Poly[[diaqua[μ5-(R,S)-2-({2-[(1,2-di­carboxyl­atoeth­yl)amino]­eth­yl}amino)­butane­dioato]cobaltate(III)sodium] di­hydrate]

Olena K Trunova; Anatolij V Dudko; Tamara O Makotryk; Olena V Osadcha; Vasily I Pekhnyo; Ganna V Shovkova

doi:10.1107/S160053681104013X

. 2011 Oct 22;67(Pt 11):m1547–m1548. doi: 10.1107/S160053681104013X

Poly[[diaqua[μ₅-(R,S)-2-({2-[(1,2-dicarboxylatoethyl)amino]ethyl}amino)butanedioato]cobaltate(III)sodium] dihydrate]

Olena K Trunova ^a,^*, Anatolij V Dudko ^a, Tamara O Makotryk ^a, Olena V Osadcha ^a, Vasily I Pekhnyo ^a, Ganna V Shovkova ^a

PMCID: PMC3246970 PMID: 22219790

Abstract

In the asymmetric unit of the title coordination polymer, {[CoNa(C₁₀H₁₂N₂O₈)(H₂O)₂]·2H₂O}_n, the Co^II ion is coordinated in a distorted octahedral environment, defined by two N atoms and four carboxylate O atoms. Two Co^II ions and two 2-({2-[(1,2-dicarboxylatoethyl)amino]ethyl}amino)butanedioate (EDDS) ligands form a dimeric complex dianion [Co₂(EDDS)₂]. These dimeric units are connected via Na⁺ ions, forming a three-dimensional polymeric structure. In the crystal, the ligand N—H groups and the coordinated and solvent water molecules are involved in intermolecular N—H⋯O and O—H⋯O hydrogen bonding, reinforcing the three-dimensional polymeric structure.

Related literature

For the synthesis and applications of EDDS and its complexes, see: Jones & Williams (2001 ▶); Kos & Leštan (2003 ▶); Mazurenko & Trunova (2001 ▶); Meers et al. (2005 ▶); Shadchina et al. (2008 ▶); Tandy et al. (2004 ▶, 2006 ▶); Vandevivere et al. (2001 ▶). For related structures, see: Horn et al. (1993 ▶); Pavelčík et al. (1980 ▶). For standard bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[CoNa(C₁₀H₁₂N₂O₈)(H₂O)₂]·2H₂O
M _r = 442.20
Orthorhombic,
a = 10.0207 (2) Å
b = 15.6475 (2) Å
c = 20.3837 (4) Å
V = 3196.14 (10) Å³
Z = 8
Mo Kα radiation
μ = 1.17 mm⁻¹
T = 100 K
0.32 × 0.28 × 0.13 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: numerical (SADABS; Sheldrick, 1996 ▶) T _min = 0.706, T _max = 0.863
11219 measured reflections
3161 independent reflections
2549 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.065
S = 0.97
3161 reflections
265 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2010 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681104013X/lh5329sup1.cif

e-67-m1547-sup1.cif^{(24.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681104013X/lh5329Isup2.hkl

e-67-m1547-Isup2.hkl^{(152KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O7ⁱ	0.84 (2)	2.21 (2)	2.830 (2)	130.6 (18)
N2—H2N⋯O6ⁱⁱ	0.82 (2)	2.16 (2)	2.809 (2)	137.0 (18)
O9—H91⋯O11	0.84 (2)	1.92 (2)	2.741 (2)	166 (2)
O9—H92⋯O2ⁱⁱⁱ	0.80 (3)	2.08 (3)	2.853 (2)	162 (3)
O10—H101⋯O8	0.83 (2)	2.18 (3)	2.972 (2)	160 (2)
O10—H102⋯O2^iv	0.82 (3)	2.04 (3)	2.853 (2)	175 (3)
O11—H111⋯O1	0.79 (3)	2.26 (3)	3.004 (2)	158 (3)
O11—H112⋯O12ⁱⁱⁱ	0.96 (3)	1.77 (3)	2.706 (3)	164 (2)
O12—H121⋯O1	0.77 (3)	2.05 (3)	2.793 (2)	161 (3)
O12—H122⋯O4^v	0.76 (3)	2.04 (3)	2.788 (2)	167 (3)

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

Acknowledgments

The authors gratefully acknowledge the support of this work by the Ukrainian National Academy of Sciences.

supplementary crystallographic information

Comment

Ethylenediamine-N,N'-disuccinic acid and its coordination compounds with different 3 d-metals have attracted much interest due to their potential and practical applications in biochemistry. EDDS can be applied for some technical purposes: for the extraction of heavy metals from soils as an efficient biodegradable chelating agents (Tandy et al., 2004; Tandy et al., 2006), in replacement of edta in soil washing and phytoextraction (Vandevivere et al., 2001; Kos & Leštan, 2003; Meers et al. 2005) or for radionuclide decontamination in the pulp and paper-making industry (Jones & Williams, 2001). Biologically active complexes are widely used in plant growing and animal industries (Mazurenko & Trunova 2001; Shadchina et al. 2008). The biodegradable strong transition metal chelant [S,S] stereoisomer of ethylenediamine disuccinate was investigated for its applicability for the washing extraction of heavy metals from soil, sewage sludge, and harbor sediment (Vandevivere et al., 2001).

In the course of our investigations the title compound was prepared and structurally characterized. The asymmetric unit of the title compound is shown in Fig. 1. The Co^II ion forms a distorted octahedral [CoN₂O₄] environment defined by sets of three five-membered (Co1/O1/C1/C2/N1;/Co1/N1/C3/C4/N2; Co1/N2/C5/C6/O3) and a six-membered (Co1/N2/C5/C7/C8/O5) metallocycle. The sixth O donor from a centrosymmetrically related [Co(edds)]^- complex ion forms a 12-membered macrocycle, as a result a dimeric unit is produced (Fig. 2). The Co-O, Co-N, Na-O bond lengths are in normal ranges and have a good correlation with literature data (Allen et al., 1987; Pavelčík et al., 1980; Horn et al., 1993). The Co1···Co1(-x, -y+1, -z) distance is 5.265 Å, which excludes the possibility of any interaction between the ions. In the crystal the compound exists as a polymeric structure, in which the monomers are interconnected by Na⁺ ions (Fig. 2). The Na⁺ ions are five-coordinate, with a distorted trigonal-bipyramidal coordination geometry formed by oxygen atoms, two of which belong to water molecules and the other three to oxygen atoms of the ligand which do not take part in the coordination of the Coⁱⁱ ion. Intermolecular N—H···O and O—H···O hydrogen bonds in the crystal structure form a three-dimensional supramolecular network which stabilizes the structure (Fig.3, Table 1).

Experimental

A mixture of CoCl₂.6H₂O (2.38 g, 10 mmol) and EDDS (2.92 g, 10 mmol) were dissolved in distilled water (10 ml). The pH was then adjusted to 4.5 by concentrated NaOH solution. Reaction mixture was refluxed with stirring for 24 h. After cooling to room temperature diethyl ether was added into the solution giving a powder crude product. Precipitate was filtered of and washed with methanol for several times (yield 86%). The resulting residue was dissolved in water and was stored in a dark place for slow evaporation. After 4 days suitable crystals for X-ray data collection were obtained.