Quaternary chalcogenides BaRE2In2Ch7 (RE = La–Nd; Ch = S, Se) containing InCh5 trigonal bipyramids

Wenlong Yin; Abishek K. Iyer; Xinsong Lin; Chao Li; Jiyong Yao; Arthur Mar

doi:10.1039/C6DT02385A

Quaternary chalcogenides BaRE₂In₂Ch₇ (RE = La–Nd; Ch = S, Se) containing InCh₅ trigonal bipyramids†

Wenlong Yin,^ab Abishek K. Iyer,^a Xinsong Lin,^c Chao Li,^d Jiyong Yao^d and Arthur Mar*^a

* Corresponding authors

^a Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2
E-mail: arthur.mar@ualberta.ca
Fax: +1-780-492-8231

^b Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900, People's Republic of China

^c Centre for Oil Sands Sustainability, Northern Alberta Institute of Technology, Edmonton, Alberta, Canada T6N 1E5

^d Center for Crystal Research and Development, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, People's Republic of China

Abstract

Eight new quaternary chalcogenides BaRE₂In₂Ch₇ (RE = La–Nd; Ch = S, Se) have been prepared by reactions of BaCh, In₂Ch₃, RE, and Ch at high temperatures. They adopt orthorhombic structures (space group Pbam, Z = 2; a = 11.6300(8)–11.5895(7) Å, b = 12.4202(9)–12.3001(8) Å, c = 4.0689(3)–4.0028(2) Å for the sulfides; a = 12.1515(6)–12.1358(10) Å, b = 12.9367(7)–12.8510(11) Å, c = 4.1966(2)–4.1363(4) Å for the selenides) containing one-dimensional anionic [In₂Ch₇] ribbons of corner-sharing InCh₅ trigonal bipyramids, separated by Ba and RE cations. The structure is an ordered variant of the rare Eu₃Sn₂S₇-type with Ba atoms occupying larger sites with nearly cubic geometry and RE atoms occupying smaller sites with bicapped trigonal prismatic geometry. The InCh₅ trigonal bipyramids, which are unusual, exhibit four shorter In–Ch bonds and a fifth longer one. Band structure calculations indicate that BaLa₂In₂S₇ is a direct gap semiconductor, and corroborate the description of the In coordination as CN4 + 1. On the basis of the optical absorption spectra, band gaps were estimated to be 1.87(2) eV for BaLa₂In₂S₇ and 1.66(2) eV for BaLa₂In₂Se₇.

Article information

https://doi.org/10.1039/C6DT02385A

Article type

Paper

Submitted

15 Jun 2016

Accepted

08 Jul 2016

First published

08 Jul 2016

Download Citation

Dalton Trans., 2016,45, 12329-12337

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Quaternary chalcogenides BaRE₂In₂Ch₇ (RE = La–Nd; Ch = S, Se) containing InCh₅ trigonal bipyramids

W. Yin, A. K. Iyer, X. Lin, C. Li, J. Yao and A. Mar, Dalton Trans., 2016, 45, 12329 DOI: 10.1039/C6DT02385A

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