Silver(I) Ethynide Coordination Networks and Clusters Assembled with <i>tert</i>-Butylphosphonic Acid

Variation of the reaction conditions with AgCCR (R = Ph, C6H4OCH3-4, tBu), tBuPO3H2, and AgX (X = NO3, BF4) as starting materials afforded four new silver­(I) ethynide complexes incorporating the tert-butylphosphonate ligand, namely, 3AgCCPh·Ag2tBuPO3·AgtBuPO3H·2AgNO3 (1), 2AgCCC6H4OCH3-4·Ag2tBuPO3·2AgNO3 (2), [{Ag5(NO3@Ag18)­Ag5}­(tBuCC)16(tBuPO3)4(H2O)3]­[{Ag5(NO3@Ag18)­Ag5} (tBuCC)16(tBuPO3)4(H2O)4]·​3SiF6·​4.5H2O·​3.5MeOH (3), and [{Ag8(Cl@Ag14)}­(tBuCC)14­(tBuPO3)2­F2(H2O)2]­BF4·3.5H2O (4). Single-crystal X-ray analysis revealed that complexes 1 and 2 display different layer-type coordination networks, while 3 and 4 contain high-nuclearity silver­(I) composite clusters enclosing nitrate and chloride template ions, respectively, that are supported by tBuPO32– ligands.