Poly[[trans-diaqua­bis(μ₂-biphenyl-2,2′-dicarboxyl­ato)bis­(μ₂-4,4′-bipyri­dine)dicobalt(II)] biphenyl-2,2′-di­carb­oxylic acid disolvate]

In the title compound, {[Co₂(C₁₄H₈O₄)₂(C₁₀H₈N₂)₂(H₂O)₂]·2C₁₄H₁₀O₄}_n, each Co^II ion is six-coordinate in a slightly distorted octa­hedral geometry. Both Co^II ions are located on twofold axes. One is surrounded by two O atoms from two biphenyl-2,2′-dicarboxyl­ate (dpa) dianions, two N atoms from two 4,4′-bipyridine (bpy) ligands and two water mol­ecules, while the second is surrounded by four O atoms from two dpa dianions and two N atoms from two bpy ligands. The coordinated dpa dianion functions as a κ³-bridge between the two Co^II ions. One carboxyl­ate group of a dpa dianion bridges two adjacent Co^II ions, and one O atom of the other carboxyl­ate group also chelates to a Co^II ion. The Co^II ions are bridged by dpa dianions and bpy ligands to form a chiral sheet. There are several strong inter­molecular hydrogen bonds between the H₂dpa solvent mol­ecule and the chiral sheet, which result in a sandwich structure.

S1. Comment

2,2'-Biphenyldicarboxylate (dpa) has the capability of affording new coordination polymers (Xu et al., 2006) for several reasons. Firstly, the freedom of rotation about the biphenyl central bond enables dpa to link metal ions or clusters into macrocycles or helical chains (Wang et al., 2002, 2005; Wang, Hong et al., 2003). Secondly, the dpa ligand contains two bridging moieties, which can lead to a variety of coordination modes with metals and provides abundant structural motifs (Wang, Zheng et al., 2003; Lu & Schauss, 2003; Rueff et al., 2002). Finally, it can act not only as a hydrogen-bond donor but also as an acceptor, which makes it a candidate for the construction of supramolecular networks. Many metal–organic frameworks based on the dpa ligand have been reported (Hu et al., 2007; Rueff et al., 2003; Wang et al., 2004; Yin et al., 2007). However, it is interesting that in all these dpa-containing structures, only a few simple coordination modes are known, although a variety are anticipated in metal–organic frameworks under appropriate conditions. Here, the title compound, {[Co(bpy)(dpa)(H₂O)].H₂dpa}_n (bpy is 4,4'-bipyridine), (I), represents a novel example.

As shown in Fig. 1, the asymmetric unit of (I) consists of two crystallographically unique Co^II atoms located on two-fold axes. Both are six-coordinate in a slightly distorted octahedral geometry, but the environments of the two are different. Ion Co1 is surrounded by two O atoms from two dpa dianions, two N atoms from two trans monodentate bpy ligands, and two water molecules (O5) occupying the axial positions. The N—Co1 bond lengths are 2.125 (3) and 2.177 (3) Å, which are typical metal–N distances (Wang et al., 2004), and the Co1—O distances are 2.067 (2) and 2.107 (2) Å, which fall within the typical range of Co—O bond lengths for octahedra (Rueff et al., 2003, 2002; Hu et al., 2007). The O5—Co1—O5(-x, -y + 1, z) bond angle is 178.20 (14)°, which is close to linear, and the N—Co—O bond angles range from 85.67 (7) to 94.33 (7)°, consistent with the distorted octahedral coordination environment of Co1. Ion Co2 is six-coordinated by two chelating carboxylate groups of two dpa dianions, with Co2—O2 and Co2—O3 distances of 2.085 (19) and 2.179 (2) Å, respectively, and by two N atoms of two bpy ligands in trans-positions, with Co2—N distances of 2.129 (3) and 2.161 (3) Å. Atoms O2 and O2ⁱ [symmetry code: (i) -x, -y + 2, z] are located in axial positions, with an O2—Co—O2ⁱ angle of 176.67 (11)°, whereas the N—Co2—O bond angles around the Co2 centre range from 85.43 (5) to 94.57 (5)°. Just as for ion Co1, all the bond lengths and angles fall within commonly observed ranges (Wang et al., 2004).

Ions Co1 and Co2 are bridged by a dpa dianion, which adopts an anti conformation and acts as a µ₃-bridge, forming a one-dimensional chain along the b axis, as shown in Fig. 2. The Co···Co separation across the dpa bridge is 5.176 (4) Å. One carboxylate group of a dpa dianion bridges two adjacent Co^II ions, and one of the O atoms of the other carboxylate group also bonds to a Co^II ion. Due to steric hindrance, the dihedral angle between the carboxylic acid group [There is no carboxylic acid group except in the solvate - please clarify by reference to specific atoms] and the linking phenyl ring [48.4 (4)°] is larger than that between the carboxylate group and the linking phenyl ring [Again, please clarify by reference to specific atoms] [34.58 (3)°] (Wang et al., 2004). The chains are further connected by bpy ligands to form a two-dimensional chiral structure (Fig. 2). The two pyridyl rings in bpy are not coplanar, the dihedral angle being 156.9 (3)°. The structure can be regarded as grid sheets with a (4,4) net topology, which is constructed through Co^II centres bridged by dpa dianions along the b axis and bpy ligands along the c axis.

The most striking feature of (I) is that adjacent two-dimensional sheets are parallel and stacked without interpenetrating, to generate nanoscale rectangular channels which are not filled with solvent molecules. There are uncoordinated H₂dpa solvent molecules between adjacent two-dimensional sheets, and there are multi-molecular interactions between the solvent H₂dpa molecules and the two-dimensional sheets. Hydrogen-bonding interactions extend the two-dimensional sheets and solvent H₂dpa molecules into a three-dimensional sandwich structure.

S2. Experimental

An aqueous solution (10 ml) of cobalt sulfate heptahydrate (0.85 g, 3.02 mmol) was added dropwise to a solution (10 ml) of dimethylformamide containing 4,4'-bipyridine (0.47 g, 3.01 mmol), 2,2'-diphenyldicarboxylic acid (0.73 g, 3.01 mmol) and 2,2'-dithiosalicylic acid (0.92 g, 3.00 mmol) at room temperature. The reaction mixture was filtered and the filtrate was left to stand for about four weeks until red single crystals were obtained (yield 53% based on Co). Red block-shaped crystals of (I) suitable for X-ray diffraction were collected by filtration, washed with water and ethanol, and finally dried in air.

S3. Refinement

The water and carboxylic acid H atoms were refined subject to the restraint O—H = 0.82 (5) Å. All other H atoms were included in the refinement in calculated positions in the riding-model approximation, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. Atoms labelled with an asterisk (*) are at the symmetry position (x, y, z - 1) and those labelled with a hash sign (#) are at the symmetry position (x, y, z - 2).
	Fig. 2. A perspective view of the two-dimensional sheet of (I), along the c axis. [Please provide correct figure]

Poly[[trans-diaquabis(µ₂-biphenyl-2,2'-dicarboxylato)bis(µ₂-4,4'- bipyridine)dicobalt(II)] biphenyl-2,2'-dicarboxylic acid disolvate]

Crystal data

[Co2(C14H8O4)2(C10H8N2)2(H2O)2]·2C14H10O4	F(000) = 1476
Mr = 1431.11	Dx = 1.447 Mg m^−3
Orthorhombic, P21212	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P22ab	Cell parameters from 5858 reflections
a = 10.1264 (10) Å	θ = 1.8–25.1°
b = 28.487 (3) Å	µ = 0.58 mm^−1
c = 11.3835 (11) Å	T = 298 K
V = 3283.8 (6) Å^3	Block, red
Z = 4	0.40 × 0.17 × 0.08 mm

Data collection

Bruker APEX CCD area-detector diffractometer	5840 independent reflections
Radiation source: X-ray tube	5236 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ϕ and ω scan	θmax = 25.1°, θmin = 1.8°
Absorption correction: integration (SADABS; Bruker, 2001)	h = −11→12
Tmin = 0.89, Tmax = 0.95	k = −34→32
17371 measured reflections	l = −13→13

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)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.0488P)^2 + 0.3862P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
5840 reflections	Δρmax = 0.61 e Å^−3
468 parameters	Δρmin = −0.42 e Å^−3
4 restraints	Absolute structure: Flack (1983), with 1476 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.013 (15)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Co1	0.5000	0.0000	0.62712 (4)	0.02339 (14)
Co2	1.0000	0.0000	0.72147 (4)	0.02310 (14)
C1	0.7549 (3)	0.05627 (10)	0.6450 (3)	0.0217 (7)
C2	0.8355 (3)	0.09575 (11)	0.5926 (3)	0.0257 (7)
C3	0.8471 (3)	0.09872 (12)	0.4709 (3)	0.0353 (8)
H3	0.7973	0.0790	0.4232	0.042*
C4	0.9320 (4)	0.13080 (14)	0.4210 (3)	0.0465 (10)
H4	0.9414	0.1320	0.3398	0.056*
C5	1.0027 (5)	0.16078 (12)	0.4905 (3)	0.0483 (9)
H5	1.0597	0.1825	0.4565	0.058*
C6	0.9895 (4)	0.15887 (11)	0.6103 (3)	0.0423 (8)
H6	1.0370	0.1797	0.6569	0.051*
C7	0.9062 (3)	0.12634 (11)	0.6635 (3)	0.0282 (7)
C8	0.8906 (3)	0.12515 (11)	0.7937 (3)	0.0308 (7)
C9	0.7710 (4)	0.13858 (13)	0.8454 (4)	0.0463 (10)
H9	0.7003	0.1469	0.7976	0.056*
C10	0.7560 (4)	0.13972 (15)	0.9653 (4)	0.0573 (12)
H10	0.6758	0.1485	0.9985	0.069*
C11	0.8610 (5)	0.12769 (14)	1.0354 (4)	0.0563 (11)
H11	0.8514	0.1285	1.1166	0.068*
C12	0.9799 (4)	0.11453 (12)	0.9877 (3)	0.0423 (9)
H12	1.0501	0.1067	1.0365	0.051*
C13	0.9953 (4)	0.11290 (10)	0.8664 (3)	0.0335 (7)
C14	1.1220 (3)	0.09543 (12)	0.8135 (3)	0.0299 (7)
C15	0.8872 (3)	0.00113 (14)	0.9702 (2)	0.0312 (6)
H15	0.8078	0.0020	0.9292	0.037*
C16	0.8829 (3)	0.00113 (14)	1.0913 (2)	0.0317 (7)
H16	0.8021	0.0019	1.1300	0.038*
C17	1.0000	0.0000	1.1553 (3)	0.0286 (9)
C18	1.0000	0.0000	1.2848 (3)	0.0287 (9)
C19	1.0953 (3)	0.02377 (12)	1.3493 (3)	0.0321 (8)
H19	1.1617	0.0403	1.3108	0.039*
C20	1.0918 (3)	0.02296 (12)	1.4694 (3)	0.0321 (8)
H20	1.1569	0.0393	1.5102	0.038*
C21	0.4776 (4)	0.03882 (11)	0.8747 (3)	0.0356 (8)
H21	0.4638	0.0665	0.8333	0.043*
C22	0.4735 (4)	0.04065 (12)	0.9956 (3)	0.0361 (9)
H22	0.4534	0.0686	1.0340	0.043*
C23	0.5000	0.0000	1.0595 (3)	0.0297 (9)
C24	0.5000	0.0000	1.1889 (3)	0.0309 (9)
C25	0.5204 (4)	0.04059 (11)	1.2533 (3)	0.0389 (9)
H25	0.5349	0.0689	1.2149	0.047*
C26	0.5192 (4)	0.03899 (12)	1.3745 (3)	0.0393 (9)
H26	0.5326	0.0668	1.4154	0.047*
C27	0.3764 (4)	0.15065 (13)	0.4153 (4)	0.0417 (9)
C28	0.4632 (3)	0.18346 (12)	0.3475 (3)	0.0385 (9)
C29	0.5976 (4)	0.17791 (14)	0.3584 (4)	0.0485 (10)
H29	0.6310	0.1570	0.4136	0.058*
C30	0.6831 (4)	0.20302 (15)	0.2886 (4)	0.0573 (11)
H30	0.7738	0.1992	0.2970	0.069*
C31	0.6343 (4)	0.23356 (15)	0.2068 (4)	0.0570 (11)
H31	0.6917	0.2496	0.1572	0.068*
C32	0.5004 (5)	0.24065 (12)	0.1979 (3)	0.0453 (8)
H32	0.4686	0.2623	0.1437	0.054*
C33	0.4111 (3)	0.21627 (11)	0.2680 (3)	0.0334 (8)
C34	0.2692 (3)	0.22840 (11)	0.2601 (3)	0.0330 (8)
C35	0.2130 (4)	0.25924 (12)	0.3396 (3)	0.0409 (9)
H35	0.2623	0.2690	0.4041	0.049*
C36	0.0873 (4)	0.27574 (14)	0.3262 (4)	0.0513 (10)
H36	0.0510	0.2957	0.3823	0.062*
C37	0.0146 (5)	0.26283 (14)	0.2299 (4)	0.0589 (11)
H37	−0.0695	0.2751	0.2187	0.071*
C38	0.0660 (4)	0.23178 (14)	0.1501 (4)	0.0561 (11)
H38	0.0160	0.2228	0.0853	0.067*
C39	0.1929 (4)	0.21344 (12)	0.1650 (3)	0.0412 (9)
C40	0.2414 (4)	0.17543 (13)	0.0868 (4)	0.0466 (10)
H5A	0.378 (5)	0.0798 (12)	0.602 (4)	0.070*
H5B	0.303 (4)	0.0552 (17)	0.664 (4)	0.070*
H7A	0.284 (5)	0.1323 (15)	0.281 (3)	0.070*
H9A	0.235 (5)	0.1561 (13)	−0.065 (4)	0.070*
N1	0.5000	0.0000	1.4359 (3)	0.0279 (7)
N2	0.5000	0.0000	0.8138 (3)	0.0286 (7)
N3	1.0000	0.0000	0.9085 (3)	0.0264 (7)
N4	1.0000	0.0000	1.5316 (3)	0.0280 (7)
O1	0.6378 (2)	0.05326 (7)	0.6134 (2)	0.0302 (6)
O2	0.81146 (19)	0.02930 (7)	0.71615 (17)	0.0263 (5)
O3	1.1170 (2)	0.06391 (7)	0.73674 (18)	0.0284 (5)
O4	1.2301 (2)	0.11247 (9)	0.8483 (2)	0.0455 (7)
O5	0.3586 (2)	0.05426 (9)	0.6242 (2)	0.0312 (6)
O6	0.3950 (3)	0.14281 (10)	0.5180 (3)	0.0628 (8)
O7	0.2842 (3)	0.12818 (10)	0.3567 (3)	0.0533 (7)
O8	0.2910 (3)	0.13965 (9)	0.1284 (2)	0.0610 (8)
O9	0.2217 (3)	0.18213 (9)	−0.0238 (3)	0.0564 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0238 (3)	0.0343 (3)	0.0120 (3)	−0.0021 (3)	0.000	0.000
Co2	0.0220 (3)	0.0350 (3)	0.0123 (3)	0.0003 (3)	0.000	0.000
C1	0.0241 (17)	0.0260 (16)	0.0150 (15)	0.0018 (12)	0.0013 (13)	−0.0026 (12)
C2	0.0211 (16)	0.0302 (16)	0.0258 (17)	0.0061 (13)	−0.0007 (13)	0.0044 (14)
C3	0.0321 (19)	0.045 (2)	0.0290 (19)	0.0014 (16)	−0.0021 (15)	0.0094 (16)
C4	0.047 (2)	0.057 (2)	0.035 (2)	0.006 (2)	0.0106 (18)	0.0179 (19)
C5	0.045 (2)	0.0418 (19)	0.057 (2)	0.000 (2)	0.016 (3)	0.0216 (17)
C6	0.034 (2)	0.0352 (17)	0.057 (2)	−0.0078 (18)	−0.001 (2)	0.0012 (15)
C7	0.0249 (17)	0.0247 (16)	0.0351 (19)	0.0049 (13)	−0.0010 (14)	0.0033 (14)
C8	0.0302 (18)	0.0261 (17)	0.036 (2)	−0.0026 (14)	0.0013 (15)	−0.0064 (14)
C9	0.040 (2)	0.045 (2)	0.054 (3)	0.0062 (17)	0.0027 (19)	−0.010 (2)
C10	0.047 (3)	0.065 (3)	0.060 (3)	0.006 (2)	0.019 (2)	−0.013 (2)
C11	0.066 (3)	0.063 (3)	0.040 (2)	−0.002 (2)	0.014 (2)	−0.022 (2)
C12	0.049 (3)	0.046 (2)	0.0316 (18)	−0.0006 (18)	−0.0003 (18)	−0.0106 (15)
C13	0.0382 (17)	0.0304 (15)	0.0318 (17)	−0.0021 (17)	0.001 (2)	−0.0086 (12)
C14	0.0319 (19)	0.0337 (18)	0.0242 (18)	0.0023 (15)	−0.0003 (14)	0.0000 (14)
C15	0.0263 (15)	0.0476 (17)	0.0198 (14)	−0.0012 (19)	−0.0023 (12)	0.001 (2)
C16	0.0247 (15)	0.0521 (18)	0.0184 (14)	−0.002 (2)	0.0025 (11)	−0.0005 (19)
C17	0.035 (2)	0.038 (2)	0.0124 (19)	−0.005 (3)	0.000	0.000
C18	0.030 (2)	0.039 (2)	0.017 (2)	0.001 (3)	0.000	0.000
C19	0.0293 (18)	0.047 (2)	0.0198 (17)	−0.0099 (15)	0.0053 (14)	0.0019 (15)
C20	0.0308 (18)	0.0467 (19)	0.0186 (17)	−0.0077 (15)	−0.0045 (14)	−0.0040 (15)
C21	0.050 (2)	0.0373 (17)	0.0192 (16)	0.0046 (17)	−0.0047 (16)	0.0014 (13)
C22	0.050 (3)	0.0390 (18)	0.0194 (16)	0.0066 (16)	−0.0008 (15)	−0.0032 (13)
C23	0.032 (2)	0.044 (2)	0.0126 (19)	0.000 (3)	0.000	0.000
C24	0.033 (2)	0.041 (2)	0.019 (2)	0.003 (3)	0.000	0.000
C25	0.062 (3)	0.0350 (17)	0.0199 (16)	−0.0041 (18)	−0.0003 (17)	0.0058 (13)
C26	0.056 (3)	0.0427 (18)	0.0194 (16)	−0.0020 (18)	−0.0036 (17)	−0.0030 (13)
C27	0.041 (2)	0.040 (2)	0.044 (2)	0.0026 (17)	−0.0015 (18)	0.0047 (18)
C28	0.040 (2)	0.0349 (18)	0.041 (2)	−0.0021 (15)	0.0000 (16)	0.0034 (16)
C29	0.045 (2)	0.048 (2)	0.052 (3)	0.0033 (19)	−0.003 (2)	0.008 (2)
C30	0.032 (2)	0.065 (3)	0.075 (3)	−0.002 (2)	0.004 (2)	0.011 (2)
C31	0.050 (3)	0.060 (3)	0.060 (3)	−0.001 (2)	0.014 (2)	0.013 (2)
C32	0.052 (2)	0.0448 (19)	0.0385 (19)	0.003 (2)	−0.003 (2)	0.0052 (15)
C33	0.040 (2)	0.0294 (17)	0.0312 (19)	−0.0028 (15)	−0.0017 (15)	−0.0043 (15)
C34	0.042 (2)	0.0236 (16)	0.0330 (19)	−0.0019 (15)	−0.0028 (16)	0.0037 (14)
C35	0.043 (2)	0.040 (2)	0.040 (2)	−0.0060 (17)	0.0014 (18)	−0.0026 (17)
C36	0.048 (3)	0.048 (2)	0.058 (3)	0.0008 (19)	0.014 (2)	−0.003 (2)
C37	0.039 (2)	0.052 (2)	0.085 (3)	0.008 (2)	−0.003 (3)	−0.002 (2)
C38	0.052 (3)	0.052 (2)	0.065 (3)	−0.006 (2)	−0.023 (2)	0.000 (2)
C39	0.044 (2)	0.0357 (19)	0.044 (2)	−0.0011 (16)	−0.0079 (17)	0.0009 (17)
C40	0.052 (3)	0.041 (2)	0.047 (2)	−0.0043 (18)	−0.015 (2)	−0.0095 (18)
N1	0.0315 (19)	0.0408 (19)	0.0115 (16)	0.000 (2)	0.000	0.000
N2	0.0280 (18)	0.038 (2)	0.0201 (17)	−0.001 (2)	0.000	0.000
N3	0.0231 (17)	0.0376 (18)	0.0185 (17)	0.000 (2)	0.000	0.000
N4	0.0303 (18)	0.0400 (19)	0.0137 (16)	0.000 (2)	0.000	0.000
O1	0.0239 (13)	0.0376 (13)	0.0290 (14)	−0.0052 (10)	−0.0059 (10)	0.0050 (11)
O2	0.0238 (11)	0.0352 (12)	0.0198 (11)	0.0027 (9)	−0.0009 (9)	0.0047 (10)
O3	0.0304 (12)	0.0316 (11)	0.0231 (12)	0.0001 (10)	0.0058 (10)	−0.0050 (10)
O4	0.0311 (14)	0.0568 (17)	0.0487 (17)	0.0008 (12)	−0.0061 (12)	−0.0207 (14)
O5	0.0253 (14)	0.0426 (14)	0.0258 (14)	0.0020 (11)	0.0055 (10)	0.0050 (12)
O6	0.081 (2)	0.0600 (19)	0.0472 (19)	−0.0118 (16)	−0.0086 (16)	0.0176 (15)
O7	0.0526 (17)	0.0498 (16)	0.0575 (18)	−0.0129 (13)	−0.0074 (16)	0.0053 (15)
O8	0.093 (2)	0.0387 (15)	0.0513 (18)	0.0164 (15)	−0.0215 (16)	−0.0135 (13)
O9	0.081 (2)	0.0441 (16)	0.0441 (17)	−0.0032 (15)	−0.0147 (15)	−0.0124 (14)

Geometric parameters (Å, º)

Co1—O1^i	2.067 (2)	C20—H20	0.9300
Co1—O1	2.067 (2)	C21—N2	1.325 (3)
Co1—O5	2.107 (2)	C21—C22	1.378 (4)
Co1—O5^i	2.107 (2)	C21—H21	0.9300
Co1—N2	2.125 (3)	C22—C23	1.394 (4)
Co1—N1^ii	2.177 (3)	C22—H22	0.9300
Co2—O2^iii	2.0847 (19)	C23—C22^i	1.394 (4)
Co2—O2	2.0847 (19)	C23—C24	1.473 (5)
Co2—N3	2.129 (3)	C24—C25	1.384 (4)
Co2—N4^ii	2.161 (3)	C24—C25^i	1.384 (4)
Co2—O3	2.179 (2)	C25—C26	1.380 (4)
Co2—O3^iii	2.179 (2)	C25—H25	0.9300
C1—O1	1.242 (4)	C26—N1	1.327 (4)
C1—O2	1.254 (3)	C26—H26	0.9300
C1—C2	1.513 (4)	C27—O6	1.205 (4)
C2—C7	1.386 (4)	C27—O7	1.315 (5)
C2—C3	1.393 (4)	C27—C28	1.498 (5)
C3—C4	1.378 (5)	C28—C29	1.375 (5)
C3—H3	0.9300	C28—C33	1.404 (5)
C4—C5	1.366 (6)	C29—C30	1.376 (6)
C4—H4	0.9300	C29—H29	0.9300
C5—C6	1.372 (5)	C30—C31	1.366 (6)
C5—H5	0.9300	C30—H30	0.9300
C6—C7	1.391 (5)	C31—C32	1.375 (6)
C6—H6	0.9300	C31—H31	0.9300
C7—C8	1.491 (5)	C32—C33	1.391 (5)
C8—C13	1.390 (5)	C32—H32	0.9300
C8—C9	1.400 (5)	C33—C34	1.480 (5)
C9—C10	1.373 (6)	C34—C35	1.384 (5)
C9—H9	0.9300	C34—C39	1.397 (5)
C10—C11	1.373 (6)	C35—C36	1.366 (5)
C10—H10	0.9300	C35—H35	0.9300
C11—C12	1.373 (6)	C36—C37	1.371 (6)
C11—H11	0.9300	C36—H36	0.9300
C12—C13	1.390 (4)	C37—C38	1.370 (6)
C12—H12	0.9300	C37—H37	0.9300
C13—C14	1.502 (5)	C38—C39	1.397 (5)
C14—O3	1.254 (4)	C38—H38	0.9300
C14—O4	1.261 (4)	C39—C40	1.486 (5)
C15—N3	1.341 (3)	C40—O8	1.231 (4)
C15—C16	1.379 (4)	C40—O9	1.289 (5)
C15—H15	0.9300	N1—C26^i	1.327 (4)
C16—C17	1.392 (3)	N1—Co1^iv	2.177 (3)
C16—H16	0.9300	N2—C21^i	1.325 (3)
C17—C16^iii	1.392 (3)	N3—C15^iii	1.341 (3)
C17—C18	1.474 (5)	N4—C20^iii	1.339 (4)
C18—C19	1.389 (4)	N4—Co2^iv	2.161 (3)
C18—C19^iii	1.389 (4)	O5—H5A	0.79 (3)
C19—C20	1.368 (4)	O5—H5B	0.72 (4)
C19—H19	0.9300	O7—H7A	0.87 (3)
C20—N4	1.339 (4)	O9—H9A	0.89 (4)
O1^i—Co1—O1	171.35 (13)	C20—C19—H19	119.9
O1^i—Co1—O5	94.51 (8)	C18—C19—H19	119.9
O1—Co1—O5	85.35 (8)	N4—C20—C19	123.7 (3)
O1^i—Co1—O5^i	85.35 (8)	N4—C20—H20	118.2
O1—Co1—O5^i	94.51 (8)	C19—C20—H20	118.2
O5—Co1—O5^i	178.20 (14)	N2—C21—C22	124.0 (3)
O1^i—Co1—N2	94.33 (7)	N2—C21—H21	118.0
O1—Co1—N2	94.33 (7)	C22—C21—H21	118.0
O5—Co1—N2	90.90 (7)	C21—C22—C23	118.9 (3)
O5^i—Co1—N2	90.90 (7)	C21—C22—H22	120.5
O1^i—Co1—N1^ii	85.67 (7)	C23—C22—H22	120.5
O1—Co1—N1^ii	85.67 (7)	C22^i—C23—C22	117.1 (4)
O5—Co1—N1^ii	89.10 (7)	C22^i—C23—C24	121.46 (18)
O5^i—Co1—N1^ii	89.10 (7)	C22—C23—C24	121.46 (18)
N2—Co1—N1^ii	180.000 (1)	C25—C24—C25^i	116.1 (4)
O2^iii—Co2—O2	176.67 (11)	C25—C24—C23	121.96 (18)
O2^iii—Co2—N3	91.66 (6)	C25^i—C24—C23	121.96 (18)
O2—Co2—N3	91.66 (6)	C26—C25—C24	120.0 (3)
O2^iii—Co2—N4^ii	88.34 (6)	C26—C25—H25	120.0
O2—Co2—N4^ii	88.34 (6)	C24—C25—H25	120.0
N3—Co2—N4^ii	180.000 (1)	N1—C26—C25	123.7 (3)
O2^iii—Co2—O3	80.72 (8)	N1—C26—H26	118.1
O2—Co2—O3	99.55 (8)	C25—C26—H26	118.1
N3—Co2—O3	85.43 (5)	O6—C27—O7	120.9 (4)
N4^ii—Co2—O3	94.57 (5)	O6—C27—C28	121.6 (4)
O2^iii—Co2—O3^iii	99.55 (8)	O7—C27—C28	117.3 (3)
O2—Co2—O3^iii	80.72 (8)	C29—C28—C33	120.4 (3)
N3—Co2—O3^iii	85.43 (5)	C29—C28—C27	117.5 (3)
N4^ii—Co2—O3^iii	94.57 (5)	C33—C28—C27	121.8 (3)
O3—Co2—O3^iii	170.85 (11)	C28—C29—C30	120.7 (4)
O1—C1—O2	125.5 (3)	C28—C29—H29	119.6
O1—C1—C2	116.9 (3)	C30—C29—H29	119.6
O2—C1—C2	117.6 (3)	C31—C30—C29	119.8 (4)
C7—C2—C3	119.8 (3)	C31—C30—H30	120.1
C7—C2—C1	121.1 (3)	C29—C30—H30	120.1
C3—C2—C1	118.9 (3)	C30—C31—C32	120.0 (4)
C4—C3—C2	120.2 (3)	C30—C31—H31	120.0
C4—C3—H3	119.9	C32—C31—H31	120.0
C2—C3—H3	119.9	C31—C32—C33	121.7 (3)
C5—C4—C3	120.2 (3)	C31—C32—H32	119.2
C5—C4—H4	119.9	C33—C32—H32	119.2
C3—C4—H4	119.9	C32—C33—C28	117.2 (3)
C4—C5—C6	120.0 (4)	C32—C33—C34	118.6 (3)
C4—C5—H5	120.0	C28—C33—C34	124.0 (3)
C6—C5—H5	120.0	C35—C34—C39	118.2 (4)
C5—C6—C7	121.2 (4)	C35—C34—C33	120.5 (3)
C5—C6—H6	119.4	C39—C34—C33	120.9 (3)
C7—C6—H6	119.4	C36—C35—C34	121.9 (4)
C2—C7—C6	118.6 (3)	C36—C35—H35	119.0
C2—C7—C8	120.6 (3)	C34—C35—H35	119.0
C6—C7—C8	120.8 (3)	C35—C36—C37	119.8 (4)
C13—C8—C9	118.5 (3)	C35—C36—H36	120.1
C13—C8—C7	121.1 (3)	C37—C36—H36	120.1
C9—C8—C7	120.2 (3)	C38—C37—C36	120.0 (4)
C10—C9—C8	121.4 (4)	C38—C37—H37	120.0
C10—C9—H9	119.3	C36—C37—H37	120.0
C8—C9—H9	119.3	C37—C38—C39	120.7 (4)
C11—C10—C9	119.1 (4)	C37—C38—H38	119.7
C11—C10—H10	120.5	C39—C38—H38	119.7
C9—C10—H10	120.5	C38—C39—C34	119.3 (4)
C10—C11—C12	121.2 (4)	C38—C39—C40	120.3 (4)
C10—C11—H11	119.4	C34—C39—C40	120.2 (3)
C12—C11—H11	119.4	O8—C40—O9	124.2 (4)
C11—C12—C13	120.0 (4)	O8—C40—C39	120.5 (4)
C11—C12—H12	120.0	O9—C40—C39	115.2 (4)
C13—C12—H12	120.0	C26^i—N1—C26	116.4 (3)
C12—C13—C8	119.8 (4)	C26^i—N1—Co1^iv	121.78 (17)
C12—C13—C14	120.4 (3)	C26—N1—Co1^iv	121.78 (17)
C8—C13—C14	119.7 (3)	C21—N2—C21^i	116.8 (3)
O3—C14—O4	121.9 (3)	C21—N2—Co1	121.58 (17)
O3—C14—C13	118.9 (3)	C21^i—N2—Co1	121.58 (17)
O4—C14—C13	119.2 (3)	C15^iii—N3—C15	116.8 (3)
N3—C15—C16	123.4 (3)	C15^iii—N3—Co2	121.59 (16)
N3—C15—H15	118.3	C15—N3—Co2	121.59 (16)
C16—C15—H15	118.3	C20^iii—N4—C20	116.2 (3)
C15—C16—C17	119.7 (3)	C20^iii—N4—Co2^iv	121.91 (17)
C15—C16—H16	120.1	C20—N4—Co2^iv	121.91 (17)
C17—C16—H16	120.1	C1—O1—Co1	132.3 (2)
C16—C17—C16^iii	116.9 (3)	C1—O2—Co2	133.02 (19)
C16—C17—C18	121.56 (17)	C14—O3—Co2	132.5 (2)
C16^iii—C17—C18	121.56 (17)	Co1—O5—H5A	121 (4)
C19—C18—C19^iii	116.1 (4)	Co1—O5—H5B	123 (4)
C19—C18—C17	121.93 (18)	H5A—O5—H5B	111 (5)
C19^iii—C18—C17	121.93 (18)	C27—O7—H7A	116 (3)
C20—C19—C18	120.2 (3)	C40—O9—H9A	112 (3)
O1—C1—C2—C7	128.1 (3)	C32—C33—C34—C35	−96.3 (4)
O2—C1—C2—C7	−52.2 (4)	C28—C33—C34—C35	79.6 (5)
O1—C1—C2—C3	−57.3 (4)	C32—C33—C34—C39	76.3 (4)
O2—C1—C2—C3	122.5 (3)	C28—C33—C34—C39	−107.8 (4)
C7—C2—C3—C4	2.4 (5)	C39—C34—C35—C36	−1.1 (5)
C1—C2—C3—C4	−172.4 (3)	C33—C34—C35—C36	171.6 (3)
C2—C3—C4—C5	−1.9 (6)	C34—C35—C36—C37	−2.0 (6)
C3—C4—C5—C6	0.3 (6)	C35—C36—C37—C38	2.9 (6)
C4—C5—C6—C7	0.8 (6)	C36—C37—C38—C39	−0.8 (6)
C3—C2—C7—C6	−1.2 (5)	C37—C38—C39—C34	−2.4 (6)
C1—C2—C7—C6	173.4 (3)	C37—C38—C39—C40	172.3 (4)
C3—C2—C7—C8	177.2 (3)	C35—C34—C39—C38	3.3 (5)
C1—C2—C7—C8	−8.2 (4)	C33—C34—C39—C38	−169.5 (3)
C5—C6—C7—C2	−0.3 (5)	C35—C34—C39—C40	−171.4 (3)
C5—C6—C7—C8	−178.8 (4)	C33—C34—C39—C40	15.9 (5)
C2—C7—C8—C13	115.7 (3)	C38—C39—C40—O8	−129.7 (4)
C6—C7—C8—C13	−65.9 (4)	C34—C39—C40—O8	44.9 (6)
C2—C7—C8—C9	−67.3 (4)	C38—C39—C40—O9	47.2 (5)
C6—C7—C8—C9	111.1 (4)	C34—C39—C40—O9	−138.2 (4)
C13—C8—C9—C10	−0.1 (6)	C25—C26—N1—C26^i	−0.2 (3)
C7—C8—C9—C10	−177.2 (4)	C25—C26—N1—Co1^iv	179.8 (3)
C8—C9—C10—C11	0.4 (6)	C22—C21—N2—C21^i	−1.5 (3)
C9—C10—C11—C12	−0.2 (7)	C22—C21—N2—Co1	178.5 (3)
C10—C11—C12—C13	−0.4 (6)	O1^i—Co1—N2—C21	−125.8 (2)
C11—C12—C13—C8	0.7 (5)	O1—Co1—N2—C21	54.2 (2)
C11—C12—C13—C14	−175.8 (3)	O5—Co1—N2—C21	−31.2 (2)
C9—C8—C13—C12	−0.5 (5)	O5^i—Co1—N2—C21	148.8 (2)
C7—C8—C13—C12	176.6 (3)	N1^ii—Co1—N2—C21	102 (61)
C9—C8—C13—C14	176.1 (3)	O1^i—Co1—N2—C21^i	54.2 (2)
C7—C8—C13—C14	−6.8 (5)	O1—Co1—N2—C21^i	−125.8 (2)
C12—C13—C14—O3	128.2 (3)	O5—Co1—N2—C21^i	148.8 (2)
C8—C13—C14—O3	−48.4 (4)	O5^i—Co1—N2—C21^i	−31.2 (2)
C12—C13—C14—O4	−51.1 (5)	N1^ii—Co1—N2—C21^i	−78 (53)
C8—C13—C14—O4	132.4 (3)	C16—C15—N3—C15^iii	−0.1 (3)
N3—C15—C16—C17	0.1 (6)	C16—C15—N3—Co2	179.9 (3)
C15—C16—C17—C16^iii	−0.1 (3)	O2^iii—Co2—N3—C15^iii	22.0 (2)
C15—C16—C17—C18	179.9 (3)	O2—Co2—N3—C15^iii	−158.0 (2)
C16—C17—C18—C19	−143.4 (2)	N4^ii—Co2—N3—C15^iii	178 (100)
C16^iii—C17—C18—C19	36.6 (2)	O3—Co2—N3—C15^iii	−58.5 (2)
C16—C17—C18—C19^iii	36.6 (2)	O3^iii—Co2—N3—C15^iii	121.5 (2)
C16^iii—C17—C18—C19^iii	−143.4 (2)	O2^iii—Co2—N3—C15	−158.0 (2)
C19^iii—C18—C19—C20	−0.1 (2)	O2—Co2—N3—C15	22.0 (2)
C17—C18—C19—C20	179.9 (2)	N4^ii—Co2—N3—C15	−2 (100)
C18—C19—C20—N4	0.1 (5)	O3—Co2—N3—C15	121.5 (2)
N2—C21—C22—C23	3.0 (5)	O3^iii—Co2—N3—C15	−58.5 (2)
C21—C22—C23—C22^i	−1.4 (2)	C19—C20—N4—C20^iii	−0.1 (2)
C21—C22—C23—C24	178.6 (2)	C19—C20—N4—Co2^iv	179.9 (2)
C22^i—C23—C24—C25	156.8 (3)	O2—C1—O1—Co1	−15.3 (5)
C22—C23—C24—C25	−23.2 (3)	C2—C1—O1—Co1	164.5 (2)
C22^i—C23—C24—C25^i	−23.2 (3)	O1^i—Co1—O1—C1	−117.5 (3)
C22—C23—C24—C25^i	156.8 (3)	O5—Co1—O1—C1	153.0 (3)
C25^i—C24—C25—C26	−0.2 (3)	O5^i—Co1—O1—C1	−28.8 (3)
C23—C24—C25—C26	179.8 (3)	N2—Co1—O1—C1	62.5 (3)
C24—C25—C26—N1	0.4 (6)	N1^ii—Co1—O1—C1	−117.5 (3)
O6—C27—C28—C29	48.0 (6)	O1—C1—O2—Co2	140.4 (3)
O7—C27—C28—C29	−127.6 (4)	C2—C1—O2—Co2	−39.3 (4)
O6—C27—C28—C33	−137.2 (4)	O2^iii—Co2—O2—C1	−31.1 (3)
O7—C27—C28—C33	47.3 (5)	N3—Co2—O2—C1	148.9 (3)
C33—C28—C29—C30	−2.5 (6)	N4^ii—Co2—O2—C1	−31.1 (3)
C27—C28—C29—C30	172.4 (4)	O3—Co2—O2—C1	63.2 (3)
C28—C29—C30—C31	−0.5 (7)	O3^iii—Co2—O2—C1	−126.1 (3)
C29—C30—C31—C32	2.8 (7)	O4—C14—O3—Co2	137.5 (3)
C30—C31—C32—C33	−2.1 (6)	C13—C14—O3—Co2	−41.8 (4)
C31—C32—C33—C28	−0.9 (5)	O2^iii—Co2—O3—C14	−121.4 (3)
C31—C32—C33—C34	175.3 (4)	O2—Co2—O3—C14	61.9 (3)
C29—C28—C33—C32	3.2 (5)	N3—Co2—O3—C14	−29.0 (3)
C27—C28—C33—C32	−171.5 (3)	N4^ii—Co2—O3—C14	151.0 (3)
C29—C28—C33—C34	−172.8 (4)	O3^iii—Co2—O3—C14	−29.0 (3)
C27—C28—C33—C34	12.5 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6	0.79 (3)	2.04 (3)	2.821 (4)	167 (5)
O7—H7A···O8	0.87 (3)	1.75 (3)	2.620 (4)	177 (5)
O9—H9A···O4^v	0.89 (4)	1.59 (4)	2.462 (4)	168 (5)
O5—H5B···O3^vi	0.72 (4)	2.08 (4)	2.775 (3)	164 (5)

Symmetry codes: (v) x−1, y, z−1; (vi) x−1, y, z.