The reactions of sodium nitroprusside [Na2Fe(CN)5NO • 2H2O] with organotin have been studied. Six new organotin-cyanometalate compounds, [Ph3Sn]2[Fe(CN)5NO] (1), [Bz3Sn]2[Fe(CN)5NO](Bz=C6H5- CH2-) ( 2), [Bz2Sn] [Fe(CN)5NO] (3), [(Bz3Sn)2CN]2 [Fe(CN)5NO] (4), [Bz2SnOSn(MeO)Bz2]2 [Fe(CN)5-NO] • 3CH2Cl2 (5), and [Bz2SnOSn(EtO)Bz2]2 [Fe(CN)5NO] • 3CH2Cl2 (6), have been isolated in these reactions and characterized by the X-ray diffraction method. Each of compounds 1,2,3,and 4shows a 2D polymeric structure containing planar four-connected [Fe(CN)5NO]2- anions. Compound 4 is the first organotin-cyanometalatecompound containing a superlong-CN-R3Sn-CN-SnR3-NC-spacer. Compounds 5 and 6 are the first examples of organotin-cyanometalate compounds of organooxotin clusters, in which the organooxotin clusters are bridged by cyanometalate anions to generate a novel 1D polymeric chain structure.