μ-Acetato-μ-aqua-μ-hydroxido-bis­[(1,10-phenanthroline)copper(II)] dinitrate monohydrate

The triply bridged title dinuclear copper(II) compound, [Cu₂(C₂H₃O₂)(OH)(C₁₂H₈N₂)₂(H₂O)](NO₃)₂·H₂O, (I), consists of a [Cu₂(μ₂-CH₃COO)(μ₂-OH)(phen)₂(μ₂-OH₂)]²⁺ cation (phen is 1,10-phenanthroline), two uncoordinated nitrate anions and one water mol­ecule. The title cation contains a distorted square-pyramidal arrangement around each metal centre with a CuN₂O₃ chromophore. In the dinuclear unit, both Cu^II ions are linked through a hydroxide bridge and a triatomic bridging carboxyl­ate group, and at the axial positions through a water mol­ecule. The phenanthroline groups in neighbouring dinuclear units inter­digitate along the [010] direction, generating several π–π contacts which give rise to planar arrays parallel to (001). These are in turn connected by hydrogen bonds involving the aqua and hydroxide groups as donors with the nitrate anions as acceptors. Comparisons are made with isostructural compounds having similar cationic units but different counter-ions; the role of hydrogen bonding in the overall three-dimensional structure and its ultimate effect on the cell dimensions are discussed.

S1. Comment

Since the seminal work on copper acetate monohydrate reported by Bleaney & Bowers (1952), interest in magnetic dimeric (or dinuclear) compounds has been maintained for the past 60 years, from different perspectives. This work has contributed to the field of molecular magnetic materials (Kahn, 1993), to the understanding of correlations between exchange couplings and bond structure, and helped in the design of new polynuclear molecular magnets. The fact that weakly interacting AFM dimeric magnetic materials display Bose–Einstein condensation at relatively high T [T = temperature?] triggered considerable research by the materials and physics community (Giamarchi et al., 2008). The discovery of high-T superconductors also stimulated interest in interacting quantum spin systems providing information about elementary excitations, quantum phase transitions and critical phenomena. Many studies of dimeric materials have been reported in this context. Our interest in dimeric materials is directed towards the effects of weak interactions between molecular units (Napolitano et al., 2008; Perec et al., 2010). Since the stacking of phenanthroline rings is a potential source of weak intermolecular exchange couplings we have been looking for new compounds where dinuclear units are coupled by this type of interaction. During our study the triply bridged dinuclear copper(II) title compound, [Cu₂(C₂H₃O₂)(OH)(H₂O)(C₁₂H₈N₂)₂] .2NO₃.H₂O, (I), was obtained (Figs. 1–3).

The molecule consists of a [Cu₂(µ₂-CH₃COO-κ²-O',O")(µ₂-OH)(µ₂-OH₂)(phen)₂]²⁺ dinuclear cation (phen = 1,10-phenanthroline), two uncoordinated L^- anions (L = NO₃) and one water molecule of crystallization (Fig. 1). It contains a distorted square-pyramidal arrangement at each copper(II) ion, in such a way that the two pyramidal CuN₂O₃ chromophores share one edge. Both Cu^II ions are linked [Cu1···Cu2 2.9559 (5) Å] at two equatorial positions through a hydroxo bridge [Cu—O_hydroxo 1.928 (2), 1.919 (2) Å for Cu1, Cu2, respectively], a triatomic carboxylato bridge [Cu—O_carboxylato 1.935 (2), 1.940 (2) Å for Cu1, Cu2, respectively], and at the axial position through a water molecule [Cu—O_water 2.344 (2), 2.332 (2) Å for Cu1, Cu2, respectively]. The coordination of each copper centre is completed by a chelating phen-N,N' [Cu—N_phen 2.007 (3), 2.023 (2) Å and 1.994 (3), 2.016 (2) Å, [for Cu1 and Cu2 ?], respectively]; the resulting bond valency for both cations is 2.16, 2.20 as calculated using PLATON (Spek, 2009). The polyhedron around Cu1 is slightly more regular than the Cu2 one, displaying clear differences in the (ideally equal) trans O—Cu—N basal angles [6.62 (16)° versus 16.48 (18)°, respectively], the deviation from planarity in the basal plane [0.032 (2) Å for N2A versus 0.205 (2) Å for N1B], the departure of the apical axis from the vertical [8.22 (12) versus. 20.4 (2)°], and (perhaps as a summary) their τ parameters (as defined in Addison et al., 1984, and calculated with the program PLATON): 0.11 versus 0.27.

The ligands are basically featureless; none of the phen groups depart significantly from planarity [maximum deviations 0.028 (3) Å for C2A; 0.037 (3) Å for C11B] and the C—O bonds in the acetato group display an almost perfect resonance [O1C ≐ C1C 1.249 (4); O2C ≐ C1C 1.252 (4) Å].

Cu₂(OH)(H₂O)(carboxylate) is a well known cluster and a search in the v5.32 (2011) version of the Cambridge Structural Database (CSD; Allen, 2002) revealed several structures incorporating the moiety [e.g. CITLOH, CITLEX and YAFZUA01 (Youngme et al., 2008); YEMNIO and YEMNEK (Chailuecha et al., 2006); DIXGEX (Chen et al., 2008); JEJCIK (Christou et al., 1990); OLOVOA (Chadjistamatis et al., 2003); QAHDUY (Sgarabotto et al., 1999); YINJEL (Chen et al., 2007) etc., just to mention a few]. The comparative analysis within this set discloses coordination distances in a modest spread (Cu—O_hydroxo 1.908–1.933 Å; Cu—O_carboxylato 1.925–1.993 Å; Cu—O_water 2.321–2.415 Å) showing the values found for (I) to be within these ranges; the intercationic distance for (I), instead, appears distinctly shorter [Cu···Cu range 2.990–3.124 Å, versus Cu1···Cu2 2.9559 (5) Å in (I)].

A view of the Cu₂(OH)(H₂O)(carboxylate) clusters is provided in Fig. 4 and presented as overlapping Cu₂(OH)(H₂O)(carboxylate) clusters, where only the Cu–(OH)–Cu bridge has been fitted, the remaining atoms omitted for clarity: it is obvious that a very reasonable match is observed for the carboxylates, while a much larger spread is observed for the aqua bridge. This may have to do with the weaker binding of the O_water to the cations as well as the hydrogen-bonding ability of water. This makes it prone to disrupting interactions and modifying the ideal geometry.

Regarding the packing arrangement, the way in which the dinuclear units aggregate into a three-dimensional supramolecular structure is describable (for clarity) as a two-step process. The first step is achieved via the stacking of interweaved dinuclear units to form two-dimensional structures parallel to (001) (Fig. 2). The forces involved are several π···π interactions between the stacked phenanthroline groups, as summarized in Table 2. These interactions are not evenly distributed, but there are zones with additional stronger bonds (labelled `A' in Fig. 2, entries 1–3 in Table 2) defining chains which run along the b-axis direction; these chains are in turn connected by weaker/fewer links (zones labelled `B', entries 4–5 in Table 2) to form a broad two-dimensional structure. Secondly, a number of hydrogen bonds involving the hydroxido/aqueous groups as donors and the O atoms of the NO₃^- counterions as acceptors are present (Table 1). Fig. 3 shows a packing view rotated by 90° [compared] to that presented in Fig. 2, where the planar arrays are seen in projection, and the hydrogen-bonding network can be clearly observed. It is apparent that the cohesion provided by these interactions is partly `intra'-planar (providing for the plane stability) as well as `inter'-planar, assisting the plane-to-plane linkage.

More detailed comparisons can be made of the three-dimensional structure in (I) with two isostructural analogues (already considered earlier) which have the same phenanthroline ligand but different L counteranions, viz. L = BF₄^-, (II) (CITLOH, Youngme et al., 2008), and L = ClO₄^-, (III) (YEMNIO, Chailuecha et al., 2006). Both structures share the same dinuclear unit as (I) [mean square deviations 0.075 (2), and 0.116 (2) Å, respectively] and are also interweaved in analogous π-bonded layers, but differing in the remaining interactions aggregating into a three-dimensional structure. It is relevant to stress for the following discussion that this hydrogen-bonding system appears stronger and more clearly defined in (I) than in either of the (II), (III) analogues, since the O-atom acceptors in the NO₃^- counterions (I) are fairly well behaved while those in the BF₄^- (II) and ClO₄^- (III) analogues appear heavily disordered.

Comparison of the cell dimensions for all three structures (Table 3) yields information regarding the interactions governing the crystal packing and the way they operate [figures in brackets give the percentage differences with (I)]. It can be seen that along the c axis there are negligible differences between all three structures, while significant differences are noted along a and b. This fact correlates with the disposition and structure of the packing `leitmotiv' shown in Fig 2. The c direction is, in principle, defined by the width of the planes and this is basically associated with the volume occupied by the dinuclear unit; counterions lodge at the intermolecular voids and even if they provide interplanar cohesion, they do not appear to affect the mean planar width. Thus, the `c'-axis length would be limited by the `bumping' of basically uncompressible planes. The remaining two directions, on the other hand, are contained in the plane and along them the structure shows no significant cohesion forces able to oppose the strain introduced by any additional forces, e.g. hydrogen bonding. Thus, structure (I), with stronger and better defined `intra'-planar hydrogen-bonding interactions than (II) and (III) (see above) presents a detectable `shrinkage' of the planes in both the a and b directions, a fact directly ascribable to the internal hydrogen-bonding network and the flexibility of π···π interactions to adapt to them. It is worth noting the highly hydrophilic character of both NO₃ ^- anions, in particular nitrate D, where O3D, for instance, accepts four hydrogen bonds of different types and strength.

Our structural results show promise in the search for new dinuclear materials with weak interactions between moieties; however, we have not yet overcome the problem of the specimens being too small for EPR measurements, and are at present devoted to the growth of single crystals of adequate size and quality.

Related literature

For related literature, see: Addison et al. (1984); Allen (2002); Bleaney & Bowers (1952); Chadjistamatis et al. (2003); Chailuecha et al. (2006); Chen et al. (2007, 2008); Christou et al. (1990); Giamarchi et al. (2008); Kahn (1993); Napolitano et al. (2008); Perec et al. (2010); Sgarabotto et al. (1999); Spek (2009); Youngme et al. (2008).

S2. Experimental

All chemicals were purchased from Sigma and used as received. A solution of sodium acetate NaCH₃COO (4 mM, 0.328 g) in 40 ml of water was prepared and its pH adjusted to 3.5–4 with a 10% solution of HNO₃. Under continuous agitation, equimolar quantities of 1,10-phenanthroline and copper nitrate were added to this solution; after complete dissolution its pH was adjusted to 4.5–5 with 1 N solution of NaOH and 10% HNO₃. This solution was filtered and left to evaporate at room temperature. Small crystals suitable for X-ray diffraction were obtained after circa 3 weeks.

S3. Refinement

Even if the geometry of the counterions allowed the groups to be initially interpreted either as acetate or nitrate, final bond lengths as well as the lack of methyl H atoms in the difference maps confirmed NO₃ with the correct assignment. All the H atoms could be found in a difference Fourier map. Those attached to C were placed at calculated positions (C—H 0.93 Å, CH₃ 0.96 Å) and allowed to ride. Those attached to O were further refined with restrained O—H 0.85 Å and H···H 1.35 Å distances. In all cases displacement factors were taken as U(H)_isot = 1.2/1.5U(host)_equiv.

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009).

Figures

	Fig. 1. Molecular view of (I) with displacement ellipsoids drawn at the 30% level. Hydrogen bonds are shown as double broken lines. Symmetry codes: (i) x - 1, y, z; (ii) -x + 3/2, -y + 1, z - 1/2.
	Fig. 2. Packing diagram of (I) viewed along [001], showing how the dinuclear units are linked by π···π bonding into planes parallel to (001).
	Fig. 3. Packing diagram of (I), viewed along [100] and rotated by 90° to the view in Fig. 2 showing the hydrogen-bonding interactions. The (001) sheets are shown in projection as vertical structures (marked by square brackets).
	Fig. 4. Comparison of the Cu2(OH)(H2O)(carboxylate) group in (I) (heavy lining) with similar ones from the literature, (the structure code (s) and within brackets the CSD RefCode(s) and Reference are stated). a, c, i: (CITLOH; CITLEX; YAFZUA01; Youngme et al., 2008); b, h: (YEMNIO; YEMNEK; Chailuecha et al., 2006); d: (DIXGEX; Chen et al., 2008); e: (JEJCIK; Christou et al., 1990; f: (OLOVOA; Chadjistamatis et al., 2003); g: (QAHDUY; Sgarabotto et al., 1999); j: (YINJEL; Chen et al., 2007).

µ-Acetato-µ-aqua-µ-hydroxido-bis[(1,10-phenanthroline)copper(II)] dinitrate monohydrate

Crystal data

[Cu2(C2H3O2)(OH)(C12H8N2)2(H2O)](NO3)2·H2O	F(000) = 1472
Mr = 723.59	Dx = 1.716 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7244 reflections
a = 8.15051 (15) Å	θ = 4.1–25.6°
b = 17.4091 (3) Å	µ = 1.59 mm^−1
c = 19.7447 (4) Å	T = 292 K
V = 2801.63 (9) Å^3	Block, blue
Z = 4	0.35 × 0.20 × 0.15 mm

Data collection

Oxford Diffraction Gemini CCD S Ultra diffractometer	5135 independent reflections
Radiation source: fine-focus sealed tube	3791 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω scans, thick slices	θmax = 26.3°, θmin = 2.6°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −10→9
Tmin = 0.54, Tmax = 0.73	k = −21→21
16045 measured reflections	l = −23→24

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.054	w = 1/[σ^2(Fo^2) + (0.0274P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.91	(Δ/σ)max = 0.001
5135 reflections	Δρmax = 0.26 e Å^−3
422 parameters	Δρmin = −0.25 e Å^−3
7 restraints	Absolute structure: Flack, 1983. 1687 Friedel pairs measured
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.001 (9)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.09622 (5)	0.532730 (19)	0.181451 (18)	0.03940 (11)
Cu2	0.04714 (5)	0.695859 (19)	0.217691 (18)	0.03840 (11)
O1	−0.0627 (3)	0.59866 (10)	0.22448 (11)	0.0387 (5)
H1	−0.153 (2)	0.5978 (16)	0.2049 (13)	0.030 (9)*
N1A	0.1297 (3)	0.46454 (14)	0.26321 (12)	0.0403 (6)
N2A	0.2467 (4)	0.45533 (14)	0.13881 (14)	0.0433 (7)
C1A	0.0727 (4)	0.47228 (18)	0.32564 (16)	0.0530 (8)
H1A	0.0102	0.5153	0.3364	0.064*
C2A	0.1043 (6)	0.4170 (2)	0.37637 (18)	0.0646 (11)
H2A	0.0626	0.4230	0.4199	0.078*
C3A	0.1962 (5)	0.3551 (2)	0.3602 (2)	0.0640 (12)
H3A	0.2167	0.3183	0.3933	0.077*
C4A	0.2615 (5)	0.34476 (18)	0.29565 (19)	0.0492 (9)
C5A	0.3601 (5)	0.28082 (18)	0.2737 (3)	0.0645 (12)
H5A	0.3830	0.2413	0.3040	0.077*
C6A	0.4197 (5)	0.27719 (18)	0.2102 (2)	0.0661 (11)
H6A	0.4837	0.2353	0.1979	0.079*
C7A	0.3879 (5)	0.33519 (17)	0.16159 (19)	0.0507 (9)
C8A	0.4440 (5)	0.3360 (2)	0.0950 (2)	0.0682 (11)
H8A	0.5109	0.2965	0.0794	0.082*
C9A	0.4018 (5)	0.3939 (2)	0.0528 (2)	0.0641 (11)
H9A	0.4395	0.3942	0.0083	0.077*
C10A	0.3023 (4)	0.45284 (19)	0.07600 (19)	0.0551 (9)
H10A	0.2736	0.4921	0.0463	0.066*
C11A	0.2883 (4)	0.39749 (17)	0.18166 (19)	0.0413 (8)
C12A	0.2256 (4)	0.40279 (16)	0.24843 (19)	0.0420 (9)
N1B	0.1693 (3)	0.79646 (14)	0.22013 (14)	0.0415 (6)
N2B	0.0001 (3)	0.72297 (13)	0.31385 (13)	0.0374 (6)
C1B	0.2522 (5)	0.83158 (18)	0.1721 (2)	0.0519 (9)
H1B	0.2577	0.8087	0.1296	0.062*
C2B	0.3319 (5)	0.9013 (2)	0.1818 (2)	0.0623 (10)
H2B	0.3925	0.9238	0.1471	0.075*
C3B	0.3189 (5)	0.9362 (2)	0.2439 (2)	0.0566 (11)
H3B	0.3675	0.9839	0.2506	0.068*
C4B	0.2345 (4)	0.90151 (17)	0.29681 (18)	0.0458 (9)
C5B	0.2111 (5)	0.9323 (2)	0.3632 (2)	0.0584 (11)
H5B	0.2579	0.9796	0.3738	0.070*
C6B	0.1252 (5)	0.8959 (2)	0.4102 (2)	0.0622 (11)
H6B	0.1135	0.9183	0.4527	0.075*
C7B	0.0494 (5)	0.82292 (18)	0.39747 (16)	0.0470 (9)
C8B	−0.0457 (5)	0.78212 (19)	0.44369 (16)	0.0547 (9)
H8B	−0.0618	0.8010	0.4872	0.066*
C9B	−0.1150 (5)	0.71428 (19)	0.42458 (16)	0.0527 (9)
H9B	−0.1793	0.6867	0.4549	0.063*
C10B	−0.0888 (5)	0.68649 (18)	0.35924 (15)	0.0464 (8)
H10B	−0.1364	0.6399	0.3472	0.056*
C11B	0.0699 (4)	0.79070 (16)	0.33261 (15)	0.0393 (8)
C12B	0.1608 (4)	0.83026 (16)	0.28255 (18)	0.0400 (8)
O1C	0.0622 (3)	0.57733 (12)	0.09282 (10)	0.0496 (6)
O2C	0.0325 (3)	0.70113 (11)	0.11975 (10)	0.0485 (6)
C1C	0.0387 (5)	0.6464 (2)	0.07864 (17)	0.0484 (9)
C2C	0.0125 (6)	0.6669 (2)	0.00525 (17)	0.0838 (16)
H2CA	0.0900	0.6395	−0.0222	0.126*
H2CB	0.0278	0.7211	−0.0008	0.126*
H2CC	−0.0969	0.6531	−0.0080	0.126*
N1D	0.5583 (6)	0.62141 (19)	0.0885 (2)	0.0694 (10)
O1D	0.6265 (8)	0.5984 (3)	0.0407 (2)	0.168 (2)
O2D	0.4321 (5)	0.6575 (2)	0.0863 (2)	0.1437 (17)
O3D	0.6074 (5)	0.60806 (17)	0.14612 (18)	0.0964 (11)
N1E	0.4211 (5)	0.5970 (2)	0.38412 (17)	0.0704 (10)
O1E	0.3242 (6)	0.6491 (2)	0.38830 (19)	0.1283 (15)
O2E	0.4594 (5)	0.57261 (18)	0.33056 (16)	0.1121 (13)
O3E	0.4739 (7)	0.5703 (3)	0.4343 (2)	0.185 (2)
O1W	0.2877 (3)	0.62337 (13)	0.21961 (13)	0.0465 (5)
H1WA	0.365 (3)	0.6326 (19)	0.1926 (12)	0.070*
H1WB	0.331 (4)	0.609 (2)	0.2563 (9)	0.070*
O2W	0.6949 (5)	0.4782 (3)	−0.0556 (2)	0.1205 (12)
H2WA	0.697 (7)	0.512 (3)	−0.023 (3)	0.181*
H2WB	0.798 (2)	0.472 (4)	−0.063 (3)	0.181*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0451 (2)	0.03186 (19)	0.0412 (2)	0.00363 (18)	0.00070 (19)	0.00110 (16)
Cu2	0.0461 (3)	0.0317 (2)	0.0375 (2)	0.00065 (19)	0.00004 (18)	0.00016 (16)
O1	0.0360 (15)	0.0397 (12)	0.0404 (13)	−0.0002 (10)	0.0018 (12)	−0.0036 (9)
N1A	0.0398 (16)	0.0349 (14)	0.0462 (17)	−0.0043 (14)	−0.0058 (12)	0.0033 (12)
N2A	0.0482 (18)	0.0333 (15)	0.0483 (17)	0.0039 (14)	−0.0027 (14)	−0.0022 (13)
C1A	0.060 (2)	0.053 (2)	0.046 (2)	−0.004 (2)	−0.0040 (19)	0.0058 (17)
C2A	0.082 (3)	0.061 (2)	0.050 (2)	−0.015 (3)	−0.006 (2)	0.0122 (18)
C3A	0.068 (3)	0.051 (3)	0.073 (3)	−0.021 (2)	−0.034 (2)	0.025 (2)
C4A	0.045 (2)	0.042 (2)	0.060 (3)	−0.0103 (17)	−0.0183 (19)	0.0061 (17)
C5A	0.063 (3)	0.0284 (18)	0.102 (3)	−0.0005 (17)	−0.037 (3)	0.007 (2)
C6A	0.057 (3)	0.038 (2)	0.104 (3)	0.0094 (18)	−0.034 (3)	−0.015 (2)
C7A	0.043 (2)	0.0311 (17)	0.078 (3)	−0.0005 (16)	−0.016 (2)	−0.0119 (17)
C8A	0.053 (3)	0.056 (2)	0.096 (3)	0.009 (2)	0.002 (2)	−0.035 (2)
C9A	0.059 (3)	0.056 (2)	0.077 (3)	0.003 (2)	0.020 (2)	−0.020 (2)
C10A	0.059 (2)	0.045 (2)	0.062 (3)	0.0027 (18)	0.0057 (19)	−0.0059 (18)
C11A	0.0328 (19)	0.0343 (18)	0.057 (2)	−0.0064 (15)	−0.0125 (19)	−0.0070 (17)
C12A	0.037 (2)	0.0248 (18)	0.064 (2)	−0.0085 (16)	−0.0166 (18)	0.0026 (15)
N1B	0.0458 (16)	0.0342 (14)	0.0446 (16)	−0.0001 (12)	−0.0023 (14)	0.0089 (15)
N2B	0.0418 (16)	0.0300 (13)	0.0403 (14)	0.0051 (11)	−0.0039 (13)	0.0023 (12)
C1B	0.052 (2)	0.047 (2)	0.056 (2)	0.0092 (17)	0.005 (2)	0.0053 (17)
C2B	0.044 (2)	0.057 (2)	0.086 (3)	−0.0016 (18)	−0.005 (2)	0.024 (2)
C3B	0.046 (2)	0.0313 (19)	0.093 (3)	0.0042 (17)	−0.010 (2)	0.007 (2)
C4B	0.035 (2)	0.0362 (19)	0.066 (3)	0.0065 (16)	−0.0145 (17)	0.0028 (17)
C5B	0.053 (3)	0.040 (2)	0.083 (3)	0.0015 (19)	−0.022 (2)	−0.016 (2)
C6B	0.067 (3)	0.055 (2)	0.065 (3)	0.010 (2)	−0.022 (2)	−0.021 (2)
C7B	0.049 (2)	0.045 (2)	0.047 (2)	0.0154 (18)	−0.0167 (19)	−0.0050 (15)
C8B	0.070 (3)	0.056 (2)	0.0381 (19)	0.024 (2)	−0.0118 (19)	−0.0042 (16)
C9B	0.064 (3)	0.056 (2)	0.0383 (19)	0.0179 (19)	0.0061 (18)	0.0078 (16)
C10B	0.050 (2)	0.0412 (19)	0.0481 (19)	0.0131 (19)	−0.0031 (17)	0.0048 (15)
C11B	0.041 (2)	0.0325 (16)	0.0447 (19)	0.0117 (15)	−0.0156 (16)	−0.0012 (14)
C12B	0.0408 (19)	0.0292 (16)	0.050 (2)	0.0067 (14)	−0.0091 (18)	−0.0018 (16)
O1C	0.0681 (18)	0.0401 (13)	0.0404 (13)	0.0073 (13)	−0.0013 (12)	0.0015 (9)
O2C	0.0723 (17)	0.0350 (11)	0.0381 (12)	0.0057 (13)	−0.0045 (11)	0.0026 (10)
C1C	0.051 (2)	0.055 (2)	0.039 (2)	0.0018 (19)	0.0025 (18)	0.0013 (17)
C2C	0.142 (5)	0.074 (3)	0.036 (2)	0.010 (3)	−0.003 (2)	0.0054 (17)
N1D	0.080 (3)	0.064 (2)	0.064 (2)	0.000 (2)	0.005 (2)	0.0021 (18)
O1D	0.215 (5)	0.189 (4)	0.099 (3)	0.018 (4)	0.066 (4)	−0.036 (3)
O2D	0.081 (3)	0.167 (4)	0.183 (4)	0.041 (3)	0.011 (3)	0.081 (3)
O3D	0.108 (3)	0.079 (2)	0.102 (2)	0.017 (2)	−0.018 (2)	−0.0126 (17)
N1E	0.084 (3)	0.083 (2)	0.044 (2)	0.023 (2)	−0.018 (2)	−0.0060 (18)
O1E	0.148 (4)	0.121 (3)	0.116 (3)	0.058 (3)	0.019 (3)	0.004 (2)
O2E	0.159 (4)	0.114 (2)	0.063 (2)	0.066 (2)	−0.015 (2)	−0.0183 (17)
O3E	0.217 (6)	0.259 (5)	0.080 (3)	0.132 (4)	−0.057 (3)	−0.019 (3)
O1W	0.0427 (14)	0.0495 (13)	0.0474 (14)	−0.0005 (11)	0.0012 (12)	0.0018 (12)
O2W	0.123 (3)	0.134 (3)	0.104 (3)	0.010 (2)	−0.009 (2)	0.017 (2)

Geometric parameters (Å, º)

Cu1—O1	1.928 (2)	N2B—C11B	1.361 (4)
Cu1—O1C	1.935 (2)	C1B—C2B	1.391 (5)
Cu1—N2A	2.007 (3)	C1B—H1B	0.9300
Cu1—N1A	2.022 (2)	C2B—C3B	1.372 (5)
Cu1—O1W	2.344 (2)	C2B—H2B	0.9300
Cu2—O1	1.919 (2)	C3B—C4B	1.389 (5)
Cu2—O2C	1.940 (2)	C3B—H3B	0.9300
Cu2—N2B	1.994 (3)	C4B—C12B	1.407 (4)
Cu2—N1B	2.015 (2)	C4B—C5B	1.429 (5)
Cu2—O1W	2.332 (2)	C5B—C6B	1.324 (5)
O1—H1	0.83 (3)	C5B—H5B	0.9300
N1A—C1A	1.324 (4)	C6B—C7B	1.435 (5)
N1A—C12A	1.360 (4)	C6B—H6B	0.9300
N2A—C10A	1.321 (4)	C7B—C8B	1.392 (5)
N2A—C11A	1.358 (4)	C7B—C11B	1.408 (4)
C1A—C2A	1.413 (4)	C8B—C9B	1.362 (5)
C1A—H1A	0.9300	C8B—H8B	0.9300
C2A—C3A	1.349 (6)	C9B—C10B	1.394 (4)
C2A—H2A	0.9300	C9B—H9B	0.9300
C3A—C4A	1.394 (5)	C10B—H10B	0.9300
C3A—H3A	0.9300	C11B—C12B	1.414 (4)
C4A—C12A	1.406 (4)	O1C—C1C	1.249 (4)
C4A—C5A	1.440 (5)	O2C—C1C	1.253 (4)
C5A—C6A	1.346 (5)	C1C—C2C	1.508 (4)
C5A—H5A	0.9300	C2C—H2CA	0.9600
C6A—C7A	1.418 (5)	C2C—H2CB	0.9600
C6A—H6A	0.9300	C2C—H2CC	0.9600
C7A—C8A	1.393 (5)	N1D—O1D	1.166 (5)
C7A—C11A	1.412 (4)	N1D—O2D	1.206 (5)
C8A—C9A	1.352 (5)	N1D—O3D	1.229 (4)
C8A—H8A	0.9300	N1E—O3E	1.176 (4)
C9A—C10A	1.386 (5)	N1E—O2E	1.182 (4)
C9A—H9A	0.9300	N1E—O1E	1.205 (4)
C10A—H10A	0.9300	O1W—H1WA	0.84 (4)
C11A—C12A	1.417 (5)	O1W—H1WB	0.84 (4)
N1B—C1B	1.315 (4)	O2W—H2WA	0.87 (4)
N1B—C12B	1.367 (4)	O2W—H2WB	0.87 (4)
N2B—C10B	1.316 (4)
O1—Cu1—O1C	93.62 (9)	C1B—N1B—Cu2	129.8 (2)
O1—Cu1—N2A	174.29 (10)	C12B—N1B—Cu2	111.7 (2)
O1C—Cu1—N2A	88.72 (10)	C10B—N2B—C11B	117.6 (3)
O1—Cu1—N1A	95.08 (10)	C10B—N2B—Cu2	129.8 (2)
O1C—Cu1—N1A	167.71 (10)	C11B—N2B—Cu2	112.6 (2)
N2A—Cu1—N1A	81.85 (11)	N1B—C1B—C2B	123.1 (4)
O1—Cu1—O1W	84.55 (8)	N1B—C1B—H1B	118.4
O1C—Cu1—O1W	96.67 (9)	C2B—C1B—H1B	118.4
N2A—Cu1—O1W	100.36 (10)	C3B—C2B—C1B	118.2 (4)
N1A—Cu1—O1W	92.79 (9)	C3B—C2B—H2B	120.9
O1—Cu2—O2C	94.74 (9)	C1B—C2B—H2B	120.9
O1—Cu2—N2B	93.00 (9)	C2B—C3B—C4B	121.3 (3)
O2C—Cu2—N2B	157.88 (9)	C2B—C3B—H3B	119.4
O1—Cu2—N1B	174.35 (10)	C4B—C3B—H3B	119.4
O2C—Cu2—N1B	90.76 (10)	C3B—C4B—C12B	116.3 (3)
N2B—Cu2—N1B	82.33 (10)	C3B—C4B—C5B	126.4 (3)
O1—Cu2—O1W	85.07 (8)	C12B—C4B—C5B	117.3 (3)
O2C—Cu2—O1W	95.37 (9)	C6B—C5B—C4B	122.2 (3)
N2B—Cu2—O1W	105.93 (9)	C6B—C5B—H5B	118.9
N1B—Cu2—O1W	93.12 (9)	C4B—C5B—H5B	118.9
Cu2—O1—Cu1	100.41 (10)	C5B—C6B—C7B	122.0 (3)
Cu2—O1—H1	113 (2)	C5B—C6B—H6B	119.0
Cu1—O1—H1	112 (2)	C7B—C6B—H6B	119.0
C1A—N1A—C12A	118.8 (3)	C8B—C7B—C11B	117.3 (3)
C1A—N1A—Cu1	129.5 (2)	C8B—C7B—C6B	125.2 (3)
C12A—N1A—Cu1	111.7 (2)	C11B—C7B—C6B	117.4 (3)
C10A—N2A—C11A	118.3 (3)	C9B—C8B—C7B	119.4 (3)
C10A—N2A—Cu1	128.7 (2)	C9B—C8B—H8B	120.3
C11A—N2A—Cu1	112.9 (2)	C7B—C8B—H8B	120.3
N1A—C1A—C2A	121.8 (3)	C8B—C9B—C10B	119.6 (3)
N1A—C1A—H1A	119.1	C8B—C9B—H9B	120.2
C2A—C1A—H1A	119.1	C10B—C9B—H9B	120.2
C3A—C2A—C1A	118.5 (4)	N2B—C10B—C9B	123.2 (3)
C3A—C2A—H2A	120.7	N2B—C10B—H10B	118.4
C1A—C2A—H2A	120.7	C9B—C10B—H10B	118.4
C2A—C3A—C4A	122.1 (3)	N2B—C11B—C7B	122.9 (3)
C2A—C3A—H3A	118.9	N2B—C11B—C12B	116.8 (3)
C4A—C3A—H3A	118.9	C7B—C11B—C12B	120.3 (3)
C3A—C4A—C12A	115.7 (3)	N1B—C12B—C4B	122.6 (3)
C3A—C4A—C5A	126.1 (4)	N1B—C12B—C11B	116.6 (3)
C12A—C4A—C5A	118.2 (4)	C4B—C12B—C11B	120.9 (3)
C6A—C5A—C4A	121.2 (3)	C1C—O1C—Cu1	127.7 (2)
C6A—C5A—H5A	119.4	C1C—O2C—Cu2	127.4 (2)
C4A—C5A—H5A	119.4	O1C—C1C—O2C	126.4 (3)
C5A—C6A—C7A	122.1 (3)	O1C—C1C—C2C	117.7 (3)
C5A—C6A—H6A	118.9	O2C—C1C—C2C	115.9 (3)
C7A—C6A—H6A	118.9	C1C—C2C—H2CA	109.4
C8A—C7A—C11A	116.5 (3)	C1C—C2C—H2CB	109.5
C8A—C7A—C6A	126.0 (4)	H2CA—C2C—H2CB	109.5
C11A—C7A—C6A	117.5 (4)	C1C—C2C—H2CC	109.5
C9A—C8A—C7A	120.4 (3)	H2CA—C2C—H2CC	109.5
C9A—C8A—H8A	119.8	H2CB—C2C—H2CC	109.5
C7A—C8A—H8A	119.8	O1D—N1D—O2D	123.9 (5)
C8A—C9A—C10A	119.8 (4)	O1D—N1D—O3D	122.0 (5)
C8A—C9A—H9A	120.1	O2D—N1D—O3D	114.1 (4)
C10A—C9A—H9A	120.1	O3E—N1E—O2E	121.0 (4)
N2A—C10A—C9A	122.4 (3)	O3E—N1E—O1E	118.7 (4)
N2A—C10A—H10A	118.8	O2E—N1E—O1E	120.3 (4)
C9A—C10A—H10A	118.8	Cu2—O1W—Cu1	78.42 (7)
N2A—C11A—C7A	122.6 (3)	Cu2—O1W—H1WA	121 (2)
N2A—C11A—C12A	116.2 (3)	Cu1—O1W—H1WA	115 (2)
C7A—C11A—C12A	121.2 (3)	Cu2—O1W—H1WB	122 (2)
N1A—C12A—C4A	123.0 (3)	Cu1—O1W—H1WB	111 (2)
N1A—C12A—C11A	117.3 (3)	H1WA—O1W—H1WB	107 (3)
C4A—C12A—C11A	119.7 (3)	H2WA—O2W—H2WB	102 (3)
C1B—N1B—C12B	118.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3D^i	0.83 (3)	2.28 (3)	3.107 (4)	174 (3)
O1W—H1WA···O2D	0.84 (4)	2.21 (3)	2.943 (5)	145 (3)
O1W—H1WA···O3D	0.84 (4)	2.22 (3)	2.994 (5)	153 (3)
O1W—H1WB···O2E	0.84 (4)	1.91 (3)	2.745 (4)	171 (3)
O2W—H2WA···O1D	0.87 (4)	2.05 (3)	2.881 (6)	161 (6)
O2W—H2WB···O3E^ii	0.87 (4)	1.99 (2)	2.835 (6)	164 (7)
C5A—H5A···O3D^iii	0.93	2.52	3.408 (5)	160
C5B—H5B···O3D^iv	0.93	2.52	3.402 (5)	158
C6B—H6B···O3E^v	0.93	2.51	3.359 (6)	152

Symmetry codes: (i) x−1, y, z; (ii) −x+3/2, −y+1, z−1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1/2; (v) x−1/2, −y+3/2, −z+1.