Nd3NCl6 and Nd4NS3Cl3: Two derivatives of neodymium nitride with discrete units of edge-shared ([N2Nd6](12+)) and isolated [NNd4](9+) tetrahedra, respectively
M. Meyer et al., Nd3NCl6 and Nd4NS3Cl3: Two derivatives of neodymium nitride with discrete units of edge-shared ([N2Nd6](12+)) and isolated [NNd4](9+) tetrahedra, respectively, Z ANORG A C, 626(5), 2000, pp. 1205-1210
Citations number
41
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
For the preparation of Nd3NCl6 (orthorhombic, Pbca; a = 1049.71(8), b = 110
6.83(8), c = 1621.1(1) pm; Z = 8) and Nd4NS3Cl3 (hexagonal, P6(3)mc; a = 92
2.78(6), c = 683.06(4) pm; Z = 2) elemental neodymium is reacted with sodiu
m azide (NaN3), neodymium trichloride (NdCl3) and in the case of Nd4NS3Cl3
additionally with sulfur in evacuated silica tubes at 750 degrees C (Nd3NCl
6) and 850 degrees C (Nd4NS3Cl3), respectively. Thereby the hydrolysis-sens
itive nitride chloride forms coarse, brick-shaped single crystals, while th
ose of the insensitive nitride sulfide chloride emerge hexagonally and pill
ar-shaped. The pale violet compounds each exhibit [NNd4] tetrahedra as char
acteristic structural features, which are connected via a common edge to fo
rm discrete pairs of tetrahedra ([N2Nd6](12+)) in Nd3NCl6 and are present i
n Nd4NS3Cl3 even as isolated [NNd4](9+) units. Their three-dimensional cros
s-linkage as well as the charge-balance regulation proceed solely through C
l- anions in the nitride chloride, but through equimolar amounts of S2- and
Cl- anions in the nitride sulfide chloride. The crystal structure of Nd3NC
l6 shows three crystallographically independent Nd3+ cations, each of which
is eightfold coordinated by anions (Nd1: 2 N3- + 6Cl(-); Nd2 and Nd3: 1 N3
- + 7 Cl-). Only two different kinds of Nd3+ underlie the structure of Nd4N
S3Cl3: Nd1 is surrounded by one N3-, Six S2- and three Cl- with CN = 10, wh
ereas one N3-. four S2- and three Cl- only are coordinating Nd2 with CN = 8
.