A coordination polymer consisting of two different one-dimensional copper(II) chains

The title compound, catena-poly[[[di­aqua­(methanol-[kappa]O)cop­per(II)]-[mu]-N-(4-methyl­pyrimidin-2-yl-[kappa]N¹)pyrazin-2-amine-[kappa]²N¹:N⁴] [[aqua­(aqua/methanol-[kappa]O)(perchlorato-[kappa]O)cop­per(II)]-[mu]-N-(4-methyl­pyrimidin-2-yl-[kappa]N¹)pyrazin-2-amine-[kappa]²N¹:N⁴] tris­(perchlorate) methanol monosolvate 1.419-hy­drate], {[Cu(C₉H₉N₅)(CH₃OH)(H₂O)₂][Cu(C₉H₉N₅)(ClO₄)(CH₃OH)_0.581(H₂O)_1.419](ClO₄)₃·CH₃OH·1.419H₂O}_n, is a one-dimensional straight-chain polymer of N-(4-methyl­py­rimidin-2-yl)pyrazin-2-amine (L) with Cu(ClO₄)₂. The complex con­sists of two crystallographically independent one-dimensional chains in which the Cu^II atoms exhibit two different octa­hedral coordination geometries. The L ligand coordinates to two Cu^II centres in a tridentate manner, with the pyrazine ring acting as a bridge linking the Cu^II coordination units and building an infinite one-dimensional chain. Extensive hydrogen bonding among perchlorate anions, water mol­ecules and L ligands results in three-dimensional networks.

S1. Introduction

Metal–organic frameworks have been studied extensively over the past several decades (Cairns et al., 2008; Dalrymple & Shimizu, 2007; Xie et al., 2004) because of their potential applications in a wide range of areas, including catalysis, separation science, gas storage, drug delivery, molecule-based optical and magnetic materials etc. (Kesanli & Lin, 2003; Brammer, 2004; Gimeno & Vilar, 2006; Kitagawa & Matsuda, 2007). The factors affecting the structure and packing of molecules in crystallization are intricate and are still not clearly understood. Different structures can result from changes to any one of a numbers of factors, i.e. solvent, acidity, ratio of the rea­cta­nts, carbon backbone of the ligand and so on (Ouellette et al., 2007; Zhao et al., 2008). Nitro­gen-containing heterocyclic ligands have proved to be extremely versatile, with the abilities to build extended networks with different coordination modes and to mediate significant magnetic inter­actions between paramagnetic centres separated by more than 6 Å (Carranza et al., 2004). A wide variety of nitro­gen-containing heterocyclic ligands have been used to construct coordination polymers, such as pyrrole, pyrazole, pyridine, pyrimidine, pyrazine, and so on (Wang et al., 2008; Ismayilov et al., 2006). Originally designed for the synthesis of extended metal atom chain complexes (EMACs), oligo-α-pyridyl­amine compounds have been shown to be excellent coordination ligands. Recently, a series of modified ligands, viz. oligo-α-pyrazyl/pyrimidyl/pyridyl­amine, have been developed by grafting pyrazine or pyrimidine into the ligands instead of pyridine rings (Ismayilov et al., 2007; Wang et al., 2007, 2012). Containing more atoms capable of coordination, these molecules showed abundant coordination modes, especially in the construction of one-, two- and three-dimensional coordination polymers. Here, a one-dimensional copper(II) complex of N-(4-methyl­pyrimidin-2-yl)pyrazin-2-amine (L) is reported, namely {[Cu(L)(MeOH)(H₂O)₂][Cu(ClO₄)(L)(MeOH/H₂O)₂(H₂O)](ClO₄)₃.MeOH.1.419H₂O}_n, (1), which provides a rare case consisting of two independent one-dimensional chains with different coordination geometries.

S2. Experimental

S2.1. Synthesis and crystallization

A mixture of N-(4-methyl­pyrimidin-2-yl)pyrazin-2-amine (0.10 g, 0.58 mmol) and Cu(ClO₄)₂.6H₂O (0.24 g, 0.65 mmol) in methanol (50 ml) was stirred overnight. The solution was then filtered to remove insoluble impurities and concentrated under vacuum. Slow evaporation of the solution gave crystals suitable for X-ray diffraction.

S2.2. Refinement

The equatorial plane of the Cu2 complex found in the chain is defined by three N atoms (N6, N7 and N10) and by the coordinated disordered water/methanol molecules (O5, O5–C20) with 0.419 (6) water and 0.581 (6) methanol occupancies. A perchlorate anion coordinated to Cu2 as an axial ligand is disordered over two positions (Cl4/O18/O21 and Cl4'/O18'/O21') and was treated with 0.529 (4) and 0.471 (4) occupancies. Atoms O21 and O21' were restrained to have similar displacement parameters. The displacement parameters of the atoms in the disordered perchlorate anion were constrained to be equivalent. One uncoordinated methanol solvent molecule was found to be disordered over the two positions O23/C21 and O23'/C21' and were treated with 0.581 (6) and 0.419 (6) occupancies, respectively. Bond distances involving non-H atoms in the disordered methanol molecules were subjected to distance restraints. The C—O distances within the two components of the disordered methanol solvent molecule (O23—C21 and O23'—C21') are restrained to 1.45 (1) Å and the methanol molecule was modeled with isotropic displacement parameters. Water atom O24 had a short contact of 2.14 Å with methanol atom O23. The free variable for the occupancy factor of uncoordinated water molecule O24 was applied and the occupancy was 0.419 (6) and the atom was refined with an isotropic displacement parameter. H atoms bonded to the coordinated and uncoordinated water molecules were located in difference Fourier maps and the O—H and H···H distances were restrained to be 0.85 (2) and 1.35 (2) Å, respectively. The U_iso(H) values were set at 1.5U_eq(O). H atoms bonded to C and N atoms were positioned geometrically and refined using a riding model, with C—H = 0.95–0.98 Å and N—H = 0.88 Å, and with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(methyl C). The refinement of the H atoms of the methanol solvent molecule required the inclusion of inter­molecular restraints to avoid convergence to unreasonable inter­molecular H···H distances. The inter­molecular H···H shortest contact distances were restrained to 2.25 (2) Å.

S3. Results and discussion

The reaction of N-(4-methyl­pyrimidin-2-yl)pyrazin-2-amine (L) with Cu(ClO₄)₂ results in a coordination polymer consisting of two crystallographically independent one-dimensional chains along the c axis, denoted chains (I) and (II); the atom-numbering scheme is shown in Fig. 1. In chain (I), the Cu1 atom is o­cta­hedrally coordinated by two pyrazine N atoms [N1 and N2ⁱ; symmetry code: (i) x, -y+1/2, z+1/2] that are trans to each other, two cis water molecules, a pyrimidine N atom and a methanol O atom. The axial positions are occupied by one water molecule (O2) and one methanol molecule (O3). Elongation occurs along the axial positions due to the Jahn–Teller effect, which is typical for a Cu^II complex (electronic configuration d⁹). This phenomenon was observed in both chains. The coordination geometry and bond lengths are consistent with data reported previously for similar complexes (Wang et al., 2008; Ismayilov et al., 20060 (Table 2). The L ligand acts as a tridentate ligand, coordinating to atom Cu1 via two N atoms and bridging to a symmetry-related Cu1ⁱⁱ atom via the second N atom (N2) of the pyrazine ring [symmetry code: (ii) x, -y+3/2, z-1/2]. Thus, through the pyrazine ring, the coordination units form an infinite one-dimensional straight chain polymer. Atoms N3 and N4 both remain uncoordinated. The straight chain structure is similar to that obtained from middle-ring pyrazine-containing oligo-α-pyridyl­amino ligands, where it was reported that the methyl group and pyrimidine ring contribute little to the formation of the polymer of analogous ligands (Wang et al., 2008).

The Cu^II atom (Cu2) in chain (II) also adopts a six-coordinate o­cta­hedral geometry, in which the coordination mode of the L ligand is the same as that in chain (I), i.e.. the L ligand coordinates to atom Cu2 as a tridentate ligand, chelating to one Cu centre via a pyrazine and a pyrimidine N atom, with the second pyrazine N atom (N7) coordinating to a symmetry-related Cu2^iv atom, thus creating an infinite one-dimensional straight chain [symmetry code: (iv) x, -y+3/2, z+1/2]. Atom Cu2 is o­cta­hedrally coordinated by two pyrazine N atoms (N6 and N7ⁱⁱ) that are trans to each other, a water molecule (O4), a coordinated disordered water/methanol molecule [O5: 0.419 (6) water and 0.581 (6) methanol], a pyrimidine N atom and a perchlorate anion. The perchlorate anion coordinates weakly to atom Cu2 with a relatively long Cu2—O19 distance (Table 2). This weak coordination bond is presumably due to the poor coordination ability of perchlorate counter-ions and the Jahn–Teller effect of the Cu centre, and has been observed in other related complexes with even longer Cu—O distances of 2.573 (5) and 2.588 (2) Å (Wang et al., 2008; Ismayilov et al., 2006).

Extensive hydrogen bonding is observed among the perchlorate anions, water molecules and L ligands (Table 3, and Figs. 2 and 3). The one-dimensional straight chains are linked along the a axis through inter­chain water–perchlorate O2···O7 hydrogen-bonding inter­actions. This is propagated by a water–perchlorate O1···O20ⁱⁱⁱ hydrogen bond [symmetry code: (iii) -x, -y+1, -z+1] resulting in a two-dimensional sheet parallel to the ac plane. The resulting two-dimensional sheet is then hydrogen bonded to other sheets through inter­actions with the inter­stitial perchlorate anions and water molecules. Atoms N3 and N8 and coordinated water molecule O2 form hydrogen bonds to the inter­stital perchlorate counter-anions. Coordinated water molecule O1 forms a hydrogen bond to water molecule O22, which in turn forms a hydrogen bond to the inter­stitial perchlorate anions. This series of hydrogen bonds among the components of the structure results in the three-dimensional hydrogen-bonded network.

In summary, with five N atoms, the L ligand shows a versatile and rich coordination chemistry and supra­molecular structure constructed by hydrogen bonds, which allows for a variety of potentially tunable coordination polymers.

Related literature

For related literature, see: Brammer (2004); Cairns et al. (2008); Carranza et al. (2004); Dalrymple & Shimizu (2007); Gimeno & Vilar (2006); Ismayilov et al. (2006, 2007); Kesanli & Lin (2003); Kitagawa & Matsuda (2007); Ouellette et al. (2007); Wang et al. (2007, 2008, 2012); Xie et al. (2004); Zhao et al. (2008).

Computing details

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The asymmetric unit of (1). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The two-dimensional hydrogen-bonding network between perchlorate anions and water molecules. H atoms not involved in these interactions, the disordered atoms, and the uncoordinated water and methanol molecules have been omitted for clarity. [Symmetry codes: (i) x, -y+1/2, z + 1/2; (iii) -x, -y+1, -z+1.]
	Fig. 3. The interchain hydrogen-bonding interactions along the b axis. H atoms not involved in these interactions, the disordered atoms, and the uncoordinated water and methanol molecules have been omitted for clarity. [Symmetry codes: (i) x, -y+1/2, z+1/2; (iv) x,y-1, z.]

catena-Poly[[[diaqua(methanol-κO)copper(II)]-µ-N-(4-methylpyrimidin-2-yl-κN¹)pyrazin-2-amine-κ²N¹:N⁴] [[aqua(aqua/methanol-κO)(perchlorato-κO)copper(II)]-µ-N-(4-methylpyrimidin-2-yl-κN¹)pyrazin-2-amine-κ²N¹:N⁴] tris(perchlorate) methanol monosolvate 1.42-hydrate]

Crystal data

[Cu(C9H9N5)(CH4O)(H2O)2] [Cu(ClO4)(C9H9N5)(CH4O)0.581(H2O)1.419]·(ClO4)3·CH4O·1.419H2O	F(000) = 2176
Mr = 1068.32	Dx = 1.759 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7928 reflections
a = 15.0769 (4) Å	θ = 1.0–27.5°
b = 20.0774 (7) Å	µ = 1.42 mm^−1
c = 13.7166 (3) Å	T = 150 K
β = 103.7105 (15)°	Needle, green
V = 4033.8 (2) Å^3	0.40 × 0.08 × 0.08 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	7928 independent reflections
Radiation source: fine-focus sealed tube	4878 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
ω scans	θmax = 26.0°, θmin = 1.4°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −16→18
Tmin = 0.783, Tmax = 0.898	k = −24→24
20877 measured reflections	l = −16→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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.194	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0962P)^2 + 8.0361P] where P = (Fo^2 + 2Fc^2)/3
7921 reflections	(Δ/σ)max = 0.001
601 parameters	Δρmax = 1.49 e Å^−3
237 restraints	Δρmin = −0.60 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	0.24119 (4)	0.24519 (3)	0.51225 (4)	0.02431 (19)
O1	0.1476 (3)	0.17418 (19)	0.4858 (3)	0.0346 (9)
H1A	0.099 (3)	0.171 (3)	0.504 (5)	0.052*
H1B	0.164 (4)	0.1347 (15)	0.476 (5)	0.052*
O2	0.3559 (3)	0.1663 (2)	0.5367 (3)	0.0438 (11)
H2A	0.401 (3)	0.175 (3)	0.512 (5)	0.066*
H2B	0.367 (4)	0.1284 (18)	0.563 (5)	0.066*
O3	0.1274 (3)	0.3285 (2)	0.4792 (3)	0.0381 (10)
H3	0.148 (5)	0.3649 (19)	0.504 (5)	0.057*
N1	0.2440 (3)	0.2494 (2)	0.3661 (3)	0.0249 (10)
N2	0.2362 (3)	0.2546 (2)	0.1611 (3)	0.0244 (10)
N3	0.2831 (3)	0.3629 (2)	0.3754 (3)	0.0308 (11)
H3B	0.2665	0.4005	0.3433	0.037*
N4	0.3698 (3)	0.4282 (2)	0.4965 (3)	0.0364 (12)
N5	0.3342 (3)	0.3178 (2)	0.5367 (3)	0.0256 (10)
C1	0.2263 (4)	0.1943 (3)	0.3057 (4)	0.0289 (12)
H1	0.2156	0.1530	0.3347	0.035*
C2	0.2233 (4)	0.1964 (3)	0.2062 (4)	0.0284 (12)
H2	0.2122	0.1566	0.1676	0.034*
C3	0.2521 (4)	0.3086 (3)	0.2166 (4)	0.0240 (11)
H3A	0.2592	0.3501	0.1861	0.029*
C4	0.2586 (4)	0.3061 (3)	0.3211 (4)	0.0246 (12)
C5	0.3308 (4)	0.3688 (3)	0.4748 (4)	0.0307 (13)
C6	0.4242 (4)	0.4360 (3)	0.5879 (4)	0.0436 (16)
C7	0.4430 (4)	0.3814 (3)	0.6539 (4)	0.0407 (15)
H7	0.4867	0.3846	0.7162	0.049*
C8	0.3962 (4)	0.3235 (3)	0.6255 (4)	0.0321 (13)
H8A	0.4075	0.2863	0.6694	0.039*
C9	0.4607 (6)	0.5034 (4)	0.6165 (5)	0.058 (2)
H9A	0.4163	0.5368	0.5834	0.088*
H9B	0.5180	0.5093	0.5955	0.088*
H9C	0.4720	0.5086	0.6894	0.088*
C10	0.0332 (5)	0.3237 (4)	0.4573 (7)	0.069 (2)
H10A	0.0135	0.2859	0.4122	0.104*
H10B	0.0063	0.3648	0.4246	0.104*
H10C	0.0132	0.3170	0.5195	0.104*
Cu2	0.21091 (5)	0.74407 (3)	0.35222 (5)	0.0314 (2)
O4	0.3197 (3)	0.6650 (3)	0.3799 (3)	0.0570 (13)
H4A	0.326 (5)	0.6226 (15)	0.401 (6)	0.086*
H4B	0.372 (3)	0.680 (3)	0.410 (6)	0.086*
O5	0.1129 (3)	0.6763 (2)	0.3244 (3)	0.0468 (11)
H5A	0.1365	0.6327	0.3316	0.070*	0.581 (6)
H5B	0.1265	0.6351	0.3271	0.070*	0.419 (6)
H5C	0.0573	0.6883	0.3095	0.070*	0.419 (6)
N6	0.2088 (3)	0.7471 (2)	0.4994 (3)	0.0333 (11)
N7	0.2035 (3)	0.7511 (2)	0.7007 (3)	0.0307 (11)
N8	0.2358 (3)	0.8621 (2)	0.5065 (3)	0.0372 (12)
H8	0.2110	0.8984	0.5243	0.045*
N9	0.3231 (4)	0.9309 (3)	0.4372 (3)	0.0414 (13)
N10	0.2998 (3)	0.8186 (2)	0.3796 (3)	0.0336 (11)
C11	0.1976 (4)	0.6916 (3)	0.5510 (4)	0.0363 (14)
H11	0.1908	0.6501	0.5169	0.044*
C12	0.1955 (4)	0.6927 (3)	0.6494 (4)	0.0338 (13)
H12	0.1885	0.6523	0.6827	0.041*
C13	0.2141 (4)	0.8063 (3)	0.6515 (4)	0.0329 (13)
H13	0.2188	0.8479	0.6853	0.039*
C14	0.2185 (4)	0.8042 (3)	0.5504 (4)	0.0339 (14)
C15	0.2876 (4)	0.8699 (3)	0.4377 (4)	0.0377 (14)
C16	0.3843 (4)	0.9398 (3)	0.3808 (4)	0.0432 (16)
C17	0.4113 (4)	0.8867 (3)	0.3298 (4)	0.0423 (15)
H17	0.4596	0.8917	0.2967	0.051*
C18	0.3671 (4)	0.8272 (3)	0.3279 (4)	0.0408 (15)
H18	0.3829	0.7912	0.2905	0.049*
C19	0.4186 (5)	1.0089 (3)	0.3769 (5)	0.0538 (18)
H19A	0.4118	1.0334	0.4365	0.081*
H19B	0.3833	1.0311	0.3165	0.081*
H19C	0.4831	1.0076	0.3751	0.081*
C20	0.0241 (10)	0.6773 (9)	0.2594 (13)	0.096 (6)	0.581 (6)
H20A	−0.0098	0.7157	0.2756	0.144*	0.581 (6)
H20B	−0.0082	0.6362	0.2682	0.144*	0.581 (6)
H20C	0.0292	0.6806	0.1897	0.144*	0.581 (6)
Cl1	0.51320 (11)	0.25412 (9)	0.39226 (11)	0.0487 (4)
O6	0.4680 (12)	0.2977 (12)	0.311 (2)	0.067 (3)	0.529 (4)
O7	0.4467 (12)	0.1983 (13)	0.383 (2)	0.087 (5)	0.529 (4)
O8	0.519 (3)	0.2965 (18)	0.479 (3)	0.096 (7)	0.529 (4)
O9	0.594 (5)	0.232 (4)	0.364 (7)	0.062 (8)	0.529 (4)
O6'	0.4429 (14)	0.2814 (14)	0.323 (2)	0.067 (3)	0.471 (4)
O7'	0.4815 (14)	0.1874 (15)	0.412 (3)	0.087 (5)	0.471 (4)
O8'	0.530 (4)	0.275 (2)	0.492 (3)	0.096 (7)	0.471 (4)
O9'	0.597 (5)	0.245 (4)	0.372 (7)	0.062 (8)	0.471 (4)
Cl2	0.16421 (14)	1.00590 (9)	0.14498 (14)	0.0593 (5)
O10	0.2430 (13)	0.9673 (10)	0.1895 (14)	0.123 (5)	0.529 (4)
O11	0.0965 (11)	1.0527 (10)	0.1714 (18)	0.131 (5)	0.529 (4)
O12	0.1906 (9)	1.0492 (6)	0.0696 (10)	0.075 (3)	0.529 (4)
O13	0.095 (4)	0.964 (2)	0.094 (3)	0.091 (7)	0.529 (4)
O10'	0.1981 (14)	0.9653 (11)	0.2331 (16)	0.123 (5)	0.471 (4)
O11'	0.2328 (13)	1.0390 (10)	0.1210 (19)	0.131 (5)	0.471 (4)
O12'	0.1376 (11)	1.0513 (8)	0.2088 (12)	0.075 (3)	0.471 (4)
O13'	0.111 (4)	0.963 (3)	0.073 (4)	0.091 (7)	0.471 (4)
Cl3	0.31322 (13)	0.50533 (8)	0.18346 (12)	0.0520 (5)
O14	0.3617 (5)	0.4525 (3)	0.1520 (6)	0.103 (2)
O15	0.3650 (3)	0.5642 (2)	0.1892 (4)	0.0614 (14)
O16	0.2979 (5)	0.4876 (4)	0.2777 (5)	0.113 (2)
O17	0.2262 (3)	0.5154 (3)	0.1168 (4)	0.0720 (16)
Cl4	−0.0025 (3)	0.8313 (2)	0.3368 (4)	0.0454 (9)	0.529 (4)
O18	−0.0398 (8)	0.7668 (5)	0.2987 (9)	0.081 (2)	0.529 (4)
O21	−0.065 (3)	0.8814 (15)	0.289 (4)	0.075 (6)	0.529 (4)
Cl4'	0.0220 (4)	0.8598 (3)	0.3574 (4)	0.0454 (9)	0.471 (4)
O18'	0.0519 (9)	0.9249 (6)	0.3854 (10)	0.081 (2)	0.471 (4)
O21'	−0.063 (3)	0.8579 (17)	0.293 (5)	0.075 (6)	0.471 (4)
O19	0.0872 (3)	0.8326 (2)	0.3155 (3)	0.0492 (12)
O20	0.0115 (3)	0.8273 (3)	0.4454 (3)	0.0667 (15)
O22	0.1824 (4)	1.0554 (2)	0.4236 (4)	0.0693 (15)
H22A	0.1600	1.0270	0.4633	0.104*
H22B	0.2293	1.0291	0.4190	0.104*
O23	0.1186 (7)	0.5546 (5)	0.3929 (8)	0.088 (3)*	0.581 (6)
H23	0.0858	0.5803	0.3511	0.132*	0.581 (6)
C21	0.0965 (11)	0.4832 (6)	0.3612 (14)	0.104 (5)*	0.581 (6)
H21A	0.0453	0.4823	0.3020	0.156*	0.581 (6)
H21B	0.0799	0.4588	0.4161	0.156*	0.581 (6)
H21C	0.1500	0.4623	0.3451	0.156*	0.581 (6)
O23'	0.1203 (9)	0.5724 (7)	0.2475 (11)	0.088 (3)*	0.419 (6)
H23'	0.1139	0.5691	0.1849	0.132*	0.419 (6)
C21'	0.0982 (18)	0.5154 (10)	0.3055 (18)	0.104 (5)*	0.419 (6)
H21D	0.0849	0.5316	0.3680	0.156*	0.419 (6)
H21E	0.1503	0.4848	0.3213	0.156*	0.419 (6)
H21F	0.0447	0.4920	0.2658	0.156*	0.419 (6)
O24	0.2614 (14)	0.5562 (10)	0.4416 (15)	0.129 (7)*	0.419 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0288 (4)	0.0303 (4)	0.0164 (3)	−0.0012 (3)	0.0105 (3)	0.0005 (3)
O1	0.037 (2)	0.041 (2)	0.032 (2)	−0.0096 (19)	0.0195 (18)	−0.0068 (19)
O2	0.045 (3)	0.050 (3)	0.044 (3)	0.014 (2)	0.025 (2)	0.017 (2)
O3	0.033 (3)	0.045 (2)	0.038 (2)	0.008 (2)	0.0115 (19)	0.000 (2)
N1	0.027 (2)	0.031 (2)	0.020 (2)	0.0012 (19)	0.0121 (18)	0.0029 (19)
N2	0.022 (2)	0.033 (2)	0.020 (2)	−0.0003 (19)	0.0080 (18)	0.0037 (19)
N3	0.043 (3)	0.027 (2)	0.024 (2)	0.000 (2)	0.011 (2)	0.0003 (19)
N4	0.049 (3)	0.041 (3)	0.023 (3)	−0.012 (2)	0.017 (2)	−0.006 (2)
N5	0.030 (3)	0.033 (2)	0.017 (2)	−0.001 (2)	0.0124 (19)	−0.0011 (19)
C1	0.038 (3)	0.028 (3)	0.025 (3)	−0.001 (2)	0.015 (2)	0.001 (2)
C2	0.037 (3)	0.028 (3)	0.023 (3)	0.000 (2)	0.012 (2)	−0.002 (2)
C3	0.031 (3)	0.024 (3)	0.020 (3)	0.000 (2)	0.011 (2)	−0.002 (2)
C4	0.026 (3)	0.030 (3)	0.019 (3)	0.001 (2)	0.009 (2)	0.001 (2)
C5	0.038 (3)	0.035 (3)	0.024 (3)	−0.001 (3)	0.017 (2)	−0.002 (2)
C6	0.048 (4)	0.057 (4)	0.033 (3)	−0.021 (3)	0.023 (3)	−0.012 (3)
C7	0.037 (4)	0.056 (4)	0.030 (3)	−0.009 (3)	0.010 (3)	−0.008 (3)
C8	0.033 (3)	0.045 (3)	0.022 (3)	−0.004 (3)	0.014 (2)	−0.004 (2)
C9	0.086 (6)	0.058 (4)	0.034 (4)	−0.031 (4)	0.018 (4)	−0.013 (3)
C10	0.056 (5)	0.057 (5)	0.096 (6)	0.009 (4)	0.022 (4)	0.019 (4)
Cu2	0.0319 (4)	0.0487 (4)	0.0156 (3)	−0.0025 (3)	0.0101 (3)	−0.0005 (3)
O4	0.047 (3)	0.084 (4)	0.039 (3)	0.020 (3)	0.009 (2)	0.001 (3)
O5	0.044 (3)	0.061 (3)	0.036 (2)	−0.008 (2)	0.010 (2)	0.006 (2)
N6	0.031 (3)	0.055 (3)	0.017 (2)	−0.008 (2)	0.0119 (19)	−0.003 (2)
N7	0.027 (3)	0.051 (3)	0.016 (2)	0.000 (2)	0.0091 (19)	0.004 (2)
N8	0.047 (3)	0.045 (3)	0.025 (2)	−0.005 (2)	0.019 (2)	0.003 (2)
N9	0.053 (3)	0.053 (3)	0.022 (3)	−0.012 (3)	0.018 (2)	0.001 (2)
N10	0.032 (3)	0.051 (3)	0.019 (2)	−0.005 (2)	0.010 (2)	0.004 (2)
C11	0.034 (3)	0.053 (4)	0.023 (3)	−0.008 (3)	0.007 (2)	−0.004 (3)
C12	0.038 (4)	0.042 (3)	0.023 (3)	−0.006 (3)	0.010 (3)	0.000 (3)
C13	0.033 (3)	0.051 (4)	0.017 (3)	−0.003 (3)	0.011 (2)	−0.001 (3)
C14	0.032 (3)	0.053 (4)	0.019 (3)	−0.003 (3)	0.011 (2)	−0.001 (3)
C15	0.034 (3)	0.057 (4)	0.023 (3)	−0.007 (3)	0.008 (3)	0.005 (3)
C16	0.044 (4)	0.058 (4)	0.027 (3)	−0.009 (3)	0.009 (3)	0.006 (3)
C17	0.036 (4)	0.059 (4)	0.037 (3)	−0.005 (3)	0.018 (3)	0.011 (3)
C18	0.032 (3)	0.067 (4)	0.026 (3)	0.002 (3)	0.013 (3)	0.003 (3)
C19	0.064 (5)	0.059 (4)	0.046 (4)	−0.010 (4)	0.029 (4)	−0.001 (3)
C20	0.065 (11)	0.099 (12)	0.107 (13)	−0.045 (9)	−0.017 (9)	0.000 (10)
Cl1	0.0301 (8)	0.0845 (12)	0.0340 (8)	0.0032 (8)	0.0128 (7)	−0.0045 (8)
O6	0.034 (8)	0.112 (10)	0.056 (6)	0.007 (7)	0.013 (7)	0.006 (5)
O7	0.068 (12)	0.104 (8)	0.105 (16)	−0.003 (8)	0.054 (12)	0.007 (6)
O8	0.052 (11)	0.176 (19)	0.056 (7)	0.034 (14)	0.003 (6)	−0.048 (11)
O9	0.037 (5)	0.10 (2)	0.057 (11)	0.014 (10)	0.029 (7)	0.004 (13)
O6'	0.034 (8)	0.112 (10)	0.056 (6)	0.007 (7)	0.013 (7)	0.006 (5)
O7'	0.068 (12)	0.104 (8)	0.105 (16)	−0.003 (8)	0.054 (12)	0.007 (6)
O8'	0.052 (11)	0.176 (19)	0.056 (7)	0.034 (14)	0.003 (6)	−0.048 (11)
O9'	0.037 (5)	0.10 (2)	0.057 (11)	0.014 (10)	0.029 (7)	0.004 (13)
Cl2	0.0694 (13)	0.0465 (10)	0.0619 (11)	−0.0094 (9)	0.0150 (9)	−0.0062 (9)
O10	0.129 (12)	0.085 (5)	0.121 (12)	0.018 (8)	−0.041 (8)	0.017 (7)
O11	0.094 (9)	0.097 (8)	0.232 (16)	−0.018 (6)	0.100 (10)	−0.028 (8)
O12	0.086 (8)	0.052 (4)	0.094 (7)	−0.004 (5)	0.036 (5)	−0.001 (4)
O13	0.108 (15)	0.080 (4)	0.075 (14)	−0.035 (7)	0.004 (9)	−0.002 (7)
O10'	0.129 (12)	0.085 (5)	0.121 (12)	0.018 (8)	−0.041 (8)	0.017 (7)
O11'	0.094 (9)	0.097 (8)	0.232 (16)	−0.018 (6)	0.100 (10)	−0.028 (8)
O12'	0.086 (8)	0.052 (4)	0.094 (7)	−0.004 (5)	0.036 (5)	−0.001 (4)
O13'	0.108 (15)	0.080 (4)	0.075 (14)	−0.035 (7)	0.004 (9)	−0.002 (7)
Cl3	0.0618 (12)	0.0478 (9)	0.0450 (10)	−0.0084 (8)	0.0104 (8)	0.0099 (8)
O14	0.097 (5)	0.059 (4)	0.152 (6)	0.004 (3)	0.030 (4)	−0.026 (4)
O15	0.068 (3)	0.041 (3)	0.063 (3)	−0.013 (2)	−0.008 (3)	0.005 (2)
O16	0.139 (6)	0.136 (6)	0.074 (4)	0.004 (5)	0.042 (4)	0.058 (4)
O17	0.058 (4)	0.081 (4)	0.073 (4)	−0.022 (3)	0.006 (3)	0.018 (3)
Cl4	0.037 (2)	0.053 (3)	0.049 (2)	0.0054 (17)	0.0181 (16)	0.0052 (19)
O18	0.084 (6)	0.060 (5)	0.104 (7)	−0.007 (4)	0.035 (5)	−0.016 (4)
O21	0.041 (3)	0.097 (19)	0.086 (6)	0.021 (12)	0.014 (3)	0.049 (16)
Cl4'	0.037 (2)	0.053 (3)	0.049 (2)	0.0054 (17)	0.0181 (16)	0.0052 (19)
O18'	0.084 (6)	0.060 (5)	0.104 (7)	−0.007 (4)	0.035 (5)	−0.016 (4)
O21'	0.041 (3)	0.097 (19)	0.086 (6)	0.021 (12)	0.014 (3)	0.049 (16)
O19	0.034 (3)	0.081 (3)	0.034 (2)	−0.004 (2)	0.0124 (19)	0.000 (2)
O20	0.058 (3)	0.100 (4)	0.050 (3)	0.004 (3)	0.031 (2)	0.014 (3)
O22	0.103 (4)	0.041 (3)	0.065 (3)	0.003 (3)	0.023 (3)	0.006 (2)

Geometric parameters (Å, º)

Cu1—O1	1.978 (4)	N9—C16	1.350 (8)
Cu1—N5	1.995 (4)	N10—C15	1.342 (8)
Cu1—N1	2.017 (4)	N10—C18	1.379 (7)
Cu1—N2^i	2.060 (4)	C11—C12	1.358 (8)
Cu1—O2	2.311 (4)	C11—H11	0.9500
Cu1—O3	2.362 (4)	C12—H12	0.9500
O1—H1A	0.840 (19)	C13—C14	1.405 (7)
O1—H1B	0.850 (19)	C13—H13	0.9500
O2—H2A	0.85 (2)	C16—C17	1.389 (9)
O2—H2B	0.842 (19)	C16—C19	1.485 (9)
O3—C10	1.384 (8)	C17—C18	1.365 (9)
O3—H3	0.84 (2)	C17—H17	0.9500
N1—C4	1.338 (6)	C18—H18	0.9500
N1—C1	1.369 (7)	C19—H19A	0.9800
N2—C3	1.314 (6)	C19—H19B	0.9800
N2—C2	1.359 (6)	C19—H19C	0.9800
N2—Cu1^ii	2.060 (4)	C20—H5C	0.7794
N3—C4	1.364 (7)	C20—H20A	0.9800
N3—C5	1.388 (7)	C20—H20B	0.9800
N3—H3B	0.8800	C20—H20C	0.9800
N4—C5	1.331 (7)	Cl1—O6'	1.36 (2)
N4—C6	1.335 (8)	Cl1—O9'	1.37 (6)
N5—C5	1.323 (7)	Cl1—O8'	1.39 (4)
N5—C8	1.354 (7)	Cl1—O9	1.43 (5)
C1—C2	1.356 (7)	Cl1—O6	1.45 (2)
C1—H1	0.9500	Cl1—O8	1.45 (3)
C2—H2	0.9500	Cl1—O7'	1.47 (3)
C3—C4	1.414 (7)	Cl1—O7	1.49 (2)
C3—H3A	0.9500	Cl2—O11'	1.334 (18)
C6—C7	1.408 (9)	Cl2—O12'	1.388 (17)
C6—C9	1.477 (9)	Cl2—O13	1.40 (3)
C7—C8	1.367 (8)	Cl2—O13'	1.41 (4)
C7—H7	0.9500	Cl2—O10	1.428 (16)
C8—H8A	0.9500	Cl2—O10'	1.447 (18)
C9—H9A	0.9800	Cl2—O12	1.476 (13)
C9—H9B	0.9800	Cl2—O11	1.494 (18)
C9—H9C	0.9800	Cl3—O15	1.408 (5)
C10—H10A	0.9800	Cl3—O16	1.411 (6)
C10—H10B	0.9800	Cl3—O14	1.412 (6)
C10—H10C	0.9800	Cl3—O17	1.425 (5)
Cu2—O5	1.978 (4)	Cl4—O21	1.43 (2)
Cu2—N10	1.985 (5)	Cl4—O19	1.450 (6)
Cu2—N6	2.027 (4)	Cl4—O20	1.456 (6)
Cu2—N7^iii	2.057 (4)	Cl4—O18	1.459 (11)
Cu2—O4	2.249 (5)	Cl4'—O19	1.365 (7)
Cu2—O19	2.539 (5)	Cl4'—O21'	1.37 (5)
O4—H4A	0.90 (2)	Cl4'—O18'	1.405 (12)
O4—H4B	0.86 (2)	Cl4'—O20	1.414 (7)
O5—C20	1.422 (14)	O22—H22A	0.9072
O5—H5A	0.9407	O22—H22B	0.8979
O5—H5B	0.8499	O23—C21	1.511 (9)
O5—H5C	0.8500	O23—H23	0.8400
N6—C14	1.333 (7)	C21—H21A	0.9800
N6—C11	1.352 (7)	C21—H21B	0.9800
N7—C13	1.327 (7)	C21—H21C	0.9800
N7—C12	1.357 (7)	O23'—C21'	1.476 (10)
N7—Cu2^iv	2.057 (4)	O23'—H23'	0.8436
N8—C14	1.361 (7)	C21'—H21D	0.9800
N8—C15	1.369 (7)	C21'—H21E	0.9800
N8—H8	0.8800	C21'—H21F	0.9800
N9—C15	1.336 (8)
O1—Cu1—N5	178.91 (18)	N6—C14—C13	121.3 (5)
O1—Cu1—N1	91.70 (17)	N8—C14—C13	118.1 (5)
N5—Cu1—N1	87.55 (17)	N9—C15—N10	126.1 (5)
O1—Cu1—N2^i	89.49 (16)	N9—C15—N8	113.8 (5)
N5—Cu1—N2^i	91.23 (16)	N10—C15—N8	120.1 (5)
N1—Cu1—N2^i	177.36 (17)	N9—C16—C17	120.6 (6)
O1—Cu1—O2	90.52 (17)	N9—C16—C19	115.9 (6)
N5—Cu1—O2	90.26 (18)	C17—C16—C19	123.5 (6)
N1—Cu1—O2	88.96 (16)	C18—C17—C16	118.8 (6)
N2^i—Cu1—O2	93.39 (16)	C18—C17—H17	120.6
O1—Cu1—O3	91.25 (17)	C16—C17—H17	120.6
N5—Cu1—O3	87.93 (16)	C17—C18—N10	121.0 (6)
N1—Cu1—O3	87.97 (16)	C17—C18—H18	119.5
N2^i—Cu1—O3	89.65 (15)	N10—C18—H18	119.5
O2—Cu1—O3	176.50 (14)	C16—C19—H19A	109.5
Cu1—O1—H1A	130 (4)	C16—C19—H19B	109.5
Cu1—O1—H1B	119 (4)	H19A—C19—H19B	109.5
H1A—O1—H1B	106 (3)	C16—C19—H19C	109.5
Cu1—O2—H2A	117 (4)	H19A—C19—H19C	109.5
Cu1—O2—H2B	138 (4)	H19B—C19—H19C	109.5
H2A—O2—H2B	105 (3)	O5—C20—H20A	109.5
C10—O3—Cu1	130.8 (4)	H5C—C20—H20A	80.6
C10—O3—H3	115 (5)	O5—C20—H20B	109.5
Cu1—O3—H3	111 (5)	H5C—C20—H20B	111.3
C4—N1—C1	116.0 (4)	H20A—C20—H20B	109.5
C4—N1—Cu1	122.6 (3)	O5—C20—H20C	109.5
C1—N1—Cu1	121.4 (3)	H5C—C20—H20C	131.3
C3—N2—C2	118.1 (4)	H20A—C20—H20C	109.5
C3—N2—Cu1^ii	121.9 (3)	H20B—C20—H20C	109.5
C2—N2—Cu1^ii	119.7 (3)	O6'—Cl1—O9'	121 (4)
C4—N3—C5	128.2 (5)	O6'—Cl1—O8'	120 (2)
C4—N3—H3B	115.9	O9'—Cl1—O8'	106 (6)
C5—N3—H3B	115.9	O6'—Cl1—O9	120 (4)
C5—N4—C6	117.1 (5)	O9'—Cl1—O9	12 (6)
C5—N5—C8	115.1 (5)	O8'—Cl1—O9	113 (4)
C5—N5—Cu1	122.6 (4)	O6'—Cl1—O6	22.4 (10)
C8—N5—Cu1	121.4 (4)	O9'—Cl1—O6	102 (4)
C2—C1—N1	122.6 (5)	O8'—Cl1—O6	121 (2)
C2—C1—H1	118.7	O9—Cl1—O6	105 (4)
N1—C1—H1	118.7	O6'—Cl1—O8	103 (2)
C1—C2—N2	120.7 (5)	O9'—Cl1—O8	111 (4)
C1—C2—H2	119.6	O8'—Cl1—O8	19 (3)
N2—C2—H2	119.6	O9—Cl1—O8	121 (4)
N2—C3—C4	121.2 (5)	O6—Cl1—O8	101.8 (17)
N2—C3—H3A	119.4	O6'—Cl1—O7'	105.2 (13)
C4—C3—H3A	119.4	O9'—Cl1—O7'	106 (4)
N1—C4—N3	120.8 (4)	O8'—Cl1—O7'	95 (3)
N1—C4—C3	121.2 (5)	O9—Cl1—O7'	96 (3)
N3—C4—C3	117.9 (5)	O6—Cl1—O7'	125.2 (13)
N5—C5—N4	127.0 (5)	O8—Cl1—O7'	110 (2)
N5—C5—N3	119.7 (5)	O6'—Cl1—O7	81.2 (12)
N4—C5—N3	113.3 (5)	O9'—Cl1—O7	121 (4)
N4—C6—C7	119.8 (5)	O8'—Cl1—O7	106 (3)
N4—C6—C9	117.7 (6)	O9—Cl1—O7	110 (3)
C7—C6—C9	122.5 (6)	O6—Cl1—O7	101.8 (11)
C8—C7—C6	117.9 (6)	O8—Cl1—O7	115 (3)
C8—C7—H7	121.1	O7'—Cl1—O7	24.1 (12)
C6—C7—H7	121.1	O11'—Cl2—O12'	100.6 (11)
N5—C8—C7	121.9 (5)	O11'—Cl2—O13	135.4 (19)
N5—C8—H8A	119.1	O12'—Cl2—O13	115 (2)
C7—C8—H8A	119.1	O11'—Cl2—O13'	118.5 (19)
C6—C9—H9A	109.5	O12'—Cl2—O13'	130 (3)
C6—C9—H9B	109.5	O13—Cl2—O13'	18 (3)
H9A—C9—H9B	109.5	O11'—Cl2—O10	76.1 (12)
C6—C9—H9C	109.5	O12'—Cl2—O10	114.9 (11)
H9A—C9—H9C	109.5	O13—Cl2—O10	110 (3)
H9B—C9—H9C	109.5	O13'—Cl2—O10	104 (3)
O3—C10—H10A	109.5	O11'—Cl2—O10'	110.2 (13)
O3—C10—H10B	109.5	O12'—Cl2—O10'	86.6 (12)
H10A—C10—H10B	109.5	O13—Cl2—O10'	99 (2)
O3—C10—H10C	109.5	O13'—Cl2—O10'	105 (3)
H10A—C10—H10C	109.5	O10—Cl2—O10'	40.9 (10)
H10B—C10—H10C	109.5	O11'—Cl2—O12	35.0 (10)
O5—Cu2—N10	174.5 (2)	O12'—Cl2—O12	102.8 (8)
O5—Cu2—N6	91.49 (18)	O13—Cl2—O12	107.5 (19)
N10—Cu2—N6	87.57 (18)	O13'—Cl2—O12	94 (2)
O5—Cu2—N7^iii	88.76 (17)	O10—Cl2—O12	106.5 (9)
N10—Cu2—N7^iii	91.61 (18)	O10'—Cl2—O12	144.8 (11)
N6—Cu2—N7^iii	174.1 (2)	O11'—Cl2—O11	111.1 (10)
O5—Cu2—O4	91.6 (2)	O12'—Cl2—O11	28.1 (10)
N10—Cu2—O4	93.9 (2)	O13—Cl2—O11	91 (2)
N6—Cu2—O4	92.05 (19)	O13'—Cl2—O11	105 (3)
N7^iii—Cu2—O4	93.84 (18)	O10—Cl2—O11	141.7 (13)
O5—Cu2—O19	87.92 (18)	O10'—Cl2—O11	106.1 (13)
N10—Cu2—O19	86.63 (18)	O12—Cl2—O11	96.4 (10)
N6—Cu2—O19	89.55 (17)	O15—Cl3—O16	111.7 (4)
N7^iii—Cu2—O19	84.56 (16)	O15—Cl3—O14	109.1 (4)
O4—Cu2—O19	178.34 (15)	O16—Cl3—O14	107.4 (5)
Cu2—O4—H4A	137 (5)	O15—Cl3—O17	109.3 (3)
Cu2—O4—H4B	112 (5)	O16—Cl3—O17	107.3 (4)
H4A—O4—H4B	100 (3)	O14—Cl3—O17	112.0 (4)
C20—O5—Cu2	131.3 (7)	O21—Cl4—O19	116 (2)
C20—O5—H5A	110.8	O21—Cl4—O20	115 (2)
Cu2—O5—H5A	111.9	O19—Cl4—O20	106.9 (4)
C20—O5—H5B	102.9	O21—Cl4—O18	107.7 (19)
Cu2—O5—H5B	119.9	O19—Cl4—O18	104.0 (6)
Cu2—O5—H5C	120.1	O20—Cl4—O18	105.5 (6)
H5A—O5—H5C	128.0	O19—Cl4'—O21'	112 (3)
H5B—O5—H5C	120.0	O19—Cl4'—O18'	105.7 (6)
C14—N6—C11	116.5 (4)	O21'—Cl4'—O18'	113.1 (16)
C14—N6—Cu2	121.6 (4)	O19—Cl4'—O20	114.3 (5)
C11—N6—Cu2	122.0 (4)	O21'—Cl4'—O20	105 (2)
C13—N7—C12	117.6 (4)	O18'—Cl4'—O20	106.8 (7)
C13—N7—Cu2^iv	119.4 (4)	Cl4'—O19—Cl4	28.7 (2)
C12—N7—Cu2^iv	122.8 (4)	Cl4'—O19—Cu2	139.9 (3)
C14—N8—C15	127.1 (5)	Cl4—O19—Cu2	128.6 (3)
C14—N8—H8	116.4	Cl4'—O20—Cl4	28.29 (19)
C15—N8—H8	116.4	H22A—O22—H22B	94.7
C15—N9—C16	117.0 (5)	O23—C21—H21A	109.5
C15—N10—C18	115.5 (5)	O23—C21—H21B	109.5
C15—N10—Cu2	120.6 (4)	H21A—C21—H21B	109.5
C18—N10—Cu2	122.9 (4)	O23—C21—H21C	109.5
N6—C11—C12	122.8 (5)	H21A—C21—H21C	109.5
N6—C11—H11	118.6	H21B—C21—H21C	109.5
C12—C11—H11	118.6	C21'—O23'—H23'	120.2
N7—C12—C11	120.7 (5)	O23'—C21'—H21D	109.5
N7—C12—H12	119.7	O23'—C21'—H21E	109.5
C11—C12—H12	119.7	H21D—C21'—H21E	109.5
N7—C13—C14	121.1 (5)	O23'—C21'—H21F	109.5
N7—C13—H13	119.4	H21D—C21'—H21F	109.5
C14—C13—H13	119.4	H21E—C21'—H21F	109.5
N6—C14—N8	120.7 (5)
O1—Cu1—O3—C10	3.9 (6)	O4—Cu2—N10—C15	−134.8 (4)
N5—Cu1—O3—C10	−176.9 (6)	O19—Cu2—N10—C15	46.8 (4)
N1—Cu1—O3—C10	95.5 (6)	N6—Cu2—N10—C18	148.9 (5)
N2^i—Cu1—O3—C10	−85.6 (6)	N7^iii—Cu2—N10—C18	−37.0 (5)
O1—Cu1—N1—C4	146.4 (4)	O4—Cu2—N10—C18	57.0 (5)
N5—Cu1—N1—C4	−32.8 (4)	O19—Cu2—N10—C18	−121.5 (4)
O2—Cu1—N1—C4	−123.1 (4)	C14—N6—C11—C12	0.3 (9)
O3—Cu1—N1—C4	55.2 (4)	Cu2—N6—C11—C12	−179.7 (4)
O1—Cu1—N1—C1	−30.3 (4)	C13—N7—C12—C11	−0.6 (8)
N5—Cu1—N1—C1	150.5 (4)	Cu2^iv—N7—C12—C11	−175.2 (4)
O2—Cu1—N1—C1	60.2 (4)	N6—C11—C12—N7	1.0 (9)
O3—Cu1—N1—C1	−121.5 (4)	C12—N7—C13—C14	−1.1 (8)
N1—Cu1—N5—C5	40.5 (4)	Cu2^iv—N7—C13—C14	173.7 (4)
N2^i—Cu1—N5—C5	−137.2 (4)	C11—N6—C14—N8	175.9 (5)
O2—Cu1—N5—C5	129.4 (4)	Cu2—N6—C14—N8	−4.1 (8)
O3—Cu1—N5—C5	−47.6 (4)	C11—N6—C14—C13	−2.0 (8)
N1—Cu1—N5—C8	−150.4 (4)	Cu2—N6—C14—C13	178.0 (4)
N2^i—Cu1—N5—C8	32.0 (4)	C15—N8—C14—N6	−35.1 (9)
O2—Cu1—N5—C8	−61.4 (4)	C15—N8—C14—C13	142.9 (6)
O3—Cu1—N5—C8	121.6 (4)	N7—C13—C14—N6	2.5 (9)
C4—N1—C1—C2	−0.2 (8)	N7—C13—C14—N8	−175.5 (5)
Cu1—N1—C1—C2	176.7 (4)	C16—N9—C15—N10	−7.3 (9)
N1—C1—C2—N2	−1.4 (8)	C16—N9—C15—N8	171.7 (5)
C3—N2—C2—C1	0.4 (8)	C18—N10—C15—N9	11.6 (9)
C2—N2—C3—C4	2.1 (8)	Cu2—N10—C15—N9	−157.5 (5)
Cu1^ii—N2—C3—C4	−172.7 (4)	C18—N10—C15—N8	−167.4 (5)
C1—N1—C4—N3	−175.4 (5)	Cu2—N10—C15—N8	23.5 (7)
Cu1—N1—C4—N3	7.7 (7)	C14—N8—C15—N9	−154.6 (6)
C1—N1—C4—C3	2.6 (7)	C14—N8—C15—N10	24.5 (9)
Cu1—N1—C4—C3	−174.3 (4)	C15—N9—C16—C17	−2.8 (9)
C5—N3—C4—N1	28.6 (8)	C15—N9—C16—C19	176.6 (6)
C5—N3—C4—C3	−149.5 (5)	N9—C16—C17—C18	7.7 (9)
N2—C3—C4—N1	−3.7 (8)	C19—C16—C17—C18	−171.7 (6)
N2—C3—C4—N3	174.4 (5)	C16—C17—C18—N10	−3.1 (9)
C8—N5—C5—N4	−11.9 (8)	C15—N10—C18—C17	−5.8 (8)
Cu1—N5—C5—N4	157.9 (5)	Cu2—N10—C18—C17	163.0 (4)
C8—N5—C5—N3	167.6 (5)	O21'—Cl4'—O19—Cl4	−44.8 (16)
Cu1—N5—C5—N3	−22.6 (7)	O18'—Cl4'—O19—Cl4	−168.4 (11)
C6—N4—C5—N5	5.7 (9)	O20—Cl4'—O19—Cl4	74.4 (8)
C6—N4—C5—N3	−173.8 (5)	O21'—Cl4'—O19—Cu2	−126.0 (16)
C4—N3—C5—N5	−20.6 (8)	O18'—Cl4'—O19—Cu2	110.5 (8)
C4—N3—C5—N4	159.0 (5)	O20—Cl4'—O19—Cu2	−6.7 (8)
C5—N4—C6—C7	4.4 (8)	O21—Cl4—O19—Cl4'	67 (3)
C5—N4—C6—C9	−174.2 (6)	O20—Cl4—O19—Cl4'	−63.0 (7)
N4—C6—C7—C8	−7.2 (9)	O18—Cl4—O19—Cl4'	−174.4 (11)
C9—C6—C7—C8	171.3 (6)	O21—Cl4—O19—Cu2	−167 (2)
C5—N5—C8—C7	8.2 (7)	O20—Cl4—O19—Cu2	62.6 (5)
Cu1—N5—C8—C7	−161.7 (4)	O18—Cl4—O19—Cu2	−48.8 (7)
C6—C7—C8—N5	0.6 (8)	O5—Cu2—O19—Cl4'	72.3 (6)
N6—Cu2—O5—C20	119.7 (11)	N10—Cu2—O19—Cl4'	−106.8 (6)
N7^iii—Cu2—O5—C20	−54.4 (11)	N6—Cu2—O19—Cl4'	−19.2 (6)
O4—Cu2—O5—C20	−148.2 (11)	N7^iii—Cu2—O19—Cl4'	161.3 (6)
O19—Cu2—O5—C20	30.2 (11)	O5—Cu2—O19—Cl4	34.9 (4)
O5—Cu2—N6—C14	−141.1 (5)	N10—Cu2—O19—Cl4	−144.2 (4)
N10—Cu2—N6—C14	33.5 (5)	N6—Cu2—O19—Cl4	−56.6 (4)
O4—Cu2—N6—C14	127.2 (5)	N7^iii—Cu2—O19—Cl4	123.9 (4)
O19—Cu2—N6—C14	−53.2 (5)	O19—Cl4'—O20—Cl4	−76.4 (8)
O5—Cu2—N6—C11	38.8 (5)	O21'—Cl4'—O20—Cl4	47 (2)
N10—Cu2—N6—C11	−146.6 (5)	O18'—Cl4'—O20—Cl4	167.1 (11)
O4—Cu2—N6—C11	−52.8 (5)	O21—Cl4—O20—Cl4'	−70 (2)
O19—Cu2—N6—C11	126.8 (4)	O19—Cl4—O20—Cl4'	60.6 (7)
N6—Cu2—N10—C15	−42.9 (4)	O18—Cl4—O20—Cl4'	171.0 (11)
N7^iii—Cu2—N10—C15	131.3 (4)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2; (iii) x, −y+3/2, z−1/2; (iv) x, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O20^v	0.84 (2)	1.94 (2)	2.779 (6)	173 (5)
O1—H1B···O22^vi	0.85 (2)	1.79 (3)	2.626 (6)	166 (7)
O2—H2A···O7	0.85 (2)	2.09 (5)	2.84 (3)	147 (6)
O2—H2B···O14^i	0.84 (2)	2.04 (3)	2.852 (7)	161 (6)
N3—H3B···O16	0.88	2.07	2.874 (8)	151
O3—H3···O12^iv	0.84 (2)	1.98 (2)	2.812 (13)	176 (7)
O4—H4B···O8^vii	0.86 (2)	2.01 (5)	2.83 (4)	160 (8)
O4—H4A···O24	0.90 (2)	1.81 (5)	2.57 (2)	141 (7)
O5—H5B···O23	0.85	1.87	2.612 (11)	145
N8—H8···O17^iv	0.88	2.13	2.910 (7)	148
O22—H22A···O17^iv	0.91	2.27	2.941 (7)	130
O22—H22B···N9	0.90	2.40	3.256 (7)	158
O23—H23···O5	0.84	2.02	2.612 (11)	127

Symmetry codes: (i) x, −y+1/2, z+1/2; (iv) x, −y+3/2, z+1/2; (v) −x, −y+1, −z+1; (vi) x, y−1, z; (vii) −x+1, −y+1, −z+1.