Poly[[(μ4-benzene-1,3,5-tri-carboxyl-ato-κ(4) O (1):O (1'):O (2):O (3))bis-(2,2-bi-pyridine-κ(2) N,N')(μ2-hydroxido)dicopper(II)] trihydrate].

In the title two-dimensional coordination polymer, {[Cu2(C9H3O6)(OH)(C10H8N2)2]·3H2O} n , each of the two independent Cu(II) atoms is coordinated by a bridging OH group, two O atoms from two benzene-1,3,5-tri-carboxyl-ate (L) ligands and two N atoms from a 2,2- bi-pyridine (bipy) ligand in a distorted square-pyramidal geometry. Each L ligand coordinates four Cu(II) atoms, thus forming a polymeric layer parallel to the bc plane with bipy molecules protruding up and down. The lattice water mol-ecules involved in O-H⋯· O hydrogen bonding are situated in the inner part of each layer. The crystal packing is consolidated by π-π inter-actions between the aromatic rings of bipy ligands from neigbouring layers [inter-centroid distance = 3.762 (3) Å].

Related literature

For general background, see: Napolitano et al. (2008 ▶). For a coordination polymer containing n class="Chemical">benzene­tricarboxlyate, see: Wang et al. (2005 ▶). For Cu—O bond-length data, see: Janiak et al. (2008 ▶); Rogan et al. (2011 ▶). For related structures, see: Christou et al. (1990 ▶); Tokii et al. (1992 ▶).

Experimental

Crystal data

[Cu2(C9H3O6)(OH)(C10n class="Species">H8N2)2]·3H2O

M = 717.62

Monoclinic,

a = 16.493 (1) Å

b = 9.7017 (5) Å

c = 17.908 (1) Å

β = 102.426 (6)°

V = 2798.1 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.59 mm−1

T = 150 K

0.2 × 0.2 × 0.1 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.760, T max = 0.810

11267 measured reflections

6245 independent reflections

4210 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.099

S = 0.94

6245 reflections

434 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.45 e Å−3

Δρmin = −0.66 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis n class="Disease">RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELX2013 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814013877/cv5448sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814013877/cv5448Isup2.hkl

CCDC reference: 921256

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Cu2(C9H3O6)(OH)(C10H8N2)2]·3H2O	F(000) = 1456
Mr = 717.62	Dx = 1.703 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.493 (1) Å	Cell parameters from 4560 reflections
b = 9.7017 (5) Å	θ = 4.2–28.8°
c = 17.908 (1) Å	µ = 1.59 mm−1
β = 102.426 (6)°	T = 150 K
V = 2798.1 (3) Å3	Prismatic, blue
Z = 4	0.2 × 0.2 × 0.1 mm

Oxford Diffraction Xcalibur Sapphire3 diffractometer	6245 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4210 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Detector resolution: 16.4547 pixels mm-1	θmax = 28.9°, θmin = 2.3°
ω scan	h = −20→18
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −10→12
Tmin = 0.760, Tmax = 0.810	l = −24→20
11267 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)] = 0.042	Hydrogen site location: mixed
wR(F2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	w = 1/[σ2(Fo2) + (0.0493P)2] where P = (Fo2 + 2Fc2)/3
6245 reflections	(Δ/σ)max = 0.001
434 parameters	Δρmax = 1.45 e Å−3
1 restraint	Δρmin = −0.66 e Å−3

Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

	x	y	z	Uiso*/Ueq
Cu1	0.15663 (3)	1.12441 (4)	0.51735 (2)	0.01664 (11)
Cu2	0.34511 (3)	0.94695 (4)	0.52697 (2)	0.01641 (11)
N1	0.06719 (18)	1.2037 (3)	0.56556 (15)	0.0193 (6)
N2	0.11195 (18)	0.9485 (3)	0.55432 (16)	0.0205 (6)
N3	0.45778 (18)	0.8754 (3)	0.57948 (15)	0.0184 (6)
N4	0.40277 (18)	1.1262 (3)	0.56267 (15)	0.0177 (6)
O1	0.17136 (15)	1.2007 (2)	0.96699 (12)	0.0212 (6)
O2	0.24185 (15)	1.0324 (2)	0.48006 (12)	0.0192 (5)
O3	0.24286 (15)	1.1348 (2)	0.63702 (12)	0.0179 (5)
O4	0.30490 (15)	0.9281 (2)	0.64187 (12)	0.0173 (5)
O5	0.13890 (16)	1.3084 (2)	0.85481 (13)	0.0247 (6)
O6	0.31266 (15)	0.7355 (2)	0.98045 (12)	0.0208 (5)
O7	0.3028 (2)	0.6298 (2)	0.86878 (14)	0.0352 (7)
OW1	0.3559 (2)	0.6465 (3)	0.67326 (16)	0.0298 (7)
OW2	0.1725 (3)	0.5142 (4)	0.76325 (19)	0.0457 (9)
OW3	0.2372 (2)	1.4313 (3)	0.64258 (18)	0.0349 (7)
C1	0.0448 (2)	1.3358 (4)	0.5645 (2)	0.0235 (8)
H1	0.0702	1.3998	0.5364	0.028*
C2	−0.0140 (2)	1.3825 (4)	0.6028 (2)	0.0303 (9)
H2	−0.0294	1.4770	0.6004	0.036*
C3	−0.0502 (3)	1.2912 (4)	0.6446 (2)	0.0351 (10)
H3	−0.0898	1.3218	0.6725	0.042*
C4	−0.0276 (3)	1.1533 (4)	0.6451 (2)	0.0340 (10)
H4	−0.0527	1.0873	0.6722	0.041*
C5	0.0316 (2)	1.1135 (4)	0.60598 (18)	0.0219 (8)
C6	0.0611 (2)	0.9704 (4)	0.6032 (2)	0.0227 (8)
C7	0.0414 (3)	0.8645 (4)	0.6488 (2)	0.0314 (9)
H7	0.0059	0.8809	0.6831	0.038*
C8	0.0744 (3)	0.7355 (4)	0.6431 (2)	0.0381 (11)
H8	0.0622	0.6621	0.6741	0.046*
C9	0.1252 (3)	0.7130 (4)	0.5925 (2)	0.0319 (9)
H9	0.1481	0.6244	0.5880	0.038*
C10	0.1423 (2)	0.8217 (4)	0.5483 (2)	0.0253 (8)
H10	0.1764	0.8061	0.5126	0.030*
C11	0.4853 (2)	0.7458 (4)	0.5792 (2)	0.0246 (8)
H11	0.4533	0.6805	0.5458	0.030*
C12	0.5594 (3)	0.7043 (4)	0.6264 (2)	0.0313 (9)
H12	0.5795	0.6131	0.6234	0.038*
C13	0.6037 (3)	0.7976 (4)	0.6779 (2)	0.0334 (10)
H13	0.6527	0.7695	0.7129	0.040*
C14	0.5763 (2)	0.9309 (4)	0.6779 (2)	0.0278 (9)
H14	0.6066	0.9970	0.7121	0.033*
C15	0.5031 (2)	0.9676 (3)	0.62682 (19)	0.0190 (7)
C16	0.4712 (2)	1.1104 (3)	0.61762 (19)	0.0197 (8)
C17	0.5086 (2)	1.2213 (4)	0.6617 (2)	0.0272 (9)
H17	0.5558	1.2073	0.7019	0.033*
C18	0.4759 (3)	1.3511 (4)	0.6460 (2)	0.0294 (9)
H18	0.4998	1.4281	0.6755	0.035*
C19	0.4070 (2)	1.3679 (4)	0.5859 (2)	0.0279 (9)
H19	0.3850	1.4572	0.5724	0.033*
C20	0.3711 (2)	1.2534 (4)	0.5464 (2)	0.0229 (8)
H20	0.3229	1.2645	0.5069	0.027*
C21	0.2685 (2)	1.0230 (3)	0.66996 (17)	0.0139 (7)
C22	0.2545 (2)	1.0030 (3)	0.75023 (17)	0.0144 (7)
C23	0.2148 (2)	1.1040 (3)	0.78405 (17)	0.0147 (7)
H23	0.1922	1.1824	0.7551	0.018*
C24	0.2075 (2)	1.0922 (3)	0.85994 (17)	0.0140 (7)
C25	0.2373 (2)	0.9754 (3)	0.90225 (18)	0.0151 (7)
H25	0.2345	0.9684	0.9545	0.018*
C26	0.2715 (2)	0.8687 (3)	0.86660 (18)	0.0156 (7)
C27	0.2982 (2)	0.7339 (3)	0.90773 (19)	0.0194 (8)
C28	0.2803 (2)	0.8831 (3)	0.79174 (18)	0.0155 (7)
H28	0.3043	0.8103	0.7683	0.019*
C29	0.1689 (2)	1.2103 (3)	0.89620 (18)	0.0164 (7)
H1W1	0.319 (3)	0.597 (4)	0.665 (2)	0.023 (13)*
H2W1	0.331 (3)	0.719 (5)	0.656 (2)	0.048 (15)*
H1W3	0.247 (4)	1.359 (5)	0.646 (3)	0.06 (2)*
H2W3	0.210 (2)	1.441 (4)	0.679 (2)	0.025 (11)*
H1W2	0.167 (3)	0.445 (5)	0.785 (3)	0.040 (14)*
H2W2	0.213 (4)	0.554 (6)	0.786 (3)	0.07 (2)*
HO2	0.230 (3)	1.033 (4)	0.42861 (17)	0.046 (13)*

	U11	U22	U33	U12	U13	U23
Cu1	0.0200 (2)	0.0156 (2)	0.0150 (2)	−0.00017 (19)	0.00539 (16)	0.00193 (16)
Cu2	0.0206 (2)	0.0145 (2)	0.0144 (2)	0.00010 (19)	0.00470 (16)	−0.00173 (16)
N1	0.0169 (16)	0.0198 (16)	0.0206 (15)	0.0001 (13)	0.0025 (12)	0.0030 (12)
N2	0.0188 (17)	0.0179 (15)	0.0238 (15)	−0.0013 (13)	0.0020 (12)	0.0047 (12)
N3	0.0219 (17)	0.0127 (14)	0.0219 (15)	0.0010 (13)	0.0074 (12)	0.0013 (12)
N4	0.0194 (16)	0.0145 (14)	0.0212 (15)	−0.0003 (13)	0.0089 (12)	−0.0005 (12)
O1	0.0297 (16)	0.0224 (13)	0.0139 (12)	−0.0009 (11)	0.0103 (10)	−0.0014 (10)
O2	0.0231 (14)	0.0219 (13)	0.0126 (12)	0.0059 (11)	0.0037 (10)	0.0001 (10)
O3	0.0273 (14)	0.0140 (12)	0.0129 (11)	0.0038 (11)	0.0055 (10)	0.0039 (9)
O4	0.0269 (15)	0.0121 (12)	0.0143 (11)	0.0023 (10)	0.0073 (10)	−0.0004 (9)
O5	0.0297 (16)	0.0229 (13)	0.0206 (13)	0.0099 (12)	0.0034 (11)	−0.0018 (10)
O6	0.0289 (15)	0.0148 (12)	0.0171 (12)	−0.0018 (11)	0.0014 (10)	0.0057 (9)
O7	0.073 (2)	0.0154 (13)	0.0258 (14)	0.0123 (14)	0.0284 (14)	0.0069 (11)
OW1	0.0338 (19)	0.0219 (16)	0.0319 (16)	0.0027 (15)	0.0034 (13)	0.0036 (13)
OW2	0.072 (3)	0.036 (2)	0.0321 (18)	0.017 (2)	0.0165 (19)	0.0101 (16)
OW3	0.045 (2)	0.0226 (17)	0.0410 (18)	0.0011 (15)	0.0173 (15)	−0.0035 (14)
C1	0.023 (2)	0.023 (2)	0.0257 (19)	0.0012 (16)	0.0068 (15)	0.0026 (15)
C2	0.030 (2)	0.031 (2)	0.031 (2)	0.0102 (19)	0.0102 (17)	−0.0026 (17)
C3	0.027 (2)	0.053 (3)	0.029 (2)	0.015 (2)	0.0134 (17)	0.0054 (19)
C4	0.025 (2)	0.045 (3)	0.034 (2)	0.002 (2)	0.0132 (18)	0.0188 (19)
C5	0.017 (2)	0.031 (2)	0.0164 (17)	−0.0006 (16)	0.0000 (14)	0.0075 (15)
C6	0.017 (2)	0.024 (2)	0.0252 (19)	−0.0016 (16)	0.0003 (15)	0.0075 (15)
C7	0.027 (2)	0.035 (2)	0.032 (2)	−0.0047 (19)	0.0059 (17)	0.0130 (18)
C8	0.032 (3)	0.030 (2)	0.047 (3)	−0.010 (2)	−0.003 (2)	0.0211 (19)
C9	0.027 (2)	0.019 (2)	0.044 (2)	−0.0035 (17)	−0.0032 (18)	0.0053 (17)
C10	0.021 (2)	0.0183 (19)	0.033 (2)	−0.0046 (16)	−0.0033 (16)	0.0037 (15)
C11	0.023 (2)	0.0162 (18)	0.037 (2)	0.0001 (16)	0.0105 (16)	−0.0020 (15)
C12	0.036 (3)	0.020 (2)	0.042 (2)	0.0066 (19)	0.0158 (19)	0.0030 (17)
C13	0.020 (2)	0.033 (2)	0.045 (2)	0.0023 (19)	0.0013 (17)	0.0094 (19)
C14	0.023 (2)	0.029 (2)	0.029 (2)	−0.0034 (18)	0.0017 (16)	0.0028 (16)
C15	0.018 (2)	0.0194 (18)	0.0217 (18)	−0.0025 (15)	0.0086 (14)	−0.0011 (14)
C16	0.018 (2)	0.0201 (18)	0.0233 (18)	−0.0016 (16)	0.0092 (15)	−0.0012 (14)
C17	0.025 (2)	0.026 (2)	0.030 (2)	−0.0043 (17)	0.0042 (16)	−0.0067 (16)
C18	0.033 (2)	0.023 (2)	0.034 (2)	−0.0073 (18)	0.0109 (18)	−0.0060 (16)
C19	0.029 (2)	0.0156 (19)	0.044 (2)	−0.0005 (17)	0.0174 (18)	0.0015 (17)
C20	0.024 (2)	0.0190 (18)	0.0282 (19)	0.0001 (16)	0.0112 (15)	0.0012 (15)
C21	0.0168 (18)	0.0121 (16)	0.0116 (15)	−0.0035 (14)	0.0005 (13)	−0.0018 (12)
C22	0.0155 (19)	0.0145 (16)	0.0133 (16)	−0.0006 (14)	0.0035 (13)	−0.0012 (13)
C23	0.0167 (18)	0.0128 (16)	0.0129 (16)	−0.0013 (14)	−0.0005 (13)	0.0010 (12)
C24	0.0152 (18)	0.0133 (16)	0.0142 (16)	0.0002 (13)	0.0050 (13)	−0.0027 (12)
C25	0.0182 (19)	0.0152 (17)	0.0123 (15)	−0.0033 (14)	0.0045 (13)	0.0010 (12)
C26	0.0146 (18)	0.0143 (17)	0.0175 (16)	−0.0002 (14)	0.0024 (13)	0.0006 (13)
C27	0.019 (2)	0.0190 (18)	0.0234 (19)	0.0050 (15)	0.0113 (15)	0.0090 (14)
C28	0.0168 (18)	0.0148 (16)	0.0158 (16)	0.0001 (15)	0.0053 (13)	−0.0003 (13)
C29	0.0131 (18)	0.0173 (18)	0.0183 (17)	−0.0004 (14)	0.0021 (13)	−0.0071 (14)

Cu1—O2	1.903 (2)	C3—H3	0.9500
Cu1—O1i	1.961 (2)	C4—C5	1.373 (5)
Cu1—N1	2.015 (3)	C4—H4	0.9500
Cu1—N2	2.026 (3)	C5—C6	1.476 (5)
Cu1—O3	2.305 (2)	C6—C7	1.393 (5)
Cu1—O5i	2.935 (2)	C7—C8	1.377 (6)
Cu1—Cu2	3.5251 (6)	C7—H7	0.9500
Cu2—O2	1.918 (2)	C8—C9	1.377 (6)
Cu2—O6ii	1.980 (2)	C8—H8	0.9500
Cu2—N3	2.017 (3)	C9—C10	1.383 (5)
Cu2—N4	2.019 (3)	C9—H9	0.9500
Cu2—O4	2.301 (2)	C10—H10	0.9500
Cu2—O7ii	2.866 (2)	C11—C12	1.388 (5)
N1—C1	1.332 (4)	C11—H11	0.9500
N1—C5	1.348 (4)	C12—C13	1.382 (5)
N2—C10	1.340 (4)	C12—H12	0.9500
N2—C6	1.353 (5)	C13—C14	1.369 (5)
N3—C11	1.337 (4)	C13—H13	0.9500
N3—C15	1.343 (4)	C14—C15	1.396 (5)
N4—C16	1.337 (4)	C14—H14	0.9500
N4—C20	1.348 (4)	C15—C16	1.479 (5)
O1—C29	1.263 (4)	C16—C17	1.397 (5)
O1—Cu1iii	1.961 (2)	C17—C18	1.375 (5)
O2—HO2	0.90 (2)	C17—H17	0.9500
O3—C21	1.263 (4)	C18—C19	1.396 (6)
O4—C21	1.261 (4)	C18—H18	0.9500
O5—C29	1.242 (4)	C19—C20	1.380 (5)
O6—C27	1.272 (4)	C19—H19	0.9500
O6—Cu2iv	1.980 (2)	C20—H20	0.9500
O7—C27	1.239 (4)	C21—C22	1.517 (4)
OW1—H1W1	0.76 (4)	C22—C23	1.389 (4)
OW1—H2W1	0.84 (5)	C22—C28	1.396 (4)
OW2—H1W2	0.79 (4)	C23—C24	1.395 (4)
OW2—H2W2	0.79 (6)	C23—H23	0.9500
OW3—H1W3	0.72 (5)	C24—C25	1.393 (4)
OW3—H2W3	0.89 (4)	C24—C29	1.522 (4)
C1—C2	1.380 (5)	C25—C26	1.397 (4)
C1—H1	0.9500	C25—H25	0.9500
C2—C3	1.376 (5)	C26—C28	1.386 (4)
C2—H2	0.9500	C26—C27	1.518 (4)
C3—C4	1.389 (6)	C28—H28	0.9500
O2—Cu1—O1i	94.05 (10)	N1—C5—C4	122.1 (3)
O2—Cu1—N1	173.34 (10)	N1—C5—C6	114.1 (3)
O1i—Cu1—N1	92.36 (10)	C4—C5—C6	123.9 (3)
O2—Cu1—N2	93.86 (11)	N2—C6—C7	121.2 (3)
O1i—Cu1—N2	165.70 (11)	N2—C6—C5	115.1 (3)
N1—Cu1—N2	80.24 (12)	C7—C6—C5	123.7 (3)
O2—Cu1—O3	89.55 (9)	C8—C7—C6	118.8 (4)
O1i—Cu1—O3	106.08 (9)	C8—C7—H7	120.6
N1—Cu1—O3	86.97 (10)	C6—C7—H7	120.6
N2—Cu1—O3	85.88 (10)	C7—C8—C9	119.9 (4)
O2—Cu1—O5i	71.33 (8)	C7—C8—H8	120.1
O1i—Cu1—O5i	49.27 (8)	C9—C8—H8	120.1
N1—Cu1—O5i	114.46 (9)	C8—C9—C10	118.9 (4)
N2—Cu1—O5i	123.06 (9)	C8—C9—H9	120.5
O3—Cu1—O5i	145.28 (8)	C10—C9—H9	120.5
O2—Cu1—Cu2	22.78 (7)	N2—C10—C9	121.8 (4)
O1i—Cu1—Cu2	104.47 (7)	N2—C10—H10	119.1
N1—Cu1—Cu2	152.20 (8)	C9—C10—H10	119.1
N2—Cu1—Cu2	87.22 (9)	N3—C11—C12	121.7 (3)
O3—Cu1—Cu2	67.34 (6)	N3—C11—H11	119.1
O5i—Cu1—Cu2	93.18 (5)	C12—C11—H11	119.1
O2—Cu2—O6ii	93.88 (10)	C13—C12—C11	119.0 (3)
O2—Cu2—N3	174.49 (11)	C13—C12—H12	120.5
O6ii—Cu2—N3	91.55 (10)	C11—C12—H12	120.5
O2—Cu2—N4	94.59 (11)	C14—C13—C12	119.5 (4)
O6ii—Cu2—N4	165.79 (11)	C14—C13—H13	120.3
N3—Cu2—N4	79.91 (11)	C12—C13—H13	120.3
O2—Cu2—O4	91.51 (9)	C13—C14—C15	118.6 (4)
O6ii—Cu2—O4	101.62 (9)	C13—C14—H14	120.7
N3—Cu2—O4	88.26 (10)	C15—C14—H14	120.7
N4—Cu2—O4	89.54 (9)	N3—C15—C14	122.0 (3)
O2—Cu2—O7ii	71.02 (9)	N3—C15—C16	114.7 (3)
O6ii—Cu2—O7ii	50.63 (8)	C14—C15—C16	123.3 (3)
N3—Cu2—O7ii	112.05 (10)	N4—C16—C17	121.8 (3)
N4—Cu2—O7ii	122.32 (9)	N4—C16—C15	114.4 (3)
O4—Cu2—O7ii	143.84 (8)	C17—C16—C15	123.8 (3)
O2—Cu2—Cu1	22.60 (7)	C18—C17—C16	119.0 (4)
O6ii—Cu2—Cu1	105.09 (7)	C18—C17—H17	120.5
N3—Cu2—Cu1	154.86 (8)	C16—C17—H17	120.5
N4—Cu2—Cu1	86.86 (8)	C17—C18—C19	118.8 (4)
O4—Cu2—Cu1	70.23 (6)	C17—C18—H18	120.6
O7ii—Cu2—Cu1	93.09 (6)	C19—C18—H18	120.6
C1—N1—C5	118.8 (3)	C20—C19—C18	119.3 (3)
C1—N1—Cu1	125.9 (2)	C20—C19—H19	120.3
C5—N1—Cu1	115.2 (2)	C18—C19—H19	120.3
C10—N2—C6	119.4 (3)	N4—C20—C19	121.5 (3)
C10—N2—Cu1	125.3 (2)	N4—C20—H20	119.2
C6—N2—Cu1	113.5 (2)	C19—C20—H20	119.2
C11—N3—C15	119.0 (3)	O4—C21—O3	125.5 (3)
C11—N3—Cu2	127.0 (2)	O4—C21—C22	117.8 (3)
C15—N3—Cu2	113.4 (2)	O3—C21—C22	116.6 (3)
C16—N4—C20	119.4 (3)	C23—C22—C28	118.3 (3)
C16—N4—Cu2	113.6 (2)	C23—C22—C21	120.3 (3)
C20—N4—Cu2	125.9 (2)	C28—C22—C21	121.3 (3)
C29—O1—Cu1iii	114.7 (2)	C22—C23—C24	121.0 (3)
Cu1—O2—Cu2	134.61 (12)	C22—C23—H23	119.5
Cu1—O2—HO2	110 (3)	C24—C23—H23	119.5
Cu2—O2—HO2	115 (3)	C25—C24—C23	120.2 (3)
C21—O3—Cu1	118.31 (19)	C25—C24—C29	120.8 (3)
C21—O4—Cu2	123.51 (19)	C23—C24—C29	119.0 (3)
C27—O6—Cu2iv	113.2 (2)	C24—C25—C26	119.0 (3)
H1W1—OW1—H2W1	98 (4)	C24—C25—H25	120.5
H1W2—OW2—H2W2	109 (5)	C26—C25—H25	120.5
H1W3—OW3—H2W3	101 (5)	C28—C26—C25	120.2 (3)
N1—C1—C2	122.0 (3)	C28—C26—C27	118.5 (3)
N1—C1—H1	119.0	C25—C26—C27	121.3 (3)
C2—C1—H1	119.0	O7—C27—O6	124.4 (3)
C3—C2—C1	119.5 (4)	O7—C27—C26	118.4 (3)
C3—C2—H2	120.2	O6—C27—C26	117.2 (3)
C1—C2—H2	120.2	C26—C28—C22	121.0 (3)
C2—C3—C4	118.4 (4)	C26—C28—H28	119.5
C2—C3—H3	120.8	C22—C28—H28	119.5
C4—C3—H3	120.8	O5—C29—O1	125.3 (3)
C5—C4—C3	119.2 (4)	O5—C29—C24	118.2 (3)
C5—C4—H4	120.4	O1—C29—C24	116.5 (3)
C3—C4—H4	120.4
C5—N1—C1—C2	−0.6 (5)	C14—C15—C16—N4	176.3 (3)
Cu1—N1—C1—C2	−176.2 (3)	N3—C15—C16—C17	179.3 (3)
N1—C1—C2—C3	1.0 (6)	C14—C15—C16—C17	−3.5 (5)
C1—C2—C3—C4	−1.6 (6)	N4—C16—C17—C18	−2.7 (5)
C2—C3—C4—C5	1.9 (6)	C15—C16—C17—C18	177.1 (3)
C1—N1—C5—C4	0.8 (5)	C16—C17—C18—C19	−0.6 (5)
Cu1—N1—C5—C4	176.9 (3)	C17—C18—C19—C20	3.1 (6)
C1—N1—C5—C6	−179.9 (3)	C16—N4—C20—C19	−0.9 (5)
Cu1—N1—C5—C6	−3.8 (4)	Cu2—N4—C20—C19	166.0 (3)
C3—C4—C5—N1	−1.5 (6)	C18—C19—C20—N4	−2.5 (5)
C3—C4—C5—C6	179.3 (4)	Cu2—O4—C21—O3	6.5 (5)
C10—N2—C6—C7	1.7 (5)	Cu2—O4—C21—C22	−173.1 (2)
Cu1—N2—C6—C7	−163.8 (3)	Cu1—O3—C21—O4	53.4 (4)
C10—N2—C6—C5	179.6 (3)	Cu1—O3—C21—C22	−127.0 (2)
Cu1—N2—C6—C5	14.2 (4)	O4—C21—C22—C23	−180.0 (3)
N1—C5—C6—N2	−7.0 (4)	O3—C21—C22—C23	0.4 (5)
C4—C5—C6—N2	172.3 (4)	O4—C21—C22—C28	−0.5 (5)
N1—C5—C6—C7	170.9 (3)	O3—C21—C22—C28	179.9 (3)
C4—C5—C6—C7	−9.8 (6)	C28—C22—C23—C24	5.8 (5)
N2—C6—C7—C8	−0.3 (6)	C21—C22—C23—C24	−174.7 (3)
C5—C6—C7—C8	−178.1 (3)	C22—C23—C24—C25	−2.5 (5)
C6—C7—C8—C9	−0.6 (6)	C22—C23—C24—C29	175.6 (3)
C7—C8—C9—C10	0.2 (6)	C23—C24—C25—C26	−2.5 (5)
C6—N2—C10—C9	−2.1 (5)	C29—C24—C25—C26	179.4 (3)
Cu1—N2—C10—C9	161.5 (3)	C24—C25—C26—C28	4.2 (5)
C8—C9—C10—N2	1.1 (6)	C24—C25—C26—C27	−174.6 (3)
C15—N3—C11—C12	−0.1 (5)	Cu2iv—O6—C27—O7	0.6 (5)
Cu2—N3—C11—C12	−170.4 (3)	Cu2iv—O6—C27—C26	179.1 (2)
N3—C11—C12—C13	3.5 (6)	C28—C26—C27—O7	−21.4 (5)
C11—C12—C13—C14	−4.1 (6)	C25—C26—C27—O7	157.4 (3)
C12—C13—C14—C15	1.5 (6)	C28—C26—C27—O6	160.0 (3)
C11—N3—C15—C14	−2.6 (5)	C25—C26—C27—O6	−21.2 (5)
Cu2—N3—C15—C14	168.9 (3)	C25—C26—C28—C22	−0.8 (5)
C11—N3—C15—C16	174.6 (3)	C27—C26—C28—C22	178.0 (3)
Cu2—N3—C15—C16	−13.9 (4)	C23—C22—C28—C26	−4.1 (5)
C13—C14—C15—N3	2.0 (5)	C21—C22—C28—C26	176.4 (3)
C13—C14—C15—C16	−175.0 (3)	Cu1iii—O1—C29—O5	−18.6 (4)
C20—N4—C16—C17	3.5 (5)	Cu1iii—O1—C29—C24	160.4 (2)
Cu2—N4—C16—C17	−164.9 (3)	C25—C24—C29—O5	−175.9 (3)
C20—N4—C16—C15	−176.3 (3)	C23—C24—C29—O5	6.0 (5)
Cu2—N4—C16—C15	15.3 (3)	C25—C24—C29—O1	5.1 (5)
N3—C15—C16—N4	−0.9 (4)	C23—C24—C29—O1	−173.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
OW1—H1W1···OW3v	0.76 (4)	2.09 (4)	2.834 (5)	168 (4)
OW1—H2W1···O4	0.84 (5)	2.08 (5)	2.878 (4)	159 (4)
OW3—H1W3···O3	0.72 (5)	2.18 (5)	2.880 (4)	165 (6)
OW3—H2W3···OW2vi	0.89 (4)	1.88 (4)	2.729 (5)	161 (4)
OW2—H1W2···O5v	0.79 (4)	1.94 (5)	2.716 (5)	164 (4)
OW2—H2W2···O7	0.79 (6)	2.01 (6)	2.774 (6)	163 (6)
O2—HO2···O5i	0.90 (2)	2.35 (3)	2.943 (3)	123 (3)
O2—HO2···O7ii	0.90 (2)	2.37 (4)	2.884 (3)	116 (3)

Compound	Cu···Cu
(1)	3.5251 (6)
Cu2(µ-OH)(µ-H2O)(µ-OAc)(bpy)2](ClO4)2a	3.035 (2)
[Cu2(µ-OAc)3(bpy)2](ClO4)a	3.392 (1)
[Cu2(phen)2(µ-OH)(µ-OAc)](NO3)2.H2Ob	3.017 (2)
[Cu2(phen)2(µ-OH)(µ-O2CEt)](NO3)2.H2Ob	3.015 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW1—H1W1⋯OW3i	0.76 (4)	2.09 (4)	2.834 (5)	168 (4)
OW1—H2W1⋯O4	0.84 (5)	2.08 (5)	2.878 (4)	159 (4)
OW3—H1W3⋯O3	0.72 (5)	2.18 (5)	2.880 (4)	165 (6)
OW3—H2W3⋯OW2ii	0.89 (4)	1.88 (4)	2.729 (5)	161 (4)
OW2—H1W2⋯O5i	0.79 (4)	1.94 (5)	2.716 (5)	164 (4)
OW2—H2W2⋯O7	0.79 (6)	2.01 (6)	2.774 (6)	163 (6)
O2—HO2⋯O5iii	0.90 (2)	2.35 (3)	2.943 (3)	123 (3)
O2—HO2⋯O7iv	0.90 (2)	2.37 (4)	2.884 (3)	116 (3)

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