[{Cu(phen)₂}(μ-malato){Cu(phen)(NO₃)}](NO₃)·4H₂O: malate acting as a tetra­dentate and dibridging ligand in a dinuclear copper complex

The crystal structure of the title compound, μ-2-hydroxy­butane­dioato-1κ²O⁴,O^4′:2κ³O¹,O²,O⁴-nitrato-2κO-tris­(1,10-phen­anthroline)-1κ⁴N,N′;2κ²N,N′-dicopper(II) nitrate tetra­hydrate, [Cu₂(C₄H₃O₅)(NO₃)(C₁₂H₈N₂)₃](NO₃)·4H₂O, contains an unsymmetrical dinuclear copper complex with Cu(phen)₂ and Cu(phen)(NO₃) moieties (phen is 1,10-phenanthroline) bridged by a malate (2-hydroxy­butane­dioate) ligand, which acts as a double-bridging and tetra­dentate ligand. As a result of this double-bridging action, especially the direct coordination of the O atom of one carboxyl­ate group of malate to the two Cu atoms, the Cu...Cu distance is only 4.199 (1) Å and the two phen planes are roughly parallel [the shortest inter­planar distance is 3.28 (1) Å], exhibiting an obvious intra­molecular π–π stacking inter­action.

S1. Comment

Malate has been found to be a versatile ligand in coordination compounds as it can exhibit many types of coordination modes due to the presence of two carboxyl groups and one hydroxyl group. In some mononuclear complexes, e.g. Na₃[WO₂H(S-mal)₂] (Zhou et al., 2001) and M₃[MoO₂H(S-mal)₂]·H₂O (M is K or Na; Zhou et al., 2002), as well as in binuclear complexes such as K₂[VO(O₂)(C₄H₄O₅)]₂·2H₂O (Justino et al., 2003) and Cs₂[{VO₂(mal)}₂]·2H₂O (Biagioli et al., 2000), the malate anion acts as a bidentate ligand, coordinating to the metal through two O atoms from the hydroxyl group and the adjacent carboxylate group. In some binuclear complexes, such as Mn₂[(C₄H₄O₅)(H₂O)₂]₂·2H₂O (Liu et al., 2004), [Zn(Hmal)(1,10-phen)(H₂O)]_n, [Cu(Hmal)(2,20-bipy)]_n.3nH₂O (He et al., 2004) or (NH₄)₂[VO(O₂)(C₄H₄O₅)]₂·2H₂O (Djordjevic et al., 1995), the malate anion is a tridentate ligand, coordinating to the metal ion through the hydroxyl O atom and two terminal carboxylate O atoms. In the trinuclear complex [Cu^I/Cu^II₂(mal)(SO₄)(bpy)₂·H₂O]_n (Lah et al., 2003), the malate anion connects the two crystallographically independent Cu^II ions by monodentate coordination of the two terminal carboxylate groups and through the hydroxyl O atom, which serves as a bridge between the two metal centres. Here, we report the crystal structure of (I), in which the malate ligand acts as a double bridging and tetradentate agent.

Some features of the molecular geometry of (I) are listed in Table 1 and the molecular conformation is illustrated in Fig. 1. The asymmetric unit of (I) consists of a [Cu₂(phen)₃(malate)(NO₃)] cation, a nitrate anion and four water molecules. In the cation, the coordination geometries around atoms Cu1 and Cu2 can be described as distorted octahedra with obvious Jahn–Teller distortion. Atom Cu1 is coordinated by four N atoms from two phen ligands and two O atoms from the same carboxylate group of the malate ligand, with atoms N1, N2, N3 and O4 in equatorial positions and N4 and O5 at the Jahn–Teller axis. Atom Cu2 is coordinated by two N atoms from the third phen ligand and four O atoms, of which the N atoms and the two O atoms from the hydroxyl group and the other carboxylate group of the malate form the equatorial plane while the O atom of a nitrate and atom O4, shared with Cu1, occupy the Jahn–Teller axis. The two coordinated moieties are thus connected not only through the malate dianion as a bridge, but also through atom O4 of one carboxylate group of the malate ligand as another bridge directly coordinating to the two Cu²⁺ ions of the two moieties, forming an unsymmetric dinuclear copper complex. Therefore, the malate ligand plays the role of a double-bridging and tetradentate agent in this cation.

The bridging atom O4 links the two octahedra, with the Cu1—O4—Cu2 angle being 131.8 (1)°. As the result of this bridging action by atom O4, the two coordinated moieties are very close, with a Cu···Cu distance of 4.199 (1) Å. The two phen planes between the two moieties are roughly parallel, with a closest distance of 3.28 (1) Å, exhibiting an obvious intramolecular π–π stacking interaction.

Because of this double-bridging action, the structure of (I) obviously differs from that of the previously reported analogous complex, [Cu₂(IDA)(phen)₃](ClO₄)₂CH₃OH (IDA is iminodiacetate; Wei et al., 2004), where the similar [Cu(phen)₂] and [Cu(phen)] moieties are bridged by the IDA ligand, but the two O atoms of one carboxylate group of the IDA ligand are coordinated to the two Cu²⁺ ions, making these ions five-coordinated in a distorted trigonal bipyramid or square pyramid, and no intramolecular π–π stacking interaction exists in this compound. Thus, the structure of the cation of (I) is unusual.

Details of the hydrogen-bonding geometry and crystal packing of (I) are listed in Table 2 and illustrated in Figs. 1 and 2. Only O—H···O hydrogen bonds are observed in (I). In the crystal packing, four complex cations are stacked in each cell (Fig. 2), making the phenanthroline rings partly overlapped with distances in the range 3.36 (1)–3.47 (1) Å, presenting intermolecular π–π stacking interactions. Therefore, hydrogen bonds and both inter- and intramolecular π–π stacking interactions stabilize the crystal structure of (I).

S2. Experimental

All chemicals were of reagent grade and commercially available from the Beijing Chemical Reagents Company, China, and were used without further purification. Addition of malic acid (1 mmol) to an aqueous solution (10 ml) of Cu(NO)₃·3H₂O (1 mmol) gave a solution of pH 1.5. 1,10-Phenanthroline (1 mmol) was slowly added to the solution with continuously stirring. The mixture was then adjusted to pH 3.0 with a dilute solution of KOH and kept at room temperature. Several days later, blue block-shaped single crystals of (I) were isolated.

S3. Refinement

H atoms attached to O atoms were located in difference Fourier maps and refined with a global U_iso(H) value. The O—H distances are in the range 0.768–0.835 Å. H atoms attached to C atoms were placed in geometrically idealized positions, with Csp³—H = 0.97 and Csp²—H = 0.93 Å, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C). Atoms O9, O10, O11, O15 from the nitrate anion and the solvate water were found to be disordered and were modelled over two sets of positions using restraints on their anisotropic displacement parameters. The major and minor disorder components had refined occupancies of 64.9 (5)% and 35.1 (5)%, respectively.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC.

Figures

	Fig. 1. The structure of (I), showing the atom-labelling scheme and with displacement ellipsoids drawn at the 20% probability level. Hydrogen bonds are shown as dashed lines. The minor disorder components and H atoms have been omitted for clarity.
	Fig. 2. Hydrogen bonds (dashed lines) and π–π stacking interactions in (I). [Symmetry codes: (i) x, 3/2 - y, 1/2 + z; (ii) 1 - x, -1/2 + y, 1/2 - z; (iii) 1 - x, 1 - y, 1 - z.]

µ-2-hydroxybutanedioato-1κ²O⁴,O^4':2κ²O²,O²-nitrato-2κO- tris(1,10-phenanthroline)-1κ⁴N,N';2κ²N,N'-dicopper(II) nitrate tetrahydrate

Crystal data

[Cu2(C4H3O5)(C12H8N2)3(NO3)](NO3)·4H2O	F(000) = 2040
Mr = 995.85	Dx = 1.603 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3837 reflections
a = 12.448 (3) Å	θ = 2.0–23.7°
b = 14.878 (4) Å	µ = 1.11 mm^−1
c = 22.483 (6) Å	T = 298 K
β = 97.655 (5)°	Block, blue
V = 4127.1 (19) Å^3	0.15 × 0.12 × 0.10 mm
Z = 4

Data collection

Bruker SMART 1K CCD area-detector diffractometer	7256 independent reflections
Radiation source: fine-focus sealed tube	4946 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
φ and ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −14→14
Tmin = 0.851, Tmax = 0.897	k = −17→13
20979 measured reflections	l = −26→26

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)] = 0.049	Hydrogen site location: difmap (water O-H) and geom (others)
wR(F^2) = 0.137	H-atom parameters constrained
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0837P)^2] where P = (Fo^2 + 2Fc^2)/3
7256 reflections	(Δ/σ)max = 0.001
623 parameters	Δρmax = 0.88 e Å^−3
67 restraints	Δρmin = −0.33 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)
Cu1	0.26891 (4)	0.77180 (3)	0.06025 (2)	0.04803 (17)
Cu2	0.33851 (4)	0.56518 (4)	0.18676 (2)	0.05783 (19)
N1	0.4188 (3)	0.7846 (2)	0.03826 (14)	0.0502 (8)
N2	0.2395 (3)	0.8732 (2)	−0.00208 (14)	0.0496 (8)
N3	0.1174 (2)	0.7660 (2)	0.08023 (14)	0.0472 (8)
N4	0.2902 (3)	0.8387 (2)	0.14685 (14)	0.0504 (8)
N5	0.4019 (3)	0.6504 (2)	0.25032 (14)	0.0515 (8)
N6	0.2006 (3)	0.5996 (2)	0.21593 (14)	0.0521 (8)
N7	0.3161 (3)	0.3774 (3)	0.27150 (18)	0.0653 (10)
N8	0.1541 (5)	0.1159 (4)	0.0993 (3)	0.132 (2)
O1	0.4740 (2)	0.53914 (19)	0.15952 (12)	0.0574 (7)
O2	0.5455 (3)	0.4773 (2)	0.08528 (14)	0.0868 (10)
O3	0.2807 (2)	0.46947 (19)	0.13151 (12)	0.0658 (8)
H3A	0.2760	0.4206	0.1483	0.099*
O4	0.3013 (2)	0.64122 (17)	0.08438 (12)	0.0537 (7)
O5	0.2297 (2)	0.6350 (2)	−0.01031 (12)	0.0656 (8)
O6	0.3646 (3)	0.4493 (2)	0.26914 (15)	0.0878 (11)
O7	0.2519 (3)	0.3521 (3)	0.22784 (19)	0.1112 (14)
O8	0.3338 (3)	0.3280 (2)	0.31584 (16)	0.0992 (12)
O12	0.2397 (3)	0.1527 (2)	0.25610 (17)	0.0986 (11)
H12A	0.2312	0.1959	0.2785	0.148*
H12B	0.2598	0.1735	0.2252	0.148*
O13	0.7305 (3)	0.5859 (3)	0.12647 (16)	0.1046 (13)
H13A	0.6817	0.5541	0.1081	0.157*
H13B	0.7173	0.5868	0.1614	0.157*
O14	0.8978 (4)	0.4685 (3)	0.09737 (19)	0.1372 (17)
H14A	0.8742	0.4961	0.1247	0.206*
H14B	0.8466	0.4476	0.0746	0.206*
O9A	0.1680 (15)	0.0423 (7)	0.1233 (6)	0.275 (7)	0.649 (7)
O9B	0.1209 (14)	0.0369 (8)	0.0810 (11)	0.205 (10)	0.351 (7)
O10A	0.1195 (8)	0.1251 (7)	0.0460 (3)	0.171 (4)	0.649 (7)
O10B	0.0835 (10)	0.1778 (8)	0.0944 (8)	0.152 (6)	0.351 (7)
O11A	0.1849 (12)	0.1882 (7)	0.1272 (5)	0.235 (6)	0.649 (7)
O11B	0.2388 (8)	0.1190 (11)	0.1335 (5)	0.120 (5)	0.351 (7)
O15A	0.1286 (8)	0.3490 (7)	0.0934 (4)	0.196 (5)	0.649 (7)
H51A	0.0846	0.3080	0.0965	0.294*
H52A	0.1017	0.3954	0.0895	0.294*
O15B	0.0492 (10)	0.4550 (8)	0.0435 (5)	0.159 (7)	0.351 (7)
C1	0.5075 (3)	0.7389 (3)	0.0601 (2)	0.0644 (12)
H1	0.5028	0.6961	0.0898	0.077*
C2	0.6063 (4)	0.7533 (3)	0.0399 (2)	0.0722 (13)
H2	0.6664	0.7197	0.0557	0.087*
C3	0.6160 (3)	0.8165 (3)	−0.0031 (2)	0.0665 (12)
H3	0.6823	0.8258	−0.0169	0.080*
C4	0.5248 (3)	0.8671 (3)	−0.02619 (17)	0.0548 (10)
C5	0.4282 (3)	0.8473 (3)	−0.00378 (16)	0.0487 (9)
C6	0.3307 (3)	0.8961 (3)	−0.02584 (16)	0.0484 (9)
C7	0.5254 (4)	0.9350 (3)	−0.0707 (2)	0.0667 (12)
H7	0.5899	0.9486	−0.0855	0.080*
C8	0.4346 (4)	0.9799 (3)	−0.0919 (2)	0.0686 (13)
H8	0.4372	1.0236	−0.1212	0.082*
C9	0.3340 (4)	0.9615 (3)	−0.06999 (19)	0.0571 (11)
C10	0.2362 (4)	1.0043 (3)	−0.0909 (2)	0.0731 (13)
H10	0.2334	1.0478	−0.1207	0.088*
C11	0.1448 (4)	0.9813 (3)	−0.0669 (2)	0.0778 (14)
H11	0.0796	1.0098	−0.0803	0.093*
C12	0.1483 (4)	0.9155 (3)	−0.0225 (2)	0.0621 (11)
H12	0.0851	0.9010	−0.0069	0.075*
C13	0.0330 (3)	0.7275 (3)	0.0478 (2)	0.0585 (11)
H13	0.0431	0.7003	0.0118	0.070*
C14	−0.0688 (4)	0.7261 (3)	0.0652 (2)	0.0726 (13)
H14	−0.1254	0.6971	0.0416	0.087*
C15	−0.0864 (4)	0.7672 (3)	0.1170 (2)	0.0709 (13)
H15	−0.1554	0.7672	0.1286	0.085*
C16	−0.0002 (3)	0.8097 (3)	0.15292 (19)	0.0568 (11)
C17	0.1023 (3)	0.8067 (2)	0.13273 (17)	0.0457 (9)
C18	0.1938 (3)	0.8456 (2)	0.16808 (17)	0.0490 (9)
C19	−0.0088 (4)	0.8527 (3)	0.2097 (2)	0.0735 (13)
H19	−0.0757	0.8549	0.2237	0.088*
C20	0.0772 (4)	0.8890 (3)	0.2421 (2)	0.0742 (14)
H20	0.0692	0.9161	0.2786	0.089*
C21	0.1797 (4)	0.8876 (3)	0.22288 (19)	0.0593 (11)
C22	0.2739 (5)	0.9248 (3)	0.2555 (2)	0.0757 (14)
H22	0.2702	0.9526	0.2922	0.091*
C23	0.3689 (4)	0.9201 (3)	0.2335 (2)	0.0750 (14)
H23	0.4303	0.9464	0.2546	0.090*
C24	0.3761 (4)	0.8757 (3)	0.17884 (19)	0.0639 (12)
H24	0.4430	0.8722	0.1648	0.077*
C25	0.5041 (3)	0.6752 (3)	0.26621 (19)	0.0640 (12)
H25	0.5567	0.6548	0.2437	0.077*
C26	0.5352 (4)	0.7303 (3)	0.3150 (2)	0.0704 (13)
H26	0.6073	0.7474	0.3244	0.085*
C27	0.4603 (4)	0.7592 (3)	0.3489 (2)	0.0644 (12)
H27	0.4811	0.7960	0.3819	0.077*
C28	0.3513 (4)	0.7341 (3)	0.33476 (17)	0.0541 (10)
C29	0.3265 (3)	0.6794 (2)	0.28444 (16)	0.0453 (9)
C30	0.2187 (3)	0.6518 (2)	0.26627 (16)	0.0456 (9)
C31	0.2661 (4)	0.7599 (3)	0.36729 (19)	0.0669 (13)
H31	0.2814	0.7960	0.4011	0.080*
C32	0.1641 (4)	0.7330 (3)	0.3500 (2)	0.0682 (13)
H32	0.1100	0.7505	0.3724	0.082*
C33	0.1364 (3)	0.6784 (3)	0.29836 (19)	0.0555 (10)
C34	0.0307 (4)	0.6492 (3)	0.2762 (2)	0.0711 (13)
H34	−0.0271	0.6641	0.2965	0.085*
C35	0.0134 (4)	0.5999 (3)	0.2254 (2)	0.0711 (13)
H35	−0.0567	0.5827	0.2101	0.085*
C36	0.0997 (3)	0.5748 (3)	0.1963 (2)	0.0645 (12)
H36	0.0867	0.5396	0.1619	0.077*
C37	0.4691 (4)	0.4941 (3)	0.11147 (19)	0.0588 (11)
C38	0.3565 (4)	0.4566 (3)	0.0879 (2)	0.0684 (13)
H38	0.3634	0.3920	0.0806	0.082*
C39	0.3063 (4)	0.5000 (3)	0.03117 (18)	0.0673 (12)
H39A	0.2417	0.4664	0.0159	0.081*
H39B	0.3565	0.4948	0.0018	0.081*
C40	0.2752 (3)	0.5984 (3)	0.03554 (19)	0.0532 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0419 (3)	0.0545 (3)	0.0476 (3)	−0.0057 (2)	0.0057 (2)	0.0058 (2)
Cu2	0.0454 (3)	0.0758 (4)	0.0528 (3)	−0.0018 (2)	0.0084 (2)	−0.0173 (3)
N1	0.0435 (19)	0.056 (2)	0.0506 (19)	−0.0068 (15)	0.0037 (15)	0.0063 (16)
N2	0.048 (2)	0.049 (2)	0.0518 (19)	−0.0025 (16)	0.0059 (16)	0.0005 (15)
N3	0.0403 (18)	0.0521 (19)	0.0488 (19)	−0.0042 (15)	0.0051 (15)	0.0010 (15)
N4	0.051 (2)	0.051 (2)	0.0470 (18)	−0.0119 (16)	0.0001 (16)	0.0020 (15)
N5	0.0440 (19)	0.060 (2)	0.0497 (19)	−0.0066 (16)	0.0041 (15)	−0.0060 (16)
N6	0.0432 (19)	0.056 (2)	0.057 (2)	−0.0014 (15)	0.0061 (16)	−0.0049 (17)
N7	0.068 (3)	0.067 (3)	0.064 (3)	−0.003 (2)	0.022 (2)	−0.004 (2)
N8	0.125 (5)	0.150 (6)	0.127 (5)	−0.018 (5)	0.043 (4)	−0.004 (5)
O1	0.0483 (16)	0.074 (2)	0.0494 (16)	0.0076 (14)	0.0059 (13)	−0.0077 (14)
O2	0.077 (2)	0.119 (3)	0.070 (2)	0.013 (2)	0.0291 (19)	−0.0203 (19)
O3	0.089 (2)	0.0599 (18)	0.0520 (17)	−0.0195 (16)	0.0198 (16)	−0.0039 (14)
O4	0.0565 (17)	0.0488 (16)	0.0536 (17)	−0.0053 (13)	−0.0003 (13)	0.0042 (13)
O5	0.076 (2)	0.071 (2)	0.0492 (17)	0.0078 (16)	0.0048 (15)	0.0145 (15)
O6	0.110 (3)	0.073 (2)	0.075 (2)	−0.016 (2)	−0.007 (2)	0.0049 (18)
O7	0.105 (3)	0.113 (3)	0.108 (3)	−0.036 (2)	−0.014 (3)	0.017 (2)
O8	0.144 (4)	0.077 (2)	0.080 (2)	0.001 (2)	0.028 (2)	0.017 (2)
O12	0.071 (2)	0.105 (3)	0.121 (3)	−0.006 (2)	0.017 (2)	0.011 (2)
O13	0.107 (3)	0.126 (3)	0.080 (2)	−0.025 (2)	0.010 (2)	0.015 (2)
O14	0.150 (4)	0.132 (4)	0.115 (3)	−0.021 (3)	−0.037 (3)	0.001 (3)
O9A	0.303 (11)	0.251 (10)	0.268 (11)	0.065 (9)	0.026 (9)	0.066 (8)
O9B	0.195 (13)	0.212 (13)	0.201 (13)	0.033 (9)	−0.001 (9)	−0.008 (9)
O10A	0.180 (7)	0.208 (8)	0.114 (6)	−0.019 (6)	−0.020 (5)	0.035 (6)
O10B	0.117 (9)	0.168 (10)	0.174 (10)	0.030 (8)	0.027 (8)	0.008 (8)
O11A	0.228 (9)	0.240 (9)	0.220 (9)	−0.011 (8)	−0.036 (7)	−0.049 (8)
O11B	0.077 (7)	0.169 (10)	0.107 (7)	−0.006 (7)	−0.012 (6)	−0.023 (7)
O15A	0.212 (8)	0.197 (7)	0.168 (7)	−0.127 (6)	−0.015 (6)	0.014 (5)
O15B	0.130 (9)	0.169 (10)	0.186 (10)	−0.035 (7)	0.044 (8)	−0.027 (8)
C1	0.047 (3)	0.076 (3)	0.068 (3)	−0.003 (2)	−0.001 (2)	0.013 (2)
C2	0.044 (3)	0.090 (4)	0.081 (3)	−0.003 (2)	0.002 (2)	0.006 (3)
C3	0.049 (3)	0.081 (3)	0.072 (3)	−0.016 (2)	0.016 (2)	−0.010 (3)
C4	0.055 (3)	0.063 (3)	0.048 (2)	−0.015 (2)	0.0126 (19)	−0.006 (2)
C5	0.053 (2)	0.049 (2)	0.043 (2)	−0.0107 (19)	0.0044 (18)	−0.0030 (18)
C6	0.057 (3)	0.045 (2)	0.044 (2)	−0.0104 (19)	0.0082 (19)	−0.0034 (18)
C7	0.069 (3)	0.074 (3)	0.061 (3)	−0.023 (3)	0.022 (2)	0.000 (2)
C8	0.086 (4)	0.060 (3)	0.062 (3)	−0.021 (3)	0.018 (3)	0.008 (2)
C9	0.068 (3)	0.048 (2)	0.056 (3)	−0.008 (2)	0.010 (2)	0.000 (2)
C10	0.091 (4)	0.058 (3)	0.071 (3)	0.002 (3)	0.012 (3)	0.018 (2)
C11	0.086 (4)	0.062 (3)	0.084 (3)	0.018 (3)	0.004 (3)	0.011 (3)
C12	0.058 (3)	0.060 (3)	0.069 (3)	0.005 (2)	0.012 (2)	0.007 (2)
C13	0.043 (2)	0.072 (3)	0.059 (3)	−0.009 (2)	0.004 (2)	−0.007 (2)
C14	0.048 (3)	0.091 (4)	0.077 (3)	−0.010 (2)	0.000 (2)	−0.007 (3)
C15	0.037 (2)	0.083 (3)	0.093 (4)	0.005 (2)	0.009 (2)	0.015 (3)
C16	0.058 (3)	0.051 (2)	0.064 (3)	0.013 (2)	0.016 (2)	0.011 (2)
C17	0.049 (2)	0.041 (2)	0.047 (2)	−0.0010 (17)	0.0069 (18)	0.0084 (18)
C18	0.055 (3)	0.042 (2)	0.049 (2)	−0.0030 (18)	0.0055 (19)	0.0042 (18)
C19	0.075 (3)	0.070 (3)	0.080 (3)	0.023 (3)	0.029 (3)	0.004 (3)
C20	0.096 (4)	0.066 (3)	0.065 (3)	0.023 (3)	0.023 (3)	−0.005 (2)
C21	0.080 (3)	0.041 (2)	0.056 (3)	0.003 (2)	0.005 (2)	0.000 (2)
C22	0.107 (4)	0.062 (3)	0.056 (3)	−0.009 (3)	0.004 (3)	−0.010 (2)
C23	0.093 (4)	0.059 (3)	0.065 (3)	−0.024 (3)	−0.017 (3)	−0.003 (2)
C24	0.063 (3)	0.065 (3)	0.060 (3)	−0.019 (2)	−0.007 (2)	0.008 (2)
C25	0.044 (2)	0.085 (3)	0.063 (3)	−0.006 (2)	0.005 (2)	−0.002 (2)
C26	0.056 (3)	0.083 (3)	0.069 (3)	−0.016 (2)	−0.005 (2)	−0.002 (3)
C27	0.075 (3)	0.055 (3)	0.058 (3)	−0.011 (2)	−0.008 (2)	−0.005 (2)
C28	0.068 (3)	0.050 (2)	0.043 (2)	0.005 (2)	0.003 (2)	0.0009 (19)
C29	0.049 (2)	0.045 (2)	0.042 (2)	0.0010 (18)	0.0059 (18)	0.0027 (17)
C30	0.046 (2)	0.045 (2)	0.047 (2)	0.0019 (17)	0.0110 (18)	0.0011 (18)
C31	0.088 (4)	0.064 (3)	0.048 (3)	0.012 (3)	0.006 (2)	−0.005 (2)
C32	0.080 (4)	0.067 (3)	0.063 (3)	0.019 (3)	0.028 (3)	0.005 (2)
C33	0.055 (3)	0.054 (3)	0.059 (3)	0.008 (2)	0.015 (2)	0.007 (2)
C34	0.053 (3)	0.069 (3)	0.096 (4)	0.009 (2)	0.028 (3)	0.011 (3)
C35	0.045 (3)	0.061 (3)	0.106 (4)	−0.005 (2)	0.006 (3)	0.001 (3)
C36	0.050 (3)	0.064 (3)	0.077 (3)	−0.003 (2)	−0.001 (2)	−0.010 (2)
C37	0.062 (3)	0.059 (3)	0.053 (3)	0.013 (2)	−0.001 (2)	0.004 (2)
C38	0.083 (3)	0.051 (3)	0.067 (3)	0.009 (2)	−0.004 (3)	−0.006 (2)
C39	0.081 (3)	0.062 (3)	0.055 (3)	0.006 (2)	−0.003 (2)	−0.006 (2)
C40	0.049 (2)	0.052 (3)	0.059 (3)	−0.0023 (19)	0.011 (2)	0.006 (2)

Geometric parameters (Å, º)

Cu1—N3	1.998 (3)	C6—C9	1.394 (5)
Cu1—N1	2.002 (3)	C7—C8	1.344 (6)
Cu1—O4	2.043 (3)	C7—H7	0.9300
Cu1—N2	2.059 (3)	C8—C9	1.432 (6)
Cu1—N4	2.171 (3)	C8—H8	0.9300
Cu1—O5	2.587 (3)	C9—C10	1.398 (6)
Cu1—Cu2	4.199 (1)	C10—C11	1.366 (7)
Cu2—O1	1.909 (3)	C10—H10	0.9300
Cu2—O3	1.962 (3)	C11—C12	1.393 (6)
Cu2—N6	1.985 (3)	C11—H11	0.9300
Cu2—N5	1.993 (3)	C12—H12	0.9300
Cu2—O6	2.519 (3)	C13—C14	1.375 (6)
Cu2—O4	2.551 (3)	C13—H13	0.9300
N1—C1	1.333 (5)	C14—C15	1.359 (7)
N1—C5	1.344 (5)	C14—H14	0.9300
N2—C12	1.326 (5)	C15—C16	1.405 (6)
N2—C6	1.361 (5)	C15—H15	0.9300
N3—C13	1.326 (5)	C16—C17	1.410 (5)
N3—C17	1.362 (5)	C16—C19	1.444 (6)
N4—C24	1.327 (5)	C17—C18	1.422 (5)
N4—C18	1.353 (5)	C18—C21	1.414 (6)
N5—C25	1.327 (5)	C19—C20	1.328 (7)
N5—C29	1.359 (5)	C19—H19	0.9300
N6—C36	1.326 (5)	C20—C21	1.401 (6)
N6—C30	1.367 (5)	C20—H20	0.9300
N7—O6	1.233 (5)	C21—C22	1.410 (6)
N7—O8	1.235 (5)	C22—C23	1.342 (7)
N7—O7	1.239 (5)	C22—H22	0.9300
N8—O11B	1.220 (7)	C23—C24	1.410 (6)
N8—O9A	1.222 (7)	C23—H23	0.9300
N8—O10A	1.226 (6)	C24—H24	0.9300
N8—O10B	1.268 (7)	C25—C26	1.383 (6)
N8—O11A	1.278 (7)	C25—H25	0.9300
N8—O9B	1.295 (7)	C26—C27	1.351 (6)
O1—C37	1.265 (5)	C26—H26	0.9300
O2—C37	1.210 (5)	C27—C28	1.401 (6)
O3—C38	1.463 (5)	C27—H27	0.9300
O3—H3A	0.8250	C28—C29	1.395 (5)
O4—C40	1.274 (5)	C28—C31	1.419 (6)
O12—H12A	0.8320	C29—C30	1.411 (5)
O12—H12B	0.8295	C30—C33	1.387 (5)
O13—H13A	0.8349	C31—C32	1.339 (7)
O13—H13B	0.8227	C31—H31	0.9300
O14—H14A	0.8248	C32—C33	1.421 (6)
O14—H14B	0.8234	C32—H32	0.9300
O15A—H51A	0.8290	C33—C34	1.412 (6)
O15A—H52A	0.7676	C34—C35	1.349 (6)
O5—C40	1.235 (4)	C34—H34	0.9300
C1—C2	1.383 (6)	C35—C36	1.383 (6)
C1—H1	0.9300	C35—H35	0.9300
C2—C3	1.366 (6)	C36—H36	0.9300
C2—H2	0.9300	C37—C38	1.536 (6)
C3—C4	1.404 (6)	C38—C39	1.490 (6)
C3—H3	0.9300	C38—H38	0.9800
C4—C5	1.396 (5)	C39—C40	1.521 (6)
C4—C7	1.423 (6)	C39—H39A	0.9700
C5—C6	1.445 (5)	C39—H39B	0.9700
N3—Cu1—N1	176.73 (13)	C6—C9—C10	116.7 (4)
N3—Cu1—O4	93.35 (12)	C6—C9—C8	119.2 (4)
N1—Cu1—O4	89.90 (12)	C10—C9—C8	124.1 (4)
N3—Cu1—N2	95.57 (12)	C11—C10—C9	119.2 (4)
N1—Cu1—N2	81.33 (13)	C11—C10—H10	120.4
O4—Cu1—N2	152.72 (11)	C9—C10—H10	120.4
N3—Cu1—N4	79.86 (12)	C10—C11—C12	120.7 (5)
N1—Cu1—N4	99.89 (12)	C10—C11—H11	119.7
O4—Cu1—N4	101.64 (11)	C12—C11—H11	119.7
N2—Cu1—N4	105.28 (12)	N2—C12—C11	121.7 (4)
N3—Cu1—O5	89.86 (11)	N2—C12—H12	119.2
N1—Cu1—O5	91.66 (11)	C11—C12—H12	119.2
O4—Cu1—O5	55.18 (10)	N3—C13—C14	122.9 (4)
N2—Cu1—O5	99.06 (11)	N3—C13—H13	118.5
N4—Cu1—O5	154.32 (10)	C14—C13—H13	118.5
O1—Cu2—O3	85.12 (12)	C15—C14—C13	119.7 (4)
O1—Cu2—N6	176.67 (13)	C15—C14—H14	120.1
O3—Cu2—N6	97.79 (13)	C13—C14—H14	120.1
O1—Cu2—N5	94.41 (12)	C14—C15—C16	119.8 (4)
O3—Cu2—N5	172.92 (13)	C14—C15—H15	120.1
N6—Cu2—N5	82.90 (13)	C16—C15—H15	120.1
O1—Cu2—O6	93.68 (12)	C15—C16—C17	117.1 (4)
O3—Cu2—O6	88.25 (12)	C15—C16—C19	124.5 (4)
N6—Cu2—O6	88.04 (13)	C17—C16—C19	118.3 (4)
N5—Cu2—O6	84.73 (12)	N3—C17—C16	121.9 (3)
O1—Cu2—O4	82.09 (10)	N3—C17—C18	118.2 (3)
O3—Cu2—O4	75.14 (10)	C16—C17—C18	120.0 (4)
N6—Cu2—O4	97.06 (11)	N4—C18—C21	124.1 (4)
N5—Cu2—O4	111.82 (11)	N4—C18—C17	117.0 (3)
O6—Cu2—O4	163.11 (10)	C21—C18—C17	118.9 (4)
C1—N1—C5	117.8 (4)	C20—C19—C16	121.1 (5)
C1—N1—Cu1	127.9 (3)	C20—C19—H19	119.4
C5—N1—Cu1	114.3 (3)	C16—C19—H19	119.4
C12—N2—C6	117.7 (3)	C19—C20—C21	121.6 (4)
C12—N2—Cu1	130.6 (3)	C19—C20—H20	119.2
C6—N2—Cu1	111.7 (2)	C21—C20—H20	119.2
C13—N3—C17	118.5 (3)	C20—C21—C22	124.2 (4)
C13—N3—Cu1	126.7 (3)	C20—C21—C18	120.0 (4)
C17—N3—Cu1	114.8 (2)	C22—C21—C18	115.8 (4)
C24—N4—C18	117.8 (4)	C23—C22—C21	120.1 (4)
C24—N4—Cu1	132.0 (3)	C23—C22—H22	120.0
C18—N4—Cu1	110.1 (2)	C21—C22—H22	120.0
C25—N5—C29	118.0 (3)	C22—C23—C24	120.4 (4)
C25—N5—Cu2	130.1 (3)	C22—C23—H23	119.8
C29—N5—Cu2	111.7 (2)	C24—C23—H23	119.8
C36—N6—C30	118.5 (4)	N4—C24—C23	121.8 (4)
C36—N6—Cu2	129.9 (3)	N4—C24—H24	119.1
C30—N6—Cu2	111.5 (2)	C23—C24—H24	119.1
O6—N7—O8	121.1 (4)	N5—C25—C26	122.3 (4)
O6—N7—O7	119.8 (4)	N5—C25—H25	118.8
O8—N7—O7	119.0 (4)	C26—C25—H25	118.8
O11B—N8—O9A	72.4 (10)	C27—C26—C25	119.7 (4)
O11B—N8—O10A	140.6 (10)	C27—C26—H26	120.2
O9A—N8—O10A	122.8 (8)	C25—C26—H26	120.2
O11B—N8—O10B	123.9 (8)	C26—C27—C28	120.4 (4)
O9A—N8—O10B	138.2 (13)	C26—C27—H27	119.8
O10A—N8—O10B	71.6 (9)	C28—C27—H27	119.8
O11B—N8—O11A	58.8 (7)	C29—C28—C27	116.3 (4)
O9A—N8—O11A	121.5 (8)	C29—C28—C31	118.4 (4)
O10A—N8—O11A	115.3 (7)	C27—C28—C31	125.3 (4)
O10B—N8—O11A	65.8 (8)	N5—C29—C28	123.2 (4)
O11B—N8—O9B	116.6 (8)	N5—C29—C30	116.5 (3)
O9A—N8—O9B	49.3 (9)	C28—C29—C30	120.3 (4)
O10A—N8—O9B	74.6 (11)	N6—C30—C33	122.8 (4)
O10B—N8—O9B	116.3 (8)	N6—C30—C29	116.8 (3)
O11A—N8—O9B	169.2 (14)	C33—C30—C29	120.4 (4)
C37—O1—Cu2	115.9 (3)	C32—C31—C28	121.0 (4)
C38—O3—Cu2	107.7 (2)	C32—C31—H31	119.5
C38—O3—H3A	106.5	C28—C31—H31	119.5
Cu2—O3—H3A	113.0	C31—C32—C33	121.7 (4)
C40—O4—Cu1	103.2 (2)	C31—C32—H32	119.2
C40—O4—Cu2	123.4 (2)	C33—C32—H32	119.2
Cu1—O4—Cu2	131.84 (12)	C30—C33—C34	116.5 (4)
N7—O6—Cu2	127.5 (3)	C30—C33—C32	118.2 (4)
H12A—O12—H12B	107.2	C34—C33—C32	125.3 (4)
H13A—O13—H13B	104.8	C35—C34—C33	120.2 (4)
H14A—O14—H14B	109.2	C35—C34—H34	119.9
H51A—O15A—H52A	112.8	C33—C34—H34	119.9
C40—O5—Cu1	78.9 (2)	C34—C35—C36	120.0 (4)
N1—C1—C2	121.9 (4)	C34—C35—H35	120.0
N1—C1—H1	119.0	C36—C35—H35	120.0
C2—C1—H1	119.0	N6—C36—C35	122.0 (4)
C3—C2—C1	120.4 (4)	N6—C36—H36	119.0
C3—C2—H2	119.8	C35—C36—H36	119.0
C1—C2—H2	119.8	O2—C37—O1	125.0 (4)
C2—C3—C4	119.2 (4)	O2—C37—C38	119.8 (4)
C2—C3—H3	120.4	O1—C37—C38	115.2 (4)
C4—C3—H3	120.4	O3—C38—C39	106.4 (4)
C5—C4—C3	116.5 (4)	O3—C38—C37	111.2 (4)
C5—C4—C7	119.4 (4)	C39—C38—C37	113.4 (4)
C3—C4—C7	124.2 (4)	O3—C38—H38	108.6
N1—C5—C4	124.1 (4)	C39—C38—H38	108.6
N1—C5—C6	116.3 (3)	C37—C38—H38	108.6
C4—C5—C6	119.6 (4)	C38—C39—C40	116.3 (4)
N2—C6—C9	124.0 (4)	C38—C39—H39A	108.2
N2—C6—C5	116.5 (3)	C40—C39—H39A	108.2
C9—C6—C5	119.5 (4)	C38—C39—H39B	108.2
C8—C7—C4	121.2 (4)	C40—C39—H39B	108.2
C8—C7—H7	119.4	H39A—C39—H39B	107.4
C4—C7—H7	119.4	O5—C40—O4	122.3 (4)
C7—C8—C9	121.1 (4)	O5—C40—C39	117.6 (4)
C7—C8—H8	119.4	O4—C40—C39	120.0 (4)
C9—C8—H8	119.4
O4—Cu1—N1—C1	−26.6 (4)	N1—C5—C6—N2	−0.4 (5)
N2—Cu1—N1—C1	179.4 (4)	C4—C5—C6—N2	180.0 (3)
N4—Cu1—N1—C1	75.2 (4)	N1—C5—C6—C9	−179.3 (3)
O5—Cu1—N1—C1	−81.7 (4)	C4—C5—C6—C9	1.1 (5)
Cu2—Cu1—N1—C1	−0.5 (4)	C5—C4—C7—C8	−0.5 (6)
O4—Cu1—N1—C5	153.4 (3)	C3—C4—C7—C8	178.6 (4)
N2—Cu1—N1—C5	−0.7 (3)	C4—C7—C8—C9	0.5 (7)
N4—Cu1—N1—C5	−104.8 (3)	N2—C6—C9—C10	−0.9 (6)
O5—Cu1—N1—C5	98.2 (3)	C5—C6—C9—C10	177.9 (4)
N3—Cu1—N2—C12	−2.6 (4)	N2—C6—C9—C8	−179.8 (4)
N1—Cu1—N2—C12	178.4 (4)	C5—C6—C9—C8	−1.0 (6)
O4—Cu1—N2—C12	105.9 (4)	C7—C8—C9—C6	0.2 (6)
N4—Cu1—N2—C12	−83.6 (4)	C7—C8—C9—C10	−178.6 (4)
O5—Cu1—N2—C12	88.1 (4)	C6—C9—C10—C11	0.9 (7)
N3—Cu1—N2—C6	179.4 (2)	C8—C9—C10—C11	179.8 (4)
N1—Cu1—N2—C6	0.5 (2)	C9—C10—C11—C12	−0.5 (7)
O4—Cu1—N2—C6	−72.1 (4)	C6—N2—C12—C11	0.1 (6)
N4—Cu1—N2—C6	98.4 (3)	Cu1—N2—C12—C11	−177.8 (3)
O5—Cu1—N2—C6	−89.8 (2)	C10—C11—C12—N2	0.0 (7)
O4—Cu1—N3—C13	−76.6 (3)	C17—N3—C13—C14	−0.7 (6)
N2—Cu1—N3—C13	77.6 (3)	Cu1—N3—C13—C14	179.5 (3)
N4—Cu1—N3—C13	−177.8 (4)	N3—C13—C14—C15	1.5 (7)
O5—Cu1—N3—C13	−21.5 (3)	C13—C14—C15—C16	−1.0 (7)
O4—Cu1—N3—C17	103.6 (3)	C14—C15—C16—C17	−0.3 (6)
N2—Cu1—N3—C17	−102.2 (3)	C14—C15—C16—C19	−177.8 (4)
N4—Cu1—N3—C17	2.4 (2)	C13—N3—C17—C16	−0.7 (5)
O5—Cu1—N3—C17	158.7 (3)	Cu1—N3—C17—C16	179.2 (3)
N3—Cu1—N4—C24	−178.7 (4)	C13—N3—C17—C18	178.2 (4)
N1—Cu1—N4—C24	−2.0 (4)	Cu1—N3—C17—C18	−2.0 (4)
O4—Cu1—N4—C24	89.9 (4)	C15—C16—C17—N3	1.1 (6)
N2—Cu1—N4—C24	−85.7 (4)	C19—C16—C17—N3	178.8 (4)
O5—Cu1—N4—C24	113.5 (4)	C15—C16—C17—C18	−177.7 (4)
N3—Cu1—N4—C18	−2.5 (2)	C19—C16—C17—C18	0.0 (5)
N1—Cu1—N4—C18	174.2 (2)	C24—N4—C18—C21	−1.7 (6)
O4—Cu1—N4—C18	−93.8 (2)	Cu1—N4—C18—C21	−178.5 (3)
N2—Cu1—N4—C18	90.6 (2)	C24—N4—C18—C17	179.0 (3)
O5—Cu1—N4—C18	−70.3 (4)	Cu1—N4—C18—C17	2.2 (4)
O1—Cu2—N5—C25	−1.3 (4)	N3—C17—C18—N4	−0.3 (5)
N6—Cu2—N5—C25	−179.3 (4)	C16—C17—C18—N4	178.5 (3)
O6—Cu2—N5—C25	92.0 (4)	N3—C17—C18—C21	−179.6 (3)
O4—Cu2—N5—C25	−84.6 (4)	C16—C17—C18—C21	−0.8 (5)
O1—Cu2—N5—C29	−175.0 (3)	C15—C16—C19—C20	177.8 (4)
N6—Cu2—N5—C29	6.9 (3)	C17—C16—C19—C20	0.3 (6)
O6—Cu2—N5—C29	−81.7 (3)	C16—C19—C20—C21	0.2 (7)
O4—Cu2—N5—C29	101.7 (2)	C19—C20—C21—C22	−179.8 (4)
O3—Cu2—N6—C36	−9.6 (4)	C19—C20—C21—C18	−1.0 (7)
N5—Cu2—N6—C36	177.6 (4)	N4—C18—C21—C20	−178.0 (4)
O6—Cu2—N6—C36	−97.5 (4)	C17—C18—C21—C20	1.3 (6)
O4—Cu2—N6—C36	66.3 (4)	N4—C18—C21—C22	0.9 (6)
O3—Cu2—N6—C30	165.7 (3)	C17—C18—C21—C22	−179.9 (4)
N5—Cu2—N6—C30	−7.2 (3)	C20—C21—C22—C23	179.8 (4)
O6—Cu2—N6—C30	77.7 (3)	C18—C21—C22—C23	1.0 (6)
O4—Cu2—N6—C30	−118.5 (3)	C21—C22—C23—C24	−2.0 (7)
O3—Cu2—O1—C37	16.6 (3)	C18—N4—C24—C23	0.6 (6)
N5—Cu2—O1—C37	−170.5 (3)	Cu1—N4—C24—C23	176.6 (3)
O6—Cu2—O1—C37	104.5 (3)	C22—C23—C24—N4	1.2 (7)
O4—Cu2—O1—C37	−59.1 (3)	C29—N5—C25—C26	−1.3 (6)
O1—Cu2—O3—C38	−19.8 (2)	Cu2—N5—C25—C26	−174.7 (3)
N6—Cu2—O3—C38	158.6 (2)	N5—C25—C26—C27	1.3 (7)
O6—Cu2—O3—C38	−113.6 (3)	C25—C26—C27—C28	−0.3 (7)
O4—Cu2—O3—C38	63.3 (2)	C26—C27—C28—C29	−0.5 (6)
N3—Cu1—O4—C40	91.1 (2)	C26—C27—C28—C31	179.6 (4)
N1—Cu1—O4—C40	−88.5 (2)	C25—N5—C29—C28	0.5 (6)
N2—Cu1—O4—C40	−17.9 (4)	Cu2—N5—C29—C28	175.0 (3)
N4—Cu1—O4—C40	171.5 (2)	C25—N5—C29—C30	180.0 (4)
O5—Cu1—O4—C40	3.6 (2)	Cu2—N5—C29—C30	−5.5 (4)
N3—Cu1—O4—Cu2	−74.60 (17)	C27—C28—C29—N5	0.4 (6)
N1—Cu1—O4—Cu2	105.80 (17)	C31—C28—C29—N5	−179.6 (4)
N2—Cu1—O4—Cu2	176.40 (19)	C27—C28—C29—C30	−179.1 (3)
N4—Cu1—O4—Cu2	5.73 (18)	C31—C28—C29—C30	0.9 (6)
O5—Cu1—O4—Cu2	−162.1 (2)	C36—N6—C30—C33	1.4 (6)
O1—Cu2—O4—C40	78.3 (3)	Cu2—N6—C30—C33	−174.4 (3)
O3—Cu2—O4—C40	−8.7 (3)	C36—N6—C30—C29	−177.8 (4)
N6—Cu2—O4—C40	−105.0 (3)	Cu2—N6—C30—C29	6.4 (4)
N5—Cu2—O4—C40	169.9 (3)	N5—C29—C30—N6	−0.6 (5)
O6—Cu2—O4—C40	1.9 (5)	C28—C29—C30—N6	178.9 (3)
O1—Cu2—O4—Cu1	−118.41 (17)	N5—C29—C30—C33	−179.9 (3)
O3—Cu2—O4—Cu1	154.56 (19)	C28—C29—C30—C33	−0.3 (6)
N6—Cu2—O4—Cu1	58.34 (18)	C29—C28—C31—C32	−0.5 (6)
N5—Cu2—O4—Cu1	−26.8 (2)	C27—C28—C31—C32	179.5 (4)
O6—Cu2—O4—Cu1	165.1 (3)	C28—C31—C32—C33	−0.5 (7)
O8—N7—O6—Cu2	−177.1 (3)	N6—C30—C33—C34	−0.5 (6)
O7—N7—O6—Cu2	6.0 (6)	C29—C30—C33—C34	178.7 (4)
O1—Cu2—O6—N7	−109.0 (4)	N6—C30—C33—C32	−179.8 (4)
O3—Cu2—O6—N7	−24.0 (4)	C29—C30—C33—C32	−0.6 (6)
N6—Cu2—O6—N7	73.9 (4)	C31—C32—C33—C30	1.1 (6)
N5—Cu2—O6—N7	156.9 (4)	C31—C32—C33—C34	−178.2 (4)
O4—Cu2—O6—N7	−34.2 (7)	C30—C33—C34—C35	−1.4 (6)
N3—Cu1—O5—C40	−97.9 (2)	C32—C33—C34—C35	177.8 (4)
N1—Cu1—O5—C40	85.0 (2)	C33—C34—C35—C36	2.5 (7)
O4—Cu1—O5—C40	−3.7 (2)	C30—N6—C36—C35	−0.4 (6)
N2—Cu1—O5—C40	166.5 (2)	Cu2—N6—C36—C35	174.5 (3)
N4—Cu1—O5—C40	−32.2 (4)	C34—C35—C36—N6	−1.5 (7)
Cu2—Cu1—O5—C40	−11.8 (2)	Cu2—O1—C37—O2	174.2 (4)
C5—N1—C1—C2	−1.3 (6)	Cu2—O1—C37—C38	−8.3 (5)
Cu1—N1—C1—C2	178.7 (3)	Cu2—O3—C38—C39	−103.8 (3)
N1—C1—C2—C3	0.8 (7)	Cu2—O3—C38—C37	20.2 (4)
C1—C2—C3—C4	0.5 (7)	O2—C37—C38—O3	168.9 (4)
C2—C3—C4—C5	−1.3 (6)	O1—C37—C38—O3	−8.8 (5)
C2—C3—C4—C7	179.6 (4)	O2—C37—C38—C39	−71.2 (5)
C1—N1—C5—C4	0.4 (6)	O1—C37—C38—C39	111.1 (4)
Cu1—N1—C5—C4	−179.5 (3)	O3—C38—C39—C40	55.5 (5)
C1—N1—C5—C6	−179.3 (3)	C37—C38—C39—C40	−67.1 (5)
Cu1—N1—C5—C6	0.8 (4)	Cu1—O5—C40—O4	5.8 (3)
C3—C4—C5—N1	0.9 (6)	Cu1—O5—C40—C39	−170.4 (4)
C7—C4—C5—N1	−180.0 (4)	Cu1—O4—C40—O5	−7.4 (4)
C3—C4—C5—C6	−179.5 (3)	Cu2—O4—C40—O5	159.9 (3)
C7—C4—C5—C6	−0.3 (6)	Cu1—O4—C40—C39	168.8 (3)
C12—N2—C6—C9	0.4 (6)	Cu2—O4—C40—C39	−24.0 (5)
Cu1—N2—C6—C9	178.6 (3)	C38—C39—C40—O5	−177.3 (4)
C12—N2—C6—C5	−178.5 (3)	C38—C39—C40—O4	6.3 (6)
Cu1—N2—C6—C5	−0.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O7	0.83	2.11	2.841 (5)	147
O12—H12A···O8	0.83	2.43	3.092 (5)	137
O12—H12A···O7	0.83	2.62	3.043 (6)	113
O12—H12B···O11A	0.83	2.29	2.936 (13)	136
O12—H12B···O11B	0.83	2.20	2.801 (13)	130
O13—H13A···O2	0.83	2.05	2.864 (5)	164
O13—H13B···O12^i	0.82	2.10	2.799 (5)	142
O14—H14A···O13	0.82	2.24	2.859 (6)	133
O14—H14B···O5^ii	0.82	2.03	2.810 (5)	157
O15A—H51A···O11A	0.83	2.23	2.578 (16)	105

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z.