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M{sub 2}X intermetallics: Nonmetal insertion in a h.c.-like metallic distribution

Journal Article · · Journal of Solid State Chemistry
 [1];  [2]
  1. E.N.S.C., Rennes (France). Lab. de Physicochimie Analytique et Theorique
  2. Lab. de Chimie due Solide et Inorganique Moleculaire, Rennes (France)

A simple structural model is proposed on the basis of an ideal hexagonal close-packing (AB){sup {infinity}} of the metal atoms M. The metalloid atoms X, located in an ordered manner in the metallic planes with the stacking sequence ..(A){sup {infinity}}.. or ..(B){sup {infinity}}.., generate two types of elementary units called units U{sub I} and U{sub II}. These units are hexagonal prisms with the fundamental vectors a{sub 0}, b{sub 0}, c{sub 0} and the elementary volume V{sub 0}. When the exclusive occurrence of U{sub I} (or U{sub II}) only yields 6-prismatic and triangular sites of metalloid atoms X, additional tetrahedral and pyramidal sites of X atoms are present when units U{sub I} and U{sub II} exist simultaneously. The structures of compounds with the general formula M{sub 2}X (M = 3d, 4d, 5d and (or) 4f, 5f elements, X = B, P, As, Sb, Si, Ge, {hor_ellipsis}) are described in terms of intergrowth mechanisms. Binary, ternary, or even quaternary structures of compounds, with M/X ratios equal or close to two, appear as superstructures of the elementary units. Insofar as no ordering is considered along the stacking direction, the vectorial combinations of the fundamental vectors in the form A = h.a{sub 0}+s.b{sub 0}, B = k.a{sub 0}+t.b{sub 0}, C = c{sub 0} result in supercells with the volume V = (h.t {minus} k.s).V{sub 0}. The attainable symmetry (hexagonal, tetragonal, orthorhombic, monoclinic, {hor_ellipsis}) strongly depends on the particular values of the integers h, s, k, t. The criteria of occurrence of various series of compounds are presented together with their crystallographic features and structural relationships are emphasized. Moreover, the model demonstrates that numerous compounds with the predicted unit cell parameters should be obtained in each crystal system.

OSTI ID:
642180
Journal Information:
Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 2 Vol. 135; ISSN 0022-4596; ISSN JSSCBI
Country of Publication:
United States
Language:
English

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