Bis[[mu]₃-cis-N-(2-amino­prop­yl)-N'-(2-carboxyl­atophen­yl)oxamidato(3-)]bis­(2,2'-bipyridine)dichloridotetra­copper(II) dihydrate

The title complex, bis­[[mu]₃-cis-N-(2-amino­prop­yl)-N'-(2-carboxyl­atophen­yl)oxamidato(3-)]-1:2:4[kappa]⁷N,N',N'',O:O',O'':O''';2:3:4[kappa]⁷O''':N,N',N'',O:O',O''-bis­(2,2'-bipyridine)-2[kappa]²N,N';4[kappa]²N,N'-dichlorido-1[kappa]Cl,3[kappa]Cl-tetra­copper(II) dihydrate, [Cu₄(C₁₂H₁₂N₃O₄)₂Cl₂(C₁₀H₈N₂)₂]·2H₂O, consists of a neutral cyclic tetra­copper(II) system having an embedded centre of inversion and two solvent water mol­ecules. The coordination of each Cu^II atom is square-pyramidal. The separations of Cu^II atoms bridged by cis-N-(2-amino­prop­yl)-N'-(2-carboxyl­ato­phen­yl)oxamidate(3-) and carboxyl groups are 5.2096 (4) and 5.1961 (5) Å, respectively. A three-dimensional supra­molecular structure involving hydrogen bonding and aromatic stacking is observed.

S1. Comment

It is known that N,N'-bis(substituted)oxamides could be good candidates in forming polynuclear complexes, because their coordinating ability toward transition-metal ions can be modified and tuned by changing the nature of the amide substituents (Ojima & Nonoyama, 1988). A typical feature of these ligands is an easy transformation of cis–trans conformations, which makes it practical to design tunable molecular materials with desired properties (Ruiz et al., 1999). To date, many polynuclear complexes containing oxamide bridges have been synthesized and their properties studied extensively (Messori et al., 2003; Wang et al., 2004). Compared with studies dealing with symmetrical N,N'-bis(substituted)oxamide polynuclear systems, relatively few studies dealing with dissymmetrical N,N'-bis(substituted)oxamide polynuclear complexes have been reported, owing to difficulties in the synthesis (Matović et al., 2005; Zang et al., 2003). However, the fact that those complexes bridged by dissymmetrical N,N'-bis(substituted)oxamides have shown predominant properties (Costes et al., 2000; Erxleben, 2001; Larionova et al., 1997; Pei et al., 1989, 1991) stimulated us to design and synthesize new polynuclear complexes with dissymmetrical N,N'-bis(substituted)oxamides to explore their special structures and functionalities. In continuation of our earlier work (Li et al., 2003, 2004; Liu et al., 2008), in this paper, a novel tetranuclear copper(II) complex bridged by an asymmetrical oxamide ligand, cis-N-(2-aminopropyl)-N'-(2-carboxylatophenyl)oxamidate(3-) (oxbm), and end-capped with 2,2'-bipyridine (bpy), namely, [Cu₄(oxbm)₂(bpy)₂Cl₂].2H₂O, (I), has been synthesized, and the crystal structure of the complex is reported here.

A perspective view of complex (I) is depicted in Fig. 1, and selected bond lengths and angles are listed in Table 1. As shown in Fig. 1, the asymmetric unit can be considered as a cis-oxamide-bridged dinuclear copper(II) complex linked with a solvent water molecule by an O—H···Cl hydrogen bond, [Cu₂(oxbm)(bpy)Cl].H₂O. Through carboxyl bridges, a pair of units assemble to form a circular tetranuclear system with inversion symmetry. The cis-oxamide group coordinates to atoms Cu1 and Cu2 in an usual mode with bite angles of 83.40 (9) and 85.23 (8)°, respectively. The carboxyl group bridges Cu atoms in a nonplanar skew–skew fashion. The Cu1—O1—C1—O2 and Cu2ⁱ—O2—C1—O1 torsion angles [symmetry code: (i) -x + 1, -y, -z + 1; Table 1] are similar to those found in other complexes with skew–skew carboxyl bridges (Duan et al., 2006; Tong et al., 1997). The Cu···Cu separations through the oxamide and carboxyl bridges are 5.2096 (4) and 5.1961 (5) Å, respectively. To date, seven cyclic tetranuclear complexes with symmetrical oxamide bridges have been synthesized and structurally characterized (Abbati et al., 1999; Li et al., 2008; Ribas et al., 1998; Zhu et al., 2007). However, the title complex is the first instance of a dissymmetrical oxamide.

Atoms Cu1 and Cu2 are both in square-pyramidal coordination geometries with τ values of 0.08 and 0.03 (Addison et al., 1984), respectively. Atom Cu1 resides in an inner site of the cis-oxbm^3- ligand; the basal plane is defined by atoms N1, N2, N3 and O1, and from the least-squares plane ddefined by these atoms the maximum displacement is 0.1073 (15) Å for N2 and the displacement of atom Cu1 is 0.2403 (13) Å. The apical position is occupied by atom Cl1. Atom Cu2 coordinates to the exo-cis O atoms of the oxbm^3- ligand (O3 and O4), and the N atoms (N4 and N5) of the bpy ligand complete the basal plane, from which the maximum deviation is 0.0190 (12) Å (N4). The apical site is occupied by a carboxyl O atom (O2ⁱ). Atom Cu2 is pulled 0.2101 (12) Å out of the basal plane by the apical O2ⁱ atom.

The oxbm^3- ligand chelates atom Cu1 to form two five-membered and a six-membered chelate rings. One of the five-membered rings is planar, and the other has an envelope conformation puckered on the chiral C11 atom, the puckering parameters (Cremer & Pople, 1975) being Q = 0.399 (3) Å and ϕ = 114.2 (4)°. The six-membered ring adopts a boat conformation with puckering parameters Q = 0.304 (3) Å, θ = 87.9 (6)° and ϕ = 300.8 (5)°. The Cu1—N1 and Cu1—N2 bonds are shorter than the Cu1—N3 bond (Table 1), which is consistent with the stronger donor ability of the deprotonated amide N atom compared with the primary amine N atom (Jubert et al., 2002).

In the crystal structure, neutral tetranuclear complexes and solvent water molecules are connected by classical hydrogen bonds into a one-dimensional chain parallel to the a axis (Table 2). The chains are linked through non-classical C—H···Cl hydrogen bonds into a two-dimensional hydrogen-bonding network extending along the (011) plane (Fig. 2). Moreover, offset π–π stacking is observed between the pyridine ring containing N4 and the phenyl ring belonging to a neighbouring complex, the nearest separation being 3.421 (4) Å for atom C6^iv [symmetry code: (iv) x, y, z - 1; Fig. 3]. The stackings dominate the interactions between the hydrogen-bond layers and hold them together to create a three-dimensional supramolecular structure.

Related literature

For related literature, see: Abbati et al. (1999); Addison et al. (1984); Costes et al. (2000); Cremer & Pople (1975); Duan et al. (2006); Erxleben (2001); Jubert et al. (2002); Larionova et al. (1997); Li et al. (2003, 2004, 2008); Liu et al. (2008); Matović et al. (2005); Messori et al. (2003); Ojima & Nonoyama (1988); Pei et al. (1989, 1991); Ribas et al. (1998); Ruiz et al. (1999); Tao et al. (2003); Tong et al. (1997); Wang et al. (2004); Zang et al. (2003); Zhu et al. (2007).

S2. Experimental

All reagents were of analytical reagent grade and were used without further purification. The Na[Cu(oxbm)] ligand was prepared according to the method described by Tao et al. (2003). The title complex, [Cu₂(oxbm)(bpy)Cl]₂.2H₂O was obtained as follows. A methanol (5 ml) solution of CuCl₂.2H₂O (0.0085 g, 0.05 mmol) was added dropwise into an aqueous solution (5 ml) of Na[Cu(oxbm)] (0.0349 g, 0.1 mmol) with continuous stirring. The mixture was stirred quickly for an hour and then 2,2'-bipyridine (0.0078 g, 0.05 mmol) in methanol (5 ml) was added dropwise. The solution obtained was further stirred at 333 K for 6 h. The resulting solution was then filtered and the filtrate was allowed to stand at room temperature for one week to give well shaped green crystals suitable for X-ray analysis (yield 72%). Elemental analysis for C₄₄H₄₄Cl₂Cu₄N₁₀O₁₀, calculated: C 44.11, H 3.70, N 11.69%; found: C 44.31, H 3.78, N 11.71%.

S3. Refinement

The methyl group is disordered over two positions, C12A and C12B, whose occupancy factors were refined and then fixed at 0.7 and 0.3, respectively. The C11—C12B bond length of was restrained to a reasonable C—C value, and the C10···C12A and C10···C12B distances of were limited to be equal, as were the N3···C12A and N3···C12B distances. Water H atoms were found in a difference Fourier map and were treated as riding, with fixed U_iso(H) values of 0.08 Ų. The remaining H atoms were placed in calculated positions with N—H distance of 0.90 Å and C—H distances of 0.93 (aromatic), 0.96 (methyl), 0.97 (methylene) or 0.98 Å (methine), and refined in riding mode, with U_iso(H) set at 1.2U_eq(C,N) or 1.5U_eq(methyl C).

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, 2008a); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008a); molecular graphics: XP (Siemens, 1994) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. For clarity, the atoms of the asymmetric residue unit and its counterpart are represented in different styles, and the bonds of C12B are depicted with open lines. Dashed lines indicate hydrogen bonds. [Symmetry code: (i) -x +1, -y, -z +1.]
	Fig. 2. A view of the two-dimensional hydrogen-bonding structure of (I). Hydrogen bonds are shown as dotted lines; H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (ii) -x + 2, -y, -z + 1; (iii) -x + 1, -y + 1, -z]
	Fig. 3. A view showing the π–π stacking interactions along the c axis, viewed perpendicular to the pyridine plane. H atoms and water molecules have been omitted for clarity. [Symmetry codes: (iv) x, y, z - 1.]

bis[µ₃-cis-N-(2-aminopropyl)-N'-(2- carboxylatophenyl)oxamidato(3-)]-1:2:4κ⁷N,N',N'', O:O',O":O''';2:4:3κ⁷O''':O', O":N,N',N'',O-bis(2,2'-bipyridine)- 2κ²N,N';4κ²N,N'-dichlorido-1κCl,3κCl- tetracopper(II) dihydrate

Crystal data

[Cu4(C12H12N3O4)2Cl2(C10H8N2)2]·2H2O	Z = 1
Mr = 1197.95	F(000) = 608
Triclinic, P1	Dx = 1.701 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.9622 (1) Å	Cell parameters from 7568 reflections
b = 11.1330 (2) Å	θ = 2.4–27.6°
c = 11.2876 (2) Å	µ = 1.98 mm^−1
α = 67.072 (1)°	T = 298 K
β = 69.842 (1)°	Block, green
γ = 72.688 (1)°	0.28 × 0.22 × 0.17 mm
V = 1169.57 (3) Å^3

Data collection

Bruker APEX area-detector diffractometer	5441 independent reflections
Radiation source: fine-focus sealed tube	4353 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
phi and ω scans	θmax = 27.7°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b)	h = −14→14
Tmin = 0.607, Tmax = 0.730	k = −14→14
16602 measured reflections	l = −14→14

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0413P)^2 + 1.5166P] where P = (Fo^2 + 2Fc^2)/3
5441 reflections	(Δ/σ)max = 0.001
328 parameters	Δρmax = 0.98 e Å^−3
3 restraints	Δρmin = −0.78 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	Occ. (<1)
Cu1	0.77756 (3)	0.05900 (4)	0.44379 (3)	0.03567 (11)
Cu2	0.45722 (3)	0.28278 (3)	0.13513 (3)	0.03533 (10)
Cl1	0.85509 (9)	0.27782 (9)	0.41557 (9)	0.0578 (2)
O1	0.75838 (19)	−0.0232 (2)	0.63187 (19)	0.0425 (5)
O2	0.6451 (2)	−0.1184 (2)	0.83390 (19)	0.0398 (5)
O3	0.44344 (18)	0.2359 (2)	0.32489 (19)	0.0373 (4)
O4	0.63968 (19)	0.1901 (2)	0.12240 (18)	0.0383 (4)
O5	1.0895 (3)	0.2385 (3)	0.1443 (3)	0.0651 (7)
H5A	1.0391	0.2643	0.2171	0.080*
H5B	1.1616	0.2081	0.1601	0.080*
N1	0.5857 (2)	0.1356 (2)	0.4648 (2)	0.0313 (5)
N2	0.7760 (2)	0.0862 (3)	0.2650 (2)	0.0391 (6)
N3	0.9681 (2)	−0.0300 (3)	0.3808 (2)	0.0441 (6)
H3A	1.0227	0.0273	0.3543	0.053*
H3B	0.9919	−0.1009	0.4477	0.053*
N4	0.4793 (3)	0.3625 (3)	−0.0577 (2)	0.0440 (6)
N5	0.2875 (3)	0.4153 (3)	0.1380 (3)	0.0450 (6)
C1	0.6514 (3)	−0.0291 (3)	0.7237 (3)	0.0325 (6)
C2	0.5284 (3)	0.0757 (3)	0.7064 (3)	0.0316 (5)
C3	0.4974 (2)	0.1543 (3)	0.5842 (3)	0.0310 (5)
C4	0.3812 (3)	0.2504 (3)	0.5856 (3)	0.0433 (7)
H4	0.3592	0.3025	0.5059	0.052*
C5	0.2983 (3)	0.2691 (4)	0.7037 (3)	0.0527 (8)
H5	0.2227	0.3350	0.7022	0.063*
C6	0.3269 (3)	0.1908 (4)	0.8236 (3)	0.0500 (8)
H6	0.2706	0.2026	0.9031	0.060*
C7	0.4399 (3)	0.0950 (3)	0.8238 (3)	0.0408 (7)
H7	0.4582	0.0411	0.9048	0.049*
C8	0.5542 (3)	0.1770 (3)	0.3515 (3)	0.0312 (5)
C9	0.6666 (3)	0.1484 (3)	0.2351 (3)	0.0321 (5)
C10	0.8970 (3)	0.0388 (3)	0.1771 (3)	0.0445 (7)
H10A	0.9459	0.1099	0.1217	0.053*
H10B	0.8772	0.0049	0.1200	0.053*
C11	0.9770 (3)	−0.0721 (4)	0.2685 (3)	0.0551 (9)
H11B	0.9308	−0.1471	0.3074	0.066*	0.70
H11A	1.0698	−0.0789	0.2168	0.066*	0.30
C12A	1.1116 (5)	−0.1214 (6)	0.1989 (5)	0.0626 (15)	0.70
H12A	1.1550	−0.1911	0.2621	0.094*	0.70
H12B	1.1602	−0.0501	0.1549	0.094*	0.70
H12C	1.1076	−0.1551	0.1342	0.094*	0.70
C12B	0.9513 (17)	−0.2058 (7)	0.3121 (14)	0.092 (5)	0.30
H12D	0.9839	−0.2389	0.2379	0.137*	0.30
H12E	0.8578	−0.2037	0.3467	0.137*	0.30
H12F	0.9952	−0.2627	0.3804	0.137*	0.30
C13	0.5817 (4)	0.3278 (4)	−0.1497 (4)	0.0610 (10)
H13	0.6515	0.2617	−0.1235	0.073*
C14	0.5882 (5)	0.3881 (5)	−0.2864 (4)	0.0762 (13)
H14	0.6606	0.3642	−0.3515	0.091*
C15	0.4814 (6)	0.4844 (4)	−0.3182 (4)	0.0753 (13)
H15	0.4825	0.5264	−0.4076	0.090*
C16	0.3749 (5)	0.5208 (4)	−0.2256 (4)	0.0664 (11)
H16	0.3042	0.5862	−0.2504	0.080*
C17	0.3743 (4)	0.4577 (3)	−0.0925 (3)	0.0506 (9)
C18	0.2666 (3)	0.4848 (3)	0.0172 (4)	0.0476 (8)
C19	0.1460 (4)	0.5739 (4)	0.0047 (5)	0.0687 (12)
H19	0.1321	0.6236	−0.0791	0.082*
C20	0.0518 (4)	0.5863 (5)	0.1146 (6)	0.0826 (14)
H20	−0.0285	0.6438	0.1074	0.099*
C21	0.0730 (4)	0.5152 (5)	0.2367 (5)	0.0785 (13)
H21	0.0080	0.5238	0.3133	0.094*
C22	0.1931 (3)	0.4297 (4)	0.2454 (4)	0.0574 (9)
H22	0.2079	0.3810	0.3290	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02575 (17)	0.0496 (2)	0.02596 (17)	0.00529 (14)	−0.01248 (13)	−0.01034 (14)
Cu2	0.03379 (18)	0.0419 (2)	0.02658 (17)	−0.00226 (14)	−0.01659 (14)	−0.00315 (14)
Cl1	0.0507 (5)	0.0529 (5)	0.0608 (5)	−0.0018 (4)	−0.0240 (4)	−0.0067 (4)
O1	0.0294 (10)	0.0571 (13)	0.0289 (10)	0.0011 (9)	−0.0138 (8)	−0.0026 (9)
O2	0.0403 (11)	0.0438 (11)	0.0292 (10)	−0.0081 (9)	−0.0158 (8)	0.0006 (8)
O3	0.0282 (9)	0.0502 (12)	0.0296 (10)	0.0039 (8)	−0.0151 (8)	−0.0105 (8)
O4	0.0334 (10)	0.0532 (12)	0.0258 (9)	−0.0028 (9)	−0.0129 (8)	−0.0096 (8)
O5	0.0536 (15)	0.0720 (17)	0.0689 (17)	0.0010 (13)	−0.0351 (13)	−0.0145 (14)
N1	0.0244 (10)	0.0417 (12)	0.0231 (10)	0.0004 (9)	−0.0092 (8)	−0.0078 (9)
N2	0.0282 (11)	0.0575 (15)	0.0285 (12)	0.0046 (10)	−0.0115 (9)	−0.0164 (11)
N3	0.0329 (12)	0.0540 (15)	0.0382 (13)	0.0111 (11)	−0.0171 (10)	−0.0148 (11)
N4	0.0519 (15)	0.0498 (15)	0.0297 (12)	−0.0150 (12)	−0.0162 (11)	−0.0034 (11)
N5	0.0436 (14)	0.0383 (13)	0.0547 (16)	0.0007 (11)	−0.0311 (13)	−0.0069 (12)
C1	0.0347 (14)	0.0373 (14)	0.0274 (13)	−0.0072 (11)	−0.0153 (11)	−0.0056 (11)
C2	0.0309 (13)	0.0364 (13)	0.0266 (12)	−0.0058 (11)	−0.0106 (10)	−0.0069 (10)
C3	0.0259 (12)	0.0398 (14)	0.0253 (12)	−0.0032 (10)	−0.0083 (10)	−0.0091 (10)
C4	0.0356 (15)	0.0536 (18)	0.0316 (14)	0.0056 (13)	−0.0118 (12)	−0.0118 (13)
C5	0.0388 (16)	0.063 (2)	0.0429 (18)	0.0118 (15)	−0.0093 (14)	−0.0205 (16)
C6	0.0437 (17)	0.066 (2)	0.0341 (16)	−0.0028 (15)	−0.0025 (13)	−0.0217 (15)
C7	0.0437 (16)	0.0504 (17)	0.0252 (13)	−0.0074 (13)	−0.0101 (12)	−0.0090 (12)
C8	0.0276 (12)	0.0364 (13)	0.0271 (12)	−0.0025 (10)	−0.0118 (10)	−0.0061 (10)
C9	0.0303 (13)	0.0406 (14)	0.0246 (12)	−0.0045 (11)	−0.0098 (10)	−0.0089 (10)
C10	0.0336 (15)	0.063 (2)	0.0337 (15)	0.0079 (13)	−0.0111 (12)	−0.0225 (14)
C11	0.0495 (19)	0.063 (2)	0.0463 (18)	0.0181 (16)	−0.0200 (15)	−0.0255 (16)
C12A	0.042 (3)	0.084 (4)	0.055 (3)	0.020 (2)	−0.016 (2)	−0.036 (3)
C12B	0.112 (14)	0.058 (9)	0.117 (14)	0.004 (9)	−0.066 (12)	−0.024 (9)
C13	0.068 (2)	0.073 (3)	0.0412 (19)	−0.021 (2)	−0.0147 (17)	−0.0124 (17)
C14	0.098 (3)	0.094 (3)	0.040 (2)	−0.046 (3)	0.001 (2)	−0.021 (2)
C15	0.119 (4)	0.067 (3)	0.047 (2)	−0.034 (3)	−0.041 (3)	0.0037 (19)
C16	0.108 (3)	0.050 (2)	0.046 (2)	−0.019 (2)	−0.042 (2)	0.0016 (16)
C17	0.074 (2)	0.0365 (16)	0.0495 (19)	−0.0190 (15)	−0.0427 (18)	0.0069 (13)
C18	0.0547 (19)	0.0343 (15)	0.057 (2)	−0.0049 (13)	−0.0352 (17)	−0.0029 (14)
C19	0.072 (3)	0.046 (2)	0.086 (3)	−0.0003 (18)	−0.054 (3)	0.0016 (19)
C20	0.052 (2)	0.069 (3)	0.109 (4)	0.017 (2)	−0.035 (3)	−0.018 (3)
C21	0.049 (2)	0.076 (3)	0.094 (3)	0.016 (2)	−0.023 (2)	−0.027 (3)
C22	0.0433 (18)	0.060 (2)	0.061 (2)	0.0070 (16)	−0.0201 (17)	−0.0166 (18)

Geometric parameters (Å, º)

Cu1—Cl1	2.6832 (10)	C6—C7	1.372 (4)
Cu1—N1	1.988 (2)	C6—H6	0.9300
Cu1—N2	1.925 (2)	C7—H7	0.9300
Cu1—N3	2.035 (2)	C8—C9	1.524 (4)
Cu1—O1	1.9188 (19)	C10—C11	1.531 (4)
Cu2—N4	1.961 (2)	C10—H10A	0.9700
Cu2—N5	2.000 (3)	C10—H10B	0.9700
Cu2—O2^i	2.276 (2)	C11—C12B	1.456 (7)
Cu2—O3	1.9586 (19)	C11—C12A	1.466 (5)
Cu2—O4	1.9430 (19)	C11—H11B	0.9800
O1—C1	1.269 (3)	C11—H11A	0.9800
O2—C1	1.248 (3)	C12A—H11A	0.5960
O2—Cu2^i	2.276 (2)	C12A—H12A	0.9600
O3—C8	1.273 (3)	C12A—H12B	0.9600
O4—C9	1.280 (3)	C12A—H12C	0.9600
O5—H5A	0.9167	C12B—H12D	0.9600
O5—H5B	0.8134	C12B—H12E	0.9600
N1—C8	1.310 (3)	C12B—H12F	0.9600
N1—C3	1.414 (3)	C13—C14	1.408 (5)
N2—C9	1.279 (3)	C13—H13	0.9300
N2—C10	1.451 (3)	C14—C15	1.375 (7)
N3—C11	1.479 (4)	C14—H14	0.9300
N3—H3A	0.9000	C15—C16	1.352 (7)
N3—H3B	0.9000	C15—H15	0.9300
N4—C13	1.318 (5)	C16—C17	1.387 (5)
N4—C17	1.365 (4)	C16—H16	0.9300
N5—C22	1.324 (5)	C17—C18	1.445 (5)
N5—C18	1.341 (4)	C18—C19	1.412 (5)
C1—C2	1.511 (4)	C19—C20	1.338 (7)
C2—C7	1.399 (4)	C19—H19	0.9300
C2—C3	1.410 (3)	C20—C21	1.356 (7)
C3—C4	1.399 (4)	C20—H20	0.9300
C4—C5	1.383 (4)	C21—C22	1.386 (5)
C4—H4	0.9300	C21—H21	0.9300
C5—C6	1.379 (5)	C22—H22	0.9300
C5—H5	0.9300
N1—Cu1—N2	83.40 (9)	N1—C8—C9	115.1 (2)
O3—Cu2—O4	85.23 (8)	N2—C9—O4	129.2 (3)
O1—Cu1—N2	159.82 (11)	N2—C9—C8	114.2 (2)
O1—Cu1—N1	93.77 (8)	O4—C9—C8	116.6 (2)
O1—Cu1—N3	97.86 (9)	N2—C10—C11	105.8 (2)
N2—Cu1—N3	82.10 (10)	N2—C10—H10A	110.6
N1—Cu1—N3	164.39 (10)	C11—C10—H10A	110.6
O1—Cu1—Cl1	97.77 (7)	N2—C10—H10B	110.6
N2—Cu1—Cl1	102.41 (9)	C11—C10—H10B	110.6
N1—Cu1—Cl1	97.27 (7)	H10A—C10—H10B	108.7
N3—Cu1—Cl1	91.45 (9)	C12B—C11—C12A	87.8 (8)
O4—Cu2—N4	95.30 (10)	C12B—C11—N3	112.6 (6)
O3—Cu2—N4	168.64 (10)	C12A—C11—N3	115.1 (3)
O4—Cu2—N5	166.56 (10)	C12B—C11—C10	117.4 (6)
O3—Cu2—N5	95.10 (10)	C12A—C11—C10	114.2 (3)
N4—Cu2—N5	81.76 (12)	N3—C11—C10	108.7 (3)
O4—Cu2—O2^i	101.63 (8)	C12A—C11—H11B	106.0
O3—Cu2—O2^i	94.04 (8)	N3—C11—H11B	106.0
N4—Cu2—O2^i	96.96 (9)	C10—C11—H11B	106.0
N5—Cu2—O2^i	91.75 (9)	C12B—C11—H11A	104.3
C1—O1—Cu1	127.26 (17)	N3—C11—H11A	106.5
C1—O2—Cu2^i	114.78 (17)	C10—C11—H11A	106.5
C8—O3—Cu2	111.56 (17)	H11B—C11—H11A	122.6
C9—O4—Cu2	111.12 (17)	C11—C12A—H12A	109.5
H5A—O5—H5B	102.6	H11A—C12A—H12A	119.0
C8—N1—C3	124.3 (2)	C11—C12A—H12B	109.5
C8—N1—Cu1	111.55 (17)	H11A—C12A—H12B	81.6
C3—N1—Cu1	123.92 (16)	C11—C12A—H12C	109.5
C9—N2—C10	126.4 (2)	H11A—C12A—H12C	123.0
C9—N2—Cu1	115.30 (19)	C11—C12B—H12D	109.5
C10—N2—Cu1	118.28 (18)	C11—C12B—H12E	109.5
C11—N3—Cu1	108.06 (19)	H12D—C12B—H12E	109.5
C11—N3—H3A	110.1	C11—C12B—H12F	109.5
Cu1—N3—H3A	110.1	H12D—C12B—H12F	109.5
C11—N3—H3B	110.1	H12E—C12B—H12F	109.5
Cu1—N3—H3B	110.1	N4—C13—C14	121.7 (4)
H3A—N3—H3B	108.4	N4—C13—H13	119.1
C13—N4—C17	120.6 (3)	C14—C13—H13	119.1
C13—N4—Cu2	125.4 (2)	C15—C14—C13	116.2 (4)
C17—N4—Cu2	113.9 (2)	C15—C14—H14	121.9
C22—N5—C18	119.4 (3)	C13—C14—H14	121.9
C22—N5—Cu2	126.3 (2)	C16—C15—C14	123.1 (4)
C18—N5—Cu2	114.0 (2)	C16—C15—H15	118.4
O2—C1—O1	121.3 (2)	C14—C15—H15	118.4
O2—C1—C2	117.4 (2)	C15—C16—C17	118.0 (4)
O1—C1—C2	121.2 (2)	C15—C16—H16	121.0
C7—C2—C3	118.5 (2)	C17—C16—H16	121.0
C7—C2—C1	115.6 (2)	N4—C17—C16	120.3 (4)
C3—C2—C1	125.9 (2)	N4—C17—C18	115.5 (3)
C4—C3—C2	118.5 (2)	C16—C17—C18	124.1 (3)
C4—C3—N1	122.3 (2)	N5—C18—C19	120.2 (4)
C2—C3—N1	119.2 (2)	N5—C18—C17	114.6 (3)
C5—C4—C3	121.1 (3)	C19—C18—C17	125.1 (3)
C5—C4—H4	119.4	C20—C19—C18	119.3 (4)
C3—C4—H4	119.4	C20—C19—H19	120.3
C6—C5—C4	120.6 (3)	C18—C19—H19	120.3
C6—C5—H5	119.7	C19—C20—C21	120.2 (4)
C4—C5—H5	119.7	C19—C20—H20	119.9
C7—C6—C5	118.9 (3)	C21—C20—H20	119.9
C7—C6—H6	120.5	C20—C21—C22	119.0 (4)
C5—C6—H6	120.5	C20—C21—H21	120.5
C6—C7—C2	122.3 (3)	C22—C21—H21	120.5
C6—C7—H7	118.8	N5—C22—C21	121.8 (4)
C2—C7—H7	118.8	N5—C22—H22	119.1
O3—C8—N1	129.6 (2)	C21—C22—H22	119.1
O3—C8—C9	115.3 (2)
Cu1—O1—C1—O2	155.8 (2)	Cu1—N1—C3—C4	154.7 (2)
Cu2^i—O2—C1—O1	−103.9 (3)	C8—N1—C3—C2	162.3 (3)
N2—Cu1—O1—C1	−75.0 (4)	Cu1—N1—C3—C2	−24.0 (4)
N1—Cu1—O1—C1	6.1 (3)	C2—C3—C4—C5	0.4 (5)
N3—Cu1—O1—C1	−163.5 (3)	N1—C3—C4—C5	−178.2 (3)
Cl1—Cu1—O1—C1	104.0 (2)	C3—C4—C5—C6	−1.7 (6)
O4—Cu2—O3—C8	3.68 (19)	C4—C5—C6—C7	0.8 (6)
N4—Cu2—O3—C8	−89.5 (5)	C5—C6—C7—C2	1.3 (5)
N5—Cu2—O3—C8	−162.8 (2)	C3—C2—C7—C6	−2.4 (5)
O2^i—Cu2—O3—C8	105.04 (19)	C1—C2—C7—C6	177.0 (3)
O3—Cu2—O4—C9	−2.40 (19)	Cu2—O3—C8—N1	176.9 (3)
N4—Cu2—O4—C9	166.2 (2)	Cu2—O3—C8—C9	−4.1 (3)
N5—Cu2—O4—C9	89.6 (5)	C3—N1—C8—O3	−2.4 (5)
O2^i—Cu2—O4—C9	−95.55 (19)	Cu1—N1—C8—O3	−176.8 (3)
O1—Cu1—N1—C8	−165.6 (2)	C3—N1—C8—C9	178.6 (2)
N2—Cu1—N1—C8	−5.7 (2)	Cu1—N1—C8—C9	4.2 (3)
N3—Cu1—N1—C8	−27.4 (5)	C10—N2—C9—O4	−4.7 (5)
Cl1—Cu1—N1—C8	96.05 (19)	Cu1—N2—C9—O4	173.6 (2)
O1—Cu1—N1—C3	20.0 (2)	C10—N2—C9—C8	176.0 (3)
N2—Cu1—N1—C3	179.9 (2)	Cu1—N2—C9—C8	−5.8 (3)
N3—Cu1—N1—C3	158.2 (3)	Cu2—O4—C9—N2	−178.4 (3)
Cl1—Cu1—N1—C3	−78.4 (2)	Cu2—O4—C9—C8	0.9 (3)
O1—Cu1—N2—C9	89.4 (3)	O3—C8—C9—N2	−178.3 (3)
N1—Cu1—N2—C9	6.4 (2)	N1—C8—C9—N2	0.8 (4)
N3—Cu1—N2—C9	−179.3 (2)	O3—C8—C9—O4	2.2 (4)
Cl1—Cu1—N2—C9	−89.6 (2)	N1—C8—C9—O4	−178.6 (2)
O1—Cu1—N2—C10	−92.2 (3)	C9—N2—C10—C11	−158.0 (3)
N1—Cu1—N2—C10	−175.1 (3)	Cu1—N2—C10—C11	23.7 (3)
N3—Cu1—N2—C10	−0.9 (2)	Cu1—N3—C11—C12B	−89.7 (7)
Cl1—Cu1—N2—C10	88.8 (2)	Cu1—N3—C11—C12A	171.8 (3)
O1—Cu1—N3—C11	136.3 (2)	Cu1—N3—C11—C10	42.2 (3)
N2—Cu1—N3—C11	−23.3 (2)	N2—C10—C11—C12B	87.2 (8)
N1—Cu1—N3—C11	−1.5 (5)	N2—C10—C11—C12A	−172.1 (4)
Cl1—Cu1—N3—C11	−125.7 (2)	N2—C10—C11—N3	−42.1 (4)
O4—Cu2—N4—C13	13.3 (3)	C17—N4—C13—C14	1.0 (6)
O3—Cu2—N4—C13	105.5 (5)	Cu2—N4—C13—C14	178.4 (3)
N5—Cu2—N4—C13	−179.9 (3)	N4—C13—C14—C15	−0.4 (6)
O2^i—Cu2—N4—C13	−89.1 (3)	C13—C14—C15—C16	−0.1 (7)
O4—Cu2—N4—C17	−169.1 (2)	C14—C15—C16—C17	0.1 (7)
O3—Cu2—N4—C17	−76.9 (6)	C13—N4—C17—C16	−1.0 (5)
N5—Cu2—N4—C17	−2.3 (2)	Cu2—N4—C17—C16	−178.7 (3)
O2^i—Cu2—N4—C17	88.4 (2)	C13—N4—C17—C18	178.5 (3)
O4—Cu2—N5—C22	−104.9 (5)	Cu2—N4—C17—C18	0.8 (4)
O3—Cu2—N5—C22	−14.2 (3)	C15—C16—C17—N4	0.4 (5)
N4—Cu2—N5—C22	176.8 (3)	C15—C16—C17—C18	−179.0 (4)
O2^i—Cu2—N5—C22	80.1 (3)	C22—N5—C18—C19	1.0 (5)
O4—Cu2—N5—C18	81.8 (5)	Cu2—N5—C18—C19	174.7 (3)
O3—Cu2—N5—C18	172.6 (2)	C22—N5—C18—C17	−177.9 (3)
N4—Cu2—N5—C18	3.6 (2)	Cu2—N5—C18—C17	−4.1 (4)
O2^i—Cu2—N5—C18	−93.2 (2)	N4—C17—C18—N5	2.2 (4)
Cu2^i—O2—C1—C2	79.0 (3)	C16—C17—C18—N5	−178.3 (3)
Cu1—O1—C1—C2	−27.2 (4)	N4—C17—C18—C19	−176.5 (3)
O2—C1—C2—C7	24.4 (4)	C16—C17—C18—C19	2.9 (6)
O1—C1—C2—C7	−152.7 (3)	N5—C18—C19—C20	−1.3 (6)
O2—C1—C2—C3	−156.3 (3)	C17—C18—C19—C20	177.4 (4)
O1—C1—C2—C3	26.7 (4)	C18—C19—C20—C21	1.0 (7)
C7—C2—C3—C4	1.5 (4)	C19—C20—C21—C22	−0.3 (8)
C1—C2—C3—C4	−177.8 (3)	C18—N5—C22—C21	−0.3 (6)
C7—C2—C3—N1	−179.8 (3)	Cu2—N5—C22—C21	−173.2 (3)
C1—C2—C3—N1	0.9 (4)	C20—C21—C22—N5	−0.1 (7)
C8—N1—C3—C4	−19.1 (4)

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
O5—H5A···Cl1	0.92	2.47	3.335 (3)	159
O5—H5B···O2^ii	0.81	2.07	2.870 (3)	168
N3—H3B···Cl1^ii	0.90	2.55	3.406 (2)	158
N3—H3A···O1^ii	0.90	2.44	3.172 (3)	138
C16—H16···Cl1^iii	0.93	2.70	3.549 (4)	152

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