Supra­molecular architecture of metal-organic frameworks involving dinuclear copper paddle-wheel complexes

The two centrosymmetric dinuclear copper paddle-wheel complexes tetra­kis­([mu]-4-hy­droxy­benzoato-[kappa]²O:O')bis­[aqua­copper(II)] di­methyl­formamide disolvate dihydrate, [Cu₂(C₇H₅O₃)₄(H₂O)₂]·2C₃H₇NO·2H₂O, (I), and tetra­kis­([mu]-4-meth­oxy­benzoato-[kappa]²O:O')bis­[(di­methyl­formamide-[kappa]O)copper(II)], [Cu₂(C₈H₇O₃)₄(C₃H₇NO)₂], (II), crystallize with half of the dinuclear paddle-wheel cage unit in the asymmetric unit and, in addition, complex (I) has one di­methyl­formamide (DMF) and one water solvent mol­ecule in the asymmetric unit. In both (I) and (II), two Cu^II ions are bridged by four syn,syn-[eta]¹:[eta]¹:[mu] carboxyl­ate groups, showing a paddle-wheel cage-type structure with a square-pyramidal coordination geometry. The equatorial positions of (I) and (II) are occupied by the carboxyl­ate groups of 4-hy­droxy- and 4-meth­oxy­benzoate ligands, and the axial positions are occupied by aqua and DMF ligands, respectively. The three-dimensional supra­molecular metal-organic framework of (I) consists of three different R₂²(20) and an R₄⁴(36) ring motif formed via O-H...O and OW-HW...O hydrogen bonds. Complex (II) simply packs as mol­ecular species.

S1. Introduction

The coordination chemistry of copper complexes involving carboxyl­ate groups which show flexible coordination modes toward metal cations, such as monodentate, chelate and η¹:η¹:µ bridging ligands in syn–syn, syn–anti and anti–anti conformations, has been studied for a long time. Dinuclear copper(II) complexes with carboxyl­ate O:O'-bridges are widely known for intra­molecular magnetic exchange and magneto-structural correlation studies (Kato & Muto, 1988; Melnik, 1982; Sesto et al., 2000). In many examples, copper(II) carboxyl­ates prefer the dinuclear paddle-wheel cage structure. Approximately 250 structures containing the Cu₂(RCOO)₄ core can be found in the Cambridge Structural Database (Allen, 2002), of which 186 are of the Cu₂(RCOO)₄(L)₂ type, where L is an apical ligand with an O- or N-donor atom (Allen et al., 1983).

Ever since the first tetra­carboxyl­ate-bridged copper(II) dimer structure was reported for copper(II) acetate dihydrate [Cu₂(MeCO₂)₄(H₂O)₂] (van Niekerk & Schoening, 1953), a variety of carboxyl­ate groups have been used in the design of paddle-wheel cage compounds (Catterick & Thornton, 1977; Porter et al., 1986).

Dimeric copper(II) carboxyl­ates and their adducts are good models for the design of anti-inflammatory drugs (Demertzi et al., 2004; Weder et al., 1999) and for magnetic exchange studies between paramagnetic molecules (Sundberg et al., 1996).

We report two copper dinuclear paddle-wheel complexes, namely tetra­kis(µ₂-4-hy­droxy­benzoato-κ²O:O')bis­[aqua­copper(II)] di­methyl­formamide disolvate dihydrate, (I), and tetra­kis(µ₂-4-meth­oxy­benzoato-κ²O:O')bis­[(di­methyl­formamide-κO)copper(II)], (II).

S2. Experimental

S2.1. Synthesis and crystallization

Complexes (I) and (II) were prepared by mixing hot aqueous solutions (10 ml) of copper nitrate hexahydrate (Loba; 73.9 mg, 0.25 mmol) with hot ethano­lic solutions (10 ml) of 4-HBA (Loba; 34.5 mg, 0.5 mmol) or 4-MBA (Sisco; 38 mg, 0.5 mmol) in 1:2 ratios. In each case, the resulting reaction mixture was stirred for 20 min. To the hot reaction mixture, di­methyl­formamide (10 ml) was added and stirring was continued for another 30 min at 318 K. After a few weeks, green prismatic crystals of (I) and (II) were obtained from their mother solutions.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The water H atoms for (I) were located in difference Fourier maps and refined freely. Water H atoms were restrained to have O—H distances of 0.89 (2) Å and H···H distances of 1.36 (1) Å. All other H atoms were positioned geometrically and were refined using riding model. The O—H and C—H bond lengths are 0.82 Å for O—H, 0.93 Å for methine C—H and 0.96 Å for methyl C—H. The U_iso(H) values were set at 1.2U_eq(C) for aromatic and at 1.5U_eq(C,O) for methyl and hy­droxy H atoms.

S3. Results and discussion

The asymmetric unit of (I) contains half a molecule of the dinuclear paddle-wheel unit [the molecules crystallize about an inversion center at (0, 0, 1)], one di­methyl­formamide (DMF) solvent molecule and one water molecule (Fig. 1). The asymmetric unit of (II) contains half a molecule of the dinuclear paddle-wheel unit; the molecules crystalize about an inversion center at (0.5, 0.5, 0) (Fig. 2). In both (I) and (II), the two Cu^II ions are bridged by four syn,syn-η¹:η¹:µ carboxyl­ate groups, showing a paddle-wheel cage type with a square-pyramidal geometry (Reger et al.,2012). In each of (I) and (II), the dinuclear copper unit sits about an inversion centre, so that one half of the unit is related to the other.

In complex (I), each Cu^II ion is coordinated with four different O atoms from the carboxyl­ate groups of 4-hy­droxy­benzoate (4HBA) ligands which occupy the equatorial positions; the axial position is occupied by a water O atom (O1w) to form a paddle-wheel building block. In complex (II), each Cu^II ion is coordinated with four different carboxyl­ate O atoms of 4-meth­oxy­benzoate (4MBA) ligands in the equatorial positions; the axial position is occupied by DMF atom O5 to form a paddle-wheel cage unit. As expected, the axial Cu—O(H₂O) bond length in (I) and Cu—O(4DMF) bond length in (II) are notably longer than the basal distances between the Cu atoms and the carboxyl­ate O atoms of 4HBA and 4MBA (Tables 2 and 3). This clearly indicates that there is a slight distortion from ideal square-pyramidal geometry which is due to Jahn–Teller distortion. In both (I) and (II), the central Cu^II atom moves above the equatorial (eq) O₄ plane towards the axial (ax) H₂O ligand in (I) and towards the DMF ligand in (II). The displacement distances of (I) and (II) are 0.149 and 0.158 Å, respectively. This displacement induces deviations from the ideal bond angles of 90 (α) and 180° (β) (where α = O_ax—Cu—O_eq and β = O_eq—Cu—O_eq). The values of α and β are 91.59 (5)–99.17 (5) and 168.95 (5)–169.14 (5)° for (I), and 92.83 (9)–98.81 (9) and 168.35 (9)–168.57 (9)° for (II). The deviations of the Cu—Cu—O_ax and Cu—Cu—O_eq bond angles from 180 and 90°, respectively, are also evidence for Jahn–Teller distortion. The corresponding values are 177.34 (4) and 83.00 (4)–86.28 (4)° for (I), and 173.20 (7) and 81.14 (7)–87.47 (6)° for (II), respectively. Jahn–Teller distortion is quite common for a series of copper(II) carboxyl­ate-type complexes reported in the literature (reference?).

The Cu···Cu separations in the dinuclear copper units in (I) and (II) are 2.6047 (3) and 2.6279 (7) Å, respectively, and these values are in close agreement with reported values (Youngme et al., 2008; Luo et al., 2008; Burrows et al., 2008). There are some general trends that can be seen by comparison of several copper acetate-type complexes from the literature (Reinen & Friebel, 1984; Sundberg et al., 1996). Both (I) and (II) agree with this general trend. We have tabulated (Table 4) some copper acetate-type complexes and verified the generalization with complexes (I) and (II). From the table, we concluded that if the Cu···Cu distance decreases, the Cu—O_ax distance increases and vice versa. For dimeric copper paddle-wheel complexes, a shortening or lengthening of the Cu···Cu distance is compensated by an elongation or compression of the Cu—O_ax bond length. The O_ax—Cu···Cu—O_ax distance is almost the same as that of sum of the Cu···Cu and Cu—O_ax distances. The nature of the substituent on the carboxyl­ate ligand strongly influences the pK_a value of the acid, the O—C—O angle in the bridge and the Cu···Cu distance. Electron-withdrawing groups lower the pK_a value, increase the acidity (which enhances the Cu···Cu distance), widen the O—C—O angle and increase? the displacement of the Cu^II atom out of the mean O₄ plane, or vice versa for electron-donating groups.

In (I), two centrosymmetric dinuclear paddle-wheel units in the same and adjacent planes are connected by three different R₂²(20) ring motifs formed via two pairs of Ow—Hw···O and a pair of O—H···O hydrogen bonds (Table 5). The first two R₂²(20) ring motifs link the coordinated water molecule (O1w) with atoms O6ⁱⁱⁱ and O3^iv of 4HBA in the same and adjacent planes, respectively, and the ring motifs extend along the b and c axes [symmetry codes: (iii) x, y+1, z; (iv) x+1, y, z-1]. The formation of the two R₂²(20) ring motifs are shown Fig. 3. The R₂²(20) ring motif shown in the middle connects two adjacent planes together. Further neighbouring paddle-wheel units inter­act via O—H···O hydrogen bonds by linking coordinated hy­droxy atom O3 and carboxyl­ate atom O4ⁱⁱ of two different 4HBA ligands which are nearly perpendicular to each other (86.43°) to form the third R₂²(20) ring motif [symmetry code: (ii) -x, -y, -z+3]. The lattice water molecule O2w links coordinated carboxyl­ate atom O2^vi of 4HBA and DMF atom O7 through Ow—Hw···O hydrogen bonds [symmetry code: (vi) -x, -y+1, -z+2]. Hy­droxy atom O6 of 4HBA links the noncoordinated atom O2w^v via an O—H···Ow hydrogen bond [symmetry code: (v) -x+1, -y, -z+2]. These hydrogen bonds link the symmetry-related coordinated water molecules and coordinated 4HBA ligands of four paddle-wheel units together to generate an R₄⁴(36) ring motif. Two centrosymmetric DMF solvent molecules are in the inter­stitial pockets [R₄⁴(36) ring motif]. The alternative occurrence of R₂²(20) and R₄⁴(36) motifs develop an extended three-dimensional supra­molecular metal–organic framework (MOF).

In complex (II), as the hydrogen-bond acceptor sites are blocked by a methyl group, the molecular packing is not governed by standard hydrogen bonds. Complex (II) packs in a regular array of molecules.

Related literature

For related literature, see: Allen et al. (1983); Bruker (2008); Burrows et al. (2008); Cason (2004); Catterick & Thornton (1977); Demertzi et al. (2004); Kato & Muto (1988); Luo et al. (2008); Macrae et al. (2008); Melnik (1982); Porter et al. (1986); Reger et al. (2012); Sesto et al. (2000); Sheldrick (2008); Spek (2009); Sundberg et al. (1996); Van Niekerk & Schoening (1953); Weder et al. (1999); Westrip (2010); Youngme et al. (2008).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009), Mercury (Macrae et al., 2008) and POVRay (Cason, 2004); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The asymmetric unit of complex (I), shown with 50% probability displacement ellipsoids. [Symmetry code: (i) -x, -y, -z+2.]
	Fig. 2. The asymmetric unit of complex (II), shown with 50% probability displacement ellipsoids. [Symmetry code: (i) -x+1, -y+1, -z.]
	Fig. 3. Supramolecular extended three-dimensional network of complex (I) formed via O—H···O and Ow—Hw···O hydrogen bonds. [Symmetry codes: (ii) -x, -y, -z+3; (iii) x, y+1, z; (iv) x+1, y, z-1; (v) -x+1, -y, -z+2; (vi) -x, -y+1, -z+2.]

(I) Tetrakis(µ₂-4-hydroxybenzoato-κ²O:O')bis[aquacopper(II)] dimethylformamide disolvate dihydrate

Crystal data

[Cu2(C7H5O3)4(H2O)2]·2C3H7NO·2H2O	Z = 1
Mr = 893.80	F(000) = 462
Triclinic, P1	Dx = 1.505 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6946 (2) Å	Cell parameters from 7410 reflections
b = 10.4874 (2) Å	θ = 2.0–34.2°
c = 10.6819 (2) Å	µ = 1.16 mm^−1
α = 82.458 (1)°	T = 296 K
β = 66.951 (1)°	Prism, green
γ = 81.904 (1)°	0.07 × 0.06 × 0.05 mm
V = 985.92 (3) Å^3

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	7410 independent reflections
Radiation source: fine-focus sealed tube	6012 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ and ω scans	θmax = 34.2°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→14
Tmin = 0.923, Tmax = 0.944	k = −16→15
25865 measured reflections	l = −16→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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0595P)^2 + 0.1947P] where P = (Fo^2 + 2Fc^2)/3
7410 reflections	(Δ/σ)max = 0.001
269 parameters	Δρmax = 0.87 e Å^−3
6 restraints	Δρmin = −0.46 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	0.12523 (2)	0.04275 (2)	0.98664 (2)	0.0231 (1)
O1	0.02547 (14)	0.07665 (14)	1.17865 (12)	0.0362 (4)
O1W	0.32575 (15)	0.12007 (15)	0.97081 (15)	0.0412 (4)
O2	−0.19177 (14)	0.00829 (14)	1.19902 (12)	0.0380 (4)
O3	−0.35748 (14)	0.10062 (16)	1.81253 (12)	0.0417 (4)
O4	0.18360 (14)	−0.13767 (12)	1.04773 (14)	0.0344 (4)
O5	−0.02961 (15)	−0.20825 (12)	1.06350 (15)	0.0393 (4)
O6	0.2989 (2)	−0.74078 (13)	1.19313 (19)	0.0515 (5)
C1	−0.10823 (18)	0.05123 (15)	1.24698 (15)	0.0270 (4)
C2	−0.17307 (18)	0.07130 (16)	1.39481 (16)	0.0277 (4)
C3	−0.3109 (2)	0.0260 (2)	1.47762 (18)	0.0412 (6)
C4	−0.3706 (2)	0.0372 (2)	1.61579 (19)	0.0427 (6)
C5	−0.29251 (18)	0.09474 (18)	1.67455 (16)	0.0309 (4)
C6	−0.15588 (19)	0.14203 (18)	1.59360 (17)	0.0333 (5)
C7	−0.09568 (19)	0.12926 (18)	1.45465 (17)	0.0318 (4)
C8	0.09771 (18)	−0.22693 (16)	1.07056 (16)	0.0279 (4)
C9	0.15242 (19)	−0.36133 (16)	1.10561 (17)	0.0299 (4)
C10	0.2905 (2)	−0.38989 (18)	1.1190 (2)	0.0398 (6)
C11	0.3411 (2)	−0.51542 (18)	1.1498 (2)	0.0426 (6)
C12	0.2537 (2)	−0.61547 (17)	1.1657 (2)	0.0374 (5)
C13	0.1162 (2)	−0.58870 (19)	1.1515 (2)	0.0444 (6)
C14	0.0658 (2)	−0.46248 (18)	1.1226 (2)	0.0385 (5)
O7	0.3696 (5)	0.5656 (5)	0.7052 (6)	0.192 (3)
N1	0.2926 (3)	0.4283 (3)	0.6114 (3)	0.0798 (10)
C15	0.3065 (7)	0.5469 (5)	0.6250 (8)	0.160 (3)
C16	0.2181 (10)	0.3964 (13)	0.5339 (8)	0.326 (7)
C17	0.3537 (9)	0.3237 (7)	0.6676 (9)	0.253 (5)
O2W	0.4439 (2)	0.76965 (19)	0.7709 (2)	0.0675 (7)
H1W	0.314 (2)	0.158 (2)	1.0370 (18)	0.0490*
H2W	0.4217 (18)	0.105 (2)	0.927 (2)	0.0490*
H3	−0.36350	−0.01250	1.43870	0.0490*
H3A	−0.29280	0.10840	1.84180	0.0630*
H4	−0.46280	0.00650	1.66980	0.0510*
H6	−0.10480	0.18230	1.63270	0.0400*
H6A	0.38590	−0.74670	1.18860	0.0770*
H7	−0.00310	0.15950	1.40080	0.0380*
H10	0.35000	−0.32350	1.10710	0.0480*
H11	0.43310	−0.53300	1.15990	0.0510*
H13	0.05790	−0.65540	1.16130	0.0530*
H14	−0.02710	−0.44490	1.11440	0.0460*
H15	0.27150	0.61600	0.57770	0.1920*
H16A	0.29040	0.36400	0.45070	0.4910*
H16B	0.16000	0.47200	0.51280	0.4910*
H16C	0.15220	0.33130	0.58460	0.4910*
H17A	0.34780	0.34150	0.75560	0.3800*
H17B	0.29930	0.25080	0.67770	0.3800*
H17C	0.45720	0.30470	0.60940	0.3800*
H3W	0.406 (3)	0.710 (2)	0.751 (3)	0.0810*
H4W	0.378 (3)	0.827 (2)	0.801 (3)	0.0810*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0228 (1)	0.0257 (1)	0.0224 (1)	−0.0018 (1)	−0.0099 (1)	−0.0036 (1)
O1	0.0321 (6)	0.0513 (8)	0.0250 (6)	−0.0090 (5)	−0.0066 (5)	−0.0110 (5)
O1W	0.0288 (6)	0.0579 (9)	0.0393 (7)	−0.0110 (6)	−0.0098 (5)	−0.0148 (6)
O2	0.0339 (6)	0.0580 (8)	0.0248 (6)	−0.0093 (6)	−0.0099 (5)	−0.0114 (5)
O3	0.0312 (6)	0.0736 (10)	0.0229 (6)	−0.0083 (6)	−0.0101 (5)	−0.0101 (6)
O4	0.0362 (6)	0.0263 (6)	0.0474 (7)	−0.0019 (5)	−0.0244 (6)	0.0001 (5)
O5	0.0341 (6)	0.0306 (6)	0.0572 (8)	−0.0021 (5)	−0.0243 (6)	0.0037 (6)
O6	0.0673 (10)	0.0266 (7)	0.0762 (11)	0.0055 (6)	−0.0469 (9)	−0.0057 (7)
C1	0.0307 (7)	0.0277 (7)	0.0232 (7)	0.0010 (6)	−0.0118 (6)	−0.0038 (5)
C2	0.0281 (7)	0.0317 (8)	0.0240 (7)	−0.0013 (6)	−0.0107 (6)	−0.0039 (6)
C3	0.0334 (8)	0.0682 (13)	0.0279 (8)	−0.0167 (8)	−0.0125 (7)	−0.0091 (8)
C4	0.0321 (8)	0.0714 (14)	0.0271 (8)	−0.0189 (9)	−0.0089 (7)	−0.0055 (8)
C5	0.0285 (7)	0.0420 (9)	0.0235 (7)	−0.0001 (6)	−0.0119 (6)	−0.0046 (6)
C6	0.0319 (8)	0.0437 (9)	0.0284 (8)	−0.0064 (7)	−0.0128 (6)	−0.0096 (7)
C7	0.0296 (7)	0.0394 (9)	0.0274 (7)	−0.0070 (6)	−0.0101 (6)	−0.0049 (6)
C8	0.0322 (7)	0.0282 (7)	0.0251 (7)	0.0001 (6)	−0.0136 (6)	−0.0034 (6)
C9	0.0336 (8)	0.0261 (7)	0.0316 (8)	0.0009 (6)	−0.0157 (6)	−0.0019 (6)
C10	0.0373 (9)	0.0300 (8)	0.0566 (12)	−0.0022 (7)	−0.0242 (8)	0.0003 (8)
C11	0.0409 (10)	0.0319 (9)	0.0615 (13)	0.0027 (7)	−0.0294 (9)	−0.0013 (8)
C12	0.0489 (10)	0.0275 (8)	0.0414 (9)	0.0028 (7)	−0.0249 (8)	−0.0047 (7)
C13	0.0510 (11)	0.0290 (9)	0.0638 (13)	−0.0043 (8)	−0.0335 (10)	−0.0023 (8)
C14	0.0405 (9)	0.0302 (8)	0.0539 (11)	−0.0018 (7)	−0.0286 (8)	−0.0024 (8)
O7	0.163 (4)	0.183 (4)	0.281 (6)	−0.025 (3)	−0.111 (4)	−0.104 (4)
N1	0.0809 (18)	0.0665 (16)	0.0754 (17)	−0.0111 (14)	−0.0104 (14)	−0.0063 (13)
C15	0.111 (4)	0.091 (4)	0.199 (7)	0.005 (3)	0.014 (4)	0.008 (4)
C16	0.173 (7)	0.68 (2)	0.157 (7)	−0.111 (11)	−0.020 (6)	−0.204 (11)
C17	0.166 (7)	0.162 (6)	0.288 (10)	0.013 (5)	0.012 (6)	0.127 (6)
O2W	0.0478 (9)	0.0554 (11)	0.0954 (15)	0.0111 (8)	−0.0288 (10)	−0.0056 (10)

Geometric parameters (Å, º)

Cu1—O1	1.9519 (12)	C4—C5	1.390 (3)
Cu1—O1W	2.1484 (16)	C5—C6	1.387 (3)
Cu1—O4	1.9974 (13)	C6—C7	1.383 (2)
Cu1—O2^i	1.9533 (12)	C8—C9	1.488 (2)
Cu1—O5^i	1.9622 (14)	C9—C14	1.394 (3)
O1—C1	1.261 (2)	C9—C10	1.389 (3)
O2—C1	1.269 (2)	C10—C11	1.383 (3)
O3—C5	1.363 (2)	C11—C12	1.392 (3)
O4—C8	1.277 (2)	C12—C13	1.386 (3)
O5—C8	1.252 (2)	C13—C14	1.384 (3)
O6—C12	1.357 (2)	C3—H3	0.9300
O1W—H2W	0.86 (2)	C4—H4	0.9300
O1W—H1W	0.818 (19)	C6—H6	0.9300
O3—H3A	0.8200	C7—H7	0.9300
O6—H6A	0.8200	C10—H10	0.9300
O7—C15	1.279 (9)	C11—H11	0.9300
O2W—H3W	0.86 (3)	C13—H13	0.9300
O2W—H4W	0.81 (3)	C14—H14	0.9300
N1—C15	1.302 (6)	C15—H15	0.9300
N1—C16	1.389 (10)	C16—H16B	0.9600
N1—C17	1.355 (9)	C16—H16C	0.9600
C1—C2	1.485 (2)	C16—H16A	0.9600
C2—C7	1.395 (3)	C17—H17C	0.9600
C2—C3	1.392 (3)	C17—H17A	0.9600
C3—C4	1.373 (3)	C17—H17B	0.9600
Cu1···O2	3.0595 (14)	C10···O3^ii	3.416 (3)
Cu1···O5	3.0720 (14)	C11···C11^x	3.482 (3)
Cu1···O3^ii	3.7302 (14)	C11···O2W^vii	3.376 (3)
Cu1···O4^i	3.1647 (15)	C12···O2W^vii	3.406 (3)
Cu1···O1^i	3.1520 (14)	C14···C14^xi	3.542 (3)
Cu1···H4W^iii	3.30 (3)	C1···H4W^vi	2.95 (3)
Cu1···H17B	3.6400	C3···H3^xii	2.9400
Cu1···H3A^ii	3.0600	C4···H3^xii	2.9100
O1···O1W	2.943 (2)	C4···H17C^viii	3.0600
O1···O4	2.7448 (19)	C5···H2W^viii	3.02 (2)
O1···C8	3.415 (2)	C7···H15^vi	3.0200
O1···Cu1^i	3.1520 (14)	C8···H3A^ii	2.8900
O1···O5^i	2.7558 (19)	C10···H3A^ii	3.0400
O1W···O2^i	3.126 (2)	C12···H1W^iii	2.78 (2)
O1W···O4	3.076 (2)	C14···H14^xi	3.0000
O1W···O6^iv	2.856 (2)	C15···H3W	2.79 (3)
O1W···O1	2.943 (2)	C15···H17C^xiii	3.0700
O1W···O3^v	2.860 (2)	H1W···C12^iv	2.78 (2)
O1W···O3^ii	3.124 (2)	H1W···H6A^iv	2.3700
O1W···O5^i	3.036 (2)	H1W···O6^iv	2.040 (19)
O2···O2W^vi	3.079 (3)	H2W···C5^v	3.02 (2)
O2···O5	2.7928 (19)	H2W···H3A^v	2.5600
O2···O1W^i	3.126 (2)	H2W···O3^v	2.00 (2)
O2···C8^i	3.344 (2)	H3···O2	2.4500
O2···Cu1	3.0595 (14)	H3···C3^xii	2.9400
O2···O4^i	2.7790 (18)	H3···H3^xii	2.4400
O2W···O2^vi	3.079 (3)	H3···C4^xii	2.9100
O2W···O6^vii	2.639 (3)	H3···H4^xii	2.3800
O2W···C11^vii	3.376 (3)	H3A···O1W^ii	2.8800
O2W···O4^iv	3.206 (2)	H3A···O4^ii	1.9400
O2W···C12^vii	3.406 (3)	H3A···H2W^viii	2.5600
O2W···O7	2.611 (6)	H3A···H6	2.3800
O3···C10^ii	3.416 (3)	H3A···Cu1^ii	3.0600
O3···Cu1^ii	3.7302 (14)	H3A···C8^ii	2.8900
O3···O1W^viii	2.860 (2)	H3A···C10^ii	3.0400
O3···O4^ii	2.744 (2)	H3A···H10^ii	2.3300
O3···O1W^ii	3.124 (2)	H3W···C15	2.79 (3)
O4···O2^i	2.7790 (18)	H3W···H6A^vii	2.4400
O4···O3^ii	2.744 (2)	H3W···H11^vii	2.5800
O4···Cu1^i	3.1647 (15)	H3W···O7	1.77 (2)
O4···C1	3.357 (2)	H4···O2W^xiv	2.7100
O4···O1W	3.076 (2)	H4···H4W^xiv	2.5100
O4···O1	2.7448 (19)	H4···H3^xii	2.3800
O4···O2W^iii	3.206 (2)	H4W···H6A^vii	2.3600
O5···O1W^i	3.036 (2)	H4W···O4^iv	2.61 (3)
O5···O1^i	2.7558 (19)	H4W···Cu1^iv	3.30 (3)
O5···Cu1	3.0720 (14)	H4W···C1^vi	2.95 (3)
O5···C1^i	3.349 (2)	H4W···H4^ix	2.5100
O5···O2	2.7928 (19)	H4W···O2^vi	2.32 (3)
O5···C1	3.387 (2)	H6···H3A	2.3800
O6···O1W^iii	2.856 (2)	H6A···H11	2.3100
O6···O2W^vii	2.639 (3)	H6A···H4W^vii	2.3600
O7···O2W	2.611 (6)	H6A···H1W^iii	2.3700
O1···H7	2.5300	H6A···H3W^vii	2.4400
O1···H1W	2.80 (2)	H6A···O2W^vii	1.8400
O1···H13^iv	2.8500	H7···O1	2.5300
O1W···H3A^ii	2.8800	H10···H3A^ii	2.3300
O2···H3	2.4500	H10···O3^ii	2.6100
O2···H4W^vi	2.32 (3)	H10···O4	2.5300
O2W···H6A^vii	1.8400	H11···H6A	2.3100
O2W···H11^vii	2.7400	H11···O2W^vii	2.7400
O2W···H4^ix	2.7100	H11···O7^vii	2.7700
O3···H10^ii	2.6100	H11···H3W^vii	2.5800
O3···H2W^viii	2.00 (2)	H13···O1^iii	2.8500
O4···H3A^ii	1.9400	H14···C14^xi	3.0000
O4···H4W^iii	2.61 (3)	H14···O5	2.4700
O4···H10	2.5300	H15···C7^vi	3.0200
O5···H14	2.4700	H15···H16B	2.2900
O6···H1W^iii	2.040 (19)	H16A···H17B	2.5800
O7···H17A	2.3600	H16B···H15	2.2900
O7···H11^vii	2.7700	H16C···H17B	2.0700
O7···H3W	1.77 (2)	H17A···O7	2.3600
C1···C8	3.592 (2)	H17B···Cu1	3.6400
C6···C7^ii	3.429 (3)	H17B···H16C	2.0700
C7···C7^ii	3.322 (3)	H17B···H16A	2.5800
C7···C6^ii	3.429 (3)	H17C···C4^v	3.0600
C8···C1	3.592 (2)	H17C···C15^xiii	3.0700
O1—Cu1—O1W	91.59 (6)	C8—C9—C10	121.59 (16)
O1—Cu1—O4	88.05 (6)	C8—C9—C14	119.89 (17)
O1—Cu1—O2^i	169.14 (6)	C9—C10—C11	121.08 (18)
O1—Cu1—O5^i	89.51 (6)	C10—C11—C12	119.73 (19)
O1W—Cu1—O4	95.72 (6)	O6—C12—C13	117.74 (18)
O1W—Cu1—O2^i	99.17 (6)	C11—C12—C13	119.89 (17)
O1W—Cu1—O5^i	95.12 (6)	O6—C12—C11	122.4 (2)
O2^i—Cu1—O4	89.40 (6)	C12—C13—C14	119.85 (19)
O4—Cu1—O5^i	168.95 (6)	C9—C14—C13	120.94 (19)
O2^i—Cu1—O5^i	91.00 (6)	C2—C3—H3	119.00
Cu1—O1—C1	121.14 (12)	C4—C3—H3	119.00
Cu1^i—O2—C1	124.61 (11)	C5—C4—H4	120.00
Cu1—O4—C8	120.84 (12)	C3—C4—H4	120.00
Cu1^i—O5—C8	126.23 (12)	C7—C6—H6	120.00
H1W—O1W—H2W	107 (2)	C5—C6—H6	120.00
Cu1—O1W—H1W	113.1 (14)	C6—C7—H7	120.00
Cu1—O1W—H2W	137.0 (13)	C2—C7—H7	120.00
C5—O3—H3A	109.00	C9—C10—H10	119.00
C12—O6—H6A	110.00	C11—C10—H10	119.00
H3W—O2W—H4W	109 (3)	C10—C11—H11	120.00
C16—N1—C17	113.3 (7)	C12—C11—H11	120.00
C15—N1—C16	123.3 (7)	C14—C13—H13	120.00
C15—N1—C17	123.4 (5)	C12—C13—H13	120.00
O1—C1—O2	124.76 (14)	C9—C14—H14	120.00
O1—C1—C2	118.05 (16)	C13—C14—H14	120.00
O2—C1—C2	117.19 (15)	O7—C15—N1	118.1 (6)
C3—C2—C7	118.76 (15)	N1—C15—H15	121.00
C1—C2—C3	119.62 (16)	O7—C15—H15	121.00
C1—C2—C7	121.55 (16)	N1—C16—H16A	109.00
C2—C3—C4	121.17 (18)	N1—C16—H16B	109.00
C3—C4—C5	119.67 (18)	H16A—C16—H16B	109.00
C4—C5—C6	120.09 (16)	H16A—C16—H16C	109.00
O3—C5—C4	116.40 (16)	N1—C16—H16C	110.00
O3—C5—C6	123.52 (17)	H16B—C16—H16C	109.00
C5—C6—C7	119.93 (17)	N1—C17—H17B	109.00
C2—C7—C6	120.38 (17)	N1—C17—H17C	109.00
O4—C8—O5	123.74 (16)	N1—C17—H17A	109.00
O4—C8—C9	118.34 (17)	H17A—C17—H17C	109.00
O5—C8—C9	117.91 (16)	H17B—C17—H17C	109.00
C10—C9—C14	118.50 (17)	H17A—C17—H17B	109.00
O1W—Cu1—O1—C1	178.42 (14)	C7—C2—C3—C4	−0.2 (3)
O4—Cu1—O1—C1	−85.91 (14)	C1—C2—C3—C4	176.76 (18)
O5^i—Cu1—O1—C1	83.31 (14)	C3—C2—C7—C6	−0.5 (3)
O1—Cu1—O4—C8	89.64 (13)	C1—C2—C7—C6	−177.35 (17)
O1W—Cu1—O4—C8	−178.96 (13)	C2—C3—C4—C5	0.0 (3)
O2^i—Cu1—O4—C8	−79.80 (13)	C3—C4—C5—O3	−178.97 (18)
O1W—Cu1—O2^i—C1^i	−174.10 (14)	C3—C4—C5—C6	0.8 (3)
O4—Cu1—O2^i—C1^i	90.21 (14)	C4—C5—C6—C7	−1.5 (3)
O1—Cu1—O5^i—C8^i	−87.26 (15)	O3—C5—C6—C7	178.31 (18)
O1W—Cu1—O5^i—C8^i	−178.81 (15)	C5—C6—C7—C2	1.3 (3)
Cu1—O1—C1—O2	−3.4 (2)	O5—C8—C9—C10	−178.31 (17)
Cu1—O1—C1—C2	175.91 (11)	O5—C8—C9—C14	3.2 (2)
Cu1^i—O2—C1—O1	6.0 (2)	O4—C8—C9—C14	−175.90 (16)
Cu1^i—O2—C1—C2	−173.29 (11)	O4—C8—C9—C10	2.6 (2)
Cu1—O4—C8—O5	−3.6 (2)	C8—C9—C14—C13	178.21 (17)
Cu1—O4—C8—C9	175.43 (11)	C8—C9—C10—C11	−179.12 (17)
Cu1^i—O5—C8—O4	1.3 (2)	C14—C9—C10—C11	−0.6 (3)
Cu1^i—O5—C8—C9	−177.75 (11)	C10—C9—C14—C13	−0.3 (3)
C17—N1—C15—O7	−6.4 (10)	C9—C10—C11—C12	1.0 (3)
C16—N1—C15—O7	176.0 (7)	C10—C11—C12—C13	−0.4 (3)
O1—C1—C2—C7	6.7 (2)	C10—C11—C12—O6	178.60 (19)
O2—C1—C2—C3	9.2 (2)	O6—C12—C13—C14	−179.57 (19)
O1—C1—C2—C3	−170.16 (17)	C11—C12—C13—C14	−0.5 (3)
O2—C1—C2—C7	−173.97 (17)	C12—C13—C14—C9	0.9 (3)

Symmetry codes: (i) −x, −y, −z+2; (ii) −x, −y, −z+3; (iii) x, y−1, z; (iv) x, y+1, z; (v) x+1, y, z−1; (vi) −x, −y+1, −z+2; (vii) −x+1, −y, −z+2; (viii) x−1, y, z+1; (ix) x+1, y+1, z−1; (x) −x+1, −y−1, −z+2; (xi) −x, −y−1, −z+2; (xii) −x−1, −y, −z+3; (xiii) −x+1, −y+1, −z+1; (xiv) x−1, y−1, z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O6^iv	0.818 (19)	2.040 (19)	2.856 (2)	175.7 (16)
O1W—H2W···O3^v	0.86 (2)	2.00 (2)	2.860 (2)	171 (2)
O3—H3A···O4^ii	0.82	1.94	2.744 (2)	165
O2W—H3W···O7	0.86 (3)	1.77 (2)	2.611 (6)	166 (3)
O2W—H4W···O2^vi	0.81 (3)	2.32 (3)	3.079 (3)	157 (3)
O6—H6A···O2W^vii	0.82	1.84	2.639 (3)	164
C3—H3···O2	0.93	2.45	2.760 (2)	100

Symmetry codes: (ii) −x, −y, −z+3; (iv) x, y+1, z; (v) x+1, y, z−1; (vi) −x, −y+1, −z+2; (vii) −x+1, −y, −z+2.

(II) Tetrakis(µ-4-methoxybenzoato-κ²O:O')bis[(dimethylformamide-κO)copper(II)]

Crystal data

[Cu2(C8H7O3)4(C3H7NO)2]	F(000) = 908
Mr = 877.84	Dx = 1.450 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3473 reflections
a = 12.2001 (2) Å	θ = 1.7–24.9°
b = 18.1548 (4) Å	µ = 1.13 mm^−1
c = 9.2514 (2) Å	T = 296 K
β = 101.042 (1)°	Prism, green
V = 2011.16 (7) Å^3	0.09 × 0.07 × 0.06 mm
Z = 2

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	3473 independent reflections
Radiation source: fine-focus sealed tube	2564 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ϕ and ω scans	θmax = 24.9°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→14
Tmin = 0.905, Tmax = 0.936	k = −21→21
32954 measured reflections	l = −10→10

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0481P)^2 + 1.0802P] where P = (Fo^2 + 2Fc^2)/3
3473 reflections	(Δ/σ)max = 0.001
257 parameters	Δρmax = 0.57 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	0.55072 (3)	0.45201 (2)	0.09644 (4)	0.0597 (2)
O1	0.5703 (2)	0.51884 (14)	−0.1977 (2)	0.0779 (9)
O2	0.54988 (19)	0.61824 (13)	0.0277 (3)	0.0739 (9)
O3	0.6394 (2)	0.53650 (13)	0.1882 (2)	0.0736 (9)
O4	0.65873 (18)	0.43842 (12)	−0.0319 (2)	0.0668 (8)
O5	0.61516 (19)	0.36784 (12)	0.2586 (2)	0.0666 (8)
O6	0.8945 (3)	0.82733 (17)	0.4535 (4)	0.1168 (14)
O7	0.9425 (2)	0.4022 (2)	−0.5281 (3)	0.1168 (14)
N1	0.6014 (3)	0.31144 (16)	0.4744 (3)	0.0726 (10)
C1	0.6227 (3)	0.60117 (19)	0.1390 (4)	0.0640 (11)
C2	0.6927 (3)	0.66211 (19)	0.2184 (4)	0.0644 (12)
C3	0.7845 (4)	0.6489 (2)	0.3284 (5)	0.0927 (16)
C4	0.8480 (4)	0.7046 (2)	0.4012 (5)	0.1026 (17)
C5	0.8221 (3)	0.7752 (2)	0.3684 (5)	0.0856 (16)
C6	0.7328 (4)	0.7916 (2)	0.2640 (6)	0.105 (2)
C7	0.6689 (4)	0.7345 (2)	0.1865 (5)	0.1001 (19)
C8	0.8634 (4)	0.8996 (3)	0.4348 (6)	0.123 (3)
C9	0.6465 (3)	0.47266 (18)	−0.1526 (4)	0.0614 (11)
C10	0.7268 (3)	0.45676 (17)	−0.2509 (3)	0.0575 (11)
C11	0.8200 (3)	0.41320 (19)	−0.2048 (4)	0.0687 (12)
C12	0.8919 (3)	0.3972 (2)	−0.2976 (4)	0.0830 (16)
C13	0.8694 (3)	0.4237 (2)	−0.4419 (4)	0.0761 (14)
C14	0.7777 (3)	0.46720 (19)	−0.4891 (4)	0.0673 (11)
C15	0.7082 (3)	0.48357 (18)	−0.3941 (3)	0.0633 (11)
C16	0.9174 (4)	0.4211 (3)	−0.6809 (5)	0.130 (2)
C17	0.5726 (3)	0.35971 (18)	0.3678 (3)	0.0667 (11)
C18	0.6927 (4)	0.2616 (2)	0.4730 (4)	0.0965 (19)
C19	0.5465 (4)	0.3088 (2)	0.6006 (4)	0.1023 (18)
H3	0.80380	0.60040	0.35390	0.1110*
H4	0.90960	0.69340	0.47390	0.1230*
H6	0.71330	0.84050	0.24290	0.1260*
H7	0.60900	0.74640	0.11180	0.1210*
H8A	0.91960	0.93020	0.49230	0.1840*
H8B	0.79360	0.90690	0.46640	0.1840*
H8C	0.85510	0.91250	0.33270	0.1840*
H11	0.83410	0.39450	−0.10950	0.0820*
H12	0.95530	0.36890	−0.26470	0.1000*
H14	0.76290	0.48540	−0.58490	0.0810*
H15	0.64660	0.51360	−0.42620	0.0760*
H16A	0.97430	0.40170	−0.72900	0.1950*
H16B	0.91470	0.47370	−0.69120	0.1950*
H16C	0.84640	0.40050	−0.72520	0.1950*
H17	0.51380	0.39100	0.37590	0.0800*
H18A	0.74780	0.26810	0.56120	0.1450*
H18B	0.72550	0.27170	0.38870	0.1450*
H18C	0.66570	0.21180	0.46810	0.1450*
H19A	0.51470	0.26080	0.60710	0.1540*
H19B	0.48840	0.34520	0.58930	0.1540*
H19C	0.60010	0.31860	0.68890	0.1540*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0766 (3)	0.0623 (3)	0.0426 (2)	0.0156 (2)	0.0175 (2)	0.0121 (2)
O1	0.0916 (17)	0.0874 (17)	0.0626 (14)	0.0321 (15)	0.0349 (13)	0.0212 (13)
O2	0.0820 (16)	0.0734 (15)	0.0649 (15)	0.0057 (12)	0.0104 (12)	0.0175 (12)
O3	0.0984 (17)	0.0638 (15)	0.0551 (14)	0.0105 (12)	0.0056 (12)	0.0053 (11)
O4	0.0788 (15)	0.0724 (15)	0.0524 (13)	0.0143 (12)	0.0205 (11)	0.0101 (11)
O5	0.0876 (16)	0.0639 (14)	0.0488 (13)	0.0102 (12)	0.0147 (11)	0.0113 (11)
O6	0.114 (2)	0.078 (2)	0.158 (3)	0.0109 (18)	0.025 (2)	−0.011 (2)
O7	0.100 (2)	0.171 (3)	0.094 (2)	0.042 (2)	0.0551 (18)	0.021 (2)
N1	0.100 (2)	0.0635 (18)	0.0499 (16)	−0.0109 (16)	0.0030 (15)	0.0124 (14)
C1	0.075 (2)	0.069 (2)	0.0538 (19)	0.0150 (18)	0.0268 (17)	0.0077 (17)
C2	0.068 (2)	0.066 (2)	0.065 (2)	0.0118 (17)	0.0276 (17)	0.0068 (17)
C3	0.111 (3)	0.069 (2)	0.090 (3)	0.014 (2)	−0.001 (2)	−0.004 (2)
C4	0.110 (3)	0.080 (3)	0.107 (3)	0.018 (3)	−0.006 (3)	−0.009 (3)
C5	0.073 (2)	0.083 (3)	0.102 (3)	0.011 (2)	0.020 (2)	−0.009 (2)
C6	0.112 (4)	0.058 (2)	0.141 (4)	0.005 (2)	0.018 (3)	0.017 (3)
C7	0.091 (3)	0.078 (3)	0.123 (4)	0.003 (2)	0.000 (3)	0.024 (3)
C8	0.116 (4)	0.110 (4)	0.148 (5)	0.013 (3)	0.037 (3)	0.014 (3)
C9	0.070 (2)	0.064 (2)	0.0528 (19)	0.0036 (17)	0.0185 (16)	0.0000 (16)
C10	0.0631 (19)	0.0606 (19)	0.0503 (18)	−0.0012 (15)	0.0150 (14)	−0.0030 (15)
C11	0.073 (2)	0.078 (2)	0.056 (2)	0.0074 (18)	0.0145 (17)	0.0075 (17)
C12	0.068 (2)	0.105 (3)	0.080 (3)	0.020 (2)	0.024 (2)	0.010 (2)
C13	0.073 (2)	0.094 (3)	0.068 (2)	−0.001 (2)	0.0306 (19)	0.000 (2)
C14	0.068 (2)	0.084 (2)	0.0511 (19)	−0.0009 (18)	0.0147 (16)	0.0056 (17)
C15	0.066 (2)	0.071 (2)	0.0534 (19)	0.0057 (17)	0.0131 (16)	0.0024 (16)
C16	0.138 (4)	0.184 (5)	0.087 (3)	0.035 (4)	0.068 (3)	0.014 (3)
C17	0.086 (2)	0.063 (2)	0.0487 (19)	−0.0012 (17)	0.0072 (17)	0.0094 (16)
C18	0.128 (4)	0.072 (3)	0.076 (3)	0.009 (2)	−0.014 (2)	0.012 (2)
C19	0.155 (4)	0.101 (3)	0.052 (2)	−0.033 (3)	0.023 (2)	0.015 (2)

Geometric parameters (Å, º)

Cu1—O3	1.973 (2)	C10—C15	1.389 (4)
Cu1—O4	1.951 (2)	C11—C12	1.371 (5)
Cu1—O5	2.180 (2)	C12—C13	1.396 (5)
Cu1—O1^i	1.967 (2)	C13—C14	1.371 (5)
Cu1—O2^i	1.978 (3)	C14—C15	1.366 (5)
O1—C9	1.262 (4)	C3—H3	0.9300
O2—C1	1.263 (4)	C4—H4	0.9300
O3—C1	1.262 (4)	C6—H6	0.9300
O4—C9	1.262 (4)	C7—H7	0.9300
O5—C17	1.230 (4)	C8—H8A	0.9600
O6—C5	1.425 (5)	C8—H8B	0.9600
O6—C8	1.368 (6)	C8—H8C	0.9600
O7—C13	1.362 (5)	C11—H11	0.9300
O7—C16	1.430 (5)	C12—H12	0.9300
N1—C17	1.316 (4)	C14—H14	0.9300
N1—C18	1.437 (6)	C15—H15	0.9300
N1—C19	1.454 (5)	C16—H16A	0.9600
C1—C2	1.501 (5)	C16—H16B	0.9600
C2—C3	1.382 (6)	C16—H16C	0.9600
C2—C7	1.366 (5)	C17—H17	0.9300
C3—C4	1.370 (6)	C18—H18A	0.9600
C4—C5	1.341 (5)	C18—H18B	0.9600
C5—C6	1.344 (7)	C18—H18C	0.9600
C6—C7	1.408 (6)	C19—H19A	0.9600
C9—C10	1.487 (5)	C19—H19B	0.9600
C10—C11	1.384 (5)	C19—H19C	0.9600
Cu1···O1	3.030 (2)	C6···H8B	2.8100
Cu1···O2	3.084 (2)	C8···H16A^xi	3.0000
Cu1···O3^i	3.165 (2)	C8···H6	2.5300
Cu1···O4^i	3.203 (2)	C9···H8B^viii	2.9100
Cu1···H14^ii	3.5800	C10···H19C^ix	2.9400
Cu1···H18C^iii	3.5900	C10···H8C^viii	2.8700
O1···Cu1	3.030 (2)	C12···H18A^ix	3.0700
O1···O2	2.805 (3)	C14···H16B	2.7400
O1···C1	3.403 (4)	C14···H3^ix	2.8700
O1···C1^i	3.328 (4)	C14···H16C	2.7600
O1···O3^i	2.766 (3)	C16···H14	2.5200
O1···O5^i	3.030 (3)	C17···H7^vi	3.0600
O1···C17^i	3.054 (4)	C18···H19C^iii	3.0300
O2···O1	2.805 (3)	C19···H7^vi	2.7000
O2···C9^i	3.295 (4)	H3···O3	2.5600
O2···Cu1	3.084 (2)	H3···C14^ii	2.8700
O2···O4^i	2.752 (3)	H3···H14^ii	2.2400
O2···O5^i	3.015 (3)	H4···O7^iv	2.4800
O3···C14^ii	3.378 (4)	H6···C8	2.5300
O3···C9	3.376 (4)	H6···H8B	2.4300
O3···O5	3.156 (3)	H6···H8C	2.2000
O3···O1^i	2.766 (3)	H7···O2	2.5100
O3···O4	2.749 (3)	H7···N1^v	2.8000
O3···Cu1^i	3.165 (2)	H7···C17^v	3.0600
O4···C1	3.419 (4)	H7···C19^v	2.7000
O4···O5	3.114 (3)	H7···H19A^v	2.3000
O4···O2^i	2.752 (3)	H8B···C6	2.8100
O4···Cu1^i	3.203 (2)	H8B···H6	2.4300
O4···O3	2.749 (3)	H8B···C1^vii	2.8600
O5···C14^ii	3.296 (4)	H8B···C9^vii	2.9100
O5···O2^i	3.015 (3)	H8C···C6	2.6600
O5···O1^i	3.030 (3)	H8C···H6	2.2000
O5···O4	3.114 (3)	H8C···H16A^xi	2.4600
O5···O3	3.156 (3)	H8C···C10^vii	2.8700
O7···C4^iv	3.244 (5)	H11···O4	2.5100
O1···H17^i	2.4100	H14···Cu1^ix	3.5800
O1···H15	2.4700	H14···O3^ix	2.5200
O2···H19A^v	2.9200	H14···C3^ix	3.1000
O2···H7	2.5100	H14···C16	2.5200
O3···H3	2.5600	H14···H3^ix	2.2400
O3···H14^ii	2.5200	H14···H16B	2.2700
O4···H18C^iii	2.7300	H14···H16C	2.3700
O4···H11	2.5100	H15···O1	2.4700
O5···H18B	2.3800	H16A···C8^xii	3.0000
O5···H16C^ii	2.8600	H16A···H8C^xii	2.4600
O5···H19A^iii	2.8700	H16B···C14	2.7400
O7···H4^iv	2.4800	H16B···H14	2.2700
N1···H7^vi	2.8000	H16C···O5^ix	2.8600
C1···C9^i	3.572 (5)	H16C···C14	2.7600
C4···O7^iv	3.244 (5)	H16C···H14	2.3700
C8···C9^vii	3.495 (6)	H17···H19B	2.2200
C8···C10^vii	3.381 (6)	H17···O1^i	2.4100
C9···C8^viii	3.495 (6)	H18A···C12^ii	3.0700
C9···C1^i	3.572 (5)	H18A···H19C	2.5100
C10···C8^viii	3.381 (6)	H18B···O5	2.3800
C10···C19^ix	3.576 (5)	H18C···H19A	2.6000
C14···C17^ix	3.249 (5)	H18C···Cu1^xiii	3.5900
C14···O5^ix	3.296 (4)	H18C···O4^xiii	2.7300
C14···O3^ix	3.378 (4)	H19A···H18C	2.6000
C15···C17^ix	3.354 (4)	H19A···O2^vi	2.9200
C17···C14^ii	3.249 (5)	H19A···H7^vi	2.3000
C17···C15^ii	3.354 (4)	H19A···O5^xiii	2.8700
C19···C10^ii	3.576 (5)	H19B···H17	2.2200
C1···H8B^viii	2.8600	H19B···C2^x	3.0900
C2···H19B^x	3.0900	H19C···C10^ii	2.9400
C3···H14^ii	3.1000	H19C···H18A	2.5100
C6···H8C	2.6600	H19C···C18^xiii	3.0300
O3—Cu1—O4	88.94 (9)	C10—C15—C14	122.0 (3)
O3—Cu1—O5	98.81 (8)	O5—C17—N1	127.0 (3)
O1^i—Cu1—O3	89.18 (10)	C2—C3—H3	119.00
O2^i—Cu1—O3	168.34 (10)	C4—C3—H3	119.00
O4—Cu1—O5	97.68 (9)	C3—C4—H4	120.00
O1^i—Cu1—O4	168.57 (9)	C5—C4—H4	120.00
O2^i—Cu1—O4	88.94 (10)	C5—C6—H6	120.00
O1^i—Cu1—O5	93.76 (9)	C7—C6—H6	120.00
O2^i—Cu1—O5	92.84 (9)	C2—C7—H7	119.00
O1^i—Cu1—O2^i	90.64 (10)	C6—C7—H7	119.00
Cu1^i—O1—C9	126.4 (2)	O6—C8—H8A	109.00
Cu1^i—O2—C1	125.2 (2)	O6—C8—H8B	110.00
Cu1—O3—C1	122.1 (2)	O6—C8—H8C	109.00
Cu1—O4—C9	119.8 (2)	H8A—C8—H8B	109.00
Cu1—O5—C17	119.7 (2)	H8A—C8—H8C	109.00
C5—O6—C8	116.1 (4)	H8B—C8—H8C	109.00
C13—O7—C16	118.0 (3)	C10—C11—H11	120.00
C17—N1—C18	120.6 (3)	C12—C11—H11	119.00
C17—N1—C19	121.7 (3)	C11—C12—H12	120.00
C18—N1—C19	117.6 (3)	C13—C12—H12	120.00
O2—C1—O3	124.2 (3)	C13—C14—H14	120.00
O2—C1—C2	117.6 (3)	C15—C14—H14	120.00
O3—C1—C2	118.2 (3)	C10—C15—H15	119.00
C1—C2—C3	122.5 (3)	C14—C15—H15	119.00
C1—C2—C7	121.7 (4)	O7—C16—H16A	109.00
C3—C2—C7	115.8 (4)	O7—C16—H16B	109.00
C2—C3—C4	122.4 (4)	O7—C16—H16C	109.00
C3—C4—C5	120.5 (4)	H16A—C16—H16B	109.00
O6—C5—C4	114.6 (4)	H16A—C16—H16C	109.00
O6—C5—C6	125.6 (3)	H16B—C16—H16C	110.00
C4—C5—C6	119.9 (4)	O5—C17—H17	117.00
C5—C6—C7	119.8 (4)	N1—C17—H17	116.00
C2—C7—C6	121.6 (4)	N1—C18—H18A	109.00
O1—C9—O4	125.1 (3)	N1—C18—H18B	109.00
O1—C9—C10	117.2 (3)	N1—C18—H18C	109.00
O4—C9—C10	117.7 (3)	H18A—C18—H18B	110.00
C9—C10—C11	121.4 (3)	H18A—C18—H18C	110.00
C9—C10—C15	120.6 (3)	H18B—C18—H18C	110.00
C11—C10—C15	118.0 (3)	N1—C19—H19A	110.00
C10—C11—C12	121.0 (3)	N1—C19—H19B	110.00
C11—C12—C13	119.6 (3)	N1—C19—H19C	109.00
O7—C13—C12	115.5 (3)	H19A—C19—H19B	109.00
O7—C13—C14	124.4 (3)	H19A—C19—H19C	109.00
C12—C13—C14	120.2 (3)	H19B—C19—H19C	109.00
C13—C14—C15	119.3 (3)
O4—Cu1—O3—C1	89.3 (3)	O2—C1—C2—C3	−170.9 (4)
O5—Cu1—O3—C1	−173.1 (3)	O2—C1—C2—C7	9.5 (6)
O1^i—Cu1—O3—C1	−79.5 (3)	O3—C1—C2—C3	9.8 (6)
O3—Cu1—O4—C9	−88.0 (2)	O3—C1—C2—C7	−169.8 (4)
O5—Cu1—O4—C9	173.3 (2)	C1—C2—C3—C4	−179.7 (4)
O2^i—Cu1—O4—C9	80.6 (2)	C7—C2—C3—C4	0.0 (7)
O3—Cu1—O5—C17	86.5 (2)	C1—C2—C7—C6	178.2 (4)
O4—Cu1—O5—C17	176.6 (2)	C3—C2—C7—C6	−1.5 (7)
O1^i—Cu1—O5—C17	−3.3 (2)	C2—C3—C4—C5	0.6 (7)
O2^i—Cu1—O5—C17	−94.1 (2)	C3—C4—C5—O6	179.4 (4)
O3—Cu1—O1^i—C9^i	85.9 (3)	C3—C4—C5—C6	0.4 (7)
O5—Cu1—O1^i—C9^i	−175.3 (3)	O6—C5—C6—C7	179.2 (4)
O4—Cu1—O2^i—C1^i	−89.8 (3)	C4—C5—C6—C7	−1.9 (7)
O5—Cu1—O2^i—C1^i	172.6 (3)	C5—C6—C7—C2	2.5 (7)
Cu1^i—O1—C9—O4	−1.6 (5)	O1—C9—C10—C11	172.9 (3)
Cu1^i—O1—C9—C10	177.4 (2)	O1—C9—C10—C15	−9.1 (5)
Cu1^i—O2—C1—O3	−1.7 (5)	O4—C9—C10—C11	−8.0 (5)
Cu1^i—O2—C1—C2	179.1 (2)	O4—C9—C10—C15	170.0 (3)
Cu1—O3—C1—O2	−0.6 (5)	C9—C10—C11—C12	178.2 (3)
Cu1—O3—C1—C2	178.6 (2)	C15—C10—C11—C12	0.2 (5)
Cu1—O4—C9—O1	2.9 (5)	C9—C10—C15—C14	−177.0 (3)
Cu1—O4—C9—C10	−176.1 (2)	C11—C10—C15—C14	1.0 (5)
Cu1—O5—C17—N1	179.6 (3)	C10—C11—C12—C13	−1.6 (5)
C8—O6—C5—C4	−172.9 (4)	C11—C12—C13—O7	−177.0 (3)
C8—O6—C5—C6	6.1 (7)	C11—C12—C13—C14	1.9 (5)
C16—O7—C13—C12	173.5 (4)	O7—C13—C14—C15	178.1 (3)
C16—O7—C13—C14	−5.3 (6)	C12—C13—C14—C15	−0.7 (5)
C18—N1—C17—O5	1.2 (6)	C13—C14—C15—C10	−0.7 (5)
C19—N1—C17—O5	178.1 (3)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y, z+1; (iii) x, −y+1/2, z−1/2; (iv) −x+2, −y+1, −z; (v) −x+1, y+1/2, −z+1/2; (vi) −x+1, y−1/2, −z+1/2; (vii) x, −y+3/2, z+1/2; (viii) x, −y+3/2, z−1/2; (ix) x, y, z−1; (x) −x+1, −y+1, −z+1; (xi) −x+2, y+1/2, −z−1/2; (xii) −x+2, y−1/2, −z−1/2; (xiii) x, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O7^iv	0.93	2.48	3.244 (5)	139
C14—H14···O3^ix	0.93	2.52	3.378 (4)	154
C17—H17···O1^i	0.93	2.41	3.054 (4)	126
C18—H18B···O5	0.96	2.38	2.798 (4)	105

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