STUDIES ON SOLID STATE REACTIONS OF COORDINATION COMPOUNDS(LXⅡ)Solid state synthesis and crystal structure of the complex ICu_(0.84)Au_(0.16)(PPh_3)_2(SC(Ph)NHPh)CIJ·0.5CS_2

[Cu_(0.84)Au_(0.16)(PPh_3)_2(SC(Ph)NHPh)Cl]·0.5CS_2=,Mr=895.79,monoclinic,space group P2_1/a,a=17.231(3),b=14.611(2),c=18.000(3) ,β=105.56(2)°,V=4365(1) ~3, Z=4,D_c=1.37g/cm^3.,λ(MoK_α)=0.71073 ,μ=12.15cm^(-1),F(000)=1855,R=0.052, R_W=0.045 for 3930 observed reflections with Ⅰ>1.5σ(Ⅰ).The central metal atom has a dis. torted tetrahedral geometry with bond lengths Cu-S=2.384(2) (Au-S=2.389(4)), Cu-Cl=2.481(3)(Au-Cl=2.474(1))and Cu-P=2.269(2)-2.289(2)(Au-P=2.270(4)-2.279(4)) .

Solid State Synthesis and Crystal Structure of 3-Methyl-1-phenyl-4-phenylbenzoylmethylene-5-pyrazolone

The solid state thermal reaction of benzil with 3-methyl-1-phenyl-5-pyrazolone gave the title compound 1 (C_24H_18N_2O_2) and its isomer 2. The crystal structure of the title compound has been determined by X-ray analysis. The crystal belongs to monoclinic system, space group P2_1/n, with cell parameters a = 7. 479 ( 1 ), b =16. 992(1), c=15. 165(1) A , β= 100. 99(1)°, V= 1891. 9 A￣3, M_r=366. 42, Z=4, D_c= 1. 286 g/cm￣3, μ= 6. 236 cm￣-1, F(000) = 768. In the molecule of 1, benzoyl group and CO group of five-member ring are in cis-positions, the interaction of oxygen atoms leads to the noncoplanarity.

Synthesis and Crystal Structure of an Incomplete Cubane-type Mo_3S_4 Cluster with the N-N-O Type Tridentate Ligand: {Mo_3S_4[NH_2CH_2CH(O)CH_2NH_2]_3}(DTP)·(H_2O)_2·(DMF)

A new cluster {Mo3S4[NH2CH2CH(O)CH2NH2]3}(DTP)?(H2O)2?(DMF) (DTP = diethyldithiophosphate) has been synthesized via ligand substitution reaction of Mo3S4(DTP)4(H2O) with an alkaline ligand 1,3-diamino-2-propanol(DAPROH) in a mixed organic solvent, and its crys- tal structure was determined with the following data: Mo3S6PC16H48O8N7, Mr = 977.76, triclinic, space group P1, Z = 2, a = 10.319(2), b = 12.843(3), c = 15.335(3) ?, α = 65.26(3), β = 82.18(3), γ = 70.67(3)o, V = 1741.7(6) ?3, Dc = 1.864 g/cm3, μ = 1.517 mm-1, F(000) = 988, the final R = 0.0794 and wR = 0.2111 for 6318 observed reflections (I>2σ(I)). The structure analysis indicates that all DTP ligands of Mo3S4(DTP)4(H2O) are replaced and each DAPRO molecule acts as a tri- dentate ligand chelating to each Mo atom of the Mo3S4 core. Different from the precursor, the clus- ter symmetry is elevated to C3. In addition, the UV-spectrum of the title compound was measured.

Synthesis and Crystal Structure of Sm Cu_(7.73)In_(3.27): a New 3D Framework Based on [Cu_5In_4M_4](M=Cu/In) Cluster

A new intermetallic compound, SmCuT.vslns.27, has been synthesized by solid-state reaction of the corresponding pure elements at high temperature, and structurally characterized by single-crystal X-ray diffraction study. SmCu7.731n3.27 crystallizes in tetragonal space group P4/mbm with a = 8.6213（4）, c = 10.2538（9）, V= 762.13（8） A3, Z = 4, M,. = 1018.90, Dc= 8.880 g/cm3,μ = 38.244 mm-1, F（000） = 1789, and the final R = 0.0374 and wR = 0.0836 for 514 observed reflections with I 〉 2σ（I）. The structure of SmCu7.69In3.31 belongs to a new structure type and features a three-dimensional （3D） [Cusln2M4] （M = Cu/In） framework composed of [CusinnM4] clusters interconnected via sharing In atoms as well as Cu-ln and In-In bonds. The Sm atoms are located in the one-dimensional （1 D） tunnels along the c-axis. The structural relationship of the title compound with other similar Sm-Cu-In phases was also studied. Band structure calculations based on Density Functional Theory （DFT） method indicate that SmCuT.69In3.31 is metallic.

Studies on solid state reactions of coordination compounds——XLⅦ.Solid state syntheses and crystal structures of cluster compounds {Cu_3MoS_3I}(PPh_3)_3S and {Cu_3WS_3Br} (PPh_3)_3S

Reactions of [NH_4]_2[MS_4](M=Mo,W),CuX(X=Br,I)and PPh_3 in the solid state produced four mixed-metal sulfur containing clusters{Cu_3MS_3X}(PPh_3)_3S(M=Mo,W;X=Br,I),two of which (1:M=Mo,X=I;2:M=W,X=Br)were structurally determined.Crystals of 1 and 2 are triclinic, space group P(1:a=11.895(3),b=13.107(1),c=20.473(2),α=74.95(6),β=84.87(8),γ=64.27(7)°, Z=2,V=2776.1 ,Rw=0.064 for 6443 observed reflections.2:α=11.876 (1),b=13.065 (2),c= 20.325(2),α=74.95(1),β=85.39(1),γ=64.09(1)°,Z=2,V=2737.3,R_w=0.055 for 5303 observed reflections).The results of the structure determination showed that the central units of the two cubane- like cluster compounds are composed of four metal atoms and four non-metal atoms situated at alter- nate comers.The differences of cubane-like cluster compounds obtained from solid state reactions and from solution reactions are discussed.

The Crystal Structure Study of CaSrFe0.75Co0.75Mn0.5O6−δ by Neutron Diffraction

The crystal structure of CaSrFe0.75Co0.75Mn0.5O6−δ is investigated through neutron diffraction techniques in this study. The material is synthesized using a solid-state synthesis method at a temperature of 1200˚C. Neutron diffraction data is subjected to Rietveld refinement, and a comparative analysis with X-ray diffraction (XRD) data is performed to unravel the structural details of the material. The findings reveal that the synthesized material exhibits a cubic crystal structure with a Pm-3m phase. The neutron diffraction results offer valuable insights into the arrangement of atoms within the lattice, contributing to a comprehensive understanding of the material’s structural properties. This research enhances our knowledge of CaSrFe0.75Co0.75Mn0.5O6−δ, with potential implications for its applications in various technological and scientific domains.

METAL CLUSTERS SYNTHESIZED BY SOLID STATE REACTION——PREPARATION AND CRYSTAL STRUCTURE OF TWO MIXED METAL CLUSTERS,Ni_2Nb_2Te_4(Ⅰ) AND Ni_2Ta-2Te_4(Ⅱ)

The two title compounds obtained by solid state reaction at high temperature were char-acierized as isomorphism by single--crystal X--ray diffraction. The space group of both crys-tals is C_(2v)~4-Pma2, with lattice constants a = 7.955(1), b=6.258 (1), c=7 .203(2)A forI, and a =7.914 (1), b=6.237 (1), c=7.236 (1) ? for Ⅱ, Z=2. The structures were de-termined by normal method and refined to the final R = 0.074 and 0.083, respectively. Theresults show that the structure may be regarded as building by cluster unit with formulaNi_2M_2Te_4 (M =Nb or Ta) in which two Ni atoms and two M atoms form a rhombus, whilethe Te atoms are distorted tetrahedrally coordinated with both kinds of metal atoms. In thecluster unit there exist interactions between Ni atoms as well as between Ni and M atoms.In addition, all the cluster units are linked together not only by bridging Te atoms, but alsoby weaker metal-metal interactions, so as to form two--dimensional network. Therefore, thestructure may be represented by the formula [Ni_2M_2(μ_4--Te)_(6/3) (μ_4--Te)_(4/2) ]_∞. A preliminarymeasurement of electric conductivity shows that the crystals of the two title compounds aremetallic but their conductivities are anisotropic; those parallel to the a-b axes are about10~3Ω^(-1)·cm^(-1), whereas those along the c axis are about 10Ω^(-1)·cm^(-1).

Synthesis and Crystal Structure of Gd_3(BsiO_6) (SiO_4)

The title compound Gd3BSi2O10 crystallizes in orthorhombic system,space group Pbca, with dimensions of a= 9. 630(1), b= 6. 959(1), c= 22. 792(3) A,V= 1527. 4(4) A 3, Z=8, Mr= 698. 73, Dc= 6.08 g/cm3, F(000) =2440, p= 262.5 cm-1, R=0. 047,,Rw=0. 053, based on 3750 with I≥3. 0 1(I) observed independent reflections. The structure contains two kinds of isolated anions: (BSi (1)O6)5- and(Si(2)O4)4- independently forming isolated sheets arranged alternately along the c axis. The Polyhedra of three crystallographically independent rare earth atoms Gd (1),Gd (2), Gd(3) are connected through edges-shared each other to form a three dimensional network structure.

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 and Chemical Bonding of a New Binary Lu-Sn Phase: Lu_(11)Sn_(10)

A new tetragonal phase of LunSnl0 is obtained from high temperature reaction of the pure elements in a welded tantalum tube. Its crystal structure was established by single-crystal X-ray diffraction. Lu11Sn10 crystallizes in the tetragonal space group 14/mmm （No. 139） with a = 11.2953（18）, c = 16.424（4） A, V= 2095.5（7）A3, Z= 4, Mr = 3111.57, Dc = 9.863 g/cm^3, p = 62.897 -1 mm , F（000） = 5124, and the final R = 0.0348 and wR = 0.0894 for 706 observed reflections with 1 〉 2σ（I）. The structure of LullSnl0 may be derived from the HonGel0 structural type. It is isostructural with DyllSn10, featuring a three-dimensional （3D） framework composed of [Sn4] squares and [Sn2] dimers interlinked via Sn-Sn bonds with two types of one-dimensional （1D） tunnels along the c-axis, which are occupied by isolated Sn atoms, [Sn2] dimers and all the Lu atoms Band structure calculation based on density functional theory method indicates that LUllSn10 is metallic.

Syntheses and Crystal Structures of Two AlxRE3(Si1-yAly)S7(RE=Sm and Gd)Compounds

Two new quaternary rare-earth chalcogenides,Al_（0.42）Sm_3（Si_（0.74）Al_（0.26））S_7（1） and Al_（0.38）Gd_3（Si_（0.86）Al_（0.14））S_7（2）,have been synthesized by a facile solid-state route with boron as the reducing reagent.They crystallize in the noncentrosymmetric hexagonal space group P6_3,belonging to the Ce_6Al_（3.33）S_（14） structure-type.Their 3-D structures feature 3-D frameworks constructed by RES_8 bicapped trigonal prisms,and Al and Si occupy the octahedral and tetrahedral voids,respectively.Al（2） and Si（1） co-occupying the 2b site and Al（1） partially occupying the 2a site have to be considered for the stability of the structures and charge balances.The Ce_6Al_（3.33）S_（14） structure-type compounds with their rich compositions and traits are discussed.The diffuse reflectance spectrum measurement of 2 indicates that it has an energy gap of 2.13 eV.

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.

Synthesis,Crystal Structure,and Optical Property of Zero-dimensional Quaternary Thioborate：Ba9B3GaS15

A new zero-dimensional（0D） thioborate Ba_9B_3GaS_（15） has been discovered by conventional high-temperature solid-state reaction. The compound crystallizes in orthorhombic space group Pbca with a = 8.4759（8）,b = 22.266（2）,c = 31.426（3） ？,V = 5931（2） ？~3,Z = 8,Mr = 1819.11,Dc = 4.075 g/cm3,μ = 13.684 mm^（-1）,F（000） = 6320,S = 1.034,（Δρ）max = 5.039,（Δρ）min = –5.409 e/？~3,the final R = 0.0362 and w R = 0.1053 for 19243 observed reflections with I 〉 2σ（I）. The structure is constructed by discrete [BS_3]^（3–） trigonal planes and isolated [GaS_4]^（5–） tetrahedra with Ba^（2＋） and isolated S^（2–） filled among them. The UV-Vis-near-IR spectrum reveals a wide band gap of 3.15 eV that agrees with the electronic structure calculation.

Synthesis,Crystal Structure and Optical Properties of KPr(MoO_4)_2 with the Scheelite-type Structure

Solid-state reaction of praseodymium （III） oxide,K2CO3 and MoO3 at high temperature leads to a potassium lanthanide double molybdate,namely,KPr（MoO4）2. The structural and optical properties of the title compound have been investigated by means of single-crystal X-ray diffraction and spectroscopic measurements at room temperature. KPr（MoO4）2 crystallizes in tetragonal,space group I41/a with a = 5.401（3）,c = 12.044（10）,Z = 2 and R （I 〉 2σ（I）） = 0.0416. It features the famous scheelite-type structure （CaWO4）,which can be thought as the substitution of two Ca^2＋ ions in CaWO4 by a couple of K^＋ and Pr^3＋ ions in a statistical manner,and W^6＋ by Mo^6＋ cations.

Synthesis,Crystal Structure and Luminescent Properties of TbCu(TeO_3)_2Cl

TbCu（TeO3）2Cl was obtained in high yield from high temperature solid-state reacion of Tb407, CuO, CuCl2 and TeO2 in a 1：2：2：8 molar ratio at 710 ℃ in an evacuated quartz tube. Its structure was established by single-crystal X-ray diffraction. The title compound crystallizes in monoclinic, space group P21/c, with a = 5.409（2）, b = 14.994（6）, c = 9.183（4）A, β = 98.884（5）°, V = 735.8（5） A^3 and Z = 4. TbCu（TeO3）2Cl is isostructural with LnCu（TeO3）2X （Ln = Dy, X= Cl; Ln = Er, X = Cl, Br）. Its structure features a three-dimensional （3D） network built from Tb（Ⅲ） and Cu（Ⅱ） ions interconnected by tellurite and chloride anions; the chloride anion and the lone-pair electrons of the tellurium（Ⅳ） ions are oriented toward the cavities of the tunnels in the network. Solid-state luminescent spectrum of TbCu（TeO3）2Cl shows a strong emission band at 545 nm with a luminescent life time of 291 μs.

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.

Preparation of Multistage Sheet-cluster ZnO Photoanode via a Solid State Reaction and Its Property in DSSCs

Different precursors were prepared via a simple low heat solid state reaction（LHSSR） upon changing the ligands. The ZnO photoanode films were obtained by the doctor blade technique, and their composition, thermal decomposition process and morphologies were identified by means of X-ray diffraction（XRD）, thermal gravimetric analysis-differential thermal analysis（TGA-SDTA） and scanning electron microscope（SEM）. The results show that the morphologies of ZnO photoanodes are irregular block, regular lamellar and irregular sheet-cluster, and the multistage structure can be found in all the photoanodes. Furthermore, there exists a genetic effect of morphology between the precursors and the corresponding photoanodes. The optimum power conversion efficiency of the sheet-cluster ZnO photoanode was 3.12% with the short circuit current density（dsc） being 11.23 mA/cm2. The multistage sheet-cluster structure could result in the increase of the scattering of the incident light and provide a rapid electronic transmission channel to reduce the risk of electronic recombination. A beneficial enlightenment was obtained to simplify the process and the photoanode films with various morphologies can be prepared with lower price in the further research.

Syntheses,Structures and Band Gaps of KLnSiS_4(Ln=Sm,Yb)

Two new quaternary sulfides, KSmSiS4 （1） and KYbSiS4 （2）, have been synthesized by high-temperature solid-state reaction. Single,crystal X-ray diffraction analyses indicate that both compounds crystallize in the space group P21/m, and the crystal data are as follows： a = 6.426（11）, b = 6.582（11）, c = 8.602（15）A, β= 107.90（13）°, Z = 2, V= 346.2（10） A^3, Dc = 3.317 g/cm^3, F（000） = 318,μ（MoKα） = 10.334 mm^-1, the final R = 0.0559 and wR = 0.1370 for 1; and α= 6.3244（10）, b = 6.5552（10）, c = 8.5701（15）A, β= 108.001（13）°, Z = 2, V = 337.91（9） A^3, De= 3.621 g/cm^3, F（000） = 334, μ（MoKα） = 15.737 mm^-1, the final R = 0.0422 and wR = 0.0960 for 2. The KLnSiS4 （Ln = Sm, Yb） structure consists of corrugated ∞^2 [LnSiS4]^- layers which are formed by edge-sharing LnS8 bicapped trigonal prisms and SiS4 tetrahedra. The K^＋ cations are located in the cavities defined by S2 anions between the ∞^2[LnSiS4]^- layers. Band-gap analyses show that compounds 1 and 2 are semiconductors with optical band-gaps of 2.40 and 2.34 eV, respectively.

Structure and Magnetic Properties of a New Oxohalogenide Compound Ba_7CoV_6O_(21)Cl_4

A new oxohalogenide compound BaTCoV6021C14 was synthesized by a conven- tional high-temperature solid state reaction. The title compound is found to crystallize in the orthorhombic system of space group Cmcm with a = 16.726（4）, b = 10.568（3）, c = 14.808（4） A, V = 2617.4（12） A3, Z= 2, Mr = 1803.68, Dc= 3.411 g/cm3,/t= 11.396 mm1, F（000） = 3172, the final R = 0.0314 and wR = 0.0750 for 1531 observed reflections with I 〉 2δ（/）. Co2＋ ions are coordinated by four O and two Cl atoms, forming a COO4C12 octahedron, while V atoms are tetrahedrally coordinated, forming （V207）4＂ groups. The structure of Ba7CoV6021Ch exhibits a pseudo-one- dimensional chain running along the c-axis. Magnetic measurements confirm that Ba7CoV6021Cl4 shows a paramagnetic behavior down to 2 K.