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Title: The synthesis and structure of new transition metal lithium calcium nitride compounds

Abstract

Three new nitrides, Li{sub 3}Ca{sub 2}V{sub 0.79}Nb{sub 0.21}N{sub 4}, Li{sub 2}Ca{sub 2.67}Nb{sub 0.33}N{sub 3} and Li{sub 12}Ca{sub 9}W{sub 5}N{sub 20}, were synthesized in sealed niobium tubes using lithium nitride as a flux at temperatures ranging from 800 Degree-Sign C to 1050 Degree-Sign C. In all of these compounds, the transition metals are coordinated tetrahedrally by nitrogen; these tetrahedra are isolated from each other. Bullet Li{sub 3}Ca{sub 2}V{sub 0.79}Nb{sub 0.21}N{sub 4}, space group P2{sub 1}/m (no. 11), cell parameters a=5.7669(8) A, b=6.9123(9) A, c=6.0116(12) A, {beta}=90.727(9) Degree-Sign , Z=2, has a shared vanadium/niobium tetrahedral position which shares vertices with the tetrahedrally-coordinated lithium position. Bullet Li{sub 2}Ca{sub 2.67}Nb{sub 0.33}N{sub 3}, space group Req /o(3, Macron )m (no. 166), cell parameters a=3.6311(2) A, c=29.459(3) A, Z=3, contains a disordered tetrahedral calcium/niobium position, an octahedral calcium position and a triangularly coordinated lithium position. Bullet Li{sub 12}Ca{sub 9}W{sub 5}N{sub 20}, space group C2/c (no. 15), cell parameters a=27.7347(19) A, b=8.6652(6) A, c=10.7685(7) A, {beta}=110.314(2) Degree-Sign , Z=4, contains three crystallographically different tungsten positions as well as one disordered lithium position. - Graphical abstract: Crystal structure of Li{sub 3}Ca{sub 2}V{sub 0.79}Nb{sub 0.21}N{sub 4} depicting the chains of edge-sharing LiN{sub 4} (light hatching) and (V/Nb)N{sub 4} (darkmore » hatching) tetrahedra viewed approximately along the [100] direction. Calcium atoms are shown as open circles and nitrogen atoms are colored black. Highlights: Black-Right-Pointing-Pointer Three new lithium calcium nitrides are synthesized. Black-Right-Pointing-Pointer Lithium nitride flux used in synthesis. Black-Right-Pointing-Pointer Structures contain isolated tetrahedrally coordinated transition metals. Black-Right-Pointing-Pointer Li{sub 12}Ca{sub 9}W{sub 5}N{sub 20} contains three crystallographically different W positions.« less

Authors:
 [1];  [2]; ;  [1]
  1. Department of Chemistry, Cornell University, Baker Laboratory, Ithaca, New York 14853 (United States)
  2. Department of Chemistry, Ithaca College, 953 Danby Road, Ithaca, New York 14850 (United States)
Publication Date:
OSTI Identifier:
22131189
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 197; Other Information: Copyright (c) 2012 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; CALCIUM; CALCIUM NITRIDES; DIFFRACTION; LITHIUM; MONOCLINIC LATTICES; NIOBIUM; NITROGEN; SPACE GROUPS; SYNTHESIS; TUNGSTEN; VANADIUM

Citation Formats

Hunting, Janet L., E-mail: jhunting@ithaca.edu, Department of Chemistry, Ithaca College, 953 Danby Road, Ithaca, New York 14850, Szymanski, Marta M., Kowalsick, Amanda L., Downie, Craig M., and DiSalvo, Francis J. The synthesis and structure of new transition metal lithium calcium nitride compounds. United States: N. p., 2013. Web. doi:10.1016/J.JSSC.2012.09.011.
Hunting, Janet L., E-mail: jhunting@ithaca.edu, Department of Chemistry, Ithaca College, 953 Danby Road, Ithaca, New York 14850, Szymanski, Marta M., Kowalsick, Amanda L., Downie, Craig M., & DiSalvo, Francis J. The synthesis and structure of new transition metal lithium calcium nitride compounds. United States. doi:10.1016/J.JSSC.2012.09.011.
Hunting, Janet L., E-mail: jhunting@ithaca.edu, Department of Chemistry, Ithaca College, 953 Danby Road, Ithaca, New York 14850, Szymanski, Marta M., Kowalsick, Amanda L., Downie, Craig M., and DiSalvo, Francis J. Tue . "The synthesis and structure of new transition metal lithium calcium nitride compounds". United States. doi:10.1016/J.JSSC.2012.09.011.
@article{osti_22131189,
title = {The synthesis and structure of new transition metal lithium calcium nitride compounds},
author = {Hunting, Janet L., E-mail: jhunting@ithaca.edu and Department of Chemistry, Ithaca College, 953 Danby Road, Ithaca, New York 14850 and Szymanski, Marta M. and Kowalsick, Amanda L. and Downie, Craig M. and DiSalvo, Francis J.},
abstractNote = {Three new nitrides, Li{sub 3}Ca{sub 2}V{sub 0.79}Nb{sub 0.21}N{sub 4}, Li{sub 2}Ca{sub 2.67}Nb{sub 0.33}N{sub 3} and Li{sub 12}Ca{sub 9}W{sub 5}N{sub 20}, were synthesized in sealed niobium tubes using lithium nitride as a flux at temperatures ranging from 800 Degree-Sign C to 1050 Degree-Sign C. In all of these compounds, the transition metals are coordinated tetrahedrally by nitrogen; these tetrahedra are isolated from each other. Bullet Li{sub 3}Ca{sub 2}V{sub 0.79}Nb{sub 0.21}N{sub 4}, space group P2{sub 1}/m (no. 11), cell parameters a=5.7669(8) A, b=6.9123(9) A, c=6.0116(12) A, {beta}=90.727(9) Degree-Sign , Z=2, has a shared vanadium/niobium tetrahedral position which shares vertices with the tetrahedrally-coordinated lithium position. Bullet Li{sub 2}Ca{sub 2.67}Nb{sub 0.33}N{sub 3}, space group Req /o(3, Macron )m (no. 166), cell parameters a=3.6311(2) A, c=29.459(3) A, Z=3, contains a disordered tetrahedral calcium/niobium position, an octahedral calcium position and a triangularly coordinated lithium position. Bullet Li{sub 12}Ca{sub 9}W{sub 5}N{sub 20}, space group C2/c (no. 15), cell parameters a=27.7347(19) A, b=8.6652(6) A, c=10.7685(7) A, {beta}=110.314(2) Degree-Sign , Z=4, contains three crystallographically different tungsten positions as well as one disordered lithium position. - Graphical abstract: Crystal structure of Li{sub 3}Ca{sub 2}V{sub 0.79}Nb{sub 0.21}N{sub 4} depicting the chains of edge-sharing LiN{sub 4} (light hatching) and (V/Nb)N{sub 4} (dark hatching) tetrahedra viewed approximately along the [100] direction. Calcium atoms are shown as open circles and nitrogen atoms are colored black. Highlights: Black-Right-Pointing-Pointer Three new lithium calcium nitrides are synthesized. Black-Right-Pointing-Pointer Lithium nitride flux used in synthesis. Black-Right-Pointing-Pointer Structures contain isolated tetrahedrally coordinated transition metals. Black-Right-Pointing-Pointer Li{sub 12}Ca{sub 9}W{sub 5}N{sub 20} contains three crystallographically different W positions.},
doi = {10.1016/J.JSSC.2012.09.011},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 197,
place = {United States},
year = {2013},
month = {1}
}