The [Re2(micro-trz-kappaN1:kappaN2)2(micro-OH)(CO)6]- (trz = 1,2,4-triazolate) organometallic anion reacts with Ag+ to afford a 2D organometallic/coordination network, [Ag[Re2(micro3-trz-kappaN1:kappaN2:kappaN4)2(micro3-OH)(CO)6]]n x 4nCH3OH, which shows dynamic structural changes triggered by solid-liquid guest exchange processes.