Square-grid coordination networks of diaqua­bis(4,4′-bipyrid­yl)copper(II) crosslinked by hydrogen bonds through two monoanions of 1-benzofuran-2,3-dicarboxylic acid and five mol­ecules of water

The title compound, poly[[[diaqua­copper(II)]-di-μ-4,4′-bi­pyri­d­yl] bis­(3-carb­oxy-1-benzofuran-2-carboxyl­ate) penta­hy­drate], {[Cu(C₁₀H₈N₂)₂(H₂O)₂](C₁₀H₅O₅)₂·5H₂O}_n, crystal­lizes in a single-framework architecture. It is composed of two-dimensional square-grid coordination networks of 1:2:2 copper–4,4′-bipyridine–water units, wherein each copper ion coordinates equatorially to four bipyridyl units and axially to two water ligands. The polymeric nets are inter­calated by layers of the benzofuran­dicarboxylic acid monoanions and additional water species. An extensive array of hydrogen bonds inter­links the various components of the structure. The Cu atom and the bipyridyl entities are located on axes of twofold rotation. This study confirms the preferred monoanionic nature of the benzofuran­dicarboxylic acid mol­ecule. It reveals a rarely observed extended coordination polymer composed only of copper ions and bipyridyl linkers, and an inter­esting hydrogen-bonding connectivity between the polymeric layers aided by the benzofuran­dicarboxylic acid and water components inter­calated in the structure.

S1. Comment

This study is part of our investigation of the supramolecular reactivity of 1-benzofuran-2,3-dicarboxylic acid. It was shown in the preceding report (Koner & Goldberg, 2009) that one carboxylic acid group can be readily de-protonated to convert this ligand into a monoanionic species (BFDC^-), while the H atom of the second carboxylic acid group is involved in an intramolecular hydrogen bond and is more difficult to ionize. It has been also shown that BFDC^- can act as a good coordinating ligand, as well as a 1- counter-ion, to 2+ and 3+ transition metal cations. This includes formation of an octahedral complex, [Cu(BFDC^-)₂(imidazole)₄] (Koner & Goldberg, 20098). In an additional experiment, the imidazole component was replaced in the reaction mixture by the 4,4'-bipyridine ligand, anticipating that the latter may provide extended connectivity features in order to afford the formation of two- or three-dimensional coordination framework instead of the discrete complexes. Coordination of BFDC^- to the copper ions was also envisioned (as in the earlier example), to account for charge balance.

The asymmetric unit of the resulting multi-component product (I) is shown in Fig. 1. Its crystal structure can be best described as composed of alternating layered zones of extended coordination and hydrogen-bonded assemblies. The former features a square grid network in which the bipyridine units line the sides of the grids, while the copper ions serve as connecting nodes (Fig. 2) Each ion has an octahedral coordination environment (Table 1), where the equatorial positions are occupied by the N-sites of four adjacent bipyridine ligands. The trans-axial positions at every site are occupied by coordinated water ligands. In accordance with the Jahn–Teller effect, the octahedra are axially distorted with longer Cu—O than Cu—N bonds (Table 1). Correspondingly, each of the bipyridine spacers binds to two adjacent six-coordinated copper ions. The Cu1/N17/C18–C23/N24 entities are located on axes of twofold rotation at (1/4, 1/4, z), while the Cu2/N25/C26–C31/N32 units are positioned on twofold axes at (1/4, -1/4, z).

The coordination networks are aligned parallel to the bc plane of the crystal, being centered at x = 1/4 and x = 3/4. The size of the grid is characterized by Cu···Cu distances of 11.144 (2) and 11.275 (2) Å between the consecutive copper ions along the b and c axes, respectively. While many coordination polymers and complexes involving transition metal ions and 4,4'-bipyridine are know, those involving square-shaped arrangement of this ligand with copper ions have been published only recently. They involve, for example, the discrete cyclo-tetrakis(µ₂-4,4'-bipyridine)copper(II) molecule (Dey et al., 2004) and the square grid-like copper-4,4'-bipyridine coordination layers of similar connectivity and coordination distances as observed in this study (Wang et al., 2007).

In the crystal structure, the polymeric layers shown in Fig. 2 are intercalated by parallel hydrogen-bonded layers centered at x = 0 and x = 1/2. These are composed of water molecules and the planar monoanionic benzofurandicarboxylic acid entities (see below). The latter are grouped in pairs in a partly overlapping manner across centers of inversion. The mean interplanar distances between the overlayed units are 3.56 (3) and 3.23 (3) Å for the more overlapping [across inversion at (1/2, 0, 0)] O33/C34–C41 and the less overlapping [across inversion at (1/2, 0, 1/2)] O48/C49–C56 aromatic fragments, respectively (Fig. 3). The hydrogen-bonded layers interact further with the coordination networks from above and below by additional hydrogen bonding of the O63, O64 and O67 water molecules to the Cu(H₂O)₂ nodes, through the coordinated O3 and O4 water ligands (Table 2). Correspondingly, the BFDC^- units approach from above and below, and partly protrude into, the void segments of the adjacent coordination networks. This in turn allows the preservation of a nearly ideal square geometry of the grid, while rhombus distortion of the network to minimize the void space has frequently been observed in other framework solids (Wang et al., 2007; George et al., 2006).

A rigorous graph-set analysis (Bernstein et al., 1995) of the hydrogen-bonded networks in this structure is quite complex, as the latter involve different types of hydrogen bonds within and between the different component species. Therefore, the current discussion is limited to the type-specification of the basic localized ring patterns. The intramolecular hydrogen bonding in the BFDC^- ligands is characterized by the S(7) descriptor. The association of the two anions of the asymmetric unit through the O63 and O66 water molecules, involving also atoms O43, O44 and O58, forms a ten-membered R₄³(10) ring with four H-atom donors and three H-atom acceptors. An adjacent ring involves the carboxylate O44 atom and the O64, O65 and O66 water molecules, and is specified as R₄⁴(8). Two further rings represent association of the anionic layers to the copper-coordinated water ligands. As shown in Fig. 3, one involves atoms O58, O59, O63, O67 and O3(-x + 1/2, -y + 1/2, z) and is defined as R₄⁴(10). The other ring is composed of atoms O4, O64, O65, O47(-x + 1, -y, -z), O3(x +1/2, -y, -z +1/2), O63(-x + 1, y - 1/2, -z +1/2) and O67 (-x + 1, y - 1/2, -z + 1/2) assembling into an R₇⁵(14) pattern. These four types of ring patterns are fused into a continuous hydrogen-bonding array, which propagates parallel to the b axis of the crystal. Similar arrays occur in a periodic manner along the ±c direction, at the interfaces between adjacent rows of the BFDC^- anions.

The intercalated crystal structure of (I) is illustrated in Fig. 4.

In summary, compound (I) exhibits a framework architecture formed by an interesting combination of coordination and hydrogen-bonding networking. It is composed of alternating layers of square grid coordination polymers of the Cu(H₂O)₂ and bipyridine species and hydrogen-bonded assemblies of BFDC^- and water molecules. These layered fragments are further interconnected to one another by hydrogen bonds from the axial copper-coordinated water ligands to water molecules of the hydrophilic zones.

Related literature

For related literature, see: Bernstein et al. (1995); Dey et al. (2004); George et al. (2006); Koner & Goldberg (2009); Wang et al. (2007).

S2. Experimental

Copper nitrate, benzofurandicarboxylic acid, 4,4'-bipyridine and all the other solvents (see below) were obtained commercially. Cu(NO₃)₂.2.5H₂O (0.058 g, 0.25 mmol) and 1-benzofuran-2,3-dicarboxylic acid (0.52 g, 0.25 mmol) were added in a glass tube to 10 ml of a 1:1 mixture of N,N'-dimethylformamide and water. A solution of 4,4'-bipyridine (0.078 g, 0.5 mmol) in 4 ml of ethanol was then layered carefully on top of the mixture. Green blocks of the title compound deposited after about one week. IR (KBr, cm^-1): 3447 (water stretching vibration); 1718 (COOH); 1630 and 1590 (COO^- asymmetric stretching); 1402 and 1323 (COO^- symmetric stretching); 1224 (m); 1093 (m); 1018 (w); 869 (m); 831 (m); 745 (w); 635 (w). The asymmetric and symmetric O—H stretching vibrations of the water of hydration appear as a broad band centered at 3447 cm^-1. The IR spectrum clearly indicates the presence of both protonated carboxyl and deprotonated carboxylate groups, as it is confirmed also by the crystallographic analyses. The series of medium or weak intensity bands within 1224–645 cm^-1 is associated with the 4,4'-bipyridyl and the benzofuran units.

S3. Refinement

H atoms bound to C atoms were located in calculated positions and were constrained to ride on their parent atoms, with C—H distances of 0.95 Å and with U_iso(H) set at 1.2U_eq(C). Most of the H atoms bound to O could be located in difference Fourier maps. The remaining H atoms, which could not be located reliably, were placed in calculated positions to optimize intermolecular hydrogen bonding. The corresponding O—H distances were then restrained to 0.85 Å, and assigned U_iso(H) values of 1.5U_eq(O) [1.2 according to CIF]. Their parameters were not refined in the final least-squares calculations. The residual electron density Fourier maps contained four peaks within 1–2 e A^-3, reflecting possible partial rotational disorder of the noncoordinated benzofurandicarboxylic acid molecules. This disorder could not be reliably modeled by discrete atoms. Six SIMU-type restraints were applied to the displacement parameters of atoms C39 and C40 atoms.

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the atom labeling scheme. The atom ellipsoids represent displacement parameters at the 40% probability level at ca 110 K. The Cu(bipyridine) units reside on axes of twofold rotation at (1/4, 1/4, z) (atoms Cu1, N17, C20, C21 and N24) and (1/4, -1/4, z) (atoms Cu2, N25, C28, C29 and N32), and only the asymmetric unit is labeled. Hydrogen bonds are indicated by dashed lines.
	Fig. 2. A wireframe illustration of the square grid coordination network, which is aligned parallel to the bc plane of the crystal structure. The Cu and O(water) atoms only are depicted by small spheres.
	Fig. 3. A face-on view of the hydrogen-bonded layer containing BFDC^- anions and water molecules centered around x = 1/2. This and the symmetry-related layer at x = 0 are aligned parallel to the bc plane of the crystal structure. Hydrogen bonds are denoted by dashed lines. The O atoms of the water molecules are denoted by small spheres; those coordinated to copper (O3 and O4) are crossed. [Symmetry codes: (i) -x + 1, y - 1/2, -z + 1/2; (ii) -x + 1, -y, -z; (iii) x + 1/2, -y, -z + 1/2; (iv) -x + 1/2, -y + 1/2, z.] Not in accord with tables
	Fig. 4. The crystal packing of (I), showing edge-on the alternating zones of the coordination networks and the hydrogen-bonded layers. The Cu atoms are denoted by small spheres; the uncoordinated water molecules are indicated as thick isolated dots. Pale wireframe and dark wireframe denote the bipyridine and BFDC^- fragments, respectively. Note that the latter are located above and below the void spaces of the copper(bipyridine)2 coordination networks.

poly[[[diaquacopper(II)]-di-µ-4,4'-bipyridyl] bis(3-carboxy-1-benzofuran-2-carboxylate) pentahydrate]

Crystal data

[Cu(C10H8N2)2(H2O)2](C10H5O5)2·5H2O	F(000) = 3784
Mr = 912.30	Dx = 1.522 Mg m^−3
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 10233 reflections
a = 15.8470 (2) Å	θ = 1.6–28.2°
b = 22.2874 (3) Å	µ = 0.63 mm^−1
c = 22.5446 (3) Å	T = 110 K
V = 7962.49 (18) Å^3	Blocks, green
Z = 8	0.40 × 0.40 × 0.30 mm

Data collection

Nonius KappaCCD diffractometer	6077 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.057
Graphite monochromator	θmax = 28.2°, θmin = 1.6°
Detector resolution: 12.8 pixels mm^-1	h = 0→20
0.7° ω scans	k = 0→29
58792 measured reflections	l = 0→29
9629 independent reflections

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.210	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.1107P)^2 + 9.1733P] where P = (Fo^2 + 2Fc^2)/3
9628 reflections	(Δ/σ)max = 0.001
564 parameters	Δρmax = 1.97 e Å^−3
6 restraints	Δρmin = −0.88 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.

The residual electron density Fourier maps contained four peaks within 1–2 e/A**3, reflecting on partial rotational disorder of the benzofuran dicarboxylic acid moieties. This disorder could not be reliably modeled by discrete atoms. Yet all the H-atoms bound to oxygen could be located on these maps.

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

	x	y	z	Uiso*/Ueq
Cu1	0.2500	0.2500	0.28210 (2)	0.01412 (15)
Cu2	0.2500	−0.2500	0.28688 (2)	0.01468 (15)
O3	0.10168 (15)	0.24724 (10)	0.28069 (9)	0.0210 (5)
H3A	0.0776	0.2759	0.2625	0.025*
H3B	0.0698	0.2479	0.3110	0.025*
O4	0.39958 (16)	−0.24054 (10)	0.28730 (9)	0.0220 (5)
H4A	0.4272	−0.2095	0.2771	0.026*
H4B	0.4394	−0.2658	0.2834	0.026*
N5	0.24911 (16)	0.15919 (12)	0.28191 (10)	0.0146 (5)
C6	0.3048 (2)	0.12751 (14)	0.31400 (13)	0.0182 (6)
H6	0.3468	0.1486	0.3357	0.022*
C7	0.3037 (2)	0.06557 (14)	0.31684 (14)	0.0210 (7)
H7	0.3437	0.0449	0.3407	0.025*
C8	0.2439 (2)	0.03357 (15)	0.28474 (12)	0.0171 (7)
C9	0.1860 (2)	0.06665 (14)	0.25098 (14)	0.0188 (6)
H9	0.1439	0.0466	0.2285	0.023*
C10	0.1904 (2)	0.12850 (14)	0.25066 (13)	0.0186 (6)
H10	0.1508	0.1504	0.2276	0.022*
C11	0.2418 (2)	−0.03304 (15)	0.28617 (13)	0.0180 (7)
C12	0.2880 (2)	−0.06514 (15)	0.32810 (13)	0.0217 (7)
H12	0.3203	−0.0445	0.3571	0.026*
C13	0.2865 (2)	−0.12704 (15)	0.32729 (13)	0.0215 (7)
H13	0.3183	−0.1480	0.3564	0.026*
N14	0.24241 (17)	−0.15910 (12)	0.28760 (10)	0.0162 (6)
C15	0.1956 (2)	−0.12850 (14)	0.24770 (14)	0.0200 (7)
H15	0.1624	−0.1503	0.2200	0.024*
C16	0.1943 (2)	−0.06652 (14)	0.24579 (14)	0.0209 (7)
H16	0.1609	−0.0466	0.2169	0.025*
N17	0.2500	0.2500	0.37392 (15)	0.0144 (7)
C18	0.3022 (2)	0.28581 (14)	0.40458 (13)	0.0188 (6)
H18	0.3391	0.3116	0.3833	0.023*
C19	0.3045 (2)	0.28667 (15)	0.46607 (13)	0.0200 (7)
H19	0.3431	0.3123	0.4860	0.024*
C20	0.2500	0.2500	0.49897 (19)	0.0169 (9)
C21	0.2500	0.2500	0.56467 (18)	0.0162 (9)
C22	0.1940 (2)	0.21464 (15)	0.59750 (13)	0.0217 (7)
H22	0.1542	0.1899	0.5776	0.026*
C23	0.1963 (2)	0.21569 (15)	0.65863 (13)	0.0208 (7)
H23	0.1580	0.1909	0.6798	0.025*
N24	0.2500	0.2500	0.68975 (15)	0.0149 (7)
N25	0.2500	−0.2500	0.37976 (15)	0.0151 (7)
C26	0.3211 (2)	−0.26045 (15)	0.41059 (14)	0.0219 (7)
H26	0.3716	−0.2686	0.3894	0.026*
C27	0.3237 (2)	−0.25988 (16)	0.47196 (14)	0.0226 (7)
H27	0.3757	−0.2662	0.4920	0.027*
C28	0.2500	−0.2500	0.50438 (19)	0.0199 (9)
C29	0.2500	−0.2500	0.57011 (19)	0.0190 (9)
C30	0.1972 (2)	−0.21243 (15)	0.60245 (14)	0.0235 (7)
H30	0.1601	−0.1858	0.5824	0.028*
C31	0.1986 (2)	−0.21377 (14)	0.66382 (13)	0.0201 (7)
H31	0.1617	−0.1880	0.6850	0.024*
N32	0.2500	−0.2500	0.69449 (15)	0.0154 (7)
O33	0.6244 (2)	−0.00834 (13)	0.05001 (13)	0.0412 (7)
C34	0.6442 (3)	−0.00789 (19)	−0.00754 (18)	0.0374 (10)
C35	0.6951 (3)	−0.0555 (2)	−0.03513 (18)	0.0437 (11)
H35	0.7178	−0.0884	−0.0136	0.052*
C36	0.7065 (3)	−0.04779 (18)	−0.09484 (18)	0.0377 (10)
H36	0.7390	−0.0764	−0.1161	0.045*
C37	0.6713 (3)	0.00168 (18)	−0.1259 (2)	0.0428 (11)
H37	0.6809	0.0044	−0.1675	0.051*
C38	0.6246 (3)	0.0456 (2)	−0.09936 (18)	0.0420 (10)
H38	0.6015	0.0784	−0.1208	0.050*
C39	0.6134 (3)	0.03897 (18)	−0.03999 (16)	0.0336 (9)
C40	0.5667 (2)	0.07630 (18)	0.00688 (15)	0.0311 (8)
C41	0.5791 (2)	0.04337 (16)	0.05673 (18)	0.0323 (8)
C42	0.5504 (3)	0.05025 (17)	0.11891 (17)	0.0338 (9)
O43	0.5128 (2)	0.09921 (13)	0.13157 (11)	0.0403 (7)
O44	0.5630 (2)	0.01036 (13)	0.15628 (14)	0.0454 (8)
C45	0.5226 (3)	0.1338 (2)	−0.00085 (16)	0.0364 (9)
O46	0.48989 (17)	0.16044 (12)	0.04495 (12)	0.0368 (6)
H46	0.4944	0.1404	0.0769	0.044*
O47	0.51959 (19)	0.15608 (14)	−0.05116 (12)	0.0459 (8)
O48	0.53586 (18)	−0.02176 (12)	0.36940 (12)	0.0348 (6)
C49	0.5443 (3)	−0.07392 (18)	0.40122 (18)	0.0370 (9)
C50	0.5236 (3)	−0.13147 (19)	0.38097 (19)	0.0416 (10)
H50	0.5035	−0.1385	0.3419	0.050*
C51	0.5341 (3)	−0.1768 (2)	0.4209 (2)	0.0478 (11)
H51	0.5220	−0.2169	0.4094	0.057*
C52	0.5621 (3)	−0.1653 (2)	0.4778 (2)	0.0460 (11)
H52	0.5646	−0.1978	0.5050	0.055*
C53	0.5863 (3)	−0.1099 (2)	0.49744 (19)	0.0458 (11)
H53	0.6089	−0.1043	0.5361	0.055*
C54	0.5762 (3)	−0.0602 (2)	0.45683 (17)	0.0380 (10)
C55	0.5901 (3)	0.00320 (19)	0.45853 (17)	0.0369 (10)
C56	0.5640 (2)	0.02506 (18)	0.40492 (15)	0.0305 (8)
C57	0.5539 (2)	0.08552 (17)	0.37688 (15)	0.0284 (8)
O58	0.51315 (17)	0.08710 (11)	0.32929 (10)	0.0306 (6)
O59	0.58640 (19)	0.12943 (13)	0.40290 (14)	0.0446 (7)
C60	0.6239 (3)	0.0341 (2)	0.51031 (19)	0.0465 (11)
O61	0.6419 (2)	0.09266 (16)	0.50486 (14)	0.0590 (9)
H61	0.6236	0.1045	0.4713	0.071*
O62	0.6374 (3)	0.00702 (15)	0.55580 (14)	0.0575 (10)
O63	0.49322 (15)	0.16130 (10)	0.23558 (10)	0.0254 (5)
H63A	0.5003	0.1389	0.2055	0.030*
H63B	0.4964	0.1359	0.2636	0.030*
O64	0.45224 (18)	−0.13367 (12)	0.23727 (12)	0.0377 (7)
H64A	0.4894	−0.1305	0.2103	0.045*
H64B	0.4491	−0.0973	0.2485	0.045*
O65	0.56775 (18)	−0.11523 (13)	0.14635 (12)	0.0384 (7)
H65A	0.5406	−0.1255	0.1155	0.046*
H65B	0.5764	−0.0780	0.1521	0.046*
O66	0.4520 (2)	−0.00921 (12)	0.25046 (13)	0.0435 (8)
H66A	0.4906	−0.0028	0.2250	0.052*
H66B	0.4728	0.0103	0.2794	0.052*
O67	0.48782 (18)	0.23463 (13)	0.38303 (12)	0.0413 (7)
H67A	0.5188	0.2041	0.3888	0.050*
H67B	0.5004	0.2631	0.4065	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0225 (3)	0.0107 (3)	0.0091 (3)	0.0004 (2)	0.000	0.000
Cu2	0.0238 (3)	0.0108 (3)	0.0095 (3)	0.0000 (2)	0.000	0.000
O3	0.0216 (12)	0.0199 (12)	0.0214 (11)	0.0043 (9)	−0.0013 (9)	0.0027 (9)
O4	0.0231 (13)	0.0199 (12)	0.0230 (12)	−0.0005 (10)	0.0025 (9)	0.0023 (9)
N5	0.0200 (14)	0.0108 (12)	0.0130 (12)	0.0004 (10)	0.0008 (10)	−0.0014 (9)
C6	0.0222 (16)	0.0149 (15)	0.0176 (14)	0.0009 (13)	−0.0040 (12)	0.0009 (12)
C7	0.0252 (18)	0.0160 (16)	0.0217 (15)	0.0029 (13)	−0.0034 (13)	0.0012 (12)
C8	0.0219 (17)	0.0144 (15)	0.0148 (14)	−0.0007 (12)	−0.0002 (12)	0.0001 (11)
C9	0.0217 (17)	0.0163 (15)	0.0185 (14)	−0.0009 (13)	−0.0032 (12)	−0.0017 (12)
C10	0.0227 (17)	0.0181 (15)	0.0150 (13)	−0.0008 (13)	−0.0043 (12)	0.0008 (12)
C11	0.0225 (17)	0.0134 (15)	0.0182 (15)	0.0000 (12)	0.0010 (12)	−0.0007 (12)
C12	0.0308 (19)	0.0188 (16)	0.0155 (14)	−0.0021 (14)	−0.0066 (13)	−0.0017 (12)
C13	0.0318 (19)	0.0151 (15)	0.0178 (15)	−0.0015 (14)	−0.0055 (13)	0.0018 (12)
N14	0.0227 (15)	0.0128 (13)	0.0131 (12)	0.0008 (10)	−0.0013 (10)	−0.0008 (10)
C15	0.0256 (17)	0.0158 (15)	0.0187 (14)	−0.0016 (13)	−0.0039 (13)	−0.0014 (12)
C16	0.0259 (18)	0.0177 (16)	0.0190 (14)	0.0012 (14)	−0.0059 (13)	0.0019 (12)
N17	0.0192 (19)	0.0152 (18)	0.0088 (15)	0.0023 (15)	0.000	0.000
C18	0.0234 (17)	0.0163 (15)	0.0166 (14)	−0.0021 (13)	0.0001 (12)	−0.0007 (12)
C19	0.0253 (17)	0.0191 (16)	0.0156 (14)	−0.0042 (14)	0.0004 (12)	−0.0011 (12)
C20	0.019 (2)	0.017 (2)	0.0140 (19)	0.0004 (18)	0.000	0.000
C21	0.021 (2)	0.016 (2)	0.0118 (19)	−0.0007 (17)	0.000	0.000
C22	0.0242 (17)	0.0248 (17)	0.0161 (14)	−0.0031 (14)	−0.0018 (12)	−0.0009 (13)
C23	0.0275 (18)	0.0199 (16)	0.0150 (14)	−0.0061 (14)	0.0026 (13)	−0.0003 (12)
N24	0.023 (2)	0.0125 (17)	0.0088 (16)	0.0013 (15)	0.000	0.000
N25	0.023 (2)	0.0121 (17)	0.0101 (16)	−0.0002 (15)	0.000	0.000
C26	0.0247 (18)	0.0254 (18)	0.0155 (14)	0.0053 (14)	0.0003 (13)	0.0021 (13)
C27	0.0249 (19)	0.0267 (18)	0.0161 (14)	0.0048 (14)	−0.0014 (13)	0.0010 (13)
C28	0.028 (3)	0.018 (2)	0.014 (2)	0.0025 (19)	0.000	0.000
C29	0.022 (2)	0.021 (2)	0.014 (2)	0.0015 (18)	0.000	0.000
C30	0.0303 (19)	0.0243 (17)	0.0158 (15)	0.0055 (15)	−0.0024 (13)	−0.0001 (13)
C31	0.0278 (18)	0.0184 (15)	0.0141 (14)	0.0034 (14)	0.0010 (12)	−0.0011 (12)
N32	0.026 (2)	0.0144 (18)	0.0058 (15)	0.0016 (15)	0.000	0.000
O33	0.0488 (19)	0.0387 (17)	0.0360 (15)	0.0044 (13)	0.0049 (14)	0.0020 (12)
C34	0.036 (2)	0.041 (2)	0.035 (2)	−0.0102 (18)	−0.0057 (17)	0.0123 (17)
C35	0.048 (3)	0.046 (3)	0.038 (2)	−0.011 (2)	0.0107 (19)	−0.0095 (19)
C36	0.040 (2)	0.031 (2)	0.042 (2)	−0.0007 (18)	0.0161 (19)	−0.0103 (17)
C37	0.040 (3)	0.038 (2)	0.051 (3)	−0.0025 (19)	0.002 (2)	−0.0088 (19)
C38	0.044 (3)	0.046 (3)	0.036 (2)	−0.006 (2)	0.0003 (19)	0.0025 (19)
C39	0.034 (2)	0.034 (2)	0.033 (2)	−0.0141 (17)	−0.0059 (16)	0.0054 (16)
C40	0.0258 (19)	0.041 (2)	0.0264 (17)	−0.0099 (16)	0.0064 (15)	−0.0065 (16)
C41	0.027 (2)	0.0227 (18)	0.047 (2)	0.0017 (15)	−0.0045 (17)	−0.0077 (16)
C42	0.039 (2)	0.028 (2)	0.0335 (19)	−0.0073 (17)	−0.0125 (17)	0.0049 (17)
O43	0.062 (2)	0.0337 (16)	0.0247 (13)	0.0007 (14)	0.0071 (13)	−0.0017 (11)
O44	0.0481 (19)	0.0383 (17)	0.0498 (18)	−0.0070 (14)	−0.0124 (15)	0.0132 (14)
C45	0.033 (2)	0.046 (2)	0.0301 (19)	−0.0168 (19)	−0.0031 (17)	0.0107 (17)
O46	0.0366 (16)	0.0272 (14)	0.0466 (16)	0.0048 (12)	0.0008 (13)	0.0090 (12)
O47	0.0457 (18)	0.0523 (19)	0.0397 (15)	−0.0180 (15)	−0.0104 (14)	0.0189 (14)
O48	0.0400 (16)	0.0300 (14)	0.0345 (14)	−0.0005 (12)	−0.0098 (12)	0.0052 (12)
C49	0.039 (2)	0.033 (2)	0.038 (2)	0.0077 (18)	0.0001 (18)	0.0085 (17)
C50	0.045 (3)	0.036 (2)	0.044 (2)	0.0030 (19)	−0.0034 (19)	−0.0016 (19)
C51	0.048 (3)	0.039 (2)	0.057 (3)	0.003 (2)	0.001 (2)	0.000 (2)
C52	0.055 (3)	0.039 (2)	0.045 (2)	0.007 (2)	0.009 (2)	0.011 (2)
C53	0.044 (3)	0.056 (3)	0.037 (2)	0.017 (2)	0.0017 (19)	0.000 (2)
C54	0.038 (2)	0.044 (2)	0.0316 (19)	0.0126 (19)	0.0083 (17)	0.0037 (18)
C55	0.033 (2)	0.052 (3)	0.0254 (19)	0.0175 (19)	−0.0008 (16)	−0.0053 (16)
C56	0.027 (2)	0.039 (2)	0.0246 (17)	0.0064 (17)	0.0026 (15)	−0.0016 (16)
C57	0.0273 (19)	0.030 (2)	0.0278 (17)	0.0055 (16)	0.0065 (15)	−0.0022 (15)
O58	0.0371 (15)	0.0312 (14)	0.0236 (12)	0.0027 (12)	−0.0005 (11)	0.0035 (10)
O59	0.0416 (17)	0.0324 (16)	0.0599 (19)	0.0051 (13)	−0.0115 (15)	−0.0157 (14)
C60	0.050 (3)	0.049 (3)	0.040 (2)	0.015 (2)	−0.013 (2)	−0.017 (2)
O61	0.071 (2)	0.057 (2)	0.0492 (19)	0.0049 (18)	−0.0283 (17)	−0.0131 (16)
O62	0.082 (3)	0.059 (2)	0.0317 (16)	0.0191 (18)	−0.0242 (17)	−0.0083 (14)
O63	0.0341 (14)	0.0185 (12)	0.0235 (11)	0.0041 (10)	0.0039 (10)	−0.0010 (10)
O64	0.0489 (18)	0.0248 (14)	0.0393 (15)	−0.0055 (13)	0.0109 (13)	−0.0011 (11)
O65	0.0466 (17)	0.0357 (15)	0.0329 (14)	0.0084 (13)	−0.0015 (12)	−0.0015 (12)
O66	0.060 (2)	0.0331 (16)	0.0371 (15)	−0.0087 (14)	−0.0022 (14)	−0.0041 (12)
O67	0.0501 (18)	0.0378 (16)	0.0361 (15)	0.0114 (14)	−0.0174 (13)	−0.0083 (12)

Geometric parameters (Å, º)

Cu1—N5^i	2.024 (3)	C29—C30^iii	1.390 (4)
Cu1—N5	2.024 (3)	C29—C30	1.390 (4)
Cu1—N17	2.070 (3)	C30—C31	1.384 (4)
Cu1—N24^ii	2.082 (3)	C30—H30	0.9500
Cu1—O3^i	2.351 (2)	C31—N32	1.339 (4)
Cu1—O3	2.351 (2)	C31—H31	0.9500
Cu2—N14^iii	2.030 (3)	N32—C31^iii	1.339 (4)
Cu2—N14	2.030 (3)	N32—Cu2^iv	2.083 (3)
Cu2—N32^ii	2.083 (3)	O33—C34	1.335 (5)
Cu2—N25	2.094 (3)	O33—C41	1.367 (5)
Cu2—O4^iii	2.380 (2)	C34—C39	1.365 (6)
Cu2—O4	2.380 (2)	C34—C35	1.471 (6)
O3—H3A	0.8500	C35—C36	1.369 (6)
O3—H3B	0.8500	C35—H35	0.9500
O4—H4A	0.8499	C36—C37	1.420 (6)
O4—H4B	0.8500	C36—H36	0.9500
N5—C6	1.342 (4)	C37—C38	1.367 (6)
N5—C10	1.352 (4)	C37—H37	0.9500
C6—C7	1.382 (4)	C38—C39	1.358 (5)
C6—H6	0.9500	C38—H38	0.9500
C7—C8	1.389 (4)	C39—C40	1.535 (5)
C7—H7	0.9500	C40—C41	1.356 (6)
C8—C9	1.403 (4)	C40—C45	1.470 (6)
C8—C11	1.485 (5)	C41—C42	1.481 (6)
C9—C10	1.380 (4)	C42—O44	1.241 (5)
C9—H9	0.9500	C42—O43	1.276 (5)
C10—H10	0.9500	C45—O47	1.239 (4)
C11—C12	1.393 (4)	C45—O46	1.299 (5)
C11—C16	1.398 (4)	O46—H46	0.8500
C12—C13	1.380 (5)	O48—C49	1.372 (5)
C12—H12	0.9500	O48—C56	1.389 (5)
C13—N14	1.341 (4)	C49—C54	1.386 (6)
C13—H13	0.9500	C49—C50	1.400 (6)
N14—C15	1.351 (4)	C50—C51	1.363 (6)
C15—C16	1.382 (4)	C50—H50	0.9500
C15—H15	0.9500	C51—C52	1.383 (6)
C16—H16	0.9500	C51—H51	0.9500
N17—C18	1.341 (4)	C52—C53	1.366 (7)
N17—C18^i	1.341 (4)	C52—H52	0.9500
C18—C19	1.387 (4)	C53—C54	1.446 (6)
C18—H18	0.9500	C53—H53	0.9500
C19—C20	1.401 (4)	C54—C55	1.431 (6)
C19—H19	0.9500	C55—C56	1.367 (5)
C20—C19^i	1.401 (4)	C55—C60	1.458 (6)
C20—C21	1.481 (6)	C56—C57	1.497 (5)
C21—C22	1.399 (4)	C57—O58	1.252 (4)
C21—C22^i	1.399 (4)	C57—O59	1.252 (5)
C22—C23	1.379 (4)	C60—O62	1.209 (6)
C22—H22	0.9500	C60—O61	1.342 (6)
C23—N24	1.342 (4)	O61—H61	0.8535
C23—H23	0.9500	O63—H63A	0.8500
N24—C23^i	1.342 (4)	O63—H63B	0.8500
N24—Cu1^iv	2.082 (3)	O64—H64A	0.8500
N25—C26^iii	1.344 (4)	O64—H64B	0.8500
N25—C26	1.344 (4)	O65—H65A	0.8501
C26—C27	1.384 (4)	O65—H65B	0.8501
C26—H26	0.9500	O66—H66A	0.8500
C27—C28	1.396 (4)	O66—H66B	0.8500
C27—H27	0.9500	O67—H67A	0.8500
C28—C27^iii	1.396 (4)	O67—H67B	0.8499
C28—C29	1.482 (6)
N5^i—Cu1—N5	179.76 (13)	C23^i—N24—Cu1^iv	121.53 (18)
N5^i—Cu1—N17	90.12 (7)	C26^iii—N25—C26	117.7 (4)
N5—Cu1—N17	90.12 (7)	C26^iii—N25—Cu2	121.14 (19)
N5^i—Cu1—N24^ii	89.88 (7)	C26—N25—Cu2	121.14 (19)
N5—Cu1—N24^ii	89.88 (7)	N25—C26—C27	122.7 (3)
N17—Cu1—N24^ii	180.0	N25—C26—H26	118.6
N5^i—Cu1—O3^i	88.10 (9)	C27—C26—H26	118.6
N5—Cu1—O3^i	91.90 (9)	C26—C27—C28	120.0 (3)
N17—Cu1—O3^i	90.77 (5)	C26—C27—H27	120.0
N24^ii—Cu1—O3^i	89.23 (5)	C28—C27—H27	120.0
N5^i—Cu1—O3	91.90 (9)	C27—C28—C27^iii	116.8 (4)
N5—Cu1—O3	88.10 (9)	C27—C28—C29	121.6 (2)
N17—Cu1—O3	90.77 (5)	C27^iii—C28—C29	121.6 (2)
N24^ii—Cu1—O3	89.23 (5)	C30^iii—C29—C30	116.7 (4)
O3^i—Cu1—O3	178.46 (11)	C30^iii—C29—C28	121.6 (2)
N14^iii—Cu2—N14	179.08 (13)	C30—C29—C28	121.6 (2)
N14^iii—Cu2—N32^ii	90.46 (7)	C31—C30—C29	120.1 (3)
N14—Cu2—N32^ii	90.46 (7)	C31—C30—H30	120.0
N14^iii—Cu2—N25	89.54 (7)	C29—C30—H30	120.0
N14—Cu2—N25	89.54 (7)	N32—C31—C30	122.6 (3)
N32^ii—Cu2—N25	180.0	N32—C31—H31	118.7
N14^iii—Cu2—O4^iii	88.31 (9)	C30—C31—H31	118.7
N14—Cu2—O4^iii	91.68 (9)	C31—N32—C31^iii	117.8 (4)
N32^ii—Cu2—O4^iii	90.23 (5)	C31—N32—Cu2^iv	121.09 (18)
N25—Cu2—O4^iii	89.77 (5)	C31^iii—N32—Cu2^iv	121.09 (18)
N14^iii—Cu2—O4	91.68 (9)	C34—O33—C41	103.0 (3)
N14—Cu2—O4	88.32 (9)	O33—C34—C39	116.3 (4)
N32^ii—Cu2—O4	90.23 (5)	O33—C34—C35	122.3 (4)
N25—Cu2—O4	89.77 (5)	C39—C34—C35	121.4 (4)
O4^iii—Cu2—O4	179.54 (10)	C36—C35—C34	113.4 (4)
Cu1—O3—H3A	115.9	C36—C35—H35	123.3
Cu1—O3—H3B	125.6	C34—C35—H35	123.3
H3A—O3—H3B	96.2	C35—C36—C37	122.1 (4)
Cu2—O4—H4A	125.8	C35—C36—H36	119.0
Cu2—O4—H4B	132.8	C37—C36—H36	119.0
H4A—O4—H4B	97.4	C38—C37—C36	123.5 (4)
C6—N5—C10	117.9 (3)	C38—C37—H37	118.2
C6—N5—Cu1	121.3 (2)	C36—C37—H37	118.2
C10—N5—Cu1	120.8 (2)	C39—C38—C37	115.1 (4)
N5—C6—C7	122.8 (3)	C39—C38—H38	122.4
N5—C6—H6	118.6	C37—C38—H38	122.4
C7—C6—H6	118.6	C38—C39—C34	124.4 (4)
C6—C7—C8	119.9 (3)	C38—C39—C40	133.0 (4)
C6—C7—H7	120.1	C34—C39—C40	102.6 (3)
C8—C7—H7	120.1	C41—C40—C45	129.7 (3)
C7—C8—C9	117.3 (3)	C41—C40—C39	102.0 (3)
C7—C8—C11	121.2 (3)	C45—C40—C39	128.3 (3)
C9—C8—C11	121.5 (3)	C40—C41—O33	116.1 (4)
C10—C9—C8	119.6 (3)	C40—C41—C42	133.2 (4)
C10—C9—H9	120.2	O33—C41—C42	110.7 (3)
C8—C9—H9	120.2	O44—C42—O43	122.4 (4)
N5—C10—C9	122.5 (3)	O44—C42—C41	121.3 (4)
N5—C10—H10	118.7	O43—C42—C41	116.3 (3)
C9—C10—H10	118.7	O47—C45—O46	121.9 (4)
C12—C11—C16	116.8 (3)	O47—C45—C40	118.4 (4)
C12—C11—C8	121.1 (3)	O46—C45—C40	119.6 (3)
C16—C11—C8	122.1 (3)	C45—O46—H46	113.5
C13—C12—C11	119.7 (3)	C49—O48—C56	107.7 (3)
C13—C12—H12	120.1	O48—C49—C54	108.8 (4)
C11—C12—H12	120.1	O48—C49—C50	125.6 (4)
N14—C13—C12	123.4 (3)	C54—C49—C50	125.6 (4)
N14—C13—H13	118.3	C51—C50—C49	115.8 (4)
C12—C13—H13	118.3	C51—C50—H50	122.1
C13—N14—C15	117.5 (3)	C49—C50—H50	122.1
C13—N14—Cu2	120.4 (2)	C50—C51—C52	120.9 (4)
C15—N14—Cu2	122.1 (2)	C50—C51—H51	119.5
N14—C15—C16	122.2 (3)	C52—C51—H51	119.5
N14—C15—H15	118.9	C53—C52—C51	124.0 (4)
C16—C15—H15	118.9	C53—C52—H52	118.0
C15—C16—C11	120.4 (3)	C51—C52—H52	118.0
C15—C16—H16	119.8	C52—C53—C54	117.1 (4)
C11—C16—H16	119.8	C52—C53—H53	121.5
C18—N17—C18^i	118.0 (4)	C54—C53—H53	121.5
C18—N17—Cu1	121.02 (18)	C49—C54—C55	107.3 (3)
C18^i—N17—Cu1	121.02 (18)	C49—C54—C53	116.4 (4)
N17—C18—C19	122.6 (3)	C55—C54—C53	136.3 (4)
N17—C18—H18	118.7	C56—C55—C54	106.4 (4)
C19—C18—H18	118.7	C56—C55—C60	130.6 (4)
C18—C19—C20	120.3 (3)	C54—C55—C60	123.0 (4)
C18—C19—H19	119.8	C55—C56—O48	109.8 (4)
C20—C19—H19	119.8	C55—C56—C57	136.6 (4)
C19—C20—C19^i	116.1 (4)	O48—C56—C57	113.5 (3)
C19—C20—C21	121.96 (19)	O58—C57—O59	126.3 (4)
C19^i—C20—C21	121.96 (19)	O58—C57—C56	116.3 (3)
C22—C21—C22^i	116.1 (4)	O59—C57—C56	117.5 (3)
C22—C21—C20	121.94 (19)	O62—C60—O61	121.7 (4)
C22^i—C21—C20	121.9 (2)	O62—C60—C55	120.6 (5)
C23—C22—C21	120.1 (3)	O61—C60—C55	117.7 (4)
C23—C22—H22	119.9	C60—O61—H61	108.1
C21—C22—H22	119.9	H63A—O63—H63B	101.2
N24—C23—C22	123.3 (3)	H64A—O64—H64B	100.0
N24—C23—H23	118.3	H65A—O65—H65B	117.9
C22—C23—H23	118.3	H66A—O66—H66B	98.8
C23—N24—C23^i	116.9 (4)	H67A—O67—H67B	111.6
C23—N24—Cu1^iv	121.53 (18)

Symmetry codes: (i) −x+1/2, −y+1/2, z; (ii) −x+1/2, y, z−1/2; (iii) −x+1/2, −y−1/2, z; (iv) −x+1/2, y, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O63^i	0.85	1.89	2.730 (3)	168
O3—H3B···O67^i	0.85	1.90	2.738 (3)	167
O4—H4A···O64	0.85	1.96	2.764 (3)	159
O4—H4B···O63^v	0.85	1.99	2.817 (3)	164
O46—H46···O43	0.85	1.56	2.410 (4)	172
O61—H61···O59	0.85	1.74	2.594 (4)	179
O63—H63A···O43	0.85	1.90	2.740 (3)	172
O63—H63B···O58	0.85	1.86	2.702 (3)	173
O64—H64A···O65	0.85	1.93	2.779 (4)	174
O64—H64B···O66	0.85	1.97	2.790 (4)	163
O65—H65A···O47^vi	0.85	1.86	2.711 (4)	174
O65—H65B···O44	0.85	1.98	2.809 (4)	164
O66—H66A···O44	0.85	1.95	2.791 (5)	170
O66—H66B···O58	0.85	2.15	2.950 (4)	158
O67—H67A···O59	0.85	2.00	2.853 (4)	177
O67—H67B···O47^vii	0.85	2.06	2.896 (4)	167

Symmetry codes: (i) −x+1/2, −y+1/2, z; (v) −x+1, y−1/2, −z+1/2; (vi) −x+1, −y, −z; (vii) x, −y+1/2, z+1/2.