Synthesis, crystal structure, and magnetic properties of a one-dimensional chain antiferromagnet NiC2O4·2NH3

Fenghua Ding; Kent J. Griffith; Chi Zhang; Jing Zhan; Hongcheng Lu; Kenneth R. Poeppelmeier

doi:10.1016/j.jssc.2022.123360

Synthesis, crystal structure, and magnetic properties of a one-dimensional chain antiferromagnet NiC₂O₄·2NH₃

Fenghua Ding, Kent J. Griffith, Chi Zhang, Jing Zhan^*, Hongcheng Lu^*, Kenneth R. Poeppelmeier^*

^*Corresponding author for this work

Chemistry

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

2 Scopus citations

Abstract

NiC₂O₄·2NH₃ was synthesized hydrothermally, and its structure was solved by single-crystal X-ray diffraction. Accordingly, NiC₂O₄·2NH₃ crystallizes in the centrosymmetric monoclinic space group C2/m (no. 12) with lattice parameters of a = 10.767(5) Å, b = 5.414(2) Å, c = 5.005(2) Å and β = 96.3(4)°. The NiO₄N₂ octahedra align in a parallel pattern through shared C₂O₄²⁻ units and thus form linear one-dimensional (1D) chains extending along the b-axis. These linear chains are separated along the a-axis by NH₃ molecules and weakly coupled with each other through hydrogen bonding. ¹H and ¹³C solid-state NMR revealed isotropic resonances at −115(3) ppm and −312(5) ppm, respectively, for NiC₂O₄·2NH₃, the ammonia protons and oxalate carbons being paramagnetically shifted via the Fermi contact interaction from d⁸ Ni(II). Room-temperature paramagnetic shift anisotropies of 400(30) ppm for ¹H and 780(40) ppm for ¹³C were determined from simulations of the spinning sideband manifolds. Magnetic susceptibility shows a broad maximum around T(χ_max) = 35 K, suggesting well-developed spin–spin correlations along the Ni–C₂O₄–Ni chains. No long-range order is observed down to 2 K, which is further confirmed by heat capacity results. The intrachain interaction J/k of −31.0 K is estimated by fitting the data with a 1D spin chain model. The isothermal magnetization curve at 2 K shows a field-induced phase transition around 5 T. The magnetization value at 9 T is only 0.087 μ_B, which is far from saturation. All magnetic results indicate NiC₂O₄·2NH₃ is a good 1D chain quantum antiferromagnet.

Original language	English (US)
Article number	123360
Journal	Journal of Solid State Chemistry
Volume	314
DOIs	https://doi.org/10.1016/j.jssc.2022.123360
State	Published - Oct 2022

Funding

Dedicated to Professor Alario- Franco on his 80th birthday. This work was supported by funding from the National Science Foundation (DMR-1904701). K.J.G. was supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. The single-crystal X-ray and solid-state NMR measurements were acquired at Northwestern University's Integrated Molecular Structure Education and Research Center (IMSERC), which is supported by grants from NSF-NSEC, NSF-MRSEC, the KECK Foundation, the State of Illinois, and Northwestern University. This work made use of the J. B. Cohen X-Ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University. We also thank Professor Weiwei Xie for her helpful comments on the manuscript and magnetic measurements. Dedicated to Professor Alario- Franco on his 80th birthday. This work was supported by funding from the National Science Foundation ( DMR-1904701 ). K.J.G. was supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. The single-crystal X-ray and solid-state NMR measurements were acquired at Northwestern University's Integrated Molecular Structure Education and Research Center (IMSERC), which is supported by grants from NSF-NSEC, NSF- MRSEC , the KECK Foundation, the State of Illinois, and Northwestern University . This work made use of the J. B. Cohen X-Ray Diffraction Facility supported by the MRSEC program of the National Science Foundation ( DMR-1720139 ) at the Materials Research Center of Northwestern University . We also thank Professor Weiwei Xie for her helpful comments on the manuscript and magnetic measurements.

Keywords

Antiferromagnetic
Crystal structures
Exploratory synthesis
One-dimensional chain
Solid-state NMR

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Ceramics and Composites
Condensed Matter Physics
Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.jssc.2022.123360

Cite this

@article{fbfaf688ed914caa931363d67c382f26,

title = "Synthesis, crystal structure, and magnetic properties of a one-dimensional chain antiferromagnet NiC2O4·2NH3",

abstract = "NiC2O4·2NH3 was synthesized hydrothermally, and its structure was solved by single-crystal X-ray diffraction. Accordingly, NiC2O4·2NH3 crystallizes in the centrosymmetric monoclinic space group C2/m (no. 12) with lattice parameters of a = 10.767(5) {\AA}, b = 5.414(2) {\AA}, c = 5.005(2) {\AA} and β = 96.3(4)°. The NiO4N2 octahedra align in a parallel pattern through shared C2O42− units and thus form linear one-dimensional (1D) chains extending along the b-axis. These linear chains are separated along the a-axis by NH3 molecules and weakly coupled with each other through hydrogen bonding. 1H and 13C solid-state NMR revealed isotropic resonances at −115(3) ppm and −312(5) ppm, respectively, for NiC2O4·2NH3, the ammonia protons and oxalate carbons being paramagnetically shifted via the Fermi contact interaction from d8 Ni(II). Room-temperature paramagnetic shift anisotropies of 400(30) ppm for 1H and 780(40) ppm for 13C were determined from simulations of the spinning sideband manifolds. Magnetic susceptibility shows a broad maximum around T(χmax) = 35 K, suggesting well-developed spin–spin correlations along the Ni–C2O4–Ni chains. No long-range order is observed down to 2 K, which is further confirmed by heat capacity results. The intrachain interaction J/k of −31.0 K is estimated by fitting the data with a 1D spin chain model. The isothermal magnetization curve at 2 K shows a field-induced phase transition around 5 T. The magnetization value at 9 T is only 0.087 μB, which is far from saturation. All magnetic results indicate NiC2O4·2NH3 is a good 1D chain quantum antiferromagnet.",

keywords = "Antiferromagnetic, Crystal structures, Exploratory synthesis, One-dimensional chain, Solid-state NMR",

author = "Fenghua Ding and Griffith, {Kent J.} and Chi Zhang and Jing Zhan and Hongcheng Lu and Poeppelmeier, {Kenneth R.}",

note = "Publisher Copyright: {\textcopyright} 2022 Elsevier Inc.",

year = "2022",

month = oct,

doi = "10.1016/j.jssc.2022.123360",

language = "English (US)",

volume = "314",

journal = "Journal of Solid State Chemistry",

issn = "0022-4596",

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TY - JOUR

T1 - Synthesis, crystal structure, and magnetic properties of a one-dimensional chain antiferromagnet NiC2O4·2NH3

AU - Ding, Fenghua

AU - Griffith, Kent J.

AU - Zhang, Chi

AU - Zhan, Jing

AU - Lu, Hongcheng

AU - Poeppelmeier, Kenneth R.

PY - 2022/10

Y1 - 2022/10

N2 - NiC2O4·2NH3 was synthesized hydrothermally, and its structure was solved by single-crystal X-ray diffraction. Accordingly, NiC2O4·2NH3 crystallizes in the centrosymmetric monoclinic space group C2/m (no. 12) with lattice parameters of a = 10.767(5) Å, b = 5.414(2) Å, c = 5.005(2) Å and β = 96.3(4)°. The NiO4N2 octahedra align in a parallel pattern through shared C2O42− units and thus form linear one-dimensional (1D) chains extending along the b-axis. These linear chains are separated along the a-axis by NH3 molecules and weakly coupled with each other through hydrogen bonding. 1H and 13C solid-state NMR revealed isotropic resonances at −115(3) ppm and −312(5) ppm, respectively, for NiC2O4·2NH3, the ammonia protons and oxalate carbons being paramagnetically shifted via the Fermi contact interaction from d8 Ni(II). Room-temperature paramagnetic shift anisotropies of 400(30) ppm for 1H and 780(40) ppm for 13C were determined from simulations of the spinning sideband manifolds. Magnetic susceptibility shows a broad maximum around T(χmax) = 35 K, suggesting well-developed spin–spin correlations along the Ni–C2O4–Ni chains. No long-range order is observed down to 2 K, which is further confirmed by heat capacity results. The intrachain interaction J/k of −31.0 K is estimated by fitting the data with a 1D spin chain model. The isothermal magnetization curve at 2 K shows a field-induced phase transition around 5 T. The magnetization value at 9 T is only 0.087 μB, which is far from saturation. All magnetic results indicate NiC2O4·2NH3 is a good 1D chain quantum antiferromagnet.

AB - NiC2O4·2NH3 was synthesized hydrothermally, and its structure was solved by single-crystal X-ray diffraction. Accordingly, NiC2O4·2NH3 crystallizes in the centrosymmetric monoclinic space group C2/m (no. 12) with lattice parameters of a = 10.767(5) Å, b = 5.414(2) Å, c = 5.005(2) Å and β = 96.3(4)°. The NiO4N2 octahedra align in a parallel pattern through shared C2O42− units and thus form linear one-dimensional (1D) chains extending along the b-axis. These linear chains are separated along the a-axis by NH3 molecules and weakly coupled with each other through hydrogen bonding. 1H and 13C solid-state NMR revealed isotropic resonances at −115(3) ppm and −312(5) ppm, respectively, for NiC2O4·2NH3, the ammonia protons and oxalate carbons being paramagnetically shifted via the Fermi contact interaction from d8 Ni(II). Room-temperature paramagnetic shift anisotropies of 400(30) ppm for 1H and 780(40) ppm for 13C were determined from simulations of the spinning sideband manifolds. Magnetic susceptibility shows a broad maximum around T(χmax) = 35 K, suggesting well-developed spin–spin correlations along the Ni–C2O4–Ni chains. No long-range order is observed down to 2 K, which is further confirmed by heat capacity results. The intrachain interaction J/k of −31.0 K is estimated by fitting the data with a 1D spin chain model. The isothermal magnetization curve at 2 K shows a field-induced phase transition around 5 T. The magnetization value at 9 T is only 0.087 μB, which is far from saturation. All magnetic results indicate NiC2O4·2NH3 is a good 1D chain quantum antiferromagnet.

KW - Antiferromagnetic

KW - Crystal structures

KW - Exploratory synthesis

KW - One-dimensional chain

KW - Solid-state NMR

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DO - 10.1016/j.jssc.2022.123360

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VL - 314

JO - Journal of Solid State Chemistry

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ER -

Synthesis, crystal structure, and magnetic properties of a one-dimensional chain antiferromagnet NiC₂O₄·2NH₃

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CCDC 2018052: Experimental Crystal Structure Determination

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Synthesis, crystal structure, and magnetic properties of a one-dimensional chain antiferromagnet NiC2O4·2NH3

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CCDC 2018052: Experimental Crystal Structure Determination

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Synthesis, crystal structure, and magnetic properties of a one-dimensional chain antiferromagnet NiC₂O₄·2NH₃