Hydroxonium hydrate tris-(2,4,6-tri-amino-1,3,5-triazin-1-ium) bis-[bis-(pyri-dine-2,6-dicarboxyl-ato)cuprate(II)] pyridine-2,6-dicarboxylic acid hexa-hydrate.

The reaction of copper(II) nitrate hexa-hydrate with pyridine-2,6-dicarboxylic acid (pydcH(2)) and 2,4,6-triamino-1,3,5-triazine (melamine) in aqueous solution in a 1:2:2 molar ratio gave the title compound, (H(5)O(2))(C(3)H(7)N(6))(3)[Cu(C(7)H(3)NO(4))(2)](2)·C(7)H(5)NO(4)·6H(2)O. The hydroxonium hydrate (H(5)O(2))(+), also known as the Zundel cation, resides on a twofold rotation axis. The O-H distance is 1.274 (14) Å, the O⋯O distance is 2.518 (5) Å, and the O-H-O angle is 162 (8)°. One of the melamine H(+) cations, the uncoordinated pydcH(2), and two water mol-ecules also reside on crystallographic twofold axes. The Cu(II) atom has a tetra-gonally distorted octa-hedral coordination environment. The structure features extensive hydrogen bonding, with 21 distinct inter-actions. There is also a centrosymmetric C=O⋯π inter-action with an O⋯centroid distance of 3.288 (3) Å. The structure is similar to a mixed-valence manganese(II/III) structure but shows inter-esting differences in the metal-atom coordination. One of the water molecules is equally disordered with respect to a twofold axis.

Related literature

For related melamine salts, see: Aghabozorg, Aghajani & Sharif (2006 ▶); Aghabozorg, Attar Gharamaleki et al. (2008 ▶); Aghabozorg, Ghadermazi et al. (2008 ▶); Aghabozorg, Manteghi & Sheshmani (2008 ▶); Aghabozorg, Zabihi et al. (2006 ▶); Agha­­jani et al. (2006 ▶); Perpétuo & Janczak (2006 ▶); Sharif et al. (2006 ▶, 2007 ▶); Zhang & Chen (2005 ▶). For a nearly isostructural manganese(II/III) structure, see: Aghabozorg, Derikvand et al. (2008 ▶).

Experimental

Crystal data

(H5O2)(C3H7N6)3[Cu(C7H3NO4)2]2·C7H5NO4·6H2O

M = 1481.19

Monoclinic,

a = 27.575 (3) Å

b = 22.814 (3) Å

c = 9.8068 (12) Å

β = 108.327 (2)°

V = 5856.5 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.84 mm−1

T = 180 (2) K

0.35 × 0.28 × 0.02 mm

Data collection

Bruker SMART APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.758, T max = 0.983

26801 measured reflections

5309 independent reflections

3805 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.096

S = 1.03

5309 reflections

531 parameters

21 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.77 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809000828/gw2056sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000828/gw2056Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(H5O2)(C3H7N6)3[Cu(C7H3NO4)2]2·C7H5NO4·6H2O	F(000) = 3048
Mr = 1481.19	Dx = 1.680 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6004 reflections
a = 27.575 (3) Å	θ = 2.8–26.1°
b = 22.814 (3) Å	µ = 0.84 mm−1
c = 9.8068 (12) Å	T = 180 K
β = 108.327 (2)°	Plate, pale blue
V = 5856.5 (13) Å3	0.35 × 0.28 × 0.02 mm
Z = 4

Bruker SMART APEXII diffractometer	5309 independent reflections
Radiation source: fine-focus sealed tube	3805 reflections with I > 2σ(I)
graphite	Rint = 0.051
Detector resolution: 8.3 pixels mm-1	θmax = 25.3°, θmin = 2.8°
ω scans	h = −33→33
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −27→27
Tmin = 0.758, Tmax = 0.983	l = −11→11
26801 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0411P)2 + 8.7866P] where P = (Fo2 + 2Fc2)/3
5309 reflections	(Δ/σ)max = 0.001
531 parameters	Δρmax = 0.26 e Å−3
21 restraints	Δρmin = −0.77 e Å−3

Experimental. The crystals cracked when cooled to 90 K so the data was collected at 180 K.

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.157851 (13)	0.631029 (17)	−0.05095 (3)	0.03071 (12)
O1	0.09962 (8)	0.63287 (9)	0.0509 (2)	0.0352 (5)
O2	0.04357 (8)	0.57153 (9)	0.0993 (2)	0.0396 (5)
O3	0.21154 (8)	0.59453 (9)	−0.1422 (2)	0.0359 (5)
O4	0.24379 (8)	0.50682 (10)	−0.1733 (2)	0.0441 (6)
O5	0.21596 (7)	0.65786 (9)	0.1601 (2)	0.0327 (5)
O6	0.25253 (8)	0.73927 (9)	0.2729 (2)	0.0362 (5)
O7	0.10282 (8)	0.65042 (10)	−0.2763 (2)	0.0374 (5)
O8	0.07941 (8)	0.72696 (9)	−0.4265 (2)	0.0377 (5)
N1	0.14634 (9)	0.54895 (11)	−0.0330 (2)	0.0280 (6)
N2	0.16513 (8)	0.71590 (11)	−0.0740 (2)	0.0291 (6)
C1	0.08130 (11)	0.58215 (13)	0.0608 (3)	0.0295 (7)
C2	0.10898 (10)	0.53146 (13)	0.0179 (3)	0.0279 (6)
C3	0.09751 (11)	0.47292 (14)	0.0232 (3)	0.0336 (7)
H3	0.0712	0.4607	0.0603	0.040*
C4	0.12506 (11)	0.43224 (15)	−0.0267 (3)	0.0377 (7)
H4	0.1177	0.3916	−0.0245	0.045*
C5	0.16359 (11)	0.45086 (15)	−0.0803 (3)	0.0366 (8)
H5	0.1826	0.4233	−0.1156	0.044*
C6	0.17368 (11)	0.50997 (14)	−0.0810 (3)	0.0296 (7)
C7	0.21347 (11)	0.53866 (14)	−0.1368 (3)	0.0327 (7)
C8	0.22339 (10)	0.71221 (14)	0.1673 (3)	0.0296 (7)
C9	0.19487 (10)	0.74812 (14)	0.0362 (3)	0.0287 (7)
C10	0.19848 (11)	0.80844 (14)	0.0269 (3)	0.0341 (7)
H10	0.2197	0.8303	0.1056	0.041*
C11	0.17062 (11)	0.83657 (15)	−0.0989 (3)	0.0364 (7)
H11	0.1724	0.8779	−0.1073	0.044*
C12	0.14016 (11)	0.80339 (14)	−0.2120 (3)	0.0333 (7)
H12	0.1210	0.8216	−0.2993	0.040*
C13	0.13815 (10)	0.74347 (14)	−0.1956 (3)	0.0289 (7)
C14	0.10436 (10)	0.70318 (14)	−0.3083 (3)	0.0301 (7)
N3	0.31880 (9)	0.69464 (11)	0.5251 (2)	0.0276 (5)
H3A	0.3001 (9)	0.7133 (11)	0.449 (2)	0.029 (8)*
N4	0.34173 (9)	0.60470 (11)	0.6466 (2)	0.0279 (5)
N5	0.37566 (9)	0.69628 (11)	0.7606 (2)	0.0283 (5)
N6	0.28551 (9)	0.60781 (12)	0.4159 (2)	0.0308 (6)
H6A	0.2790 (12)	0.5702 (5)	0.415 (3)	0.045 (10)*
H6B	0.2656 (10)	0.6283 (12)	0.344 (2)	0.038 (9)*
N7	0.39782 (10)	0.60852 (12)	0.8748 (3)	0.0348 (6)
H7A	0.4185 (10)	0.6269 (12)	0.950 (2)	0.043 (9)*
H7B	0.3957 (13)	0.5701 (5)	0.877 (4)	0.054 (11)*
N8	0.35019 (10)	0.78255 (12)	0.6365 (3)	0.0324 (6)
H8A	0.3686 (9)	0.8009 (11)	0.714 (2)	0.030 (8)*
H8B	0.3313 (11)	0.8021 (13)	0.561 (2)	0.053 (11)*
C15	0.31528 (10)	0.63496 (13)	0.5310 (3)	0.0273 (6)
C16	0.37112 (10)	0.63705 (13)	0.7578 (3)	0.0273 (6)
C17	0.34873 (10)	0.72446 (13)	0.6423 (3)	0.0270 (6)
N9	0.02898 (8)	0.83461 (10)	−0.1285 (2)	0.0271 (5)
N10	0.0000	0.74606 (16)	−0.2500	0.0301 (8)
H10A	0.0000	0.7074 (5)	−0.2500	0.057 (16)*
N11	0.0000	0.91967 (15)	−0.2500	0.0308 (8)
H11A	−0.0184 (10)	0.9405 (12)	−0.324 (2)	0.040 (9)*
N12	0.05475 (10)	0.74580 (12)	−0.0180 (3)	0.0356 (6)
H12A	0.0731 (10)	0.7644 (12)	0.059 (2)	0.036 (9)*
H12B	0.0558 (13)	0.7072 (5)	−0.020 (4)	0.053 (11)*
C18	0.0000	0.86200 (17)	−0.2500	0.0244 (8)
C19	0.02795 (10)	0.77645 (13)	−0.1311 (3)	0.0277 (6)
O9	0.06509 (9)	0.99585 (10)	−0.0244 (2)	0.0508 (7)
O10	0.09675 (8)	1.07950 (9)	0.0842 (2)	0.0334 (5)
H10B	0.1173 (12)	1.0565 (14)	0.142 (3)	0.075 (14)*
N13	0.0000	1.05523 (15)	−0.2500	0.0279 (8)
C20	0.0000	1.17795 (19)	−0.2500	0.0344 (10)
H20	0.0000	1.2196	−0.2500	0.056 (15)*
C21	0.03105 (11)	1.14704 (13)	−0.1331 (3)	0.0301 (7)
H21	0.0522	1.1670	−0.0509	0.029 (8)*
C22	0.03049 (10)	1.08601 (12)	−0.1391 (3)	0.0256 (6)
C23	0.06522 (11)	1.04884 (14)	−0.0217 (3)	0.0302 (7)
O11	0.0000	0.48788 (15)	0.2500	0.0428 (8)
H11B	−0.0111 (14)	0.5073 (16)	0.302 (4)	0.053 (11)*
O12	−0.01661 (12)	0.66299 (13)	0.1148 (3)	0.0631 (8)
H12C	−0.0356 (13)	0.6839 (16)	0.049 (3)	0.079 (14)*
H12D	0.0013 (16)	0.6374 (16)	0.092 (5)	0.100 (18)*
H12E	0.0000	0.672 (4)	0.2500	0.17 (3)*
O13	0.16865 (9)	1.01368 (11)	0.2655 (2)	0.0372 (5)
H13A	0.1944 (10)	1.0045 (19)	0.242 (4)	0.080 (15)*
H13B	0.1636 (16)	0.9829 (11)	0.306 (4)	0.079 (15)*
O14	0.28646 (9)	0.84247 (11)	0.3914 (2)	0.0411 (6)
H14A	0.2740 (12)	0.8119 (9)	0.347 (3)	0.043 (10)*
H14B	0.2899 (17)	0.8674 (14)	0.333 (4)	0.088 (16)*
O15	−0.0086 (2)	0.6313 (2)	−0.2238 (8)	0.0471 (15)	0.50
H15A	−0.006 (3)	0.599 (2)	−0.261 (12)	0.07 (3)*	0.50
H15B	−0.0385 (11)	0.630 (3)	−0.219 (8)	0.06 (3)*	0.50

	U11	U22	U33	U12	U13	U23
Cu1	0.02553 (19)	0.0436 (3)	0.02402 (18)	0.00683 (17)	0.00929 (14)	0.00601 (16)
O1	0.0351 (11)	0.0301 (12)	0.0447 (12)	0.0009 (10)	0.0189 (10)	0.0083 (10)
O2	0.0400 (13)	0.0334 (13)	0.0575 (14)	0.0033 (10)	0.0330 (11)	0.0056 (10)
O3	0.0390 (12)	0.0375 (14)	0.0356 (11)	0.0126 (10)	0.0179 (9)	0.0096 (9)
O4	0.0431 (13)	0.0424 (14)	0.0582 (14)	0.0146 (11)	0.0324 (11)	0.0096 (11)
O5	0.0311 (11)	0.0353 (13)	0.0275 (10)	−0.0019 (10)	0.0033 (9)	0.0064 (9)
O6	0.0333 (12)	0.0361 (13)	0.0323 (11)	0.0008 (10)	0.0006 (9)	0.0084 (9)
O7	0.0388 (12)	0.0390 (14)	0.0386 (12)	0.0103 (10)	0.0181 (10)	0.0129 (10)
O8	0.0362 (12)	0.0424 (14)	0.0292 (11)	0.0005 (10)	0.0030 (9)	0.0125 (9)
N1	0.0244 (12)	0.0386 (15)	0.0204 (11)	0.0077 (11)	0.0062 (10)	0.0031 (10)
N2	0.0188 (12)	0.0456 (16)	0.0245 (12)	0.0075 (11)	0.0090 (10)	0.0114 (11)
C1	0.0289 (16)	0.0325 (18)	0.0296 (15)	0.0026 (13)	0.0131 (13)	0.0048 (13)
C2	0.0241 (14)	0.0347 (18)	0.0239 (14)	0.0027 (13)	0.0060 (12)	0.0008 (12)
C3	0.0230 (15)	0.040 (2)	0.0383 (17)	−0.0007 (14)	0.0097 (13)	−0.0012 (14)
C4	0.0326 (17)	0.0346 (19)	0.0457 (18)	0.0006 (14)	0.0119 (14)	−0.0014 (14)
C5	0.0296 (17)	0.041 (2)	0.0398 (17)	0.0075 (14)	0.0112 (14)	−0.0029 (14)
C6	0.0232 (14)	0.041 (2)	0.0233 (14)	0.0080 (14)	0.0060 (12)	0.0030 (13)
C7	0.0294 (16)	0.042 (2)	0.0271 (15)	0.0100 (15)	0.0087 (13)	0.0077 (13)
C8	0.0203 (14)	0.042 (2)	0.0261 (15)	0.0044 (13)	0.0063 (12)	0.0081 (13)
C9	0.0182 (14)	0.041 (2)	0.0282 (15)	0.0036 (13)	0.0097 (12)	0.0114 (13)
C10	0.0251 (15)	0.042 (2)	0.0348 (16)	0.0002 (14)	0.0091 (13)	0.0080 (14)
C11	0.0296 (16)	0.040 (2)	0.0422 (18)	0.0022 (15)	0.0148 (14)	0.0163 (15)
C12	0.0264 (16)	0.044 (2)	0.0307 (16)	0.0057 (14)	0.0100 (13)	0.0174 (14)
C13	0.0189 (14)	0.044 (2)	0.0267 (14)	0.0051 (13)	0.0109 (12)	0.0123 (13)
C14	0.0217 (14)	0.046 (2)	0.0256 (15)	0.0066 (14)	0.0114 (12)	0.0117 (13)
N3	0.0255 (13)	0.0310 (15)	0.0249 (12)	0.0020 (11)	0.0057 (10)	0.0106 (11)
N4	0.0280 (13)	0.0319 (14)	0.0224 (12)	0.0009 (11)	0.0061 (10)	0.0054 (10)
N5	0.0284 (13)	0.0281 (15)	0.0269 (12)	0.0022 (11)	0.0065 (10)	0.0071 (10)
N6	0.0301 (14)	0.0353 (17)	0.0244 (13)	0.0012 (12)	0.0045 (11)	0.0042 (11)
N7	0.0408 (16)	0.0286 (16)	0.0273 (14)	−0.0003 (13)	−0.0003 (12)	0.0058 (11)
N8	0.0334 (15)	0.0305 (16)	0.0298 (14)	−0.0017 (12)	0.0050 (12)	0.0063 (12)
C15	0.0227 (14)	0.0336 (18)	0.0275 (14)	0.0021 (13)	0.0106 (11)	0.0055 (13)
C16	0.0252 (14)	0.0330 (18)	0.0241 (14)	0.0008 (13)	0.0084 (11)	0.0053 (12)
C17	0.0226 (14)	0.0321 (18)	0.0288 (15)	0.0009 (13)	0.0118 (12)	0.0059 (12)
N9	0.0284 (13)	0.0208 (14)	0.0283 (12)	0.0012 (10)	0.0035 (10)	0.0026 (10)
N10	0.0279 (19)	0.021 (2)	0.038 (2)	0.000	0.0060 (15)	0.000
N11	0.036 (2)	0.021 (2)	0.0269 (19)	0.000	−0.0024 (16)	0.000
N12	0.0334 (15)	0.0259 (17)	0.0409 (16)	0.0012 (12)	0.0024 (12)	0.0097 (13)
C18	0.0213 (19)	0.022 (2)	0.027 (2)	0.000	0.0041 (16)	0.000
C19	0.0234 (14)	0.0267 (18)	0.0336 (16)	0.0009 (12)	0.0097 (12)	0.0025 (12)
O9	0.0626 (16)	0.0264 (14)	0.0390 (13)	−0.0015 (11)	−0.0189 (11)	0.0011 (10)
O10	0.0322 (12)	0.0327 (13)	0.0281 (11)	−0.0022 (10)	−0.0008 (9)	−0.0058 (9)
N13	0.0258 (18)	0.029 (2)	0.0262 (17)	0.000	0.0044 (14)	0.000
C20	0.031 (2)	0.024 (3)	0.046 (3)	0.000	0.010 (2)	0.000
C21	0.0267 (15)	0.0289 (18)	0.0340 (16)	−0.0041 (13)	0.0086 (13)	−0.0063 (12)
C22	0.0241 (15)	0.0244 (17)	0.0271 (14)	−0.0020 (12)	0.0064 (12)	−0.0028 (11)
C23	0.0283 (16)	0.033 (2)	0.0260 (15)	−0.0018 (13)	0.0043 (12)	−0.0054 (12)
O11	0.062 (2)	0.030 (2)	0.042 (2)	0.000	0.0255 (18)	0.000
O12	0.087 (2)	0.069 (2)	0.0308 (14)	0.0485 (17)	0.0157 (14)	0.0130 (13)
O13	0.0320 (13)	0.0404 (15)	0.0374 (12)	0.0012 (11)	0.0086 (10)	0.0076 (10)
O14	0.0568 (15)	0.0361 (15)	0.0267 (12)	−0.0032 (12)	0.0077 (11)	0.0052 (11)
O15	0.032 (4)	0.027 (3)	0.090 (5)	0.000 (2)	0.030 (3)	0.003 (3)

Cu1—N1	1.916 (3)	N5—C16	1.357 (4)
Cu1—N2	1.967 (3)	N6—C15	1.322 (4)
Cu1—O3	2.126 (2)	N6—H6A	0.876 (13)
Cu1—O1	2.142 (2)	N6—H6B	0.88 (3)
Cu1—O5	2.2670 (19)	N7—C16	1.323 (4)
Cu1—O7	2.296 (2)	N7—H7A	0.88 (3)
O1—C1	1.279 (3)	N7—H7B	0.879 (12)
O2—C1	1.237 (3)	N8—C17	1.328 (4)
O3—C7	1.276 (4)	N8—H8A	0.88 (3)
O4—C7	1.242 (3)	N8—H8B	0.88 (3)
O5—C8	1.255 (4)	N9—C19	1.327 (4)
O6—C8	1.256 (3)	N9—C18	1.360 (3)
O7—C14	1.248 (4)	N10—C19	1.367 (3)
O8—C14	1.269 (3)	N10—C19i	1.367 (3)
N1—C2	1.339 (4)	N10—H10A	0.882 (12)
N1—C6	1.343 (4)	N11—C18	1.315 (5)
N2—C13	1.347 (3)	N11—H11A	0.88 (2)
N2—C9	1.350 (4)	N12—C19	1.323 (4)
C1—C2	1.516 (4)	N12—H12A	0.87 (3)
C2—C3	1.377 (4)	N12—H12B	0.876 (13)
C3—C4	1.383 (4)	C18—N9i	1.360 (3)
C3—H3	0.9500	O9—C23	1.209 (4)
C4—C5	1.391 (4)	O10—C23	1.325 (3)
C4—H4	0.9500	O10—H10B	0.85 (3)
C5—C6	1.377 (4)	N13—C22	1.345 (3)
C5—H5	0.9500	N13—C22i	1.345 (3)
C6—C7	1.520 (4)	C20—C21i	1.388 (4)
C8—C9	1.519 (4)	C20—C21	1.388 (4)
C9—C10	1.385 (4)	C20—H20	0.9500
C10—C11	1.388 (4)	C21—C22	1.393 (4)
C10—H10	0.9500	C21—H21	0.9500
C11—C12	1.387 (4)	C22—C23	1.506 (4)
C11—H11	0.9500	O11—H11B	0.81 (3)
C12—C13	1.379 (4)	O12—H12C	0.84 (3)
C12—H12	0.9500	O12—H12D	0.84 (3)
C13—C14	1.512 (4)	O12—H12E	1.274 (14)
N3—C15	1.367 (4)	O13—H13A	0.84 (3)
N3—C17	1.368 (4)	O13—H13B	0.84 (3)
N3—H3A	0.874 (10)	O14—H14A	0.84 (3)
N4—C15	1.332 (3)	O14—H14B	0.84 (3)
N4—C16	1.355 (4)	O15—H15A	0.84 (3)
N5—C17	1.329 (3)	O15—H15B	0.84 (3)
N1—Cu1—N2	176.51 (9)	N2—C13—C14	113.9 (3)
N1—Cu1—O3	79.24 (9)	C12—C13—C14	123.7 (2)
N2—Cu1—O3	103.15 (9)	O7—C14—O8	126.2 (3)
N1—Cu1—O1	78.83 (9)	O7—C14—C13	117.7 (2)
N2—Cu1—O1	98.79 (9)	O8—C14—C13	116.1 (3)
O3—Cu1—O1	158.06 (8)	C15—N3—C17	119.5 (2)
N1—Cu1—O5	105.67 (8)	C15—N3—H3A	119.4 (19)
N2—Cu1—O5	76.75 (8)	C17—N3—H3A	121.0 (19)
O3—Cu1—O5	95.97 (8)	C15—N4—C16	115.6 (3)
O1—Cu1—O5	89.28 (8)	C17—N5—C16	116.2 (2)
N1—Cu1—O7	101.42 (9)	C15—N6—H6A	123 (2)
N2—Cu1—O7	76.13 (8)	C15—N6—H6B	120 (2)
O3—Cu1—O7	90.42 (7)	H6A—N6—H6B	116 (3)
O1—Cu1—O7	94.57 (7)	C16—N7—H7A	122 (2)
O5—Cu1—O7	152.87 (8)	C16—N7—H7B	120 (2)
C1—O1—Cu1	112.94 (18)	H7A—N7—H7B	119 (3)
C7—O3—Cu1	113.53 (18)	C17—N8—H8A	117 (2)
C8—O5—Cu1	111.97 (16)	C17—N8—H8B	122 (2)
C14—O7—Cu1	111.32 (18)	H8A—N8—H8B	121 (3)
C2—N1—C6	121.0 (3)	N6—C15—N4	120.7 (3)
C2—N1—Cu1	119.6 (2)	N6—C15—N3	117.6 (2)
C6—N1—Cu1	119.2 (2)	N4—C15—N3	121.7 (3)
C13—N2—C9	118.8 (3)	N7—C16—N4	117.3 (3)
C13—N2—Cu1	120.9 (2)	N7—C16—N5	116.8 (3)
C9—N2—Cu1	120.15 (18)	N4—C16—N5	125.9 (2)
O2—C1—O1	126.2 (3)	N8—C17—N5	120.3 (3)
O2—C1—C2	118.7 (3)	N8—C17—N3	118.6 (2)
O1—C1—C2	115.1 (3)	N5—C17—N3	121.1 (3)
N1—C2—C3	121.0 (3)	C19—N9—C18	116.1 (2)
N1—C2—C1	112.9 (3)	C19—N10—C19i	119.1 (4)
C3—C2—C1	126.0 (3)	C19—N10—H10A	120.47 (18)
C2—C3—C4	118.7 (3)	C19i—N10—H10A	120.47 (18)
C2—C3—H3	120.7	C18—N11—H11A	123 (2)
C4—C3—H3	120.7	C19—N12—H12A	119 (2)
C3—C4—C5	119.9 (3)	C19—N12—H12B	121 (2)
C3—C4—H4	120.1	H12A—N12—H12B	120 (3)
C5—C4—H4	120.1	N11—C18—N9i	117.36 (18)
C6—C5—C4	118.7 (3)	N11—C18—N9	117.36 (18)
C6—C5—H5	120.6	N9i—C18—N9	125.3 (4)
C4—C5—H5	120.6	N12—C19—N9	120.6 (3)
N1—C6—C5	120.7 (3)	N12—C19—N10	117.6 (3)
N1—C6—C7	112.9 (3)	N9—C19—N10	121.7 (3)
C5—C6—C7	126.4 (3)	C23—O10—H10B	110 (3)
O4—C7—O3	126.5 (3)	C22—N13—C22i	117.0 (3)
O4—C7—C6	118.7 (3)	C21i—C20—C21	118.9 (4)
O3—C7—C6	114.8 (3)	C21i—C20—H20	120.5
O5—C8—O6	125.7 (3)	C21—C20—H20	120.5
O5—C8—C9	117.0 (3)	C20—C21—C22	118.5 (3)
O6—C8—C9	117.4 (3)	C20—C21—H21	120.7
N2—C9—C10	121.8 (3)	C22—C21—H21	120.7
N2—C9—C8	114.0 (3)	N13—C22—C21	123.5 (3)
C10—C9—C8	124.3 (3)	N13—C22—C23	114.2 (3)
C9—C10—C11	119.1 (3)	C21—C22—C23	122.3 (2)
C9—C10—H10	120.4	O9—C23—O10	122.8 (3)
C11—C10—H10	120.4	O9—C23—C22	123.3 (2)
C12—C11—C10	119.0 (3)	O10—C23—C22	113.9 (3)
C12—C11—H11	120.5	H12C—O12—H12D	118 (4)
C10—C11—H11	120.5	H12C—O12—H12E	130 (4)
C13—C12—C11	119.0 (3)	H12D—O12—H12E	109 (4)
C13—C12—H12	120.5	H13A—O13—H13B	102 (4)
C11—C12—H12	120.5	H14A—O14—H14B	109 (4)
N2—C13—C12	122.3 (3)	H15A—O15—H15B	102 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O6	0.87 (3)	1.90 (1)	2.766 (3)	168 (3)
N6—H6A···O4ii	0.88 (1)	2.06 (2)	2.880 (4)	155 (3)
N6—H6B···O5	0.88 (3)	2.01 (1)	2.872 (3)	167 (3)
N7—H7A···N9iii	0.88 (3)	2.09 (1)	2.965 (3)	176 (3)
N7—H7B···O9iii	0.88 (1)	2.13 (3)	2.815 (3)	134 (3)
N8—H8B···O14	0.88 (3)	1.96 (1)	2.842 (3)	177 (3)
N10—H10A···O15	0.88 (1)	1.78 (1)	2.649 (6)	167 (2)
N11—H11A···O9i	0.88 (3)	2.06 (1)	2.939 (3)	172 (3)
N12—H12A···N5iii	0.87 (3)	2.09 (1)	2.959 (4)	173 (3)
N12—H12B···O1	0.88 (1)	2.07 (2)	2.846 (3)	146 (3)
O10—H10B···O13	0.85 (3)	1.83 (3)	2.671 (3)	172 (4)
O11—H11B···O2iv	0.81 (3)	2.10 (3)	2.896 (3)	167 (4)
O12—H12C···O8i	0.84 (3)	1.72 (3)	2.555 (3)	173 (4)
O12—H12D···O2	0.84 (3)	1.89 (4)	2.700 (3)	162 (5)
O12—H12E···O12iv	1.27 (1)	1.27 (1)	2.518 (5)	162 (8)
O13—H13A···O4v	0.84 (3)	2.04 (3)	2.870 (3)	172 (4)
O13—H13B···N4iii	0.84 (3)	2.07 (2)	2.876 (3)	162 (4)
O14—H14A···O6	0.84 (3)	1.83 (1)	2.662 (3)	172 (3)
O14—H14B···O3v	0.84 (3)	2.05 (4)	2.850 (3)	160 (4)
O15—H15A···O11vi	0.84 (3)	1.98 (6)	2.748 (6)	151 (11)
O15—H15B···O7i	0.84 (3)	1.82 (2)	2.636 (5)	163 (7)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O6	0.87 (3)	1.903 (12)	2.766 (3)	168 (3)
N6—H6A⋯O4i	0.876 (13)	2.062 (17)	2.880 (4)	155 (3)
N6—H6B⋯O5	0.88 (3)	2.007 (12)	2.872 (3)	167 (3)
N7—H7A⋯N9ii	0.88 (3)	2.086 (11)	2.965 (3)	176 (3)
N7—H7B⋯O9ii	0.879 (12)	2.13 (3)	2.815 (3)	134 (3)
N8—H8B⋯O14	0.88 (3)	1.964 (11)	2.842 (3)	177 (3)
N10—H10A⋯O15	0.882 (12)	1.782 (12)	2.649 (6)	167 (2)
N11—H11A⋯O9iii	0.88 (3)	2.064 (11)	2.939 (3)	172 (3)
N12—H12A⋯N5ii	0.87 (3)	2.090 (12)	2.959 (4)	173 (3)
N12—H12B⋯O1	0.882 (12)	2.07 (2)	2.846 (3)	146 (3)
O10—H10B⋯O13	0.85 (3)	1.83 (3)	2.671 (3)	172 (4)
O11—H11B⋯O2iv	0.81 (3)	2.10 (3)	2.896 (3)	167 (4)
O12—H12C⋯O8iii	0.84 (3)	1.72 (3)	2.555 (3)	173 (4)
O12—H12D⋯O2	0.84 (3)	1.89 (4)	2.700 (3)	162 (5)
O12—H12E⋯O12iv	1.274 (14)	1.274 (14)	2.518 (5)	162 (8)
O13—H13A⋯O4v	0.84 (3)	2.04 (3)	2.870 (3)	172 (4)
O13—H13B⋯N4ii	0.84 (3)	2.066 (17)	2.876 (3)	162 (4)
O14—H14A⋯O6	0.84 (3)	1.831 (12)	2.662 (3)	172 (3)
O14—H14B⋯O3v	0.84 (3)	2.05 (4)	2.850 (3)	160 (4)
O15—H15A⋯O11vi	0.84 (3)	1.98 (6)	2.748 (6)	151 (11)
O15—H15B⋯O7iii	0.84 (3)	1.82 (2)	2.636 (5)	163 (7)

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