Abstract: | Synthesis, Crystal Structures, and Vibrational Spectra of (Mo6X)Y]2–; Xi = Cl, Br; Ya = NO3, NO2 By treatment of (Mo6X)Y]2–; Xi = Ya = Cl, Br with AgNO3 or AgNO2 by strictly exclusion of oxygene in acetone the hexanitrato and hexanitrito cluster anions (Mo6X)Y]2–, Ya = NO2, NO3 are formed. X-ray structure determinations of (Ph4As)2(Mo6Cl)(NO3)] · 2 Me2CO ( 1 ) (monoclinic, space group P21/n, a = 12.696(3), b = 21.526(1), c = 14.275(5) Å, β = 115.02(2)°, Z = 2), (n-Bu4N)2(Mo6Br)(NO3)] · 2 CH2Cl2 ( 2 ) (monoclinic, space group P21/n, a = 14.390(5), b = 11.216(5), c = 21.179(5)Å, β = 96.475(5)°, Z = 2) and (Ph4P)2(Mo6Cl)(NO2)] (3) (monoclinic, space group P21/n, a = 11.823(5), b = 13.415(5), c = 19.286(5) Å, β = 105.090(5)°, Z = 2) reveal the coordination of the ligands via O atoms with (Mo–O) bond lengths of 2.11–2.13 Å, and (MoON) angles of 122–131°. The vibrational spectra of the nitrato compounds show the typical innerligand vibrations νas(NO2) (~ 1500), νs(NO2) (~ 1270) and ν(NO) (~ 980 cm–1). The stretching vibrations ν(N=O) at 1460–1490 cm–1 and ν(N–O) in the range of 950–1000 cm–1 are characteristic for nitrito ligands coordinated via O atoms. |