Yan Hong, Matsushita Yoshitaka, Chikamatsu Akira, Hasegawa Tetsuya, Yamaura Kazunari, Tsujimoto Yoshihiro
International Center for Materials Nanoarchitechtonics (WPI-MANA), National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan.
Graduate School of Chemical Sciences and Engineering, Hokkaido University, North 13 West 8, Kita-ku, Sapporo 060-0808, Japan.
ACS Omega. 2021 Mar 5;6(10):6842-6847. doi: 10.1021/acsomega.0c06017. eCollection 2021 Mar 16.
A new ternary chromium disulfide, BaCrS, has been grown out of BaCl molten salt. Single-crystal structure analysis revealed that it crystallizes in the centrosymmetric space group 2/ with lattice parameters: = 12.795(3) Å, = 11.3269(2) Å, = 23.2057(6) Å, β = 104.041(3)°, and = 4. BaCrS comprises four face-sharing Cr-centered octahedra with disulfide ions occupying sites on each terminal face. The resulting CrS tetramer units are isolated by nonmagnetic Ba-centered polyhedra in the plane and barium disulfide (=Ba(S)) layers along the -axis. Following the structure analysis, the title compound should be expressed as [Ba][Cr][(S)][S], 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.
一种新的三元二硫化铬BaCrS已从BaCl熔盐中生长出来。单晶结构分析表明，它结晶于中心对称空间群2/，晶格参数为：a = 12.795(3) Å，b = 11.3269(2) Å，c = 23.2057(6) Å，β = 104.041(3)°，Z = 4。BaCrS由四个共用面的以Cr为中心的八面体组成，二硫离子占据每个端面的位置。所得的CrS四聚体单元在ab平面内被非磁性的以Ba为中心的多面体以及沿c轴的二硫化钡（=Ba(S)）层隔开。通过结构分析，标题化合物应表示为[Ba][Cr][(S)][S]，这也与显示Cr原子三价态的Cr2p X射线光电子能谱一致。在采用以Cr为中心的多面体的1 - 3维框架的三元硫化铬中，首次实现了具有这些二硫离子形成的独特的基于Cr的零维结构。
