Inorganic Chemistry, Vol.34, No.10, 2671-2677, 1995
Interstitially-Stabilized Praseodymium(III) Compounds Na2Pr4Br9No and Pr8Br13N3O - Structures on the Border Between Salts and Clusters
The title compounds are obtained in high yields after appropriate reactions in sealed Nb tubing at similar to 750-950 degrees C in nonreduced systems but only when both O and N sources are included in the appropriate proportions. The structures of both have been established by single crystal means. (Na2Pr4Br9NO : P2(1)/m, Z = 2, a = 8.543(4) Angstrom, b = 11.707(3) Angstrom, c = 9.697(4) Angstrom, beta = 106.49(3)degrees, R, R(w) = 3.7, 4.9%. Pr8Br13N3O : C2/c, Z = 4, a = 21.967(8) Angstrom, b = 8.355(2) Angstrom, c = 16.889(7), beta = 119.40(3)degrees, R, R(w) = 2.9, 3.1%.) The former is isotypic (but not isoelectronic) with the known Na2Pr4Cl9O(2). Both phases contain infinite zigzag chains of N- and O-centered Pr-4 tetrahedra sharing trans edges, and both appear to be Pr-III valence compounds. They can also be geometrically related to reduced compounds like Pr4I5Ru with infinite octahedral chains and are thus on the borderline between reduced, metal-rich cluster phases and "simple" salts.