Bis[N,N'-(2-chloro­benzyl­idene)­ethylene­diamine-[kappa]²N,N']copper(I) dichlorido­cuprate(I) acetonitrile solvate

The 1:1 adduct of N,N'-bis­(2-chloro­benzyl­idene)ethylene­diamine (cb₂en) with copper(I) chloride proves to be an ionic compound with Cu^I-centred cations and anions, [Cu(C₁₆H₁₄Cl₂N₂)₂][CuCl₂]·CH₃CN. In the cation, the Cu^I atom has a flattened tetra­hedral coordination geometry, with a small bite angle for the chelating ligands, which form a double-helical arrangement around the metal centre. The anion is almost linear, as expected. The packing of the cations involves inter­molecular [pi]-[pi] inter­actions, which lead to columns of translationally related cations along the shortest unit-cell axis, with anions and solvent mol­ecules in channels between them.

S1. Comment

The coordination chemistry of copper(I) complexes has received increased attention over the last few decades. This is mainly due to the potential application of these complexes in catalytic processes (Fife et al., 1985; Bowker et al., 1988; Bowmarker et al. 2000), photosensitization reactions (Horváth, 1994; Kutal, 1990), light-harvesting studies (Rosi et al., 1999; Dietrich-Buchecker & Sauvage, 1987) and the design of supramolecular arrays (Meghdadi et al., 2002; Foster et al. 2000). Reaction of copper(I) halides, CuX, with nitrogen-based ligands (L) yields CuXL_n adducts. The steric, electronic and conformational effects imparted by the coordinated ligands play an important role in influencing the properties of the resulting metal complexes. A thorough understanding of these effects can serve as the basis for the rational design of complexes with specific and predictable properties. The number of ligands bound to the monovalent Cu^I ion is greatly influenced by both the chemical nature and the geometry of the ligand L, and the particular choice of halogen X (Lange et al., 2000). Although structural reports on [Cu^IL₄]⁺ complex cations (where L is an N-donor ligand) are numerous (Alcon et al., 2000; Miller & Karpishin, 1999; Panja et al., 2002), there are a limited number of studies of copper(I) complexes with isolated linear dihalidocuprate(I) anions (Amirnasr et al., 2005; Mirkhani et al., 2004). The structures of halidocuprate(I) compounds are exceptionally varied, and the nature of the cation plays an important role in determining the coordination number of Cu^I in halidocuprates and the tendency of the anions to form extended structures (Andersson & Jagner, 1989; Hasselgren et al., 1999). Thus, bulky cations with well screened charges tend to favour the formation of discrete anions in which Cu^I has a low coordination number. It has been recognized that cation properties, such as size, shape and the distribution of positive charge, are of importance for the anion configurations adopted by halidocuprates(I).

In this context, we decided to examine the nature of the complex formed with an unconjugated diimine ligand. The title complex, (I), was prepared by reacting the bidentate ligand N,N'-bis(2-chlorobenzylidene)ethylenediamine (cb₂en) with CuCl. The structure determination of (I) is consistent with the stoichiometry of a 1:1 copper(I) chloride–ligand adduct, [CuCl(L)]. The structural connectivity, however, is that of an ionic complex, the asymmetric unit of the structure comprising a bis(ligand)copper(I) cation and a dichloridocuprate(I) anion, together with a molecule of acetonitrile solvent, [L₂Cu]⁺[CuCl₂]^-·MeCN (Fig. 1).

The anion of (I) has no crystallographic symmetry, and one Cl atom is disordered over two sites. Neither of these gives a completely linear coordination (Table 1). The geometry is in good agreement with that of several other previous examples (Kaiser et al., 1974; Engelhardt et al., 1984).

The cation of (I) has a markedly flattened tetrahedral geometry and also lies in a general position with no crystallographic symmetry. The angles at the Cu^I atom in the cation are similar to the corresponding angles for ethylenediamine complexes (Engelhardt et al., 1984), with a small bite angle for the chelating ligand. The two ligands form a double-helical arrangement around the Cu^I atom. Within the cation, the two benzene rings of each ligand are almost parallel to those of the other, with dihedral angles of 2.73 (16)° for rings C1–C6 and C27–C32, and 0.38 (17)° for rings C11–C16 and C17–C22, with interplanar spacings of about 3.6 Å in each case. This does not give rise to intramolecular π–π stacking, since the pairs of rings are substantially displaced laterally, the centroid-to-centroid distances being 4.877 (4) and 4.846 (4) Å, respectively. However, the same pairs of rings are similarly close to parallel in adjacent molecules along the short a axis (dihedral angles are the same by symmetry), and here there is intermolecular π–π stacking (Fig. 2), the centroid-to-centroid distances being 3.645 (3) and 3.536 (3) Å, respectively, and the interplanar spacings being 3.532 and 3.523 Å, respectively. This stacking produces columns of cations along the a axis, with anions and solvent molecules occupying the channels between them (Fig. 3).

Related literature

For related literature, see: Alcon et al. (2000); Amirnasr et al. (2005); Andersson & Jagner (1989); Bowker et al. (1988); Bowmarker et al. (2000); Bruker (2005); Dietrich-Buchecker & Sauvage (1987); Engelhardt et al. (1984); Fife et al. (1985); Foster et al. (2000); Hasselgren et al. (1999); Horváth (1994); Kaiser et al. (1974); Kutal (1990); Lange et al. (2000); Meghdadi et al. (2002); Miller & Karpishin (1999); Mirkhani et al. (2004); Panja et al. (2002); Rosi et al. (1999).

S2. Experimental

The title compound was prepared by the reaction of CuCl and cb₂en (molar ratio 1:1) in an acetonitrile solution at room temperature. The solution was then concentrated under vacuum. Red crystals of (I) were formed by vapour diffusion of diethyl ether into the concentrated solution.

S3. Refinement

The small size and weak diffraction of the crystals necessitated the use of synchrotron radiation. The crystal was found to be a non-merohedral rotation twin about (100), with symmetry-inequivalent reflections overlapping in the diffraction pattern, making it impossible to merge equivalent reflections before the refinement with SHELXL HKLF5 style data (SHELXTL; Bruker, 2005). The twin law is (1 0 0/ 0 - 1 0/ -0.8867 0 - 1). A number of reflections were rejected in the data processing because of problems with spot shape or masking by the beamstop. The deposited structure factors are in the format generated by the undocumented LIST 7 instruction of SHELXTL (and SHELXL97), in which the contributions of the twin components are identified following refinement of the twin fraction; this was 0.5415:0.4585 (5).

All H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.95–0.99 Å, with U_iso(H) = 1.2U_eq(C) [1.5U_eq(C) for methyl H atoms]. One Cl atom of the anion was modelled as disordered over two positions, with occupancy factors 0.55:0.45 (2). Twofold disorder was also found for the CH₂CH₂ bridge of one of the ligands in the cation, with occupancy factors 0.515:0.485 (15); restraints were applied to the displacement parameters of these disordered atoms.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Bruker, 2005); program(s) used to refine structure: SHELXTL (Bruker, 2005); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL (Bruker, 2005) and local programs.

Figures

	Fig. 1. The asymmetric unit of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity, and only one component is shown for each disordered group.
	Fig. 2. The stacking of cations of (I) via π–π interactions.
	Fig. 3. The crystal packing in (I), viewed along the a axis, showing the columns of cations, with anions and solvent molecules in channels.

Bis[N,N'-(2-chlorobenzylidene)ethylenediamine-κ²N,N']copper(I) dichloridocuprate(I) acetonitrile solvate

Crystal data

[Cu(C16H14Cl2N2)2][CuCl2]·C2H3N	F(000) = 1720
Mr = 849.42	Dx = 1.590 Mg m^−3
Monoclinic, P21/n	Synchrotron radiation, λ = 0.8462 Å
Hall symbol: -P 2yn	Cell parameters from 1720 reflections
a = 7.845 (5) Å	θ = 3.7–33.3°
b = 16.965 (10) Å	µ = 1.68 mm^−1
c = 26.915 (15) Å	T = 120 K
β = 97.896 (9)°	Block, orange
V = 3548 (4) Å^3	0.10 × 0.10 × 0.10 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	30485 independent reflections
Radiation source: Daresbury SRS station 16.2SMX	15283 reflections with I > 2σ(I)
Silicon 111 monochromator	Rint = 0.000
thin–slice ω scans	θmax = 31.9°, θmin = 4.2°
Absorption correction: multi-scan (TWINABS; Bruker, 2004)	h = −9→9
Tmin = 0.730, Tmax = 0.850	k = −21→21
30485 measured reflections	l = −33→33

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H-atom parameters constrained
S = 0.79	w = 1/[σ^2(Fo^2) + (0.0359P)^2] where P = (Fo^2 + 2Fc^2)/3
30485 reflections	(Δ/σ)max = 0.005
456 parameters	Δρmax = 0.71 e Å^−3
24 restraints	Δρmin = −0.84 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.27850 (5)	0.24353 (3)	0.624256 (15)	0.01994 (11)
Cu2	0.24837 (6)	0.25659 (3)	0.320108 (17)	0.03667 (14)
Cl1	0.54531 (12)	−0.06468 (6)	0.68760 (4)	0.0346 (3)
Cl2	0.17607 (15)	0.55829 (6)	0.68610 (5)	0.0560 (4)
Cl3	0.42641 (13)	0.54910 (6)	0.55917 (4)	0.0389 (3)
Cl4	0.15693 (12)	−0.06374 (6)	0.56177 (3)	0.0285 (2)
Cl5	0.15291 (12)	0.24529 (6)	0.38838 (3)	0.0353 (2)
Cl6	0.3896 (19)	0.2678 (2)	0.2565 (2)	0.0429 (19)	0.55 (2)
Cl6A	0.3021 (17)	0.2747 (3)	0.24772 (18)	0.0314 (16)	0.45 (2)
N1	0.4113 (4)	0.17874 (18)	0.67975 (11)	0.0312 (8)
N2	0.2138 (4)	0.31162 (17)	0.68051 (11)	0.0237 (7)
N3	0.3661 (3)	0.30304 (17)	0.56702 (11)	0.0200 (7)
N4	0.1356 (3)	0.18205 (17)	0.56960 (10)	0.0195 (7)
N5	0.7040 (4)	0.2583 (2)	0.48590 (14)	0.0431 (9)
C1	0.5758 (4)	−0.0059 (2)	0.63605 (14)	0.0208 (9)
C2	0.6331 (4)	−0.0427 (2)	0.59556 (14)	0.0226 (9)
H2A	0.6550	−0.0978	0.5965	0.027*
C3	0.6584 (4)	0.0003 (2)	0.55406 (14)	0.0266 (10)
H3A	0.6958	−0.0247	0.5259	0.032*
C4	0.6282 (4)	0.0818 (2)	0.55377 (14)	0.0256 (9)
H4A	0.6448	0.1124	0.5253	0.031*
C5	0.5743 (4)	0.1175 (2)	0.59511 (13)	0.0205 (9)
H5A	0.5564	0.1729	0.5946	0.025*
C6	0.5454 (4)	0.0751 (2)	0.63731 (13)	0.0171 (8)
C7	0.4939 (5)	0.1137 (2)	0.68146 (14)	0.0302 (10)
H7A	0.5235	0.0891	0.7132	0.036*
C8	0.4227 (15)	0.2261 (6)	0.7287 (3)	0.017 (3)	0.485 (14)
H8A	0.5132	0.2669	0.7298	0.021*	0.485 (14)
H8B	0.4510	0.1908	0.7580	0.021*	0.485 (14)
C8A	0.3345 (15)	0.1978 (6)	0.7264 (3)	0.020 (3)	0.515 (14)
H8AA	0.4101	0.1792	0.7567	0.024*	0.515 (14)
H8AB	0.2200	0.1729	0.7255	0.024*	0.515 (14)
C9	0.2456 (15)	0.2646 (6)	0.7296 (3)	0.021 (3)	0.485 (14)
H9A	0.1554	0.2241	0.7308	0.025*	0.485 (14)
H9B	0.2472	0.2999	0.7590	0.025*	0.485 (14)
C9A	0.3195 (14)	0.2863 (5)	0.7264 (3)	0.020 (2)	0.515 (14)
H9AA	0.2665	0.3037	0.7559	0.024*	0.515 (14)
H9AB	0.4353	0.3103	0.7286	0.024*	0.515 (14)
C10	0.1506 (4)	0.3805 (2)	0.68212 (14)	0.0279 (10)
H10A	0.1546	0.4052	0.7139	0.033*
C11	0.0711 (4)	0.4240 (2)	0.63727 (15)	0.0238 (9)
C12	−0.0142 (4)	0.3837 (2)	0.59701 (15)	0.0262 (10)
H12A	−0.0178	0.3277	0.5976	0.031*
C13	−0.0948 (5)	0.4237 (3)	0.55571 (16)	0.0357 (11)
H13A	−0.1538	0.3956	0.5280	0.043*
C14	−0.0889 (5)	0.5055 (3)	0.55494 (18)	0.0458 (13)
H14A	−0.1425	0.5331	0.5263	0.055*
C15	−0.0085 (5)	0.5463 (3)	0.5942 (2)	0.0458 (13)
H15A	−0.0070	0.6023	0.5937	0.055*
C16	0.0720 (5)	0.5052 (2)	0.63543 (16)	0.0329 (11)
C17	0.5256 (4)	0.4950 (2)	0.60984 (15)	0.0250 (9)
C18	0.6097 (5)	0.5350 (2)	0.65003 (17)	0.0325 (11)
H18A	0.6123	0.5909	0.6500	0.039*
C19	0.6905 (5)	0.4936 (2)	0.69041 (16)	0.0342 (11)
H19A	0.7506	0.5208	0.7183	0.041*
C20	0.6839 (4)	0.4117 (2)	0.69030 (14)	0.0256 (9)
H20A	0.7381	0.3830	0.7184	0.031*
C21	0.5994 (4)	0.3725 (2)	0.64982 (13)	0.0207 (9)
H21A	0.5982	0.3165	0.6498	0.025*
C22	0.5159 (4)	0.4126 (2)	0.60896 (14)	0.0193 (9)
C23	0.4375 (4)	0.3703 (2)	0.56447 (14)	0.0248 (9)
H23A	0.4396	0.3936	0.5325	0.030*
C24	0.3069 (4)	0.2628 (2)	0.51925 (12)	0.0235 (9)
H24A	0.3920	0.2224	0.5127	0.028*
H24B	0.2966	0.3015	0.4914	0.028*
C25	0.1333 (4)	0.2241 (2)	0.52152 (12)	0.0266 (10)
H25A	0.0418	0.2647	0.5182	0.032*
H25B	0.1077	0.1864	0.4934	0.032*
C26	0.0824 (4)	0.1117 (2)	0.56783 (13)	0.0203 (9)
H26A	0.0503	0.0882	0.5359	0.024*
C27	0.0679 (4)	0.0644 (2)	0.61281 (13)	0.0179 (8)
C28	0.0179 (4)	0.0987 (2)	0.65588 (13)	0.0184 (9)
H28A	−0.0019	0.1540	0.6565	0.022*
C29	−0.0034 (4)	0.0539 (2)	0.69757 (13)	0.0224 (9)
H29A	−0.0386	0.0784	0.7262	0.027*
C30	0.0263 (4)	−0.0265 (2)	0.69768 (13)	0.0213 (9)
H30A	0.0139	−0.0570	0.7266	0.026*
C31	0.0731 (4)	−0.0616 (2)	0.65649 (13)	0.0206 (9)
H31A	0.0927	−0.1169	0.6565	0.025*
C32	0.0928 (4)	−0.0171 (2)	0.61401 (13)	0.0168 (8)
C33	0.6915 (4)	0.2562 (2)	0.44344 (19)	0.0338 (10)
C34	0.6791 (4)	0.2547 (2)	0.38894 (14)	0.0401 (10)
H34A	0.6162	0.3014	0.3749	0.060*
H34B	0.6178	0.2071	0.3760	0.060*
H34C	0.7950	0.2548	0.3792	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0275 (2)	0.0170 (3)	0.0153 (2)	0.0016 (2)	0.00302 (18)	0.0026 (2)
Cu2	0.0576 (3)	0.0208 (3)	0.0306 (3)	−0.0078 (3)	0.0024 (2)	0.0008 (3)
Cl1	0.0369 (6)	0.0301 (6)	0.0369 (6)	0.0058 (5)	0.0058 (5)	0.0179 (5)
Cl2	0.0636 (8)	0.0274 (7)	0.0813 (10)	−0.0044 (6)	0.0249 (7)	−0.0206 (7)
Cl3	0.0535 (7)	0.0248 (6)	0.0416 (7)	0.0138 (5)	0.0178 (6)	0.0146 (5)
Cl4	0.0406 (6)	0.0252 (6)	0.0200 (5)	0.0038 (5)	0.0058 (4)	−0.0064 (4)
Cl5	0.0502 (6)	0.0235 (6)	0.0324 (6)	0.0059 (5)	0.0065 (4)	−0.0036 (5)
Cl6	0.047 (5)	0.0357 (15)	0.0489 (18)	−0.0119 (19)	0.015 (2)	0.0140 (13)
Cl6A	0.024 (4)	0.0340 (17)	0.0347 (17)	−0.0061 (18)	−0.0009 (19)	0.0068 (12)
N1	0.043 (2)	0.033 (2)	0.0170 (19)	0.0180 (17)	0.0032 (16)	0.0064 (15)
N2	0.032 (2)	0.0207 (19)	0.0170 (18)	0.0054 (15)	−0.0024 (15)	−0.0025 (14)
N3	0.0168 (17)	0.0213 (19)	0.0230 (19)	0.0038 (14)	0.0063 (14)	0.0057 (14)
N4	0.0256 (18)	0.0197 (19)	0.0135 (17)	0.0025 (15)	0.0037 (13)	0.0014 (13)
N5	0.038 (2)	0.026 (2)	0.066 (3)	0.0021 (18)	0.010 (2)	0.007 (2)
C1	0.016 (2)	0.024 (2)	0.021 (2)	−0.0007 (17)	0.0006 (17)	0.0096 (18)
C2	0.019 (2)	0.014 (2)	0.034 (2)	0.0006 (17)	0.0008 (18)	0.0044 (18)
C3	0.026 (2)	0.032 (3)	0.022 (2)	0.0100 (19)	0.0026 (18)	−0.0023 (19)
C4	0.025 (2)	0.024 (2)	0.027 (2)	0.0031 (18)	0.0018 (18)	0.0095 (19)
C5	0.019 (2)	0.018 (2)	0.024 (2)	0.0073 (17)	0.0014 (17)	0.0041 (17)
C6	0.011 (2)	0.018 (2)	0.020 (2)	0.0034 (16)	−0.0032 (16)	0.0025 (17)
C7	0.041 (3)	0.031 (3)	0.016 (2)	0.010 (2)	−0.0018 (19)	0.0081 (18)
C8	0.023 (4)	0.021 (4)	0.010 (3)	−0.006 (3)	0.007 (3)	0.001 (3)
C8A	0.023 (4)	0.022 (4)	0.014 (3)	0.002 (3)	−0.003 (3)	−0.002 (3)
C9	0.026 (4)	0.031 (4)	0.005 (3)	−0.011 (3)	0.001 (3)	0.005 (3)
C9A	0.023 (4)	0.020 (4)	0.018 (4)	−0.008 (3)	0.007 (3)	−0.004 (3)
C10	0.027 (2)	0.028 (3)	0.028 (2)	0.0022 (19)	0.0027 (19)	−0.0145 (19)
C11	0.018 (2)	0.027 (2)	0.029 (2)	0.0058 (19)	0.0119 (18)	0.0048 (19)
C12	0.020 (2)	0.023 (2)	0.037 (3)	0.0069 (18)	0.0086 (19)	0.002 (2)
C13	0.027 (2)	0.047 (3)	0.035 (3)	0.011 (2)	0.011 (2)	0.004 (2)
C14	0.038 (3)	0.060 (4)	0.042 (3)	0.031 (3)	0.018 (2)	0.021 (3)
C15	0.046 (3)	0.020 (3)	0.081 (4)	0.015 (2)	0.041 (3)	0.012 (3)
C16	0.033 (3)	0.020 (2)	0.051 (3)	0.006 (2)	0.023 (2)	0.002 (2)
C17	0.017 (2)	0.032 (3)	0.029 (3)	0.0038 (19)	0.0140 (18)	0.011 (2)
C18	0.032 (3)	0.019 (2)	0.051 (3)	−0.001 (2)	0.022 (2)	0.001 (2)
C19	0.023 (2)	0.042 (3)	0.040 (3)	−0.010 (2)	0.012 (2)	−0.009 (2)
C20	0.021 (2)	0.028 (2)	0.029 (2)	−0.0051 (18)	0.0076 (18)	0.0014 (19)
C21	0.017 (2)	0.020 (2)	0.026 (2)	−0.0020 (17)	0.0062 (17)	0.0038 (17)
C22	0.017 (2)	0.019 (2)	0.025 (2)	−0.0032 (17)	0.0125 (17)	0.0078 (18)
C23	0.021 (2)	0.030 (3)	0.023 (2)	0.0068 (19)	0.0043 (18)	0.0100 (18)
C24	0.027 (2)	0.031 (2)	0.0126 (18)	0.0032 (19)	0.0035 (16)	0.0064 (18)
C25	0.038 (3)	0.021 (2)	0.018 (2)	0.0033 (18)	−0.0037 (18)	0.0051 (17)
C26	0.021 (2)	0.024 (2)	0.016 (2)	−0.0046 (18)	0.0014 (17)	−0.0018 (16)
C27	0.017 (2)	0.022 (2)	0.014 (2)	−0.0009 (17)	0.0030 (16)	−0.0018 (17)
C28	0.018 (2)	0.016 (2)	0.022 (2)	0.0040 (16)	0.0035 (17)	−0.0015 (16)
C29	0.024 (2)	0.030 (2)	0.014 (2)	0.0045 (18)	0.0055 (16)	−0.0016 (18)
C30	0.023 (2)	0.019 (2)	0.023 (2)	−0.0054 (17)	0.0064 (17)	0.0068 (17)
C31	0.016 (2)	0.013 (2)	0.032 (2)	0.0020 (17)	0.0011 (17)	0.0000 (17)
C32	0.013 (2)	0.018 (2)	0.020 (2)	0.0013 (16)	0.0037 (16)	−0.0052 (16)
C33	0.017 (2)	0.013 (2)	0.073 (3)	0.0064 (19)	0.014 (2)	0.006 (3)
C34	0.039 (2)	0.024 (2)	0.058 (3)	0.008 (2)	0.008 (2)	0.013 (2)

Geometric parameters (Å, º)

Cu1—N1	2.024 (3)	C10—C11	1.478 (5)
Cu1—N2	2.024 (3)	C11—C12	1.375 (5)
Cu1—N3	2.039 (3)	C11—C16	1.378 (5)
Cu1—N4	2.014 (3)	C12—H12A	0.950
Cu2—Cl5	2.0862 (14)	C12—C13	1.380 (5)
Cu2—Cl6	2.171 (5)	C13—H13A	0.950
Cu2—Cl6A	2.072 (4)	C13—C14	1.388 (5)
Cl1—C1	1.752 (4)	C14—H14A	0.950
Cl2—C16	1.741 (4)	C14—C15	1.346 (6)
Cl3—C17	1.737 (4)	C15—H15A	0.950
Cl4—C32	1.747 (3)	C15—C16	1.387 (6)
N1—C7	1.277 (4)	C17—C18	1.367 (5)
N1—C8	1.535 (8)	C17—C22	1.399 (5)
N1—C8A	1.502 (8)	C18—H18A	0.950
N2—C9	1.534 (8)	C18—C19	1.373 (5)
N2—C9A	1.456 (9)	C19—H19A	0.950
N2—C10	1.272 (4)	C19—C20	1.390 (5)
N3—C23	1.278 (4)	C20—H20A	0.950
N3—C24	1.473 (4)	C20—C21	1.368 (5)
N4—C25	1.475 (4)	C21—H21A	0.950
N4—C26	1.264 (4)	C21—C22	1.380 (5)
N5—C33	1.134 (5)	C22—C23	1.457 (5)
C1—C2	1.384 (5)	C23—H23A	0.950
C1—C6	1.397 (5)	C24—H24A	0.990
C2—H2A	0.950	C24—H24B	0.990
C2—C3	1.371 (5)	C24—C25	1.521 (4)
C3—H3A	0.950	C25—H25A	0.990
C3—C4	1.402 (5)	C25—H25B	0.990
C4—H4A	0.950	C26—H26A	0.950
C4—C5	1.384 (5)	C26—C27	1.470 (4)
C5—H5A	0.950	C27—C28	1.401 (4)
C5—C6	1.389 (4)	C27—C32	1.395 (5)
C6—C7	1.461 (5)	C28—H28A	0.950
C7—H7A	0.950	C28—C29	1.385 (4)
C8—H8A	0.990	C29—H29A	0.950
C8—H8B	0.990	C29—C30	1.384 (5)
C8—C9	1.539 (16)	C30—H30A	0.950
C8A—H8AA	0.990	C30—C31	1.353 (4)
C8A—H8AB	0.990	C31—H31A	0.950
C8A—C9A	1.505 (14)	C31—C32	1.397 (5)
C9—H9A	0.990	C33—C34	1.457 (5)
C9—H9B	0.990	C34—H34A	0.980
C9A—H9AA	0.990	C34—H34B	0.980
C9A—H9AB	0.990	C34—H34C	0.980
C10—H10A	0.950
N1—Cu1—N2	85.09 (12)	C11—C12—C13	120.6 (4)
N1—Cu1—N3	129.33 (12)	H12A—C12—C13	119.7
N1—Cu1—N4	115.87 (13)	C12—C13—H13A	120.3
N2—Cu1—N3	115.33 (12)	C12—C13—C14	119.4 (4)
N2—Cu1—N4	132.11 (11)	H13A—C13—C14	120.3
N3—Cu1—N4	85.18 (12)	C13—C14—H14A	119.5
Cl5—Cu2—Cl6	170.5 (4)	C13—C14—C15	121.0 (4)
Cl5—Cu2—Cl6A	170.3 (4)	H14A—C14—C15	119.5
Cu1—N1—C7	134.7 (3)	C14—C15—H15A	120.6
Cu1—N1—C8	108.2 (3)	C14—C15—C16	118.9 (4)
Cu1—N1—C8A	106.0 (3)	H15A—C15—C16	120.6
C7—N1—C8	116.8 (4)	Cl2—C16—C11	119.5 (3)
C7—N1—C8A	114.6 (4)	Cl2—C16—C15	118.6 (4)
Cu1—N2—C9	108.7 (4)	C11—C16—C15	121.8 (4)
Cu1—N2—C9A	107.1 (4)	Cl3—C17—C18	118.3 (3)
Cu1—N2—C10	133.5 (3)	Cl3—C17—C22	119.8 (3)
C9—N2—C10	117.8 (4)	C18—C17—C22	121.9 (4)
C9A—N2—C10	114.9 (4)	C17—C18—H18A	120.2
Cu1—N3—C23	132.8 (3)	C17—C18—C19	119.5 (4)
Cu1—N3—C24	109.4 (2)	H18A—C18—C19	120.2
C23—N3—C24	117.1 (3)	C18—C19—H19A	120.1
Cu1—N4—C25	109.2 (2)	C18—C19—C20	119.7 (4)
Cu1—N4—C26	131.7 (2)	H19A—C19—C20	120.1
C25—N4—C26	117.3 (3)	C19—C20—H20A	119.9
Cl1—C1—C2	117.5 (3)	C19—C20—C21	120.2 (4)
Cl1—C1—C6	119.9 (3)	H20A—C20—C21	119.9
C2—C1—C6	122.6 (3)	C20—C21—H21A	119.4
C1—C2—H2A	120.0	C20—C21—C22	121.3 (4)
C1—C2—C3	120.0 (3)	H21A—C21—C22	119.4
H2A—C2—C3	120.0	C17—C22—C21	117.4 (4)
C2—C3—H3A	120.5	C17—C22—C23	121.4 (4)
C2—C3—C4	119.1 (4)	C21—C22—C23	120.8 (3)
H3A—C3—C4	120.5	N3—C23—C22	122.3 (3)
C3—C4—H4A	120.1	N3—C23—H23A	118.9
C3—C4—C5	119.8 (4)	C22—C23—H23A	118.9
H4A—C4—C5	120.1	N3—C24—H24A	109.7
C4—C5—H5A	118.9	N3—C24—H24B	109.7
C4—C5—C6	122.2 (3)	N3—C24—C25	110.0 (3)
H5A—C5—C6	118.9	H24A—C24—H24B	108.2
C1—C6—C5	116.2 (3)	H24A—C24—C25	109.7
C1—C6—C7	121.9 (3)	H24B—C24—C25	109.7
C5—C6—C7	121.8 (3)	N4—C25—C24	109.9 (3)
N1—C7—C6	123.6 (3)	N4—C25—H25A	109.7
N1—C7—H7A	118.2	N4—C25—H25B	109.7
C6—C7—H7A	118.2	C24—C25—H25A	109.7
N1—C8—H8A	110.4	C24—C25—H25B	109.7
N1—C8—H8B	110.4	H25A—C25—H25B	108.2
N1—C8—C9	106.8 (8)	N4—C26—H26A	118.4
H8A—C8—H8B	108.6	N4—C26—C27	123.2 (3)
H8A—C8—C9	110.4	H26A—C26—C27	118.4
H8B—C8—C9	110.4	C26—C27—C28	121.1 (3)
N1—C8A—H8AA	110.8	C26—C27—C32	122.2 (3)
N1—C8A—H8AB	110.8	C28—C27—C32	116.6 (3)
N1—C8A—C9A	104.8 (9)	C27—C28—H28A	119.3
H8AA—C8A—H8AB	108.9	C27—C28—C29	121.4 (3)
H8AA—C8A—C9A	110.8	H28A—C28—C29	119.3
H8AB—C8A—C9A	110.8	C28—C29—H29A	119.9
N2—C9—C8	104.3 (7)	C28—C29—C30	120.3 (3)
N2—C9—H9A	110.9	H29A—C29—C30	119.9
N2—C9—H9B	110.9	C29—C30—H30A	120.1
C8—C9—H9A	110.9	C29—C30—C31	119.8 (3)
C8—C9—H9B	110.9	H30A—C30—C31	120.1
H9A—C9—H9B	108.9	C30—C31—H31A	119.8
N2—C9A—C8A	109.3 (8)	C30—C31—C32	120.3 (3)
N2—C9A—H9AA	109.8	H31A—C31—C32	119.8
N2—C9A—H9AB	109.8	Cl4—C32—C27	119.0 (3)
C8A—C9A—H9AA	109.8	Cl4—C32—C31	119.3 (3)
C8A—C9A—H9AB	109.8	C27—C32—C31	121.6 (3)
H9AA—C9A—H9AB	108.3	N5—C33—C34	178.6 (5)
N2—C10—H10A	118.2	C33—C34—H34A	109.5
N2—C10—C11	123.6 (4)	C33—C34—H34B	109.5
H10A—C10—C11	118.2	C33—C34—H34C	109.5
C10—C11—C12	120.0 (4)	H34A—C34—H34B	109.5
C10—C11—C16	121.7 (4)	H34A—C34—H34C	109.5
C12—C11—C16	118.2 (4)	H34B—C34—H34C	109.5
C11—C12—H12A	119.7
N2—Cu1—N1—C7	173.7 (4)	Cu1—N2—C9A—C8A	−39.7 (11)
N2—Cu1—N1—C8	−12.8 (5)	C10—N2—C9A—C8A	160.5 (8)
N2—Cu1—N1—C8A	20.7 (5)	N1—C8A—C9A—N2	58.0 (12)
N3—Cu1—N1—C7	−67.3 (4)	Cu1—N2—C10—C11	13.9 (6)
N3—Cu1—N1—C8	106.2 (5)	C9—N2—C10—C11	−163.3 (6)
N3—Cu1—N1—C8A	139.7 (5)	C9A—N2—C10—C11	166.7 (6)
N4—Cu1—N1—C7	38.8 (4)	N2—C10—C11—C12	32.2 (5)
N4—Cu1—N1—C8	−147.7 (5)	N2—C10—C11—C16	−151.3 (4)
N4—Cu1—N1—C8A	−114.3 (5)	C10—C11—C12—C13	177.4 (3)
N1—Cu1—N2—C9	−18.2 (5)	C16—C11—C12—C13	0.8 (5)
N1—Cu1—N2—C9A	10.1 (5)	C11—C12—C13—C14	0.1 (6)
N1—Cu1—N2—C10	164.5 (4)	C12—C13—C14—C15	−1.2 (6)
N3—Cu1—N2—C9	−149.7 (5)	C13—C14—C15—C16	1.3 (6)
N3—Cu1—N2—C9A	−121.4 (5)	C10—C11—C16—Cl2	2.5 (5)
N3—Cu1—N2—C10	32.9 (4)	C10—C11—C16—C15	−177.3 (3)
N4—Cu1—N2—C9	102.6 (5)	C12—C11—C16—Cl2	179.1 (3)
N4—Cu1—N2—C9A	131.0 (5)	C12—C11—C16—C15	−0.7 (6)
N4—Cu1—N2—C10	−74.7 (4)	C14—C15—C16—Cl2	179.9 (3)
N1—Cu1—N3—C23	−80.8 (4)	C14—C15—C16—C11	−0.3 (6)
N1—Cu1—N3—C24	110.1 (2)	Cl3—C17—C18—C19	−179.5 (3)
N2—Cu1—N3—C23	24.6 (4)	C22—C17—C18—C19	1.4 (6)
N2—Cu1—N3—C24	−144.5 (2)	C17—C18—C19—C20	−0.9 (5)
N4—Cu1—N3—C23	159.4 (3)	C18—C19—C20—C21	1.0 (5)
N4—Cu1—N3—C24	−9.7 (2)	C19—C20—C21—C22	−1.6 (5)
N1—Cu1—N4—C25	−146.6 (2)	C20—C21—C22—C17	2.0 (5)
N1—Cu1—N4—C26	17.4 (4)	C20—C21—C22—C23	175.3 (3)
N2—Cu1—N4—C25	105.4 (2)	Cl3—C17—C22—C21	179.0 (3)
N2—Cu1—N4—C26	−90.7 (3)	Cl3—C17—C22—C23	5.7 (5)
N3—Cu1—N4—C25	−14.8 (2)	C18—C17—C22—C21	−1.9 (5)
N3—Cu1—N4—C26	149.2 (3)	C18—C17—C22—C23	−175.2 (3)
Cl1—C1—C2—C3	179.6 (3)	Cu1—N3—C23—C22	17.5 (5)
C6—C1—C2—C3	−1.5 (5)	C24—N3—C23—C22	−174.1 (3)
C1—C2—C3—C4	1.1 (5)	C17—C22—C23—N3	−151.8 (3)
C2—C3—C4—C5	0.2 (5)	C21—C22—C23—N3	35.1 (5)
C3—C4—C5—C6	−1.2 (5)	Cu1—N3—C24—C25	31.7 (3)
C4—C5—C6—C1	0.8 (5)	C23—N3—C24—C25	−139.3 (3)
C4—C5—C6—C7	177.9 (3)	Cu1—N4—C25—C24	36.0 (3)
Cl1—C1—C6—C5	179.4 (3)	C26—N4—C25—C24	−130.6 (3)
Cl1—C1—C6—C7	2.2 (5)	N3—C24—C25—N4	−45.2 (4)
C2—C1—C6—C5	0.6 (5)	Cu1—N4—C26—C27	20.8 (5)
C2—C1—C6—C7	−176.6 (3)	C25—N4—C26—C27	−176.3 (3)
Cu1—N1—C7—C6	14.4 (6)	N4—C26—C27—C28	36.1 (5)
C8—N1—C7—C6	−158.7 (6)	N4—C26—C27—C32	−147.7 (3)
C8A—N1—C7—C6	165.8 (6)	C26—C27—C28—C29	177.1 (3)
C1—C6—C7—N1	−155.8 (4)	C32—C27—C28—C29	0.8 (5)
C5—C6—C7—N1	27.2 (6)	C27—C28—C29—C30	0.6 (5)
Cu1—N1—C8—C9	41.2 (10)	C28—C29—C30—C31	−1.3 (5)
C7—N1—C8—C9	−143.9 (7)	C29—C30—C31—C32	0.5 (5)
Cu1—N1—C8A—C9A	−46.2 (10)	C26—C27—C32—Cl4	4.2 (4)
C7—N1—C8A—C9A	154.6 (7)	C26—C27—C32—C31	−177.9 (3)
Cu1—N2—C9—C8	44.6 (10)	C28—C27—C32—Cl4	−179.5 (3)
C9A—N2—C9—C8	−46.6 (12)	C28—C27—C32—C31	−1.6 (5)
C10—N2—C9—C8	−137.6 (7)	C30—C31—C32—Cl4	178.9 (3)
N1—C8—C9—N2	−55.7 (11)	C30—C31—C32—C27	1.0 (5)