Synthesis, structure, and properties of nickel complexes with nitrilotris(methylenephosphonic acid) [Ni(H 2 O)3N(CH2PO 3
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CTURE OF ORGANIC COMPOUNDS
Synthesis, Structure, and Properties of Nickel Complexes with Nitrilotris(methylenephosphonic acid) [Ni(H2O)3N(CH2PO3H)3] and Na4[Ni(H2O)N(CH2PO3)3] ⋅ 11H2O N. V. Somova*, F. F. Chausovb,c**, R. M. Zakirovac, and I. V. Fedotovac*** a
Lobachevsky Nizhny Novgorod State University, Gagarina pr. 23, Nizhny Novgorod, 603950 Russia Institute, Ural Branch, Russian Academy of Sciences, ul. Kirova 132, Izhevsk, 426000 Russia c Udmurt State University, ul. Universitetskaya 1, Izhevsk, 426034 Russia * e-mail: [email protected] ** e-mail: [email protected] *** e-mail: [email protected]
bPhysico-Technical
Received April 24, 2015
Abstract—Nitrilotris(methylenephosphonato)triaquanickel and tetrasodium nitrilotris(methylenephosphonato)aquanickelate undecahydrate were synthesized and characterized. The crystal of [Ni(H2O)3N(CH2PO3H)3] is composed of linear coordination polymers and belongs to sp. gr. P21/c, Z = 4, a = 9.17120(10) Å, b = 16.05700(10) Å, c = 9.70890(10) Å, β = 115.830(2)°. The Ni atom is in an octahedral coordination formed by two oxygen atoms of one phosphonate ligand, one oxygen atom of another ligand molecule, and three water molecules in a meridional configuration. The crystal of Na4[Ni(H2O)N(CH2PO3)3] ⋅ 11H2O has an island dimeric chelate structure and belongs to sp. gr. С2/c, Z = 8, a = 18.7152(2) Å, b = 12.05510(10) Å, c = 21.1266(2) Å, β = 104.4960(10)°. The Ni atom has a slightly distorted octahedral coordination involving one nitrogen atom and closes three five-membered N–C–P–O–Ni rings sharing the Ni–N bond. DOI: 10.1134/S1063774516020243
INTRODUCTION Zinc and copper salts and complexes of organophosphonic acids are widely used in engineering applications as salt-precipitation inhibitors [1, 2] and corrosion inhibitors [3–5], as well as effective bactericides [6]. The structures and properties of these compounds have not been studied for a long time, which led to the dispersion and unpredictability of the results of industrial application of products produced by different manufacturers [7]. A false equalization of coordination compounds, the structures of which differ from each other and from salts of organophosphonic acids, was used by competitors for defamation [8]. Quite recently, structural studies [9–11] have demonstrated the diversity of structures formed by nitrilotris(methylenephosphonic acid) (N(CH2PO3)3H6, NTP) upon coordination to zinc and copper. This provided the basis for industrial routes to the highly selective synthesis of salt-precipitation and corrosion inhibitors and bactericides with specified structures and properties [12, 13]. Meanwhile, zinc and copper complexes with NTP give a narrow range of inhibitors, the thermal stability of NTP derivatives with copper being low [14]. Therefore, an extension of the range of NTP derivatives with 3d metals as potential inhibitors and bactericides is of considerable interest. Nickel is
one of the main components of doped steels [15]. Hence, the structures of the reaction products of NTP with Ni2+ are of obvious interest for
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