The three-dimensional coordination polymers [{(n-C4H9)(3)Sn}(3)M(CN)(6)] (M = Fe. Co) were synthesized by slow interdiffusion of aqueous solutions of K-3[M(CN)(6)] and THF solutions of (C4H9)(3)SnCl. The structures were determined by single-crystal X-ray crystallography (M = Fe, cubic, P4(1)31, n = 17.338(1) Angstrom, Z = 4; M = Co, cubic. P4(3)32, a = 17.260(1) Angstrom, Z = 4). The compounds are examples of guest-free cyanide-bridged 3-D neutral networks and are composed of nearly planar Bu3Sn units linked together with slightly distorted octahedral M(CN)(6) fragments through the cyanide N atoms. ignoring the butyl groups. each M(CN)(6) octahedron is center-shared with six neighbors through Sn, and each M atom is a vertex for three three-membered rings and fifteen five-membered rings. The butyl groups are disordered over three positions. with their trigonal arrangement preserved. The [{(n-C4H9)(3)Sn}(3)M(CN)(6)] compounds crystallize in chiral space groups. and they are essentially isostructural enantiomers with similar cell dimensions.