AbstractAlthough racemic allylbenzylmethylphenylammonium iodide 1b displays spontaneous resolution crystallizing in a homochiral mode as a conglomerate, its phosphonium analogue rac‐2b crystallizes in a heterochiral lattice forming racemic compound in the solid state. The more pronounced conformation freedom for 2b molecules manifests itself by multiple molecules crystallization (Z′ = 3) of (S)‐2b with the three independent molecules having different conformation. Chirality, 2009. © 2008 Wiley‐Liss, Inc.