Poly[[sesqui­[μ₂-1,4-bis­(imidazol-1-ylmeth­yl)benzene-κ²N:N′](carbonato-κ²O,O′)copper(II)] 1,4-bis­(imidazol-1-ylmeth­yl)benzene hemisolvate penta­hydrate]

The asymmetric unit of the title compound, {[Cu(CO₃)(C₁₄H₁₄N₄)_1.5]·0.5C₁₄H₁₄N₄·5H₂O}_n, contains one Cu^II cation in a slightly distorted square-pyramidal coordination environment, one CO₃²⁻ anion, one full and two half 1,4-bis­(imidazol-1-ylmeth­yl)benzene (bix) ligands, one half-mol­ecule of which is uncoordinated, and five uncoordinated water mol­ecules. One of the coordinated bix ligands and the uncoordinated bix mol­ecule are situated about centers of symmetry, located at the centers of the benzene rings. The coordinated bix ligands link the copper(II) ions into a [Cu(bix)_1.5]_n mol­ecular ladder. These mol­ecular ladders do not form inter­penetrated ladders but are arranged in an ABAB parallel terrace, i.e. with the ladders arranged one above another, with sequence A translated with respect to B by 8 Å. To best of our knowledge, this arrangement has not been observed in any of the mol­ecular ladder frameworks synthesized to date. The coordination environment of the Cu^II atom is completed by two O atoms of the CO₃²⁻ anion. The framework is further strengthened by extensive O—H...O and O—H...N hydrogen bonds involving the water mol­ecules, the O atoms of the CO₃²⁻ anion and the N atoms of the bix ligands. This study describes the first example of a mol­ecular ladder coordination polymer based on bix and therefore demonstrates further the usefulness of bix as a versatile multidentate ligand for constructing coordination polymers with inter­esting architectures.

S1. Comment

Owing to their fascinating properties and potential applications to gas storage, molecular sieves, size- or shape-selective catalysis, and ion exchange (Noro et al., 2000; Eddaoudi et al., 2002) in functional materials, the construction of organic–inorganic open framework complexes with variable cavities or channels has attracted considerable interest in the past decade (Tong et al., 1999; Wu et al., 2006; Zhang et al., 2006). These studies have shown that the careful selection of appropriate multidentate bridging ligands is helpful not only to tailor effectively the polymer architectures but also to realize various applications. The use of long bidentate nitrogen ligand spacers has afforded very interesting structural motifs, such as double helices (Carlucci et al., 1997), multiple sheets (Hennigar et al., 1997), interpenetrated ladders (Fujita et al., 1998) and other noteworthy species. Many of the architectures reported to date, however, are based on rigid, linear, linker, bidentate nitrogen ligands, with efforts only recently being focused on the use of ligands showing conformational flexibility (Carlucci et al., 2000). In addition, the design of coordination polymers from flexible ligands is highly influenced by factors such as the nature of coordination of the metal ion, the length and flexibility of the organic ligand, the metal–ligand ratio, and the possible influences of the counter-anion and solvent. Recently, we have begun to work on the architectures of polymeric structures containing flexible ligands. We describe here the synthesis and structure of a new metal–organic molecular ladder, (I), formed from bix ligands and copper sulfate.

The X-ray diffraction analysis reveals the title complex is a unique `parallel terrace' molecular ladder structure with molecular formula {[Cu(CO₃)(C₁₄H₁₄N₄)_1.5].0.5C₁₄H₁₄N₄.5H₂O}_n. Each Cu center in the title complex is five-coordinated, with one N atom from a bix ligand located in the apical position, and two bix N atoms and two O atoms from the CO₃^2- anion located in the basal plane, as shown in Fig. 1. The τ value for the coordination environment of the Cu atom is 0.36, showing that the Cu atom is in a slightly distorted square-pyramidal arrangement (τ ranges between 0 and 1 for square-pyramidal and trigonal–bipyramidal structures, respectively (Addision & Rao, 1984 ). The Cu—N distances range from 1.963 (5) to 2.123 (5) Å, and the Cu—O distances are 1.966 (3) and 1.993 (3) Å. The bix ligands link the copper(II) ions into a [Cu(bix)_1.5]_n ladder. The bix ligands adopt two different conformations (A and B) in the ladder: the sides of the ladder adopt conformation A, with a dihedral angle of the two imidazol rings of 46°; the rungs of the ladder adopt conformation B, where the dihedral angle of the two imidazol rings is 0°, as the two imidazol ring are almost [or exactly if angle is 0°?] parallel to each other. The CO₃^2- ligands not only act as a µ₂-bridge through two O atoms to complete the coordination geometry of Cu^II but also act to balance the charge in the structure.

Generally, molecular ladders occur in a T-shaped unit, formed by quasi-octahedrally or octahedrally coordinated metal centers and rod-like ligands, and exhibit the phenomenon of interpenetration (Fujita et al., 1995; Blake et al.,1997). Large cavities between the rungs of the ladders encourage the inclusion of discrete symmetry-related ladders. Interpenetration was found to be perpendicular to the orientation of the original ladder to generate a three-dimensional polycatenated structure (Hennigar et al., 1997). Another interpenetrating example of a molecular ladder was decribed by Blake et al. (1997). The packing of polymer (I) is very interesting. As shown in Fig. 2, the molecular ladders do not form an interpenetrated structure. Each ladder has two ladders above it, so as to fill the spaces between the rungs of the ladder, and the ladders are arranged in an ABAB parallel terrace sequence as A is translated with respect to B by ca 8 Å . To the authors' knowledge, this fascinating (one-dimensional-to-one-dimensional) parallel terrace array shows a type of arrangement of molecular ladder that has not been observed in any of the molecular ladder frameworks synthesized to date. The structure is further stabilized by extensive O—H···N hydrogen bonds involving the water molecules, the carbonate O atoms and the N atoms of the bix ligands, as shown in Fig. 3. When O—H···O hydrogen bonds between the uncoordinated water molecules and the CO₃^2- ligands, and O—H···N hydrogen bonds between the uncoordinated water molecules and the bix ligands, are omitted, one-dimensional water chains emerge. As shown in Fig. 4, the one-dimensional water chain is built up from four- and six-membered rings arranged alternately. The one-dimensional water chain stucture constitutes a potential form of water that is poorly understood (Liu & Xu, 2005). Many fundamental biological processes appear to depend on the unique properties of water chains. However, the nature for acquiring the structural constraints in stabilizing one-dimensional chains is not fully understood (Cheruzel et al., 2003). The one-dimensional water chains reported here represent a rare example.

Finally, it is worth mentioning that the CO₃^2- anion may be formed by an in situ oxidation reaction from the bix ligand or originate from atmospheric carbon dioxide, as there were no carbon complexes except the bix ligands and carbon dioxide in the starting reaction mixture. The bond lengths C29—O1 [1.289 (5) Å], C29—O2 [1.276 (5) Å] and C29—O3 [1.241 (5) Å], and the O—C—O angles O1—C29—O2 [113.3 (4)°], O2—C29—O3 [122.3 (4)°] and O1—C29—O3[124.4 (4)°] for the CO₃^2- anion are comparable to those reported in the complex [Co(C₃H₁₀N₂)₂(CO₃)]Cl.H₂O (Zhu & Chen, 1999). When using CuCO₃ instead of CuSO₄, the title compound could not be obtained, indicating that SO₄ may play an important role in the formation of the title compound, although it did not appear in the molecular formula of the final compound.

Related literature

For related literature, see: Blake et al. (1997); Carlucci et al. (1997, 2000); Cheruzel et al. (2003); Eddaoudi, Kim, Rosi, Vodak, Wachter, Keeffe, Yaghi & Science (2002); Fujita et al. (1995, 1998); Hennigar et al. (1997); Liu, Xu & CrystEngComm (2005); Noro, Kitagawa, Kondo, Seki, Angew & Chem (2000); Tong et al. (1999); Wu et al. (2006); Zhang et al. (2006); Zhu, Chen & Acta Cryst (1999).

S2. Experimental

A mixture of CuSO₄.5H₂O (0.50 mmol, 0.14 g), bix (1.00 mmol, 0.24 g) and water (15 ml) was stirred vigorously while the pH value was adjusted to 6 by the addition of 10% NaOH. The mixture was then heated at 433 K for 3 d in a sealed 25 ml Teflon-lined stainless steel vessel under autogenous pressure. After cooling to room temperature at 50 K h^-1, blue prismatic crystals were isolated, which were washed with ethanol and dried in air (yield 42%, based on Cu). Elemental analyses found: C 50.45, H 5.72, N 16.21%; calculated: C 50.47, H 5.55, N16.23%. IR (KBr, cm^-1): 3415 (m), 3102 (m), 1645 (m), 1566 (s), 1521 (w), 1442 (m), 1386 (m), 1300 (m), 1245 (m), 1090 (m), 1024 (m), 952 (w), 878 (w), 848 (w), 742 (w), 718 (w), 659 (m), 622 (w), 517 (w), 466 (w).

S3. Refinement

C-bound H atoms were positioned geometrically and treated using a riding model, fixing the C—H bond lengths at 0.97 and 0.93 Å for CH₂ and aromatic CH groups, respectively [U_iso(H) = 1.2U_eq(C)]. Water H atoms were located from difference maps and refined with O—H distance restraints of 0.86 (5) Å [U_iso(H) = 1.2U_eq(O)].

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994) and XPREP in SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The local coordination around the Cu^II ion in (I). Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x - 1, y - 1, z; (viii) -x - 1, -y, -z + 1.]
	Fig. 2. Parallel terrace arrangement of the molecular ladder in (I). H atoms, uncoordinated bix ligands and water molecules have been omitted for clarity.
	Fig. 3. The crystal packing of (I). Hydrogen bonds are shown as dashed lines; uncoordinated bix ligands and H atoms have been omitted for clarity.
	Fig. 4. The one-dimensional water chains in (I). Dashed lines represent hydrogen bonds.

Poly[(carbonato-κ²O,O')bis[µ₂-1,4-bis(imidazol-1-ylmethyl)benzene-κ²N:N']copper(II) 1,4-bis(imidazol-1-ylmethyl)benzene hemisolvate pentahydrate]

Crystal data

[Cu(CO3)(C14H14N4)1.5]·0.5C14H14N4·5H2O	Z = 2
Mr = 690.22	F(000) = 722
Triclinic, P1	Dx = 1.432 Mg m^−3
a = 12.2286 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.4976 (7) Å	Cell parameters from 3621 reflections
c = 12.951 Å	θ = 2.1–27.5°
α = 103.759 (15)°	µ = 0.74 mm^−1
β = 98.726 (12)°	T = 293 K
γ = 118.767 (9)°	Prism, blue
V = 1600.8 (3) Å^3	0.20 × 0.15 × 0.05 mm

Data collection

Bruker P4 diffractometer	7352 independent reflections
Radiation source: fine-focus sealed tube	5723 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −15→15
Tmin = 0.875, Tmax = 0.963	k = −16→11
12466 measured reflections	l = −15→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0584P)^2 + 0.5166P] where P = (Fo^2 + 2Fc^2)/3
7352 reflections	(Δ/σ)max = 0.019
49 parameters	Δρmax = 0.52 e Å^−3
7 restraints	Δρmin = −0.60 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	−0.11200 (8)	−0.28708 (6)	0.48515 (6)	0.0453 (3)
N1	−0.3282 (5)	−0.0384 (5)	0.9232 (4)	0.0725 (12)
N2	−0.4264 (4)	−0.2533 (4)	0.8619 (3)	0.0557 (9)
N3	0.0714 (5)	−0.1632 (4)	0.6140 (4)	0.0424 (11)
N4	0.2303 (3)	0.0233 (3)	0.7483 (3)	0.0415 (7)
N5	0.8359 (3)	0.5612 (3)	0.5314 (3)	0.0428 (7)
N6	0.8253 (3)	0.4506 (3)	0.6415 (3)	0.0463 (8)
N7	−0.2950 (3)	−0.1077 (3)	0.6222 (3)	0.0433 (7)
N8	−0.2250 (3)	−0.2319 (3)	0.5537 (3)	0.0430 (7)
O1	−0.0943 (4)	−0.3591 (3)	0.3383 (3)	0.0674 (9)
O1W	−1.1623 (9)	−0.5795 (8)	1.1702 (8)	0.117 (3)
H1WA	−1.129 (13)	−0.616 (11)	1.196 (10)	0.140*
H1WB	−1.131 (12)	−0.506 (7)	1.223 (8)	0.140*
O2	−0.0688 (4)	−0.1707 (3)	0.3986 (3)	0.0675 (9)
O2W	−0.9612 (6)	−0.6079 (5)	0.9426 (4)	0.1035 (15)
H2WA	−0.974 (7)	−0.667 (5)	0.886 (5)	0.124*
H2WB	−0.903 (6)	−0.536 (4)	0.947 (6)	0.124*
O3	−0.0379 (4)	−0.2304 (4)	0.2367 (3)	0.0807 (11)
O3W	−0.0683 (4)	−0.1886 (4)	0.8758 (4)	0.0832 (11)
H3WA	−0.006 (5)	−0.200 (6)	0.888 (6)	0.100*
H3WB	−0.040 (6)	−0.120 (5)	0.861 (6)	0.100*
O4W	−0.0247 (6)	−0.0662 (5)	0.1206 (4)	0.0935 (13)
H4WA	−0.011 (7)	−0.097 (7)	0.168 (4)	0.112*
H4WB	−0.032 (7)	−0.111 (6)	0.058 (3)	0.112*
O5W	−1.1286 (5)	−0.7671 (4)	1.0416 (4)	0.0802 (11)
H5WA	−1.071 (5)	−0.714 (5)	1.021 (5)	0.096*
H5WB	−1.205 (4)	−0.838 (4)	1.014 (6)	0.096*
C1	−0.3116 (5)	−0.1361 (5)	0.9027 (4)	0.0637 (12)
H1A	−0.2297	−0.1260	0.9148	0.076*
C2	−0.4582 (7)	−0.0946 (6)	0.8938 (5)	0.0736 (15)
H2A	−0.5000	−0.0489	0.8984	0.088*
C3	−0.5204 (5)	−0.2246 (6)	0.8569 (4)	0.0693 (14)
H3A	−0.6108	−0.2841	0.8325	0.083*
C4	−0.4431 (7)	−0.3818 (6)	0.8307 (5)	0.0818 (17)
H4A	−0.3635	−0.3732	0.8181	0.098*
H4B	−0.5142	−0.4394	0.7609	0.098*
C5	−0.4728 (5)	−0.4436 (4)	0.9190 (4)	0.0592 (12)
C6	−0.5981 (5)	−0.5073 (5)	0.9264 (4)	0.0653 (13)
H6A	−0.6656	−0.5127	0.8766	0.078*
C7	−0.3750 (5)	−0.4369 (5)	0.9931 (5)	0.0648 (13)
H7A	−0.2899	−0.3943	0.9893	0.078*
C8	0.1314 (4)	−0.0337 (4)	0.6538 (3)	0.0423 (8)
H8A	0.1065	0.0119	0.6191	0.051*
C9	0.1411 (4)	−0.1866 (4)	0.6916 (4)	0.0480 (9)
H9A	0.1229	−0.2691	0.6873	0.058*
C10	0.2382 (4)	−0.0732 (4)	0.7735 (4)	0.0521 (10)
H10A	0.2981	−0.0631	0.8346	0.063*
C11	0.3150 (4)	0.1639 (4)	0.8132 (4)	0.0528 (10)
H11A	0.3305	0.1775	0.8923	0.063*
H11B	0.2700	0.2063	0.7949	0.063*
C12	0.4446 (4)	0.2264 (4)	0.7913 (3)	0.0440 (9)
C13	0.4592 (4)	0.2732 (4)	0.7052 (3)	0.0487 (9)
H13A	0.3871	0.2648	0.6591	0.058*
C14	0.5783 (4)	0.3324 (4)	0.6859 (4)	0.0492 (10)
H14A	0.5858	0.3636	0.6273	0.059*
C15	0.6872 (4)	0.3459 (4)	0.7531 (3)	0.0439 (9)
C16	0.6727 (4)	0.2975 (4)	0.8392 (3)	0.0489 (10)
H16A	0.7443	0.3045	0.8846	0.059*
C17	0.5533 (4)	0.2391 (4)	0.8581 (3)	0.0495 (10)
H17A	0.5453	0.2076	0.9166	0.059*
C18	0.8222 (4)	0.4160 (5)	0.7411 (4)	0.0611 (13)
H18A	0.8791	0.4952	0.8065	0.073*
H18B	0.8573	0.3608	0.7393	0.073*
C19	0.8401 (4)	0.5607 (4)	0.6332 (3)	0.0442 (9)
H19A	0.8519	0.6287	0.6921	0.053*
C20	0.8095 (5)	0.3755 (4)	0.5380 (4)	0.0642 (13)
H20A	0.7967	0.2928	0.5179	0.077*
C21	0.8160 (5)	0.4440 (4)	0.4707 (4)	0.0555 (11)
H21A	0.8083	0.4162	0.3952	0.067*
C22	−0.2002 (4)	−0.1122 (4)	0.5867 (3)	0.0421 (8)
H22A	−0.1258	−0.0399	0.5854	0.051*
C23	−0.3431 (4)	−0.3077 (4)	0.5691 (4)	0.0498 (10)
H23A	−0.3859	−0.3973	0.5533	0.060*
C24	−0.3877 (4)	−0.2322 (4)	0.6108 (4)	0.0504 (10)
H24A	−0.4657	−0.2593	0.6282	0.061*
C25	−0.3009 (5)	0.0088 (4)	0.6623 (4)	0.0535 (11)
H25A	−0.2159	0.0862	0.6762	0.064*
H25B	−0.3207	0.0145	0.7325	0.064*
C26	−0.4039 (4)	0.0048 (4)	0.5786 (3)	0.0409 (8)
C27	−0.5209 (4)	−0.0204 (4)	0.5969 (3)	0.0483 (10)
H27A	−0.5363	−0.0342	0.6621	0.058*
C28	−0.3843 (4)	0.0252 (4)	0.4814 (4)	0.0476 (9)
H28A	−0.3059	0.0426	0.4679	0.057*
C29	−0.0661 (4)	−0.2529 (4)	0.3205 (3)	0.0499 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0706 (5)	0.0298 (4)	0.0429 (4)	0.0280 (4)	0.0248 (3)	0.0182 (3)
N1	0.094 (3)	0.070 (3)	0.068 (3)	0.052 (3)	0.025 (2)	0.032 (2)
N2	0.093 (3)	0.068 (2)	0.068 (2)	0.049 (2)	0.0243 (18)	0.0350 (18)
N3	0.044 (3)	0.033 (2)	0.050 (3)	0.020 (2)	0.017 (2)	0.016 (2)
N4	0.0395 (17)	0.0359 (17)	0.0440 (17)	0.0157 (14)	0.0184 (14)	0.0130 (13)
N5	0.057 (2)	0.0290 (15)	0.0456 (17)	0.0223 (15)	0.0216 (15)	0.0170 (13)
N6	0.0435 (18)	0.0423 (18)	0.057 (2)	0.0194 (15)	0.0187 (15)	0.0310 (16)
N7	0.0500 (19)	0.0460 (18)	0.0457 (18)	0.0334 (16)	0.0147 (15)	0.0185 (14)
N8	0.0471 (18)	0.0393 (17)	0.0491 (18)	0.0269 (15)	0.0146 (14)	0.0182 (14)
O1	0.086 (4)	0.043 (2)	0.038 (3)	0.028 (3)	0.042 (3)	0.024 (2)
O1W	0.109 (4)	0.082 (3)	0.127 (5)	0.057 (3)	0.017 (3)	−0.012 (3)
O2	0.088 (4)	0.043 (2)	0.039 (3)	0.026 (3)	0.041 (3)	0.026 (2)
O2W	0.137 (4)	0.082 (3)	0.097 (4)	0.057 (3)	0.055 (3)	0.036 (3)
O3	0.128 (3)	0.065 (2)	0.054 (2)	0.045 (2)	0.044 (2)	0.0370 (17)
O3W	0.090 (3)	0.083 (3)	0.099 (3)	0.056 (3)	0.039 (2)	0.040 (2)
O4W	0.150 (4)	0.092 (3)	0.084 (3)	0.081 (3)	0.061 (3)	0.052 (3)
O5W	0.097 (3)	0.076 (3)	0.089 (3)	0.051 (2)	0.048 (2)	0.043 (2)
C1	0.066 (3)	0.078 (4)	0.059 (3)	0.045 (3)	0.020 (2)	0.029 (3)
C2	0.106 (5)	0.091 (4)	0.073 (3)	0.076 (4)	0.043 (3)	0.047 (3)
C3	0.067 (3)	0.092 (4)	0.063 (3)	0.047 (3)	0.026 (2)	0.038 (3)
C4	0.069 (5)	0.088 (3)	0.060 (3)	0.051 (4)	0.027 (3)	0.037 (3)
C5	0.083 (3)	0.044 (2)	0.051 (2)	0.036 (2)	0.023 (2)	0.0126 (19)
C6	0.076 (3)	0.055 (3)	0.060 (3)	0.039 (3)	0.009 (2)	0.014 (2)
C7	0.069 (3)	0.050 (3)	0.073 (3)	0.032 (2)	0.026 (3)	0.016 (2)
C8	0.044 (2)	0.0319 (18)	0.050 (2)	0.0183 (16)	0.0173 (17)	0.0177 (16)
C9	0.049 (2)	0.041 (2)	0.065 (3)	0.0273 (19)	0.024 (2)	0.0270 (19)
C10	0.046 (2)	0.055 (3)	0.058 (3)	0.025 (2)	0.0143 (19)	0.028 (2)
C11	0.051 (2)	0.038 (2)	0.051 (2)	0.0141 (18)	0.0206 (19)	0.0041 (17)
C12	0.043 (2)	0.0319 (19)	0.039 (2)	0.0123 (16)	0.0095 (16)	0.0050 (15)
C13	0.040 (2)	0.046 (2)	0.047 (2)	0.0165 (18)	0.0040 (17)	0.0159 (18)
C14	0.044 (2)	0.050 (2)	0.046 (2)	0.0176 (19)	0.0077 (17)	0.0279 (18)
C15	0.040 (2)	0.039 (2)	0.045 (2)	0.0136 (16)	0.0079 (16)	0.0223 (16)
C16	0.046 (2)	0.049 (2)	0.047 (2)	0.0196 (19)	0.0075 (17)	0.0276 (18)
C17	0.057 (2)	0.045 (2)	0.040 (2)	0.0195 (19)	0.0161 (18)	0.0210 (17)
C18	0.044 (2)	0.063 (3)	0.040 (3)	0.023 (2)	0.016 (2)	0.021 (3)
C19	0.052 (2)	0.0351 (19)	0.044 (2)	0.0204 (17)	0.0200 (17)	0.0169 (16)
C20	0.093 (4)	0.039 (2)	0.075 (3)	0.040 (2)	0.035 (3)	0.028 (2)
C21	0.084 (3)	0.033 (2)	0.054 (2)	0.032 (2)	0.029 (2)	0.0178 (18)
C22	0.043 (2)	0.038 (2)	0.050 (2)	0.0243 (17)	0.0148 (17)	0.0190 (17)
C23	0.047 (2)	0.043 (2)	0.062 (3)	0.0242 (19)	0.0141 (19)	0.0258 (19)
C24	0.048 (2)	0.057 (3)	0.059 (3)	0.032 (2)	0.0224 (19)	0.031 (2)
C25	0.066 (3)	0.055 (3)	0.049 (2)	0.044 (2)	0.014 (2)	0.0121 (19)
C26	0.049 (2)	0.0372 (19)	0.045 (2)	0.0291 (17)	0.0181 (16)	0.0127 (16)
C27	0.064 (3)	0.056 (2)	0.049 (2)	0.042 (2)	0.033 (2)	0.0275 (19)
C28	0.048 (2)	0.054 (2)	0.061 (2)	0.035 (2)	0.0307 (19)	0.028 (2)
C29	0.067 (3)	0.039 (2)	0.041 (2)	0.025 (2)	0.0167 (19)	0.0196 (17)

Geometric parameters (Å, º)

Cu1—N5^i	1.963 (3)	C4—H4A	0.9700
Cu1—O2	1.966 (3)	C4—H4B	0.9700
Cu1—O1	1.993 (3)	C5—C7	1.369 (7)
Cu1—N8	2.041 (3)	C5—C6	1.378 (7)
Cu1—N3	2.123 (5)	C6—C7^iii	1.383 (8)
Cu1—C29	2.369 (4)	C6—H6A	0.9300
N1—C1	1.304 (7)	C7—C6^iii	1.383 (8)
N1—C2	1.334 (7)	C7—H7A	0.9300
N2—C1	1.350 (7)	C8—H8A	0.9300
N2—C3	1.357 (6)	C9—C10	1.352 (6)
N2—C4	1.461 (6)	C9—H9A	0.9300
N3—C8	1.324 (5)	C10—H10A	0.9300
N3—C9	1.394 (7)	C11—C12	1.501 (6)
N4—C8	1.332 (5)	C11—H11A	0.9700
N4—C10	1.364 (5)	C11—H11B	0.9700
N4—C11	1.466 (5)	C12—C13	1.374 (6)
N5—C19	1.314 (5)	C12—C17	1.387 (6)
N5—C21	1.369 (5)	C13—C14	1.376 (6)
N5—Cu1^ii	1.963 (3)	C13—H13A	0.9300
N6—C19	1.333 (5)	C14—C15	1.387 (5)
N6—C20	1.365 (6)	C14—H14A	0.9300
N6—C18	1.454 (5)	C15—C16	1.385 (5)
N7—C22	1.331 (5)	C15—C18	1.506 (6)
N7—C24	1.367 (6)	C16—C17	1.376 (6)
N7—C25	1.465 (5)	C16—H16A	0.9300
N8—C22	1.317 (5)	C17—H17A	0.9300
N8—C23	1.373 (5)	C18—H18A	0.9700
O1—C29	1.289 (5)	C18—H18B	0.9700
O1W—H1WA	0.83 (16)	C19—H19A	0.9300
O1W—H1WB	0.86 (5)	C20—C21	1.345 (6)
O2—C29	1.276 (5)	C20—H20A	0.9300
O2W—H2WA	0.83 (10)	C21—H21A	0.9300
O2W—H2WB	0.82 (5)	C22—H22A	0.9300
O3—C29	1.241 (5)	C23—C24	1.349 (6)
O3W—H3WA	0.84 (10)	C23—H23A	0.9300
O3W—H3WB	0.85 (9)	C24—H24A	0.9300
O4W—H4WA	0.84 (10)	C25—C26	1.505 (6)
O4W—H4WB	0.83 (4)	C25—H25A	0.9700
O5W—H5WA	0.84 (5)	C25—H25B	0.9700
O5W—H5WB	0.86 (5)	C26—C28	1.376 (6)
C1—H1A	0.9300	C26—C27	1.381 (5)
C2—C3	1.334 (8)	C27—C28^iv	1.386 (6)
C2—H2A	0.9300	C27—H27A	0.9300
C3—H3A	0.9300	C28—C27^iv	1.386 (6)
C4—C5	1.521 (7)	C28—H28A	0.9300
N5^i—Cu1—O2	163.80 (13)	N3—C9—H9A	124.8
N5^i—Cu1—O1	98.53 (13)	C9—C10—N4	105.9 (4)
O2—Cu1—O1	65.57 (13)	C9—C10—H10A	127.1
N5^i—Cu1—N8	96.19 (13)	N4—C10—H10A	127.1
O2—Cu1—N8	95.13 (14)	N4—C11—C12	112.7 (3)
O1—Cu1—N8	141.92 (15)	N4—C11—H11A	109.0
N5^i—Cu1—N3	94.9 (2)	C12—C11—H11A	109.0
O2—Cu1—N3	94.3 (2)	N4—C11—H11B	109.0
O1—Cu1—N3	112.5 (2)	C12—C11—H11B	109.0
N8—Cu1—N3	100.90 (19)	H11A—C11—H11B	107.8
N5^i—Cu1—C29	131.49 (14)	C13—C12—C17	118.2 (4)
O2—Cu1—C29	32.60 (13)	C13—C12—C11	121.1 (4)
O1—Cu1—C29	32.98 (13)	C17—C12—C11	120.7 (4)
N8—Cu1—C29	121.67 (14)	C12—C13—C14	121.3 (4)
N3—Cu1—C29	105.22 (14)	C12—C13—H13A	119.4
C1—N1—C2	104.6 (5)	C14—C13—H13A	119.4
C1—N2—C3	104.9 (4)	C13—C14—C15	120.6 (4)
C1—N2—C4	126.7 (5)	C13—C14—H14A	119.7
C3—N2—C4	128.4 (5)	C15—C14—H14A	119.7
C8—N3—C9	103.1 (4)	C16—C15—C14	118.4 (4)
C8—N3—Cu1	122.7 (4)	C16—C15—C18	118.0 (3)
C9—N3—Cu1	132.3 (3)	C14—C15—C18	123.5 (4)
C8—N4—C10	107.5 (3)	C17—C16—C15	120.5 (4)
C8—N4—C11	126.2 (4)	C17—C16—H16A	119.7
C10—N4—C11	126.3 (4)	C15—C16—H16A	119.7
C19—N5—C21	105.9 (3)	C16—C17—C12	121.0 (4)
C19—N5—Cu1^ii	126.4 (3)	C16—C17—H17A	119.5
C21—N5—Cu1^ii	126.3 (3)	C12—C17—H17A	119.5
C19—N6—C20	106.7 (4)	N6—C18—C15	114.0 (3)
C19—N6—C18	126.2 (4)	N6—C18—H18A	108.7
C20—N6—C18	127.0 (4)	C15—C18—H18A	108.7
C22—N7—C24	107.5 (3)	N6—C18—H18B	108.7
C22—N7—C25	126.1 (4)	C15—C18—H18B	108.7
C24—N7—C25	126.4 (4)	H18A—C18—H18B	107.6
C22—N8—C23	105.4 (3)	N5—C19—N6	111.5 (3)
C22—N8—Cu1	125.2 (3)	N5—C19—H19A	124.3
C23—N8—Cu1	129.3 (3)	N6—C19—H19A	124.3
C29—O1—Cu1	89.7 (2)	C21—C20—N6	107.0 (4)
H1WA—O1W—H1WB	106 (7)	C21—C20—H20A	126.5
C29—O2—Cu1	91.3 (2)	N6—C20—H20A	126.5
H2WA—O2W—H2WB	112 (5)	C20—C21—N5	108.9 (4)
H3WA—O3W—H3WB	107 (4)	C20—C21—H21A	125.5
H4WA—O4W—H4WB	110 (5)	N5—C21—H21A	125.5
H5WA—O5W—H5WB	140 (7)	N8—C22—N7	111.5 (4)
N1—C1—N2	112.6 (5)	N8—C22—H22A	124.3
N1—C1—H1A	123.7	N7—C22—H22A	124.3
N2—C1—H1A	123.7	C24—C23—N8	109.6 (4)
C3—C2—N1	111.3 (5)	C24—C23—H23A	125.2
C3—C2—H2A	124.4	N8—C23—H23A	125.2
N1—C2—H2A	124.4	C23—C24—N7	106.0 (4)
C2—C3—N2	106.7 (5)	C23—C24—H24A	127.0
C2—C3—H3A	126.7	N7—C24—H24A	127.0
N2—C3—H3A	126.7	N7—C25—C26	111.4 (3)
N2—C4—C5	113.1 (4)	N7—C25—H25A	109.3
N2—C4—H4A	109.0	C26—C25—H25A	109.3
C5—C4—H4A	109.0	N7—C25—H25B	109.3
N2—C4—H4B	109.0	C26—C25—H25B	109.3
C5—C4—H4B	109.0	H25A—C25—H25B	108.0
H4A—C4—H4B	107.8	C28—C26—C27	118.3 (4)
C7—C5—C6	118.5 (5)	C28—C26—C25	120.8 (4)
C7—C5—C4	120.5 (5)	C27—C26—C25	120.9 (4)
C6—C5—C4	121.0 (5)	C26—C27—C28^iv	120.4 (4)
C5—C6—C7^iii	121.0 (5)	C26—C27—H27A	119.8
C5—C6—H6A	119.5	C28^iv—C27—H27A	119.8
C7^iii—C6—H6A	119.5	C26—C28—C27^iv	121.3 (4)
C5—C7—C6^iii	120.5 (5)	C26—C28—H28A	119.3
C5—C7—H7A	119.7	C27^iv—C28—H28A	119.3
C6^iii—C7—H7A	119.7	O3—C29—O2	122.3 (4)
N4—C8—N3	112.9 (4)	O3—C29—O1	124.4 (4)
N4—C8—H8A	123.8	O2—C29—O1	113.3 (4)
N3—C8—H8A	123.8	O3—C29—Cu1	177.6 (4)
C10—C9—N3	110.4 (4)	O2—C29—Cu1	56.1 (2)
C10—C9—H9A	124.8	O1—C29—Cu1	57.3 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O5W	0.83 (16)	2.40 (11)	2.780 (10)	108 (10)
O1W—H1WB···O1^v	0.86 (5)	1.87 (5)	2.722 (8)	170 (13)
O2W—H2WA···O3^vi	0.83 (10)	1.88 (6)	2.687 (9)	163 (10)
O2W—H2WB···O1W^vii	0.82 (5)	2.29 (9)	2.964 (14)	140 (10)
O3W—H3WA···O5W^iii	0.84 (10)	2.02 (5)	2.834 (9)	163 (10)
O3W—H3WB···O4W^viii	0.85 (9)	2.00 (5)	2.803 (9)	160 (10)
O4W—H4WA···O3	0.84 (10)	2.00 (6)	2.779 (8)	156 (10)
O4W—H4WB···O3W^ix	0.83 (4)	2.21 (5)	3.012 (10)	162 (9)
O5W—H5WA···O2W	0.84 (5)	1.99 (5)	2.808 (10)	166 (10)
O5W—H5WB···N1^i	0.86 (5)	2.09 (6)	2.868 (10)	151 (9)

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