Ba3Zr2Cu4S9: the first quaternary phase of the Ba–Zr–Cu–S system

Barman, Sayani and Jana, Subhendu and Panigrahi, Gopabandhu and Yadav, Sweta and Niranjan, Manish K. and Prakash, Jai (2022) Ba3Zr2Cu4S9: the first quaternary phase of the Ba–Zr–Cu–S system. New Journal of Chemistry. ISSN 1144-0546

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We report the synthesis of red-colored crystals of Ba3Zr2Cu4S9via a high-temperature reaction of elements at 1223 K. The title compound is the first quaternary phase of the Ba-Zr-Cu-S system. A single-crystal X-ray diffraction study has elucidated its crystal structure, which shows that it crystallizes in a new structure type in the centrosymmetric triclinic P1̄ space group with cell dimensions of a = 6.9150(3) Å, b = 10.3863(5) Å, c = 12.2417(6) Å, α = 109.524(1)°, β = 105.132(2)°, and γ = 96.809(2)° with Z = 2. The asymmetric unit of the structure contains a total of eighteen crystallographic distinct atomic positions: 3 × Ba, 2 × Zr, 4 × Cu, and 9 × S. All these atoms are present at the general positions. The structure is best described as pseudo-two-dimensional with infinite layers of ∝2[Zr2Cu4S9]6− and Ba2+ cations occupy the space between two such layers. The Zr atoms are bonded with six S atoms to form ZrS6 octahedra. Each Cu(2) and Cu(4) atom sits at the center of a distorted tetrahedron of sulfur atoms. Interestingly, the Cu(1) and Cu(3) atoms are only three coordinated and form distorted CuS3 trigonal polyhedra. The ab initio DFT calculations are performed to explore the electronic structure and the optical properties. An experimental optical bandgap study established the semiconducting nature (Eg = 1.9(1) eV) of a polycrystalline Ba3Zr2Cu4S9 sample in agreement with the theoretical DFT study. The computed cell constants and atomic positions are found to be in good agreement with the experiments. The computed bandgap is indirect with a ∼1.1 to 1.5 eV magnitude. The COHP values are obtained to assess the relative strength of chemical bonding between atoms. The relative charge transfer between bonding atoms is estimated from the analysis of the Bader charge. © 2022 The Royal Society of Chemistry.

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IITH Creators:
IITH CreatorsORCiD
Niranjan, Manish K
Prakash, Jai
Item Type: Article
Additional Information: J. P. thanks DST-SERB, the Government of India (GOI) for the financial support under the core research grant (Grant number: CRG/2021/0003641), and IIT Hyderabad for research facilities; S. B. thanks CSIR, India, for a JRF fellowship; S. J. and G. P. thank the Ministry of Education (MOE), GOI, and IIT Hyderabad for the research fellowships; S. Y. thanks MOE, GOI for the prime minister research fellowship (PMRF). The authors also acknowledge DST-FIST(SR/FST/PSI-215/2016) for the computational resources.
Uncontrolled Keywords: Atomic positions; Centrosymmetric; Colored crystals; Crystals structures; High-temperature reaction; Quaternary phasis; S-systems; Single-crystal X-ray diffraction studies; Structure type; Title compounds
Subjects: Physics
Divisions: Department of Chemistry
Department of Physics
Depositing User: . LibTrainee 2021
Date Deposited: 16 Aug 2022 08:47
Last Modified: 16 Aug 2022 08:47
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