) and 0.092 (7) for (II). The apical Cu—­Cl bond length is 2.852 (1) Å for (I) and 2.971 (2) Å for (II). The basal Cu—Cl and Cu—N average bonds lengths are 2.2673 (9) and 2.030 (2) Å, respectively, for (I), and 2.280 (2) and 2.038 (6) Å for (II). The mol­ecules of (I) are linked by one C—H...Cl hydrogen bond into a complex [10] sheet. The mol­ecules of (II) are linked by one C—H...Cl and one N—H...O hydrogen bond into a complex [100] sheet.

S1. Comment

Dinuclear transition metal complexes have received much attention because of their relevance as models for active sites of biomolecules, such as hemocyanin, tyrosinase and copper oxidases (Pradeep et al., 2005; Sorrell, 1989), and also because of the correlation between the structure and the magnetic behaviour (Schuitema et al., 2002; Rodríguez et al., 2000). Among these dinuclear transition metal complexes, some anions, such as OH^-, RO^-, RCO₂^-, Cl^- and Br^-, are often used as bridging ligands (Christou et al., 2000). For dichloro-bridged dinuclear copper systems, many complexes have been reported in the literature and different magnetic behaviours are observed (Rodríguez et al., 2000; Schuitema et al., 2002; Tuna et al., 1999), and the magneto-structural correlation, which relates the magnetic interaction to ϕ/R, has been established (Marsh et al., 1982). Copper complexes containing diimines also have been extensively studied and reported owing to their potential applications (Alvesa et al., 2004). Previously, our group has reported the structures of some transition metal complexes with diimines (Han et al., 2006; Liu et al., 2007; Xia et al., 2007; Yang et al., 2007). For this reason, we have synthesized two new dichloro-bridged dinuclear copper complexes with diimines, [Cu₂Cl₂(C₁₇H₂₀N₂Cl₂)₂Cl₂], (I), and [Cu₂Cl₂(C₁₉H₂₂N₂O₄)₂Cl₂], (II). In this paper, we report the synthesis and structures of complexes (I) and (II).

Complexes (I) and (II) have similar coordination environments (Fig. 1 and Fig. 2). In each complex, the asymmetric unit consists of one half-molecule; two copper centers are bridged by a pair of chloride atoms, resulting in a complex with a centrosymmetric structure containing a parallelogram Cu(µ-Cl)₂Cu core. The Cu···Cu separation of 3.4285 (8) Å for (I) is smaller than those values reported in two dichloro-bridged dinuclear copper(II) complexes, viz. [Cu₂ (5-aminomethyl-3-methylpyrazole)₂Cl₄] [Cu···Cu = 3.479 (4) Å; Schuitema et al., 2002] and {[CuL²Cl₂]₂[ClO₄]₂} [where L is 1-(imidazol-4-ylmethyl)-l,5-diazacyclooctane; Cu···Cu = 3.494 (8) Å; Bu et al., 2001], in which magnetic coupling between the copper centers can be observed; but the Cu···Cu separation of 3.565 (2) Å for (II) is longer than those of two dichloro-bridged dinuclear copper(II) complexes mentioned above. The Cu—Cl—Cu angles are 83.36 (3)° for (I) and 84.39 (7)° for (II); these values are smaller than those of the two dichloro-bridged dinuclear copper(II) complexes mentioned above, in which the Cu—Cl—Cu angles range from 85.33 (15) to 88.81 (5)°. Each Cu atom is five-coordinated by two N atoms of one ligand and three Cl atoms, and the coordination polyhedron around the Cu atom may be described as a slightly distorted square pyramid with τ values (Addison et al., 1984) of 0.155 (3) for (I) and 0.092 (7) for (II), where τ is defined as (β - α)/60, and β and α are the largest coordination angles (τ = 0 for a regular square-pyramidal geometry and τ = 1 for trigonal–bipyramidal geometry). The apical position is occupied by one elongated bridging Cl atom, and the apical Cu—Cl bond distances are 2.852 (1) Å for (I), and 2.971 (2) Å for (II); these values are longer than those of the two dichloro-bridged dinuclear copper(II) complexes mentioned above, in which the apical Cu—Cl bond distances range from 2.6571 (14) to 2.829 (4) Å. The basal planes are defined by atoms Cl1, Cl2, N1 and N2; atoms Cu1 are shifted by 0.106 (1) Å for (I) and 0.050 (3) Å for (II) from the basal planes toward the apical Cl1A atom. The basal Cu—Cl and Cu–N average bond lengths are 2.2673 (9) and 2.030 (2) Å in (I), and 2.280 (2) and 2.038 (6) Å in (II) (see in Table 1 and Table 3).

Generally, the dichloro-bridged dinuclear copper complexes with square-pyramidal geometry exhibit three different geometries with regard to the relative arrangement of square pyramids, viz. perpendicular bases (type I), parallel bases (type II) and coplanar bases (type III) (Rodríguez et al., 2000). In the parallel bases case, two square pyramids share a base-to-apex edge, so that a Cl atom situated at the vertex of one base becomes the apical vertex of the other square pyramid. The symmetric arrangements of the Cu(µ-Cl)₂Cu cores in complexes (I) and (II) belong to type II; the two intramolecular basal planes are strictly parallel, with an interplanar spacing of 2.731 (6) Å for (I) and 2.82 (3) Å for (II), corresponding to a plane offset of 2.07 (1) Å for (I) and 2.18 (4) Å for (II); the dihedral angles between the parallelogram Cu(µ-Cl)₂Cu core and the basal plane are 87.27 (4)° for (I) and 86.85 (8)° for (II).

Some theoretical analysis and real experiments concerning the magneto-structural correlation for dichloro-bridged dinuclear copper(II) complexes can be found in the literature (Schuitema et al., 2002; Rodríguez et al., 2000; Tuna et al., 1999). Marsh et al. (1982) have shown that the exchange coupling interaction depends on the magnitude of the angle at the Cu—Cl—Cu bridge, ϕ, as well as the apical Cu—Cl bond length, R. It was found that for values of the quotient ϕ/R that are lower than 32.6° Å^-1 and higher than 34.88° Å^-1, the exchange interaction is antiferromagnetic. For values falling between these limits, the exchange interaction was found to be ferromagnetic. In the cases of (I) and (II), the values of the quotient ϕ/R are 29.23 (2) and 28.40 (4)° Å^-1, respectively, both quotients are below the border value of 32.6° Å^-1, suggesting an antiferromagnetic interaction between the two copper(II) ions.

In the crystal structures of (I) and (II), the molecules are stabilized by a pair of intramolecular N—H···Cl hydrogen bonds (Figs. 1 and 2, and Tables 2 and 4). In (I), the molecules are linked by a single intermolecular C—H···Cl hydrogen bond, atom C11 at (x, y, z) in molecule centred at (1/2, 1/2, 1/2) acts as hydrogen-bond donor, via H11b, to atom Cl2 at (3/2 - x, -1/2 + y, 3/2 - z) in the molecule centred at (1, 0, 1), and propagation is via inversion, the screw axis and translation generating a complex sheet in [101] (Fig. 3 and Table 2).

In (II), the molecules are linked by one intermolecular C—H···Cl and one N—H···O hydrogen bonds, atoms C12 and N2 at (x, y, z) in the molecule centred at (1/2, 1/2, 1/2) act as hydrogen-bond donors, via H12B [12 A in Table 4] and H2, to atoms Cl2 and O3 at (3/2 - x, -1/2 + y, 3/2 - z) [or (-x + 1, y - 1/2, -z + 1/2)?] in the molecule centred at [1, 0, 1], and propagation via a screw axis and translation generates a complex sheet in [100] (Fig. 4 and Table 4).

Related literature

For related literature, see: Addison et al. (1984); Alvesa et al. (2004); Bu et al. (2001); Christou et al. (2000); Han et al. (2006); Liu et al. (2007); Marsh et al. (1982); Pradeep et al. (2005); Rodríguez et al. (2000); Schuitema et al. (2002); Sorrell (1989); Tuna et al. (1999); Xia et al. (2007); Yang et al. (2007).

S2. Experimental

For the preparation of complex (I), to a solution containing N,N-bis(4-chlorobenzyl)propane-1,2-diamine (0.96 g, 3 mmol) and ethanol (20 ml), a solution of copper chloride (0.48 g, 3 mmol) and ethanol(10 ml) was added dropwise with stirring. The reaction mixture was stirred for 3 h at 333–343 K and then left to cool at room temperature; the solid obtained was filtered off, washed successively with chloroform (3 × 3 ml) and ethanol (3 × 3 ml), and dried at room temperature. Green crystals of complex (I) suitable for X-ray structure analysis were obtained by slow evaporation of a dimethylformamide–ethanol (1:10) solution containing the product over a period of three weeks (yield 0.98 g, 68%; m.p.466–469 K). Analysis calculated for [Cu₂Cl₄(C₁₇H₂₀N₂Cl₂)₂]: C 44.61, H 4.40, N 6.12%; found: C 45.22, H 4.28, N 5.88%. IR (KBr, cm^-1): 3450, 3162, 2946, 1599, 1551, 1492, 1440, 1089, 1013, 922, 810, 704, 566.

In same method, green crystals of complex(II) suitable for X-ray structure analysis also were obtained (yield 1.18 g, 71%; m.p.509– 512 K). Analysis calculated for [Cu₂Cl₄(C₁₉H₂₂N₂O₄)₂]: C 47.86%, H 4.65%, N 5.87%; found: C 48.48%, H 4.49%, N 6.02%. IR(KBr, disk,cm^-1): 3464, 3250, 2932, 1599, 1553, 1493,1447, 1252, 1034, 922, 812, 767, 704.

S3. Refinement

All H atoms were located in difference Fourier maps and treated as riding atoms, with C—H distances of 0.98 Å (methine), 0.93 Å (aryl), 0.96 Å (methyl) and 0.97 Å (methylene), N—H distances of 0.91 Å, and with U_iso(H) values of 1.2U_eq(C,N) (aryl, methylene, imine) and 1.5U_eq(C) (methyl). The value of R_int for complex (II) is high (R_int = 0.162) because of the poor crystal quality, resulting in broad diffraction peaks.

Computing details

For both compounds, data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures

	Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. For clarity, H atoms have been omitted. Dashed lines indicate hydrogen bonds. [Symmetry code: (*) -x + 1, -y + 1, -z + 1.]
	Fig. 2. The molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. For clarity, H atoms have been omitted. Dashed lines indicate hydrogen bonds. [Symmetry code: (*) -x + 1, -y + 1, -z + 1.]
	Fig. 3. Part of the crystal structure of (I), showing the formation of a [101] sheet. For clarity, H atoms have been omitted. Dashed lines indicate hydrogen bonds. [Symmetry code: (*) -x + 3/2, y - 1/2, -z + 3/2.]
	Fig. 4. Part of the crystal structure of compound (II), showing the formation of a [100] sheet. For clarity, H atoms have been omitted. Dashed lines indicate hydrogen bonds. [Symmetry code: (*) -x + 1, y - 1/2, -z + 1/2.]

(I) di-µ-chlorido-bis{[N,N'-bis(4-chlorobenzyl)propane-1,2- diamine]chloridocopper(II)}

Crystal data

[Cu2Cl4(C17H20Cl2N2)2]	F(000) = 932
Mr = 915.38	Dx = 1.568 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3324 reflections
a = 14.4217 (15) Å	θ = 2.6–27.0°
b = 9.5445 (13) Å	µ = 1.68 mm^−1
c = 15.6198 (19) Å	T = 298 K
β = 115.647 (2)°	Block, green
V = 1938.2 (4) Å^3	0.54 × 0.50 × 0.46 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	3417 independent reflections
Radiation source: fine-focus sealed tube	2484 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ϕ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→17
Tmin = 0.464, Tmax = 0.512	k = −11→6
8896 measured reflections	l = −17→18

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0306P)^2 + 0.7906P] where P = (Fo^2 + 2Fc^2)/3
3417 reflections	(Δ/σ)max = 0.001
218 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.28 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	0.56093 (3)	0.40517 (4)	0.60255 (3)	0.03284 (13)
Cl3	−0.02417 (7)	0.36440 (11)	0.64146 (8)	0.0634 (3)
Cl4	0.64329 (11)	0.57123 (13)	1.04591 (9)	0.0884 (4)
Cl2	0.71211 (6)	0.39329 (8)	0.59008 (6)	0.0409 (2)
Cl1	0.54872 (6)	0.64141 (8)	0.59685 (6)	0.0408 (2)
N1	0.41881 (18)	0.3830 (2)	0.59727 (18)	0.0321 (6)
H1	0.3741	0.4288	0.5443	0.038*
N2	0.58206 (18)	0.2072 (2)	0.65562 (18)	0.0341 (6)
H2	0.5980	0.1546	0.6152	0.041*
C1	0.3954 (2)	0.2317 (3)	0.5811 (2)	0.0402 (8)
H1A	0.3831	0.2074	0.5167	0.048*
H1B	0.3337	0.2104	0.5887	0.048*
C2	0.4843 (2)	0.1465 (3)	0.6509 (2)	0.0378 (8)
H2A	0.4852	0.1560	0.7137	0.045*
C3	0.4726 (3)	−0.0085 (3)	0.6246 (3)	0.0621 (11)
H3A	0.4653	−0.0194	0.5609	0.093*
H3B	0.4127	−0.0451	0.6288	0.093*
H3C	0.5324	−0.0586	0.6676	0.093*
C4	0.4061 (2)	0.4434 (3)	0.6791 (2)	0.0397 (8)
H4A	0.4227	0.5424	0.6837	0.048*
H4B	0.4547	0.3987	0.7369	0.048*
C5	0.2992 (2)	0.4263 (3)	0.6723 (2)	0.0362 (8)
C6	0.2757 (3)	0.3200 (4)	0.7195 (2)	0.0487 (9)
H6	0.3277	0.2597	0.7581	0.058*
C7	0.1771 (3)	0.3006 (4)	0.7109 (3)	0.0514 (9)
H7	0.1624	0.2272	0.7423	0.062*
C8	0.1014 (2)	0.3911 (3)	0.6555 (2)	0.0403 (8)
C9	0.1223 (2)	0.4988 (3)	0.6087 (2)	0.0415 (8)
H9	0.0704	0.5605	0.5719	0.050*
C10	0.2204 (2)	0.5156 (3)	0.6163 (2)	0.0389 (8)
H10	0.2340	0.5878	0.5835	0.047*
C11	0.6707 (2)	0.1899 (3)	0.7513 (2)	0.0419 (8)
H11A	0.7342	0.2094	0.7463	0.050*
H11B	0.6732	0.0935	0.7717	0.050*
C12	0.6634 (2)	0.2852 (3)	0.8247 (2)	0.0351 (7)
C13	0.6297 (2)	0.2365 (3)	0.8902 (2)	0.0428 (8)
H13	0.6126	0.1423	0.8894	0.051*
C14	0.6210 (3)	0.3239 (4)	0.9559 (2)	0.0485 (9)
H14	0.5973	0.2898	0.9987	0.058*
C15	0.6478 (3)	0.4636 (4)	0.9580 (2)	0.0485 (9)
C16	0.6818 (3)	0.5153 (4)	0.8952 (3)	0.0485 (9)
H16	0.6995	0.6093	0.8970	0.058*
C17	0.6894 (2)	0.4259 (3)	0.8287 (2)	0.0433 (8)
H17	0.7124	0.4608	0.7858	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0315 (2)	0.0285 (2)	0.0380 (2)	0.00195 (16)	0.01460 (18)	0.00274 (17)
Cl3	0.0484 (6)	0.0729 (7)	0.0793 (8)	−0.0070 (5)	0.0374 (6)	−0.0075 (5)
Cl4	0.1269 (11)	0.0784 (8)	0.0701 (8)	−0.0054 (7)	0.0522 (8)	−0.0269 (6)
Cl2	0.0319 (4)	0.0447 (5)	0.0463 (5)	0.0029 (3)	0.0172 (4)	0.0037 (4)
Cl1	0.0483 (5)	0.0277 (4)	0.0456 (5)	−0.0011 (3)	0.0196 (4)	−0.0034 (3)
N1	0.0276 (13)	0.0317 (15)	0.0323 (15)	−0.0003 (10)	0.0087 (12)	0.0028 (11)
N2	0.0398 (15)	0.0279 (14)	0.0352 (16)	0.0053 (11)	0.0168 (13)	0.0007 (11)
C1	0.043 (2)	0.040 (2)	0.039 (2)	−0.0101 (15)	0.0188 (17)	−0.0075 (15)
C2	0.048 (2)	0.0312 (18)	0.0366 (19)	−0.0052 (15)	0.0206 (17)	−0.0005 (14)
C3	0.086 (3)	0.035 (2)	0.072 (3)	−0.0058 (18)	0.040 (3)	−0.0029 (18)
C4	0.0383 (19)	0.041 (2)	0.038 (2)	0.0031 (14)	0.0149 (16)	−0.0040 (15)
C5	0.0352 (18)	0.0377 (19)	0.0348 (19)	0.0024 (14)	0.0143 (16)	−0.0036 (15)
C6	0.048 (2)	0.053 (2)	0.045 (2)	0.0156 (17)	0.0207 (19)	0.0130 (18)
C7	0.061 (2)	0.050 (2)	0.056 (2)	−0.0002 (18)	0.037 (2)	0.0118 (18)
C8	0.0390 (19)	0.045 (2)	0.040 (2)	−0.0017 (16)	0.0204 (17)	−0.0097 (16)
C9	0.039 (2)	0.038 (2)	0.042 (2)	0.0070 (14)	0.0133 (17)	−0.0002 (15)
C10	0.043 (2)	0.0337 (19)	0.039 (2)	−0.0008 (15)	0.0166 (17)	0.0000 (15)
C11	0.0400 (19)	0.0366 (19)	0.045 (2)	0.0133 (15)	0.0147 (17)	0.0104 (16)
C12	0.0300 (17)	0.0380 (19)	0.0298 (18)	0.0056 (14)	0.0057 (15)	0.0031 (14)
C13	0.049 (2)	0.0336 (19)	0.039 (2)	−0.0019 (15)	0.0127 (17)	0.0076 (15)
C14	0.057 (2)	0.054 (2)	0.037 (2)	−0.0022 (18)	0.0220 (19)	0.0035 (17)
C15	0.053 (2)	0.047 (2)	0.039 (2)	0.0031 (17)	0.0142 (18)	−0.0049 (17)
C16	0.057 (2)	0.033 (2)	0.050 (2)	−0.0066 (16)	0.0184 (19)	−0.0021 (17)
C17	0.0411 (19)	0.046 (2)	0.041 (2)	−0.0028 (15)	0.0166 (17)	0.0079 (16)

Geometric parameters (Å, º)

Cu1—N1	2.026 (2)	C4—H4B	0.9700
Cu1—N2	2.033 (2)	C5—C6	1.380 (4)
Cu1—Cl1	2.2604 (9)	C5—C10	1.386 (4)
Cu1—Cl2	2.2742 (9)	C6—C7	1.382 (4)
Cu1—Cl1^i	2.852 (1)	C6—H6	0.9300
Cu1—Cu1^i	3.4285 (8)	C7—C8	1.367 (5)
Cl3—C8	1.747 (3)	C7—H7	0.9300
Cl4—C15	1.739 (4)	C8—C9	1.368 (4)
Cl1—Cu1^i	2.852 (1)	C9—C10	1.377 (4)
N1—C1	1.480 (4)	C9—H9	0.9300
N1—C4	1.484 (4)	C10—H10	0.9300
N1—H1	0.9100	C11—C12	1.503 (4)
N2—C2	1.496 (4)	C11—H11A	0.9700
N2—C11	1.497 (4)	C11—H11B	0.9700
N2—H2	0.9100	C12—C13	1.388 (4)
C1—C2	1.511 (4)	C12—C17	1.389 (4)
C1—H1A	0.9700	C13—C14	1.371 (4)
C1—H1B	0.9700	C13—H13	0.9300
C2—C3	1.525 (4)	C14—C15	1.385 (5)
C2—H2A	0.9800	C14—H14	0.9300
C3—H3A	0.9600	C15—C16	1.365 (5)
C3—H3B	0.9600	C16—C17	1.384 (5)
C3—H3C	0.9600	C16—H16	0.9300
C4—C5	1.508 (4)	C17—H17	0.9300
C4—H4A	0.9700
N1—Cu1—N2	83.69 (9)	N1—C4—H4A	108.8
N1—Cu1—Cl1	92.41 (7)	C5—C4—H4A	108.8
N2—Cu1—Cl1	159.84 (8)	N1—C4—H4B	108.8
N1—Cu1—Cl2	169.01 (7)	C5—C4—H4B	108.8
N2—Cu1—Cl2	90.49 (7)	H4A—C4—H4B	107.7
Cl1—Cu1—Cl2	96.18 (3)	C6—C5—C10	117.8 (3)
N1—Cu1—Cl1^i	82.32 (7)	C6—C5—C4	121.4 (3)
N2—Cu1—Cl1^i	102.40 (7)	C10—C5—C4	120.8 (3)
Cl1—Cu1—Cl1^i	96.64 (3)	C5—C6—C7	121.8 (3)
Cl2—Cu1—Cl1^i	89.87 (3)	C5—C6—H6	119.1
N1—Cu1—Cu1^i	85.22 (7)	C7—C6—H6	119.1
N2—Cu1—Cu1^i	142.90 (7)	C8—C7—C6	118.8 (3)
Cl1—Cu1—Cu1^i	55.73 (2)	C8—C7—H7	120.6
Cl2—Cu1—Cu1^i	93.96 (3)	C6—C7—H7	120.6
Cl1^i—Cu1—Cu1^i	40.912 (18)	C7—C8—C9	120.9 (3)
Cu1—Cl1—Cu1^i	83.36 (3)	C7—C8—Cl3	119.2 (3)
C1—N1—C4	115.0 (2)	C9—C8—Cl3	119.9 (3)
C1—N1—Cu1	105.09 (17)	C8—C9—C10	119.8 (3)
C4—N1—Cu1	115.12 (18)	C8—C9—H9	120.1
C1—N1—H1	107.1	C10—C9—H9	120.1
C4—N1—H1	107.1	C9—C10—C5	120.9 (3)
Cu1—N1—H1	107.1	C9—C10—H10	119.5
C2—N2—C11	112.8 (2)	C5—C10—H10	119.5
C2—N2—Cu1	111.59 (18)	N2—C11—C12	112.5 (2)
C11—N2—Cu1	114.93 (18)	N2—C11—H11A	109.1
C2—N2—H2	105.5	C12—C11—H11A	109.1
C11—N2—H2	105.5	N2—C11—H11B	109.1
Cu1—N2—H2	105.5	C12—C11—H11B	109.1
N1—C1—C2	110.0 (2)	H11A—C11—H11B	107.8
N1—C1—H1A	109.7	C13—C12—C17	117.7 (3)
C2—C1—H1A	109.7	C13—C12—C11	121.5 (3)
N1—C1—H1B	109.7	C17—C12—C11	120.8 (3)
C2—C1—H1B	109.7	C14—C13—C12	121.5 (3)
H1A—C1—H1B	108.2	C14—C13—H13	119.2
N2—C2—C1	108.3 (2)	C12—C13—H13	119.2
N2—C2—C3	112.4 (3)	C13—C14—C15	119.2 (3)
C1—C2—C3	111.5 (3)	C13—C14—H14	120.4
N2—C2—H2A	108.1	C15—C14—H14	120.4
C1—C2—H2A	108.1	C16—C15—C14	121.0 (3)
C3—C2—H2A	108.1	C16—C15—Cl4	120.1 (3)
C2—C3—H3A	109.5	C14—C15—Cl4	118.8 (3)
C2—C3—H3B	109.5	C15—C16—C17	119.1 (3)
H3A—C3—H3B	109.5	C15—C16—H16	120.5
C2—C3—H3C	109.5	C17—C16—H16	120.5
H3A—C3—H3C	109.5	C16—C17—C12	121.5 (3)
H3B—C3—H3C	109.5	C16—C17—H17	119.2
N1—C4—C5	113.6 (2)	C12—C17—H17	119.2
N1—Cu1—Cl1—Cu1^i	−82.54 (7)	N1—C1—C2—N2	−44.7 (3)
N2—Cu1—Cl1—Cu1^i	−160.8 (2)	N1—C1—C2—C3	−168.9 (3)
Cl2—Cu1—Cl1—Cu1^i	90.59 (3)	C1—N1—C4—C5	−58.2 (3)
Cl1^i—Cu1—Cl1—Cu1^i	0.0	Cu1—N1—C4—C5	179.4 (2)
N2—Cu1—N1—C1	−30.59 (19)	N1—C4—C5—C6	98.5 (4)
Cl1—Cu1—N1—C1	169.26 (18)	N1—C4—C5—C10	−80.0 (4)
Cl2—Cu1—N1—C1	27.8 (5)	C10—C5—C6—C7	0.9 (5)
Cl1^i—Cu1—N1—C1	72.88 (18)	C4—C5—C6—C7	−177.7 (3)
Cu1^i—Cu1—N1—C1	113.95 (18)	C5—C6—C7—C8	−1.2 (5)
N2—Cu1—N1—C4	96.9 (2)	C6—C7—C8—C9	0.3 (5)
Cl1—Cu1—N1—C4	−63.2 (2)	C6—C7—C8—Cl3	178.2 (3)
Cl2—Cu1—N1—C4	155.3 (3)	C7—C8—C9—C10	0.9 (5)
Cl1^i—Cu1—N1—C4	−159.6 (2)	Cl3—C8—C9—C10	−176.9 (2)
Cu1^i—Cu1—N1—C4	−118.5 (2)	C8—C9—C10—C5	−1.3 (5)
N1—Cu1—N2—C2	7.23 (19)	C6—C5—C10—C9	0.4 (5)
Cl1—Cu1—N2—C2	87.0 (3)	C4—C5—C10—C9	178.9 (3)
Cl2—Cu1—N2—C2	−163.42 (19)	C2—N2—C11—C12	−72.7 (3)
Cl1^i—Cu1—N2—C2	−73.45 (19)	Cu1—N2—C11—C12	56.7 (3)
Cu1^i—Cu1—N2—C2	−66.2 (2)	N2—C11—C12—C13	101.1 (3)
N1—Cu1—N2—C11	−122.7 (2)	N2—C11—C12—C17	−78.3 (4)
Cl1—Cu1—N2—C11	−43.0 (3)	C17—C12—C13—C14	0.8 (5)
Cl2—Cu1—N2—C11	66.60 (19)	C11—C12—C13—C14	−178.7 (3)
Cl1^i—Cu1—N2—C11	156.57 (18)	C12—C13—C14—C15	−1.0 (5)
Cu1^i—Cu1—N2—C11	163.82 (15)	C13—C14—C15—C16	0.6 (5)
C4—N1—C1—C2	−78.2 (3)	C13—C14—C15—Cl4	−176.5 (3)
Cu1—N1—C1—C2	49.4 (3)	C14—C15—C16—C17	−0.1 (5)
C11—N2—C2—C1	148.8 (3)	Cl4—C15—C16—C17	176.9 (3)
Cu1—N2—C2—C1	17.7 (3)	C15—C16—C17—C12	0.0 (5)
C11—N2—C2—C3	−87.4 (3)	C13—C12—C17—C16	−0.3 (5)
Cu1—N2—C2—C3	141.5 (2)	C11—C12—C17—C16	179.2 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2^i	0.91	2.57	3.450 (3)	164
C11—H11B···Cl2^ii	0.97	2.82	3.659 (3)	145
C13—H13···Cl3^iii	0.93	2.89	3.810 (3)	170

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

(II) di-µ-chlorido-bis{[N,N'-bis(3,4-methylenedioxybenzyl)propane-1,2- diamine]chloridocopper(II)}

Crystal data

[Cu2Cl4(C19H22N2O4)2]	F(000) = 980
Mr = 953.65	Dx = 1.487 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2094 reflections
a = 12.2965 (13) Å	θ = 2.5–24.1°
b = 11.0554 (12) Å	µ = 1.30 mm^−1
c = 15.822 (2) Å	T = 298 K
β = 98.140 (2)°	Block, green
V = 2129.2 (4) Å^3	0.45 × 0.37 × 0.31 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	3730 independent reflections
Radiation source: fine-focus sealed tube	2008 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.162
ϕ and ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→6
Tmin = 0.592, Tmax = 0.688	k = −13→13
10028 measured reflections	l = −18→18

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.217	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.059P)^2 + 3.0479P] where P = (Fo^2 + 2Fc^2)/3
3730 reflections	(Δ/σ)max < 0.001
254 parameters	Δρmax = 1.12 e Å^−3
0 restraints	Δρmin = −0.64 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	0.54541 (8)	0.43043 (8)	0.40956 (6)	0.0360 (3)
Cl1	0.56158 (18)	0.63216 (17)	0.43920 (13)	0.0444 (6)
Cl2	0.37692 (16)	0.44497 (17)	0.32916 (12)	0.0384 (5)
O1	1.1333 (6)	0.2222 (7)	0.5665 (5)	0.079 (2)
O2	1.1506 (6)	0.2989 (7)	0.7031 (4)	0.081 (2)
O3	0.6540 (5)	0.6293 (6)	0.1355 (4)	0.067 (2)
O4	0.8296 (5)	0.5707 (6)	0.1196 (4)	0.0583 (17)
N1	0.6829 (5)	0.3962 (6)	0.4935 (4)	0.0381 (16)
H1	0.6713	0.4287	0.5443	0.046*
N2	0.5678 (5)	0.2588 (5)	0.3672 (4)	0.0348 (16)
H2	0.5091	0.2159	0.3800	0.042*
C1	0.6828 (7)	0.2600 (7)	0.5049 (5)	0.042 (2)
H1A	0.6247	0.2363	0.5371	0.050*
H1B	0.7524	0.2337	0.5362	0.050*
C2	0.6649 (7)	0.2016 (7)	0.4170 (5)	0.039 (2)
H2A	0.7289	0.2201	0.3888	0.047*
C3	0.6573 (9)	0.0639 (7)	0.4251 (6)	0.066 (3)
H3A	0.5965	0.0436	0.4543	0.099*
H3B	0.7241	0.0336	0.4569	0.099*
H3C	0.6467	0.0283	0.3692	0.099*
C4	0.7857 (7)	0.4469 (8)	0.4740 (6)	0.049 (2)
H4A	0.7796	0.5344	0.4729	0.059*
H4B	0.7969	0.4206	0.4174	0.059*
C5	0.8847 (6)	0.4120 (7)	0.5363 (5)	0.041 (2)
C6	0.9618 (7)	0.3294 (8)	0.5136 (6)	0.049 (2)
H6	0.9549	0.2969	0.4589	0.059*
C7	1.0472 (7)	0.2982 (9)	0.5739 (6)	0.052 (2)
C8	1.0592 (7)	0.3451 (9)	0.6557 (6)	0.053 (2)
C9	0.9841 (7)	0.4247 (9)	0.6800 (6)	0.060 (3)
H9	0.9912	0.4551	0.7353	0.072*
C10	0.8966 (7)	0.4585 (8)	0.6185 (6)	0.054 (3)
H10	0.8451	0.5134	0.6330	0.065*
C11	1.1997 (8)	0.2212 (11)	0.6477 (7)	0.075 (3)
H11A	1.2732	0.2491	0.6424	0.090*
H11B	1.2048	0.1397	0.6705	0.090*
C12	0.5659 (7)	0.2435 (7)	0.2716 (5)	0.042 (2)
H12A	0.5853	0.1608	0.2598	0.050*
H12B	0.4920	0.2581	0.2430	0.050*
C13	0.6429 (7)	0.3269 (7)	0.2362 (5)	0.0350 (19)
C14	0.6058 (7)	0.4436 (7)	0.2080 (5)	0.041 (2)
H14	0.5359	0.4704	0.2149	0.049*
C15	0.6743 (8)	0.5138 (7)	0.1712 (5)	0.043 (2)
C16	0.7790 (7)	0.4808 (7)	0.1605 (5)	0.041 (2)
C17	0.8188 (8)	0.3702 (8)	0.1886 (5)	0.050 (2)
H17	0.8900	0.3463	0.1831	0.060*
C18	0.7476 (7)	0.2941 (7)	0.2262 (5)	0.043 (2)
H18	0.7728	0.2181	0.2451	0.051*
C19	0.7520 (8)	0.6666 (8)	0.1051 (6)	0.056 (2)
H19A	0.7810	0.7388	0.1351	0.068*
H19B	0.7371	0.6850	0.0447	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0484 (7)	0.0262 (5)	0.0315 (6)	0.0033 (5)	−0.0014 (4)	−0.0017 (4)
Cl1	0.0587 (14)	0.0258 (10)	0.0474 (12)	−0.0026 (10)	0.0033 (10)	−0.0019 (9)
Cl2	0.0439 (12)	0.0357 (11)	0.0339 (11)	0.0037 (9)	−0.0006 (9)	0.0004 (9)
O1	0.068 (5)	0.100 (6)	0.069 (5)	0.028 (4)	0.003 (4)	−0.019 (4)
O2	0.063 (5)	0.102 (6)	0.068 (5)	0.026 (4)	−0.020 (4)	−0.024 (4)
O3	0.072 (5)	0.044 (4)	0.089 (5)	0.010 (4)	0.026 (4)	0.028 (4)
O4	0.064 (4)	0.051 (4)	0.064 (4)	−0.004 (4)	0.022 (3)	0.006 (3)
N1	0.053 (4)	0.034 (4)	0.027 (3)	0.015 (3)	0.003 (3)	−0.001 (3)
N2	0.049 (4)	0.028 (3)	0.025 (3)	0.003 (3)	−0.004 (3)	−0.001 (3)
C1	0.061 (6)	0.034 (4)	0.029 (4)	0.004 (4)	0.000 (4)	0.011 (4)
C2	0.049 (5)	0.031 (4)	0.034 (5)	0.008 (4)	−0.004 (4)	0.004 (4)
C3	0.096 (8)	0.029 (5)	0.067 (7)	0.004 (5)	−0.011 (6)	0.002 (4)
C4	0.050 (6)	0.046 (5)	0.055 (6)	−0.006 (5)	0.016 (5)	0.005 (4)
C5	0.037 (5)	0.033 (5)	0.051 (5)	−0.003 (4)	0.000 (4)	−0.004 (4)
C6	0.047 (5)	0.059 (6)	0.041 (5)	−0.008 (5)	0.008 (4)	−0.004 (5)
C7	0.039 (5)	0.054 (6)	0.062 (6)	0.001 (5)	0.010 (5)	−0.009 (5)
C8	0.037 (5)	0.059 (6)	0.062 (6)	−0.003 (5)	0.000 (5)	−0.010 (5)
C9	0.051 (6)	0.066 (7)	0.059 (6)	0.004 (5)	−0.004 (5)	−0.027 (5)
C10	0.041 (5)	0.045 (5)	0.075 (7)	0.005 (4)	0.002 (5)	−0.019 (5)
C11	0.055 (7)	0.084 (8)	0.083 (8)	0.022 (6)	0.004 (6)	0.010 (7)
C12	0.063 (6)	0.036 (5)	0.023 (4)	0.009 (4)	−0.005 (4)	−0.006 (4)
C13	0.044 (5)	0.037 (4)	0.022 (4)	0.005 (4)	0.000 (4)	0.003 (3)
C14	0.043 (5)	0.040 (5)	0.041 (5)	0.008 (4)	0.012 (4)	0.004 (4)
C15	0.058 (6)	0.034 (4)	0.040 (5)	0.008 (4)	0.014 (4)	0.006 (4)
C16	0.047 (5)	0.039 (5)	0.037 (5)	0.001 (4)	0.006 (4)	−0.002 (4)
C17	0.053 (6)	0.054 (6)	0.044 (5)	0.007 (5)	0.011 (5)	−0.011 (5)
C18	0.053 (6)	0.036 (5)	0.036 (5)	0.006 (4)	−0.001 (4)	0.000 (4)
C19	0.067 (7)	0.045 (5)	0.060 (6)	−0.004 (5)	0.015 (5)	0.006 (5)

Geometric parameters (Å, º)

Cu1—N1	2.032 (6)	C4—C5	1.504 (11)
Cu1—N2	2.044 (6)	C4—H4A	0.9700
Cu1—Cl2	2.278 (2)	C4—H4B	0.9700
Cu1—Cl1	2.282 (2)	C5—C10	1.387 (12)
Cu1—Cl1^i	2.971 (2)	C5—C6	1.399 (11)
Cu1—Cu1^i	3.565 (2)	C6—C7	1.360 (12)
Cl1—Cu1^i	2.971 (2)	C6—H6	0.9300
O1—C7	1.371 (10)	C7—C8	1.382 (12)
O1—C11	1.420 (12)	C8—C9	1.369 (12)
O2—C8	1.360 (10)	C9—C10	1.395 (12)
O2—C11	1.422 (12)	C9—H9	0.9300
O3—C15	1.404 (10)	C10—H10	0.9300
O3—C19	1.422 (10)	C11—H11A	0.9700
O4—C16	1.381 (10)	C11—H11B	0.9700
O4—C19	1.423 (10)	C12—C13	1.486 (11)
N1—C4	1.456 (10)	C12—H12A	0.9700
N1—C1	1.517 (10)	C12—H12B	0.9700
N1—H1	0.9100	C13—C18	1.369 (11)
N2—C2	1.477 (9)	C13—C14	1.419 (10)
N2—C12	1.519 (9)	C14—C15	1.338 (11)
N2—H2	0.9100	C14—H14	0.9300
C1—C2	1.521 (10)	C15—C16	1.373 (11)
C1—H1A	0.9700	C16—C17	1.368 (11)
C1—H1B	0.9700	C17—C18	1.405 (12)
C2—C3	1.531 (11)	C17—H17	0.9300
C2—H2A	0.9800	C18—H18	0.9300
C3—H3A	0.9600	C19—H19A	0.9700
C3—H3B	0.9600	C19—H19B	0.9700
C3—H3C	0.9600
N1—Cu1—N2	84.5 (2)	H4A—C4—H4B	107.6
N1—Cu1—Cl2	170.0 (2)	C10—C5—C6	119.8 (8)
N2—Cu1—Cl2	92.1 (2)	C10—C5—C4	119.2 (8)
N1—Cu1—Cl1	90.4 (2)	C6—C5—C4	121.0 (8)
N2—Cu1—Cl1	164.3 (2)	C7—C6—C5	118.0 (8)
Cl2—Cu1—Cl1	95.26 (8)	C7—C6—H6	121.0
N1—Cu1—Cl1^i	81.5 (2)	C5—C6—H6	121.0
N2—Cu1—Cl1^i	98.3 (2)	C6—C7—O1	128.7 (9)
Cl2—Cu1—Cl1^i	89.70 (7)	C6—C7—C8	122.1 (9)
Cl1—Cu1—Cl1^i	95.61 (7)	O1—C7—C8	109.2 (8)
N1—Cu1—Cu1^i	83.2 (2)	O2—C8—C9	128.6 (9)
N2—Cu1—Cu1^i	137.40 (18)	O2—C8—C7	110.2 (8)
Cl2—Cu1—Cu1^i	93.11 (6)	C9—C8—C7	121.2 (9)
Cl1—Cu1—Cu1^i	56.04 (6)	C8—C9—C10	117.4 (9)
Cl1^i—Cu1—Cu1^i	39.57 (4)	C8—C9—H9	121.3
Cu1—Cl1—Cu1^i	84.39 (7)	C10—C9—H9	121.3
C7—O1—C11	106.2 (7)	C5—C10—C9	121.6 (8)
C8—O2—C11	106.0 (7)	C5—C10—H10	119.2
C15—O3—C19	106.8 (7)	C9—C10—H10	119.2
C16—O4—C19	106.0 (6)	O1—C11—O2	108.3 (8)
C4—N1—C1	115.0 (6)	O1—C11—H11A	110.0
C4—N1—Cu1	117.2 (5)	O2—C11—H11A	110.0
C1—N1—Cu1	104.4 (5)	O1—C11—H11B	110.0
C4—N1—H1	106.5	O2—C11—H11B	110.0
C1—N1—H1	106.5	H11A—C11—H11B	108.4
Cu1—N1—H1	106.5	C13—C12—N2	112.7 (6)
C2—N2—C12	112.4 (6)	C13—C12—H12A	109.1
C2—N2—Cu1	111.0 (4)	N2—C12—H12A	109.1
C12—N2—Cu1	116.5 (4)	C13—C12—H12B	109.1
C2—N2—H2	105.3	N2—C12—H12B	109.1
C12—N2—H2	105.3	H12A—C12—H12B	107.8
Cu1—N2—H2	105.3	C18—C13—C14	118.1 (8)
N1—C1—C2	108.3 (6)	C18—C13—C12	122.6 (7)
N1—C1—H1A	110.0	C14—C13—C12	119.3 (7)
C2—C1—H1A	110.0	C15—C14—C13	118.1 (8)
N1—C1—H1B	110.0	C15—C14—H14	121.0
C2—C1—H1B	110.0	C13—C14—H14	121.0
H1A—C1—H1B	108.4	C14—C15—C16	124.0 (8)
N2—C2—C1	108.0 (6)	C14—C15—O3	128.0 (8)
N2—C2—C3	114.6 (7)	C16—C15—O3	108.0 (8)
C1—C2—C3	110.4 (7)	C17—C16—C15	119.8 (8)
N2—C2—H2A	107.9	C17—C16—O4	129.2 (8)
C1—C2—H2A	107.9	C15—C16—O4	111.1 (7)
C3—C2—H2A	107.9	C16—C17—C18	117.2 (8)
C2—C3—H3A	109.5	C16—C17—H17	121.4
C2—C3—H3B	109.5	C18—C17—H17	121.4
H3A—C3—H3B	109.5	C13—C18—C17	122.9 (8)
C2—C3—H3C	109.5	C13—C18—H18	118.5
H3A—C3—H3C	109.5	C17—C18—H18	118.5
H3B—C3—H3C	109.5	O3—C19—O4	108.1 (7)
N1—C4—C5	114.1 (7)	O3—C19—H19A	110.1
N1—C4—H4A	108.7	O4—C19—H19A	110.1
C5—C4—H4A	108.7	O3—C19—H19B	110.1
N1—C4—H4B	108.7	O4—C19—H19B	110.1
C5—C4—H4B	108.7	H19A—C19—H19B	108.4
N1—Cu1—Cl1—Cu1^i	−81.51 (19)	C5—C6—C7—C8	0.2 (14)
N2—Cu1—Cl1—Cu1^i	−152.2 (6)	C11—O1—C7—C6	179.7 (10)
Cl2—Cu1—Cl1—Cu1^i	90.21 (7)	C11—O1—C7—C8	1.0 (11)
Cl1^i—Cu1—Cl1—Cu1^i	0.0	C11—O2—C8—C9	−179.8 (11)
N2—Cu1—N1—C4	101.1 (6)	C11—O2—C8—C7	1.3 (11)
Cl2—Cu1—N1—C4	171.3 (8)	C6—C7—C8—O2	179.8 (9)
Cl1—Cu1—N1—C4	−64.0 (6)	O1—C7—C8—O2	−1.4 (11)
Cl1^i—Cu1—N1—C4	−159.6 (6)	C6—C7—C8—C9	0.8 (15)
Cu1^i—Cu1—N1—C4	−119.7 (6)	O1—C7—C8—C9	179.6 (9)
N2—Cu1—N1—C1	−27.4 (5)	O2—C8—C9—C10	179.9 (9)
Cl2—Cu1—N1—C1	42.8 (13)	C7—C8—C9—C10	−1.3 (15)
Cl1—Cu1—N1—C1	167.5 (5)	C6—C5—C10—C9	−0.1 (14)
Cl1^i—Cu1—N1—C1	71.9 (5)	C4—C5—C10—C9	177.0 (8)
Cu1^i—Cu1—N1—C1	111.8 (5)	C8—C9—C10—C5	1.0 (14)
N1—Cu1—N2—C2	0.8 (5)	C7—O1—C11—O2	−0.2 (11)
Cl2—Cu1—N2—C2	−169.7 (5)	C8—O2—C11—O1	−0.7 (12)
Cl1—Cu1—N2—C2	72.3 (8)	C2—N2—C12—C13	−77.2 (8)
Cl1^i—Cu1—N2—C2	−79.7 (5)	Cu1—N2—C12—C13	52.6 (8)
Cu1^i—Cu1—N2—C2	−72.8 (6)	N2—C12—C13—C18	94.1 (9)
N1—Cu1—N2—C12	−129.5 (6)	N2—C12—C13—C14	−88.7 (8)
Cl2—Cu1—N2—C12	59.9 (5)	C18—C13—C14—C15	1.7 (11)
Cl1—Cu1—N2—C12	−58.1 (9)	C12—C13—C14—C15	−175.6 (7)
Cl1^i—Cu1—N2—C12	149.9 (5)	C13—C14—C15—C16	−1.2 (13)
Cu1^i—Cu1—N2—C12	156.8 (4)	C13—C14—C15—O3	177.1 (8)
C4—N1—C1—C2	−80.3 (8)	C19—O3—C15—C14	179.6 (9)
Cu1—N1—C1—C2	49.5 (7)	C19—O3—C15—C16	−1.8 (9)
C12—N2—C2—C1	158.9 (6)	C14—C15—C16—C17	−0.2 (13)
Cu1—N2—C2—C1	26.3 (7)	O3—C15—C16—C17	−178.9 (7)
C12—N2—C2—C3	−77.7 (9)	C14—C15—C16—O4	179.2 (8)
Cu1—N2—C2—C3	149.8 (6)	O3—C15—C16—O4	0.5 (10)
N1—C1—C2—N2	−50.7 (9)	C19—O4—C16—C17	−179.7 (9)
N1—C1—C2—C3	−176.6 (7)	C19—O4—C16—C15	1.0 (9)
C1—N1—C4—C5	−53.5 (9)	C15—C16—C17—C18	1.2 (12)
Cu1—N1—C4—C5	−176.7 (5)	O4—C16—C17—C18	−178.1 (8)
N1—C4—C5—C10	−69.7 (10)	C14—C13—C18—C17	−0.7 (12)
N1—C4—C5—C6	107.3 (9)	C12—C13—C18—C17	176.5 (7)
C10—C5—C6—C7	−0.5 (13)	C16—C17—C18—C13	−0.7 (12)
C4—C5—C6—C7	−177.5 (8)	C15—O3—C19—O4	2.4 (10)
C5—C6—C7—O1	−178.4 (9)	C16—O4—C19—O3	−2.1 (9)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2^i	0.91	2.58	3.476 (6)	169
N2—H2···O3^ii	0.91	2.20	3.075 (9)	160
C12—H12A···Cl2^ii	0.97	2.84	3.774 (8)	162
C11—H11A···Cl1^iii	0.97	2.87	3.779 (11)	156

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