Synthesis, crystal growth, structural and magnetic characterization of NH4MCl2(HCOO), M=(Fe, Co, Ni)

Greenfield, Joshua T.; Ovidiu Garlea, V.; Kamali, Saeed; Chen, Michael; Kovnir, Kirill

doi:10.1016/j.jssc.2015.09.016

Title: Synthesis, crystal growth, structural and magnetic characterization of NH₄MCl₂(HCOO), M=(Fe, Co, Ni)

Abstract

In this paper, an ambient-pressure solution route and an improved solvothermal synthetic method have been developed to produce polycrystalline powders and large single crystals of NH₄MCl₂(HCOO) (M=Fe, Co, Ni). The magnetic structure of the 1D linear chain compound NH₄FeCl₂(HCOO) has been determined by low-temperature neutron powder diffraction, revealing ferromagnetic intra-chain interactions and antiferromagnetic inter-chain interactions. Finally, the newly-reported Co and Ni analogs are isostructural with NH₄FeCl₂(HCOO), but there are significant differences in the magnetic properties of each compound; the Ni analog behaves similarly to the Fe compound but with stronger magnetic coupling, exhibiting antiferromagnetic ordering (T_N=8.5 K) and a broad metamagnetic transition between 2 and 5 T, while the Co analog does not order magnetically above 2 K, despite strong antiferromagnetic nearest-neighbor interactions.

Authors:

Greenfield, Joshua T. ^[1]; Ovidiu Garlea, V. ^[2]; Kamali, Saeed ^[3]; Chen, Michael ^[1]; Kovnir, Kirill ^[1]

Univ. of California, Davis, CA (United States). Dept. of Chemistry
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Quantum Condensed Matter Division
Univ. of Tennessee Space Inst. (UTSI), Tullahoma, TN (United States). Mechanical, Aerospace and Biomedical Engineering Dept.

Publication Date:: Thu Sep 24 00:00:00 EDT 2015

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Univ. of California, Davis (United States)

OSTI Identifier:: 1261278

Alternate Identifier(s):: OSTI ID: 1244122

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Journal of Solid State Chemistry

Additional Journal Information:: Journal Volume: 236; Journal ID: ISSN 0022-4596

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Solvothermal synthesis; Crystal growth; Low-dimensional magnetism; Neutron diffraction; Mossbauer spectroscopy; Magnetic structure

Citation Formats


                    Greenfield, Joshua T., Ovidiu Garlea, V., Kamali, Saeed, Chen, Michael, and Kovnir, Kirill. Synthesis, crystal growth, structural and magnetic characterization of NH4MCl2(HCOO), M=(Fe, Co, Ni).  United States: N. p., 2015. 
        Web.  doi:10.1016/j.jssc.2015.09.016.

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                    Greenfield, Joshua T., Ovidiu Garlea, V., Kamali, Saeed, Chen, Michael, & Kovnir, Kirill. Synthesis, crystal growth, structural and magnetic characterization of NH4MCl2(HCOO), M=(Fe, Co, Ni).  United States.  https://doi.org/10.1016/j.jssc.2015.09.016

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                    Greenfield, Joshua T., Ovidiu Garlea, V., Kamali, Saeed, Chen, Michael, and Kovnir, Kirill. 2015.  
        "Synthesis, crystal growth, structural and magnetic characterization of NH4MCl2(HCOO), M=(Fe, Co, Ni)".  United States.  https://doi.org/10.1016/j.jssc.2015.09.016.  https://www.osti.gov/servlets/purl/1261278.

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@article{osti_1261278,

  title        = {Synthesis, crystal growth, structural and magnetic characterization of NH4MCl2(HCOO), M=(Fe, Co, Ni)},

  author       = {Greenfield, Joshua T. and Ovidiu Garlea, V. and Kamali, Saeed and Chen, Michael and Kovnir, Kirill},

  abstractNote = {In this paper, an ambient-pressure solution route and an improved solvothermal synthetic method have been developed to produce polycrystalline powders and large single crystals of NH4MCl2(HCOO) (M=Fe, Co, Ni). The magnetic structure of the 1D linear chain compound NH4FeCl2(HCOO) has been determined by low-temperature neutron powder diffraction, revealing ferromagnetic intra-chain interactions and antiferromagnetic inter-chain interactions. Finally, the newly-reported Co and Ni analogs are isostructural with NH4FeCl2(HCOO), but there are significant differences in the magnetic properties of each compound; the Ni analog behaves similarly to the Fe compound but with stronger magnetic coupling, exhibiting antiferromagnetic ordering (TN=8.5 K) and a broad metamagnetic transition between 2 and 5 T, while the Co analog does not order magnetically above 2 K, despite strong antiferromagnetic nearest-neighbor interactions.},

  doi          = {10.1016/j.jssc.2015.09.016},

  url          = {https://www.osti.gov/biblio/1261278},
  journal      = {Journal of Solid State Chemistry},

  issn         = {0022-4596},

  number       = ,

  volume       = 236,

  place        = {United States},

  year         = {Thu Sep 24 00:00:00 EDT 2015},

  month        = {Thu Sep 24 00:00:00 EDT 2015}

}

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https://doi.org/10.1016/j.jssc.2015.09.016

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Cited by: 4 works

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Figures / Tables:

Figure 1.: A: Polycrystalline powders and B: single crystals of NH₄MCl₂(HCOO) (M = Fe, Co, Ni), produced from ambient-pressure synthesis and solvothermal recrystallization, respectively. C: Room-temperature PXRD patterns for each compound, with calculated peak positions (>1% total intensity) indicated by tick marks below the patterns. Fe: magenta; Co: blue; Ni:more »

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Works referenced in this record:

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The magneto-structural correlation of two novel 1D antiferromagnetic chains with different magnetic behaviors
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Two Chain Compounds of [M(N ₃ ) ₂ (HCOO)][(CH ₃ ) ₂ NH ₂ ] (M = Fe and Co) with a Mixed Azido/Formato Bridge Displaying Metamagnetic Behavior
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Works referencing / citing this record:

Three coordination frameworks with copper formate based low dimensional motifs: synthesis, structure and magnetic properties
journal, January 2017

Bovill, Sally M.; Dixey, Richard J. C.; Saines, Paul J.
CrystEngComm, Vol. 19, Issue 13
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Neutron Instruments for Research in Coordination Chemistry: Neutron Instruments for Research in Coordination Chemistry
journal, January 2019

Xue, Zi-Ling; Ramirez-Cuesta, Anibal J.; Brown, Craig M.
European Journal of Inorganic Chemistry, Vol. 2019, Issue 8
https://doi.org/10.1002/ejic.201801076

Insertion of CS ₂ into the Mg–H bond: synthesis and structural characterization of the magnesium dithioformate complex, [Tism ^PriBenz ]Mg(κ ² -S ₂ CH)
journal, January 2018

Rauch, Michael; Parkin, Gerard
Dalton Transactions, Vol. 47, Issue 36
https://doi.org/10.1039/c8dt01947a

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Title: Synthesis, crystal growth, structural and magnetic characterization of NH4MCl2(HCOO), M=(Fe, Co, Ni)

Abstract

Citation Formats

Figures / Tables:

The Role of Hydrothermal Synthesis in Preparative Chemistry journal, December 1985

Formate-Based Magnetic Metal-Organic Frameworks Templated by Protonated Amines journal, March 2010

The magneto-structural correlation of two novel 1D antiferromagnetic chains with different magnetic behaviors journal, November 2011

Constructing magnetic molecular solids by employing three-atom ligands as bridges journal, January 2008

A Highly Anisotropic Cobalt(II)-Based Single-Chain Magnet: Exploration of Spin Canting in an Antiferromagnetic Array journal, October 2008

Coexistence of Magnetic and Electric Orderings in the Metal–Formate Frameworks of [NH 4 ][M(HCOO) 3 ] journal, September 2011

NH 4 FeCl 2 (HCOO): Synthesis, Structure, and Magnetism of a Novel Low-Dimensional Magnetic Material journal, February 2014

A short history of SHELX journal, December 2007

Recent advances in magnetic structure determination by neutron powder diffraction journal, October 1993

A new protocol for the determination of magnetic structures using simulated annealing and representational analysis (SARAh) journal, March 2000

Symmetry-Based Computational Tools for Magnetic Crystallography journal, July 2015

Analytical expression for the Mössbauer line shape of 57Fe in the presence of mixed hyperfine interactions journal, May 1985

Two Chain Compounds of [M(N 3 ) 2 (HCOO)][(CH 3 ) 2 NH 2 ] (M = Fe and Co) with a Mixed Azido/Formato Bridge Displaying Metamagnetic Behavior journal, April 2006

Synthesis of [NH 4 ]MnCl 2 (OAc) and [NH 4 ] 2 MnCl 4 (H 2 O) 2 by Solvothermal Dehydration and Structure/Property Correlations in a One-Dimensional Antiferromagnet journal, April 2004

Cobalt(II) metamagnet built from ferromagnetic chains with mixed bis(azido)(carboxylate) bridges journal, June 2012

Three coordination frameworks with copper formate based low dimensional motifs: synthesis, structure and magnetic properties journal, January 2017

Neutron Instruments for Research in Coordination Chemistry: Neutron Instruments for Research in Coordination Chemistry journal, January 2019

Insertion of CS 2 into the Mg–H bond: synthesis and structural characterization of the magnesium dithioformate complex, [Tism PriBenz ]Mg(κ 2 -S 2 CH) journal, January 2018

Title: Synthesis, crystal growth, structural and magnetic characterization of NH₄MCl₂(HCOO), M=(Fe, Co, Ni)

The Role of Hydrothermal Synthesis in Preparative Chemistry
journal, December 1985

Formate-Based Magnetic Metal-Organic Frameworks Templated by Protonated Amines
journal, March 2010

The magneto-structural correlation of two novel 1D antiferromagnetic chains with different magnetic behaviors
journal, November 2011

Constructing magnetic molecular solids by employing three-atom ligands as bridges
journal, January 2008

A Highly Anisotropic Cobalt(II)-Based Single-Chain Magnet: Exploration of Spin Canting in an Antiferromagnetic Array
journal, October 2008

Coexistence of Magnetic and Electric Orderings in the Metal–Formate Frameworks of [NH ₄ ][M(HCOO) ₃ ]
journal, September 2011

NH ₄ FeCl ₂ (HCOO): Synthesis, Structure, and Magnetism of a Novel Low-Dimensional Magnetic Material
journal, February 2014

A short history of SHELX
journal, December 2007

Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993

A new protocol for the determination of magnetic structures using simulated annealing and representational analysis (SARAh)
journal, March 2000

Symmetry-Based Computational Tools for Magnetic Crystallography
journal, July 2015

Analytical expression for the Mössbauer line shape of 57Fe in the presence of mixed hyperfine interactions
journal, May 1985

Two Chain Compounds of [M(N ₃ ) ₂ (HCOO)][(CH ₃ ) ₂ NH ₂ ] (M = Fe and Co) with a Mixed Azido/Formato Bridge Displaying Metamagnetic Behavior
journal, April 2006

Synthesis of [NH ₄ ]MnCl ₂ (OAc) and [NH ₄ ] ₂ MnCl ₄ (H ₂ O) ₂ by Solvothermal Dehydration and Structure/Property Correlations in a One-Dimensional Antiferromagnet
journal, April 2004

Cobalt(II) metamagnet built from ferromagnetic chains with mixed bis(azido)(carboxylate) bridges
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journal, January 2018