catena-Poly[[tetra­kis(μ-propionato-κ²O:O′)dicopper(II)]-μ-3-pyridylmethanol-κ²N:O-[bis­(propionato-κO)bis­(3-pyridylmethanol-κN)copper(II)]-μ-3-pyridylmethanol-κO:N]

The title compound, [Cu₃(C₃H₅O₂)₆(C₆H₇NO)₄]_n, is composed of polymeric chains formed by alternating centrosymmetric Cu₂(μ-CH₃CH₂CO₂)₄ and Cu(C₃H₅O₂)₂(C₆H₇NO)₂ units. These elemental units are linked by two bridging 3-pyridylmethanol (3PM) ligands. The Cu₂(μ-CH₃CH₂CO₂)₄ group presents a centrosymmetric tetra­bridged structure with four syn–syn bridging propionate ligands to which two 3PM mol­ecules are bonded (through N), occupying the apical positions of each square-pyramidal polyhedron around the Cu^II ions. The remaining mononuclear group is centred around a third Cu^II ion, which lies on a symmetry centre and is bound to two monodentate propionate groups (through O), two monodentate 3PM mol­ecules (through N) and two bridging 3PM mol­ecules (through O), thus completing a square-bipyramidal CuO₂N₂O₂ coordination.

S1. Comment

3-Pyridylmethanol (3PM) is a non-steroidal anti-inflammatory agent in current use. It can act as an effective ligand in coordination compounds, where it presents a variety of binding modes. In the monomeric structures [CuCl₂(3PM)₄], (II) (Moncol et al., 2004), and [Cu(2-nitrobenzoato)₂(3PM)₂(H₂O)₂], (III) (Stachová et al., 2006), 3PM behaves as a terminal ligand, coordinating through the N atom of its pyridine ring. An analogous binding mode is found in dimeric [Cu₂(µ-CH₃CO₂)₄(3PM)₂]·CH₂Cl₂, (IV) (Melník et al., 1985), where the Cu^II atoms are bridged into pairs by four acetate groups to form two crystallographically independent binuclear molecules, with the N atoms of the 3PM ligands situated at the vertices of a slightly deformed square pyramid around the cations. More complex intermolecular interactions are achieved in complexes of general formula [Cu(RCO₂)₂(µ-3PM)₂]_n. For RCO₂ = salicylate, (V) (Hoang et al., 1992, Maroszová, Moncol et al., 2006), 4-chlorosalicylate, (VI) (Maroszová, Martiška et al., 2006), flufenamate, (VII) (Lörinc et al., 2004), clofibriate, (VIII) (Moncol et al., 2001), or 2-chlorobenzoate, (IX) (Moncol et al., 2006), a two-dimensional sheet is built up with Cu^II ions linked by bridging 3PM ligands. When RCO₂ = trichloroacetate, (X) (Múdra et al., 2003), dichloroacetate, (XI) (Múdra et al., 2003), 3-nitrobenzoate, (XII) (Stachová et al., 2005), 3,5-dinitrobenzoate, (XIII) (Stachová et al., 2006), niflumate, (XIV) (Valach et al., 1997), or 2-methylthionicotinate, (XV) (Moncol et al., 2006), the result is a one-dimensional coordination polymer. Finally, the crystal structure of [Cu₃(2-chloronicotinate)₆(µ-3PM)₄(3PM)₂]_n, (XVI) (Moncol et al., 2006), consists of one-dimensional `accordion chain' coordination polymers with different coordination environments around the Cu^II ions (square bipyramidal and square pyramidal).

The crystal structure of (I) consists of zigzag chains (Fig. 1.) that are formed by alternating dinuclear Cu₂(µ-CH₃CH₂CO₂)₄ and mononuclear Cu(CH₃CH₂CO₂)₂(3PM)₂ units linked by bridging 3PM molecules. The dimeric unit is formed around a symmetry centre and presents a tetrabridged paddle-wheel structure with four syn–syn bridging propionates. The Cu2···Cu2ⁱ [symmetry code: (i) -x, 1 - y, 1 - z] distance is 2.6367 (12) Å, very similar to the values found in other dimeric copper(II) propionate complexes (range 2.569–2.655 Å; Melník et al., 1998). The τ value (Addison et al., 1984) is 0.005 for atom Cu2, which is typical for a square-pyramidal geometry. The basal plane consists of four O atoms, O4, O5ⁱ, O6 and O7ⁱ, at distances of 1.958 (3)–1.964 (3) Å. The apical site is occupied by the N atom of the 3PM pyridine ring [Cu2—N2 = 2.176 (3) Å]. Atom Cu2 is displaced from the least-squares plane defined by the basal atoms by 0.207 (1) Å towards the apical N atom. The Cu(CH₃CH₂CO₂)₂(3PM)₂ unit also has a centrosymmetric structure, with a CuO₂N₂O₂ square-bipyramidal coordination around atom Cu1, which lies at the symmetry centre. The environment is defined by two O atoms from two unidentate propionate groups, two N atoms from two unidentate 3PM molecules and two O atoms from two bridging 3PM molecules. The basal plane is built up by a pair of carboxylate O atoms [Cu1—O1 = 1.954 (2) Å] and a pair of N atoms [Cu1—N1 = 2.003 (2) Å] from the pyridine rings in the terminal neutral 3-pyridylmethanol molecules. The axial positions are occupied by two hydroxyl O atoms [Cu1—O8 = 2.502 (3) Å] from the bridging 3PM ligands.

Intramolecular hydrogen bonds [O8···O2 = 2.625 (5) Å] create a six-membered metallocycle and stabilize the molecular structure of the chain building units. The crystal structure of (I) consists of zigzag one-dimensional chains (Fig. 2), which are connected by intermolecular hydrogen bonds [O3···O2ⁱⁱⁱ = 2.768 (5) Å; symmetry code: x + 1, y, z] to form two-dimensional sheets.

The structure of (I) can be compared with the dimeric structure of (IV) mentioned above and the polymeric structures (V)–(XV). The Cu2···Cu2ⁱ distance and the average Cu2—O_carb and Cu2—N2 bond distances of the Cu₂(µ-CH₃CH₂CO₂)₄ unit are very similar to the bond distances in (IV), where the molecular structure consists of two crystallographically independent molecules of Cu₂(CH₃CO₂)₄(3PM)₂. The Cu···Cu distance, and average Cu—O_carb (acetate anions) and Cu—N_ax (N atom of the pyridine ring of 3PM) bond lengths in the two independent dimers of (IV) are 2.654 (1), 1.963 (4) and 2.197 (5) Å, and 2.634 (1), 1.969 (4) and 2.152 (5) Å, respectively. The geometry of the Cu(CH₃CH₂CO₂)₂(3PM)₂ unit and the bond distances are very similar to the molecular structure of complexes with the formula [Cu(RCO₂)₂(µ-3PM)₂]_n, (V)–(XV). The present crystal structure can be considered as the connecting link between two types of structures of copper(II) carboxylate adducts with 3-pyridylmethanol (dimeric and polymeric).

Related literature

For related literature, see: Addison et al. (1984); Battaglia & Corradi (1986); Hoang et al. (1992); Lörinc et al. (2004); Múdra et al. (2003); Maroszová, Martiška, Valigura, Koman & Głowiak (2006); Maroszová, Moncol, Koman, Melník & Głowiak (2006); Melník et al. (1985, 1998); Moncol et al. (2001, 2004, 2006); Sheldrick (1997); Stachová et al. (2005, 2006); Valach et al. (1997).

S2. Experimental

Cu(CH₃CH₂CO₂)₂·H₂O was prepared as described by Battaglia & Corradi (1986). Compound (I) was prepared by treating 3-pyridylmethanol with Cu(CH₃CH₂CO₂)₂·H₂O in a 2:3 molar ratio in hot methanol. The resulting solution was filtered and the filtrate left to stand at room temperature, allowing fine green crystals to precipitate out. These crystals were filtered off, washed with cold methanol and dried at room temperature. Crystals of (I) suitable for structural determination were obtained by recrystallizing the crude product from methanol with a small amount of acetone (yield 70%). Analysis, found: C 47.56, H 5.68, N 5.30, Cu 17.82%; C₄₂H₅₈Cu₃N₄O₁₆ requires: C 47.34, H 5.49, N 5.26, Cu 17.89%.

S3. Refinement

All H atoms attached to C atoms were placed in calculated positions with C—H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl groups, respectively. The hydroxyl H atom was positioned using the AFIX 147 facility in SHELXL97 (Sheldrick, 1997) (O—H = 0.82 Å). In all cases, U_iso(H) = xU_iso(C,O), where x = 1.2 for aromatic and methylene H, and 1.5 for methyl and hydroxyl H.

Computing details

Data collection: P2₁ Software (Syntex, 1973); cell refinement: P2₁ Software; data reduction: XP21 (Pavelčík, 1993); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and XP in SHELXTL (Sheldrick, 1998); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures

	Fig. 1. A perspective view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) -x, 1 - y, 1 - z; (ii) -x, -y, -z.]
	Fig. 2. The O—H···O hydrogen bonds in the crystal structure of (I). [Symmetry code: (iii) x + 1, y, z.]

catena-Poly[[tetrakis(µ-propionato-κ²O:O')dicopper(II)]-µ-3- pyridylmethanol-κ²N:O-[bis(propionato-κO)bis(µ-3-pyridylmethanol- κ²N,O)copper(II)]-µ-3-pyridylmethanol-κO:N]

Crystal data

[Cu3(C6H7NO)4(C3H5O2)6]	Z = 1
Mr = 1065.54	F(000) = 553
Triclinic, P1	Dx = 1.507 Mg m^−3 Dm = 1.50 Mg m^−3 Dm measured by flotation
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 8.194 (2) Å	Cell parameters from 25 reflections
b = 9.959 (2) Å	θ = 5.2–11.6°
c = 15.358 (3) Å	µ = 1.42 mm^−1
α = 104.27 (3)°	T = 293 K
β = 103.99 (3)°	Rectangular prism, green
γ = 91.10 (3)°	0.45 × 0.40 × 0.30 mm
V = 1174.4 (4) Å^3

Data collection

Syntex P21 diffractometer	3645 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.035
Graphite monochromator	θmax = 27.6°, θmin = 1.4°
θ/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = −12→12
Tmin = 0.576, Tmax = 0.654	l = −19→19
5808 measured reflections	2 standard reflections every 100 reflections
5428 independent reflections	intensity decay: 15%

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.153	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.103P)^2] where P = (Fo^2 + 2Fc^2)/3
5428 reflections	(Δ/σ)max < 0.001
300 parameters	Δρmax = 0.76 e Å^−3
0 restraints	Δρmin = −0.70 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	0.0000	0.0000	0.0000	0.04309 (17)
Cu2	−0.08880 (5)	0.48991 (4)	0.41438 (3)	0.04171 (15)
N1	0.1691 (4)	0.1037 (3)	0.11617 (19)	0.0426 (7)
N2	−0.2456 (4)	0.4675 (3)	0.27445 (19)	0.0431 (6)
O1	−0.0104 (3)	−0.1549 (3)	0.05617 (18)	0.0509 (6)
O2	−0.2367 (4)	−0.1215 (4)	0.1079 (3)	0.0839 (10)
O3	0.5601 (4)	−0.1069 (3)	0.2295 (2)	0.0713 (8)
H3O	0.6143	−0.1131	0.1904	0.107*
O4	−0.0106 (4)	0.3028 (3)	0.38880 (19)	0.0616 (7)
O5	0.1414 (4)	0.3211 (3)	0.5329 (2)	0.0612 (7)
O6	−0.2710 (3)	0.4164 (3)	0.45697 (19)	0.0567 (7)
O7	−0.1223 (3)	0.4353 (3)	0.60164 (19)	0.0603 (7)
O8	−0.2244 (3)	0.1192 (3)	0.06742 (19)	0.0589 (7)
H8O	−0.2520	0.0424	0.0724	0.088*
C1	−0.1125 (5)	−0.1846 (4)	0.0973 (3)	0.0512 (9)
C2	−0.0819 (7)	−0.3103 (5)	0.1365 (4)	0.0822 (15)
H2A	−0.0941	−0.2853	0.1996	0.099*
H2B	−0.1695	−0.3834	0.1005	0.099*
C3	0.0782 (10)	−0.3655 (8)	0.1376 (7)	0.140 (3)
H3A	0.0942	−0.3881	0.0759	0.210*
H3B	0.0817	−0.4479	0.1597	0.210*
H3C	0.1663	−0.2976	0.1781	0.210*
C4	0.2984 (4)	0.0411 (4)	0.1572 (2)	0.0436 (8)
H4	0.3061	−0.0525	0.1310	0.052*
C5	0.4184 (4)	0.1070 (4)	0.2349 (2)	0.0449 (8)
C6	0.4030 (5)	0.2451 (4)	0.2750 (2)	0.0493 (9)
H6	0.4825	0.2941	0.3283	0.059*
C7	0.2698 (5)	0.3081 (4)	0.2353 (3)	0.0529 (9)
H7	0.2561	0.4001	0.2625	0.063*
C8	0.1561 (5)	0.2367 (4)	0.1556 (3)	0.0479 (8)
H8	0.0677	0.2821	0.1282	0.057*
C9	0.5635 (5)	0.0319 (5)	0.2768 (3)	0.0679 (12)
H9A	0.6687	0.0798	0.2783	0.081*
H9B	0.5619	0.0368	0.3405	0.081*
C10	0.0850 (5)	0.2571 (4)	0.4502 (3)	0.0519 (9)
C11	0.1405 (7)	0.1136 (5)	0.4207 (4)	0.0819 (15)
H11A	0.2568	0.1236	0.4175	0.098*
H11B	0.1396	0.0678	0.4695	0.098*
C12	0.0474 (9)	0.0230 (6)	0.3351 (5)	0.136 (3)
H12A	−0.0473	−0.0238	0.3451	0.204*
H12B	0.1189	−0.0444	0.3116	0.204*
H12C	0.0080	0.0761	0.2909	0.204*
C13	−0.2545 (5)	0.4028 (4)	0.5368 (3)	0.0501 (9)
C14	−0.4064 (5)	0.3461 (5)	0.5597 (4)	0.0683 (12)
H14A	−0.4350	0.4167	0.6085	0.082*
H14B	−0.5009	0.3298	0.5052	0.082*
C15	−0.3874 (9)	0.2213 (7)	0.5888 (7)	0.138 (3)
H15A	−0.3582	0.1504	0.5415	0.206*
H15B	−0.4915	0.1917	0.5994	0.206*
H15C	−0.2996	0.2375	0.6453	0.206*
C16	−0.2530 (4)	0.3513 (4)	0.2078 (2)	0.0437 (8)
H16	−0.1794	0.2846	0.2204	0.052*
C17	−0.3636 (4)	0.3245 (4)	0.1213 (2)	0.0441 (8)
C18	−0.4732 (5)	0.4234 (4)	0.1039 (3)	0.0509 (9)
H18	−0.5514	0.4087	0.0466	0.061*
C19	−0.4657 (5)	0.5434 (4)	0.1717 (3)	0.0546 (9)
H19	−0.5381	0.6117	0.1611	0.066*
C20	−0.3514 (5)	0.5615 (4)	0.2547 (3)	0.0473 (8)
H20	−0.3468	0.6440	0.3001	0.057*
C21	−0.3676 (6)	0.1906 (4)	0.0478 (3)	0.0643 (11)
H21A	−0.4666	0.1310	0.0424	0.077*
H21B	−0.3780	0.2117	−0.0115	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0457 (3)	0.0385 (3)	0.0375 (3)	−0.0032 (2)	0.0010 (2)	0.0060 (2)
Cu2	0.0364 (2)	0.0450 (3)	0.0365 (2)	0.00480 (17)	0.00507 (16)	0.00131 (17)
N1	0.0441 (15)	0.0375 (15)	0.0375 (14)	−0.0005 (12)	0.0042 (12)	0.0000 (12)
N2	0.0417 (15)	0.0442 (16)	0.0388 (15)	0.0060 (12)	0.0087 (12)	0.0035 (12)
O1	0.0553 (15)	0.0432 (14)	0.0519 (15)	−0.0001 (11)	0.0068 (12)	0.0149 (11)
O2	0.070 (2)	0.095 (3)	0.108 (3)	0.0291 (19)	0.038 (2)	0.049 (2)
O3	0.0648 (19)	0.0631 (18)	0.091 (2)	0.0228 (15)	0.0229 (17)	0.0251 (17)
O4	0.0688 (18)	0.0528 (16)	0.0506 (16)	0.0195 (14)	0.0055 (14)	−0.0010 (13)
O5	0.0655 (17)	0.0505 (15)	0.0564 (17)	0.0140 (13)	0.0037 (14)	0.0039 (13)
O6	0.0397 (13)	0.0731 (19)	0.0503 (15)	−0.0061 (12)	0.0061 (11)	0.0093 (13)
O7	0.0423 (14)	0.087 (2)	0.0501 (15)	−0.0012 (14)	0.0084 (12)	0.0188 (14)
O8	0.0570 (16)	0.0524 (16)	0.0625 (17)	0.0091 (13)	0.0192 (13)	0.0016 (13)
C1	0.047 (2)	0.049 (2)	0.055 (2)	0.0019 (16)	0.0061 (17)	0.0164 (17)
C2	0.076 (3)	0.074 (3)	0.112 (4)	0.008 (3)	0.025 (3)	0.053 (3)
C3	0.135 (6)	0.124 (6)	0.200 (8)	0.064 (5)	0.048 (6)	0.104 (6)
C4	0.0433 (18)	0.0422 (18)	0.0420 (18)	0.0084 (14)	0.0111 (15)	0.0040 (14)
C5	0.0381 (17)	0.051 (2)	0.0435 (18)	0.0020 (15)	0.0102 (14)	0.0080 (15)
C6	0.0447 (19)	0.050 (2)	0.0420 (19)	−0.0056 (16)	0.0026 (15)	0.0001 (15)
C7	0.056 (2)	0.0371 (18)	0.055 (2)	0.0005 (16)	0.0110 (18)	−0.0037 (16)
C8	0.0485 (19)	0.0392 (18)	0.049 (2)	0.0057 (15)	0.0067 (16)	0.0045 (15)
C9	0.054 (2)	0.073 (3)	0.067 (3)	0.015 (2)	0.000 (2)	0.015 (2)
C10	0.045 (2)	0.048 (2)	0.059 (2)	0.0083 (16)	0.0147 (18)	0.0043 (18)
C11	0.083 (3)	0.052 (3)	0.091 (4)	0.024 (2)	0.007 (3)	−0.005 (2)
C12	0.126 (5)	0.076 (4)	0.144 (6)	0.040 (4)	−0.030 (5)	−0.028 (4)
C13	0.0406 (19)	0.044 (2)	0.065 (2)	0.0019 (15)	0.0188 (18)	0.0081 (17)
C14	0.048 (2)	0.075 (3)	0.084 (3)	−0.004 (2)	0.023 (2)	0.019 (2)
C15	0.100 (5)	0.117 (5)	0.256 (10)	0.037 (4)	0.082 (6)	0.120 (6)
C16	0.0398 (17)	0.0473 (19)	0.0393 (17)	0.0104 (14)	0.0061 (14)	0.0056 (15)
C17	0.0385 (17)	0.0489 (19)	0.0416 (18)	0.0053 (14)	0.0079 (14)	0.0077 (15)
C18	0.0431 (19)	0.063 (2)	0.0422 (19)	0.0082 (17)	0.0011 (15)	0.0153 (17)
C19	0.050 (2)	0.051 (2)	0.062 (2)	0.0174 (17)	0.0112 (18)	0.0176 (18)
C20	0.0477 (19)	0.0430 (19)	0.049 (2)	0.0069 (15)	0.0131 (16)	0.0061 (15)
C21	0.070 (3)	0.058 (2)	0.046 (2)	0.014 (2)	−0.0010 (19)	−0.0050 (18)

Geometric parameters (Å, º)

Cu1—O1	1.954 (2)	C5—C9	1.513 (5)
Cu1—O1^i	1.954 (2)	C6—C7	1.360 (5)
Cu1—N1^i	2.003 (3)	C6—H6	0.9300
Cu1—N1	2.003 (3)	C7—C8	1.366 (5)
Cu1—O8	2.502 (3)	C7—H7	0.9300
Cu2—O5^ii	1.958 (3)	C8—H8	0.9300
Cu2—O4	1.960 (3)	C9—H9A	0.9700
Cu2—O7^ii	1.963 (3)	C9—H9B	0.9700
Cu2—O6	1.964 (3)	C10—O5	1.241 (5)
Cu2—N2	2.176 (3)	C10—C11	1.503 (5)
Cu2—Cu2^ii	2.6367 (12)	C11—C12	1.424 (7)
N1—C8	1.332 (4)	C11—H11A	0.9700
N1—C4	1.343 (5)	C11—H11B	0.9700
N2—C20	1.328 (4)	C12—H12A	0.9600
N2—C16	1.333 (4)	C12—H12B	0.9600
O1—C1	1.234 (5)	C12—H12C	0.9600
O2—C1	1.229 (5)	C13—O7	1.255 (5)
O3—C9	1.390 (5)	C13—C14	1.508 (5)
O3—H3O	0.8200	C14—C15	1.420 (7)
O4—C10	1.257 (5)	C14—H14A	0.9700
O5—Cu2^ii	1.958 (3)	C14—H14B	0.9700
O6—C13	1.243 (5)	C15—H15A	0.9600
O7—Cu2^ii	1.963 (3)	C15—H15B	0.9600
O8—C21	1.393 (5)	C15—H15C	0.9600
O8—H8O	0.8200	C16—C17	1.375 (5)
C1—C2	1.518 (6)	C16—H16	0.9300
C2—C3	1.430 (8)	C17—C18	1.377 (5)
C2—H2A	0.9700	C17—C21	1.513 (5)
C2—H2B	0.9700	C18—C19	1.368 (6)
C3—H3A	0.9600	C18—H18	0.9300
C3—H3B	0.9600	C19—C20	1.355 (5)
C3—H3C	0.9600	C19—H19	0.9300
C4—C5	1.358 (5)	C20—H20	0.9300
C4—H4	0.9300	C21—H21A	0.9700
C5—C6	1.383 (5)	C21—H21B	0.9700
O1—Cu1—O1^i	180.00 (12)	C5—C6—H6	120.5
O1—Cu1—N1^i	91.13 (11)	C6—C7—C8	120.2 (3)
O1^i—Cu1—N1^i	88.87 (11)	C6—C7—H7	119.9
O1—Cu1—N1	88.87 (11)	C8—C7—H7	119.9
O1^i—Cu1—N1	91.13 (11)	N1—C8—C7	121.5 (3)
N1^i—Cu1—N1	180.00 (13)	N1—C8—H8	119.2
O1—Cu1—O8	93.37 (11)	C7—C8—H8	119.2
O1^i—Cu1—O8	86.63 (11)	O3—C9—C5	114.2 (3)
N1^i—Cu1—O8	92.18 (11)	O3—C9—H9A	108.7
N1—Cu1—O8	87.82 (11)	C5—C9—H9A	108.7
O1—Cu1—O8^iii	161.26 (8)	O3—C9—H9B	108.7
O1^i—Cu1—O8^iii	18.74 (8)	C5—C9—H9B	108.7
N1^i—Cu1—O8^iii	107.04 (9)	H9A—C9—H9B	107.6
N1—Cu1—O8^iii	72.96 (9)	O5—C10—O4	125.8 (4)
O8—Cu1—O8^iii	81.66 (8)	O5—C10—C11	116.8 (4)
O5^ii—Cu2—O4	167.87 (12)	O4—C10—C11	117.4 (4)
O5^ii—Cu2—O7^ii	89.98 (14)	C12—C11—C10	118.5 (5)
O4—Cu2—O7^ii	89.51 (13)	C12—C11—H11A	107.7
O5^ii—Cu2—O6	89.31 (13)	C10—C11—H11A	107.7
O4—Cu2—O6	88.64 (13)	C12—C11—H11B	107.7
O7^ii—Cu2—O6	167.83 (11)	C10—C11—H11B	107.7
O5^ii—Cu2—N2	96.61 (12)	H11A—C11—H11B	107.1
O4—Cu2—N2	95.44 (11)	C11—C12—H12A	109.5
O7^ii—Cu2—N2	98.49 (11)	C11—C12—H12B	109.5
O6—Cu2—N2	93.67 (11)	H12A—C12—H12B	109.5
O5^ii—Cu2—Cu2^ii	83.81 (9)	C11—C12—H12C	109.5
O4—Cu2—Cu2^ii	84.09 (9)	H12A—C12—H12C	109.5
O7^ii—Cu2—Cu2^ii	84.36 (9)	H12B—C12—H12C	109.5
O6—Cu2—Cu2^ii	83.48 (8)	O6—C13—O7	125.5 (3)
N2—Cu2—Cu2^ii	177.12 (8)	O6—C13—C14	118.0 (4)
C8—N1—C4	117.9 (3)	O7—C13—C14	116.5 (4)
C8—N1—Cu1	121.0 (2)	C15—C14—C13	115.7 (4)
C4—N1—Cu1	121.1 (2)	C15—C14—H14A	108.4
C20—N2—C16	117.2 (3)	C13—C14—H14A	108.4
C20—N2—Cu2	121.5 (2)	C15—C14—H14B	108.4
C16—N2—Cu2	120.9 (2)	C13—C14—H14B	108.4
C1—O1—Cu1	129.6 (3)	H14A—C14—H14B	107.4
C9—O3—H3O	109.5	C14—C15—H15A	109.5
C10—O4—Cu2	122.7 (2)	C14—C15—H15B	109.5
C13—O6—Cu2	124.0 (2)	H15A—C15—H15B	109.5
C21—O8—Cu1	143.7 (3)	C14—C15—H15C	109.5
C21—O8—H8O	109.5	H15A—C15—H15C	109.5
Cu1—O8—H8O	85.2	H15B—C15—H15C	109.5
O2—C1—O1	125.2 (4)	N2—C16—C17	123.6 (3)
O2—C1—C2	118.0 (4)	N2—C16—H16	118.2
O1—C1—C2	116.8 (4)	C17—C16—H16	118.2
C3—C2—C1	116.2 (5)	C16—C17—C18	117.6 (3)
C3—C2—H2A	108.2	C16—C17—C21	121.7 (3)
C1—C2—H2A	108.2	C18—C17—C21	120.7 (3)
C3—C2—H2B	108.2	C19—C18—C17	119.2 (3)
C1—C2—H2B	108.2	C19—C18—H18	120.4
H2A—C2—H2B	107.4	C17—C18—H18	120.4
C2—C3—H3A	109.5	C20—C19—C18	119.2 (4)
C2—C3—H3B	109.5	C20—C19—H19	120.4
H3A—C3—H3B	109.5	C18—C19—H19	120.4
C2—C3—H3C	109.5	N2—C20—C19	123.3 (3)
H3A—C3—H3C	109.5	N2—C20—H20	118.3
H3B—C3—H3C	109.5	C19—C20—H20	118.4
N1—C4—C5	123.6 (3)	O8—C21—C17	113.0 (3)
N1—C4—H4	118.2	O8—C21—H21A	109.0
C5—C4—H4	118.2	C17—C21—H21A	109.0
C4—C5—C6	117.8 (3)	O8—C21—H21B	109.0
C4—C5—C9	121.2 (3)	C17—C21—H21B	109.0
C6—C5—C9	121.0 (3)	H21A—C21—H21B	107.8
C7—C6—C5	118.9 (3)	C13—O7—Cu2^ii	122.7 (3)
C7—C6—H6	120.5	C10—O5—Cu2^ii	123.6 (3)
O1—Cu1—N1—C8	−134.3 (3)	Cu1—O1—C1—C2	−177.7 (3)
O1^i—Cu1—N1—C8	45.7 (3)	O2—C1—C2—C3	−169.1 (6)
N1^i—Cu1—N1—C8	28 (87)	O1—C1—C2—C3	11.6 (8)
O8—Cu1—N1—C8	−40.9 (3)	C8—N1—C4—C5	−1.9 (5)
O8^iii—Cu1—N1—C8	41.1 (3)	Cu1—N1—C4—C5	178.6 (3)
O1—Cu1—N1—C4	45.2 (3)	N1—C4—C5—C6	2.0 (6)
O1^i—Cu1—N1—C4	−134.8 (3)	N1—C4—C5—C9	−178.6 (4)
N1^i—Cu1—N1—C4	−153 (87)	C4—C5—C6—C7	0.0 (6)
O8—Cu1—N1—C4	138.6 (3)	C9—C5—C6—C7	−179.5 (4)
O8^iii—Cu1—N1—C4	−139.4 (3)	C5—C6—C7—C8	−1.9 (6)
O5^ii—Cu2—N2—C20	−8.4 (3)	C4—N1—C8—C7	−0.1 (5)
O4—Cu2—N2—C20	170.3 (3)	Cu1—N1—C8—C7	179.4 (3)
O7^ii—Cu2—N2—C20	−99.4 (3)	C6—C7—C8—N1	2.0 (6)
O6—Cu2—N2—C20	81.3 (3)	C4—C5—C9—O3	−0.4 (6)
Cu2^ii—Cu2—N2—C20	89.8 (16)	C6—C5—C9—O3	179.0 (4)
O5^ii—Cu2—N2—C16	179.3 (3)	Cu2—O4—C10—O5	0.2 (6)
O4—Cu2—N2—C16	−2.0 (3)	Cu2—O4—C10—C11	−177.9 (3)
O7^ii—Cu2—N2—C16	88.3 (3)	O5—C10—C11—C12	163.7 (6)
O6—Cu2—N2—C16	−91.0 (3)	O4—C10—C11—C12	−18.1 (8)
Cu2^ii—Cu2—N2—C16	−82.5 (16)	Cu2—O6—C13—O7	1.2 (6)
O1^i—Cu1—O1—C1	16 (41)	Cu2—O6—C13—C14	179.4 (3)
N1^i—Cu1—O1—C1	−83.2 (3)	O6—C13—C14—C15	120.5 (6)
N1—Cu1—O1—C1	96.8 (3)	O7—C13—C14—C15	−61.1 (7)
O8—Cu1—O1—C1	9.1 (3)	C20—N2—C16—C17	−0.3 (5)
O8^iii—Cu1—O1—C1	82.9 (4)	Cu2—N2—C16—C17	172.3 (3)
O5^ii—Cu2—O4—C10	−3.9 (8)	N2—C16—C17—C18	−0.7 (6)
O7^ii—Cu2—O4—C10	83.7 (3)	N2—C16—C17—C21	−179.8 (4)
O6—Cu2—O4—C10	−84.3 (3)	C16—C17—C18—C19	1.1 (6)
N2—Cu2—O4—C10	−177.8 (3)	C21—C17—C18—C19	−179.8 (4)
Cu2^ii—Cu2—O4—C10	−0.7 (3)	C17—C18—C19—C20	−0.5 (6)
O5^ii—Cu2—O6—C13	−83.9 (3)	C16—N2—C20—C19	1.0 (6)
O4—Cu2—O6—C13	84.2 (3)	Cu2—N2—C20—C19	−171.6 (3)
O7^ii—Cu2—O6—C13	2.8 (8)	C18—C19—C20—N2	−0.6 (6)
N2—Cu2—O6—C13	179.6 (3)	Cu1—O8—C21—C17	−131.5 (3)
Cu2^ii—Cu2—O6—C13	0.0 (3)	C16—C17—C21—O8	−16.0 (6)
O1—Cu1—O8—C21	−137.6 (4)	C18—C17—C21—O8	164.9 (4)
O1^i—Cu1—O8—C21	42.4 (4)	O6—C13—O7—Cu2^ii	−2.0 (6)
N1^i—Cu1—O8—C21	−46.4 (4)	C14—C13—O7—Cu2^ii	179.7 (3)
N1—Cu1—O8—C21	133.6 (4)	O4—C10—O5—Cu2^ii	0.8 (6)
O8^iii—Cu1—O8—C21	60.5 (4)	C11—C10—O5—Cu2^ii	178.9 (3)
Cu1—O1—C1—O2	3.1 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O2^iv	0.82	1.95	2.768 (5)	174
O8—H8O···O2	0.82	1.84	2.625 (5)	160

Symmetry code: (iv) x+1, y, z.