Bis{μ-6,6′-dimeth­oxy-2,2′-[propane-1,2-diylbis(imino­methyl­ene)]­diphenol­ato}­bis­[aqua­copper(II)] dihydrate

In the title compound, [Cu₂(C₁₉H₂₄N₂O₄)₂(H₂O)₂]·2H₂O, the asymmetric unit consists of one half of the bis­{μ-6,6′-dimeth­oxy-2,2′-[propane-1,2-diylbis(imino­methyl­ene)]­di­phenol­ato}­bis­[aqua­copper(II)] complex and two water mol­ecules. Two Cu^II centres are bridged through a pair of phenolate groups, resulting in a complex with a centrosymmetric structure, with the centre of inversion at the middle of the Cu₂O₂ plane. The Cu atoms are in a slightly distorted square-pyramidal coordination environment (τ = 0.07). The average equatorial Cu—O bond length and the axial Cu—O bond length are 1.928 (3) and 2.486 (3) Å, respectively. The Cu—O(water) bond length is 2.865 (4) Å, so the compound could be described as having a weakly coordinating water mol­ecule at each Cu^II ion and two solvent water mol­ecules per dimetallic unit. The Cu...Cu distance and Cu—O—Cu angle are 3.0901 (10) Å and 87.56 (10)°, respectively. The mol­ecules are linked into a sheet by O—H...O and C—H...O hydrogen bonds parallel to the [001] plane.

S1. Comment

Binuclear transition metal complexes have attracted much attention because of their potential applications, for example as active sites in metalloproteins and enzymes (Elmali et al., 2004) and as new inorganic functional materials showing molecular ferromagnetism (Gupta et al., 2005). Among these binuclear transition metal complexes, OH^-, RO^-, RCO₂^-, Cl^-, Br^- and other groups are often used as bridging ligands (Christou et al., 2000). In particular, magnetostructural correlations in dicopper(II) complexes bridged by pairs of phenoxide or alkoxide groups show that the major factors controlling the intramolecular spin coupling between the metal centres are the bridged Cu—O—Cu angle (Elmali et al., 2004) and other features, such as the Cu—O distances and the distortion index (τ) of the Cu^II atoms, which can lead to increased ferromagnetic contributions (Xie et al., 2003) [Original sentence not clear - please check rephrasing]. These complexes are able to stabilize the Cu₂O₂ core portion by forming square-pyramidal CuO₂N₃ coordination sites or square-planar CuO₂N₂ coordination sites (Herres et al., 2005). In the light of this, we have synthesized some new ligands with diamino moieties (Xia et al., 2006; Xia, Liu, Yang & Wang, 2007). 6,6'-Dimethoxy-2,2'-(propane-1,2-diyldiiminodimethylene)diphenol (H₂L) is a versatile ligand that, due to its conformational flexibility, can form a tetradentate chelating mode through its N and O atoms (Liu et al., 2007; Xia, Liu, Wang & Yang, 2007) or a bridging coordination mode towards many metals, resulting in complexes with different stereochemistries. In this paper, we report the synthesis and structure of the title phenoxide-bridged dicopper(II) H₂L complex, (I).

In complex (I), two copper atoms are bridged by a pair of phenoxide O atoms, with each copper atom five-coordinated by two nitrogen and three oxygen atoms (Fig. 1). The coordination polyhedron around the Cu atom may be described as square based pyramidal. The distortion index τ (Addison et al., 1984) is 0.07 (where τ = 0 for a square pyramidal geometry and τ = 1 for trigonal bipyramidal geometry), with an apical Cu1—O1A distance of 2.486 (3) Å. The basal plane is formed by atoms O1, N1, N2, and O3. Atom Cu1 is shifted by 0.0752 (16) Å from the basal plane toward the apical atom O1A.

In the complex, it can be observed that the distance between water atom O5 and atom Cu1 is 2.865 (4) Å, and the atom O5 is situated at the apical point of a pseudo-octahedral geometry, which is similar to what was observed in another diphenoxide-bridged dicopper(II) complex, [Cu₂L(N₃)]₂ ·2H₂O (L is a macrocyclic ligand; Chattopadhyay et al., 2007). Thus, the compound (I) can be described as having a weakly coordinating water molecule at each copper ion and two lattice water molecules per dimetallic unit.

The two intramolecular basal planes are strictly parallel, with an interplanar spacing of 2.528 (13) Å, corresponding to a plane offset of 1.838 Å. The dihedral angles between the basal plane with the phenyl rings C5—C10 and C13—C18 are 31.10 (16)° and 23.37 (18)°, respectively, and the dihedral angle between the square-plane Cu₂O₂ and the basal plane is 87.62 (7)°. The Cu—N bond lengths range from 1.992 (3) Å to 2.011 (3) Å, and the average equatorial Cu1—O bond length is 1.928 (3) Å, whereas the axial Cu1—O1A bond length is 2.486 (3) Å. This axial elongation is a consequence of the Jahn-Teller effect of copper(II), indicating that the spin-unpaired electron is located in the d_{x2 - y2} orbital and that the d_z2 orbital contains spin-paired electrons. Thus, the magnetic exchange is propagated principally via the d_{x2 - y2} orbital of the Cu^II ions which interacts with the appropriate orbital of the O atoms of the bridging phenoxide groups.

The Cu···Cu separation is 3.0901 (10) Å, consistent with the value of 3.091 Å reported for the diphenoxide-bridged dicopper(II) complex [Cu₂L(H₂O)₂](SO₄)₂·2H₂O (where L are derivatives of the 4-methyl-2,6-diformylphenol with 1,3-diamine-2-propanol; Venegas-Yazigi et al., 2006), but longer than the value of 2.9133 (10) Å reported for another diphenoxide-bridged dicopper(II) complex, [Cu₂L(N₃)₂]·2H₂O (whereL are derivatives of the 4-methyl-2,6-diformylphenol with ethane-1,2-diamine; Chattopadhyay et al., 2007). The Cu–O–Cu bridging angles of 87.56 (10)° are smaller than those of the two diphenoxide-bridged dicopper(II) complexes mentioned above [104.08° and 99.65 (15)°, respectively]. It is well known that the strength of antiferromagnetic coupling depends mainly on the Cu–O–Cu bridging angle in dicopper(II) complexes equatorially bridged by a pair of phenoxide O atoms (Thompson et al., 1996). Magnetostructural correlation of such complexes has been reported by Thompson et al. using macrocyclic ligands. They predicted that the antiferromagnetism of such an equatorial-equatorial interaction of tetragonally distorted dicopper(II) complexes should prevail until the Cu–O–Cu angle is as small as 77°. The title compound is an axial-equatorial interaction of tetragonally distorted dicopper(II) complexes, the Cu–O–Cu angle is much smaller than that found in the systems studied by Thompson et al. (99–105°), but it would still be predicted to be antiferromagnetic in nature.

In the crystal structure, the molecules of compound (I) are linked into complex sheets by means of four independent O—H···O hydrogen bonds and two C—H···O hydrogen bond (Table 2), but the formation of the sheets is readily described in terms of simpler substructure motifs. Atom C1 in the molecule at (1/2 - x, 1/2 + y, z) and C12 in the molecule at (1/2 + x, 1/2 - y, 1 - z) acts as hydrogen bond donor to atom O6 in the molecule at (x, y, z) and O5 in the molecule at (1/2 + x, 1/2 - y, 1 - z),respectively. Although the H atoms bonded to the water moelcule O5 cannot be determined reliably, it appears from the intermolecular O—O distances that the atom O5 at (1/2 + x, 1/2 - y, 1 - z) acts as hydrogen bond donor to atom O6 in the molecule at (x, y, z) with a distance of 2.722 (5) Å. At the same time, atom O6 in the molecule at (x, y, z) acts as hydrogen bond donor to, respectively, atoms O1, O2 and O3 in the molecule at (x, y, z), so forming a R₁² ring (Bernstein et al., 1995). The combination of these two motifs then forms a sheet parallel to the [001] plane and generated by the n-glide plane at y = 1/2 (Fig. 2). There are no direction-specific interactions between adjacent sheets.

Related literature

For related literature, see: Bernstein et al. (1995); Chattopadhyay et al. (2007); Christou et al. (2000); Elmali et al. (2004); Gupta et al. (2005); Herres et al. (2005); Liu et al. (2007); Thompson et al. (1996); Venegas-Yazigi, Cortés, Paredes-García, Peña, Ibañez, Baggio & Spodine (2006); Xia et al. (2006); Xia, Liu, Wang & Yang (2007); Xia, Liu, Yang & Wang (2007); Xie et al. (2003).

S2. Experimental

The ligand was produced according to the literature method of Xia, Liu, Yang & Wang (2007). Complex (I) was prepared as follows. The ligand (0.693 g, 2 mmol) was dissolved in ethanol (10 ml) and an aqueous solution (10 ml) of cupric chloride (0.341 g, 2 mmol) was added. The reaction mixture was stirred for 2 h at 323 K. The solution was then cooled slowly to room temperature and filtered. Green crystals suitable for X-ray diffraction were obtained by evaporation of an ethanol solution (yield 0.48 g, 51%; m.p. 514–516 K). Analysis, calculated for C₃₈H₅₆N₄O₁₂Cu₂: C 51.40, H 6.36, N 6.31%; found: C 51.56, H 6.57, N 6.15%. Spectroscopic analysis: IR (KBr disk, ν, cm^-1): 3426 (w), 3246 (m), 2932 (w), 1598 (w), 1562 (m), 1482 (s), 1452 (s), 1291 (m), 1241 (s), 1070 (s), 719 (m); UV–vis [λ (nm), ε (mol^-1 cm^-1), CH₃OH): 247 (27225), 284 (16575), 334 (1990), 405 (2038), 581 (510).

S3. Refinement

All H atoms were located in difference Fourier maps, except those bonded to O5 which could not be determined reliably. H atoms bonded to C and N atoms were treated as riding atoms, with C—H distances of 0.93 Å (aryl), 0.96 Å (methyl), 0.97 Å(methylene), 0.98 Å(tertiary C—H) and N—H distances of 0.91 Å (amine), and with U_iso(H) = 1.2U_eq(C,N) (aryl, methylene, tertiary C—H, amine) and 1.5U_eq(C) (methyl). The H atoms bonded to O6 were refined isotropically with the bond lengths restrained to be the same and 1.5U_eq(O).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures

	Fig. 1. The molecular structure of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Unlabelled atoms and those labelled with the suffix A are related to labelled atoms by the symmetry code (1 - x, - y, 1 - z).
	Fig. 2. The crystal structure of (I), showing the formation of hydrogen-bonded sheets via C—H···O and O—H···O interactions. For clarity, H atoms not involved in the hydrogen bonding have been omitted. Dashed lines indicate hydrogen bonds. [Symmetry codes: (B) 1/2 - x, 1/2 + y, z, (C) 1/2 + x, 1/2 - y, 1 - z].

Bis[µ-6,6'-dimethoxy-2,2'-[propane-1,2-diylbis(iminomethylene)]diphenolato]bis[aquacopper(II)] dihydrate

Crystal data

[Cu2(C19H24N2O4)2(H2O)2]·2H2O	F(000) = 1864
Mr = 887.95	Dx = 1.457 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3604 reflections
a = 10.3214 (16) Å	θ = 2.5–25.3°
b = 16.474 (2) Å	µ = 1.12 mm^−1
c = 23.812 (2) Å	T = 298 K
V = 4048.7 (9) Å^3	Block, green
Z = 4	0.28 × 0.21 × 0.10 mm

Data collection

Siemens SMART 1000 CCD area-detector diffractometer	3572 independent reflections
Radiation source: fine-focus sealed tube	2280 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
ϕ and ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→12
Tmin = 0.745, Tmax = 0.897	k = −19→14
15892 measured reflections	l = −26→28

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0479P)^2 + 5.003P] where P = (Fo^2 + 2Fc^2)/3
3572 reflections	(Δ/σ)max = 0.015
259 parameters	Δρmax = 0.66 e Å^−3
2 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	0.36537 (4)	0.02807 (3)	0.52068 (2)	0.03528 (17)
N1	0.2869 (3)	−0.0630 (2)	0.47741 (15)	0.0455 (9)
H1	0.3516	−0.0950	0.4639	0.055*
N2	0.2538 (3)	−0.00709 (19)	0.58547 (14)	0.0383 (8)
H2	0.3023	−0.0405	0.6075	0.046*
O1	0.4532 (2)	0.06352 (17)	0.45276 (11)	0.0387 (7)
O2	0.5725 (3)	0.14505 (18)	0.37395 (13)	0.0559 (8)
O3	0.4361 (3)	0.11917 (16)	0.55978 (11)	0.0448 (7)
O4	0.6239 (3)	0.20060 (19)	0.60627 (13)	0.0574 (9)
O5	0.1789 (4)	0.1519 (2)	0.49601 (17)	0.0869 (12)
O6	0.4973 (4)	0.23289 (19)	0.48119 (16)	0.0668 (10)
H6B	0.510 (6)	0.195 (3)	0.4555 (19)	0.100*
H6A	0.487 (6)	0.205 (3)	0.5131 (16)	0.100*
C1	0.2070 (4)	−0.1114 (3)	0.5167 (2)	0.0533 (12)
H1B	0.2607	−0.1521	0.5348	0.064*
H1C	0.1392	−0.1392	0.4961	0.064*
C2	0.1461 (4)	−0.0567 (3)	0.5614 (2)	0.0479 (11)
H2A	0.0849	−0.0200	0.5428	0.058*
C3	0.0726 (5)	−0.1059 (3)	0.6051 (2)	0.0686 (15)
H3A	0.1313	−0.1421	0.6238	0.103*
H3B	0.0057	−0.1368	0.5870	0.103*
H3C	0.0344	−0.0698	0.6321	0.103*
C4	0.2141 (4)	−0.0306 (3)	0.4303 (2)	0.0586 (13)
H4A	0.1505	0.0076	0.4445	0.070*
H4B	0.1673	−0.0747	0.4125	0.070*
C5	0.2948 (4)	0.0113 (3)	0.38661 (18)	0.0454 (11)
C6	0.4048 (4)	0.0574 (2)	0.40104 (17)	0.0386 (10)
C7	0.4656 (4)	0.1006 (3)	0.35687 (19)	0.0471 (11)
C8	0.4227 (5)	0.0973 (3)	0.3019 (2)	0.0649 (14)
H8	0.4662	0.1256	0.2739	0.078*
C9	0.3163 (6)	0.0524 (3)	0.2894 (2)	0.0725 (16)
H9	0.2863	0.0508	0.2526	0.087*
C10	0.2525 (5)	0.0093 (3)	0.3303 (2)	0.0623 (14)
H10	0.1804	−0.0216	0.3207	0.075*
C11	0.6202 (6)	0.2071 (3)	0.3377 (2)	0.0836 (18)
H11A	0.6540	0.1829	0.3041	0.125*
H11B	0.6877	0.2366	0.3564	0.125*
H11C	0.5509	0.2434	0.3282	0.125*
C12	0.2107 (4)	0.0620 (3)	0.62087 (19)	0.0488 (11)
H12A	0.1534	0.0419	0.6500	0.059*
H12B	0.1621	0.0999	0.5979	0.059*
C13	0.3225 (4)	0.1057 (2)	0.64766 (17)	0.0423 (10)
C14	0.4263 (4)	0.1329 (2)	0.61492 (17)	0.0385 (10)
C15	0.5268 (4)	0.1766 (3)	0.64176 (19)	0.0464 (11)
C16	0.5220 (5)	0.1925 (3)	0.6981 (2)	0.0670 (15)
H16	0.5878	0.2221	0.7152	0.080*
C17	0.4184 (6)	0.1642 (3)	0.7296 (2)	0.0794 (17)
H17	0.4159	0.1741	0.7680	0.095*
C18	0.3203 (5)	0.1221 (3)	0.7048 (2)	0.0620 (14)
H18	0.2510	0.1042	0.7265	0.074*
C19	0.7270 (5)	0.2473 (3)	0.6295 (2)	0.0726 (16)
H19A	0.6921	0.2940	0.6483	0.109*
H19B	0.7839	0.2646	0.5999	0.109*
H19C	0.7745	0.2147	0.6558	0.109*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0308 (3)	0.0373 (3)	0.0378 (3)	−0.0047 (2)	−0.0007 (2)	−0.0058 (2)
N1	0.0393 (19)	0.045 (2)	0.052 (2)	−0.0037 (17)	−0.0008 (18)	−0.0033 (19)
N2	0.0297 (16)	0.035 (2)	0.050 (2)	−0.0021 (15)	−0.0035 (16)	0.0006 (17)
O1	0.0378 (15)	0.0462 (17)	0.0323 (15)	−0.0035 (13)	−0.0054 (12)	−0.0027 (13)
O2	0.060 (2)	0.055 (2)	0.053 (2)	−0.0037 (17)	0.0008 (16)	0.0194 (17)
O3	0.0559 (18)	0.0458 (18)	0.0325 (16)	−0.0163 (15)	0.0040 (13)	−0.0054 (14)
O4	0.060 (2)	0.062 (2)	0.0503 (19)	−0.0252 (17)	−0.0040 (16)	−0.0124 (16)
O5	0.095 (3)	0.070 (3)	0.096 (3)	0.017 (2)	−0.016 (2)	0.006 (2)
O6	0.094 (3)	0.043 (2)	0.063 (2)	0.005 (2)	0.002 (2)	−0.0005 (18)
C1	0.049 (3)	0.046 (3)	0.065 (3)	−0.013 (2)	−0.004 (2)	−0.006 (3)
C2	0.033 (2)	0.049 (3)	0.062 (3)	−0.011 (2)	−0.003 (2)	0.007 (2)
C3	0.054 (3)	0.071 (4)	0.081 (4)	−0.016 (3)	0.006 (3)	0.013 (3)
C4	0.045 (3)	0.060 (3)	0.070 (3)	−0.008 (2)	−0.019 (2)	−0.009 (3)
C5	0.046 (3)	0.049 (3)	0.041 (3)	0.007 (2)	−0.009 (2)	−0.008 (2)
C6	0.041 (2)	0.036 (2)	0.039 (2)	0.0114 (19)	−0.0049 (19)	−0.008 (2)
C7	0.051 (3)	0.043 (3)	0.047 (3)	0.013 (2)	−0.002 (2)	−0.001 (2)
C8	0.080 (4)	0.075 (4)	0.039 (3)	0.008 (3)	−0.006 (3)	0.006 (3)
C9	0.091 (4)	0.084 (4)	0.042 (3)	0.012 (4)	−0.019 (3)	−0.009 (3)
C10	0.064 (3)	0.071 (4)	0.052 (3)	0.001 (3)	−0.018 (3)	−0.017 (3)
C11	0.099 (4)	0.077 (4)	0.075 (4)	−0.009 (3)	−0.004 (3)	0.042 (3)
C12	0.041 (2)	0.052 (3)	0.053 (3)	0.002 (2)	0.013 (2)	−0.002 (2)
C13	0.053 (3)	0.035 (2)	0.039 (2)	0.003 (2)	0.006 (2)	−0.004 (2)
C14	0.047 (2)	0.029 (2)	0.040 (3)	0.000 (2)	0.0002 (19)	−0.0037 (19)
C15	0.053 (3)	0.041 (3)	0.045 (3)	−0.004 (2)	−0.001 (2)	−0.003 (2)
C16	0.085 (4)	0.069 (4)	0.047 (3)	−0.017 (3)	−0.004 (3)	−0.019 (3)
C17	0.106 (5)	0.095 (4)	0.037 (3)	−0.018 (4)	0.006 (3)	−0.019 (3)
C18	0.074 (3)	0.065 (3)	0.047 (3)	−0.008 (3)	0.016 (3)	−0.009 (3)
C19	0.065 (3)	0.079 (4)	0.074 (4)	−0.032 (3)	−0.014 (3)	−0.008 (3)

Geometric parameters (Å, º)

Cu1—O3	1.911 (3)	C4—C5	1.501 (6)
Cu1—O1	1.944 (3)	C4—H4A	0.9700
Cu1—N1	1.992 (3)	C4—H4B	0.9700
Cu1—N2	2.011 (3)	C5—C6	1.409 (6)
Cu1—O1^i	2.486 (3)	C5—C10	1.411 (6)
Cu1—O5	2.865 (4)	C6—C7	1.416 (6)
Cu1—Cu1^i	3.0901 (10)	C7—C8	1.382 (6)
N1—C4	1.452 (5)	C8—C9	1.357 (7)
N1—C1	1.481 (5)	C8—H8	0.9300
N1—H1	0.9100	C9—C10	1.374 (7)
N2—C12	1.484 (5)	C9—H9	0.9300
N2—C2	1.494 (5)	C10—H10	0.9300
N2—H2	0.9100	C11—H11A	0.9600
O1—C6	1.333 (4)	C11—H11B	0.9600
O1—Cu1^i	2.486 (3)	C11—H11C	0.9600
O2—C7	1.385 (5)	C12—C13	1.502 (6)
O2—C11	1.425 (5)	C12—H12A	0.9700
O3—C14	1.336 (5)	C12—H12B	0.9700
O4—C15	1.369 (5)	C13—C18	1.388 (6)
O4—C19	1.425 (5)	C13—C14	1.398 (6)
O6—H6B	0.89 (3)	C14—C15	1.416 (6)
O6—H6A	0.90 (3)	C15—C16	1.368 (6)
C1—C2	1.528 (6)	C16—C17	1.386 (7)
C1—H1B	0.9700	C16—H16	0.9300
C1—H1C	0.9700	C17—C18	1.361 (7)
C2—C3	1.522 (6)	C17—H17	0.9300
C2—H2A	0.9800	C18—H18	0.9300
C3—H3A	0.9600	C19—H19A	0.9600
C3—H3B	0.9600	C19—H19B	0.9600
C3—H3C	0.9600	C19—H19C	0.9600
O3—Cu1—O1	89.51 (11)	N1—C4—H4A	108.6
O3—Cu1—N1	177.11 (14)	C5—C4—H4A	108.6
O1—Cu1—N1	89.18 (13)	N1—C4—H4B	108.6
O3—Cu1—N2	94.07 (12)	C5—C4—H4B	108.6
O1—Cu1—N2	172.84 (12)	H4A—C4—H4B	107.6
N1—Cu1—N2	86.96 (14)	C6—C5—C10	119.6 (4)
O3—Cu1—O1^i	93.73 (11)	C6—C5—C4	121.8 (4)
O1—Cu1—O1^i	92.44 (10)	C10—C5—C4	118.5 (4)
N1—Cu1—O1^i	88.89 (12)	O1—C6—C5	124.6 (4)
N2—Cu1—O1^i	93.51 (11)	O1—C6—C7	118.8 (4)
O3—Cu1—O5	78.30 (12)	C5—C6—C7	116.5 (4)
O1—Cu1—O5	85.92 (12)	C8—C7—O2	123.6 (4)
N1—Cu1—O5	99.04 (13)	C8—C7—C6	122.8 (5)
N2—Cu1—O5	88.73 (13)	O2—C7—C6	113.6 (4)
O1^i—Cu1—O5	171.87 (10)	C9—C8—C7	119.3 (5)
O3—Cu1—Cu1^i	92.69 (9)	C9—C8—H8	120.4
O1—Cu1—Cu1^i	53.50 (8)	C7—C8—H8	120.4
N1—Cu1—Cu1^i	88.60 (10)	C8—C9—C10	120.9 (5)
N2—Cu1—Cu1^i	132.33 (10)	C8—C9—H9	119.6
O1^i—Cu1—Cu1^i	38.94 (6)	C10—C9—H9	119.6
O5—Cu1—Cu1^i	138.75 (9)	C9—C10—C5	120.9 (5)
C4—N1—C1	113.5 (3)	C9—C10—H10	119.5
C4—N1—Cu1	109.4 (3)	C5—C10—H10	119.5
C1—N1—Cu1	107.7 (3)	O2—C11—H11A	109.5
C4—N1—H1	108.7	O2—C11—H11B	109.5
C1—N1—H1	108.7	H11A—C11—H11B	109.5
Cu1—N1—H1	108.7	O2—C11—H11C	109.5
C12—N2—C2	114.5 (3)	H11A—C11—H11C	109.5
C12—N2—Cu1	112.7 (2)	H11B—C11—H11C	109.5
C2—N2—Cu1	106.8 (3)	N2—C12—C13	112.3 (3)
C12—N2—H2	107.5	N2—C12—H12A	109.2
C2—N2—H2	107.5	C13—C12—H12A	109.2
Cu1—N2—H2	107.5	N2—C12—H12B	109.2
C6—O1—Cu1	124.8 (3)	C13—C12—H12B	109.2
C6—O1—Cu1^i	118.1 (2)	H12A—C12—H12B	107.9
Cu1—O1—Cu1^i	87.56 (10)	C18—C13—C14	119.8 (4)
C7—O2—C11	118.4 (4)	C18—C13—C12	119.8 (4)
C14—O3—Cu1	125.6 (2)	C14—C13—C12	120.3 (4)
C15—O4—C19	117.6 (4)	O3—C14—C13	123.5 (4)
H6B—O6—H6A	104 (5)	O3—C14—C15	118.3 (4)
N1—C1—C2	110.6 (3)	C13—C14—C15	118.2 (4)
N1—C1—H1B	109.5	C16—C15—O4	125.2 (4)
C2—C1—H1B	109.5	C16—C15—C14	120.9 (4)
N1—C1—H1C	109.5	O4—C15—C14	113.9 (4)
C2—C1—H1C	109.5	C15—C16—C17	119.6 (5)
H1B—C1—H1C	108.1	C15—C16—H16	120.2
N2—C2—C3	113.5 (4)	C17—C16—H16	120.2
N2—C2—C1	106.5 (3)	C18—C17—C16	120.7 (5)
C3—C2—C1	111.5 (4)	C18—C17—H17	119.6
N2—C2—H2A	108.4	C16—C17—H17	119.6
C3—C2—H2A	108.4	C17—C18—C13	120.8 (5)
C1—C2—H2A	108.4	C17—C18—H18	119.6
C2—C3—H3A	109.5	C13—C18—H18	119.6
C2—C3—H3B	109.5	O4—C19—H19A	109.5
H3A—C3—H3B	109.5	O4—C19—H19B	109.5
C2—C3—H3C	109.5	H19A—C19—H19B	109.5
H3A—C3—H3C	109.5	O4—C19—H19C	109.5
H3B—C3—H3C	109.5	H19A—C19—H19C	109.5
N1—C4—C5	114.7 (3)	H19B—C19—H19C	109.5
O1—Cu1—N1—C4	−57.5 (3)	N1—C4—C5—C6	−35.7 (6)
N2—Cu1—N1—C4	116.5 (3)	N1—C4—C5—C10	149.3 (4)
O1^i—Cu1—N1—C4	−149.9 (3)	Cu1—O1—C6—C5	−12.4 (5)
O5—Cu1—N1—C4	28.3 (3)	Cu1^i—O1—C6—C5	95.9 (4)
Cu1^i—Cu1—N1—C4	−111.0 (3)	Cu1—O1—C6—C7	166.8 (3)
O1—Cu1—N1—C1	178.7 (3)	Cu1^i—O1—C6—C7	−85.0 (4)
N2—Cu1—N1—C1	−7.3 (3)	C10—C5—C6—O1	−179.9 (4)
O1^i—Cu1—N1—C1	86.2 (3)	C4—C5—C6—O1	5.2 (6)
O5—Cu1—N1—C1	−95.6 (3)	C10—C5—C6—C7	0.9 (6)
Cu1^i—Cu1—N1—C1	125.2 (3)	C4—C5—C6—C7	−174.0 (4)
O3—Cu1—N2—C12	30.6 (3)	C11—O2—C7—C8	17.4 (6)
N1—Cu1—N2—C12	−146.7 (3)	C11—O2—C7—C6	−163.4 (4)
O1^i—Cu1—N2—C12	124.6 (3)	O1—C6—C7—C8	179.5 (4)
O5—Cu1—N2—C12	−47.6 (3)	C5—C6—C7—C8	−1.3 (6)
Cu1^i—Cu1—N2—C12	128.0 (2)	O1—C6—C7—O2	0.3 (5)
O3—Cu1—N2—C2	157.2 (3)	C5—C6—C7—O2	179.6 (3)
N1—Cu1—N2—C2	−20.1 (3)	O2—C7—C8—C9	−179.6 (4)
O1^i—Cu1—N2—C2	−108.8 (2)	C6—C7—C8—C9	1.4 (7)
O5—Cu1—N2—C2	79.0 (3)	C7—C8—C9—C10	−1.1 (8)
Cu1^i—Cu1—N2—C2	−105.4 (2)	C8—C9—C10—C5	0.8 (8)
O3—Cu1—O1—C6	−143.2 (3)	C6—C5—C10—C9	−0.7 (7)
N1—Cu1—O1—C6	34.2 (3)	C4—C5—C10—C9	174.4 (5)
O1^i—Cu1—O1—C6	123.1 (3)	C2—N2—C12—C13	175.5 (4)
O5—Cu1—O1—C6	−64.9 (3)	Cu1—N2—C12—C13	−62.2 (4)
Cu1^i—Cu1—O1—C6	123.1 (3)	N2—C12—C13—C18	−130.7 (4)
O3—Cu1—O1—Cu1^i	93.72 (11)	N2—C12—C13—C14	52.0 (5)
N1—Cu1—O1—Cu1^i	−88.86 (11)	Cu1—O3—C14—C13	−28.9 (5)
O1^i—Cu1—O1—Cu1^i	0.0	Cu1—O3—C14—C15	150.6 (3)
O5—Cu1—O1—Cu1^i	172.02 (10)	C18—C13—C14—O3	179.6 (4)
O1—Cu1—O3—C14	−173.3 (3)	C12—C13—C14—O3	−3.1 (6)
N2—Cu1—O3—C14	12.9 (3)	C18—C13—C14—C15	0.1 (6)
O1^i—Cu1—O3—C14	−80.9 (3)	C12—C13—C14—C15	177.5 (4)
O5—Cu1—O3—C14	100.8 (3)	C19—O4—C15—C16	−1.4 (7)
Cu1^i—Cu1—O3—C14	−119.9 (3)	C19—O4—C15—C14	178.0 (4)
C4—N1—C1—C2	−87.8 (5)	O3—C14—C15—C16	180.0 (4)
Cu1—N1—C1—C2	33.5 (4)	C13—C14—C15—C16	−0.5 (6)
C12—N2—C2—C3	−69.3 (5)	O3—C14—C15—O4	0.5 (6)
Cu1—N2—C2—C3	165.2 (3)	C13—C14—C15—O4	180.0 (4)
C12—N2—C2—C1	167.6 (4)	O4—C15—C16—C17	−179.5 (5)
Cu1—N2—C2—C1	42.1 (4)	C14—C15—C16—C17	1.1 (8)
N1—C1—C2—N2	−51.0 (5)	C15—C16—C17—C18	−1.2 (9)
N1—C1—C2—C3	−175.3 (4)	C16—C17—C18—C13	0.8 (9)
C1—N1—C4—C5	−173.9 (4)	C14—C13—C18—C17	−0.3 (7)
Cu1—N1—C4—C5	65.7 (4)	C12—C13—C18—C17	−177.6 (5)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···O5	0.97	2.58	3.338 (6)	135
C1—H1C···O6^ii	0.97	2.56	3.427 (5)	149
O6—H6A···O3	0.90 (3)	1.87 (3)	2.723 (4)	158 (5)
O6—H6B···O2	0.89 (3)	2.20 (3)	3.036 (5)	156 (5)
O6—H6B···O1	0.89 (3)	2.24 (5)	2.907 (4)	131 (5)
N2—H2···O2^i	0.91	2.20	3.052 (4)	156
N1—H1···O4^i	0.91	2.43	3.155 (5)	137
N1—H1···O3^i	0.91	2.30	3.133 (4)	153

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