{μ-N,N′-Bis[2-(dimethyl­amino)­ethyl]­oxamidato(2–)-κ⁶N,N′,O′:N′′,N′′′,O}bis­[(2,2′-bipyridine-κ²N,N′)copper(II)] bis­(perchlorate)

In the crystal structure of the title complex, [Cu₂(C₁₀H₂₀N₄O₂)(C₁₀H₈N₂)₂](ClO₄)₂, the deprotonated dmaeoxd²⁻ ligand {H₂dmaeoxd is N,N′-bis­[2-(dimethyl­amino)­ethyl]­oxamide} occupies an inversion centre at the mid-point of the central C—C bond and is thus in a trans conformation. The two Cu^II atoms are located in slightly distorted square-based pyramidal environments. The binuclear units inter­act with each other via π–π inter­actions to form a one-dimensional chain extending in the c direction.

S1. Comment

There has been a great interest in the crystal engineering of self-assembled supramolecular architectures formed through relatively weak interactions such as hydrogen bonds and π–π stacking interactions (Blake et al., 1999; Lin et al., 2003). It is well known that N,N'-bis(substituent)oxamides could be good candidates for the formation of polynuclear complexes, because their coordinating ability towards transition metal ions can be modified and tuned by changing the nature of the amide substituents (Ojima & Nonoyama, 1988). A typical feature of these ligands is an easy transformation of cis–trans conformations, which makes it practical to design tunable molecular materials with desired properties (Chen et al., 1998). To date, many polynuclear complexes containing oxamide-bridges have been synthesized and their properties studied extensively (Messori et al., 2003; Wang et al., 2004). However, as far as we are aware, there are few studies of the influence of substituents in the amine groups of the bridging ligand on their coordination environments and supramolecular structures. Taking into account the above facts and in continuation of our work on polynuclear complexes with bridging oxamide groups (Li et al., 2003, 2004), we chose N,N'-bis[2-(dimethylamino)ethyl]oxamide (H₂dmaeoxd) as bridging ligand and 2,2'-bipyridine as terminal ligand to synthesize the title binuclear copper(II) complex formulated as [Cu(dmaeoxd)(bpy)₂](ClO₄)₂, (I). The influence of the methyl substituents in the amine groups of the bridging ligand on the structures is also discussed.

The molecular structure of (I) (Fig. 1) consists of a centrosymmetric dinuclear copper(II) cation and two uncoordinated perchlorate anions. The [Cu₂(dmaeoxd)(bpy)₂]²⁺ cation has a transoid conformation and occupies a special inversion centre at the middle of the C15—C15ⁱ bond [symmetry code: (i) -x, -y, 2 - z], which is similar to another complex, [Cu(apox)(bpy)₂](NO₃)₂, (II) [H₂(apox) is N,N'-bis(3-aminopropyl)oxamide; Boyd & Rickard, 2006]. The N4/O1/C15/C15ⁱ/N4ⁱ/O1ⁱ bridging group is planar, and atom Cu1 is displaced by 0.069 (4) Å from this plane. The Cu···Cu separation through the bridge is 5.249 (2) Å. Within the oxamide fragment, the C—O and C—N bonds have partial double-bond character [N4—C15 = 1.292 (4) and C15—O1 = 1.263 (3) Å, Table 1], while the length of the C15—C15ⁱ single bond [1.533 (5) Å] is between the value of 1.541 (3) Å in [H₄dmaeoxd](NO₃)₂ (Sun et al., 2006) and that of 1.520 Å in compound (II).

Due to the rigidity of the ligands, the pentacoordinated Cu^II atom has a distorted square-pyramidal geometry. Atom N1 of the bpy ligand occupies the apical position, while the other N atom, N2, as well as two N atoms (N3, N4) and one O atom (O1ⁱ) from the dmaeoxd ligand, form the basal coordination plane, with a maximum deviation of 0.0238 (13) Å for atom N4. Atom Cu1 is displaced out of the basal plane towards the apex by 0.0751 (17) Å. The axial Cu1—N1 distance of 2.218 (3) Å is significantly longer than those in the basal plane. The bis-tridentate dmaeoxd ligand produces two five-membered chelate rings with each Cu^II atom. The ring formed by the ethylenediamine fragment adopts a twist form, with puckering parameters (Cremer & Pople, 1975) of ϕ = 56.7 (4)° and Q = 0.448 (3) Å. In the ring, the Cu1—N3 (amine) distance [2.092 (3) Å] is longer than the Cu1—N4 (amidic) distance [1.903 (2) Å] by 0.189 (4) Å. This difference is larger than that of 0.0698 (18) Å in compound (II), in which the corresponding Cu—N bonds are in a six-membered ring. The dihedral angle between the oxamide bridge and the coordination basal plane is 8.07 (15)°, which is much smaller than the angle of 19.7° in compound (II).

The terminal bpy ligand is present in the usual chelating bidentate mode with a bite angle of 78.36 (10)°. The C5—N1, C6—N2 and C5—C6 distances of 1.332 (4), 1.351 (4) and 1.494 (4) Å, respectively, are typical C═N and Csp²—Csp² values. The 12-atom plane of the bpy ligand (r.m.s. deviation 0.0238 Å) is nearly perpendicular to the oxamide bridge, with a dihedral angle of 84.03 (7)°, which is larger than the angle of 72.5° in compound (II).

Compared with compound (II), the bpy ligands of the title compound do not contribute to C—H···O hydrogen bonds. In addition, due to the substitution of the H atoms of the primary amine by a methyl group, the dmaeoxd ligand does not participate in any hydrogen bonds, which is different from eight other reported binuclear complexes bridged by oxen [H₂oxen is N,N'-bis(2-aminoethyl)oxamide] (Cambridge Structural Database, Version?; Allen, 2002). The pyridine rings of the bpy ligand are involved in offset π–π stacking interactions, by means of which, as shown in Fig. 2, the [Cu₂(dmaeoxd)(bpy)₂]²⁺ cations assemble into a two-dimensional supramolecular structure parallel to the bc plane. The nearest separation is 3.405 (5) Å to atom C10ⁱⁱⁱ [symmetry code: (iii) -x, -y, 1 - z]. Further investigation concerning the influence of substituents on supramolecular structure is in progress in our laboratory.

Related literature

For related literature, see: Allen (2002); Blake et al. (1999); Boyd & Rickard (2006); Chen et al. (1998); Cremer & Pople (1975); Li et al. (2003, 2004); Lin et al. (2003); Messori et al. (2003); Ojima & Nonoyama (1988); Ojima & Yamada (1970); Sun et al. (2006); Wang et al. (2004).

S2. Experimental

All reagents were of AR grade and were used without further purification. The H₂dmaeoxd ligand was synthesized according to the method of Ojima & Yamada (1970). [Cu(dmaeoxd)(bpy)₂](ClO₄)₂ was obtained as follows. To a solution of H₂dmaeoxd (0.0230 g, 0.1 mmol) in methanol (10 ml) were added successively piperidine (0.2 mmol) and a solution of Cu(ClO₄)₂·6H₂O (0.0741 g, 0.2 mmol) in methanol (5 ml). After stirring for 20 min, bpy (0.0312 g, 0.2 mmol) in methanol (5 ml) was added. The reaction mixture was stirred at 333 K for a further 2 h. The green precipitate which formed was collected by suction filtration, washed several times with methanol and diethyl ether, and dried over P₂O₅ under reduced pressure (yield 0.0637 g, 73%). Green crystals of the title compound suitable for X-ray analysis were obtained from a methanol–acetonitrile (1:1 v/v) mixture by slow evaporation for one week at room temperature. Analysis, calculated for C₃₀H₃₆Cl₂N₈O₁₀Cu₂ (%): C 41.58, H 4.19, N 12.93%; found: C 41.52, H 4.14, N 12.92%. Spectroscopic analysis: IR (KBr pellet, γ, cm^-1): 1648 (vs), 1474 (m), 1442 (s), 1090 (vs), 770 (m), 623 (s).

S3. Refinement

All H atoms were positioned geometrically, with C—H distances of 0.93 (sp²C—H), 0.97 (CH₂) or 0.96 Å (CH₃). They were then treated using a riding model, with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(methyl C).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (i) -x, -y, 2 - z.]
	Fig. 2. A view showing the π–π stacking interactions, viewed down the c axis. H atoms and the ClO4^- anion have been omitted for clarity. [Symmetry codes: (i) -x, -y, 2 - z; (ii) -x, 1 - y, 1 - z; (iii) -x, -y, 1 - z.]

{µ-N,N'-Bis[2-(dimethylamino)ethyl]oxamidato(2-)-κ⁶N,N',O':N'',N''',O}bis[(2,2'-bipyridine-κ²N,N')copper(II)] bis(perchlorate)

Crystal data

[Cu2(C10H20N4O2)(C10H8N2)2](ClO4)2	Z = 1
Mr = 866.67	F(000) = 444
Triclinic, P1	Dx = 1.610 Mg m^−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6631 (17) Å	Cell parameters from 2853 reflections
b = 10.144 (2) Å	θ = 2.4–27.7°
c = 10.569 (2) Å	µ = 1.41 mm^−1
α = 79.73 (3)°	T = 298 K
β = 78.02 (3)°	Block, green
γ = 87.08 (3)°	0.22 × 0.16 × 0.13 mm
V = 893.9 (3) Å^3

Data collection

Bruker APEX area-detector diffractometer	3189 independent reflections
Radiation source: fine-focus sealed tube	2778 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
ϕ and ω scans	θmax = 25.2°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→10
Tmin = 0.747, Tmax = 0.838	k = −12→7
4847 measured reflections	l = −12→12

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0678P)^2 + 0.3896P] where P = (Fo^2 + 2Fc^2)/3
3189 reflections	(Δ/σ)max = 0.001
235 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.40 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	0.13801 (4)	0.14679 (4)	0.77887 (3)	0.04023 (15)
O1	0.0559 (2)	−0.0280 (2)	1.15406 (18)	0.0450 (5)
N1	−0.0220 (3)	0.3240 (3)	0.7625 (3)	0.0495 (6)
N2	0.1150 (3)	0.1671 (2)	0.5931 (2)	0.0385 (5)
N3	0.3601 (3)	0.2320 (3)	0.7507 (2)	0.0481 (6)
N4	0.1634 (3)	0.1025 (3)	0.9562 (2)	0.0424 (6)
C1	−0.0927 (5)	0.3934 (4)	0.8552 (4)	0.0676 (10)
H1	−0.0594	0.3793	0.9348	0.081*
C2	−0.2129 (5)	0.4850 (4)	0.8378 (4)	0.0705 (11)
H2	−0.2607	0.5307	0.9049	0.085*
C3	−0.2603 (4)	0.5073 (4)	0.7205 (4)	0.0675 (10)
H3	−0.3388	0.5706	0.7052	0.081*
C4	−0.1901 (4)	0.4348 (3)	0.6252 (4)	0.0546 (8)
H4	−0.2216	0.4477	0.5449	0.066*
C5	−0.0724 (3)	0.3424 (3)	0.6498 (3)	0.0397 (6)
C6	0.0064 (3)	0.2565 (3)	0.5534 (3)	0.0381 (6)
C7	−0.0291 (4)	0.2644 (3)	0.4309 (3)	0.0501 (7)
H7	−0.1045	0.3258	0.4045	0.060*
C8	0.0474 (4)	0.1813 (4)	0.3482 (3)	0.0548 (8)
H8	0.0225	0.1847	0.2662	0.066*
C9	0.1602 (4)	0.0938 (4)	0.3867 (3)	0.0543 (8)
H9	0.2153	0.0389	0.3305	0.065*
C10	0.1911 (4)	0.0881 (3)	0.5101 (3)	0.0477 (7)
H10	0.2671	0.0276	0.5368	0.057*
C11	0.3788 (5)	0.3565 (4)	0.6500 (4)	0.0726 (11)
H11A	0.4754	0.3992	0.6495	0.109*
H11B	0.2914	0.4164	0.6707	0.109*
H11C	0.3815	0.3341	0.5651	0.109*
C12	0.4884 (5)	0.1379 (5)	0.7137 (5)	0.0783 (12)
H12A	0.5874	0.1758	0.7146	0.117*
H12B	0.4884	0.1211	0.6272	0.117*
H12C	0.4734	0.0554	0.7751	0.117*
C13	0.3610 (5)	0.2690 (4)	0.8806 (3)	0.0636 (10)
H13A	0.2941	0.3474	0.8920	0.076*
H13B	0.4674	0.2907	0.8847	0.076*
C14	0.3006 (4)	0.1517 (4)	0.9907 (3)	0.0578 (9)
H14A	0.3809	0.0818	0.9960	0.069*
H14B	0.2720	0.1818	1.0747	0.069*
C15	0.0627 (3)	0.0201 (3)	1.0343 (3)	0.0383 (6)
Cl1	0.35087 (11)	−0.25757 (10)	0.77526 (10)	0.0666 (3)
O11	0.4172 (6)	−0.2598 (8)	0.6467 (4)	0.202 (3)
O12	0.4653 (5)	−0.2779 (6)	0.8502 (5)	0.154 (2)
O13	0.2628 (6)	−0.1442 (5)	0.7901 (6)	0.162 (2)
O14	0.2401 (7)	−0.3631 (5)	0.8124 (5)	0.1421 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0457 (2)	0.0484 (2)	0.0292 (2)	−0.00128 (16)	−0.01167 (14)	−0.00859 (15)
O1	0.0515 (11)	0.0576 (13)	0.0303 (10)	−0.0070 (10)	−0.0158 (8)	−0.0089 (9)
N1	0.0554 (15)	0.0515 (16)	0.0449 (14)	0.0055 (12)	−0.0102 (11)	−0.0185 (12)
N2	0.0410 (12)	0.0443 (13)	0.0321 (11)	0.0006 (10)	−0.0095 (9)	−0.0093 (10)
N3	0.0480 (14)	0.0586 (16)	0.0380 (13)	−0.0084 (12)	−0.0077 (11)	−0.0078 (11)
N4	0.0482 (13)	0.0507 (14)	0.0323 (12)	−0.0050 (12)	−0.0149 (10)	−0.0091 (10)
C1	0.080 (3)	0.073 (2)	0.055 (2)	0.010 (2)	−0.0111 (18)	−0.0311 (18)
C2	0.066 (2)	0.064 (2)	0.082 (3)	0.0085 (19)	0.001 (2)	−0.037 (2)
C3	0.0507 (19)	0.057 (2)	0.094 (3)	0.0063 (17)	−0.0091 (19)	−0.019 (2)
C4	0.0467 (17)	0.0515 (19)	0.067 (2)	0.0026 (15)	−0.0153 (15)	−0.0089 (16)
C5	0.0388 (14)	0.0378 (15)	0.0423 (15)	−0.0060 (12)	−0.0072 (12)	−0.0059 (12)
C6	0.0379 (14)	0.0414 (15)	0.0361 (14)	−0.0077 (12)	−0.0081 (11)	−0.0066 (12)
C7	0.0573 (18)	0.0532 (18)	0.0446 (17)	−0.0005 (15)	−0.0231 (14)	−0.0060 (14)
C8	0.070 (2)	0.066 (2)	0.0344 (15)	−0.0090 (18)	−0.0192 (14)	−0.0117 (14)
C9	0.063 (2)	0.065 (2)	0.0394 (16)	−0.0040 (17)	−0.0080 (14)	−0.0219 (15)
C10	0.0516 (17)	0.0524 (18)	0.0412 (16)	0.0063 (14)	−0.0099 (13)	−0.0151 (14)
C11	0.074 (2)	0.075 (3)	0.067 (2)	−0.021 (2)	−0.0193 (19)	0.003 (2)
C12	0.056 (2)	0.086 (3)	0.093 (3)	0.004 (2)	−0.009 (2)	−0.025 (2)
C13	0.066 (2)	0.079 (3)	0.0515 (19)	−0.0226 (19)	−0.0153 (16)	−0.0175 (18)
C14	0.0598 (19)	0.077 (2)	0.0423 (17)	−0.0174 (18)	−0.0217 (15)	−0.0070 (16)
C15	0.0448 (15)	0.0435 (15)	0.0306 (13)	0.0023 (12)	−0.0130 (12)	−0.0113 (11)
Cl1	0.0624 (5)	0.0731 (6)	0.0720 (6)	0.0187 (5)	−0.0241 (4)	−0.0263 (5)
O11	0.131 (4)	0.391 (10)	0.075 (3)	0.017 (5)	−0.002 (3)	−0.046 (4)
O12	0.115 (3)	0.243 (6)	0.143 (4)	0.059 (4)	−0.086 (3)	−0.085 (4)
O13	0.133 (4)	0.105 (3)	0.286 (7)	0.050 (3)	−0.087 (4)	−0.092 (4)
O14	0.203 (5)	0.108 (3)	0.130 (4)	−0.038 (3)	−0.078 (3)	0.003 (3)

Geometric parameters (Å, º)

Cu1—N4	1.903 (2)	C6—C7	1.379 (4)
Cu1—N2	1.988 (2)	C7—C8	1.371 (5)
Cu1—O1^i	2.045 (2)	C7—H7	0.9300
Cu1—N3	2.092 (3)	C8—C9	1.362 (5)
Cu1—N1	2.218 (3)	C8—H8	0.9300
O1—C15	1.263 (3)	C9—C10	1.375 (4)
O1—Cu1^i	2.045 (2)	C9—H9	0.9300
N1—C5	1.332 (4)	C10—H10	0.9300
N1—C1	1.335 (4)	C11—H11A	0.9600
N2—C10	1.343 (4)	C11—H11B	0.9600
N2—C6	1.351 (4)	C11—H11C	0.9600
N3—C12	1.464 (5)	C12—H12A	0.9600
N3—C13	1.488 (4)	C12—H12B	0.9600
N3—C11	1.492 (5)	C12—H12C	0.9600
N4—C15	1.292 (4)	C13—C14	1.537 (5)
N4—C14	1.449 (4)	C13—H13A	0.9700
C1—C2	1.379 (6)	C13—H13B	0.9700
C1—H1	0.9300	C14—H14A	0.9700
C2—C3	1.364 (6)	C14—H14B	0.9700
C2—H2	0.9300	C15—C15^i	1.533 (5)
C3—C4	1.375 (5)	Cl1—O13	1.362 (4)
C3—H3	0.9300	Cl1—O11	1.364 (4)
C4—C5	1.382 (4)	Cl1—O12	1.379 (4)
C4—H4	0.9300	Cl1—O14	1.421 (5)
C5—C6	1.494 (4)
N4—Cu1—N2	172.37 (10)	C8—C7—H7	120.2
N4—Cu1—O1^i	83.44 (9)	C6—C7—H7	120.2
N2—Cu1—O1^i	92.92 (9)	C9—C8—C7	119.7 (3)
N4—Cu1—N3	82.92 (10)	C9—C8—H8	120.2
N2—Cu1—N3	99.63 (10)	C7—C8—H8	120.2
O1^i—Cu1—N3	164.14 (10)	C8—C9—C10	118.9 (3)
N4—Cu1—N1	108.19 (10)	C8—C9—H9	120.6
N2—Cu1—N1	78.36 (10)	C10—C9—H9	120.6
O1^i—Cu1—N1	88.81 (10)	N2—C10—C9	122.1 (3)
N3—Cu1—N1	103.12 (11)	N2—C10—H10	119.0
C15—O1—Cu1^i	109.10 (17)	C9—C10—H10	119.0
C5—N1—C1	118.3 (3)	N3—C11—H11A	109.5
C5—N1—Cu1	111.13 (19)	N3—C11—H11B	109.5
C1—N1—Cu1	129.2 (3)	H11A—C11—H11B	109.5
C10—N2—C6	118.9 (2)	N3—C11—H11C	109.5
C10—N2—Cu1	123.1 (2)	H11A—C11—H11C	109.5
C6—N2—Cu1	117.68 (18)	H11B—C11—H11C	109.5
C12—N3—C13	111.8 (3)	N3—C12—H12A	109.5
C12—N3—C11	109.0 (3)	N3—C12—H12B	109.5
C13—N3—C11	108.4 (3)	H12A—C12—H12B	109.5
C12—N3—Cu1	112.1 (2)	N3—C12—H12C	109.5
C13—N3—Cu1	103.15 (19)	H12A—C12—H12C	109.5
C11—N3—Cu1	112.3 (2)	H12B—C12—H12C	109.5
C15—N4—C14	124.8 (2)	N3—C13—C14	109.8 (3)
C15—N4—Cu1	116.41 (18)	N3—C13—H13A	109.7
C14—N4—Cu1	118.5 (2)	C14—C13—H13A	109.7
N1—C1—C2	122.7 (4)	N3—C13—H13B	109.7
N1—C1—H1	118.6	C14—C13—H13B	109.7
C2—C1—H1	118.6	H13A—C13—H13B	108.2
C3—C2—C1	118.8 (3)	N4—C14—C13	105.7 (3)
C3—C2—H2	120.6	N4—C14—H14A	110.6
C1—C2—H2	120.6	C13—C14—H14A	110.6
C2—C3—C4	118.9 (3)	N4—C14—H14B	110.6
C2—C3—H3	120.6	C13—C14—H14B	110.6
C4—C3—H3	120.6	H14A—C14—H14B	108.7
C3—C4—C5	119.5 (3)	O1—C15—N4	129.1 (2)
C3—C4—H4	120.3	O1—C15—C15^i	118.8 (3)
C5—C4—H4	120.3	N4—C15—C15^i	112.2 (3)
N1—C5—C4	121.7 (3)	O13—Cl1—O11	111.7 (4)
N1—C5—C6	115.4 (2)	O13—Cl1—O12	113.2 (3)
C4—C5—C6	122.9 (3)	O11—Cl1—O12	110.1 (3)
N2—C6—C7	120.7 (3)	O13—Cl1—O14	104.8 (3)
N2—C6—C5	116.2 (2)	O11—Cl1—O14	105.4 (4)
C7—C6—C5	123.0 (3)	O12—Cl1—O14	111.1 (3)
C8—C7—C6	119.6 (3)
N4—Cu1—N1—C5	−166.3 (2)	C1—C2—C3—C4	2.0 (6)
N2—Cu1—N1—C5	9.7 (2)	C2—C3—C4—C5	−0.8 (5)
O1^i—Cu1—N1—C5	−83.6 (2)	C1—N1—C5—C4	2.8 (5)
N3—Cu1—N1—C5	107.0 (2)	Cu1—N1—C5—C4	170.8 (2)
N4—Cu1—N1—C1	0.1 (3)	C1—N1—C5—C6	−177.0 (3)
N2—Cu1—N1—C1	176.1 (3)	Cu1—N1—C5—C6	−9.0 (3)
O1^i—Cu1—N1—C1	82.8 (3)	C3—C4—C5—N1	−1.7 (5)
N3—Cu1—N1—C1	−86.6 (3)	C3—C4—C5—C6	178.1 (3)
O1^i—Cu1—N2—C10	−94.2 (2)	C10—N2—C6—C7	1.6 (4)
N3—Cu1—N2—C10	76.0 (2)	Cu1—N2—C6—C7	−172.3 (2)
N1—Cu1—N2—C10	177.6 (3)	C10—N2—C6—C5	−179.3 (3)
O1^i—Cu1—N2—C6	79.4 (2)	Cu1—N2—C6—C5	6.9 (3)
N3—Cu1—N2—C6	−110.3 (2)	N1—C5—C6—N2	2.3 (4)
N1—Cu1—N2—C6	−8.8 (2)	C4—C5—C6—N2	−177.5 (3)
N4—Cu1—N3—C12	92.2 (3)	N1—C5—C6—C7	−178.6 (3)
N2—Cu1—N3—C12	−80.5 (3)	C4—C5—C6—C7	1.6 (4)
O1^i—Cu1—N3—C12	61.3 (4)	N2—C6—C7—C8	−0.4 (5)
N1—Cu1—N3—C12	−160.7 (2)	C5—C6—C7—C8	−179.5 (3)
N4—Cu1—N3—C13	−28.2 (2)	C6—C7—C8—C9	−1.4 (5)
N2—Cu1—N3—C13	159.0 (2)	C7—C8—C9—C10	2.0 (5)
O1^i—Cu1—N3—C13	−59.1 (4)	C6—N2—C10—C9	−1.0 (4)
N1—Cu1—N3—C13	78.9 (2)	Cu1—N2—C10—C9	172.5 (2)
N4—Cu1—N3—C11	−144.7 (3)	C8—C9—C10—N2	−0.8 (5)
N2—Cu1—N3—C11	42.6 (3)	C12—N3—C13—C14	−74.2 (4)
O1^i—Cu1—N3—C11	−175.6 (3)	C11—N3—C13—C14	165.7 (3)
N1—Cu1—N3—C11	−37.6 (3)	Cu1—N3—C13—C14	46.4 (3)
O1^i—Cu1—N4—C15	2.8 (2)	C15—N4—C14—C13	−167.2 (3)
N3—Cu1—N4—C15	−169.1 (2)	Cu1—N4—C14—C13	19.3 (4)
N1—Cu1—N4—C15	89.4 (2)	N3—C13—C14—N4	−44.0 (4)
O1^i—Cu1—N4—C14	176.8 (3)	Cu1^i—O1—C15—N4	177.9 (3)
N3—Cu1—N4—C14	5.0 (2)	Cu1^i—O1—C15—C15^i	−1.9 (4)
N1—Cu1—N4—C14	−96.6 (3)	C14—N4—C15—O1	4.1 (5)
C5—N1—C1—C2	−1.4 (6)	Cu1—N4—C15—O1	177.7 (2)
Cu1—N1—C1—C2	−167.0 (3)	C14—N4—C15—C15^i	−176.1 (3)
N1—C1—C2—C3	−1.0 (6)	Cu1—N4—C15—C15^i	−2.4 (4)

Symmetry code: (i) −x, −y, −z+2.