Piperazine-dithiocarbamate of potassium (K(2)DTC(2)pz) was used as a new precursor for the spontaneous deposition of sulfur on the Au(100) surface in alkaline solution. Two new sulfur phases were studied by scanning tunneling microscopy (STM). These phases were formed by six sulfur atoms (S6 phase, hexamer) and by four sulfur atoms (S-4 phase, tetramer with (root 7 x root 7) structure), and they were observed in coexistence with the well-known quasi-square patterns formed by eight sulfur atoms (S8 phase, octomer). A model was proposed where sulfur multilayers were formed by a (root 7 x root 7) phase adsorbed directly on the gold surface while one of the other structures: hexamers or octomers were deposited on top. Sulfur layers were formed on gold terraces, vacancies and islands produced by lifting reconstructed surface. Sequential high-resolution STM images allowed the direct observation of the dynamic of the octomers, while the (root 7 x root 7) structure remained static. Images also showed the reversible association/dissociation of the octomer. (C) 2014 Elsevier B.V. All rights reserved.