[Cu(phen)₂([mu]-IDA)Cu(phen)](ClO₄)₂·CH₃OH: tridentate and monodentate binding to two copper(II) species by a bridging ligand

The stoichiometric reaction of 1,10-phenanthroline (phen), imino­di­acetic acid (IDA-H₂) and Cu(ClO₄)₂ in a H₂O-CH₃OH (2:1) solution yields [mu]-imino­diacetato-2:1[kappa]⁴O,N,O':O''-tris(1,10-phenanthroline)-1[kappa]⁴N,N';2[kappa]²N,N'-dicopper(II) diperchlorate methanol solvate, [Cu₂(C₄H₅NO₄)(C₁₂H₈N₂)₃](ClO₄)₂·CH₃OH. The IDA ligand bridges the two Cu^II ions via a carboxyl­ate group and uses one further N and an O atom of the second carboxylate group to complete a fac-tridentate coordination at one Cu centre. A phen ligand completes a distorted square-pyramidal coordination at this metal atom, although there is weak coordination by a perchlorate O atom at a sixth position. The second Cu centre has a distorted trigonal-bipyramidal coordination to two phen moieties and a carboxyl­ate O atom.

S1. Comment

On account of the tridentate chelating property of the iminodiacetate (IDA) ligand and the flexibility of the Cu^II coordination stereochemistry, extensive research has been devoted to the structures of a variety of {Cu(IDA)(H₂O)₂}_n mixed-ligand complexes of Cu^II, with IDA-like groups as primary ligands and N-heterocyclic donors as auxiliary ligands (Bugella-Altamirano Choquesillo et al., 2002; Bugella-Altamirano González et al., 2002; Chatterjee & Stephen, 2001; de la Cueva et al., 1998). Such ternary complexes are bio-inorganic model compounds for mono- and dinuclear copper proteins. In this context, the Cu^II complex serves as a metal centre, while the tridentate IDA ligand or IDA derivative acts as a protein-like moiety and the N-heterocyclic donors play the role of substrate or inhibitor. All mixed-ligand complexes having a Cu:IDA-like:N-heterocyclic donor ratio of 1:1:2 exhibit an IDA-like ligand in a fac-chelating conformation. In contrast, complexes with an equimolar Cu:IDA-like:N-heterocyclic donor ratio (1:1:1) have the Cu^II ion in a distorted square-pyramidal coordination (4 + 1 type), or more rarely in an elongated octahedral coordination (4 + 2 or 4 + 1+1 type), and the IDA-like ligand adopts a mer-tridentate chelating role (Brandi-Blanco et al., 2003; Román-Alpiste et al., 1999). It was demonstrated that the stoichiometry and coordination character of the auxiliary ligand influence the coordination geometry of IDA. Compared with 2,2'-bipyridyl (Abarca et al., 1993), 1,10-phenanthroline (phen) possesses a stronger coordination ability. On this basis, we selected phen as the secondary ligand and synthesized the title dinuclear Cu^II complex, (I). \sch

The molecular structure and crystal packing of (I) are illustrated in Figs. 1–3. Selected geometric parameters are listed in Table 1. In this new mixed-ligand dinuclear complex, IDA serves as a bridging ligand linking two different moieties, Cu(phen)₂]²⁺ and [Cu(phen)]²⁺, via a carboxylate group. Unexpectedly, the two Cu^II ions exhibit totally different coordination geometries. The coordination polyhedron around Cu1 can be described as a distorted trigonal bipyramid, similar to those reported previously (Boys & Escobar, 1981; Anderson, 1975; Wei & Yang, 2004).

We are primarily interested in the coordination around Cu2, which shows a distorted square pyramid with a bidentate phen ligand and an O,N,O'-tridentate chelating IDA ligand. Atom O2 of IDA occupies the apical position. The atoms in the basal plane, N6, N7 from phen, and N5 and O4 from IDA, are displaced from the least-squares plane by −0.24 (2)–0.23 (3) Å, with a tetrahedral distortion. Atom Cu2 is displaced by 0.13 (4) Å from the mean plane towards atom O2, a distance almost twice as far as the value reported for compound (II), (2,2'-bipyridyl)(iminodiacetato)copper(II) hexahydrate (Abarca et al., 1993).

All phen ligands in (I) have a nearly planar conformation [maximum deviation 0.048 (6) Å]. Atom N7 of phen is in a trans position to atom N5 of IDA. The entry of atom N6 forces the IDA-Cu2 chelate ring to bend along the Cu2—N5 bond. Thus, the IDA ligand forms two five-membered chelate rings sharing the Cu2—N5 bond, with a dihedral angle of 71.34 (19)°, adopting a fac-tridentate chelating role in accordance with the 1:1:2 coordination rule. In addition, atom Cu2 is weakly coordinated by a sixth atom, O8 of the ClO₄⁻ anion, with a Cu2—O8 distance of 3.232 (11) Å (Fig. 3). Therefore, the overall coordination configuration around Cu2 is actually a distorted octahedron. Thus, IDA plays dual roles, as a tridentate chelate to Cu2 and as a bridge between Cu1 and Cu2.

In this dinuclear complex, it is noticeable that the source of the tridentate chelate atoms of IDA is different from those of the earlier reported complexes. In the latter, no matter which conformation IDA assumes, mer or fac, the carboxylate group is distorted by coordination so that the longer C—O bond is bound to the metal. However, in (I), one carboxylate group binds to two Cu atoms, and it is notable that the longer C—O bond is bound to Cu1 and the shorter to Cu2, where it is part of the tridentate coordination. This is in accord with the corresponding Cu—O bonds, that to Cu2 being longer than that to Cu1. Furthermore, while the binding to Cu1 takes place in the equatorial plane of the trigonal bipyramid, that to Cu2 lies on the Jahn-Teller axis (along with the perchlorate) and would be expected to lengthened.

Details of the hydrogen-bonding geometry of (I) are listed in Table 2. As illustrated in Fig. 2, the packing has a network of hydrogen bonds. These are mainly formed between methanol molecules, the N5 atom of IDA and the O atoms of the ClO₄⁻ anion.

Furthermore, a more interesting phenomenon observed is shown in Fig. 3. Pairs of phen ligands from neighbouring complexes are interleaved to form a stack along the b axis. Phen planes (1) (C13A—C24A/N3A/N4A) and (2) (C13—C24/N3/N4) are symmetry-related and oriented in a parallel fashion, the shortest interatomic distance C18—C20(1 − x, −y, 1 − z) being 3.294 (11) Å, which is shorter than the distance (3.4 Å) between neighbouring base pairs in DNA (Neidle, 1999), indicating significant π–π packing interactions. Phen plane (3) (C29—C40/N6/N7) is non-parallel to plane (1), the angle between them being 20.0 (5)°. The shortest interatomic distance, C19—C33(1 − x, −y, 1 − z), is 3.126 (11) Å, showing an even stronger π–π stacking interaction. Therefore, π–π stacking interactions dominate throughout the crystal of (I), stabilizing the crystal packing together with hydrogen-bonding interactions.

S2. Experimental

1,10-Phenanthroline (0.0793 g, 0.4 mmol), iminodiacetic acid (0.0266 g, 0.2 mmol) and Cu(ClO₄)₂ (0.0766 g, 0.4 mmol) were dissolved in an H₂O:CH₃OH (2:1) solution. The mixture was refluxed for 30 min with stirring and then cooled slowly, before being filtered and kept at room temperature. Blue block-shaped crystals of (I) grew after two weeks.

S3. Refinement

All H atoms were treated as riding atoms, with C—H(CH) = 0.93, C—H(CH₂) = 0.97, C—H(CH₃) = 0.96, N—H(NH) = 0.80 and O—H(OH) = 0.96 Å, and with U_iso(H) = 1.2U_eq(CH, NH, CH₂) or 1.5U_eq(CH₃, OH).

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 molecular structure of (I), with the atomic labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms, solvent molecules and counterions have been omitted for clarity.
	Fig. 2. The hydrogen-bonding network and octahedral coordination geometry around Cu2. [Symmetry code: (i) 1 + x, y, z]. Please clarify - symmetry code does not match that in Table 2 for N5···O13^i.
	Fig. 3. The π–π stacking interaction in (I). Solvent molecules and counterions have been omitted for clarity. [Symmetry code: (ii) 1 − x,-y,1 − z].

µ-iminodiacetato-1:2κ⁴O,N,O':O''-tris(1,10-phenanthroline)- 1κ⁴N,N';2κ²N,N'-dicopper(II) diperchlorate methanol solvate

Crystal data

[Cu2(C4H5NO4)(C12H8N2)3](ClO4)2·CH4O	Z = 2
Mr = 1029.74	F(000) = 1048
Triclinic, P1	Dx = 1.638 Mg m^−3
Hall symbol: -P 1	Melting point: none K
a = 10.511 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.707 (4) Å	Cell parameters from 2337 reflections
c = 15.551 (5) Å	θ = 2.3–22.0°
α = 72.785 (4)°	µ = 1.22 mm^−1
β = 82.336 (4)°	T = 297 K
γ = 78.048 (5)°	Block, blue
V = 2087.6 (11) Å^3	0.30 × 0.30 × 0.30 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer	7184 independent reflections
Radiation source: fine-focus sealed tube	4501 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ϕ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −11→12
Tmin = 0.710, Tmax = 0.710	k = −7→16
8597 measured reflections	l = −18→18

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)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.179	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0826P)^2] where P = (Fo^2 + 2Fc^2)/3
7184 reflections	(Δ/σ)max < 0.001
587 parameters	Δρmax = 0.71 e Å^−3
0 restraints	Δρmin = −0.43 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	0.52692 (7)	0.06800 (6)	0.21839 (5)	0.0445 (3)
Cu2	0.41049 (7)	0.44114 (6)	0.25825 (5)	0.0475 (3)
Cl1	0.1402 (2)	0.72913 (18)	0.27285 (13)	0.0705 (6)
Cl2	0.9659 (2)	0.21298 (19)	0.26841 (17)	0.0813 (6)
O1	0.3918 (4)	0.1873 (3)	0.1719 (3)	0.0452 (10)
O2	0.4595 (4)	0.2821 (3)	0.2437 (3)	0.0477 (11)
O3	0.4989 (6)	0.6167 (4)	0.0196 (3)	0.0880 (18)
O4	0.5131 (5)	0.5153 (4)	0.1597 (3)	0.0685 (14)
O5	0.1024 (6)	0.6730 (6)	0.3583 (4)	0.129 (3)
O6	0.0293 (8)	0.7674 (8)	0.2251 (5)	0.163 (4)
O7	0.1845 (8)	0.8141 (6)	0.2763 (7)	0.169 (4)
O8	0.2448 (8)	0.6728 (7)	0.2352 (6)	0.173 (4)
O9	0.8432 (8)	0.1944 (7)	0.3038 (6)	0.157 (3)
O10	1.0270 (6)	0.1373 (6)	0.2242 (5)	0.119 (2)
O11	1.0420 (9)	0.2326 (8)	0.3205 (7)	0.189 (4)
O12	0.9278 (10)	0.3097 (6)	0.2020 (6)	0.176 (4)
O13	0.9918 (8)	0.5167 (11)	0.2051 (7)	0.240 (6)
H13A	1.0346	0.4527	0.1926	0.361*
N1	0.6604 (5)	0.1122 (4)	0.1192 (3)	0.0462 (13)
N2	0.5346 (5)	−0.0461 (4)	0.1473 (3)	0.0419 (12)
N3	0.4122 (5)	0.0051 (4)	0.3236 (3)	0.0450 (13)
N4	0.6684 (5)	−0.0125 (4)	0.3069 (4)	0.0469 (13)
N5	0.2834 (5)	0.4564 (4)	0.1685 (3)	0.0468 (13)
H5	0.2110	0.4748	0.1874	0.056*
N6	0.2935 (5)	0.4191 (4)	0.3758 (3)	0.0450 (13)
N7	0.5441 (5)	0.4197 (4)	0.3433 (3)	0.0456 (13)
C1	0.7217 (6)	0.1912 (5)	0.1079 (5)	0.0575 (18)
H1	0.6940	0.2359	0.1441	0.069*
C2	0.8237 (7)	0.2086 (6)	0.0451 (5)	0.066 (2)
H2	0.8681	0.2622	0.0406	0.079*
C3	0.8597 (7)	0.1466 (7)	−0.0110 (5)	0.065 (2)
H3	0.9264	0.1603	−0.0561	0.078*
C4	0.7986 (6)	0.0631 (6)	−0.0021 (4)	0.0517 (18)
C5	0.6986 (6)	0.0493 (5)	0.0649 (4)	0.0428 (15)
C6	0.6304 (6)	−0.0360 (5)	0.0789 (4)	0.0418 (15)
C7	0.8281 (6)	−0.0054 (7)	−0.0568 (4)	0.064 (2)
H7	0.8946	0.0042	−0.1028	0.077*
C8	0.7646 (7)	−0.0831 (7)	−0.0454 (5)	0.066 (2)
H8	0.7868	−0.1260	−0.0836	0.079*
C9	0.6633 (6)	−0.1016 (6)	0.0243 (4)	0.0517 (17)
C10	0.5919 (7)	−0.1815 (6)	0.0416 (5)	0.0593 (19)
H10	0.6093	−0.2269	0.0057	0.071*
C11	0.4988 (7)	−0.1931 (6)	0.1090 (5)	0.062 (2)
H11	0.4530	−0.2475	0.1212	0.074*
C12	0.4703 (6)	−0.1238 (5)	0.1611 (4)	0.0492 (17)
H12	0.4040	−0.1320	0.2073	0.059*
C13	0.7968 (7)	−0.0233 (6)	0.2963 (6)	0.067 (2)
H13	0.8361	0.0088	0.2407	0.080*
C14	0.8743 (8)	−0.0803 (7)	0.3650 (7)	0.082 (3)
H14	0.9646	−0.0876	0.3554	0.098*
C15	0.8183 (11)	−0.1259 (6)	0.4465 (7)	0.081 (3)
H15	0.8703	−0.1627	0.4937	0.098*
C16	0.6839 (9)	−0.1180 (5)	0.4604 (6)	0.064 (2)
C17	0.6148 (7)	−0.0626 (5)	0.3865 (4)	0.0451 (16)
C18	0.4768 (7)	−0.0517 (5)	0.3947 (4)	0.0477 (17)
C19	0.6167 (11)	−0.1647 (6)	0.5433 (5)	0.077 (3)
H19	0.6639	−0.2022	0.5928	0.093*
C20	0.4893 (11)	−0.1559 (6)	0.5512 (5)	0.076 (3)
H20	0.4481	−0.1862	0.6066	0.092*
C21	0.4125 (9)	−0.1011 (5)	0.4769 (5)	0.0579 (19)
C22	0.2786 (10)	−0.0881 (6)	0.4794 (6)	0.076 (3)
H22	0.2316	−0.1187	0.5320	0.092*
C23	0.2161 (8)	−0.0317 (7)	0.4064 (6)	0.078 (2)
H23	0.1260	−0.0247	0.4081	0.093*
C24	0.2850 (7)	0.0169 (6)	0.3277 (5)	0.0573 (18)
H24	0.2403	0.0579	0.2779	0.069*
C25	0.3888 (6)	0.2706 (5)	0.1923 (4)	0.0413 (15)
C26	0.2836 (6)	0.3577 (5)	0.1498 (5)	0.0539 (18)
H26A	0.2939	0.3683	0.0849	0.065*
H26B	0.1995	0.3372	0.1713	0.065*
C27	0.3194 (8)	0.5383 (5)	0.0888 (4)	0.064 (2)
H27A	0.2584	0.6023	0.0873	0.077*
H27B	0.3122	0.5190	0.0347	0.077*
C28	0.4556 (8)	0.5567 (6)	0.0885 (6)	0.066 (2)
C29	0.1672 (6)	0.4183 (5)	0.3893 (5)	0.0527 (17)
H29	0.1181	0.4332	0.3400	0.063*
C30	0.1058 (7)	0.3952 (6)	0.4769 (6)	0.064 (2)
H30	0.0169	0.3937	0.4849	0.077*
C31	0.1730 (7)	0.3756 (6)	0.5484 (5)	0.063 (2)
H31	0.1312	0.3625	0.6062	0.075*
C32	0.3066 (7)	0.3751 (5)	0.5357 (5)	0.0522 (17)
C33	0.3618 (6)	0.3983 (5)	0.4478 (4)	0.0435 (15)
C34	0.4986 (6)	0.3970 (5)	0.4303 (4)	0.0436 (15)
C35	0.3912 (9)	0.3505 (5)	0.6063 (5)	0.066 (2)
H35	0.3556	0.3354	0.6658	0.079*
C36	0.5209 (8)	0.3482 (6)	0.5904 (5)	0.066 (2)
H36	0.5733	0.3312	0.6383	0.079*
C37	0.5763 (7)	0.3717 (5)	0.5009 (5)	0.0552 (18)
C38	0.7118 (7)	0.3691 (6)	0.4760 (6)	0.067 (2)
H38	0.7698	0.3522	0.5206	0.081*
C39	0.7567 (8)	0.3907 (6)	0.3892 (6)	0.074 (2)
H39	0.8455	0.3888	0.3733	0.089*
C40	0.6704 (7)	0.4159 (6)	0.3235 (5)	0.062 (2)
H40	0.7024	0.4308	0.2632	0.074*
C41	0.8982 (17)	0.5854 (13)	0.1220 (16)	0.304 (14)
H41A	0.8369	0.6385	0.1416	0.457*
H41B	0.8520	0.5405	0.1061	0.457*
H41C	0.9517	0.6168	0.0704	0.457*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0514 (5)	0.0414 (5)	0.0408 (5)	−0.0131 (4)	0.0031 (4)	−0.0108 (4)
Cu2	0.0504 (5)	0.0492 (5)	0.0461 (5)	−0.0153 (4)	0.0052 (4)	−0.0176 (4)
Cl1	0.0690 (13)	0.0864 (15)	0.0556 (12)	−0.0275 (12)	0.0082 (10)	−0.0150 (11)
Cl2	0.0690 (14)	0.0806 (16)	0.0964 (17)	−0.0165 (12)	0.0146 (12)	−0.0348 (14)
O1	0.053 (3)	0.039 (3)	0.047 (3)	−0.011 (2)	−0.007 (2)	−0.013 (2)
O2	0.062 (3)	0.043 (3)	0.041 (2)	−0.002 (2)	−0.017 (2)	−0.016 (2)
O3	0.141 (5)	0.070 (4)	0.059 (3)	−0.054 (4)	0.033 (3)	−0.021 (3)
O4	0.070 (3)	0.083 (4)	0.052 (3)	−0.031 (3)	0.011 (3)	−0.013 (3)
O5	0.100 (5)	0.182 (7)	0.065 (4)	−0.040 (5)	0.000 (3)	0.030 (4)
O6	0.135 (6)	0.255 (11)	0.094 (5)	−0.036 (7)	−0.054 (5)	−0.020 (6)
O7	0.141 (7)	0.113 (6)	0.275 (10)	−0.072 (5)	0.051 (7)	−0.082 (7)
O8	0.169 (7)	0.164 (8)	0.187 (8)	−0.027 (6)	0.087 (6)	−0.097 (7)
O9	0.147 (6)	0.174 (8)	0.185 (7)	−0.079 (6)	0.088 (6)	−0.112 (6)
O10	0.086 (4)	0.152 (6)	0.130 (5)	0.022 (4)	−0.003 (4)	−0.089 (5)
O11	0.170 (8)	0.239 (11)	0.215 (9)	0.034 (7)	−0.076 (7)	−0.169 (9)
O12	0.228 (9)	0.095 (6)	0.177 (8)	−0.026 (6)	−0.013 (7)	0.001 (6)
O13	0.110 (6)	0.386 (18)	0.187 (9)	0.035 (9)	−0.040 (7)	−0.064 (10)
N1	0.043 (3)	0.048 (3)	0.044 (3)	−0.012 (3)	−0.001 (2)	−0.005 (3)
N2	0.047 (3)	0.039 (3)	0.041 (3)	−0.010 (3)	0.003 (2)	−0.015 (2)
N3	0.055 (3)	0.049 (3)	0.038 (3)	−0.020 (3)	0.006 (3)	−0.018 (3)
N4	0.056 (4)	0.035 (3)	0.053 (4)	−0.008 (3)	−0.010 (3)	−0.014 (3)
N5	0.052 (3)	0.036 (3)	0.047 (3)	0.000 (3)	−0.003 (2)	−0.011 (3)
N6	0.046 (3)	0.039 (3)	0.052 (3)	−0.007 (3)	0.003 (3)	−0.020 (3)
N7	0.043 (3)	0.053 (3)	0.053 (3)	−0.012 (3)	−0.003 (3)	−0.030 (3)
C1	0.059 (4)	0.053 (4)	0.056 (4)	−0.016 (4)	−0.002 (4)	−0.006 (4)
C2	0.054 (5)	0.075 (6)	0.062 (5)	−0.025 (4)	−0.005 (4)	0.001 (5)
C3	0.044 (4)	0.092 (6)	0.040 (4)	−0.015 (4)	−0.005 (3)	0.015 (4)
C4	0.043 (4)	0.066 (5)	0.033 (4)	−0.008 (4)	0.001 (3)	0.003 (4)
C5	0.042 (4)	0.047 (4)	0.035 (3)	0.000 (3)	−0.008 (3)	−0.008 (3)
C6	0.036 (3)	0.048 (4)	0.035 (3)	0.000 (3)	−0.007 (3)	−0.006 (3)
C7	0.039 (4)	0.104 (7)	0.040 (4)	−0.001 (4)	0.001 (3)	−0.015 (4)
C8	0.064 (5)	0.089 (6)	0.045 (4)	−0.002 (5)	−0.003 (4)	−0.027 (4)
C9	0.052 (4)	0.067 (5)	0.036 (4)	−0.001 (4)	−0.004 (3)	−0.020 (4)
C10	0.068 (5)	0.066 (5)	0.054 (5)	−0.009 (4)	−0.011 (4)	−0.033 (4)
C11	0.077 (5)	0.054 (5)	0.069 (5)	−0.023 (4)	−0.008 (4)	−0.029 (4)
C12	0.051 (4)	0.051 (4)	0.048 (4)	−0.013 (4)	−0.003 (3)	−0.015 (3)
C13	0.060 (5)	0.055 (5)	0.087 (6)	−0.008 (4)	−0.015 (4)	−0.022 (4)
C14	0.057 (5)	0.072 (6)	0.120 (8)	0.007 (5)	−0.036 (6)	−0.033 (6)
C15	0.120 (8)	0.044 (5)	0.086 (7)	0.011 (5)	−0.052 (6)	−0.025 (5)
C16	0.089 (6)	0.039 (4)	0.075 (6)	−0.002 (4)	−0.026 (5)	−0.029 (4)
C17	0.058 (4)	0.032 (4)	0.049 (4)	−0.007 (3)	−0.012 (3)	−0.015 (3)
C18	0.079 (5)	0.032 (4)	0.035 (4)	−0.014 (4)	0.000 (3)	−0.012 (3)
C19	0.149 (9)	0.032 (4)	0.046 (5)	−0.003 (6)	−0.012 (6)	−0.011 (4)
C20	0.153 (9)	0.034 (4)	0.039 (5)	−0.018 (6)	0.011 (6)	−0.012 (4)
C21	0.102 (6)	0.034 (4)	0.044 (4)	−0.023 (4)	0.007 (4)	−0.019 (3)
C22	0.116 (8)	0.060 (5)	0.060 (5)	−0.043 (5)	0.032 (5)	−0.026 (5)
C23	0.071 (5)	0.100 (7)	0.078 (6)	−0.040 (5)	0.022 (5)	−0.045 (6)
C24	0.060 (5)	0.067 (5)	0.051 (4)	−0.020 (4)	0.002 (4)	−0.022 (4)
C25	0.052 (4)	0.041 (4)	0.030 (3)	−0.015 (3)	0.005 (3)	−0.007 (3)
C26	0.052 (4)	0.042 (4)	0.066 (5)	−0.006 (3)	−0.021 (3)	−0.008 (4)
C27	0.093 (6)	0.042 (4)	0.049 (4)	−0.014 (4)	−0.006 (4)	0.000 (4)
C28	0.093 (6)	0.053 (5)	0.057 (5)	−0.024 (5)	0.020 (5)	−0.026 (4)
C29	0.047 (4)	0.054 (4)	0.056 (4)	−0.004 (3)	−0.004 (3)	−0.017 (4)
C30	0.046 (4)	0.061 (5)	0.080 (6)	−0.011 (4)	0.011 (4)	−0.018 (4)
C31	0.069 (5)	0.061 (5)	0.058 (5)	−0.018 (4)	0.024 (4)	−0.024 (4)
C32	0.069 (5)	0.040 (4)	0.054 (4)	−0.013 (4)	0.001 (4)	−0.023 (3)
C33	0.059 (4)	0.034 (4)	0.042 (4)	−0.010 (3)	0.000 (3)	−0.018 (3)
C34	0.050 (4)	0.042 (4)	0.048 (4)	−0.009 (3)	−0.006 (3)	−0.025 (3)
C35	0.100 (6)	0.051 (5)	0.049 (5)	−0.015 (5)	0.001 (4)	−0.019 (4)
C36	0.084 (6)	0.065 (5)	0.062 (5)	−0.015 (5)	−0.015 (4)	−0.032 (4)
C37	0.067 (5)	0.043 (4)	0.066 (5)	−0.017 (4)	−0.001 (4)	−0.027 (4)
C38	0.064 (5)	0.063 (5)	0.086 (6)	−0.005 (4)	−0.029 (5)	−0.032 (5)
C39	0.053 (5)	0.091 (6)	0.095 (7)	−0.015 (4)	−0.003 (5)	−0.052 (5)
C40	0.052 (4)	0.076 (5)	0.068 (5)	−0.020 (4)	0.006 (4)	−0.036 (4)
C41	0.168 (15)	0.164 (16)	0.54 (4)	−0.041 (13)	−0.05 (2)	−0.02 (2)

Geometric parameters (Å, º)

Cu1—O1	1.956 (4)	C10—C11	1.332 (9)
Cu1—N1	1.984 (5)	C10—H10	0.9300
Cu1—N3	1.986 (5)	C11—C12	1.386 (9)
Cu1—N4	2.071 (5)	C11—H11	0.9300
Cu1—N2	2.150 (5)	C12—H12	0.9300
Cu2—O4	1.907 (5)	C13—C14	1.374 (10)
Cu2—N7	1.975 (5)	C13—H13	0.9300
Cu2—N5	1.997 (5)	C14—C15	1.352 (11)
Cu2—N6	2.043 (5)	C14—H14	0.9300
Cu2—O2	2.205 (4)	C15—C16	1.386 (11)
Cl1—O7	1.358 (7)	C15—H15	0.9300
Cl1—O8	1.375 (7)	C16—C17	1.380 (9)
Cl1—O5	1.376 (5)	C16—C19	1.424 (11)
Cl1—O6	1.390 (7)	C17—C18	1.420 (9)
Cl2—O11	1.326 (8)	C18—C21	1.412 (9)
Cl2—O9	1.377 (7)	C19—C20	1.311 (11)
Cl2—O10	1.410 (6)	C19—H19	0.9300
Cl2—O12	1.437 (8)	C20—C21	1.427 (11)
O1—C25	1.266 (7)	C20—H20	0.9300
O2—C25	1.224 (7)	C21—C22	1.378 (11)
O3—C28	1.238 (8)	C22—C23	1.337 (11)
O4—C28	1.256 (9)	C22—H22	0.9300
O13—C41	1.66 (2)	C23—C24	1.395 (9)
O13—H13A	0.9600	C23—H23	0.9300
N1—C1	1.328 (8)	C24—H24	0.9300
N1—C5	1.348 (8)	C25—C26	1.506 (8)
N2—C12	1.326 (7)	C26—H26A	0.9700
N2—C6	1.360 (7)	C26—H26B	0.9700
N3—C24	1.309 (8)	C27—C28	1.504 (10)
N3—C18	1.327 (8)	C27—H27A	0.9700
N4—C13	1.320 (8)	C27—H27B	0.9700
N4—C17	1.339 (7)	C29—C30	1.402 (9)
N5—C26	1.465 (8)	C29—H29	0.9300
N5—C27	1.472 (7)	C30—C31	1.327 (9)
N5—H5	0.7965	C30—H30	0.9300
N6—C29	1.318 (7)	C31—C32	1.391 (9)
N6—C33	1.338 (8)	C31—H31	0.9300
N7—C40	1.316 (8)	C32—C33	1.382 (8)
N7—C34	1.340 (7)	C32—C35	1.425 (9)
C1—C2	1.361 (9)	C33—C34	1.425 (8)
C1—H1	0.9300	C34—C37	1.375 (9)
C2—C3	1.357 (10)	C35—C36	1.348 (10)
C2—H2	0.9300	C35—H35	0.9300
C3—C4	1.390 (10)	C36—C37	1.406 (9)
C3—H3	0.9300	C36—H36	0.9300
C4—C5	1.378 (8)	C37—C38	1.421 (10)
C4—C7	1.408 (10)	C38—C39	1.336 (10)
C5—C6	1.442 (8)	C38—H38	0.9300
C6—C9	1.377 (9)	C39—C40	1.376 (10)
C7—C8	1.328 (10)	C39—H39	0.9300
C7—H7	0.9300	C40—H40	0.9300
C8—C9	1.420 (9)	C41—H41A	0.9600
C8—H8	0.9300	C41—H41B	0.9600
C9—C10	1.395 (9)	C41—H41C	0.9600
O1—Cu1—N1	94.56 (18)	N4—C13—C14	122.0 (8)
O1—Cu1—N3	93.7 (2)	N4—C13—H13	119.0
N1—Cu1—N3	171.7 (2)	C14—C13—H13	119.0
O1—Cu1—N4	152.25 (19)	C15—C14—C13	119.6 (8)
N1—Cu1—N4	91.9 (2)	C15—C14—H14	120.2
N3—Cu1—N4	81.1 (2)	C13—C14—H14	120.2
O1—Cu1—N2	109.21 (18)	C14—C15—C16	120.5 (8)
N1—Cu1—N2	80.3 (2)	C14—C15—H15	119.7
N3—Cu1—N2	96.21 (19)	C16—C15—H15	119.7
N4—Cu1—N2	98.48 (19)	C17—C16—C15	115.7 (8)
O4—Cu2—N7	92.2 (2)	C17—C16—C19	119.9 (8)
O4—Cu2—N5	86.5 (2)	C15—C16—C19	124.4 (9)
N7—Cu2—N5	176.2 (2)	N4—C17—C16	124.4 (7)
O4—Cu2—N6	156.0 (2)	N4—C17—C18	116.3 (6)
N7—Cu2—N6	81.2 (2)	C16—C17—C18	119.3 (7)
N5—Cu2—N6	101.3 (2)	N3—C18—C21	122.1 (7)
O4—Cu2—O2	102.52 (19)	N3—C18—C17	118.1 (6)
N7—Cu2—O2	95.05 (18)	C21—C18—C17	119.8 (7)
N5—Cu2—O2	81.80 (18)	C20—C19—C16	121.2 (8)
N6—Cu2—O2	101.02 (17)	C20—C19—H19	119.4
O7—Cl1—O8	104.6 (5)	C16—C19—H19	119.4
O7—Cl1—O5	110.5 (6)	C19—C20—C21	121.6 (8)
O8—Cl1—O5	111.0 (5)	C19—C20—H20	119.2
O7—Cl1—O6	105.5 (6)	C21—C20—H20	119.2
O8—Cl1—O6	117.6 (6)	C22—C21—C18	116.5 (7)
O5—Cl1—O6	107.5 (4)	C22—C21—C20	125.3 (8)
O11—Cl2—O9	118.3 (6)	C18—C21—C20	118.1 (8)
O11—Cl2—O10	114.2 (5)	C23—C22—C21	120.2 (7)
O9—Cl2—O10	109.6 (4)	C23—C22—H22	119.9
O11—Cl2—O12	105.8 (6)	C21—C22—H22	119.9
O9—Cl2—O12	98.2 (6)	C22—C23—C24	120.6 (8)
O10—Cl2—O12	109.2 (5)	C22—C23—H23	119.7
C25—O1—Cu1	118.7 (4)	C24—C23—H23	119.7
C25—O2—Cu2	110.7 (4)	N3—C24—C23	120.2 (7)
C28—O4—Cu2	114.5 (5)	N3—C24—H24	119.9
C41—O13—H13A	109.1	C23—C24—H24	119.9
C1—N1—C5	118.7 (5)	O2—C25—O1	125.4 (6)
C1—N1—Cu1	125.6 (5)	O2—C25—C26	120.9 (6)
C5—N1—Cu1	115.4 (4)	O1—C25—C26	113.7 (6)
C12—N2—C6	117.4 (5)	N5—C26—C25	114.4 (5)
C12—N2—Cu1	132.5 (4)	N5—C26—H26A	108.7
C6—N2—Cu1	110.1 (4)	C25—C26—H26A	108.7
C24—N3—C18	120.4 (6)	N5—C26—H26B	108.7
C24—N3—Cu1	126.2 (5)	C25—C26—H26B	108.7
C18—N3—Cu1	113.4 (4)	H26A—C26—H26B	107.6
C13—N4—C17	117.7 (6)	N5—C27—C28	112.6 (6)
C13—N4—Cu1	131.1 (5)	N5—C27—H27A	109.1
C17—N4—Cu1	111.1 (4)	C28—C27—H27A	109.1
C26—N5—C27	114.0 (5)	N5—C27—H27B	109.1
C26—N5—Cu2	111.8 (4)	C28—C27—H27B	109.1
C27—N5—Cu2	105.3 (4)	H27A—C27—H27B	107.8
C26—N5—H5	106.2	O3—C28—O4	125.3 (8)
C27—N5—H5	108.9	O3—C28—C27	117.0 (8)
Cu2—N5—H5	110.6	O4—C28—C27	117.6 (7)
C29—N6—C33	118.3 (6)	N6—C29—C30	121.0 (6)
C29—N6—Cu2	129.8 (5)	N6—C29—H29	119.5
C33—N6—Cu2	111.8 (4)	C30—C29—H29	119.5
C40—N7—C34	118.7 (6)	C31—C30—C29	120.8 (7)
C40—N7—Cu2	126.9 (5)	C31—C30—H30	119.6
C34—N7—Cu2	114.0 (4)	C29—C30—H30	119.6
N1—C1—C2	122.0 (7)	C30—C31—C32	119.1 (7)
N1—C1—H1	119.0	C30—C31—H31	120.5
C2—C1—H1	119.0	C32—C31—H31	120.5
C3—C2—C1	119.0 (7)	C33—C32—C31	117.5 (7)
C3—C2—H2	120.5	C33—C32—C35	117.5 (7)
C1—C2—H2	120.5	C31—C32—C35	124.9 (7)
C2—C3—C4	121.1 (7)	N6—C33—C32	123.2 (6)
C2—C3—H3	119.4	N6—C33—C34	116.4 (6)
C4—C3—H3	119.4	C32—C33—C34	120.3 (6)
C5—C4—C3	116.0 (7)	N7—C34—C37	123.7 (6)
C5—C4—C7	118.4 (7)	N7—C34—C33	116.4 (6)
C3—C4—C7	125.5 (7)	C37—C34—C33	119.9 (6)
N1—C5—C4	123.0 (6)	C36—C35—C32	122.7 (7)
N1—C5—C6	117.4 (5)	C36—C35—H35	118.7
C4—C5—C6	119.6 (6)	C32—C35—H35	118.7
N2—C6—C9	123.5 (6)	C35—C36—C37	119.4 (7)
N2—C6—C5	116.4 (6)	C35—C36—H36	120.3
C9—C6—C5	120.1 (6)	C37—C36—H36	120.3
C8—C7—C4	122.5 (6)	C34—C37—C36	120.2 (7)
C8—C7—H7	118.8	C34—C37—C38	115.4 (7)
C4—C7—H7	118.8	C36—C37—C38	124.4 (7)
C7—C8—C9	120.8 (7)	C39—C38—C37	120.6 (7)
C7—C8—H8	119.6	C39—C38—H38	119.7
C9—C8—H8	119.6	C37—C38—H38	119.7
C6—C9—C10	116.6 (6)	C38—C39—C40	119.4 (7)
C6—C9—C8	118.6 (7)	C38—C39—H39	120.3
C10—C9—C8	124.8 (7)	C40—C39—H39	120.3
C11—C10—C9	120.5 (7)	N7—C40—C39	122.2 (7)
C11—C10—H10	119.7	N7—C40—H40	118.9
C9—C10—H10	119.7	C39—C40—H40	118.9
C10—C11—C12	119.8 (7)	O13—C41—H41A	109.5
C10—C11—H11	120.1	O13—C41—H41B	109.5
C12—C11—H11	120.1	H41A—C41—H41B	109.5
N2—C12—C11	122.2 (6)	O13—C41—H41C	109.5
N2—C12—H12	118.9	H41A—C41—H41C	109.5
C11—C12—H12	118.9	H41B—C41—H41C	109.5
N1—Cu1—O1—C25	−85.2 (4)	C9—C10—C11—C12	1.7 (11)
N3—Cu1—O1—C25	95.6 (4)	C6—N2—C12—C11	0.3 (9)
N4—Cu1—O1—C25	17.7 (6)	Cu1—N2—C12—C11	−175.2 (5)
N2—Cu1—O1—C25	−166.5 (4)	C10—C11—C12—N2	−1.2 (11)
O4—Cu2—O2—C25	−86.8 (4)	C17—N4—C13—C14	−2.4 (10)
N7—Cu2—O2—C25	179.8 (4)	Cu1—N4—C13—C14	179.5 (5)
N5—Cu2—O2—C25	−2.3 (4)	N4—C13—C14—C15	−1.1 (12)
N6—Cu2—O2—C25	97.8 (4)	C13—C14—C15—C16	2.0 (12)
N7—Cu2—O4—C28	−172.1 (5)	C14—C15—C16—C17	0.5 (11)
N5—Cu2—O4—C28	11.4 (5)	C14—C15—C16—C19	178.9 (7)
N6—Cu2—O4—C28	−98.9 (7)	C13—N4—C17—C16	5.2 (9)
O2—Cu2—O4—C28	92.2 (5)	Cu1—N4—C17—C16	−176.3 (5)
O1—Cu1—N1—C1	71.8 (5)	C13—N4—C17—C18	−178.3 (6)
N4—Cu1—N1—C1	−81.2 (5)	Cu1—N4—C17—C18	0.2 (7)
N2—Cu1—N1—C1	−179.4 (5)	C15—C16—C17—N4	−4.2 (10)
O1—Cu1—N1—C5	−114.8 (4)	C19—C16—C17—N4	177.2 (6)
N4—Cu1—N1—C5	92.2 (4)	C15—C16—C17—C18	179.4 (6)
N2—Cu1—N1—C5	−6.0 (4)	C19—C16—C17—C18	0.9 (9)
O1—Cu1—N2—C12	−87.5 (6)	C24—N3—C18—C21	−0.1 (9)
N1—Cu1—N2—C12	−179.0 (6)	Cu1—N3—C18—C21	178.6 (5)
N3—Cu1—N2—C12	8.7 (6)	C24—N3—C18—C17	179.6 (6)
N4—Cu1—N2—C12	90.5 (6)	Cu1—N3—C18—C17	−1.7 (7)
O1—Cu1—N2—C6	96.7 (4)	N4—C17—C18—N3	1.0 (8)
N1—Cu1—N2—C6	5.2 (4)	C16—C17—C18—N3	177.7 (5)
N3—Cu1—N2—C6	−167.1 (4)	N4—C17—C18—C21	−179.3 (5)
N4—Cu1—N2—C6	−85.3 (4)	C16—C17—C18—C21	−2.6 (9)
O1—Cu1—N3—C24	27.4 (5)	C17—C16—C19—C20	−0.2 (11)
N4—Cu1—N3—C24	180.0 (6)	C15—C16—C19—C20	−178.6 (8)
N2—Cu1—N3—C24	−82.4 (5)	C16—C19—C20—C21	1.2 (12)
O1—Cu1—N3—C18	−151.2 (4)	N3—C18—C21—C22	0.5 (9)
N4—Cu1—N3—C18	1.3 (4)	C17—C18—C21—C22	−179.2 (6)
N2—Cu1—N3—C18	99.0 (4)	N3—C18—C21—C20	−176.7 (6)
O1—Cu1—N4—C13	−101.6 (7)	C17—C18—C21—C20	3.6 (9)
N1—Cu1—N4—C13	1.9 (6)	C19—C20—C21—C22	−179.9 (8)
N3—Cu1—N4—C13	177.4 (6)	C19—C20—C21—C18	−3.0 (11)
N2—Cu1—N4—C13	82.4 (6)	C18—C21—C22—C23	0.4 (11)
O1—Cu1—N4—C17	80.2 (5)	C20—C21—C22—C23	177.4 (7)
N1—Cu1—N4—C17	−176.3 (4)	C21—C22—C23—C24	−1.7 (12)
N3—Cu1—N4—C17	−0.8 (4)	C18—N3—C24—C23	−1.2 (10)
N2—Cu1—N4—C17	−95.8 (4)	Cu1—N3—C24—C23	−179.8 (5)
O4—Cu2—N5—C26	108.2 (4)	C22—C23—C24—N3	2.1 (11)
N6—Cu2—N5—C26	−94.6 (4)	Cu2—O2—C25—O1	−178.6 (5)
O2—Cu2—N5—C26	5.0 (4)	Cu2—O2—C25—C26	−1.2 (7)
O4—Cu2—N5—C27	−16.1 (4)	Cu1—O1—C25—O2	−4.5 (8)
N6—Cu2—N5—C27	141.0 (4)	Cu1—O1—C25—C26	177.9 (4)
O2—Cu2—N5—C27	−119.3 (4)	C27—N5—C26—C25	112.2 (6)
O4—Cu2—N6—C29	105.4 (7)	Cu2—N5—C26—C25	−7.1 (7)
N7—Cu2—N6—C29	−179.1 (6)	O2—C25—C26—N5	5.6 (8)
N5—Cu2—N6—C29	−1.9 (6)	O1—C25—C26—N5	−176.7 (5)
O2—Cu2—N6—C29	−85.6 (6)	C26—N5—C27—C28	−104.6 (6)
O4—Cu2—N6—C33	−77.8 (7)	Cu2—N5—C27—C28	18.3 (6)
N7—Cu2—N6—C33	−2.3 (4)	Cu2—O4—C28—O3	172.4 (6)
N5—Cu2—N6—C33	174.9 (4)	Cu2—O4—C28—C27	−3.0 (8)
O2—Cu2—N6—C33	91.1 (4)	N5—C27—C28—O3	172.8 (6)
O4—Cu2—N7—C40	−26.6 (6)	N5—C27—C28—O4	−11.4 (9)
N6—Cu2—N7—C40	176.5 (6)	C33—N6—C29—C30	−0.6 (9)
O2—Cu2—N7—C40	76.1 (6)	Cu2—N6—C29—C30	176.0 (5)
O4—Cu2—N7—C34	160.1 (4)	N6—C29—C30—C31	1.3 (11)
N6—Cu2—N7—C34	3.3 (4)	C29—C30—C31—C32	−2.0 (11)
O2—Cu2—N7—C34	−97.1 (4)	C30—C31—C32—C33	1.9 (10)
C5—N1—C1—C2	−1.8 (9)	C30—C31—C32—C35	−176.9 (7)
Cu1—N1—C1—C2	171.4 (5)	C29—N6—C33—C32	0.6 (9)
N1—C1—C2—C3	3.5 (10)	Cu2—N6—C33—C32	−176.6 (5)
C1—C2—C3—C4	−3.3 (11)	C29—N6—C33—C34	178.2 (6)
C2—C3—C4—C5	1.5 (10)	Cu2—N6—C33—C34	1.0 (7)
C2—C3—C4—C7	179.7 (7)	C31—C32—C33—N6	−1.2 (10)
C1—N1—C5—C4	−0.1 (9)	C35—C32—C33—N6	177.6 (6)
Cu1—N1—C5—C4	−174.0 (4)	C31—C32—C33—C34	−178.8 (6)
C1—N1—C5—C6	179.8 (5)	C35—C32—C33—C34	0.0 (9)
Cu1—N1—C5—C6	5.9 (7)	C40—N7—C34—C37	1.2 (10)
C3—C4—C5—N1	0.2 (9)	Cu2—N7—C34—C37	175.0 (5)
C7—C4—C5—N1	−178.1 (6)	C40—N7—C34—C33	−177.6 (6)
C3—C4—C5—C6	−179.7 (5)	Cu2—N7—C34—C33	−3.7 (7)
C7—C4—C5—C6	2.0 (9)	N6—C33—C34—N7	1.7 (8)
C12—N2—C6—C9	0.0 (9)	C32—C33—C34—N7	179.5 (5)
Cu1—N2—C6—C9	176.5 (5)	N6—C33—C34—C37	−177.1 (6)
C12—N2—C6—C5	179.8 (5)	C32—C33—C34—C37	0.7 (9)
Cu1—N2—C6—C5	−3.7 (6)	C33—C32—C35—C36	−0.7 (10)
N1—C5—C6—N2	−1.1 (8)	C31—C32—C35—C36	178.1 (7)
C4—C5—C6—N2	178.8 (5)	C32—C35—C36—C37	0.6 (11)
N1—C5—C6—C9	178.7 (5)	N7—C34—C37—C36	−179.5 (6)
C4—C5—C6—C9	−1.4 (9)	C33—C34—C37—C36	−0.8 (10)
C5—C4—C7—C8	−1.0 (10)	N7—C34—C37—C38	−1.0 (10)
C3—C4—C7—C8	−179.1 (7)	C33—C34—C37—C38	177.8 (6)
C4—C7—C8—C9	−0.7 (11)	C35—C36—C37—C34	0.2 (10)
N2—C6—C9—C10	0.5 (9)	C35—C36—C37—C38	−178.2 (7)
C5—C6—C9—C10	−179.3 (6)	C34—C37—C38—C39	0.3 (11)
N2—C6—C9—C8	179.6 (5)	C36—C37—C38—C39	178.7 (7)
C5—C6—C9—C8	−0.2 (9)	C37—C38—C39—C40	0.1 (12)
C7—C8—C9—C6	1.3 (10)	C34—N7—C40—C39	−0.7 (11)
C7—C8—C9—C10	−179.7 (7)	Cu2—N7—C40—C39	−173.7 (5)
C6—C9—C10—C11	−1.3 (10)	C38—C39—C40—N7	0.1 (12)
C8—C9—C10—C11	179.7 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O12	0.96	2.41	3.064 (17)	125
N5—H5···O13^i	0.80	2.26	3.027 (11)	163

Symmetry code: (i) x−1, y, z.