Aqua[N-(6-carboxylato-κO-pyridine-2-carbonyl-κN)-L-histidinato-κ²N,N′]copper(II)

The title compound, [Cu(C₁₃H₁₀N₄O₅)(H₂O)], is an asymmetric and pentacoordinated square-pyramidal copper(II) complex, with a water mol­ecule occupying an apical position. It consists of syn and anti isomers of the apical water mol­ecule with respect to the metal-free carboxyl group on the equatorial ligand. The crystal structure of this complex is a rare example of conformational isomerization, in which the two isomers cocrystallize in a 1:3 ratio of syn to anti mol­ecules in the same lattice.

S1. Comment

In the context of a study on the characteristic ligancy of asymmetric metal complexes, we have focused on the molecular and crystal structure of asymmetric copper(II) complexes. We report here the characteristic molecular conformation and crystal structure of the title compound, (I). \sch

The atoms and atom groups of the equatorial tetradentate ligand in (I) are almost coplanar, except for the methylene group, the inclined imidazole ring and the metal-free carboxyl group. The six-membered chelate ring formed by the imidazole ring and the amide group during the metal coordination of (I) has a twisted half-chair conformation, in accordance with the axial preference of the carboxyl substituent (Ertan & Csoregh, 1995; Uehara et al., 1999).

The apical water molecule has syn and anti coordination modes with respect to the axial carboxyl group. It is noteworthy that the unit cell consists of the isomers with a 1:3 ratio of syn to anti molecules (Fig. 2). The best mean basal plane of the first anti isomer, defined by O1, N1, N2 and N4, is planar to within 0.02 (3) Å, and atom Cu1 is displaced by 0.17 (3) Å toward the apical water molecule from this basal plane. For the Cu2 and Cu3 complexes, the corresponding values of the best mean basal plane are 0.04 (5) and 0.04 (5) Å, respectively, and the displacements of the Cu atoms are 0.16 (5) and 0.17 (5) Å, respectively.

The coordination geometry of the syn isomer around the Cu atom is almost the same as those of the anti isomers, except for the situation of the apical water molecule. The best mean basal plane of the syn isomer, defined by O19, N13, N14 and N16, is planar to within 0.06 (6) Å, and atom Cu4 is displaced by 0.12 (6) Å toward the apical water molecule. The equatorial conformation of the syn isomer is basically the same as those of the anti isomers, but with a somewhat different inclination angle between the imidazole ring and the basal plane. The inclined angle (25°) of the imidazole ring to the basal plane of the syn isomer is larger than those of the anti isomers, which are 3.6 (6)–5.7 (6)°.

The distances between each apical water molecule and the respective Cu atom of the anti isomers are 2.347 (2), 2.296 (2) and 2.275 (3) Å, and that of the syn isomer is 2.333 (2) Å. Those bond lengths are comparable with the corresponding distances in analogous pentacoordinated copper(II) complexes: 2.2681 (18) Å for the glycolato complex (Medina et al., 2000), 2.309 (3) Å for the propanediaminato complex (Arıcı et al., 1999), 2.355 (4) Å for the glycinate complex (Alvarez-Larena et al., 1995) and 2.294 (6) Å for the L-glutamate complex (Antorini et al., 1983).

The O23···O24 bond lengths indicate the existence of a significant OH···O hydrogen-bonding interaction between the apical water molecule and the carboxyl group in the syn isomer. Therefore, the O24—Cu4—N14 angle of the syn isomer [95.9 (1)°] is smaller than the corresponding angles of the anti isomers [98.45 (9)–106.43 (9)°].

The C═C distances in the oxalic acid moieties of the syn and anti isomers are in the range 1.507 (4)–1.520 (4) Å. These distances are similar to the value of 1.526 Å observed for the C═C distance in [Cu(C₂₁H₁₇N₃O₅)(H₂O)] (ref?), in which the oxalic acid moieties coordinate to the Cu^II.

The O3···O16 and O4···O9 bond lengths are 2.553 (3) and 2.538 (3) Å, respectively. These distances indicate the existence of a significant OH···O hydrogen-bonding interaction between each anti isomer.

Related literature

For related literature, see: Alvarez-Larena, Brianso-Penalva & Piniella (1995); Antorini et al. (1983); Arıcı, Ercan, Atakol & Cakırer (1999); Ertan & Csoregh (1995); Medina et al. (2000); Uehara et al. (1999).

S2. Experimental

A solution of L-histidine (20 mmol) in 0.5M NaOH solution (vol?) and a 2M NaOH solution (vol?) were added dropwise to a suspension of 2,6-pyridinedicarbonyl dichloride (20 mmol) in CH₂Cl₂ (vol?) with stirring over 0.5 h, and then the mixture was stirred for an additional 3 h at room temperature. 6M HCl was added to the separated water phase until a pH of 4 was reached. CuSO₄·5H₂O (18 mmol) was added to the resultant reaction mixture. Compound (I) precipitated as blue crystals after several days. Crystals of (I) suitable for single-crystal X-ray analysis were obtained from a high-performance liquid chromatography purification on an ODS column (ODS is ?), followed by slow evaporation of the solvent at room temperature. Please define ODS, and provide missing volumes of reagents.

S3. Refinement

The H atoms of the H₂O and COOH groups were not fixed because they could not be found from the difference Fourier map. All other H atoms were refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku, 2001); program(s) used to solve structure: SIR97 (Altomare, 1998); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure.

Figures

	Fig. 1. The molecular structure of the four isomers in (I), showing the atom-numbering scheme and with 30% probability displacement ellipsoids. H atoms have been omitted for clarity.
	Fig. 2. The packing of the molecules of (I).

(I)

Crystal data

[CuH2O(C13H10N4O5)]	Dx = 1.725 Mg m^−3
Mr = 383.81	Mo Kα radiation, λ = 0.7107 Å
Monoclinic, P21	Cell parameters from 9082 reflections
a = 15.983 (1) Å	θ = 3.1–27.5°
b = 6.5095 (4) Å	µ = 1.52 mm^−1
c = 29.068 (1) Å	T = 123 K
β = 102.2801 (5)°	Plate, blue
V = 2955.0 (3) Å^3	0.2 × 0.2 × 0.1 mm
Z = 8

Data collection

Rigaku Mercury CCD area-detector diffractometer	11052 reflections with F^2 > 2σ(F^2)
Detector resolution: 7.32 pixels mm^-1	Rint = 0.076
ω scans	θmax = 27.5°
Absorption correction: multi-scan (Blessing, 1995)	h = −20→19
Tmin = 0.731, Tmax = 0.859	k = −8→7
21831 measured reflections	l = −37→37
12299 independent reflections

Refinement

Refinement on F^2	Weighting scheme based on measured s.u.'s w = 1/σ^2(Fo^2)
R[F^2 > 2σ(F^2)] = 0.032	(Δ/σ)max = 0.001
wR(F^2) = 0.074	Δρmax = 0.90 e Å^−3
S = 1.34	Δρmin = −1.03 e Å^−3
12299 reflections	Absolute structure: 5197 Friedel pairs (Flack, 1983)
902 parameters	Absolute structure parameter: 0.015 (7)
H-atom parameters constrained

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 using reflections with F² > -10.0 σ(F²). The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt). The refinements were performed by using Crystals for crystallographic refinements program. All calculations were performed using the CrystalStructure crystallographic software package.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.43081 (2)	0.06196 (9)	0.09286 (1)	0.01431 (9)
Cu2	0.34920 (2)	0.30055 (7)	0.40252 (1)	0.01451 (8)
Cu3	0.15413 (2)	0.30124 (8)	0.59784 (1)	0.01438 (8)
Cu4	0.05818 (2)	−0.02717 (9)	0.91237 (1)	0.01572 (9)
O1	0.4033 (1)	0.0706 (4)	0.02019 (7)	0.0171 (5)
O2	0.4694 (1)	0.0818 (4)	−0.04060 (8)	0.0189 (5)
O3	0.6335 (1)	−0.0404 (4)	0.20011 (8)	0.0235 (6)
O4	0.4446 (2)	−0.2760 (4)	0.25307 (9)	0.0313 (7)
O5	0.4513 (2)	−0.3827 (4)	0.18127 (9)	0.0364 (8)
O6	0.4229 (1)	0.4218 (3)	0.09466 (8)	0.0172 (6)
O7	0.3901 (1)	0.3174 (4)	0.47506 (7)	0.0176 (5)
O8	0.5116 (1)	0.3157 (4)	0.53063 (7)	0.0194 (6)
O9	0.4463 (1)	0.3606 (3)	0.28488 (8)	0.0195 (6)
O10	0.1985 (2)	0.6975 (4)	0.26435 (9)	0.0323 (7)
O11	0.2932 (2)	0.7406 (4)	0.3303 (1)	0.0394 (8)
O12	0.3423 (1)	−0.0487 (4)	0.41197 (8)	0.0195 (5)
O13	0.1135 (1)	0.3248 (4)	0.52531 (7)	0.0178 (5)
O14	−0.0077 (1)	0.3302 (4)	0.46963 (7)	0.0196 (6)
O15	0.0583 (1)	0.3989 (3)	0.71444 (8)	0.0209 (6)
O16	0.3093 (2)	0.7021 (4)	0.73136 (9)	0.0311 (7)
O17	0.2092 (2)	0.7383 (4)	0.66695 (9)	0.0383 (8)
O18	0.1557 (1)	−0.0448 (4)	0.58705 (8)	0.0206 (5)
O19	0.0858 (1)	−0.0456 (4)	0.98501 (7)	0.0175 (5)
O20	0.0207 (1)	−0.0895 (4)	1.04550 (8)	0.0195 (6)
O21	−0.1465 (1)	−0.0556 (4)	0.80300 (8)	0.0262 (6)
O22	0.0509 (2)	−0.2372 (4)	0.74557 (8)	0.0320 (7)
O23	0.0520 (2)	−0.3737 (4)	0.8152 (1)	0.050 (1)
O24	0.0881 (1)	−0.3772 (4)	0.90989 (8)	0.0191 (6)
N1	0.5442 (2)	0.0548 (5)	0.0809 (1)	0.0155 (6)
N2	0.4953 (2)	0.0167 (4)	0.1580 (1)	0.0176 (8)
N4	0.3195 (2)	0.0083 (4)	0.1059 (1)	0.0162 (7)
N3	0.1837 (2)	−0.0598 (5)	0.10103 (9)	0.0174 (7)
N5	0.4708 (1)	0.3140 (4)	0.40762 (9)	0.0144 (6)
N6	0.3517 (2)	0.3447 (4)	0.33558 (9)	0.0176 (7)
N7	0.0961 (2)	0.3483 (4)	0.40633 (9)	0.0166 (7)
N8	0.2268 (1)	0.3245 (4)	0.39420 (9)	0.0159 (6)
N9	0.0328 (1)	0.3274 (4)	0.59242 (9)	0.0142 (6)
N10	0.1522 (2)	0.3454 (4)	0.66480 (9)	0.0173 (7)
N11	0.4078 (1)	0.3284 (4)	0.59412 (9)	0.0165 (7)
N12	0.2771 (1)	0.3152 (4)	0.60622 (8)	0.0154 (6)
N13	−0.0549 (2)	−0.0535 (5)	0.92409 (9)	0.0167 (7)
N14	−0.0079 (2)	−0.0076 (4)	0.8461 (1)	0.0188 (7)
N15	0.3050 (2)	0.0587 (5)	0.9032 (1)	0.0181 (6)
N16	0.1663 (2)	0.0518 (5)	0.8989 (1)	0.0181 (7)
C1	0.4690 (2)	0.0756 (5)	0.0021 (1)	0.0143 (7)
C2	0.5548 (2)	0.0729 (6)	0.0374 (1)	0.0153 (7)
C3	0.6362 (2)	0.0811 (5)	0.0280 (1)	0.0168 (8)
C4	0.7058 (2)	0.0702 (6)	0.0664 (1)	0.0191 (8)
C5	0.6926 (2)	0.0459 (6)	0.1120 (1)	0.0185 (8)
C6	0.6092 (2)	0.0377 (5)	0.1183 (1)	0.0159 (8)
C7	0.5797 (2)	0.0024 (4)	0.1636 (1)	0.0171 (8)
C8	0.4586 (2)	−0.0176 (5)	0.1989 (1)	0.0172 (7)
C9	0.4518 (2)	−0.2471 (5)	0.2096 (1)	0.0199 (8)
C10	0.3698 (2)	0.0862 (5)	0.1928 (1)	0.0176 (7)
C11	0.3037 (2)	0.0164 (4)	0.1510 (1)	0.0140 (8)
C12	0.2191 (2)	−0.0270 (6)	0.1482 (1)	0.0186 (7)
C13	0.2462 (2)	−0.0384 (6)	0.0770 (1)	0.0157 (7)
C14	0.4716 (2)	0.3151 (5)	0.4886 (1)	0.0150 (7)
C15	0.5219 (2)	0.3148 (5)	0.4503 (1)	0.0146 (7)
C16	0.6100 (2)	0.3206 (5)	0.4546 (1)	0.0168 (7)
C17	0.6423 (2)	0.3235 (5)	0.4137 (1)	0.0190 (8)
C18	0.5868 (2)	0.3225 (5)	0.3694 (1)	0.0175 (8)
C19	0.4998 (2)	0.3188 (5)	0.3679 (1)	0.0156 (7)
C20	0.4277 (2)	0.3407 (4)	0.3246 (1)	0.0152 (8)
C21	0.2768 (2)	0.3953 (5)	0.2987 (1)	0.0154 (8)
C22	0.2586 (2)	0.6270 (6)	0.2994 (1)	0.0234 (9)
C23	0.1988 (2)	0.2713 (5)	0.3061 (1)	0.0181 (8)
C24	0.1699 (2)	0.3152 (5)	0.3509 (1)	0.0152 (7)
C25	0.0889 (2)	0.3326 (5)	0.3584 (1)	0.0169 (8)
C26	0.1800 (2)	0.3434 (4)	0.4265 (1)	0.0161 (8)
C27	0.0322 (2)	0.3269 (5)	0.5114 (1)	0.0147 (7)
C28	−0.0185 (2)	0.3290 (5)	0.5500 (1)	0.0145 (7)
C29	−0.1064 (2)	0.3381 (4)	0.5454 (1)	0.0168 (8)
C30	−0.1389 (2)	0.3434 (4)	0.5865 (1)	0.0191 (8)
C31	−0.0834 (2)	0.3429 (5)	0.6307 (1)	0.0186 (8)
C32	0.0039 (2)	0.3373 (4)	0.6323 (1)	0.0155 (8)
C33	0.0759 (2)	0.3607 (4)	0.6753 (1)	0.0165 (8)
C34	0.2273 (2)	0.3986 (5)	0.7009 (1)	0.0166 (8)
C35	0.2468 (2)	0.6271 (5)	0.6984 (1)	0.0215 (9)
C36	0.3044 (2)	0.2674 (5)	0.6946 (1)	0.0170 (8)
C37	0.3339 (2)	0.3040 (5)	0.6496 (1)	0.0150 (7)
C38	0.4150 (2)	0.3153 (5)	0.6422 (1)	0.0162 (7)
C39	0.3239 (2)	0.3279 (5)	0.5739 (1)	0.0155 (7)
C40	0.0206 (2)	−0.0665 (5)	1.0030 (1)	0.0168 (8)
C41	−0.0653 (2)	−0.0651 (5)	0.9676 (1)	0.0156 (8)
C42	−0.1466 (2)	−0.0767 (5)	0.9772 (1)	0.0211 (9)
C43	−0.2164 (2)	−0.0683 (5)	0.9389 (1)	0.0216 (9)
C44	−0.2039 (2)	−0.0531 (6)	0.8929 (1)	0.0207 (8)
C45	−0.1207 (2)	−0.0475 (5)	0.8866 (1)	0.0168 (8)
C46	−0.0920 (2)	−0.0363 (5)	0.8405 (1)	0.0192 (8)
C47	0.0286 (2)	−0.0077 (5)	0.8045 (1)	0.0199 (8)
C48	0.0445 (2)	−0.2253 (5)	0.7893 (1)	0.0206 (8)
C49	0.1105 (2)	0.1236 (5)	0.8118 (1)	0.0221 (8)
C50	0.1806 (2)	0.0744 (6)	0.8536 (1)	0.0177 (7)
C51	0.2669 (2)	0.0772 (6)	0.8564 (1)	0.0213 (8)
C52	0.2434 (2)	0.0425 (5)	0.9279 (1)	0.0180 (8)
H1	0.6444	0.0926	−0.0034	0.020*
H2	0.7625	0.0799	0.0614	0.024*
H3	0.7398	0.0359	0.1381	0.021*
H4	0.4956	0.0437	0.2252	0.020*
H5	0.3484	0.0590	0.2203	0.021*
H6	0.3773	0.2301	0.1899	0.021*
H7	0.1904	−0.0338	0.1737	0.023*
H8	0.1255	−0.0916	0.08791	0.021*
H9	0.2387	−0.0544	0.0439	0.019*
H10	0.6474	0.3221	0.4848	0.020*
H11	0.7025	0.3265	0.4159	0.024*
H12	0.6082	0.3241	0.3413	0.022*
H13	0.2884	0.3602	0.2690	0.018*
H14	0.1524	0.2999	0.2806	0.021*
H15	0.2130	0.1295	0.3059	0.021*
H16	0.0373	0.3335	0.3351	0.020*
H17	0.0501	0.3604	0.42217	0.020*
H18	0.2025	0.3525	0.4594	0.019*
H19	−0.1436	0.3407	0.5152	0.020*
H20	−0.1991	0.3474	0.5844	0.023*
H21	−0.1048	0.3464	0.6588	0.024*
H22	0.2156	0.3694	0.7309	0.020*
H23	0.3510	0.2965	0.7200	0.020*
H24	0.2892	0.1267	0.6955	0.020*
H25	0.4666	0.3142	0.6655	0.019*
H26	0.4539	0.3365	0.57825	0.020*
H27	0.3013	0.3356	0.5410	0.019*
H28	−0.1544	−0.0892	1.0086	0.024*
H29	−0.2730	−0.0738	0.9442	0.026*
H30	−0.2511	−0.0459	0.8668	0.023*
H31	−0.0124	0.0531	0.7798	0.023*
H32	0.1337	0.1083	0.7845	0.026*
H33	0.0943	0.2627	0.8146	0.026*
H34	0.2952	0.0888	0.8309	0.026*
H35	0.3649	0.0577	0.9160	0.022*
H36	0.2530	0.0272	0.9611	0.021*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0096 (2)	0.0199 (2)	0.0130 (2)	−0.0002 (2)	0.0015 (1)	0.0014 (2)
Cu2	0.0093 (2)	0.0225 (2)	0.0117 (2)	0.0001 (1)	0.0022 (1)	0.0009 (1)
Cu3	0.0090 (2)	0.0226 (2)	0.0116 (2)	0.0001 (1)	0.0022 (1)	−0.0014 (1)
Cu4	0.0119 (2)	0.0206 (2)	0.0136 (2)	0.0015 (2)	0.0004 (1)	−0.0011 (2)
O1	0.013 (1)	0.025 (1)	0.014 (1)	0.001 (1)	0.0046 (8)	0.001 (1)
O2	0.018 (1)	0.023 (1)	0.017 (1)	0.002 (1)	0.0054 (9)	−0.001 (1)
O3	0.018 (1)	0.032 (1)	0.018 (1)	0.004 (1)	−0.0029 (9)	0.001 (1)
O4	0.053 (2)	0.026 (1)	0.017 (1)	−0.003 (1)	0.013 (1)	0.002 (1)
O5	0.068 (2)	0.022 (1)	0.021 (1)	−0.006 (1)	0.014 (1)	−0.002 (1)
O6	0.015 (1)	0.017 (1)	0.021 (1)	−0.0001 (8)	0.0051 (9)	−0.0001 (9)
O7	0.0090 (9)	0.029 (1)	0.015 (1)	−0.0017 (9)	0.0021 (8)	−0.002 (1)
O8	0.014 (1)	0.028 (1)	0.015 (1)	−0.003 (1)	0.0014 (8)	−0.002 (1)
O9	0.023 (1)	0.021 (1)	0.016 (1)	−0.0013 (8)	0.0079 (9)	0.0008 (8)
O10	0.038 (2)	0.023 (1)	0.030 (1)	0.006 (1)	−0.006 (1)	0.002 (1)
O11	0.055 (2)	0.028 (2)	0.028 (1)	−0.004 (1)	−0.005 (1)	−0.008 (1)
O12	0.015 (1)	0.022 (1)	0.020 (1)	0.0002 (9)	0.0007 (9)	−0.001 (1)
O13	0.010 (1)	0.029 (1)	0.014 (1)	0.0006 (9)	0.0021 (8)	0.0001 (9)
O14	0.012 (1)	0.030 (1)	0.015 (1)	0.0030 (9)	−0.0001 (9)	0.0014 (9)
O15	0.023 (1)	0.025 (1)	0.017 (1)	0.0027 (9)	0.0090 (9)	−0.0010 (9)
O16	0.036 (1)	0.021 (1)	0.031 (1)	−0.007 (1)	−0.005 (1)	−0.002 (1)
O17	0.051 (2)	0.029 (1)	0.028 (1)	0.004 (1)	−0.007 (1)	0.008 (1)
O18	0.016 (1)	0.023 (1)	0.021 (1)	0.001 (1)	0.0000 (9)	−0.000 (1)
O19	0.012 (1)	0.025 (1)	0.016 (1)	−0.002 (1)	0.0034 (8)	−0.003 (1)
O20	0.013 (1)	0.030 (1)	0.016 (1)	0.0017 (9)	0.0020 (9)	−0.0023 (9)
O21	0.024 (1)	0.033 (1)	0.017 (1)	−0.001 (1)	−0.0050 (9)	−0.002 (1)
O22	0.053 (2)	0.029 (1)	0.017 (1)	0.004 (1)	0.012 (1)	−0.001 (1)
O23	0.109 (3)	0.022 (1)	0.024 (1)	0.018 (2)	0.024 (2)	0.003 (1)
O24	0.015 (1)	0.023 (1)	0.018 (1)	0.0011 (9)	0.0019 (9)	0.0021 (9)
N1	0.016 (1)	0.013 (1)	0.017 (1)	−0.002 (1)	0.003 (1)	0.000 (1)
N2	0.016 (1)	0.023 (2)	0.012 (1)	−0.0006 (9)	−0.001 (1)	0.0020 (9)
N4	0.014 (1)	0.018 (2)	0.016 (1)	0.0014 (9)	0.002 (1)	−0.0013 (9)
N3	0.014 (1)	0.019 (2)	0.020 (1)	−0.003 (1)	0.004 (1)	−0.001 (1)
N5	0.015 (1)	0.013 (1)	0.016 (1)	−0.002 (1)	0.0044 (9)	0.001 (1)
N6	0.015 (1)	0.026 (2)	0.012 (1)	0.002 (1)	0.003 (1)	0.002 (1)
N7	0.012 (1)	0.018 (2)	0.019 (1)	0.0015 (9)	0.003 (1)	0.001 (1)
N8	0.015 (1)	0.019 (1)	0.013 (1)	0.002 (1)	0.003 (1)	0.001 (1)
N9	0.013 (1)	0.014 (1)	0.016 (1)	0.001 (1)	0.005 (1)	−0.001 (1)
N10	0.013 (1)	0.028 (2)	0.012 (1)	−0.000 (1)	0.003 (1)	−0.003 (1)
N11	0.011 (1)	0.020 (1)	0.018 (1)	0.000 (1)	0.003 (1)	0.000 (1)
N12	0.013 (1)	0.019 (1)	0.014 (1)	−0.001 (1)	0.003 (1)	−0.001 (1)
N13	0.015 (1)	0.015 (1)	0.018 (1)	0.002 (1)	−0.001 (1)	−0.007 (1)
N14	0.023 (1)	0.021 (2)	0.011 (1)	0.003 (1)	0.000 (1)	−0.001 (1)
N15	0.018 (1)	0.017 (1)	0.020 (1)	−0.002 (1)	0.006 (1)	0.002 (1)
N16	0.019 (1)	0.016 (1)	0.018 (1)	0.002 (1)	0.001 (1)	0.001 (1)
C1	0.014 (1)	0.011 (1)	0.019 (1)	0.002 (1)	0.004 (1)	0.000 (1)
C2	0.016 (1)	0.012 (1)	0.018 (2)	−0.001 (1)	0.003 (1)	−0.003 (1)
C3	0.015 (1)	0.013 (2)	0.023 (2)	0.001 (1)	0.007 (1)	−0.002 (1)
C4	0.012 (1)	0.015 (1)	0.032 (2)	0.001 (1)	0.009 (1)	−0.004 (2)
C5	0.013 (1)	0.014 (2)	0.027 (2)	0.001 (1)	−0.001 (1)	−0.003 (1)
C6	0.015 (1)	0.010 (2)	0.022 (2)	0.001 (1)	0.000 (1)	−0.001 (1)
C7	0.016 (1)	0.016 (2)	0.017 (2)	0.001 (1)	−0.001 (1)	−0.001 (1)
C8	0.016 (1)	0.020 (2)	0.014 (2)	−0.001 (1)	0.001 (1)	−0.001 (1)
C9	0.019 (2)	0.026 (2)	0.014 (1)	−0.001 (1)	0.002 (1)	0.001 (1)
C10	0.019 (1)	0.018 (2)	0.016 (1)	−0.000 (1)	0.003 (1)	0.001 (1)
C11	0.015 (1)	0.012 (2)	0.016 (2)	0.001 (1)	0.003 (1)	0.001 (1)
C12	0.019 (1)	0.019 (1)	0.019 (2)	0.002 (1)	0.006 (1)	0.002 (1)
C13	0.013 (1)	0.019 (1)	0.016 (1)	0.001 (1)	0.004 (1)	0.001 (1)
C14	0.012 (1)	0.017 (1)	0.016 (1)	−0.001 (1)	0.003 (1)	−0.001 (1)
C15	0.013 (1)	0.013 (1)	0.018 (1)	−0.002 (1)	0.003 (1)	0.000 (1)
C16	0.012 (1)	0.015 (2)	0.023 (2)	−0.001 (1)	0.001 (1)	0.001 (1)
C17	0.013 (1)	0.017 (2)	0.029 (2)	−0.002 (1)	0.008 (1)	−0.002 (1)
C18	0.020 (2)	0.013 (2)	0.022 (2)	−0.000 (1)	0.011 (1)	0.001 (1)
C19	0.017 (1)	0.014 (1)	0.017 (1)	0.001 (1)	0.007 (1)	0.003 (1)
C20	0.017 (1)	0.011 (2)	0.018 (2)	−0.000 (1)	0.005 (1)	0.001 (1)
C21	0.015 (1)	0.020 (2)	0.011 (1)	0.001 (1)	0.000 (1)	−0.001 (1)
C22	0.026 (2)	0.024 (2)	0.017 (2)	−0.000 (1)	−0.001 (1)	−0.001 (1)
C23	0.018 (1)	0.018 (2)	0.017 (2)	0.001 (1)	0.002 (1)	−0.001 (1)
C24	0.013 (1)	0.016 (1)	0.016 (1)	0.002 (1)	0.001 (1)	0.002 (1)
C25	0.013 (1)	0.017 (2)	0.019 (2)	0.002 (1)	0.000 (1)	−0.000 (1)
C26	0.010 (1)	0.017 (2)	0.020 (2)	0.003 (1)	0.002 (1)	0.000 (1)
C27	0.010 (1)	0.017 (2)	0.017 (2)	0.002 (1)	0.003 (1)	0.001 (1)
C28	0.013 (1)	0.012 (2)	0.018 (2)	0.002 (1)	0.003 (1)	−0.001 (1)
C29	0.012 (1)	0.016 (2)	0.021 (2)	0.001 (1)	0.002 (1)	0.000 (1)
C30	0.012 (1)	0.019 (2)	0.028 (2)	0.002 (1)	0.008 (1)	0.001 (1)
C31	0.018 (2)	0.017 (2)	0.024 (2)	0.000 (1)	0.011 (1)	−0.002 (1)
C32	0.015 (1)	0.015 (2)	0.018 (2)	0.001 (1)	0.007 (1)	−0.001 (1)
C33	0.020 (2)	0.015 (2)	0.016 (2)	0.002 (1)	0.006 (1)	−0.000 (1)
C34	0.018 (1)	0.019 (2)	0.013 (2)	−0.001 (1)	0.003 (1)	−0.000 (1)
C35	0.025 (2)	0.021 (2)	0.019 (2)	0.001 (1)	0.004 (1)	−0.001 (1)
C36	0.018 (1)	0.018 (2)	0.014 (1)	0.001 (1)	0.000 (1)	0.001 (1)
C37	0.013 (1)	0.014 (1)	0.016 (1)	−0.001 (1)	−0.000 (1)	−0.002 (1)
C38	0.014 (1)	0.015 (2)	0.019 (2)	0.000 (1)	0.002 (1)	−0.000 (1)
C39	0.011 (1)	0.019 (2)	0.017 (1)	−0.004 (1)	0.004 (1)	−0.001 (1)
C40	0.012 (1)	0.017 (2)	0.021 (2)	0.000 (1)	0.001 (1)	−0.005 (1)
C41	0.013 (1)	0.015 (2)	0.018 (2)	0.002 (1)	0.001 (1)	−0.004 (1)
C42	0.015 (1)	0.023 (2)	0.023 (2)	−0.002 (1)	0.001 (1)	−0.005 (1)
C43	0.011 (1)	0.023 (2)	0.030 (2)	−0.002 (1)	0.003 (1)	−0.009 (1)
C44	0.014 (1)	0.014 (2)	0.030 (2)	0.002 (1)	−0.005 (1)	−0.007 (1)
C45	0.017 (1)	0.011 (2)	0.020 (2)	0.000 (1)	−0.002 (1)	−0.003 (1)
C46	0.021 (2)	0.014 (1)	0.019 (2)	0.004 (1)	−0.004 (1)	−0.002 (1)
C47	0.021 (2)	0.020 (2)	0.017 (2)	0.006 (1)	0.001 (1)	−0.001 (1)
C48	0.024 (2)	0.022 (2)	0.016 (1)	−0.000 (1)	0.002 (1)	−0.001 (1)
C49	0.027 (2)	0.022 (2)	0.017 (2)	0.002 (1)	0.003 (1)	0.004 (1)
C50	0.022 (2)	0.014 (1)	0.016 (2)	−0.002 (1)	0.004 (1)	−0.001 (1)
C51	0.025 (2)	0.020 (2)	0.020 (2)	−0.004 (1)	0.008 (1)	0.000 (2)
C52	0.017 (2)	0.016 (2)	0.020 (2)	−0.001 (1)	0.001 (1)	0.000 (1)

Geometric parameters (Å, º)

Cu1—O1	2.065 (2)	N16—C50	1.392 (4)
Cu1—O6	2.347 (2)	N16—C52	1.338 (4)
Cu1—N1	1.917 (3)	C1—C2	1.528 (4)
Cu1—N2	1.976 (3)	C2—C3	1.388 (4)
Cu1—N4	1.928 (3)	C3—C4	1.401 (4)
Cu2—O7	2.073 (2)	C3—H1	0.95
Cu2—O12	2.296 (2)	C4—C5	1.395 (5)
Cu2—N5	1.920 (2)	C4—H2	0.95
Cu2—N6	1.975 (3)	C5—C6	1.384 (4)
Cu2—N8	1.926 (2)	C5—H3	0.95
Cu3—O13	2.076 (2)	C6—C7	1.508 (5)
Cu3—O18	2.275 (3)	C8—C9	1.535 (5)
Cu3—N9	1.920 (2)	C8—C10	1.549 (4)
Cu3—N10	1.974 (3)	C8—H4	0.95
Cu3—N12	1.930 (2)	C10—C11	1.500 (4)
Cu4—O19	2.067 (2)	C10—H5	0.95
Cu4—O24	2.333 (2)	C10—H6	0.95
Cu4—N13	1.917 (3)	C11—C12	1.368 (4)
Cu4—N14	1.993 (3)	C12—H7	0.95
Cu4—N16	1.922 (3)	C13—H9	0.95
O1—C1	1.272 (3)	C14—C15	1.507 (4)
O2—C1	1.243 (4)	C15—C16	1.386 (4)
O3—C7	1.248 (4)	C16—C17	1.396 (4)
O4—C9	1.306 (4)	C16—H10	0.95
O5—C9	1.206 (4)	C17—C18	1.399 (4)
O7—C14	1.278 (3)	C17—H11	0.95
O8—C14	1.252 (3)	C18—C19	1.382 (4)
O9—C20	1.259 (4)	C18—H12	0.95
O10—C22	1.324 (4)	C19—C20	1.521 (4)
O11—C22	1.205 (4)	C21—C22	1.537 (5)
O13—C27	1.276 (3)	C21—C23	1.538 (4)
O14—C27	1.247 (4)	C21—H13	0.95
O15—C33	1.253 (4)	C23—C24	1.499 (4)
O16—C35	1.321 (4)	C23—H14	0.95
O17—C35	1.220 (4)	C23—H15	0.95
O19—C40	1.269 (4)	C24—C25	1.362 (4)
O20—C40	1.245 (4)	C25—H16	0.95
O21—C46	1.249 (4)	C26—H18	0.95
O22—C48	1.299 (4)	C27—C28	1.517 (4)
O23—C48	1.215 (4)	C28—C29	1.384 (4)
N1—C2	1.314 (4)	C29—C30	1.403 (4)
N1—C6	1.341 (4)	C29—H19	0.95
N2—C7	1.326 (4)	C30—C31	1.397 (4)
N2—C8	1.450 (4)	C30—H20	0.95
N4—C11	1.387 (4)	C31—C32	1.387 (4)
N4—C13	1.323 (4)	C31—H21	0.95
N3—C12	1.385 (4)	C32—C33	1.517 (4)
N3—C13	1.342 (4)	C34—C35	1.525 (5)
N3—H8	0.95	C34—C36	1.543 (4)
N5—C15	1.331 (4)	C34—H22	0.95
N5—C19	1.332 (4)	C36—C37	1.500 (4)
N6—C20	1.321 (4)	C36—H23	0.95
N6—C21	1.464 (4)	C36—H24	0.95
N7—C25	1.376 (4)	C37—C38	1.360 (4)
N7—C26	1.344 (4)	C38—H25	0.95
N7—H17	0.95	C39—H27	0.95
N8—C24	1.389 (4)	C40—C41	1.530 (4)
N8—C26	1.326 (4)	C41—C42	1.388 (4)
N9—C28	1.327 (4)	C42—C43	1.401 (4)
N9—C32	1.337 (4)	C42—H28	0.95
N10—C33	1.322 (4)	C43—C44	1.398 (5)
N10—C34	1.458 (4)	C43—H29	0.95
N11—C38	1.380 (4)	C44—C45	1.380 (4)
N11—C39	1.346 (4)	C44—H30	0.95
N11—H26	0.95	C45—C46	1.506 (4)
N12—C37	1.391 (3)	C47—C48	1.521 (4)
N12—C39	1.321 (4)	C47—C49	1.540 (5)
N13—C41	1.312 (4)	C47—H31	0.95
N13—C45	1.345 (4)	C49—C50	1.501 (4)
N14—C46	1.333 (4)	C49—H32	0.95
N14—C47	1.450 (4)	C49—H33	0.95
N15—C51	1.371 (4)	C50—C51	1.365 (4)
N15—C52	1.341 (4)	C51—H34	0.95
N15—H35	0.95	C52—H36	0.95
Cu4···O20^i	3.444 (2)	N3···C43^x	3.582 (5)
O1···N15^ii	3.431 (4)	N3···C43^vii	3.481 (4)
O1···C3^iii	3.484 (4)	N3···C44^x	3.228 (5)
O1···C52^ii	3.294 (4)	N3···C44^vii	3.315 (5)
O2···O6^iii	2.770 (3)	N3···C45^x	3.373 (4)
O2···N1^iv	3.285 (4)	N3···C45^vii	3.524 (5)
O2···N15^ii	2.788 (4)	N3···H30^x	3.41
O2···C1^iii	3.551 (4)	N3···H30^vii	3.58
O2···C1^iv	3.476 (4)	N7···C29^x	3.596 (4)
O2···C2^iii	3.339 (5)	N7···C29^vii	3.474 (4)
O2···C2^iv	3.224 (5)	N7···C30^x	3.354 (4)
O2···C52^ii	3.542 (4)	N7···C30^vii	3.292 (4)
O3···O16^v	2.553 (3)	N7···C31^x	3.454 (4)
O3···C34^v	3.265 (4)	N7···C31^vii	3.387 (4)
O3···C35^v	3.338 (4)	N8···C30^x	3.525 (4)
O3···C36^v	3.260 (4)	N8···H20^x	3.22
O3···C51^v	3.541 (4)	N8···H20^vii	3.51
O4···O9^vi	2.538 (3)	N9···H17^x	3.31
O4···C20^vi	3.296 (4)	N11···C16^v	3.584 (4)
O4···C22^vi	3.571 (4)	N11···C16^viii	3.490 (4)
O4···C38^v	3.428 (4)	N11···C17^v	3.379 (4)
O5···O6^vi	2.771 (3)	N11···C17^viii	3.317 (4)
O5···O9^vi	3.460 (3)	N11···C18^v	3.455 (4)
O6···C43^vii	3.236 (4)	N11···C18^viii	3.382 (4)
O6···C44^vii	3.599 (4)	N11···C19^viii	3.591 (4)
O8···O12^viii	2.712 (3)	N12···C17^v	3.543 (4)
O8···C14^v	3.327 (4)	N15···C1^xi	3.456 (4)
O8···C14^viii	3.319 (4)	N15···C4^v	3.316 (5)
O8···C15^v	3.369 (4)	N15···C4^viii	3.459 (5)
O8···C15^viii	3.358 (4)	N15···C5^v	3.368 (5)
O9···C9^ix	3.376 (4)	N15···C5^viii	3.203 (5)
O10···O21^vii	2.559 (3)	N15···C6^viii	3.514 (4)
O10···C46^vii	3.507 (4)	C1···C1^iii	3.412 (5)
O10···H7^ix	3.14	C1···C1^iv	3.412 (5)
O11···O12^ix	2.708 (3)	C1···C2^iii	3.462 (5)
O12···C30^x	3.335 (4)	C1···C2^iv	3.429 (5)
O14···O18^vii	2.704 (3)	C4···C52^v	3.525 (5)
O14···C27^x	3.359 (4)	C4···C52^viii	3.176 (5)
O14···C27^vii	3.317 (4)	C5···C51^v	3.212 (5)
O14···C28^x	3.354 (4)	C6···C51^v	3.581 (5)
O14···C28^vii	3.338 (4)	C11···C44^vii	3.341 (4)
O15···O22^ix	2.548 (3)	C12···C44^vii	3.298 (5)
O15···O23^ix	3.302 (3)	C12···C45^vii	3.544 (5)
O15···C48^ix	3.313 (4)	C13···C43^x	3.499 (5)
O16···C7^viii	3.444 (4)	C13···C43^vii	3.116 (5)
O17···O18^ix	2.697 (3)	C13···C44^x	3.564 (5)
O18···C17^v	3.344 (4)	C13···C44^vii	3.385 (5)
O19···O20^i	3.443 (3)	C14···C14^v	3.406 (5)
O19···N3^xi	3.403 (3)	C14···C14^viii	3.406 (5)
O19···C13^xi	3.288 (4)	C16···C39^v	3.531 (4)
O19···C41^i	3.461 (4)	C17···C39^v	3.278 (4)
O19···C42^i	3.318 (4)	C17···C39^viii	3.335 (4)
O20···O24^i	2.752 (3)	C18···C37^viii	3.469 (5)
O20···N3^xi	2.763 (3)	C18···C38^v	3.318 (4)
O20···N13^xii	3.162 (4)	C18···C38^viii	3.225 (4)
O20···C13^xi	3.540 (3)	C19···C38^v	3.585 (5)
O20···C40^xii	3.416 (4)	C19···C38^viii	3.544 (5)
O20···C41^xii	3.218 (4)	C20···H25^viii	3.50
O20···C41^i	3.524 (4)	C24···C31^x	3.459 (4)
O21···C21^x	3.250 (4)	C25···C30^x	3.577 (4)
O21···C22^x	3.348 (4)	C25···C31^x	3.206 (4)
O21···C23^x	3.301 (4)	C25···C31^vii	3.340 (4)
O22···C25^x	3.386 (4)	C25···C32^x	3.583 (4)
O22···C33^vi	3.395 (4)	C26···C29^vii	3.582 (4)
O23···O24	2.692 (3)	C26···C30^x	3.325 (4)
O23···C49^vi	3.411 (4)	C26···C30^vii	3.326 (4)
O24···C4^v	3.236 (4)	C27···C27^x	3.435 (5)
O24···C40^xii	3.581 (4)	C27···C27^vii	3.435 (5)
O24···C42^xii	3.468 (4)	C40···C40^xii	3.318 (5)
N4···C43^vii	3.330 (4)	C40···C40^i	3.318 (5)
N4···C44^vii	3.405 (4)	C40···C41^xii	3.393 (4)
N3···C40^ii	3.429 (4)	C40···C41^i	3.411 (4)
O1—Cu1—O6	89.71 (9)	N3—C13—H9	125
O1—Cu1—N1	79.5 (1)	O7—C14—O8	125.2 (3)
O6—Cu1—N1	94.95 (11)	O7—C14—C15	116.2 (2)
O1—Cu1—N2	159.8 (1)	O8—C14—C15	118.7 (3)
O6—Cu1—N2	98.45 (9)	N5—C15—C14	111.8 (2)
N1—Cu1—N2	81.36 (12)	N5—C15—C16	119.7 (3)
O1—Cu1—N4	101.62 (11)	C14—C15—C16	128.5 (3)
O6—Cu1—N4	96.87 (9)	C15—C16—C17	118.4 (3)
N1—Cu1—N4	168.13 (12)	C15—C16—H10	121
N2—Cu1—N4	95.74 (12)	C17—C16—H10	121
O7—Cu2—O12	86.75 (8)	C16—C17—C18	120.4 (3)
O7—Cu2—N5	79.86 (9)	C16—C17—H11	120
O12—Cu2—N5	96.3 (1)	C18—C17—H11	120
O7—Cu2—N6	157.80 (9)	C17—C18—C19	117.8 (3)
O12—Cu2—N6	105.88 (9)	C17—C18—H12	121
N5—Cu2—N6	80.6 (1)	C19—C18—H12	121
O7—Cu2—N8	102.45 (9)	N5—C19—C18	120.4 (3)
O12—Cu2—N8	91.3 (1)	N5—C19—C20	112.2 (3)
N5—Cu2—N8	172.25 (12)	C18—C19—C20	127.1 (3)
N6—Cu2—N8	95.6 (1)	O9—C20—N6	128.9 (3)
O13—Cu3—O18	86.75 (8)	O9—C20—C19	119.0 (3)
O13—Cu3—N9	79.48 (9)	N6—C20—C19	112.1 (3)
O18—Cu3—N9	96.72 (9)	N6—C21—C22	109.8 (2)
O13—Cu3—N10	157.44 (9)	N6—C21—C23	109.9 (3)
O18—Cu3—N10	106.43 (9)	C22—C21—C23	110.7 (3)
N9—Cu3—N10	80.8 (1)	N6—C21—H13	109
O13—Cu3—N12	102.43 (9)	C22—C21—H13	109
O18—Cu3—N12	91.3 (1)	C23—C21—H13	109
N9—Cu3—N12	171.83 (12)	O10—C22—O11	120.3 (3)
N10—Cu3—N12	95.6 (1)	O10—C22—C21	116.1 (3)
O19—Cu4—O24	88.53 (9)	O11—C22—C21	123.6 (3)
O19—Cu4—N13	79.5 (1)	C21—C23—C24	115.5 (3)
O24—Cu4—N13	97.2 (1)	C21—C23—H14	108
O19—Cu4—N14	160.9 (1)	C24—C23—H14	108
O24—Cu4—N14	95.9 (1)	C21—C23—H15	108
N13—Cu4—N14	81.47 (11)	C24—C23—H15	108
O19—Cu4—N16	102.61 (11)	H14—C23—H15	110
O24—Cu4—N16	93.19 (11)	N8—C24—C23	122.1 (3)
N13—Cu4—N16	169.46 (13)	N8—C24—C25	108.2 (3)
N14—Cu4—N16	95.74 (12)	C23—C24—C25	129.4 (3)
Cu1—O1—C1	114.16 (19)	N7—C25—C24	106.9 (3)
Cu2—O7—C14	113.16 (18)	N7—C25—H16	127
Cu3—O13—C27	113.56 (19)	C24—C25—H16	127
Cu4—O19—C40	114.27 (19)	N7—C26—N8	110.7 (3)
Cu1—N1—C2	119.5 (2)	N7—C26—H18	125
Cu1—N1—C6	117.0 (2)	N8—C26—H18	125
C2—N1—C6	123.5 (3)	O13—C27—O14	125.7 (3)
Cu1—N2—C7	116.0 (2)	O13—C27—C28	115.7 (3)
Cu1—N2—C8	126.1 (2)	O14—C27—C28	118.6 (3)
C7—N2—C8	117.8 (3)	N9—C28—C27	111.4 (2)
Cu1—N4—C11	122.6 (2)	N9—C28—C29	120.3 (3)
Cu1—N4—C13	130.3 (2)	C27—C28—C29	128.2 (3)
C11—N4—C13	107.1 (3)	C28—C29—C30	118.0 (3)
C12—N3—C13	107.8 (3)	C28—C29—H19	121
C12—N3—H8	126	C30—C29—H19	121
C13—N3—H8	126	C29—C30—C31	120.4 (3)
Cu2—N5—C15	118.9 (2)	C29—C30—H20	120
Cu2—N5—C19	117.8 (2)	C31—C30—H20	120
C15—N5—C19	123.3 (3)	C30—C31—C32	117.9 (3)
Cu2—N6—C20	116.6 (2)	C30—C31—H21	121
Cu2—N6—C21	124.7 (2)	C32—C31—H21	121
C20—N6—C21	118.6 (3)	N9—C32—C31	120.2 (3)
C25—N7—C26	107.5 (3)	N9—C32—C33	112.2 (3)
C25—N7—H17	126	C31—C32—C33	127.3 (3)
C26—N7—H17	126	O15—C33—N10	128.5 (3)
Cu2—N8—C24	124.2 (2)	O15—C33—C32	119.3 (3)
Cu2—N8—C26	129.1 (2)	N10—C33—C32	112.1 (3)
C24—N8—C26	106.7 (2)	N10—C34—C35	110.1 (3)
Cu3—N9—C28	119.4 (2)	N10—C34—C36	109.8 (3)
Cu3—N9—C32	117.5 (2)	C35—C34—C36	111.0 (3)
C28—N9—C32	123.0 (3)	N10—C34—H22	109
Cu3—N10—C33	116.6 (2)	C35—C34—H22	109
Cu3—N10—C34	124.1 (2)	C36—C34—H22	109
C33—N10—C34	118.3 (3)	O16—C35—O17	120.0 (3)
C38—N11—C39	107.6 (2)	O16—C35—C34	117.2 (3)
C38—N11—H26	126	O17—C35—C34	122.7 (3)
C39—N11—H26	126	C34—C36—C37	115.1 (3)
Cu3—N12—C37	124.3 (2)	C34—C36—H23	108
Cu3—N12—C39	128.9 (2)	C37—C36—H23	108
C37—N12—C39	106.8 (2)	C34—C36—H24	108
Cu4—N13—C41	119.6 (2)	C37—C36—H24	108
Cu4—N13—C45	117.2 (2)	H23—C36—H24	110
C41—N13—C45	123.1 (3)	N12—C37—C36	122.2 (2)
Cu4—N14—C46	115.0 (2)	N12—C37—C38	108.3 (3)
Cu4—N14—C47	125.6 (2)	C36—C37—C38	129.3 (3)
C46—N14—C47	118.2 (3)	N11—C38—C37	106.7 (3)
C51—N15—C52	108.4 (3)	N11—C38—H25	127
C51—N15—H35	126	C37—C38—H25	127
C52—N15—H35	126	N11—C39—N12	110.7 (3)
Cu4—N16—C50	123.9 (2)	N11—C39—H27	125
Cu4—N16—C52	127.4 (2)	N12—C39—H27	125
C50—N16—C52	106.7 (3)	O19—C40—O20	126.4 (3)
O1—C1—O2	126.4 (3)	O19—C40—C41	114.9 (3)
O1—C1—C2	115.0 (3)	O20—C40—C41	118.7 (3)
O2—C1—C2	118.5 (2)	N13—C41—C40	111.7 (3)
N1—C2—C1	111.5 (2)	N13—C41—C42	120.8 (3)
N1—C2—C3	120.8 (3)	C40—C41—C42	127.5 (3)
C1—C2—C3	127.7 (3)	C41—C42—C43	117.4 (3)
C2—C3—C4	117.3 (3)	C41—C42—H28	121
C2—C3—H1	121	C43—C42—H28	121
C4—C3—H1	121	C42—C43—C44	120.8 (3)
C3—C4—C5	120.6 (3)	C42—C43—H29	120
C3—C4—H2	120	C44—C43—H29	120
C5—C4—H2	120	C43—C44—C45	117.8 (3)
C4—C5—C6	118.3 (3)	C43—C44—H30	121
C4—C5—H3	121	C45—C44—H30	121
C6—C5—H3	121	N13—C45—C44	120.0 (3)
N1—C6—C5	119.5 (3)	N13—C45—C46	112.9 (3)
N1—C6—C7	112.8 (3)	C44—C45—C46	127.1 (3)
C5—C6—C7	127.7 (3)	O21—C46—N14	128.3 (3)
O3—C7—N2	128.3 (3)	O21—C46—C45	118.9 (3)
O3—C7—C6	119.2 (3)	N14—C46—C45	112.9 (3)
N2—C7—C6	112.4 (3)	N14—C47—C48	111.4 (3)
N2—C8—C9	112.0 (3)	N14—C47—C49	111.5 (3)
N2—C8—C10	111.0 (3)	C48—C47—C49	111.5 (3)
C9—C8—C10	110.2 (3)	N14—C47—H31	107
N2—C8—H4	108	C48—C47—H31	107
C9—C8—H4	108	C49—C47—H31	108
C10—C8—H4	108	O22—C48—O23	122.8 (3)
O4—C9—O5	124.5 (3)	O22—C48—C47	113.1 (3)
O4—C9—C8	111.2 (3)	O23—C48—C47	124.1 (3)
O5—C9—C8	124.3 (3)	C47—C49—C50	117.3 (3)
C8—C10—C11	115.5 (3)	C47—C49—H32	107
C8—C10—H5	108	C50—C49—H32	107
C11—C10—H5	108	C47—C49—H33	108
C8—C10—H6	108	C50—C49—H33	108
C11—C10—H6	108	H32—C49—H33	110
H5—C10—H6	109	N16—C50—C49	122.9 (3)
N4—C11—C10	122.6 (3)	N16—C50—C51	108.1 (3)
N4—C11—C12	108.3 (3)	C49—C50—C51	128.1 (3)
C10—C11—C12	128.8 (3)	N15—C51—C50	106.8 (3)
N3—C12—C11	106.3 (3)	N15—C51—H34	127
N3—C12—H7	127	C50—C51—H34	127
C11—C12—H7	127	N15—C52—N16	110.0 (3)
N4—C13—N3	110.5 (3)	N15—C52—H36	125
N4—C13—H9	125	N16—C52—H36	125
O6—Cu1—O1—C1	92.5 (4)	C25—N7—C26—N8	−0.3 (5)
N1—Cu1—O1—C1	−2.6 (4)	Cu2—N8—C24—C23	4.1 (5)
N2—Cu1—O1—C1	−21.9 (5)	Cu2—N8—C24—C25	178.5 (2)
N4—Cu1—O1—C1	−170.6 (4)	C26—N8—C24—C23	−173.4 (4)
O1—Cu1—N1—C2	4.9 (4)	C26—N8—C24—C25	1.1 (5)
O1—Cu1—N1—C6	−177.2 (4)	Cu2—N8—C26—N7	−177.8 (2)
O6—Cu1—N1—C2	−83.9 (5)	C24—N8—C26—N7	−0.5 (5)
O6—Cu1—N1—C6	94.0 (4)	Cu3—N9—C28—C27	−4.9 (4)
N2—Cu1—N1—C2	178.3 (5)	Cu3—N9—C28—C29	177.0 (3)
N2—Cu1—N1—C6	−3.8 (5)	C32—N9—C28—C27	177.1 (4)
N4—Cu1—N1—C2	101.7 (6)	C32—N9—C28—C29	−1.0 (6)
N4—Cu1—N1—C6	−80.3 (7)	Cu3—N9—C32—C31	−175.8 (3)
O1—Cu1—N2—C7	19.0 (4)	Cu3—N9—C32—C33	9.4 (4)
O1—Cu1—N2—C8	−156.0 (3)	C28—N9—C32—C31	2.2 (6)
O6—Cu1—N2—C7	−94.0 (4)	C28—N9—C32—C33	−172.6 (4)
O6—Cu1—N2—C8	91.1 (2)	Cu3—N10—C33—O15	−176.0 (3)
N1—Cu1—N2—C7	−0.2 (2)	Cu3—N10—C33—C32	0.8 (4)
N1—Cu1—N2—C8	−175.1 (5)	C34—N10—C33—O15	−7.0 (7)
N4—Cu1—N2—C7	168.2 (4)	C34—N10—C33—C32	169.9 (4)
N4—Cu1—N2—C8	−6.7 (6)	Cu3—N10—C34—C35	79.4 (4)
O1—Cu1—N4—C11	−171.1 (4)	Cu3—N10—C34—C36	−43.1 (4)
O1—Cu1—N4—C13	8.1 (6)	C33—N10—C34—C35	−88.8 (5)
O6—Cu1—N4—C11	−80.0 (2)	C33—N10—C34—C36	148.8 (4)
O6—Cu1—N4—C13	99.2 (5)	C39—N11—C38—C37	0.9 (5)
N1—Cu1—N4—C11	94.3 (6)	C38—N11—C39—N12	−0.1 (5)
N1—Cu1—N4—C13	−86.5 (7)	Cu3—N12—C37—C36	3.6 (4)
N2—Cu1—N4—C11	19.3 (2)	Cu3—N12—C37—C38	179.0 (2)
N2—Cu1—N4—C13	−161.5 (5)	C39—N12—C37—C36	−173.9 (4)
O12—Cu2—O7—C14	92.8 (4)	C39—N12—C37—C38	1.4 (5)
N5—Cu2—O7—C14	−4.1 (4)	Cu3—N12—C39—N11	−178.2 (2)
N6—Cu2—O7—C14	−33.0 (4)	C37—N12—C39—N11	−0.8 (5)
N8—Cu2—O7—C14	−176.6 (4)	Cu4—N13—C41—C40	−3.1 (4)
O7—Cu2—N5—C15	3.8 (4)	Cu4—N13—C41—C42	177.6 (3)
O7—Cu2—N5—C19	−177.2 (4)	C45—N13—C41—C40	−179.2 (4)
O12—Cu2—N5—C15	−81.8 (4)	C45—N13—C41—C42	1.5 (7)
O12—Cu2—N5—C19	97.2 (4)	Cu4—N13—C45—C44	−176.1 (3)
N6—Cu2—N5—C15	173.1 (4)	Cu4—N13—C45—C46	4.3 (4)
N6—Cu2—N5—C19	−7.9 (4)	C41—N13—C45—C44	0.1 (7)
O7—Cu2—N6—C20	35.6 (4)	C41—N13—C45—C46	−179.5 (4)
O7—Cu2—N6—C21	−139.8 (6)	Cu4—N14—C46—O21	−171.1 (3)
O12—Cu2—N6—C20	−87.1 (4)	Cu4—N14—C46—C45	8.2 (4)
O12—Cu2—N6—C21	97.4 (4)	C47—N14—C46—O21	−3.3 (7)
N5—Cu2—N6—C20	6.8 (4)	C47—N14—C46—C45	176.0 (4)
N5—Cu2—N6—C21	−168.7 (4)	Cu4—N14—C47—C48	84.1 (4)
N8—Cu2—N6—C20	180.0 (4)	Cu4—N14—C47—C49	−41.1 (4)
N8—Cu2—N6—C21	4.5 (5)	C46—N14—C47—C48	−82.2 (5)
O7—Cu2—N8—C24	−177.9 (4)	C46—N14—C47—C49	152.5 (4)
O7—Cu2—N8—C26	−1.1 (5)	C52—N15—C51—C50	0.7 (5)
O12—Cu2—N8—C24	−91.0 (4)	C51—N15—C52—N16	−0.6 (6)
O12—Cu2—N8—C26	85.9 (5)	Cu4—N16—C50—C49	25.4 (5)
N6—Cu2—N8—C24	15.1 (5)	Cu4—N16—C50—C51	−164.2 (2)
N6—Cu2—N8—C26	−168.0 (4)	C52—N16—C50—C49	−170.1 (4)
O18—Cu3—O13—C27	91.9 (4)	C52—N16—C50—C51	0.3 (5)
N9—Cu3—O13—C27	−5.6 (4)	Cu4—N16—C52—N15	164.0 (2)
N10—Cu3—O13—C27	−35.2 (4)	C50—N16—C52—N15	0.2 (5)
N12—Cu3—O13—C27	−177.5 (4)	O1—C1—C2—N1	3.4 (5)
O13—Cu3—N9—C28	5.7 (4)	O1—C1—C2—C3	−178.6 (4)
O13—Cu3—N9—C32	−176.2 (4)	O2—C1—C2—N1	−176.5 (4)
O18—Cu3—N9—C28	−79.7 (4)	O2—C1—C2—C3	1.5 (7)
O18—Cu3—N9—C32	98.4 (4)	N1—C2—C3—C4	−0.3 (6)
N10—Cu3—N9—C28	174.7 (4)	C1—C2—C3—C4	−178.1 (4)
N10—Cu3—N9—C32	−7.2 (4)	C2—C3—C4—C5	1.8 (7)
O13—Cu3—N10—C33	32.7 (4)	C3—C4—C5—C6	−1.4 (7)
O13—Cu3—N10—C34	−135.7 (6)	C4—C5—C6—N1	−0.6 (7)
O18—Cu3—N10—C33	−91.2 (4)	C4—C5—C6—C7	176.8 (4)
O18—Cu3—N10—C34	100.5 (4)	N1—C6—C7—O3	171.6 (4)
N9—Cu3—N10—C33	3.2 (4)	N1—C6—C7—N2	−6.6 (6)
N9—Cu3—N10—C34	−165.2 (4)	C5—C6—C7—O3	−5.9 (8)
N12—Cu3—N10—C33	175.8 (4)	C5—C6—C7—N2	175.9 (5)
N12—Cu3—N10—C34	7.4 (5)	N2—C8—C9—O4	160.2 (4)
O13—Cu3—N12—C37	−179.4 (4)	N2—C8—C9—O5	−21.2 (6)
O13—Cu3—N12—C39	−2.5 (5)	C10—C8—C9—O4	−75.7 (5)
O18—Cu3—N12—C37	−92.5 (4)	C10—C8—C9—O5	103.0 (5)
O18—Cu3—N12—C39	84.5 (5)	N2—C8—C10—C11	59.0 (5)
N10—Cu3—N12—C39	−168.9 (4)	C9—C8—C10—C11	−65.8 (5)
O24—Cu4—O19—C40	−96.9 (4)	C8—C10—C11—N4	−50.3 (6)
N13—Cu4—O19—C40	0.7 (4)	C8—C10—C11—C12	137.4 (5)
N14—Cu4—O19—C40	6.8 (5)	N4—C11—C12—N3	−0.5 (5)
N16—Cu4—O19—C40	170.1 (4)	C10—C11—C12—N3	172.7 (4)
O19—Cu4—N13—C41	1.6 (4)	O7—C14—C15—N5	−0.9 (5)
O19—Cu4—N13—C45	177.9 (4)	O7—C14—C15—C16	177.3 (4)
O24—Cu4—N13—C41	88.7 (4)	O8—C14—C15—N5	179.9 (3)
O24—Cu4—N13—C45	−94.9 (4)	O8—C14—C15—C16	−1.9 (6)
N14—Cu4—N13—C41	−176.4 (4)	N5—C15—C16—C17	−0.6 (6)
N14—Cu4—N13—C45	−0.0 (5)	C14—C15—C16—C17	−178.6 (4)
N16—Cu4—N13—C41	−100.8 (7)	C15—C16—C17—C18	0.6 (6)
N16—Cu4—N13—C45	75.5 (7)	C16—C17—C18—C19	0.1 (6)
O19—Cu4—N14—C46	−11.1 (5)	C17—C18—C19—N5	−0.8 (6)
O19—Cu4—N14—C47	−177.8 (3)	C17—C18—C19—C20	172.7 (4)
O24—Cu4—N14—C46	91.6 (4)	N5—C19—C20—O9	175.5 (4)
O24—Cu4—N14—C47	−75.2 (2)	N5—C19—C20—N6	−1.7 (5)
N13—Cu4—N14—C46	−4.9 (2)	C18—C19—C20—O9	1.6 (7)
N13—Cu4—N14—C47	−171.6 (5)	C18—C19—C20—N6	−175.6 (4)
N16—Cu4—N14—C46	−174.6 (4)	N6—C21—C22—O10	172.6 (4)
N16—Cu4—N14—C47	18.6 (6)	N6—C21—C22—O11	−10.5 (6)
O19—Cu4—N16—C50	176.9 (4)	C23—C21—C22—O10	−65.9 (6)
O19—Cu4—N16—C52	15.7 (6)	C23—C21—C22—O11	111.0 (5)
O24—Cu4—N16—C50	87.7 (5)	N6—C21—C23—C24	63.1 (5)
O24—Cu4—N16—C52	−73.5 (5)	C22—C21—C23—C24	−58.4 (6)
N13—Cu4—N16—C50	−82.8 (7)	C21—C23—C24—N8	−47.2 (6)
N13—Cu4—N16—C52	116.0 (6)	C21—C23—C24—C25	139.6 (5)
N14—Cu4—N16—C50	−8.5 (6)	N8—C24—C25—N7	−1.2 (4)
N14—Cu4—N16—C52	−169.7 (5)	C23—C24—C25—N7	172.7 (4)
Cu1—O1—C1—O2	−179.8 (3)	O13—C27—C28—N9	−0.2 (5)
Cu1—O1—C1—C2	0.3 (4)	O13—C27—C28—C29	177.7 (4)
Cu2—O7—C14—O8	−177.1 (3)	O14—C27—C28—N9	−179.3 (3)
Cu2—O7—C14—C15	3.8 (4)	O14—C27—C28—C29	−1.3 (6)
Cu3—O13—C27—O14	−176.4 (3)	N9—C28—C29—C30	−0.6 (6)
Cu3—O13—C27—C28	4.6 (4)	C27—C28—C29—C30	−178.4 (4)
Cu4—O19—C40—O20	176.8 (3)	C28—C29—C30—C31	1.0 (6)
Cu4—O19—C40—C41	−2.4 (4)	C29—C30—C31—C32	0.1 (6)
Cu1—N1—C2—C1	−5.9 (4)	C30—C31—C32—N9	−1.7 (6)
Cu1—N1—C2—C3	176.0 (3)	C30—C31—C32—C33	172.2 (4)
C6—N1—C2—C1	176.4 (4)	N9—C32—C33—O15	170.8 (4)
C6—N1—C2—C3	−1.8 (7)	N9—C32—C33—N10	−6.4 (5)
Cu1—N1—C6—C5	−175.6 (3)	C31—C32—C33—O15	−3.6 (7)
Cu1—N1—C6—C7	6.7 (4)	C31—C32—C33—N10	179.2 (4)
C2—N1—C6—C5	2.2 (7)	N10—C34—C35—O16	174.9 (4)
C2—N1—C6—C7	−175.5 (4)	N10—C34—C35—O17	−7.4 (6)
Cu1—N2—C7—O3	−174.3 (3)	C36—C34—C35—O16	−63.3 (5)
Cu1—N2—C7—C6	3.7 (4)	C36—C34—C35—O17	114.4 (5)
C8—N2—C7—O3	1.0 (7)	N10—C34—C36—C37	64.3 (5)
C8—N2—C7—C6	179.0 (4)	C35—C34—C36—C37	−57.6 (5)
Cu1—N2—C8—C9	95.6 (3)	C34—C36—C37—N12	−46.2 (6)
Cu1—N2—C8—C10	−28.1 (4)	C34—C36—C37—C38	139.5 (5)
C7—N2—C8—C9	−79.2 (5)	N12—C37—C38—N11	−1.5 (4)
C7—N2—C8—C10	157.1 (4)	C36—C37—C38—N11	173.5 (4)
Cu1—N4—C11—C10	5.8 (5)	O19—C40—C41—N13	3.6 (5)
Cu1—N4—C11—C12	179.5 (2)	O19—C40—C41—C42	−177.2 (4)
C13—N4—C11—C10	−173.6 (4)	O20—C40—C41—N13	−175.7 (3)
C13—N4—C11—C12	0.1 (5)	O20—C40—C41—C42	3.5 (6)
Cu1—N4—C13—N3	−179.0 (2)	N13—C41—C42—C43	−2.1 (6)
C11—N4—C13—N3	0.4 (5)	C40—C41—C42—C43	178.7 (4)
C13—N3—C12—C11	0.7 (5)	C41—C42—C43—C44	1.3 (6)
C12—N3—C13—N4	−0.6 (5)	C42—C43—C44—C45	0.3 (7)
Cu2—N5—C15—C14	−2.8 (4)	C43—C44—C45—N13	−1.0 (7)
Cu2—N5—C15—C16	178.8 (3)	C43—C44—C45—C46	178.6 (4)
C19—N5—C15—C14	178.2 (4)	N13—C45—C46—O21	171.2 (4)
C19—N5—C15—C16	−0.1 (6)	N13—C45—C46—N14	−8.2 (6)
Cu2—N5—C19—C18	−178.1 (3)	C44—C45—C46—O21	−8.4 (8)
Cu2—N5—C19—C20	7.5 (4)	C44—C45—C46—N14	172.2 (5)
C15—N5—C19—C18	0.8 (6)	N14—C47—C48—O22	159.5 (4)
C15—N5—C19—C20	−173.6 (4)	N14—C47—C48—O23	−21.5 (6)
Cu2—N6—C20—O9	178.6 (3)	C49—C47—C48—O22	−75.3 (5)
Cu2—N6—C20—C19	−4.6 (4)	C49—C47—C48—O23	103.7 (5)
C21—N6—C20—O9	−5.7 (7)	N14—C47—C49—C50	54.5 (5)
C21—N6—C20—C19	171.1 (4)	C48—C47—C49—C50	−70.6 (5)
Cu2—N6—C21—C22	82.2 (4)	C47—C49—C50—N16	−49.5 (7)
Cu2—N6—C21—C23	−39.8 (4)	C47—C49—C50—C51	142.1 (5)
C20—N6—C21—C22	−93.2 (5)	N16—C50—C51—N15	−0.6 (5)
C20—N6—C21—C23	144.8 (4)	C49—C50—C51—N15	169.1 (4)
C26—N7—C25—C24	0.9 (5)

Symmetry codes: (i) −x, y+1/2, −z+2; (ii) x, y, z−1; (iii) −x+1, y−1/2, −z; (iv) −x+1, y+1/2, −z; (v) −x+1, y−1/2, −z+1; (vi) x, y−1, z; (vii) −x, y+1/2, −z+1; (viii) −x+1, y+1/2, −z+1; (ix) x, y+1, z; (x) −x, y−1/2, −z+1; (xi) x, y, z+1; (xii) −x, y−1/2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H8···O20^ii	0.95	1.86	2.763 (3)	159
N7—H17···O14	0.95	1.83	2.730 (3)	158
N11—H26···O8	0.95	1.82	2.732 (3)	159
N15—H35···O2^xi	0.95	1.87	2.788 (4)	161

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