Bis­(azido-κN)[(6R,7S,8S,14S)-(–)-sparteine-κ²N,N′]copper(II)

In the title compound, [Cu(N₃)₂(C₁₅H₂₆N₂)], the chiral alkaloid (−)-l-sparteine (Sp) acts as a bidentate ligand, with two azide ligands occupying the remaining coordination sites, forming a distorted CuN₄ tetrahedron. The dihedral angle between the N_Sp—Cu—N_Sp and N_azide—Cu—N_azide planes is 55.3 (2)°. Principal dimensions include Cu—N_Sp = 2.011 (6) and 2.025 (5) Å, and Cu—N_azide = 1.939 (6) and 1.934 (7) Å. The mid-point of the N_Sp...N_Sp line does not lie exactly in the N_azide—Cu—N_azide plane, but is tilted towards one of the N_Sp atoms by 0.026 Å.

S1. Comment

There exist three diastereomers of sparteine: (-)-sparteine (6R,7S,8S,14S) (C₁₅H₂₆N₂), (-)-α-isosparteine (6R,7S,8S,14R) (α-C₁₅H₂₆N₂) and (-)-β-isosparteine (6S,7S,8S,14S) (β-C₁₅H₂₆N₂). These sparteine ligands have attracted research attention and have been intensively utilized in medicinal chemistry (Cady et al., 1977) and asymmetric synthesis of the chiral compounds (Beak et al., 1996; Kretchmer, 1972; Mason & Peacock, 1973). Many crystal structures of copper(II) complexes with the neutral alkaloid sparteine diastereomers have been reported (Childers et al., 1975; Choi et al., 1995; Kim et al., 2001, 2002; Lee et al., 1998, 2000; Lopez et al., 1998). The sparteine copper(II) complexes that have been reported, with one exception (Lee et al., 1998), are four-coordinate and tetrahedrally distorted (Childers et al., 1975; Choi et al., 1995; Kim et al., 2001, 2002; Lee et al., 2000; Lopez et al., 1998) from the ligand-field favorable square-planar geometry (Figgis, 1966). The pseudo-tetrahedral geometry around the Cu(II) center of these complexes is due to the steric requirements imposed by the bulky sparteine ligand. However, the role of anionic ligand, L, in these complexes of the type [Cu(L)₂(C₁₅H₂₆N₂)] is also important in the ultimate molecular structure. We determined the crystal structure of the title compound, (I), in order to evaluate the extent of distortion imposed by the (-)-sparteine ligand compared with that imposed by the (-)-α-isosparteine. Actually, the extent of distortion towards a tetrahedron in (I) was higher than that in the (-)-α-isosparteine complex (Kim et al., 2002).

In complex (I), the (-)-sparteine acts as a bidentate, with two azide ligands occupying the remaining coordination sites, forming a distorted CuN₄ tetrahedron (Fig. 1). The coordinated (-)-sparteine ligand in complex (I) consists of one terminal ring folded down over the metal (endo) and another terminal ring folded back away from the metal (exo), identical to the conformation of the free ligand (Boschmann et al., 1974; Wrobleski & Long, 1977). Two azide anions are bound terminally to the copper(II). The dihedral angle between the N1—Cu—N9 and N18—Cu—N21 planes in (I) is 55.3 (2)°, whereas that in Cu(N₃)₂(α-C₁₅H₂₆N₂) is 50.2 (2)° (Kim et al., 2002). This smaller dihedral angle can be visualized as a balance between the crystal field stabilization effect and the steric effect of (-)-sparteine.

One of the parameters associated with the distortion of the tetrahedron is the 'tilt' of the bidentate sparteine ligand with respect to the N18—Cu—N21 plane. In complex (I), the mid-point of the N1—N9 line does not exactly lie on the N18—Cu—N21 plane but is tilted towards atom N1 only by 0.026 Å (1.8% of half of the N1—N9 distance). Similarly, the mid-point of the N18—N21 line is tilted towards atom N18 by 0.045 Å (3.0% of half of the N18—N21 distance). However, in Cu(N₃)₂(α-C₁₅H₂₆N₂), the mid-point of the N1—N9 line is tilted towards atom N1 by 0.103 Å (7.2% of half of the N1—N9 distance) and that of the N18—N21 line is greatly tilted towards atom N18 by 0.264 Å (17.7% of half of the N18—N21 distance). In complex (I), the N1—Cu—N18 and N9—Cu—N21 angles differ by 2.1°, and similarly the N1—Cu—N21 and N9—Cu—N18 angles differ by only 2.2°. These results clearly indicate that the distortion towards a tetrahedron for the complex (I) is quite symmetrically twisted.

The Cu(II)-azide distances (Table 1) found in complex (I) agree with the Cu(II)—N distances found in copper(II) complexes containing a terminally bound azide ligand (Goher et al., 2001; Grove et al., 2001; Kim et al., 2002). The coordinating azide anions are nearly linear, but the (Cu)—N—N bonds are longer than the (Cu—N)—N—N bonds. This result suggests that the covalency in Cu(II)-azide bonding is appreciable and that the main contribution to the ground-state geometry of the coordinated azide is provided by the two canonical structures —N ═N⁺ ═N^- ←→ —N^-—N⁺≡N. This result is quite similar to that found in the [Cu(N₃)₂(α-C₁₅H₂₆N₂)] complex (Kim et al., 2002).

S2. Experimental

The precursor copper(II) complex, [Cu(NO₃)₂(C₁₅H₂₆N₂)], was prepared by mixing an ethanol–triethylorthoformate (5:1 v/v) solution of copper(II) nitrate hemipentahydrate with a stoichiometric amount of (-)-sparteine at room temperature for 2 h. The resulting blue precipitate was filtered, washed with cold absolute ethanol and then dried in a vacuum. The title complex, (I), was prepared from the substitution reaction of [Cu(NO₃)₂(C₁₅H₂₆N₂)] with a stoichiometric amount of NaN₃ in an ethanol-triethylorthoformate (5:1 v/v) solution. The dark-brown precipitate was filtered, washed with cold absolute ethanol and then dried in a vacuum. The single crystals were obtained by recrystallization at about 278 K from a dichloromethane–triethylorthoformate (5:1 v/v) solution. Analysis: calculated for CuC₁₅H₂₆N₈ C 47.17, H 6.86, N 29.34%; found C 47.83, H 6.91, N, 29.59%.

S3. Refinement

Positional parameters of the H atoms on the sparteine ligand were calculated geometrically and constrained to ride on their attached atoms. Their isotropic displacement parameters were fixed at 1.2 times the equivalent isotropic displacement parameters of their parent atoms. The absolute configuration of (I) was known from the known configuration of the starting material and was confirmed by the value [-0.06 (3)] of the Flack parameter.

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. ORTEP-3 (Farrugia, 1997) diagram of (I) showing the atom-numbering scheme and 30% probability ellipsoids. H atoms have been omitted for clarity.

(diazido-N)[(-)-sparteine-N,N']copper(II)

Crystal data

[Cu(N3)2(C15H26N2)]	F(000) = 804
Mr = 381.98	Dx = 1.455 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 40 reflections
a = 8.2870 (9) Å	θ = 5.0–12.6°
b = 14.061 (3) Å	µ = 1.27 mm^−1
c = 14.9685 (15) Å	T = 296 K
V = 1744.2 (5) Å^3	Irregular, dark brown
Z = 4	0.44 × 0.42 × 0.32 mm

Data collection

Bruker P4 diffractometer	2061 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.040
Graphite monochromator	θmax = 27.5°, θmin = 2.0°
2θ/ω scans	h = −1→10
Absorption correction: ψ scan (North et al., 1968)	k = −1→18
Tmin = 0.882, Tmax = 0.938	l = −19→19
5383 measured reflections	3 standard reflections every 97 reflections
4004 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.059	w = 1/[σ^2(Fo^2) + (0.0588P)^2 + 0.8943P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.171	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.90 e Å^−3
4004 reflections	Δρmin = −0.52 e Å^−3
218 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0055 (12)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1712 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.06 (3)

Special details

Geometry. All su values (except the su in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell su values are taken into account individually in the estimation of su values in distances, angles and torsion angles; correlations between su values in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell su values is used for estimating su values 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
Cu	0.40214 (10)	0.39560 (6)	0.68303 (5)	0.0493 (3)
N1	0.1687 (7)	0.3582 (4)	0.6933 (4)	0.0582 (16)
C2	0.1499 (10)	0.2837 (7)	0.7643 (6)	0.077 (3)
H2A	0.0369	0.2667	0.7698	0.093*
H2B	0.1854	0.3092	0.8212	0.093*
C3	0.2479 (12)	0.1953 (7)	0.7419 (6)	0.084 (3)
H3A	0.3618	0.2112	0.7406	0.101*
H3B	0.2316	0.1476	0.7878	0.101*
C4	0.1977 (15)	0.1553 (7)	0.6518 (6)	0.101 (3)
H4A	0.0876	0.1321	0.6550	0.121*
H4B	0.2672	0.1024	0.6359	0.121*
C5	0.2103 (13)	0.2330 (6)	0.5812 (6)	0.087 (3)
H5A	0.3222	0.2518	0.5747	0.105*
H5B	0.1738	0.2081	0.5242	0.105*
C6	0.1104 (12)	0.3189 (6)	0.6057 (5)	0.069 (2)
H6	−0.0007	0.2970	0.6147	0.082*
C7	0.1059 (9)	0.3948 (6)	0.5338 (5)	0.068 (2)
H7	0.0583	0.3661	0.4803	0.082*
C8	0.0746 (11)	0.5180 (6)	0.6470 (6)	0.074 (2)
H8	0.0057	0.5702	0.6675	0.089*
N9	0.3465 (6)	0.4869 (4)	0.5830 (3)	0.0461 (14)
C10	0.5026 (9)	0.5312 (5)	0.5553 (5)	0.059 (2)
H10A	0.5652	0.4841	0.5232	0.071*
H10B	0.5625	0.5480	0.6086	0.071*
C11	0.4881 (11)	0.6180 (6)	0.4978 (6)	0.075 (2)
H11A	0.4394	0.6010	0.4411	0.090*
H11B	0.5946	0.6437	0.4860	0.090*
C12	0.3853 (12)	0.6927 (6)	0.5438 (5)	0.074 (2)
H12A	0.4402	0.7153	0.5970	0.088*
H12B	0.3696	0.7464	0.5041	0.088*
C13	0.2251 (12)	0.6517 (6)	0.5690 (6)	0.075 (2)
H13A	0.1649	0.6377	0.5151	0.090*
H13B	0.1648	0.6988	0.6027	0.090*
C14	0.2391 (10)	0.5613 (5)	0.6247 (5)	0.057 (2)
H14	0.2890	0.5794	0.6815	0.068*
C15	0.0760 (11)	0.4447 (7)	0.7207 (6)	0.077 (3)
H15A	0.1246	0.4719	0.7738	0.093*
H15B	−0.0340	0.4268	0.7351	0.093*
C16	0.2685 (10)	0.4365 (5)	0.5071 (5)	0.0565 (19)
H16A	0.3388	0.3857	0.4867	0.068*
H16B	0.2535	0.4805	0.4579	0.068*
C17	−0.0058 (11)	0.4764 (8)	0.5634 (7)	0.092 (3)
H17A	−0.0144	0.5242	0.5169	0.110*
H17B	−0.1128	0.4527	0.5771	0.110*
N18	0.4472 (8)	0.4002 (6)	0.8101 (4)	0.0748 (18)
N19	0.5818 (9)	0.4085 (5)	0.8335 (4)	0.0695 (18)
N20	0.7068 (12)	0.4112 (7)	0.8642 (6)	0.117 (3)
N21	0.6048 (9)	0.3481 (5)	0.6371 (4)	0.0694 (18)
N22	0.6664 (7)	0.2785 (5)	0.6687 (4)	0.0621 (17)
N23	0.7313 (10)	0.2115 (6)	0.6922 (6)	0.095 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0417 (4)	0.0607 (5)	0.0454 (4)	0.0009 (5)	0.0009 (4)	0.0030 (4)
N1	0.043 (3)	0.072 (4)	0.060 (4)	−0.001 (3)	0.008 (3)	0.013 (3)
C2	0.057 (5)	0.096 (7)	0.078 (5)	−0.011 (5)	0.010 (4)	0.027 (5)
C3	0.073 (6)	0.076 (6)	0.103 (7)	−0.013 (6)	0.007 (6)	0.035 (6)
C4	0.129 (10)	0.066 (6)	0.107 (7)	−0.027 (7)	−0.010 (7)	0.000 (5)
C5	0.101 (7)	0.070 (6)	0.091 (6)	−0.022 (6)	−0.005 (6)	−0.002 (5)
C6	0.059 (5)	0.077 (5)	0.069 (5)	−0.021 (5)	−0.007 (5)	0.002 (4)
C7	0.057 (4)	0.082 (5)	0.066 (4)	−0.016 (6)	−0.020 (4)	0.006 (5)
C8	0.061 (6)	0.075 (5)	0.086 (6)	0.022 (5)	0.028 (5)	0.007 (5)
N9	0.044 (3)	0.048 (3)	0.046 (3)	0.003 (3)	0.001 (3)	−0.003 (3)
C10	0.049 (4)	0.054 (4)	0.073 (5)	−0.003 (4)	0.003 (4)	0.008 (4)
C11	0.078 (6)	0.060 (5)	0.086 (6)	0.004 (5)	0.019 (5)	0.019 (5)
C12	0.088 (6)	0.056 (4)	0.076 (5)	−0.001 (5)	−0.009 (6)	0.012 (4)
C13	0.093 (7)	0.056 (5)	0.076 (5)	0.020 (5)	0.019 (5)	0.012 (4)
C14	0.068 (6)	0.050 (4)	0.052 (4)	0.015 (4)	0.006 (4)	−0.005 (4)
C15	0.060 (5)	0.096 (6)	0.075 (5)	0.014 (5)	0.033 (5)	0.011 (5)
C16	0.059 (5)	0.063 (5)	0.048 (4)	0.002 (4)	−0.006 (4)	−0.007 (4)
C17	0.044 (5)	0.112 (8)	0.119 (8)	0.006 (6)	−0.008 (5)	0.032 (7)
N18	0.056 (4)	0.113 (5)	0.055 (3)	0.001 (4)	−0.006 (3)	0.007 (5)
N19	0.074 (5)	0.067 (4)	0.068 (4)	−0.019 (4)	−0.021 (4)	0.007 (3)
N20	0.118 (7)	0.107 (7)	0.128 (7)	−0.041 (7)	−0.062 (6)	0.034 (6)
N21	0.063 (4)	0.075 (4)	0.070 (4)	0.021 (4)	0.019 (4)	0.017 (4)
N22	0.048 (3)	0.067 (4)	0.071 (4)	0.002 (3)	0.006 (3)	0.016 (4)
N23	0.092 (6)	0.080 (5)	0.115 (6)	0.017 (5)	−0.006 (6)	0.030 (5)

Geometric parameters (Å, º)

Cu—N1	2.011 (6)	C8—H8	0.9800
Cu—N9	2.025 (5)	N9—C10	1.495 (9)
Cu—N18	1.939 (6)	N9—C14	1.508 (8)
Cu—N21	1.934 (7)	N9—C16	1.488 (8)
N1—C2	1.500 (9)	C10—C11	1.498 (10)
N1—C6	1.504 (9)	C10—H10A	0.9700
N1—C15	1.495 (10)	C10—H10B	0.9700
C2—C3	1.523 (12)	C11—C12	1.518 (11)
C2—H2A	0.9700	C11—H11A	0.9700
C2—H2B	0.9700	C11—H11B	0.9700
C3—C4	1.519 (12)	C12—C13	1.495 (12)
C3—H3A	0.9700	C12—H12A	0.9700
C3—H3B	0.9700	C12—H12B	0.9700
C4—C5	1.523 (11)	C13—C14	1.524 (9)
C4—H4A	0.9700	C13—H13A	0.9700
C4—H4B	0.9700	C13—H13B	0.9700
C5—C6	1.510 (12)	C14—H14	0.9800
C5—H5A	0.9700	C15—H15A	0.9700
C5—H5B	0.9700	C15—H15B	0.9700
C6—C7	1.516 (11)	C16—H16A	0.9700
C6—H6	0.9800	C16—H16B	0.9700
C7—C16	1.523 (10)	C17—H17A	0.9700
C7—C17	1.539 (12)	C17—H17B	0.9700
C7—H7	0.9800	N18—N19	1.175 (8)
C8—C15	1.509 (11)	N19—N20	1.134 (10)
C8—C14	1.531 (11)	N21—N22	1.200 (8)
C8—C17	1.533 (12)	N22—N23	1.140 (9)
N1—Cu—N9	90.2 (2)	C10—N9—C14	109.7 (6)
N1—Cu—N18	96.8 (3)	C16—N9—Cu	111.2 (4)
N1—Cu—N21	140.6 (3)	C10—N9—Cu	105.8 (4)
N9—Cu—N18	138.4 (3)	C14—N9—Cu	105.6 (4)
N9—Cu—N21	98.9 (2)	N9—C10—C11	115.5 (7)
N18—Cu—N21	101.1 (3)	N9—C10—H10A	108.4
C15—N1—C2	108.7 (6)	C11—C10—H10A	108.4
C15—N1—C6	111.9 (6)	N9—C10—H10B	108.4
C2—N1—C6	109.1 (6)	C11—C10—H10B	108.4
C15—N1—Cu	107.6 (5)	H10A—C10—H10B	107.5
C2—N1—Cu	109.7 (5)	C10—C11—C12	110.4 (7)
C6—N1—Cu	109.8 (5)	C10—C11—H11A	109.6
N1—C2—C3	111.1 (7)	C12—C11—H11A	109.6
N1—C2—H2A	109.4	C10—C11—H11B	109.6
C3—C2—H2A	109.4	C12—C11—H11B	109.6
N1—C2—H2B	109.4	H11A—C11—H11B	108.1
C3—C2—H2B	109.4	C13—C12—C11	110.2 (7)
H2A—C2—H2B	108.0	C13—C12—H12A	109.6
C4—C3—C2	110.6 (9)	C11—C12—H12A	109.6
C4—C3—H3A	109.5	C13—C12—H12B	109.6
C2—C3—H3A	109.5	C11—C12—H12B	109.6
C4—C3—H3B	109.5	H12A—C12—H12B	108.1
C2—C3—H3B	109.5	C12—C13—C14	113.1 (8)
H3A—C3—H3B	108.1	C12—C13—H13A	109.0
C3—C4—C5	109.4 (7)	C14—C13—H13A	109.0
C3—C4—H4A	109.8	C12—C13—H13B	109.0
C5—C4—H4A	109.8	C14—C13—H13B	109.0
C3—C4—H4B	109.8	H13A—C13—H13B	107.8
C5—C4—H4B	109.8	N9—C14—C13	113.4 (6)
H4A—C4—H4B	108.2	N9—C14—C8	109.8 (6)
C6—C5—C4	111.6 (8)	C13—C14—C8	112.6 (7)
C6—C5—H5A	109.3	N9—C14—H14	106.9
C4—C5—H5A	109.3	C13—C14—H14	106.9
C6—C5—H5B	109.3	C8—C14—H14	106.9
C4—C5—H5B	109.3	N1—C15—C8	111.0 (6)
H5A—C5—H5B	108.0	N1—C15—H15A	109.4
N1—C6—C5	109.3 (7)	C8—C15—H15A	109.4
N1—C6—C7	111.6 (6)	N1—C15—H15B	109.4
C5—C6—C7	113.9 (7)	C8—C15—H15B	109.4
N1—C6—H6	107.3	H15A—C15—H15B	108.0
C5—C6—H6	107.3	N9—C16—C7	111.6 (6)
C7—C6—H6	107.3	N9—C16—H16A	109.3
C6—C7—C16	115.8 (7)	C7—C16—H16A	109.3
C6—C7—C17	109.6 (7)	N9—C16—H16B	109.3
C16—C7—C17	108.7 (7)	C7—C16—H16B	109.3
C6—C7—H7	107.5	H16A—C16—H16B	108.0
C16—C7—H7	107.5	C8—C17—C7	104.9 (7)
C17—C7—H7	107.5	C8—C17—H17A	110.8
C15—C8—C14	115.1 (7)	C7—C17—H17A	110.8
C15—C8—C17	109.9 (8)	C8—C17—H17B	110.8
C14—C8—C17	111.1 (7)	C7—C17—H17B	110.8
C15—C8—H8	106.7	H17A—C17—H17B	108.8
C14—C8—H8	106.7	Cu—N18—N19	118.7 (6)
C17—C8—H8	106.7	N18—N19—N20	172.6 (9)
C16—N9—C10	111.2 (6)	Cu—N21—N22	120.7 (5)
C16—N9—C14	113.0 (6)	N21—N22—N23	174.4 (9)
N21—Cu—N1—C15	−167.4 (5)	C14—N9—C10—C11	−52.3 (9)
N18—Cu—N1—C15	75.8 (5)	Cu—N9—C10—C11	−165.8 (6)
N9—Cu—N1—C15	−63.1 (5)	N9—C10—C11—C12	56.0 (11)
N21—Cu—N1—C2	74.5 (7)	C10—C11—C12—C13	−54.7 (10)
N18—Cu—N1—C2	−42.4 (6)	C11—C12—C13—C14	54.0 (9)
N9—Cu—N1—C2	178.8 (5)	C16—N9—C14—C13	−75.8 (9)
N21—Cu—N1—C6	−45.4 (7)	C10—N9—C14—C13	48.9 (9)
N18—Cu—N1—C6	−162.2 (5)	Cu—N9—C14—C13	162.6 (6)
N9—Cu—N1—C6	58.9 (5)	C16—N9—C14—C8	51.2 (8)
C15—N1—C2—C3	−177.5 (7)	C10—N9—C14—C8	175.9 (6)
C6—N1—C2—C3	60.2 (9)	Cu—N9—C14—C8	−70.5 (6)
Cu—N1—C2—C3	−60.1 (8)	C12—C13—C14—N9	−52.3 (10)
N1—C2—C3—C4	−57.7 (9)	C12—C13—C14—C8	−177.8 (7)
C2—C3—C4—C5	54.5 (11)	C15—C8—C14—N9	67.9 (9)
C3—C4—C5—C6	−56.6 (12)	C17—C8—C14—N9	−57.8 (8)
C15—N1—C6—C5	179.1 (7)	C15—C8—C14—C13	−164.7 (7)
C2—N1—C6—C5	−60.6 (9)	C17—C8—C14—C13	69.6 (9)
Cu—N1—C6—C5	59.7 (7)	C2—N1—C15—C8	−173.4 (7)
C15—N1—C6—C7	52.3 (9)	C6—N1—C15—C8	−52.9 (9)
C2—N1—C6—C7	172.6 (7)	Cu—N1—C15—C8	67.8 (8)
Cu—N1—C6—C7	−67.2 (8)	C14—C8—C15—N1	−65.8 (10)
C4—C5—C6—N1	59.8 (10)	C17—C8—C15—N1	60.5 (10)
C4—C5—C6—C7	−174.6 (8)	C10—N9—C16—C7	−177.5 (6)
N1—C6—C7—C16	64.8 (10)	C14—N9—C16—C7	−53.7 (8)
C5—C6—C7—C16	−59.5 (10)	Cu—N9—C16—C7	64.8 (7)
N1—C6—C7—C17	−58.7 (9)	C6—C7—C16—N9	−63.3 (9)
C5—C6—C7—C17	177.1 (7)	C17—C7—C16—N9	60.6 (8)
N21—Cu—N9—C16	82.8 (5)	C15—C8—C17—C7	−64.5 (9)
N18—Cu—N9—C16	−159.2 (5)	C14—C8—C17—C7	64.1 (9)
N1—Cu—N9—C16	−58.6 (5)	C6—C7—C17—C8	63.4 (9)
N21—Cu—N9—C10	−38.1 (5)	C16—C7—C17—C8	−64.2 (8)
N18—Cu—N9—C10	79.9 (5)	N21—Cu—N18—N19	25.7 (8)
N1—Cu—N9—C10	−179.6 (5)	N1—Cu—N18—N19	170.4 (7)
N21—Cu—N9—C14	−154.3 (5)	N9—Cu—N18—N19	−91.6 (8)
N18—Cu—N9—C14	−36.3 (6)	N18—Cu—N21—N22	50.2 (7)
N1—Cu—N9—C14	64.2 (5)	N1—Cu—N21—N22	−65.3 (8)
C16—N9—C10—C11	73.4 (8)	N9—Cu—N21—N22	−166.5 (6)