Lithium-Filled Double-Deck Layered Structure of the RELixCu2-yP2 (RE = La, Pr, Nd, Gd, Er; 0.82 ≤ x ≤ 1; 1.19 ≤ y ≤ 1.54) Series: Experimental and Theoretical Studies

• Published in: European journal of inorganic chemistry 2015-06, Vol.2015 (17), p.2786-2793
• Main Authors: Jang, Eunyoung, Nam, Gnu, Woo, Hyein, Lee, Junseong, Han, Mi-Kyung, Kim, Sung-Jin, You, Tae-Soo
• Format: Article
• Language: English
• Subjects: Crystal structure; Diffraction; Layered structues; NMR spectroscopy; Structure calculation; Thermal conductivity; Zintl phases
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201500387

Five rare‐earth metal containing quaternary phosphides in the RELixCu2–yP2 (RE = La, Pr, Nd, Gd, Er; 0.82 ≤ x ≤ 1; 1.19 ≤ y ≤ 1.54) series were synthesized by using high‐temperature synthetic methods, and they were characterized by single‐crystal X‐ray diffraction. The title compounds crystallize in the trigonal space group P$\bar {3}$m1 (Z = 1, Pearson code hP6) with four crystallographically independent atomic positions. The overall crystal structure can be described as a “Li‐filled” CaAl2Si2‐type structure, in which a partially occupied Li site is embedded within the “double‐deck” layers formed by two anionic components. Tight‐binding linear muffin‐tin orbital calculations including density of states, crystal orbital Hamilton population, and electron localization function analyses provided rationales for the overall electronic structure and chemical bonding of the title phase. PrLi0.98(5)Cu1.54(1)P2 indicated an antiferromagnetic interaction of Pr at a relatively low temperature with a paramagnetic Curie temperature of –6.8 K and a thermal conductivity of 3.2 W mK–1 at 323 K. Five rare‐earth metal containing quaternary phosphide compounds show the “Li‐filled” double‐deck‐layered structure, in which the Cu and P atoms consist of 2D puckered hexagonal double‐deck layers.