Poly[μ2-aqua-μ4-(2-{3-[(6-chloro­pyridin-3-yl)meth­yl]-2-oxoimidazolidin-1-yl}acetato)-sodium]

Rajni Kant; Vivek K Gupta; Kamini Kapoor; Chetan S Shripanavar; Kaushik Banerjee; Madhukar B Deshmukh

doi:10.1107/S1600536812025007

. 2012 Jun 13;68(Pt 7):m891–m892. doi: 10.1107/S1600536812025007

Poly[μ₂-aqua-μ₄-(2-{3-[(6-chloropyridin-3-yl)methyl]-2-oxoimidazolidin-1-yl}acetato)-sodium]

Rajni Kant ^a,^*, Vivek K Gupta ^a, Kamini Kapoor ^a, Chetan S Shripanavar ^b, Kaushik Banerjee ^c, Madhukar B Deshmukh ^b

PMCID: PMC3393166 PMID: 22807734

Abstract

In the title compound, [Na(C₁₁H₁₁ClN₃O₃)(H₂O)]_n, there are two independent Na^I ions, one of which lies on an inversion center and is coordinated in a slightly distorted octahedral environment. The other Na^I ion lies on a twofold rotation axis and is cooordinated in a slightly distorted trigonal–bipyramidal coordination environment. In the organic ligand, the imidazolidine ring adopts a half-chair conformation. The Na^I ions bridge organic ligands and water molecules, forming a two-dimensional structure parallel to (100). There are intermolecular O—H⋯O and weak C—H⋯O hydrogen bonds within the two-dimensional structure.

Related literature

For background to the insecticidal applications of imidacloprid {systematic name: N-[1-[(6-chloro-3-pyridyl)methyl]-4,5-dihydroimidazol-2-yl]nitramide}, see: Legocki & Polec (2008 ▶); Kovganko & Kashkan (2004 ▶); Zhao et al. (2009 ▶); Tanner et al. (2010 ▶); Xu et al. (2010 ▶). For ring conformations, see: Duax & Norton (1975 ▶). For related structures, see: Kapoor et al. (2011 ▶, 2012 ▶); Kant et al. (2012 ▶).

Experimental

Crystal data

[Na(C₁₁H₁₁ClN₃O₃)(H₂O)]
M _r = 309.68
Monoclinic,
a = 45.655 (2) Å
b = 4.9113 (2) Å
c = 12.5205 (7) Å
β = 102.184 (5)°
V = 2744.2 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.1 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.836, T _max = 1.000
9498 measured reflections
2678 independent reflections
1909 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.112
S = 1.02
2678 reflections
191 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812025007/lh5481sup1.cif

e-68-0m891-sup1.cif^{(29KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812025007/lh5481Isup2.hkl

e-68-0m891-Isup2.hkl^{(128.9KB, 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
O1W—H1W⋯O12ⁱ	0.80 (4)	2.02 (4)	2.826 (3)	179 (3)
O1W—H2W⋯O15ⁱⁱ	0.84 (4)	2.02 (4)	2.822 (2)	158 (3)
C10—H10B⋯O12ⁱⁱⁱ	0.97	2.54	3.279 (3)	133
C13—H13B⋯O16ⁱⁱ	0.97	2.49	3.265 (3)	137

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

Acknowledgments

RK acknowledges the Department of Science & Technology for the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003. He is also thankful to the University of Jammu, Jammu, India, for financial support.

supplementary crystallographic information

Comment

For the development of nicotinoid insecticides the crucial turning-point could be traced back to the work done by the scientists from Nihon Tokushu Noyaku Seizo K and Nippon Bayer (Legocki & Polec, 2008). Insects become resistant to insecticides due to continuous use and hence it is imperative to introduce new molecules having novel mode of action (Kovganko & Kashkan, 2004). The outstanding development of neonicotinoid insecticides has been achieved for the modern crop protection, consumer products, and animal health markets between 1990 and today reflects the enormous importance of this chemical class (Zhao et al., 2009). Neonicotinoids have low toxicity toward mammals and no teratogenic or mutagenic effects (Xu et al., 2010). The biological activity and agricultural uses of neonicotinoid insecticides are enormous (Zhao et al., 2009). From investigations it is revealed that the neonicotinoids are converted into numerous and variable metabolites in plants as well as in mammals (Tanner et al., 2010).

The asymmetric unit is shown in Fig. 1. The bond lengths and angles observed in (I) show normal values and are comparable to those in related structures (Kapoor et al., 2011; Kant et al., 2012). There are two independent Na^I ions, one of which lies on an inversion center and is coordinated in a slightly disotorted octahedral environment. The other Na^I ion lies on a twofold rotation axis and is cooordinated in a slightly distorted trigonal bipyramidal coordination environment. In the organic ligand the imidazole ring adopts half-chair conformation (asymmetry parameter: ΔC₂(C9—C10) = 2.31). The Na^I ions bridge organic ligands and solvent water molecules to form a two-dimensional structure parallel to (100). There are intermolecular O—H···O and weak C—H···O hydrogen bonds within the two-dimensional structure.

Experimental

Ethyl[3-[(6-chloropyridin-3-yl)methyl]-2-(nitroimino)imidazolidin -1-yl]acetate (0.341 g m, 0.001 mol) was dissolved in 5 ml methanol and 5 ml 1 N NaOH solution was added. The reaction mixture was refluxed on a water bath at 343K for 12 h, and then cooled. The compound was re-precipitated upon neutralization with 1 N HCl. The compound was dissolved in methanol and crystallized in a fume hood at room temperature by the process of slow evaporation.

m.p. 575 K IR (KBr) ν_max: 3421, 3300, 2872, 2930, 1668, 1606 cm^-1. LC—MS/MS: 270, 252, 224, 149, 126 m/z.