A mixed bridged trinuclear copper(II)-1,10-phenanthroline complex with a linear structure

The title compound, diaqua-1[kappa]O,3[kappa]O-di-[mu]-hydroxido-1:2[kappa]²O:O,2:3[kappa]²O:O-di-[mu]-methacrylato-1:2[kappa]²O:O',2:3[kappa]²O:O'-bis­(1,10-phenanthroline)-1[kappa]²N,N';3[kappa]²N,N'-tricopper(II) dinitrate dihydrate, [Cu₃(C₄H₅O₂)₂(OH)₂(C₁₂H₈N₂)₂(H₂O)₂](NO₃)₂·2H₂O, has the central Cu atom on an inversion centre. The three Cu^II atoms are in a linear arrangement linked by meth­acrylate and hydroxide groups. The coordination environments of the Cu^II ions are five-coordinated distorted square-pyramidal for the outer Cu atoms and four-coordinated square-planar for the central Cu atom. All nitrate ions, hydroxide groups and water mol­ecules are linked by hydrogen bonds, forming a linear structure. The complex exhibits ferromagnetic exchange coupling, which is helpful in elucidating magnetic inter­actions between copper ions and other metallic ions in heteronuclear complexes.

S1. Comment

Molecular magnetic compounds have recently attracted attention and have been developed to a large extent (Miller & Drillon, 2001a,b, 2002; Bruda et al., 2006; Narasimha et al., 2006). In particular, ferromagnetic exchange coupling in the mixed bridged unit Cu^II–RO/RCO₂–Cu^II leads to a quartet ground state for the trinuclear system (Haase & Gehring, 1985). Because various ligands show different abilities for mediating electronic effects between copper ions, these coordination compounds display rich magnetic behaviour over various temperature ranges (Rao et al., 2004; Setifi et al., 2006; Chen et al., 2006; Das et al., 2006; Tao et al., 2006). Efforts to obtain new compounds in which rare earth ions are coupled magnetically to transition metal ions and/or organic radicals are increasing rapidly (Mishra et al., 2005; Mori et al., 2005, 2006; Costes, Dahan & Wernsdorfer, 2006; Costes, Auchel et al., 2006; Murugesu et al., 2006; Yeung et al., 2006). However, it is difficult to clarify what contributes most to the magnetic interaction between rare earth and transition metal ions, because a change in magnetic properties depends on many factors.

In recent years, we have pursued a research project investigating the structures and properties of heteronuclear complexes of rare earth and transition metals bridged by carboxyl groups (Wu et al., 2002a,b, 2003, 2004; Zhu et al., 2005). The title complex, (I), was obtained during the preparation of a dysprosium–copper carboxyl compound. Its structure and magnetic properties are promising for the elucidation of the magnetic interaction between different 4f and 3d metallic ions in heteroneuclear complexes.

The molecular structure and intramolecular arrangement of (I) are shown in Fig. 1. The symmetric centre of the molecule is situated at atom Cu1. The coordination environments that surround the Cu^II ions can be divided into two types. Atom Cu2 is in a CuN₂O₃ environment formed by two N atoms of a bidentate phenanthroline ligand and three O atoms from a water molecule, an α-methylacrylate group and a hydroxyl group, composing a distorted square-pyramidal geometry. Atoms O1, O2, N1 and N2 are in the equatorial plane and atom O5 occupies the vertex of the square-pyramid. Atom Cu1 is coordinated by atoms O1, O1ⁱⁱⁱ, O3 and O3ⁱⁱⁱ, which constitute a square plane [symmetry code: (iii) 1 - x, -y, -z]. It is noted that atoms O5 and O5ⁱⁱⁱ of the water molecules occupy the axial sites of an octahedral polyhedron if atom Cu1 is considered as six-coordinated (dashed lines in Fig. 1). The Cu1—O5 distance is 2.567 Å. Three Cu^II ions in the molecule are in a linear arrangement linked by α-methylacrylate and hydroxyl groups to give two mixed bridged Cu2–OH/RCOO–Cu1 units with a Cu2···Cu1 distance of 3.0275 Å. As Table 1 shows, the Cu—O bond lengths in the square planes are similar, with an average bond length of 1.9468 Å. The axial Cu—O distance is 2.287 (2) Å, which is obviously longer than those in the square planes. The two Cu—N distances are nearly the same, with an average value of 2.021 Å. All bond lengths are in agreement with those in other reports (Gehring et al., 1993; Setifi et al., 2006; Tao et al., 2006). Electronic delocalization in the OCO fragment is complete, with two almost equivalent CO bond lengths [1.265 (4) Å for C31—O2 and 1.262 (3) Å for C31—O3]. The phenanthroline ligand adopts a bidentate coordination mode and possesses local C_2v symmetry.

A packing diagram for complex (I) is shown in Fig. 2. The copper complex cations are associated with their identical neighbours through stacking of the phenanthroline aromatic rings in an `offset' manner. There is no evidence, however, of strong π–π stacking interactions. The aryl rings of neighbouring phenanthroline ligands are approximately parallel, with a dihedral angle of 0.82° and an approximate perpendicular distance of 3.687 Å.

Hydrogen bonds play an important role in the stability of the crystal structure of (I). As Fig. 3 shows, there are also many intermolecular hydrogen bonds between O atoms of the water molecules and O atoms of the nitrate ions or hydroxyl groups. Atoms O1, O4, O5ⁱ, O6ⁱⁱ, N3ⁱⁱ and O8ⁱⁱ are interlinked by hydrogen bonds to form a six-ring cycle [symmetry codes: (i) -1 + x, y, z; (ii) -x, -y, -z]. Atoms O1ⁱⁱ, O4ⁱⁱ, O5ⁱⁱⁱ, O6, N3 and O8 are also joined together by hydrogen bonds to form another six-ring cycle. Meanwhile, there are two cycles linked by hydrogen bonds between atoms O4 and O8, and O4ⁱⁱ and O8ⁱⁱ. These hydrogen bonds form a one-dimensional structure along the a axis, which is advantageous for decreasing the energy. The hydrogen-bond distances are in the range 2.731–2.968 Å, with an average of 2.873 Å, which is in good agreement with typical values for O—H···O interactions [Reference?].

Related literature

For related literature, see: Bruda et al. (2006); Chen et al. (2006); Costes, Auchel, Dahan, Peyrou, Shova & Wernsdorfer (2006); Costes, Dahan & Wernsdorfer (2006); Das et al. (2006); Gehring et al. (1993); Haase & Gehring (1985); Miller & Drillon (2001a, 2001b, 2002); Mishra et al. (2005); Mori et al. (2005, 2006); Murugesu et al. (2006); Narasimha et al. (2006); Rao et al. (2004); Setifi et al. (2006); Tao et al. (2006); Wu et al. (2002a, 2002b, 2003, 2004); Yeung et al. (2006); Zhu et al. (2005).

S2. Experimental

An aqueous solution (1 ml) of Cu(NO₃)₂ (188 mg, 1 mmol) was added to a solution of Dy(C₄H₅O₂)₃(H₂O)₆ (81.7 mg, 0.16 mmol) in water (3 ml) with stirring. An ethanol solution (1 ml) of phenanthroline (15.1 mg, 0.076 mmol) was added to the mixture. The resulting solution was filtered and the filtrate was allowed to stand at room temperature. After two weeks, blue needle crystals of (I) suitable for X-ray crystallographic study were obtained.

Temperature-dependent magnetic susceptibilities were collected from the pure crystal sample in the 5–300 K range using a Quantum Design PPMS-9 magnetometer in an applied field of 20 kOe (1 Oe = 79.58 A m^-1). An effective magnetic moment of 3.589 µ_B was observed at 300 K. With decreasing temperature, the µ_eff(T) functions increase and reach 3.859 µ_B at 18 K, and then decrease rapidly to 3.54 µ_B at 5 K. Such behaviour is characteristic of predominantly ferromagnetic exchange coupling in Cu^II₃ systems (Haase & Gehring, 1985). The observed susceptibility data are well fitted to the Curie–Weiss law [χ_m = C/(T - θ)], with Weiss constant θ = 3.52 K. IR: ν(OH) 3650–2900, ν(C═C) 1645, ν(COO)_as 1541, ν(COO)_s 1426, ν(NO₃) 1384 cm^-1.

S3. Refinement

The H atoms of the hydrocarbon groups were placed in calculated positions, with C—H = 0.96 Å for the methyl group or 0.93 Å for the terminal CH₂ group, and they were included in the final cycles of refinement in a riding model, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). H atoms from water molecules were located in a difference Fourier map, and their coordinates and displacement parameters were fixed during structure refinement, using a riding model, with U_iso(H) = 1.2 U_eq(O).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: CrystalStructure (Rigaku/MSC & Rigaku, 2002); data reduction: CrystalStructure (Rigaku/MSC & Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Unlabelled atoms are related to labelled atoms by the symmetry code ? [Please complete].
	Fig. 2. A packing diagram for complex (I), viewed along the b axis, showing the π–π interactions between the phenanthroline rings. Water molecules and nitrate ions have been omitted for clarity.
	Fig. 3. Intermolecular hydrogen bonds, along the a axis. C atoms of the phenanthroline ligands have been omitted for clarity. [Symmetry codes: (i) -1 + x, y, z; (ii) -x, -y, -z; (iii) 1 - x, -y, -z.]

diaqua-1κO,3κO-di-µ-methacrylato-1:2κ²O:O',2:3κ²O:O'-bis(1,10-phenanthroline)-1κ²N,N';3κ²N,N'-di-µ-hydroxido-1:2κ²O:O,2:3κ²O:O-tricopper(II) dinitrate dihydrate

Crystal data

[Cu3(C4H5O2)2(OH)2(C12H8N2)2(H2O)2](NO3)2·2H2O	Z = 1
Mr = 951.29	F(000) = 485
Triclinic, P1	Dx = 1.712 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 7.3779 (5) Å	Cell parameters from 6352 reflections
b = 11.1570 (9) Å	θ = 3.0–27.4°
c = 12.5830 (9) Å	µ = 1.80 mm^−1
α = 71.081 (2)°	T = 293 K
β = 81.596 (2)°	Needle, blue
γ = 70.529 (2)°	0.35 × 0.08 × 0.02 mm
V = 922.94 (12) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	4172 independent reflections
Radiation source: fine-focus sealed tube	3356 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 10.0 pixels mm^-1	θmax = 27.4°, θmin = 3.0°
ω scans	h = −8→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −14→14
Tmin = 0.572, Tmax = 0.965	l = −16→16
8975 measured reflections

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) = 0.120	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0675P)^2 + 0.1148P] where P = (Fo^2 + 2Fc^2)/3
4172 reflections	(Δ/σ)max = 0.002
271 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.53 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	0.5000	0.0000	0.0000	0.02985 (14)
Cu2	0.57035 (5)	−0.03202 (3)	−0.23383 (3)	0.03213 (13)
O1	0.3649 (3)	0.01196 (19)	−0.12575 (16)	0.0323 (4)
O2	0.6478 (4)	−0.2161 (2)	−0.14337 (19)	0.0486 (6)
O3	0.6092 (3)	−0.1945 (2)	0.03045 (18)	0.0408 (5)
O4	0.1068 (3)	−0.1396 (3)	−0.0591 (2)	0.0497 (6)
O5	0.7678 (3)	0.0296 (2)	−0.1518 (2)	0.0456 (5)
N3	0.1086 (4)	−0.3237 (3)	0.2507 (2)	0.0457 (6)
O6	0.2592 (4)	−0.3094 (3)	0.2669 (3)	0.0919 (11)
O7	0.0654 (5)	−0.4231 (3)	0.3049 (3)	0.0816 (10)
O8	−0.0003 (4)	−0.2339 (3)	0.1781 (2)	0.0663 (8)
N1	0.5011 (3)	0.1456 (2)	−0.3527 (2)	0.0350 (5)
N2	0.7326 (3)	−0.0881 (3)	−0.3643 (2)	0.0398 (6)
C1	0.3902 (5)	0.2629 (3)	−0.3434 (3)	0.0488 (8)
H1	0.3363	0.2695	−0.2732	0.059*
C2	0.5825 (4)	0.1392 (3)	−0.4559 (2)	0.0386 (7)
C3	0.7076 (4)	0.0115 (4)	−0.4616 (3)	0.0417 (7)
C4	0.8479 (5)	−0.2074 (4)	−0.3662 (4)	0.0569 (9)
H4	0.8666	−0.2773	−0.2999	0.068*
C5	0.3514 (6)	0.3769 (4)	−0.4355 (4)	0.0647 (11)
H5	0.2723	0.4575	−0.4259	0.078*
C6	0.4281 (6)	0.3709 (4)	−0.5388 (4)	0.0710 (13)
H6	0.4016	0.4470	−0.6003	0.085*
C7	0.5486 (5)	0.2484 (4)	−0.5521 (3)	0.0570 (10)
C8	0.6394 (7)	0.2266 (6)	−0.6575 (3)	0.0798 (16)
H8	0.6136	0.2970	−0.7234	0.096*
C9	0.7585 (7)	0.1086 (7)	−0.6625 (3)	0.0774 (15)
H9	0.8173	0.0996	−0.7314	0.093*
C10	0.7979 (5)	−0.0036 (5)	−0.5657 (3)	0.0586 (11)
C11	0.9204 (6)	−0.1309 (6)	−0.5639 (4)	0.0724 (14)
H11	0.9857	−0.1462	−0.6296	0.087*
C12	0.9435 (6)	−0.2309 (5)	−0.4672 (5)	0.0748 (14)
H12	1.0224	−0.3158	−0.4665	0.090*
C31	0.6521 (4)	−0.2627 (3)	−0.0375 (2)	0.0353 (6)
C32	0.7148 (5)	−0.4106 (3)	0.0115 (3)	0.0451 (7)
C33	0.7374 (7)	−0.4870 (4)	−0.0560 (4)	0.0749 (13)
H33A	0.7736	−0.5791	−0.0263	0.090*
H33B	0.7169	−0.4476	−0.1324	0.090*
C34	0.7444 (7)	−0.4644 (4)	0.1339 (3)	0.0701 (12)
H34A	0.7215	−0.3923	0.1649	0.105*
H34B	0.8742	−0.5216	0.1467	0.105*
H34C	0.6566	−0.5142	0.1694	0.105*
H101	0.2523	0.0843	−0.1435	0.039*
H401	0.0815	−0.1654	0.0183	0.060*
H402	0.2111	−0.1153	−0.0748	0.060*
H501	0.8906	−0.0176	−0.1295	0.055*
H502	0.7712	0.1197	−0.1819	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0354 (3)	0.0272 (2)	0.0258 (2)	−0.00682 (19)	−0.00484 (18)	−0.00762 (18)
Cu2	0.0365 (2)	0.0313 (2)	0.0262 (2)	−0.00690 (15)	−0.00155 (13)	−0.00885 (14)
O1	0.0308 (9)	0.0351 (10)	0.0288 (10)	−0.0063 (8)	−0.0027 (7)	−0.0098 (8)
O2	0.0700 (16)	0.0313 (11)	0.0370 (12)	−0.0051 (10)	−0.0045 (11)	−0.0099 (9)
O3	0.0563 (13)	0.0285 (10)	0.0346 (11)	−0.0087 (9)	−0.0084 (9)	−0.0069 (9)
O4	0.0498 (13)	0.0625 (15)	0.0404 (12)	−0.0247 (11)	−0.0043 (10)	−0.0111 (11)
O5	0.0424 (12)	0.0473 (13)	0.0479 (13)	−0.0181 (10)	−0.0097 (10)	−0.0079 (11)
N3	0.0432 (15)	0.0442 (15)	0.0459 (16)	−0.0101 (12)	−0.0027 (12)	−0.0110 (13)
O6	0.0605 (18)	0.075 (2)	0.135 (3)	−0.0251 (15)	−0.0338 (19)	−0.008 (2)
O7	0.080 (2)	0.0606 (18)	0.088 (2)	−0.0295 (16)	−0.0158 (17)	0.0135 (17)
O8	0.0517 (15)	0.0621 (17)	0.0552 (16)	0.0008 (13)	−0.0044 (12)	0.0042 (13)
N1	0.0345 (12)	0.0355 (12)	0.0321 (12)	−0.0116 (10)	−0.0040 (9)	−0.0042 (10)
N2	0.0337 (13)	0.0510 (15)	0.0418 (14)	−0.0125 (11)	0.0018 (10)	−0.0249 (13)
C1	0.0439 (17)	0.0383 (17)	0.060 (2)	−0.0129 (14)	−0.0046 (15)	−0.0072 (16)
C2	0.0372 (15)	0.0538 (18)	0.0283 (14)	−0.0236 (14)	−0.0051 (11)	−0.0049 (13)
C3	0.0344 (15)	0.067 (2)	0.0357 (16)	−0.0253 (14)	0.0029 (12)	−0.0221 (15)
C4	0.0449 (19)	0.060 (2)	0.071 (3)	−0.0074 (16)	0.0002 (17)	−0.036 (2)
C5	0.056 (2)	0.0388 (19)	0.086 (3)	−0.0116 (16)	−0.013 (2)	0.0006 (19)
C6	0.063 (2)	0.064 (3)	0.068 (3)	−0.031 (2)	−0.027 (2)	0.027 (2)
C7	0.053 (2)	0.078 (3)	0.0394 (18)	−0.0393 (19)	−0.0147 (15)	0.0094 (17)
C8	0.082 (3)	0.135 (5)	0.0292 (19)	−0.072 (3)	−0.0093 (19)	0.009 (2)
C9	0.071 (3)	0.152 (5)	0.034 (2)	−0.068 (3)	0.0116 (18)	−0.032 (3)
C10	0.049 (2)	0.113 (3)	0.0416 (19)	−0.050 (2)	0.0131 (15)	−0.039 (2)
C11	0.051 (2)	0.122 (4)	0.078 (3)	−0.041 (3)	0.028 (2)	−0.074 (3)
C12	0.048 (2)	0.095 (4)	0.106 (4)	−0.017 (2)	0.014 (2)	−0.074 (3)
C31	0.0396 (15)	0.0266 (13)	0.0387 (16)	−0.0095 (11)	−0.0045 (12)	−0.0077 (12)
C32	0.0504 (18)	0.0294 (15)	0.0510 (19)	−0.0092 (13)	0.0002 (14)	−0.0100 (14)
C33	0.108 (4)	0.0334 (19)	0.077 (3)	−0.011 (2)	−0.007 (3)	−0.0188 (19)
C34	0.099 (3)	0.0317 (18)	0.058 (2)	−0.0074 (19)	−0.005 (2)	0.0023 (17)

Geometric parameters (Å, º)

Cu1—O1^i	1.9369 (19)	C2—C7	1.393 (5)
Cu1—O1	1.9369 (19)	C2—C3	1.433 (5)
Cu1—O3	1.973 (2)	C3—C10	1.415 (4)
Cu1—O3^i	1.973 (2)	C4—C12	1.418 (6)
Cu1—Cu2^i	3.0275 (4)	C4—H4	0.9300
Cu1—Cu2	3.0275 (4)	C5—C6	1.352 (6)
Cu2—O1	1.9295 (19)	C5—H5	0.9300
Cu2—O2	1.932 (2)	C6—C7	1.408 (6)
Cu2—N1	2.012 (2)	C6—H6	0.9300
Cu2—N2	2.028 (2)	C7—C8	1.452 (6)
Cu2—O5	2.286 (2)	C8—C9	1.333 (7)
O1—H101	0.939	C8—H8	0.9300
O2—C31	1.265 (4)	C9—C10	1.417 (7)
O3—C31	1.262 (3)	C9—H9	0.9300
O4—H401	0.931	C10—C11	1.401 (7)
O4—H402	0.874	C11—C12	1.344 (7)
O5—H501	0.915	C11—H11	0.9300
O5—H502	0.960	C12—H12	0.9300
N3—O7	1.216 (4)	C31—C32	1.494 (4)
N3—O6	1.228 (4)	C32—C33	1.344 (5)
N3—O8	1.252 (4)	C32—C34	1.480 (5)
N1—C1	1.324 (4)	C33—H33A	0.9300
N1—C2	1.363 (4)	C33—H33B	0.9300
N2—C4	1.325 (4)	C34—H34A	0.9600
N2—C3	1.347 (4)	C34—H34B	0.9600
C1—C5	1.392 (5)	C34—H34C	0.9600
C1—H1	0.9300
O1^i—Cu1—O1	180.00 (11)	C5—C1—H1	118.9
O1^i—Cu1—O3	89.19 (8)	N1—C2—C7	123.2 (3)
O1—Cu1—O3	90.81 (8)	N1—C2—C3	116.2 (3)
O1^i—Cu1—O3^i	90.81 (8)	C7—C2—C3	120.6 (3)
O1—Cu1—O3^i	89.19 (8)	N2—C3—C10	123.8 (3)
O3—Cu1—O3^i	180.00 (15)	N2—C3—C2	116.5 (3)
O1^i—Cu1—Cu2^i	38.37 (5)	C10—C3—C2	119.7 (3)
O1—Cu1—Cu2^i	141.63 (5)	N2—C4—C12	121.5 (4)
O3—Cu1—Cu2^i	102.61 (6)	N2—C4—H4	119.2
O3^i—Cu1—Cu2^i	77.39 (6)	C12—C4—H4	119.2
O1^i—Cu1—Cu2	141.63 (5)	C6—C5—C1	120.4 (4)
O1—Cu1—Cu2	38.37 (5)	C6—C5—H5	119.8
O3—Cu1—Cu2	77.39 (6)	C1—C5—H5	119.8
O3^i—Cu1—Cu2	102.61 (6)	C5—C6—C7	119.2 (3)
Cu2^i—Cu1—Cu2	180.000 (17)	C5—C6—H6	120.4
O1—Cu2—O2	90.89 (9)	C7—C6—H6	120.4
O1—Cu2—N1	97.49 (9)	C2—C7—C6	117.0 (4)
O2—Cu2—N1	169.20 (10)	C2—C7—C8	117.5 (4)
O1—Cu2—N2	164.93 (9)	C6—C7—C8	125.4 (4)
O2—Cu2—N2	88.74 (10)	C9—C8—C7	121.9 (4)
N1—Cu2—N2	81.41 (11)	C9—C8—H8	119.1
O1—Cu2—O5	90.64 (8)	C7—C8—H8	119.1
O2—Cu2—O5	94.88 (10)	C8—C9—C10	121.7 (4)
N1—Cu2—O5	91.82 (9)	C8—C9—H9	119.2
N2—Cu2—O5	104.40 (9)	C10—C9—H9	119.2
O1—Cu2—Cu1	38.55 (6)	C11—C10—C9	125.2 (4)
O2—Cu2—Cu1	79.42 (6)	C11—C10—C3	116.3 (4)
N1—Cu2—Cu1	111.36 (7)	C9—C10—C3	118.5 (4)
N2—Cu2—Cu1	155.17 (7)	C12—C11—C10	120.0 (3)
O5—Cu2—Cu1	55.67 (6)	C12—C11—H11	120.0
Cu2—O1—Cu1	103.08 (9)	C10—C11—H11	120.0
Cu2—O1—H101	124.01	C11—C12—C4	120.2 (4)
Cu1—O1—H101	115.55	C11—C12—H12	119.9
C31—O2—Cu2	128.47 (19)	C4—C12—H12	119.9
C31—O3—Cu1	129.10 (19)	O3—C31—O2	125.3 (3)
H401—O4—H402	110.6	O3—C31—C32	117.1 (3)
Cu2—O5—H501	127.89	O2—C31—C32	117.5 (3)
Cu2—O5—H502	117.26	C33—C32—C34	123.7 (3)
H501—O5—H502	103.5	C33—C32—C31	119.1 (3)
O7—N3—O6	120.5 (3)	C34—C32—C31	117.1 (3)
O7—N3—O8	120.6 (3)	C32—C33—H33A	120.0
O6—N3—O8	119.0 (3)	C32—C33—H33B	120.0
C1—N1—C2	117.8 (3)	H33A—C33—H33B	120.0
C1—N1—Cu2	129.2 (2)	C32—C34—H34A	109.5
C2—N1—Cu2	112.9 (2)	C32—C34—H34B	109.5
C4—N2—C3	118.1 (3)	H34A—C34—H34B	109.5
C4—N2—Cu2	128.9 (3)	C32—C34—H34C	109.5
C3—N2—Cu2	112.9 (2)	H34A—C34—H34C	109.5
N1—C1—C5	122.2 (4)	H34B—C34—H34C	109.5
N1—C1—H1	118.9

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H101···O8^ii	0.94	2.03	2.970 (4)	177
O4—H401···O8	0.93	1.99	2.910 (3)	171
O4—H402···O1	0.87	2.00	2.819 (4)	156
O5—H501···O4^iii	0.92	1.84	2.731 (4)	166
O5—H502···O6^i	0.96	1.99	2.936 (4)	168

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