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Acta Cryst. (2007). E63, m2597    [ doi:10.1107/S1600536807045904 ]

Hexaaquacobalt(II) 4-hydroxybenzenesulfonate dihydrate

J.-M. Du, Q. Li, W. Li, H.-M. Lin and G.-C. Guo

Abstract top

In the title compound, [Co(H2O)6](C6H6O4S)2·2H2O, the CoII ion lies on an inversion center and is octahedrally coordinated by six water molecules. Two independent water molecules in the [Co(H2O)6]2+ cation are disordered over two sites, with half occupancy for each site. The 4-hydroxybenzenesulfonate (L-) anion does not coordinate to the cobalt ion but rather acts as a counter-ion. The asymmetric unit is completed by an uncoordinated water molecule. The crystal structure is composed of alternating layers of [Co(H2O)6]2+ cations and L- anions, with the lattice water molecules located in channels along the a direction. The [Co(H2O)6]2+ cations, L- anions and solvent water molecules are connected through a complex pattern of hydrogen-bonding interactions.

Comment top

The crystal structures of [Co(H2O)6]2+ with 3-carboxy-4-hydroxybenzenesulfonate as counter-ion (Ma et al., 2003) and [Co(NH3)6]3+ with 4-hydroxybenzenesulfonate (Sharma et al., 2006) have been reported. We have now characterized the title compound, [Co(H2O)6]2+ 4-hydroxybenzenesulfonate as a dihydrate, for which we report the synthesis and the crystal structure (Scheme, I).

As shown in Fig. 1, the asymmetric unit of (I) consists of one L− anion, one-half hexaaquacobalt(II) cation as well as one lattice water molecule. The CoII ion is located on an inversion center, and all other atoms are in general positions. The Co1 atom displays a slightly distorted octahedral environment, coordinated by six water molecules with the Co—O bond lengths ranging from 2.0574 (11) to 2.1032 (10) Å, similar to those found in the above cited hexaaquacobalt compound (Ma et al., 2003). The 4-hydroxybenzenesulfonate anion acts as a counter-ion, with normal bond lengths (Sharma et al., 2006).

The crystal structure of (I) can be regarded as a H-bonding 3-D framework, composed of alternating layers of [Co(H2O)6]2+ cations and L− sulfonate anions, with the lattice water molecules located in the channels along the [100] direction (Fig. 2). Within the sulfonate layers, the L− anions are connected to form a zigzag chain along the [010] direction through the inter-molecular O3···O4 H-bonds, with O3···O4 separation of 2.7543 (10) Å. The chains are bridged by hexaaquacobalt(II) cations through the O1W···O4 and O2W···O3 H-bonds [O1W···O4 = 2.7609 (9); O2WA···O3 = 2.8625 (12) Å] to form the 3-D framework. The O4W lattice water molecules H-bond to the O2W and O3W coordinated water molecules, and O1 and O2 atoms of L− anions, to further stabilize the crystal structure.

Related literature top

For related literature, see: Ma et al. (2003); Sharma et al. (2006).

Experimental top

A mixture of HL (549 mg, 1 mmol) and CoCO3 (60 mg, 0.5 mmol) was added into 15 ml water and stirred at room temperature for 1 h. Red crystals of (I) suitable for single-crystal X-ray diffraction analysis were obtained after leaving the solution to stand at room temperature for several days (56% yield based on CoCO3).

Refinement top

Water molecules O2W and O3W were found to be disordered over two positions, and refined with site occupancies 1/2 for O2WA, O2WB, O3WA and O3WB. Water H atoms and hydroxyl H4 atom were located in a difference Fourier map and refined with a regularized geometry, the O—H and H···H distances being restrained to 0.85 (1) and 1.34 (2) Å, respectively, and with Uiso(H) = 1.5Ueq(carrier O). The C-bonded H atoms were placed in idealized positions and allowed to ride on their respective parent atoms, with C—H distances constrained to 0.93 Å, and Uiso(H) = 1.2Ueq(carrier C).

Computing details top

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXTL (Siemens, 1994); program(s) used to refine structure: SHELXTL (Siemens, 1994); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXTL (Siemens, 1994).

Figures top
[Figure 1] Fig. 1. ORTEP drawing with 30% probability thermal ellipsoids. Hydrogen atoms are omitted for clarity, as disordered 'B' sites for O2W and O3W.
[Figure 2] Fig. 2. 3-D packing diagram viewed along the [100] direction with the dashed lines representing the O···O contacts for H-bonds. The H-bonds around the O4W atoms are omitted for clarity. All H atoms and disordered O atoms have been omitted.
Hexaaquacobalt(II) 4-hydroxybenzenesulfonate dihydrate top
Crystal data top
[Co(H2O)6](C6H6O4S)2·2H2OF000 = 570
Mr = 549.38Dx = 1.704 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5365 reflections
a = 5.843 (2) Åθ = 2.3–27.5º
b = 7.224 (3) ŵ = 1.07 mm−1
c = 25.459 (9) ÅT = 293 (2) K
β = 94.8370 (10)ºPrism, red
V = 1070.8 (7) Å30.40 × 0.30 × 0.20 mm
Z = 2
Data collection top
Rigaku Mercury CCD
diffractometer		2427 independent reflections
Radiation source: rotating anode generator2051 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.031
T = 293(2) Kθmax = 27.5º
ω scansθmin = 2.9º
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2002)		h = −7→7
Tmin = 0.673, Tmax = 0.814k = −7→9
7850 measured reflectionsl = −32→32
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.090  w = 1/[σ2(Fo2) + (0.0458P)2 + 0.0596P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.009
2427 reflectionsΔρmax = 0.75 e Å−3
199 parametersΔρmin = −0.57 e Å−3
18 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Co(H2O)6](C6H6O4S)2·2H2OV = 1070.8 (7) Å3
Mr = 549.38Z = 2
Monoclinic, P21/cMo Kα
a = 5.843 (2) ŵ = 1.07 mm−1
b = 7.224 (3) ÅT = 293 (2) K
c = 25.459 (9) Å0.40 × 0.30 × 0.20 mm
β = 94.8370 (10)º
Data collection top
Rigaku Mercury CCD
diffractometer		2427 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2002)		2051 reflections with I > 2σ(I)
Tmin = 0.673, Tmax = 0.814Rint = 0.031
7850 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03418 restraints
wR(F2) = 0.090H atoms treated by a mixture of
independent and constrained refinement
S = 1.03Δρmax = 0.75 e Å−3
2427 reflectionsΔρmin = −0.57 e Å−3
199 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Co10.00001.00001.00000.01164 (3)
O1W−0.14944 (9)0.91860 (7)0.926835 (19)0.03708 (16)
H1WA−0.1214 (11)0.8278 (5)0.90746 (18)0.056*
H1WB−0.2298 (8)0.9937 (5)0.9076 (2)0.056*
O2WA0.03598 (15)1.26230 (12)0.96743 (3)0.0185 (2)0.50
H2WA0.0732 (10)1.2458 (13)0.93638 (13)0.028*0.50
H2WB−0.0793 (6)1.3331 (7)0.9643 (4)0.028*0.50
O2WB0.16007 (14)1.23240 (13)0.97331 (3)0.0186 (2)0.50
H2WC0.2844 (6)1.2132 (14)0.99136 (19)0.028*0.50
H2WD0.1907 (13)1.2767 (10)0.94403 (13)0.028*0.50
O3WA0.29704 (14)0.84098 (11)0.99253 (3)0.0149 (2)0.50
H3WA0.4229 (6)0.8969 (7)0.9974 (4)0.022*0.50
H3WB0.3033 (15)0.7408 (5)1.0096 (2)0.022*0.50
O3WB0.31335 (15)0.92872 (14)0.97466 (4)0.0284 (3)0.50
H3WC0.3241 (16)0.8382 (5)0.95388 (19)0.043*0.50
H3WD0.4383 (6)0.9879 (7)0.9752 (5)0.043*0.50
S10.19699 (3)0.55915 (2)0.865589 (6)0.01538 (4)
O1−0.04225 (7)0.60173 (6)0.873004 (17)0.01916 (12)
O20.36032 (8)0.67549 (6)0.897272 (17)0.02085 (12)
O30.24658 (8)0.36089 (6)0.873832 (16)0.02103 (12)
O40.35295 (8)0.67622 (7)0.642301 (17)0.02172 (12)
H40.4713 (12)0.7379 (11)0.6375 (3)0.033*
C10.23829 (10)0.60609 (8)0.79905 (2)0.01407 (15)
C20.07181 (11)0.55567 (9)0.75978 (2)0.01730 (16)
H2A−0.06620.50510.76860.021*
C30.11117 (11)0.58080 (9)0.70694 (2)0.01842 (17)
H3A−0.00050.54860.68030.022*
C40.32027 (11)0.65489 (8)0.69470 (2)0.01541 (15)
C50.48649 (11)0.70370 (9)0.73403 (2)0.01702 (16)
H5A0.62510.75320.72520.020*
C60.44820 (11)0.67946 (8)0.78660 (2)0.01726 (16)
H6A0.56040.71150.81310.021*
O4W−0.30549 (11)1.49300 (7)0.96527 (3)0.0577 (2)
H4WA−0.2574 (11)1.5769 (6)0.98621 (17)0.087*
H4WB−0.4113 (7)1.5371 (9)0.94433 (18)0.087*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.01328 (5)0.01141 (5)0.01034 (5)0.00068 (4)0.00169 (4)0.00001 (4)
O1W0.0524 (3)0.0345 (3)0.0210 (2)0.0267 (2)−0.0169 (2)−0.0160 (2)
O2WA0.0286 (4)0.0132 (4)0.0146 (4)0.0043 (4)0.0066 (3)0.0016 (3)
O2WB0.0186 (4)0.0219 (4)0.0154 (4)−0.0024 (4)0.0016 (3)0.0043 (4)
O3WA0.0150 (4)0.0159 (4)0.0139 (4)0.0008 (3)0.0016 (3)−0.0006 (3)
O3WB0.0135 (4)0.0342 (5)0.0379 (5)−0.0018 (4)0.0050 (4)−0.0190 (5)
S10.02079 (7)0.01546 (7)0.01016 (6)0.00447 (6)0.00284 (6)−0.00033 (6)
O10.0213 (2)0.0205 (2)0.01664 (19)0.00334 (19)0.00750 (17)−0.00017 (18)
O20.0234 (2)0.0258 (2)0.01320 (19)0.0017 (2)0.00036 (18)−0.00523 (18)
O30.0315 (2)0.0187 (2)0.01380 (19)0.0059 (2)0.00675 (18)0.00249 (18)
O40.0250 (2)0.0289 (2)0.01156 (19)−0.0076 (2)0.00335 (18)0.00095 (18)
C10.0184 (3)0.0134 (3)0.0106 (2)0.0033 (2)0.0022 (2)−0.0001 (2)
C20.0147 (3)0.0210 (3)0.0165 (3)0.0015 (3)0.0033 (2)0.0027 (2)
C30.0163 (3)0.0252 (3)0.0133 (3)−0.0005 (3)−0.0015 (2)0.0009 (3)
C40.0209 (3)0.0144 (3)0.0114 (2)0.0020 (3)0.0041 (2)0.0006 (2)
C50.0171 (3)0.0155 (3)0.0186 (3)−0.0037 (3)0.0025 (2)0.0023 (2)
C60.0213 (3)0.0135 (3)0.0164 (3)−0.0029 (3)−0.0022 (3)−0.0006 (2)
O4W0.0375 (3)0.0214 (3)0.1061 (5)−0.0087 (2)−0.0417 (3)0.0174 (3)
Geometric parameters (Å, °) top
Co1—O3WB2.0574 (11)O3WB—H3WD0.845 (4)
Co1—O3WBi2.0574 (11)S1—O11.4591 (7)
Co1—O2WB2.0645 (11)S1—O21.4621 (6)
Co1—O2WBi2.0645 (11)S1—O31.4728 (8)
Co1—O1W2.0745 (8)S1—C11.7640 (8)
Co1—O1Wi2.0745 (8)O4—C41.3721 (9)
Co1—O2WA2.0861 (11)O4—H40.840 (8)
Co1—O2WAi2.0861 (11)C1—C21.3836 (9)
Co1—O3WA2.1032 (10)C1—C61.3969 (10)
Co1—O3WAi2.1032 (10)C2—C31.3956 (10)
O1W—H1WA0.845 (4)C2—H2A0.9300
O1W—H1WB0.846 (4)C3—C41.3931 (10)
O2WA—H2WA0.846 (4)C3—H3A0.9300
O2WA—H2WB0.844 (4)C4—C51.3806 (9)
O2WB—H2WC0.838 (4)C5—C61.3868 (10)
O2WB—H2WD0.844 (4)C5—H5A0.9300
O3WA—H3WA0.839 (4)C6—H6A0.9300
O3WA—H3WB0.843 (4)O4W—H4WA0.840 (4)
O3WB—H3WC0.847 (4)O4W—H4WB0.844 (4)
O3WB—Co1—O3WBi180.000 (1)O2WAi—Co1—O3WAi110.40 (4)
O3WB—Co1—O2WB70.15 (4)O3WA—Co1—O3WAi180.00 (4)
O3WBi—Co1—O2WB109.85 (4)Co1—O1W—H1WA131.0 (4)
O3WB—Co1—O2WBi109.85 (4)Co1—O1W—H1WB120.6 (3)
O3WBi—Co1—O2WBi70.15 (4)H1WA—O1W—H1WB106.6 (5)
O2WB—Co1—O2WBi180.0Co1—O2WA—H2WA106.6 (6)
O3WB—Co1—O1W88.04 (4)Co1—O2WA—H2WB118.8 (4)
O3WBi—Co1—O1W91.96 (4)H2WA—O2WA—H2WB105.2 (7)
O2WB—Co1—O1W95.91 (3)Co1—O2WB—H2WC94.6 (6)
O2WBi—Co1—O1W84.09 (3)Co1—O2WB—H2WD137.3 (5)
O3WB—Co1—O1Wi91.96 (4)H2WC—O2WB—H2WD108.0 (7)
O3WBi—Co1—O1Wi88.04 (4)Co1—O3WA—H3WA116.3 (4)
O2WB—Co1—O1Wi84.09 (3)Co1—O3WA—H3WB115.0 (6)
O2WBi—Co1—O1Wi95.91 (3)H3WA—O3WA—H3WB109.7 (8)
O1W—Co1—O1Wi180.0Co1—O3WB—H3WC120.3 (7)
O3WB—Co1—O2WA88.88 (4)Co1—O3WB—H3WD131.2 (5)
O3WBi—Co1—O2WA91.12 (4)H3WC—O3WB—H3WD107.0 (9)
O2WB—Co1—O2WA21.07 (3)O1—S1—O2113.29 (3)
O2WBi—Co1—O2WA158.93 (3)O1—S1—O3111.45 (3)
O1W—Co1—O2WA87.10 (3)O2—S1—O3111.65 (3)
O1Wi—Co1—O2WA92.90 (3)O1—S1—C1107.09 (3)
O3WB—Co1—O2WAi91.12 (4)O2—S1—C1106.47 (3)
O3WBi—Co1—O2WAi88.88 (4)O3—S1—C1106.41 (3)
O2WB—Co1—O2WAi158.93 (3)C4—O4—H4112.6 (5)
O2WBi—Co1—O2WAi21.07 (3)C2—C1—C6120.88 (6)
O1W—Co1—O2WAi92.90 (3)C2—C1—S1119.90 (5)
O1Wi—Co1—O2WAi87.10 (3)C6—C1—S1118.99 (4)
O2WA—Co1—O2WAi180.000 (1)C1—C2—C3119.96 (6)
O3WB—Co1—O3WA21.88 (4)C1—C2—H2A120.0
O3WBi—Co1—O3WA158.12 (4)C3—C2—H2A120.0
O2WB—Co1—O3WA90.81 (4)C4—C3—C2118.98 (6)
O2WBi—Co1—O3WA89.19 (4)C4—C3—H3A120.5
O1W—Co1—O3WA92.99 (3)C2—C3—H3A120.5
O1Wi—Co1—O3WA87.01 (3)O4—C4—C5121.96 (6)
O2WA—Co1—O3WA110.40 (4)O4—C4—C3117.21 (5)
O2WAi—Co1—O3WA69.60 (4)C5—C4—C3120.83 (6)
O3WB—Co1—O3WAi158.12 (4)C4—C5—C6120.46 (6)
O3WBi—Co1—O3WAi21.88 (4)C4—C5—H5A119.8
O2WB—Co1—O3WAi89.19 (4)C6—C5—H5A119.8
O2WBi—Co1—O3WAi90.81 (4)C5—C6—C1118.89 (5)
O1W—Co1—O3WAi87.01 (3)C5—C6—H6A120.6
O1Wi—Co1—O3WAi92.99 (3)C1—C6—H6A120.6
O2WA—Co1—O3WAi69.60 (4)H4WA—O4W—H4WB108.5 (6)
O1—S1—C1—C2−41.52 (6)C1—C2—C3—C40.72 (10)
O2—S1—C1—C2−163.00 (5)C2—C3—C4—O4179.56 (6)
O3—S1—C1—C277.78 (6)C2—C3—C4—C5−0.24 (10)
O1—S1—C1—C6143.96 (5)O4—C4—C5—C6−179.69 (6)
O2—S1—C1—C622.48 (6)C3—C4—C5—C60.10 (10)
O3—S1—C1—C6−96.74 (6)C4—C5—C6—C1−0.42 (9)
C6—C1—C2—C3−1.07 (10)C2—C1—C6—C50.91 (9)
S1—C1—C2—C3−175.48 (5)S1—C1—C6—C5175.37 (5)
Symmetry codes: (i) −x, −y+2, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O10.845 (4)1.928 (4)2.7667 (11)171.4 (4)
O1W—H1WB···O4ii0.846 (4)1.927 (4)2.7609 (9)168.0 (5)
O2WA—H2WA···O3iii0.846 (4)2.127 (6)2.8625 (12)145.2 (8)
O2WA—H2WB···O4W0.844 (4)1.757 (4)2.5967 (12)172.7 (8)
O3WA—H3WB···O4Wi0.843 (4)1.806 (4)2.6398 (14)169.6 (5)
O3WB—H3WC···O20.847 (4)1.886 (5)2.7193 (13)167.9 (5)
O4—H4···O3iv0.840 (8)1.916 (7)2.7543 (10)175.6 (8)
O4W—H4WA···O2WBv0.840 (4)1.785 (4)2.6227 (13)175.6 (4)
O4W—H4WA···O2WAv0.840 (4)2.040 (5)2.8436 (12)160.1 (6)
O4W—H4WB···O2vi0.844 (4)1.986 (5)2.8244 (10)171.9 (6)
O2WB—H2WD···O3iii0.844 (4)1.941 (4)2.7833 (13)175.1 (6)
O3WB—H3WD···O3WBvii0.845 (4)1.945 (8)2.6474 (19)139.8 (11)
Symmetry codes: (ii) −x, y+1/2, −z+3/2; (iii) x, y+1, z; (i) −x, −y+2, −z+2; (iv) −x+1, y+1/2, −z+3/2; (v) −x, −y+3, −z+2; (vi) x−1, y+1, z; (vii) −x+1, −y+2, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O10.845 (4)1.928 (4)2.7667 (11)171.4 (4)
O1W—H1WB···O4i0.846 (4)1.927 (4)2.7609 (9)168.0 (5)
O2WA—H2WA···O3ii0.846 (4)2.127 (6)2.8625 (12)145.2 (8)
O2WA—H2WB···O4W0.844 (4)1.757 (4)2.5967 (12)172.7 (8)
O3WA—H3WB···O4Wiii0.843 (4)1.806 (4)2.6398 (14)169.6 (5)
O3WB—H3WC···O20.847 (4)1.886 (5)2.7193 (13)167.9 (5)
O4—H4···O3iv0.840 (8)1.916 (7)2.7543 (10)175.6 (8)
O4W—H4WA···O2WBv0.840 (4)1.785 (4)2.6227 (13)175.6 (4)
O4W—H4WA···O2WAv0.840 (4)2.040 (5)2.8436 (12)160.1 (6)
O4W—H4WB···O2vi0.844 (4)1.986 (5)2.8244 (10)171.9 (6)
O2WB—H2WD···O3ii0.844 (4)1.941 (4)2.7833 (13)175.1 (6)
O3WB—H3WD···O3WBvii0.845 (4)1.945 (8)2.6474 (19)139.8 (11)
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) x, y+1, z; (iii) −x, −y+2, −z+2; (iv) −x+1, y+1/2, −z+3/2; (v) −x, −y+3, −z+2; (vi) x−1, y+1, z; (vii) −x+1, −y+2, −z+2.
Acknowledgements top

We gratefully acknowledge financial support by the NSF of Fujian Province (E0510031).

references
References top

Ma, J.-F., Yang, J. & Liu, J.-F. (2003). Acta Cryst. E59, m481–m482.

Rigaku (2002). CrystalClear. Version 1.35. Rigaku Corporation, Tokyo, Japan.

Sharma, R. P., Bala, R., Sharma, R. & Bond, A. D. (2006). Acta Cryst. E62, m2113–m2115.

Siemens (1994). SHELXTL. Release 5.03. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.