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Ni_(2)M^(Ⅱ)Te^(Ⅳ)_(2)O_(2)(PO_(4))_(2)(OH)_(4)(M^(Ⅱ)=Ni,Zn):Synthesis,Crystal Structure,and Magnetic Properties

Chinese Journal of Structural Chemistry 2021年第11期40卷 1439-1448,1406页

作者： CHEN Jia-Ze ZHUANG Rong-Chuan MI Jin-Xiao HUANG Ya-Xi Fujian Key Laboratory of Advanced Materials(Xiamen University) Department of Materials Science and EngineeringCollege of MaterialsXiamen UniversityXiamen 361005China State Key Laboratory of Comprehensive Utilization of Low-grade Refractory Gold Ores Shanghang 364200China

Two isostructural tellurite phosphates Ni_(2)M^(Ⅱ)Te^(Ⅳ)_(2)O_(2)(PO_(4))_(2)(OH)_(4)(M^(Ⅱ)=Ni,Zn)have been synthesized via hydrothermal *** of them crystalize in monoclinic space group C2/m(No.12).For Ni_(2)ZnTe^(Ⅳ)_(2)O_(2)(PO_(4))_(2)(OH)_(4),a=19.3247(10),b=5.9697(3),c=4.7737(2)Å,β=103.637(5)°,V=535.18(5)Å^(3),Z=2,M_(r)=727.94,S=1.103,D_(c)=4.517 g·cm^(-3),μ(Mo Kα)=11.434 mm^(-1) and F(000)=672,the final R=0.0369and wR=0.1086 for 639 observed reflections with I>2σ(I).The crystal structure of Ni_(2)M^(Ⅱ)Te^(Ⅳ)_(2)O_(2)(PO_(4))_(2)(OH)_(4)(M^(Ⅱ)=Ni,Zn)features a 3D framework composed of[Ni_(2)O_(2)(PO_(4))_(2)]^(6-)layers interconnected by[MTe_(2)O_(2)(OH)_(4)]^(2+)single *** magnetic susceptibility results at low temperature of the two title compounds confirm that Zn(1)completely occupies the Ni(2)position but not partially substitutes both Ni(1)and Ni(2)position ***,the acentric TeO_(3)(OH)_(2) tetragonal pyramids are aligned in an antiparallel manner,resulting in the crystallization of centrosymmetric(C2/m)crystal structure instead of the non-centrosymmetric crystal *** investigation of the origin of centrosymmetric crystal structure with strong dipole moment units provides deeper understanding for future rational design for non-centrosymmetric crystal structure.

关键词： tellurite phosphate crystal structure stereo-chemically active lone pair centrosymmetric

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Ni₂M^IITe^IV₂O₂(PO₄)₂(OH)₄(M^II= Ni, Zn): Synthesis, crystal structure, and magnetic properties

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Jiegou Huaxue 2021年第11期40卷 1439-1448页

作者： Chen, Jia-Ze Zhuang, Rong-Chuan Mi, Jin-Xiao Huang, Ya-Xi Fujian Key Laboratory of Advanced Materials (Xiamen University) Department of Materials Scienceand Engineering College of Materials Xiamen University Xiamen 361005 China State Key Laboratory of Comprehensive Utilization of Low-grade Refractory Gold Ores Shanghang 364200 China

Two isostructural tellurite phosphates Ni2MIITeIV2O2(PO4)2(OH)4(MII= Ni, Zn) havebeen synthe-sized via hydrothermal method. Both of them crystalize in monoclinic space group C2/m(No. 12). For Ni2ZnTeIV2O2(PO4)2(OH)4,a= 19.3247(10),b= 5.9697(3), c= 4.7737(2)Å, β= 103.637(5)°, V= 535.18(5)Å3, Z= 2, Mr= 727.94, S= 1.103, Dc= 4.517 g-cm-3, μ(MoKα) = 11.434 mm-1and F(000) = 672, the final R= 0.0369and wR= 0.1086for 639 observed reflections with I> 2σ(I). The crystal structure of Ni2MIITeIV2O2(PO4)2(OH)4(MII= Ni, Zn) features a 3Dframework composed of [Ni2O2(PO4)2]6-layers interconnected by [MTe2O2(OH)4]2+single chains. Different magnetic susceptibility results at low temperature of the two title compounds confirm that Zn(1) completely occupies the Ni(2) position but not partially substitutesboth Ni(1) and Ni(2) positionatoms. Additionally, the acentric TeO3(OH)2tetragonal pyramids are aligned in an antiparallel manner,resultinginthe crystallization of centrosymmetric (C2/m) crystal structureinstead ofthenon-centrosymmetric crystal structure. The investigation of the origin of centrosymmetric crystal structurewith strong dipole moment units provides deeper understandingfor future rational design for non-centrosymmetric crystal structure. © 2021 Fujian Institute of Research of the Structure of Matter. All rights reserved.

关键词： Centrosymmetric Crystal structure Phosphate stereo-chemically active lone pair Tellurite

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