本論文以固態長晶法合成出四種結構的化合物，分別為Pb4In5.84Ga0.66S13 (1)、Sn4In5.78Ga0.72S13 (2)、Ba3SnSb2Se8 (3) 和Ba2SnSbSe4.5 (4)。化合物1晶系為Monoclinic C2/m，晶格常數為：a = 27.7882(17) Å, b = 3.8613(2) Å, c = 19.2502(11) Å, ß = 91.817(1)゜。化合物2晶系為Monoclinic C2/m，晶格常數為：a = 27.7954(16) Å, b = 3.8613(2) Å, c = 19.2502(11) Å, ß = 91.817(10)゜。化合物1、2兩者呈現等結構，皆由InS6八面體、InS5四角錐和GaS4四面體形成三維骨架結構，維持了Pb-In-S三元系統中常見似NaCl和CdI2-block的結構區塊特徵，此外In(6)的位置為In+/In3+混價所形成[In(6)2]4+之共價對(covalent pairs)。化合物3晶系為Orthorhombic Pnma，晶格常數為：a = 12.714(2) Å, b = 4.5428(8) Å, c = 29.569(5) Å。結構中是以SbSe6八面體、SbSe5四角錐和SnSe4四面體，各別形成沿b軸方向延伸的鏈狀結構，此結構在相關文獻[32]Inorg. Chem. 2012, 51, 13328已被發表。然而在同一Ba-Sn-Sb-Se系統中，我們發現有別於化合物3分子式的另一化合物4，晶系為Monoclinic C2/m，晶格常數為：a = 12.722(1) Å, b = 4.6949(4) Å, c = 32.838(3) Å，目前正在進行單晶X光繞射分析，期許未來有良好發展。

New metal chalcogenides in the systems of Pb4In5.84Ga0.66S13(1) 、Sn4In5.78Ga0.72S13 (2)、Ba3SnSb2Se8 (3) and Ba2SnSbSe4.5 (4) were synthesized by solid-state reaction, and their structures were determined by single-crystal X-ray diffraction. Compounds 1 and 2 crystallize in Monoclinic space group C2/m. Compounds 1 and 2 are isostructural, the framworks consists of three major building blocks formed by InS6 octahedra, InS5 square pyramidal and GaS4 tetrahedra. The structure retains the original framework of Pb-In-S ternary chalcogenides system composed of NaCl-type and CdI2-type blocks. Compounds 3 crystallize in Orthorhombic space group Pnma. The framwork consists of SbSe5 square pyramidal, SbSe4 tetrahedra and SnSe4 tetrahedra. Consistently, the results are good agreement with structure reported in 2012. Noticeably, the copounds 4 were peculiarly found in synthesis of Ba-Sn-Sb-Se quaternary chalcogenides. Accordingly, Compounds 4 structures would be determinded by single-crystal X-ray diffraction so as to gain the in-depth understanding of uniqu structure.

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