The coordination polymers poly[μ-4,4′-bipyrid­yl-di-μ-formato-copper(II)] and catena-poly[[[diaqua­(1-benzofuran-2,3-dicarboxyl­ato)copper(II)]-μ-1,2-di-4-pyridylethane] dihydrate]

The title compounds, [Cu(CHO₂)₂(C₁₀H₈N₂)]_n, (I), and {[Cu(C₁₀H₄O₅)(C₁₂H₁₂N₂)(H₂O)₂]·2H₂O}_n, (II), are composed of one-dimensional linear coordination polymers involving copper(II) ions and bidentate bipyridyl species. In (I), the polymeric chains are located on twofold rotation axes at (x, x, 0) and are arranged in layered zones centered at z = 0, , ½ and parallel to the ab plane of the tetra­gonal crystal. Weak coordination of the formate anions of one layer to the copper centers of neighboring layers imparts a three-dimensional connectivity to this structure. In (II), the polymeric chains propagate parallel to the a axis of the crystal. Noncoordinated water mol­ecules link the chains through O—H...O hydrogen bonding in directions perpendicular to c, imparting to the entire structure three-dimensional connectivity. The metal ions adopt distorted octa­hedral and square-based pyramidal environments in (I) and (II), respectively. This study indicates that, under the given conditions, extended coordination involves Cu^II centers associating with the bipyridyl ligands rather than with the competing benzofuran­dicarboxyl­ate entities.

S1. Comment

This study is part of our exploratory search for multidentate polycarboxylic acid ligands that can be utilized, in combination with metal ions, in the construction of framework solids (Goldberg, 2005). In earlier reports we investigated the supramolecular reactivity of a novel, previously unexplored ligand, 1-benzofuran-2,3-dicarboxylic acid (BFDC) (Koner & Goldberg, 2009a,b). It was shown that in reactions of BFDC with various metal ions, carried out under mild conditions, this ligand converts readily into a monoanionic species (BFDC^-) by deprotonation of one carboxylic group. The H atom in the second carboxylic group is then involved in an intramolecular hydrogen bond to the carboxylate function. BFDC^- was found to act as a good coordinating ligand, as well as a singly charged noncoordinated counter-anion to 2+ and 3+ transition metal cations (Koner & Goldberg, 2009a,b). It has also been shown that in more forcing (strongly basic) reaction environments it is possible to doubly deprotonate this ligand to a dianion, BFDC^2-, which can then function as a bridging ligand in the construction of extended coordination networks with an oxophilic metal ion such as La^III (Koner & Goldberg, 2009c). In subsequent investigations we have examined the reactivity of BFDC^2- towards Cu^II ions in the presence of dipyridyl ligands. As no coordination polymers have been obtained thus far by direct reaction between the benzofurandicarboxylic acid and copper ion moieties, we introduced (in addition to the BFDC) different bipyridine reagents into the reaction mixtures, anticipating that the latter might provide additional connectivity features and assist in the formation of polymeric aggregates (see Experimental). Here we report the structural features of two compounds synthesized in the above context: catena-poly[[diformatocopper(II)]-µ-4,4'-bipyridyl], (I), and catena-poly[[[diaqua(1-benzofuran-2,3-dicarboxylato)copper(II)]-µ-1, 2-di-4-pyridylethane] dihydrate], (II).

Displacement ellipsoid plots of the structures of (I) and (II) are depicted in Figs. 1 and 2, respectively. Disappointingly, in neither case was the BFDC^2- ligand involved in the formation of the polymer. It has not been incorporated into (I) at all, while in (II) it plays the role of a counter-ion coordinated to only one metal site. Instead, the two structures contain linear coordination polymers composed of alternating Cu^II ions and the respective bipyridyl ligands. Structure (I) resulted from the reaction of copper nitrate with 4,4'-bipyridine, BFDC and sodium hydroxide in a DMF (N,N-dimethylformamide)–water solvent environment. It turned out that in these experimental conditions, the DMF was hydrolysed to dimethylamine with the release of the formate (HCO₂^-) anion (Burrows et al., 2005; Muniappan et al., 2007), and the latter was incorporated into the crystal structure along with the copper ions. The FT IR (Fourier transform infrared?) spectrum of the solid product (see Experimental) was difficult to analyse due to partial overlap between absorption bands of the 4,4'-bipyridyl ligand (Litvinov et al., 2005; Popov et al., 1961) and the formate anion (Ito & Bernstein, 1956). It revealed typical signals for symmetric and asymmetric vibrations of the COO^- group and [for?] to ring vibrations of the coordinated 4,4'-bipyridyl ligand, as well as C—O and C—N stretch vibrations in the 1200–1300 cm^-1 region which could not be assigned to a specific group. The [Cu(CHO₂)₂–(4,4'-bipyridyl)]_n linear coordination polymer which formed is shown in Fig. 3. The polymer is located on a twofold rotation axis at (x, x, 0), with the metal ion and the N···N axis of the bipyridyl ligand positioned on it. The two formate anions are directed sideways. The polymers are aligned side by side in layers parallel to the ab plane of the tetragonal crystal (Fig. 3). The layers are centered at the z = 0, 1/4, 1/2 and 3/4 levels of the unit cell. Polymeric arrays located at z = 0 and 1/2 propagate along the [110] axis, while those at the z = 1/4 and 3/4 levels extend along the [110] axis (Fig. 4). Coordination of the pyridyl ligands and the two formate anions to the Cu^II ions define a square-based planar geometry [##AUTHOR: this metal centre is octahedral, not square planar - please re-word] with the corresponding Cu—N and Cu—O bond distances being around 2.0 Å (Table 1). A distorted octahedral environment around the metal ions is completed by two mutually trans axial Cu—O4 [2.468 (3) Å] bonds from adjacent polymeric arrays (Fig. 4). Thus, the O2 donor of every formate anion binds to the copper ion of a given polymeric chain, while the O4 donor is more weakly coordinated to a neighboring array. This corresponds to a strong Jahn–Teller effect, associated with a considerable axial distortion of the octahedral environment around the copper ions. The resulting intercoordinated structure thus represents a single-framework coordination polymer, with an unexpected connectivity scheme. There are no apparent voids in this architecture. The [(µ₂-4,4'-bipyridyl-N,N')copper]_n and [(µ₂-formato-O,O')copper]_n coordination polymers are abundant in the literature; a search of the Cambridge Structural Database (CSD; Allen, 2002; version 5.30, November 2008) revealed 438 and 57 hits, respectively, for these motifs. However, the simultaneous inter-coordination of copper ions via the two ligands into polymeric architectures has not been observed before.

The use of copper chloride instead of the copper nitrate in the second experiment with the 1,2-bis(4'-bipyridyl)ethane is associated with the replacement of the CHO₂^- anions by BFDC^2-. The polymeric arrangement of the constituent species in (II) is illustrated in Fig. 5. The copper(II) ion in this compound occupies a general position and is five coordinate with a square-based pyramidal geometry. The two mutually trans N-pyridyl donors, the monocoordinated carboxylate donor, and the O31 water molecule define the base of the pyramid, with Cu—O and Cu—N bonds of around 2.0 Å (Table 2). The O32 molecule of water coordinated at the apical site is more distant, as expected (Table 2). [##AUTHOR: it would be normal here to specify how far, and in what direction, the metal atom lies out of the basal plane.] The polymeric arrays propagate along the a axis (##AUTHOR: is "a-axis" correct?) of the crystal and are aligned parallel to the ab plane. The side-coordinated bulky BFDC^2- ligands impart an irregular shape to the polymeric arrays, apparently preventing close packing next to one another and inducing the incorporation of noncoordinated molecules of water as crystallization solvent in order to fill the interchain space. The latter are involved in hydrogen bonds with the surrounding polymers, interacting with the free carboxylate site of BFDC^2- and the Cu-bound water ligands (Table 3). The resulting structure thus combines coordination polymerization and hydrogen bonding between the constituent moieties (Fig. 6). Coordination polymers involving copper ions and the 1,2-bis(4-pyridyl)ethane ligand are also known, although to a much lesser extent than those with 4,4'-bipyridine; the CSD (Allen, 2002) lists a few tens of structures with the former versus hundreds with the latter (see above). However, in most of the reported examples the polymeric arrays are not in a fully extended form due to the flexibility of this ligand about the central CH₂—CH₂ bond (e.g. Power et al., 1998; Carlucci et al., 2000; Noro et al., 2006). Coordination complexes and polymers of copper with the divalent BFDC^2- ligand as counter-ion have not been reported before.

With a single exceptional example (Koner & Goldberg, 2009c), it is tentatively evident from our studies that the benzofurandicarboxylic acid has a low capacity to act as a bridging ligand and induce the formation of coordination polymers with transition metal ions. Copper(II) ions reveal a preference for N-donor over O-donor ligands, and thus more readily form coordination polymers with the bipyridyl moieties. The trans-disposition of the N sites in the bipyridine ligand, as opposed to the cis-disposition of the carboxylic functions in BFDC, may also favor coordination polymerization with the former. With Cu^II, both BFDC^1- (Koner & Goldberg, 2009a) and BFDC^2- (this study) play the role of coordinating counter-ions only. A somewhat more favorable situation has been experienced with La^III ions, which are characterized by a considerably higher affinity for oxo ligands, as is reflected in a recent report of a two-dimensional coordination network composed of La₂(BFDC^2-)₃ building blocks (Koner & Goldberg, 2009c).

Related literature

For related literature, see: Allen (2002); Burrows et al. (2005); Carlucci et al. (2000); Goldberg (2005); Ito & Bernstein (1956); Koner & Goldberg (2009a, 2009b, 2009c); Litvinov et al. (2005); Muniappan et al. (2007); Noro et al. (2006); Popov et al. (1961); Power et al. (1998).

S2. Experimental

##AUTHOR: Some re-wording here - please check.

All the reactants and solvents (see below) were obtained commercially. For (I), an aqueous solution (4 ml) of Cu(NO₃)₂.2.5H₂O (0.058 g, 0.25 mmol) was added dropwise with stirring to a solution containing 2,3-benzenofurandicarboxylic acid (0.052 g, 0.25 mmol) and NaOH (0.02 g, 0.5 mmol) in 1:1 DMF/H₂O (10 ml). The color of the solution changed from (##AUTHOR: from which colour?) to bluish-green. To this solution, 4,4'-bipyridine (0.078 g, 0.5 mmol) dissolved in DMF (5 ml) was added dropwise with stirring. The reaction mixture was then stirred further for 1 h, filtered, and the filtrate left undisturbed to allow slow evaporation. After a few days, green crystals were deposited, filtered, washed with DMF and air-dried. IR (KBr, cm^-1): (A) 1598s (ν_as of OCO^-),1380m (ν_s of OCO^-); (B) 1491m, 1402m, 1323s, ring stretching of the coordinated 4,4'-bipyridyl ligand. (C) 1308, 1298, 1270, 1224 and 1205, a series of bands associated with C—O and C—N stretching in the two ligands. For (II), CuCl₂.2(H₂O) (0.043 g, 0.25 mmol) was initially mixed with NaOH (0.02 g, 0.5 mmol) in water (10 ml), to yield Cu(OH)₂. The Cu(OH)₂ (0.25 mmol), 2,3-benzofurandicarboxylic acid (0.052 g, 0.25 mmol) and 1,2-bis(4-pyridyl)ethane (0.092 g, 0.5 mmol) were then dissolved in ammonia (25% v/v, 3 ml). Slow evaporation from the resulting solution at ambient temperature yielded blue single crystals of the final product. IR (KBr, cm^-1): 3383 (broad band of water O—H stretching modes), 1635s and 1609m (ν_as OCO), 1556s and 1487m (ν_s OCO).

S3. Refinement

The 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 and 0.99 Å and with U_iso(H) = 1.2 U_eq(C). H atoms bound to O atoms in (II) were either located in difference Fourier maps, or positioned to optimize intermolecular hydrogen bonding. All the O—H bond lengths were first restrained to 0.90 (2) Å, but then kept fixed in final least-squares cycles with U_iso(H) = 1.2 U_eq(O).

Computing details

For both compounds, 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: ORTEP-III (Burnett & Johnson, 1996); Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. #AUTHOR: some changes to text in these captions Fig. 1. Molecular structure of compound (I). It is located on a twofold rotation axis at (x, x, 0), and only atoms of the symmetric unit are labeled. Atoms Cu1, N5, C8, C9 and N12 are located on this symmetry axis. The atom ellipsoids represent displacement parameters at the 50% probability level at ca 110 K. [##AUTHOR: why ca 110 K?] Cu1 is further coordinated to a translation-related bipyridyl species. It is also approached by two symmetry-related formate anions at somewhat longer distances (Table 1), generating a distorted octahedral coordination.
	Fig. 2. Displacement ellipsoid plot of the asymmetric unit of compound (II), showing the atom-labeling scheme. The ellipsoids represent the 50% probability level at ca 110 K. [##AUTHOR: why ca 110 K?] H atoms, except for those of the water molecules, are omitted. Hydrogen bonds (Table 3) are denoted by dashed lines. Cu1 is further coordinated to a translation-related bipyridyl species (Table 2), generating a square-based pyramidal coordination.
	Fig. 3. Coordination polymers in (I), located at z = 1/4 in the unit cell (see text). This wireframe representation, with only the Cu^II ions depicted as small spheres, is a projection down the c axis. H atoms are omitted for clarity.
	Fig. 4. (a) The Cu^II ions in (I) are depicted as small spheres. Note that the polymeric chains at the consecutive z levels (0,1/4,1/2,3/4) of the unit cell propagate in perpendicular directions. Note also the cross-linking between the different polymers by the formate anions; (b) an expanded view of the octahedral environment of the copper(II) ion. The long trans-axial Cu—O bonds in the distorted octahedron are indicated by asterisks.
	Fig. 5. Ball-and-stick illustration of the fully extended coordination polymer in (II). Note the square-based pyramidal coordination environment around the copper(II) ions.
	Fig. 6. The copper(II) ions in (II) and the noncoordinated water molecules are depicted as small spheres. The hydrogen bonding between them is marked by dotted lines. On the right-hand side of the figure hydrogen bonds between the solvent water molecules and the polymeric arrays are also marked.

(I) poly[µ-4,4'-bipyridyl-di-µ-formato-copper(II)]

Crystal data

[Cu(CHO2)2(C10H8N2)]	Dx = 1.839 Mg m^−3
Mr = 309.76	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P41212	Cell parameters from 1314 reflections
Hall symbol: P 4abw 2nw	θ = 1.4–27.9°
a = 7.8505 (1) Å	µ = 1.96 mm^−1
c = 18.1513 (5) Å	T = 110 K
V = 1118.67 (4) Å^3	Prism, blue
Z = 4	0.30 × 0.20 × 0.15 mm
F(000) = 628

Data collection

Nonius KappaCCD diffractometer	1331 independent reflections
Radiation source: fine-focus sealed tube	1248 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 12.8 pixels mm^-1	θmax = 27.9°, θmin = 2.8°
1 deg. ϕ scans	h = −10→10
Absorption correction: multi-scan (Blessing, 1995)	k = −9→9
Tmin = 0.590, Tmax = 0.757	l = −18→23
6143 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.059P)^2 + 0.855P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.096	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 1.04 e Å^−3
1331 reflections	Δρmin = −0.65 e Å^−3
89 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0073 (17)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.04 (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	1.26627 (4)	0.26627 (4)	0.0000	0.01512 (18)
O2	1.1303 (3)	0.3879 (3)	0.07594 (13)	0.0205 (5)
C3	1.1710 (4)	0.5157 (4)	0.11449 (17)	0.0206 (7)
H3	1.2827	0.5597	0.1079	0.025*
O4	1.0792 (3)	0.5887 (3)	0.15995 (13)	0.0221 (5)
N5	1.0870	0.0870	0.0000	0.0162 (7)
C6	0.9193 (4)	0.1239 (4)	0.00905 (19)	0.0196 (6)
H6	0.8889	0.2399	0.0162	0.023*
C7	0.7894 (4)	0.0044 (4)	0.00865 (17)	0.0188 (6)
H7	0.6738	0.0380	0.0141	0.023*
C8	0.8331 (4)	−0.1669 (4)	0.0000	0.0159 (8)
C9	0.6992 (4)	−0.3008 (4)	0.0000	0.0144 (8)
C10	0.5533 (4)	−0.2852 (4)	−0.04349 (17)	0.0182 (6)
H10	0.5372	−0.1873	−0.0734	0.022*
C11	0.4330 (4)	−0.4128 (4)	−0.04267 (17)	0.0181 (6)
H11	0.3358	−0.4021	−0.0735	0.022*
N12	0.4478 (3)	−0.5522 (3)	0.0000	0.0160 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0131 (2)	0.0131 (2)	0.0192 (3)	−0.00253 (19)	0.00209 (13)	−0.00209 (13)
O2	0.0164 (11)	0.0168 (11)	0.0284 (12)	−0.0036 (9)	0.0021 (9)	−0.0061 (9)
C3	0.0162 (15)	0.0201 (16)	0.0255 (16)	−0.0016 (13)	0.0018 (12)	−0.0034 (13)
O4	0.0203 (11)	0.0210 (11)	0.0248 (11)	0.0025 (10)	0.0013 (9)	−0.0043 (9)
N5	0.0141 (10)	0.0141 (10)	0.0204 (17)	−0.0018 (13)	−0.0004 (12)	0.0004 (12)
C6	0.0126 (13)	0.0151 (14)	0.0310 (17)	0.0027 (11)	−0.0007 (12)	−0.0037 (12)
C7	0.0139 (13)	0.0169 (13)	0.0255 (16)	0.0007 (12)	−0.0012 (13)	−0.0008 (13)
C8	0.0164 (12)	0.0164 (12)	0.0149 (18)	−0.0035 (15)	−0.0028 (12)	0.0028 (12)
C9	0.0138 (12)	0.0138 (12)	0.0155 (18)	0.0039 (14)	0.0032 (11)	−0.0032 (11)
C10	0.0182 (14)	0.0151 (14)	0.0213 (15)	0.0003 (12)	0.0000 (11)	0.0003 (12)
C11	0.0138 (14)	0.0166 (14)	0.0240 (15)	−0.0004 (11)	−0.0010 (12)	0.0019 (12)
N12	0.0145 (10)	0.0145 (10)	0.0190 (17)	0.0006 (13)	0.0041 (11)	−0.0041 (11)

Geometric parameters (Å, º)

Cu1—O2	1.988 (2)	C6—H6	0.9500
Cu1—O4^i	2.468 (3)	C7—C8	1.397 (3)
Cu1—N5	1.9903 (5)	C7—H7	0.9500
Cu1—N12^ii	2.015 (3)	C8—C9	1.487 (6)
O2—C3	1.264 (4)	C9—C10	1.396 (4)
C3—O4	1.237 (4)	C10—C11	1.377 (4)
C3—H3	0.9500	C10—H10	0.9500
N5—C6	1.358 (3)	C11—N12	1.346 (3)
C6—C7	1.386 (4)	C11—H11	0.9500
O2—Cu1—O2^iii	175.39 (13)	C8—C7—H7	120.9
O2—Cu1—N5	87.70 (6)	C6—C7—H7	120.9
O2—Cu1—N12^ii	92.30 (6)	C7—C8—C7^iii	119.1 (4)
N5—Cu1—N12^ii	180.0	C7—C8—C9	120.46 (19)
C3—O2—Cu1	129.0 (2)	C10—C9—C10^iii	117.6 (4)
O4—C3—O2	126.1 (3)	C10—C9—C8	121.2 (2)
O4—C3—H3	117.0	C11—C10—C9	119.5 (3)
O2—C3—H3	117.0	C11—C10—H10	120.3
C6^iii—N5—C6	115.4 (2)	C9—C10—H10	120.3
C6—N5—Cu1	122.32 (12)	N12—C11—C10	122.6 (3)
N5—C6—C7	124.6 (2)	N12—C11—H11	118.7
N5—C6—H6	117.7	C10—C11—H11	118.7
C7—C6—H6	117.7	C11—N12—C11^iii	118.1 (4)
C8—C7—C6	118.1 (3)	C11—N12—Cu1^iv	120.96 (19)

Symmetry codes: (i) −x+5/2, y−1/2, −z+1/4; (ii) x+1, y+1, z; (iii) y+1, x−1, −z; (iv) x−1, y−1, z.

(II) catena-poly[[[diaqua(1-benzofuran-2,3-dicarboxylato)copper(II)]-µ- 1,2-di-4-pyridylethane] dihydrate]

Crystal data

[Cu(C10H4O5)(C12H12N2)(H2O)2]·2H2O	F(000) = 1084
Mr = 523.97	Dx = 1.552 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5078 reflections
a = 13.3333 (3) Å	θ = 1.4–27.9°
b = 15.1250 (3) Å	µ = 1.03 mm^−1
c = 11.9108 (2) Å	T = 110 K
β = 110.9824 (7)°	Prism, blue
V = 2242.73 (8) Å^3	0.40 × 0.25 × 0.20 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	5329 independent reflections
Radiation source: fine-focus sealed tube	3899 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
Detector resolution: 12.8 pixels mm^-1	θmax = 27.9°, θmin = 2.3°
1 deg. ϕ and ω scans	h = −17→16
Absorption correction: multi-scan (Blessing, 1995)	k = −19→0
Tmin = 0.683, Tmax = 0.820	l = 0→15
18429 measured 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.141	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0858P)^2] where P = (Fo^2 + 2Fc^2)/3
5329 reflections	(Δ/σ)max = 0.001
307 parameters	Δρmax = 0.80 e Å^−3
0 restraints	Δρmin = −0.83 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	0.36126 (3)	0.23473 (2)	0.60351 (3)	0.01696 (13)
O2	0.29595 (15)	0.18012 (13)	0.44165 (16)	0.0194 (4)
O3	0.27857 (16)	0.06147 (13)	0.54377 (16)	0.0231 (4)
C4	0.1799 (2)	0.06463 (18)	0.3353 (2)	0.0176 (6)
C5	0.0670 (2)	0.05405 (18)	0.3131 (2)	0.0184 (6)
C6	0.0000 (2)	0.06911 (19)	0.3789 (2)	0.0218 (6)
H6	0.0280	0.0926	0.4580	0.026*
C7	−0.1079 (2)	0.04877 (19)	0.3254 (2)	0.0231 (6)
H7	−0.1540	0.0561	0.3698	0.028*
C8	−0.1505 (2)	0.01747 (19)	0.2066 (2)	0.0228 (6)
H8	−0.2255	0.0065	0.1712	0.027*
C9	−0.0858 (2)	0.00217 (19)	0.1393 (2)	0.0215 (6)
H9	−0.1142	−0.0183	0.0586	0.026*
C10	0.0228 (2)	0.01875 (18)	0.1977 (2)	0.0198 (6)
O11	0.10146 (15)	0.00451 (13)	0.14996 (16)	0.0205 (4)
C12	0.1970 (2)	0.03324 (18)	0.2371 (2)	0.0189 (6)
C13	0.2982 (2)	0.02230 (19)	0.2113 (2)	0.0205 (6)
C14	0.2593 (2)	0.10290 (19)	0.4488 (2)	0.0194 (6)
O15	0.29016 (16)	−0.00579 (14)	0.10919 (17)	0.0248 (5)
O16	0.38236 (15)	0.04371 (13)	0.29652 (16)	0.0226 (4)
N17	0.51119 (19)	0.21458 (16)	0.6054 (2)	0.0197 (5)
C18	0.5884 (2)	0.2757 (2)	0.6587 (3)	0.0279 (7)
H18	0.5696	0.3266	0.6936	0.033*
C19	0.6914 (3)	0.2668 (2)	0.6640 (3)	0.0338 (8)
H19	0.7427	0.3112	0.7023	0.041*
C20	0.7228 (2)	0.1935 (2)	0.6138 (3)	0.0282 (7)
C21	0.6431 (2)	0.13121 (19)	0.5585 (2)	0.0224 (6)
H21	0.6598	0.0803	0.5218	0.027*
C22	0.5402 (2)	0.14334 (19)	0.5570 (2)	0.0199 (6)
H22	0.4876	0.0995	0.5202	0.024*
C23	0.8368 (3)	0.1811 (2)	0.6220 (4)	0.0411 (9)
H23A	0.8822	0.1693	0.7067	0.049*
H23B	0.8407	0.1287	0.5739	0.049*
C24	0.8807 (3)	0.2594 (3)	0.5783 (4)	0.0418 (9)
H24A	0.8726	0.3119	0.6240	0.050*
H24B	0.8358	0.2694	0.4929	0.050*
C25	0.9958 (2)	0.2542 (2)	0.5877 (3)	0.0239 (6)
C26	1.0714 (2)	0.2018 (2)	0.6728 (3)	0.0250 (6)
H26	1.0506	0.1670	0.7271	0.030*
C27	1.1762 (2)	0.2004 (2)	0.6782 (2)	0.0221 (6)
H27	1.2267	0.1652	0.7383	0.027*
N28	1.21064 (19)	0.24653 (15)	0.6023 (2)	0.0185 (5)
C29	1.1378 (2)	0.2970 (2)	0.5196 (2)	0.0215 (6)
H29	1.1604	0.3303	0.4653	0.026*
C30	1.0319 (2)	0.3026 (2)	0.5102 (3)	0.0230 (6)
H30	0.9835	0.3396	0.4508	0.028*
O31	0.41935 (19)	0.26374 (16)	0.7807 (2)	0.0345 (5)
H31A	0.4592	0.2181	0.8218	0.041*
H31B	0.4496	0.3179	0.7914	0.041*
O32	0.36172 (16)	0.36795 (14)	0.51047 (17)	0.0257 (5)
H32A	0.3386	0.4165	0.5376	0.031*
H32B	0.4196	0.3803	0.4913	0.031*
O33	0.42844 (18)	−0.02449 (15)	0.73691 (18)	0.0319 (5)
H33A	0.3819	0.0054	0.6748	0.038*
H33B	0.4859	−0.0254	0.7141	0.038*
O34	0.52177 (19)	0.09979 (16)	0.91024 (19)	0.0351 (5)
H34A	0.5921	0.0861	0.9356	0.042*
H34B	0.4814	0.0521	0.8778	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01330 (19)	0.0211 (2)	0.01723 (19)	−0.00048 (13)	0.00634 (13)	−0.00199 (12)
O2	0.0160 (10)	0.0238 (11)	0.0191 (9)	−0.0044 (8)	0.0073 (7)	−0.0025 (8)
O3	0.0231 (11)	0.0244 (11)	0.0183 (9)	0.0014 (8)	0.0030 (8)	0.0014 (8)
C4	0.0167 (14)	0.0159 (14)	0.0189 (13)	−0.0011 (11)	0.0047 (10)	0.0016 (10)
C5	0.0190 (14)	0.0157 (13)	0.0200 (13)	−0.0014 (11)	0.0062 (10)	0.0007 (10)
C6	0.0236 (15)	0.0231 (15)	0.0181 (13)	−0.0001 (12)	0.0067 (11)	−0.0020 (11)
C7	0.0214 (15)	0.0244 (16)	0.0257 (14)	0.0011 (12)	0.0110 (11)	0.0006 (11)
C8	0.0163 (14)	0.0213 (15)	0.0286 (15)	−0.0046 (11)	0.0056 (11)	0.0006 (12)
C9	0.0220 (15)	0.0181 (14)	0.0218 (13)	−0.0023 (11)	0.0045 (11)	−0.0010 (11)
C10	0.0216 (15)	0.0171 (14)	0.0212 (13)	0.0012 (11)	0.0084 (11)	0.0018 (11)
O11	0.0162 (10)	0.0261 (11)	0.0186 (9)	−0.0027 (8)	0.0056 (7)	−0.0025 (8)
C12	0.0169 (14)	0.0206 (14)	0.0172 (12)	−0.0021 (11)	0.0036 (10)	−0.0007 (11)
C13	0.0213 (15)	0.0201 (14)	0.0201 (13)	0.0013 (11)	0.0075 (11)	0.0015 (11)
C14	0.0132 (13)	0.0244 (15)	0.0211 (13)	0.0019 (11)	0.0068 (10)	−0.0026 (11)
O15	0.0240 (11)	0.0303 (12)	0.0222 (10)	−0.0014 (9)	0.0107 (8)	−0.0035 (8)
O16	0.0174 (10)	0.0268 (11)	0.0233 (10)	−0.0021 (8)	0.0069 (8)	−0.0030 (8)
N17	0.0148 (11)	0.0249 (13)	0.0195 (11)	0.0001 (9)	0.0062 (9)	−0.0012 (9)
C18	0.0210 (16)	0.0278 (17)	0.0350 (17)	−0.0050 (12)	0.0100 (13)	−0.0109 (13)
C19	0.0186 (16)	0.0313 (18)	0.051 (2)	−0.0078 (13)	0.0118 (14)	−0.0115 (15)
C20	0.0203 (15)	0.0222 (16)	0.0447 (18)	−0.0013 (12)	0.0147 (13)	−0.0013 (13)
C21	0.0224 (15)	0.0205 (15)	0.0261 (14)	0.0031 (12)	0.0107 (11)	−0.0010 (11)
C22	0.0197 (14)	0.0205 (14)	0.0209 (13)	0.0003 (11)	0.0092 (11)	0.0001 (11)
C23	0.0197 (17)	0.0322 (19)	0.076 (3)	0.0008 (14)	0.0233 (17)	−0.0015 (17)
C24	0.0233 (17)	0.044 (2)	0.067 (3)	0.0089 (15)	0.0262 (17)	0.0222 (18)
C25	0.0173 (15)	0.0241 (16)	0.0335 (16)	0.0029 (11)	0.0131 (12)	0.0007 (12)
C26	0.0239 (16)	0.0273 (16)	0.0289 (15)	0.0011 (13)	0.0156 (12)	0.0044 (12)
C27	0.0201 (15)	0.0243 (15)	0.0237 (13)	0.0030 (12)	0.0101 (11)	0.0019 (11)
N28	0.0155 (11)	0.0234 (13)	0.0174 (11)	0.0004 (9)	0.0068 (9)	−0.0008 (9)
C29	0.0189 (14)	0.0225 (15)	0.0231 (14)	−0.0014 (12)	0.0074 (11)	0.0013 (11)
C30	0.0170 (14)	0.0244 (15)	0.0271 (14)	0.0030 (12)	0.0071 (11)	0.0043 (12)
O31	0.0324 (13)	0.0358 (13)	0.0330 (12)	0.0011 (10)	0.0088 (10)	−0.0011 (10)
O32	0.0255 (11)	0.0227 (11)	0.0326 (11)	0.0002 (9)	0.0151 (9)	0.0014 (9)
O33	0.0274 (12)	0.0399 (13)	0.0303 (11)	0.0084 (10)	0.0126 (9)	0.0119 (10)
O34	0.0343 (13)	0.0359 (13)	0.0377 (12)	0.0081 (10)	0.0160 (10)	0.0017 (10)

Geometric parameters (Å, º)

Cu1—O2	1.9887 (18)	C20—C21	1.396 (4)
Cu1—O31	2.019 (2)	C20—C23	1.499 (4)
Cu1—O32	2.301 (2)	C21—C22	1.378 (4)
Cu1—N17	2.014 (2)	C21—H21	0.9500
Cu1—N28^i	2.011 (2)	C22—H22	0.9500
O2—C14	1.281 (3)	C23—C24	1.495 (5)
O3—C14	1.236 (3)	C23—H23A	0.9900
C4—C12	1.355 (4)	C23—H23B	0.9900
C4—C5	1.440 (4)	C24—C25	1.501 (5)
C4—C14	1.503 (4)	C24—H24A	0.9900
C5—C10	1.393 (4)	C24—H24B	0.9900
C5—C6	1.402 (4)	C25—C30	1.391 (4)
C6—C7	1.383 (4)	C25—C26	1.393 (4)
C6—H6	0.9500	C26—C27	1.376 (4)
C7—C8	1.405 (4)	C26—H26	0.9500
C7—H7	0.9500	C27—N28	1.346 (4)
C8—C9	1.391 (4)	C27—H27	0.9500
C8—H8	0.9500	N28—C29	1.346 (4)
C9—C10	1.387 (4)	N28—Cu1^ii	2.011 (2)
C9—H9	0.9500	C29—C30	1.379 (4)
C10—O11	1.377 (3)	C29—H29	0.9500
O11—C12	1.393 (3)	C30—H30	0.9500
C12—C13	1.498 (4)	O31—H31A	0.9010
C13—O15	1.256 (3)	O31—H31B	0.9012
C13—O16	1.256 (3)	O32—H32A	0.8995
N17—C22	1.342 (4)	O32—H32B	0.8994
N17—C18	1.360 (4)	O33—H33A	0.8994
C18—C19	1.359 (5)	O33—H33B	0.8994
C18—H18	0.9500	O34—H34A	0.8998
C19—C20	1.394 (5)	O34—H34B	0.8996
C19—H19	0.9500
O2—Cu1—O31	167.04 (9)	C18—C19—H19	119.6
O2—Cu1—O32	88.43 (7)	C20—C19—H19	119.6
O2—Cu1—N17	92.08 (9)	C19—C20—C21	116.4 (3)
O2—Cu1—N28^i	86.58 (9)	C19—C20—C23	121.6 (3)
O31—Cu1—O32	104.30 (9)	C21—C20—C23	121.9 (3)
O31—Cu1—N17	90.78 (10)	C22—C21—C20	120.2 (3)
O31—Cu1—N28^i	89.79 (10)	C22—C21—H21	119.9
O32—Cu1—N17	87.94 (9)	C20—C21—H21	119.9
O32—Cu1—N28^i	95.38 (8)	N17—C22—C21	122.7 (3)
N17—Cu1—N28^i	176.38 (10)	N17—C22—H22	118.7
C14—O2—Cu1	111.04 (16)	C21—C22—H22	118.7
C12—C4—C5	106.9 (2)	C24—C23—C20	113.1 (3)
C12—C4—C14	129.0 (2)	C24—C23—H23A	109.0
C5—C4—C14	124.1 (2)	C20—C23—H23A	109.0
C10—C5—C6	119.0 (3)	C24—C23—H23B	109.0
C10—C5—C4	105.6 (2)	C20—C23—H23B	109.0
C6—C5—C4	135.4 (3)	H23A—C23—H23B	107.8
C7—C6—C5	118.2 (3)	C23—C24—C25	116.8 (3)
C7—C6—H6	120.9	C23—C24—H24A	108.1
C5—C6—H6	120.9	C25—C24—H24A	108.1
C6—C7—C8	121.2 (3)	C23—C24—H24B	108.1
C6—C7—H7	119.4	C25—C24—H24B	108.1
C8—C7—H7	119.4	H24A—C24—H24B	107.3
C9—C8—C7	121.7 (3)	C30—C25—C26	116.8 (3)
C9—C8—H8	119.1	C30—C25—C24	120.7 (3)
C7—C8—H8	119.1	C26—C25—C24	122.6 (3)
C10—C9—C8	115.7 (3)	C27—C26—C25	120.1 (3)
C10—C9—H9	122.2	C27—C26—H26	120.0
C8—C9—H9	122.2	C25—C26—H26	120.0
O11—C10—C9	125.3 (3)	N28—C27—C26	123.0 (3)
O11—C10—C5	110.6 (2)	N28—C27—H27	118.5
C9—C10—C5	124.1 (3)	C26—C27—H27	118.5
C10—O11—C12	105.8 (2)	C27—N28—C29	117.1 (2)
C4—C12—O11	111.2 (2)	C27—N28—Cu1^ii	121.92 (19)
C4—C12—C13	131.2 (2)	C29—N28—Cu1^ii	120.85 (19)
O11—C12—C13	117.6 (2)	N28—C29—C30	123.0 (3)
O15—C13—O16	127.7 (3)	N28—C29—H29	118.5
O15—C13—C12	117.7 (2)	C30—C29—H29	118.5
O16—C13—C12	114.5 (2)	C29—C30—C25	120.1 (3)
O3—C14—O2	124.3 (2)	C29—C30—H30	120.0
O3—C14—C4	118.5 (3)	C25—C30—H30	120.0
O2—C14—C4	117.0 (2)	Cu1—O31—H31A	109.4
C22—N17—C18	117.4 (2)	Cu1—O31—H31B	109.2
C22—N17—Cu1	123.62 (19)	H31A—O31—H31B	118.1
C18—N17—Cu1	119.0 (2)	Cu1—O32—H32A	118.8
C19—C18—N17	122.5 (3)	Cu1—O32—H32B	117.0
C19—C18—H18	118.7	H32A—O32—H32B	110.9
N17—C18—H18	118.7	H33A—O33—H33B	99.9
C18—C19—C20	120.8 (3)	H34A—O34—H34B	110.5

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O31—H31B···O16^iii	0.90	2.29	2.971 (3)	133
O31—H31A···O34	0.90	2.09	2.981 (3)	168
O32—H32A···O15^iii	0.90	1.83	2.728 (3)	172
O32—H32B···O34^iv	0.90	1.95	2.836 (3)	166
O33—H33A···O3	0.90	1.87	2.772 (3)	176
O33—H33B···O16^v	0.90	1.83	2.707 (3)	165
O34—H34A···O15^v	0.90	2.20	2.963 (3)	143
O34—H34B···O33	0.90	1.95	2.739 (3)	145

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