Hexaaqua­cobalt(II) bis­(2,2′-sulfanediyldiacetato-κ3O,S,O′)cobaltate(II) tetra­hydrate

Wang, H.; Gao, S.; Ng, S.W.

doi:10.1107/S1600536811040979

metal-organic compounds

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Volume 67| Part 11| November 2011| Page m1521

doi:10.1107/S1600536811040979

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Hexaaquacobalt(II) bis(2,2′-sulfanediyldiacetato-κ³O,S,O′)cobaltate(II) tetrahydrate

Huang Wang,^a Shan Gao ^a and Seik Weng Ng ^b,^c ^*

^aKey Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Heilongjiang University, Harbin 150080, People's Republic of China, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 3 October 2011; accepted 5 October 2011; online 12 October 2011)

The two Co^II atoms in the title salt, [Co(H₂O)₆][Co(C₄H₄O₄S)₂]·4H₂O, exist in an octahedral coordination environment. In the cation, the Co atom is surrounded by six water molecules, and in the anion, it is bis-O,S,O′-chelated by the thioacetate ligands. The cations, anions and uncoordinated water molecules are linked by O—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For the isotypic nickel(II) analog, see: Pan et al. (2005 ).

Experimental

Crystal data

[Co(H₂O)₆][Co(C₄H₄O₄S)₂]·4H₂O
M_r = 594.28
Monoclinic, C c
a = 18.8627 (9) Å
b = 13.5779 (7) Å
c = 8.9535 (4) Å
β = 101.403 (1)°
V = 2247.87 (19) Å³
Z = 4
Mo Kα radiation
μ = 1.74 mm⁻¹
T = 293 K
0.18 × 0.14 × 0.14 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.745, T_max = 0.793
10837 measured reflections
4978 independent reflections
4802 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.067
S = 1.01
4978 reflections
331 parameters
56 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.58 e Å⁻³
Absolute structure: Flack (1983 ), 2402 Friedel pairs
Flack parameter: 0.02 (1)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H11⋯O2	0.84 (1)	1.89 (2)	2.707 (4)	162 (5)
O1w—H12⋯O6ⁱ	0.84 (1)	1.95 (1)	2.791 (4)	173 (5)
O2w—H21⋯O8wⁱⁱ	0.84 (1)	2.08 (2)	2.824 (3)	147 (3)
O2w—H22⋯O4ⁱⁱⁱ	0.85 (1)	1.98 (1)	2.813 (3)	170 (4)
O3w—H31⋯O4^iv	0.83 (1)	1.87 (2)	2.671 (3)	163 (5)
O3w—H32⋯O8^v	0.83 (1)	1.85 (2)	2.666 (3)	168 (5)
O4w—H41⋯O7w^vi	0.85 (1)	2.06 (2)	2.880 (4)	162 (4)
O4w—H42⋯O8^vii	0.85 (1)	1.96 (1)	2.805 (3)	173 (4)
O5w—H51⋯O9wⁱⁱⁱ	0.83 (1)	1.84 (2)	2.657 (4)	166 (3)
O5w—H52⋯O5ⁱ	0.84 (1)	1.89 (1)	2.721 (3)	179 (5)
O6w—H61⋯O1	0.83 (1)	1.91 (2)	2.726 (3)	166 (4)
O6w—H62⋯O10w	0.84 (1)	1.91 (1)	2.746 (3)	177 (4)
O7w—H71⋯O2	0.83 (1)	2.18 (4)	2.828 (4)	135 (5)
O7w—H72⋯O8w	0.84 (1)	1.96 (2)	2.777 (4)	165 (5)
O8w—H81⋯O6ⁱ	0.85 (1)	1.91 (1)	2.751 (3)	172 (5)
O8w—H82⋯O3^viii	0.84 (1)	2.13 (1)	2.965 (3)	168 (4)
O9w—H91⋯O3	0.84 (1)	2.08 (5)	2.797 (4)	142 (8)
O9w—H92⋯O10w	0.85 (1)	2.12 (8)	2.759 (5)	132 (9)
O10w—H101⋯O7w^vi	0.84 (1)	2.02 (2)	2.831 (4)	162 (4)
O10w—H102⋯O7^vii	0.84 (1)	1.93 (2)	2.701 (3)	152 (4)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (v) $[x, -y, z-{\script{1\over 2}}]$ ; (vi) $[x, -y+1, z-{\script{1\over 2}}]$ ; (vii) x, y, z-1; (viii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811040979/bt5666sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811040979/bt5666Isup2.hkl

checkCIF report

Comment top

First-row transition metal dications form a plethora of metal dicarboxylates; in some cases, a a direct metal–carboxylate bond is formed and in other cases, the product consists of hexaaquametal cations and carboxylate ions, the anion interacting indirectly in an outer-sphere type of coordination. Thioacetic acid yields several metal carboxylates; the reaction of the deprotonated acid with cobalt(II) ions gives the hexaaquacobalt(II) di(carboxylato)cobaltate(II) (Scheme I, Fig. 1). The two Co^II atoms in the salt exist in octahedral coordination environments. That in the cation is surrounded by water water molecules; that in the anion is O,S,O'-chelated by the thioacetate ligands. The cations, anions and lattice water molecules are linked by O···H···O into a three-dimensional network (Table 1). The salt is isostructural with the nickel(II) analog (Pan et al., 2005).

Related literature top

For the isotypic nickel(II) analog, see: Pan et al. (2005).

Experimental top

Cobalt diacetate (1 mmol) was added to an aqueous solution of thiodiacetic acid acid (1 mmol) that was earlier been treated with 1M sodium hydroxide to a pH of 6. The filtered solution was set aside for several days, after which pink prismatic crystals separated from solution.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of Co(H₂O)₆^2+.Co(C₄H₄O₄S)^2–.4H₂O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Hexaaquacobalt(II) bis(2,2'-sulfanediyldiacetato-κ³O,S,O')cobaltate(II) tetrahydrate top

Crystal data top

[Co(H₂O)₆][Co(C₄H₄O₄S)₂]·4H₂O	F(000) = 1224
M_r = 594.28	D_x = 1.756 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 10500 reflections
a = 18.8627 (9) Å	θ = 3.0–27.5°
b = 13.5779 (7) Å	µ = 1.74 mm⁻¹
c = 8.9535 (4) Å	T = 293 K
β = 101.403 (1)°	Prism, pink
V = 2247.87 (19) Å³	0.18 × 0.14 × 0.14 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	4978 independent reflections
Radiation source: fine-focus sealed tube	4802 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −24→24
T_min = 0.745, T_max = 0.793	k = −17→17
10837 measured reflections	l = −11→11

Refinement top

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)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.067	w = 1/[σ²(F_o²) + (0.0456P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
4978 reflections	Δρ_max = 0.74 e Å⁻³
331 parameters	Δρ_min = −0.58 e Å⁻³
56 restraints	Absolute structure: Flack (1983), 2402 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (1)

Crystal data top

[Co(H₂O)₆][Co(C₄H₄O₄S)₂]·4H₂O	V = 2247.87 (19) Å³
M_r = 594.28	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 18.8627 (9) Å	µ = 1.74 mm⁻¹
b = 13.5779 (7) Å	T = 293 K
c = 8.9535 (4) Å	0.18 × 0.14 × 0.14 mm
β = 101.403 (1)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	4978 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	4802 reflections with I > 2σ(I)
T_min = 0.745, T_max = 0.793	R_int = 0.025
10837 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.067	Δρ_max = 0.74 e Å⁻³
S = 1.01	Δρ_min = −0.58 e Å⁻³
4978 reflections	Absolute structure: Flack (1983), 2402 Friedel pairs
331 parameters	Absolute structure parameter: 0.02 (1)
56 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.500004 (19)	0.23844 (2)	0.50001 (4)	0.02113 (8)
Co2	0.756568 (19)	0.19476 (2)	0.24733 (4)	0.02289 (8)
S1	0.49039 (3)	0.40580 (5)	0.60363 (7)	0.02473 (13)
S2	0.51526 (3)	0.06991 (5)	0.40430 (7)	0.02585 (14)
O1	0.58222 (12)	0.30010 (14)	0.4126 (3)	0.0343 (5)
O2	0.65276 (15)	0.4269 (2)	0.3849 (4)	0.0643 (9)
O3	0.42627 (11)	0.29204 (14)	0.3183 (2)	0.0302 (4)
O4	0.35388 (11)	0.40998 (15)	0.2070 (3)	0.0346 (5)
O5	0.41625 (11)	0.17334 (15)	0.5790 (3)	0.0328 (4)
O6	0.35800 (12)	0.04251 (16)	0.6378 (3)	0.0415 (5)
O7	0.57090 (12)	0.18662 (14)	0.6866 (2)	0.0335 (5)
O8	0.65760 (11)	0.08440 (14)	0.7929 (2)	0.0317 (4)
O1W	0.75186 (17)	0.34735 (15)	0.2392 (4)	0.0485 (5)
H11	0.728 (2)	0.380 (3)	0.293 (5)	0.073*
H12	0.782 (2)	0.385 (3)	0.211 (5)	0.073*
O2W	0.75883 (13)	0.19813 (16)	0.4850 (3)	0.0376 (5)
H21	0.771 (2)	0.2564 (10)	0.510 (4)	0.056*
H22	0.7864 (19)	0.1600 (19)	0.545 (4)	0.056*
O3W	0.75775 (13)	0.04584 (14)	0.2516 (4)	0.0444 (5)
H31	0.7904 (18)	0.013 (3)	0.226 (6)	0.067*
H32	0.7261 (18)	0.010 (3)	0.276 (6)	0.067*
O4W	0.75304 (12)	0.19686 (15)	0.0065 (3)	0.0348 (5)
H41	0.751 (2)	0.2540 (13)	−0.033 (4)	0.052*
H42	0.7221 (18)	0.162 (2)	−0.053 (4)	0.052*
O5W	0.86746 (11)	0.19782 (15)	0.2686 (3)	0.0348 (5)
H51	0.8928 (18)	0.201 (3)	0.3561 (19)	0.052*
H52	0.883 (2)	0.237 (3)	0.210 (3)	0.052*
O6W	0.64320 (11)	0.19108 (14)	0.2156 (3)	0.0309 (4)
H61	0.631 (2)	0.223 (3)	0.287 (3)	0.046*
H62	0.629 (2)	0.221 (2)	0.133 (2)	0.046*
O7W	0.71149 (19)	0.6167 (2)	0.3620 (4)	0.0693 (8)
H71	0.712 (3)	0.566 (3)	0.414 (6)	0.104*
H72	0.746 (2)	0.616 (4)	0.314 (5)	0.104*
O8W	0.81452 (15)	0.64657 (18)	0.1837 (3)	0.0516 (6)
H81	0.832 (2)	0.5909 (17)	0.168 (6)	0.077*
H82	0.8486 (16)	0.682 (3)	0.231 (5)	0.077*
O9W	0.45875 (19)	0.2664 (5)	0.0292 (4)	0.1126 (15)
H91	0.456 (5)	0.247 (6)	0.117 (4)	0.169*
H92	0.494 (4)	0.237 (7)	0.002 (9)	0.169*
O10W	0.59157 (12)	0.2904 (2)	−0.0509 (3)	0.0421 (5)
H101	0.622 (2)	0.329 (2)	−0.077 (4)	0.063*
H102	0.585 (2)	0.242 (2)	−0.111 (4)	0.063*
C1	0.60292 (15)	0.3899 (2)	0.4351 (4)	0.0316 (6)
C2	0.56550 (18)	0.4557 (2)	0.5315 (4)	0.0398 (7)
H2A	0.5485	0.5136	0.4716	0.048*
H2B	0.6015	0.4777	0.6179	0.048*
C3	0.41322 (17)	0.4397 (2)	0.4608 (4)	0.0353 (7)
H3A	0.3710	0.4386	0.5074	0.042*
H3B	0.4198	0.5071	0.4307	0.042*
C4	0.39701 (13)	0.37693 (18)	0.3173 (3)	0.0247 (5)
C5	0.40418 (15)	0.0819 (2)	0.5766 (3)	0.0276 (5)
C6	0.44673 (16)	0.0137 (2)	0.4915 (3)	0.0318 (6)
H6A	0.4126	−0.0197	0.4124	0.038*
H6B	0.4698	−0.0362	0.5622	0.038*
C7	0.60916 (13)	0.11060 (19)	0.6845 (3)	0.0248 (5)
C8	0.59746 (16)	0.0475 (2)	0.5424 (3)	0.0321 (6)
H8A	0.5978	−0.0210	0.5731	0.039*
H8B	0.6382	0.0572	0.4925	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02393 (15)	0.01925 (16)	0.02064 (14)	0.00472 (13)	0.00543 (11)	0.00147 (13)
Co2	0.02136 (14)	0.02034 (16)	0.02750 (15)	0.00004 (12)	0.00615 (12)	0.00000 (13)
S1	0.0264 (3)	0.0259 (3)	0.0225 (3)	0.0038 (2)	0.0062 (2)	−0.0031 (2)
S2	0.0306 (3)	0.0268 (3)	0.0203 (3)	0.0052 (2)	0.0051 (2)	−0.0030 (2)
O1	0.0363 (10)	0.0275 (10)	0.0447 (11)	0.0001 (8)	0.0219 (9)	−0.0066 (8)
O2	0.0666 (17)	0.0410 (14)	0.104 (2)	−0.0081 (12)	0.0631 (18)	−0.0073 (14)
O3	0.0382 (10)	0.0246 (9)	0.0259 (9)	0.0114 (8)	0.0019 (8)	−0.0031 (7)
O4	0.0375 (11)	0.0308 (10)	0.0320 (11)	0.0121 (8)	−0.0018 (9)	−0.0002 (8)
O5	0.0366 (10)	0.0242 (9)	0.0430 (11)	0.0008 (8)	0.0213 (9)	−0.0030 (9)
O6	0.0427 (11)	0.0304 (11)	0.0578 (14)	−0.0002 (9)	0.0252 (10)	0.0057 (10)
O7	0.0432 (11)	0.0285 (10)	0.0254 (9)	0.0162 (8)	−0.0017 (8)	−0.0049 (8)
O8	0.0317 (10)	0.0308 (10)	0.0290 (11)	0.0083 (8)	−0.0026 (8)	−0.0004 (8)
O1W	0.0592 (13)	0.0229 (10)	0.0758 (16)	−0.0026 (11)	0.0435 (12)	−0.0015 (12)
O2W	0.0467 (12)	0.0348 (11)	0.0289 (10)	0.0014 (9)	0.0018 (10)	0.0009 (8)
O3W	0.0284 (9)	0.0185 (9)	0.0899 (16)	0.0008 (8)	0.0198 (10)	−0.0002 (12)
O4W	0.0392 (11)	0.0359 (12)	0.0292 (10)	−0.0013 (8)	0.0064 (9)	−0.0026 (8)
O5W	0.0235 (9)	0.0429 (12)	0.0384 (12)	−0.0063 (8)	0.0072 (9)	0.0058 (9)
O6W	0.0275 (10)	0.0327 (10)	0.0327 (10)	0.0042 (8)	0.0065 (9)	−0.0027 (8)
O7W	0.087 (2)	0.0499 (15)	0.078 (2)	0.0073 (15)	0.0313 (17)	−0.0139 (14)
O8W	0.0566 (14)	0.0336 (12)	0.0609 (16)	0.0021 (10)	0.0030 (12)	−0.0041 (11)
O9W	0.0498 (17)	0.246 (4)	0.0406 (16)	0.022 (2)	0.0068 (15)	−0.022 (2)
O10W	0.0409 (11)	0.0512 (13)	0.0338 (11)	0.0057 (10)	0.0065 (10)	−0.0110 (10)
C1	0.0323 (14)	0.0249 (13)	0.0419 (16)	0.0005 (11)	0.0180 (13)	−0.0007 (11)
C2	0.0387 (15)	0.0305 (15)	0.055 (2)	−0.0056 (12)	0.0212 (14)	−0.0114 (14)
C3	0.0349 (14)	0.0317 (14)	0.0363 (16)	0.0129 (11)	0.0000 (13)	−0.0073 (12)
C4	0.0259 (12)	0.0232 (11)	0.0253 (12)	0.0035 (9)	0.0061 (10)	0.0003 (10)
C5	0.0295 (12)	0.0253 (12)	0.0275 (13)	0.0035 (10)	0.0041 (11)	0.0021 (10)
C6	0.0416 (15)	0.0213 (12)	0.0339 (14)	0.0011 (10)	0.0112 (12)	−0.0018 (10)
C7	0.0238 (11)	0.0230 (11)	0.0276 (13)	0.0032 (9)	0.0053 (11)	0.0000 (10)
C8	0.0319 (13)	0.0335 (14)	0.0282 (14)	0.0124 (11)	−0.0007 (11)	−0.0077 (11)

Geometric parameters (Å, º) top

Co1—O7	2.0472 (19)	O3W—H31	0.831 (11)
Co1—O1	2.049 (2)	O3W—H32	0.830 (11)
Co1—O3	2.0532 (19)	O4W—H41	0.851 (11)
Co1—O5	2.054 (2)	O4W—H42	0.850 (11)
Co1—S1	2.4746 (7)	O5W—H51	0.834 (11)
Co1—S2	2.4801 (7)	O5W—H52	0.835 (11)
Co2—O3W	2.0224 (19)	O6W—H61	0.834 (11)
Co2—O5W	2.063 (2)	O6W—H62	0.840 (11)
Co2—O1W	2.075 (2)	O7W—H71	0.834 (11)
Co2—O6W	2.101 (2)	O7W—H72	0.841 (11)
Co2—O2W	2.120 (2)	O8W—H81	0.847 (11)
Co2—O4W	2.145 (2)	O8W—H82	0.844 (11)
S1—C3	1.797 (3)	O9W—H91	0.843 (11)
S1—C2	1.802 (3)	O9W—H92	0.845 (11)
S2—C8	1.807 (3)	O10W—H101	0.843 (11)
S2—C6	1.806 (3)	O10W—H102	0.839 (11)
O1—C1	1.283 (3)	C1—C2	1.511 (4)
O2—C1	1.227 (4)	C2—H2A	0.9700
O3—C4	1.277 (3)	C2—H2B	0.9700
O4—C4	1.233 (3)	C3—C4	1.522 (4)
O5—C5	1.261 (4)	C3—H3A	0.9700
O6—C5	1.238 (4)	C3—H3B	0.9700
O7—C7	1.262 (3)	C5—C6	1.525 (4)
O8—C7	1.246 (3)	C6—H6A	0.9700
O1W—H11	0.843 (11)	C6—H6B	0.9700
O1W—H12	0.843 (11)	C7—C8	1.514 (4)
O2W—H21	0.843 (11)	C8—H8A	0.9700
O2W—H22	0.845 (11)	C8—H8B	0.9700

O7—Co1—O1	91.74 (10)	Co2—O4W—H41	115 (3)
O7—Co1—O3	177.79 (10)	Co2—O4W—H42	120 (3)
O1—Co1—O3	89.88 (9)	H41—O4W—H42	106 (2)
O7—Co1—O5	89.64 (10)	Co2—O5W—H51	118 (3)
O1—Co1—O5	177.55 (10)	Co2—O5W—H52	115 (3)
O3—Co1—O5	88.79 (9)	H51—O5W—H52	111 (2)
O7—Co1—S1	95.40 (6)	Co2—O6W—H61	108 (3)
O1—Co1—S1	83.40 (6)	Co2—O6W—H62	104 (3)
O3—Co1—S1	83.29 (5)	H61—O6W—H62	110 (2)
O5—Co1—S1	98.49 (6)	H71—O7W—H72	111 (5)
O7—Co1—S2	82.13 (5)	H81—O8W—H82	108 (2)
O1—Co1—S2	95.56 (6)	H91—O9W—H92	109 (9)
O3—Co1—S2	99.21 (6)	H101—O10W—H102	109 (2)
O5—Co1—S2	82.63 (6)	O2—C1—O1	124.3 (3)
S1—Co1—S2	177.30 (3)	O2—C1—C2	116.4 (3)
O3W—Co2—O5W	90.64 (9)	O1—C1—C2	119.3 (3)
O3W—Co2—O1W	178.12 (12)	C1—C2—S1	118.1 (2)
O5W—Co2—O1W	91.07 (10)	C1—C2—H2A	107.8
O3W—Co2—O6W	89.20 (8)	S1—C2—H2A	107.8
O5W—Co2—O6W	177.57 (10)	C1—C2—H2B	107.8
O1W—Co2—O6W	89.06 (10)	S1—C2—H2B	107.8
O3W—Co2—O2W	90.26 (12)	H2A—C2—H2B	107.1
O5W—Co2—O2W	95.05 (9)	C4—C3—S1	117.2 (2)
O1W—Co2—O2W	90.35 (11)	C4—C3—H3A	108.0
O6W—Co2—O2W	87.38 (9)	S1—C3—H3A	108.0
O3W—Co2—O4W	91.75 (12)	C4—C3—H3B	108.0
O5W—Co2—O4W	85.52 (9)	S1—C3—H3B	108.0
O1W—Co2—O4W	87.63 (11)	H3A—C3—H3B	107.2
O6W—Co2—O4W	92.06 (9)	O4—C4—O3	123.4 (2)
O2W—Co2—O4W	177.91 (8)	O4—C4—C3	117.6 (2)
C3—S1—C2	103.43 (17)	O3—C4—C3	119.0 (2)
C3—S1—Co1	94.45 (10)	O6—C5—O5	123.9 (3)
C2—S1—Co1	95.16 (10)	O6—C5—C6	116.4 (2)
C8—S2—C6	102.94 (15)	O5—C5—C6	119.7 (3)
C8—S2—Co1	93.51 (9)	C5—C6—S2	116.86 (19)
C6—S2—Co1	95.67 (9)	C5—C6—H6A	108.1
C1—O1—Co1	123.92 (19)	S2—C6—H6A	108.1
C4—O3—Co1	123.34 (17)	C5—C6—H6B	108.1
C5—O5—Co1	124.48 (19)	S2—C6—H6B	108.1
C7—O7—Co1	123.53 (18)	H6A—C6—H6B	107.3
Co2—O1W—H11	122 (4)	O8—C7—O7	123.7 (3)
Co2—O1W—H12	126 (4)	O8—C7—C8	117.1 (2)
H11—O1W—H12	108 (2)	O7—C7—C8	119.1 (2)
Co2—O2W—H21	104 (3)	C7—C8—S2	116.28 (18)
Co2—O2W—H22	121 (3)	C7—C8—H8A	108.2
H21—O2W—H22	108 (2)	S2—C8—H8A	108.2
Co2—O3W—H31	123 (3)	C7—C8—H8B	108.2
Co2—O3W—H32	126 (3)	S2—C8—H8B	108.2
H31—O3W—H32	111 (2)	H8A—C8—H8B	107.4

O7—Co1—S1—C3	−167.18 (14)	O1—Co1—O7—C7	−78.5 (2)
O1—Co1—S1—C3	101.68 (14)	O5—Co1—O7—C7	99.5 (2)
O3—Co1—S1—C3	11.02 (13)	S1—Co1—O7—C7	−162.0 (2)
O5—Co1—S1—C3	−76.74 (14)	S2—Co1—O7—C7	16.9 (2)
O7—Co1—S1—C2	88.87 (14)	Co1—O1—C1—O2	178.9 (3)
O1—Co1—S1—C2	−2.26 (14)	Co1—O1—C1—C2	0.1 (4)
O3—Co1—S1—C2	−92.93 (14)	O2—C1—C2—S1	178.4 (3)
O5—Co1—S1—C2	179.32 (14)	O1—C1—C2—S1	−2.7 (4)
O7—Co1—S2—C8	−17.84 (13)	C3—S1—C2—C1	−92.7 (3)
O1—Co1—S2—C8	73.15 (13)	Co1—S1—C2—C1	3.2 (3)
O3—Co1—S2—C8	163.94 (13)	C2—S1—C3—C4	79.5 (3)
O5—Co1—S2—C8	−108.50 (13)	Co1—S1—C3—C4	−16.9 (3)
O7—Co1—S2—C6	85.55 (12)	Co1—O3—C4—O4	178.4 (2)
O1—Co1—S2—C6	176.55 (12)	Co1—O3—C4—C3	−4.2 (4)
O3—Co1—S2—C6	−92.67 (12)	S1—C3—C4—O4	−165.9 (2)
O5—Co1—S2—C6	−5.11 (12)	S1—C3—C4—O3	16.6 (4)
O7—Co1—O1—C1	−93.6 (2)	Co1—O5—C5—O6	172.7 (2)
O3—Co1—O1—C1	84.9 (2)	Co1—O5—C5—C6	−8.8 (4)
S1—Co1—O1—C1	1.6 (2)	O6—C5—C6—S2	−179.0 (2)
S2—Co1—O1—C1	−175.9 (2)	O5—C5—C6—S2	2.3 (4)
O1—Co1—O3—C4	−89.2 (2)	C8—S2—C6—C5	98.2 (2)
O5—Co1—O3—C4	92.9 (2)	Co1—S2—C6—C5	3.3 (2)
S1—Co1—O3—C4	−5.8 (2)	Co1—O7—C7—O8	172.3 (2)
S2—Co1—O3—C4	175.2 (2)	Co1—O7—C7—C8	−6.5 (4)
O7—Co1—O5—C5	−73.5 (2)	O8—C7—C8—S2	166.7 (2)
O3—Co1—O5—C5	108.1 (2)	O7—C7—C8—S2	−14.4 (4)
S1—Co1—O5—C5	−168.9 (2)	C6—S2—C8—C7	−75.0 (3)
S2—Co1—O5—C5	8.6 (2)	Co1—S2—C8—C7	21.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O2	0.84 (1)	1.89 (2)	2.707 (4)	162 (5)
O1w—H12···O6ⁱ	0.84 (1)	1.95 (1)	2.791 (4)	173 (5)
O2w—H21···O8wⁱⁱ	0.84 (1)	2.08 (2)	2.824 (3)	147 (3)
O2w—H22···O4ⁱⁱⁱ	0.85 (1)	1.98 (1)	2.813 (3)	170 (4)
O3w—H31···O4^iv	0.83 (1)	1.87 (2)	2.671 (3)	163 (5)
O3w—H32···O8^v	0.83 (1)	1.85 (2)	2.666 (3)	168 (5)
O4w—H41···O7w^vi	0.85 (1)	2.06 (2)	2.880 (4)	162 (4)
O4w—H42···O8^vii	0.85 (1)	1.96 (1)	2.805 (3)	173 (4)
O5w—H51···O9wⁱⁱⁱ	0.83 (1)	1.84 (2)	2.657 (4)	166 (3)
O5w—H52···O5ⁱ	0.84 (1)	1.89 (1)	2.721 (3)	179 (5)
O6w—H61···O1	0.83 (1)	1.91 (2)	2.726 (3)	166 (4)
O6w—H62···O10w	0.84 (1)	1.91 (1)	2.746 (3)	177 (4)
O7w—H71···O2	0.83 (1)	2.18 (4)	2.828 (4)	135 (5)
O7w—H72···O8w	0.84 (1)	1.96 (2)	2.777 (4)	165 (5)
O8w—H81···O6ⁱ	0.85 (1)	1.91 (1)	2.751 (3)	172 (5)
O8w—H82···O3^viii	0.84 (1)	2.13 (1)	2.965 (3)	168 (4)
O9w—H91···O3	0.84 (1)	2.08 (5)	2.797 (4)	142 (8)
O9w—H92···O10w	0.85 (1)	2.12 (8)	2.759 (5)	132 (9)
O10w—H101···O7w^vi	0.84 (1)	2.02 (2)	2.831 (4)	162 (4)
O10w—H102···O7^vii	0.84 (1)	1.93 (2)	2.701 (3)	152 (4)

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

Experimental details

Crystal data
Chemical formula	[Co(H₂O)₆][Co(C₄H₄O₄S)₂]·4H₂O
M_r	594.28
Crystal system, space group	Monoclinic, Cc
Temperature (K)	293
a, b, c (Å)	18.8627 (9), 13.5779 (7), 8.9535 (4)
β (°)	101.403 (1)
V (Å³)	2247.87 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.74
Crystal size (mm)	0.18 × 0.14 × 0.14

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.745, 0.793
No. of measured, independent and observed [I > 2σ(I)] reflections	10837, 4978, 4802
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.067, 1.01
No. of reflections	4978
No. of parameters	331
No. of restraints	56
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.58
Absolute structure	Flack (1983), 2402 Friedel pairs
Absolute structure parameter	0.02 (1)

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O2	0.84 (1)	1.89 (2)	2.707 (4)	162 (5)
O1w—H12···O6ⁱ	0.84 (1)	1.95 (1)	2.791 (4)	173 (5)
O2w—H21···O8wⁱⁱ	0.84 (1)	2.08 (2)	2.824 (3)	147 (3)
O2w—H22···O4ⁱⁱⁱ	0.85 (1)	1.98 (1)	2.813 (3)	170 (4)
O3w—H31···O4^iv	0.83 (1)	1.87 (2)	2.671 (3)	163 (5)
O3w—H32···O8^v	0.83 (1)	1.85 (2)	2.666 (3)	168 (5)
O4w—H41···O7w^vi	0.85 (1)	2.06 (2)	2.880 (4)	162 (4)
O4w—H42···O8^vii	0.85 (1)	1.96 (1)	2.805 (3)	173 (4)
O5w—H51···O9wⁱⁱⁱ	0.83 (1)	1.84 (2)	2.657 (4)	166 (3)
O5w—H52···O5ⁱ	0.84 (1)	1.89 (1)	2.721 (3)	179 (5)
O6w—H61···O1	0.83 (1)	1.91 (2)	2.726 (3)	166 (4)
O6w—H62···O10w	0.84 (1)	1.91 (1)	2.746 (3)	177 (4)
O7w—H71···O2	0.83 (1)	2.18 (4)	2.828 (4)	135 (5)
O7w—H72···O8w	0.84 (1)	1.96 (2)	2.777 (4)	165 (5)
O8w—H81···O6ⁱ	0.85 (1)	1.91 (1)	2.751 (3)	172 (5)
O8w—H82···O3^viii	0.84 (1)	2.13 (1)	2.965 (3)	168 (4)
O9w—H91···O3	0.84 (1)	2.08 (5)	2.797 (4)	142 (8)
O9w—H92···O10w	0.85 (1)	2.12 (8)	2.759 (5)	132 (9)
O10w—H101···O7w^vi	0.84 (1)	2.02 (2)	2.831 (4)	162 (4)
O10w—H102···O7^vii	0.84 (1)	1.93 (2)	2.701 (3)	152 (4)

Acknowledgements

This work was supported by the Key Project of the Natural Science Foundation of Heilongjiang Province (No. ZD200903), the Innovation Team of the Education Bureau of Heilongjiang Province (No. 2010 t d03), the Key Project of the Education Bureau of Heilongjiang Province (No. 12511z023) and the University of Malaya.

References

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