Tetra-μ-aqua-octaaqua-bis(μ-4-chloro-pyridine-2,6-dicarboxyl-ato)bis-(4-chloro-pyridine-2,6-dicarboxyl-ato)tri-cobalt(II)disodium(I) bis-[triaqua-bis(4-chloro-pyridine-2,6-dicarboxyl-ato)cobalt(II)] hexa-hydrate.

The title compound, [Co(3)Na(2)(C(7)H(2)ClNO(4))(4)(H(2)O)(12)][Co(C(7)H(2)ClNO(4))(H(2)O)(3)](2)·6H(2)O, consists of a centrosymmetric dimer of [Co(II)(dipicCl)(2)](2-) complex dianions [dipicCl is 4-chloro-pyridine-2,6-dicarboxyl-ate] bridged by an [Na(2)Co(II)(H(2)O)(12)](4+) tetra-cationic cluster, two independent [Co(dipicCl)(H(2)O)(3)] complexes, and six water mol-ecules of crystallization. The metals are all six-coordinate with distorted octahedral geometries. The [Co(II)(dipicCl)(H(2)O)(3)] complexes are neutral, with one tridentate ligand and three water molecules. The [Co(II)(dipicCl)(2)](2-) complexes each have two tridentate ligands. The [Na(2)Co(II)(H(2)O)(12)](4+) cluster has a central Co(II) ion which is coordinated to six water molecules and lies on a crystallographic inversion center. Four of the water molecules bridge to two sodium ions, each of which have three other water molecules coordinated along with an O atom from the [Co(II)(dipicCl)(2)](2-) complex. In the crystal structure, the various units are linked by O-H⋯O hydrogen bonds, forming a three-dimensional network. Two water molecules are disordered equally over two positions.

Related literature

For related literature, see: Anagnostopoulos (1975 ▶); Cassellato & Vigato (1978 ▶); Chatterjee, Ghosh, Wu & Mak (1998 ▶); Chatterjee, Maji, Ghosh & Mak (1998 ▶); Hartkamp (1962 ▶); Lukes & Jurecek (1948 ▶); Chatterjee et al. (1997 ▶); Crans et al. (2000 ▶, 2003 ▶, 2006 ▶); D’Ascenzo, Marino, Sabbatini & Bica (1978 ▶); Du et al. (2006 ▶); Furst et al. (1978 ▶); Ghosh et al. (1978 ▶); Lamture et al. (1995 ▶); Liu et al. (2006 ▶); Su et al. (2005 ▶); Yang et al. (2002 ▶); Zhou et al. (2004 ▶).

Experimental

Crystal data

[Co3Na2(C7H2ClNO4)4(H2O)12][Co(C7H2ClNO4)(H2O)3]2·6H2O

M = 1970.29

Triclinic,

a = 9.1539 (18) Å

b = 14.475 (3) Å

c = 15.476 (3) Å

α = 62.54 (3)°

β = 83.32 (3)°

γ = 80.19 (3)°

V = 1791.4 (6) Å3

Z = 1

Mo Kα radiation

μ = 1.48 mm−1

T = 153 (2) K

0.34 × 0.19 × 0.11 mm

Data collection

Rigaku Mercury CCD diffractometer

Absorption correction: multi-scan (REQAB; Rigaku/MSC 2006 ▶) T min = 0.633, T max = 0.854

12735 measured reflections

6520 independent reflections

5060 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.086

S = 1.04

6520 reflections

583 parameters

24 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.58 e Å−3

Δρmin = −0.38 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2006 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Bruker, 2000 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067141/su2035sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067141/su2035Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Co3Na2(C7H2ClNO4)4(H2O)12][Co(C7H2ClNO4)(H2O)3]2·6H2O	Z = 1
Mr = 1970.29	F000 = 997
Triclinic, P1	Dx = 1.826 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 9.1539 (18) Å	Cell parameters from 5409 reflections
b = 14.475 (3) Å	θ = 3.7–26.4º
c = 15.476 (3) Å	µ = 1.48 mm−1
α = 62.54 (3)º	T = 153 (2) K
β = 83.32 (3)º	Rod, purple
γ = 80.19 (3)º	0.34 × 0.19 × 0.11 mm
V = 1791.4 (6) Å3

Rigaku Mercury CCD diffractometer	6520 independent reflections
Radiation source: Sealed Tube	5060 reflections with I > 2σ(I)
Monochromator: Graphite Monochromator	Rint = 0.024
Detector resolution: 14.6306 pixels mm-1	θmax = 25.5º
T = 153(2) K	θmin = 3.2º
ω scans	h = −11→11
Absorption correction: multi-scan(REQAB; Rigaku/MSC 2006)	k = −15→17
Tmin = 0.633, Tmax = 0.854	l = −16→18
12735 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.086	w = 1/[σ2(Fo2) + (0.0467P)2 + 0.1717P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
6520 reflections	Δρmax = 0.58 e Å−3
583 parameters	Δρmin = −0.38 e Å−3
24 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.27302 (4)	0.83775 (3)	0.19235 (3)	0.01340 (10)
Cl1	0.34541 (10)	0.46841 (7)	0.63440 (6)	0.0316 (2)
Cl2	0.21294 (9)	1.22256 (6)	−0.24098 (6)	0.02708 (19)
N1	0.3011 (3)	0.71984 (18)	0.32895 (18)	0.0138 (5)
N2	0.2483 (3)	0.95501 (18)	0.05598 (18)	0.0138 (5)
O1	0.1696 (2)	0.71166 (16)	0.19327 (16)	0.0188 (5)
O2	0.3910 (2)	0.90072 (16)	0.26077 (16)	0.0186 (5)
O3	0.1353 (2)	0.54304 (16)	0.28689 (17)	0.0220 (5)
O4	0.4945 (2)	0.86338 (17)	0.39863 (16)	0.0230 (5)
O5	0.0749 (2)	0.93466 (16)	0.20562 (16)	0.0194 (5)
O6	0.4625 (2)	0.80119 (15)	0.11290 (15)	0.0169 (4)
O7	−0.0654 (2)	1.08848 (16)	0.12304 (16)	0.0203 (5)
O8	0.5652 (2)	0.85418 (16)	−0.03851 (16)	0.0210 (5)
C1	0.1770 (3)	0.6265 (2)	0.2730 (2)	0.0163 (6)
C2	0.2456 (3)	0.6301 (2)	0.3554 (2)	0.0165 (6)
C3	0.2570 (4)	0.5501 (2)	0.4498 (2)	0.0212 (7)
H3	0.2162	0.4861	0.4693	0.025*
C4	0.3296 (3)	0.5654 (2)	0.5155 (2)	0.0203 (7)
C5	0.3905 (3)	0.6572 (2)	0.4871 (2)	0.0185 (7)
H5	0.4434	0.6669	0.5317	0.022*
C6	0.3722 (3)	0.7337 (2)	0.3927 (2)	0.0151 (6)
C7	0.4242 (3)	0.8415 (2)	0.3475 (2)	0.0156 (6)
C8	0.0404 (3)	1.0182 (2)	0.1294 (2)	0.0151 (6)
C9	0.1373 (3)	1.0341 (2)	0.0390 (2)	0.0143 (6)
C10	0.1218 (3)	1.1194 (2)	−0.0532 (2)	0.0159 (6)
H10	0.0435	1.1768	−0.0658	0.019*
C11	0.2245 (3)	1.1174 (2)	−0.1258 (2)	0.0165 (6)
C12	0.3385 (3)	1.0352 (2)	−0.1082 (2)	0.0165 (6)
H12	0.4085	1.0340	−0.1590	0.020*
C13	0.3468 (3)	0.9550 (2)	−0.0140 (2)	0.0144 (6)
C14	0.4697 (3)	0.8627 (2)	0.0210 (2)	0.0153 (6)
Co3	0.67155 (4)	0.11941 (3)	0.36043 (3)	0.01259 (10)
Cl3	1.12718 (10)	0.29703 (7)	0.52031 (6)	0.0343 (2)
N3	0.8057 (2)	0.17914 (18)	0.41349 (18)	0.0125 (5)
O9	0.7150 (2)	−0.00397 (15)	0.50786 (15)	0.0156 (4)
O10	0.6749 (2)	0.27965 (16)	0.24966 (15)	0.0164 (4)
O11	0.8694 (2)	−0.05463 (16)	0.62997 (16)	0.0185 (5)
O12	0.8157 (2)	0.41056 (16)	0.19307 (16)	0.0195 (5)
O13	0.4629 (2)	0.16346 (16)	0.42191 (16)	0.0165 (4)
H13A	0.395 (3)	0.124 (2)	0.432 (3)	0.025*
H13B	0.477 (4)	0.159 (3)	0.4786 (17)	0.025*
O14	0.8596 (2)	0.06266 (18)	0.30523 (17)	0.0208 (5)
H14A	0.950 (2)	0.061 (3)	0.320 (3)	0.031*
H14B	0.870 (4)	0.074 (3)	0.2449 (16)	0.031*
O15	0.5546 (2)	0.06640 (18)	0.29292 (17)	0.0225 (5)
H15A	0.477 (3)	0.103 (3)	0.263 (3)	0.034*
H15B	0.538 (4)	0.0025 (17)	0.326 (3)	0.034*
C15	0.8112 (3)	0.0107 (2)	0.5519 (2)	0.0144 (6)
C16	0.8614 (3)	0.1193 (2)	0.5014 (2)	0.0135 (6)
C17	0.9592 (3)	0.1542 (2)	0.5388 (2)	0.0177 (6)
H17	0.9956	0.1127	0.6031	0.021*
C18	1.0013 (3)	0.2528 (2)	0.4775 (2)	0.0177 (7)
C19	0.9472 (3)	0.3142 (2)	0.3847 (2)	0.0181 (7)
H19	0.9778	0.3818	0.3430	0.022*
C20	0.8469 (3)	0.2737 (2)	0.3550 (2)	0.0146 (6)
C21	0.7745 (3)	0.3273 (2)	0.2569 (2)	0.0138 (6)
Co2	0.5000	0.5000	0.0000	0.01317 (13)
O16	0.7253 (2)	0.51517 (17)	0.00124 (16)	0.0170 (4)
H16A	0.758 (4)	0.477 (2)	0.0607 (16)	0.025*
H16B	0.778 (4)	0.497 (3)	−0.037 (2)	0.025*
O17	0.4626 (2)	0.66360 (16)	−0.08005 (16)	0.0156 (4)
H17A	0.424 (4)	0.674 (3)	−0.1328 (18)	0.023*
H17B	0.394 (3)	0.689 (3)	−0.051 (2)	0.023*
O18	0.4605 (2)	0.51588 (17)	0.12724 (16)	0.0203 (5)
H18A	0.528 (3)	0.540 (3)	0.142 (3)	0.030*
H18B	0.439 (4)	0.464 (2)	0.1846 (18)	0.030*
Na1	0.69526 (12)	0.70953 (9)	−0.05481 (9)	0.0185 (3)
O19	0.6582 (3)	0.63560 (18)	0.12553 (18)	0.0242 (5)
H19A	0.740 (3)	0.621 (3)	0.154 (3)	0.036*
H19B	0.614 (4)	0.686 (2)	0.137 (3)	0.036*
O20	0.2393 (2)	0.73840 (18)	−0.99731 (17)	0.0240 (5)
H20A	0.183 (4)	0.795 (2)	−1.031 (3)	0.036*
H20B	0.225 (4)	0.724 (3)	−0.9359 (16)	0.036*
O21	0.0629 (3)	0.52400 (19)	−0.87565 (18)	0.0259 (5)
H21A	0.083 (4)	0.538 (3)	−0.830 (2)	0.039*
H21B	0.001 (4)	0.479 (3)	−0.845 (3)	0.039*
O22	0.9464 (3)	0.6958 (2)	−0.0502 (2)	0.0404 (7)
H22A	0.994 (5)	0.749 (3)	−0.084 (3)	0.061*
H22B	0.997 (5)	0.650 (3)	0.000 (2)	0.061*
O23	0.3333 (6)	0.3650 (4)	−0.7100 (4)	0.0199 (11)	0.50
H23A	0.376 (4)	0.311 (2)	−0.661 (2)	0.030*
H23B	0.278 (4)	0.398 (3)	−0.680 (3)	0.030*
O23'	0.3847 (7)	0.3859 (5)	−0.6866 (5)	0.0347 (14)	0.50
O24	0.7164 (5)	0.7828 (4)	−0.2286 (3)	0.0232 (10)	0.50
H24A	0.766 (4)	0.833 (2)	−0.270 (3)	0.035*
H24B	0.685 (6)	0.826 (4)	−0.203 (4)	0.035*
O24'	0.7025 (6)	0.8604 (4)	−0.2068 (4)	0.0271 (12)	0.50

	U11	U22	U33	U12	U13	U23
Co1	0.01611 (19)	0.0112 (2)	0.0106 (2)	−0.00180 (15)	−0.00031 (15)	−0.00306 (16)
Cl1	0.0474 (5)	0.0228 (4)	0.0135 (4)	−0.0051 (4)	−0.0029 (4)	0.0016 (3)
Cl2	0.0288 (4)	0.0243 (4)	0.0135 (4)	−0.0013 (3)	−0.0002 (3)	0.0029 (3)
N1	0.0164 (12)	0.0101 (12)	0.0146 (14)	−0.0010 (9)	0.0002 (10)	−0.0056 (10)
N2	0.0147 (11)	0.0126 (13)	0.0147 (14)	−0.0022 (9)	−0.0016 (10)	−0.0063 (10)
O1	0.0228 (11)	0.0158 (11)	0.0169 (12)	−0.0044 (8)	−0.0016 (9)	−0.0059 (9)
O2	0.0230 (10)	0.0168 (11)	0.0157 (12)	−0.0073 (9)	−0.0009 (9)	−0.0056 (9)
O3	0.0290 (11)	0.0156 (11)	0.0225 (13)	−0.0086 (9)	−0.0014 (10)	−0.0074 (9)
O4	0.0306 (12)	0.0241 (12)	0.0176 (12)	−0.0115 (9)	−0.0010 (10)	−0.0096 (10)
O5	0.0193 (10)	0.0170 (11)	0.0159 (12)	0.0027 (8)	0.0021 (9)	−0.0047 (9)
O6	0.0172 (10)	0.0153 (11)	0.0144 (12)	−0.0004 (8)	0.0011 (8)	−0.0046 (9)
O7	0.0197 (10)	0.0205 (12)	0.0151 (12)	0.0059 (9)	−0.0005 (9)	−0.0062 (9)
O8	0.0194 (10)	0.0206 (12)	0.0209 (13)	−0.0007 (9)	0.0062 (9)	−0.0099 (10)
C1	0.0173 (14)	0.0166 (16)	0.0170 (17)	−0.0027 (12)	0.0009 (12)	−0.0095 (13)
C2	0.0210 (14)	0.0129 (15)	0.0161 (17)	−0.0028 (11)	0.0012 (12)	−0.0073 (12)
C3	0.0330 (17)	0.0128 (16)	0.0166 (17)	−0.0070 (13)	0.0004 (14)	−0.0046 (13)
C4	0.0292 (16)	0.0146 (16)	0.0104 (16)	−0.0008 (12)	0.0014 (13)	−0.0012 (13)
C5	0.0214 (15)	0.0188 (16)	0.0153 (17)	−0.0029 (12)	0.0000 (13)	−0.0078 (13)
C6	0.0184 (14)	0.0167 (16)	0.0112 (15)	−0.0025 (11)	0.0007 (12)	−0.0075 (12)
C7	0.0173 (14)	0.0160 (16)	0.0149 (17)	−0.0039 (11)	0.0032 (12)	−0.0085 (13)
C8	0.0162 (14)	0.0160 (15)	0.0141 (16)	−0.0026 (12)	−0.0018 (12)	−0.0071 (13)
C9	0.0157 (14)	0.0146 (15)	0.0134 (16)	−0.0039 (11)	−0.0012 (12)	−0.0064 (12)
C10	0.0169 (14)	0.0134 (15)	0.0162 (16)	−0.0020 (11)	−0.0013 (12)	−0.0057 (12)
C11	0.0189 (14)	0.0152 (15)	0.0110 (16)	−0.0076 (12)	−0.0027 (12)	0.0001 (12)
C12	0.0153 (14)	0.0197 (16)	0.0144 (16)	−0.0070 (12)	0.0023 (12)	−0.0066 (13)
C13	0.0140 (13)	0.0168 (15)	0.0161 (16)	−0.0036 (11)	0.0006 (12)	−0.0104 (13)
C14	0.0141 (13)	0.0162 (16)	0.0167 (17)	−0.0028 (11)	−0.0008 (12)	−0.0081 (13)
Co3	0.01322 (19)	0.0124 (2)	0.0116 (2)	−0.00269 (14)	−0.00176 (15)	−0.00440 (16)
Cl3	0.0461 (5)	0.0309 (5)	0.0254 (5)	−0.0225 (4)	−0.0155 (4)	−0.0033 (4)
N3	0.0096 (11)	0.0129 (12)	0.0136 (13)	0.0003 (9)	−0.0001 (9)	−0.0055 (10)
O9	0.0152 (10)	0.0157 (11)	0.0147 (11)	−0.0038 (8)	−0.0029 (8)	−0.0047 (9)
O10	0.0165 (10)	0.0153 (11)	0.0153 (11)	−0.0036 (8)	−0.0033 (8)	−0.0040 (9)
O11	0.0189 (10)	0.0166 (11)	0.0148 (12)	−0.0026 (8)	−0.0051 (9)	−0.0016 (9)
O12	0.0219 (10)	0.0173 (11)	0.0140 (12)	−0.0070 (9)	−0.0028 (9)	−0.0007 (9)
O13	0.0151 (10)	0.0163 (11)	0.0160 (12)	−0.0039 (8)	−0.0001 (9)	−0.0050 (9)
O14	0.0167 (10)	0.0305 (13)	0.0165 (12)	0.0007 (9)	−0.0026 (9)	−0.0125 (10)
O15	0.0251 (11)	0.0213 (13)	0.0236 (13)	−0.0082 (10)	−0.0036 (10)	−0.0098 (10)
C15	0.0167 (13)	0.0134 (15)	0.0121 (16)	−0.0013 (11)	0.0009 (12)	−0.0055 (12)
C16	0.0109 (13)	0.0156 (15)	0.0132 (16)	−0.0012 (11)	−0.0008 (11)	−0.0059 (12)
C17	0.0194 (14)	0.0175 (16)	0.0140 (16)	−0.0033 (12)	−0.0036 (12)	−0.0044 (13)
C18	0.0194 (14)	0.0188 (16)	0.0172 (17)	−0.0078 (12)	−0.0032 (12)	−0.0076 (13)
C19	0.0202 (15)	0.0144 (15)	0.0191 (17)	−0.0058 (12)	−0.0017 (13)	−0.0056 (13)
C20	0.0141 (13)	0.0139 (15)	0.0125 (16)	−0.0019 (11)	−0.0001 (11)	−0.0033 (12)
C21	0.0135 (13)	0.0143 (15)	0.0137 (16)	−0.0014 (11)	−0.0005 (12)	−0.0065 (12)
Co2	0.0134 (3)	0.0121 (3)	0.0124 (3)	−0.0013 (2)	−0.0015 (2)	−0.0041 (2)
O16	0.0163 (10)	0.0193 (12)	0.0137 (12)	−0.0009 (8)	−0.0021 (9)	−0.0062 (9)
O17	0.0171 (10)	0.0149 (11)	0.0134 (12)	0.0013 (8)	−0.0037 (9)	−0.0058 (9)
O18	0.0285 (12)	0.0184 (12)	0.0125 (12)	−0.0052 (9)	0.0003 (10)	−0.0054 (9)
Na1	0.0182 (6)	0.0175 (6)	0.0186 (7)	−0.0023 (5)	−0.0006 (5)	−0.0072 (5)
O19	0.0289 (12)	0.0181 (12)	0.0245 (14)	0.0041 (10)	−0.0058 (10)	−0.0101 (10)
O20	0.0261 (12)	0.0253 (13)	0.0157 (12)	0.0068 (9)	−0.0024 (10)	−0.0081 (10)
O21	0.0260 (12)	0.0349 (14)	0.0227 (14)	−0.0129 (10)	0.0017 (10)	−0.0155 (11)
O22	0.0240 (13)	0.0384 (17)	0.0504 (19)	−0.0080 (11)	−0.0110 (12)	−0.0095 (14)
O23	0.023 (3)	0.016 (3)	0.019 (3)	0.003 (2)	−0.001 (2)	−0.008 (2)
O23'	0.035 (3)	0.022 (3)	0.035 (4)	−0.001 (2)	0.011 (3)	−0.006 (3)
O24	0.024 (2)	0.028 (3)	0.018 (3)	−0.012 (2)	0.0065 (19)	−0.009 (2)
O24'	0.027 (3)	0.027 (3)	0.020 (3)	−0.005 (2)	0.005 (2)	−0.006 (2)

Co1—N2	2.016 (3)	O14—H14A	0.879 (19)
Co1—N1	2.024 (3)	O14—H14B	0.866 (19)
Co1—O6	2.143 (2)	O15—H15A	0.854 (19)
Co1—O2	2.147 (2)	O15—H15B	0.858 (19)
Co1—O5	2.147 (2)	C15—C16	1.524 (4)
Co1—O1	2.188 (2)	C16—C17	1.391 (4)
Cl1—C4	1.729 (3)	C17—C18	1.392 (4)
Cl2—C11	1.730 (3)	C17—H17	0.9600
N1—C2	1.341 (4)	C18—C19	1.391 (4)
N1—C6	1.347 (4)	C19—C20	1.388 (4)
N2—C13	1.326 (4)	C19—H19	0.9600
N2—C9	1.341 (4)	C20—C21	1.523 (4)
O1—C1	1.279 (4)	Co2—O18i	2.070 (2)
O2—C7	1.255 (4)	Co2—O18	2.070 (2)
O3—C1	1.244 (4)	Co2—O17	2.092 (2)
O4—C7	1.248 (4)	Co2—O17i	2.092 (2)
O5—C8	1.263 (4)	Co2—O16i	2.114 (2)
O6—C14	1.285 (4)	Co2—O16	2.114 (2)
O7—C8	1.256 (4)	Co2—Na1i	3.4979 (15)
O8—C14	1.228 (4)	Co2—Na1	3.4979 (15)
O8—Na1	2.331 (3)	O16—Na1	2.507 (3)
C1—C2	1.511 (4)	O16—H16A	0.884 (19)
C2—C3	1.386 (4)	O16—H16B	0.833 (19)
C3—C4	1.392 (5)	O17—Na1	2.459 (2)
C3—H3	0.9600	O17—H17A	0.866 (19)
C4—C5	1.388 (4)	O17—H17B	0.855 (18)
C5—C6	1.375 (4)	O18—H18A	0.862 (19)
C5—H5	0.9600	O18—H18B	0.883 (19)
C6—C7	1.523 (4)	Na1—O22	2.280 (3)
C8—C9	1.510 (4)	Na1—O24'	2.362 (6)
C9—C10	1.394 (4)	Na1—O24	2.390 (5)
C10—C11	1.386 (4)	Na1—O19	2.490 (3)
C10—H10	0.9600	Na1—H24B	2.13 (6)
C11—C12	1.387 (4)	O19—H19A	0.852 (19)
C12—C13	1.383 (4)	O19—H19B	0.861 (19)
C12—H12	0.9600	O20—H20A	0.857 (19)
C13—C14	1.519 (4)	O20—H20B	0.872 (19)
Co3—O15	2.026 (2)	O21—H21A	0.862 (19)
Co3—N3	2.045 (2)	O21—H21B	0.860 (19)
Co3—O14	2.047 (2)	O22—H22A	0.872 (19)
Co3—O10	2.160 (2)	O22—H22B	0.87 (2)
Co3—O13	2.164 (2)	O23—O23'	0.795 (7)
Co3—O9	2.183 (2)	O23—H23A	0.872 (19)
Cl3—C18	1.732 (3)	O23—H23B	0.877 (19)
N3—C16	1.337 (4)	O23'—H23A	0.98 (3)
N3—C20	1.337 (4)	O23'—H23B	0.97 (3)
O9—C15	1.273 (4)	O24—O24'	1.297 (7)
O10—C21	1.276 (3)	O24—H24A	0.874 (18)
O11—C15	1.250 (4)	O24—H24B	0.88 (2)
O12—C21	1.241 (3)	O24'—H24A	1.27 (4)
O13—H13A	0.869 (18)	O24'—H24B	0.52 (4)
O13—H13B	0.873 (19)
N2—Co1—N1	179.17 (9)	N3—C20—C19	120.9 (3)
N2—Co1—O6	76.81 (9)	N3—C20—C21	113.2 (2)
N1—Co1—O6	102.47 (9)	C19—C20—C21	125.9 (3)
N2—Co1—O2	103.45 (9)	O12—C21—O10	126.6 (3)
N1—Co1—O2	76.18 (9)	O12—C21—C20	118.8 (2)
O6—Co1—O2	95.69 (8)	O10—C21—C20	114.6 (2)
N2—Co1—O5	76.44 (10)	O18i—Co2—O18	180.00 (12)
N1—Co1—O5	104.26 (10)	O18i—Co2—O17	90.81 (9)
O6—Co1—O5	153.20 (8)	O18—Co2—O17	89.19 (9)
O2—Co1—O5	88.90 (9)	O18i—Co2—O17i	89.19 (9)
N2—Co1—O1	104.41 (9)	O18—Co2—O17i	90.81 (9)
N1—Co1—O1	75.95 (9)	O17—Co2—O17i	180.000 (1)
O6—Co1—O1	89.72 (8)	O18i—Co2—O16i	88.93 (9)
O2—Co1—O1	152.13 (8)	O18—Co2—O16i	91.07 (9)
O5—Co1—O1	98.48 (8)	O17—Co2—O16i	92.68 (9)
C2—N1—C6	121.0 (3)	O17i—Co2—O16i	87.32 (9)
C2—N1—Co1	119.6 (2)	O18i—Co2—O16	91.07 (9)
C6—N1—Co1	119.39 (19)	O18—Co2—O16	88.93 (9)
C13—N2—C9	121.4 (3)	O17—Co2—O16	87.32 (9)
C13—N2—Co1	119.1 (2)	O17i—Co2—O16	92.68 (9)
C9—N2—Co1	119.4 (2)	O16i—Co2—O16	180.00 (14)
C1—O1—Co1	115.42 (19)	O18i—Co2—Na1i	79.08 (7)
C7—O2—Co1	116.71 (18)	O18—Co2—Na1i	100.92 (7)
C8—O5—Co1	115.56 (18)	O17—Co2—Na1i	136.21 (6)
C14—O6—Co1	115.74 (19)	O17i—Co2—Na1i	43.79 (6)
C14—O8—Na1	132.80 (19)	O16i—Co2—Na1i	45.20 (7)
O3—C1—O1	125.9 (3)	O16—Co2—Na1i	134.80 (7)
O3—C1—C2	118.8 (3)	O18i—Co2—Na1	100.92 (7)
O1—C1—C2	115.2 (2)	O18—Co2—Na1	79.08 (7)
N1—C2—C3	120.8 (3)	O17—Co2—Na1	43.79 (6)
N1—C2—C1	113.5 (3)	O17i—Co2—Na1	136.21 (6)
C3—C2—C1	125.7 (3)	O16i—Co2—Na1	134.80 (7)
C2—C3—C4	117.9 (3)	O16—Co2—Na1	45.20 (7)
C2—C3—H3	121.1	Na1i—Co2—Na1	180.0
C4—C3—H3	121.1	Co2—O16—Na1	98.04 (9)
C5—C4—C3	121.2 (3)	Co2—O16—H16A	110 (2)
C5—C4—Cl1	119.2 (3)	Na1—O16—H16A	114 (2)
C3—C4—Cl1	119.6 (2)	Co2—O16—H16B	111 (3)
C6—C5—C4	117.5 (3)	Na1—O16—H16B	113 (2)
C6—C5—H5	121.2	H16A—O16—H16B	110 (3)
C4—C5—H5	121.2	Co2—O17—Na1	100.14 (9)
N1—C6—C5	121.6 (3)	Co2—O17—H17A	104 (2)
N1—C6—C7	112.0 (3)	Na1—O17—H17A	131 (2)
C5—C6—C7	126.3 (3)	Co2—O17—H17B	110 (2)
O4—C7—O2	126.0 (3)	Na1—O17—H17B	106 (2)
O4—C7—C6	118.4 (3)	H17A—O17—H17B	105 (3)
O2—C7—C6	115.7 (3)	Co2—O18—H18A	116 (3)
O7—C8—O5	125.7 (3)	Co2—O18—H18B	124 (3)
O7—C8—C9	118.1 (3)	H18A—O18—H18B	101 (3)
O5—C8—C9	116.2 (3)	O22—Na1—O8	114.12 (11)
N2—C9—C10	121.0 (3)	O22—Na1—O24'	89.33 (16)
N2—C9—C8	112.2 (3)	O8—Na1—O24'	71.02 (15)
C10—C9—C8	126.8 (3)	O22—Na1—O24	89.85 (14)
C11—C10—C9	116.9 (3)	O8—Na1—O24	99.61 (14)
C11—C10—H10	121.6	O24'—Na1—O24	31.68 (18)
C9—C10—H10	121.6	O22—Na1—O17	155.17 (11)
C10—C11—C12	122.0 (3)	O8—Na1—O17	90.42 (8)
C10—C11—Cl2	118.9 (2)	O24'—Na1—O17	95.61 (15)
C12—C11—Cl2	119.1 (2)	O24—Na1—O17	82.00 (12)
C13—C12—C11	117.0 (3)	O22—Na1—O19	93.27 (11)
C13—C12—H12	121.5	O8—Na1—O19	78.70 (9)
C11—C12—H12	121.5	O24'—Na1—O19	147.79 (15)
N2—C13—C12	121.7 (3)	O24—Na1—O19	176.85 (13)
N2—C13—C14	113.6 (3)	O17—Na1—O19	95.32 (9)
C12—C13—C14	124.6 (3)	O22—Na1—O16	87.95 (10)
O8—C14—O6	126.6 (3)	O8—Na1—O16	147.57 (9)
O8—C14—C13	118.8 (3)	O24'—Na1—O16	135.71 (16)
O6—C14—C13	114.6 (3)	O24—Na1—O16	104.09 (14)
O15—Co3—N3	173.05 (9)	O17—Na1—O16	71.57 (8)
O15—Co3—O14	87.23 (9)	O19—Na1—O16	76.49 (9)
N3—Co3—O14	87.62 (9)	O22—Na1—Co2	124.68 (9)
O15—Co3—O10	99.86 (9)	O8—Na1—Co2	117.26 (6)
N3—Co3—O10	75.88 (9)	O24'—Na1—Co2	125.49 (14)
O14—Co3—O10	94.18 (9)	O24—Na1—Co2	100.42 (12)
O15—Co3—O13	87.85 (9)	O17—Na1—Co2	36.07 (5)
N3—Co3—O13	97.62 (9)	O19—Na1—Co2	78.16 (7)
O14—Co3—O13	173.53 (8)	O16—Na1—Co2	36.76 (5)
O10—Co3—O13	90.79 (9)	O22—Na1—H24B	94.7 (14)
O15—Co3—O9	109.07 (9)	O8—Na1—H24B	78.5 (7)
N3—Co3—O9	75.73 (9)	O24'—Na1—H24B	11.9 (10)
O14—Co3—O9	91.55 (9)	O24—Na1—H24B	21.5 (6)
O10—Co3—O9	150.74 (8)	O17—Na1—H24B	86.3 (14)
O13—Co3—O9	86.10 (9)	O19—Na1—H24B	157.2 (6)
C16—N3—C20	121.5 (3)	O16—Na1—H24B	125.2 (6)
C16—N3—Co3	119.51 (19)	Co2—Na1—H24B	114.0 (12)
C20—N3—Co3	118.6 (2)	Na1—O19—H19A	112 (3)
C15—O9—Co3	115.55 (17)	Na1—O19—H19B	107 (3)
C21—O10—Co3	115.63 (18)	H19A—O19—H19B	102 (4)
Co3—O13—H13A	114 (2)	H20A—O20—H20B	109 (4)
Co3—O13—H13B	110 (2)	H21A—O21—H21B	100 (4)
H13A—O13—H13B	106 (3)	Na1—O22—H22A	122 (3)
Co3—O14—H14A	124 (3)	Na1—O22—H22B	123 (3)
Co3—O14—H14B	122 (3)	H22A—O22—H22B	110 (4)
H14A—O14—H14B	104 (3)	O23'—O23—H23A	72 (3)
Co3—O15—H15A	121 (3)	O23'—O23—H23B	70 (3)
Co3—O15—H15B	115 (3)	H23A—O23—H23B	101 (4)
H15A—O15—H15B	109 (4)	O23—O23'—H23A	57.8 (18)
O11—C15—O9	126.9 (3)	O23—O23'—H23B	58.8 (18)
O11—C15—C16	117.6 (3)	H23A—O23'—H23B	88 (3)
O9—C15—C16	115.4 (3)	O24'—O24—Na1	73.0 (3)
N3—C16—C17	121.8 (3)	O24'—O24—H24A	68 (3)
N3—C16—C15	113.0 (2)	Na1—O24—H24A	129 (3)
C17—C16—C15	125.2 (3)	O24'—O24—H24B	17 (3)
C16—C17—C18	116.2 (3)	Na1—O24—H24B	62 (4)
C16—C17—H17	121.9	H24A—O24—H24B	85 (4)
C18—C17—H17	121.9	O24—O24'—Na1	75.3 (3)
C19—C18—C17	122.3 (3)	O24—O24'—H24A	39.8 (10)
C19—C18—Cl3	120.3 (2)	Na1—O24'—H24A	108.9 (13)
C17—C18—Cl3	117.4 (2)	O24—O24'—H24B	29 (4)
C20—C19—C18	117.2 (3)	Na1—O24'—H24B	58 (7)
C20—C19—H19	121.4	H24A—O24'—H24B	69 (5)
C18—C19—H19	121.4

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O9ii	0.869 (18)	1.95 (2)	2.778 (3)	160 (3)
O13—H13B···O4iii	0.873 (19)	1.82 (2)	2.687 (3)	174 (3)
O14—H14A···O11iv	0.879 (19)	1.88 (2)	2.747 (3)	171 (4)
O14—H14B···O7v	0.866 (19)	1.84 (2)	2.688 (3)	167 (4)
O15—H15A···O24'i	0.854 (19)	1.83 (2)	2.650 (6)	161 (4)
O15—H15A···O24i	0.854 (19)	2.13 (2)	2.939 (5)	158 (4)
O15—H15B···O4vi	0.858 (19)	1.885 (19)	2.743 (3)	178 (4)
O16—H16A···O12	0.884 (19)	1.91 (2)	2.791 (3)	172 (4)
O16—H16B···O21vii	0.833 (19)	1.95 (2)	2.761 (3)	165 (3)
O17—H17A···O10i	0.866 (19)	1.89 (2)	2.752 (3)	170 (3)
O17—H17B···O20viii	0.855 (18)	1.776 (19)	2.628 (3)	174 (4)
O18—H18A···O19	0.862 (19)	1.89 (2)	2.701 (3)	157 (4)
O18—H18B···O23'viii	0.883 (19)	1.84 (2)	2.703 (7)	165 (4)
O18—H18B···O23viii	0.883 (19)	1.90 (2)	2.753 (6)	162 (3)
O19—H19B···O6	0.861 (19)	1.89 (3)	2.679 (3)	151 (4)
O20—H20A···O7ix	0.857 (19)	1.89 (2)	2.732 (3)	170 (4)
O21—H21A···O3x	0.862 (19)	1.96 (2)	2.816 (3)	170 (4)
O20—H20B···O1x	0.872 (19)	1.94 (2)	2.802 (3)	171 (4)
O21—H21B···O12xi	0.860 (19)	2.01 (2)	2.837 (3)	161 (4)
O22—H22A···O7xii	0.872 (19)	2.33 (3)	3.136 (4)	154 (4)
O22—H22B···O21xiii	0.87 (2)	2.02 (2)	2.862 (4)	164 (4)
O22—H22A···O20xiii	0.872 (19)	2.69 (5)	3.127 (3)	112 (4)
O23—H23A···O13x	0.872 (19)	1.99 (2)	2.825 (6)	159 (4)
O23'—H23B···O3x	0.97 (3)	2.14 (3)	2.854 (6)	129 (3)
O24—H24A···O11xiv	0.874 (18)	1.95 (2)	2.820 (5)	176 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13A⋯O9i	0.869 (18)	1.95 (2)	2.778 (3)	160 (3)
O13—H13B⋯O4ii	0.873 (19)	1.82 (2)	2.687 (3)	174 (3)
O14—H14A⋯O11iii	0.879 (19)	1.88 (2)	2.747 (3)	171 (4)
O14—H14B⋯O7iv	0.866 (19)	1.84 (2)	2.688 (3)	167 (4)
O15—H15A⋯O24′v	0.854 (19)	1.83 (2)	2.650 (6)	161 (4)
O15—H15A⋯O24v	0.854 (19)	2.13 (2)	2.939 (5)	158 (4)
O15—H15B⋯O4vi	0.858 (19)	1.885 (19)	2.743 (3)	178 (4)
O16—H16A⋯O12	0.884 (19)	1.91 (2)	2.791 (3)	172 (4)
O16—H16B⋯O21vii	0.833 (19)	1.95 (2)	2.761 (3)	165 (3)
O17—H17A⋯O10v	0.866 (19)	1.89 (2)	2.752 (3)	170 (3)
O17—H17B⋯O20viii	0.855 (18)	1.776 (19)	2.628 (3)	174 (4)
O18—H18A⋯O19	0.862 (19)	1.89 (2)	2.701 (3)	157 (4)
O18—H18B⋯O23′viii	0.883 (19)	1.84 (2)	2.703 (7)	165 (4)
O18—H18B⋯O23viii	0.883 (19)	1.90 (2)	2.753 (6)	162 (3)
O19—H19B⋯O6	0.861 (19)	1.89 (3)	2.679 (3)	151 (4)
O20—H20A⋯O7ix	0.857 (19)	1.89 (2)	2.732 (3)	170 (4)
O21—H21A⋯O3x	0.862 (19)	1.96 (2)	2.816 (3)	170 (4)
O20—H20B⋯O1x	0.872 (19)	1.94 (2)	2.802 (3)	171 (4)
O21—H21B⋯O12xi	0.860 (19)	2.01 (2)	2.837 (3)	161 (4)
O22—H22A⋯O7xii	0.872 (19)	2.33 (3)	3.136 (4)	154 (4)
O22—H22B⋯O21xiii	0.87 (2)	2.02 (2)	2.862 (4)	164 (4)
O22—H22A⋯O20xiii	0.872 (19)	2.69 (5)	3.127 (3)	112 (4)
O23—H23A⋯O13x	0.872 (19)	1.99 (2)	2.825 (6)	159 (4)
O23′—H23B⋯O3x	0.97 (3)	2.14 (3)	2.854 (6)	129 (3)
O24—H24A⋯O11xiv	0.874 (18)	1.95 (2)	2.820 (5)	176 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) ; (xi) ; (xii) ; (xiii) ; (xiv) .