Poly[[μ-aqua-bis­(μ-4,4′-bipyridine-κ2 N:N′)bis­(μ-3-hy­droxy­adamantane-1-carboxyl­ato-κ2 O:O′)bis­(3-hy­droxy­adamantane-1-carboxyl­ato-κO)dicobalt(II)] hepta­hydrate]

Jin-Bei Shen; Xiao-Yong Wu; Xiao-Ju Chen; Guo-Liang Zhao

doi:10.1107/S1600536811012475

. 2011 Apr 7;67(Pt 5):m558–m559. doi: 10.1107/S1600536811012475

Poly[[μ-aqua-bis(μ-4,4′-bipyridine-κ² N:N′)bis(μ-3-hydroxyadamantane-1-carboxylato-κ² O:O′)bis(3-hydroxyadamantane-1-carboxylato-κO)dicobalt(II)] heptahydrate]

Jin-Bei Shen ^a, Xiao-Yong Wu ^a, Xiao-Ju Chen ^a, Guo-Liang Zhao ^a,^b,^*

PMCID: PMC3089202 PMID: 21754291

Abstract

The title coordination compound, {[Co(C₁₁H₁₅O₃)₄(C₁₀H₈N₂)₂(H₂O)]·7H₂O}_n, consists of a pair of Co^II atoms, four 3-hydroxyadamantane-1-carboxylate anions (L), one water molecule, two bridging 4,4′-bipyridine (4,4′-bpy) ligands and seven uncoordinated water molecules. Both of the Co^II ions are coordinated in a distorted octahedral geometry. Four L ligands bind to each pair of Co^II atoms in a plane, two of which bridge the two Co^II atoms as bidentate groups while the other two coordinate to a single Co^II atom in a monodentate mode. Two half-molecules of 4,4′-bipyridine coordinate the Co^II atoms from the upside and underside. The packing features extensice O—H⋯O hydrogen bonding.

Related literature

For a related nickel complex, see: Hu et al. (2011 ▶). For other complexes based on adamantane-1-carboxylic acid, see: Milios et al. (2007 ▶); Korlyukov et al. (2008 ▶); Zhu et al. (2005 ▶).

Experimental

Crystal data

[Co(C₁₁H₁₅O₃)₄(C₁₀H₈N₂)₂(H₂O)]·7H₂O
M _r = 1355.28
Monoclinic,
a = 12.0201 (3) Å
b = 20.7463 (5) Å
c = 17.6353 (3) Å
β = 132.806 (1)°
V = 3226.45 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 296 K
0.20 × 0.13 × 0.04 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.909, T _max = 0.979
42213 measured reflections
11001 independent reflections
9720 reflections with I > 2σ(I)
R _int = 0.050

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.083
S = 1.03
11001 reflections
797 parameters
27 restraints
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.34 e Å⁻³
Absolute structure: Flack (1983 ▶), 5293 Friedel pairs
Flack parameter: −0.003 (9)

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012475/om2417sup1.cif

e-67-0m558-sup1.cif^{(54.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012475/om2417Isup2.hkl

e-67-0m558-Isup2.hkl^{(537.9KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co1—O7	2.019 (2)
Co1—O11	2.068 (2)
Co1—O5	2.1277 (19)
Co1—N1	2.145 (2)
Co1—O1W	2.1603 (18)
Co1—N4	2.161 (2)
Co2—O4	2.022 (2)
Co2—O2	2.072 (2)
Co2—O8	2.110 (2)
Co2—N2	2.154 (2)
Co2—O1W	2.1813 (19)
Co2—N3	2.198 (2)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O1	0.85	1.78	2.623 (3)	168
O1W—H1WA⋯O2	0.85	2.56	2.968 (3)	111
O1W—H1WB⋯O10	0.95	1.69	2.623 (3)	164
O3W—H3WA⋯O5W	0.85	2.01	2.844 (5)	166
O3W—H3WB⋯O8W	0.85	2.12	2.973 (5)	179
O12—H12A⋯O4W	0.82	2.03	2.836 (4)	170
O6W—H6WA⋯O2W	0.85	2.08	2.865 (8)	154
O6—H6C⋯O8W	0.82	2.10	2.923 (4)	180
O6W—H6WB⋯O7W	0.85	2.08	2.920 (7)	167
O7W—H7WB⋯O5	0.85	2.07	2.794 (3)	143
O7W—H7WA⋯O11	0.85	2.12	2.908 (3)	155
O3—H3C⋯O6ⁱ	0.82	2.07	2.884 (4)	176
O9—H9B⋯O7Wⁱⁱ	0.82	2.04	2.864 (4)	178
O2W—H2WA⋯O3ⁱⁱⁱ	0.85	2.03	2.881 (6)	179
O4W—H4WA⋯O8^iv	0.84	2.10	2.943 (3)	176
O4W—H4WB⋯O1^iv	0.82	2.09	2.843 (4)	152
O5W—H5WA⋯O12^v	0.85	2.00	2.849 (4)	180
O5W—H5WB⋯O9^vi	0.85	2.11	2.927 (4)	163
O8W—H8WA⋯O1^vii	0.83	2.08	2.882 (4)	163
O8W—H8WB⋯O10^vii	0.85	2.01	2.857 (4)	173
O2W—H2WA⋯O3ⁱⁱⁱ	0.85	2.03	2.881 (6)	179

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

supplementary crystallographic information

Comment

The fascinating structures of adamantane-1- carboxylic acid complexes coupled with their special functionality have attracted a great deal of interest (Zhu et al., 2005; Milios et al., 2007; Korlyukov et al., 2008). Recently, we reported the structure of a nickel complex with 3-hydroxyadamantane-1-carboxylic acid and 4,4'-bpy (Hu et al., 2011). As an extension of our work in this field, we describe a new Co^II complex.

The structure of the Co complex is shown in Fig. 1. It is constructed by a central cobalt unit, and each unit consists of a pair of Co^II centers, four 3- hydroxy-adamantane-1-carboxylic acid anions (L), one water molecule, two bridging 4,4'-bpy ligands and seven uncoordinated water molecules. Four L ligands bind to each pair of Co^II center in a plane, two of which bridge the two Co^II centers as bidentate bridging ligands, while the other two coordinate to a single Co^II center in monodentate mode. Two half parts of 4,4' -bipyridine coordinate Co(1) and Co(2) from the upside and underside. One coordinated water molecule bridges the Co(1) and Co(2) with a similar bond length [Co(1)—O(1W) = 2.160 (3)Å, Co(2)—O(1W) = 2.181 (6)Å]. The structure demonstrates that both of the Co^II ions coordinate in a distorted octahedral geometry. The Co—O (from carboxylic and water oxygen) distances are all within the range 2.019 (2)-2.127 (3)Å, and the Co—N distances range from 2.145 (2)-2.198 (3)Å. The selected bond lengths and angles for the complex are listed in Table 1.

The binuclear unit is further supported by hydrogen bonding interactions involving the non-coordinated oxygen atoms of the two monodentate L ligands, one bridging water molecule and seven uncoordinated water molecules. The hydrogen bonds are listed in Table 2.

Experimental

Reagents and solvents used were of commercially available quality and without purified before using. A mixture of 3-hydroxyadamantane-1-carboxylic acid (0.3924 g, 2 mmol), CoSO₄^.7H₂O (0.2811 g, 1 mmol), 4,4'-bipyridine (0.1562 g, 1 mmol) and water (16 ml) was sealed in a 25 ml stainless steel reactor with a Teflon liner and heated at 160 K for 2 d and then cooled to room temperature over 3 d. The resulting pink crystals suitable for X-ray diffraction were obtained and collected by filtration, washed with water, and evaporated in air for one month.