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Title: The synthesis and structural characterization of the new ternary nitrides: Ca{sub 4}TiN{sub 4} and Ca{sub 5}NbN{sub 5}

Abstract

The ternary nitrides, Ca{sub 4}TiN{sub 4} and Ca{sub 5}NbN{sub 5}, were synthesized in sealed niobium tubes using lithium nitride as a flux at 900 and 1050 deg. C, respectively. The structures of both compounds were solved from single-crystal X-ray diffraction data. Ca{sub 4}TiN{sub 4} is the first example of a calcium group IV nitride; it crystallizes in the triclinic space group P1-bar (No. 2) with cell parameters a=5.9757(5) A, b=6.0129(5) A, c=6.0116(12) A, {alpha}=71.565(4){sup o}, {beta}=79.471(4){sup o}, {gamma}=68.258(4){sup o} and Z=2. Ca{sub 4}TiN{sub 4} is isostructural with Na{sub 4}TiO{sub 4} and contains tetrahedral TiN{sub 4} units connected through edges and corners to CaN{sub 4} tetrahedra and CaN{sub 5} square pyramids. Ca{sub 5}NbN{sub 5} crystallizes in the monoclinic space group C2/m (No. 12) with cell parameters a=11.922(7) A, b=6.878(5) A, c=8.936(7) A, {beta}=101.22(3){sup o} and Z=4. Ca{sub 5}NbN{sub 5} is isostructural with Ba{sub 5}NbN{sub 5}; the structure contains NbN{sub 4} tetrahedra that share vertices with CaN{sub 5} trigonal bipyramids.

Authors:
 [1];  [2];  [2];  [2];  [2]
  1. Department of Chemistry, Cornell University, Ithaca, NY 14853 (United States), E-mail: jhunting@fandm.edu
  2. Department of Chemistry, Cornell University, Ithaca, NY 14853 (United States)
Publication Date:
OSTI Identifier:
21015615
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 1; Other Information: DOI: 10.1016/j.jssc.2006.09.018; PII: S0022-4596(06)00528-7; Copyright (c) 2006 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; CALCIUM NITRIDES; LITHIUM NITRIDES; MONOCLINIC LATTICES; MONOCRYSTALS; NIOBIUM NITRIDES; SPACE GROUPS; SYNTHESIS; TITANIUM NITRIDES; X-RAY DIFFRACTION

Citation Formats

Hunting, Janet L., Szymanski, Marta M., Johnson, Philip E., Brenhin Kellar, C., and DiSalvo, Francis J. The synthesis and structural characterization of the new ternary nitrides: Ca{sub 4}TiN{sub 4} and Ca{sub 5}NbN{sub 5}. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2006.09.018.
Hunting, Janet L., Szymanski, Marta M., Johnson, Philip E., Brenhin Kellar, C., & DiSalvo, Francis J. The synthesis and structural characterization of the new ternary nitrides: Ca{sub 4}TiN{sub 4} and Ca{sub 5}NbN{sub 5}. United States. doi:10.1016/j.jssc.2006.09.018.
Hunting, Janet L., Szymanski, Marta M., Johnson, Philip E., Brenhin Kellar, C., and DiSalvo, Francis J. Mon . "The synthesis and structural characterization of the new ternary nitrides: Ca{sub 4}TiN{sub 4} and Ca{sub 5}NbN{sub 5}". United States. doi:10.1016/j.jssc.2006.09.018.
@article{osti_21015615,
title = {The synthesis and structural characterization of the new ternary nitrides: Ca{sub 4}TiN{sub 4} and Ca{sub 5}NbN{sub 5}},
author = {Hunting, Janet L. and Szymanski, Marta M. and Johnson, Philip E. and Brenhin Kellar, C. and DiSalvo, Francis J.},
abstractNote = {The ternary nitrides, Ca{sub 4}TiN{sub 4} and Ca{sub 5}NbN{sub 5}, were synthesized in sealed niobium tubes using lithium nitride as a flux at 900 and 1050 deg. C, respectively. The structures of both compounds were solved from single-crystal X-ray diffraction data. Ca{sub 4}TiN{sub 4} is the first example of a calcium group IV nitride; it crystallizes in the triclinic space group P1-bar (No. 2) with cell parameters a=5.9757(5) A, b=6.0129(5) A, c=6.0116(12) A, {alpha}=71.565(4){sup o}, {beta}=79.471(4){sup o}, {gamma}=68.258(4){sup o} and Z=2. Ca{sub 4}TiN{sub 4} is isostructural with Na{sub 4}TiO{sub 4} and contains tetrahedral TiN{sub 4} units connected through edges and corners to CaN{sub 4} tetrahedra and CaN{sub 5} square pyramids. Ca{sub 5}NbN{sub 5} crystallizes in the monoclinic space group C2/m (No. 12) with cell parameters a=11.922(7) A, b=6.878(5) A, c=8.936(7) A, {beta}=101.22(3){sup o} and Z=4. Ca{sub 5}NbN{sub 5} is isostructural with Ba{sub 5}NbN{sub 5}; the structure contains NbN{sub 4} tetrahedra that share vertices with CaN{sub 5} trigonal bipyramids.},
doi = {10.1016/j.jssc.2006.09.018},
journal = {Journal of Solid State Chemistry},
number = 1,
volume = 180,
place = {United States},
year = {Mon Jan 15 00:00:00 EST 2007},
month = {Mon Jan 15 00:00:00 EST 2007}
}
  • Tetrameric [(C{sub 5}Me{sub 5})MF{sub 3}{sub 4}] (M = Zr, Hf) react smoothly with Me{sub 3}SiCl in CH{sub 2}Cl{sub 2} at room temperature to give [((C{sub 5}Me{sub 5})ZrF{sub 2}Cl){sub 4}] (1) and [((C{sub 5}Me{sub 5})HfF{sub 2}Cl){sub 4}] (2), respectively in high yield. Treatment of [((C{sub 5}Me{sub 5})MF{sub 3}){sub 4}] (M = Zr, Hf) with Me{sub 2}AlCl in toluene gives mixtures of 1 and [(C{sub 5}Me{sub 5}){sub 4}Zr{sub 4}({mu}-F){sub 2}({mu}-F{sub 2}){sub 2}({mu}-Cl){sub 2}Cl{sub 4}] (3), and 2 and [(C{sub 5}Me{sub 5}){sub 4}Hf{sub 4}({mu}-F){sub 2}({mu}-F{sub 2}){sub 2}({mu}-Cl){sub 2}Cl{sub 4}] (4), respectively, in an approximately 1:1 molar ratio. Metallocene type complexes [(C{sub 5}Me{sub 4}Et){submore » 2}ZrCl{sub 2}] and [(C{sub 5}Me{sub 5}){sub 2}HfCl{sub 2}] react with 1 equiv of Me{sub 3}SnF to give [(C{sub 5}Me{sub 4}Et){sub 2}ZrClF] (5) and [(C{sub 5}Me{sub 5}){sub 2}HfClF] (6), respectively. The complexes 1-6 were characterized by spectroscopic methods ({sup 1}H and {sup 19}F NMR and mass spectrometry). The solid state structures of 1, 3, and 5 were determined by single-crystal X-ray diffraction analyses.« less
  • Reported are the synthesis and the structural characterization of four new polar intermetallic phases, which exist only with mixed alkaline-earth and rare-earth metal cations in narrow homogeneity ranges. (Sr{sub 1-x}Ca{sub x}){sub 5}In{sub 3}Ge{sub 6} and (Eu{sub 1-x}Yb{sub x}){sub 5}In{sub 3}Ge{sub 6} (x{approx}0.7) crystallize in the orthorhombic space group Pnma with two formula units per unit cell (own structure type, Pearson symbol oP56). The lattice parameters are as follows: a=13.109(3)-13.266(3) A, b=4.4089(9)-4.4703(12) A, and c=23.316(5)-23.557(6) A. (Sr{sub 1-x}Ca{sub x}){sub 3}In{sub 2}Ge{sub 4} and (Sr{sub 1-x}Yb{sub x}){sub 3}In{sub 2}Ge{sub 4} (x{approx}0.4-0.5) adopt another novel monoclinic structure-type (space group C2/m, Z=4, Pearson symbolmore » mS36) with lattice parameters in the range a=19.978(2)-20.202(2) A, b=4.5287(5)-4.5664(5) A, c=10.3295(12)-10.3447(10) A, and {beta}=98.214(2)-98.470(2){sup o}, depending on the metal cations and their ratio. The polyanionic sub-structures in both cases are based on chains of InGe{sub 4} corner-shared tetrahedra. The A{sub 5}In{sub 3}Ge{sub 6} structure (A=Sr/Ca or Sr/Yb) also features Ge{sub 4} tetramers, and isolated In atoms in nearly square-planar environment, while the A{sub 3}In{sub 2}Ge{sub 4} structure (A=Sr/Ca or Eu/Yb) contains zig-zag chains of In and Ge strings with intricate topology of cis- and trans-bonds. The experimental results have been complemented by tight-binding linear muffin-tin orbital (LMTO) band structure calculations. - Graphical abstract: The anion sub-network of A{sub 5}In{sub 3}Ge{sub 6} is based upon tetrahedral [InGe{sub 4}] chains, Ge{sub 4} tetramers isosteric with 1,3-cis-butadiene, and distorted square-planar [InGe{sub 4}] fragments. The structure of A{sub 3}In{sub 2}Ge{sub 4} is a combination of infinite Ge chains with cis- and trans-bonds in a complex (tttctc){sub n} pattern, tetrahedral [InGe{sub 4}] chains, and In zig-zag chains.« less
  • Ten new ternary phosphides and arsenides with empirical formulae AE{sub 3}Al{sub 2}Pn{sub 4} and AE{sub 3}Ga{sub 2}Pn{sub 4} (AE=Ca, Sr, Ba, Eu; Pn=P, As) have been synthesized using molten Ga, Al, and Pb fluxes. They have been structurally characterized by single-crystal and powder X-ray diffraction to form with two different structures-Ca{sub 3}Al{sub 2}P{sub 4}, Sr{sub 3}Al{sub 2}As{sub 4}, Eu{sub 3}Al{sub 2}P{sub 4}, Eu{sub 3}Al{sub 2}As{sub 4}, Ca{sub 3}Ga{sub 2}P{sub 4}, Sr{sub 3}Ga{sub 2}P{sub 4}, Sr{sub 3}Ga{sub 2}As{sub 4}, and Eu{sub 3}Ga{sub 2}As{sub 4} crystallize with the Ca{sub 3}Al{sub 2}As{sub 4} structure type (space group C2/c, Z=4); Ba{sub 3}Al{sub 2}P{sub 4}more » and Ba{sub 3}Al{sub 2}As{sub 4} adopt the Na{sub 3}Fe{sub 2}S{sub 4} structure type (space group Pnma, Z=4). The polyanions in both structures are made up of TrPn{sub 4} tetrahedra, which share common corners and edges to form {sup 2}{sub {infinity}}[TrPn{sub 2}]{sub 3-} layers in the phases with the Ca{sub 3}Al{sub 2}As{sub 4} structure, and {sup 1}{sub {infinity}}[TrPn{sub 2}]{sub 3-} chains in Ba{sub 3}Al{sub 2}P{sub 4} and Ba{sub 3}Al{sub 2}As{sub 4} with the Na{sub 3}Fe{sub 2}S{sub 4} structure type. The valence electron count for all of these compounds follows the Zintl-Klemm rules. Electronic band structure calculations confirm them to be semiconductors. - Graphical abstract: AE{sub 3}Al{sub 2}Pn{sub 4} and AE{sub 3}Ga{sub 2}Pn{sub 4} (AE=Ca, Sr, Ba, Eu; Pn=P, As) crystallize in two different structures-Ca{sub 3}Al{sub 2}P{sub 4}, Sr{sub 3}Al{sub 2}As{sub 4}, Eu{sub 3}Al{sub 2}P{sub 4}, Eu{sub 3}Al{sub 2}As{sub 4}, Ca{sub 3}Ga{sub 2}P{sub 4}, Sr{sub 3}Ga{sub 2}P{sub 4}, Sr{sub 3}Ga{sub 2}As{sub 4}, and Eu{sub 3}Ga{sub 2}As{sub 4}, are isotypic with the previously reported Ca{sub 3}Al{sub 2}As{sub 4} (space group C2/c (No. 15)), while Ba{sub 3}Al{sub 2}P{sub 4} and Ba{sub 3}Al{sub 2}As{sub 4} adopt a different structure known for Na{sub 3}Fe{sub 2}S{sub 4} (space group Pnma (No. 62). The polyanions in both structures are made up of TrPn{sub 4} tetrahedra, which by sharing common corners and edges, form {sup 2}{sub {infinity}}[TrPn{sub 2}]{sub 3-}layers in the former and {sup 1}{sub {infinity}}[TrPn{sub 2}]{sub 3-} chains in Ba{sub 3}Al{sub 2}P{sub 4} and Ba{sub 3}Al{sub 2}As{sub 4}. Highlights: Black-Right-Pointing-Pointer AE{sub 3}Ga{sub 2}Pn{sub 4} (AE=Ca, Sr, Ba, Eu; Pn=P, As) are new ternary pnictides. Black-Right-Pointing-Pointer Ba{sub 3}Al{sub 2}P{sub 4} and Ba{sub 3}Al{sub 2}As{sub 4} adopt the Na{sub 3}Fe{sub 2}S{sub 4} structure type. Black-Right-Pointing-Pointer The Sr- and Ca-compounds crystallize with the Ca{sub 3}Al{sub 2}As{sub 4} structure type. Black-Right-Pointing-Pointer The valence electron count for all title compounds follows the Zintl-Klemm rules.« less
  • Trace amounts of H/sub 2/O and limited exposure to air of reaction mixtures of UCl/sub 4/ and 12-crown-4, 15-crown-5, benzo-15-crown-5, 18-crown-6, or dibenzo-18-crown-6 in 1:3 mixtures of CH/sub 3/OH and CH/sub 3/CN resulted in the hydrolysis and oxidation of UCl/sub 4/ to (UO/sub 2/Cl/sub 4/)/sup 2/minus//. In the presence of these crown ethers, it has been possible to isolate intermediate products via crystallization of crown complexes of the (UO/sub 2/Cl/sub 4/)/sup 2/minus// ion, the (UCl/sub 6/)/sup 2/minus// ion, and (UO/sub 2/Cl/sub 2/(OH/sub 2/)/sub 3/). The neutral moiety crystallizes as a hydrogen-bonded crown ether complex; however, crown ether complexation of amore » counterion, either an ammonium ion formed during the oxidation of U(IV) or a Na/sup +/ ion leached from glass reaction vessels, resulted in novel crystalline complexes of the ionic species. ((NH/sub 4/)(15-crown-5)/sub 2/)/sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2CH/sub 3/CN, ((NH/sub 4/)(benzo-15-crown-5)/sub 2/)/sub 2/(UCl/sub 6/) /times/ 4CH/sub 3/CN, and ((NH/sub 4/)(dibenzo-18-crown-6))/sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2CH/sub 3/CN have been structurally characterized by single-crystal X-ray diffraction techniques. The results of all the crystal studies are presented in detail. The ammonium ions interact with the crown ethers via hydrogen-bonding and electrostatic interactions. 15-Crown-5 and benzo-15-crown-5 form 2:1 sandwich cations, allowing no H/sub 4/N/sup +//hor ellipsis/(UO/sub 2/Cl/sub 4/)/sup 2/minus// interaction. The dibenzo-18-crown-6 complexed ammonium ions are 1:1 and form bifurcated hydrogen bonds with the chlorine atoms in the (UO/sub 2/Cl/sub 4/)/sup /minus// anion. The formation of (Na(12-crown-4)/sub 2//sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2OHMe and (UO/sub 2/Cl/sub 2/(OH)/sub 2/)/sub 3/) /times/ 18-crown-6 /times/ H/sub 2/O /times/ OHMe has been confirmed by preliminary single-crystal X-ray diffraction studies.« less
  • A new three-dimensional open-framework gallophosphate: [H{sub 3}N(CH{sub 2}){sub 2}NH{sub 3}]{sub 1/2}.[Ga{sub 5} (PO{sub 4}){sub 4}(OH){sub 4}] has been prepared by hydro(solvo)thermal synthesis in presence of ethylenediamine (en) as structure-directing agent. Its structure was determined by means of single-crystal X-ray diffraction analysis with the following crystal data: monoclinic space group C2/m, a=10.1604(9)A, b=12.0085(15)A, c=7.1892(7)A, {beta}=90.797(6){sup o}, V=877.08(16)A{sup 3}, Z=2, R{sub 1}=0.0264, wR{sub 2}=0.0764. The total numbers of measured reflections and unique reflections were 3508 and 1300, respectively. It is built up from a new secondary building unit (SBU) Ga{sub 4}P{sub 4}O{sub 20}(OH){sub 4}, in which Ga atoms exhibit distorted trigonal bipyramidalmore » coordination and P atoms are in tetrahedral coordination. The SBU Ga{sub 4}P{sub 4}O{sub 20}(OH){sub 4} are linked into a layer by bridge oxygen atoms. The GaO{sub 4}(OH){sub 2} octahedra link the layers into a three-dimentional framework. Diprotonated ethylenediamine was found in the channel of the framework. The material was characterized by IR spectroscopy, {sup 1}H NMR spectra, thermogravimetric and differential thermal analyses and elemental analysis.« less