catena-Poly[[(2,2′-diamino-4,4′-bithia­zole){μ₃-cis-N-(2-carboxyl­ato­phenyl)-N′-[3-(dimethyl­amino)­propyl]ox­ami­dato(3−)}dicopper(II)] nitrate 0.6-hydrate]

The title complex, {[Cu₂(C₁₄H₁₆N₃O₄)(C₆H₆N₄S₂)]NO₃·0.6H₂O}_n, is a one-dimensional copper(II) coordination polymer bridged by cis-oxamide and carboxyl­ate groups. The asymmetric unit is composed of a dinuclear copper(II) cation, [Cu₂(dmapob)(dabt)]⁺ {dmapob is N-(2-carboxyl­ato­phenyl)-N′-[3-(dimethyl­amino)­propyl]oxamidate and dabt is 2,2′-diamino-4,4′-bithia­zole}, one nitrate anion and one partially occupied site for a solvent water mol­ecule. The two Cu^II ions are located in square-planar and square-pyramidal coordination environments, respectively. The separations of the Cu atoms bridged by oxamide and carboxyl­ate groups are 5.2053 (3) and 5.0971 (4) Å, respectively. The complex chains are linked by classical hydrogen bonds to form a layer and then assembled by π–π stacking inter­actions into a three-dimensional network. The influence of the terminal ligand on the structure of the complex is discussed.

S1. Comment

Polymeric metal complexes, due to their novel structures, special properties and potential applications as metalloenzymes and catalysts, are of current interest, attracting increasing research effort (Miller & Epstein, 1994; Zhan et al., 2007). A successful strategy to construct polymeric metal complexes is self-assembly of metal ions and ligands with versatile coordination modes (Chen et al., 1998). N,N'-Bis(substituted)oxamides have played a key role in the design and synthesis of polymetallic systems, because their coordination abilities towards transition metal ions can be modified by changing the nature of the amide substituents (Ojima & Nonoyama, 1988). One of the outstanding characteristics of these ligands is the easy transformation of cis–trans conformations, which makes it practical to design tunable molecular materials with extended structures and desired properties (Ruiz et al., 1999). To date, many polymeric structures based on symmetrical N,N'-bis(substituted)oxamides have been reported (Costes et al., 1999; Gulbrandsen et al., 1993; Jiang et al., 2009; Li et al., 2008; Lloret et al., 1993; Nakatani et al., 1991; Rangmathan et al., 1995; Pei et al., 1988; Zhang et al., 2001). In contrast, due to the difficulty of synthesis, reports of complexes based on disymmetrical N,N'-bis(substituted)oxamides are few (Pei et al., 1989; Zang et al., 2003). To the best of our knowledge, only a two-dimensional copper(II)–manganese(II) polymer, {[Cu(oxbe)]Mn(H₂O)[Cu(oxbe)(DMF)].DMF.H₂O}_n, [oxbe is N-benzoato-N'-(2-aminoethyl)oxamide and DMF is dimethylformamide], (II), bridged simultaneously by disymmetrical cis-oxamide and carboxylate groups on the benzoate, has been reported (Zang et al., 2003), and no one-dimensional copper(II) complexes bridged by disymmetrical N,N'-bis(substituted)oxamides with the same coordination mode are known to date. However, complexes bridged by disymmetrical N,N'-bis(substituted)oxamides have shown magnetic properties (Larionova et al., 1997; Matović et al., 2005; Pei et al., 1989, 1991; Zang et al., 2003) and this prompted us to design and synthesize new polynuclear complexes.

Recently, we have synthesized a series of disymmetrical N,N'-bis(substituted)oxamide-bridged polynuclear metal complexes (Gu et al., 2009; Li et al., 2003, 2004; Liu et al., 2008). As an extension of our earlier research work and in order to investigate further the effect of terminal ligands on forming coordination polymers, we used N-(2-carboxylatophenyl)-N'-[3-(dimethylamino)propyl]oxamidate (dmapob) as a bridging ligand and 2,2'-diamino-4,4'-bithiazole (dabt) as a terminal ligand to synthesize the title novel one-dimensional copper(II) complex, (I).

Compound (I) exists as a one-dimensional coordination polymer extending along the b axis, constructed by the cis-oxamide and carboxylate groups connecting the Cu^II ions, and this structural unit can be considered as a cis-oxamide-bridged binuclear copper(II) fragment with dabt as the terminal ligand. An uncoordinated nitrate anion and a (depleted) solvent water molecule link to the chain through N—H···O and O—H···O hydrogen bonds (Fig. 1 and Table 2). In the binuclear fragment, the cis-oxamide group bridges the Cu^II ions in the usual chelating mode, with bite angles of 84.73 (9) for Cu1 and 83.74 (8)° for Cu2. Atoms Cu1 and Cu2 are 5.2050 (5) Å apart through the oxamide bridge. The binuclear fragments are bridged by the carboxylate groups in a nonplanar skew–skew fashion. The torsion angles Cu1—O1—C1—O2 [-148.5 (2)°] and Cu2ⁱⁱ—O2—C1—O1 [95.0 (3)°] [symmetry code: (ii) -x + 2, y + 1/2, -z + 1/2; Table 1] are similar to those found in other complexes with such carboxylate groups (Duan et al., 2006; Tong et al., 1997). The Cu···Cu separation through the carboxylate bridge is 5.0970 (5) Å.

The coordination environments of the two Cu^II ions are different. Atom Cu1, at the inner site of the cis-dmapob ligand, is located in a distorted [CuN₃O] square-planar environment. The maximum displacement of the coordination atoms from their least-squares plane is 0.1990 (13) Å for atom N1, and the displacement of atom Cu1 from this plane is 0.1067 (11) Å. Atom Cu2 is in a slightly distorted [CuN₃O₂] square-pyramidal coordination geometry with a τ value of 0.11 [Reference for definition of τ?]. The basal plane consists of two exo O atoms from the oxamide group and two N atoms from the dabt ligand, with a maximum deviation from the least-squares plane of 0.0588 (9) Å (atom N5). The apical position is occupied by a carboxyl O atom [O2ⁱ; symmetry code: (i) -x + 2, y - 1/2, -z + 1/2]. In this disposition, atom Cu2 is displaced 0.1881 (10) Å out of the basal plane towards the apical site.

The oxamide ligand coordinates to atom Cu1 in a tetradentate manner, forming one five- and two six-membered chelate rings (Fig. 1). The five-membered ring is planar. Regarding the two six-membered rings, the one formed by the propylenediamine fragment adopts a half-chair conformation, with puckering parameters (Cremer & Pople, 1975) of Q = 0.539 (3) Å, θ = 127.3 (3)° and ϕ = 30.3 (5)°. The second six-membered ring has a boat conformation, with puckering parameters Q = 0.332 (3) Å, θ = 89.0 (3)° and ϕ = 119.7 (4)°. The Cu1—N1 and Cu1—N2 bonds are shorter than Cu1—N3, which is consistent with the stronger donor abilities of the sp² N atoms over the sp³-hybridized N atoms (Jubert et al., 2002).

In the crystal structure, the (depleted) solvent water molecules and nitrate ions are assembled into a one-dimensional hydrogen-bonded chain parallel to the complex polymers (Fig. 2 and Table 2). The latter link to the chains through hydrogen bonds involving the amino groups of the dabt ligands, which gives rise to a two-dimensional classical hydrogen-bonding structure parallel to the (010) plane. Besides the hydrogen bonds, the layer contains an aromatic π–π stacking interaction between the thiazole ring containing atom S1 and the benzene ring of the dmapob ligand related by the symmetry operation (-x + 2, y - 1/2, -z + 1/2), (i). The smallest separation is 3.325 (3) Å (C2ⁱ, Table 3). Moreover, there is another kind of π–π interaction between the layers. It also involves the same S1-thiazole and benzene rings, but now the symmetry operation is (-x + 2, -y + 1, -z) (v). The minimum distance is 3.215 (4) Å (Table 3, C5^v to the thiazole ring).

On comparing complex (I) with the copper(II)–manganese(II) heterotrinuclear polymer, (II), reported by Zang et al. (2003), it can be seen that the two complexes have a similar skeleton, viz. an oxamidate bridging structure. Both of them are simultaneously bridged by disymmetrical cis-oxamide and carboxylate groups on benzoates, and the main difference resides in the terminal ligand (dabt) in complex (I), which generates two distinct results. Firstly, the chelating terminal ligand reduces the number of coordination sites of the metal ions used for coordinating to the bridging groups, and this has an influence on the dimensionality of the complex polymer. As shown in Fig. 3, in complex (II), the structural unit is a heterotrinuclear Cu^II–Mn^II–Cu^II fragment, which leaves two uncoordinated O atoms of the coordinated carboxylate groups of atoms Cu1 and Cu2 and two spare coordination sites on atoms Cu2 and Mn. Consequently, complex (II) exists as a two-dimensional polymer, while in the unit of (I) only one donor O atom and one spare coordination site remain, thus giving rise to a one-dimensional complex chain. Secondly, the aromatic terminal ligands also affect the supramolecular structure due to π–π stacking interactions. In complex (II), the two-dimensional complex polymers are assembled only by hydrogen bonds to form a three-dimensional network. However, in complex (I), as depicted above, the aromatic stacking interactions make an important contribution to the three-dimensional supramolecular structure. This is a clear example of how terminal ligands may strongly affect the construction of metal complex polymers by influencing the coordination sites and intermolecular interactions, and further investigations on the subject are proceeding in our laboratory.

S2. Experimental

All chemicals were of analytical reagent grade. H₃dmapob (0.0147 g, 0.05 mmol) was dissolved in methanol (5 ml). Piperidine (0.75 ml, 0.15 mmol) and a solution of Cu(NO₃)₂.3H₂O (0.0242 g, 0.10 mmol) in methanol (5 ml) were added with continuous stirring. After 0.5 h, a solution of dabt (0.01 g, 0.05 mmol) in methanol (5 ml) was added dropwise. The reaction mixture was stirred at 333 K for 6 h and filtered. Green block-shaped crystals of (I) of suitable size for X-ray diffraction analysis were obtained by slow evaporation of the filtrate at room temperature for three weeks (yield 63%). Elemental analysis, calculated for C₂₀H_23.2Cu₂N₈O_7.6S₂: C 23.18, H 2.25, N 10.8%; found: C 25.02, H 2.46, N 10.03%.

S3. Refinement

The occupation of the depleted solvent water molecule (O8) was initially refined, and then fixed in the final stages of refinement. Water and amino H atoms were found in an electron-density difference map. Water H atoms were further idealized, with O—H = 0.82Å, and treated as riding, with U_iso(H) = 1.2 or 1.5U_eq(O). Amino H atoms were refined with N—H restrained to 0.84 (2)Å and free isotropic displacement factors. The remaining H atoms were placed in calculated positions, with C—H = 0.93 (aromatic), 0.96 (methyl) and 0.97 Å (methylene), and refined in riding mode, with U_iso(H) = 1.2 or 1.5U_eq(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, 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. Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) -x + 2, y - 1/2, -z + 1/2; (ii) -x + 2, y + 1/2, -z + 1/2.]
	Fig. 2. The two-dimensional hydrogen-bonded structure of (I), parallel to (001), viewed perpendicular to the plane of the thiazole ring containing atom S1 of the dabt ligand. Hydrogen bonds are shown as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity. Note that the solvent water molecule O8 is depleted, with an occupancy factor of 0.60. [Symmetry codes: (ii) -x + 2, y + 1/2, -z + 1/2; (iii) -x + 1, y - 1/2, -z + 1/2; (iv) x - 1, y, z.]
	Fig. 3. A schematic drawing of the bridging skeletons in complex polymers (I) and (II).

catena-Poly[[(2,2'-diamino-4,4'-bithiazole){µ₃-cis-N- (2-carboxylatophenyl)-N'-[3- (dimethylamino)propyl]oxamidato(3-)}dicopper(II)] nitrate 0.6-hydrate]

Crystal data

[Cu2(C14H16N3O4)(C6H6N4S2)]NO3·0.6H2O	F(000) = 1400
Mr = 688.51	Dx = 1.787 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5918 reflections
a = 12.6991 (3) Å	θ = 2.8–27.6°
b = 14.0263 (3) Å	µ = 1.89 mm^−1
c = 15.0300 (3) Å	T = 296 K
β = 107.103 (2)°	Block, green
V = 2558.77 (10) Å^3	0.42 × 0.15 × 0.06 mm
Z = 4

Data collection

Bruker APEX CCD area-detector diffractometer	5918 independent reflections
Radiation source: fine-focus sealed tube	4589 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ϕ and ω scans	θmax = 27.7°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −16→5
Tmin = 0.505, Tmax = 0.895	k = −18→12
11743 measured reflections	l = −18→19

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.052P)^2 + 0.209P] where P = (Fo^2 + 2Fc^2)/3
5918 reflections	(Δ/σ)max = 0.001
380 parameters	Δρmax = 0.44 e Å^−3
2 restraints	Δρmin = −0.31 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.

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 > 2sigma(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	0.80644 (2)	0.77569 (2)	0.06620 (2)	0.03570 (10)
Cu2	0.92063 (2)	0.422539 (19)	0.14770 (2)	0.03447 (10)
S1	0.73503 (6)	0.15529 (5)	0.17342 (5)	0.04937 (19)
S2	1.22572 (6)	0.24913 (5)	0.15945 (6)	0.05001 (19)
O1	0.89280 (15)	0.88794 (12)	0.10392 (15)	0.0511 (5)
O2	1.03816 (15)	0.96004 (12)	0.19550 (12)	0.0433 (4)
O3	0.98983 (13)	0.53969 (11)	0.12039 (12)	0.0373 (4)
O4	0.78541 (14)	0.49798 (12)	0.10834 (13)	0.0433 (4)
N1	0.94052 (15)	0.69787 (13)	0.08385 (13)	0.0303 (4)
N2	0.73403 (16)	0.65385 (14)	0.07024 (15)	0.0380 (5)
N3	0.66686 (18)	0.85655 (15)	0.03676 (15)	0.0419 (5)
N4	0.84917 (16)	0.30036 (13)	0.15780 (14)	0.0333 (4)
N5	1.04864 (16)	0.33884 (13)	0.15382 (14)	0.0345 (4)
N6	0.6681 (2)	0.33799 (19)	0.1545 (2)	0.0506 (6)
N7	1.1913 (2)	0.43835 (18)	0.1410 (2)	0.0532 (6)
C1	0.9972 (2)	0.89549 (17)	0.13940 (18)	0.0364 (5)
C2	1.0730 (2)	0.82771 (16)	0.11232 (16)	0.0343 (5)
C3	1.04591 (19)	0.73288 (16)	0.08606 (15)	0.0310 (5)
C4	1.1236 (2)	0.67630 (17)	0.06215 (16)	0.0358 (5)
H4	1.1058	0.6138	0.0431	0.043*
C5	1.2265 (2)	0.7112 (2)	0.06621 (18)	0.0436 (6)
H5	1.2776	0.6718	0.0511	0.052*
C6	1.2536 (2)	0.8043 (2)	0.0926 (2)	0.0494 (7)
H6	1.3225	0.8283	0.0946	0.059*
C7	1.1775 (2)	0.86128 (19)	0.11587 (19)	0.0438 (6)
H7	1.1963	0.9238	0.1344	0.053*
C8	0.92245 (19)	0.60850 (16)	0.09978 (16)	0.0303 (5)
C9	0.80415 (19)	0.58473 (17)	0.09291 (17)	0.0334 (5)
C10	0.6168 (2)	0.6315 (2)	0.0569 (2)	0.0546 (8)
H10A	0.6110	0.5857	0.1036	0.066*
H10B	0.5858	0.6027	−0.0038	0.066*
C11	0.5523 (2)	0.7191 (2)	0.0642 (2)	0.0574 (8)
H11A	0.5758	0.7413	0.1282	0.069*
H11B	0.4750	0.7021	0.0494	0.069*
C12	0.5638 (2)	0.7999 (2)	0.0018 (2)	0.0552 (8)
H12A	0.5608	0.7740	−0.0588	0.066*
H12B	0.5013	0.8424	−0.0067	0.066*
C13	0.6695 (3)	0.9296 (2)	−0.0339 (2)	0.0605 (8)
H13A	0.6078	0.9718	−0.0425	0.091*
H13B	0.6657	0.8988	−0.0918	0.091*
H13C	0.7367	0.9654	−0.0131	0.091*
C14	0.6659 (3)	0.9085 (2)	0.1222 (2)	0.0595 (8)
H14A	0.7301	0.9482	0.1421	0.089*
H14B	0.6659	0.8635	0.1704	0.089*
H14C	0.6010	0.9474	0.1095	0.089*
C15	0.7502 (2)	0.27719 (17)	0.16171 (17)	0.0370 (5)
C16	0.8684 (2)	0.13758 (18)	0.17172 (19)	0.0453 (6)
H16	0.9026	0.0784	0.1761	0.054*
C17	0.9161 (2)	0.22087 (16)	0.16315 (16)	0.0348 (5)
C18	1.0277 (2)	0.24175 (16)	0.16122 (17)	0.0352 (5)
C19	1.1126 (2)	0.18436 (19)	0.16539 (19)	0.0446 (6)
H19	1.1110	0.1184	0.1708	0.053*
C20	1.1497 (2)	0.35367 (18)	0.15132 (18)	0.0391 (6)
N8	0.4748 (3)	0.4700 (3)	0.2113 (2)	0.0708 (8)
O5	0.4399 (3)	0.3879 (2)	0.1945 (2)	0.1055 (10)
O6	0.5700 (3)	0.4876 (3)	0.2522 (2)	0.1182 (12)
O7	0.4099 (3)	0.5346 (3)	0.1799 (3)	0.1353 (14)
O8	0.5261 (3)	0.2093 (3)	0.2242 (3)	0.0782 (12)	0.60
H8A	0.4898	0.2564	0.2287	0.117*	0.60
H8B	0.5165	0.1675	0.2592	0.117*	0.60
H6A	0.683 (2)	0.394 (2)	0.158 (2)	0.046 (9)*
H6B	0.620 (3)	0.319 (2)	0.177 (2)	0.050 (9)*
H7A	1.154 (2)	0.4860 (16)	0.146 (2)	0.052 (9)*
H7B	1.2590 (15)	0.4452 (19)	0.1480 (18)	0.040 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03122 (16)	0.02373 (16)	0.04998 (19)	0.00493 (12)	0.00857 (13)	0.00315 (12)
Cu2	0.03250 (16)	0.02073 (15)	0.04951 (19)	0.00206 (12)	0.01100 (13)	0.00255 (12)
S1	0.0498 (4)	0.0288 (3)	0.0703 (5)	−0.0064 (3)	0.0189 (4)	0.0028 (3)
S2	0.0416 (4)	0.0389 (4)	0.0706 (5)	0.0130 (3)	0.0182 (3)	0.0037 (3)
O1	0.0385 (10)	0.0233 (9)	0.0883 (14)	0.0031 (8)	0.0135 (10)	−0.0034 (9)
O2	0.0535 (11)	0.0253 (9)	0.0514 (11)	−0.0015 (8)	0.0161 (9)	−0.0007 (8)
O3	0.0331 (9)	0.0223 (8)	0.0564 (11)	0.0053 (7)	0.0132 (8)	0.0074 (7)
O4	0.0328 (9)	0.0263 (9)	0.0698 (12)	−0.0002 (7)	0.0133 (8)	0.0077 (8)
N1	0.0302 (10)	0.0215 (9)	0.0386 (11)	0.0015 (8)	0.0094 (8)	0.0016 (8)
N2	0.0283 (10)	0.0284 (11)	0.0559 (13)	0.0032 (9)	0.0100 (9)	0.0050 (9)
N3	0.0372 (11)	0.0330 (11)	0.0529 (13)	0.0091 (9)	0.0094 (10)	0.0060 (10)
N4	0.0352 (11)	0.0244 (10)	0.0401 (11)	0.0009 (9)	0.0109 (8)	−0.0011 (8)
N5	0.0342 (10)	0.0258 (10)	0.0423 (11)	0.0029 (9)	0.0092 (8)	0.0000 (8)
N6	0.0414 (14)	0.0324 (14)	0.0832 (19)	−0.0023 (11)	0.0262 (13)	0.0013 (12)
N7	0.0363 (14)	0.0356 (13)	0.090 (2)	0.0043 (11)	0.0224 (13)	0.0085 (12)
C1	0.0404 (14)	0.0221 (11)	0.0471 (14)	−0.0006 (10)	0.0135 (11)	0.0071 (10)
C2	0.0373 (13)	0.0291 (12)	0.0366 (12)	−0.0024 (10)	0.0107 (10)	0.0052 (10)
C3	0.0330 (12)	0.0274 (12)	0.0316 (12)	0.0011 (10)	0.0081 (9)	0.0060 (9)
C4	0.0398 (13)	0.0308 (13)	0.0381 (13)	0.0025 (11)	0.0135 (10)	0.0036 (10)
C5	0.0395 (14)	0.0498 (16)	0.0470 (15)	0.0061 (12)	0.0214 (12)	0.0045 (12)
C6	0.0387 (15)	0.0539 (17)	0.0611 (18)	−0.0061 (13)	0.0235 (13)	0.0064 (14)
C7	0.0426 (15)	0.0369 (14)	0.0530 (16)	−0.0078 (12)	0.0155 (12)	0.0021 (12)
C8	0.0302 (12)	0.0264 (11)	0.0344 (12)	0.0023 (10)	0.0094 (9)	−0.0001 (9)
C9	0.0304 (12)	0.0275 (12)	0.0414 (13)	−0.0012 (10)	0.0092 (10)	0.0011 (10)
C10	0.0305 (14)	0.0420 (16)	0.090 (2)	0.0002 (12)	0.0153 (14)	0.0061 (15)
C11	0.0310 (14)	0.0492 (17)	0.092 (2)	0.0030 (13)	0.0183 (15)	0.0025 (16)
C12	0.0383 (15)	0.0471 (17)	0.072 (2)	0.0104 (13)	0.0027 (13)	0.0059 (15)
C13	0.0598 (19)	0.0473 (17)	0.074 (2)	0.0233 (15)	0.0194 (16)	0.0221 (15)
C14	0.062 (2)	0.0535 (18)	0.067 (2)	0.0051 (16)	0.0236 (16)	−0.0116 (15)
C15	0.0434 (14)	0.0278 (12)	0.0397 (13)	−0.0033 (11)	0.0118 (11)	−0.0012 (10)
C16	0.0483 (16)	0.0266 (13)	0.0593 (17)	0.0049 (12)	0.0132 (13)	0.0027 (12)
C17	0.0403 (13)	0.0253 (12)	0.0366 (13)	0.0031 (10)	0.0079 (10)	−0.0005 (10)
C18	0.0407 (13)	0.0256 (12)	0.0370 (13)	0.0041 (11)	0.0080 (10)	0.0003 (10)
C19	0.0467 (15)	0.0316 (13)	0.0554 (16)	0.0078 (12)	0.0151 (12)	0.0024 (12)
C20	0.0384 (14)	0.0348 (13)	0.0435 (14)	0.0072 (11)	0.0110 (11)	0.0020 (11)
N8	0.0547 (18)	0.080 (2)	0.086 (2)	0.0145 (18)	0.0337 (16)	−0.0034 (18)
O5	0.110 (3)	0.086 (2)	0.136 (3)	−0.016 (2)	0.062 (2)	−0.015 (2)
O6	0.071 (2)	0.140 (3)	0.124 (3)	0.018 (2)	−0.0012 (17)	−0.052 (2)
O7	0.071 (2)	0.101 (3)	0.229 (4)	0.020 (2)	0.037 (2)	0.025 (3)
O8	0.076 (3)	0.083 (3)	0.084 (3)	0.003 (2)	0.036 (2)	0.010 (2)

Geometric parameters (Å, º)

Cu1—N1	1.9737 (18)	C2—C7	1.395 (3)
Cu1—N2	1.950 (2)	C2—C3	1.401 (3)
Cu1—N3	2.040 (2)	C3—C4	1.394 (3)
Cu2—N4	1.9658 (19)	C4—C5	1.379 (4)
Cu2—N5	1.9853 (19)	C4—H4	0.9300
Cu1—O1	1.9072 (18)	C5—C6	1.379 (4)
Cu2—O2^i	2.3192 (18)	C5—H5	0.9300
Cu2—O4	1.9547 (17)	C6—C7	1.376 (4)
Cu2—O3	1.9629 (16)	C6—H6	0.9300
S1—C16	1.719 (3)	C7—H7	0.9300
S1—C15	1.735 (2)	C8—C9	1.512 (3)
S2—C19	1.724 (3)	C10—C11	1.499 (4)
S2—C20	1.740 (3)	C10—H10A	0.9700
O1—C1	1.280 (3)	C10—H10B	0.9700
O2—C1	1.242 (3)	C11—C12	1.505 (4)
O2—Cu2^ii	2.3192 (18)	C11—H11A	0.9700
O3—C8	1.266 (3)	C11—H11B	0.9700
O4—C9	1.274 (3)	C12—H12A	0.9700
N1—C8	1.309 (3)	C12—H12B	0.9700
N1—C3	1.417 (3)	C13—H13A	0.9600
N2—C9	1.293 (3)	C13—H13B	0.9600
N2—C10	1.476 (3)	C13—H13C	0.9600
N3—C14	1.479 (4)	C14—H14A	0.9600
N3—C13	1.483 (3)	C14—H14B	0.9600
N3—C12	1.489 (4)	C14—H14C	0.9600
N4—C15	1.316 (3)	C16—C17	1.340 (3)
N4—C17	1.390 (3)	C16—H16	0.9300
N5—C20	1.312 (3)	C17—C18	1.456 (4)
N5—C18	1.398 (3)	C18—C19	1.332 (3)
N6—C15	1.326 (3)	C19—H19	0.9300
N6—H6A	0.80 (3)	N8—O6	1.210 (4)
N6—H6B	0.82 (3)	N8—O7	1.222 (4)
N7—C20	1.327 (3)	N8—O5	1.233 (4)
N7—H7A	0.831 (17)	O8—H8A	0.8188
N7—H7B	0.841 (17)	O8—H8B	0.8205
C1—C2	1.492 (3)
O1—Cu1—N2	161.70 (9)	C5—C6—H6	120.4
O1—Cu1—N1	91.07 (8)	C6—C7—C2	121.7 (2)
N2—Cu1—N1	84.68 (8)	C6—C7—H7	119.1
O1—Cu1—N3	89.57 (8)	C2—C7—H7	119.1
N2—Cu1—N3	96.11 (8)	O3—C8—N1	129.2 (2)
N1—Cu1—N3	175.36 (8)	O3—C8—C9	115.8 (2)
O4—Cu2—O3	83.74 (7)	N1—C8—C9	115.0 (2)
O4—Cu2—N4	96.36 (8)	O4—C9—N2	127.8 (2)
O3—Cu2—N4	172.37 (8)	O4—C9—C8	115.7 (2)
O4—Cu2—N5	165.60 (8)	N2—C9—C8	116.5 (2)
O3—Cu2—N5	95.39 (7)	N2—C10—C11	111.6 (2)
N4—Cu2—N5	82.60 (8)	N2—C10—H10A	109.3
O4—Cu2—O2^i	95.76 (7)	C11—C10—H10A	109.3
O3—Cu2—O2^i	92.38 (7)	N2—C10—H10B	109.3
N4—Cu2—O2^i	95.20 (7)	C11—C10—H10B	109.3
N5—Cu2—O2^i	98.63 (7)	H10A—C10—H10B	108.0
C16—S1—C15	90.10 (13)	C10—C11—C12	114.6 (3)
C19—S2—C20	89.66 (13)	C10—C11—H11A	108.6
C1—O1—Cu1	128.82 (16)	C12—C11—H11A	108.6
C1—O2—Cu2^ii	116.66 (15)	C10—C11—H11B	108.6
C8—O3—Cu2	112.17 (15)	C12—C11—H11B	108.6
C9—O4—Cu2	112.18 (15)	H11A—C11—H11B	107.6
C8—N1—C3	122.88 (19)	N3—C12—C11	114.7 (2)
C8—N1—Cu1	111.31 (15)	N3—C12—H12A	108.6
C3—N1—Cu1	125.67 (15)	C11—C12—H12A	108.6
C9—N2—C10	117.8 (2)	N3—C12—H12B	108.6
C9—N2—Cu1	111.78 (16)	C11—C12—H12B	108.6
C10—N2—Cu1	130.36 (17)	H12A—C12—H12B	107.6
C14—N3—C13	106.8 (2)	N3—C13—H13A	109.5
C14—N3—C12	109.8 (2)	N3—C13—H13B	109.5
C13—N3—C12	108.6 (2)	H13A—C13—H13B	109.5
C14—N3—Cu1	108.29 (17)	N3—C13—H13C	109.5
C13—N3—Cu1	109.77 (17)	H13A—C13—H13C	109.5
C12—N3—Cu1	113.43 (16)	H13B—C13—H13C	109.5
C15—N4—C17	112.0 (2)	N3—C14—H14A	109.5
C15—N4—Cu2	133.42 (17)	N3—C14—H14B	109.5
C17—N4—Cu2	114.55 (16)	H14A—C14—H14B	109.5
C20—N5—C18	111.6 (2)	N3—C14—H14C	109.5
C20—N5—Cu2	134.40 (17)	H14A—C14—H14C	109.5
C18—N5—Cu2	114.03 (16)	H14B—C14—H14C	109.5
C15—N6—H6A	117 (2)	N4—C15—N6	125.1 (2)
C15—N6—H6B	115 (2)	N4—C15—S1	112.56 (19)
H6A—N6—H6B	118 (3)	N6—C15—S1	122.3 (2)
C20—N7—H7A	117 (2)	C17—C16—S1	110.5 (2)
C20—N7—H7B	121.0 (19)	C17—C16—H16	124.7
H7A—N7—H7B	119 (3)	S1—C16—H16	124.7
O2—C1—O1	121.2 (2)	C16—C17—N4	114.8 (2)
O2—C1—C2	118.4 (2)	C16—C17—C18	130.4 (2)
O1—C1—C2	120.4 (2)	N4—C17—C18	114.8 (2)
C7—C2—C3	118.9 (2)	C19—C18—N5	115.0 (2)
C7—C2—C1	117.2 (2)	C19—C18—C17	131.0 (2)
C3—C2—C1	123.9 (2)	N5—C18—C17	114.0 (2)
C4—C3—C2	118.7 (2)	C18—C19—S2	110.8 (2)
C4—C3—N1	122.2 (2)	C18—C19—H19	124.6
C2—C3—N1	119.2 (2)	S2—C19—H19	124.6
C5—C4—C3	121.3 (2)	N5—C20—N7	124.9 (2)
C5—C4—H4	119.3	N5—C20—S2	113.06 (19)
C3—C4—H4	119.3	N7—C20—S2	122.1 (2)
C6—C5—C4	120.1 (2)	O6—N8—O7	120.4 (4)
C6—C5—H5	119.9	O6—N8—O5	122.6 (4)
C4—C5—H5	119.9	O7—N8—O5	116.9 (4)
C7—C6—C5	119.3 (2)	H8A—O8—H8B	109.3
C7—C6—H6	120.4
N2—Cu1—O1—C1	67.0 (4)	C8—N1—C3—C2	−149.9 (2)
N1—Cu1—O1—C1	−9.1 (2)	Cu1—N1—C3—C2	25.4 (3)
N3—Cu1—O1—C1	175.5 (2)	C2—C3—C4—C5	1.7 (3)
O4—Cu2—O3—C8	5.89 (16)	N1—C3—C4—C5	−178.9 (2)
N4—Cu2—O3—C8	97.1 (6)	C3—C4—C5—C6	−1.3 (4)
N5—Cu2—O3—C8	171.45 (16)	C4—C5—C6—C7	0.8 (4)
O2^i—Cu2—O3—C8	−89.65 (16)	C5—C6—C7—C2	−0.8 (4)
O3—Cu2—O4—C9	−6.00 (17)	C3—C2—C7—C6	1.3 (4)
N4—Cu2—O4—C9	−178.33 (17)	C1—C2—C7—C6	179.8 (2)
N5—Cu2—O4—C9	−93.3 (3)	Cu2—O3—C8—N1	174.9 (2)
O2^i—Cu2—O4—C9	85.77 (17)	Cu2—O3—C8—C9	−4.7 (2)
O1—Cu1—N1—C8	155.23 (17)	C3—N1—C8—O3	1.1 (4)
N2—Cu1—N1—C8	−6.94 (16)	Cu1—N1—C8—O3	−174.8 (2)
N3—Cu1—N1—C8	−106.9 (10)	C3—N1—C8—C9	−179.19 (19)
O1—Cu1—N1—C3	−20.53 (19)	Cu1—N1—C8—C9	4.9 (2)
N2—Cu1—N1—C3	177.30 (19)	Cu2—O4—C9—N2	−176.6 (2)
N3—Cu1—N1—C3	77.4 (10)	Cu2—O4—C9—C8	5.1 (3)
O1—Cu1—N2—C9	−69.4 (3)	C10—N2—C9—O4	−2.3 (4)
N1—Cu1—N2—C9	7.79 (18)	Cu1—N2—C9—O4	174.5 (2)
N3—Cu1—N2—C9	−176.81 (18)	C10—N2—C9—C8	176.1 (2)
O1—Cu1—N2—C10	106.9 (3)	Cu1—N2—C9—C8	−7.2 (3)
N1—Cu1—N2—C10	−176.0 (3)	O3—C8—C9—O4	−0.2 (3)
N3—Cu1—N2—C10	−0.6 (3)	N1—C8—C9—O4	−179.9 (2)
O1—Cu1—N3—C14	−57.43 (19)	O3—C8—C9—N2	−178.8 (2)
N2—Cu1—N3—C14	105.14 (19)	N1—C8—C9—N2	1.5 (3)
N1—Cu1—N3—C14	−155.4 (9)	C9—N2—C10—C11	160.1 (3)
O1—Cu1—N3—C13	58.8 (2)	Cu1—N2—C10—C11	−16.0 (4)
N2—Cu1—N3—C13	−138.60 (19)	N2—C10—C11—C12	53.2 (4)
N1—Cu1—N3—C13	−39.1 (11)	C14—N3—C12—C11	−66.6 (3)
O1—Cu1—N3—C12	−179.5 (2)	C13—N3—C12—C11	177.0 (2)
N2—Cu1—N3—C12	−17.0 (2)	Cu1—N3—C12—C11	54.7 (3)
N1—Cu1—N3—C12	82.5 (10)	C10—C11—C12—N3	−79.3 (3)
O4—Cu2—N4—C15	−15.8 (2)	C17—N4—C15—N6	−177.2 (2)
O3—Cu2—N4—C15	−106.2 (6)	Cu2—N4—C15—N6	3.7 (4)
N5—Cu2—N4—C15	178.6 (2)	C17—N4—C15—S1	0.6 (3)
O2^i—Cu2—N4—C15	80.6 (2)	Cu2—N4—C15—S1	−178.51 (13)
O4—Cu2—N4—C17	165.08 (16)	C16—S1—C15—N4	−0.5 (2)
O3—Cu2—N4—C17	74.7 (6)	C16—S1—C15—N6	177.4 (2)
N5—Cu2—N4—C17	−0.46 (16)	C15—S1—C16—C17	0.2 (2)
O2^i—Cu2—N4—C17	−98.52 (16)	S1—C16—C17—N4	0.0 (3)
O4—Cu2—N5—C20	92.5 (4)	S1—C16—C17—C18	178.0 (2)
O3—Cu2—N5—C20	6.7 (2)	C15—N4—C17—C16	−0.4 (3)
N4—Cu2—N5—C20	179.3 (3)	Cu2—N4—C17—C16	178.86 (18)
O2^i—Cu2—N5—C20	−86.6 (2)	C15—N4—C17—C18	−178.7 (2)
O4—Cu2—N5—C18	−86.5 (3)	Cu2—N4—C17—C18	0.5 (3)
O3—Cu2—N5—C18	−172.30 (16)	C20—N5—C18—C19	0.8 (3)
N4—Cu2—N5—C18	0.29 (16)	Cu2—N5—C18—C19	179.98 (18)
O2^i—Cu2—N5—C18	94.46 (16)	C20—N5—C18—C17	−179.3 (2)
Cu2^ii—O2—C1—O1	95.1 (2)	Cu2—N5—C18—C17	−0.1 (3)
Cu2^ii—O2—C1—C2	−86.2 (2)	C16—C17—C18—C19	1.6 (5)
Cu1—O1—C1—O2	−148.44 (19)	N4—C17—C18—C19	179.6 (3)
Cu1—O1—C1—C2	33.0 (3)	C16—C17—C18—N5	−178.3 (3)
O2—C1—C2—C7	−27.7 (3)	N4—C17—C18—N5	−0.3 (3)
O1—C1—C2—C7	150.9 (2)	N5—C18—C19—S2	−0.4 (3)
O2—C1—C2—C3	150.7 (2)	C17—C18—C19—S2	179.7 (2)
O1—C1—C2—C3	−30.7 (4)	C20—S2—C19—C18	0.0 (2)
C7—C2—C3—C4	−1.6 (3)	C18—N5—C20—N7	177.4 (3)
C1—C2—C3—C4	180.0 (2)	Cu2—N5—C20—N7	−1.6 (4)
C7—C2—C3—N1	178.9 (2)	C18—N5—C20—S2	−0.8 (3)
C1—C2—C3—N1	0.5 (3)	Cu2—N5—C20—S2	−179.76 (13)
C8—N1—C3—C4	30.7 (3)	C19—S2—C20—N5	0.5 (2)
Cu1—N1—C3—C4	−154.06 (18)	C19—S2—C20—N7	−177.7 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8A···O5	0.82	1.97	2.717 (5)	152
O8—H8B···O7^iii	0.82	2.16	2.838 (6)	140
N6—H6A···O4	0.80 (3)	2.22 (3)	2.889 (3)	140 (3)
N6—H6B···O5	0.82 (3)	2.56 (3)	3.206 (4)	136 (3)
N6—H6B···O8	0.82 (3)	2.19 (3)	2.953 (5)	154 (3)
N7—H7A···O3	0.83 (2)	2.15 (2)	2.863 (3)	144 (3)
N7—H7B···O5^iv	0.84 (2)	2.34 (2)	3.101 (4)	151 (2)
N7—H7B···O7^iv	0.84 (2)	2.22 (2)	2.986 (4)	151 (2)

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