3,5-Diamino-4H-1,2,4-triazol-1-ium (6-carb-oxy-pyridine-2-carboxyl-ato)(pyridine-2,6-dicarboxyl-ato)cuprate(II) trihydrate.

In the complex anion of the title compound, (C(2)H(6)N(5))[Cu(C(7)H(4)NO(4))(C(7)H(3)NO(4))]·3H(2)O, the Cu(II) atom is coordinated by tridentate 6-carb-oxy-pyridine-2-carboxyl-ate and pyridine-2,6-dicarboxyl-ate ligands and is surrounded by four O atoms in the equatorial plane and two N atoms in axial positions in a distorted octa-hedral geometry. In the crystal, the components are linked into a three dimensional network by O-H⋯O, N-H⋯O, N-H⋯N and C-H⋯O hydrogen bonds and a π-π inter-action with a centroid-centroid distance of 3.6080 (8) Å.

Related literature

For general background to and applications of supra­molecular arrangements, see: Lehn (1995 ▶); Aghajani et al. (2009 ▶); Tshuva & Lippard (2004 ▶); Kuzelka et al. (2003 ▶). For crystal structures of related complexes, see: Aghabozorg et al. (2007 ▶); Ramos Silva et al. (2008 ▶); Wang et al. (2004 ▶); MacDonald et al. (2004 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

(C2H6N5)[Cu(C7H4NO4)(C7H3NO4)]·3H2O

M = 548.92

Orthorhombic,

a = 11.3091 (2) Å

b = 14.9442 (3) Å

c = 24.6045 (5) Å

V = 4158.29 (14) Å3

Z = 8

Mo Kα radiation

μ = 1.13 mm−1

T = 100 K

0.54 × 0.20 × 0.07 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.583, T max = 0.921

55434 measured reflections

9184 independent reflections

6619 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.098

S = 1.05

9184 reflections

368 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.61 e Å−3

Δρmin = −0.62 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811011147/is2693sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011147/is2693Isup2.hkl

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

(C2H6N5)[Cu(C7H4NO4)(C7H3NO4)]·3H2O	Dx = 1.754 Mg m−3
Mr = 548.92	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9982 reflections
a = 11.3091 (2) Å	θ = 2.4–34.3°
b = 14.9442 (3) Å	µ = 1.13 mm−1
c = 24.6045 (5) Å	T = 100 K
V = 4158.29 (14) Å3	Block, blue
Z = 8	0.54 × 0.20 × 0.07 mm
F(000) = 2248

Bruker SMART APEXII DUO CCD area-detector diffractometer	9184 independent reflections
Radiation source: fine-focus sealed tube	6619 reflections with I > 2σ(I)
graphite	Rint = 0.040
φ and ω scans	θmax = 35.2°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −16→18
Tmin = 0.583, Tmax = 0.921	k = −24→24
55434 measured reflections	l = −35→39

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0419P)2 + 1.6423P] where P = (Fo2 + 2Fc2)/3
9184 reflections	(Δ/σ)max = 0.001
368 parameters	Δρmax = 0.61 e Å−3
0 restraints	Δρmin = −0.62 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) 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
Cu1	0.215732 (15)	0.157389 (11)	0.147781 (7)	0.00961 (5)
O1	0.08015 (9)	0.08189 (7)	0.18273 (4)	0.0134 (2)
O2	0.36032 (9)	0.18850 (7)	0.10156 (4)	0.01296 (19)
O3	0.07633 (9)	0.24435 (7)	0.10732 (4)	0.01269 (19)
O4	0.35335 (9)	0.12522 (7)	0.21908 (4)	0.0141 (2)
O5	−0.02108 (10)	−0.04545 (7)	0.16838 (5)	0.0178 (2)
O6	0.49003 (10)	0.12228 (8)	0.04550 (5)	0.0209 (2)
O7	−0.02109 (9)	0.37240 (7)	0.12527 (4)	0.0146 (2)
O8	0.43168 (10)	0.20192 (7)	0.28899 (4)	0.0153 (2)
N1	0.22886 (10)	0.04926 (8)	0.10717 (5)	0.0101 (2)
N2	0.21368 (10)	0.26548 (8)	0.19377 (5)	0.0093 (2)
N3	0.74524 (12)	0.52025 (8)	0.08876 (5)	0.0135 (2)
N4	0.57456 (11)	0.54813 (8)	0.04709 (5)	0.0132 (2)
N5	0.61177 (11)	0.45979 (8)	0.03913 (5)	0.0131 (2)
N6	0.66479 (13)	0.66858 (9)	0.09430 (6)	0.0173 (3)
N7	0.77259 (13)	0.36686 (10)	0.06458 (7)	0.0211 (3)
C1	0.06033 (13)	0.00591 (9)	0.15837 (6)	0.0122 (2)
C2	0.14997 (12)	−0.01609 (9)	0.11494 (6)	0.0102 (2)
C3	0.15723 (12)	−0.09465 (9)	0.08511 (6)	0.0120 (2)
H3A	0.1014	−0.1397	0.0895	0.014*
C4	0.25034 (13)	−0.10441 (9)	0.04841 (6)	0.0126 (3)
H4A	0.2568	−0.1565	0.0280	0.015*
C5	0.33380 (12)	−0.03646 (9)	0.04217 (6)	0.0125 (3)
H5A	0.3973	−0.0430	0.0185	0.015*
C6	0.31922 (12)	0.04136 (9)	0.07243 (6)	0.0110 (2)
C7	0.39802 (13)	0.12317 (10)	0.07216 (6)	0.0128 (3)
C8	0.05761 (12)	0.31610 (9)	0.13374 (6)	0.0109 (2)
C9	0.14039 (12)	0.33297 (9)	0.18110 (6)	0.0096 (2)
C10	0.14068 (12)	0.41254 (9)	0.21033 (6)	0.0121 (2)
H10A	0.0887	0.4585	0.2013	0.015*
C11	0.21941 (12)	0.42253 (9)	0.25307 (6)	0.0127 (2)
H11A	0.2219	0.4757	0.2727	0.015*
C12	0.29478 (12)	0.35219 (9)	0.26639 (6)	0.0122 (2)
H12A	0.3481	0.3574	0.2950	0.015*
C13	0.28853 (12)	0.27413 (9)	0.23597 (6)	0.0108 (2)
C14	0.36167 (12)	0.19255 (9)	0.24695 (6)	0.0116 (2)
C15	0.65778 (12)	0.58205 (9)	0.07748 (6)	0.0123 (3)
C16	0.71346 (12)	0.44283 (10)	0.06413 (6)	0.0125 (2)
O1W	0.54413 (15)	0.26343 (9)	0.16261 (7)	0.0380 (4)
O2W	0.64627 (12)	0.10349 (10)	0.18324 (6)	0.0293 (3)
O3W	0.08779 (10)	0.22067 (8)	−0.00591 (5)	0.0171 (2)
H1O8	0.467 (2)	0.1503 (17)	0.2979 (11)	0.054 (8)*
H1N3	0.7969 (19)	0.5288 (15)	0.1077 (9)	0.032 (6)*
H1N5	0.5722 (17)	0.4258 (14)	0.0218 (9)	0.023 (5)*
H1N6	0.7083 (18)	0.6739 (15)	0.1215 (10)	0.028 (6)*
H2N6	0.5929 (19)	0.6983 (14)	0.0952 (8)	0.026 (5)*
H1N7	0.7412 (19)	0.3244 (14)	0.0499 (8)	0.022 (5)*
H2N7	0.837 (2)	0.3643 (15)	0.0799 (9)	0.033 (6)*
H1W1	0.491 (2)	0.2500 (19)	0.1436 (11)	0.049 (8)*
H2W1	0.546 (2)	0.3146 (17)	0.1640 (10)	0.031 (6)*
H1W2	0.611 (3)	0.157 (2)	0.1794 (14)	0.076 (10)*
H2W2	0.618 (3)	0.0882 (19)	0.2141 (13)	0.067 (9)*
H1W3	0.054 (2)	0.2667 (17)	−0.0225 (10)	0.044 (7)*
H2W3	0.082 (2)	0.2265 (15)	0.0251 (11)	0.037 (7)*

	U11	U22	U33	U12	U13	U23
Cu1	0.01071 (8)	0.00748 (8)	0.01064 (8)	0.00011 (6)	0.00135 (6)	−0.00198 (6)
O1	0.0145 (5)	0.0100 (4)	0.0157 (5)	−0.0004 (4)	0.0043 (4)	−0.0022 (4)
O2	0.0146 (5)	0.0096 (4)	0.0147 (5)	−0.0009 (4)	0.0026 (4)	−0.0022 (4)
O3	0.0147 (5)	0.0113 (4)	0.0122 (5)	−0.0003 (4)	−0.0010 (4)	−0.0022 (4)
O4	0.0171 (5)	0.0100 (4)	0.0151 (5)	0.0020 (4)	−0.0017 (4)	−0.0012 (4)
O5	0.0169 (5)	0.0141 (5)	0.0223 (6)	−0.0037 (4)	0.0070 (4)	−0.0014 (4)
O6	0.0181 (5)	0.0179 (5)	0.0268 (6)	−0.0039 (4)	0.0116 (5)	−0.0058 (5)
O7	0.0134 (5)	0.0142 (5)	0.0163 (5)	0.0027 (4)	−0.0024 (4)	0.0013 (4)
O8	0.0183 (5)	0.0120 (5)	0.0157 (5)	0.0036 (4)	−0.0069 (4)	−0.0006 (4)
N1	0.0104 (5)	0.0095 (5)	0.0104 (5)	0.0004 (4)	0.0003 (4)	−0.0007 (4)
N2	0.0095 (5)	0.0088 (5)	0.0096 (5)	0.0003 (4)	0.0006 (4)	0.0002 (4)
N3	0.0120 (5)	0.0125 (5)	0.0160 (6)	−0.0003 (4)	−0.0038 (5)	−0.0010 (5)
N4	0.0125 (5)	0.0118 (5)	0.0155 (6)	0.0013 (4)	−0.0004 (4)	−0.0013 (4)
N5	0.0123 (5)	0.0108 (5)	0.0161 (6)	0.0001 (4)	−0.0026 (4)	−0.0020 (4)
N6	0.0174 (6)	0.0127 (6)	0.0217 (7)	0.0010 (5)	−0.0021 (5)	−0.0050 (5)
N7	0.0168 (7)	0.0120 (6)	0.0346 (8)	0.0021 (5)	−0.0115 (6)	−0.0028 (5)
C1	0.0141 (6)	0.0089 (6)	0.0136 (6)	0.0012 (5)	0.0017 (5)	0.0002 (5)
C2	0.0099 (6)	0.0090 (6)	0.0118 (6)	0.0008 (5)	0.0003 (4)	−0.0003 (4)
C3	0.0134 (6)	0.0089 (6)	0.0139 (6)	−0.0001 (5)	−0.0004 (5)	−0.0001 (5)
C4	0.0142 (6)	0.0109 (6)	0.0127 (6)	0.0019 (5)	−0.0017 (5)	−0.0017 (5)
C5	0.0126 (6)	0.0124 (6)	0.0125 (6)	0.0022 (5)	0.0008 (5)	−0.0021 (5)
C6	0.0115 (6)	0.0101 (6)	0.0113 (6)	0.0013 (5)	0.0009 (5)	−0.0005 (5)
C7	0.0143 (6)	0.0113 (6)	0.0128 (6)	−0.0008 (5)	0.0013 (5)	−0.0011 (5)
C8	0.0112 (6)	0.0110 (6)	0.0105 (6)	−0.0016 (5)	0.0007 (5)	0.0023 (5)
C9	0.0097 (5)	0.0086 (6)	0.0106 (6)	−0.0001 (4)	0.0007 (4)	−0.0001 (4)
C10	0.0122 (6)	0.0087 (6)	0.0155 (7)	0.0017 (5)	0.0005 (5)	−0.0010 (5)
C11	0.0141 (6)	0.0090 (6)	0.0150 (6)	0.0004 (5)	0.0008 (5)	−0.0026 (5)
C12	0.0134 (6)	0.0111 (6)	0.0122 (6)	−0.0001 (5)	−0.0018 (5)	−0.0018 (5)
C13	0.0108 (6)	0.0106 (6)	0.0108 (6)	0.0014 (5)	−0.0004 (5)	−0.0005 (4)
C14	0.0118 (6)	0.0116 (6)	0.0114 (6)	−0.0001 (5)	0.0003 (5)	0.0019 (5)
C15	0.0119 (6)	0.0116 (6)	0.0136 (6)	0.0010 (5)	0.0008 (5)	0.0003 (5)
C16	0.0116 (6)	0.0112 (6)	0.0146 (7)	−0.0005 (5)	−0.0020 (5)	0.0000 (5)
O1W	0.0469 (9)	0.0118 (6)	0.0554 (10)	−0.0030 (6)	−0.0334 (8)	0.0027 (6)
O2W	0.0308 (7)	0.0313 (7)	0.0256 (7)	0.0163 (6)	0.0061 (6)	0.0020 (6)
O3W	0.0232 (6)	0.0141 (5)	0.0140 (6)	0.0026 (4)	0.0017 (4)	−0.0017 (4)

Cu1—N1	1.9057 (12)	N6—H2N6	0.93 (2)
Cu1—N2	1.9723 (12)	N7—C16	1.318 (2)
Cu1—O2	2.0453 (10)	N7—H1N7	0.81 (2)
Cu1—O1	2.0889 (10)	N7—H2N7	0.82 (2)
Cu1—O3	2.2727 (10)	C1—C2	1.509 (2)
Cu1—O4	2.3939 (10)	C2—C3	1.3870 (19)
O1—C1	1.3034 (17)	C3—C4	1.395 (2)
O2—C7	1.2877 (17)	C3—H3A	0.9300
O3—C8	1.2716 (17)	C4—C5	1.395 (2)
O4—C14	1.2213 (17)	C4—H4A	0.9300
O5—C1	1.2237 (17)	C5—C6	1.3907 (19)
O6—C7	1.2301 (17)	C5—H5A	0.9300
O7—C8	1.2425 (17)	C6—C7	1.513 (2)
O8—C14	1.3102 (17)	C8—C9	1.516 (2)
O8—H1O8	0.90 (3)	C9—C10	1.3896 (19)
N1—C2	1.3365 (17)	C10—C11	1.386 (2)
N1—C6	1.3375 (18)	C10—H10A	0.9300
N2—C9	1.3422 (17)	C11—C12	1.3925 (19)
N2—C13	1.3459 (17)	C11—H11A	0.9300
N3—C16	1.3547 (19)	C12—C13	1.3878 (19)
N3—C15	1.3813 (19)	C12—H12A	0.9300
N3—H1N3	0.76 (2)	C13—C14	1.4978 (19)
N4—C15	1.3045 (18)	O1W—H1W1	0.78 (3)
N4—N5	1.3994 (17)	O1W—H2W1	0.77 (2)
N5—C16	1.3285 (18)	O2W—H1W2	0.90 (3)
N5—H1N5	0.80 (2)	O2W—H2W2	0.85 (3)
N6—C15	1.3602 (19)	O3W—H1W3	0.89 (3)
N6—H1N6	0.83 (2)	O3W—H2W3	0.77 (3)
N1—Cu1—N2	174.99 (5)	C2—C3—C4	118.42 (13)
N1—Cu1—O2	80.73 (4)	C2—C3—H3A	120.8
N2—Cu1—O2	98.17 (4)	C4—C3—H3A	120.8
N1—Cu1—O1	79.34 (4)	C3—C4—C5	120.39 (13)
N2—Cu1—O1	101.40 (4)	C3—C4—H4A	119.8
O2—Cu1—O1	159.80 (4)	C5—C4—H4A	119.8
N1—Cu1—O3	108.01 (4)	C6—C5—C4	118.01 (13)
N2—Cu1—O3	76.99 (4)	C6—C5—H5A	121.0
O2—Cu1—O3	100.43 (4)	C4—C5—H5A	121.0
O1—Cu1—O3	88.85 (4)	N1—C6—C5	120.44 (13)
N1—Cu1—O4	99.40 (4)	N1—C6—C7	112.42 (12)
N2—Cu1—O4	75.63 (4)	C5—C6—C7	127.13 (13)
O2—Cu1—O4	86.18 (4)	O6—C7—O2	126.01 (14)
O1—Cu1—O4	93.85 (4)	O6—C7—C6	119.46 (13)
O3—Cu1—O4	152.47 (4)	O2—C7—C6	114.53 (12)
C1—O1—Cu1	114.05 (9)	O7—C8—O3	127.20 (13)
C7—O2—Cu1	113.87 (9)	O7—C8—C9	117.30 (13)
C8—O3—Cu1	111.94 (9)	O3—C8—C9	115.50 (12)
C14—O4—Cu1	107.22 (9)	N2—C9—C10	121.43 (13)
C14—O8—H1O8	111.8 (17)	N2—C9—C8	115.77 (12)
C2—N1—C6	122.47 (12)	C10—C9—C8	122.80 (12)
C2—N1—Cu1	119.51 (9)	C11—C10—C9	119.10 (13)
C6—N1—Cu1	118.00 (9)	C11—C10—H10A	120.4
C9—N2—C13	119.69 (12)	C9—C10—H10A	120.4
C9—N2—Cu1	119.31 (9)	C10—C11—C12	119.38 (13)
C13—N2—Cu1	120.92 (9)	C10—C11—H11A	120.3
C16—N3—C15	106.92 (12)	C12—C11—H11A	120.3
C16—N3—H1N3	128.6 (17)	C13—C12—C11	118.45 (13)
C15—N3—H1N3	124.2 (17)	C13—C12—H12A	120.8
C15—N4—N5	103.28 (11)	C11—C12—H12A	120.8
C16—N5—N4	112.06 (12)	N2—C13—C12	121.93 (12)
C16—N5—H1N5	127.6 (14)	N2—C13—C14	114.09 (12)
N4—N5—H1N5	120.4 (14)	C12—C13—C14	123.97 (12)
C15—N6—H1N6	111.6 (15)	O4—C14—O8	125.31 (13)
C15—N6—H2N6	114.3 (13)	O4—C14—C13	121.79 (13)
H1N6—N6—H2N6	117.0 (19)	O8—C14—C13	112.90 (12)
C16—N7—H1N7	116.6 (15)	N4—C15—N6	125.87 (13)
C16—N7—H2N7	119.6 (16)	N4—C15—N3	111.84 (13)
H1N7—N7—H2N7	124 (2)	N6—C15—N3	122.19 (13)
O5—C1—O1	125.68 (13)	N7—C16—N5	127.42 (14)
O5—C1—C2	120.75 (13)	N7—C16—N3	126.69 (13)
O1—C1—C2	113.57 (12)	N5—C16—N3	105.89 (13)
N1—C2—C3	120.22 (12)	H1W1—O1W—H2W1	107 (3)
N1—C2—C1	112.99 (12)	H1W2—O2W—H2W2	100 (3)
C3—C2—C1	126.79 (12)	H1W3—O3W—H2W3	109 (2)
N1—Cu1—O1—C1	−6.84 (10)	N1—C2—C3—C4	1.9 (2)
N2—Cu1—O1—C1	178.21 (10)	C1—C2—C3—C4	−176.87 (13)
O2—Cu1—O1—C1	−16.30 (18)	C2—C3—C4—C5	0.1 (2)
O3—Cu1—O1—C1	101.73 (10)	C3—C4—C5—C6	−1.6 (2)
O4—Cu1—O1—C1	−105.69 (10)	C2—N1—C6—C5	0.6 (2)
N1—Cu1—O2—C7	−5.71 (10)	Cu1—N1—C6—C5	179.32 (10)
N2—Cu1—O2—C7	169.34 (10)	C2—N1—C6—C7	−178.28 (12)
O1—Cu1—O2—C7	3.71 (18)	Cu1—N1—C6—C7	0.41 (15)
O3—Cu1—O2—C7	−112.48 (10)	C4—C5—C6—N1	1.3 (2)
O4—Cu1—O2—C7	94.47 (10)	C4—C5—C6—C7	−179.91 (14)
N1—Cu1—O3—C8	176.48 (9)	Cu1—O2—C7—O6	−171.91 (13)
N2—Cu1—O3—C8	−3.90 (9)	Cu1—O2—C7—C6	7.35 (15)
O2—Cu1—O3—C8	−99.97 (9)	N1—C6—C7—O6	173.99 (13)
O1—Cu1—O3—C8	98.08 (9)	C5—C6—C7—O6	−4.8 (2)
O4—Cu1—O3—C8	1.95 (14)	N1—C6—C7—O2	−5.33 (18)
N1—Cu1—O4—C14	174.94 (10)	C5—C6—C7—O2	175.84 (14)
N2—Cu1—O4—C14	−4.45 (9)	Cu1—O3—C8—O7	−172.04 (12)
O2—Cu1—O4—C14	95.00 (10)	Cu1—O3—C8—C9	7.09 (14)
O1—Cu1—O4—C14	−105.24 (9)	C13—N2—C9—C10	0.7 (2)
O3—Cu1—O4—C14	−10.33 (14)	Cu1—N2—C9—C10	−176.17 (10)
N2—Cu1—N1—C2	103.6 (6)	C13—N2—C9—C8	−178.69 (12)
O2—Cu1—N1—C2	−178.65 (11)	Cu1—N2—C9—C8	4.45 (16)
O1—Cu1—N1—C2	4.64 (10)	O7—C8—C9—N2	171.23 (12)
O3—Cu1—N1—C2	−80.62 (11)	O3—C8—C9—N2	−7.99 (18)
O4—Cu1—N1—C2	96.82 (10)	O7—C8—C9—C10	−8.1 (2)
N2—Cu1—N1—C6	−75.1 (6)	O3—C8—C9—C10	172.64 (13)
O2—Cu1—N1—C6	2.62 (10)	N2—C9—C10—C11	0.7 (2)
O1—Cu1—N1—C6	−174.09 (11)	C8—C9—C10—C11	−179.93 (13)
O3—Cu1—N1—C6	100.66 (10)	C9—C10—C11—C12	−1.2 (2)
O4—Cu1—N1—C6	−81.90 (10)	C10—C11—C12—C13	0.3 (2)
N1—Cu1—N2—C9	175.3 (5)	C9—N2—C13—C12	−1.7 (2)
O2—Cu1—N2—C9	98.28 (10)	Cu1—N2—C13—C12	175.13 (10)
O1—Cu1—N2—C9	−86.74 (10)	C9—N2—C13—C14	177.65 (12)
O3—Cu1—N2—C9	−0.61 (10)	Cu1—N2—C13—C14	−5.54 (16)
O4—Cu1—N2—C9	−177.83 (11)	C11—C12—C13—N2	1.2 (2)
N1—Cu1—N2—C13	−1.5 (6)	C11—C12—C13—C14	−178.06 (13)
O2—Cu1—N2—C13	−78.54 (11)	Cu1—O4—C14—O8	−177.73 (12)
O1—Cu1—N2—C13	96.45 (11)	Cu1—O4—C14—C13	3.18 (16)
O3—Cu1—N2—C13	−177.43 (11)	N2—C13—C14—O4	0.74 (19)
O4—Cu1—N2—C13	5.36 (10)	C12—C13—C14—O4	−179.95 (14)
C15—N4—N5—C16	0.02 (16)	N2—C13—C14—O8	−178.46 (12)
Cu1—O1—C1—O5	−172.99 (12)	C12—C13—C14—O8	0.9 (2)
Cu1—O1—C1—C2	7.53 (15)	N5—N4—C15—N6	176.70 (14)
C6—N1—C2—C3	−2.3 (2)	N5—N4—C15—N3	0.33 (16)
Cu1—N1—C2—C3	179.01 (10)	C16—N3—C15—N4	−0.57 (17)
C6—N1—C2—C1	176.63 (12)	C16—N3—C15—N6	−177.08 (14)
Cu1—N1—C2—C1	−2.03 (16)	N4—N5—C16—N7	−179.65 (15)
O5—C1—C2—N1	176.49 (13)	N4—N5—C16—N3	−0.36 (16)
O1—C1—C2—N1	−4.00 (17)	C15—N3—C16—N7	179.84 (15)
O5—C1—C2—C3	−4.6 (2)	C15—N3—C16—N5	0.54 (16)
O1—C1—C2—C3	174.87 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H1O8···O1i	0.90 (3)	1.71 (2)	2.5536 (15)	157 (2)
N3—H1N3···O2Wii	0.76 (2)	2.26 (2)	2.9081 (19)	144 (2)
N5—H1N5···O3Wiii	0.80 (2)	2.23 (2)	2.8310 (17)	132.3 (18)
N5—H1N5···N4iv	0.80 (2)	2.40 (2)	2.9925 (18)	131.2 (19)
N6—H1N6···O2Wii	0.83 (2)	2.47 (2)	3.209 (2)	147.6 (19)
N6—H2N6···O3v	0.93 (2)	2.06 (2)	2.9699 (17)	168.7 (19)
N7—H1N7···O3Wiii	0.81 (2)	2.15 (2)	2.8570 (19)	145 (2)
N7—H2N7···O7vi	0.82 (2)	1.96 (2)	2.7714 (18)	170 (2)
O1W—H1W1···O2	0.79 (2)	2.03 (3)	2.7985 (19)	168 (3)
O1W—H2W1···O5v	0.77 (3)	2.11 (3)	2.8715 (17)	171 (2)
O2W—H1W2···O1W	0.90 (3)	1.81 (3)	2.703 (2)	173 (3)
O2W—H2W2···O1i	0.85 (3)	2.58 (3)	3.3968 (18)	162 (3)
O3W—H1W3···O6vii	0.89 (3)	1.90 (3)	2.7712 (17)	169 (2)
O3W—H2W3···O3	0.77 (3)	2.04 (3)	2.8113 (16)	177 (2)
C5—H5A···O6viii	0.93	2.35	3.2042 (18)	153
C12—H12A···O7i	0.93	2.47	3.3960 (17)	176

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H1O8⋯O1i	0.90 (3)	1.71 (2)	2.5536 (15)	157 (2)
N3—H1N3⋯O2Wii	0.76 (2)	2.26 (2)	2.9081 (19)	144 (2)
N5—H1N5⋯O3Wiii	0.80 (2)	2.23 (2)	2.8310 (17)	132.3 (18)
N5—H1N5⋯N4iv	0.80 (2)	2.40 (2)	2.9925 (18)	131.2 (19)
N6—H1N6⋯O2Wii	0.83 (2)	2.47 (2)	3.209 (2)	147.6 (19)
N6—H2N6⋯O3v	0.93 (2)	2.06 (2)	2.9699 (17)	168.7 (19)
N7—H1N7⋯O3Wiii	0.81 (2)	2.15 (2)	2.8570 (19)	145 (2)
N7—H2N7⋯O7vi	0.82 (2)	1.96 (2)	2.7714 (18)	170 (2)
O1W—H1W1⋯O2	0.79 (2)	2.03 (3)	2.7985 (19)	168 (3)
O1W—H2W1⋯O5v	0.77 (3)	2.11 (3)	2.8715 (17)	171 (2)
O2W—H1W2⋯O1W	0.90 (3)	1.81 (3)	2.703 (2)	173 (3)
O2W—H2W2⋯O1i	0.85 (3)	2.58 (3)	3.3968 (18)	162 (3)
O3W—H1W3⋯O6vii	0.89 (3)	1.90 (3)	2.7712 (17)	169 (2)
O3W—H2W3⋯O3	0.77 (3)	2.04 (3)	2.8113 (16)	177 (2)
C5—H5A⋯O6viii	0.93	2.35	3.2042 (18)	153
C12—H12A⋯O7i	0.93	2.47	3.3960 (17)	176

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