Poly[di-μ2-aqua-μ5-(pyridine-2,6-dicarboxyl­ato)-μ3-(pyridine-2,6-dicarboxyl­ato)-cobalt(II)disodium]

Boyko, A.N.; Golenya, I.A.; Izotova, Y.A.; Haukka, M.; Prisyazhnaya, E.V.

doi:10.1107/S1600536811048252

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1782-m1783

https://doi.org/10.1107/S1600536811048252

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Poly[di-μ₂-aqua-μ₅-(pyridine-2,6-dicarboxylato)-μ₃-(pyridine-2,6-dicarboxylato)-cobalt(II)disodium]

Alexander N. Boyko,^a Irina A. Golenya,^a ^* Yulia A. Izotova,^b Matti Haukka ^c and Elena V. Prisyazhnaya ^d

^aKiev National Taras Shevchenko University, Department of Chemistry, Volodymyrska Street 64, 01601 Kiev, Ukraine, ^bDepartment of Chemistry, St Petersburg State University, Universitetsky Pr. 26, 198504 Stary Petergof, Russian Federation, ^cUniversity of Joensuu, Department of Chemistry, PO Box 111, FI-80101 Joensuu, Finland, and ^dKyiv National University of Construction and Architecture, Department of Chemistry, Povitroflotsky Avenue 31, 03680 Kiev, Ukraine
^*Correspondence e-mail: igolenya@ua.fm

(Received 6 November 2011; accepted 14 November 2011; online 19 November 2011)

In the title compound, [CoNa₂(C₇H₃NO₄)₂(H₂O)₂]_n, the Co^II atom is coordinated by two pyridine N atoms and four carboxylate O atoms from two doubly deprotonated pyridine-2,6-dicarboxylate ligands in a distorted octahedral geometry. One Na⁺ cation is coordinated by three carboxylate O atoms and two water molecules and the other is coordinated by five carboxylate O atoms and two water molecules in an irregular geometry. The bis(pyridine-2,6-dicarboxylato)cobalt complex units are connected by Na⁺ cations and bridging water molecules into a three-dimensional coordination network. O—H⋯O hydrogen bonds are formed between the water molecules and the carboxylate O atoms.

Related literature

For hydrolytic decomposition of hydroxamate ligands upon complex formation, see: Dobosz et al. (1999 ); Świątek-Kozłowska et al. (2000 ). For related structures, see: Fritsky et al. (2001 ); Krämer & Fritsky (2000 ); Mokhir et al. (2002 ); Moroz et al. (2010 ); Sachse et al. (2008 ); Sliva et al. (1997 ); Wörl et al. (2005a ,b ). For the preparation of the ligand, see: Świątek-Kozłowska et al. (2002 ).

Experimental

Crystal data

[CoNa₂(C₇H₃NO₄)₂(H₂O)₂]
M_r = 471.15
Orthorhombic, P n a 2₁
a = 7.9540 (3) Å
b = 13.2187 (3) Å
c = 15.1475 (3) Å
V = 1592.63 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.20 mm⁻¹
T = 120 K
0.17 × 0.10 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.826, T_max = 0.931
22979 measured reflections
3640 independent reflections
3388 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.054
S = 1.07
3640 reflections
264 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.32 e Å⁻³
Absolute structure: Flack (1983 ), 1749 Friedel pairs
Flack parameter: 0.017 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9A⋯O7ⁱ	0.84	1.94	2.742 (2)	159
O9—H9B⋯O4ⁱⁱ	0.85	1.90	2.717 (2)	162
O10—H10A⋯O3	0.86	1.88	2.725 (2)	166
O10—H10B⋯O4ⁱⁱⁱ	0.91	2.12	2.993 (2)	159
Symmetry codes: (i) x-1, y, z; (ii) $[-x-1, -y, z+{\script{1\over 2}}]$ ; (iii) $[-x, -y, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811048252/hy2486sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811048252/hy2486Isup2.hkl

checkCIF report

Comment top

Hydroxamic acids are widely used in synthesis of polynuclear compounds and coordination polymers. However, when the synthesis is conducted in alkaline conditions, hydrolytic decomposition of the hydroxamate function resulting in the formation of carboxylic groups sometimes occurs (Dobosz et al., 1999; Świątek-Kozłowska et al., 2000). Herein we report the crystal structure of the title compound obtained as a result of hydrolytic decomposition of pyridine-2,6-dihydroxamic acid in the course of formation of the anionic complex with cobalt(II) in the presence of sodium hydroxide.

In the title compound, the Co^II atom is coordinated by two pyridine N atoms and four carboxylate O atoms from two doubly deprotonated pyridine-2,6-dicarboxylate ligands in a distorted octahedral geometry (Fig. 1). The Co—O bond lengths are in a range of 2.1235 (17)–2.2065 (14) Å, which clearly indicates that the central ion is in bivalent state (Sliva et al., 1997). The Na ions are coordinated by O atoms of pyridine-2,6-dicarboxylate ligands and two water molecules in irregular geometries. Na1 atom is in a strongly distorted square-pyramidal environment, while Na2 atom exhibits a coordination number 7 and its geometry approaches to a distorted pentagonal-bipyramidal. The Na—O bond lengths lie in a range of 2.2756 (11)–2.7557 (17) Å, which is normal for sodium ions (Mokhir et al., 2002; Świątek-Kozłowska et al., 2000). The C9—O3 and C9—O7 bond lengths [1.284 (2) and 1.240 (2) Å] are typical for a monodentately coordinated carboxylate (Wörl et al., 2005a,b). The C—N and C—C bond lengths in the pyridine rings are normal for 2-substituted pyridine derivatives (Fritsky et al., 2001; Krämer & Fritsky, 2000; Moroz et al., 2010; Sachse et al., 2008).

In the crystal packing (Fig. 2), the bis(pyridine-2,6-dicarboxylato)cobalt(II) complex units are connected by the sodium ions and water molecules into a three-dimensional coordination network. The two water molecules bridge the sodium ions and form intermolecular hydrogen bonds (Table 1).

Related literature top

For hydrolytic decomposition of hydroxamate ligands upon complex formation, see: Dobosz et al. (1999); Świątek-Kozłowska et al. (2000). For related structures, see: Fritsky et al. (2001); Krämer & Fritsky (2000); Mokhir et al. (2002); Moroz et al. (2010); Sachse et al. (2008); Sliva et al. (1997); Wörl et al. (2005a,b). For the preparation of the ligand, see: Świątek-Kozłowska et al. (2002).

Experimental top

Cobalt(II) perchlorate hexahydrate (0.0365 g, 0.1 mmol) was dissolved in methanol (5 ml) and mixed with a solution of pyridine-2,6-dihydroxamic acid (0.0197 g, 0.1 mmol) synthesized according to Świątek-Kozłowska et al. (2002) in H₂O, and then to the obtained mixture solution sodium hydroxide (0.1 M, 1 ml) was added. The mixture was stirred for 30 min and filtered. The insoluble material was dissolved in DMSO (3 ml) and set aside for crystallization by slow diffusion of isopropanol vapours into the formed solution. The greenish yellow crystals formed in 5–7 days were filtered off, washed with isopropanol and dried (yield: 78%).

Structure description top

For hydrolytic decomposition of hydroxamate ligands upon complex formation, see: Dobosz et al. (1999); Świątek-Kozłowska et al. (2000). For related structures, see: Fritsky et al. (2001); Krämer & Fritsky (2000); Mokhir et al. (2002); Moroz et al. (2010); Sachse et al. (2008); Sliva et al. (1997); Wörl et al. (2005a,b). For the preparation of the ligand, see: Świątek-Kozłowska et al. (2002).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoinds are shown at the 50% probability level. Hydrogen bonds are indicated by dashed lines. [Symmetry codes: (i) 1/2+x, 1/2-y, z; (ii) -x, -y, 1/2+z; (iii) -1/2-x, 1/2+y, 1/2+z.]
	Fig. 2. A view of the crystal packing for the title compound.

Poly[di-µ₂-aqua-µ₅-(pyridine-2,6-dicarboxylato)-µ₃-(pyridine- 2,6-dicarboxylato)-cobalt(II)disodium] top

Crystal data top

[CoNa₂(C₇H₃NO₄)₂(H₂O)₂]	F(000) = 948
M_r = 471.15	D_x = 1.965 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 14413 reflections
a = 7.9540 (3) Å	θ = 1.0–27.5°
b = 13.2187 (3) Å	µ = 1.20 mm⁻¹
c = 15.1475 (3) Å	T = 120 K
V = 1592.63 (8) Å³	Block, green-yellow
Z = 4	0.17 × 0.10 × 0.06 mm

Data collection top

Nonius KappaCCD diffractometer	3640 independent reflections
Radiation source: fine-focus sealed tube	3388 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.037
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
φ and ω scans with κ offset	h = −10→10
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	k = −17→15
T_min = 0.826, T_max = 0.931	l = −19→19
22979 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.054	w = 1/[σ²(F_o²) + (0.0247P)² + 0.349P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
3640 reflections	Δρ_max = 0.30 e Å⁻³
264 parameters	Δρ_min = −0.32 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1749 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.017 (10)

Crystal data top

[CoNa₂(C₇H₃NO₄)₂(H₂O)₂]	V = 1592.63 (8) Å³
M_r = 471.15	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 7.9540 (3) Å	µ = 1.20 mm⁻¹
b = 13.2187 (3) Å	T = 120 K
c = 15.1475 (3) Å	0.17 × 0.10 × 0.06 mm

Data collection top

Nonius KappaCCD diffractometer	3640 independent reflections
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	3388 reflections with I > 2σ(I)
T_min = 0.826, T_max = 0.931	R_int = 0.037
22979 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.054	Δρ_max = 0.30 e Å⁻³
S = 1.07	Δρ_min = −0.32 e Å⁻³
3640 reflections	Absolute structure: Flack (1983), 1749 Friedel pairs
264 parameters	Absolute structure parameter: 0.017 (10)
1 restraint

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

	x	y	z	U_iso*/U_eq
Co1	−0.05451 (3)	−0.010675 (17)	0.25557 (2)	0.01076 (7)
Na1	−0.07221 (11)	0.28100 (6)	0.49042 (5)	0.01966 (19)
Na2	−0.26548 (10)	0.06445 (7)	0.52208 (6)	0.0212 (2)
O1	−0.24152 (18)	0.05370 (10)	0.34732 (9)	0.0146 (3)
O2	0.1115 (2)	0.00400 (10)	0.14651 (11)	0.0163 (4)
O3	0.1244 (2)	−0.00136 (10)	0.36280 (10)	0.0141 (3)
O4	−0.21550 (19)	−0.09844 (10)	0.16519 (10)	0.0158 (3)
O5	−0.30854 (18)	0.20122 (10)	0.41058 (9)	0.0162 (3)
O6	0.18157 (18)	0.10750 (11)	0.03583 (9)	0.0183 (3)
O7	0.23230 (19)	−0.09423 (11)	0.47351 (9)	0.0180 (3)
O8	−0.2541 (2)	−0.25677 (11)	0.11508 (9)	0.0188 (3)
O9	−0.55522 (17)	0.05090 (11)	0.53885 (10)	0.0160 (3)
H9A	−0.5987	0.0012	0.5123	0.024*
H9B	−0.6164	0.0561	0.5846	0.024*
O10	0.01645 (19)	0.11758 (10)	0.49835 (10)	0.0164 (3)
H10A	0.0629	0.0876	0.4541	0.025*
H10B	0.0745	0.0949	0.5461	0.025*
N1	−0.0691 (2)	0.13931 (12)	0.22358 (10)	0.0109 (3)
N2	−0.0236 (2)	−0.15690 (12)	0.29271 (11)	0.0112 (3)
C1	−0.1490 (2)	0.20301 (14)	0.27769 (12)	0.0120 (4)
C2	−0.2419 (2)	0.14940 (15)	0.35081 (13)	0.0126 (4)
C3	−0.1404 (2)	0.30715 (14)	0.26432 (15)	0.0158 (4)
H3	−0.1946	0.3527	0.3036	0.019*
C4	−0.0503 (3)	0.34270 (15)	0.19181 (14)	0.0153 (4)
H4	−0.0429	0.4134	0.1812	0.018*
C5	0.0285 (3)	0.27576 (16)	0.13529 (14)	0.0151 (4)
H5	0.0879	0.2992	0.0849	0.018*
C6	0.0182 (3)	0.17334 (15)	0.15435 (13)	0.0121 (4)
C7	0.1110 (3)	0.09008 (15)	0.10677 (13)	0.0136 (4)
C8	0.0704 (3)	−0.17728 (16)	0.36365 (13)	0.0121 (4)
C9	0.1491 (3)	−0.08438 (15)	0.40480 (13)	0.0136 (4)
C10	0.0974 (3)	−0.27604 (15)	0.39155 (14)	0.0153 (4)
H10	0.1621	−0.2900	0.4429	0.018*
C11	0.0270 (3)	−0.35394 (15)	0.34216 (13)	0.0149 (4)
H11	0.0446	−0.4222	0.3594	0.018*
C12	−0.0685 (2)	−0.33259 (14)	0.26795 (15)	0.0148 (4)
H12	−0.1161	−0.3854	0.2335	0.018*
C13	−0.0928 (2)	−0.23155 (14)	0.24533 (14)	0.0120 (4)
C14	−0.1961 (3)	−0.19475 (15)	0.16881 (13)	0.0131 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01387 (12)	0.00901 (11)	0.00941 (12)	0.00019 (9)	0.00036 (12)	0.00034 (13)
Na1	0.0260 (5)	0.0149 (4)	0.0181 (4)	−0.0034 (3)	0.0049 (3)	−0.0026 (3)
Na2	0.0140 (4)	0.0243 (5)	0.0251 (4)	0.0016 (3)	0.0007 (4)	0.0109 (4)
O1	0.0164 (8)	0.0128 (7)	0.0147 (7)	−0.0013 (6)	0.0015 (6)	0.0004 (6)
O2	0.0214 (9)	0.0125 (8)	0.0151 (9)	0.0016 (6)	0.0058 (7)	0.0001 (6)
O3	0.0164 (9)	0.0130 (8)	0.0130 (9)	−0.0006 (6)	−0.0009 (7)	−0.0006 (5)
O4	0.0194 (8)	0.0142 (7)	0.0137 (7)	−0.0007 (6)	−0.0030 (6)	0.0014 (6)
O5	0.0180 (8)	0.0181 (7)	0.0124 (7)	0.0024 (6)	0.0024 (6)	−0.0020 (6)
O6	0.0217 (8)	0.0203 (8)	0.0130 (7)	−0.0022 (6)	0.0057 (6)	0.0004 (6)
O7	0.0194 (8)	0.0201 (8)	0.0145 (8)	0.0017 (6)	−0.0067 (6)	−0.0003 (6)
O8	0.0254 (8)	0.0168 (8)	0.0141 (7)	−0.0049 (6)	−0.0050 (6)	−0.0016 (6)
O9	0.0162 (7)	0.0137 (7)	0.0181 (7)	−0.0016 (6)	0.0037 (6)	−0.0029 (6)
O10	0.0184 (8)	0.0186 (7)	0.0120 (7)	0.0018 (6)	−0.0001 (6)	−0.0010 (6)
N1	0.0121 (9)	0.0111 (8)	0.0095 (7)	0.0003 (7)	−0.0010 (6)	−0.0010 (6)
N2	0.0117 (8)	0.0112 (8)	0.0108 (8)	0.0002 (7)	0.0008 (6)	0.0001 (6)
C1	0.0104 (9)	0.0138 (9)	0.0118 (10)	0.0012 (8)	−0.0021 (7)	−0.0012 (7)
C2	0.0118 (10)	0.0154 (10)	0.0106 (9)	0.0019 (8)	−0.0016 (8)	−0.0011 (8)
C3	0.0164 (9)	0.0128 (8)	0.0180 (11)	0.0029 (7)	−0.0012 (9)	−0.0014 (9)
C4	0.0182 (11)	0.0090 (9)	0.0185 (10)	0.0005 (8)	−0.0042 (8)	0.0049 (8)
C5	0.0162 (11)	0.0169 (10)	0.0123 (10)	−0.0014 (8)	−0.0024 (8)	0.0045 (8)
C6	0.0115 (10)	0.0136 (10)	0.0114 (10)	−0.0008 (8)	−0.0011 (8)	−0.0006 (8)
C7	0.0121 (10)	0.0163 (10)	0.0125 (10)	−0.0029 (8)	−0.0009 (8)	−0.0016 (8)
C8	0.0105 (11)	0.0145 (10)	0.0111 (10)	0.0005 (7)	0.0029 (7)	0.0008 (8)
C9	0.0112 (10)	0.0160 (10)	0.0137 (10)	0.0021 (8)	0.0023 (8)	0.0001 (8)
C10	0.0152 (10)	0.0158 (11)	0.0150 (10)	0.0030 (8)	0.0025 (8)	0.0040 (8)
C11	0.0165 (11)	0.0116 (10)	0.0167 (10)	0.0039 (8)	0.0025 (8)	0.0040 (8)
C12	0.0167 (10)	0.0115 (8)	0.0163 (11)	−0.0002 (7)	0.0064 (8)	−0.0033 (8)
C13	0.0124 (9)	0.0128 (8)	0.0108 (10)	0.0001 (7)	0.0029 (8)	−0.0025 (8)
C14	0.0134 (10)	0.0140 (9)	0.0119 (9)	−0.0006 (8)	0.0038 (8)	0.0036 (8)

Geometric parameters (Å, º) top

Co1—N2	2.0281 (16)	O9—H9A	0.8440
Co1—N1	2.0443 (17)	O9—H9B	0.8492
Co1—O2	2.1235 (17)	O10—H10A	0.8618
Co1—O3	2.1631 (17)	O10—H10B	0.9091
Co1—O4	2.2044 (15)	N1—C6	1.336 (3)
Co1—O1	2.2065 (14)	N1—C1	1.336 (2)
Na1—O10	2.2757 (16)	N2—C8	1.337 (3)
Na1—O9ⁱ	2.3439 (16)	N2—C13	1.339 (2)
Na1—O8ⁱⁱ	2.3924 (16)	C1—C3	1.393 (3)
Na1—O5ⁱ	2.4324 (16)	C1—C2	1.508 (3)
Na1—O5	2.4715 (16)	C3—C4	1.393 (3)
Na2—O9	2.3254 (16)	C3—H3	0.9500
Na2—O10	2.3772 (17)	C4—C5	1.382 (3)
Na2—O6ⁱⁱⁱ	2.3780 (17)	C4—H4	0.9500
Na2—O2ⁱⁱⁱ	2.4232 (18)	C5—C6	1.387 (3)
Na2—O5	2.4978 (16)	C5—H5	0.9500
Na2—O1	2.6579 (17)	C6—C7	1.508 (3)
Na2—O8ⁱⁱ	2.7557 (17)	C8—C10	1.389 (3)
O1—C2	1.266 (2)	C8—C9	1.513 (3)
O2—C7	1.287 (2)	C10—C11	1.391 (3)
O3—C9	1.284 (2)	C10—H10	0.9500
O4—C14	1.284 (2)	C11—C12	1.386 (3)
O5—C2	1.253 (2)	C11—H11	0.9500
O6—C7	1.234 (2)	C12—C13	1.392 (3)
O7—C9	1.240 (2)	C12—H12	0.9500
O8—C14	1.244 (2)	C13—C14	1.502 (3)

N2—Co1—N1	175.53 (7)	C14—O8—Na2^vi	151.48 (14)
N2—Co1—O2	103.15 (6)	Na1^vi—O8—Na2^vi	78.94 (5)
N1—Co1—O2	76.24 (6)	Na2—O9—Na1^v	87.13 (5)
N2—Co1—O3	76.47 (6)	Na2—O9—H9A	114.5
N1—Co1—O3	99.21 (6)	Na1^v—O9—H9A	124.4
O2—Co1—O3	99.78 (5)	Na2—O9—H9B	130.6
N2—Co1—O4	75.00 (6)	Na1^v—O9—H9B	98.4
N1—Co1—O4	109.28 (6)	H9A—O9—H9B	102.5
O2—Co1—O4	85.76 (6)	Na1—O10—Na2	89.78 (6)
O3—Co1—O4	151.46 (5)	Na1—O10—H10A	121.9
N2—Co1—O1	105.94 (6)	Na2—O10—H10A	112.7
N1—Co1—O1	74.76 (6)	Na1—O10—H10B	120.8
O2—Co1—O1	150.91 (5)	Na2—O10—H10B	105.1
O3—Co1—O1	87.05 (6)	H10A—O10—H10B	104.4
O4—Co1—O1	101.68 (5)	C6—N1—C1	121.13 (17)
O10—Na1—O9ⁱ	149.94 (7)	C6—N1—Co1	118.90 (13)
O10—Na1—O8ⁱⁱ	86.51 (6)	C1—N1—Co1	119.52 (13)
O9ⁱ—Na1—O8ⁱⁱ	89.09 (5)	C8—N2—C13	120.84 (17)
O10—Na1—O5ⁱ	81.42 (6)	C8—N2—Co1	118.88 (14)
O9ⁱ—Na1—O5ⁱ	90.82 (5)	C13—N2—Co1	120.26 (13)
O8ⁱⁱ—Na1—O5ⁱ	155.57 (6)	N1—C1—C3	120.67 (17)
O10—Na1—O5	81.75 (5)	N1—C1—C2	112.81 (17)
O9ⁱ—Na1—O5	126.98 (6)	C3—C1—C2	126.53 (17)
O8ⁱⁱ—Na1—O5	81.84 (5)	O5—C2—O1	125.27 (18)
O5ⁱ—Na1—O5	116.98 (6)	O5—C2—C1	118.75 (17)
O9—Na2—O10	166.94 (6)	O1—C2—C1	115.96 (17)
O9—Na2—O6ⁱⁱⁱ	101.24 (6)	C1—C3—C4	118.24 (18)
O10—Na2—O6ⁱⁱⁱ	91.77 (5)	C1—C3—H3	120.9
O9—Na2—O2ⁱⁱⁱ	112.79 (7)	C4—C3—H3	120.9
O10—Na2—O2ⁱⁱⁱ	75.58 (6)	C5—C4—C3	120.39 (19)
O6ⁱⁱⁱ—Na2—O2ⁱⁱⁱ	55.47 (5)	C5—C4—H4	119.8
O9—Na2—O5	89.64 (6)	C3—C4—H4	119.8
O10—Na2—O5	79.24 (5)	C4—C5—C6	118.01 (19)
O6ⁱⁱⁱ—Na2—O5	142.14 (6)	C4—C5—H5	121.0
O2ⁱⁱⁱ—Na2—O5	149.95 (6)	C6—C5—H5	121.0
O9—Na2—O1	100.12 (6)	N1—C6—C5	121.52 (19)
O10—Na2—O1	78.32 (5)	N1—C6—C7	112.57 (17)
O6ⁱⁱⁱ—Na2—O1	90.91 (5)	C5—C6—C7	125.74 (19)
O2ⁱⁱⁱ—Na2—O1	135.93 (6)	O6—C7—O2	124.80 (19)
O5—Na2—O1	51.32 (4)	O6—C7—C6	120.17 (18)
O9—Na2—O8ⁱⁱ	93.80 (6)	O2—C7—C6	115.02 (17)
O10—Na2—O8ⁱⁱ	76.74 (5)	N2—C8—C10	121.37 (19)
O6ⁱⁱⁱ—Na2—O8ⁱⁱ	139.38 (6)	N2—C8—C9	113.53 (17)
O2ⁱⁱⁱ—Na2—O8ⁱⁱ	83.92 (6)	C10—C8—C9	125.01 (19)
O5—Na2—O8ⁱⁱ	74.50 (5)	O7—C9—O3	125.97 (19)
O1—Na2—O8ⁱⁱ	123.43 (5)	O7—C9—C8	118.77 (18)
C7ⁱⁱⁱ—Na2—O8ⁱⁱ	112.28 (6)	O3—C9—C8	115.24 (17)
C2—O1—Co1	114.40 (12)	C8—C10—C11	118.04 (19)
C2—O1—Na2	84.54 (11)	C8—C10—H10	121.0
Co1—O1—Na2	134.13 (6)	C11—C10—H10	121.0
C7—O2—Co1	116.28 (13)	C12—C11—C10	120.42 (18)
C7—O2—Na2^iv	88.16 (12)	C12—C11—H11	119.8
Co1—O2—Na2^iv	152.28 (7)	C10—C11—H11	119.8
C9—O3—Co1	115.10 (13)	C11—C12—C13	118.10 (19)
C14—O4—Co1	115.19 (13)	C11—C12—H12	121.0
C2—O5—Na1^v	140.98 (13)	C13—C12—H12	121.0
C2—O5—Na1	105.37 (12)	N2—C13—C12	121.21 (18)
Na1^v—O5—Na1	111.79 (6)	N2—C13—C14	113.58 (16)
C2—O5—Na2	92.00 (12)	C12—C13—C14	125.21 (18)
Na1^v—O5—Na2	81.48 (5)	O8—C14—O4	125.53 (19)
Na1—O5—Na2	82.74 (5)	O8—C14—C13	119.63 (17)
C7—O6—Na2^iv	91.47 (12)	O4—C14—C13	114.84 (17)
C14—O8—Na1^vi	126.37 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9A···O7^vii	0.84	1.94	2.742 (2)	159
O9—H9B···O4^viii	0.85	1.90	2.717 (2)	162
O10—H10A···O3	0.86	1.88	2.725 (2)	166
O10—H10B···O4ⁱⁱⁱ	0.91	2.12	2.993 (2)	159

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

Experimental details

Crystal data
Chemical formula	[CoNa₂(C₇H₃NO₄)₂(H₂O)₂]
M_r	471.15
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	120
a, b, c (Å)	7.9540 (3), 13.2187 (3), 15.1475 (3)
V (Å³)	1592.63 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.20
Crystal size (mm)	0.17 × 0.10 × 0.06

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.826, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	22979, 3640, 3388
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.054, 1.07
No. of reflections	3640
No. of parameters	264
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.32
Absolute structure	Flack (1983), 1749 Friedel pairs
Absolute structure parameter	0.017 (10)

Computer programs: COLLECT (Nonius, 1998), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9A···O7ⁱ	0.84	1.94	2.742 (2)	159
O9—H9B···O4ⁱⁱ	0.85	1.90	2.717 (2)	162
O10—H10A···O3	0.86	1.88	2.725 (2)	166
O10—H10B···O4ⁱⁱⁱ	0.91	2.12	2.993 (2)	159

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

Acknowledgements

Financial support from the State Fund for Fundamental Research of Ukraine (grant No. F40.3/041) and the Russian Foundation for Basic Research (grant No. 11-03-90417) is gratefully acknowledged.

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