A dihydroxidotetra­copper(II) framework supported by 4,4′-(adamantane-1,3-diyl)bis­(1,2,4-triazole) and benzene-1,3,5-tricarboxyl­ate bridges

The new bifunctional ligand 4,4′-(adamantane-1,3-diyl)bis­(1,2,4-triazole) (tr₂ad) and benzene-1,3,5-tricarboxyl­ate sus­tain complementary coordination bridging for the three-dimensional framework of poly[[bis­[μ₃-4,4′-(adamantane-1,3-diyl)bis­(1,2,4-triazole)-κ³N¹:N²:N^1′]bis­(μ₄-benzene-1,3,5-tricarboxyl­ato-κ⁴O¹:O^1′:O³:O⁵)di-μ₃-hydroxido-κ⁶O:O:O-tetra­copper(II)] dihydrate], {[Cu₄(C₉H₃O₆)₂(OH)₂(C₁₄H₁₈N₆)₂]·2H₂O}_n. The net node is a centrosymmetric (μ₃-OH)₂Cu₄ cluster [Cu—O = 1.9525 (14)–2.0770 (15) Å and Cu...Cu = 3.0536 (5) Å] involving two independent copper ions in tetra­gonal pyramidal CuO₄N and trigonal bipyramidal CuO₃N₂ environments. One carboxyl­ate group of the anion is bridging and the other two are monodentate, leading to the connection of three hydroxide clusters and the generation of neutral coordination layers separated by 9.3583 (5) Å. The inter­layer linkage is effected by μ₃-tr₂ad ligands, with one triazole group N¹:N²-bridging and the second monodentate [Cu—N = 1.9893 (19), 2.010 (2) and 2.411 (2) Å]. In total, the hydroxide clusters are linked to six close neighbors within the carboxyl­ate layer and to four neighbors via tr₂ad bridges. Hydrogen bonding of solvent water mol­ecules to noncoordinated triazole N atoms and carboxyl­ate groups provides two additional links for the net, which adopts a 12-connected topology corresponding to hexa­gonal closest packing. The study also introduces a new type of bis­(triazole) ligand, which may find wider applications for supra­molecular synthesis.

S1. Comment

1,2,4-Triazole and its derivatives commonly adopt multiple N¹,N²-coordination bridges that effectively transmit magnetic interaction between paramagnetic metal centers (van Koningsbruggen et al., 1997), and these features are essential for the preparation of polynuclear complexes exhibiting diverse magnetic properties (Kahn et al., 1992). For connecting many metal ions, the triazole bridges are especially applicable in combination with short-distance inorganic (OH or Cl) or organic (RCO₂^- or RPO₃^2-) links. They are complementary in their coordination preferences and may act synergetically in the generation of complicated polynuclear motifs, as was revealed by the structure of hydroxotricopper(II) complexes with 4-amino-1,2,4-triazoles (Liu et al., 2003). Further attractive possibilities for the extension of the polynuclear ensembles and their propagation into the lattice could be provided by the cooperation of triazole and polyfunctional anionic linkers, such as polycarboxylates (Zhai et al., 2007), and also by employing organic modules bearing multiple triazole groups (Lysenko et al., 2006). In this way, benzene-1,3,5-tricarboxylate and flexible 1,2-bis(1,2,4-triazol-4-yl)ethane were used for the preparation of highly connected topologies involving Ni₃ and Zn₃ units (Habib et al., 2008). However, since the multivalency of the building block and inherently defined and proper binding geometry are equally important prerequisites from the design perspective, a suitable paradigm for new polytriazolyl ligands may be found with geometrically rigid molecular platforms (cf. adamantane functionalized at the bridgehead positions) rather than using the flexible aliphatic spacers. In this context, we have examined systems combining the aforementioned components; we report here the structure of a new coordination polymer, (I), that features assembly of a polynuclear copper(II)–hydroxide cluster and its propagation by combination of trifunctional benzene-1,3,5-tricarboxylate and bifuctional adamantane-1,3-bis(1,2,4-triazol-4-yl) (tr₂ad) bridges.

In (I), the three-dimensional framework architecture is organized by interconnection of copper(II) ions by three types of links, namely µ₃-hydroxide, µ₃-tr₂ad and µ₄-C₆H₃(CO₂)₃. The unique portion of the structure includes two Cu ions, one each of the hydroxide, bis(triazole) and carboxylate ligands, and a solvent water molecule. Two characteristic Cu₃(µ₃-OH) fragments share a Cu2···Cu2ⁱⁱⁱ edge [symmetry code: (iii) -x + 1, -y + 1, -z + 1], yielding a tetranuclear Cu₄(µ₃-OH)₂ hydroxo cluster situated across an inversion center (Fig. 1). In the cluster, two pairs of Cu1···Cu2 and Cu1···Cu2ⁱⁱⁱ edges are bridged by bidentate carboxylate and triazole groups, respectively, and the coordination also involves four monodentate carboxy O- and two triazole N-atom donors. This polynuclear ensemble formed by a set of hydroxide, carboxylate and azole bridges has several close precedents for molecular copper(II) species, such as pivalate complexes with 4-amino- and 4-tert-butyl-1,2,4-triazoles (Zhou et al., 2005) and mixed-anion benzoate–pyrazolyde compounds (Mezei et al., 2004). Therefore, the present cluster may be regarded as a predictable feature of the system and it demonstrates an attractive supramolecular synthon for crystal design. Within the central Cu₂O₂ rhomb of the cluster, the Cu2···Cu2ⁱⁱⁱ separation is relatively short [3.0536 (5) Å] and only slightly exceeds the shortest Cu···Cu distance found for Cu₄(µ₃-OH)₂ units [2.864 (1) Å; Knuuttila, 1982].

The µ₃-OH group sustains two short [Cu—O = 1.9525 (14) and 1.9715 (14) Å] and one slightly longer [Cu2—O1ⁱⁱⁱ = 2.0770 (15) Å] coordination bonds. Divergence of these parameters was much more appreciable for a molecular 4-tert-butyl-1,2,4-triazole analog [Cu—O = 1.927 (5)–2.302 (5) Å; Zhou et al., 2005]; however, the relatively strong coordination interactions with the hydroxo group in the title compound facilitate elongation of one of the Cu—N bonds. Thus the typically Jahn–Teller-distorted CuO₄N tetragonal pyramid around Cu1 involves four basal O-atom donors [one hydroxide and three carboxylate groups; Cu—O = 1.9153 (17)–1.9993 (17) Å] and a distal triazole N atom at the apex [Cu1—N2ⁱⁱⁱ = 2.411 (2) Å]. A second unique copper ion adopts a distorted trigonal–bipyramidal CuO₃N₂ coordination with a monodentate triazole N atom in the equatorial position [Cu—N4^iv = 2.010 (2) Å; symmetry code: (iv) -x + 1/2, y + 1/2, -z + 3/2; Fig. 1].

The carboxylate groups of the anion display three different coordination modes. The first (containing atom C15) is O²,O³-bidentate bridging between two copper ions; the second carboxylate group (C16) acts as a single coordination donor and accepts a strong hydrogen bond from an adjacent hydroxo group [Cu1—O4ⁱⁱ 1.9993 (17) Å; O1—H1W···O5ⁱⁱ = 2.652 (2) Å; symmetry code: (ii) -x + 1/2, y + 1/2, -z + 1/2; Table 2], while the remaining carboxylate group (C17) is coordinated monodentately. The tr₂ad ligand, one triazole group of which is N¹,N²-bidentate while the other is monodentate, connects two clusters, and the significant size of the adamantane spacer effects long-distance bridging [Cu2···Cu2^vii = 11.63 Å; symmetry code: (vii) -x + 1/2, y - 1/2, -z + 3/2].

Thus, the interconnection of the clusters is supported either by carboxylate or by tr₂ad bridges, and these generate two distinct topologies, which connect with each other through common net nodes. Firstly, interconnection of the Cu₄(µ₃-OH)₂ units by bis(triazole) bridges yields a corrugated (4,4)-net, which is parallel to the (101) plane, with a distance between the centroids of the linked clusters of 13.60 (s.u.?) Å. Secondly, each cluster is bonded to six close neighbors by three-connecting carboxylate groups, yielding a neutral coordination layer parallel to the (101) plane (Fig. 2). Its topology may be represented in the form of a regular hexagonal lattice with the hydroxide–copper clusters as six-connected nodes; furthermore, considering the ligands also as three-connected net points, a 3,6-coordinated "Kagome dual" (kgd) isohedral lattice is found with two types of nodes. Such a layer is unprecedented for metal–tricarboxylate complexes, although it may be compared with a three-dimensional eight-connected framework involving closely related [Fe₄(µ₃-OH)₂]¹⁰⁺ clusters (Choi et al., 2007). These covalent layers are separated by 9.36 (s.u.?) Å and are linked by neutral tr₂ad bridges (Fig. 3). Such a type of `pillared' structure may favor the accommodation of guest molecules between the layers, in the same way as for clays or organic clay mimics (Biradha et al., 1998).

The organic bridges support the connection of the Cu₄(µ₃-OH)₂ units to ten close neighbors, and this is one of the highest net node coordinations yet observed for metal-organic polymers. One example of a 12-connected coordination topology is known (Li et al., 2005). Two more links for the network in (I) are provided by hydrogen bonding. Thus, the solvent water molecules are incorporated into the interlayer space and are involved in bonding with noncoordinated triazole N atoms and carboxylate O4 atoms [O8—H3W···O4 = 2.974 (3) Å; O8—H2W···N5^v = 3.093 (4) Å; symmetry code: (v) -x + 1, -y, -z + 1]. This is accompanied by weak C—H···O bonding of the triazole ring [C···O = 3.078 (3) and 3.098 (3) Å; Table 2 and Fig. 3], which together support additional links between the clusters related by translation parallel to the x axis (symmetry code: x - 1, y, z). Therefore, the entire supramolecular architecture in (I) may be regarded as a 12-connected net corresponding to hexagonal closest packing (hcp) (Fig. 4).

In brief, the title compound reveals a potential for the construction of highly-connected coordination frameworks utilizing polynuclear secondary building blocks and complementary carboxylate and triazole bridges. The study introduces also a new type of bis(triazole) ligand, which may find wider applications for supramolecular synthesis.

Related literature

For related literature, see: Biradha et al. (1998); Choi et al. (2007); Habib et al. (2008); Kahn et al. (1992); Knuuttila (1982); Koningsbruggen et al. (1997); Li et al. (2005); Liu et al. (2003); Lysenko et al. (2006); Mezei et al. (2004); Zhou et al. (2005).

S2. Experimental

The tr₂ad ligand was prepared in 70% yield by reacting adamantane-1,3-diamine and dimethylformamide azine in boiling xylene in the presence of TsOH as catalyst; the product was crystallized from water as the trihydrate tr₂ad.3H₂O. For the synthesis of the title compound, Cu(AcO)₂.H₂O (6.0 mg, 0.03 mmol) 1,3,5-benzenetricarboxylic acid (6.3 mg, 0.03 mmol), tr₂ad.3H₂O (8.9 mg, 0.03 mmol) and water (7 ml) in a Teflon vessel were placed in a steel autoclave, heated at 453 K for 24 h and then cooled to room temperature over a period of 48 h, affording light-green plates of (I) (yield 85%, 8.1 mg).

S3. Refinement

All H atoms were located from difference maps and then refined as riding, with O—H distances constrained to 0.85 Å, C—H(aromatic) distances constrained to 0.94 Å and C—H(adamantane) distances constrained to 0.98 Å, and with U_iso(H) equal to 1.2U_eq(C) or 1.5U_eq(O). H atoms of the water molecule were also located and then fixed with O—H bond distances of 0.85 Å and an H—O—H bond angle of 108°. The U values of the water molecule are appreciably larger than those of the rest of the structure.

Computing details

Data collection: IPDS Software (Stoe & Cie, 2000); cell refinement: IPDS Software (Stoe & Cie, 2000); data reduction: IPDS Software (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Version 1.70.01; Farrugia, 1999).

Figures

	Fig. 1. The structure of (I), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) x - 1/2, -y + 1/2, z - 1/2; (ii) -x + 1/2, y + 1/2, -z + 1/2; (iii) -x + 1, -y + 1, -z + 1; (iv) -x + 1/2, y + 1/2, -z + 3/2.]
	Fig. 2. The carboxylate-bridged subtopology in the structure of (I), in the form of a planar 3,6-connected net supported by dihydroxotetracopper(II) and 1,3,5-benzenetricarboxylate nodes. O atoms are shaded gray and dashed lines indicate hydrogen bonds. [Symmetry codes: (ii) -x + 1/2, y + 1/2, -z + 1/2; (iii) -x + 1, -y + 1, -z + 1.]
	Fig. 3. The interconnection of metal/carboxylate layers (which are orthogonal to the plane of the figure) by tr2ad ligands in (I), showing a set of O—H···O, O—H···N and C—H···O bonds. Note that hydrogen-bonded water molecules (O8) provide additional links between the hydroxide–copper clusters. Dashed lines indicate hydrogen bonding, O atoms are shaded gray, N and Cu atoms are shown as crossed circles, and methylene H atoms have been omitted for clarity. [Symmetry codes: (v) -x + 1, -y, -z + 1; (vi) x, y, z + 1.]
	Fig. 4. A schematic representation of the three-dimensional topology in (I), in the form of a 12-connected framework (hexagonal closest packing) that considers the hydroxide–copper clusters as the net nodes. Bold lines show links to carboxylate-bridged nodes, open lines are bis(triazole) bridges and dashed lines indicate hydrogen bonding with solvent water molecules.

poly[bis[µ3-adamantane-1,3-bis(1,2,4-triazol-4-yl)-κ3N:N':N''] -bis(µ4-benzene-1,3,5-tricarboxylato-κ4O:O':O'':O''') -bis(µ3-hydroxido)tetracopper(II) dihydrate]

Crystal data

[Cu4(OH)2(C14H18N6)2(C9H3O6)2]·2H2O	F(000) = 1304
Mr = 1279.12	Dx = 1.798 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.1122 (5) Å	Cell parameters from 8000 reflections
b = 18.9068 (7) Å	θ = 2.2–26.0°
c = 13.3503 (5) Å	µ = 1.87 mm^−1
β = 112.241 (2)°	T = 213 K
V = 2362.53 (17) Å^3	Plate, green
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Stoe IPDS diffractometer	4592 independent reflections
Radiation source: fine-focus sealed tube	3851 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
ϕ oscillation scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]	h = −12→12
Tmin = 0.684, Tmax = 0.821	k = −22→22
18636 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0578P)^2] where P = (Fo^2 + 2Fc^2)/3
4592 reflections	(Δ/σ)max = 0.002
352 parameters	Δρmax = 1.18 e Å^−3
0 restraints	Δρmin = −0.56 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	0.26068 (3)	0.469671 (15)	0.29288 (2)	0.01235 (9)
Cu2	0.40469 (3)	0.491597 (15)	0.56472 (2)	0.01273 (9)
O1	0.38520 (16)	0.52312 (3)	0.42053 (12)	0.0124 (3)
H1W	0.3640	0.5668	0.4129	0.019*
O2	0.37469 (17)	0.38473 (9)	0.35256 (12)	0.0164 (3)
O3	0.34082 (19)	0.38453 (9)	0.51024 (13)	0.0190 (4)
O4	0.36772 (17)	0.05199 (9)	0.27104 (13)	0.0185 (4)
O5	0.22279 (18)	0.14151 (9)	0.18524 (13)	0.0208 (4)
O6	0.63940 (19)	0.08103 (10)	0.66757 (13)	0.0235 (4)
O7	0.56927 (18)	0.16865 (10)	0.75040 (13)	0.0218 (4)
O8	0.6695 (3)	0.0031 (2)	0.3479 (3)	0.0921 (13)
H2W	0.6844	−0.0024	0.2899	0.138*
H3W	0.5838	0.0169	0.3313	0.138*
N1	0.4618 (2)	0.45631 (11)	0.71565 (15)	0.0156 (4)
N2	0.5829 (2)	0.48624 (11)	0.79143 (16)	0.0181 (4)
N3	0.5146 (2)	0.39676 (11)	0.86645 (15)	0.0146 (4)
N4	0.2352 (2)	0.06286 (12)	0.92189 (16)	0.0193 (4)
N5	0.3266 (2)	0.05384 (12)	0.86811 (18)	0.0251 (5)
N6	0.3607 (2)	0.16003 (11)	0.94429 (16)	0.0179 (4)
C1	0.4231 (2)	0.40341 (14)	0.76151 (18)	0.0178 (5)
H1	0.3436	0.3742	0.7270	0.021*
C2	0.6118 (3)	0.44991 (13)	0.88059 (18)	0.0179 (5)
H2	0.6892	0.4591	0.9457	0.021*
C3	0.2562 (3)	0.12622 (14)	0.9650 (2)	0.0201 (5)
H3	0.2055	0.1454	1.0048	0.024*
C4	0.4014 (3)	0.11254 (15)	0.8839 (2)	0.0260 (6)
H4	0.4736	0.1209	0.8571	0.031*
C5	0.5063 (2)	0.34774 (13)	0.95240 (17)	0.0136 (5)
C6	0.4337 (2)	0.27796 (13)	0.90010 (18)	0.0151 (5)
H6A	0.4878	0.2555	0.8614	0.018*
H6B	0.3366	0.2873	0.8483	0.018*
C7	0.4292 (2)	0.22883 (13)	0.99125 (18)	0.0155 (5)
C8	0.3430 (3)	0.26460 (14)	1.0501 (2)	0.0203 (5)
H8A	0.3366	0.2330	1.1063	0.024*
H8B	0.2458	0.2745	0.9987	0.024*
C9	0.4166 (3)	0.33403 (14)	1.1017 (2)	0.0234 (5)
H9	0.3613	0.3568	1.1402	0.028*
C10	0.4222 (3)	0.38384 (14)	1.0120 (2)	0.0200 (5)
H10A	0.3251	0.3945	0.9612	0.024*
H10B	0.4687	0.4284	1.0439	0.024*
C11	0.6588 (2)	0.33215 (14)	1.03202 (19)	0.0186 (5)
H11A	0.7070	0.3764	1.0636	0.022*
H11B	0.7133	0.3094	0.9938	0.022*
C12	0.6528 (3)	0.28298 (15)	1.1224 (2)	0.0243 (6)
H12	0.7512	0.2734	1.1742	0.029*
C13	0.5813 (3)	0.21293 (14)	1.0720 (2)	0.0221 (5)
H13A	0.5776	0.1810	1.1287	0.027*
H13B	0.6365	0.1899	1.0347	0.027*
C14	0.5684 (3)	0.31884 (16)	1.1820 (2)	0.0288 (6)
H14A	0.6153	0.3631	1.2147	0.035*
H14B	0.5650	0.2880	1.2400	0.035*
C15	0.3710 (2)	0.35469 (13)	0.43742 (17)	0.0135 (4)
C16	0.3224 (2)	0.11582 (13)	0.26474 (17)	0.0139 (5)
C17	0.5770 (2)	0.13964 (13)	0.66935 (18)	0.0144 (5)
C18	0.4072 (2)	0.27715 (13)	0.44860 (18)	0.0140 (5)
C19	0.3638 (2)	0.23499 (13)	0.35561 (18)	0.0144 (5)
H19	0.3162	0.2557	0.2874	0.017*
C20	0.3907 (2)	0.16211 (13)	0.36334 (18)	0.0144 (5)
C21	0.4669 (2)	0.13240 (13)	0.46532 (18)	0.0146 (5)
H21	0.4912	0.0842	0.4708	0.018*
C22	0.5069 (2)	0.17396 (13)	0.55891 (17)	0.0134 (4)
C23	0.4751 (2)	0.24598 (13)	0.55069 (18)	0.0134 (4)
H23	0.4992	0.2737	0.6136	0.016*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01570 (15)	0.00763 (17)	0.00932 (14)	−0.00101 (10)	−0.00024 (10)	0.00026 (10)
Cu2	0.01599 (15)	0.01211 (17)	0.00947 (14)	0.00338 (10)	0.00409 (11)	0.00196 (10)
O1	0.0156 (7)	0.0088 (9)	0.0112 (7)	0.0024 (6)	0.0032 (6)	−0.0001 (6)
O2	0.0228 (8)	0.0091 (9)	0.0152 (8)	0.0017 (6)	0.0048 (7)	0.0016 (6)
O3	0.0304 (9)	0.0103 (9)	0.0174 (8)	−0.0019 (7)	0.0101 (7)	−0.0020 (6)
O4	0.0198 (8)	0.0093 (9)	0.0204 (8)	0.0008 (6)	0.0008 (7)	−0.0033 (7)
O5	0.0274 (9)	0.0113 (9)	0.0141 (8)	0.0004 (7)	−0.0030 (7)	−0.0011 (6)
O6	0.0320 (10)	0.0127 (10)	0.0154 (8)	0.0066 (7)	−0.0027 (7)	0.0002 (7)
O7	0.0236 (9)	0.0277 (11)	0.0146 (8)	0.0039 (7)	0.0079 (7)	0.0023 (7)
O8	0.0381 (15)	0.126 (3)	0.091 (2)	0.0069 (17)	0.0012 (15)	−0.063 (2)
N1	0.0172 (9)	0.0150 (11)	0.0131 (9)	−0.0002 (8)	0.0039 (7)	0.0004 (8)
N2	0.0225 (10)	0.0155 (11)	0.0134 (9)	−0.0032 (8)	0.0037 (8)	0.0000 (8)
N3	0.0159 (9)	0.0147 (11)	0.0120 (9)	−0.0023 (8)	0.0038 (7)	0.0012 (8)
N4	0.0237 (10)	0.0174 (12)	0.0192 (10)	−0.0051 (8)	0.0107 (8)	−0.0018 (8)
N5	0.0300 (11)	0.0202 (13)	0.0325 (12)	−0.0062 (9)	0.0203 (10)	−0.0065 (10)
N6	0.0227 (10)	0.0137 (12)	0.0202 (10)	−0.0043 (8)	0.0114 (8)	−0.0007 (8)
C1	0.0161 (11)	0.0207 (14)	0.0135 (11)	−0.0025 (9)	0.0020 (9)	0.0032 (9)
C2	0.0231 (12)	0.0141 (13)	0.0134 (11)	−0.0046 (9)	0.0035 (9)	−0.0002 (9)
C3	0.0258 (12)	0.0175 (14)	0.0209 (12)	−0.0068 (10)	0.0135 (10)	−0.0040 (10)
C4	0.0319 (14)	0.0207 (15)	0.0346 (14)	−0.0059 (11)	0.0231 (12)	−0.0058 (11)
C5	0.0156 (11)	0.0135 (13)	0.0111 (10)	−0.0012 (9)	0.0044 (8)	0.0027 (8)
C6	0.0164 (11)	0.0149 (13)	0.0134 (10)	−0.0022 (9)	0.0051 (8)	−0.0007 (9)
C7	0.0180 (11)	0.0126 (13)	0.0162 (11)	−0.0041 (9)	0.0067 (9)	−0.0025 (9)
C8	0.0263 (12)	0.0181 (14)	0.0216 (12)	−0.0047 (10)	0.0148 (10)	−0.0015 (10)
C9	0.0356 (14)	0.0179 (14)	0.0238 (12)	−0.0056 (11)	0.0194 (11)	−0.0041 (10)
C10	0.0261 (12)	0.0141 (13)	0.0229 (12)	−0.0008 (10)	0.0127 (10)	−0.0013 (10)
C11	0.0153 (11)	0.0193 (14)	0.0174 (11)	−0.0037 (9)	0.0018 (9)	0.0036 (10)
C12	0.0212 (12)	0.0254 (15)	0.0176 (12)	−0.0042 (10)	−0.0025 (9)	0.0091 (10)
C13	0.0219 (12)	0.0181 (14)	0.0238 (12)	0.0011 (10)	0.0058 (10)	0.0091 (10)
C14	0.0429 (16)	0.0270 (16)	0.0141 (12)	−0.0148 (12)	0.0080 (11)	−0.0008 (10)
C15	0.0121 (10)	0.0107 (12)	0.0133 (10)	−0.0024 (8)	−0.0001 (8)	−0.0007 (8)
C16	0.0171 (11)	0.0116 (13)	0.0117 (10)	−0.0024 (9)	0.0042 (9)	−0.0004 (9)
C17	0.0131 (10)	0.0099 (12)	0.0161 (11)	−0.0029 (8)	0.0011 (9)	0.0020 (9)
C18	0.0148 (10)	0.0101 (12)	0.0151 (11)	−0.0004 (8)	0.0034 (8)	0.0007 (8)
C19	0.0181 (11)	0.0107 (12)	0.0116 (10)	0.0001 (8)	0.0023 (9)	0.0015 (8)
C20	0.0156 (10)	0.0125 (13)	0.0131 (10)	−0.0004 (8)	0.0031 (8)	−0.0005 (9)
C21	0.0160 (11)	0.0076 (12)	0.0168 (11)	0.0018 (8)	0.0022 (9)	0.0013 (9)
C22	0.0109 (10)	0.0139 (12)	0.0125 (10)	−0.0005 (8)	0.0012 (8)	0.0020 (9)
C23	0.0140 (10)	0.0120 (12)	0.0122 (10)	−0.0016 (8)	0.0026 (8)	−0.0014 (8)

Geometric parameters (Å, º)

Cu1—O6^i	1.9153 (17)	C5—C11	1.534 (3)
Cu1—O2	1.9616 (16)	C5—C6	1.542 (3)
Cu1—O1	1.9715 (14)	C6—C7	1.545 (3)
Cu1—O4^ii	1.9993 (17)	C6—H6A	0.9800
Cu1—N2^iii	2.411 (2)	C6—H6B	0.9800
Cu2—O1	1.9525 (14)	C7—C8	1.534 (3)
Cu2—N1	1.9893 (19)	C7—C13	1.537 (3)
Cu2—N4^iv	2.010 (2)	C8—C9	1.537 (4)
Cu2—O1^iii	2.0770 (15)	C8—H8A	0.9800
Cu2—O3	2.1652 (18)	C8—H8B	0.9800
Cu2—Cu2^iii	3.0536 (5)	C9—C14	1.531 (4)
O1—H1W	0.8500	C9—C10	1.541 (3)
O2—C15	1.280 (3)	C9—H9	0.9900
O3—C15	1.257 (3)	C10—H10A	0.9800
O4—C16	1.282 (3)	C10—H10B	0.9800
O5—C16	1.252 (3)	C11—C12	1.543 (3)
O6—C17	1.280 (3)	C11—H11A	0.9800
O7—C17	1.242 (3)	C11—H11B	0.9800
O8—H2W	0.8500	C12—C14	1.528 (4)
O8—H3W	0.8500	C12—C13	1.537 (4)
N1—C1	1.308 (3)	C12—H12	0.9900
N1—N2	1.380 (3)	C13—H13A	0.9800
N2—C2	1.308 (3)	C13—H13B	0.9800
N3—C1	1.361 (3)	C14—H14A	0.9800
N3—C2	1.368 (3)	C14—H14B	0.9800
N3—C5	1.502 (3)	C15—C18	1.505 (3)
N4—C3	1.311 (3)	C16—C20	1.513 (3)
N4—N5	1.379 (3)	C17—C22	1.519 (3)
N5—C4	1.314 (4)	C18—C19	1.399 (3)
N6—C3	1.350 (3)	C18—C23	1.403 (3)
N6—C4	1.370 (3)	C19—C20	1.401 (3)
N6—C7	1.495 (3)	C19—H19	0.9400
C1—H1	0.9400	C20—C21	1.403 (3)
C2—H2	0.9400	C21—C22	1.400 (3)
C3—H3	0.9400	C21—H21	0.9400
C4—H4	0.9400	C22—C23	1.394 (3)
C5—C10	1.528 (3)	C23—H23	0.9400
O6^i—Cu1—O2	91.64 (7)	N6—C7—C8	109.58 (18)
O6^i—Cu1—O1	179.15 (6)	N6—C7—C13	107.8 (2)
O2—Cu1—O1	89.07 (5)	C8—C7—C13	109.81 (19)
O6^i—Cu1—O4^ii	85.36 (7)	N6—C7—C6	109.87 (18)
O2—Cu1—O4^ii	175.99 (7)	C8—C7—C6	109.3 (2)
O1—Cu1—O4^ii	93.96 (5)	C13—C7—C6	110.49 (18)
O6^i—Cu1—N2^iii	94.68 (7)	C7—C8—C9	109.47 (19)
O2—Cu1—N2^iii	94.82 (7)	C7—C8—H8A	109.8
O1—Cu1—N2^iii	84.78 (7)	C9—C8—H8A	109.8
O4^ii—Cu1—N2^iii	88.08 (7)	C7—C8—H8B	109.8
O1—Cu2—N1	169.48 (7)	C9—C8—H8B	109.8
O1—Cu2—N4^iv	94.09 (6)	H8A—C8—H8B	108.2
N1—Cu2—N4^iv	94.53 (8)	C14—C9—C8	109.9 (2)
O1—Cu2—O1^iii	81.51 (6)	C14—C9—C10	109.7 (2)
N1—Cu2—O1^iii	87.98 (7)	C8—C9—C10	109.1 (2)
N4^iv—Cu2—O1^iii	144.16 (7)	C14—C9—H9	109.4
O1—Cu2—O3	92.77 (5)	C8—C9—H9	109.4
N1—Cu2—O3	87.83 (7)	C10—C9—H9	109.4
N4^iv—Cu2—O3	121.73 (8)	C5—C10—C9	108.9 (2)
O1^iii—Cu2—O3	94.07 (5)	C5—C10—H10A	109.9
O1—Cu2—Cu2^iii	42.28 (4)	C9—C10—H10A	109.9
N1—Cu2—Cu2^iii	127.20 (6)	C5—C10—H10B	109.9
N4^iv—Cu2—Cu2^iii	126.65 (6)	C9—C10—H10B	109.9
O1^iii—Cu2—Cu2^iii	39.23 (4)	H10A—C10—H10B	108.3
O3—Cu2—Cu2^iii	94.54 (5)	C5—C11—C12	109.30 (19)
Cu2—O1—Cu1	119.26 (6)	C5—C11—H11A	109.8
Cu2—O1—Cu2^iii	98.49 (6)	C12—C11—H11A	109.8
Cu1—O1—Cu2^iii	108.00 (6)	C5—C11—H11B	109.8
Cu2—O1—H1W	110.0	C12—C11—H11B	109.8
Cu1—O1—H1W	110.2	H11A—C11—H11B	108.3
Cu2^iii—O1—H1W	110.1	C14—C12—C13	110.4 (2)
C15—O2—Cu1	120.86 (15)	C14—C12—C11	109.6 (2)
C15—O3—Cu2	123.39 (15)	C13—C12—C11	109.1 (2)
C16—O4—Cu1^v	123.11 (14)	C14—C12—H12	109.2
C17—O6—Cu1^vi	125.05 (15)	C13—C12—H12	109.2
H2W—O8—H3W	108.4	C11—C12—H12	109.2
C1—N1—N2	108.06 (18)	C12—C13—C7	108.6 (2)
C1—N1—Cu2	135.00 (17)	C12—C13—H13A	110.0
N2—N1—Cu2	116.22 (15)	C7—C13—H13A	110.0
C2—N2—N1	106.42 (19)	C12—C13—H13B	110.0
C2—N2—Cu1^iii	130.24 (17)	C7—C13—H13B	110.0
N1—N2—Cu1^iii	110.87 (13)	H13A—C13—H13B	108.4
C1—N3—C2	104.31 (19)	C12—C14—C9	109.2 (2)
C1—N3—C5	129.09 (19)	C12—C14—H14A	109.8
C2—N3—C5	126.36 (19)	C9—C14—H14A	109.8
C3—N4—N5	108.2 (2)	C12—C14—H14B	109.8
C3—N4—Cu2^vii	125.16 (16)	C9—C14—H14B	109.8
N5—N4—Cu2^vii	126.62 (16)	H14A—C14—H14B	108.3
C4—N5—N4	105.7 (2)	O3—C15—O2	125.6 (2)
C3—N6—C4	104.0 (2)	O3—C15—C18	118.8 (2)
C3—N6—C7	126.9 (2)	O2—C15—C18	115.6 (2)
C4—N6—C7	128.5 (2)	O5—C16—O4	125.0 (2)
N1—C1—N3	110.2 (2)	O5—C16—C20	118.0 (2)
N1—C1—H1	124.9	O4—C16—C20	116.96 (19)
N3—C1—H1	124.9	O7—C17—O6	126.3 (2)
N2—C2—N3	111.0 (2)	O7—C17—C22	119.8 (2)
N2—C2—H2	124.5	O6—C17—C22	113.8 (2)
N3—C2—H2	124.5	C19—C18—C23	119.8 (2)
N4—C3—N6	110.6 (2)	C19—C18—C15	119.0 (2)
N4—C3—H3	124.7	C23—C18—C15	121.1 (2)
N6—C3—H3	124.7	C18—C19—C20	120.5 (2)
N5—C4—N6	111.4 (2)	C18—C19—H19	119.7
N5—C4—H4	124.3	C20—C19—H19	119.7
N6—C4—H4	124.3	C19—C20—C21	119.0 (2)
N3—C5—C10	108.97 (19)	C19—C20—C16	119.5 (2)
N3—C5—C11	108.42 (18)	C21—C20—C16	121.0 (2)
C10—C5—C11	109.66 (19)	C22—C21—C20	120.6 (2)
N3—C5—C6	109.67 (17)	C22—C21—H21	119.7
C10—C5—C6	110.75 (19)	C20—C21—H21	119.7
C11—C5—C6	109.32 (19)	C23—C22—C21	119.9 (2)
C5—C6—C7	107.97 (18)	C23—C22—C17	120.2 (2)
C5—C6—H6A	110.1	C21—C22—C17	119.9 (2)
C7—C6—H6A	110.1	C22—C23—C18	120.0 (2)
C5—C6—H6B	110.1	C22—C23—H23	120.0
C7—C6—H6B	110.1	C18—C23—H23	120.0
H6A—C6—H6B	108.4
N1—Cu2—O1—Cu1	115.5 (4)	C4—N6—C7—C8	178.5 (2)
N4^iv—Cu2—O1—Cu1	−99.58 (8)	C3—N6—C7—C13	107.8 (3)
O1^iii—Cu2—O1—Cu1	116.22 (6)	C4—N6—C7—C13	−62.1 (3)
O3—Cu2—O1—Cu1	22.52 (7)	C3—N6—C7—C6	−131.7 (2)
Cu2^iii—Cu2—O1—Cu1	116.22 (6)	C4—N6—C7—C6	58.4 (3)
N1—Cu2—O1—Cu2^iii	−0.7 (4)	C5—C6—C7—N6	−179.46 (18)
N4^iv—Cu2—O1—Cu2^iii	144.20 (7)	C5—C6—C7—C8	60.3 (2)
O1^iii—Cu2—O1—Cu2^iii	0.0	C5—C6—C7—C13	−60.6 (2)
O3—Cu2—O1—Cu2^iii	−93.70 (6)	N6—C7—C8—C9	178.0 (2)
O2—Cu1—O1—Cu2	−57.64 (7)	C13—C7—C8—C9	59.8 (3)
O4^ii—Cu1—O1—Cu2	119.73 (7)	C6—C7—C8—C9	−61.6 (3)
N2^iii—Cu1—O1—Cu2	−152.56 (8)	C7—C8—C9—C14	−59.4 (3)
O2—Cu1—O1—Cu2^iii	53.47 (6)	C7—C8—C9—C10	60.9 (3)
O4^ii—Cu1—O1—Cu2^iii	−129.16 (6)	N3—C5—C10—C9	−178.86 (19)
N2^iii—Cu1—O1—Cu2^iii	−41.46 (6)	C11—C5—C10—C9	−60.3 (3)
O6^i—Cu1—O2—C15	−111.37 (17)	C6—C5—C10—C9	60.4 (2)
O1—Cu1—O2—C15	69.11 (17)	C14—C9—C10—C5	60.7 (3)
N2^iii—Cu1—O2—C15	153.79 (17)	C8—C9—C10—C5	−59.8 (3)
O1—Cu2—O3—C15	34.37 (18)	N3—C5—C11—C12	178.9 (2)
N1—Cu2—O3—C15	−135.12 (18)	C10—C5—C11—C12	60.0 (3)
N4^iv—Cu2—O3—C15	130.90 (18)	C6—C5—C11—C12	−61.6 (3)
O1^iii—Cu2—O3—C15	−47.30 (18)	C5—C11—C12—C14	−59.7 (3)
Cu2^iii—Cu2—O3—C15	−7.96 (18)	C5—C11—C12—C13	61.2 (3)
O1—Cu2—N1—C1	−119.4 (4)	C14—C12—C13—C7	60.3 (3)
N4^iv—Cu2—N1—C1	95.7 (2)	C11—C12—C13—C7	−60.2 (3)
O1^iii—Cu2—N1—C1	−120.2 (2)	N6—C7—C13—C12	−179.17 (19)
O3—Cu2—N1—C1	−26.0 (2)	C8—C7—C13—C12	−59.8 (3)
Cu2^iii—Cu2—N1—C1	−120.0 (2)	C6—C7—C13—C12	60.8 (3)
O1—Cu2—N1—N2	49.5 (5)	C13—C12—C14—C9	−60.2 (3)
N4^iv—Cu2—N1—N2	−95.39 (17)	C11—C12—C14—C9	60.0 (3)
O1^iii—Cu2—N1—N2	48.79 (16)	C8—C9—C14—C12	59.3 (3)
O3—Cu2—N1—N2	142.94 (17)	C10—C9—C14—C12	−60.7 (3)
Cu2^iii—Cu2—N1—N2	48.89 (19)	Cu2—O3—C15—O2	−36.9 (3)
C1—N1—N2—C2	−0.2 (3)	Cu2—O3—C15—C18	142.69 (17)
Cu2—N1—N2—C2	−172.02 (16)	Cu1—O2—C15—O3	−25.7 (3)
C1—N1—N2—Cu1^iii	146.21 (16)	Cu1—O2—C15—C18	154.69 (15)
Cu2—N1—N2—Cu1^iii	−25.59 (19)	Cu1^v—O4—C16—O5	−35.7 (3)
C3—N4—N5—C4	1.4 (3)	Cu1^v—O4—C16—C20	141.37 (16)
Cu2^vii—N4—N5—C4	−177.69 (19)	Cu1^vi—O6—C17—O7	−9.8 (3)
N2—N1—C1—N3	0.1 (3)	Cu1^vi—O6—C17—C22	170.73 (15)
Cu2—N1—C1—N3	169.67 (17)	O3—C15—C18—C19	144.2 (2)
C2—N3—C1—N1	0.1 (3)	O2—C15—C18—C19	−36.1 (3)
C5—N3—C1—N1	174.7 (2)	O3—C15—C18—C23	−31.6 (3)
N1—N2—C2—N3	0.3 (3)	O2—C15—C18—C23	148.0 (2)
Cu1^iii—N2—C2—N3	−137.13 (18)	C23—C18—C19—C20	−1.6 (3)
C1—N3—C2—N2	−0.2 (3)	C15—C18—C19—C20	−177.5 (2)
C5—N3—C2—N2	−175.0 (2)	C18—C19—C20—C21	−2.5 (3)
N5—N4—C3—N6	−1.3 (3)	C18—C19—C20—C16	170.1 (2)
Cu2^vii—N4—C3—N6	177.83 (16)	O5—C16—C20—C19	−13.5 (3)
C4—N6—C3—N4	0.6 (3)	O4—C16—C20—C19	169.2 (2)
C7—N6—C3—N4	−171.2 (2)	O5—C16—C20—C21	158.9 (2)
N4—N5—C4—N6	−1.0 (3)	O4—C16—C20—C21	−18.4 (3)
C3—N6—C4—N5	0.3 (3)	C19—C20—C21—C22	4.4 (3)
C7—N6—C4—N5	172.0 (2)	C16—C20—C21—C22	−168.1 (2)
C1—N3—C5—C10	−89.6 (3)	C20—C21—C22—C23	−2.1 (3)
C2—N3—C5—C10	84.0 (3)	C20—C21—C22—C17	174.3 (2)
C1—N3—C5—C11	151.1 (2)	O7—C17—C22—C23	20.7 (3)
C2—N3—C5—C11	−35.3 (3)	O6—C17—C22—C23	−159.8 (2)
C1—N3—C5—C6	31.8 (3)	O7—C17—C22—C21	−155.7 (2)
C2—N3—C5—C6	−154.6 (2)	O6—C17—C22—C21	23.8 (3)
N3—C5—C6—C7	179.26 (18)	C21—C22—C23—C18	−2.0 (3)
C10—C5—C6—C7	−60.4 (2)	C17—C22—C23—C18	−178.5 (2)
C11—C5—C6—C7	60.5 (2)	C19—C18—C23—C22	3.9 (3)
C3—N6—C7—C8	−11.6 (3)	C15—C18—C23—C22	179.7 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···O5^ii	0.85	1.90	2.652 (2)	147
O8—H2W···N5^viii	0.85	2.29	3.093 (4)	158
O8—H3W···O4	0.85	2.13	2.974 (3)	173
C4—H4···O7	0.94	2.20	3.078 (3)	156
C3—H3···O5^ix	0.94	2.35	3.098 (3)	136

Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (viii) −x+1, −y, −z+1; (ix) x, y, z+1.