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

Trunova, O.K.; Dudko, A.V.; Makotryk, T.O.; Osadcha, O.V.; Pekhnyo, V.I.; Shovkova, G.V.

doi:10.1107/S160053681104013X

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages m1547-m1548

doi:10.1107/S160053681104013X

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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 and Ganna V. Shovkova ^a

^aInstitute of General and Inorganic Chemistry, NAS Ukraine, Kyiv, prosp. Palladina 32/34, 03680, Ukraine
^*Correspondence e-mail: trunova@ionc.kiev.ua

(Received 29 August 2011; accepted 29 September 2011; online 22 October 2011)

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, P b c a
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[F² > 2σ(F²)] = 0.029
wR(F²) = 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

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)
Symmetry codes: (i) -x, -y+1, -z; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z; (iv) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681104013X/lh5329sup1.cif

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

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top

	Fig. 1. The asymmetric unit of the title compound with ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Part of the polymeric structure of the title compound formed by sodium ions.
	Fig. 3. Crystal packing of title compound, projected along the a axis. Dashed lines indicate hydrogen bonds.

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

Crystal data top

[CoNa(C₁₀H₁₂N₂O₈)(H₂O)₂]·2H₂O	F(000) = 1824
M_r = 442.20	D_x = 1.838 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4049 reflections
a = 10.0207 (2) Å	θ = 2.6–26.1°
b = 15.6475 (2) Å	µ = 1.17 mm⁻¹
c = 20.3837 (4) Å	T = 100 K
V = 3196.14 (10) Å³	Diamond, violet
Z = 8	0.32 × 0.28 × 0.13 mm

Data collection top

Bruker SMART APEXII diffractometer	3161 independent reflections
Radiation source: fine-focus sealed tube	2549 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ϕ and ω scans	θ_max = 26.1°, θ_min = 2.0°
Absorption correction: numerical (SADABS; Sheldrick, 1996)	h = −7→12
T_min = 0.706, T_max = 0.863	k = −19→19
11219 measured reflections	l = −25→21

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ²(F_o²) + (0.0324P)²] where P = (F_o² + 2F_c²)/3
3161 reflections	(Δ/σ)_max < 0.001
265 parameters	Δρ_max = 0.34 e Å⁻³
1 restraint	Δρ_min = −0.50 e Å⁻³

Crystal data top

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

Data collection top

Bruker SMART APEXII diffractometer	3161 independent reflections
Absorption correction: numerical (SADABS; Sheldrick, 1996)	2549 reflections with I > 2σ(I)
T_min = 0.706, T_max = 0.863	R_int = 0.042
11219 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	1 restraint
wR(F²) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	Δρ_max = 0.34 e Å⁻³
3161 reflections	Δρ_min = −0.50 e Å⁻³
265 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Co1	0.09689 (3)	0.387117 (14)	0.083088 (13)	0.00826 (9)
Na1	0.39217 (9)	0.53940 (5)	0.21505 (4)	0.0178 (2)
C1	0.1871 (2)	0.38312 (11)	−0.04223 (10)	0.0104 (4)
C2	0.0531 (2)	0.33752 (11)	−0.04526 (9)	0.0100 (4)
H2	0.0712	0.2749	−0.0414	0.012*
C3	−0.1234 (2)	0.29948 (11)	0.03843 (10)	0.0120 (5)
H3A	−0.0830	0.2418	0.0400	0.014*
H3B	−0.2034	0.2975	0.0099	0.014*
C4	−0.1601 (2)	0.32957 (12)	0.10675 (10)	0.0130 (5)
H4A	−0.2192	0.3801	0.1038	0.016*
H4B	−0.2088	0.2838	0.1302	0.016*
C5	0.0280 (2)	0.28136 (11)	0.18052 (10)	0.0111 (4)
H5	−0.0412	0.2455	0.2027	0.013*
C6	0.1054 (2)	0.22824 (12)	0.13122 (10)	0.0118 (4)
C7	0.1248 (2)	0.31881 (11)	0.23126 (10)	0.0123 (5)
H7A	0.0714	0.3483	0.2653	0.015*
H7B	0.1714	0.2707	0.2529	0.015*
C8	0.2302 (2)	0.38128 (11)	0.20641 (10)	0.0124 (5)
C9	0.0287 (2)	0.55445 (11)	0.13005 (10)	0.0106 (4)
C10	0.0175 (2)	0.64820 (11)	0.11074 (10)	0.0111 (4)
H10A	0.1083	0.6729	0.1082	0.013*
H10B	−0.0317	0.6792	0.1455	0.013*
N1	−0.02558 (17)	0.36314 (9)	0.01328 (8)	0.0087 (4)
H1N	−0.065 (2)	0.4093 (12)	0.0043 (10)	0.010*
N2	−0.03629 (17)	0.35219 (10)	0.14370 (8)	0.0102 (4)
H2N	−0.057 (2)	0.3904 (12)	0.1691 (11)	0.012*
O1	0.22354 (14)	0.41008 (8)	0.01494 (6)	0.0105 (3)
O2	0.25654 (16)	0.39053 (8)	−0.09163 (7)	0.0163 (3)
O3	0.15026 (14)	0.27071 (7)	0.08149 (6)	0.0113 (3)
O4	0.12621 (15)	0.15144 (8)	0.14003 (7)	0.0158 (3)
O5	0.22710 (14)	0.41130 (8)	0.14795 (7)	0.0119 (3)
O6	0.31703 (15)	0.40383 (8)	0.24573 (7)	0.0184 (4)
O7	0.04285 (14)	0.50388 (7)	0.08043 (6)	0.0107 (3)
O8	0.02390 (15)	0.53288 (8)	0.18835 (7)	0.0156 (3)
O9	0.56412 (18)	0.49111 (10)	0.15130 (8)	0.0245 (4)
H91	0.537 (3)	0.4471 (15)	0.1319 (11)	0.037*
H92	0.605 (3)	0.5215 (16)	0.1272 (14)	0.037*
O10	0.22692 (18)	0.62299 (10)	0.26905 (8)	0.0214 (4)
H101	0.162 (3)	0.5949 (15)	0.2558 (12)	0.032*
H102	0.229 (3)	0.6165 (15)	0.3088 (13)	0.032*
O11	0.49078 (18)	0.36011 (9)	0.06961 (9)	0.0253 (4)
H111	0.415 (3)	0.3726 (17)	0.0657 (14)	0.038*
H112	0.539 (3)	0.3836 (15)	0.0329 (11)	0.038*
O12	0.33610 (19)	0.57331 (10)	0.01853 (8)	0.0241 (4)
H121	0.320 (3)	0.5253 (16)	0.0228 (13)	0.036*
H122	0.348 (3)	0.5872 (17)	0.0539 (14)	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.00957 (17)	0.00764 (12)	0.00757 (14)	0.00002 (11)	−0.00016 (12)	0.00084 (11)
Na1	0.0234 (5)	0.0147 (4)	0.0153 (4)	0.0012 (4)	0.0001 (4)	0.0032 (3)
C1	0.0113 (12)	0.0080 (8)	0.0119 (10)	0.0028 (8)	−0.0009 (9)	0.0029 (8)
C2	0.0141 (12)	0.0078 (8)	0.0082 (10)	0.0000 (8)	0.0013 (9)	−0.0007 (8)
C3	0.0110 (12)	0.0123 (8)	0.0126 (11)	−0.0031 (8)	−0.0009 (9)	0.0017 (8)
C4	0.0081 (12)	0.0163 (9)	0.0145 (11)	−0.0004 (9)	−0.0002 (9)	0.0017 (8)
C5	0.0118 (12)	0.0109 (8)	0.0105 (10)	0.0002 (8)	−0.0009 (9)	0.0036 (8)
C6	0.0103 (12)	0.0137 (9)	0.0114 (10)	−0.0008 (9)	−0.0040 (9)	0.0008 (8)
C7	0.0142 (13)	0.0125 (9)	0.0103 (10)	0.0026 (9)	−0.0011 (9)	−0.0008 (8)
C8	0.0142 (13)	0.0097 (8)	0.0134 (11)	0.0043 (8)	−0.0005 (10)	0.0002 (8)
C9	0.0048 (12)	0.0128 (9)	0.0143 (11)	−0.0016 (8)	−0.0008 (9)	0.0000 (8)
C10	0.0135 (13)	0.0106 (9)	0.0092 (10)	−0.0004 (8)	0.0006 (9)	−0.0007 (8)
N1	0.0099 (10)	0.0072 (7)	0.0089 (9)	0.0014 (7)	−0.0001 (7)	0.0011 (7)
N2	0.0103 (10)	0.0099 (7)	0.0104 (9)	0.0017 (7)	−0.0001 (8)	−0.0010 (7)
O1	0.0091 (8)	0.0117 (6)	0.0107 (7)	−0.0014 (6)	0.0005 (6)	0.0008 (6)
O2	0.0159 (9)	0.0223 (7)	0.0107 (8)	−0.0029 (6)	0.0031 (7)	−0.0004 (6)
O3	0.0126 (8)	0.0099 (6)	0.0114 (7)	0.0018 (6)	0.0007 (6)	0.0014 (6)
O4	0.0241 (10)	0.0095 (6)	0.0138 (8)	0.0018 (6)	−0.0011 (7)	0.0015 (6)
O5	0.0116 (9)	0.0137 (6)	0.0103 (7)	−0.0014 (6)	−0.0021 (6)	0.0013 (6)
O6	0.0203 (9)	0.0198 (7)	0.0153 (8)	−0.0051 (6)	−0.0078 (7)	0.0024 (6)
O7	0.0138 (8)	0.0086 (6)	0.0097 (7)	0.0011 (6)	−0.0005 (6)	0.0008 (6)
O8	0.0229 (10)	0.0156 (6)	0.0083 (7)	0.0033 (6)	0.0017 (7)	0.0016 (6)
O9	0.0310 (12)	0.0211 (8)	0.0214 (9)	−0.0064 (7)	0.0051 (8)	−0.0005 (7)
O10	0.0232 (10)	0.0246 (8)	0.0163 (8)	−0.0030 (7)	−0.0002 (8)	0.0023 (7)
O11	0.0174 (10)	0.0180 (7)	0.0405 (11)	0.0026 (7)	0.0020 (9)	−0.0021 (7)
O12	0.0380 (12)	0.0140 (7)	0.0202 (9)	−0.0057 (7)	−0.0033 (9)	0.0003 (7)

Geometric parameters (Å, º) top

Co1—O5	1.8957 (14)	C5—C7	1.534 (3)
Co1—O3	1.8987 (12)	C5—H5	1.0000
Co1—N2	1.8990 (17)	C6—O4	1.233 (2)
Co1—O7	1.9064 (12)	C6—O3	1.293 (2)
Co1—O1	1.9155 (13)	C7—C8	1.526 (3)
Co1—N1	1.9161 (17)	C7—H7A	0.9900
Na1—O9	2.2866 (19)	C7—H7B	0.9900
Na1—O4ⁱ	2.3336 (15)	C8—O6	1.234 (2)
Na1—O6	2.3363 (15)	C8—O5	1.281 (2)
Na1—O8ⁱⁱ	2.3728 (16)	C9—O8	1.236 (2)
Na1—O10	2.3800 (19)	C9—O7	1.292 (2)
Na1—O5	2.9368 (15)	C9—C10	1.523 (2)
Na1—H101	2.60 (3)	C10—C2ⁱⁱⁱ	1.527 (3)
C1—O2	1.229 (2)	C10—H10A	0.9900
C1—O1	1.292 (2)	C10—H10B	0.9900
C1—C2	1.522 (3)	N1—H1N	0.84 (2)
C2—N1	1.485 (2)	N2—H2N	0.82 (2)
C2—C10ⁱⁱⁱ	1.527 (3)	O4—Na1^iv	2.3336 (15)
C2—H2	1.0000	O8—Na1^v	2.3728 (16)
C3—N1	1.489 (2)	O9—H91	0.84 (2)
C3—C4	1.515 (3)	O9—H92	0.80 (3)
C3—H3A	0.9900	O10—H101	0.83 (2)
C3—H3B	0.9900	O10—H102	0.82 (3)
C4—N2	1.494 (3)	O11—H111	0.79 (3)
C4—H4A	0.9900	O11—H112	0.96 (3)
C4—H4B	0.9900	O12—H121	0.77 (3)
C5—N2	1.486 (2)	O12—H122	0.76 (3)
C5—C6	1.517 (3)

O5—Co1—O3	90.55 (6)	N2—C5—C6	107.20 (16)
O5—Co1—N2	95.02 (7)	N2—C5—C7	109.25 (15)
O3—Co1—N2	86.16 (6)	C6—C5—C7	109.43 (17)
O5—Co1—O7	91.37 (6)	N2—C5—H5	110.3
O3—Co1—O7	177.39 (6)	C6—C5—H5	110.3
N2—Co1—O7	95.43 (6)	C7—C5—H5	110.3
O5—Co1—O1	90.70 (6)	O4—C6—O3	123.80 (19)
O3—Co1—O1	88.91 (6)	O4—C6—C5	121.60 (18)
N2—Co1—O1	172.47 (6)	O3—C6—C5	114.56 (15)
O7—Co1—O1	89.30 (5)	C8—C7—C5	117.30 (17)
O5—Co1—N1	176.22 (7)	C8—C7—H7A	108.0
O3—Co1—N1	88.84 (6)	C5—C7—H7A	108.0
N2—Co1—N1	88.66 (7)	C8—C7—H7B	108.0
O7—Co1—N1	89.12 (6)	C5—C7—H7B	108.0
O1—Co1—N1	85.56 (7)	H7A—C7—H7B	107.2
O9—Na1—O4ⁱ	86.29 (6)	O6—C8—O5	121.08 (19)
O9—Na1—O6	95.44 (6)	O6—C8—C7	117.10 (18)
O4ⁱ—Na1—O6	146.32 (6)	O5—C8—C7	121.79 (18)
O9—Na1—O8ⁱⁱ	92.19 (6)	O8—C9—O7	126.13 (17)
O4ⁱ—Na1—O8ⁱⁱ	128.32 (6)	O8—C9—C10	120.57 (17)
O6—Na1—O8ⁱⁱ	85.30 (5)	O7—C9—C10	113.31 (16)
O9—Na1—O10	165.64 (6)	C9—C10—C2ⁱⁱⁱ	113.63 (15)
O4ⁱ—Na1—O10	80.52 (6)	C9—C10—H10A	108.8
O6—Na1—O10	98.69 (6)	C2ⁱⁱⁱ—C10—H10A	108.8
O8ⁱⁱ—Na1—O10	91.54 (6)	C9—C10—H10B	108.8
O9—Na1—O5	86.23 (5)	C2ⁱⁱⁱ—C10—H10B	108.8
O4ⁱ—Na1—O5	99.39 (5)	H10A—C10—H10B	107.7
O6—Na1—O5	47.42 (5)	C2—N1—C3	116.47 (14)
O8ⁱⁱ—Na1—O5	132.10 (5)	C2—N1—Co1	108.02 (12)
O10—Na1—O5	101.46 (6)	C3—N1—Co1	107.29 (12)
O9—Na1—H101	163.8 (6)	C2—N1—H1N	107.7 (15)
O4ⁱ—Na1—H101	83.6 (5)	C3—N1—H1N	109.9 (14)
O6—Na1—H101	86.1 (5)	Co1—N1—H1N	107.0 (14)
O8ⁱⁱ—Na1—H101	104.0 (6)	C5—N2—C4	115.98 (15)
O10—Na1—H101	18.5 (5)	C5—N2—Co1	103.81 (12)
O5—Na1—H101	83.0 (6)	C4—N2—Co1	108.90 (13)
O2—C1—O1	123.23 (19)	C5—N2—H2N	109.7 (15)
O2—C1—C2	120.69 (18)	C4—N2—H2N	106.2 (16)
O1—C1—C2	116.04 (17)	Co1—N2—H2N	112.4 (15)
N1—C2—C1	108.02 (15)	C1—O1—Co1	113.93 (13)
N1—C2—C10ⁱⁱⁱ	114.61 (16)	C6—O3—Co1	112.44 (12)
C1—C2—C10ⁱⁱⁱ	112.07 (16)	C6—O4—Na1^iv	144.52 (14)
N1—C2—H2	107.3	C8—O5—Co1	126.31 (13)
C1—C2—H2	107.3	C8—O5—Na1	78.66 (11)
C10ⁱⁱⁱ—C2—H2	107.3	Co1—O5—Na1	148.08 (6)
N1—C3—C4	105.57 (15)	C8—O6—Na1	108.23 (12)
N1—C3—H3A	110.6	C9—O7—Co1	126.58 (12)
C4—C3—H3A	110.6	C9—O8—Na1^v	143.85 (14)
N1—C3—H3B	110.6	Na1—O9—H91	107.0 (17)
C4—C3—H3B	110.6	Na1—O9—H92	122.9 (19)
H3A—C3—H3B	108.8	H91—O9—H92	111 (2)
N2—C4—C3	109.59 (17)	Na1—O10—H101	95.7 (18)
N2—C4—H4A	109.8	Na1—O10—H102	112.1 (18)
C3—C4—H4A	109.8	H101—O10—H102	106 (3)
N2—C4—H4B	109.8	H111—O11—H112	108 (3)
C3—C4—H4B	109.8	H121—O12—H122	102 (3)
H4A—C4—H4B	108.2

O2—C1—C2—N1	−161.41 (17)	N1—Co1—O1—C1	−14.24 (13)
O1—C1—C2—N1	20.9 (2)	O4—C6—O3—Co1	179.19 (16)
O2—C1—C2—C10ⁱⁱⁱ	−34.2 (2)	C5—C6—O3—Co1	−3.1 (2)
O1—C1—C2—C10ⁱⁱⁱ	148.05 (16)	O5—Co1—O3—C6	76.97 (13)
N1—C3—C4—N2	−46.74 (19)	N2—Co1—O3—C6	−18.03 (14)
N2—C5—C6—O4	−152.14 (19)	O1—Co1—O3—C6	167.66 (13)
C7—C5—C6—O4	89.5 (2)	N1—Co1—O3—C6	−106.76 (14)
N2—C5—C6—O3	30.1 (2)	O3—C6—O4—Na1^iv	169.60 (14)
C7—C5—C6—O3	−88.3 (2)	C5—C6—O4—Na1^iv	−7.9 (4)
N2—C5—C7—C8	−53.7 (2)	O6—C8—O5—Co1	−177.17 (13)
C6—C5—C7—C8	63.4 (2)	C7—C8—O5—Co1	0.7 (3)
C5—C7—C8—O6	−172.07 (17)	O6—C8—O5—Na1	−19.22 (17)
C5—C7—C8—O5	10.0 (3)	C7—C8—O5—Na1	158.64 (18)
O8—C9—C10—C2ⁱⁱⁱ	−146.6 (2)	O3—Co1—O5—C8	−64.38 (16)
O7—C9—C10—C2ⁱⁱⁱ	33.4 (2)	N2—Co1—O5—C8	21.81 (16)
C1—C2—N1—C3	−150.78 (16)	O7—Co1—O5—C8	117.39 (15)
C10ⁱⁱⁱ—C2—N1—C3	83.5 (2)	O1—Co1—O5—C8	−153.29 (15)
C1—C2—N1—Co1	−30.05 (16)	O3—Co1—O5—Na1	159.72 (13)
C10ⁱⁱⁱ—C2—N1—Co1	−155.76 (12)	N2—Co1—O5—Na1	−114.09 (13)
C4—C3—N1—C2	164.59 (16)	O7—Co1—O5—Na1	−18.51 (13)
C4—C3—N1—Co1	43.47 (17)	O1—Co1—O5—Na1	70.80 (13)
O3—Co1—N1—C2	−64.06 (11)	O9—Na1—O5—C8	112.60 (12)
N2—Co1—N1—C2	−150.24 (12)	O4ⁱ—Na1—O5—C8	−161.79 (12)
O7—Co1—N1—C2	114.30 (11)	O6—Na1—O5—C8	11.67 (11)
O1—Co1—N1—C2	24.94 (11)	O8ⁱⁱ—Na1—O5—C8	23.07 (14)
O3—Co1—N1—C3	62.25 (12)	O10—Na1—O5—C8	−79.65 (12)
N2—Co1—N1—C3	−23.93 (12)	O9—Na1—O5—Co1	−102.28 (13)
O7—Co1—N1—C3	−119.39 (12)	O4ⁱ—Na1—O5—Co1	−16.67 (14)
O1—Co1—N1—C3	151.24 (12)	O6—Na1—O5—Co1	156.79 (15)
C6—C5—N2—C4	78.7 (2)	O8ⁱⁱ—Na1—O5—Co1	168.18 (11)
C7—C5—N2—C4	−162.84 (17)	O10—Na1—O5—Co1	65.47 (14)
C6—C5—N2—Co1	−40.72 (17)	O5—C8—O6—Na1	25.3 (2)
C7—C5—N2—Co1	77.76 (16)	C7—C8—O6—Na1	−152.67 (13)
C3—C4—N2—C5	−88.7 (2)	O9—Na1—O6—C8	−92.30 (14)
C3—C4—N2—Co1	27.91 (17)	O4ⁱ—Na1—O6—C8	−0.8 (2)
O5—Co1—N2—C5	−57.29 (12)	O8ⁱⁱ—Na1—O6—C8	175.94 (14)
O3—Co1—N2—C5	32.93 (12)	O10—Na1—O6—C8	85.10 (14)
O7—Co1—N2—C5	−149.15 (12)	O5—Na1—O6—C8	−12.52 (12)
N1—Co1—N2—C5	121.86 (12)	O8—C9—O7—Co1	−14.0 (3)
O5—Co1—N2—C4	178.59 (11)	C10—C9—O7—Co1	165.99 (13)
O3—Co1—N2—C4	−91.20 (12)	O5—Co1—O7—C9	−40.90 (16)
O7—Co1—N2—C4	86.72 (12)	N2—Co1—O7—C9	54.28 (17)
O2—C1—O1—Co1	−178.47 (14)	O1—Co1—O7—C9	−131.58 (16)
C2—C1—O1—Co1	−0.80 (19)	N1—Co1—O7—C9	142.85 (17)
O5—Co1—O1—C1	165.23 (12)	O7—C9—O8—Na1^v	−123.2 (2)
O3—Co1—O1—C1	74.69 (13)	C10—C9—O8—Na1^v	56.8 (3)
O7—Co1—O1—C1	−103.41 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O7ⁱⁱⁱ	0.84 (2)	2.21 (2)	2.830 (2)	130.6 (18)
N2—H2N···O6^v	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···O2^vi	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^vii	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···O12^vi	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···O4ⁱ	0.76 (3)	2.04 (3)	2.788 (2)	167 (3)

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

Experimental details

Crystal data
Chemical formula	[CoNa(C₁₀H₁₂N₂O₈)(H₂O)₂]·2H₂O
M_r	442.20
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	10.0207 (2), 15.6475 (2), 20.3837 (4)
V (Å³)	3196.14 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.17
Crystal size (mm)	0.32 × 0.28 × 0.13

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Numerical (SADABS; Sheldrick, 1996)
T_min, T_max	0.706, 0.863
No. of measured, independent and observed [I > 2σ(I)] reflections	11219, 3161, 2549
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.620

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.065, 0.97
No. of reflections	3161
No. of parameters	265
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.50

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2010), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

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)

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

Acknowledgements

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

References

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