(Aqua-2κO)bis­(2,2′-bipyridine-1κ²N,N′){μ-N-[3-(dimethyl­amino)­propyl]-N′-(2-oxido­phenyl)oxamidato(3−)-1:2κ²O,O′:κ⁴O′′,N,N′,N′′}copper(II)nickel(II) perchlorate

The title complex, [CuNi(C₁₃H₁₆N₃O₃)(C₁₀H₈N₂)₂(H₂O)]ClO₄, has a cis-oxamide-bridged heterobinuclear cation, with a Cu...Ni separation of 5.3297 (6) Å, counterbalanced by a disordered perchlorate anion. The Cu^II and Ni^II cations are located in square-pyramidal and octa­hedral coordination environments, respectively. The complex mol­ecules are assembled into a three-dimensional supra­molecular structure through hydrogen bonds and π–π stacking inter­actions. The influence of the two types of metal cation on the supra­molecular structure is discussed.

S1. Comment

The design and synthesis of heterometal systems with two different paramagnetic centres has been an active field of research (Li, Wu et al., 2004; Tercero et al., 2002; Wang et al., 2004; Willett et al., 1985). Interest in this field is aimed at understanding the nature of electronic exchange coupling through multiatom bridging ligands, and mimicking the active sites and functions of biological substances, as well as designing and preparing new magnetic materials (Baron et al., 1996; Li, Wu et al., 2004 or Li, Yan & Guan, 2004). One of the best strategies for constructing heterobinuclear species is the `complex as ligand' approach, using a complex which contains a potential donor group capable of coordinating to another metal cation (Cronin et al., 1999; Fukita et al., 2001). (N,N'-Disubstituted oxamide)copper(II) mononuclear complexes are a very suitable type of ligand for designing heterometallic species due to their ability to coordinate to metal cations as bidentate ligands through their carbonyl O atoms (Ruiz et al., 1999). To date, several heterobinuclear complexes based on symmetric N,N'-disubstituted oxamide ligands with interesting magnetic properties have been reported (Brewer et al., 2001; Li, Wu et al., 2004; Li, Yan & Guan, 2004; Nakatani et al., 1989, 1991; Nie et al., 2010; Sun et al., 2007; Tang et al., 2002, 2003; Wang et al., 2004). In contrast, little work has been carried out on assemblies of heterobinuclear complexes containing asymmetric N,N'-disubstituted oxamides (Larionova et al., 1997; Pei et al., 1991), owing to the difficulty of their synthesis. To the best of our knowledge, no heterobinuclear copper(II)–nickel(II) complex bridged by an asymmetric N,N'-disubstituted oxamide containing a phenolate group has hitherto been reported.

Recently, Gao & Wang (2010) reported a binuclear copper(II) complex bridged by N-[3-(dimethylamino)propyl]-N'-(2-oxidophenyl)oxamidate (pdmapo) and end-capped with 1,10-phenanthroline (phen), namely [Cu(pdmapo)(H₂O)Cu(phen)]NO₃, (II), but in order to provide more examples of pdmapo-bridged binuclear complexes and to better understand the factors affecting the supramolecular structures of these complexes, it is necessary to synthesize a series of binuclear complexes of essentially the same structure except for the metal cations. In this paper, we have selected the mononuclear copper(II) complex, Na[Cu(pdmapo)].1.5H₂O, as the bridging ligand and 2,2'-bipyridine (bpy) as the terminal ligand, to synthesize the title new heterobinuclear copper(II)–nickel(II) complex, formulated as [Cu(pdmapo)(H₂O)Ni(bpy)₂]ClO₄, (I), and we compare the crystal structure of (I) with that of (II).

Compound (I) consists of a heterobinuclear [Cu(pdmapo)(H₂O)Ni(bpy)₂]⁺ cation and an uncoordinated perchlorate anion (Fig. 1). The complex cation can be described as a cis-oxamide-bridged binuclear Cu^II–Ni^II fragment, in which the Cu^II and Ni^II cations are at the inner and exo sites of the oxamide bridge, respectively. The Cu···Ni separation is 5.3297 (6) Å. The Cu^II cation has an {N₃O₂} square-pyramidal geometry with a τ value of 0.1 (Addison et al., 1984). The basal plane is defined by four coordination atoms from the oxamide ligand, with a maximum deviation from the least-squares plane of 0.1630 (15) Å (for atom N1). The apical position is occupied by a water molecule (O4), with a Cu—O bond length of 2.456 (3) Å (Table 1). The Cu^II cation is displaced 0.1976 (15) Å from the basal plane. The Cu1—N1 and Cu1—N2 bonds are shorter than Cu1—N3, which is consistent with the stronger donor abilities of N atoms in sp² hybridization than in sp³ (Jubert et al., 2002). The Ni^II cation is chelated by two exo-O atoms of the oxamide group and two bpy terminal ligands, viz. in an {N₄O₂} octahedral environment. The equatorial plane is composed of atoms O2, N4, N6 and N7, with a maximum displacement of 0.0667 (14) Å (for atom N7), from which the Ni^II cation deviates by 0.0280 (14) Å.

The oxamide ligand (pdmapo^3-) chelates the Cu^II and Ni^II cations with bite angles of 83.15 (10) and 81.98 (8)°, respectively. Within the bridging oxamide fragment, the C7—O2 [1.260 (4) Å], C8—O3 [1.274 (3) Å], C7—N1 [1.313 (4)Å] and C8—N2 [1.305 (4) Å] bond lengths imply partial double-bond character, similar to those in many other oxamidate complexes (Lloret et al., 1989; Real et al., 1993). The six-membered chelate ring formed by the propylenediamine fragment adopts a screw-boat conformation, with puckering parameters (Cremer & Pople, 1975) of Q = 0.649 (4) Å, θ = 108.8 (4)° and ϕ = 23.4 (3)°, while all other chelate rings around the two metal cations are almost planar. The two bpy ligands around the Ni^II cation are in a cis arrangement.

As shown in Fig. 2, complex cations related by the symmetry operation (-x + 1, -y + 1, -z) [symmetry code (i)] are associated into pairs by hydrogen bonds between the coordinated water molecule and phenolic O atoms (Table 2). In this arrangement, a Cu1···Cu1ⁱ separation of 5.5492 (9) Å is observed. These pairs are, in turn, joined by the disordered Cl2 perchlorate anions to result in a one-dimensional hydrogen-bonded structure parallel to the b axis.

There are also offset aromatic stacking interactions between the bpy ligands, linking the chains together (Fig. 3). The pyridine ring containing atom N4 and that at (-x, -y + 1, -z) [symmetry code (iv)] are parallel, with a centroid-to-centroid distance of 3.641 (2) Å and a slippage of 1.500 Å. The smallest separation is between atom C16^iv and the reference py(N4) ring [3.315 (5) Å]. In addition, another π–π stacking interaction occurs between the bpy ligand containing atoms N6 and N7 and that at (-x + 1, -y + 1, -z + 1) [symmetry code (v)]. The N6- and N7^v-containing rings have a dihedral angle of 3.9 (2)°, with a centroid-to-centroid distance of 3.770 (3) Å. The nearest separations are 3.345 (5) [C30^v to py(N6)] and 3.357 (5) Å [C27^v to py(N7)]. As a result, a three-dimensional supramolecular structure is completed in the crystal structure.

As already stated, the same bridging ligand, cis-pdmapo^3-, has also been used in complex (II) with a binuclear copper(II) cation (Gao & Wang, 2010), in which the Cu^II cations at the inner and exo sites of the pdmapo^3- anion are in square-planar and square-pyramidal environments, respectively. The exo Cu^II cation coordinates to a phen ligand and a water molecule. However, in complex (I), the coordinated water molecule is transferred to the inner Cu^II cation. In addition, the exo metal cation, nickel(II), uses two bpy as terminal ligands because Ni^II cations usually prefer six coordination to five, as is the case for the exo Cu^II cation in (II). These differences lead to distinct supramolecular structures. Complex (I) has a three-dimensional supramolecular structure of classical hydrogen bonding and π–π stacking interactions depicted as above. In complex (II), instead (according to our own analysis of the freely available crystallographic data), there is just a one-dimensional hydrogen-bonded chain parallel to [101]; the cations give rise to dimers through classical hydrogen bonds. The dimers and nitrate anions further build up a two-dimensional structure extending along the (010) plane by C—H···O hydrogen bonds and π–π stacking interactions. This is a clear example of how metal cations may play an important role in the way supramolecular structures are built up.

Related literature

For related literature, see: Addison et al. (1984); Baron et al. (1996); Brewer et al. (2001); Cremer & Pople (1975); Cronin et al. (1999); Fukita et al. (2001); Gao & Wang (2010); Jubert et al. (2002); Larionova et al. (1997); Li, Wu, Yan & Zhu (2004); Li, Yan & Guan (2004); Lloret et al. (1989); Nakatani et al. (1989, 1991); Nie et al. (2010); Pei et al. (1991); Real et al. (1993); Ruiz et al. (1999); Sheldrick (2008); Sun et al. (2007); Tang et al. (2002, 2003); Tercero et al. (2002); Wang et al. (2004); Willett et al. (1985).

S2. Experimental

All chemicals were of analytical reagent grade. The Na[Cu(pdmapo)].1.5H₂O ligand was prepared according to the method of Pei et al. (1991). The title complex was obtained as follows. A methanol (5 ml) solution of Ni(ClO₄)₂.6H₂O (0.0183 g, 0.05 mmol) was added dropwise to an aqueous solution (5 ml) of Na[Cu(pdmapo)].1.5H₂O (0.0192 g, 0.05 mmol) with continuous stirring. The mixture was stirred quickly for 0.5 h and then bpy (0.0156 g, 0.1 mmol) in methanol (5 ml) was added dropwise. The solution obtained was stirred at 333 K for 6 h and filtered. Green block-shaped crystals of (I) suitable for X-ray analysis were obtained from the filtrate by slow evaporation at room temperature for 17 d (yield 65%). Elemental analysis, calculated for C₃₃H₃₄ClCuN₇NiO₈: C 48.67, H 4.21, N 12.04%; found: C 48.93, H 4.27, N 11.51%.

S3. Refinement

Both perchlorate anions (Cl1 and Cl2) are disordered around inversion centres at (1/2,1/2,0) and (0,1,1/2), respectively, and correspondingly their occupancies were constrained to 0.5. The Cl—O and O—O distances were restrained by similarity conditions (SADI 0.2 in SHELXL97; Sheldrick, 2008). Water H atoms were found in a difference Fourier map and further refined with restrained distances O—H = 0.85 (1) Å and H···H = 1.35 (1) Å. The isotropic displacement parameters were refined freely. Other H atoms were placed in calculated positions, with C—H = 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methylene), and refined in riding mode, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). The methyl groups were allowed to rotate freely around the C—N bond.

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The disordered parts of the equally populated perchlorate anions have been drawn with different styles for clarity. [Symmetry code: (i) -x + 1, -y + 1, -z; (ii) -x, -y + 2, -z + 1.]
	Fig. 2. A view of the one-dimensional hydrogen-bonded structure of (I), parallel to the b axis. Only one of the two half-occupied perchlorate anions is drawn for clarity. [Symmetry code: (i) -x + 1, -y + 1, -z; (iii) -x + 1, -y + 2, -z.]
	Fig. 3. The π–π stacking interactions in (I), viewed down the a axis. H atoms and perchlorate anions have been omitted for clarity. [Symmetry codes: (iv) -x, -y + 1, -z; (v) -x + 1, -y + 1, -z + 1.]

(Aqua-2κO)bis(2,2'-bipyridine-1κ²N,N'){µ-N- [3-(dimethylamino)propyl]-N'-(2-oxidophenyl)oxamidato(3-)- 1:2κ²O,O':κ⁴O'',N,N',N''} copper(II)nickel(II) perchlorate

Crystal data

[CuNi(C13H16N3O3)(C10H8N2)2(H2O)]ClO4	Z = 2
Mr = 814.37	F(000) = 838
Triclinic, P1	Dx = 1.528 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.4692 (5) Å	Cell parameters from 3159 reflections
b = 11.8976 (5) Å	θ = 2.6–23.3°
c = 15.1818 (7) Å	µ = 1.27 mm^−1
α = 92.261 (3)°	T = 296 K
β = 109.043 (3)°	Block, green
γ = 112.911 (3)°	0.24 × 0.15 × 0.15 mm
V = 1770.51 (15) Å^3

Data collection

Bruker APEX area-detector diffractometer	8178 independent reflections
Radiation source: fine-focus sealed tube	4749 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
ϕ and ω scans	θmax = 27.9°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −15→14
Tmin = 0.751, Tmax = 0.833	k = −15→15
15761 measured reflections	l = −19→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0597P)^2] where P = (Fo^2 + 2Fc^2)/3
8178 reflections	(Δ/σ)max < 0.001
515 parameters	Δρmax = 0.46 e Å^−3
45 restraints	Δρmin = −0.40 e Å^−3

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	Occ. (<1)
Cu1	0.54940 (4)	0.94857 (4)	0.18183 (3)	0.04840 (15)
Ni1	0.24661 (4)	0.57388 (4)	0.30638 (3)	0.04288 (14)
O1	0.4933 (3)	1.0777 (2)	0.13145 (18)	0.0584 (6)
O2	0.2463 (2)	0.7333 (2)	0.25978 (16)	0.0497 (6)
O3	0.4338 (2)	0.63997 (19)	0.29168 (15)	0.0434 (5)
O4	0.4630 (3)	0.8237 (3)	0.0227 (2)	0.0739 (8)
H4A	0.474 (5)	0.854 (3)	−0.025 (2)	0.099 (17)*
H4B	0.470 (4)	0.756 (2)	0.017 (3)	0.078 (16)*
N1	0.3811 (3)	0.8913 (2)	0.20327 (19)	0.0436 (6)
N2	0.5643 (2)	0.8058 (2)	0.23912 (19)	0.0437 (6)
N3	0.7501 (3)	1.0436 (3)	0.2046 (2)	0.0546 (8)
N4	0.1397 (3)	0.4731 (2)	0.1682 (2)	0.0490 (7)
N5	0.0459 (3)	0.5237 (3)	0.2946 (2)	0.0568 (8)
N6	0.2647 (3)	0.4264 (3)	0.36910 (19)	0.0456 (7)
N7	0.3371 (3)	0.6570 (3)	0.4491 (2)	0.0547 (8)
C1	0.3730 (4)	1.0605 (3)	0.1340 (2)	0.0480 (8)
C2	0.3049 (3)	0.9596 (3)	0.1739 (2)	0.0447 (8)
C3	0.1808 (4)	0.9393 (3)	0.1790 (3)	0.0563 (9)
H3	0.1396	0.8756	0.2074	0.068*
C4	0.1180 (5)	1.0141 (4)	0.1415 (3)	0.0764 (13)
H4	0.0325	0.9984	0.1425	0.092*
C5	0.1806 (5)	1.1113 (4)	0.1029 (3)	0.0733 (13)
H5	0.1368	1.1607	0.0778	0.088*
C6	0.3075 (4)	1.1369 (3)	0.1008 (3)	0.0628 (11)
H6	0.3502	1.2055	0.0770	0.075*
C7	0.3499 (3)	0.7903 (3)	0.2397 (2)	0.0416 (8)
C8	0.4579 (3)	0.7399 (3)	0.2587 (2)	0.0391 (7)
C9	0.6710 (3)	0.7631 (3)	0.2544 (3)	0.0516 (9)
H9A	0.6314	0.6772	0.2225	0.062*
H9B	0.7148	0.7675	0.3217	0.062*
C10	0.7766 (4)	0.8438 (3)	0.2158 (3)	0.0602 (10)
H10A	0.8505	0.8184	0.2309	0.072*
H10B	0.7347	0.8301	0.1472	0.072*
C11	0.8340 (3)	0.9800 (3)	0.2554 (3)	0.0595 (10)
H11A	0.8438	0.9900	0.3215	0.071*
H11B	0.9243	1.0207	0.2533	0.071*
C12	0.7713 (4)	1.0667 (4)	0.1145 (3)	0.0747 (12)
H12A	0.7469	0.9892	0.0759	0.112*
H12B	0.8653	1.1204	0.1281	0.112*
H12C	0.7152	1.1056	0.0810	0.112*
C13	0.7959 (4)	1.1643 (4)	0.2652 (4)	0.0861 (14)
H13A	0.8909	1.2134	0.2783	0.129*
H13B	0.7825	1.1507	0.3238	0.129*
H13C	0.7442	1.2074	0.2330	0.129*
C14	0.1933 (4)	0.4464 (3)	0.1097 (3)	0.0585 (10)
H14	0.2874	0.4745	0.1308	0.070*
C15	0.1143 (5)	0.3782 (4)	0.0183 (3)	0.0731 (12)
H15	0.1542	0.3611	−0.0218	0.088*
C16	−0.0246 (6)	0.3368 (4)	−0.0113 (4)	0.0890 (17)
H16	−0.0803	0.2909	−0.0723	0.107*
C17	−0.0810 (4)	0.3628 (4)	0.0485 (3)	0.0727 (13)
H17	−0.1751	0.3340	0.0290	0.087*
C18	0.0029 (3)	0.4325 (3)	0.1388 (3)	0.0551 (10)
C19	−0.0472 (3)	0.4691 (3)	0.2073 (3)	0.0586 (10)
C20	−0.1815 (4)	0.4509 (4)	0.1846 (4)	0.0859 (15)
H20	−0.2453	0.4127	0.1236	0.103*
C21	−0.2191 (5)	0.4885 (5)	0.2510 (5)	0.1000 (18)
H21	−0.3091	0.4764	0.2357	0.120*
C22	−0.1271 (5)	0.5441 (5)	0.3401 (5)	0.1016 (17)
H22	−0.1518	0.5706	0.3868	0.122*
C23	0.0067 (4)	0.5598 (4)	0.3591 (4)	0.0811 (13)
H23	0.0712	0.5975	0.4199	0.097*
C24	0.2219 (3)	0.3108 (3)	0.3256 (3)	0.0581 (10)
H24	0.1832	0.2922	0.2597	0.070*
C25	0.2319 (4)	0.2170 (4)	0.3734 (3)	0.0714 (12)
H25	0.1998	0.1369	0.3405	0.086*
C26	0.2903 (4)	0.2444 (4)	0.4710 (3)	0.0786 (13)
H26	0.2979	0.1827	0.5051	0.094*
C27	0.3367 (4)	0.3629 (4)	0.5170 (3)	0.0655 (11)
H27	0.3782	0.3833	0.5829	0.079*
C28	0.3217 (3)	0.4529 (3)	0.4652 (2)	0.0492 (9)
C29	0.3653 (3)	0.5832 (4)	0.5089 (2)	0.0539 (9)
C30	0.4299 (4)	0.6277 (5)	0.6063 (3)	0.0798 (14)
H30	0.4507	0.5764	0.6474	0.096*
C31	0.4626 (5)	0.7498 (6)	0.6408 (4)	0.1030 (18)
H31	0.5046	0.7815	0.7058	0.124*
C32	0.4327 (5)	0.8231 (5)	0.5788 (4)	0.0975 (16)
H32	0.4543	0.9055	0.6009	0.117*
C33	0.3706 (4)	0.7746 (4)	0.4841 (3)	0.0763 (12)
H33	0.3509	0.8255	0.4422	0.092*
Cl1	0.0908 (3)	0.8999 (3)	0.47311 (18)	0.0861 (7)	0.50
O5	0.0854 (9)	0.8854 (8)	0.3851 (5)	0.137 (3)	0.50
O6	0.0175 (11)	0.9659 (11)	0.4820 (7)	0.171 (4)	0.50
O7	0.2209 (7)	0.9679 (6)	0.5332 (6)	0.124 (3)	0.50
O8	0.0413 (9)	0.7917 (6)	0.5007 (5)	0.142 (3)	0.50
Cl2	0.5093 (11)	0.5178 (8)	−0.0044 (8)	0.0829 (17)	0.50
O9	0.4630 (19)	0.3965 (10)	−0.0017 (13)	0.261 (11)	0.50
O10	0.5026 (8)	0.5359 (9)	−0.0969 (5)	0.119 (3)	0.50
O11	0.6448 (8)	0.5849 (12)	0.0541 (6)	0.150 (4)	0.50
O12	0.4342 (8)	0.5725 (9)	0.0201 (6)	0.106 (3)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0455 (2)	0.0406 (3)	0.0570 (3)	0.01421 (18)	0.0200 (2)	0.0231 (2)
Ni1	0.0399 (2)	0.0375 (3)	0.0431 (3)	0.00924 (18)	0.01359 (19)	0.01315 (19)
O1	0.0651 (15)	0.0447 (14)	0.0673 (17)	0.0234 (12)	0.0247 (13)	0.0293 (12)
O2	0.0443 (12)	0.0434 (13)	0.0650 (16)	0.0180 (10)	0.0244 (11)	0.0213 (11)
O3	0.0416 (11)	0.0366 (12)	0.0486 (13)	0.0141 (9)	0.0143 (10)	0.0208 (10)
O4	0.092 (2)	0.071 (2)	0.065 (2)	0.0366 (18)	0.0316 (17)	0.0324 (16)
N1	0.0450 (14)	0.0365 (15)	0.0496 (17)	0.0177 (12)	0.0164 (13)	0.0165 (13)
N2	0.0385 (14)	0.0411 (16)	0.0517 (17)	0.0157 (12)	0.0174 (13)	0.0183 (13)
N3	0.0497 (16)	0.0415 (17)	0.063 (2)	0.0107 (13)	0.0194 (15)	0.0181 (15)
N4	0.0478 (16)	0.0383 (16)	0.0497 (18)	0.0126 (12)	0.0102 (14)	0.0172 (13)
N5	0.0497 (17)	0.0527 (19)	0.067 (2)	0.0162 (14)	0.0265 (17)	0.0233 (16)
N6	0.0403 (14)	0.0439 (17)	0.0406 (16)	0.0090 (12)	0.0108 (12)	0.0141 (13)
N7	0.0533 (17)	0.0492 (19)	0.0483 (18)	0.0096 (14)	0.0180 (14)	0.0042 (15)
C1	0.062 (2)	0.0350 (19)	0.043 (2)	0.0217 (16)	0.0129 (17)	0.0074 (15)
C2	0.058 (2)	0.0330 (18)	0.0397 (19)	0.0206 (15)	0.0118 (16)	0.0061 (14)
C3	0.066 (2)	0.052 (2)	0.061 (2)	0.0333 (19)	0.0254 (19)	0.0134 (18)
C4	0.089 (3)	0.084 (3)	0.082 (3)	0.058 (3)	0.037 (3)	0.024 (3)
C5	0.105 (3)	0.078 (3)	0.065 (3)	0.070 (3)	0.027 (3)	0.023 (2)
C6	0.089 (3)	0.047 (2)	0.059 (2)	0.038 (2)	0.023 (2)	0.0190 (19)
C7	0.0406 (17)	0.0362 (18)	0.0395 (19)	0.0123 (14)	0.0093 (14)	0.0084 (15)
C8	0.0395 (16)	0.0358 (18)	0.0336 (17)	0.0118 (14)	0.0085 (14)	0.0084 (14)
C9	0.0502 (19)	0.051 (2)	0.060 (2)	0.0239 (16)	0.0238 (17)	0.0242 (18)
C10	0.054 (2)	0.060 (2)	0.073 (3)	0.0250 (18)	0.0292 (19)	0.026 (2)
C11	0.0430 (18)	0.059 (2)	0.065 (3)	0.0119 (17)	0.0176 (18)	0.019 (2)
C12	0.068 (2)	0.075 (3)	0.083 (3)	0.020 (2)	0.040 (2)	0.047 (2)
C13	0.065 (3)	0.053 (3)	0.113 (4)	0.009 (2)	0.022 (3)	−0.005 (3)
C14	0.070 (2)	0.049 (2)	0.053 (2)	0.0262 (19)	0.017 (2)	0.0180 (18)
C15	0.115 (4)	0.053 (3)	0.046 (2)	0.040 (3)	0.018 (2)	0.013 (2)
C16	0.109 (4)	0.042 (3)	0.062 (3)	0.015 (2)	−0.012 (3)	0.008 (2)
C17	0.067 (3)	0.046 (2)	0.070 (3)	0.010 (2)	−0.002 (2)	0.020 (2)
C18	0.0490 (19)	0.037 (2)	0.057 (2)	0.0078 (15)	0.0037 (18)	0.0213 (17)
C19	0.0417 (18)	0.045 (2)	0.076 (3)	0.0099 (16)	0.015 (2)	0.033 (2)
C20	0.052 (2)	0.089 (3)	0.107 (4)	0.024 (2)	0.022 (3)	0.044 (3)
C21	0.060 (3)	0.108 (4)	0.144 (5)	0.037 (3)	0.047 (4)	0.055 (4)
C22	0.080 (3)	0.102 (4)	0.150 (5)	0.041 (3)	0.073 (4)	0.037 (4)
C23	0.069 (3)	0.078 (3)	0.099 (4)	0.024 (2)	0.044 (3)	0.019 (3)
C24	0.055 (2)	0.042 (2)	0.054 (2)	0.0098 (16)	0.0061 (18)	0.0133 (18)
C25	0.063 (2)	0.049 (2)	0.082 (3)	0.0139 (19)	0.013 (2)	0.021 (2)
C26	0.071 (3)	0.072 (3)	0.088 (3)	0.026 (2)	0.025 (2)	0.051 (3)
C27	0.057 (2)	0.077 (3)	0.056 (2)	0.022 (2)	0.0195 (19)	0.035 (2)
C28	0.0368 (16)	0.057 (2)	0.044 (2)	0.0104 (15)	0.0131 (15)	0.0178 (17)
C29	0.0392 (17)	0.067 (3)	0.040 (2)	0.0088 (17)	0.0134 (16)	0.0077 (19)
C30	0.069 (3)	0.103 (4)	0.044 (2)	0.020 (3)	0.014 (2)	0.005 (2)
C31	0.094 (4)	0.115 (5)	0.057 (3)	0.016 (3)	0.016 (3)	−0.027 (3)
C32	0.102 (4)	0.080 (4)	0.080 (4)	0.018 (3)	0.026 (3)	−0.021 (3)
C33	0.087 (3)	0.056 (3)	0.074 (3)	0.019 (2)	0.030 (3)	−0.003 (2)
Cl1	0.1021 (19)	0.0856 (19)	0.0669 (16)	0.0447 (15)	0.0207 (14)	0.0172 (13)
O5	0.181 (8)	0.161 (8)	0.082 (5)	0.078 (6)	0.056 (5)	0.025 (5)
O6	0.172 (9)	0.243 (15)	0.134 (9)	0.135 (9)	0.042 (7)	0.041 (9)
O7	0.116 (6)	0.094 (5)	0.150 (7)	0.043 (5)	0.033 (6)	0.047 (5)
O8	0.175 (8)	0.090 (6)	0.111 (6)	0.015 (5)	0.046 (6)	−0.002 (5)
Cl2	0.097 (3)	0.049 (5)	0.105 (2)	0.032 (4)	0.0374 (19)	0.017 (3)
O9	0.41 (3)	0.065 (8)	0.37 (3)	0.112 (14)	0.20 (2)	0.098 (12)
O10	0.121 (6)	0.121 (7)	0.105 (6)	0.049 (5)	0.034 (5)	0.022 (5)
O11	0.102 (7)	0.193 (11)	0.113 (7)	0.049 (7)	0.007 (5)	−0.010 (7)
O12	0.102 (5)	0.091 (6)	0.144 (7)	0.046 (5)	0.061 (5)	0.025 (5)

Geometric parameters (Å, º)

Cu1—N1	1.924 (3)	C11—H11B	0.9700
Cu1—O1	1.975 (2)	C12—H12A	0.9600
Cu1—N2	1.980 (3)	C12—H12B	0.9600
Cu1—N3	2.030 (3)	C12—H12C	0.9600
Cu1—O4	2.456 (3)	C13—H13A	0.9600
Ni1—O2	2.051 (2)	C13—H13B	0.9600
Ni1—O3	2.071 (2)	C13—H13C	0.9600
Ni1—N7	2.077 (3)	C14—C15	1.387 (5)
Ni1—N6	2.077 (3)	C14—H14	0.9300
Ni1—N4	2.079 (3)	C15—C16	1.374 (7)
Ni1—N5	2.083 (3)	C15—H15	0.9300
O1—C1	1.329 (4)	C16—C17	1.362 (7)
O2—C7	1.260 (4)	C16—H16	0.9300
O3—C8	1.274 (3)	C17—C18	1.386 (5)
O4—H4A	0.85 (3)	C17—H17	0.9300
O4—H4B	0.84 (3)	C18—C19	1.466 (6)
N1—C7	1.313 (4)	C19—C20	1.388 (5)
N1—C2	1.397 (4)	C20—C21	1.343 (7)
N2—C8	1.305 (4)	C20—H20	0.9300
N2—C9	1.454 (4)	C21—C22	1.355 (7)
N3—C13	1.476 (5)	C21—H21	0.9300
N3—C12	1.484 (5)	C22—C23	1.399 (6)
N3—C11	1.491 (4)	C22—H22	0.9300
N4—C14	1.323 (5)	C23—H23	0.9300
N4—C18	1.352 (4)	C24—C25	1.376 (5)
N5—C23	1.322 (5)	C24—H24	0.9300
N5—C19	1.338 (4)	C25—C26	1.376 (6)
N6—C24	1.327 (4)	C25—H25	0.9300
N6—C28	1.354 (4)	C26—C27	1.362 (6)
N7—C33	1.334 (5)	C26—H26	0.9300
N7—C29	1.339 (4)	C27—C28	1.385 (5)
C1—C6	1.402 (5)	C27—H27	0.9300
C1—C2	1.433 (5)	C28—C29	1.480 (5)
C2—C3	1.376 (5)	C29—C30	1.392 (5)
C3—C4	1.380 (5)	C30—C31	1.384 (7)
C3—H3	0.9300	C30—H30	0.9300
C4—C5	1.371 (6)	C31—C32	1.361 (7)
C4—H4	0.9300	C31—H31	0.9300
C5—C6	1.378 (6)	C32—C33	1.362 (6)
C5—H5	0.9300	C32—H32	0.9300
C6—H6	0.9300	C33—H33	0.9300
C7—C8	1.528 (4)	Cl1—O5	1.319 (7)
C9—C10	1.528 (5)	Cl1—O8	1.336 (7)
C9—H9A	0.9700	Cl1—O7	1.351 (7)
C9—H9B	0.9700	Cl1—O6	1.386 (7)
C10—C11	1.501 (5)	Cl2—O9	1.338 (9)
C10—H10A	0.9700	Cl2—O12	1.389 (12)
C10—H10B	0.9700	Cl2—O11	1.386 (11)
C11—H11A	0.9700	Cl2—O10	1.411 (12)
N1—Cu1—O1	82.82 (11)	N3—C11—H11B	108.6
N1—Cu1—N2	83.15 (10)	C10—C11—H11B	108.6
O1—Cu1—N2	165.95 (11)	H11A—C11—H11B	107.6
N1—Cu1—N3	160.19 (12)	N3—C12—H12A	109.5
O1—Cu1—N3	96.32 (11)	N3—C12—H12B	109.5
N2—Cu1—N3	96.68 (11)	H12A—C12—H12B	109.5
O2—Ni1—O3	81.98 (8)	N3—C12—H12C	109.5
O2—Ni1—N7	94.29 (11)	H12A—C12—H12C	109.5
O3—Ni1—N7	91.62 (10)	H12B—C12—H12C	109.5
O2—Ni1—N6	173.02 (10)	N3—C13—H13A	109.5
O3—Ni1—N6	95.87 (9)	N3—C13—H13B	109.5
N7—Ni1—N6	79.10 (12)	H13A—C13—H13B	109.5
O2—Ni1—N4	90.57 (10)	N3—C13—H13C	109.5
O3—Ni1—N4	93.93 (10)	H13A—C13—H13C	109.5
N7—Ni1—N4	173.09 (11)	H13B—C13—H13C	109.5
N6—Ni1—N4	96.21 (10)	N4—C14—C15	122.4 (4)
O2—Ni1—N5	87.79 (10)	N4—C14—H14	118.8
O3—Ni1—N5	167.36 (10)	C15—C14—H14	118.8
N7—Ni1—N5	96.55 (13)	C16—C15—C14	118.0 (5)
N6—Ni1—N5	95.14 (11)	C16—C15—H15	121.0
N4—Ni1—N5	78.70 (13)	C14—C15—H15	121.0
C1—O1—Cu1	111.8 (2)	C17—C16—C15	120.1 (4)
C7—O2—Ni1	111.3 (2)	C17—C16—H16	120.0
C8—O3—Ni1	111.32 (19)	C15—C16—H16	120.0
H4A—O4—H4B	105 (4)	C16—C17—C18	119.5 (4)
C7—N1—C2	128.4 (3)	C16—C17—H17	120.2
C7—N1—Cu1	116.0 (2)	C18—C17—H17	120.2
C2—N1—Cu1	115.5 (2)	N4—C18—C17	120.5 (4)
C8—N2—C9	118.6 (3)	N4—C18—C19	115.7 (3)
C8—N2—Cu1	112.8 (2)	C17—C18—C19	123.7 (4)
C9—N2—Cu1	128.4 (2)	N5—C19—C20	121.0 (4)
C13—N3—C12	108.6 (3)	N5—C19—C18	115.7 (3)
C13—N3—C11	108.4 (3)	C20—C19—C18	123.3 (4)
C12—N3—C11	109.6 (3)	C21—C20—C19	119.7 (5)
C13—N3—Cu1	105.9 (2)	C21—C20—H20	120.1
C12—N3—Cu1	111.4 (2)	C19—C20—H20	120.1
C11—N3—Cu1	112.7 (2)	C20—C21—C22	120.6 (5)
C14—N4—C18	119.5 (3)	C20—C21—H21	119.7
C14—N4—Ni1	126.1 (2)	C22—C21—H21	119.7
C18—N4—Ni1	114.4 (3)	C21—C22—C23	117.2 (5)
C23—N5—C19	118.3 (4)	C21—C22—H22	121.4
C23—N5—Ni1	126.0 (3)	C23—C22—H22	121.4
C19—N5—Ni1	114.6 (3)	N5—C23—C22	123.2 (5)
C24—N6—C28	118.1 (3)	N5—C23—H23	118.4
C24—N6—Ni1	127.1 (2)	C22—C23—H23	118.4
C28—N6—Ni1	114.8 (2)	N6—C24—C25	123.2 (4)
C33—N7—C29	119.1 (3)	N6—C24—H24	118.4
C33—N7—Ni1	126.0 (3)	C25—C24—H24	118.4
C29—N7—Ni1	114.8 (2)	C24—C25—C26	118.6 (4)
O1—C1—C6	123.8 (3)	C24—C25—H25	120.7
O1—C1—C2	119.2 (3)	C26—C25—H25	120.7
C6—C1—C2	117.0 (4)	C27—C26—C25	119.2 (4)
C3—C2—N1	128.2 (3)	C27—C26—H26	120.4
C3—C2—C1	121.1 (3)	C25—C26—H26	120.4
N1—C2—C1	110.7 (3)	C26—C27—C28	119.5 (4)
C2—C3—C4	119.6 (4)	C26—C27—H27	120.2
C2—C3—H3	120.2	C28—C27—H27	120.2
C4—C3—H3	120.2	N6—C28—C27	121.4 (3)
C5—C4—C3	120.6 (4)	N6—C28—C29	115.1 (3)
C5—C4—H4	119.7	C27—C28—C29	123.5 (3)
C3—C4—H4	119.7	N7—C29—C30	121.1 (4)
C4—C5—C6	120.9 (4)	N7—C29—C28	116.1 (3)
C4—C5—H5	119.6	C30—C29—C28	122.8 (4)
C6—C5—H5	119.6	C31—C30—C29	118.6 (5)
C5—C6—C1	120.7 (4)	C31—C30—H30	120.7
C5—C6—H6	119.6	C29—C30—H30	120.7
C1—C6—H6	119.6	C32—C31—C30	119.3 (5)
O2—C7—N1	128.8 (3)	C32—C31—H31	120.3
O2—C7—C8	118.6 (3)	C30—C31—H31	120.3
N1—C7—C8	112.5 (3)	C31—C32—C33	119.3 (5)
O3—C8—N2	128.0 (3)	C31—C32—H32	120.3
O3—C8—C7	116.6 (3)	C33—C32—H32	120.3
N2—C8—C7	115.4 (3)	N7—C33—C32	122.5 (5)
N2—C9—C10	110.1 (3)	N7—C33—H33	118.7
N2—C9—H9A	109.6	C32—C33—H33	118.7
C10—C9—H9A	109.6	O5—Cl1—O8	112.5 (5)
N2—C9—H9B	109.6	O5—Cl1—O7	110.2 (5)
C10—C9—H9B	109.6	O8—Cl1—O7	108.8 (5)
H9A—C9—H9B	108.2	O5—Cl1—O6	110.0 (6)
C11—C10—C9	112.9 (3)	O8—Cl1—O6	108.6 (7)
C11—C10—H10A	109.0	O7—Cl1—O6	106.6 (6)
C9—C10—H10A	109.0	O9—Cl2—O12	112.8 (10)
C11—C10—H10B	109.0	O9—Cl2—O11	112.9 (10)
C9—C10—H10B	109.0	O12—Cl2—O11	107.8 (9)
H10A—C10—H10B	107.8	O9—Cl2—O10	110.1 (10)
N3—C11—C10	114.5 (3)	O12—Cl2—O10	107.1 (8)
N3—C11—H11A	108.6	O11—Cl2—O10	105.7 (8)
C10—C11—H11A	108.6
N1—Cu1—O1—C1	−1.9 (2)	C3—C4—C5—C6	−0.2 (7)
N2—Cu1—O1—C1	−4.4 (5)	C4—C5—C6—C1	3.0 (6)
N3—Cu1—O1—C1	−162.0 (2)	O1—C1—C6—C5	178.0 (3)
O3—Ni1—O2—C7	3.6 (2)	C2—C1—C6—C5	−2.8 (5)
N7—Ni1—O2—C7	94.7 (2)	Ni1—O2—C7—N1	175.9 (3)
N4—Ni1—O2—C7	−90.3 (2)	Ni1—O2—C7—C8	−4.0 (4)
N5—Ni1—O2—C7	−168.9 (2)	C2—N1—C7—O2	−2.5 (6)
O2—Ni1—O3—C8	−2.7 (2)	Cu1—N1—C7—O2	−179.3 (3)
N7—Ni1—O3—C8	−96.8 (2)	C2—N1—C7—C8	177.4 (3)
N6—Ni1—O3—C8	−176.0 (2)	Cu1—N1—C7—C8	0.6 (4)
N4—Ni1—O3—C8	87.4 (2)	Ni1—O3—C8—N2	−178.9 (3)
N5—Ni1—O3—C8	33.6 (6)	Ni1—O3—C8—C7	1.4 (3)
O1—Cu1—N1—C7	178.6 (3)	C9—N2—C8—O3	0.9 (5)
N2—Cu1—N1—C7	−2.1 (2)	Cu1—N2—C8—O3	176.6 (3)
N3—Cu1—N1—C7	−92.7 (4)	C9—N2—C8—C7	−179.4 (3)
O1—Cu1—N1—C2	1.3 (2)	Cu1—N2—C8—C7	−3.7 (3)
N2—Cu1—N1—C2	−179.3 (2)	O2—C7—C8—O3	1.8 (4)
N3—Cu1—N1—C2	90.0 (4)	N1—C7—C8—O3	−178.1 (3)
N1—Cu1—N2—C8	3.2 (2)	O2—C7—C8—N2	−177.9 (3)
O1—Cu1—N2—C8	5.8 (6)	N1—C7—C8—N2	2.2 (4)
N3—Cu1—N2—C8	163.3 (2)	C8—N2—C9—C10	173.0 (3)
N1—Cu1—N2—C9	178.4 (3)	Cu1—N2—C9—C10	−1.9 (4)
O1—Cu1—N2—C9	−179.1 (4)	N2—C9—C10—C11	54.3 (4)
N3—Cu1—N2—C9	−21.6 (3)	C13—N3—C11—C10	164.4 (3)
N1—Cu1—N3—C13	−31.6 (5)	C12—N3—C11—C10	−77.2 (4)
O1—Cu1—N3—C13	54.7 (3)	Cu1—N3—C11—C10	47.5 (4)
N2—Cu1—N3—C13	−119.9 (3)	C9—C10—C11—N3	−84.5 (4)
N1—Cu1—N3—C12	−149.6 (3)	C18—N4—C14—C15	0.3 (5)
O1—Cu1—N3—C12	−63.3 (3)	Ni1—N4—C14—C15	179.9 (3)
N2—Cu1—N3—C12	122.1 (3)	N4—C14—C15—C16	−0.5 (6)
N1—Cu1—N3—C11	86.7 (4)	C14—C15—C16—C17	−0.1 (6)
O1—Cu1—N3—C11	173.0 (2)	C15—C16—C17—C18	0.8 (6)
N2—Cu1—N3—C11	−1.6 (3)	C14—N4—C18—C17	0.5 (5)
O2—Ni1—N4—C14	95.7 (3)	Ni1—N4—C18—C17	−179.2 (3)
O3—Ni1—N4—C14	13.7 (3)	C14—N4—C18—C19	−178.5 (3)
N6—Ni1—N4—C14	−82.7 (3)	Ni1—N4—C18—C19	1.9 (3)
N5—Ni1—N4—C14	−176.7 (3)	C16—C17—C18—N4	−1.0 (5)
O2—Ni1—N4—C18	−84.7 (2)	C16—C17—C18—C19	177.9 (4)
O3—Ni1—N4—C18	−166.7 (2)	C23—N5—C19—C20	0.1 (5)
N6—Ni1—N4—C18	96.9 (2)	Ni1—N5—C19—C20	−168.3 (3)
N5—Ni1—N4—C18	2.9 (2)	C23—N5—C19—C18	179.3 (3)
O2—Ni1—N5—C23	−83.9 (3)	Ni1—N5—C19—C18	10.9 (4)
O3—Ni1—N5—C23	−119.8 (5)	N4—C18—C19—N5	−8.6 (4)
N7—Ni1—N5—C23	10.1 (4)	C17—C18—C19—N5	172.5 (3)
N6—Ni1—N5—C23	89.7 (3)	N4—C18—C19—C20	170.6 (3)
N4—Ni1—N5—C23	−175.0 (4)	C17—C18—C19—C20	−8.3 (5)
O2—Ni1—N5—C19	83.4 (2)	N5—C19—C20—C21	0.1 (6)
O3—Ni1—N5—C19	47.5 (6)	C18—C19—C20—C21	−179.1 (4)
N7—Ni1—N5—C19	177.5 (2)	C19—C20—C21—C22	−0.1 (8)
N6—Ni1—N5—C19	−103.0 (2)	C20—C21—C22—C23	0.0 (8)
N4—Ni1—N5—C19	−7.6 (2)	C19—N5—C23—C22	−0.2 (6)
O3—Ni1—N6—C24	−92.3 (3)	Ni1—N5—C23—C22	166.7 (4)
N7—Ni1—N6—C24	177.2 (3)	C21—C22—C23—N5	0.2 (7)
N4—Ni1—N6—C24	2.4 (3)	C28—N6—C24—C25	0.4 (5)
N5—Ni1—N6—C24	81.5 (3)	Ni1—N6—C24—C25	−176.5 (3)
O3—Ni1—N6—C28	90.8 (2)	N6—C24—C25—C26	−0.6 (6)
N7—Ni1—N6—C28	0.3 (2)	C24—C25—C26—C27	−0.3 (6)
N4—Ni1—N6—C28	−174.6 (2)	C25—C26—C27—C28	1.4 (6)
N5—Ni1—N6—C28	−95.4 (2)	C24—N6—C28—C27	0.8 (5)
O2—Ni1—N7—C33	2.4 (3)	Ni1—N6—C28—C27	178.0 (3)
O3—Ni1—N7—C33	84.4 (3)	C24—N6—C28—C29	−179.2 (3)
N6—Ni1—N7—C33	−179.9 (3)	Ni1—N6—C28—C29	−1.9 (4)
N5—Ni1—N7—C33	−85.9 (3)	C26—C27—C28—N6	−1.7 (5)
O2—Ni1—N7—C29	−176.2 (2)	C26—C27—C28—C29	178.3 (3)
O3—Ni1—N7—C29	−94.1 (2)	C33—N7—C29—C30	−0.6 (5)
N6—Ni1—N7—C29	1.6 (2)	Ni1—N7—C29—C30	178.0 (3)
N5—Ni1—N7—C29	95.6 (2)	C33—N7—C29—C28	178.3 (3)
Cu1—O1—C1—C6	−178.6 (3)	Ni1—N7—C29—C28	−3.1 (4)
Cu1—O1—C1—C2	2.2 (4)	N6—C28—C29—N7	3.3 (4)
C7—N1—C2—C3	2.2 (6)	C27—C28—C29—N7	−176.6 (3)
Cu1—N1—C2—C3	179.0 (3)	N6—C28—C29—C30	−177.7 (3)
C7—N1—C2—C1	−177.3 (3)	C27—C28—C29—C30	2.3 (5)
Cu1—N1—C2—C1	−0.5 (3)	N7—C29—C30—C31	1.1 (6)
O1—C1—C2—C3	179.2 (3)	C28—C29—C30—C31	−177.7 (4)
C6—C1—C2—C3	0.0 (5)	C29—C30—C31—C32	−0.9 (7)
O1—C1—C2—N1	−1.2 (4)	C30—C31—C32—C33	0.3 (8)
C6—C1—C2—N1	179.6 (3)	C29—N7—C33—C32	−0.1 (6)
N1—C2—C3—C4	−176.8 (3)	Ni1—N7—C33—C32	−178.5 (4)
C1—C2—C3—C4	2.7 (5)	C31—C32—C33—N7	0.2 (8)
C2—C3—C4—C5	−2.7 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O1^i	0.85 (3)	1.92 (2)	2.763 (4)	176 (4)
O4—H4B···O9^ii	0.84 (3)	2.23 (2)	3.087 (18)	167 (4)
O4—H4B···O12	0.84 (3)	2.07 (2)	2.871 (10)	160 (4)
C15—H15···O11^ii	0.93	2.36	3.176 (12)	146
C21—H21···O10^iii	0.93	2.47	3.226 (10)	139
C26—H26···O7^iv	0.93	2.46	3.322 (8)	154
C27—H27···O3^v	0.93	2.49	3.233 (4)	138

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