Layered Carbodiimides A2M(CN2)3 with Tetravalent Cations M = Sn, Zr, and Hf

被引:23
作者
Dolabdjian, Konstantin [1 ]
Castro, Cristina [1 ,2 ]
Meyer, Hans-Juergen [1 ]
机构
[1] Abt Festkorperchem & Theoret Anorgan Chem, Inst Anorgan Chem, Morgenstelle 18, D-72076 Tubingen, Germany
[2] Univ Oxford, Inorgan Chem Lab, South Parks Rd, Oxford OX1 3QR, England
关键词
Carbodiimides; Solid-state reactions; Metathesis; Structure elucidation; CRYSTAL-STRUCTURE DETERMINATION; RARE-EARTH CARBODIIMIDES; HOMOLEPTIC TETRACYANAMIDOGERMANATES; MAGNETIC-PROPERTIES; TRANSITION-METAL; CYANAMIDE; 1ST; LUMINESCENCE; REFINEMENT; LI2ZRO3;
D O I
10.1002/ejic.201800183
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The ternary carbodiimides Li2Sn(CN2)(3), Na2Sn(CN2)(3), Li2Zr(CN2)(3) and Li2Hf(CN2)(3) were synthesized and their crystal structures were solved and refined by means of powder X-ray diffraction [Li2Zr(CN2)(3) and Li2Hf(CN2)(3) crystallize in R (3) over barc, whereas Li2Sn(CN2)(3) and Na2Sn(CN2)(3) crystallize in Pnna]. All structures are characterized by alternating layers of carbodiimide units and metal atoms, although cations show distinct distributions within layers. All three lithium metal carbodiimides reveal partial occupations of Li+ and M4+ on opposite sites in the order of 10 % (at room temperature). This and the general structural assembly exhibit analogies to the corresponding ternary oxides A(2)MO(3). Furthermore, all A(2)Sn(CN2)(3) structures can be related to the hierarchical NiAs type structure by space group theory via group-subgroup relationship.
引用
收藏
页码:1624 / 1630
页数:7
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