Uncommon silver coordination environments occupied exclusively by Ag⋯H–B interactions, namely Ag⋯(H–B)4 and Ag⋯(H–B)6 centres, were observed in two novel coordination polymers, [Ag(pim)(Cobdc)][Ag(Cobdc)] (1) (pim = pimelonitrile, CN(CH2)5CN, and Cobdc = cobalt(III) bis(dicarbollide) anion, [Co(C2B9H11)2]−) and [Ag3(sub)2(Cobdc)3] (2) (sub = suberonitrile, CN(CH2)6CN). The Ag⋯(H–B)4 centre was observed in compound 1 and shows a geometry that resembles an extremely distorted tetrahedron, while a highly distorted octahedral centre Ag⋯(H–B)6 was found in 2. The two compounds were isolated as crystalline materials, their structures established by single crystal X-ray diffraction and also characterized by CHN elemental analysis and infrared spectroscopy. The compounds 1 and 2 feature neutral 1D and 2D coordination polymers, [Ag(pim)(Cobdc)]1∞ and [Ag3(sub)2(Cobdc)3]2∞, respectively.
