[(Pyridine-2,6-dicarboxyl-ato)copper(II)]-μ-(pyridine-2,6-dicarboxyl-ato)-[bis-(ethyl-enediamine)-copper(II)]-μ-(pyridine-2,6-dicarboxyl-ato)-[(pyridine-2,6-dicarboxyl-ato)copper(II)] ethyl-enediamine monosolvate tetra-hydrate.

The title compound, [Cu(3)(C(7)H(3)NO(4))(4)(C(2)H(8)N(2))(2)]·C(2)H(8)N(2)·4H(2)O, was obtained by the reaction of copper(II) acetate dihydrate with pyridine-2,6-dicarb-oxy-lic acid (H(2)dipic) and ethyl-enediamine (en) in an aqueous solution. All of the Cu(II) atoms in the trinuclear centrosymmetric title complex are six-coordinated in a distorted octa-hedral geometry with N(2)O(4) and N(4)O(2) environments for the outer and central Cu(II) atoms, respectively. Various inter-actions, including numerous O-H⋯O and C-H⋯O hydrogen bonds and C-O⋯π stacking of the pyridine and carboxyl-ate groups [O⋯centroid distances = 3.669 (2) and 3.668 (2) Å] are observed in the crystal structure.

Related literature

For metal complexes formed by pyridine­dicarb­oxy­lic acids, see: Aghabozorg et al. (2006 ▶); Burdock (1996 ▶); Douki et al. (2005 ▶); Kazuhiro et al. (1994 ▶); Murakami et al. (2003) ▶; Park et al. (2007 ▶); Xie et al. (2006 ▶).

Experimental

Crystal data

[Cu3(C7H3NO4)4(C2H8N2)2]·C2H8N2·4H2O

M = 1105.43

Monoclinic,

a = 8.152 (2) Å

b = 20.538 (5) Å

c = 12.736 (3) Å

β = 93.44 (2)°

V = 2128.5 (10) Å3

Z = 2

Mo Kα radiation

μ = 1.58 mm−1

T = 293 K

0.51 × 0.28 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007) ▶ T min = 0.583, T max = 0.747

35349 measured reflections

9453 independent reflections

6734 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.100

S = 1.02

9453 reflections

336 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.48 e Å−3

Δρmin = −0.47 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: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812022039/qm2066sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812022039/qm2066Isup2.hkl

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

[Cu3(C7H3NO4)4(C2H8N2)2]·C2H8N2·4H2O	F(000) = 1134
Mr = 1105.43	Dx = 1.725 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8052 reflections
a = 8.152 (2) Å	θ = 2.6–32.5°
b = 20.538 (5) Å	µ = 1.58 mm−1
c = 12.736 (3) Å	T = 293 K
β = 93.44 (2)°	Irregular, blue
V = 2128.5 (10) Å3	0.51 × 0.28 × 0.12 mm
Z = 2

Bruker APEXII CCD diffractometer	9453 independent reflections
Radiation source: fine-focus sealed tube	6734 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ and ω scans	θmax = 35.2°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −13→13
Tmin = 0.583, Tmax = 0.747	k = −33→33
35349 measured reflections	l = −20→20

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) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0528P)2 + 0.1097P] where P = (Fo2 + 2Fc2)/3
9453 reflections	(Δ/σ)max = 0.003
336 parameters	Δρmax = 0.48 e Å−3
5 restraints	Δρmin = −0.47 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.41369 (2)	0.734887 (8)	0.553105 (12)	0.02551 (5)
N1	0.38865 (14)	0.73453 (5)	0.39949 (8)	0.02225 (19)
O5	0.26265 (15)	0.81147 (5)	0.60629 (9)	0.0362 (2)
O3	0.58419 (15)	0.81797 (6)	0.50570 (8)	0.0368 (2)
N2	0.44168 (14)	0.72476 (5)	0.70320 (8)	0.02212 (19)
C2	0.29612 (16)	0.68844 (6)	0.35084 (10)	0.0236 (2)
C6	0.46747 (16)	0.77861 (6)	0.34388 (10)	0.0233 (2)
C9	0.36906 (16)	0.76619 (6)	0.76552 (10)	0.0229 (2)
O1	0.21166 (16)	0.65984 (5)	0.51771 (8)	0.0374 (3)
O2	0.15002 (16)	0.59160 (5)	0.38441 (9)	0.0401 (3)
C13	0.53495 (16)	0.67598 (6)	0.74101 (10)	0.0240 (2)
C10	0.38875 (18)	0.75991 (7)	0.87363 (11)	0.0302 (3)
H10	0.3384	0.7889	0.9177	0.036*
O7	0.58610 (16)	0.65866 (6)	0.56406 (8)	0.0401 (3)
O6	0.21260 (16)	0.86312 (6)	0.75532 (11)	0.0468 (3)
C3	0.27609 (18)	0.68619 (7)	0.24224 (10)	0.0270 (2)
H3	0.2112	0.6542	0.2089	0.032*
C1	0.21182 (18)	0.64213 (6)	0.42338 (11)	0.0277 (3)
O4	0.62267 (16)	0.87514 (5)	0.36029 (9)	0.0413 (3)
C5	0.45307 (18)	0.77855 (7)	0.23509 (10)	0.0276 (3)
H5	0.5090	0.8091	0.1969	0.033*
C7	0.56691 (17)	0.82794 (7)	0.40915 (11)	0.0269 (2)
C4	0.35429 (19)	0.73235 (7)	0.18424 (11)	0.0296 (3)
H4	0.3405	0.7323	0.1112	0.036*
C11	0.48516 (19)	0.70947 (9)	0.91474 (11)	0.0353 (3)
H11	0.5004	0.7044	0.9872	0.042*
C12	0.55921 (18)	0.66641 (8)	0.84784 (11)	0.0312 (3)
H12	0.6234	0.6321	0.8745	0.037*
C8	0.27279 (17)	0.81864 (7)	0.70493 (12)	0.0290 (3)
Cu2	0.0000	0.5000	0.5000	0.03467 (7)
O8	0.70149 (17)	0.59043 (6)	0.68212 (10)	0.0447 (3)
C14	0.61377 (19)	0.63770 (7)	0.65613 (12)	0.0297 (3)
N4	0.06892 (19)	0.55367 (6)	0.62685 (10)	0.0333 (3)
N3	0.2066 (2)	0.45052 (7)	0.53830 (13)	0.0394 (3)
O10	0.2610 (2)	0.52256 (7)	0.21358 (10)	0.0516 (3)
C15	0.3169 (2)	0.49316 (9)	0.60259 (14)	0.0394 (3)
H15A	0.3641	0.5262	0.5591	0.047*
H15B	0.4054	0.4681	0.6370	0.047*
C16	0.2137 (3)	0.52425 (9)	0.68297 (13)	0.0442 (4)
H16A	0.1795	0.4917	0.7324	0.053*
H16B	0.2767	0.5574	0.7218	0.053*
N5	0.28169 (16)	1.02440 (7)	0.51530 (11)	0.0352 (3)
H5A	0.1986	1.0039	0.5433	0.053*
H5B	0.2551	1.0331	0.4479	0.053*
H5C	0.3024	1.0615	0.5498	0.053*
O9	0.0509 (2)	0.94330 (9)	0.60524 (16)	0.0669 (5)
C17	0.4283 (2)	0.98283 (8)	0.52329 (15)	0.0388 (3)
H17A	0.4057	0.9423	0.4860	0.047*
H17B	0.4562	0.9726	0.5966	0.047*
H4A	−0.003 (2)	0.5641 (9)	0.6683 (15)	0.033 (5)*
H3A	0.181 (3)	0.4176 (11)	0.5774 (18)	0.049 (6)*
H4B	0.098 (3)	0.5904 (10)	0.6056 (18)	0.050 (6)*
H3B	0.249 (3)	0.4324 (11)	0.491 (2)	0.054 (6)*
H10A	0.273 (3)	0.4821 (7)	0.2364 (17)	0.055 (6)*
H10B	0.228 (3)	0.5469 (10)	0.2693 (18)	0.079 (8)*
H9A	−0.027 (3)	0.9446 (15)	0.645 (2)	0.082 (10)*
H9B	0.095 (4)	0.9106 (12)	0.640 (2)	0.099 (11)*

	U11	U22	U33	U12	U13	U23
Cu1	0.03397 (10)	0.02360 (8)	0.01879 (7)	0.00059 (6)	0.00018 (6)	0.00041 (6)
N1	0.0263 (5)	0.0217 (4)	0.0186 (4)	−0.0015 (4)	0.0007 (4)	0.0018 (4)
O5	0.0444 (6)	0.0339 (5)	0.0293 (5)	0.0062 (5)	−0.0055 (4)	0.0029 (4)
O3	0.0466 (6)	0.0369 (5)	0.0262 (5)	−0.0096 (5)	−0.0049 (4)	0.0008 (4)
N2	0.0255 (5)	0.0208 (4)	0.0200 (4)	0.0013 (4)	0.0007 (4)	−0.0013 (4)
C2	0.0280 (6)	0.0219 (5)	0.0209 (5)	−0.0012 (4)	0.0006 (4)	−0.0001 (4)
C6	0.0249 (6)	0.0219 (5)	0.0232 (5)	−0.0001 (4)	0.0017 (4)	0.0024 (4)
C9	0.0227 (5)	0.0232 (5)	0.0228 (5)	0.0000 (4)	0.0015 (4)	−0.0028 (4)
O1	0.0582 (7)	0.0317 (5)	0.0227 (4)	−0.0143 (5)	0.0058 (5)	0.0006 (4)
O2	0.0550 (7)	0.0317 (5)	0.0341 (6)	−0.0186 (5)	0.0084 (5)	−0.0054 (4)
C13	0.0267 (6)	0.0227 (5)	0.0230 (5)	0.0017 (5)	0.0038 (5)	0.0012 (4)
C10	0.0312 (7)	0.0365 (7)	0.0233 (6)	0.0025 (6)	0.0040 (5)	−0.0056 (5)
O7	0.0601 (8)	0.0373 (6)	0.0235 (5)	0.0146 (5)	0.0066 (5)	−0.0020 (4)
O6	0.0555 (7)	0.0349 (6)	0.0494 (7)	0.0197 (5)	−0.0035 (6)	−0.0106 (5)
C3	0.0325 (7)	0.0269 (6)	0.0214 (5)	−0.0002 (5)	−0.0006 (5)	−0.0038 (5)
C1	0.0349 (7)	0.0232 (5)	0.0251 (6)	−0.0056 (5)	0.0029 (5)	0.0002 (5)
O4	0.0551 (7)	0.0306 (5)	0.0385 (6)	−0.0163 (5)	0.0059 (5)	0.0026 (5)
C5	0.0321 (7)	0.0289 (6)	0.0221 (5)	0.0011 (5)	0.0042 (5)	0.0061 (5)
C7	0.0276 (6)	0.0241 (5)	0.0290 (6)	−0.0013 (5)	0.0018 (5)	0.0007 (5)
C4	0.0358 (7)	0.0349 (7)	0.0181 (5)	0.0043 (6)	0.0024 (5)	0.0000 (5)
C11	0.0363 (8)	0.0512 (9)	0.0185 (5)	0.0044 (7)	0.0014 (5)	0.0025 (6)
C12	0.0319 (7)	0.0354 (7)	0.0264 (6)	0.0074 (6)	0.0021 (5)	0.0077 (5)
C8	0.0278 (6)	0.0244 (6)	0.0342 (7)	0.0022 (5)	−0.0038 (5)	−0.0017 (5)
Cu2	0.03599 (14)	0.03264 (13)	0.03617 (14)	0.00045 (10)	0.00872 (11)	−0.01548 (11)
O8	0.0584 (8)	0.0315 (5)	0.0455 (7)	0.0218 (5)	0.0139 (6)	0.0061 (5)
C14	0.0377 (7)	0.0231 (5)	0.0287 (6)	0.0051 (5)	0.0064 (5)	−0.0012 (5)
N4	0.0461 (7)	0.0260 (5)	0.0292 (6)	−0.0023 (5)	0.0151 (5)	−0.0052 (5)
N3	0.0467 (8)	0.0333 (7)	0.0395 (7)	0.0063 (6)	0.0122 (6)	−0.0102 (6)
O10	0.0888 (11)	0.0350 (6)	0.0313 (6)	0.0095 (7)	0.0053 (6)	0.0035 (5)
C15	0.0423 (9)	0.0407 (8)	0.0352 (8)	0.0023 (7)	0.0036 (7)	−0.0012 (7)
C16	0.0643 (12)	0.0405 (8)	0.0279 (7)	0.0044 (8)	0.0033 (7)	−0.0041 (6)
N5	0.0316 (6)	0.0360 (6)	0.0377 (7)	−0.0032 (5)	−0.0007 (5)	−0.0016 (5)
O9	0.0400 (7)	0.0670 (10)	0.0921 (12)	−0.0022 (7)	−0.0090 (8)	0.0472 (9)
C17	0.0366 (8)	0.0355 (7)	0.0447 (9)	−0.0001 (6)	0.0070 (7)	0.0026 (7)

Cu1—N2	1.9228 (11)	C4—H4	0.9300
Cu1—N1	1.9549 (11)	C11—C12	1.391 (2)
Cu1—O7	2.1030 (11)	C11—H11	0.9300
Cu1—O5	2.1328 (11)	C12—H12	0.9300
Cu1—O1	2.2808 (11)	Cu2—N3i	2.0019 (16)
Cu1—O3	2.3041 (11)	Cu2—N3	2.0019 (16)
N1—C6	1.3375 (16)	Cu2—N4	2.0080 (13)
N1—C2	1.3390 (17)	Cu2—N4i	2.0080 (13)
O5—C8	1.2626 (18)	O8—C14	1.2389 (17)
O3—C7	1.2461 (18)	N4—C16	1.473 (2)
N2—C9	1.3271 (16)	N4—H4A	0.843 (19)
N2—C13	1.3303 (16)	N4—H4B	0.84 (2)
C2—C3	1.3837 (18)	N3—C15	1.469 (2)
C2—C1	1.5188 (18)	N3—H3A	0.87 (2)
C6—C5	1.3834 (18)	N3—H3B	0.80 (2)
C6—C7	1.5146 (19)	O10—H10A	0.883 (15)
C9—C10	1.3826 (19)	O10—H10B	0.921 (16)
C9—C8	1.5162 (19)	C15—C16	1.505 (2)
O1—C1	1.2553 (17)	C15—H15A	0.9700
O2—C1	1.2439 (17)	C15—H15B	0.9700
C13—C12	1.3772 (19)	C16—H16A	0.9700
C13—C14	1.5109 (18)	C16—H16B	0.9700
C10—C11	1.384 (2)	N5—C17	1.467 (2)
C10—H10	0.9300	N5—H5A	0.8900
O7—C14	1.2567 (18)	N5—H5B	0.8900
O6—C8	1.2350 (18)	N5—H5C	0.8900
C3—C4	1.381 (2)	O9—H9A	0.831 (17)
C3—H3	0.9300	O9—H9B	0.875 (17)
O4—C7	1.2520 (17)	C17—C17ii	1.516 (3)
C5—C4	1.380 (2)	C17—H17A	0.9700
C5—H5	0.9300	C17—H17B	0.9700
N2—Cu1—N1	173.52 (4)	C10—C11—H11	119.9
N2—Cu1—O7	79.31 (4)	C12—C11—H11	119.9
N1—Cu1—O7	95.33 (4)	C13—C12—C11	118.20 (13)
N2—Cu1—O5	78.49 (4)	C13—C12—H12	120.9
N1—Cu1—O5	107.04 (4)	C11—C12—H12	120.9
O7—Cu1—O5	157.55 (4)	O6—C8—O5	126.80 (14)
N2—Cu1—O1	99.47 (4)	O6—C8—C9	118.08 (13)
N1—Cu1—O1	76.64 (4)	O5—C8—C9	115.12 (12)
O7—Cu1—O1	88.96 (5)	N3i—Cu2—N3	180.0
O5—Cu1—O1	97.89 (5)	N3i—Cu2—N4	96.20 (6)
N2—Cu1—O3	107.65 (4)	N3—Cu2—N4	83.80 (6)
N1—Cu1—O3	76.64 (4)	N3i—Cu2—N4i	83.80 (6)
O7—Cu1—O3	99.06 (5)	N3—Cu2—N4i	96.20 (6)
O5—Cu1—O3	84.60 (5)	N4—Cu2—N4i	180.00 (6)
O1—Cu1—O3	152.68 (4)	O8—C14—O7	125.87 (13)
C6—N1—C2	120.58 (11)	O8—C14—C13	118.69 (13)
C6—N1—Cu1	120.18 (9)	O7—C14—C13	115.42 (12)
C2—N1—Cu1	119.20 (8)	C16—N4—Cu2	110.04 (10)
C8—O5—Cu1	113.42 (9)	C16—N4—H4A	111.8 (13)
C7—O3—Cu1	110.25 (9)	Cu2—N4—H4A	118.2 (13)
C9—N2—C13	122.16 (11)	C16—N4—H4B	106.9 (15)
C9—N2—Cu1	119.64 (9)	Cu2—N4—H4B	107.7 (16)
C13—N2—Cu1	118.20 (8)	H4A—N4—H4B	101.2 (19)
N1—C2—C3	121.04 (12)	C15—N3—Cu2	108.13 (10)
N1—C2—C1	115.09 (11)	C15—N3—H3A	107.5 (15)
C3—C2—C1	123.82 (12)	Cu2—N3—H3A	108.0 (14)
N1—C6—C5	121.00 (12)	C15—N3—H3B	114.6 (17)
N1—C6—C7	114.86 (11)	Cu2—N3—H3B	116.4 (17)
C5—C6—C7	124.12 (12)	H3A—N3—H3B	101 (2)
N2—C9—C10	120.42 (12)	H10A—O10—H10B	106.7 (17)
N2—C9—C8	112.77 (11)	N3—C15—C16	106.47 (15)
C10—C9—C8	126.78 (12)	N3—C15—H15A	110.4
C1—O1—Cu1	110.04 (9)	C16—C15—H15A	110.4
N2—C13—C12	120.68 (12)	N3—C15—H15B	110.4
N2—C13—C14	113.03 (11)	C16—C15—H15B	110.4
C12—C13—C14	126.20 (12)	H15A—C15—H15B	108.6
C9—C10—C11	118.42 (12)	N4—C16—C15	107.96 (13)
C9—C10—H10	120.8	N4—C16—H16A	110.1
C11—C10—H10	120.8	C15—C16—H16A	110.1
C14—O7—Cu1	113.50 (9)	N4—C16—H16B	110.1
C4—C3—C2	118.76 (13)	C15—C16—H16B	110.1
C4—C3—H3	120.6	H16A—C16—H16B	108.4
C2—C3—H3	120.6	C17—N5—H5A	109.5
O2—C1—O1	126.87 (13)	C17—N5—H5B	109.5
O2—C1—C2	117.84 (12)	H5A—N5—H5B	109.5
O1—C1—C2	115.30 (11)	C17—N5—H5C	109.5
C4—C5—C6	118.86 (12)	H5A—N5—H5C	109.5
C4—C5—H5	120.6	H5B—N5—H5C	109.5
C6—C5—H5	120.6	H9A—O9—H9B	91 (3)
O3—C7—O4	126.50 (14)	N5—C17—C17ii	110.25 (17)
O3—C7—C6	117.18 (12)	N5—C17—H17A	109.6
O4—C7—C6	116.32 (13)	C17ii—C17—H17A	109.6
C5—C4—C3	119.72 (12)	N5—C17—H17B	109.6
C5—C4—H4	120.1	C17ii—C17—H17B	109.6
C3—C4—H4	120.1	H17A—C17—H17B	108.1
C10—C11—C12	120.11 (13)
O7—Cu1—N1—C6	−100.17 (11)	C8—C9—C10—C11	−178.36 (14)
O5—Cu1—N1—C6	77.88 (11)	N2—Cu1—O7—C14	6.88 (11)
O1—Cu1—N1—C6	172.17 (11)	N1—Cu1—O7—C14	−169.43 (11)
O3—Cu1—N1—C6	−2.10 (10)	O5—Cu1—O7—C14	15.4 (2)
O7—Cu1—N1—C2	77.69 (10)	O1—Cu1—O7—C14	−92.96 (12)
O5—Cu1—N1—C2	−104.25 (10)	O3—Cu1—O7—C14	113.29 (12)
O1—Cu1—N1—C2	−9.96 (10)	N1—C2—C3—C4	0.3 (2)
O3—Cu1—N1—C2	175.77 (11)	C1—C2—C3—C4	177.64 (13)
N2—Cu1—O5—C8	6.16 (10)	Cu1—O1—C1—O2	160.26 (14)
N1—Cu1—O5—C8	−177.35 (10)	Cu1—O1—C1—C2	−20.20 (16)
O7—Cu1—O5—C8	−2.43 (19)	N1—C2—C1—O2	−166.87 (13)
O1—Cu1—O5—C8	104.28 (11)	C3—C2—C1—O2	15.7 (2)
O3—Cu1—O5—C8	−103.11 (11)	N1—C2—C1—O1	13.55 (19)
N2—Cu1—O3—C7	−177.91 (10)	C3—C2—C1—O1	−163.89 (14)
N1—Cu1—O3—C7	7.14 (10)	N1—C6—C5—C4	0.6 (2)
O7—Cu1—O3—C7	100.50 (10)	C7—C6—C5—C4	−177.81 (13)
O5—Cu1—O3—C7	−101.83 (10)	Cu1—O3—C7—O4	169.07 (13)
O1—Cu1—O3—C7	−5.07 (16)	Cu1—O3—C7—C6	−10.36 (15)
O7—Cu1—N2—C9	174.33 (11)	N1—C6—C7—O3	9.37 (19)
O5—Cu1—N2—C9	−2.34 (10)	C5—C6—C7—O3	−172.16 (14)
O1—Cu1—N2—C9	−98.55 (10)	N1—C6—C7—O4	−170.12 (13)
O3—Cu1—N2—C9	78.13 (11)	C5—C6—C7—O4	8.4 (2)
O7—Cu1—N2—C13	−5.37 (10)	C6—C5—C4—C3	−1.9 (2)
O5—Cu1—N2—C13	177.95 (11)	C2—C3—C4—C5	1.5 (2)
O1—Cu1—N2—C13	81.74 (10)	C9—C10—C11—C12	−0.2 (2)
O3—Cu1—N2—C13	−101.58 (10)	N2—C13—C12—C11	−0.7 (2)
C6—N1—C2—C3	−1.7 (2)	C14—C13—C12—C11	175.45 (14)
Cu1—N1—C2—C3	−179.57 (10)	C10—C11—C12—C13	0.6 (2)
C6—N1—C2—C1	−179.23 (12)	Cu1—O5—C8—O6	171.92 (14)
Cu1—N1—C2—C1	2.91 (15)	Cu1—O5—C8—C9	−8.36 (16)
C2—N1—C6—C5	1.2 (2)	N2—C9—C8—O6	−173.61 (13)
Cu1—N1—C6—C5	179.08 (10)	C10—C9—C8—O6	4.7 (2)
C2—N1—C6—C7	179.77 (11)	N2—C9—C8—O5	6.65 (18)
Cu1—N1—C6—C7	−2.39 (15)	C10—C9—C8—O5	−175.07 (14)
C13—N2—C9—C10	0.1 (2)	Cu1—O7—C14—O8	174.91 (13)
Cu1—N2—C9—C10	−179.56 (10)	Cu1—O7—C14—C13	−6.97 (17)
C13—N2—C9—C8	178.54 (11)	N2—C13—C14—O8	−178.92 (13)
Cu1—N2—C9—C8	−1.15 (15)	C12—C13—C14—O8	4.7 (2)
N2—Cu1—O1—C1	−157.62 (10)	N2—C13—C14—O7	2.82 (19)
N1—Cu1—O1—C1	17.09 (10)	C12—C13—C14—O7	−173.59 (15)
O7—Cu1—O1—C1	−78.64 (11)	N3i—Cu2—N4—C16	173.36 (12)
O5—Cu1—O1—C1	122.82 (10)	N3—Cu2—N4—C16	−6.64 (12)
O3—Cu1—O1—C1	29.29 (16)	N4—Cu2—N3—C15	−22.24 (11)
C9—N2—C13—C12	0.3 (2)	N4i—Cu2—N3—C15	157.76 (11)
Cu1—N2—C13—C12	−179.98 (11)	Cu2—N3—C15—C16	45.93 (16)
C9—N2—C13—C14	−176.31 (12)	Cu2—N4—C16—C15	33.54 (17)
Cu1—N2—C13—C14	3.39 (15)	N3—C15—C16—N4	−52.17 (18)
N2—C9—C10—C11	−0.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O1	0.84 (2)	2.07 (2)	2.8697 (17)	160 (2)
O10—H10B···O2	0.92 (2)	1.87 (2)	2.7927 (17)	176 (3)
N5—H5A···O9	0.89	1.93	2.808 (2)	167
O9—H9B···O5	0.88 (2)	2.50 (2)	3.211 (2)	139 (3)
O9—H9B···O6	0.88 (2)	1.96 (2)	2.793 (2)	159 (3)
N3—H3A···O6iii	0.87 (2)	2.51 (2)	3.218 (2)	138.5 (18)
O9—H9A···O10iv	0.83 (2)	2.10 (2)	2.893 (3)	160 (3)
N5—H5B···O9v	0.89	2.59	3.106 (2)	118
N5—H5B···O10vi	0.89	2.06	2.9151 (19)	160
N5—H5C···O4ii	0.89	1.82	2.6882 (18)	166
N4—H4A···O8vii	0.843 (19)	2.482 (19)	3.2079 (19)	144.8 (17)
O10—H10A···O8viii	0.88 (2)	1.82 (2)	2.6824 (17)	165 (2)
N3—H3B···O8viii	0.80 (2)	2.31 (3)	3.0664 (19)	156 (2)
N3—H3B···O7viii	0.80 (2)	2.43 (2)	3.1383 (17)	147 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯O1	0.84 (2)	2.07 (2)	2.8697 (17)	160 (2)
O10—H10B⋯O2	0.92 (2)	1.87 (2)	2.7927 (17)	176 (3)
N5—H5A⋯O9	0.89	1.93	2.808 (2)	167
O9—H9B⋯O5	0.88 (2)	2.50 (2)	3.211 (2)	139 (3)
O9—H9B⋯O6	0.88 (2)	1.96 (2)	2.793 (2)	159 (3)
N3—H3A⋯O6i	0.87 (2)	2.51 (2)	3.218 (2)	138.5 (18)
O9—H9A⋯O10ii	0.83 (2)	2.10 (2)	2.893 (3)	160 (3)
N5—H5B⋯O9iii	0.89	2.59	3.106 (2)	118
N5—H5B⋯O10iv	0.89	2.06	2.9151 (19)	160
N5—H5C⋯O4v	0.89	1.82	2.6882 (18)	166
N4—H4A⋯O8vi	0.843 (19)	2.482 (19)	3.2079 (19)	144.8 (17)
O10—H10A⋯O8vii	0.88 (2)	1.82 (2)	2.6824 (17)	165 (2)
N3—H3B⋯O8vii	0.80 (2)	2.31 (3)	3.0664 (19)	156 (2)
N3—H3B⋯O7vii	0.80 (2)	2.43 (2)	3.1383 (17)	147 (2)

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