(–)-α-Isosparteine copper(II) diazide

In the title complex, [Cu(N₃)₂(C₁₅H₂₆N₂)], the Cu atom is surrounded by the two N atoms of the chelating (−)-α-isosparteine ligand and another two N atoms from the two azide anions, forming a distorted CuN₄ tetrahedron. The two azide anions are terminally bound to the Cu^II atom, and the dihedral angle between the N_sparteine—Cu—N_sparteine and N_azide—Cu—N_azide planes is 50.0 (2)°.

S1. Comment

The crystal structures of several copper(II) complexes with the neutral alkaloid (-)-sparteine (C₁₅H₂₆N₂) and its diastereomer, (-)-β-isosparteine, have been determined by several workers (Childers et al., 1975; Choi et al., 1995; Kim et al., 2001; Lee et al., 1998, 2000; Lopez et al., 1998). It has been recognized that, with one exception (Lee et al., 1998), sparteine copper(II) complexes are four-coordinate and tetrahedrally distorted (Childers et al., 1975; Choi et al., 1995; Kim et al., 2001; Lee et al., 2000; Lopez et al., 1998). The pseudo-tetrahedral geometry around the Cu^II centre of these complexes is due to the steric requirements imposed by the bulky chelating sparteine ligand. However, the anionic ligands L in these complexes of the type [Cu(L)₂(C₁₅H₂₆N₂)] are also important in controlling the molecular structures. The X-ray crystallographic structures of sparteine copper(II) complexes have shown that the average dihedral angles between the L₂Cu and N₂Cu planes in these complexes are in the range 31.7–87.3° (Childers et al., 1975; Choi et al., 1995; Kim et al., 2001; Lee et al., 2000; Lopez et al., 1998). (-)-α-Isosparteine, one of three diastereomers of sparteine, has been reported to react with Cu^II halides to produce the corresponding stable complexes (Boschmann et al., 1974), although no structures of (-)-α-isosparteine copper(II) complexes have been reported. The present investigation of (-)-α-isosparteine copper(II) diazide, (I), was also prompted by the possibility of the complex having a tetrahedrally distorted Cu^IIN₄ chromophore, and the likely influence of the azide anion on the molecular structure. \sch

In complex (I), the Cu atom is surrounded by two N atoms (N1 and N9) of the chelating (-)-α-isosparteine ligand and by two N atoms (N18 and N21) of the two azide anions, forming a distorted CuN₄ tetrahedron. All four of the six-membered rings in the coordinated (-)-α-isosparteine are in the chair conformation. The conformation of the coordinated (-)-α-isosparteine in (I) consists of two terminal rings folded down over the Cu^II (endo), identical to the conformation of the free ligand (Boschmann et al., 1974; Wrobleski & Long, 1977).

The molecule of (I) possesses a nearly perfect twofold axis of rotation along a line through atoms C17 and Cu. Two azide anions are bound terminally to the Cu^II. The N1—Cu—N9 plane is twisted by 50.0 (2)° from the N18—Cu—N21 plane.

The Cu^II-azide distances (Table 1) found in (I) are similar to the Cu^II—N distances found in other copper(II) complexes containing a terminally bound azide ligand (references?). The Cu—N_sparteine bond lengths of approximately 2.0 Å have previously been established for several other sparteine copper(II) complexes (Childers et al., 1975; Choi et al., 1995; Kim et al., 2001; Lee et al., 1998; Lee et al., 2000; Lopez et al., 1998).

The coordinating azide anions are nearly linear, but the (Cu)—N—N bonds are longer than the (Cu—N)—N—N bonds. This result, together with the nonlinear M—N—N angle, suggest that the covalency in copper(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^- \leftrightarrow –N^-—N⁺≡N.

S2. Experimental

(-)-α-Isosparteine was derived from commercially available (-)-sparteine by the literature method of Leonard & Beyler (1950). The precursor copper(II) complex, [Cu(NO₃)₂(C₁₅H₂₆N₂)], was prepared in a glove box by mixing a solution of copper(II) nitrate in ethanol-triethylorthoformate (5:1 v/v) with a stoichiometric amount of (-)-α-isosparteine. The resulting blue precipitate was filtered, washed with cold absolute ethanol and dried in a vacuum. Complex (I) was prepared by the reaction of [Cu(NO₃)₂(C₁₅H₂₆N₂)] with a stoichiometric amount of NaN₃ in an ethanol-triethylorthoformate (5:1 v/v) solution. Single crystals of (I) were obtained by recrystallization at about 278 K from a solution in dichloromethane-triethylorthoformate (5:1 v/v) under carbon tetrachloride vapour.

S3. Refinement

The positional parameters of the H atoms on the sparteine ligand were calculated geometrically and constrained to ride on their attached atoms, with C—H = 0.97–0.98 Å and U_iso(H) = 1.2U_eq(C).

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 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A view of the molecule of (I) showing the atom-numbering scheme and 30% probability displacement ellipsoids. H atoms have been omitted for clarity.

(Diazido-N)[(-)-α-isosparteine-N,N']copper(II)

Crystal data

[Cu(N3)2(C15H26N2)]	F(000) = 804
Mr = 381.98	Dx = 1.489 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 40 reflections
a = 8.1517 (16) Å	θ = 6.2–12.6°
b = 13.4955 (12) Å	µ = 1.30 mm^−1
c = 15.486 (2) Å	T = 296 K
V = 1703.6 (4) Å^3	Block, dark brown
Z = 4	0.38 × 0.22 × 0.20 mm

Data collection

Bruker P4 diffractometer	1431 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
Graphite monochromator	θmax = 27.5°, θmin = 2.0°
2θ/ω scans	h = −1→10
Absorption correction: ψ scan (North et al., 1968)	k = −1→17
Tmin = 0.717, Tmax = 0.772	l = −1→20
2930 measured reflections	3 standard reflections every 97 min
2741 independent reflections	intensity decay: 0.0%

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)] = 0.052	w = 1/[σ^2(Fo^2) + (0.0101P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.087	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.68 e Å^−3
2741 reflections	Δρmin = −0.42 e Å^−3
218 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0032 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 497 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.00 (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
Cu	0.90547 (12)	0.93690 (7)	0.64989 (5)	0.0398 (3)
N1	0.8474 (6)	1.0047 (4)	0.5363 (3)	0.0356 (15)
C2	0.9999 (8)	1.0420 (5)	0.4926 (4)	0.048 (2)
H2A	0.9708	1.0699	0.4370	0.058*
H2B	1.0735	0.9867	0.4825	0.058*
C3	1.0881 (10)	1.1198 (5)	0.5456 (5)	0.054 (2)
H3A	1.1818	1.1447	0.5136	0.064*
H3B	1.1277	1.0906	0.5989	0.064*
C4	0.9696 (10)	1.2058 (6)	0.5662 (5)	0.064 (3)
H4A	1.0231	1.2528	0.6042	0.076*
H4B	0.9404	1.2399	0.5132	0.076*
C5	0.8161 (10)	1.1662 (6)	0.6091 (5)	0.060 (3)
H5A	0.8447	1.1357	0.6638	0.072*
H5B	0.7412	1.2205	0.6206	0.072*
C6	0.7338 (9)	1.0912 (5)	0.5520 (5)	0.043 (2)
H6	0.7142	1.1231	0.4961	0.052*
C7	0.5687 (9)	1.0531 (6)	0.5847 (5)	0.048 (2)
H7	0.4972	1.1110	0.5913	0.057*
C8	0.6005 (10)	0.8978 (5)	0.5091 (4)	0.047 (2)
H8	0.5539	0.8542	0.4649	0.056*
N9	0.6614 (7)	0.9066 (4)	0.6680 (3)	0.0409 (17)
C10	0.6341 (9)	0.8532 (6)	0.7513 (4)	0.058 (3)
H10A	0.5175	0.8426	0.7595	0.070*
H10B	0.6734	0.8939	0.7986	0.070*
C11	0.7227 (11)	0.7533 (7)	0.7529 (5)	0.071 (3)
H11A	0.8402	0.7647	0.7516	0.085*
H11B	0.6970	0.7196	0.8065	0.085*
C12	0.6758 (12)	0.6869 (6)	0.6776 (5)	0.084 (4)
H12A	0.5621	0.6666	0.6828	0.101*
H12B	0.7440	0.6280	0.6772	0.101*
C13	0.7006 (11)	0.7456 (6)	0.5941 (5)	0.064 (3)
H13A	0.8161	0.7610	0.5873	0.077*
H13B	0.6670	0.7054	0.5453	0.077*
C14	0.6023 (11)	0.8410 (5)	0.5949 (5)	0.047 (2)
H14	0.4884	0.8230	0.6079	0.057*
C15	0.7699 (8)	0.9307 (6)	0.4786 (4)	0.0444 (19)
H15A	0.8407	0.8731	0.4747	0.053*
H15B	0.7602	0.9588	0.4212	0.053*
C16	0.5711 (10)	0.9999 (5)	0.6717 (4)	0.049 (2)
H16A	0.6212	1.0427	0.7145	0.059*
H16B	0.4592	0.9868	0.6897	0.059*
C17	0.4891 (8)	0.9864 (6)	0.5183 (5)	0.057 (2)
H17A	0.3810	0.9660	0.5374	0.069*
H17B	0.4783	1.0206	0.4635	0.069*
N18	1.1086 (8)	0.8752 (5)	0.6090 (3)	0.0503 (18)
N19	1.1597 (7)	0.8046 (5)	0.6476 (4)	0.0447 (16)
N20	1.2175 (10)	0.7362 (5)	0.6814 (4)	0.071 (2)
N21	0.9608 (7)	0.9549 (6)	0.7701 (3)	0.056 (2)
N22	1.0945 (9)	0.9402 (5)	0.7974 (3)	0.0443 (15)
N23	1.2228 (8)	0.9254 (6)	0.8278 (4)	0.060 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0370 (5)	0.0503 (5)	0.0322 (4)	0.0032 (6)	−0.0009 (5)	0.0000 (6)
N1	0.032 (4)	0.043 (4)	0.032 (3)	−0.001 (3)	0.001 (3)	−0.004 (3)
C2	0.042 (4)	0.061 (6)	0.042 (4)	−0.008 (5)	−0.001 (4)	0.009 (4)
C3	0.045 (5)	0.059 (5)	0.058 (5)	−0.016 (6)	−0.011 (6)	0.016 (4)
C4	0.072 (7)	0.044 (5)	0.075 (6)	−0.004 (5)	−0.020 (6)	0.004 (5)
C5	0.076 (7)	0.043 (5)	0.060 (6)	0.008 (5)	0.012 (6)	−0.006 (5)
C6	0.039 (5)	0.050 (6)	0.042 (5)	0.016 (4)	−0.006 (4)	0.010 (4)
C7	0.029 (5)	0.044 (5)	0.069 (5)	0.017 (5)	−0.002 (4)	−0.003 (5)
C8	0.042 (4)	0.059 (5)	0.039 (4)	−0.010 (5)	−0.008 (5)	−0.001 (4)
N9	0.038 (4)	0.053 (4)	0.031 (3)	0.007 (3)	0.014 (3)	0.003 (3)
C10	0.050 (6)	0.076 (6)	0.048 (5)	−0.004 (5)	0.014 (5)	0.025 (5)
C11	0.068 (7)	0.077 (7)	0.068 (6)	−0.003 (7)	0.005 (6)	0.031 (6)
C12	0.077 (7)	0.044 (5)	0.132 (10)	−0.010 (6)	−0.009 (7)	0.025 (6)
C13	0.070 (7)	0.038 (5)	0.085 (7)	−0.007 (6)	−0.010 (6)	0.001 (5)
C14	0.044 (5)	0.042 (5)	0.056 (5)	0.003 (5)	−0.007 (5)	0.005 (4)
C15	0.050 (5)	0.054 (5)	0.029 (3)	−0.017 (5)	−0.004 (4)	−0.006 (4)
C16	0.046 (5)	0.053 (5)	0.048 (5)	0.012 (5)	0.020 (4)	−0.001 (4)
C17	0.030 (4)	0.086 (7)	0.056 (5)	−0.004 (5)	−0.008 (4)	0.014 (5)
N18	0.045 (4)	0.068 (4)	0.038 (3)	0.017 (5)	0.009 (4)	0.012 (3)
N19	0.034 (4)	0.055 (4)	0.045 (4)	−0.003 (3)	0.006 (4)	−0.010 (4)
N20	0.086 (6)	0.060 (5)	0.067 (5)	0.021 (5)	−0.002 (5)	0.009 (4)
N21	0.047 (4)	0.090 (6)	0.031 (3)	0.008 (5)	−0.007 (3)	−0.011 (4)
N22	0.058 (4)	0.045 (4)	0.030 (3)	−0.005 (6)	0.000 (4)	−0.004 (4)
N23	0.051 (4)	0.069 (5)	0.062 (5)	−0.004 (5)	−0.015 (4)	−0.004 (5)

Geometric parameters (Å, º)

Cu—N21	1.931 (5)	C8—H8	0.9800
Cu—N18	1.958 (6)	N9—C16	1.460 (8)
Cu—N1	2.039 (5)	N9—C10	1.494 (7)
Cu—N9	2.050 (5)	N9—C14	1.516 (8)
N1—C15	1.482 (8)	C10—C11	1.530 (10)
N1—C2	1.502 (7)	C10—H10A	0.9700
N1—C6	1.510 (7)	C10—H10B	0.9700
C2—C3	1.514 (8)	C11—C12	1.520 (10)
C2—H2A	0.9700	C11—H11A	0.9700
C2—H2B	0.9700	C11—H11B	0.9700
C3—C4	1.543 (9)	C12—C13	1.529 (9)
C3—H3A	0.9700	C12—H12A	0.9700
C3—H3B	0.9700	C12—H12B	0.9700
C4—C5	1.514 (9)	C13—C14	1.517 (10)
C4—H4A	0.9700	C13—H13A	0.9700
C4—H4B	0.9700	C13—H13B	0.9700
C5—C6	1.502 (9)	C14—H14	0.9800
C5—H5A	0.9700	C15—H15A	0.9700
C5—H5B	0.9700	C15—H15B	0.9700
C6—C7	1.527 (9)	C16—H16A	0.9700
C6—H6	0.9800	C16—H16B	0.9700
C7—C17	1.513 (9)	C17—H17A	0.9700
C7—C16	1.527 (9)	C17—H17B	0.9700
C7—H7	0.9800	N18—N19	1.200 (7)
C8—C17	1.508 (8)	N19—N20	1.161 (8)
C8—C15	1.526 (9)	N21—N22	1.186 (8)
C8—C14	1.533 (9)	N22—N23	1.164 (8)
N21—Cu—N18	99.6 (2)	C10—N9—C14	108.4 (6)
N21—Cu—N1	146.1 (3)	C16—N9—Cu	108.8 (4)
N18—Cu—N1	96.2 (2)	C10—N9—Cu	111.0 (4)
N21—Cu—N9	96.9 (2)	C14—N9—Cu	108.8 (5)
N18—Cu—N9	141.2 (3)	N9—C10—C11	111.6 (6)
N1—Cu—N9	89.0 (2)	N9—C10—H10A	109.3
C15—N1—C2	107.9 (5)	C11—C10—H10A	109.3
C15—N1—C6	110.9 (5)	N9—C10—H10B	109.3
C2—N1—C6	108.8 (5)	C11—C10—H10B	109.3
C15—N1—Cu	108.5 (4)	H10A—C10—H10B	108.0
C2—N1—Cu	110.3 (4)	C12—C11—C10	112.8 (7)
C6—N1—Cu	110.5 (4)	C12—C11—H11A	109.0
N1—C2—C3	112.4 (6)	C10—C11—H11A	109.0
N1—C2—H2A	109.1	C12—C11—H11B	109.0
C3—C2—H2A	109.1	C10—C11—H11B	109.0
N1—C2—H2B	109.1	H11A—C11—H11B	107.8
C3—C2—H2B	109.1	C11—C12—C13	108.1 (6)
H2A—C2—H2B	107.9	C11—C12—H12A	110.1
C2—C3—C4	109.6 (6)	C13—C12—H12A	110.1
C2—C3—H3A	109.7	C11—C12—H12B	110.1
C4—C3—H3A	109.7	C13—C12—H12B	110.1
C2—C3—H3B	109.7	H12A—C12—H12B	108.4
C4—C3—H3B	109.7	C14—C13—C12	111.3 (7)
H3A—C3—H3B	108.2	C14—C13—H13A	109.4
C5—C4—C3	110.1 (6)	C12—C13—H13A	109.4
C5—C4—H4A	109.6	C14—C13—H13B	109.4
C3—C4—H4A	109.6	C12—C13—H13B	109.4
C5—C4—H4B	109.6	H13A—C13—H13B	108.0
C3—C4—H4B	109.6	N9—C14—C13	109.5 (6)
H4A—C4—H4B	108.2	N9—C14—C8	111.0 (6)
C6—C5—C4	110.4 (7)	C13—C14—C8	115.0 (7)
C6—C5—H5A	109.6	N9—C14—H14	107.0
C4—C5—H5A	109.6	C13—C14—H14	107.0
C6—C5—H5B	109.6	C8—C14—H14	107.0
C4—C5—H5B	109.6	N1—C15—C8	113.3 (6)
H5A—C5—H5B	108.1	N1—C15—H15A	108.9
C5—C6—N1	110.0 (6)	C8—C15—H15A	108.9
C5—C6—C7	115.2 (7)	N1—C15—H15B	108.9
N1—C6—C7	109.5 (6)	C8—C15—H15B	108.9
C5—C6—H6	107.3	H15A—C15—H15B	107.7
N1—C6—H6	107.3	N9—C16—C7	112.2 (5)
C7—C6—H6	107.3	N9—C16—H16A	109.2
C17—C7—C6	110.7 (6)	C7—C16—H16A	109.2
C17—C7—C16	108.9 (7)	N9—C16—H16B	109.2
C6—C7—C16	116.1 (6)	C7—C16—H16B	109.2
C17—C7—H7	106.9	H16A—C16—H16B	107.9
C6—C7—H7	106.9	C8—C17—C7	106.1 (6)
C16—C7—H7	106.9	C8—C17—H17A	110.5
C17—C8—C15	110.1 (6)	C7—C17—H17A	110.5
C17—C8—C14	108.7 (6)	C8—C17—H17B	110.5
C15—C8—C14	113.9 (7)	C7—C17—H17B	110.5
C17—C8—H8	108.0	H17A—C17—H17B	108.7
C15—C8—H8	108.0	N19—N18—Cu	118.1 (5)
C14—C8—H8	108.0	N20—N19—N18	175.7 (8)
C16—N9—C10	107.9 (5)	N22—N21—Cu	122.5 (5)
C16—N9—C14	111.8 (6)	N23—N22—N21	177.0 (7)
N21—Cu—N1—C15	−161.8 (5)	C14—N9—C10—C11	57.9 (8)
N18—Cu—N1—C15	80.5 (5)	Cu—N9—C10—C11	−61.6 (7)
N9—Cu—N1—C15	−61.0 (4)	N9—C10—C11—C12	−55.6 (9)
N21—Cu—N1—C2	80.2 (6)	C10—C11—C12—C13	52.9 (10)
N18—Cu—N1—C2	−37.4 (5)	C11—C12—C13—C14	−56.7 (10)
N9—Cu—N1—C2	−178.9 (5)	C16—N9—C14—C13	179.8 (6)
N21—Cu—N1—C6	−40.1 (6)	C10—N9—C14—C13	−61.4 (8)
N18—Cu—N1—C6	−157.7 (4)	Cu—N9—C14—C13	59.5 (7)
N9—Cu—N1—C6	60.8 (4)	C16—N9—C14—C8	51.8 (9)
C15—N1—C2—C3	179.0 (6)	C10—N9—C14—C8	170.7 (7)
C6—N1—C2—C3	58.7 (7)	Cu—N9—C14—C8	−68.4 (7)
Cu—N1—C2—C3	−62.6 (6)	C12—C13—C14—N9	62.3 (9)
N1—C2—C3—C4	−55.9 (8)	C12—C13—C14—C8	−172.0 (7)
C2—C3—C4—C5	54.5 (9)	C17—C8—C14—N9	−58.9 (9)
C3—C4—C5—C6	−57.9 (8)	C15—C8—C14—N9	64.2 (9)
C4—C5—C6—N1	61.2 (8)	C17—C8—C14—C13	176.2 (6)
C4—C5—C6—C7	−174.5 (6)	C15—C8—C14—C13	−60.7 (9)
C15—N1—C6—C5	−178.8 (6)	C2—N1—C15—C8	−171.6 (6)
C2—N1—C6—C5	−60.3 (7)	C6—N1—C15—C8	−52.6 (8)
Cu—N1—C6—C5	60.9 (6)	Cu—N1—C15—C8	68.9 (7)
C15—N1—C6—C7	53.6 (7)	C17—C8—C15—N1	57.0 (8)
C2—N1—C6—C7	172.1 (5)	C14—C8—C15—N1	−65.4 (8)
Cu—N1—C6—C7	−66.7 (6)	C10—N9—C16—C7	−171.2 (6)
C5—C6—C7—C17	174.2 (6)	C14—N9—C16—C7	−52.0 (8)
N1—C6—C7—C17	−61.2 (7)	Cu—N9—C16—C7	68.3 (7)
C5—C6—C7—C16	−61.0 (9)	C17—C7—C16—N9	59.3 (8)
N1—C6—C7—C16	63.6 (8)	C6—C7—C16—N9	−66.3 (9)
N21—Cu—N9—C16	85.9 (5)	C15—C8—C17—C7	−60.4 (8)
N18—Cu—N9—C16	−159.2 (4)	C14—C8—C17—C7	65.0 (8)
N1—Cu—N9—C16	−60.6 (4)	C6—C7—C17—C8	64.1 (8)
N21—Cu—N9—C10	−32.7 (5)	C16—C7—C17—C8	−64.7 (7)
N18—Cu—N9—C10	82.2 (6)	N21—Cu—N18—N19	51.6 (6)
N1—Cu—N9—C10	−179.2 (5)	N1—Cu—N18—N19	−158.5 (6)
N21—Cu—N9—C14	−152.0 (5)	N9—Cu—N18—N19	−62.3 (7)
N18—Cu—N9—C14	−37.1 (6)	N18—Cu—N21—N22	8.1 (9)
N1—Cu—N9—C14	61.6 (4)	N1—Cu—N21—N22	−108.6 (8)
C16—N9—C10—C11	179.2 (6)	N9—Cu—N21—N22	152.9 (8)