Flux Crystal Growth, Crystal Structure, and Magnetic Properties of a Ternary Chromium Disulfide Ba9Cr4S19 with Unusual Cr4S15 Tetramer Units

Hong Yan; Yoshitaka Matsushita; Akira Chikamatsu; Tetsuya Hasegawa; Kazunari Yamaura; Yoshihiro Tsujimoto

doi:10.1021/acsomega.0c06017

Flux Crystal Growth, Crystal Structure, and Magnetic Properties of a Ternary Chromium Disulfide Ba₉Cr₄S₁₉ with Unusual Cr₄S₁₅ Tetramer Units

ACS Omega. 2021 Mar 5;6(10):6842-6847. doi: 10.1021/acsomega.0c06017. eCollection 2021 Mar 16.

Authors

Hong Yan^{1

2}, Yoshitaka Matsushita³, Akira Chikamatsu⁴, Tetsuya Hasegawa⁴, Kazunari Yamaura^{1

2}, Yoshihiro Tsujimoto^{1

2}

Affiliations

¹ International Center for Materials Nanoarchitechtonics (WPI-MANA), National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan.
² Graduate School of Chemical Sciences and Engineering, Hokkaido University, North 13 West 8, Kita-ku, Sapporo 060-0808, Japan.
³ Materials Analysis Station, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba 305-0047, Japan.
⁴ Department of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.

Abstract

A new ternary chromium disulfide, Ba₉Cr₄S₁₉, has been grown out of BaCl₂ molten salt. Single-crystal structure analysis revealed that it crystallizes in the centrosymmetric space group C 2/c with lattice parameters: a = 12.795(3) Å, b = 11.3269(2) Å, c = 23.2057(6) Å, β = 104.041(3)°, and Z = 4. Ba₉Cr₄S₁₉ comprises four face-sharing Cr-centered octahedra with disulfide ions occupying sites on each terminal face. The resulting Cr₄S₁₅ tetramer units are isolated by nonmagnetic Ba-centered polyhedra in the ab plane and barium disulfide (=Ba₄(S₂)₂) layers along the c-axis. Following the structure analysis, the title compound should be expressed as [Ba²⁺]₉[Cr³⁺]₄[(S₂)^2-]₄[S^2-]₁₁, which is also consistent with Cr2p X-ray photoemission spectra showing trivalent states of the Cr atoms. The unique Cr-based zero-dimensional structure with the formation of these disulfide ions can be achieved for the first time in ternary chromium sulfides, which adopt 1-3 dimensional frameworks of Cr-centered polyhedra.