Poly­[[di­aqua­tris(μ₆-benzene-1,2,4,5-tetra­carboxyl­ato)­tris(μ₂-4,4′-bi­pyridine)­hexacopper(II)] dihydrate]

The hydro­thermal reaction of an aqueous solution of Cu(CH₃COO)₂·H₂O, 1,2,4,5-benzene­tetra­carboxylic acid and 4,4′-bi­pyridine gave rise to the interesting title three-dimensional polymer {[Cu₆(btec)₃(4,4′-bpy)₃(H₂O)₂]·2H₂O}_n (btec is 1,2,4,5-benzene­tetra­carboxyl­ate, C₁₀H₂O₈⁴⁻, and 4,4′-bpy is 4,4′-bi­pyridine, C₁₀H₈N₂), in which each btec ligand links six copper(II) cations into a lamellar [Cu₆(btec)₃(H₂O)₂]_n sub­polymer framework. There are two distinct diamine units and two distinct carboxylate units, with one of each lying across an inversion centre.

S1. Comment

The design of metal-organic materials with large tunnels and cavities has been extensively developed, due to their intriguing structural diversities and potential applications as microporous solids for molecular adsorption, ion exchange and heterogeneous catalysis. Recent elaboration has shown that hydrothermal reaction at relatively low temperature and autogeneous pressure provides a powerful tool for the construction of such materials. In particular, multidentate benzenecarboxylate ligands and the rod-like 4,4'-bpy ligand have been shown to be good building blocks in the design of materials with desired topologies under the hydrothermal reaction. Recently, some compounds constructed by 1,2,4,5-benzenetetracarboxylic acid (H₄btec) and 4,4'-bpy have been reported (Cao et al., 2002; Wu et al., 2001, 2002). Here, we present the title novel compound, (I), {[Cu₆(btec)₃(4,4'-bpy)₃(H₂O)₂]·2H₂O}_n. \sch

The present crystal structure analysis reveals that (I) is a neutral three-dimensional polymer, which is very different from the structure of [Cu₂(btec)_4/4{Cu(Hbtec)_2/2(4,4-Hbpy)(H₂O)₂}₂·4H₂O]_n (Cao et al., 2002). The hexanuclear species [Cu₆(btec)₃(4,4'-bpy)₃(H₂O)₂] constitutes the basic building block (Fig.1).

The most interesting feature of (I) is that the btec ligands exhibit two different coordination modes. One has a symmetric coordination mode, with two para carboxylate groups linking four Cu1 ions in a bidentate bridging coordination, with the Cu1—Cu1ⁱ distance being 2.8246 (14) Å [symmetry code: (i) 2 − x, 1 − y, 1 − z], while the remaining two carboxylate groups link the two Cu3 ions in the axial positions in a monodentate mode. The other btec ligand has an asymmetric coordination mode, with each para carboxylate group linking atoms Cu2 and Cu3 in a bidentate bridging coordination, with a Cu2—Cu3 distance of 3.0464 (10) Å, while the remaining two carboxylate groups link atoms Cu2 and Cu1 in axial positions in a monodentate mode (Figs. 1 and 2).

Atom Cu1 adopts a distorted tetrahedral coordination environment, consisting of one 4,4'-bpy N donor and three carboxylate O atoms. Atom Cu2 has a coordination mode similar to that for Cu1, except that these three carboxylate O atoms are all from three asymmetrically coordinated btec ligands. Atom Cu3 has a square-pyramidal coordination, with the basal plane consisting of one N donor and three O donors from three carboxylate groups of three individual btec anions. The apical site is occupied by an O donor from a coordinated water molecule.

As shown in Fig.2, each btec ligand connects another four asymmetrically and two symmetrically coordinated ligands by six Cu^II cations into an infinite two-dimensional lamellar [Cu₆(btec)₃(H₂O)₂]_n subpolymer framework. These lamellae are integrated by 4,4'-bpy ligands to form a three-dimensional architecture, with vacancy dimensions of about 5.8 × 10.9 Å (Fig.3). These vacancies are filled with water molecules.

S2. Experimental

A mixture of Cu(CH₃COO)₂·H₂O (0.303 g,1.5 mmol), 1,2,4,5-benzenetetracarboxylic acid (0.064 g, 0.25 mmol) and 4,4'-bpy (0.039 g, 0.25 mmol) was dissolved in H₂O (18 ml) and kept at 418 K for 3 d in a 23 ml Teflon-lined bomb. After slow cooling of the reaction mixture to room temperature, blue crystals of (I) appeared.

S3. Refinement

H atoms bonded to C atoms were located theoretically, with C—H distances of 0.93 Å, and treated as riding atoms, with U_iso(H) = 1.2U_eq(C). Please check added text. H atoms bonded to O atoms were located in difference maps and refined isotropically; the four O—H distances involving the water molecules were restrained from 0.79 to 0.82 Å.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1994); data reduction: XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the ??% probability level and H atoms have been omitted for clarity [symmetry codes: (i) 2 − x, 1 − y, 1 − z; (ii) x, 1 + y, z; (iii) 2 − x, 2 − y, 1 − z; (iv) 2 − x, 1 − y, −z].
	Fig. 2. A view of a lamellar sheet in (I), down the [100] face of the subpolymer.
	Fig. 3. The packing structure in (I), viewed along the [001] face.

Poly[[diaquatris(µ₆-benzene-1,2,4,5-tetracarboxylato)tris(µ₂-4,4'- bipyridine)hexacopper(II)] dihydrate]

Crystal data

[Cu6(C10H2O8)3(C10H8N2)3(H2O)2]·2H2O	Z = 1
Mr = 1672.20	F(000) = 838
Triclinic, P1	Dx = 1.976 Mg m^−3
a = 10.2545 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.8207 (8) Å	Cell parameters from 2833 reflections
c = 13.7264 (10) Å	θ = 1.5–25.1°
α = 91.305 (1)°	µ = 2.34 mm^−1
β = 90.461 (2)°	T = 293 K
γ = 112.655 (2)°	Prism, blue
V = 1404.97 (17) Å^3	0.36 × 0.20 × 0.16 mm

Data collection

Siemens SMART CCD area-detector diffractometer	4938 independent reflections
Radiation source: fine-focus sealed tube	3554 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ϕ and ω scans	θmax = 25.1°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→12
Tmin = 0.523, Tmax = 0.688	k = −11→12
7378 measured reflections	l = −15→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
4938 reflections	(Δ/σ)max = 0.006
463 parameters	Δρmax = 0.86 e Å^−3
0 restraints	Δρmin = −0.55 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.85137 (7)	0.44331 (7)	0.50733 (5)	0.0173 (2)
Cu2	0.88223 (8)	0.12335 (7)	0.19502 (5)	0.0190 (2)
Cu3	1.19740 (8)	0.24913 (7)	0.15456 (5)	0.0218 (2)
O1	0.9421 (4)	0.4765 (4)	0.3818 (3)	0.0205 (9)
O1W	1.4814 (6)	0.0578 (6)	0.1287 (4)	0.0459 (15)
H1WA	1.430 (9)	−0.015 (8)	0.097 (6)	0.069*
H1WB	1.547 (10)	0.082 (9)	0.097 (6)	0.069*
O2	0.7331 (5)	0.4742 (4)	0.3371 (3)	0.0293 (11)
O2W	1.4004 (5)	0.2611 (5)	0.1941 (3)	0.0291 (11)
H2WB	1.390 (8)	0.251 (7)	0.255 (5)	0.044*
H2WA	1.437 (8)	0.211 (7)	0.177 (5)	0.044*
O3	0.9062 (4)	0.9559 (4)	0.1982 (3)	0.0203 (9)
O4	1.1232 (4)	1.0313 (4)	0.1349 (3)	0.0195 (9)
O5	1.0722 (5)	0.8573 (4)	−0.0563 (3)	0.0217 (10)
O6	1.2825 (5)	0.8663 (4)	−0.0051 (3)	0.0321 (11)
O7	1.1304 (4)	0.3977 (4)	0.1492 (3)	0.0220 (10)
O8	0.9049 (4)	0.3103 (4)	0.2000 (3)	0.0206 (9)
O11	0.8853 (4)	0.6372 (4)	0.5197 (3)	0.0184 (9)
O12	1.1173 (4)	0.7244 (4)	0.4845 (3)	0.0183 (9)
O13	1.1202 (4)	1.2093 (4)	0.2852 (3)	0.0195 (9)
O14	1.3088 (5)	1.2185 (4)	0.3729 (3)	0.0288 (11)
N1	0.7105 (5)	0.3978 (5)	0.6105 (3)	0.0201 (11)
N2	0.2702 (5)	0.2803 (5)	1.0193 (3)	0.0219 (12)
N3	0.7430 (5)	0.0756 (5)	0.3046 (3)	0.0183 (11)
C1	0.6215 (7)	0.4603 (6)	0.6188 (4)	0.0246 (14)
H1	0.6220	0.5203	0.5712	0.030*
C2	0.5282 (7)	0.4399 (6)	0.6951 (4)	0.0249 (15)
H2	0.4680	0.4858	0.6984	0.030*
C3	0.5259 (6)	0.3509 (6)	0.7659 (4)	0.0206 (13)
C4	0.6180 (6)	0.2843 (6)	0.7565 (4)	0.0242 (15)
H4	0.6190	0.2231	0.8027	0.029*
C5	0.7065 (7)	0.3095 (6)	0.6792 (4)	0.0268 (15)
H5	0.7665	0.2637	0.6736	0.032*
C6	0.4324 (6)	0.3265 (6)	0.8515 (4)	0.0208 (13)
C7	0.3892 (7)	0.4246 (6)	0.8910 (4)	0.0268 (15)
H7	0.4134	0.5065	0.8610	0.032*
C8	0.3109 (7)	0.3994 (6)	0.9743 (4)	0.0239 (14)
H8	0.2849	0.4663	1.0008	0.029*
C9	0.3079 (7)	0.1866 (6)	0.9788 (4)	0.0232 (14)
H9	0.2784	0.1039	1.0081	0.028*
C10	0.3876 (7)	0.2042 (6)	0.8966 (4)	0.0263 (15)
H10	0.4111	0.1351	0.8716	0.032*
C21	0.9319 (6)	0.5839 (5)	0.2369 (4)	0.0148 (12)
C22	0.9316 (6)	0.7111 (6)	0.2302 (4)	0.0177 (13)
H22	0.8790	0.7386	0.2742	0.021*
C23	1.0074 (6)	0.7988 (5)	0.1599 (4)	0.0154 (12)
C24	1.0800 (6)	0.7546 (6)	0.0906 (4)	0.0163 (13)
C25	1.0817 (6)	0.6285 (6)	0.0973 (4)	0.0187 (13)
H25	1.1320	0.6002	0.0520	0.022*
C26	1.0096 (6)	0.5413 (6)	0.1711 (4)	0.0155 (13)
C27	0.8576 (7)	0.5019 (5)	0.3224 (4)	0.0174 (13)
C28	1.0127 (6)	0.9408 (6)	0.1624 (4)	0.0151 (12)
C29	1.1537 (7)	0.8365 (6)	0.0038 (4)	0.0219 (15)
C30	1.0159 (6)	0.4060 (6)	0.1737 (4)	0.0169 (13)
C31	0.6705 (7)	0.1526 (6)	0.3265 (4)	0.0244 (14)
H31	0.6849	0.2274	0.2893	0.029*
C32	0.5753 (7)	0.1260 (6)	0.4018 (4)	0.0231 (14)
H32	0.5290	0.1833	0.4146	0.028*
C33	0.5483 (6)	0.0136 (6)	0.4587 (4)	0.0209 (13)
C34	0.6209 (7)	−0.0671 (6)	0.4333 (4)	0.0258 (15)
H34	0.6060	−0.1440	0.4681	0.031*
C35	0.7145 (7)	−0.0356 (6)	0.3576 (4)	0.0224 (14)
H35	0.7599	−0.0930	0.3422	0.027*
C36	1.0002 (6)	0.7313 (5)	0.5032 (4)	0.0148 (13)
C37	0.9987 (6)	0.8695 (5)	0.5033 (4)	0.0149 (12)
C38	1.0841 (6)	0.9638 (6)	0.4377 (4)	0.0186 (13)
H38	1.1421	0.9396	0.3962	0.022*
C39	1.0839 (6)	1.0899 (6)	0.4332 (4)	0.0169 (13)
C40	1.1799 (7)	1.1836 (6)	0.3590 (4)	0.0170 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0218 (4)	0.0142 (4)	0.0182 (4)	0.0091 (3)	0.0109 (3)	0.0045 (3)
Cu2	0.0272 (5)	0.0142 (4)	0.0181 (4)	0.0103 (3)	0.0133 (3)	0.0052 (3)
Cu3	0.0310 (5)	0.0239 (4)	0.0170 (4)	0.0172 (4)	0.0133 (3)	0.0078 (3)
O1	0.029 (2)	0.020 (2)	0.015 (2)	0.0114 (19)	0.0104 (18)	0.0041 (17)
O1W	0.037 (3)	0.055 (4)	0.048 (3)	0.020 (3)	0.011 (3)	−0.010 (3)
O2	0.022 (3)	0.036 (3)	0.031 (3)	0.012 (2)	0.011 (2)	0.015 (2)
O2W	0.029 (3)	0.044 (3)	0.020 (2)	0.019 (2)	0.014 (2)	0.003 (2)
O3	0.030 (2)	0.013 (2)	0.022 (2)	0.0128 (19)	0.0100 (18)	0.0023 (17)
O4	0.025 (2)	0.013 (2)	0.023 (2)	0.0097 (19)	0.0141 (18)	0.0029 (17)
O5	0.033 (3)	0.021 (2)	0.018 (2)	0.017 (2)	0.0142 (19)	0.0098 (18)
O6	0.029 (3)	0.032 (3)	0.034 (3)	0.011 (2)	0.017 (2)	0.008 (2)
O7	0.029 (3)	0.016 (2)	0.025 (2)	0.014 (2)	0.0114 (19)	0.0049 (18)
O8	0.027 (2)	0.011 (2)	0.025 (2)	0.0073 (19)	0.0154 (19)	0.0044 (17)
O11	0.026 (2)	0.012 (2)	0.019 (2)	0.0094 (19)	0.0113 (18)	0.0027 (17)
O12	0.021 (2)	0.012 (2)	0.025 (2)	0.0083 (18)	0.0103 (18)	0.0048 (17)
O13	0.023 (2)	0.023 (2)	0.014 (2)	0.0102 (19)	0.0127 (17)	0.0086 (17)
O14	0.023 (3)	0.035 (3)	0.026 (2)	0.007 (2)	0.009 (2)	0.012 (2)
N1	0.023 (3)	0.017 (3)	0.021 (3)	0.008 (2)	0.010 (2)	0.004 (2)
N2	0.026 (3)	0.022 (3)	0.017 (3)	0.009 (2)	0.007 (2)	0.005 (2)
N3	0.022 (3)	0.019 (3)	0.015 (2)	0.010 (2)	0.005 (2)	0.002 (2)
C1	0.029 (4)	0.027 (4)	0.024 (3)	0.017 (3)	0.010 (3)	0.008 (3)
C2	0.027 (4)	0.027 (4)	0.027 (3)	0.017 (3)	0.015 (3)	0.009 (3)
C3	0.020 (3)	0.019 (3)	0.020 (3)	0.005 (3)	0.006 (3)	−0.001 (3)
C4	0.023 (3)	0.034 (4)	0.019 (3)	0.014 (3)	0.012 (3)	0.012 (3)
C5	0.025 (4)	0.033 (4)	0.030 (4)	0.019 (3)	0.010 (3)	0.002 (3)
C6	0.018 (3)	0.029 (4)	0.015 (3)	0.008 (3)	0.005 (2)	0.002 (3)
C7	0.032 (4)	0.027 (4)	0.020 (3)	0.009 (3)	0.015 (3)	0.012 (3)
C8	0.026 (4)	0.028 (4)	0.024 (3)	0.017 (3)	0.014 (3)	0.004 (3)
C9	0.031 (4)	0.020 (3)	0.023 (3)	0.015 (3)	0.009 (3)	0.003 (3)
C10	0.030 (4)	0.024 (4)	0.025 (3)	0.010 (3)	0.012 (3)	0.000 (3)
C21	0.021 (3)	0.012 (3)	0.012 (3)	0.007 (3)	0.008 (2)	0.007 (2)
C22	0.022 (3)	0.017 (3)	0.013 (3)	0.007 (3)	0.008 (2)	0.000 (2)
C23	0.018 (3)	0.014 (3)	0.016 (3)	0.008 (3)	0.005 (2)	0.003 (2)
C24	0.014 (3)	0.015 (3)	0.016 (3)	0.000 (2)	0.010 (2)	0.007 (2)
C25	0.027 (3)	0.019 (3)	0.013 (3)	0.011 (3)	0.012 (3)	0.005 (2)
C26	0.021 (3)	0.020 (3)	0.009 (3)	0.012 (3)	0.007 (2)	0.000 (2)
C27	0.032 (4)	0.011 (3)	0.015 (3)	0.014 (3)	0.005 (3)	−0.002 (2)
C28	0.027 (3)	0.018 (3)	0.003 (2)	0.011 (3)	0.004 (2)	0.003 (2)
C29	0.037 (4)	0.008 (3)	0.017 (3)	0.005 (3)	0.015 (3)	0.003 (2)
C30	0.028 (4)	0.017 (3)	0.007 (3)	0.010 (3)	0.005 (2)	0.003 (2)
C31	0.024 (3)	0.018 (3)	0.031 (4)	0.007 (3)	0.008 (3)	0.001 (3)
C32	0.031 (4)	0.020 (3)	0.024 (3)	0.015 (3)	0.013 (3)	0.009 (3)
C33	0.026 (3)	0.025 (3)	0.015 (3)	0.013 (3)	0.001 (3)	−0.001 (3)
C34	0.030 (4)	0.025 (4)	0.028 (3)	0.015 (3)	0.013 (3)	0.010 (3)
C35	0.027 (4)	0.019 (3)	0.026 (3)	0.014 (3)	0.014 (3)	0.007 (3)
C36	0.028 (4)	0.016 (3)	0.003 (2)	0.011 (3)	0.007 (2)	0.003 (2)
C37	0.021 (3)	0.012 (3)	0.013 (3)	0.007 (3)	0.004 (2)	0.002 (2)
C38	0.023 (3)	0.017 (3)	0.017 (3)	0.008 (3)	0.007 (2)	−0.002 (2)
C39	0.025 (3)	0.018 (3)	0.009 (3)	0.010 (3)	0.001 (2)	0.000 (2)
C40	0.029 (4)	0.016 (3)	0.013 (3)	0.016 (3)	0.007 (3)	0.000 (2)

Geometric parameters (Å, º)

Cu1—O1	1.939 (4)	C1—H1	0.9300
Cu1—N1	1.963 (5)	C2—C3	1.378 (8)
Cu1—O12^i	1.966 (4)	C2—H2	0.9300
Cu1—O11	1.993 (4)	C3—C4	1.396 (8)
Cu1—Cu1^i	2.8245 (14)	C3—C6	1.486 (8)
Cu2—O3^ii	1.922 (4)	C4—C5	1.365 (8)
Cu2—O8	1.945 (4)	C4—H4	0.9300
Cu2—O5^iii	1.961 (4)	C5—H5	0.9300
Cu2—N3	2.017 (5)	C6—C10	1.385 (8)
Cu2—Cu3	3.0464 (10)	C6—C7	1.399 (9)
Cu3—O13^ii	1.955 (4)	C7—C8	1.374 (8)
Cu3—O7	1.979 (4)	C7—H7	0.9300
Cu3—N2^iv	1.994 (5)	C8—H8	0.9300
Cu3—O2W	2.102 (5)	C9—C10	1.371 (8)
Cu3—O4^ii	2.190 (4)	C9—H9	0.9300
O1—C27	1.294 (7)	C10—H10	0.9300
O1W—H1WA	0.86 (8)	C21—C22	1.383 (8)
O1W—H1WB	0.76 (9)	C21—C26	1.392 (7)
O2—C27	1.213 (7)	C21—C27	1.512 (7)
O2W—H2WB	0.85 (7)	C22—C23	1.386 (7)
O2W—H2WA	0.80 (7)	C22—H22	0.9300
O3—C28	1.266 (7)	C23—C24	1.399 (8)
O3—Cu2^v	1.922 (4)	C23—C28	1.516 (7)
O4—C28	1.247 (7)	C24—C25	1.376 (8)
O4—Cu3^v	2.190 (4)	C24—C29	1.524 (7)
O5—C29	1.254 (8)	C25—C26	1.408 (7)
O5—Cu2^iii	1.961 (4)	C25—H25	0.9300
O6—C29	1.240 (8)	C26—C30	1.491 (7)
O7—C30	1.260 (7)	C31—C32	1.384 (8)
O8—C30	1.271 (7)	C31—H31	0.9300
O11—C36	1.251 (7)	C32—C33	1.398 (8)
O12—C36	1.260 (7)	C32—H32	0.9300
O12—Cu1^i	1.966 (4)	C33—C34	1.389 (8)
O13—C40	1.270 (7)	C33—C33^vii	1.471 (11)
O13—Cu3^v	1.955 (4)	C34—C35	1.377 (8)
O14—C40	1.239 (7)	C34—H34	0.9300
N1—C1	1.333 (7)	C35—H35	0.9300
N1—C5	1.347 (7)	C36—C37	1.501 (7)
N2—C9	1.329 (7)	C37—C39^viii	1.397 (8)
N2—C8	1.357 (7)	C37—C38	1.409 (7)
N2—Cu3^vi	1.994 (5)	C38—C39	1.367 (8)
N3—C31	1.344 (7)	C38—H38	0.9300
N3—C35	1.354 (7)	C39—C37^viii	1.397 (8)
C1—C2	1.388 (8)	C39—C40	1.527 (8)
O1—Cu1—N1	163.4 (2)	C7—C6—C3	122.3 (5)
O1—Cu1—O12^i	90.11 (16)	C8—C7—C6	119.7 (6)
N1—Cu1—O12^i	94.51 (18)	C8—C7—H7	120.2
O1—Cu1—O11	88.98 (15)	C6—C7—H7	120.2
N1—Cu1—O11	91.90 (18)	N2—C8—C7	122.2 (6)
O12^i—Cu1—O11	160.41 (17)	N2—C8—H8	118.9
O1—Cu1—Cu1^i	58.56 (13)	C7—C8—H8	118.9
N1—Cu1—Cu1^i	137.85 (16)	N2—C9—C10	124.2 (6)
O12^i—Cu1—Cu1^i	82.81 (12)	N2—C9—H9	117.9
O11—Cu1—Cu1^i	80.04 (12)	C10—C9—H9	117.9
O3^ii—Cu2—O8	166.52 (18)	C9—C10—C6	119.0 (6)
O3^ii—Cu2—O5^iii	91.78 (16)	C9—C10—H10	120.5
O8—Cu2—O5^iii	88.36 (16)	C6—C10—H10	120.5
O3^ii—Cu2—N3	93.51 (18)	C22—C21—C26	119.5 (5)
O8—Cu2—N3	92.69 (17)	C22—C21—C27	117.4 (5)
O5^iii—Cu2—N3	151.87 (19)	C26—C21—C27	122.8 (5)
O3^ii—Cu2—Cu3	86.02 (13)	C21—C22—C23	122.0 (5)
O8—Cu2—Cu3	81.76 (12)	C21—C22—H22	119.0
O5^iii—Cu2—Cu3	65.68 (13)	C23—C22—H22	119.0
N3—Cu2—Cu3	142.26 (14)	C22—C23—C24	118.8 (5)
O13^ii—Cu3—O7	89.41 (16)	C22—C23—C28	119.1 (5)
O13^ii—Cu3—N2^iv	177.14 (19)	C24—C23—C28	122.0 (5)
O7—Cu3—N2^iv	92.17 (18)	C25—C24—C23	119.4 (5)
O13^ii—Cu3—O2W	95.20 (17)	C25—C24—C29	117.1 (5)
O7—Cu3—O2W	127.51 (19)	C23—C24—C29	123.5 (5)
N2^iv—Cu3—O2W	85.7 (2)	C24—C25—C26	121.8 (5)
O13^ii—Cu3—O4^ii	84.77 (15)	C24—C25—H25	119.1
O7—Cu3—O4^ii	141.58 (17)	C26—C25—H25	119.1
N2^iv—Cu3—O4^ii	92.52 (17)	C21—C26—C25	118.4 (5)
O2W—Cu3—O4^ii	90.86 (18)	C21—C26—C30	122.8 (5)
O13^ii—Cu3—Cu2	56.35 (12)	C25—C26—C30	118.8 (5)
O7—Cu3—Cu2	74.49 (12)	O2—C27—O1	124.1 (5)
N2^iv—Cu3—Cu2	121.85 (15)	O2—C27—C21	122.2 (5)
O2W—Cu3—Cu2	146.37 (13)	O1—C27—C21	113.4 (5)
O4^ii—Cu3—Cu2	70.73 (11)	O4—C28—O3	126.6 (5)
C27—O1—Cu1	106.9 (4)	O4—C28—C23	117.6 (5)
H1WA—O1W—H1WB	101 (9)	O3—C28—C23	115.7 (5)
Cu3—O2W—H2WB	100 (5)	O6—C29—O5	126.6 (5)
Cu3—O2W—H2WA	127 (6)	O6—C29—C24	118.7 (6)
H2WB—O2W—H2WA	105 (7)	O5—C29—C24	114.4 (6)
C28—O3—Cu2^v	122.3 (4)	O7—C30—O8	126.4 (5)
C28—O4—Cu3^v	130.3 (4)	O7—C30—C26	116.9 (5)
C29—O5—Cu2^iii	120.8 (4)	O8—C30—C26	116.7 (5)
C30—O7—Cu3	132.0 (4)	N3—C31—C32	123.1 (6)
C30—O8—Cu2	123.7 (4)	N3—C31—H31	118.4
C36—O11—Cu1	124.8 (4)	C32—C31—H31	118.4
C36—O12—Cu1^i	122.5 (4)	C31—C32—C33	120.5 (6)
C40—O13—Cu3^v	126.8 (4)	C31—C32—H32	119.7
C1—N1—C5	117.6 (5)	C33—C32—H32	119.7
C1—N1—Cu1	120.8 (4)	C34—C33—C32	115.6 (5)
C5—N1—Cu1	121.4 (4)	C34—C33—C33^vii	123.1 (7)
C9—N2—C8	117.3 (5)	C32—C33—C33^vii	121.3 (7)
C9—N2—Cu3^vi	116.7 (4)	C35—C34—C33	121.3 (6)
C8—N2—Cu3^vi	124.6 (4)	C35—C34—H34	119.3
C31—N3—C35	116.7 (5)	C33—C34—H34	119.3
C31—N3—Cu2	120.6 (4)	N3—C35—C34	122.6 (6)
C35—N3—Cu2	122.6 (4)	N3—C35—H35	118.7
N1—C1—C2	123.0 (6)	C34—C35—H35	118.7
N1—C1—H1	118.5	O11—C36—O12	127.9 (5)
C2—C1—H1	118.5	O11—C36—C37	116.6 (5)
C3—C2—C1	119.1 (6)	O12—C36—C37	115.5 (5)
C3—C2—H2	120.4	C39^viii—C37—C38	117.7 (5)
C1—C2—H2	120.4	C39^viii—C37—C36	122.7 (5)
C2—C3—C4	117.8 (5)	C38—C37—C36	119.6 (5)
C2—C3—C6	122.5 (6)	C39—C38—C37	121.9 (5)
C4—C3—C6	119.7 (5)	C39—C38—H38	119.1
C5—C4—C3	119.7 (6)	C37—C38—H38	119.1
C5—C4—H4	120.2	C38—C39—C37^viii	120.4 (5)
C3—C4—H4	120.2	C38—C39—C40	117.4 (5)
N1—C5—C4	122.8 (6)	C37^viii—C39—C40	122.1 (5)
N1—C5—H5	118.6	O14—C40—O13	126.3 (5)
C4—C5—H5	118.6	O14—C40—C39	116.4 (5)
C10—C6—C7	117.6 (5)	O13—C40—C39	117.0 (5)
C10—C6—C3	120.0 (6)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, y−1, z; (iii) −x+2, −y+1, −z; (iv) x+1, y, z−1; (v) x, y+1, z; (vi) x−1, y, z+1; (vii) −x+1, −y, −z+1; (viii) −x+2, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O6^ii	0.86 (8)	2.08 (9)	2.888 (8)	157 (8)
O1W—H1WB···O6^ix	0.76 (9)	2.07 (9)	2.831 (7)	175 (10)
O2W—H2WB···O14^ii	0.85 (7)	1.81 (7)	2.623 (6)	161 (7)
O2W—H2WA···O1W	0.80 (7)	1.98 (7)	2.768 (7)	166 (8)

Symmetry codes: (ii) x, y−1, z; (ix) −x+3, −y+1, −z.