μ-1,2-Bis(4-pyridyl)ethene-κ²N:N′-bis(tetraaqua­{4-[2-(4-pyridinio)­ethenyl]pyridine-κN}cobalt(II)) hexaaqua­cobalt(II) tetrakis(sulfate) octahydrate

The title compound, [Co₂(C₁₂H₁₁N₂)₂(C₁₂H₁₀N₂)(H₂O)₈][Co(H₂O)₆](SO₄)₄·8H₂O, consists of bis(4-pyridyl)ethenedicobalt(II) cations, hexaaqua­cobalt cations, sulfate anions and water solvent molecules that are linked by hydrogen bonds into a network structure. In the hexaaquacobalt cation, the six water molecules are coordinated in an octahedral geometry to the Co atom, which lies on an inversion centre. The other cation is a 1,2-bis(4-pyridyl)ethene-bridged centrosymmetric dimer, consisting of protonated 1,2-bis(4-pyridyl)­ethene cations, a bridging 1,2-bis(4-pyridyl)ethene ligand and tetraaqua­cobalt cations. Each Co atom is six-coordinated by four water molecules and two N atoms from a protonated 1,2-bis(4-pyridyl)ethene cation and the bridging 1,2-bis(4-pyridyl)­ethene ligand, and the geometry around each Co atom is octahedral.

S1. Comment

Much interest at present is focused on the deliberate construction of coordination polymers (Carlucci et al., 1994; Munakata et al., 1999; Hirsch et al., 1997; Hoskins & Robson, 1990), and a large amount of this interest has involved linear pyridyl-donor ligands. These include pyrazine (Carlucci et al., 1995), 4,4'-bipyridine (bipy; Yaghi & Li, 1996) and longer bridges (Soma & Iwamoto, 1997). Bipy has been used extensively before (Huang & Xiong, 1997); however few coordination polymers are known for the other ligands (Batten et al., 1999). Against this background, we report here the structure of the title compound to outline further studies on coordination polymers constructed through the interaction of metal ions with pyridyl-donor ligands with two-connecting geometry.

The title compound, (I), consists of [C₃₆H₄₈Co₂N₆O₈]⁶⁺ cations, hexaaquacobalt cations, sulfate anions and water solvent molecules (Fig. 1). In the C₃₆H₄₈Co₂N₆O₈]⁶⁺ cation, the Co²⁺ ion coordinates to four O atoms from four water molecules and two N atoms from a protonated 1,2-tris(4-pyridyl)-ethene and a 1,2-tris(4-pyridyl)-ethene ligand, and the geometry around the Co²⁺ ion is that of a distorted octahedron. The 1,2-tris(4-pyridyl)-ethene ligand bridges two Co²⁺ ions, forming a centrosymmetric dimer. In this dimeric cation, two 1,2-tris(4-pyridyl)-ethene ligands are protonated at one end, and the two bridging ligands act in a monodentate mode. This coordination mode is quite different from that reported by Batten et al. (1999) for [Cu{1,2-tris(4-pyridyl)-ethene}₂] ^.(BF₄)^.CH₃CN, in which the 1,2-tris(4-pyridyl)-ethene ligand coordinates in a bridging fashion. It is interesting to note that there is a six coordinated hexaaquacobalt cation to the balance charge, and there are complex hydrogen bonds in this compound (Table 2).

The C₃₆H₄₈Co₂N₆O₈]⁶⁺ cations are arranged in a parallel fashion, but only the terminal protonated 1,2-tris(4-pyridyl)-ethene ligands of each [C₃₆H₄₈Co₂N₆O₈]⁶⁺ cation are overlapped. The sulfate anions, water molecules and hexaaquacobalt cations are distributed regularly between the overlap area (Fig. 2). There are two kinds of parallel arrangement directions of [C₃₆H₄₈Co₂N₆O₈]⁶⁺ cations, which cross one another. The angle between the crossing molecules is 57.75 (3) °, and there are also significant face-to-face π–π interactions of the pyridyl rings between the molecules; the average distance is about 3.329 Å. The crossing [C₃₆H₄₈Co₂N₆O₈]⁶⁺ cations form a regular grid structure, and interact with π–π interactions, forming alternate layers. There are channels between the layer grids, and the sulfate anions, hexaaquacobalt cations, and water molecules reside in channels through the structure, interacting via numerous hydrogen bonds (Table 2 and Fig. 3).

S2. Experimental

Cobalt sulfate heptahydrate (0.6 g, 2 mmol) was dissolved in water (10 ml) and the solution was mixed with a dimethylformamide solution (10 ml) of 1,2-tris(4-pyridyl)-ethene (0.4 g, 2 mmol), trimesic acid (0.4 g, 2 mmol) and 2,2'-dithiosalicylic acid (0.6 g, 2 mmol) at 298 K. The reaction mixture was filtered; brown block-shaped crystals separated from the solution after about three months.

S3. Refinement

The uncoordinated water H atoms were refined subject to the restraint O—H = 0.82 (5) Å. The other H atoms were positioned geometrically and allowed to ride on their parent atoms at distances of 0.82 (O—H), 0.86 (N—H) and 0.93 Å (C—H), with U_iso(H) = 1.2U_eq(parent atom).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. ORTEPII (Johnson, 1976) plot of the title compound, showing 50% probability displacement ellipsoids. Only the contents of the asymmetric unit are labelled. H atoms of aromatic rings have been omitted for clarity.
	Fig. 2. The arrangement of the title compound.
	Fig. 3. The three-dimensional network formed by hydrogen-bonding interactions in the title compound, which are shown as dashed lines.

µ-1,2-Bis(4-pyridyl)ethene-κ²N:N'-bis(tetraaqua{4-[2-(4- pyridinio)ethenyl]pyridine-κN}cobalt(II)) hexaaquacobalt(II) tetrakis(sulfate) octahydrate

Crystal data

[Co2(C12H11N2)2(C12H10N2)(H2O)8][Co(H2O)6](SO4)4·8H2O	F(000) = 1566
Mr = 1506.06	Dx = 1.610 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p2ybc	Cell parameters from 5517 reflections
a = 10.2353 (8) Å	θ = 1.9–25.1°
b = 12.1885 (9) Å	µ = 1.03 mm^−1
c = 24.9647 (19) Å	T = 298 K
β = 93.895 (2)°	Block, brown
V = 3107.2 (4) Å^3	0.31 × 0.18 × 0.15 mm
Z = 2

Data collection

Bruker SMART CCD area detector diffractometer	5517 independent reflections
Radiation source: fine-focus sealed tube	4657 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
600 frames, delta ω = 2 dgr scans	θmax = 25.1°, θmin = 1.9°
Absorption correction: numerical SADABS (Sheldrick, 1996)	h = −12→12
Tmin = 0.81, Tmax = 0.85	k = −14→14
16014 measured reflections	l = −21→29

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ^2(Fo^2) + (0.0549P)^2 + 2.9068P] where P = (Fo^2 + 2Fc^2)/3
5517 reflections	(Δ/σ)max = 0.016
425 parameters	Δρmax = 0.72 e Å^−3
8 restraints	Δρmin = −0.47 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
Co1	0.16166 (6)	0.77595 (5)	0.24691 (2)	0.01992 (18)
Co2	0.5000	1.0000	0.5000	0.0275 (2)
C1	0.0961 (5)	0.8055 (4)	0.1258 (2)	0.0321 (12)
H1	0.1120	0.7304	0.1263	0.039*
C2	0.0668 (5)	0.8539 (4)	0.0773 (2)	0.0329 (12)
H2	0.0626	0.8121	0.0460	0.039*
C3	0.0431 (4)	0.9667 (4)	0.07476 (19)	0.0283 (11)
C4	0.0514 (5)	1.0220 (4)	0.1230 (2)	0.0324 (12)
H4	0.0370	1.0973	0.1235	0.039*
C5	0.0807 (5)	0.9668 (4)	0.1703 (2)	0.0310 (11)
H5	0.0849	1.0066	0.2022	0.037*
C6	0.2395 (5)	0.7533 (4)	0.36681 (19)	0.0362 (13)
H6	0.2277	0.8289	0.3651	0.043*
C7	0.2719 (6)	0.7071 (4)	0.4162 (2)	0.0389 (13)
H7	0.2819	0.7508	0.4467	0.047*
C8	0.2894 (4)	0.5937 (4)	0.41973 (19)	0.0265 (11)
C9	0.2726 (5)	0.5349 (4)	0.37270 (19)	0.0298 (11)
H9	0.2829	0.4591	0.3732	0.036*
C10	0.2403 (4)	0.5881 (4)	0.32457 (18)	0.0256 (10)
H10	0.2296	0.5465	0.2933	0.031*
C11	0.3182 (4)	0.5379 (4)	0.47104 (18)	0.0270 (11)
H11	0.3097	0.4620	0.4710	0.032*
C12	0.3552 (5)	0.5848 (4)	0.51758 (19)	0.0307 (11)
H12	0.3686	0.6603	0.5175	0.037*
C13	0.3766 (5)	0.5279 (4)	0.56884 (19)	0.0287 (11)
C14	0.4132 (5)	0.5855 (4)	0.61518 (19)	0.0317 (11)
H14	0.4279	0.6606	0.6133	0.038*
C15	0.4283 (5)	0.5337 (5)	0.6636 (2)	0.0381 (13)
H15	0.4532	0.5736	0.6944	0.046*
C17	0.3744 (5)	0.3666 (4)	0.6233 (2)	0.0406 (13)
H17	0.3625	0.2913	0.6266	0.049*
C18	0.3581 (5)	0.4144 (4)	0.5745 (2)	0.0357 (12)
H18	0.3344	0.3719	0.5444	0.043*
C19	0.0118 (5)	1.0242 (4)	0.02404 (19)	0.0314 (11)
H19	0.0079	1.1004	0.0252	0.038*
O1	0.0508 (3)	0.6368 (3)	0.22274 (13)	0.0286 (8)
H1B	−0.0270	0.6490	0.2261	0.043*
H1A	0.0863	0.6052	0.1986	0.043*
O2	0.3202 (3)	0.7055 (3)	0.20966 (13)	0.0344 (8)
H2B	0.2932	0.6564	0.1893	0.052*
H2A	0.3890	0.7242	0.2258	0.052*
O3	0.2776 (3)	0.9101 (2)	0.27277 (13)	0.0315 (8)
H3B	0.3508	0.8885	0.2831	0.047*
H3A	0.2335	0.9663	0.2702	0.047*
O4	−0.0116 (3)	0.8333 (3)	0.27725 (14)	0.0408 (9)
H4B	−0.0745	0.8131	0.2576	0.061*
H4A	0.0060	0.8677	0.3051	0.061*
O5	0.6410 (4)	0.7879 (3)	0.64893 (14)	0.0503 (10)
O6	0.7881 (3)	0.8767 (3)	0.71377 (18)	0.0494 (11)
O7	0.7452 (4)	0.6849 (3)	0.72121 (16)	0.0487 (10)
O8	0.5793 (3)	0.8159 (3)	0.73794 (14)	0.0464 (10)
O9	0.5717 (3)	0.8525 (3)	0.47054 (14)	0.0372 (9)
H9B	0.6118	0.8192	0.4950	0.056*
H9A	0.6229	0.8658	0.4475	0.056*
O10	0.5057 (4)	1.0756 (4)	0.42341 (15)	0.0565 (12)
H10B	0.4370	1.1088	0.4163	0.085*
H10A	0.5768	1.0637	0.4113	0.085*
O11	0.3104 (3)	0.9471 (3)	0.48213 (14)	0.0366 (8)
H11B	0.2782	0.9813	0.4562	0.055*
H11A	0.2682	0.9539	0.5087	0.055*
O12	0.2940 (4)	−0.0380 (3)	0.63901 (16)	0.0537 (11)
O13	0.0740 (3)	0.0222 (3)	0.64645 (14)	0.0397 (9)
O14	0.1420 (4)	−0.0409 (4)	0.56264 (15)	0.0574 (12)
O15	0.2246 (4)	0.1294 (3)	0.59775 (17)	0.0527 (11)
O16	0.1755 (5)	0.0346 (5)	0.39738 (19)	0.0684 (15)
O17	0.0495 (6)	0.1771 (4)	0.4999 (2)	0.0808 (17)
O18	0.7246 (5)	0.7350 (4)	0.54571 (18)	0.0501 (11)
O19	0.5339 (5)	0.8828 (5)	0.2999 (3)	0.0830 (19)
N1	0.1036 (4)	0.8586 (3)	0.17286 (15)	0.0271 (9)
N2	0.2240 (4)	0.6965 (3)	0.32120 (15)	0.0266 (9)
N3	0.4074 (4)	0.4263 (4)	0.66699 (17)	0.0370 (11)
H3N	0.4153	0.3947	0.6979	0.044*
S1	0.68919 (11)	0.78988 (9)	0.70511 (5)	0.0258 (3)
S2	0.18357 (11)	0.01907 (10)	0.61116 (5)	0.0278 (3)
H16A	0.105 (4)	0.022 (5)	0.387 (2)	0.042*
H16B	0.202 (6)	0.059 (5)	0.3723 (19)	0.042*
H17A	0.069 (5)	0.150 (5)	0.5287 (17)	0.042*
H17B	0.034 (6)	0.121 (4)	0.482 (2)	0.042*
H18A	0.791 (4)	0.761 (5)	0.537 (2)	0.042*
H18B	0.715 (6)	0.748 (5)	0.5755 (16)	0.042*
H19A	0.561 (6)	0.934 (4)	0.284 (3)	0.042*
H19B	0.560 (5)	0.927 (4)	0.322 (2)	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0177 (3)	0.0241 (3)	0.0173 (3)	0.0009 (2)	−0.0035 (2)	0.0006 (3)
Co2	0.0232 (5)	0.0319 (5)	0.0275 (5)	0.0042 (4)	0.0019 (4)	−0.0019 (4)
C1	0.038 (3)	0.030 (3)	0.027 (3)	−0.004 (2)	−0.004 (2)	0.000 (2)
C2	0.042 (3)	0.034 (3)	0.021 (3)	−0.007 (2)	−0.005 (2)	−0.001 (2)
C3	0.020 (2)	0.038 (3)	0.026 (3)	0.000 (2)	−0.006 (2)	0.003 (2)
C4	0.031 (3)	0.031 (3)	0.034 (3)	0.005 (2)	−0.004 (2)	0.002 (2)
C5	0.035 (3)	0.035 (3)	0.023 (3)	0.008 (2)	−0.004 (2)	−0.006 (2)
C6	0.060 (4)	0.022 (2)	0.026 (3)	0.006 (2)	−0.005 (3)	0.002 (2)
C7	0.058 (4)	0.030 (3)	0.027 (3)	0.005 (3)	−0.008 (3)	−0.004 (2)
C8	0.023 (2)	0.032 (3)	0.024 (3)	0.003 (2)	−0.003 (2)	0.005 (2)
C9	0.029 (3)	0.028 (2)	0.032 (3)	0.005 (2)	−0.002 (2)	0.000 (2)
C10	0.030 (3)	0.027 (2)	0.019 (2)	0.002 (2)	−0.004 (2)	−0.003 (2)
C11	0.028 (3)	0.028 (2)	0.026 (3)	0.001 (2)	0.001 (2)	0.006 (2)
C12	0.035 (3)	0.025 (2)	0.032 (3)	0.001 (2)	−0.001 (2)	0.005 (2)
C13	0.024 (3)	0.036 (3)	0.026 (3)	0.005 (2)	0.001 (2)	0.004 (2)
C14	0.036 (3)	0.034 (3)	0.025 (3)	−0.002 (2)	−0.001 (2)	−0.003 (2)
C15	0.039 (3)	0.052 (3)	0.023 (3)	0.002 (3)	−0.002 (2)	−0.007 (3)
C17	0.050 (3)	0.036 (3)	0.036 (3)	0.004 (3)	−0.001 (3)	0.005 (3)
C18	0.049 (3)	0.033 (3)	0.024 (3)	0.003 (2)	−0.002 (2)	−0.001 (2)
C19	0.026 (3)	0.039 (3)	0.028 (3)	0.001 (2)	−0.001 (2)	0.007 (2)
O1	0.0158 (16)	0.0341 (18)	0.036 (2)	−0.0008 (14)	0.0031 (14)	−0.0082 (16)
O2	0.0192 (17)	0.046 (2)	0.037 (2)	0.0022 (15)	−0.0059 (15)	−0.0180 (17)
O3	0.0272 (19)	0.0264 (17)	0.039 (2)	−0.0014 (14)	−0.0117 (16)	−0.0024 (17)
O4	0.0239 (18)	0.062 (3)	0.036 (2)	0.0067 (18)	−0.0029 (16)	−0.0216 (19)
O5	0.051 (2)	0.072 (3)	0.027 (2)	0.018 (2)	−0.0020 (18)	0.004 (2)
O6	0.0187 (18)	0.0325 (19)	0.097 (3)	−0.0041 (15)	0.003 (2)	−0.001 (2)
O7	0.047 (2)	0.035 (2)	0.062 (3)	0.0000 (18)	−0.016 (2)	0.006 (2)
O8	0.0216 (18)	0.081 (3)	0.037 (2)	−0.0092 (19)	0.0034 (16)	−0.023 (2)
O9	0.039 (2)	0.037 (2)	0.036 (2)	0.0047 (16)	0.0085 (17)	−0.0009 (17)
O10	0.037 (2)	0.092 (3)	0.042 (2)	0.033 (2)	0.0118 (19)	0.026 (2)
O11	0.0257 (18)	0.050 (2)	0.034 (2)	0.0009 (17)	0.0014 (15)	−0.0061 (19)
O12	0.037 (2)	0.072 (3)	0.053 (3)	0.009 (2)	0.0061 (19)	0.025 (2)
O13	0.036 (2)	0.047 (2)	0.038 (2)	−0.0005 (17)	0.0117 (17)	−0.0029 (18)
O14	0.049 (2)	0.086 (3)	0.038 (2)	−0.016 (2)	0.011 (2)	−0.022 (2)
O15	0.062 (3)	0.038 (2)	0.061 (3)	−0.0076 (19)	0.021 (2)	0.007 (2)
O16	0.042 (3)	0.106 (4)	0.054 (3)	−0.027 (3)	−0.019 (2)	0.031 (3)
O17	0.094 (4)	0.069 (3)	0.075 (4)	0.008 (3)	−0.029 (3)	0.031 (3)
O18	0.061 (3)	0.044 (2)	0.044 (3)	0.002 (2)	−0.003 (2)	−0.007 (2)
O19	0.048 (3)	0.093 (4)	0.103 (5)	0.007 (3)	−0.024 (3)	−0.052 (4)
N1	0.025 (2)	0.033 (2)	0.022 (2)	0.0023 (17)	−0.0060 (17)	0.0020 (18)
N2	0.028 (2)	0.027 (2)	0.024 (2)	0.0016 (17)	−0.0039 (17)	0.0035 (18)
N3	0.035 (2)	0.049 (3)	0.027 (2)	0.007 (2)	0.0016 (19)	0.015 (2)
S1	0.0210 (6)	0.0281 (6)	0.0278 (6)	−0.0013 (5)	−0.0014 (5)	−0.0002 (5)
S2	0.0245 (6)	0.0352 (7)	0.0239 (6)	−0.0004 (5)	0.0026 (5)	0.0049 (5)

Geometric parameters (Å, º)

Co1—O4	2.095 (3)	C14—H14	0.9300
Co1—O3	2.096 (3)	C15—N3	1.330 (7)
Co1—O1	2.106 (3)	C15—H15	0.9300
Co1—O2	2.107 (3)	C17—N3	1.334 (7)
Co1—N2	2.151 (4)	C17—C18	1.352 (7)
Co1—N1	2.153 (4)	C17—H17	0.9300
Co2—O11^i	2.065 (3)	C18—H18	0.9300
Co2—O11	2.065 (3)	C19—C19^ii	1.345 (9)
Co2—O9^i	2.094 (3)	C19—H19	0.9300
Co2—O9	2.094 (3)	O1—H1B	0.8200
Co2—O10	2.127 (4)	O1—H1A	0.8202
Co2—O10^i	2.127 (4)	O2—H2B	0.8200
C1—N1	1.339 (6)	O2—H2A	0.8201
C1—C2	1.362 (7)	O3—H3B	0.8200
C1—H1	0.9300	O3—H3A	0.8200
C2—C3	1.397 (7)	O4—H4B	0.8200
C2—H2	0.9300	O4—H4A	0.8200
C3—C4	1.377 (7)	O5—S1	1.455 (4)
C3—C19	1.464 (6)	O6—S1	1.471 (3)
C4—C5	1.375 (7)	O7—S1	1.448 (4)
C4—H4	0.9300	O8—S1	1.470 (3)
C5—N1	1.341 (6)	O9—H9B	0.8200
C5—H5	0.9300	O9—H9A	0.8201
C6—N2	1.333 (6)	O10—H10B	0.8200
C6—C7	1.374 (7)	O10—H10A	0.8200
C6—H6	0.9300	O11—H11B	0.8200
C7—C8	1.396 (7)	O11—H11A	0.8200
C7—H7	0.9300	O12—S2	1.462 (4)
C8—C9	1.376 (7)	O13—S2	1.473 (3)
C8—C11	1.462 (6)	O14—S2	1.453 (4)
C9—C10	1.385 (6)	O15—S2	1.454 (4)
C9—H9	0.9300	O16—H16A	0.76 (4)
C10—N2	1.333 (6)	O16—H16B	0.76 (4)
C10—H10	0.9300	O17—H17A	0.80 (4)
C11—C12	1.327 (6)	O17—H17B	0.82 (4)
C11—H11	0.9300	O18—H18A	0.79 (4)
C12—C13	1.459 (6)	O18—H18B	0.77 (4)
C12—H12	0.9300	O19—H19A	0.81 (4)
C13—C14	1.383 (7)	O19—H19B	0.80 (4)
C13—C18	1.405 (7)	N3—H3N	0.8600
C14—C15	1.363 (7)
O4—Co1—O3	95.94 (13)	C13—C12—H12	117.3
O4—Co1—O1	85.40 (13)	C14—C13—C18	116.5 (5)
O3—Co1—O1	177.59 (13)	C14—C13—C12	120.6 (4)
O4—Co1—O2	172.56 (13)	C18—C13—C12	122.9 (5)
O3—Co1—O2	91.00 (13)	C15—C14—C13	121.0 (5)
O1—Co1—O2	87.77 (12)	C15—C14—H14	119.5
O4—Co1—N2	92.72 (14)	C13—C14—H14	119.5
O3—Co1—N2	87.54 (14)	N3—C15—C14	120.2 (5)
O1—Co1—N2	90.39 (14)	N3—C15—H15	119.9
O2—Co1—N2	90.27 (14)	C14—C15—H15	119.9
O4—Co1—N1	87.90 (14)	N3—C17—C18	120.7 (5)
O3—Co1—N1	90.98 (14)	N3—C17—H17	119.6
O1—Co1—N1	91.08 (14)	C18—C17—H17	119.6
O2—Co1—N1	89.29 (14)	C17—C18—C13	120.4 (5)
N2—Co1—N1	178.45 (15)	C17—C18—H18	119.8
O11^i—Co2—O11	180.0	C13—C18—H18	119.8
O11^i—Co2—O9^i	90.17 (13)	C19^ii—C19—C3	125.2 (6)
O11—Co2—O9^i	89.83 (13)	C19^ii—C19—H19	117.4
O11^i—Co2—O9	89.83 (13)	C3—C19—H19	117.4
O11—Co2—O9	90.17 (13)	Co1—O1—H1B	109.5
O9^i—Co2—O9	180.00 (18)	Co1—O1—H1A	109.4
O11^i—Co2—O10	88.64 (15)	H1B—O1—H1A	129.9
O11—Co2—O10	91.36 (15)	Co1—O2—H2B	109.5
O9^i—Co2—O10	88.60 (15)	Co1—O2—H2A	109.4
O9—Co2—O10	91.40 (15)	H2B—O2—H2A	138.5
O11^i—Co2—O10^i	91.36 (15)	Co1—O3—H3B	109.5
O11—Co2—O10^i	88.64 (15)	Co1—O3—H3A	109.3
O9^i—Co2—O10^i	91.40 (15)	H3B—O3—H3A	141.2
O9—Co2—O10^i	88.60 (15)	Co1—O4—H4B	109.5
O10—Co2—O10^i	180.000 (1)	Co1—O4—H4A	109.5
N1—C1—C2	124.6 (5)	H4B—O4—H4A	141.0
N1—C1—H1	117.7	Co2—O9—H9B	109.5
C2—C1—H1	117.7	Co2—O9—H9A	109.4
C1—C2—C3	119.5 (5)	H9B—O9—H9A	108.1
C1—C2—H2	120.2	Co2—O10—H10B	109.5
C3—C2—H2	120.2	Co2—O10—H10A	109.5
C4—C3—C2	116.2 (5)	H10B—O10—H10A	140.9
C4—C3—C19	121.2 (4)	Co2—O11—H11B	109.5
C2—C3—C19	122.5 (5)	Co2—O11—H11A	109.4
C5—C4—C3	120.6 (5)	H11B—O11—H11A	112.5
C5—C4—H4	119.7	H16A—O16—H16B	100 (6)
C3—C4—H4	119.7	H17A—O17—H17B	100 (6)
N1—C5—C4	123.3 (5)	H18A—O18—H18B	111 (7)
N1—C5—H5	118.4	H19A—O19—H19B	73 (5)
C4—C5—H5	118.4	C1—N1—C5	115.8 (4)
N2—C6—C7	124.1 (4)	C1—N1—Co1	121.6 (3)
N2—C6—H6	117.9	C5—N1—Co1	122.5 (3)
C7—C6—H6	117.9	C6—N2—C10	117.0 (4)
C6—C7—C8	119.0 (5)	C6—N2—Co1	120.9 (3)
C6—C7—H7	120.5	C10—N2—Co1	121.9 (3)
C8—C7—H7	120.5	C15—N3—C17	121.1 (5)
C9—C8—C7	116.9 (4)	C15—N3—H3N	119.4
C9—C8—C11	120.7 (4)	C17—N3—H3N	119.4
C7—C8—C11	122.3 (5)	O7—S1—O5	110.8 (2)
C8—C9—C10	120.3 (4)	O7—S1—O8	109.8 (2)
C8—C9—H9	119.8	O5—S1—O8	108.6 (2)
C10—C9—H9	119.8	O7—S1—O6	109.9 (2)
N2—C10—C9	122.7 (4)	O5—S1—O6	109.8 (3)
N2—C10—H10	118.7	O8—S1—O6	107.9 (2)
C9—C10—H10	118.7	O14—S2—O15	110.2 (3)
C12—C11—C8	126.5 (4)	O14—S2—O12	109.3 (3)
C12—C11—H11	116.7	O15—S2—O12	108.9 (3)
C8—C11—H11	116.7	O14—S2—O13	108.7 (2)
C11—C12—C13	125.5 (4)	O15—S2—O13	110.9 (2)
C11—C12—H12	117.3	O12—S2—O13	108.8 (2)
N1—C1—C2—C3	0.4 (8)	C4—C5—N1—Co1	175.9 (4)
C1—C2—C3—C4	0.0 (7)	O4—Co1—N1—C1	−125.8 (4)
C1—C2—C3—C19	179.7 (4)	O3—Co1—N1—C1	138.3 (4)
C2—C3—C4—C5	−0.4 (7)	O1—Co1—N1—C1	−40.5 (4)
C19—C3—C4—C5	179.9 (4)	O2—Co1—N1—C1	47.3 (4)
C3—C4—C5—N1	0.5 (8)	N2—Co1—N1—C1	121 (5)
N2—C6—C7—C8	−0.3 (9)	O4—Co1—N1—C5	58.4 (4)
C6—C7—C8—C9	−0.1 (8)	O3—Co1—N1—C5	−37.5 (4)
C6—C7—C8—C11	−177.2 (5)	O1—Co1—N1—C5	143.8 (4)
C7—C8—C9—C10	0.3 (7)	O2—Co1—N1—C5	−128.5 (4)
C11—C8—C9—C10	177.5 (4)	N2—Co1—N1—C5	−55 (6)
C8—C9—C10—N2	−0.1 (7)	C7—C6—N2—C10	0.5 (8)
C9—C8—C11—C12	169.4 (5)	C7—C6—N2—Co1	176.2 (4)
C7—C8—C11—C12	−13.6 (8)	C9—C10—N2—C6	−0.3 (7)
C8—C11—C12—C13	176.5 (4)	C9—C10—N2—Co1	−175.9 (3)
C11—C12—C13—C14	−179.0 (5)	O4—Co1—N2—C6	−58.2 (4)
C11—C12—C13—C18	−0.9 (8)	O3—Co1—N2—C6	37.7 (4)
C18—C13—C14—C15	−0.9 (7)	O1—Co1—N2—C6	−143.6 (4)
C12—C13—C14—C15	177.3 (5)	O2—Co1—N2—C6	128.7 (4)
C13—C14—C15—N3	−0.2 (8)	N1—Co1—N2—C6	55 (6)
N3—C17—C18—C13	0.5 (8)	O4—Co1—N2—C10	117.3 (4)
C14—C13—C18—C17	0.8 (7)	O3—Co1—N2—C10	−146.9 (4)
C12—C13—C18—C17	−177.4 (5)	O1—Co1—N2—C10	31.9 (4)
C4—C3—C19—C19^ii	−172.6 (6)	O2—Co1—N2—C10	−55.9 (4)
C2—C3—C19—C19^ii	7.7 (9)	N1—Co1—N2—C10	−129 (5)
C2—C1—N1—C5	−0.4 (7)	C14—C15—N3—C17	1.5 (8)
C2—C1—N1—Co1	−176.4 (4)	C18—C17—N3—C15	−1.7 (8)
C4—C5—N1—C1	−0.1 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O6^iii	0.82	1.92	2.688 (4)	155
O1—H1A···O13^iv	0.82	2.02	2.738 (5)	145
O2—H2B···O12^iv	0.82	1.91	2.699 (5)	160
O2—H2A···O8^v	0.82	2.01	2.711 (4)	143
O3—H3B···O19	0.82	1.89	2.686 (6)	162
O3—H3A···O6^i	0.82	1.97	2.711 (5)	150
O4—H4B···O7^iii	0.82	2.00	2.781 (5)	159
O4—H4A···O13^vi	0.82	2.02	2.703 (5)	141
O9—H9B···O18	0.82	1.95	2.761 (6)	172
O10—H10B···O5^i	0.82	2.17	2.813 (5)	136
O10—H10A···O12^vii	0.82	1.91	2.698 (5)	161
O11—H11B···O16^viii	0.82	1.86	2.669 (6)	167
O11—H11A···O14^viii	0.82	1.93	2.739 (5)	169
N3—H3N···O8^ix	0.86	1.87	2.723 (5)	174
O16—H16A···O13^x	0.76 (4)	2.04 (4)	2.797 (6)	174 (6)
O16—H16B···O6^vii	0.76 (4)	2.30 (4)	3.024 (6)	161 (6)
O17—H17A···O15	0.80 (4)	2.28 (5)	2.987 (7)	147 (5)
O17—H17B···O14^x	0.82 (4)	2.28 (5)	2.936 (7)	138 (6)
O18—H18A···O17^vii	0.79 (4)	2.07 (4)	2.855 (8)	170 (6)
O18—H18B···O5	0.77 (4)	2.09 (4)	2.844 (6)	166 (6)
O19—H19B···O12^vii	0.80 (4)	2.20 (5)	2.939 (7)	155 (6)

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