Poly[[diaqua-μ-4,4′-bipyridine-di­nitratodi-μ-L-tyrosinato-dicopper(II)]: a chiral two-dimensional coordination polymer

The title compound, [Cu₂(C₉H₁₀NO₃)₂(NO₃)₂(C₁₀H₈N₂)(H₂O)₂]_n, contains Cu^II atoms and L-tyrosinate (L-tyr) and 4,4′-bipyridine (4,4′-bipy) ligands in a 2:2:1 ratio. Each Cu atom is coordinated by one amino N atom and two carboxyl­ate O atoms from two L-tyr ligands, one N atom from a 4,4′-bipy ligand, a monodentate nitrate ion and a water mol­ecule in an elongated octa­hedral geometry. Adjacent Cu atoms are bridged by the bidentate carboxyl­ate groups into a chain. These chains are further linked by the bridging 4,4′-bipy ligands, forming an undulated chiral two-dimensional sheet. O—H...O and N—H...O hydrogen bonds connect the sheets in the [100] direction. This study offers useful information for the engineering of chiral coordination polymers with amino acids and 4,4′-bipy ligands by considering the ratios of the metal ion and organic components.

S1. Comment

There is considerable interest in chiral coordination polymers, owing to their potential application in asymmetric catalysis and chiral separation (Kesanli & Lin, 2003). Although these materials can be synthesized from single chiral or achiral organic components, self-assembly based on a mixed-ligand system containing both chiral and achiral ligands is an attractive approach to the construction of chiral framework materials since it allows for facile tuning of structural, topological and functional features derived from different molecular components (Dai et al., 2005; Wang et al., 2008; Zaworotko, 2001). The 4,4'-bipyridine (4,4'-bipy) molecule is a common building block, which has been used extensively as a rigid linear linker between metal centres (Biradha et al., 2006). Amino acids such as L-tyrosine (L-tyr) are good candidates as chiral building blocks, with their amino and carboxylate groups being capable of binding to metal ions in flexible modes (Vaidhyanathan et al., 2006). We report here the title chiral two-dimensional coordination polymer, (I), which is assembled by connecting Cu–L-tyr units with 4,4'-bipy linkers.

The asymmetric unit of (I) consists of two Cu^II atoms, two deprotonated L-tyr ligands, one 4,4'-bipy ligand, two nitrate ions and two coordinated water molecules (Fig. 1). Each Cu atom is coordinated by one N atom and two carboxylate O atoms from two L-tyr ligands and one N atom from a 4,4'-bipy ligand in the equatorial plane, and by a monodentate nitrate ion and a water molecule in the axial positions. The nitrate ions and water molecules are weakly bonded to the Cu atoms, with Cu—O_nitrate distances of 2.565 (5) and 2.808 (7) Å, and Cu—O_water distances of 2.461 (4) and 2.627 (5) Å (Table 1). These axial Cu—O distances are longer than the sum of the ionic radii (Reference?), but they are still within the range of 2.2–2.9 Å known for axial Cu—O bond lengths (Zhang et al., 1996), thus displaying an elongated octahedral geometry around each Cu atom. The L-tyr ligand binds to the Cu atom in a µ-(κ³N,O:O') mode, that is, one carboxylate O atom chelates a Cu atom together with the amino N atom, and the other carboxylate O atom coordinates to another Cu atom. The hydroxyl O atom of the phenol group is uncoordinated. In this way, the L-tyr ligands bridge adjacent Cu atoms to form a chiral [Cu(L-tyr)(NO₃)(H₂O)]_n chain extending in the [001] direction. The separations between the Cu atoms in the chain are 5.180 (1) and 5.193 (1) Å. As shown in Fig. 2, these chains are further connected by the 4,4'-bipy linkers into a two-dimensional undulating sheet. Fig. 3 shows a schematic depiction of the sheet, which has a (6,3) topology (Batten & Robson, 1998), with Cu atoms as the three-connected nodes and with meshes of dimensions 9.82 × 11.06 Å. Moreover, these sheets are arranged in the [100] direction and connected by three types of hydrogen bonds (Table 2). One is formed between a hydroxyl group and a water O atom [O6—H6A···O2Wⁱⁱⁱ; symmetry code: (iii) 1 - x, 1/2 + y, 1 - z], the second involves the coordinated water molecules and nitrate ions, and the third involves the amino groups and nitrate ions.

It has been observed in the structures of [Cu(L-tyr)(1,10-phenanthroline)(H₂O)](ClO₄).H₂O (Sugimori et al., 1997) and [Cu(L-I₂tyr)(2,2'-bipyridine)(NO₃)].CH₃OH (Zhang et al., 1996) that the phenol ring of the L-tyr ligand folds back to be located over the Cu atom with an intramolecular phenol ring···Cu coordination plane interaction, whereas the two phenol rings in (I) each extend away from the Cu atoms. The phenol ring with hydroxyl atom O3 inserts itself into the mesh of the sheet to form a hydrogen bond between atom O3 and nitrate atom O11(2 - x, y - 1/2, 1 - z) of the opposite chain, while the phenol ring with hydroxyl atom O6 lies between two sheets, stabilized by a π–π interaction with a pyridyl ring of a neighbouring sheet [centroid-to-centroid distance = 3.56 (1) Å]. As a result, the channels along the [100] direction formed by the aligned meshes of the sheets are blocked by the side chains of the L-tyr ligands.

The rational design and controlled synthesis of coordination frameworks have been a challenging subject in crystal engineering. Small changes in the variables of reaction such as stoichiometry, pH value, temperature, solvent and metal source can have a profound influence on the structures of the products. For the Cu^II–amino acid–4,4'-bipy system, it seems that the ratio of Cu^II to amino acid to 4,4'-bipy is related to structural architecture. We note that a zero-dimensional dinuclear complex is formed for an L-valinate complex when the ratio is 2:2:3 (Lou & Hong, 2008), while one-dimensional helical chains have been found in L-threoninate and L-alaninate complexes with a ratio of 1:1:1, regardless of a polar or non-polar side chain (Lou et al., 2005). Two-dimensional frameworks are observed in (I), with the polar L-tyr ligand, and in a non-polar L-valinate complex (Lou et al., 2007), both of which have a ratio of 2:2:1. Clearly, despite the observed structural relevance to component ratios, further work is needed for understanding the factors affecting these structural architectures.

In conclusion, we have synthesized a two-dimensional chiral coordination polymer based on a mixed-ligand system, in which the L-tyr ligand provides a chiral source and the 4,4'-bipy ligand is used to extend the framework. This study offers helpful information for engineering this type of chiral coordination polymer by considering the ratios of metal ion and organic components.

S2. Experimental

Cu(NO₃)₂.3H₂O (0.096 g, 0.4 mmol) and L-tyrosine (0.072 g, 0.4 mmol) were dissolved in hot water (20 ml) with stirring. To this solution was added 4,4'-bipyridine (0.031 g, 0.2 mmol) in methanol (10 ml). The resulting solution was allowed to stand at room temperature and blue crystals of (I) suitable for X-ray diffraction analysis were obtained after two weeks.

S3. Refinement

H atoms bonded to O atoms were located in a difference Fourier map and fixed in the refinement, with U_iso(H) = 1.2U_eq(O). Other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 (aromatic), 0.97 (CH₂) or 0.98 (CH) Å and N—H = 0.90 Å, and with U_iso(H) = 1.2U_eq(C,N). The highest residual electron density is 0.94 Å from atom Cu2 and the deepest hole 0.93 Å from atom Cu1.

Computing details

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The asymmetric unit of (I), together with symmetry-related atoms to complete the coordination unit. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) x, y, z - 1; (ii) 2 - x, y - 1/2, 1 - z; (vi) 2 - x, y + 1/2, 1 - z.]
	Fig. 2. Ball-and-stick representation of the two-dimensional sheet in (I). H atoms have been omitted for clarity.
	Fig. 3. Schematic view of the (6,3) net in (I). Blue and pink lines represent the L-tyr and 4,4'-bipy ligands, respectively. [Colour will not be visible in the print version of the journal, so cannot be referred to specifically in the caption. Please revise the figure and caption, perhaps using dotted and dashed lines, or pale and dark ones]

Poly[[diaqua-µ-4,4'-bipyridine-dinitratodi-µ-L-tyrosinato-diaquadicopper(II)]

Crystal data

[Cu2(C9H10NO3)2(NO3)2(C10H8N2)(H2O)2]	F(000) = 824
Mr = 803.68	Dx = 1.687 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4737 reflections
a = 7.6075 (13) Å	θ = 2.4–26.1°
b = 22.281 (4) Å	µ = 1.43 mm^−1
c = 9.8205 (16) Å	T = 293 K
β = 108.150 (2)°	Prism, blue
V = 1581.8 (5) Å^3	0.33 × 0.19 × 0.17 mm
Z = 2

Data collection

Bruker SMART APEX CCD area-detector diffractometer	5584 independent reflections
Radiation source: fine-focus sealed tube	5003 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ϕ and ω scans	θmax = 25.8°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
Tmin = 0.652, Tmax = 0.791	k = −27→24
8422 measured reflections	l = −12→9

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.137	w = 1/[σ^2(Fo^2) + (0.0889P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.006
5584 reflections	Δρmax = 1.23 e Å^−3
439 parameters	Δρmin = −0.87 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 2506 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.010 (18)

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

	x	y	z	Uiso*/Ueq
Cu1	0.65447 (8)	−0.074095 (19)	0.03002 (6)	0.03088 (18)
Cu2	0.64748 (9)	−0.14898 (2)	0.52764 (6)	0.03256 (19)
O1W	0.3519 (6)	−0.0347 (2)	0.0291 (5)	0.0537 (11)
H1W	0.2866	−0.0516	0.0860	0.064*
H2W	0.2708	−0.0306	−0.0534	0.064*
O2W	0.3137 (7)	−0.1796 (2)	0.5268 (6)	0.0606 (13)
H3W	0.2491	−0.1625	0.5734	0.073*
H4W	0.2502	−0.1749	0.4368	0.073*
O1	0.6762 (5)	−0.10763 (18)	0.2227 (4)	0.0334 (8)
O2	0.5688 (5)	−0.18057 (17)	0.3307 (4)	0.0333 (8)
O3	1.0203 (7)	−0.4124 (2)	0.2408 (6)	0.0641 (13)
H3	0.9791	−0.4493	0.2326	0.077*
O4	0.6594 (6)	−0.11945 (16)	0.7187 (4)	0.0341 (9)
O5	0.6068 (6)	−0.04034 (17)	0.8366 (4)	0.0352 (9)
O6	0.5628 (7)	0.22702 (19)	0.2812 (5)	0.0599 (11)
H6A	0.6072	0.2557	0.3403	0.072*
O7	0.9706 (6)	−0.1209 (3)	0.0535 (5)	0.0673 (15)
O8	1.1001 (8)	−0.1743 (3)	0.2412 (8)	0.0839 (19)
O9	1.1833 (7)	−0.0821 (2)	0.2309 (6)	0.0644 (13)
O10	0.9665 (9)	−0.0804 (3)	0.5561 (7)	0.0867 (12)
O11	1.0682 (9)	−0.0326 (3)	0.7594 (7)	0.0867 (12)
O12	1.1989 (8)	−0.1120 (4)	0.7213 (7)	0.099 (2)
N1	0.7849 (6)	0.0017 (2)	0.1148 (5)	0.0325 (10)
N2	1.2032 (7)	0.2784 (2)	0.3938 (5)	0.0371 (11)
N3	0.5382 (6)	−0.1539 (2)	−0.0360 (5)	0.0310 (9)
H3A	0.4461	−0.1496	−0.1192	0.037*
H3B	0.6229	−0.1791	−0.0508	0.037*
N4	0.5479 (7)	−0.0687 (2)	0.4656 (4)	0.0370 (10)
H4A	0.6038	−0.0536	0.4048	0.044*
H4B	0.4261	−0.0716	0.4184	0.044*
N5	1.0848 (7)	−0.1252 (3)	0.1757 (7)	0.0527 (15)
N6	1.0791 (7)	−0.0751 (3)	0.6782 (6)	0.0542 (14)
C1	0.7881 (13)	0.0209 (3)	0.2439 (8)	0.076 (2)
H1	0.7375	−0.0038	0.2983	0.092*
C2	0.8616 (13)	0.0753 (3)	0.3024 (8)	0.076 (2)
H2	0.8581	0.0865	0.3927	0.092*
C3	0.9385 (7)	0.1119 (3)	0.2273 (6)	0.0333 (12)
C4	0.9382 (11)	0.0923 (3)	0.0942 (6)	0.0544 (19)
H4	0.9902	0.1160	0.0388	0.065*
C5	0.8613 (10)	0.0378 (3)	0.0432 (6)	0.0524 (17)
H5	0.8632	0.0257	−0.0469	0.063*
C6	1.1788 (10)	0.2348 (3)	0.4811 (7)	0.0469 (15)
H6	1.2239	0.2407	0.5797	0.056*
C7	1.0896 (10)	0.1815 (3)	0.4301 (7)	0.0459 (15)
H7	1.0761	0.1525	0.4942	0.055*
C8	1.0201 (8)	0.1711 (2)	0.2842 (6)	0.0319 (11)
C9	1.0389 (8)	0.2170 (2)	0.1946 (6)	0.0421 (13)
H9	0.9921	0.2125	0.0957	0.050*
C10	1.1284 (8)	0.2700 (2)	0.2533 (6)	0.0373 (12)
H10	1.1361	0.3008	0.1916	0.045*
C11	0.5793 (7)	−0.1544 (3)	0.2209 (5)	0.0273 (10)
C12	0.4648 (7)	−0.1786 (2)	0.0739 (5)	0.0295 (10)
H12	0.3428	−0.1600	0.0550	0.035*
C13	0.4278 (8)	−0.2456 (3)	0.0658 (6)	0.0355 (13)
H13A	0.3535	−0.2544	0.1276	0.043*
H13B	0.3527	−0.2548	−0.0314	0.043*
C14	0.5901 (7)	−0.2881 (2)	0.1050 (5)	0.0347 (11)
C15	0.5558 (8)	−0.3495 (3)	0.1026 (6)	0.0401 (14)
H15	0.4336	−0.3626	0.0722	0.048*
C16	0.6930 (9)	−0.3917 (3)	0.1429 (6)	0.0446 (13)
H16	0.6638	−0.4323	0.1370	0.054*
C17	0.8755 (9)	−0.3732 (3)	0.1924 (6)	0.0461 (13)
C18	0.9170 (9)	−0.3136 (3)	0.1911 (7)	0.0477 (14)
H18	1.0398	−0.3011	0.2195	0.057*
C19	0.7735 (7)	−0.2710 (2)	0.1467 (6)	0.0383 (11)
H19	0.8030	−0.2306	0.1455	0.046*
C20	0.6144 (7)	−0.0656 (3)	0.7252 (5)	0.0292 (11)
C21	0.5769 (7)	−0.0273 (2)	0.5900 (5)	0.0295 (10)
H21	0.6911	−0.0051	0.5987	0.035*
C22	0.4230 (9)	0.0195 (3)	0.5660 (7)	0.0388 (14)
H22A	0.3063	0.0015	0.5115	0.047*
H22B	0.4129	0.0318	0.6581	0.047*
C23	0.4578 (8)	0.0741 (2)	0.4873 (6)	0.0388 (12)
C24	0.5572 (10)	0.1221 (3)	0.5660 (6)	0.0493 (16)
H24	0.6009	0.1195	0.6655	0.059*
C25	0.5922 (10)	0.1736 (3)	0.4995 (7)	0.0515 (15)
H25	0.6569	0.2054	0.5536	0.062*
C26	0.5290 (9)	0.1770 (2)	0.3501 (6)	0.0446 (13)
C27	0.4357 (9)	0.1295 (3)	0.2729 (6)	0.0483 (14)
H27	0.3966	0.1314	0.1734	0.058*
C28	0.3982 (8)	0.0787 (2)	0.3395 (6)	0.0427 (13)
H28	0.3322	0.0472	0.2845	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0475 (4)	0.0299 (4)	0.0149 (3)	−0.0067 (3)	0.0092 (3)	−0.0019 (3)
Cu2	0.0539 (4)	0.0284 (4)	0.0141 (3)	0.0070 (3)	0.0088 (3)	0.0014 (3)
O1W	0.050 (2)	0.058 (3)	0.053 (3)	−0.0001 (19)	0.015 (2)	0.003 (2)
O2W	0.076 (3)	0.054 (3)	0.049 (3)	0.007 (2)	0.015 (2)	−0.005 (2)
O1	0.045 (2)	0.036 (2)	0.0181 (18)	−0.0086 (17)	0.0068 (16)	−0.0040 (16)
O2	0.050 (2)	0.0305 (18)	0.0195 (19)	−0.0014 (16)	0.0107 (15)	0.0016 (15)
O3	0.064 (3)	0.052 (3)	0.081 (4)	0.012 (2)	0.029 (3)	0.007 (3)
O4	0.059 (2)	0.0252 (19)	0.0195 (18)	0.0058 (16)	0.0135 (17)	0.0007 (15)
O5	0.061 (2)	0.0299 (18)	0.0149 (18)	−0.0008 (16)	0.0117 (15)	−0.0028 (15)
O6	0.092 (3)	0.051 (2)	0.036 (2)	−0.010 (2)	0.020 (2)	0.0082 (19)
O7	0.051 (3)	0.113 (4)	0.030 (2)	0.009 (3)	0.001 (2)	−0.009 (3)
O8	0.069 (3)	0.071 (4)	0.094 (5)	−0.014 (3)	−0.001 (3)	0.009 (3)
O9	0.064 (3)	0.065 (3)	0.053 (3)	−0.015 (3)	0.004 (2)	0.000 (3)
O10	0.094 (3)	0.105 (3)	0.056 (2)	0.012 (2)	0.016 (2)	0.002 (2)
O11	0.094 (3)	0.105 (3)	0.056 (2)	0.012 (2)	0.016 (2)	0.002 (2)
O12	0.080 (4)	0.116 (5)	0.076 (4)	0.049 (4)	−0.012 (3)	−0.033 (4)
N1	0.046 (3)	0.029 (2)	0.027 (2)	−0.005 (2)	0.017 (2)	−0.001 (2)
N2	0.047 (3)	0.042 (3)	0.018 (2)	−0.010 (2)	0.005 (2)	−0.007 (2)
N3	0.044 (2)	0.031 (2)	0.018 (2)	−0.006 (2)	0.0098 (17)	−0.007 (2)
N4	0.063 (3)	0.035 (2)	0.012 (2)	0.009 (2)	0.0101 (19)	0.000 (2)
N5	0.035 (3)	0.078 (4)	0.047 (3)	0.004 (3)	0.015 (2)	0.001 (3)
N6	0.050 (3)	0.079 (4)	0.030 (3)	0.004 (3)	0.008 (2)	−0.005 (3)
C1	0.138 (5)	0.064 (3)	0.057 (3)	−0.057 (3)	0.071 (4)	−0.034 (3)
C2	0.138 (5)	0.064 (3)	0.057 (3)	−0.057 (3)	0.071 (4)	−0.034 (3)
C3	0.032 (3)	0.041 (3)	0.028 (3)	−0.002 (2)	0.011 (2)	−0.002 (2)
C4	0.091 (5)	0.049 (4)	0.027 (3)	−0.035 (3)	0.024 (3)	−0.006 (3)
C5	0.076 (4)	0.064 (4)	0.018 (3)	−0.025 (3)	0.017 (3)	−0.013 (3)
C6	0.083 (4)	0.035 (3)	0.024 (3)	−0.024 (3)	0.019 (3)	−0.003 (2)
C7	0.069 (4)	0.045 (3)	0.024 (3)	−0.017 (3)	0.014 (3)	−0.002 (3)
C8	0.040 (3)	0.030 (3)	0.026 (3)	−0.006 (2)	0.012 (2)	−0.003 (2)
C9	0.054 (3)	0.041 (3)	0.024 (3)	−0.009 (2)	0.002 (2)	−0.002 (2)
C10	0.049 (3)	0.037 (3)	0.021 (2)	−0.007 (2)	0.004 (2)	0.003 (2)
C11	0.037 (2)	0.028 (2)	0.017 (2)	0.001 (2)	0.0077 (19)	−0.004 (2)
C12	0.037 (3)	0.036 (2)	0.014 (2)	−0.0042 (19)	0.0062 (19)	0.0007 (18)
C13	0.040 (3)	0.047 (4)	0.018 (3)	−0.011 (2)	0.008 (2)	−0.001 (2)
C14	0.056 (3)	0.035 (2)	0.016 (2)	−0.005 (2)	0.016 (2)	−0.001 (2)
C15	0.054 (3)	0.038 (3)	0.031 (3)	−0.013 (3)	0.016 (3)	−0.003 (2)
C16	0.066 (4)	0.040 (3)	0.035 (3)	−0.001 (3)	0.026 (3)	0.004 (2)
C17	0.066 (4)	0.049 (3)	0.029 (3)	0.010 (3)	0.022 (3)	0.005 (2)
C18	0.054 (4)	0.048 (3)	0.041 (4)	−0.003 (3)	0.014 (3)	−0.002 (3)
C19	0.050 (3)	0.031 (2)	0.034 (3)	−0.006 (2)	0.014 (2)	−0.005 (2)
C20	0.032 (2)	0.034 (3)	0.020 (2)	−0.003 (2)	0.0060 (19)	0.001 (2)
C21	0.045 (3)	0.026 (2)	0.020 (2)	0.0045 (19)	0.013 (2)	0.0011 (18)
C22	0.058 (4)	0.033 (3)	0.031 (3)	0.007 (2)	0.023 (3)	0.009 (2)
C23	0.053 (3)	0.036 (2)	0.028 (3)	0.016 (2)	0.013 (2)	0.005 (2)
C24	0.079 (4)	0.047 (3)	0.018 (3)	0.010 (3)	0.009 (3)	0.007 (2)
C25	0.075 (4)	0.038 (3)	0.034 (3)	−0.002 (3)	0.008 (3)	0.001 (2)
C26	0.062 (4)	0.041 (3)	0.034 (3)	0.003 (3)	0.019 (3)	0.009 (2)
C27	0.072 (4)	0.053 (3)	0.020 (3)	0.001 (3)	0.014 (2)	0.007 (2)
C28	0.064 (4)	0.036 (3)	0.027 (3)	0.005 (2)	0.013 (2)	0.000 (2)

Geometric parameters (Å, º)

Cu1—O5^i	1.968 (4)	C3—C4	1.378 (8)
Cu1—O1	1.993 (4)	C3—C8	1.489 (6)
Cu1—N3	2.002 (5)	C4—C5	1.372 (9)
Cu1—N1	2.004 (4)	C4—H4	0.9300
Cu1—O1W	2.461 (4)	C5—H5	0.9300
Cu1—O7	2.565 (5)	C6—C7	1.381 (8)
Cu2—N4	1.964 (5)	C6—H6	0.9300
Cu2—O4	1.964 (4)	C7—C8	1.383 (8)
Cu2—O2	1.968 (4)	C7—H7	0.9300
Cu2—N2^ii	1.989 (5)	C8—C9	1.386 (8)
Cu2—O2W	2.627 (5)	C9—C10	1.394 (7)
Cu2—O10	2.808 (7)	C9—H9	0.9300
O1W—H1W	0.9347	C10—H10	0.9300
O1W—H2W	0.8568	C11—C12	1.532 (6)
O2W—H3W	0.8582	C12—C13	1.516 (8)
O2W—H4W	0.8712	C12—H12	0.9800
O1—C11	1.274 (7)	C13—C14	1.508 (8)
O2—C11	1.251 (6)	C13—H13A	0.9700
O3—C17	1.369 (7)	C13—H13B	0.9700
O3—H3	0.8749	C14—C19	1.379 (7)
O4—C20	1.255 (7)	C14—C15	1.393 (8)
O5—C20	1.248 (6)	C15—C16	1.367 (9)
O5—Cu1^iii	1.968 (4)	C15—H15	0.9300
O6—C26	1.369 (7)	C16—C17	1.383 (9)
O6—H6A	0.8586	C16—H16	0.9300
O7—N5	1.247 (7)	C17—C18	1.368 (9)
O8—N5	1.256 (8)	C18—C19	1.409 (8)
O9—N5	1.235 (8)	C18—H18	0.9300
O10—N6	1.243 (8)	C19—H19	0.9300
O11—N6	1.257 (9)	C20—C21	1.529 (7)
O12—N6	1.202 (8)	C21—C22	1.530 (7)
N1—C5	1.316 (8)	C21—H21	0.9800
N1—C1	1.332 (8)	C22—C23	1.508 (8)
N2—C10	1.332 (7)	C22—H22A	0.9700
N2—C6	1.347 (8)	C22—H22B	0.9700
N2—Cu2^iv	1.989 (5)	C23—C28	1.383 (7)
N3—C12	1.468 (6)	C23—C24	1.396 (9)
N3—H3A	0.9000	C24—C25	1.386 (9)
N3—H3B	0.9000	C24—H24	0.9300
N4—C21	1.492 (6)	C25—C26	1.396 (8)
N4—H4A	0.9000	C25—H25	0.9300
N4—H4B	0.9000	C26—C27	1.365 (8)
C1—C2	1.382 (9)	C27—C28	1.381 (8)
C1—H1	0.9300	C27—H27	0.9300
C2—C3	1.350 (8)	C28—H28	0.9300
C2—H2	0.9300
O5^i—Cu1—O1	174.40 (16)	C7—C6—H6	118.7
O5^i—Cu1—N3	95.56 (17)	C6—C7—C8	120.4 (6)
O1—Cu1—N3	82.66 (17)	C6—C7—H7	119.8
O5^i—Cu1—N1	89.84 (17)	C8—C7—H7	119.8
O1—Cu1—N1	92.16 (17)	C7—C8—C9	116.8 (5)
N3—Cu1—N1	174.20 (19)	C7—C8—C3	121.2 (5)
O5^i—Cu1—O1W	88.24 (17)	C9—C8—C3	121.9 (5)
O1—Cu1—O1W	86.45 (16)	C10—C9—C8	119.7 (5)
N3—Cu1—O1W	89.85 (17)	C10—C9—H9	120.1
N1—Cu1—O1W	92.44 (17)	C8—C9—H9	120.1
O5^i—Cu1—O7	97.35 (16)	N2—C10—C9	123.0 (5)
O1—Cu1—O7	87.93 (16)	N2—C10—H10	118.5
N3—Cu1—O7	88.59 (19)	C9—C10—H10	118.5
N1—Cu1—O7	88.62 (18)	O2—C11—O1	124.2 (4)
O1W—Cu1—O7	174.32 (17)	O2—C11—C12	118.6 (5)
N4—Cu2—O4	83.68 (16)	O1—C11—C12	117.2 (4)
N4—Cu2—O2	92.92 (16)	N3—C12—C13	115.9 (4)
O4—Cu2—O2	165.53 (17)	N3—C12—C11	109.1 (4)
N4—Cu2—N2^ii	168.4 (2)	C13—C12—C11	115.9 (4)
O4—Cu2—N2^ii	92.94 (17)	N3—C12—H12	104.9
O2—Cu2—N2^ii	92.99 (18)	C13—C12—H12	104.9
N4—Cu2—O2W	87.51 (19)	C11—C12—H12	104.9
O4—Cu2—O2W	81.20 (16)	C14—C13—C12	118.8 (5)
O2—Cu2—O2W	84.61 (16)	C14—C13—H13A	107.6
N2^ii—Cu2—O2W	102.99 (19)	C12—C13—H13A	107.6
N4—Cu2—O10	76.9 (2)	C14—C13—H13B	107.6
O4—Cu2—O10	86.63 (17)	C12—C13—H13B	107.6
O2—Cu2—O10	106.35 (17)	H13A—C13—H13B	107.1
N2^ii—Cu2—O10	91.9 (2)	C19—C14—C15	116.3 (5)
O2W—Cu2—O10	161.19 (17)	C19—C14—C13	125.1 (5)
H1W—O1W—H2W	104.4	C15—C14—C13	118.6 (5)
H3W—O2W—H4W	105.0	C16—C15—C14	123.2 (6)
C11—O1—Cu1	114.6 (3)	C16—C15—H15	118.4
C11—O2—Cu2	126.8 (3)	C14—C15—H15	118.4
C17—O3—H3	109.9	C15—C16—C17	119.4 (5)
C20—O4—Cu2	115.9 (3)	C15—C16—H16	120.3
C20—O5—Cu1^iii	129.0 (4)	C17—C16—H16	120.3
C26—O6—H6A	111.5	C18—C17—O3	117.3 (6)
C5—N1—C1	115.6 (5)	C18—C17—C16	119.7 (6)
C5—N1—Cu1	122.5 (4)	O3—C17—C16	123.0 (5)
C1—N1—Cu1	121.8 (4)	C17—C18—C19	119.9 (6)
C10—N2—C6	117.2 (5)	C17—C18—H18	120.1
C10—N2—Cu2^iv	121.7 (4)	C19—C18—H18	120.1
C6—N2—Cu2^iv	121.1 (4)	C14—C19—C18	121.4 (5)
C12—N3—Cu1	109.0 (3)	C14—C19—H19	119.3
C12—N3—H3A	109.9	C18—C19—H19	119.3
Cu1—N3—H3A	109.9	O4—C20—O5	124.3 (5)
C12—N3—H3B	109.9	O4—C20—C21	118.0 (5)
Cu1—N3—H3B	109.9	O5—C20—C21	117.6 (5)
H3A—N3—H3B	108.3	N4—C21—C22	112.6 (4)
C21—N4—Cu2	111.4 (3)	N4—C21—C20	107.8 (4)
C21—N4—H4A	109.3	C22—C21—C20	116.2 (4)
Cu2—N4—H4A	109.3	N4—C21—H21	106.5
C21—N4—H4B	109.3	C22—C21—H21	106.5
Cu2—N4—H4B	109.3	C20—C21—H21	106.5
H4A—N4—H4B	108.0	C23—C22—C21	112.4 (5)
O9—N5—O8	120.4 (6)	C23—C22—H22A	109.1
O9—N5—O7	120.5 (6)	C21—C22—H22A	109.1
O8—N5—O7	119.0 (7)	C23—C22—H22B	109.1
O12—N6—O10	119.6 (7)	C21—C22—H22B	109.1
O12—N6—O11	119.0 (6)	H22A—C22—H22B	107.9
O10—N6—O11	121.4 (7)	C28—C23—C24	118.0 (5)
N1—C1—C2	124.2 (6)	C28—C23—C22	123.0 (5)
N1—C1—H1	117.9	C24—C23—C22	119.0 (5)
C2—C1—H1	117.9	C25—C24—C23	121.5 (5)
C3—C2—C1	119.4 (6)	C25—C24—H24	119.2
C3—C2—H2	120.3	C23—C24—H24	119.2
C1—C2—H2	120.3	C24—C25—C26	119.1 (6)
C2—C3—C4	116.9 (5)	C24—C25—H25	120.4
C2—C3—C8	122.1 (5)	C26—C25—H25	120.4
C4—C3—C8	121.0 (5)	O6—C26—C27	120.2 (5)
C5—C4—C3	120.1 (6)	O6—C26—C25	120.5 (5)
C5—C4—H4	119.9	C27—C26—C25	119.3 (5)
C3—C4—H4	119.9	C26—C27—C28	121.4 (5)
N1—C5—C4	123.7 (6)	C26—C27—H27	119.3
N1—C5—H5	118.1	C28—C27—H27	119.3
C4—C5—H5	118.1	C27—C28—C23	120.5 (5)
N2—C6—C7	122.6 (6)	C27—C28—H28	119.7
N2—C6—H6	118.7	C23—C28—H28	119.7

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O11^ii	0.87	1.90	2.761 (9)	169
O6—H6A···O2W^v	0.86	1.91	2.768 (7)	175
O1W—H1W···O9^vi	0.93	1.95	2.876 (7)	171
O1W—H2W···O11^vii	0.86	2.00	2.849 (8)	172
O2W—H4W···O8^vi	0.87	1.90	2.772 (8)	173
O2W—H3W···O12^vi	0.86	1.97	2.779 (8)	157
N3—H3A···O12^vii	0.90	2.20	3.063 (7)	159
N4—H4A···O1	0.90	2.36	2.974 (6)	126
N4—H4B···O9^vi	0.90	2.18	3.018 (7)	155

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