Crystal Structure and Magnetic Property of a Quaternary Sulfide, Al_(0.36)Sm_3Ge_(0.98)S_7

A new quaternary sulfide, Al0.36Sm3Ge0.98S7 1, has been prepared by a facile solidstate reaction, and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in the hexagonal space group P63 with a = 9.964（1）, c = 5.768（2）A, V = 495.9（1）A^3 and Z = 2. In the crystal structure of 1, Al^3＋ and Ge^4＋ occupy the octahedral and tetrahedral interspaces of the 3-D main-framework constructed by SmS8 bicapped trigonal prisms, respectively. The investigation of optical and magnetic properties of 1 indicates that its optical band gap is 2.18 eV and it shows antiferromagnetic-like interaction.

Synthesis,Crystal Structure,Physical Properties and Theoretical Studies of the New Ternary Sulfide with Closed Cavities:CsYb_7S_(11)

A novel ternary rare-earth sulfide, CsYb7S（11）, has been successfully synthesized by high-temperature solid-state reaction of an elemental mixture with modified Cs Cl flux. The single-crystal X-ray diffraction data reveal its orthorhombic symmetry in space group Cmca（no. 64） with a = 15.271（3）, b = 13.414（2）, c = 18.869（3） A°, V = 3865.2（2） A°^3, Z = 8, Mr = 1696.85, Dc = 5.832 g/cm^3, μ = 36.538 mm^-1, F（000） = 5768, the final R = 0.0225 and w R = 0.0517 for 2258 observed reflections with I 〉 2σ（I）, 2.67〈θ〈27.48o, w = 1/[σ^2（Fo^2） ＋（0.0443 P）2 ＋ 8.7453 P], where P =（Fo^2 ＋ 2Fc^2）/3, S = 1.036,（Δρ）max = 1.609 and（Δρ）min = –1.922. The remarkable structural feature is the dual tricapped Cs2@S18 cube closed cavities far apart within the three-dimensional [Yb7S（11）]-covalent bonding matrix. Magnetic susceptibility measurements show that the title compound exhibits temperature-dependent（50～300 K） para-magnetism and obey the Curie-Weiss law. Moreover, the optical gap of 2.03 Ev for CsYb7S11 was deduced from the UV/Vis reflectance spectroscopy and DFT study indicates an indirect band gap with an electronic transfer excitation of S-3p to Yb-5d orbital.

Synthesis and Crystal Structure of a New Quaternary Sulfide FeSm6Si2S14

One new quaternary rare-earth sulfide, FeSm6Si2S（14）, has been synthesized by a facile solid-state route with boron as the reducing reagent. It crystallizes in the noncentrosymmetric hexagonal space group P63, belonging to the Ce6Al（3.33）S（14） structure-type, and the AxRE3MQ7 family. Its crystal structure features a 3-D framework constructed by SmS 8 bicapped trigonal prisms, where Fe and Si atoms occupy the octahedral（2a） and tetrahedral（2c） voids, respectively. The FeS 6 octahedra are connected with each other to form a chain along the b direction. FeSm6Si2S（14） represents a new chemical composition among the large family of AxRE3MQ7 compounds. The other related compounds containing transition metal are also discussed.

Solid-state Synthesis,Crystal and Band Structures,and Optical Properties of a Novel Ternary Sulfide Eu_2Ga_2S_5

One new ternary europium gallium sulfide, Eu2Ga2S5, has been synthesized by a facile solid-state route with boron as the reducing reagent. It crystallizes in the orthorhombic space group Pbca, with a = 11.976（1）, b = 11.074（1）, c = 17.446（1）A^°, V = 1650.6（3）A^°^3, and Z = 8. Its 3-D structure is built by the connection between EuS 7 monocapped trigonal prisms and GaS 4 tetrahedra, and the latter connect with each other to form layer-like slabs. Its optical energy gap is determined to be 2.17 eV, which is also verified by the electronic band structure calculation.

Syntheses and Single-crystal Structures of Ln_3Sn_(0.25)GeS_7 (Ln=La,Sm)

Two new quaternary sulfides,La3Sn0.25GeS71 and Sm3 Sn0.25GeS72,have been synthesized by a facile solid-state reaction,and their crystal structures were determined by singlecrystal X-ray diffraction analysis.The two compounds crystallize in the P6 3 space group,and the crystal data are as follows-La3Sn0.25GeS7：a=10.3335（7）,c=5.8455（7）,Z=2;Sm3Sn0.25GeS7：a=9.999（3）,c=5.787（2）,Z=2.Single-crystal analysis indicated that the two compounds consist of three types of building blocks：LnS 8 anti-tetragonal prism,SnS 6 octahedron,and GeS 4 tetrahedron.

Syntheses and Single-crystal Structures of New Deficient Compounds in the R_6B_2C_2Q_(14)Family

Four new deficient compounds in the R6B2C2QI4 family, LasCaSn2.75S4 1, Y6A10.67Ge2S14 2, Er5.33Si4S14 3 and Er4Ge4SI4 4, have been obtained via a precursor/flux method. Single-crystal analysis indicated that their crystal structures consist of three types of building blocks： RS7 （R = La/Ca for 1, R = Y for 2, R = Er for 3 and 4） mono-triangonal prism, CS6 （C = A1 for 1, C = Sn（2） for 2, C = Si（2） for 3, C = Ge（2） for 4） octahedron, and BS4 （B = Si for 1, B = Sn（1） for 2, B = Si（1） for 3, B = Ge（1） for 4） tetrahedron, as any other compounds belong to the R6B2C2Q14 family.

Syntheses,structures and properties of five chiral quaternary sulfides,AlxLn_3(Si_yAl_(1-γ))S_7 (Ln=Y,Gd,Dy) and In_(0.33)Sm_3SiS_7

Five new quaternary isostructural rare-earth sulfides, Al0.57Gd3(Si0.27Al0.73)S7 (1), Al0.55Dy3(Si0.34Al0.66)S7 (2), Al0.50Y3(Si0.50Al0.50)S7 (3), Al0.44Gd3(Si0.70Al0.30)S7 (4) and In0.33Sm3SiS7 (5), have been synthesized by facile solid-state reactions. They crystallize in the 3-D ALn3EQ7 structure type in the hexagonal chiral space group P63. The structures feature a 3-D host framework constructed by Ln-S bicapped trigonal prisms, in which the octahedral and tetrahedral interspaces are occupied by A and E atoms, respectively. The investigation of optical and magnetic properties of 4 indicates that it is a semiconductor and behaves antiferromagnetic-like interaction.