catena-Poly[[diaquacobalt(II)]-bis(μ-3-carboxy­adamantane-1-carboxyl­ato-κ2 O 1:O 3)]

Li-Ming Tang; Jia-Hui Xu; Xiao-Yan Han; Wei Xu

doi:10.1107/S1600536809007387

. 2009 Mar 6;65(Pt 4):m375. doi: 10.1107/S1600536809007387

catena-Poly[[diaquacobalt(II)]-bis(μ-3-carboxyadamantane-1-carboxylato-κ² O ¹:O ³)]

Li-Ming Tang ^a, Jia-Hui Xu ^a, Xiao-Yan Han ^a, Wei Xu ^a,^*

PMCID: PMC2968899 PMID: 21582328

Abstract

In the title compound, [Co(C₁₂H₁₅O₄)₂(H₂O)₂]_n, adjacent Co^II atoms ( Inline graphic symmetry) are bridged by 3-carboxyadamantane-1-carboxylate anions, forming a chain running along [001]. Interchain O—H⋯O hydrogen bonds link the chains into layers parallel to (100); the layers are further connected via interlayer hydrogen bonds interactions, forming a three-dimensional framework.

Related literature

For related compounds, see: Nielsen et al. (2008 ▶); Zhao et al. (2007 ▶); Zheng et al. (2008 ▶).

Experimental

Crystal data

[Co(C₁₂H₁₅O₄)₂(H₂O)₂]
M _r = 541.44
Orthorhombic,
a = 10.718 (2) Å
b = 23.638 (5) Å
c = 9.0726 (18) Å
V = 2298.6 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 293 K
0.10 × 0.10 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.921, T _max = 0.925
20865 measured reflections
2622 independent reflections
2145 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.086
S = 1.06
2622 reflections
161 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); 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 ptcLa, I. DOI: 10.1107/S1600536809007387/ng2552sup1.cif

e-65-0m375-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809007387/ng2552Isup2.hkl

e-65-0m375-Isup2.hkl^{(128.9KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co—O1	2.0574 (12)
Co—O5	2.0956 (14)
Co—O4ⁱ	2.1061 (12)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1⋯O1ⁱⁱ	0.81	1.82	2.6058 (19)	166
O5—H2⋯O2	0.80	2.07	2.7762 (18)	147
O5—H3⋯O2ⁱⁱⁱ	0.81	2.02	2.8334 (18)	175

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Symmetry codes: (ii) Inline graphic ; (iii) .

Acknowledgments

This project was sponsored by the K. C. Wong Magna Fund of Ningbo University and supported by the Expert Project of Key Basic Research of the Ministry of Science and Technology of China (grant No. 2003CCA00800), the Zhejiang Provincial Natural Science Foundation (grant No. Z203067) and the Ningbo Municipal Natural Science Foundation (grant No. 2006 A610061).

supplementary crystallographic information

Comment

The cambridge Structural Database (Version 5.30, February 2009) lists few examples of metal (II) adamantane-1,3-dicarboxylates (Nielsen et al., 2008; Zhao et al., 2007). The dicarboxylate group is rigid, much more different from the aliphatic dicarboxylic acids (Zheng et al., 2008), effected severely by spacial steric hindrance. The asymmetric unit of the title compoud consists of one Co²⁺ cation, one aqua ligand and one Hadc^- anion (H₂adc = adamantane-1,3-dicarboxylic acid) (Fig.1). The Co atoms at the Wckoff 4a sites are crystallographically imposed by iversion center and are each located in an elongated octahedral coordination sphere defined by two aqua ligands and four carboxylate oxygen atoms from four 3-carboxyadamantane-1-carboxylate anions. The axial Co—O bond distances averaged at 2.106 (1) Å are slightly longer than the equatorial ones of 2.078 (1) Å. The trans- and cisoid O—Co—O angles fall in the regions 88.49 (5)–91.51 (5)° and 180°, respectively, exhibiting slight diviation from the corresponding values for a regular geometry (Table 1). Each carboxylate anion monodentately coordinates one Co²⁺ ion in syn fashion. Interestingly, one of the two carboxylate anions from each ligand is protonated and coordinates one Co²⁺ ion by carbonyl oxygen atom, which is rare in former reports. The Co²⁺ ions are bridged by 3-carboxyadamantane-1-carboxylate anions to form one-dimensional chains running along the [001] direction. On the basis of the interchain O—H···O hydrogen bonds (Table 2),these chains are assembled into layers parallel to (100) (Fig.2). The layers are further connected to form a three-dimensional framework via interlayer hydrogen bonds interaction.

Experimental

Adamantane-1,3-dicarboxylic acid (H₂adc) (0.0666 g, 0.3 mmol), 1 M NaOH (0.5 ml, 0.5 mmol) was consequently added to 15 mol aqueous solution, then the mixture was heated constantly at 90 °C and stirred for 30 min, yielding colorless solution, to which was added CoCl₂.6H₂O (0.2485 g, 1.0 mmol) and continually stirred for 30 min, then the purple solution (pH = 5.12) was cooled to room temperature and laid undisturbed, purple block-like crystals was afforded after two weeks.