TY - JOUR
T1 - Crystal and electronic structure of La3Zn2-xP4 - New phosphide with isolated P3- species
AU - Lincke, Hannes
AU - Nilges, Tom
AU - Johrendt, Dirk
AU - Pöttgen, Rainer
PY - 2008/8
Y1 - 2008/8
N2 - The new phosphide La3Zn2-xP4 was synthesized from lanthanum, LaZn and red phosphorous in a NaCl/KCl halide flux at 1120 K. La3Zn2-xP4 crystallizes with a new structure type: R over(3, -) m, a = 418.72(7), c = 4143.7(1) pm, wR2 = 0.0577, 1061 F2 values for La3Zn1.75P4 and a = 418.99(6), c = 4157.1(8) pm, wR2 = 0.0485, 337 F2 values for La3Zn1.88P4 with 17 variables per refinement. The P3- phosphide anions show an hhcc stacking sequence, similar to the structures of Mg3In and PuGa3. The Zn2+ and La3+ cations fill 1/4 and 3/4 of the tetrahedral and octahedral voids, respectively, in an ordered manner, leading to a layer of ZnP4 tetrahedra and triple layers of LaP6 octahedra. DFT band structural calculations verify that the lower zinc occupation stabilizes the structure close to an electron precise composition.
AB - The new phosphide La3Zn2-xP4 was synthesized from lanthanum, LaZn and red phosphorous in a NaCl/KCl halide flux at 1120 K. La3Zn2-xP4 crystallizes with a new structure type: R over(3, -) m, a = 418.72(7), c = 4143.7(1) pm, wR2 = 0.0577, 1061 F2 values for La3Zn1.75P4 and a = 418.99(6), c = 4157.1(8) pm, wR2 = 0.0485, 337 F2 values for La3Zn1.88P4 with 17 variables per refinement. The P3- phosphide anions show an hhcc stacking sequence, similar to the structures of Mg3In and PuGa3. The Zn2+ and La3+ cations fill 1/4 and 3/4 of the tetrahedral and octahedral voids, respectively, in an ordered manner, leading to a layer of ZnP4 tetrahedra and triple layers of LaP6 octahedra. DFT band structural calculations verify that the lower zinc occupation stabilizes the structure close to an electron precise composition.
KW - Chemical bonding
KW - Crystal structure
KW - Phosphide
UR - http://www.scopus.com/inward/record.url?scp=48649097947&partnerID=8YFLogxK
U2 - 10.1016/j.solidstatesciences.2007.11.012
DO - 10.1016/j.solidstatesciences.2007.11.012
M3 - Article
AN - SCOPUS:48649097947
SN - 1293-2558
VL - 10
SP - 1006
EP - 1011
JO - Solid State Sciences
JF - Solid State Sciences
IS - 8
ER -