[Di-aqua-sesqui(nitrato-κO)hemi(perchlorato-κO)copper(II)]-μ-{bis-[5-methyl-3-(pyridin-2-yl)-1H-pyrazol-4-yl] selenide}-[tri-aqua-(perchlorato-κO)copper(II)] nitrate monohydrate.

In the binuclear title complex, [Cu2(ClO4)1.5(NO3)1.5(C18H16N6Se)(H2O)5]NO3·H2O, both Cu(II) ions are hexa-coordinated by O and N atoms, thus forming axially elongated CuO4N2 octa-hedra. The equatorial plane of each octa-hedron is formed by one chelating pyrazole-pyridine fragment of the organic ligand and two water mol-ecules. The axial positions in one octa-hedron are occupied by a water mol-ecule and a monodentately coordinated perchlorate anion, while those in the other are occupied by a nitrate anion and a disordered perchlorate/nitrate anion with equal site occupancy. The pyrazole-pyridine units of the organic selenide are trans-oriented to each other with a C-Se-C angle of 96.01 (14)°. In the crystal, uncoordinated nitrate anions and the coordinating water mol-ecules are involved in O-H⋯O and N-H⋯O hydrogen bonds, forming a bridge between the pyrazole group and the coordinating water mol-ecules. Further O-H⋯O hydrogen bonds between the complex mol-ecules and a π-π stacking inter-action with a centroid-centroid distance of 3.834 (4) Å are also observed.

Related literature

For structural studies of related pyrazolylselenides, see: Seredyuk et al. (2010 ▶) and for structural studies of d-metal complexes of bis­(3,5-dimethyl-1H-pyrazol-4-yl)selenide, see: Seredyuk et al. (2007 ▶). For related structures, see: Fritsky et al. (2004 ▶); Kanderal et al. (2005 ▶); Moroz et al. (2010 ▶).

Experimental

Crystal data

[Cu2(ClO4)1.5(NO3)1.5(C18H16N6Se)(H2O)5]NO3·H2O

M = 934.72

Triclinic,

a = 9.7233 (6) Å

b = 13.1987 (7) Å

c = 13.3217 (8) Å

α = 93.510 (4)°

β = 108.858 (5)°

γ = 93.494 (4)°

V = 1608.93 (16) Å3

Z = 2

Mo Kα radiation

μ = 2.67 mm−1

T = 100 K

0.30 × 0.25 × 0.12 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.468, T max = 0.728

11167 measured reflections

7085 independent reflections

5817 reflections with I > 2σ(I)

R int = 0.073

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.113

S = 1.02

7085 reflections

498 parameters

12 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.00 e Å−3

Δρmin = −0.95 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2009 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813012178/is5261sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813012178/is5261Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813012178/is5261Isup3.cdx

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

[Cu2(ClO4)1.5(NO3)1.5(C18H16N6Se)(H2O)5]NO3·H2O	Z = 2
Mr = 934.72	F(000) = 938
Triclinic, P1	Dx = 1.929 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.7233 (6) Å	Cell parameters from 6705 reflections
b = 13.1987 (7) Å	θ = 2.6–30.3°
c = 13.3217 (8) Å	µ = 2.67 mm−1
α = 93.510 (4)°	T = 100 K
β = 108.858 (5)°	Block, green
γ = 93.494 (4)°	0.30 × 0.25 × 0.12 mm
V = 1608.93 (16) Å3

Bruker SMART APEXII CCD diffractometer	7085 independent reflections
Radiation source: fine-focus sealed tube	5817 reflections with I > 2σ(I)
Flat graphite crystal monochromator	Rint = 0.073
Detector resolution: 16 pixels mm-1	θmax = 28.4°, θmin = 3.5°
φ and ω scans	h = −10→12
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −17→17
Tmin = 0.468, Tmax = 0.728	l = −17→16
11167 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0615P)2] where P = (Fo2 + 2Fc2)/3
7085 reflections	(Δ/σ)max = 0.001
498 parameters	Δρmax = 1.00 e Å−3
12 restraints	Δρmin = −0.95 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.

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 > 2sigma(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)
Se	0.30579 (4)	0.28810 (2)	0.04893 (3)	0.01672 (10)
Cu1	0.07983 (4)	0.55346 (3)	0.31262 (3)	0.01379 (10)
Cu2	0.60531 (4)	−0.03338 (3)	0.28618 (3)	0.01818 (11)
Cl1	0.08419 (9)	0.80696 (6)	0.22351 (8)	0.02334 (19)
O1	0.2168 (3)	0.63956 (19)	0.4340 (2)	0.0209 (5)
H2O1	0.284 (4)	0.669 (3)	0.419 (4)	0.031*
H1O1	0.173 (4)	0.680 (3)	0.457 (3)	0.031*
O2	−0.0895 (2)	0.57907 (18)	0.35723 (19)	0.0166 (5)
H1O2	−0.137 (4)	0.626 (2)	0.329 (3)	0.025*
H2O2	−0.079 (4)	0.577 (3)	0.4215 (17)	0.025*
O1W	0.2383 (3)	0.01642 (19)	0.4205 (2)	0.0228 (5)
H1W1	0.181 (4)	0.059 (3)	0.428 (4)	0.034*
H2W1	0.216 (5)	−0.0443 (17)	0.397 (4)	0.034*
O3	0.1043 (3)	0.42346 (18)	0.4361 (2)	0.0192 (5)
H1O3	0.189 (3)	0.406 (3)	0.457 (3)	0.029*
H2O3	0.056 (4)	0.370 (2)	0.410 (3)	0.029*
O4	0.5283 (3)	−0.06721 (19)	0.4011 (2)	0.0214 (5)
H1O4	0.505 (5)	−0.1278 (17)	0.405 (4)	0.032*
H2O4	0.596 (4)	−0.049 (3)	0.458 (2)	0.032*
O5	0.7923 (3)	−0.08153 (19)	0.3647 (2)	0.0245 (6)
H1O5	0.802 (5)	−0.139 (2)	0.341 (4)	0.037*
H2O5	0.865 (3)	−0.045 (3)	0.362 (4)	0.037*
O6	0.0385 (3)	0.8548 (2)	0.3056 (3)	0.0499 (10)
O7	0.0311 (3)	0.8566 (2)	0.1280 (3)	0.0410 (8)
O8	0.2401 (3)	0.8125 (2)	0.2577 (2)	0.0368 (7)
O9	0.0257 (3)	0.70178 (18)	0.2037 (2)	0.0287 (6)
O10	0.4717 (3)	0.72896 (18)	0.4218 (2)	0.0255 (6)
O11	0.5918 (3)	0.59929 (17)	0.4819 (2)	0.0218 (5)
O12	0.6898 (3)	0.75338 (19)	0.5375 (2)	0.0299 (6)
O13	0.7312 (3)	−0.2750 (2)	0.2985 (3)	0.0379 (7)
O14	0.5604 (3)	−0.36909 (19)	0.1776 (2)	0.0290 (6)
O15	0.5431 (3)	−0.20641 (19)	0.1993 (2)	0.0249 (5)
N1	0.2334 (3)	0.4991 (2)	0.2624 (2)	0.0149 (5)
N2	0.3773 (3)	0.4906 (2)	0.3050 (2)	0.0159 (5)
H1N2	0.4325	0.5242	0.3628	0.019*
N3	−0.0450 (3)	0.47889 (19)	0.1744 (2)	0.0145 (5)
N4	0.4412 (3)	0.0459 (2)	0.2249 (2)	0.0169 (6)
N5	0.3236 (3)	0.0687 (2)	0.2505 (2)	0.0179 (6)
H1N5	0.2936	0.0381	0.2958	0.021*
N6	0.6606 (3)	0.0214 (2)	0.1646 (2)	0.0191 (6)
N7	0.5859 (3)	0.6952 (2)	0.4812 (2)	0.0188 (6)
N8	0.6108 (3)	−0.2844 (2)	0.2239 (2)	0.0188 (6)
C1	0.5770 (3)	0.3955 (3)	0.2785 (3)	0.0219 (7)
H1A	0.6415	0.4534	0.3163	0.033*
H1B	0.6008	0.3744	0.2163	0.033*
H1C	0.5877	0.3407	0.3239	0.033*
C2	0.4246 (4)	0.4232 (2)	0.2463 (3)	0.0161 (6)
C3	0.3034 (3)	0.3858 (2)	0.1598 (3)	0.0143 (6)
C4	0.1865 (3)	0.4339 (2)	0.1747 (3)	0.0140 (6)
C5	0.0275 (3)	0.4270 (2)	0.1190 (3)	0.0140 (6)
C6	−0.0450 (4)	0.3737 (2)	0.0211 (3)	0.0171 (6)
H6	0.0063	0.3376	−0.0152	0.021*
C7	−0.1951 (4)	0.3752 (2)	−0.0219 (3)	0.0187 (7)
H7	−0.2458	0.3391	−0.0869	0.022*
C8	−0.2691 (4)	0.4306 (3)	0.0323 (3)	0.0188 (7)
H8	−0.3695	0.4336	0.0038	0.023*
C9	−0.1901 (3)	0.4817 (2)	0.1305 (3)	0.0177 (7)
H9	−0.2395	0.5192	0.1672	0.021*
C10	0.1243 (4)	0.1828 (3)	0.2098 (3)	0.0210 (7)
H10A	0.0756	0.1312	0.2370	0.031*
H10B	0.0607	0.1990	0.1420	0.031*
H10C	0.1498	0.2428	0.2586	0.031*
C11	0.2582 (3)	0.1449 (2)	0.1969 (3)	0.0170 (6)
C12	0.3424 (3)	0.1760 (2)	0.1345 (3)	0.0151 (6)
C13	0.4547 (4)	0.1103 (2)	0.1543 (3)	0.0161 (6)
C14	0.5762 (3)	0.0938 (2)	0.1147 (3)	0.0169 (6)
C15	0.6019 (4)	0.1410 (2)	0.0314 (3)	0.0180 (7)
H15	0.5442	0.1914	−0.0008	0.022*
C16	0.7149 (4)	0.1119 (3)	−0.0031 (3)	0.0205 (7)
H16	0.7333	0.1419	−0.0594	0.025*
C17	0.8007 (4)	0.0369 (3)	0.0477 (3)	0.0228 (7)
H17	0.8768	0.0159	0.0257	0.027*
C18	0.7700 (4)	−0.0058 (3)	0.1317 (3)	0.0219 (7)
H18	0.8278	−0.0550	0.1662	0.026*
Cl2	0.8810 (3)	0.1792 (2)	0.3891 (2)	0.0147 (5)	0.50
O16	0.9609 (11)	0.0934 (7)	0.3751 (9)	0.0270 (7)	0.50
O17	0.8847 (5)	0.2502 (4)	0.3146 (5)	0.0270 (7)	0.50
O18	0.9531 (6)	0.2249 (4)	0.4990 (5)	0.0270 (7)	0.50
O19	0.7361 (11)	0.1453 (8)	0.3799 (7)	0.0270 (7)	0.50
N9	0.8701 (15)	0.1712 (11)	0.4062 (11)	0.0188 (6)	0.50
O20	0.9164 (6)	0.2618 (4)	0.4398 (6)	0.0363 (11)	0.50
O21	0.7413 (12)	0.1391 (8)	0.4031 (8)	0.0363 (11)	0.50
O22	0.9545 (12)	0.1050 (7)	0.3892 (10)	0.0363 (11)	0.50

	U11	U22	U33	U12	U13	U23
Se	0.02294 (18)	0.01469 (16)	0.01541 (17)	0.00675 (12)	0.00905 (13)	0.00297 (12)
Cu1	0.01339 (19)	0.01215 (19)	0.0161 (2)	0.00040 (14)	0.00579 (15)	−0.00181 (15)
Cu2	0.0180 (2)	0.0160 (2)	0.0223 (2)	0.00449 (15)	0.00766 (17)	0.00644 (17)
Cl1	0.0206 (4)	0.0162 (4)	0.0349 (5)	0.0012 (3)	0.0124 (4)	−0.0028 (3)
O1	0.0184 (12)	0.0196 (12)	0.0252 (13)	−0.0029 (10)	0.0102 (10)	−0.0060 (10)
O2	0.0161 (11)	0.0188 (11)	0.0161 (12)	0.0067 (9)	0.0059 (9)	0.0029 (10)
O1W	0.0244 (13)	0.0199 (12)	0.0251 (14)	−0.0013 (10)	0.0110 (11)	−0.0021 (11)
O3	0.0206 (12)	0.0156 (11)	0.0223 (13)	0.0012 (9)	0.0080 (10)	0.0033 (10)
O4	0.0241 (13)	0.0173 (12)	0.0221 (13)	−0.0002 (10)	0.0065 (10)	0.0041 (10)
O5	0.0217 (13)	0.0182 (12)	0.0334 (15)	0.0038 (10)	0.0080 (11)	0.0050 (11)
O6	0.0407 (18)	0.0424 (18)	0.072 (2)	−0.0143 (14)	0.0361 (17)	−0.0361 (18)
O7	0.0314 (16)	0.0275 (14)	0.064 (2)	0.0057 (12)	0.0119 (15)	0.0213 (15)
O8	0.0202 (14)	0.0473 (18)	0.0435 (18)	0.0056 (12)	0.0102 (12)	0.0067 (14)
O9	0.0479 (17)	0.0127 (12)	0.0239 (14)	−0.0045 (11)	0.0119 (12)	−0.0032 (10)
O10	0.0159 (12)	0.0209 (12)	0.0356 (16)	0.0022 (10)	0.0013 (11)	0.0113 (11)
O11	0.0239 (13)	0.0132 (11)	0.0247 (13)	0.0002 (9)	0.0030 (10)	0.0025 (10)
O12	0.0255 (14)	0.0192 (12)	0.0347 (16)	−0.0033 (10)	−0.0023 (11)	−0.0044 (11)
O13	0.0268 (15)	0.0255 (14)	0.0448 (18)	0.0119 (12)	−0.0116 (13)	−0.0029 (13)
O14	0.0273 (14)	0.0223 (13)	0.0324 (15)	0.0000 (11)	0.0039 (11)	−0.0017 (12)
O15	0.0233 (13)	0.0240 (13)	0.0262 (14)	0.0090 (10)	0.0041 (10)	0.0082 (11)
N1	0.0136 (13)	0.0120 (12)	0.0200 (14)	−0.0001 (10)	0.0065 (11)	0.0019 (11)
N2	0.0143 (13)	0.0152 (13)	0.0174 (14)	0.0002 (10)	0.0049 (11)	−0.0002 (11)
N3	0.0151 (13)	0.0113 (12)	0.0180 (14)	−0.0006 (10)	0.0076 (11)	−0.0014 (11)
N4	0.0208 (14)	0.0136 (13)	0.0194 (15)	0.0049 (11)	0.0094 (11)	0.0055 (11)
N5	0.0164 (13)	0.0190 (14)	0.0212 (15)	0.0012 (11)	0.0092 (11)	0.0067 (12)
N6	0.0207 (14)	0.0165 (13)	0.0205 (15)	0.0020 (11)	0.0071 (12)	0.0027 (12)
N7	0.0177 (14)	0.0167 (13)	0.0227 (15)	0.0008 (11)	0.0073 (12)	0.0036 (12)
N8	0.0166 (13)	0.0199 (14)	0.0211 (15)	0.0055 (11)	0.0067 (11)	0.0057 (11)
C1	0.0149 (16)	0.0207 (16)	0.031 (2)	0.0023 (13)	0.0085 (14)	0.0022 (15)
C2	0.0193 (16)	0.0127 (14)	0.0189 (16)	0.0009 (12)	0.0094 (13)	0.0047 (13)
C3	0.0168 (15)	0.0129 (14)	0.0156 (15)	0.0032 (12)	0.0082 (12)	0.0011 (12)
C4	0.0180 (15)	0.0105 (14)	0.0139 (15)	−0.0005 (12)	0.0060 (12)	0.0021 (12)
C5	0.0149 (15)	0.0123 (14)	0.0158 (16)	0.0012 (11)	0.0059 (12)	0.0028 (12)
C6	0.0209 (16)	0.0139 (15)	0.0168 (16)	0.0014 (12)	0.0072 (13)	−0.0030 (13)
C7	0.0225 (17)	0.0141 (15)	0.0161 (16)	−0.0009 (13)	0.0022 (13)	0.0007 (13)
C8	0.0157 (15)	0.0194 (16)	0.0186 (17)	−0.0006 (13)	0.0025 (13)	0.0011 (13)
C9	0.0171 (16)	0.0185 (16)	0.0174 (17)	−0.0007 (13)	0.0064 (13)	0.0002 (13)
C10	0.0188 (16)	0.0198 (16)	0.0272 (19)	0.0021 (13)	0.0106 (14)	0.0051 (14)
C11	0.0155 (15)	0.0162 (15)	0.0179 (16)	−0.0015 (12)	0.0043 (13)	−0.0007 (13)
C12	0.0180 (15)	0.0111 (14)	0.0146 (16)	−0.0002 (12)	0.0035 (12)	0.0009 (12)
C13	0.0201 (16)	0.0120 (14)	0.0161 (16)	0.0001 (12)	0.0057 (13)	0.0018 (12)
C14	0.0172 (15)	0.0104 (14)	0.0215 (17)	0.0004 (12)	0.0048 (13)	−0.0021 (13)
C15	0.0203 (16)	0.0126 (14)	0.0209 (17)	−0.0006 (12)	0.0069 (13)	0.0000 (13)
C16	0.0266 (18)	0.0179 (16)	0.0193 (17)	0.0003 (13)	0.0111 (14)	0.0015 (14)
C17	0.0197 (17)	0.0241 (18)	0.0263 (19)	0.0003 (14)	0.0115 (14)	−0.0037 (15)
C18	0.0218 (17)	0.0196 (16)	0.0250 (19)	0.0065 (14)	0.0079 (14)	0.0023 (14)
Cl2	0.0151 (9)	0.0085 (8)	0.0224 (13)	−0.0033 (6)	0.0107 (7)	−0.0058 (8)
O16	0.0208 (15)	0.0273 (16)	0.0354 (19)	0.0073 (12)	0.0117 (13)	0.0038 (14)
O17	0.0208 (15)	0.0273 (16)	0.0354 (19)	0.0073 (12)	0.0117 (13)	0.0038 (14)
O18	0.0208 (15)	0.0273 (16)	0.0354 (19)	0.0073 (12)	0.0117 (13)	0.0038 (14)
O19	0.0208 (15)	0.0273 (16)	0.0354 (19)	0.0073 (12)	0.0117 (13)	0.0038 (14)
N9	0.0166 (13)	0.0199 (14)	0.0211 (15)	0.0055 (11)	0.0067 (11)	0.0057 (11)
O20	0.034 (2)	0.0206 (19)	0.061 (3)	−0.0118 (16)	0.030 (2)	−0.0110 (19)
O21	0.034 (2)	0.0206 (19)	0.061 (3)	−0.0118 (16)	0.030 (2)	−0.0110 (19)
O22	0.034 (2)	0.0206 (19)	0.061 (3)	−0.0118 (16)	0.030 (2)	−0.0110 (19)

Se—C12	1.904 (3)	N4—N5	1.340 (4)
Se—C3	1.907 (3)	N5—C11	1.341 (4)
Cu1—O2	1.963 (2)	N5—H1N5	0.8600
Cu1—O1	1.969 (3)	N6—C18	1.334 (4)
Cu1—N1	1.978 (3)	N6—C14	1.360 (4)
Cu1—N3	2.005 (3)	C1—C2	1.479 (4)
Cu1—O3	2.419 (3)	C1—H1A	0.9600
Cu1—O9	2.489 (3)	C1—H1B	0.9600
Cu2—N4	1.942 (3)	C1—H1C	0.9600
Cu2—O5	1.948 (3)	C2—C3	1.394 (5)
Cu2—O4	1.972 (3)	C3—C4	1.398 (4)
Cu2—N6	2.023 (3)	C4—C5	1.477 (4)
Cu2—O15	2.445 (3)	C5—C6	1.388 (4)
Cu2—O19	2.643 (11)	C6—C7	1.387 (5)
Cl1—O7	1.426 (3)	C6—H6	0.9300
Cl1—O8	1.431 (3)	C7—C8	1.382 (5)
Cl1—O6	1.434 (3)	C7—H7	0.9300
Cl1—O9	1.443 (3)	C8—C9	1.391 (5)
O1—H2O1	0.826 (19)	C8—H8	0.9300
O1—H1O1	0.805 (19)	C9—H9	0.9300
O2—H1O2	0.834 (19)	C10—C11	1.479 (4)
O2—H2O2	0.831 (19)	C10—H10A	0.9600
O1W—H1W1	0.836 (19)	C10—H10B	0.9600
O1W—H2W1	0.832 (19)	C10—H10C	0.9600
O3—H1O3	0.831 (19)	C11—C12	1.403 (5)
O3—H2O3	0.818 (19)	C12—C13	1.404 (5)
O4—H1O4	0.829 (19)	C13—C14	1.464 (5)
O4—H2O4	0.836 (19)	C14—C15	1.388 (5)
O5—H1O5	0.823 (19)	C15—C16	1.386 (5)
O5—H2O5	0.842 (19)	C15—H15	0.9300
O10—N7	1.262 (4)	C16—C17	1.397 (5)
O11—N7	1.271 (3)	C16—H16	0.9300
O12—N7	1.232 (4)	C17—C18	1.389 (5)
O13—N8	1.260 (4)	C17—H17	0.9300
O14—N8	1.234 (4)	C18—H18	0.9300
O15—N8	1.259 (4)	Cl2—O17	1.413 (6)
N1—C4	1.340 (4)	Cl2—O19	1.415 (11)
N1—N2	1.344 (4)	Cl2—O16	1.447 (8)
N2—C2	1.346 (4)	Cl2—O18	1.475 (7)
N2—H1N2	0.8600	N9—O20	1.255 (15)
N3—C9	1.346 (4)	N9—O21	1.285 (17)
N3—C5	1.357 (4)	N9—O22	1.293 (15)
N4—C13	1.337 (4)
C12—Se—C3	96.01 (14)	O10—N7—O11	118.5 (3)
O2—Cu1—O1	93.43 (10)	O14—N8—O15	121.3 (3)
O2—Cu1—N1	168.52 (10)	O14—N8—O13	120.1 (3)
O1—Cu1—N1	94.85 (11)	O15—N8—O13	118.6 (3)
O2—Cu1—N3	92.57 (11)	C2—C1—H1A	109.5
O1—Cu1—N3	170.62 (11)	C2—C1—H1B	109.5
N1—Cu1—N3	80.28 (11)	H1A—C1—H1B	109.5
O2—Cu1—O3	81.67 (9)	C2—C1—H1C	109.5
O1—Cu1—O3	85.52 (10)	H1A—C1—H1C	109.5
N1—Cu1—O3	91.06 (10)	H1B—C1—H1C	109.5
N3—Cu1—O3	102.50 (10)	N2—C2—C3	106.6 (3)
O2—Cu1—O9	88.12 (10)	N2—C2—C1	122.8 (3)
O1—Cu1—O9	91.62 (10)	C3—C2—C1	130.5 (3)
N1—Cu1—O9	99.57 (11)	C2—C3—C4	105.2 (3)
N3—Cu1—O9	81.37 (10)	C2—C3—Se	125.1 (2)
O3—Cu1—O9	169.20 (9)	C4—C3—Se	129.7 (2)
N4—Cu2—O5	166.31 (12)	N1—C4—C3	110.2 (3)
N4—Cu2—O4	90.67 (11)	N1—C4—C5	114.8 (3)
O5—Cu2—O4	90.21 (11)	C3—C4—C5	135.0 (3)
N4—Cu2—N6	79.71 (12)	N3—C5—C6	121.7 (3)
O5—Cu2—N6	98.40 (12)	N3—C5—C4	112.7 (3)
O4—Cu2—N6	169.88 (11)	C6—C5—C4	125.6 (3)
N4—Cu2—O15	107.91 (11)	C7—C6—C5	119.0 (3)
O5—Cu2—O15	85.70 (10)	C7—C6—H6	120.5
O4—Cu2—O15	92.59 (10)	C5—C6—H6	120.5
N6—Cu2—O15	93.36 (11)	C8—C7—C6	119.7 (3)
N4—Cu2—O19	83.5 (2)	C8—C7—H7	120.2
O5—Cu2—O19	82.9 (2)	C6—C7—H7	120.2
O4—Cu2—O19	95.1 (2)	C7—C8—C9	118.5 (3)
N6—Cu2—O19	80.7 (2)	C7—C8—H8	120.7
O15—Cu2—O19	166.2 (2)	C9—C8—H8	120.7
O7—Cl1—O8	109.63 (18)	N3—C9—C8	122.4 (3)
O7—Cl1—O6	110.2 (2)	N3—C9—H9	118.8
O8—Cl1—O6	109.33 (19)	C8—C9—H9	118.8
O7—Cl1—O9	109.16 (18)	C11—C10—H10A	109.5
O8—Cl1—O9	109.82 (18)	C11—C10—H10B	109.5
O6—Cl1—O9	108.64 (17)	H10A—C10—H10B	109.5
Cu1—O1—H2O1	113 (3)	C11—C10—H10C	109.5
Cu1—O1—H1O1	110 (3)	H10A—C10—H10C	109.5
H2O1—O1—H1O1	110 (4)	H10B—C10—H10C	109.5
Cu1—O2—H1O2	115 (3)	N5—C11—C12	106.6 (3)
Cu1—O2—H2O2	117 (3)	N5—C11—C10	122.1 (3)
H1O2—O2—H2O2	114 (4)	C12—C11—C10	131.3 (3)
H1W1—O1W—H2W1	127 (4)	C11—C12—C13	104.9 (3)
Cu1—O3—H1O3	111 (3)	C11—C12—Se	124.4 (2)
Cu1—O3—H2O3	114 (3)	C13—C12—Se	130.6 (3)
H1O3—O3—H2O3	103 (4)	N4—C13—C12	109.7 (3)
Cu2—O4—H1O4	118 (3)	N4—C13—C14	114.3 (3)
Cu2—O4—H2O4	105 (3)	C12—C13—C14	136.0 (3)
H1O4—O4—H2O4	106 (4)	N6—C14—C15	121.8 (3)
Cu2—O5—H1O5	112 (3)	N6—C14—C13	112.7 (3)
Cu2—O5—H2O5	114 (3)	C15—C14—C13	125.3 (3)
H1O5—O5—H2O5	105 (4)	C16—C15—C14	119.0 (3)
Cl1—O9—Cu1	132.23 (16)	C16—C15—H15	120.5
N8—O15—Cu2	128.4 (2)	C14—C15—H15	120.5
C4—N1—N2	106.2 (3)	C15—C16—C17	119.1 (3)
C4—N1—Cu1	115.8 (2)	C15—C16—H16	120.4
N2—N1—Cu1	135.9 (2)	C17—C16—H16	120.4
N1—N2—C2	111.8 (3)	C18—C17—C16	118.7 (3)
N1—N2—H1N2	124.1	C18—C17—H17	120.7
C2—N2—H1N2	124.1	C16—C17—H17	120.7
C9—N3—C5	118.7 (3)	N6—C18—C17	122.4 (3)
C9—N3—Cu1	125.6 (2)	N6—C18—H18	118.8
C5—N3—Cu1	115.6 (2)	C17—C18—H18	118.8
C13—N4—N5	106.9 (3)	O17—Cl2—O19	111.6 (4)
C13—N4—Cu2	116.9 (2)	O17—Cl2—O16	109.9 (5)
N5—N4—Cu2	134.7 (2)	O19—Cl2—O16	110.3 (6)
N4—N5—C11	111.7 (3)	O17—Cl2—O18	110.8 (4)
N4—N5—H1N5	124.1	O19—Cl2—O18	107.5 (5)
C11—N5—H1N5	124.1	O16—Cl2—O18	106.6 (5)
C18—N6—C14	119.0 (3)	Cl2—O19—Cu2	123.9 (6)
C18—N6—Cu2	126.5 (2)	O20—N9—O21	119.1 (12)
C14—N6—Cu2	114.5 (2)	O20—N9—O22	122.0 (12)
O12—N7—O10	121.2 (3)	O21—N9—O22	118.2 (12)
O12—N7—O11	120.3 (3)
O7—Cl1—O9—Cu1	171.1 (2)	C12—Se—C3—C4	−109.6 (3)
O8—Cl1—O9—Cu1	50.8 (3)	N2—N1—C4—C3	−1.9 (3)
O6—Cl1—O9—Cu1	−68.7 (3)	Cu1—N1—C4—C3	−168.2 (2)
O2—Cu1—O9—Cl1	97.4 (2)	N2—N1—C4—C5	176.5 (2)
O1—Cu1—O9—Cl1	4.0 (2)	Cu1—N1—C4—C5	10.2 (3)
N1—Cu1—O9—Cl1	−91.2 (2)	C2—C3—C4—N1	2.1 (4)
N3—Cu1—O9—Cl1	−169.7 (2)	Se—C3—C4—N1	−178.8 (2)
O3—Cu1—O9—Cl1	78.5 (5)	C2—C3—C4—C5	−175.9 (3)
N4—Cu2—O15—N8	−170.6 (3)	Se—C3—C4—C5	3.2 (6)
O5—Cu2—O15—N8	10.9 (3)	C9—N3—C5—C6	−2.7 (5)
O4—Cu2—O15—N8	−79.1 (3)	Cu1—N3—C5—C6	−178.7 (2)
N6—Cu2—O15—N8	109.1 (3)	C9—N3—C5—C4	177.7 (3)
O19—Cu2—O15—N8	45.0 (8)	Cu1—N3—C5—C4	1.7 (3)
O2—Cu1—N1—C4	44.8 (7)	N1—C4—C5—N3	−7.7 (4)
O1—Cu1—N1—C4	−179.2 (2)	C3—C4—C5—N3	170.2 (3)
N3—Cu1—N1—C4	−7.3 (2)	N1—C4—C5—C6	172.7 (3)
O3—Cu1—N1—C4	95.2 (2)	C3—C4—C5—C6	−9.4 (6)
O9—Cu1—N1—C4	−86.7 (2)	N3—C5—C6—C7	1.1 (5)
O2—Cu1—N1—N2	−116.1 (5)	C4—C5—C6—C7	−179.3 (3)
O1—Cu1—N1—N2	20.0 (3)	C5—C6—C7—C8	1.0 (5)
N3—Cu1—N1—N2	−168.1 (3)	C6—C7—C8—C9	−1.5 (5)
O3—Cu1—N1—N2	−65.6 (3)	C5—N3—C9—C8	2.2 (5)
O9—Cu1—N1—N2	112.4 (3)	Cu1—N3—C9—C8	177.8 (2)
C4—N1—N2—C2	1.0 (3)	C7—C8—C9—N3	−0.1 (5)
Cu1—N1—N2—C2	163.1 (2)	N4—N5—C11—C12	−2.0 (4)
O2—Cu1—N3—C9	16.1 (3)	N4—N5—C11—C10	178.8 (3)
N1—Cu1—N3—C9	−172.9 (3)	N5—C11—C12—C13	1.9 (4)
O3—Cu1—N3—C9	98.2 (3)	C10—C11—C12—C13	−179.0 (3)
O9—Cu1—N3—C9	−71.6 (3)	N5—C11—C12—Se	−175.9 (2)
O2—Cu1—N3—C5	−168.2 (2)	C10—C11—C12—Se	3.2 (5)
N1—Cu1—N3—C5	2.8 (2)	C3—Se—C12—C11	53.5 (3)
O3—Cu1—N3—C5	−86.1 (2)	C3—Se—C12—C13	−123.7 (3)
O9—Cu1—N3—C5	104.1 (2)	N5—N4—C13—C12	0.1 (4)
O5—Cu2—N4—C13	70.2 (6)	Cu2—N4—C13—C12	−167.9 (2)
O4—Cu2—N4—C13	163.9 (3)	N5—N4—C13—C14	−178.1 (3)
N6—Cu2—N4—C13	−13.0 (2)	Cu2—N4—C13—C14	14.0 (4)
O15—Cu2—N4—C13	−103.2 (2)	C11—C12—C13—N4	−1.2 (4)
O19—Cu2—N4—C13	68.8 (3)	Se—C12—C13—N4	176.4 (2)
O5—Cu2—N4—N5	−93.4 (6)	C11—C12—C13—C14	176.4 (4)
O4—Cu2—N4—N5	0.2 (3)	Se—C12—C13—C14	−6.0 (6)
N6—Cu2—N4—N5	−176.6 (3)	C18—N6—C14—C15	−0.7 (5)
O15—Cu2—N4—N5	93.1 (3)	Cu2—N6—C14—C15	178.4 (2)
O19—Cu2—N4—N5	−94.9 (4)	C18—N6—C14—C13	175.9 (3)
C13—N4—N5—C11	1.2 (4)	Cu2—N6—C14—C13	−5.0 (4)
Cu2—N4—N5—C11	166.0 (2)	N4—C13—C14—N6	−5.4 (4)
N4—Cu2—N6—C18	−171.4 (3)	C12—C13—C14—N6	177.1 (4)
O5—Cu2—N6—C18	22.3 (3)	N4—C13—C14—C15	171.1 (3)
O4—Cu2—N6—C18	170.3 (5)	C12—C13—C14—C15	−6.5 (6)
O15—Cu2—N6—C18	−63.8 (3)	N6—C14—C15—C16	1.3 (5)
O19—Cu2—N6—C18	103.6 (4)	C13—C14—C15—C16	−174.9 (3)
N4—Cu2—N6—C14	9.6 (2)	C14—C15—C16—C17	−0.8 (5)
O5—Cu2—N6—C14	−156.7 (2)	C15—C16—C17—C18	−0.3 (5)
O4—Cu2—N6—C14	−8.8 (8)	C14—N6—C18—C17	−0.4 (5)
O15—Cu2—N6—C14	117.2 (2)	Cu2—N6—C18—C17	−179.4 (3)
O19—Cu2—N6—C14	−75.4 (3)	C16—C17—C18—N6	0.9 (5)
Cu2—O15—N8—O14	174.3 (2)	O17—Cl2—O19—Cu2	102.8 (5)
Cu2—O15—N8—O13	−4.6 (5)	O16—Cl2—O19—Cu2	−19.7 (8)
N1—N2—C2—C3	0.2 (4)	O18—Cl2—O19—Cu2	−135.5 (4)
N1—N2—C2—C1	−176.7 (3)	N4—Cu2—O19—Cl2	−136.8 (5)
N2—C2—C3—C4	−1.4 (3)	O5—Cu2—O19—Cl2	43.5 (5)
C1—C2—C3—C4	175.2 (3)	O4—Cu2—O19—Cl2	133.1 (5)
N2—C2—C3—Se	179.5 (2)	N6—Cu2—O19—Cl2	−56.3 (5)
C1—C2—C3—Se	−3.9 (5)	O15—Cu2—O19—Cl2	9.3 (12)
C12—Se—C3—C2	69.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H2O1···O10	0.83 (2)	1.93 (2)	2.737 (3)	164 (4)
O1—H1O1···O18i	0.81 (2)	2.00 (2)	2.801 (6)	174 (5)
O1—H1O1···O20i	0.81 (2)	1.99 (3)	2.747 (6)	155 (4)
O2—H1O2···O13ii	0.83 (2)	1.85 (2)	2.660 (3)	163 (4)
O2—H2O2···O3iii	0.83 (2)	1.99 (2)	2.805 (4)	167 (4)
O3—H1O3···O11i	0.83 (2)	2.03 (2)	2.842 (4)	166 (4)
O3—H1O3···O12i	0.83 (2)	2.47 (3)	3.130 (4)	137 (4)
O4—H1O4···O10iv	0.83 (2)	1.94 (2)	2.762 (3)	174 (4)
O4—H2O4···O1Wv	0.84 (2)	1.88 (2)	2.717 (4)	174 (5)
O5—H1O5···O13	0.82 (2)	1.87 (3)	2.617 (4)	150 (4)
O5—H2O5···O16	0.84 (2)	1.97 (3)	2.719 (11)	148 (4)
O5—H2O5···O16	0.84 (2)	1.97 (3)	2.719 (11)	148 (4)
O5—H2O5···O22	0.84 (2)	2.07 (3)	2.784 (10)	142 (4)
O1W—H2W1···O6iv	0.83 (2)	2.10 (3)	2.800 (4)	142 (4)
O1W—H1W1···O16vi	0.84 (2)	2.12 (3)	2.833 (9)	144 (4)
O1W—H1W1···O22vi	0.84 (2)	2.23 (3)	2.977 (11)	149 (4)
N2—H1N2···O11	0.86	1.98	2.829 (4)	168
N5—H1N5···O1W	0.86	1.94	2.762 (4)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H2O1⋯O10	0.83 (2)	1.93 (2)	2.737 (3)	164 (4)
O1—H1O1⋯O18i	0.81 (2)	2.00 (2)	2.801 (6)	174 (5)
O1—H1O1⋯O20i	0.81 (2)	1.99 (3)	2.747 (6)	155 (4)
O2—H1O2⋯O13ii	0.83 (2)	1.85 (2)	2.660 (3)	163 (4)
O2—H2O2⋯O3iii	0.83 (2)	1.99 (2)	2.805 (4)	167 (4)
O3—H1O3⋯O11i	0.83 (2)	2.03 (2)	2.842 (4)	166 (4)
O3—H1O3⋯O12i	0.83 (2)	2.47 (3)	3.130 (4)	137 (4)
O4—H1O4⋯O10iv	0.83 (2)	1.94 (2)	2.762 (3)	174 (4)
O4—H2O4⋯O1W v	0.84 (2)	1.88 (2)	2.717 (4)	174 (5)
O5—H1O5⋯O13	0.82 (2)	1.87 (3)	2.617 (4)	150 (4)
O5—H2O5⋯O16	0.84 (2)	1.97 (3)	2.719 (11)	148 (4)
O5—H2O5⋯O16	0.84 (2)	1.97 (3)	2.719 (11)	148 (4)
O5—H2O5⋯O22	0.84 (2)	2.07 (3)	2.784 (10)	142 (4)
O1W—H2W1⋯O6iv	0.83 (2)	2.10 (3)	2.800 (4)	142 (4)
O1W—H1W1⋯O16vi	0.84 (2)	2.12 (3)	2.833 (9)	144 (4)
O1W—H1W1⋯O22vi	0.84 (2)	2.23 (3)	2.977 (11)	149 (4)
N2—H1N2⋯O11	0.86	1.98	2.829 (4)	168
N5—H1N5⋯O1W	0.86	1.94	2.762 (4)	160

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