Coordination assemblies of Mg(II) and Ca(II) phosphites – Structural evolution from 1D to 3D framework

Aishwarya Chauhan; Priyanka Chauhan; Gabriele Kociok-Köhn; Ravi Shankar

doi:10.1016/j.molstruc.2025.144159

Coordination assemblies of Mg(II) and Ca(II) phosphites – Structural evolution from 1D to 3D framework

Aishwarya Chauhan, Priyanka Chauhan, Gabriele Kociok-Köhn, Ravi Shankar

Indian Institute of Technology Kanpur

Research output: Contribution to journal › Article › peer-review

Abstract

The study reports the synthesis of two new alkaline earth metal-phosphites, [Mg{OP(O)(OH)H)}₂]·H₂O (1) and [Ca{OP(O)(OH)H)}₂] (2) and their structural characterization by X-ray crystallography. The extended coordinative interaction between the metal ions and phosphite afforded a honeycomb three-dimensional framework in 1 with voids occupied by lattice water molecule while 2 represents a layered motif. The genesis of 1 under hydro-/solvothermal condition has been put forth by implicating the linear chain polymer, [Mg{OP(O)(OMe)H}₂(H₂O)₂] (1a) bearing hydrolysable P-OMe bond as the intermediate which is the first species to crystallize under mild reaction condition. Bulk thermolysis of 1 at 700 °C under aerial conditions afforded a biphasic mixture of the known phosphate phases, namely, magnesium tetrametaphosphate, Mg₂(PO₃)₄ and magnesium metaphosphate, Mg(PO₃)₂ comprising cyclic and linear PO₄ tetrahedra, respectively. Under similar conditions, 2 results in the formation of phase pure calcium metaphosphate, β-Ca(PO₃)₂.

Original language	English
Article number	144159
Journal	Journal of Molecular Structure
Volume	1350
Issue number	Part 2
Early online date	25 Sept 2025
DOIs	https://doi.org/10.1016/j.molstruc.2025.144159
Publication status	E-pub ahead of print - 25 Sept 2025

Data Availability Statement

Data will be made available on request.

Acknowledgements

The authors thank Aarti Gautam for assisting Rietveld refinement data.

Funding

The authors thank DST-India (SR/FST/CSII-07/2014) for funding the single-crystal diffractometer and Central Research Facility at IIT Delhi for providing instrumentation facilities. A. C. is grateful to CSIR, India [Grant no. 09/086(1492)/2021/ EMR-I] and P. C. to Indian Institute of Technology Delhi for fellowships.

Keywords

Alkaline earth metal
Coordination polymers
Hydro/solvothermal
Phosphite
Pyrolysis

ASJC Scopus subject areas

Analytical Chemistry
Spectroscopy
Organic Chemistry
Inorganic Chemistry

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title = "Coordination assemblies of Mg(II) and Ca(II) phosphites – Structural evolution from 1D to 3D framework",

abstract = "The study reports the synthesis of two new alkaline earth metal-phosphites, [Mg\{OP(O)(OH)H)\}2]·H2O (1) and [Ca\{OP(O)(OH)H)\}2] (2) and their structural characterization by X-ray crystallography. The extended coordinative interaction between the metal ions and phosphite afforded a honeycomb three-dimensional framework in 1 with voids occupied by lattice water molecule while 2 represents a layered motif. The genesis of 1 under hydro-/solvothermal condition has been put forth by implicating the linear chain polymer, [Mg\{OP(O)(OMe)H\}2(H2O)2] (1a) bearing hydrolysable P-OMe bond as the intermediate which is the first species to crystallize under mild reaction condition. Bulk thermolysis of 1 at 700 °C under aerial conditions afforded a biphasic mixture of the known phosphate phases, namely, magnesium tetrametaphosphate, Mg2(PO3)4 and magnesium metaphosphate, Mg(PO3)2 comprising cyclic and linear PO4 tetrahedra, respectively. Under similar conditions, 2 results in the formation of phase pure calcium metaphosphate, β-Ca(PO3)2.",

keywords = "Alkaline earth metal, Coordination polymers, Hydro/solvothermal, Phosphite, Pyrolysis",

author = "Aishwarya Chauhan and Priyanka Chauhan and Gabriele Kociok-K{\"o}hn and Ravi Shankar",

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AU - Chauhan, Aishwarya

AU - Chauhan, Priyanka

AU - Kociok-Köhn, Gabriele

AU - Shankar, Ravi

PY - 2025/9/25

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N2 - The study reports the synthesis of two new alkaline earth metal-phosphites, [Mg{OP(O)(OH)H)}2]·H2O (1) and [Ca{OP(O)(OH)H)}2] (2) and their structural characterization by X-ray crystallography. The extended coordinative interaction between the metal ions and phosphite afforded a honeycomb three-dimensional framework in 1 with voids occupied by lattice water molecule while 2 represents a layered motif. The genesis of 1 under hydro-/solvothermal condition has been put forth by implicating the linear chain polymer, [Mg{OP(O)(OMe)H}2(H2O)2] (1a) bearing hydrolysable P-OMe bond as the intermediate which is the first species to crystallize under mild reaction condition. Bulk thermolysis of 1 at 700 °C under aerial conditions afforded a biphasic mixture of the known phosphate phases, namely, magnesium tetrametaphosphate, Mg2(PO3)4 and magnesium metaphosphate, Mg(PO3)2 comprising cyclic and linear PO4 tetrahedra, respectively. Under similar conditions, 2 results in the formation of phase pure calcium metaphosphate, β-Ca(PO3)2.

AB - The study reports the synthesis of two new alkaline earth metal-phosphites, [Mg{OP(O)(OH)H)}2]·H2O (1) and [Ca{OP(O)(OH)H)}2] (2) and their structural characterization by X-ray crystallography. The extended coordinative interaction between the metal ions and phosphite afforded a honeycomb three-dimensional framework in 1 with voids occupied by lattice water molecule while 2 represents a layered motif. The genesis of 1 under hydro-/solvothermal condition has been put forth by implicating the linear chain polymer, [Mg{OP(O)(OMe)H}2(H2O)2] (1a) bearing hydrolysable P-OMe bond as the intermediate which is the first species to crystallize under mild reaction condition. Bulk thermolysis of 1 at 700 °C under aerial conditions afforded a biphasic mixture of the known phosphate phases, namely, magnesium tetrametaphosphate, Mg2(PO3)4 and magnesium metaphosphate, Mg(PO3)2 comprising cyclic and linear PO4 tetrahedra, respectively. Under similar conditions, 2 results in the formation of phase pure calcium metaphosphate, β-Ca(PO3)2.

KW - Alkaline earth metal

KW - Coordination polymers

KW - Hydro/solvothermal

KW - Phosphite

KW - Pyrolysis

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DO - 10.1016/j.molstruc.2025.144159

M3 - Article

AN - SCOPUS:105017114318

SN - 0022-2860

VL - 1350

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

IS - Part 2

M1 - 144159

ER -

Coordination assemblies of Mg(II) and Ca(II) phosphites – Structural evolution from 1D to 3D framework

Abstract

Data Availability Statement

Acknowledgements

Funding

Keywords

ASJC Scopus subject areas

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