catena-Poly[ammonium [aqua­bis­(μ-2,3,5,6-tetra­oxo-4-nitro­pyridin-4-ido)argentate(I)]]

Nguyen Dinh Do; Olga Kovalchukova; Adam Stash; Svetlana Strashnova

doi:10.1107/S1600536813020631

. 2013 Jul 31;69(Pt 8):m477–m478. doi: 10.1107/S1600536813020631

catena-Poly[ammonium [aquabis(μ-2,3,5,6-tetraoxo-4-nitropyridin-4-ido)argentate(I)]]

Nguyen Dinh Do ^a,^*, Olga Kovalchukova ^b, Adam Stash ^c, Svetlana Strashnova ^b

PMCID: PMC3793704 PMID: 24109291

Abstract

In the title compound, {(NH₄)[Ag(C₅HN₂O₆)₂(H₂O)]}_n, the Ag^I cation is seven-coordinated and is surrounded by four oxo O atoms of the 2,3,5,6-tetraoxo-4-nitropyridin-4-ide species [Ag—O = 2.3848 (19), 2.4931 (18), 2.5361 (18) and 2.573 (2) Å], two nitro O atoms [Ag—O = 2.644 (2) and 2.661 (2) Å], and one water molecule [Ag—O = 2.3133 (19) Å]. The pyridin-4-ide mono-anions act as polydentate bridging ligands and form a three-dimensional network that is stabilized through O—H⋯O and N—H⋯O hydrogen bonds involving the coordinating water molecule and the imide function as donator groups. The ammonium cations are located in the cavities of the framework and are also involved in hydrogen bonding to O atoms of the ligand.

Related literature

For reviews of 1,2-dicarbonyl compounds, see: Aldoshin (2008 ▶); Ohba & Okawa (2000 ▶). The synthesis and crystal structures of ammonium and sodium 2,3,5,6-tetraoxo-4-nitropyridinates have been reported previously (Palkina et al., 2000 ▶; Kuzmina et al., 2004 ▶). The structure of the organic anion in its hexaaqua metal salts is described by Kovalchukova et al. (2003 ▶ and 2013 ▶). For references to related structures of metal complexes with cyclic polyoxo compounds, see: Coronado et al. (2007 ▶); Kitagawa & Kawata (2002 ▶). graphic file with name e-69-0m477-scheme1.jpg

Experimental

Crystal data

(NH₄)[Ag(C₅HN₂O₆)₂(H₂O)]
M _r = 514.08
Monoclinic,
a = 8.784 (2) Å
b = 18.551 (4) Å
c = 9.195 (2) Å
β = 90.70 (3)°
V = 1498.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.44 mm⁻¹
T = 293 K
0.35 × 0.31 × 0.08 mm

Data collection

Enraf Nonius CAD-4 diffractometer
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983 ▶) T _min = 0.406, T _max = 0.798
2952 measured reflections
2768 independent reflections
2094 reflections with I > 2σ(I)
R _int = 0.014
3 standard reflections every 60 min intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.021
wR(F ²) = 0.066
S = 1.09
2768 reflections
283 parameters
11 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: CAD-4-PC (Enraf–Nonius, 1993 ▶); cell refinement: CAD-4-PC; data reduction: CAD-4-PC; 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: CIFTAB97 and SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813020631/pj2004sup1.cif

e-69-0m477-sup1.cif^{(18.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813020631/pj2004Isup2.hkl

e-69-0m477-Isup2.hkl^{(135.9KB, 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
N4—H4⋯O11ⁱ	0.86	2.18	2.979 (3)	155
N10—H10⋯O2	0.86	2.26	2.945 (3)	137
N10—H10⋯O3	0.86	2.29	3.030 (3)	144
O1—H11⋯O131ⁱⁱ	0.80 (3)	2.06 (3)	2.851 (3)	177 (5)
O1—H12⋯O8ⁱⁱⁱ	0.80 (3)	2.02 (3)	2.781 (2)	160 (3)
N2—H21⋯O6^iv	0.83 (2)	2.16 (2)	2.962 (3)	163 (3)
N2—H22⋯O72^v	0.83 (2)	2.20 (2)	2.998 (3)	160 (3)

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

Acknowledgments

This research was supported by the Russian Foundation for Basic Research (grant 13–03–00079).

supplementary crystallographic information

Comment

1,2-dicarbonyl compounds attract great interest because of the features of their structure and high reactivity. One of the simplest representatives of them is oxalic acid. As described by S. Aldoshin (Aldoshin, 2008), bimetallic coordination polymers based on oxalate and thiooxalate bridging ligands possess different types of magnetic activity and can intercalate complex organic molecules and ions. These have been extensively used as building units in supramolecular coordination systems (Ohba & Okawa, 2000). The replacement of oxalate anions by other 1,2-dicarbonyl cyclic compounds may be of interest from the synthetic and practical point of view. As an example (Coronado et al. 2007), the paramagnetic and chiral anion [Fe(C₅O₅)₃]^3- has been combined with the organic donor BEDT-TTF DET (bis(ethylenedithio)tetrathiafulvalene) to synthesize a novel paramagnetic semiconductor with the first chirality-induced α-phase, α-(BEDT-TTF)5[Fe(C₅O₅)₃].5H₂O, and one of the few known paramagnetic molecular metals, β-(BEDT-TTF)5[Fe(C₅O₅)₃].C₆H₅CN. The variety of coordination modes, some geometric characteristics as well as electrical, magnetic and other properties of coordinate compounds of dibenzoquinone-1,4 derivatives of a general formula H₂C₆O₄X₂ are summarised by S. Kitagawa and S. Kawata (Kitagawa & Kawata, 2002). The present paper deals with the crystal structure determination of ammonium-silver 2,3,5,6-tetraoxo-4-nitropyridinate monohydrate (NH₄)[Ag(C₅HN₂O₆)₂(H₂O)]. The molecular structure of the above substance consists of Ag(I) and ammonium cations, two crystallographically unequivalent 2,3,5,6-tetraoxo-4-nitropyridinate mono anions, and one coordinated water molecule. Each of the Ag(I) cation displays sevenfold coordination by O2, O5, O8, and O11 of the keto-groups of the organic species. The Ag—O distances are 2.3848 (19); 2.4931 (18); 2.5361 (18); and 2.573 (2) Å. Two coordinate bonds involve the O atoms of the nitro-group of the organic anion (2.644 (2) and 2.661 (2) Å). The shortest distance in the coordination sphere of Ag(I) involves the coordinated water molecule (2.3133 (19) Å). The 2,3,5,6-tetraoxo-4-nitropyridinate anions act as polydentate bridging ligands. This coordination mode leads to formation of polymer chains. The coordination does not change significantly the C—O distances of the ligand comparing with its ammonium and sodium salts (Palkina et al., 2000; Kuzmina et al., 2004). The corresponding bond lengths are in the range 1.224 (3) to 1.220 (3) Å for the nitro-diketone fragment, and 1.210 (4) to 1.215 (4) Å for the amide fragment. These two fragments of the organic mono anion are connected by an almost single C—C bonds (C2—C3 length is 1.531 (4), and C5—C6 length is 1.544 (4) Å). The ammonium cation has the outer sphere character, and forms bridging H-bonds with the O atoms of the organic anions linking the polymer chains into three-dimensional structure. The H atoms of the coordinated water molecules are also involved into the H-bonding.

Experimental

Single crystals of C₁₀H₈AgN₅O₁₃ were grown by the slow evaporation of the ethanol solution of the 1-to-1 molar mixture of silver nitrate and ammonium 2,3,5,6-tetraoxo-4-nitropyridinate.