Bis[3,6-bis(6-methyl-2-pyridyl)pyridazine-κ²N²,N³]chlorocopper(II) perchlorate

The title compound, [CuCl(C₁₆H₁₄N₄)₂]ClO₄, consists of a mononuclear complex cation and a perchlorate anion. The coordination of the copper(II) ion exhibits a trigonal bipyramidal geometry, where the equatorial plane is composed of the Cl atom and two N atoms of the two pyridazine rings, and the axial positions are occupied by the N atoms of two methyl­pyridine rings.

S1. Comment

The existence of a dinuclear complex with two 3,6-bis(6-methyl-2-pyridyl)pyridazine ligands is not thought to be possible, due to steric hindrance between the 6-methyl groups on the pyridyl rings in the intermolecular reaction. The most interesting feature of the title compound, (I), is an unusual pentacoordination of the Cu atom with the organic ligands, which showed reasonable hydrolysis reactivity for phosphodiester and DNA model compounds (Sung et al., 2000). \sch

The crystal structure of (I) can best be described as a pseudo-trigonal bipyramidal geometry, with two N atoms (N4 and N5) of the two methylpyridine rings in the axial positions and one Cl and two N atoms [Cl1, N3 and N6] in the equatorial plane. The interaxial N4—Cu—N5 angle of 173.6 (2)° is nearly linear. The Cu atom deviates slightly from the basal N₂Cl plane by 0.044 (3) Å, shifted toward the axially coordinated N4 atom.

The geometry is somewhat distorted from a perfect trigonal bipyramid, as is apparent from the observed τ value of 0.70 (values of 0 and 1 are indicative of idealized square pyramidal and trigonal bipyramidal geometries, respectively; Addison et al., 1984). The axial Cu—N bond distances [2.021 (4) and 2.030 (4) Å] are considerably longer than those in chlorobis[3,6-di(2-pyridyl)pyridazine]copper(II) chloride pentahydrate [1.970 (5) and 1.976 (5) Å; Manotti Lanfredi et al., 1982]. These long axial Cu—N distances may be due to steric hindrance between the 6-methyl groups and the pyridazine rings. It might be ascribed to the hydrolysis reactivity. The axial Cu—N bonds are not perfectly perpendicular to the CuN₂Cl plane, with N—Cu—N and N—Cu—Cl angles ranging from 79.5 (2) to 131.6 (1)°. All atoms in each of the two ligands are planar to within 0.572 (6) Å and the dihedral angle between the two ligands is 52.47 (6)°.

S2. Experimental

The ligand 3,6-bis(6-methyl-2-pyridyl)pyridazine was prepared as described previously by Sung et al. (2000). The green Cu^II complex, (I), was prepared by mixing the free ligand and CuCl₂·6H₂O in the ratio 1:2 in acetone solution and then adding NaClO₄ (1 eq.) to the solution. The final solution was left in the refrigerator for a week, after which time green crystals of (I) had formed. The crystals were washed with absolute ethanol and dried at room temperature.

S3. Refinement

The O1 atom in the perchlorate is disordered over two positions and the two split atoms, designated as O1 and O1', were refined isotropically using PART (ref?). The final occupancy factors of O1 and O1' are 0.54 (3) and 0.46 (3), respectively. The positional parameters of all H atoms were calculated geometrically and constrained to ride on their attached atoms (C—H = ?), with isotropic displacement parameters fixed at 1.2 or 1.5 (for methyl group) times the equivalent isotropic displacement parameters of their parent atoms. The highest peak and the deepest hole in the final difference density map are 0.58 e Å^-3 at 1.57 Å from O4 and -0.38 e Å^-3 at 1.22 Å from the Cu atom.

Computing details

Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); 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).

Figures

Fig. 1. ORTEP-3 for Windows (Farrugia, 1997) diagram of (I) showing 35% probability displacement ellipsoids. H atoms are drawn as small spheres of arbitrary radii.

Bis-[3,6-bis(6-methyl-2-pyridyl)pyridazine-κ²N²,N³]chlorocopper(II) perchlorate

Crystal data

[Cu(C16H14N4)2Cl]·ClO4	Z = 2
Mr = 723.06	F(000) = 742
Triclinic, P1	Dx = 1.524 Mg m^−3
a = 7.3928 (18) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.1176 (11) Å	Cell parameters from 25 reflections
c = 15.7262 (16) Å	θ = 11.4–14.3°
α = 92.439 (8)°	µ = 0.92 mm^−1
β = 96.573 (14)°	T = 293 K
γ = 104.249 (11)°	Plate, green
V = 1576.1 (4) Å^3	0.53 × 0.25 × 0.01 mm

Data collection

Enraf Nonius CAD4 diffractometer	3839 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.041
Graphite monochromator	θmax = 25.5°, θmin = 2.1°
non–profiled ω/2θ scans	h = −8→8
Absorption correction: ψ-scan (North et al., 1968)	k = −17→17
Tmin = 0.666, Tmax = 0.987	l = 0→19
6050 measured reflections	3 standard reflections every 300 min
5821 independent reflections	intensity decay: 8%

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.153	H-atom parameters constrained
S = 1.02	Calculated w = 1/[σ^2(Fo^2) + (0.0632P)^2 + 1.292P] where P = (Fo^2 + 2Fc^2)/3
5821 reflections	(Δ/σ)max < 0.001
424 parameters	Δρmax = 0.58 e Å^−3
11 restraints	Δρmin = −0.38 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	Occ. (<1)
Cu	−0.01526 (9)	0.91042 (4)	0.27180 (4)	0.0395 (2)
Cl1	0.2838 (2)	0.90723 (11)	0.32656 (9)	0.0629 (4)
N1	−0.5880 (6)	0.6905 (3)	0.5378 (3)	0.0506 (11)
N2	−0.3221 (6)	0.8009 (3)	0.3762 (2)	0.0409 (9)
N3	−0.2151 (5)	0.8878 (3)	0.3604 (2)	0.0367 (9)
N4	0.0241 (6)	1.0495 (3)	0.3231 (2)	0.0399 (9)
N5	−0.0771 (5)	0.7750 (3)	0.2113 (2)	0.0382 (9)
N6	−0.1245 (5)	0.9401 (3)	0.1529 (2)	0.0385 (9)
N7	−0.1575 (6)	1.0272 (3)	0.1356 (2)	0.0415 (10)
N8	−0.3086 (5)	1.1505 (3)	−0.0428 (2)	0.0418 (10)
C1	−0.7454 (9)	0.5994 (5)	0.6468 (4)	0.081 (2)
HC1A	−0.8193	0.5347	0.6538	0.121*
HC1B	−0.8174	0.6461	0.6561	0.121*
HC1C	−0.6334	0.6145	0.6875	0.121*
C2	−0.6922 (7)	0.6040 (4)	0.5572 (4)	0.0554 (14)
C3	−0.7405 (9)	0.5222 (5)	0.4987 (4)	0.0682 (17)
HC3	−0.8122	0.4628	0.5134	0.082*
C4	−0.6816 (8)	0.5302 (4)	0.4199 (4)	0.0649 (16)
HC4	−0.7152	0.4764	0.3799	0.078*
C5	−0.5720 (7)	0.6182 (4)	0.3991 (3)	0.0510 (13)
HC5	−0.5290	0.6247	0.3458	0.061*
C6	−0.5287 (7)	0.6958 (4)	0.4599 (3)	0.0446 (12)
C7	−0.4147 (7)	0.7943 (3)	0.4451 (3)	0.0392 (11)
C8	−0.4004 (7)	0.8763 (4)	0.5011 (3)	0.0453 (12)
HC8	−0.4620	0.8703	0.5497	0.054*
C9	−0.2963 (7)	0.9638 (4)	0.4837 (3)	0.0428 (12)
HC9	−0.2861	1.0196	0.5193	0.051*
C10	−0.2036 (6)	0.9688 (3)	0.4106 (3)	0.0376 (11)
C11	−0.0826 (7)	1.0597 (3)	0.3853 (3)	0.0409 (11)
C12	−0.0760 (8)	1.1501 (4)	0.4248 (4)	0.0568 (15)
HC12	−0.1506	1.1558	0.4676	0.068*
C13	0.0438 (9)	1.2314 (4)	0.3990 (4)	0.0712 (18)
HC13	0.0498	1.2932	0.4240	0.085*
C14	0.1542 (9)	1.2219 (4)	0.3368 (4)	0.0633 (16)
HC14	0.2356	1.2769	0.3195	0.076*
C15	0.1440 (8)	1.1293 (4)	0.2997 (3)	0.0504 (13)
C16	0.2691 (9)	1.1184 (4)	0.2339 (4)	0.0723 (18)
H16A	0.2459	1.0504	0.2149	0.108*
H16B	0.3982	1.1426	0.2586	0.108*
H16C	0.2438	1.1551	0.1860	0.108*
C17	−0.0121 (9)	0.6899 (4)	0.3402 (3)	0.0664 (17)
H17A	−0.0036	0.7533	0.3674	0.100*
H17B	0.1063	0.6735	0.3525	0.100*
H17C	−0.1088	0.6419	0.3617	0.100*
C18	−0.0590 (7)	0.6915 (4)	0.2452 (3)	0.0445 (12)
C19	−0.0801 (8)	0.6068 (4)	0.1920 (4)	0.0566 (15)
HC19	−0.0660	0.5496	0.2160	0.068*
C20	−0.1211 (8)	0.6070 (4)	0.1055 (4)	0.0591 (15)
HC20	−0.1322	0.5508	0.0702	0.071*
C21	−0.1459 (7)	0.6918 (4)	0.0707 (3)	0.0510 (13)
HC21	−0.1766	0.6934	0.0118	0.061*
C22	−0.1241 (6)	0.7738 (3)	0.1250 (3)	0.0373 (11)
C23	−0.1580 (6)	0.8657 (3)	0.0930 (3)	0.0335 (10)
C24	−0.2265 (7)	0.8769 (3)	0.0084 (3)	0.0403 (11)
HC24	−0.2484	0.8259	−0.0339	0.048*
C25	−0.2600 (6)	0.9646 (3)	−0.0102 (3)	0.0417 (11)
HC25	−0.3057	0.9749	−0.0657	0.050*
C26	−0.2243 (6)	1.0397 (3)	0.0559 (3)	0.0376 (11)
C27	−0.2599 (6)	1.1370 (3)	0.0401 (3)	0.0397 (11)
C28	−0.2464 (8)	1.2068 (4)	0.1057 (4)	0.0598 (15)
HC28	−0.2123	1.1949	0.1622	0.072*
C29	−0.2845 (9)	1.2949 (4)	0.0861 (4)	0.0699 (17)
HC29	−0.2753	1.3437	0.1292	0.084*
C30	−0.3361 (8)	1.3091 (4)	0.0019 (4)	0.0601 (15)
HC30	−0.3649	1.3674	−0.0125	0.072*
C31	−0.3455 (7)	1.2361 (4)	−0.0619 (3)	0.0465 (13)
C32	−0.3994 (8)	1.2492 (4)	−0.1552 (3)	0.0579 (15)
H32A	−0.4225	1.3128	−0.1608	0.087*
H32B	−0.5113	1.1997	−0.1773	0.087*
H32C	−0.2989	1.2434	−0.1871	0.087*
Cl2	0.2736 (3)	0.42687 (12)	0.16774 (10)	0.0739 (5)
O1	0.332 (3)	0.3423 (9)	0.1464 (6)	0.078 (4)*	0.54 (3)
O1'	0.239 (3)	0.3212 (8)	0.1428 (6)	0.065 (5)*	0.46 (3)
O2	0.1330 (9)	0.4159 (4)	0.2270 (4)	0.126 (2)
O3	0.4353 (10)	0.4847 (6)	0.2123 (5)	0.178 (3)
O4	0.2007 (10)	0.4683 (4)	0.0971 (3)	0.122 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0486 (4)	0.0422 (4)	0.0309 (3)	0.0176 (3)	0.0045 (3)	0.0043 (2)
Cl1	0.0584 (9)	0.0857 (11)	0.0490 (8)	0.0379 (8)	−0.0097 (7)	−0.0177 (7)
N1	0.050 (3)	0.061 (3)	0.046 (3)	0.018 (2)	0.011 (2)	0.012 (2)
N2	0.047 (2)	0.041 (2)	0.036 (2)	0.013 (2)	0.0082 (19)	0.0026 (18)
N3	0.042 (2)	0.040 (2)	0.032 (2)	0.0169 (19)	0.0065 (17)	0.0003 (17)
N4	0.048 (2)	0.041 (2)	0.030 (2)	0.0121 (19)	−0.0022 (18)	0.0050 (17)
N5	0.039 (2)	0.039 (2)	0.041 (2)	0.0161 (18)	0.0104 (18)	0.0073 (18)
N6	0.046 (2)	0.037 (2)	0.033 (2)	0.0115 (18)	0.0050 (18)	0.0040 (17)
N7	0.053 (3)	0.037 (2)	0.035 (2)	0.0152 (19)	0.0010 (19)	0.0044 (18)
N8	0.040 (2)	0.049 (2)	0.040 (2)	0.0151 (19)	0.0085 (18)	0.0145 (19)
C1	0.081 (5)	0.097 (5)	0.071 (4)	0.022 (4)	0.030 (4)	0.039 (4)
C2	0.046 (3)	0.065 (4)	0.060 (4)	0.018 (3)	0.011 (3)	0.022 (3)
C3	0.062 (4)	0.057 (4)	0.084 (5)	0.008 (3)	0.013 (3)	0.020 (3)
C4	0.067 (4)	0.051 (4)	0.073 (4)	0.009 (3)	0.004 (3)	0.003 (3)
C5	0.054 (3)	0.048 (3)	0.052 (3)	0.014 (3)	0.005 (3)	0.006 (3)
C6	0.043 (3)	0.053 (3)	0.042 (3)	0.019 (2)	0.005 (2)	0.009 (2)
C7	0.041 (3)	0.041 (3)	0.038 (3)	0.018 (2)	−0.001 (2)	0.004 (2)
C8	0.046 (3)	0.060 (3)	0.033 (3)	0.020 (3)	0.007 (2)	−0.004 (2)
C9	0.046 (3)	0.052 (3)	0.033 (3)	0.021 (3)	0.001 (2)	−0.008 (2)
C10	0.033 (3)	0.043 (3)	0.039 (3)	0.018 (2)	−0.002 (2)	0.000 (2)
C11	0.043 (3)	0.042 (3)	0.039 (3)	0.017 (2)	−0.004 (2)	0.000 (2)
C12	0.056 (4)	0.043 (3)	0.073 (4)	0.019 (3)	0.003 (3)	−0.008 (3)
C13	0.083 (5)	0.042 (3)	0.086 (5)	0.019 (3)	−0.005 (4)	−0.007 (3)
C14	0.076 (4)	0.043 (3)	0.062 (4)	0.001 (3)	−0.003 (3)	0.018 (3)
C15	0.055 (3)	0.052 (3)	0.040 (3)	0.008 (3)	−0.002 (2)	0.012 (2)
C16	0.083 (5)	0.066 (4)	0.058 (4)	−0.003 (3)	0.014 (3)	0.011 (3)
C17	0.094 (5)	0.068 (4)	0.053 (3)	0.043 (4)	0.018 (3)	0.021 (3)
C18	0.045 (3)	0.044 (3)	0.053 (3)	0.021 (2)	0.016 (2)	0.014 (2)
C19	0.068 (4)	0.041 (3)	0.067 (4)	0.019 (3)	0.019 (3)	0.018 (3)
C20	0.072 (4)	0.042 (3)	0.064 (4)	0.015 (3)	0.013 (3)	−0.004 (3)
C21	0.061 (4)	0.041 (3)	0.050 (3)	0.010 (3)	0.009 (3)	0.002 (2)
C22	0.032 (3)	0.039 (3)	0.041 (3)	0.008 (2)	0.008 (2)	0.005 (2)
C23	0.029 (2)	0.040 (3)	0.031 (2)	0.006 (2)	0.0065 (19)	0.001 (2)
C24	0.045 (3)	0.043 (3)	0.032 (2)	0.010 (2)	0.004 (2)	−0.001 (2)
C25	0.039 (3)	0.052 (3)	0.033 (3)	0.012 (2)	0.001 (2)	0.005 (2)
C26	0.035 (3)	0.042 (3)	0.038 (3)	0.010 (2)	0.009 (2)	0.009 (2)
C27	0.037 (3)	0.046 (3)	0.038 (3)	0.012 (2)	0.006 (2)	0.009 (2)
C28	0.079 (4)	0.056 (3)	0.046 (3)	0.025 (3)	−0.006 (3)	0.003 (3)
C29	0.097 (5)	0.054 (4)	0.058 (4)	0.026 (3)	−0.007 (3)	−0.005 (3)
C30	0.070 (4)	0.044 (3)	0.070 (4)	0.022 (3)	0.004 (3)	0.014 (3)
C31	0.037 (3)	0.053 (3)	0.053 (3)	0.014 (2)	0.011 (2)	0.020 (3)
C32	0.064 (4)	0.069 (4)	0.053 (3)	0.031 (3)	0.020 (3)	0.029 (3)
Cl2	0.1064 (14)	0.0671 (10)	0.0546 (9)	0.0401 (10)	−0.0028 (9)	0.0029 (8)
O2	0.168 (6)	0.141 (5)	0.101 (4)	0.078 (4)	0.056 (4)	0.024 (4)
O3	0.134 (6)	0.212 (8)	0.155 (6)	0.021 (5)	−0.044 (5)	−0.045 (6)
O4	0.211 (7)	0.095 (4)	0.073 (3)	0.070 (4)	−0.002 (4)	0.020 (3)

Geometric parameters (Å, º)

Cu—N5	2.021 (4)	C9—C10	1.400 (6)
Cu—N4	2.030 (4)	C10—C11	1.472 (7)
Cu—N6	2.052 (4)	C11—C12	1.383 (7)
Cu—N3	2.122 (4)	C12—C13	1.374 (8)
Cu—Cl1	2.2912 (16)	C13—C14	1.366 (8)
N1—C2	1.342 (7)	C14—C15	1.388 (7)
N1—C6	1.348 (6)	C15—C16	1.492 (8)
N2—N3	1.337 (5)	C17—C18	1.497 (7)
N2—C7	1.341 (6)	C18—C19	1.395 (7)
N3—C10	1.341 (5)	C19—C20	1.360 (7)
N4—C15	1.345 (6)	C20—C21	1.381 (7)
N4—C11	1.350 (6)	C21—C22	1.374 (6)
N5—C18	1.344 (6)	C22—C23	1.478 (6)
N5—C22	1.361 (6)	C23—C24	1.398 (6)
N6—C23	1.336 (5)	C24—C25	1.358 (6)
N6—N7	1.344 (5)	C25—C26	1.407 (6)
N7—C26	1.328 (6)	C26—C27	1.488 (6)
N8—C31	1.341 (6)	C27—C28	1.373 (7)
N8—C27	1.346 (6)	C28—C29	1.381 (7)
C1—C2	1.505 (8)	C29—C30	1.373 (8)
C2—C3	1.392 (8)	C30—C31	1.390 (7)
C3—C4	1.361 (8)	C31—C32	1.508 (7)
C4—C5	1.381 (7)	Cl2—O3	1.366 (6)
C5—C6	1.373 (7)	Cl2—O4	1.393 (5)
C6—C7	1.482 (7)	Cl2—O1	1.405 (8)
C7—C8	1.399 (6)	Cl2—O2	1.459 (5)
C8—C9	1.342 (7)	Cl2—O1'	1.478 (9)
N5—Cu—N4	173.63 (15)	N4—C11—C10	116.3 (4)
N5—Cu—N6	80.37 (15)	C12—C11—C10	121.6 (5)
N4—Cu—N6	93.88 (14)	C13—C12—C11	118.1 (6)
N5—Cu—N3	100.18 (15)	C14—C13—C12	120.3 (6)
N4—Cu—N3	79.46 (15)	C13—C14—C15	119.4 (5)
N6—Cu—N3	112.91 (15)	N4—C15—C14	120.8 (5)
N5—Cu—Cl1	94.40 (11)	N4—C15—C16	119.7 (5)
N4—Cu—Cl1	91.47 (12)	C14—C15—C16	119.5 (5)
N6—Cu—Cl1	131.55 (12)	N5—C18—C19	120.3 (5)
N3—Cu—Cl1	115.41 (11)	N5—C18—C17	119.9 (4)
C2—N1—C6	117.8 (5)	C19—C18—C17	119.9 (4)
N3—N2—C7	119.2 (4)	C20—C19—C18	120.7 (5)
N2—N3—C10	121.2 (4)	C19—C20—C21	119.2 (5)
N2—N3—Cu	125.4 (3)	C22—C21—C20	118.5 (5)
C10—N3—Cu	112.6 (3)	N5—C22—C21	122.7 (4)
C15—N4—C11	119.2 (4)	N5—C22—C23	115.7 (4)
C15—N4—Cu	125.6 (3)	C21—C22—C23	121.6 (4)
C11—N4—Cu	115.2 (3)	N6—C23—C24	120.4 (4)
C18—N5—C22	118.6 (4)	N6—C23—C22	114.7 (4)
C18—N5—Cu	127.5 (3)	C24—C23—C22	124.9 (4)
C22—N5—Cu	113.6 (3)	C25—C24—C23	118.0 (4)
C23—N6—N7	122.3 (4)	C24—C25—C26	118.9 (4)
C23—N6—Cu	114.4 (3)	N7—C26—C25	121.8 (4)
N7—N6—Cu	123.3 (3)	N7—C26—C27	116.6 (4)
C26—N7—N6	118.6 (4)	C25—C26—C27	121.6 (4)
C31—N8—C27	118.3 (4)	N8—C27—C28	123.0 (4)
N1—C2—C3	121.6 (5)	N8—C27—C26	114.9 (4)
N1—C2—C1	116.2 (5)	C28—C27—C26	122.0 (4)
C3—C2—C1	122.1 (5)	C27—C28—C29	118.8 (5)
C4—C3—C2	119.3 (6)	C30—C29—C28	118.7 (5)
C3—C4—C5	120.0 (6)	C29—C30—C31	119.9 (5)
C6—C5—C4	117.6 (5)	N8—C31—C30	121.3 (5)
N1—C6—C5	123.6 (5)	N8—C31—C32	117.1 (5)
N1—C6—C7	113.5 (4)	C30—C31—C32	121.6 (5)
C5—C6—C7	122.9 (5)	O3—Cl2—O4	114.6 (5)
N2—C7—C8	121.4 (4)	O3—Cl2—O1	101.2 (9)
N2—C7—C6	116.7 (4)	O4—Cl2—O1	113.8 (5)
C8—C7—C6	121.9 (4)	O3—Cl2—O2	105.5 (4)
C9—C8—C7	119.0 (5)	O4—Cl2—O2	105.5 (4)
C8—C9—C10	118.4 (4)	O1—Cl2—O2	116.2 (7)
N3—C10—C9	120.7 (4)	O3—Cl2—O1'	125.5 (8)
N3—C10—C11	115.6 (4)	O4—Cl2—O1'	106.3 (5)
C9—C10—C11	123.7 (4)	O1—Cl2—O1'	26.7 (5)
N4—C11—C12	122.2 (5)	O2—Cl2—O1'	96.0 (7)
C7—N2—N3—C10	−2.2 (6)	C15—N4—C11—C12	1.5 (7)
C7—N2—N3—Cu	166.9 (3)	Cu—N4—C11—C12	−178.1 (4)
N5—Cu—N3—N2	9.9 (4)	C15—N4—C11—C10	−177.1 (4)
N4—Cu—N3—N2	−176.6 (4)	Cu—N4—C11—C10	3.3 (5)
N6—Cu—N3—N2	93.6 (3)	N3—C10—C11—N4	−9.4 (6)
Cl1—Cu—N3—N2	−90.0 (3)	C9—C10—C11—N4	167.9 (4)
N5—Cu—N3—C10	179.7 (3)	N3—C10—C11—C12	172.0 (4)
N4—Cu—N3—C10	−6.7 (3)	C9—C10—C11—C12	−10.6 (7)
N6—Cu—N3—C10	−96.5 (3)	N4—C11—C12—C13	0.0 (8)
Cl1—Cu—N3—C10	79.9 (3)	C10—C11—C12—C13	178.5 (5)
N5—Cu—N4—C15	−90.6 (15)	C11—C12—C13—C14	−0.8 (9)
N6—Cu—N4—C15	−65.3 (4)	C12—C13—C14—C15	0.2 (9)
N3—Cu—N4—C15	−177.9 (4)	C11—N4—C15—C14	−2.1 (7)
Cl1—Cu—N4—C15	66.5 (4)	Cu—N4—C15—C14	177.4 (4)
N5—Cu—N4—C11	89.0 (15)	C11—N4—C15—C16	177.1 (5)
N6—Cu—N4—C11	114.2 (3)	Cu—N4—C15—C16	−3.3 (7)
N3—Cu—N4—C11	1.6 (3)	C13—C14—C15—N4	1.3 (8)
Cl1—Cu—N4—C11	−113.9 (3)	C13—C14—C15—C16	−177.9 (5)
N4—Cu—N5—C18	−150.7 (13)	C22—N5—C18—C19	2.7 (7)
N6—Cu—N5—C18	−176.4 (4)	Cu—N5—C18—C19	−170.0 (4)
N3—Cu—N5—C18	−64.6 (4)	C22—N5—C18—C17	−178.5 (4)
Cl1—Cu—N5—C18	52.2 (4)	Cu—N5—C18—C17	8.8 (7)
N4—Cu—N5—C22	36.2 (16)	N5—C18—C19—C20	−0.6 (8)
N6—Cu—N5—C22	10.6 (3)	C17—C18—C19—C20	−179.4 (5)
N3—Cu—N5—C22	122.4 (3)	C18—C19—C20—C21	−1.5 (9)
Cl1—Cu—N5—C22	−120.8 (3)	C19—C20—C21—C22	1.4 (8)
N5—Cu—N6—C23	−8.2 (3)	C18—N5—C22—C21	−2.8 (7)
N4—Cu—N6—C23	174.5 (3)	Cu—N5—C22—C21	170.9 (4)
N3—Cu—N6—C23	−105.3 (3)	C18—N5—C22—C23	174.8 (4)
Cl1—Cu—N6—C23	79.1 (3)	Cu—N5—C22—C23	−11.5 (5)
N5—Cu—N6—N7	172.8 (4)	C20—C21—C22—N5	0.7 (8)
N4—Cu—N6—N7	−4.5 (4)	C20—C21—C22—C23	−176.8 (5)
N3—Cu—N6—N7	75.7 (4)	N7—N6—C23—C24	1.2 (7)
Cl1—Cu—N6—N7	−99.9 (3)	Cu—N6—C23—C24	−177.8 (3)
C23—N6—N7—C26	−0.6 (6)	N7—N6—C23—C22	−176.5 (4)
Cu—N6—N7—C26	178.4 (3)	Cu—N6—C23—C22	4.5 (5)
C6—N1—C2—C3	−0.9 (8)	N5—C22—C23—N6	4.6 (6)
C6—N1—C2—C1	176.3 (5)	C21—C22—C23—N6	−177.7 (4)
N1—C2—C3—C4	−0.3 (9)	N5—C22—C23—C24	−173.0 (4)
C1—C2—C3—C4	−177.3 (6)	C21—C22—C23—C24	4.7 (7)
C2—C3—C4—C5	1.3 (9)	N6—C23—C24—C25	−0.9 (7)
C3—C4—C5—C6	−0.9 (8)	C22—C23—C24—C25	176.5 (4)
C2—N1—C6—C5	1.2 (7)	C23—C24—C25—C26	0.1 (7)
C2—N1—C6—C7	−179.9 (4)	N6—N7—C26—C25	−0.3 (7)
C4—C5—C6—N1	−0.3 (8)	N6—N7—C26—C27	179.5 (4)
C4—C5—C6—C7	−179.1 (5)	C24—C25—C26—N7	0.6 (7)
N3—N2—C7—C8	−0.5 (7)	C24—C25—C26—C27	−179.3 (4)
N3—N2—C7—C6	−179.1 (4)	C31—N8—C27—C28	0.0 (7)
N1—C6—C7—N2	167.9 (4)	C31—N8—C27—C26	179.1 (4)
C5—C6—C7—N2	−13.2 (7)	N7—C26—C27—N8	173.4 (4)
N1—C6—C7—C8	−10.6 (7)	C25—C26—C27—N8	−6.7 (6)
C5—C6—C7—C8	168.3 (5)	N7—C26—C27—C28	−7.5 (7)
N2—C7—C8—C9	2.2 (7)	C25—C26—C27—C28	172.4 (5)
C6—C7—C8—C9	−179.4 (4)	N8—C27—C28—C29	0.0 (9)
C7—C8—C9—C10	−1.1 (7)	C26—C27—C28—C29	−179.0 (5)
N2—N3—C10—C9	3.3 (6)	C27—C28—C29—C30	0.6 (9)
Cu—N3—C10—C9	−167.1 (3)	C28—C29—C30—C31	−1.3 (9)
N2—N3—C10—C11	−179.3 (4)	C27—N8—C31—C30	−0.7 (7)
Cu—N3—C10—C11	10.4 (5)	C27—N8—C31—C32	179.9 (4)
C8—C9—C10—N3	−1.6 (7)	C29—C30—C31—N8	1.4 (9)
C8—C9—C10—C11	−178.8 (4)	C29—C30—C31—C32	−179.3 (5)