Bis[hexa­aquacobalt(II)] 25,26,27,28-tetra­hydr­oxy-2,8,14,19-tetra­thia­calix[4]arene-5,11,17,23-tetra­sulfonate monohydrate

Akashi, H.; Ichikawa, M.

doi:10.1107/S1600536808011781

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Pages m797-m798

doi:10.1107/S1600536808011781

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Bis[hexaaquacobalt(II)] 25,26,27,28-tetrahydroxy-2,8,14,19-tetrathiacalix[4]arene-5,11,17,23-tetrasulfonate monohydrate

Haruo Akashi ^a ^* and Misato Ichikawa ^a

^aResearch Institute of Natural Sciences, Okayama University of Science, Ridai-cho, Okayama 700-0005, Japan
^*Correspondence e-mail: akashi@high.ous.ac.jp

(Received 15 April 2008; accepted 24 April 2008; online 10 May 2008)

In the crystal structure of the title compound, [Co(H₂O)₆]₂(C₂₄H₁₂O₁₆S₈)·H₂O, the thiacalix[4]arenetetrasulfonate (= TCAS⁴⁻) anions adopt a cone-type conformation with an additional water molecule as a guest molecule in the hydrophobic cavity. The TCAS⁴⁻ anions are arranged in layers in an up–down fashion. These anionic layers alternate with cationic layers consisting of rather regular octahedral cations (symmetry m). Several medium O—H⋯O hydrogen-bond interactions exist between the aqua ligands of the [Co(H₂O)₆]²⁺ cations and the O atoms of the sulfonate groups. In addition to the two crystallographically different Co atoms, two S and four O atoms are situated on mirror planes.

Related literature

For the structure of sodium thiacalix[4]arene tetrasulfonate monohydrate, see: Akashi & Yamauchi (2003 ), and for the Cd salt of the same anion, see: Zhao et al. (2005 ). Assemblies of thiacalix[4]arene tetrasulfonates with several transition metal ions were described by Guo et al. (2004 ).

Experimental

Crystal data

[Co(H₂O)₆]₂(C₂₄H₁₂O₁₆S₈)·H₂O
M_r = 1164.89
Monoclinic, P 2₁ /m
a = 11.9955 (5) Å
b = 14.0628 (10) Å
c = 12.8907 (11) Å
β = 95.638 (3)°
V = 2164.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.25 mm⁻¹
T = 93 K
0.40 × 0.40 × 0.10 mm

Data collection

Rigaku R-AXIS-IV diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.767, T_max = 0.883
15194 measured reflections
4319 independent reflections
3640 reflections with F² > 2σ(F²)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.144
S = 1.00
4296 reflections
320 parameters
H-atom parameters constrained
Δρ_max = 1.65 e Å⁻³
Δρ_min = −0.81 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O9	2.079 (3)
Co1—O10	2.064 (3)
Co1—O11	2.085 (2)
Co1—O12	2.088 (2)
Co2—O13	2.076 (3)
Co2—O14	2.090 (3)
Co2—O15	2.078 (2)
Co2—O16	2.085 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H5⋯O1ⁱ	0.78	2.17	2.877 (3)	151
O2—H6⋯O1	0.88	2.26	3.082 (3)	156
O2—H6⋯O12ⁱⁱ	0.88	2.71	3.154 (3)	113
O9—H7⋯O4ⁱⁱⁱ	0.82	2.06	2.878 (3)	173
O9—H7⋯O4ⁱⁱⁱ	0.82	2.06	2.878 (3)	173
O10—H8⋯O8^iv	0.93	1.83	2.729 (2)	163
O10—H8⋯O8^iv	0.93	1.83	2.729 (2)	163
O11—H9⋯O3^v	0.81	1.95	2.741 (3)	165
O11—H10⋯O7^v	0.77	2.04	2.795 (3)	169
O12—H11⋯O5	0.91	1.86	2.764 (3)	173
O12—H12⋯O6^iv	0.82	2.00	2.812 (3)	174
O13—H13⋯O7^vi	0.81	1.95	2.739 (2)	165
O13—H13⋯O7^vi	0.81	1.95	2.739 (2)	165
O14—H14⋯O5	0.78	2.05	2.818 (2)	172
O14—H14⋯O5	0.78	2.05	2.818 (2)	172
O15—H15⋯O6^vii	0.84	1.91	2.739 (3)	170
O15—H16⋯O4^v	0.87	1.89	2.743 (3)	164
O16—H17⋯O8^viii	0.77	2.01	2.764 (3)	166
O16—H18⋯O3^viii	0.84	1.92	2.719 (3)	159
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (iv) x, y, z+1; (v) -x, -y+1, -z+1; (vi) $[-x, y-{\script{1\over 2}}, -z]$ ; (vii) -x, -y+1, -z; (viii) $[x, -y+{\script{1\over 2}}, z]$ .

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2006 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: CrystalStructure; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808011781/wm2177sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808011781/wm2177Isup2.hkl

checkCIF report

Comment top

The water soluble thiacalix[4]arene tetrasulfonate anion (= TCAS^4-) is well-known as a second-sphere ligand of various transition metal coordination compounds containing complex metal aqua cations (Zhao, 2005). In the title compound, [Co(H₂O)₆]₂(S₈C₂₄O₁₆H₁₂)^.H₂O, (I), the second-sphere TCAS^4- anionic ligands are linked to the aqua ligands of [Co(H₂O)₆] via several medium O-H···H hydrogen bonding interactions (see Table 2).

In the crystal structure of (I) the TCAS^4- molecules adopt the cone-type conformation. The Co²⁺ ions are not directly bonded to the TCAS^4- moieties, but exist as two octahedral aqua complexes, [Co(H₂O)₆]²⁺, both with m symmetry (Figure 1, Table 1). Layers of TCAS^4- anions are arranged in an up-down fashion and alternate with cationic layers that contain the [Co(H₂O)₆]²⁺ cations (Figure 2).

The TCAS^4- molecule include a water molecule as a guest-molecule in the hydrophobic cavity. Interactions between the H atoms of the aqua ligands of [Co(H₂O)₆]²⁺ and of O atoms of the TCAS^4- moieties constitute a three-dimensional hydrogen bond network, and from there the second-sphere coordination is established.

Related literature top

For the structure of sodium thiacalix[4]arene tetrasulfonate hydrate, see: Akashi & Yamauchi (2003), and for the Cd salt of the same anion, see: Zhao et al. (2005). Assemblies of thiacalix[4]arene tetrasulfonates with several transition metal ions were described by Guo et al. (2004).

Experimental top

A solution of Na₄(S₈C₂₄O₁₆H₁₂)^.14H₂O (=Na₄TCAS^.14H₂O) in 2 M HCl and a 2M HCl solution containing CoCl₂^.6H₂O were mixed in the molar ratio (Co/Na₄TCAS = 5), poured into a vial and stirred for 1 h. This solution was then kept at room temperature from which pale pink crystals of (I) were obtained within a few days. Elemental analysis of (I) is in agreement with the refined structure model. Found: C 24.85, H 2.89%; calculated for (I): C 24.74, H 3.29%.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: CrystalStructure (Rigaku/MSC, 2006); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2006).

Figures top

	Fig. 1. The molecular entities of (I) with the atom-labelling scheme and displacement ellipsoids drawn at 50% probability level. Labelling of H atoms has been omitted for clarity. [Symmetry code: (i) x, 1/2 - y, z.]
	Fig. 2. The projection of the structure of (I) along the b axis.

Bis[hexaaquacobalt(II)] 25,26,27,28-tetrahydroxy-2,8,14,19- tetrathiacalix[4]arene-5,11,17,23-tetrasulfonate monohydrate top

Crystal data top

[Co(H₂O)₆]₂(C₂₄H₁₂O₁₆S₈)·H₂O	F(000) = 1192.00
M_r = 1164.89	D_x = 1.788 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yb	Cell parameters from 14562 reflections
a = 11.9955 (5) Å	θ = 2.2–27.5°
b = 14.0628 (10) Å	µ = 1.25 mm⁻¹
c = 12.8907 (11) Å	T = 93 K
β = 95.638 (3)°	Block, pale pink
V = 2164.0 (3) Å³	0.40 × 0.40 × 0.10 mm
Z = 2

Data collection top

Rigaku R-AXIS-IV diffractometer	3640 reflections with F² > 2σ(F²)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.047
ω scans	θ_max = 25.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −15→15
T_min = 0.767, T_max = 0.883	k = −17→17
15194 measured reflections	l = −16→16
4319 independent reflections

Refinement top

Refinement on F²	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.044	w = 1/[0.0031F_o² + σ(F_o²)]/(4F_o²)
wR(F²) = 0.144	(Δ/σ)_max < 0.001
S = 1.00	Δρ_max = 1.65 e Å⁻³
4296 reflections	Δρ_min = −0.81 e Å⁻³
320 parameters

Crystal data top

[Co(H₂O)₆]₂(C₂₄H₁₂O₁₆S₈)·H₂O	V = 2164.0 (3) Å³
M_r = 1164.89	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 11.9955 (5) Å	µ = 1.25 mm⁻¹
b = 14.0628 (10) Å	T = 93 K
c = 12.8907 (11) Å	0.40 × 0.40 × 0.10 mm
β = 95.638 (3)°

Data collection top

Rigaku R-AXIS-IV diffractometer	4319 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3640 reflections with F² > 2σ(F²)
T_min = 0.767, T_max = 0.883	R_int = 0.047
15194 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	320 parameters
wR(F²) = 0.144	H-atom parameters constrained
S = 1.00	Δρ_max = 1.65 e Å⁻³
4296 reflections	Δρ_min = −0.81 e Å⁻³

Special details top

Refinement. Refinement was performed using 4296 reflections (5 < 2θ < 51°). The weighted R-factor (wR) and goodness of fit (S) are based on F². R factor (gt) are based on F. The threshold expression of F² > 2σ(F²) is used only for calculating R factor (gt).

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

	x	y	z	U_iso*/U_eq
Co1	0.04693 (6)	0.2500	0.75294 (5)	0.01428 (17)
Co2	0.00632 (6)	0.2500	0.24647 (5)	0.01639 (17)
S1	0.50722 (9)	0.7500	0.56024 (9)	0.0120 (2)
S2	0.53799 (7)	0.47539 (6)	0.25884 (6)	0.01238 (19)
S3	0.52961 (10)	0.7500	−0.04805 (9)	0.0129 (2)
S4	0.15582 (6)	0.50788 (5)	0.45489 (6)	0.00843 (18)
S5	0.17521 (6)	0.50752 (5)	−0.03055 (6)	0.00836 (18)
O1	0.60482 (18)	0.64771 (18)	0.38463 (19)	0.0174 (5)
O2	0.61612 (19)	0.64728 (17)	0.14682 (18)	0.0162 (5)
O3	0.10300 (19)	0.50174 (16)	0.34755 (17)	0.0122 (5)
O4	0.10609 (19)	0.58262 (17)	0.51376 (17)	0.0130 (5)
O5	0.15942 (19)	0.41514 (16)	0.50631 (17)	0.0135 (5)
O6	0.1697 (2)	0.50641 (16)	−0.14431 (18)	0.0132 (5)
O7	0.10106 (19)	0.57942 (16)	0.00710 (17)	0.0121 (5)
O8	0.15982 (19)	0.41379 (16)	0.01357 (17)	0.0117 (5)
O9	−0.0351 (3)	0.250000 (10)	0.6031 (2)	0.0206 (9)
O10	0.1310 (4)	0.250000 (10)	0.9006 (2)	0.0393 (12)
O11	−0.0636 (2)	0.35446 (18)	0.79486 (19)	0.0257 (6)
O12	0.1547 (2)	0.35660 (17)	0.71050 (18)	0.0184 (6)
O13	−0.0660 (4)	0.250000 (10)	0.0934 (2)	0.0380 (11)
O14	0.0769 (3)	0.250000 (10)	0.4013 (2)	0.0178 (8)
O15	−0.1064 (2)	0.35324 (17)	0.28526 (18)	0.0201 (6)
O16	0.1180 (2)	0.14395 (18)	0.21098 (19)	0.0240 (6)
O17	0.3199 (9)	0.7500	0.2349 (9)	0.154 (4)
C1	0.5066 (2)	0.6116 (2)	0.4082 (2)	0.0123 (7)
C2	0.4618 (2)	0.5311 (2)	0.3545 (2)	0.0107 (7)
C3	0.3575 (2)	0.4978 (2)	0.3728 (2)	0.0113 (7)
C4	0.2960 (2)	0.5438 (2)	0.4440 (2)	0.0103 (7)
C5	0.3419 (2)	0.6201 (2)	0.5015 (2)	0.0107 (7)
C6	0.4478 (2)	0.6531 (2)	0.4843 (2)	0.0102 (7)
C7	0.5189 (2)	0.6115 (2)	0.1034 (2)	0.0114 (7)
C8	0.4647 (2)	0.6537 (2)	0.0126 (2)	0.0098 (7)
C9	0.3610 (2)	0.6200 (2)	−0.0297 (2)	0.0093 (7)
C10	0.3118 (2)	0.5430 (2)	0.0163 (2)	0.0106 (7)
C11	0.3666 (2)	0.4982 (2)	0.1027 (2)	0.0108 (7)
C12	0.4701 (2)	0.5325 (2)	0.1461 (2)	0.0105 (7)
H1	0.3306	0.4470	0.3377	0.013*
H2	0.2996	0.6492	0.5510	0.013*
H3	0.3269	0.6542	−0.0940	0.011*
H4	0.3380	0.4414	0.1315	0.013*
H5	0.6164	0.6994	0.4048	0.021*
H6	0.6272	0.6330	0.2133	0.020*
H7	−0.0525	0.2040	0.5657	0.025*
H8	0.1529	0.2997	0.9450	0.046*
H9	−0.0875	0.3956	0.7543	0.032*
H10	−0.0648	0.3742	0.8501	0.031*
H11	0.1560	0.3806	0.6450	0.022*
H12	0.1556	0.4022	0.7502	0.022*
H13	−0.0783	0.2055	0.0540	0.045*
H14	0.1057	0.2940	0.4286	0.021*
H15	−0.1274	0.4002	0.2485	0.024*
H16	−0.0996	0.3831	0.3450	0.024*
H17	0.1182	0.1257	0.1545	0.030*
H18	0.1217	0.0916	0.2420	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0313 (4)	0.0051 (3)	0.0070 (3)	0.0000	0.0045 (2)	0.0000
Co2	0.0372 (4)	0.0050 (3)	0.0075 (3)	0.0000	0.0052 (2)	0.0000
S1	0.0131 (5)	0.0110 (5)	0.0113 (5)	0.0000	−0.0020 (4)	0.0000
S2	0.0133 (3)	0.0130 (4)	0.0113 (3)	0.0074 (2)	0.0034 (3)	0.0013 (2)
S3	0.0145 (5)	0.0112 (5)	0.0143 (5)	0.0000	0.0088 (4)	0.0000
S4	0.0107 (3)	0.0076 (3)	0.0075 (3)	0.0005 (2)	0.0029 (3)	−0.0007 (2)
S5	0.0114 (3)	0.0058 (3)	0.0080 (3)	0.0007 (2)	0.0011 (3)	−0.0010 (2)
O1	0.0095 (10)	0.0191 (12)	0.0240 (12)	−0.0005 (9)	0.0047 (10)	0.0014 (10)
O2	0.0136 (10)	0.0168 (12)	0.0181 (11)	−0.0003 (9)	0.0001 (9)	0.0011 (9)
O3	0.0180 (11)	0.0100 (12)	0.0089 (10)	−0.0007 (8)	0.0021 (9)	−0.0004 (8)
O4	0.0146 (10)	0.0111 (11)	0.0142 (10)	0.0021 (8)	0.0063 (9)	−0.0032 (8)
O5	0.0169 (11)	0.0101 (11)	0.0135 (10)	−0.0003 (9)	0.0009 (9)	0.0023 (9)
O6	0.0186 (11)	0.0106 (11)	0.0100 (10)	−0.0004 (9)	−0.0007 (9)	−0.0006 (8)
O7	0.0126 (10)	0.0092 (11)	0.0152 (10)	0.0031 (8)	0.0045 (9)	−0.0004 (8)
O8	0.0167 (11)	0.0077 (11)	0.0104 (10)	−0.0015 (8)	0.0001 (9)	0.0003 (8)
O9	0.042 (2)	0.0102 (17)	0.0094 (15)	0.0000	0.0008 (15)	0.0000
O10	0.095 (3)	0.0078 (18)	0.0115 (16)	0.0000	−0.015 (2)	0.0000
O11	0.0573 (18)	0.0121 (12)	0.0094 (10)	0.0091 (12)	0.0126 (12)	0.0010 (9)
O12	0.0365 (14)	0.0086 (11)	0.0108 (10)	−0.0018 (10)	0.0051 (10)	−0.0022 (9)
O13	0.094 (3)	0.0091 (18)	0.0086 (15)	0.0000	−0.009 (2)	0.0000
O14	0.034 (2)	0.0075 (16)	0.0118 (15)	0.0000	0.0012 (15)	0.0000
O15	0.0406 (15)	0.0089 (11)	0.0106 (10)	0.0045 (10)	0.0011 (11)	−0.0006 (9)
O16	0.0523 (17)	0.0089 (12)	0.0132 (11)	0.0059 (11)	0.0150 (12)	0.0015 (9)
O17	0.141 (9)	0.149 (9)	0.180 (10)	0.0000	0.054 (8)	0.0000
C1	0.0094 (13)	0.0123 (16)	0.0148 (14)	0.0035 (12)	−0.0011 (12)	0.0048 (12)
C2	0.0150 (15)	0.0087 (15)	0.0084 (13)	0.0059 (12)	0.0009 (12)	0.0008 (11)
C3	0.0148 (14)	0.0095 (16)	0.0098 (14)	0.0032 (12)	0.0016 (12)	0.0002 (11)
C4	0.0133 (14)	0.0071 (15)	0.0110 (13)	−0.0002 (11)	0.0031 (12)	0.0023 (11)
C5	0.0133 (14)	0.0090 (15)	0.0103 (14)	0.0042 (11)	0.0040 (12)	0.0007 (11)
C6	0.0132 (14)	0.0076 (14)	0.0092 (13)	0.0026 (11)	−0.0019 (12)	−0.0006 (11)
C7	0.0091 (13)	0.0132 (16)	0.0124 (14)	0.0043 (12)	0.0038 (12)	−0.0030 (12)
C8	0.0114 (14)	0.0091 (15)	0.0103 (13)	0.0006 (11)	0.0075 (12)	0.0006 (11)
C9	0.0101 (13)	0.0091 (15)	0.0088 (13)	0.0005 (11)	0.0008 (12)	−0.0016 (11)
C10	0.0128 (14)	0.0070 (15)	0.0123 (13)	0.0026 (11)	0.0031 (12)	−0.0004 (11)
C11	0.0175 (15)	0.0078 (15)	0.0077 (13)	0.0030 (12)	0.0040 (13)	−0.0013 (11)
C12	0.0129 (14)	0.0092 (15)	0.0097 (13)	0.0070 (11)	0.0027 (12)	−0.0008 (11)

Geometric parameters (Å, º) top

Co1—O9	2.079 (3)	C3—C4	1.392 (4)
Co1—O10	2.064 (3)	C4—C5	1.386 (4)
Co1—O11	2.085 (2)	C5—C6	1.390 (4)
Co1—O11ⁱ	2.085 (2)	C7—C8	1.413 (4)
Co1—O12	2.088 (2)	C7—C12	1.393 (4)
Co1—O12ⁱ	2.088 (2)	C8—C9	1.391 (4)
Co2—O13	2.076 (3)	C9—C10	1.394 (4)
Co2—O14	2.090 (3)	C10—C11	1.387 (4)
Co2—O15	2.078 (2)	C11—C12	1.397 (4)
Co2—O15ⁱ	2.078 (2)	O1—H5	0.779
Co2—O16	2.085 (2)	O2—H6	0.878
Co2—O16ⁱ	2.085 (2)	O9—H7	0.822
S1—C6	1.786 (3)	O9—H7ⁱ	0.822
S1—C6ⁱⁱ	1.786 (3)	O10—H8	0.925
S2—C2	1.786 (3)	O10—H8ⁱ	0.925
S2—C12	1.785 (3)	O11—H9	0.813
S3—C8	1.781 (3)	O11—H10	0.766
S3—C8ⁱⁱ	1.781 (3)	O12—H11	0.911
S4—O3	1.467 (2)	O12—H12	0.820
S4—O4	1.458 (2)	O13—H13	0.811
S4—O5	1.462 (2)	O13—H13ⁱ	0.811
S4—C4	1.775 (3)	O14—H14	0.776
S5—O6	1.462 (2)	O14—H14ⁱ	0.776
S5—O7	1.461 (2)	O15—H15	0.837
S5—O8	1.455 (2)	O15—H16	0.874
S5—C10	1.762 (3)	O16—H17	0.772
O1—C1	1.345 (3)	O16—H18	0.837
O2—C7	1.341 (3)	C3—H1	0.888
C1—C2	1.406 (4)	C5—H2	0.947
C1—C6	1.392 (4)	C9—H3	1.009
C2—C3	1.378 (4)	C11—H4	0.958

O9—Co1—O10	179.01 (18)	C3—C4—C5	120.3 (2)
O9—Co1—O11	89.19 (10)	C4—C5—C6	119.6 (2)
O9—Co1—O11ⁱ	89.19 (10)	S1—C6—C1	120.2 (2)
O9—Co1—O12	90.31 (10)	S1—C6—C5	119.3 (2)
O9—Co1—O12ⁱ	90.31 (10)	C1—C6—C5	120.4 (2)
O10—Co1—O11	91.51 (12)	O2—C7—C8	119.9 (2)
O10—Co1—O11ⁱ	91.51 (12)	O2—C7—C12	121.1 (2)
O10—Co1—O12	89.00 (12)	C8—C7—C12	119.0 (2)
O10—Co1—O12ⁱ	89.00 (12)	S3—C8—C7	119.9 (2)
O11—Co1—O11ⁱ	89.58 (11)	S3—C8—C9	119.9 (2)
O11—Co1—O12	89.31 (10)	C7—C8—C9	120.2 (2)
O11—Co1—O12ⁱ	178.79 (10)	C8—C9—C10	119.8 (2)
O11ⁱ—Co1—O12	178.79 (10)	S5—C10—C9	119.5 (2)
O11ⁱ—Co1—O12ⁱ	89.31 (10)	S5—C10—C11	119.8 (2)
O12—Co1—O12ⁱ	91.80 (10)	C9—C10—C11	120.5 (2)
O13—Co2—O14	179.19 (18)	C10—C11—C12	119.8 (2)
O13—Co2—O15	90.44 (12)	S2—C12—C7	120.3 (2)
O13—Co2—O15ⁱ	90.44 (12)	S2—C12—C11	119.1 (2)
O13—Co2—O16	90.52 (12)	C7—C12—C11	120.5 (2)
O13—Co2—O16ⁱ	90.52 (12)	C1—O1—H5	114.1
O14—Co2—O15	88.99 (9)	C7—O2—H6	111.3
O14—Co2—O15ⁱ	88.99 (9)	Co1—O9—H7	128.0
O14—Co2—O16	90.04 (10)	Co1—O9—H7ⁱ	128.0
O14—Co2—O16ⁱ	90.04 (10)	H7—O9—H7ⁱ	103.8
O15—Co2—O15ⁱ	88.64 (10)	Co1—O10—H8	130.8
O15—Co2—O16	178.36 (10)	Co1—O10—H8ⁱ	130.8
O15—Co2—O16ⁱ	90.02 (10)	H8—O10—H8ⁱ	98.2
O15ⁱ—Co2—O16	90.02 (10)	Co1—O11—H9	121.8
O15ⁱ—Co2—O16ⁱ	178.36 (10)	Co1—O11—H10	124.5
O16—Co2—O16ⁱ	91.31 (10)	H9—O11—H10	107.6
C6—S1—C6ⁱⁱ	99.56 (15)	Co1—O12—H11	125.2
C2—S2—C12	98.15 (14)	Co1—O12—H12	111.6
C8—S3—C8ⁱⁱ	99.04 (15)	H11—O12—H12	106.7
O3—S4—O4	111.87 (13)	Co2—O13—H13	129.0
O3—S4—O5	111.47 (12)	Co2—O13—H13ⁱ	129.0
O3—S4—C4	105.50 (14)	H13—O13—H13ⁱ	101.1
O4—S4—O5	113.74 (13)	Co2—O14—H14	123.7
O4—S4—C4	105.98 (14)	Co2—O14—H14ⁱ	123.7
O5—S4—C4	107.68 (13)	H14—O14—H14ⁱ	105.7
O6—S5—O7	111.83 (13)	Co2—O15—H15	125.6
O6—S5—O8	112.81 (13)	Co2—O15—H16	122.8
O6—S5—C10	107.21 (14)	H15—O15—H16	96.7
O7—S5—O8	113.11 (13)	Co2—O16—H17	120.4
O7—S5—C10	105.42 (14)	Co2—O16—H18	121.9
O8—S5—C10	105.79 (14)	H17—O16—H18	98.9
O1—C1—C2	119.6 (2)	C2—C3—H1	118.5
O1—C1—C6	121.1 (2)	C4—C3—H1	121.3
C2—C1—C6	119.2 (2)	C4—C5—H2	118.9
S2—C2—C1	119.7 (2)	C6—C5—H2	121.4
S2—C2—C3	120.2 (2)	C8—C9—H3	115.8
C1—C2—C3	120.0 (2)	C10—C9—H3	124.4
C2—C3—C4	120.2 (2)	C10—C11—H4	122.0
S4—C4—C3	119.1 (2)	C12—C11—H4	118.1
S4—C4—C5	120.5 (2)

Symmetry codes: (i) x, −y+1/2, z; (ii) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H5···O1ⁱⁱ	0.78	2.17	2.877 (3)	151
O2—H6···O1	0.88	2.26	3.082 (3)	156
O2—H6···O12ⁱⁱⁱ	0.88	2.71	3.154 (3)	113
O9—H7···O4^iv	0.82	2.06	2.878 (3)	173
O9—H7···O4^iv	0.82	2.06	2.878 (3)	173
O10—H8···O8^v	0.93	1.83	2.729 (2)	163
O10—H8···O8^v	0.93	1.83	2.729 (2)	163
O11—H9···O3^vi	0.81	1.95	2.741 (3)	165
O11—H10···O7^vi	0.77	2.04	2.795 (3)	169
O12—H11···O5	0.91	1.86	2.764 (3)	173
O12—H12···O6^v	0.82	2.00	2.812 (3)	174
O13—H13···O7^vii	0.81	1.95	2.739 (2)	165
O13—H13···O7^vii	0.81	1.95	2.739 (2)	165
O14—H14···O5	0.78	2.05	2.818 (2)	172
O14—H14···O5	0.78	2.05	2.818 (2)	172
O15—H15···O6^viii	0.84	1.91	2.739 (3)	170
O15—H16···O4^vi	0.87	1.89	2.743 (3)	164
O16—H17···O8ⁱ	0.77	2.01	2.764 (3)	166
O16—H18···O3ⁱ	0.84	1.92	2.719 (3)	159

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

Experimental details

Crystal data
Chemical formula	[Co(H₂O)₆]₂(C₂₄H₁₂O₁₆S₈)·H₂O
M_r	1164.89
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	93
a, b, c (Å)	11.9955 (5), 14.0628 (10), 12.8907 (11)
β (°)	95.638 (3)
V (Å³)	2164.0 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.25
Crystal size (mm)	0.40 × 0.40 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS-IV diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.767, 0.883
No. of measured, independent and observed [F² > 2σ(F²)] reflections	15194, 4319, 3640
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.144, 1.00
No. of reflections	4296
No. of parameters	320
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.65, −0.81

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2006), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Selected bond lengths (Å) top

Co1—O9	2.079 (3)	Co2—O13	2.076 (3)
Co1—O10	2.064 (3)	Co2—O14	2.090 (3)
Co1—O11	2.085 (2)	Co2—O15	2.078 (2)
Co1—O12	2.088 (2)	Co2—O16	2.085 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H5···O1ⁱ	0.779	2.169	2.877 (3)	151.3
O2—H6···O1	0.878	2.260	3.082 (3)	155.8
O2—H6···O12ⁱⁱ	0.878	2.706	3.154 (3)	112.9
O9—H7···O4ⁱⁱⁱ	0.822	2.061	2.878 (3)	173.1
O9—H7···O4ⁱⁱⁱ	0.822	2.061	2.878 (3)	173.1
O10—H8···O8^iv	0.925	1.830	2.729 (2)	163.4
O10—H8···O8^iv	0.925	1.830	2.729 (2)	163.4
O11—H9···O3^v	0.813	1.948	2.741 (3)	164.9
O11—H10···O7^v	0.766	2.039	2.795 (3)	168.6
O12—H11···O5	0.911	1.857	2.764 (3)	173.4
O12—H12···O6^iv	0.820	1.995	2.812 (3)	174.3
O13—H13···O7^vi	0.811	1.948	2.739 (2)	164.9
O13—H13···O7^vi	0.811	1.948	2.739 (2)	164.9
O14—H14···O5	0.776	2.048	2.818 (2)	171.8
O14—H14···O5	0.776	2.048	2.818 (2)	171.8
O15—H15···O6^vii	0.837	1.911	2.739 (3)	169.9
O15—H16···O4^v	0.874	1.892	2.743 (3)	164.0
O16—H17···O8^viii	0.772	2.009	2.764 (3)	165.6
O16—H18···O3^viii	0.837	1.919	2.719 (3)	159.4

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

Acknowledgements

This research was partially supported by the Ministry of Education, Science, Sports and Culture, Grant-in-Aid for Scientific Research, 18550063, 2007.

References

Akashi, H. & Yamauchi, T. (2003). Acta Cryst. E59, m336–m338. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Guo, Q.-L., Zhu, W.-X., Ma, S.-L., Dong, S.-J. & Xu, M.-Q. (2004). Polyhedron, 23, 1461–1466. Web of Science CSD CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2006). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, B.-T., Hu, P.-Z., Wang, J.-G., Ma, L.-F., Wang, L.-Y. & Ng, S. W. (2005). Acta Cryst. E61, m1957–m1959. Web of Science CSD CrossRef IUCr Journals Google Scholar

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Volume 64| Part 6| June 2008| Pages m797-m798

doi:10.1107/S1600536808011781

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis[hexa­aquacobalt(II)] 25,26,27,28-tetra­hydr­­oxy-2,8,14,19-tetra­thia­calix[4]arene-5,11,17,23-tetra­sulfonate monohydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Bis[hexaaquacobalt(II)] 25,26,27,28-tetrahydroxy-2,8,14,19-tetrathiacalix[4]arene-5,11,17,23-tetrasulfonate monohydrate