Sulfate-bridged dimeric trinuclear copper(II)-pyrazolate complex with three different terminal ligands.

The reaction of CuSO4·5H2O, 4-chloro-pyrazole (4-Cl-pzH) and tri-ethyl-amine (Et3N) in di-methyl-formamide (DMF) produced crystals of di-aqua-hexa-kis-(μ-4-chloro-pyrazolato-κ(2) N:N')bis-(N,N-di-methyl-formamide)di-μ3-hydroxido-bis-(μ4-sulfato-κ(4) O:O':O'':O'')hexa-copper(II) N,N-di-methyl-formamide tetra-solvate dihydrate, [Cu3(OH)(SO4)(C3H2ClN2)3(C3H7NO)(H2O)]2·4C3H7NO·2H2O. The centrosymmetric dimeric molecule consists of two trinuclear copper-pyrazolate units bridged by two sulfate ions. The title compound provides the first example of a trinuclear copper-pyrazolate complex with three different terminal ligands on the Cu atoms, and also the first example of such complex with a strongly binding basal sulfate ion. Within each trinuclear unit, the Cu(II) atoms are bridged by μ-pyrazolate groups and a central μ3-OH group, and are coordinated by terminal sulfate, H2O and DMF ligands, respectively. Moreover, the sulfate O atoms coordinate at the apical position to the Cu atoms of the symmetry-related unit, providing square-pyramidal coordination geometry around each copper cation. The metal complex and solvent mol-ecules are involved in O-H⋯O hydrogen bonds, leading to a two-dimensional network parallel to (10-1).

Chemical context

Trinuclear copper(II) complexes are primarily studied for their relevance to multicopper enzymes, such as oxidases (e.g., laccase, ascorbate oxidase, ceruloplasmin), oxygenases (e.g., tyrosinase, particulate methane monooxygenase, ammonia monooxygenase) and reductases (e.g., nitrite reductase, nitrous oxide reductase) (Solomon et al., 1996 ▸, 2014 ▸). Thus, such complexes are important targets from synthesis, redox chemistry and catalysis viewpoints (Di Nicola et al., 2009 ▸; Mimmi et al., 2004 ▸; Tsui et al., 2011 ▸; Lionetti et al., 2013 ▸; Grundner et al., 2015 ▸). Trinuclear copper(II) complexes also display inter­esting spectroscopic and magnetic properties (Boča et al., 2003 ▸; Rivera-Carrillo et al., 2008 ▸; Spielberg et al., 2015 ▸), and have been crucial in studying concepts such as spin frustration (Fu et al., 2015 ▸). The pyrazolate anion is an excellent ligand for the construction of cyclic trinuclear and higher nuclearity metal complexes, leading to a variety of mol­ecular architectures based on copper or other metals (Halcrow, 2009 ▸; Viciano-Chumillas et al., 2010 ▸).

A unique class of copper–pyrazolate complexes is defined by nanojars, based on a series of cyclic polymerization isomers, [cis-CuII(μ-OH)(μ-pz)] (pz = pyrazolate anion, n = 6–14, except 11), which incarcerate anions with large hydration energies (e.g., sulfate, phosphate, carbonate) with unprecedented strength (Fernando et al., 2012 ▸; Mezei, 2015 ▸; Ahmed, Szymczyna et al., 2016 ▸) and permits the extraction of such anions from water into aliphatic solvents (Ahmed, Calco et al., 2016 ▸). Nanojars are obtained by self-assembly from a copper salt, pyrazole and a base (needed both for deprotonating pyrazole and as a hydroxide ion source) in the presence of an anion with large hydration energy, via a trinuclear inter­mediate, which is isolable and can be converted into nanojars by adding a base (Ahmed & Mezei, 2016 ▸). Use of a strong base, such as sodium or tetra­butyl­ammonium hydroxide, allows the preparation of nanojar solutions in different organic solvents. In contrast, a weak base, such as tri­ethyl­amine, can only be employed as hydroxide source (Et3N + H2O ↔ Et3NH+ + HO−) if the nanojar product is precipitated out of the solution by dilution with excess water, in which the nanojar is not soluble (Fernando et al., 2012 ▸). Isolation of the title compound provides further evidence that in a neat organic solvent, such as N,N-di­methyl­formamide, the self-assembly process using tri­ethyl­amine halts at the trinuclear stage, due to the acidity of the conjugate acid (tri­ethyl­ammonium cation, pK a = 10.75 in H2O).

Structural commentary

The title metal complex mol­ecule, located around an inversion center, consists of two symmetry-related trinuclear copper pyrazolate units (Fig. 1 ▸) connected together by sulfate ions (Fig. 2 ▸). One O atom of the sulfate moiety coordinates to one of the three independent CuII atoms as basal donor [Cu1—O2: 1.976 (2) Å], and to the corresponding symmetry-related CuII atom as apical donor [Cu1′—O2: 2.277 (2) Å]. The other two O atoms of the sulfate moiety coordinate apically to the other two Cu atoms of the symmetry-related trinuclear unit, whereas the fourth O atom accepts a hydrogen bond from the solvent water mol­ecule (Table 1 ▸). A square–pyramidal coordination geometry around each of the CuII atoms is completed by the bridging μ-pyrazolate and μ3-OH moieties, and terminal water or di­methyl­formamide mol­ecules in basal positions. The Cu3(μ-4-Cl-pz)3 core is relatively flat, with dihedral angles between the 4-chloro­pyrazolate mean planes and the Cu3 mean plane of 1.74 (6), 7.20 (6) and 14.10 (4)°. The μ3-OH group is located 0.5615 (15) Å above the Cu3 mean plane. Bond lengths and angles within the Cu3(μ-4-Cl-pz)3 framework are similar to the ones found in related complexes (Mezei et al., 2007 ▸; Rivera-Carrillo et al., 2008 ▸). The sulfate-bridged dimeric structure presented here is reminiscent of dimeric trinuclear copper–pyrazolate complexes with bridging carboxyl­ates (Mezei et al., 2004 ▸; Casarin et al., 2005 ▸).

Figure 1

Displacement ellipsoid plot (50% probability level) of the asymmetric unit of the title complex, showing the atom-labeling scheme (DMF and H2O solvent mol­ecules omitted).

Figure 2

Dimeric structure formed by mutual apical coordination of three sulfate O atoms to the Cu atoms of the symmetry-related trinuclear copper(II)–pyrazolate complex.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O5i	0.93	2.23	3.155 (3)	170
C6—H6⋯O10ii	0.93	2.38	3.234 (4)	153
O10—H10B⋯O9iii	0.81 (2)	1.96 (2)	2.751 (3)	165 (4)
O10—H10A⋯O3iv	0.81 (2)	1.91 (2)	2.700 (3)	165 (4)
O7—H7B⋯O8v	0.83 (2)	1.83 (2)	2.658 (3)	175 (3)
O7—H7A⋯O10ii	0.80 (2)	1.83 (2)	2.625 (3)	172 (3)
O1—H1O⋯O9vi	0.78 (2)	1.95 (2)	2.711 (3)	166 (3)
O1—H1O⋯O9vi	0.78 (2)	1.95 (2)	2.711 (3)	166 (3)
O7—H7A⋯O10ii	0.80 (2)	1.83 (2)	2.625 (3)	172 (3)
O7—H7B⋯O8v	0.83 (2)	1.83 (2)	2.658 (3)	175 (3)
O10—H10A⋯O3iv	0.81 (2)	1.91 (2)	2.700 (3)	165 (4)
O10—H10B⋯O9iii	0.81 (2)	1.96 (2)	2.751 (3)	165 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Supra­molecular features

The dimeric metal complex participates in an intricate hydrogen-bond network with the solvent DMF and H2O mol­ecules. Numerical details of the hydrogen bonding are given in Table 1 ▸. The μ3-OH group donates a hydrogen bond to a solvent DMF mol­ecule [O1⋯O9: 2.711 (3) Å], whereas the coordinating water mol­ecule donates two hydrogen bonds, one to the solvent water mol­ecule [O7⋯O10: 2.625 (3) Å] and one to the other independent DMF solvent mol­ecule [O7⋯O8: 2.658 (3) Å]. The solvent water mol­ecule donates two hydrogen bonds, one to a sulfate O atom [O10⋯O3: 2.700 (3) Å] and one to a DMF solvent mol­ecule [O10⋯O9: 2.751 (3) Å]. Within the dimeric unit, π–π inter­actions are identified between pairs of pyrazolate moieties along the sulfate-bridged sides of the trinuclear units [centroid–centroid distance: 3.641 (1) Å; dihedral angle: 7.5 (1)°].

Database survey

A search of the Cambridge Structural Database (Groom et al., 2016 ▸) reveals only three trinuclear copper pyrazolate structures that contain sulfate (Zheng et al., 2008 ▸; Di Nicola et al., 2010 ▸). In all three cases, the sulfate ion coordinates weakly at the apical position of the copper cations (Cu—O bonds lengths >2.3 Å). Thus, the complex presented here is the first example of a trinuclear copper pyrazolate with the sulfate anion strongly binding at the basal position to a penta­coordinate Cu-atom [Cu1—O2: 1.976 (2) Å].

Synthesis and crystallization

Copper sulfate penta­hydrate (1.000 g), 4-chloro­pyrazole (411 mg) and Et3N (1.2 mL) were dissolved in DMF (20 mL) yielding a deep-blue solution. Dark-blue prismatic crystals of the title compound were obtained upon slow evaporation of the solvent.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. C—H hydrogen atoms were placed in idealized positions and refined using the riding-model approximation. The OH hydrogen atoms were located from difference Fourier maps; their displacement parameters were fixed to be 20% larger than those of the attached O atoms. O—H distances were restrained to 0.82 (2) Å.

Table 2

Experimental details

Crystal data
Chemical formula	[Cu6(OH)2(SO4)2(C3H2ClN2)6(C3H7NO)2(H2O)2]·4C3H7NO·2H2O
M r	1727.11
Crystal system, space group	Monoclinic, P21/n
Temperature (K)	100
a, b, c (Å)	12.7038 (1), 16.5265 (2), 16.6830 (2)
β (°)	109.774 (1)
V (Å3)	3296.05 (6)
Z	2
Radiation type	Mo Kα
μ (mm−1)	2.29
Crystal size (mm)	0.24 × 0.10 × 0.05
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 ▸)
T min, T max	0.610, 0.894
No. of measured, independent and observed [I > 2σ(I)] reflections	39853, 8504, 6351
R int	0.061
(sin θ/λ)max (Å−1)	0.676
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.035, 0.075, 1.01
No. of reflections	8504
No. of parameters	418
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.59, −0.52

Computer programs: APEX2 and SAINT (Bruker, 2014 ▸), SHELXS97 and SHELXTL (Sheldrick, 2008 ▸) and SHELXL2014 (Sheldrick, 2015 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016010719/gk2663sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016010719/gk2663Isup2.hkl

CCDC reference: 1489622

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Cu6(OH)2(SO4)2(C3H2ClN2)6(C3H7NO)2(H2O)2]·4C3H7NO·2H2O	F(000) = 1748
Mr = 1727.11	Dx = 1.740 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.7038 (1) Å	Cell parameters from 6640 reflections
b = 16.5265 (2) Å	θ = 2.6–26.9°
c = 16.6830 (2) Å	µ = 2.29 mm−1
β = 109.774 (1)°	T = 100 K
V = 3296.05 (6) Å3	Prism, blue
Z = 2	0.24 × 0.10 × 0.05 mm

Bruker APEXII CCD diffractometer	6351 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.061
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θmax = 28.7°, θmin = 1.8°
Tmin = 0.610, Tmax = 0.894	h = −17→17
39853 measured reflections	k = −20→22
8504 independent reflections	l = −22→22

Refinement on F2	5 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.075	w = 1/[σ2(Fo2) + (0.0294P)2 + 1.238P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max = 0.001
8504 reflections	Δρmax = 0.59 e Å−3
418 parameters	Δρmin = −0.52 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cu1	0.88533 (2)	0.98432 (2)	0.92266 (2)	0.01205 (7)
Cu2	0.84732 (2)	0.78607 (2)	0.89552 (2)	0.01339 (8)
Cu3	0.71256 (3)	0.89070 (2)	1.00006 (2)	0.01415 (8)
S1	1.02182 (5)	1.14500 (4)	0.90916 (4)	0.01287 (13)
Cl1	1.14671 (7)	0.88248 (5)	0.71858 (6)	0.0362 (2)
Cl2	0.50045 (6)	0.57973 (5)	0.93424 (6)	0.0375 (2)
Cl3	0.69134 (6)	1.23152 (4)	1.07089 (5)	0.02872 (17)
O1	0.78020 (14)	0.89300 (10)	0.90866 (11)	0.0124 (4)
H1O	0.7316 (19)	0.8995 (17)	0.8661 (13)	0.015*
O2	1.00215 (13)	1.06890 (10)	0.95164 (11)	0.0137 (4)
O3	0.92608 (14)	1.15827 (11)	0.83199 (12)	0.0181 (4)
O4	1.12603 (14)	1.13455 (11)	0.89049 (12)	0.0162 (4)
O5	1.03357 (14)	1.21179 (10)	0.96983 (11)	0.0156 (4)
O6	0.62509 (15)	0.88937 (11)	1.07932 (12)	0.0193 (4)
O7	0.89793 (15)	0.68175 (11)	0.86138 (13)	0.0191 (4)
H7A	0.855 (2)	0.6528 (16)	0.8274 (16)	0.023*
H7B	0.9493 (19)	0.6535 (16)	0.8930 (17)	0.023*
O8	0.07007 (16)	0.59491 (12)	−0.04174 (13)	0.0265 (5)
O9	−0.13195 (15)	0.43846 (12)	0.74393 (13)	0.0264 (5)
O10	0.24177 (18)	0.42323 (14)	0.23718 (17)	0.0412 (7)
H10A	0.293 (2)	0.401 (2)	0.2728 (19)	0.049*
H10B	0.219 (3)	0.4655 (15)	0.251 (2)	0.049*
N1	0.95307 (17)	0.92644 (13)	0.85102 (14)	0.0147 (5)
N2	0.94773 (17)	0.84403 (13)	0.84797 (14)	0.0149 (5)
N3	0.72096 (17)	0.73695 (13)	0.92013 (14)	0.0155 (5)
N4	0.67343 (17)	0.77874 (13)	0.96960 (14)	0.0154 (5)
N5	0.72004 (17)	1.00879 (13)	1.00420 (14)	0.0156 (5)
N6	0.79401 (16)	1.04688 (13)	0.97334 (14)	0.0142 (5)
N7	0.61860 (18)	0.90095 (14)	1.21195 (15)	0.0201 (5)
N8	0.21667 (19)	0.62870 (14)	0.07710 (15)	0.0218 (5)
N9	0.03464 (18)	0.37758 (13)	0.81585 (15)	0.0195 (5)
C1	1.0125 (2)	0.81766 (16)	0.80436 (17)	0.0175 (6)
H1	1.0244	0.7638	0.7937	0.021*
C2	1.0585 (2)	0.88365 (17)	0.77797 (18)	0.0196 (6)
C3	1.0202 (2)	0.95107 (17)	0.80841 (17)	0.0183 (6)
H3	1.0378	1.0045	0.8008	0.022*
C4	0.5943 (2)	0.73193 (16)	0.98217 (18)	0.0185 (6)
H4A	0.5498	0.7459	1.0143	0.022*
C5	0.5894 (2)	0.65981 (16)	0.93968 (19)	0.0207 (6)
C6	0.6705 (2)	0.66438 (16)	0.90177 (19)	0.0201 (6)
H6	0.6874	0.6241	0.8691	0.024*
C7	0.7943 (2)	1.12579 (16)	0.99150 (18)	0.0175 (6)
H7	0.8377	1.1651	0.9777	0.021*
C8	0.7200 (2)	1.13943 (16)	1.03396 (18)	0.0192 (6)
C9	0.6751 (2)	1.06498 (16)	1.04087 (18)	0.0187 (6)
H9	0.6221	1.0552	1.0668	0.022*
C10	0.6727 (2)	0.89642 (16)	1.15752 (19)	0.0199 (6)
H10	0.7504	0.8986	1.1785	0.024*
C11	0.4967 (2)	0.8972 (2)	1.1816 (2)	0.0321 (8)
H11A	0.4714	0.8602	1.1347	0.048*
H11B	0.4667	0.9500	1.1634	0.048*
H11C	0.4719	0.8790	1.2269	0.048*
C12	0.6772 (3)	0.9130 (2)	1.30266 (19)	0.0300 (7)
H12A	0.6561	0.9643	1.3197	0.045*
H12B	0.7565	0.9124	1.3138	0.045*
H12C	0.6578	0.8705	1.3342	0.045*
C13	0.1149 (2)	0.63767 (17)	0.02161 (19)	0.0216 (6)
H13	0.0728	0.6803	0.0310	0.026*
C14	0.2914 (3)	0.5656 (2)	0.0675 (2)	0.0379 (8)
H14A	0.2527	0.5324	0.0193	0.057*
H14B	0.3153	0.5328	0.1180	0.057*
H14C	0.3554	0.5899	0.0589	0.057*
C15	0.2608 (3)	0.6836 (2)	0.1482 (2)	0.0341 (8)
H15A	0.2041	0.7218	0.1485	0.051*
H15B	0.3241	0.7119	0.1428	0.051*
H15C	0.2836	0.6534	0.2005	0.051*
C16	−0.0465 (2)	0.43014 (17)	0.80778 (19)	0.0225 (6)
H16	−0.0392	0.4640	0.8539	0.027*
C17	0.1313 (2)	0.37298 (19)	0.89417 (19)	0.0273 (7)
H17A	0.1206	0.4090	0.9359	0.041*
H17B	0.1975	0.3884	0.8824	0.041*
H17C	0.1394	0.3186	0.9156	0.041*
C18	0.0309 (2)	0.32090 (18)	0.7482 (2)	0.0278 (7)
H18A	−0.0347	0.3310	0.6997	0.042*
H18B	0.0286	0.2666	0.7679	0.042*
H18C	0.0963	0.3277	0.7324	0.042*

	U11	U22	U33	U12	U13	U23
Cu1	0.00914 (14)	0.01448 (16)	0.01225 (16)	−0.00096 (12)	0.00324 (12)	−0.00052 (13)
Cu2	0.01008 (14)	0.01517 (16)	0.01420 (17)	−0.00047 (12)	0.00315 (12)	−0.00099 (13)
Cu3	0.01137 (15)	0.01748 (17)	0.01439 (17)	−0.00170 (12)	0.00540 (13)	−0.00102 (13)
S1	0.0095 (3)	0.0152 (3)	0.0120 (3)	−0.0015 (2)	0.0013 (2)	0.0007 (2)
Cl1	0.0364 (4)	0.0423 (5)	0.0444 (5)	0.0025 (4)	0.0326 (4)	−0.0004 (4)
Cl2	0.0273 (4)	0.0200 (4)	0.0715 (7)	−0.0091 (3)	0.0247 (4)	−0.0017 (4)
Cl3	0.0227 (3)	0.0219 (4)	0.0440 (5)	0.0035 (3)	0.0146 (3)	−0.0092 (3)
O1	0.0079 (8)	0.0164 (9)	0.0111 (10)	−0.0004 (7)	0.0010 (7)	−0.0014 (8)
O2	0.0103 (8)	0.0159 (9)	0.0139 (10)	−0.0013 (7)	0.0025 (7)	0.0031 (7)
O3	0.0127 (9)	0.0206 (10)	0.0144 (10)	−0.0021 (7)	−0.0039 (8)	0.0042 (8)
O4	0.0118 (8)	0.0215 (10)	0.0156 (10)	−0.0023 (7)	0.0052 (8)	−0.0007 (8)
O5	0.0130 (8)	0.0163 (9)	0.0156 (10)	−0.0003 (7)	0.0024 (7)	−0.0019 (8)
O6	0.0172 (9)	0.0256 (11)	0.0172 (11)	−0.0035 (8)	0.0088 (8)	−0.0015 (8)
O7	0.0145 (9)	0.0183 (10)	0.0205 (11)	0.0018 (7)	0.0006 (8)	−0.0050 (8)
O8	0.0224 (10)	0.0286 (11)	0.0237 (12)	0.0038 (9)	0.0014 (9)	−0.0041 (9)
O9	0.0201 (10)	0.0254 (11)	0.0236 (12)	0.0033 (8)	−0.0059 (9)	−0.0051 (9)
O10	0.0244 (12)	0.0337 (14)	0.0449 (16)	0.0136 (10)	−0.0152 (11)	−0.0228 (12)
N1	0.0117 (10)	0.0180 (11)	0.0149 (12)	−0.0020 (8)	0.0053 (9)	−0.0007 (9)
N2	0.0133 (10)	0.0160 (11)	0.0149 (12)	0.0002 (8)	0.0043 (9)	−0.0030 (9)
N3	0.0117 (10)	0.0182 (12)	0.0145 (12)	−0.0015 (8)	0.0015 (9)	0.0001 (9)
N4	0.0115 (10)	0.0198 (12)	0.0159 (12)	0.0005 (9)	0.0060 (9)	0.0016 (9)
N5	0.0115 (10)	0.0185 (12)	0.0172 (12)	−0.0012 (8)	0.0054 (9)	−0.0005 (9)
N6	0.0102 (10)	0.0181 (11)	0.0142 (12)	−0.0011 (8)	0.0040 (9)	0.0005 (9)
N7	0.0206 (12)	0.0241 (13)	0.0179 (13)	0.0045 (10)	0.0094 (10)	0.0009 (10)
N8	0.0191 (12)	0.0230 (13)	0.0195 (13)	0.0034 (10)	0.0015 (10)	0.0023 (10)
N9	0.0155 (11)	0.0210 (12)	0.0177 (13)	−0.0006 (9)	−0.0002 (10)	0.0024 (10)
C1	0.0143 (12)	0.0209 (14)	0.0164 (14)	0.0012 (10)	0.0039 (11)	−0.0029 (11)
C2	0.0148 (13)	0.0284 (15)	0.0189 (15)	0.0016 (11)	0.0101 (12)	−0.0021 (12)
C3	0.0155 (13)	0.0226 (14)	0.0188 (15)	−0.0024 (11)	0.0084 (11)	0.0005 (11)
C4	0.0122 (12)	0.0206 (14)	0.0238 (16)	−0.0019 (10)	0.0075 (11)	0.0015 (11)
C5	0.0135 (12)	0.0168 (14)	0.0310 (17)	−0.0026 (10)	0.0065 (12)	0.0027 (12)
C6	0.0163 (13)	0.0164 (14)	0.0254 (16)	0.0002 (10)	0.0040 (12)	0.0000 (12)
C7	0.0131 (12)	0.0157 (13)	0.0219 (15)	0.0007 (10)	0.0036 (11)	−0.0001 (11)
C8	0.0138 (12)	0.0187 (14)	0.0248 (16)	0.0031 (10)	0.0061 (12)	−0.0033 (12)
C9	0.0150 (13)	0.0237 (15)	0.0191 (15)	0.0034 (11)	0.0077 (11)	−0.0014 (12)
C10	0.0197 (14)	0.0207 (14)	0.0226 (16)	−0.0017 (11)	0.0114 (12)	−0.0013 (12)
C11	0.0202 (15)	0.052 (2)	0.0276 (18)	0.0047 (14)	0.0125 (14)	0.0045 (15)
C12	0.0308 (16)	0.0405 (19)	0.0193 (16)	0.0059 (14)	0.0093 (13)	−0.0009 (14)
C13	0.0174 (13)	0.0245 (15)	0.0217 (16)	0.0035 (11)	0.0051 (12)	0.0018 (12)
C14	0.0251 (16)	0.039 (2)	0.043 (2)	0.0143 (14)	0.0026 (15)	0.0005 (16)
C15	0.0299 (17)	0.0330 (18)	0.0291 (19)	−0.0012 (14)	−0.0036 (14)	−0.0036 (15)
C16	0.0213 (14)	0.0230 (15)	0.0206 (16)	−0.0041 (11)	0.0035 (12)	−0.0012 (12)
C17	0.0187 (14)	0.0349 (18)	0.0221 (17)	−0.0027 (12)	−0.0013 (12)	0.0097 (13)
C18	0.0240 (15)	0.0244 (16)	0.0324 (19)	0.0040 (12)	0.0063 (14)	0.0025 (13)

Cu1—N1	1.944 (2)	N7—C10	1.313 (3)
Cu1—N6	1.948 (2)	N7—C12	1.457 (4)
Cu1—O2	1.9760 (17)	N7—C11	1.458 (3)
Cu1—O1	1.9761 (17)	N8—C13	1.319 (3)
Cu1—O2i	2.2773 (17)	N8—C15	1.447 (4)
Cu2—N3	1.962 (2)	N8—C14	1.455 (4)
Cu2—N2	1.964 (2)	N9—C16	1.320 (3)
Cu2—O7	1.9895 (19)	N9—C18	1.455 (4)
Cu2—O1	2.0061 (17)	N9—C17	1.461 (3)
Cu2—O5i	2.2444 (18)	C1—C2	1.378 (4)
Cu3—N4	1.939 (2)	C1—H1	0.9300
Cu3—N5	1.954 (2)	C2—C3	1.380 (4)
Cu3—O1	1.9879 (18)	C3—H3	0.9300
Cu3—O6	1.9945 (18)	C4—C5	1.377 (4)
Cu3—O4i	2.2759 (18)	C4—H4A	0.9300
S1—O3	1.4579 (18)	C5—C6	1.382 (4)
S1—O4	1.4691 (18)	C6—H6	0.9300
S1—O5	1.4708 (18)	C7—C8	1.377 (4)
S1—O2	1.5055 (18)	C7—H7	0.9300
Cl1—C2	1.729 (3)	C8—C9	1.377 (4)
Cl2—C5	1.723 (3)	C9—H9	0.9300
Cl3—C8	1.726 (3)	C10—H10	0.9300
O1—H1O	0.775 (17)	C11—H11A	0.9600
O2—Cu1i	2.2774 (17)	C11—H11B	0.9600
O4—Cu3i	2.2759 (18)	C11—H11C	0.9600
O5—Cu2i	2.2444 (18)	C12—H12A	0.9600
O6—C10	1.244 (3)	C12—H12B	0.9600
O7—H7A	0.801 (17)	C12—H12C	0.9600
O7—H7B	0.831 (17)	C13—H13	0.9300
O8—C13	1.238 (3)	C14—H14A	0.9600
O9—C16	1.245 (3)	C14—H14B	0.9600
O10—H10A	0.808 (18)	C14—H14C	0.9600
O10—H10B	0.814 (18)	C15—H15A	0.9600
N1—C3	1.345 (3)	C15—H15B	0.9600
N1—N2	1.364 (3)	C15—H15C	0.9600
N2—C1	1.342 (3)	C16—H16	0.9300
N3—C6	1.345 (3)	C17—H17A	0.9600
N3—N4	1.364 (3)	C17—H17B	0.9600
N4—C4	1.340 (3)	C17—H17C	0.9600
N5—C9	1.341 (3)	C18—H18A	0.9600
N5—N6	1.368 (3)	C18—H18B	0.9600
N6—C7	1.339 (3)	C18—H18C	0.9600
N1—Cu1—N6	168.69 (9)	C16—N9—C18	121.7 (2)
N1—Cu1—O2	92.66 (8)	C16—N9—C17	121.1 (3)
N6—Cu1—O2	91.53 (8)	C18—N9—C17	117.2 (2)
N1—Cu1—O1	88.49 (8)	N2—C1—C2	108.7 (2)
N6—Cu1—O1	88.78 (8)	N2—C1—H1	125.7
O2—Cu1—O1	172.22 (7)	C2—C1—H1	125.7
N1—Cu1—O2i	96.06 (8)	C1—C2—C3	106.3 (2)
N6—Cu1—O2i	94.92 (8)	C1—C2—Cl1	127.0 (2)
O2—Cu1—O2i	82.09 (7)	C3—C2—Cl1	126.7 (2)
O1—Cu1—O2i	90.14 (7)	N1—C3—C2	108.4 (2)
N3—Cu2—N2	167.22 (9)	N1—C3—H3	125.8
N3—Cu2—O7	93.89 (8)	C2—C3—H3	125.8
N2—Cu2—O7	89.43 (8)	N4—C4—C5	108.9 (2)
N3—Cu2—O1	86.18 (8)	N4—C4—H4A	125.5
N2—Cu2—O1	88.44 (8)	C5—C4—H4A	125.5
O7—Cu2—O1	170.11 (8)	C4—C5—C6	106.1 (2)
N3—Cu2—O5i	96.85 (8)	C4—C5—Cl2	127.3 (2)
N2—Cu2—O5i	94.96 (8)	C6—C5—Cl2	126.6 (2)
O7—Cu2—O5i	97.26 (7)	N3—C6—C5	108.4 (2)
O1—Cu2—O5i	92.54 (7)	N3—C6—H6	125.8
N4—Cu3—N5	165.39 (9)	C5—C6—H6	125.8
N4—Cu3—O1	87.49 (8)	N6—C7—C8	109.0 (2)
N5—Cu3—O1	88.83 (8)	N6—C7—H7	125.5
N4—Cu3—O6	90.70 (8)	C8—C7—H7	125.5
N5—Cu3—O6	91.08 (8)	C7—C8—C9	105.8 (2)
O1—Cu3—O6	172.37 (7)	C7—C8—Cl3	126.3 (2)
N4—Cu3—O4i	96.70 (8)	C9—C8—Cl3	127.9 (2)
N5—Cu3—O4i	97.76 (8)	N5—C9—C8	109.2 (2)
O1—Cu3—O4i	96.49 (7)	N5—C9—H9	125.4
O6—Cu3—O4i	91.08 (7)	C8—C9—H9	125.4
O3—S1—O4	111.90 (11)	O6—C10—N7	123.2 (3)
O3—S1—O5	110.78 (11)	O6—C10—H10	118.4
O4—S1—O5	110.20 (10)	N7—C10—H10	118.4
O3—S1—O2	108.64 (10)	N7—C11—H11A	109.5
O4—S1—O2	107.86 (10)	N7—C11—H11B	109.5
O5—S1—O2	107.30 (10)	H11A—C11—H11B	109.5
Cu1—O1—Cu3	111.97 (8)	N7—C11—H11C	109.5
Cu1—O1—Cu2	112.98 (8)	H11A—C11—H11C	109.5
Cu3—O1—Cu2	112.15 (8)	H11B—C11—H11C	109.5
Cu1—O1—H1O	107 (2)	N7—C12—H12A	109.5
Cu3—O1—H1O	107 (2)	N7—C12—H12B	109.5
Cu2—O1—H1O	105 (2)	H12A—C12—H12B	109.5
S1—O2—Cu1	134.93 (11)	N7—C12—H12C	109.5
S1—O2—Cu1i	127.14 (10)	H12A—C12—H12C	109.5
Cu1—O2—Cu1i	97.91 (7)	H12B—C12—H12C	109.5
S1—O4—Cu3i	118.91 (11)	O8—C13—N8	126.4 (3)
S1—O5—Cu2i	125.29 (10)	O8—C13—H13	116.8
C10—O6—Cu3	120.80 (17)	N8—C13—H13	116.8
Cu2—O7—H7A	121 (2)	N8—C14—H14A	109.5
Cu2—O7—H7B	125 (2)	N8—C14—H14B	109.5
H7A—O7—H7B	108 (3)	H14A—C14—H14B	109.5
H10A—O10—H10B	118 (4)	N8—C14—H14C	109.5
C3—N1—N2	108.4 (2)	H14A—C14—H14C	109.5
C3—N1—Cu1	131.89 (19)	H14B—C14—H14C	109.5
N2—N1—Cu1	119.18 (16)	N8—C15—H15A	109.5
C1—N2—N1	108.2 (2)	N8—C15—H15B	109.5
C1—N2—Cu2	131.42 (18)	H15A—C15—H15B	109.5
N1—N2—Cu2	120.19 (15)	N8—C15—H15C	109.5
C6—N3—N4	108.4 (2)	H15A—C15—H15C	109.5
C6—N3—Cu2	132.94 (19)	H15B—C15—H15C	109.5
N4—N3—Cu2	118.57 (16)	O9—C16—N9	125.8 (3)
C4—N4—N3	108.2 (2)	O9—C16—H16	117.1
C4—N4—Cu3	130.49 (18)	N9—C16—H16	117.1
N3—N4—Cu3	121.01 (15)	N9—C17—H17A	109.5
C9—N5—N6	107.8 (2)	N9—C17—H17B	109.5
C9—N5—Cu3	133.20 (18)	H17A—C17—H17B	109.5
N6—N5—Cu3	118.53 (16)	N9—C17—H17C	109.5
C7—N6—N5	108.2 (2)	H17A—C17—H17C	109.5
C7—N6—Cu1	131.22 (18)	H17B—C17—H17C	109.5
N5—N6—Cu1	120.33 (16)	N9—C18—H18A	109.5
C10—N7—C12	121.5 (2)	N9—C18—H18B	109.5
C10—N7—C11	120.0 (2)	H18A—C18—H18B	109.5
C12—N7—C11	118.4 (2)	N9—C18—H18C	109.5
C13—N8—C15	121.4 (2)	H18A—C18—H18C	109.5
C13—N8—C14	121.6 (3)	H18B—C18—H18C	109.5
C15—N8—C14	116.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18B···O3ii	0.96	2.64	3.494 (4)	148
C17—H17C···O5ii	0.96	2.56	3.360 (3)	141
C15—H15C···N2iii	0.96	2.63	3.406 (4)	138
C13—H13···O5iv	0.93	2.23	3.155 (3)	170
C10—H10···O4i	0.93	2.30	2.971 (3)	128
C7—H7···O5	0.93	2.65	3.483 (3)	149
C7—H7···S1	0.93	2.95	3.610 (3)	129
C6—H6···O10v	0.93	2.38	3.234 (4)	153
C4—H4A···Cl3vi	0.93	2.93	3.484 (3)	119
C3—H3···O4	0.93	2.64	3.411 (3)	140
C3—H3···S1	0.93	2.99	3.616 (3)	126
O10—H10B···O9vii	0.81 (2)	1.96 (2)	2.751 (3)	165 (4)
O10—H10A···O3iii	0.81 (2)	1.91 (2)	2.700 (3)	165 (4)
O7—H7B···O8viii	0.83 (2)	1.83 (2)	2.658 (3)	175 (3)
O7—H7A···O10v	0.80 (2)	1.83 (2)	2.625 (3)	172 (3)
O1—H1O···O9ix	0.78 (2)	1.95 (2)	2.711 (3)	166 (3)
O1—H1O···O9ix	0.78 (2)	1.95 (2)	2.711 (3)	166 (3)
O7—H7A···O10v	0.80 (2)	1.83 (2)	2.625 (3)	172 (3)
O7—H7B···O8viii	0.83 (2)	1.83 (2)	2.658 (3)	175 (3)
O10—H10A···O3iii	0.81 (2)	1.91 (2)	2.700 (3)	165 (4)
O10—H10B···O9vii	0.81 (2)	1.96 (2)	2.751 (3)	165 (4)
C3—H3···S1	0.93	2.99	3.616 (3)	126
C3—H3···O4	0.93	2.64	3.411 (3)	140
C4—H4A···Cl3vi	0.93	2.93	3.484 (3)	119
C6—H6···O10v	0.93	2.38	3.234 (4)	153
C7—H7···S1	0.93	2.95	3.610 (3)	129
C7—H7···O5	0.93	2.65	3.483 (3)	149
C10—H10···O4i	0.93	2.30	2.971 (3)	128
C13—H13···O5iv	0.93	2.23	3.155 (3)	170
C15—H15C···N2iii	0.96	2.63	3.406 (4)	138
C17—H17C···O5ii	0.96	2.56	3.360 (3)	141
C18—H18B···O3ii	0.96	2.64	3.494 (4)	148