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Title: Syntheses and crystal structures of a series of new divalent metal phosphonates with imino-bis(methylphosphonic acid)

Abstract

Hydrothermal reactions of divalent transition metal salts with imino-bis(methylphosphonic acid), NH(CH{sub 2}PO{sub 3}H{sub 2}){sub 2} (H{sub 4}L) afforded three new metal phosphonates, namely, Cu[NH(CH{sub 2}PO{sub 3}H){sub 2}] 1, {l_brace}Co[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O){sub 2}{r_brace}.H{sub 2}O 2 and Mn[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O) 3. When HO{sub 2}C(CH{sub 2}){sub 3}N(CH{sub 2}PO{sub 3}H{sub 2}){sub 2} was used as the phosphonate ligand and 4,4'-bipy as the second metal linker, {l_brace}Cu{sub 4}[NH(CH{sub 2}PO{sub 3}){sub 2}]{sub 2}(4,4'-bipy)(H{sub 2}O){sub 4}{r_brace}.9H{sub 2}O 4 with a pillared layered architecture was obtained. The NH(CH{sub 2}PO{sub 3}){sub 2} anion resulted from the cleavage of the HO{sub 2}C(CH{sub 2}){sub 3}-group during the reaction. Although compounds 1-3 have a same M/L ratio (1:1), they exhibit totally different structures.Compound 1 has a linear chain structure, in which each pair of square-pyramidal coordinated copper(II) ions are bridged by two phosphonate oxygen atoms to form a Cu{sub 2}O{sub 2} dimeric unit, and such dimeric units are further interconnected via phosphonate groups to form a [010] chain. Compound 2 has a layered architecture built from CoO{sub 6} octahedra bridged by phosphonate ligands. In compound 3, the interconnection of the manganese(II) ions by bridging imino-diphosphonate ligands leads to a 3D network. Compound 4 hasmore » a pillar-layered structure, the layers composed of Cu(II) ions bridged by aminodiphosphonate ligands are interconnected by 4,4'-bipy ligands to form channels along c-axis. Several factors that affect the structures of the metal phosphonates formed have also been discussed. Compounds 2 and 3 show predominant antiferromagnetic interactions between magnetic centers. -- Graphical abstract: Four new metal phosphonates, namely, Cu[NH(CH{sub 2}PO{sub 3}H){sub 2}] 1, {l_brace}Co[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O){sub 2}{r_brace}.H{sub 2}O 2, Mn[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O) 3 and {l_brace}Cu{sub 4}[NH(CH{sub 2}PO{sub 3}){sub 2}]{sub 2}(4,4'-bipy)(H{sub 2}O){sub 4}{r_brace}.9H{sub 2}O 4 have been synthesized and structurally characterized. Compound 1 has a linear chain structure, and compound 2 is layered. Compound 3 is three dimensional whereas compound 4 has a pillar-layered structure. Compounds 2 and 3 show predominant antiferromagnetic interactions between magnetic centers.« less

Authors:
 [1];  [2];  [2];  [3]
  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002 (China)
  2. Department of Chemistry, Texas A and M University, P.O. Box 30012, College Station, TX 77843-3012 (United States)
  3. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002 (China). E-mail: mjg@ms.fjirsm.ac.cn
Publication Date:
OSTI Identifier:
20784847
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 179; Journal Issue: 1; Other Information: DOI: 10.1016/j.jssc.2005.10.015; PII: S0022-4596(05)00475-5; Copyright (c) 2005 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COPPER COMPOUNDS; COPPER IONS; CRYSTAL STRUCTURE; HYDROTHERMAL SYNTHESIS; LIGANDS; MAGNETIC PROPERTIES; MANGANESE COMPOUNDS; PHOSPHONATES

Citation Formats

Yang Bingping, Prosvirin, Andrey V., Zhao, Han-Hua, and Mao, Jiang-Gao. Syntheses and crystal structures of a series of new divalent metal phosphonates with imino-bis(methylphosphonic acid). United States: N. p., 2006. Web. doi:10.1016/j.jssc.2005.10.015.
Yang Bingping, Prosvirin, Andrey V., Zhao, Han-Hua, & Mao, Jiang-Gao. Syntheses and crystal structures of a series of new divalent metal phosphonates with imino-bis(methylphosphonic acid). United States. doi:10.1016/j.jssc.2005.10.015.
Yang Bingping, Prosvirin, Andrey V., Zhao, Han-Hua, and Mao, Jiang-Gao. Sun . "Syntheses and crystal structures of a series of new divalent metal phosphonates with imino-bis(methylphosphonic acid)". United States. doi:10.1016/j.jssc.2005.10.015.
@article{osti_20784847,
title = {Syntheses and crystal structures of a series of new divalent metal phosphonates with imino-bis(methylphosphonic acid)},
author = {Yang Bingping and Prosvirin, Andrey V. and Zhao, Han-Hua and Mao, Jiang-Gao},
abstractNote = {Hydrothermal reactions of divalent transition metal salts with imino-bis(methylphosphonic acid), NH(CH{sub 2}PO{sub 3}H{sub 2}){sub 2} (H{sub 4}L) afforded three new metal phosphonates, namely, Cu[NH(CH{sub 2}PO{sub 3}H){sub 2}] 1, {l_brace}Co[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O){sub 2}{r_brace}.H{sub 2}O 2 and Mn[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O) 3. When HO{sub 2}C(CH{sub 2}){sub 3}N(CH{sub 2}PO{sub 3}H{sub 2}){sub 2} was used as the phosphonate ligand and 4,4'-bipy as the second metal linker, {l_brace}Cu{sub 4}[NH(CH{sub 2}PO{sub 3}){sub 2}]{sub 2}(4,4'-bipy)(H{sub 2}O){sub 4}{r_brace}.9H{sub 2}O 4 with a pillared layered architecture was obtained. The NH(CH{sub 2}PO{sub 3}){sub 2} anion resulted from the cleavage of the HO{sub 2}C(CH{sub 2}){sub 3}-group during the reaction. Although compounds 1-3 have a same M/L ratio (1:1), they exhibit totally different structures.Compound 1 has a linear chain structure, in which each pair of square-pyramidal coordinated copper(II) ions are bridged by two phosphonate oxygen atoms to form a Cu{sub 2}O{sub 2} dimeric unit, and such dimeric units are further interconnected via phosphonate groups to form a [010] chain. Compound 2 has a layered architecture built from CoO{sub 6} octahedra bridged by phosphonate ligands. In compound 3, the interconnection of the manganese(II) ions by bridging imino-diphosphonate ligands leads to a 3D network. Compound 4 has a pillar-layered structure, the layers composed of Cu(II) ions bridged by aminodiphosphonate ligands are interconnected by 4,4'-bipy ligands to form channels along c-axis. Several factors that affect the structures of the metal phosphonates formed have also been discussed. Compounds 2 and 3 show predominant antiferromagnetic interactions between magnetic centers. -- Graphical abstract: Four new metal phosphonates, namely, Cu[NH(CH{sub 2}PO{sub 3}H){sub 2}] 1, {l_brace}Co[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O){sub 2}{r_brace}.H{sub 2}O 2, Mn[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O) 3 and {l_brace}Cu{sub 4}[NH(CH{sub 2}PO{sub 3}){sub 2}]{sub 2}(4,4'-bipy)(H{sub 2}O){sub 4}{r_brace}.9H{sub 2}O 4 have been synthesized and structurally characterized. Compound 1 has a linear chain structure, and compound 2 is layered. Compound 3 is three dimensional whereas compound 4 has a pillar-layered structure. Compounds 2 and 3 show predominant antiferromagnetic interactions between magnetic centers.},
doi = {10.1016/j.jssc.2005.10.015},
journal = {Journal of Solid State Chemistry},
number = 1,
volume = 179,
place = {United States},
year = {Sun Jan 15 00:00:00 EST 2006},
month = {Sun Jan 15 00:00:00 EST 2006}
}