A one-dimensional coordination polymer with a capped [Cu₄O₄] cubane core assembled from 2-(hy­droxy­methyl)pyridine

The one-dimensional coordination polymer catena-poly[[[di-μ₂-acetato-tetra­kis­[μ₃-(pyridin-2-yl)methanol­ato]tetracopper(II)]-di-μ₂-diacetamidato] aceto­nitrile monosolvate], {[Cu₄(C₆H₆NO)₄(CH₃COO)₂(C₂N₃)₂]·CH₃CN}_n, has been pre­pared from the direct reaction of 2-(hy­droxy­methyl)pyridine with Cu(OAc)₂·H₂O (OAc⁻ is acetate) in a methanol–aceto­nitrile mixture. The four Cu centres are bridged by four O atoms from discrete (pyridin-2-yl)methanol­ate ligands and two acetate groups, forming a capped [Cu₄O₄] cubane core. Each core is doubly bridged to each of two adjacent cores by [N(CN)₂]⁻ anions, resulting in one-dimensional chains. The magnetic properties of the complex were also studied.

S1. Introduction

Since the pioneering reports of Robson and co-workers (Hoskins & Robson, 1990; Seddon & Zaworotko, 1996), much attention has focused on the field of crystal engineering. Great efforts have been focused on the assembly of coordination polymers through hydrogen bonds or coordination bonds. These complexes exhibit unique geometric characteristics (e.g. large size, high symmetry, aesthetically pleasing shapes and architectures) and fascinating physical properties (e.g. optical, magnetic, electronic and fluorescent properties) (Bagai & Christou, 2009; Gatteschi & Sessoli, 2003; Risch et al., 2009). Recently, much attention has been devoted to 2-(hy­droxy­methyl)­pyridine (Hhmp) since it contains an N-donor function forming polynuclear transition metal clusters. Several Fe^II, Co^II/Co^III, Ni^II, Cu^II and Mn^II complexes have been reported based on this ligand (Christmas et al., 1993; Yang et al., 2002; Stamatatos et al., 2007; Zhang et al., 2010; Lah et al., 2006). We recently investigated a novel Mn complex, namely, [Mn₄(hmp)₆(dca)₄(H₂O)₂] (dca^- is the dicyanamide anion), with a linear Mn₄ core and single-molecule magnet properties (Li et al., 2010). Continuing our work in this field, we report here the synthesis and structural characterization of a one-dimensional copper coordination polymer assembled from Hhmp, namely {[Cu₄(hmp)₄(CH₃COO)₂(dca)₂]·CH₃CN}_n, (I).

S2. Experimental

S2.1. Synthesis and crystallization

All chemicals were of analytical grade and were obtained commercially and used without further purification. Complex (I) was synthesized by dissolving Cu(OAc)₂·H₂O (0.3997 g, 2 mmol), Hhmp (0.4905 g, 4.5 mmol) and Na[N(CN)₂] (0.1602 g, 1.8 mmol) in a methanol–aceto­nitrile mixture (20 ml, 1:1 v/v). 25% Bu₄NOH (0.9324 mg, 0.9 mmol) was added to this solution and the mixture was stirred for 5 h at room temperature. Blue crystals of (I) were obtained by diffusion in 51% yield (based on copper). Analysis, calculated for C₃₄H₃₃Cu₄N₁₁O₈ (%): H 3.37, C 41.72, N 15.74; found: H 3.32, C 41.32, N 15.71. The formation of (I) can be represented by the reaction scheme shown in Scheme 2.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were positioned in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 (aryl), 0.97 (methyl­ene) or 0.96 Å (methyl), and with U_iso(H) = U_eq(C) for methyl groups or 1.2U_eq(C) otherwise.

S3. Results and discussion

The title complex, (I), crystallizes in the monoclinic space group P2₁ and consists of [Cu₄O₄] cubane units connected by dicyanamidate ligands {dca^-, [N(CN)₂]^-}, resulting in a one-dimensional coordination chain structure. As shown in Fig. 1, the core of (I) is composed of four crystallographically independent Cu²⁺ cations, four monodeprotonated (pyridin-2-yl)methano­late (hmp^-) ligands, two κ¹,κ¹;µ₂-acetate ligands, four κ¹,κ¹;µ₂-dca^- ligands and one aceto­nitrile solvent molecule. Table 2 shows the Cu—O/N coordination distances. Atom Cu1 is in a distorted six-coordinated o­cta­hedral coordination environment where the equatorial plane is occupied by one N atom (N8) and one O atom (O8) from one hmp^- ligand, one O atom (O5) from another hmp^- ligand and one N atom (N5) from a bridging dca^- ligand. The O—Cu1—N and N—Cu1—N angles are in the range 80.78 (17)–95.2 (2)°. The axial positions are occupied by two O atoms (O4 and O7) from acetate and hmp^- ligands, with an O4—Cu1—O7 angle of 152.08 (13)°. Atom Cu2 also adopts a distorted o­cta­hedral geometry, with atoms N2 and O6 (from one hmp^- ligand), O8 (from another hmp^- ligand) and O3 (from a κ¹,κ¹;µ₂-acetate ligand) in the equatorial plane. The axial positions are occupied by atoms O5 (from one hmp^- ligand) and N7 (from a κ¹,κ¹;µ₂-dca^- bridging ligand). The O—Cu2—N and O—Cu2—O angles are in the range 81.89 (17)–98.44 (16)° in the equatorial plane and the O—Cu2—N angle along the apical positions of 169.77 (16)°, indicating the distortion of the o­cta­hedron. Atoms Cu3 and Cu4 exhibit similar coordination environments to Cu2 and Cu1, respectively. The equatorial Cu—O and Cu—N bond distances for all the metal centres are in the ranges 1.935 (4)-1.973 (3) and 1.954 (5)–2.015 (5) Å, respectively, which are close to previously reported bond lengths for Cu^II cations (Zheng 2013; Chakraborty et al., 2012; Winter et al., 2004). However, the axial bonds are elongated [2.321 (4)–2.612 (4) Å] due to Jahn–Teller distortion (Miyasaka et al., 2004).

Four O atoms from four κ³,κ¹;µ₃-hmp^- ligands bridge four Cu^II cations, resulting in a [Cu₄O₄] cubane core with Cu²⁺ cations and O atoms located at the corners. The two acetate groups adopt κ¹,κ¹;µ₂-coordination modes, connecting Cu1 and Cu2, and Cu3 and Cu4, respectively. The Cu···Cu distances and Cu—O—Cu angles within the cubane core are in the ranges 3.107(s.u.?)–3.574(s.u.?) Å [Please supply missing s.u.s] and 86.02 (12)–113.19 (19)°, respectively, indicating that the cubane is slightly distorted (Mishtu et al., 2002).

Several Ni₄, Co₄, Zn₄ and Cu₄ complexes based on the 2-(hy­droxy­methyl)­pyridine ligand have been reported (Yang et al., 2006; Lawrence et al., 2007; Zhang et al., 2013). They are discrete cubane molecules, further connected through weak inter­actions to form one-dimensional chains. However, in complex (I) the capped cubanes are linked together through κ¹,κ¹;µ₂-dca^- ligands [symmetry code: (i) x + 1, y, z + 1], resulting in one-dimensional structures parallel to [101] (Fig. 2). The Cu···Cu distances between neighbouring capped cubanes along the chain span the range 8.553(s.u.?)–8.636(s.u.?) Å. [Please supply missing s.u.s]

The temperature dependence of the magnetic susceptibilities for (I) was measured in the temperature range 2–300 K in a constant magnetic field of 0.1 T, and the results are shown as χ_MT versus T plots in Fig. 3. The χ_MT of (I) is 1.78 cm³ mol^-1 K at 300 K, somewhat higher than the spin-only value (1.50 cm³ mol^-1 K) expected for magnetically isolated high-spin Cu^II cations with g = 2.00. Upon cooling, χ_MT drops slowly down to approximately 60 K. Below 60 K, there is a sharp decrease to a minimum of 0.61 cm³ mol^-1 K at 2 K. This decrease in χ_MT suggests anti­ferromagnetic inter­actions between the Cu^II cations. Furthermore, the magnetic susceptibilities above 50 K can be fitted well by the Curie–Weiss law χ = C/(T - θ), obtaining C = 1.89 cm³ mol^-1 K and θ = -17.23 K (Fig. 3, inset). The value of θ also indicates anti­ferromagnetic inter­actions between the four Cu^II centres.

In order to investigate the magnetic coupling in this complex, an isotropic Heisenberg–Dirac–van Vleck (HDVV) Hamiltonian formalism was used (Chakraborty et al., 2012), i.e. H = -2J(S₁·S₂ + S₁·S₃ + S₁·S₄+ S₂·S₃ +S₂·S₄ + S₃·S₄).

The best parameters fitted in the temperature range 10–300 K are J = -4.97 cm^-1, g = 2.039 and zJ' = -0.017cm^-1, with the result shown as the red line in Fig. 3. It is obvious that anti­ferromagnetic inter­actions are present between the four Cu^II centres, which is consistent with the results deduced from the Curie–Weiss law.

Related literature

For related literature, see: Bagai & Christou (2009); Chakraborty et al. (2012); Christmas et al. (1993); Gatteschi & Sessoli (2003); Hoskins & Robson (1990); Lah et al. (2006); Lawrence et al. (2007); Li et al. (2010); Mishtu et al. (2002); Miyasaka et al. (2004); Risch et al. (2009); Seddon & Zaworotko (1996); Stamatatos et al. (2007); Winter et al. (2004); Yang et al. (2002, 2006); Zhang et al. (2010, 2013); Zheng (2013).

Computing details

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The coordination environments of atoms Cu1, Cu2, Cu3 and Cu4 in complex (I), with part of the atom-numbering scheme; the remaining C atoms complete the sequence in an orderly manner. The acetonitrile solvent molecule and all H atoms have been omitted for clarity. [Symmetry code: (i) x + 1, y, z + 1.] [Several labels overlap with atoms which reduces clarity. Please revise with no overlap.]
	Fig. 2. A view of the [101] one-dimensional array in complex (I), projected along [010].
	Fig. 3. The temperature dependence of χMT and 1/χM (inset) for complex (I). The solid red lines indicate the best fits obtained.

catena-Poly[[[di-µ₂-acetato-1:2κ²O:O';3:4κ²O:O'-tetrakis[µ₃-(pyridin-2-yl)methanolato-κ²N:O]-1:2:4κ⁴N,O:O:O;2:3:4κ⁴N,O:O:O;1:2:3κ⁴O:O:N,O;1:3:4κ⁴O:O:N,O-tetracopper(II)]-di-µ₂-diacetamidato-1:4'κ²N¹:N⁵;3:2'κ²N¹:N⁵] acetonitrile monosolvate]

Crystal data

[Cu4(C6H6NO)4(C2H3O2)2(C2N3)2]·C2H3N	F(000) = 988
Mr = 977.87	Dx = 1.696 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 5178 reflections
a = 10.316 (1) Å	θ = 2.4–27.0°
b = 19.7793 (19) Å	µ = 2.26 mm^−1
c = 10.6749 (11) Å	T = 298 K
β = 118.437 (2)°	Block, blue
V = 1915.3 (3) Å^3	0.45 × 0.38 × 0.21 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	8708 independent reflections
Radiation source: fine-focus sealed tube	7116 reflections with I > 2/s(I)
Graphite monochromator	Rint = 0.041
φ and ω scans	θmax = 28.3°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −13→13
Tmin = 0.430, Tmax = 0.649	k = −25→26
12122 measured reflections	l = −14→6

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.116	w = 1/[σ^2(Fo^2) + (0.0497P)^2 + 0.2828P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.004
8708 reflections	Δρmax = 0.61 e Å^−3
517 parameters	Δρmin = −0.61 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 3893 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.020 (15)

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
Cu1	0.65254 (6)	0.97572 (3)	0.15263 (6)	0.02925 (15)
Cu2	0.96465 (7)	0.91677 (3)	0.28746 (7)	0.03010 (15)
Cu3	0.81423 (7)	0.99751 (3)	−0.04408 (6)	0.02986 (15)
Cu4	0.97134 (7)	1.07710 (3)	0.24063 (7)	0.03396 (16)
N1	0.8496 (5)	0.9119 (2)	−0.1243 (4)	0.0313 (9)
N2	1.0909 (5)	0.8599 (2)	0.2332 (5)	0.0332 (10)
N3	0.5790 (6)	1.0192 (3)	−0.2445 (5)	0.0523 (15)
N4	0.3660 (7)	1.0934 (3)	−0.3473 (6)	0.075 (2)
N5	0.4516 (5)	0.9736 (3)	−0.0090 (5)	0.0465 (13)
N6	0.2252 (6)	0.9526 (5)	−0.2243 (6)	0.089 (3)
N7	0.1744 (7)	0.9255 (3)	−0.4654 (6)	0.0606 (16)
N8	0.6019 (5)	1.0352 (2)	0.2743 (5)	0.0334 (10)
N9	0.8652 (5)	1.1586 (2)	0.2604 (4)	0.0320 (10)
N10	0.1541 (5)	1.0938 (3)	−0.5835 (6)	0.0505 (14)
N11	0.4719 (15)	0.7845 (7)	0.5377 (13)	0.163 (6)
O1	0.9220 (5)	1.0546 (2)	−0.1129 (5)	0.0478 (11)
O2	1.0551 (6)	1.1219 (3)	0.0776 (6)	0.0689 (15)
O3	0.8794 (4)	0.8387 (2)	0.3343 (4)	0.0404 (10)
O4	0.6443 (5)	0.8716 (2)	0.2489 (5)	0.0468 (10)
O5	0.7398 (4)	0.93249 (19)	0.0455 (4)	0.0321 (9)
O6	1.0324 (3)	0.98834 (19)	0.2062 (4)	0.0299 (8)
O7	0.7819 (4)	1.06523 (18)	0.0697 (4)	0.0328 (8)
O8	0.8512 (4)	0.98706 (19)	0.3164 (3)	0.0288 (8)
C1	0.6906 (7)	0.8729 (3)	−0.0344 (6)	0.0407 (14)
H1A	0.5883	0.8779	−0.1060	0.049*
H1B	0.6974	0.8357	0.0275	0.049*
C2	0.7826 (6)	0.8583 (3)	−0.1047 (5)	0.0347 (12)
C3	0.7990 (9)	0.7946 (3)	−0.1484 (7)	0.0562 (18)
H3	0.7518	0.7575	−0.1343	0.067*
C4	0.8869 (10)	0.7865 (4)	−0.2136 (9)	0.069 (2)
H4	0.9002	0.7441	−0.2432	0.083*
C5	0.9526 (9)	0.8417 (4)	−0.2333 (9)	0.070 (2)
H5	1.0108	0.8373	−0.2778	0.084*
C6	0.9334 (7)	0.9045 (3)	−0.1875 (6)	0.0451 (15)
H6	0.9796	0.9421	−0.2009	0.054*
C7	1.1670 (6)	0.9726 (3)	0.2085 (7)	0.0432 (14)
H7A	1.2488	0.9893	0.2958	0.052*
H7B	1.1709	0.9940	0.1286	0.052*
C8	1.1786 (6)	0.8969 (3)	0.1996 (5)	0.0347 (12)
C9	1.2745 (7)	0.8659 (4)	0.1615 (7)	0.0472 (15)
H9	1.3352	0.8917	0.1379	0.057*
C10	1.2796 (8)	0.7963 (4)	0.1586 (8)	0.061 (2)
H10	1.3439	0.7747	0.1333	0.073*
C11	1.1887 (8)	0.7591 (4)	0.1936 (8)	0.0599 (19)
H11	1.1903	0.7121	0.1921	0.072*
C12	1.0954 (7)	0.7926 (3)	0.2307 (7)	0.0434 (14)
H12	1.0339	0.7677	0.2546	0.052*
C13	0.7119 (9)	0.7621 (4)	0.3446 (11)	0.080 (3)
H13A	0.7571	0.7588	0.4465	0.120*
H13B	0.7500	0.7273	0.3086	0.120*
H13C	0.6071	0.7570	0.3046	0.120*
C14	0.7455 (6)	0.8299 (3)	0.3043 (6)	0.0373 (12)
C15	1.1001 (10)	1.1243 (4)	−0.1319 (12)	0.087 (3)
H15A	1.1555	1.1644	−0.0875	0.131*
H15B	1.0284	1.1343	−0.2284	0.131*
H15C	1.1656	1.0897	−0.1313	0.131*
C16	1.0201 (8)	1.0992 (4)	−0.0482 (8)	0.0564 (17)
C17	0.4765 (7)	1.0514 (3)	−0.2992 (6)	0.0402 (13)
C18	0.2565 (6)	1.0900 (3)	−0.4740 (6)	0.0408 (14)
C19	0.3495 (6)	0.9626 (3)	−0.1144 (6)	0.0403 (14)
C20	0.2072 (7)	0.9390 (3)	−0.3507 (6)	0.0436 (14)
C21	0.8434 (6)	0.9978 (3)	0.4428 (5)	0.0378 (12)
H21A	0.9314	1.0210	0.5119	0.045*
H21B	0.8370	0.9548	0.4832	0.045*
C22	0.7104 (6)	1.0395 (3)	0.4098 (5)	0.0345 (12)
C23	0.6954 (7)	1.0798 (4)	0.5097 (7)	0.0504 (16)
H23	0.7696	1.0809	0.6039	0.060*
C24	0.5695 (9)	1.1178 (4)	0.4671 (8)	0.0590 (19)
H24	0.5591	1.1460	0.5314	0.071*
C25	0.4575 (8)	1.1134 (4)	0.3261 (8)	0.0553 (18)
H25	0.3713	1.1384	0.2956	0.066*
C26	0.4764 (7)	1.0717 (3)	0.2328 (7)	0.0420 (13)
H26	0.4015	1.0683	0.1392	0.050*
C27	0.7008 (7)	1.1247 (3)	0.0206 (6)	0.0373 (13)
H27A	0.5963	1.1143	−0.0260	0.045*
H27B	0.7232	1.1460	−0.0487	0.045*
C28	0.7374 (6)	1.1720 (3)	0.1423 (6)	0.0329 (12)
C29	0.6479 (7)	1.2253 (3)	0.1385 (7)	0.0479 (15)
H29	0.5597	1.2340	0.0565	0.058*
C30	0.6911 (8)	1.2650 (3)	0.2570 (8)	0.0557 (18)
H30	0.6323	1.3008	0.2563	0.067*
C31	0.8218 (8)	1.2515 (3)	0.3767 (7)	0.0480 (15)
H31	0.8536	1.2781	0.4579	0.058*
C32	0.9038 (7)	1.1983 (3)	0.3740 (6)	0.0439 (14)
H32	0.9917	1.1890	0.4558	0.053*
C33	0.5351 (11)	0.9057 (5)	0.5091 (9)	0.088 (3)
H33A	0.5635	0.9072	0.4356	0.132*
H33B	0.6151	0.9216	0.5970	0.132*
H33C	0.4505	0.9340	0.4830	0.132*
C34	0.5005 (11)	0.8391 (6)	0.5265 (9)	0.084 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0247 (3)	0.0409 (4)	0.0204 (3)	0.0012 (2)	0.0093 (2)	−0.0022 (2)
Cu2	0.0286 (3)	0.0300 (3)	0.0345 (3)	0.0029 (3)	0.0174 (3)	0.0028 (3)
Cu3	0.0335 (3)	0.0321 (3)	0.0262 (3)	−0.0009 (3)	0.0159 (3)	−0.0019 (2)
Cu4	0.0275 (3)	0.0310 (3)	0.0314 (3)	0.0025 (3)	0.0042 (3)	−0.0025 (3)
N1	0.030 (2)	0.037 (2)	0.027 (2)	0.005 (2)	0.0130 (18)	−0.0014 (19)
N2	0.029 (2)	0.037 (3)	0.034 (2)	0.0032 (19)	0.016 (2)	0.0004 (19)
N3	0.043 (3)	0.071 (4)	0.032 (3)	0.011 (3)	0.008 (2)	0.001 (3)
N4	0.060 (4)	0.073 (4)	0.049 (3)	0.032 (3)	−0.009 (3)	−0.021 (3)
N5	0.034 (2)	0.075 (4)	0.027 (2)	0.002 (3)	0.011 (2)	−0.005 (3)
N6	0.034 (3)	0.187 (8)	0.035 (3)	−0.018 (4)	0.007 (3)	−0.033 (4)
N7	0.068 (4)	0.061 (4)	0.036 (3)	0.002 (3)	0.012 (3)	−0.005 (3)
N8	0.031 (2)	0.039 (3)	0.034 (2)	0.0049 (19)	0.019 (2)	0.0023 (19)
N9	0.033 (2)	0.029 (2)	0.027 (2)	−0.0008 (18)	0.0085 (19)	−0.0018 (17)
N10	0.030 (3)	0.049 (3)	0.051 (3)	0.002 (2)	0.001 (2)	−0.009 (2)
N11	0.209 (13)	0.149 (11)	0.137 (10)	−0.064 (10)	0.086 (10)	0.025 (8)
O1	0.057 (3)	0.049 (3)	0.041 (2)	−0.008 (2)	0.026 (2)	0.001 (2)
O2	0.082 (4)	0.055 (3)	0.074 (4)	−0.011 (3)	0.040 (3)	−0.002 (3)
O3	0.032 (2)	0.038 (2)	0.050 (2)	0.0044 (17)	0.0190 (19)	0.0130 (18)
O4	0.041 (2)	0.048 (3)	0.055 (3)	0.005 (2)	0.026 (2)	0.013 (2)
O5	0.031 (2)	0.041 (2)	0.0235 (18)	−0.0053 (16)	0.0125 (16)	−0.0067 (15)
O6	0.0227 (16)	0.033 (2)	0.036 (2)	0.0014 (15)	0.0160 (15)	0.0022 (16)
O7	0.033 (2)	0.033 (2)	0.0261 (18)	0.0073 (16)	0.0091 (16)	−0.0001 (15)
O8	0.0277 (17)	0.039 (2)	0.0195 (16)	0.0022 (15)	0.0110 (14)	−0.0009 (15)
C1	0.049 (4)	0.042 (3)	0.038 (3)	−0.014 (3)	0.026 (3)	−0.017 (2)
C2	0.038 (3)	0.038 (3)	0.025 (3)	−0.006 (2)	0.012 (2)	−0.012 (2)
C3	0.079 (5)	0.039 (4)	0.055 (4)	−0.005 (3)	0.035 (4)	−0.007 (3)
C4	0.085 (6)	0.055 (5)	0.077 (5)	0.009 (4)	0.047 (5)	−0.021 (4)
C5	0.079 (6)	0.074 (6)	0.082 (6)	0.005 (4)	0.059 (5)	−0.023 (4)
C6	0.050 (4)	0.054 (4)	0.040 (3)	−0.001 (3)	0.028 (3)	−0.012 (3)
C7	0.025 (3)	0.045 (3)	0.060 (4)	0.006 (2)	0.020 (3)	0.007 (3)
C8	0.026 (3)	0.046 (3)	0.028 (3)	0.006 (2)	0.010 (2)	0.000 (2)
C9	0.043 (4)	0.057 (4)	0.050 (4)	0.006 (3)	0.028 (3)	−0.002 (3)
C10	0.059 (5)	0.066 (5)	0.070 (5)	0.008 (4)	0.041 (4)	−0.018 (4)
C11	0.057 (4)	0.048 (4)	0.086 (5)	0.005 (3)	0.043 (4)	−0.022 (4)
C12	0.045 (3)	0.036 (3)	0.053 (4)	−0.002 (3)	0.027 (3)	−0.007 (3)
C13	0.052 (5)	0.064 (5)	0.116 (7)	−0.007 (4)	0.033 (5)	0.038 (5)
C14	0.035 (3)	0.041 (3)	0.036 (3)	−0.001 (2)	0.018 (2)	0.009 (2)
C15	0.083 (6)	0.070 (6)	0.135 (9)	0.001 (5)	0.074 (7)	0.017 (5)
C16	0.058 (4)	0.045 (4)	0.060 (5)	0.006 (3)	0.023 (4)	0.004 (3)
C17	0.036 (3)	0.052 (4)	0.022 (3)	0.002 (3)	0.005 (2)	−0.006 (2)
C18	0.036 (3)	0.038 (3)	0.036 (3)	0.006 (2)	0.007 (3)	−0.006 (2)
C19	0.033 (3)	0.058 (4)	0.034 (3)	0.003 (3)	0.019 (3)	0.000 (3)
C20	0.039 (3)	0.048 (4)	0.032 (3)	−0.006 (3)	0.007 (3)	−0.004 (3)
C21	0.033 (3)	0.058 (3)	0.024 (3)	0.001 (3)	0.015 (2)	−0.006 (3)
C22	0.036 (3)	0.043 (3)	0.028 (3)	−0.004 (2)	0.018 (2)	−0.004 (2)
C23	0.055 (4)	0.063 (4)	0.041 (3)	−0.005 (3)	0.030 (3)	−0.014 (3)
C24	0.075 (5)	0.058 (5)	0.066 (5)	0.004 (4)	0.052 (4)	−0.013 (3)
C25	0.062 (5)	0.056 (4)	0.065 (5)	0.011 (3)	0.044 (4)	0.006 (3)
C26	0.040 (3)	0.046 (3)	0.044 (3)	0.009 (3)	0.023 (3)	0.005 (3)
C27	0.043 (3)	0.035 (3)	0.026 (3)	0.008 (2)	0.010 (2)	0.006 (2)
C28	0.033 (3)	0.029 (3)	0.035 (3)	0.003 (2)	0.015 (2)	0.004 (2)
C29	0.052 (4)	0.041 (3)	0.046 (3)	0.014 (3)	0.019 (3)	0.008 (3)
C30	0.061 (4)	0.044 (4)	0.061 (4)	0.017 (3)	0.029 (4)	−0.008 (3)
C31	0.064 (4)	0.040 (3)	0.045 (4)	−0.005 (3)	0.030 (3)	−0.013 (3)
C32	0.046 (4)	0.039 (3)	0.037 (3)	−0.006 (3)	0.011 (3)	−0.010 (3)
C33	0.091 (7)	0.088 (7)	0.054 (5)	−0.002 (5)	0.009 (5)	−0.017 (5)
C34	0.077 (6)	0.108 (8)	0.059 (5)	−0.009 (6)	0.027 (5)	0.012 (5)

Geometric parameters (Å, º)

Cu1—O5	1.957 (4)	C2—C3	1.381 (9)
Cu1—N5	1.967 (5)	C3—C4	1.391 (11)
Cu1—O8	1.973 (3)	C3—H3	0.9300
Cu1—N8	1.998 (5)	C4—C5	1.352 (11)
Cu1—O4	2.321 (4)	C4—H4	0.9300
Cu1—O7	2.612 (4)	C5—C6	1.384 (9)
Cu2—O8	1.935 (4)	C5—H5	0.9300
Cu2—O6	1.955 (4)	C6—H6	0.9300
Cu2—O3	1.957 (4)	C7—C8	1.508 (8)
Cu2—N2	2.003 (5)	C7—H7A	0.9700
Cu2—O5	2.538 (3)	C7—H7B	0.9700
Cu2—N7^i	2.497 (6)	C8—C9	1.380 (8)
Cu3—O7	1.941 (4)	C9—C10	1.378 (10)
Cu3—O1	1.956 (4)	C9—H9	0.9300
Cu3—O5	1.964 (4)	C10—C11	1.377 (10)
Cu3—N1	2.008 (4)	C10—H10	0.9300
Cu3—N3	2.389 (5)	C11—C12	1.373 (9)
Cu3—O6	2.551 (3)	C11—H11	0.9300
Cu4—O7	1.951 (4)	C12—H12	0.9300
Cu4—N10^i	1.954 (5)	C13—C14	1.498 (9)
Cu4—O6	1.958 (4)	C13—H13A	0.9600
Cu4—N9	2.015 (5)	C13—H13B	0.9600
Cu4—O2	2.448 (6)	C13—H13C	0.9600
Cu4—O8	2.514 (4)	C15—C16	1.557 (11)
N1—C6	1.334 (7)	C15—H15A	0.9600
N1—C2	1.336 (7)	C15—H15B	0.9600
N2—C12	1.334 (7)	C15—H15C	0.9600
N2—C8	1.339 (7)	C21—C22	1.493 (8)
N3—C17	1.130 (8)	C21—H21A	0.9700
N4—C18	1.287 (7)	C21—H21B	0.9700
N4—C17	1.301 (8)	C22—C23	1.398 (8)
N5—C19	1.137 (7)	C23—C24	1.377 (10)
N6—C19	1.275 (8)	C23—H23	0.9300
N6—C20	1.300 (8)	C24—C25	1.397 (10)
N7—C20	1.136 (8)	C24—H24	0.9300
N8—C22	1.345 (7)	C25—C26	1.377 (9)
N8—C26	1.358 (7)	C25—H25	0.9300
N9—C32	1.337 (7)	C26—H26	0.9300
N9—C28	1.347 (7)	C27—C28	1.496 (8)
N10—C18	1.145 (7)	C27—H27A	0.9700
N10—Cu4^ii	1.954 (5)	C27—H27B	0.9700
N11—C34	1.142 (14)	C28—C29	1.390 (8)
O1—C16	1.271 (8)	C29—C30	1.371 (9)
O2—C16	1.293 (9)	C29—H29	0.9300
O3—C14	1.272 (7)	C30—C31	1.372 (9)
O4—C14	1.238 (7)	C30—H30	0.9300
O5—C1	1.400 (6)	C31—C32	1.357 (9)
O6—C7	1.411 (6)	C31—H31	0.9300
O7—C27	1.393 (6)	C32—H32	0.9300
O8—C21	1.406 (6)	C33—C34	1.400 (14)
C1—C2	1.493 (8)	C33—H33A	0.9600
C1—H1A	0.9700	C33—H33B	0.9600
C1—H1B	0.9700	C33—H33C	0.9600
O5—Cu1—N5	93.67 (18)	N1—C2—C1	115.1 (5)
O5—Cu1—O8	89.70 (14)	C3—C2—C1	123.8 (6)
N5—Cu1—O8	174.6 (2)	C2—C3—C4	119.1 (7)
O5—Cu1—N8	166.61 (17)	C2—C3—H3	120.4
N5—Cu1—N8	95.2 (2)	C4—C3—H3	120.4
O8—Cu1—N8	80.78 (17)	C5—C4—C3	118.7 (7)
O5—Cu1—O4	89.71 (16)	C5—C4—H4	120.6
N5—Cu1—O4	97.1 (2)	C3—C4—H4	120.6
O8—Cu1—O4	87.14 (15)	C4—C5—C6	120.2 (7)
N8—Cu1—O4	99.13 (18)	C4—C5—H5	119.9
O5—Cu1—O7	69.31 (13)	C6—C5—H5	119.9
N5—Cu1—O7	102.24 (18)	N1—C6—C5	120.9 (6)
O8—Cu1—O7	74.97 (13)	N1—C6—H6	119.5
N8—Cu1—O7	98.93 (16)	C5—C6—H6	119.5
O4—Cu1—O7	152.08 (13)	O6—C7—C8	109.0 (5)
O8—Cu2—O6	85.54 (15)	O6—C7—H7A	109.9
O8—Cu2—O3	98.44 (16)	C8—C7—H7A	109.9
O6—Cu2—O3	169.77 (16)	O6—C7—H7B	109.9
O8—Cu2—N2	167.28 (17)	C8—C7—H7B	109.9
O6—Cu2—N2	81.89 (17)	H7A—C7—H7B	108.3
O3—Cu2—N2	93.66 (18)	N2—C8—C9	120.5 (6)
O8—Cu2—O5	75.24 (12)	N2—C8—C7	116.1 (5)
O6—Cu2—O5	78.84 (13)	C9—C8—C7	123.4 (6)
O3—Cu2—O5	93.00 (14)	C10—C9—C8	119.4 (7)
N2—Cu2—O5	100.34 (15)	C10—C9—H9	120.3
O7—Cu3—O1	97.74 (17)	C8—C9—H9	120.3
O7—Cu3—O5	85.61 (15)	C9—C10—C11	119.3 (6)
O1—Cu3—O5	169.88 (18)	C9—C10—H10	120.3
O7—Cu3—N1	165.76 (17)	C11—C10—H10	120.3
O1—Cu3—N1	94.31 (19)	C12—C11—C10	118.8 (7)
O5—Cu3—N1	81.26 (17)	C12—C11—H11	120.6
O7—Cu3—N3	91.84 (18)	C10—C11—H11	120.6
O1—Cu3—N3	94.4 (2)	N2—C12—C11	121.7 (6)
O5—Cu3—N3	95.04 (18)	N2—C12—H12	119.2
N1—Cu3—N3	94.76 (18)	C11—C12—H12	119.2
O7—Cu3—O6	73.90 (14)	C14—C13—H13A	109.5
O1—Cu3—O6	93.35 (15)	C14—C13—H13B	109.5
O5—Cu3—O6	78.35 (13)	H13A—C13—H13B	109.5
N1—Cu3—O6	97.92 (15)	C14—C13—H13C	109.5
N3—Cu3—O6	164.58 (16)	H13A—C13—H13C	109.5
O7—Cu4—N10^i	175.8 (2)	H13B—C13—H13C	109.5
O7—Cu4—O6	89.15 (14)	O4—C14—O3	126.6 (5)
N10^i—Cu4—O6	94.75 (18)	O4—C14—C13	118.4 (6)
O7—Cu4—N9	80.91 (16)	O3—C14—C13	115.0 (5)
N10^i—Cu4—N9	95.0 (2)	C16—C15—H15A	109.5
O6—Cu4—N9	167.46 (16)	C16—C15—H15B	109.5
O7—Cu4—O2	85.08 (17)	H15A—C15—H15B	109.5
N10^i—Cu4—O2	96.7 (2)	C16—C15—H15C	109.5
O6—Cu4—O2	86.37 (17)	H15A—C15—H15C	109.5
N9—Cu4—O2	100.27 (19)	H15B—C15—H15C	109.5
O7—Cu4—O8	77.75 (13)	O1—C16—O2	124.1 (7)
N10^i—Cu4—O8	102.05 (19)	O1—C16—C15	114.4 (7)
O6—Cu4—O8	71.18 (13)	O2—C16—C15	121.5 (7)
N9—Cu4—O8	99.06 (16)	N3—C17—N4	172.5 (6)
O2—Cu4—O8	151.68 (15)	N10—C18—N4	172.2 (6)
C6—N1—C2	120.0 (5)	N5—C19—N6	172.4 (7)
C6—N1—Cu3	127.0 (4)	N7—C20—N6	171.8 (7)
C2—N1—Cu3	113.0 (3)	O8—C21—C22	108.8 (4)
C12—N2—C8	120.3 (5)	O8—C21—H21A	109.9
C12—N2—Cu2	126.9 (4)	C22—C21—H21A	109.9
C8—N2—Cu2	112.7 (4)	O8—C21—H21B	109.9
C17—N3—Cu3	150.0 (5)	C22—C21—H21B	109.9
C18—N4—C17	123.2 (6)	H21A—C21—H21B	108.3
C19—N5—Cu1	164.6 (5)	N8—C22—C23	121.3 (5)
C19—N6—C20	124.8 (6)	N8—C22—C21	114.8 (5)
C22—N8—C26	119.5 (5)	C23—C22—C21	123.9 (5)
C22—N8—Cu1	113.3 (4)	C24—C23—C22	119.2 (6)
C26—N8—Cu1	127.2 (4)	C24—C23—H23	120.4
C32—N9—C28	118.0 (5)	C22—C23—H23	120.4
C32—N9—Cu4	128.6 (4)	C23—C24—C25	119.2 (6)
C28—N9—Cu4	113.4 (3)	C23—C24—H24	120.4
C18—N10—Cu4^ii	165.5 (5)	C25—C24—H24	120.4
C16—O1—Cu3	130.2 (5)	C26—C25—C24	119.1 (7)
C16—O2—Cu4	126.5 (5)	C26—C25—H25	120.4
C14—O3—Cu2	127.6 (4)	C24—C25—H25	120.4
C14—O4—Cu1	127.1 (4)	N8—C26—C25	121.6 (6)
C1—O5—Cu1	126.1 (3)	N8—C26—H26	119.2
C1—O5—Cu3	111.5 (3)	C25—C26—H26	119.2
Cu1—O5—Cu3	113.19 (19)	O7—C27—C28	110.0 (4)
C1—O5—Cu2	114.0 (3)	O7—C27—H27A	109.7
Cu1—O5—Cu2	84.88 (12)	C28—C27—H27A	109.7
Cu3—O5—Cu2	101.31 (14)	O7—C27—H27B	109.7
C7—O6—Cu2	112.9 (3)	C28—C27—H27B	109.7
C7—O6—Cu4	126.6 (3)	H27A—C27—H27B	108.2
Cu2—O6—Cu4	110.52 (16)	N9—C28—C29	121.1 (5)
C7—O6—Cu3	113.8 (3)	N9—C28—C27	114.8 (5)
Cu2—O6—Cu3	101.10 (13)	C29—C28—C27	124.1 (5)
Cu4—O6—Cu3	86.02 (12)	C30—C29—C28	119.3 (6)
C27—O7—Cu3	126.8 (3)	C30—C29—H29	120.4
C27—O7—Cu4	113.9 (3)	C28—C29—H29	120.4
Cu3—O7—Cu4	105.90 (18)	C31—C30—C29	119.4 (6)
C27—O7—Cu1	112.8 (3)	C31—C30—H30	120.3
Cu3—O7—Cu1	90.69 (14)	C29—C30—H30	120.3
Cu4—O7—Cu1	102.15 (14)	C32—C31—C30	118.5 (6)
C21—O8—Cu2	125.3 (3)	C32—C31—H31	120.7
C21—O8—Cu1	111.0 (3)	C30—C31—H31	120.7
Cu2—O8—Cu1	103.23 (16)	N9—C32—C31	123.7 (6)
C21—O8—Cu4	117.6 (3)	N9—C32—H32	118.1
Cu2—O8—Cu4	91.67 (13)	C31—C32—H32	118.1
Cu1—O8—Cu4	104.99 (14)	C34—C33—H33A	109.5
O5—C1—C2	109.7 (5)	C34—C33—H33B	109.5
O5—C1—H1A	109.7	H33A—C33—H33B	109.5
C2—C1—H1A	109.7	C34—C33—H33C	109.5
O5—C1—H1B	109.7	H33A—C33—H33C	109.5
C2—C1—H1B	109.7	H33B—C33—H33C	109.5
H1A—C1—H1B	108.2	N11—C34—C33	178.5 (12)
N1—C2—C3	121.1 (6)
O7—Cu3—N1—C6	−142.2 (7)	N1—Cu3—O7—C27	−149.5 (7)
O1—Cu3—N1—C6	5.6 (5)	N3—Cu3—O7—C27	−31.8 (5)
O5—Cu3—N1—C6	−165.2 (5)	O6—Cu3—O7—C27	154.1 (5)
N3—Cu3—N1—C6	100.4 (5)	O1—Cu3—O7—Cu4	−74.8 (2)
O6—Cu3—N1—C6	−88.4 (5)	O5—Cu3—O7—Cu4	95.63 (18)
O7—Cu3—N1—C2	35.5 (9)	N1—Cu3—O7—Cu4	72.9 (8)
O1—Cu3—N1—C2	−176.6 (4)	N3—Cu3—O7—Cu4	−169.5 (2)
O5—Cu3—N1—C2	12.5 (4)	O6—Cu3—O7—Cu4	16.50 (14)
N3—Cu3—N1—C2	−81.9 (4)	O1—Cu3—O7—Cu1	−177.61 (14)
O6—Cu3—N1—C2	89.4 (4)	O5—Cu3—O7—Cu1	−7.21 (13)
O8—Cu2—N2—C12	−159.7 (6)	N1—Cu3—O7—Cu1	−30.0 (7)
O6—Cu2—N2—C12	−168.3 (5)	N3—Cu3—O7—Cu1	87.70 (16)
O3—Cu2—N2—C12	2.4 (5)	O6—Cu3—O7—Cu1	−86.34 (12)
O5—Cu2—N2—C12	−91.3 (5)	O6—Cu4—O7—C27	−164.6 (4)
O8—Cu2—N2—C8	21.4 (10)	N9—Cu4—O7—C27	23.1 (4)
O6—Cu2—N2—C8	12.8 (4)	O2—Cu4—O7—C27	−78.2 (4)
O3—Cu2—N2—C8	−176.4 (4)	O8—Cu4—O7—C27	124.5 (4)
O5—Cu2—N2—C8	89.9 (4)	O6—Cu4—O7—Cu3	−20.83 (18)
O7—Cu3—N3—C17	10.9 (11)	N9—Cu4—O7—Cu3	166.8 (2)
O1—Cu3—N3—C17	−87.0 (11)	O2—Cu4—O7—Cu3	65.60 (19)
O5—Cu3—N3—C17	96.7 (11)	O8—Cu4—O7—Cu3	−91.75 (17)
N1—Cu3—N3—C17	178.3 (11)	O6—Cu4—O7—Cu1	73.43 (15)
O6—Cu3—N3—C17	33.0 (15)	N9—Cu4—O7—Cu1	−98.91 (17)
O5—Cu1—N5—C19	14 (2)	O2—Cu4—O7—Cu1	159.85 (17)
N8—Cu1—N5—C19	−176 (2)	O8—Cu4—O7—Cu1	2.51 (12)
O4—Cu1—N5—C19	−76 (2)	O5—Cu1—O7—C27	138.6 (3)
O7—Cu1—N5—C19	84 (2)	N5—Cu1—O7—C27	49.3 (4)
O5—Cu1—N8—C22	−59.7 (9)	O8—Cu1—O7—C27	−125.9 (3)
N5—Cu1—N8—C22	169.1 (4)	N8—Cu1—O7—C27	−48.1 (4)
O8—Cu1—N8—C22	−14.5 (4)	O4—Cu1—O7—C27	−177.8 (3)
O4—Cu1—N8—C22	71.0 (4)	O5—Cu1—O7—Cu3	7.72 (13)
O7—Cu1—N8—C22	−87.6 (4)	N5—Cu1—O7—Cu3	−81.6 (2)
O5—Cu1—N8—C26	117.7 (8)	O8—Cu1—O7—Cu3	103.20 (16)
N5—Cu1—N8—C26	−13.5 (5)	N8—Cu1—O7—Cu3	−178.93 (16)
O8—Cu1—N8—C26	162.8 (5)	O4—Cu1—O7—Cu3	51.3 (3)
O4—Cu1—N8—C26	−111.6 (5)	O5—Cu1—O7—Cu4	−98.72 (17)
O7—Cu1—N8—C26	89.8 (5)	N5—Cu1—O7—Cu4	171.96 (19)
O7—Cu4—N9—C32	166.3 (5)	O8—Cu1—O7—Cu4	−3.23 (16)
N10^i—Cu4—N9—C32	−12.7 (6)	N8—Cu1—O7—Cu4	74.64 (19)
O6—Cu4—N9—C32	128.4 (7)	O4—Cu1—O7—Cu4	−55.1 (3)
O2—Cu4—N9—C32	−110.4 (5)	O6—Cu2—O8—C21	−133.2 (4)
O8—Cu4—N9—C32	90.4 (5)	O3—Cu2—O8—C21	56.3 (4)
O7—Cu4—N9—C28	−11.8 (4)	N2—Cu2—O8—C21	−141.8 (7)
N10^i—Cu4—N9—C28	169.2 (4)	O5—Cu2—O8—C21	147.2 (4)
O6—Cu4—N9—C28	−49.7 (10)	O6—Cu2—O8—Cu1	98.70 (16)
O2—Cu4—N9—C28	71.4 (4)	O3—Cu2—O8—Cu1	−71.81 (17)
O8—Cu4—N9—C28	−87.8 (4)	N2—Cu2—O8—Cu1	90.2 (7)
O7—Cu3—O1—C16	40.5 (6)	O5—Cu2—O8—Cu1	19.09 (13)
O5—Cu3—O1—C16	−68.3 (12)	O6—Cu2—O8—Cu4	−7.12 (12)
N1—Cu3—O1—C16	−132.0 (6)	O3—Cu2—O8—Cu4	−177.63 (14)
N3—Cu3—O1—C16	132.9 (6)	N2—Cu2—O8—Cu4	−15.7 (8)
O6—Cu3—O1—C16	−33.7 (6)	O5—Cu2—O8—Cu4	−86.73 (12)
O7—Cu4—O2—C16	−39.1 (6)	O5—Cu1—O8—C21	−160.7 (4)
N10^i—Cu4—O2—C16	144.7 (6)	N8—Cu1—O8—C21	28.7 (4)
O6—Cu4—O2—C16	50.3 (6)	O4—Cu1—O8—C21	−71.0 (4)
N9—Cu4—O2—C16	−119.0 (6)	O7—Cu1—O8—C21	130.6 (4)
O8—Cu4—O2—C16	13.4 (8)	O5—Cu1—O8—Cu2	−24.21 (17)
O8—Cu2—O3—C14	38.0 (5)	N8—Cu1—O8—Cu2	165.2 (2)
O6—Cu2—O3—C14	−74.3 (11)	O4—Cu1—O8—Cu2	65.51 (17)
N2—Cu2—O3—C14	−138.1 (5)	O7—Cu1—O8—Cu2	−92.85 (16)
O5—Cu2—O3—C14	−37.5 (5)	O5—Cu1—O8—Cu4	71.17 (16)
O5—Cu1—O4—C14	48.7 (5)	N8—Cu1—O8—Cu4	−99.37 (18)
N5—Cu1—O4—C14	142.3 (5)	O4—Cu1—O8—Cu4	160.90 (16)
O8—Cu1—O4—C14	−41.0 (5)	O7—Cu1—O8—Cu4	2.54 (12)
N8—Cu1—O4—C14	−121.2 (5)	O7—Cu4—O8—C21	−127.3 (3)
O7—Cu1—O4—C14	8.5 (7)	N10^i—Cu4—O8—C21	48.4 (4)
N5—Cu1—O5—C1	−50.3 (5)	O6—Cu4—O8—C21	139.4 (3)
O8—Cu1—O5—C1	134.0 (4)	N9—Cu4—O8—C21	−48.8 (3)
N8—Cu1—O5—C1	178.4 (7)	O2—Cu4—O8—C21	178.7 (4)
O4—Cu1—O5—C1	46.8 (4)	O7—Cu4—O8—Cu2	100.81 (15)
O7—Cu1—O5—C1	−152.0 (5)	N10^i—Cu4—O8—Cu2	−83.47 (19)
N5—Cu1—O5—Cu3	93.4 (2)	O6—Cu4—O8—Cu2	7.49 (13)
O8—Cu1—O5—Cu3	−82.33 (19)	N9—Cu4—O8—Cu2	179.37 (14)
N8—Cu1—O5—Cu3	−37.9 (8)	O2—Cu4—O8—Cu2	46.8 (4)
O4—Cu1—O5—Cu3	−169.47 (19)	O7—Cu4—O8—Cu1	−3.36 (16)
O7—Cu1—O5—Cu3	−8.30 (14)	N10^i—Cu4—O8—Cu1	172.4 (2)
N5—Cu1—O5—Cu2	−166.47 (19)	O6—Cu4—O8—Cu1	−96.68 (17)
O8—Cu1—O5—Cu2	17.79 (13)	N9—Cu4—O8—Cu1	75.20 (18)
N8—Cu1—O5—Cu2	62.2 (8)	O2—Cu4—O8—Cu1	−57.3 (4)
O4—Cu1—O5—Cu2	−69.35 (13)	Cu1—O5—C1—C2	177.7 (3)
O7—Cu1—O5—Cu2	91.82 (12)	Cu3—O5—C1—C2	33.4 (6)
O7—Cu3—O5—C1	159.6 (4)	Cu2—O5—C1—C2	−80.5 (5)
O1—Cu3—O5—C1	−90.6 (10)	C6—N1—C2—C3	0.3 (8)
N1—Cu3—O5—C1	−25.9 (4)	Cu3—N1—C2—C3	−177.6 (5)
N3—Cu3—O5—C1	68.1 (4)	C6—N1—C2—C1	−179.4 (5)
O6—Cu3—O5—C1	−126.0 (4)	Cu3—N1—C2—C1	2.7 (6)
O7—Cu3—O5—Cu1	10.51 (18)	O5—C1—C2—N1	−23.7 (7)
O1—Cu3—O5—Cu1	120.3 (9)	O5—C1—C2—C3	156.6 (6)
N1—Cu3—O5—Cu1	−175.0 (2)	N1—C2—C3—C4	0.1 (10)
N3—Cu3—O5—Cu1	−81.0 (2)	C1—C2—C3—C4	179.7 (6)
O6—Cu3—O5—Cu1	84.96 (17)	C2—C3—C4—C5	−0.6 (12)
O7—Cu3—O5—Cu2	−78.73 (15)	C3—C4—C5—C6	0.8 (13)
O1—Cu3—O5—Cu2	31.1 (10)	C2—N1—C6—C5	−0.1 (9)
N1—Cu3—O5—Cu2	95.74 (16)	Cu3—N1—C6—C5	177.5 (5)
N3—Cu3—O5—Cu2	−170.20 (16)	C4—C5—C6—N1	−0.4 (12)
O6—Cu3—O5—Cu2	−4.28 (12)	Cu2—O6—C7—C8	29.2 (6)
O8—Cu2—O5—C1	−146.3 (4)	Cu4—O6—C7—C8	171.1 (3)
O6—Cu2—O5—C1	125.5 (4)	Cu3—O6—C7—C8	−85.4 (5)
O3—Cu2—O5—C1	−48.3 (4)	C12—N2—C8—C9	0.2 (8)
N2—Cu2—O5—C1	46.0 (4)	Cu2—N2—C8—C9	179.1 (4)
O8—Cu2—O5—Cu1	−18.80 (14)	C12—N2—C8—C7	−178.9 (5)
O6—Cu2—O5—Cu1	−107.08 (16)	Cu2—N2—C8—C7	0.1 (6)
O3—Cu2—O5—Cu1	79.14 (16)	O6—C7—C8—N2	−18.9 (7)
N2—Cu2—O5—Cu1	173.42 (16)	O6—C7—C8—C9	162.0 (5)
O8—Cu2—O5—Cu3	93.86 (17)	N2—C8—C9—C10	−0.2 (9)
O6—Cu2—O5—Cu3	5.58 (16)	C7—C8—C9—C10	178.8 (6)
O3—Cu2—O5—Cu3	−168.20 (17)	C8—C9—C10—C11	0.1 (11)
N2—Cu2—O5—Cu3	−73.9 (2)	C9—C10—C11—C12	−0.1 (11)
O8—Cu2—O6—C7	157.9 (4)	C8—N2—C12—C11	−0.2 (9)
O3—Cu2—O6—C7	−88.8 (9)	Cu2—N2—C12—C11	−179.0 (5)
N2—Cu2—O6—C7	−24.0 (4)	C10—C11—C12—N2	0.2 (11)
O5—Cu2—O6—C7	−126.3 (4)	Cu1—O4—C14—O3	8.5 (9)
O8—Cu2—O6—Cu4	9.77 (16)	Cu1—O4—C14—C13	−173.0 (5)
O3—Cu2—O6—Cu4	123.1 (8)	Cu2—O3—C14—O4	−6.1 (9)
N2—Cu2—O6—Cu4	−172.1 (2)	Cu2—O3—C14—C13	175.3 (5)
O5—Cu2—O6—Cu4	85.59 (16)	Cu3—O1—C16—O2	−9.4 (10)
O8—Cu2—O6—Cu3	−80.10 (14)	Cu3—O1—C16—C15	169.3 (5)
O3—Cu2—O6—Cu3	33.2 (9)	Cu4—O2—C16—O1	8.7 (10)
N2—Cu2—O6—Cu3	98.00 (17)	Cu4—O2—C16—C15	−169.9 (5)
O5—Cu2—O6—Cu3	−4.29 (12)	Cu2—O8—C21—C22	−161.1 (4)
O7—Cu4—O6—C7	132.1 (4)	Cu1—O8—C21—C22	−36.3 (6)
N10^i—Cu4—O6—C7	−49.5 (5)	Cu4—O8—C21—C22	84.6 (5)
N9—Cu4—O6—C7	169.4 (7)	C26—N8—C22—C23	1.3 (8)
O2—Cu4—O6—C7	46.9 (4)	Cu1—N8—C22—C23	178.9 (5)
O8—Cu4—O6—C7	−150.6 (4)	C26—N8—C22—C21	−179.4 (5)
O7—Cu4—O6—Cu2	−85.25 (18)	Cu1—N8—C22—C21	−1.8 (6)
N10^i—Cu4—O6—Cu2	93.2 (2)	O8—C21—C22—N8	25.0 (7)
N9—Cu4—O6—Cu2	−47.9 (8)	O8—C21—C22—C23	−155.8 (5)
O2—Cu4—O6—Cu2	−170.37 (19)	N8—C22—C23—C24	−2.6 (9)
O8—Cu4—O6—Cu2	−7.91 (13)	C21—C22—C23—C24	178.3 (6)
O7—Cu4—O6—Cu3	15.12 (13)	C22—C23—C24—C25	2.2 (10)
N10^i—Cu4—O6—Cu3	−166.41 (19)	C23—C24—C25—C26	−0.5 (10)
N9—Cu4—O6—Cu3	52.5 (8)	C22—N8—C26—C25	0.3 (9)
O2—Cu4—O6—Cu3	−70.00 (15)	Cu1—N8—C26—C25	−176.9 (5)
O8—Cu4—O6—Cu3	92.46 (11)	C24—C25—C26—N8	−0.7 (10)
O7—Cu3—O6—C7	−144.4 (4)	Cu3—O7—C27—C28	−163.7 (4)
O1—Cu3—O6—C7	−47.3 (4)	Cu4—O7—C27—C28	−28.8 (6)
O5—Cu3—O6—C7	126.9 (4)	Cu1—O7—C27—C28	87.0 (5)
N1—Cu3—O6—C7	47.6 (4)	C32—N9—C28—C29	−0.2 (8)
N3—Cu3—O6—C7	−167.4 (6)	Cu4—N9—C28—C29	178.2 (5)
O7—Cu3—O6—Cu2	94.31 (18)	C32—N9—C28—C27	−179.1 (5)
O1—Cu3—O6—Cu2	−168.59 (18)	Cu4—N9—C28—C27	−0.7 (6)
O5—Cu3—O6—Cu2	5.56 (16)	O7—C27—C28—N9	18.9 (7)
N1—Cu3—O6—Cu2	−73.76 (18)	O7—C27—C28—C29	−160.0 (6)
N3—Cu3—O6—Cu2	71.3 (7)	N9—C28—C29—C30	0.2 (10)
O7—Cu3—O6—Cu4	−15.83 (14)	C27—C28—C29—C30	179.0 (6)
O1—Cu3—O6—Cu4	81.26 (17)	C28—C29—C30—C31	0.2 (11)
O5—Cu3—O6—Cu4	−104.59 (15)	C29—C30—C31—C32	−0.7 (11)
N1—Cu3—O6—Cu4	176.09 (16)	C28—N9—C32—C31	−0.4 (9)
N3—Cu3—O6—Cu4	−38.8 (7)	Cu4—N9—C32—C31	−178.5 (5)
O1—Cu3—O7—C27	62.8 (5)	C30—C31—C32—N9	0.8 (10)
O5—Cu3—O7—C27	−126.8 (5)

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