During the last two decades, design and synthesis of novel coordination polymers are attracting more attention1. In addition, the coordination chemistry of bidentate ligands has been studied for over thirty years2. The bidentate ligands with phosphoryl and thiophosphoryl groups have been used as effective coordinating agents in the different metal chemistry. In this work two new mercury (II) coordination polymers with thiophosphoryl ligands {[C2H5O]2P(S)}2X, X = NC4H8N & NHC6H4NH are studied:{Hg(Cl)(µ-Cl)2Hg(Cl)[(S)P(OC2H5)2NC4H8NP(OC2H5)2(S)}n (1) and {Hg(Cl)(µ-Cl)2Hg(Cl)[(S)P(OC2H5)2NHC6H4NHP(OC2H5)2(S)}n (2). The coordination polymers 1 and 2are the first structural studies of themercurycoordination polymers with the ligands containingan [O]2P(S)[N] segment. Indeed, anystructure with an [O]2[N]P(S)—Hg segment was not found in the Cambridge Structural Database (CSD, version 5.35, updated in February 2014)3. In both complexes 1 and 2, the two Hg centers are within an [S][Cl]Hg(µ-Cl)2Hg[Cl][S] segment with a distorted tetrahedral environment for each Hg center. In each structure, the asymmetric unit is composed of half of the monomer related to theother halfby a C2 rotation axis. On the other hand, in complex 1 the NC4H8N part adopts a nearly chair conformation and the two P═S groups[bonded to nitrogen atoms] bond vectors in opposite side with respect to each other. In complex 2, the NHC6H4NH part is nearly planar considering the heavy atoms and the P═S groups bonded to thenitrogen atoms of the noted part adopt an anti-conformation with respect to each other. In both structures, the weak intermolecular C—H…Cl and C—H…S interactions are observed. The spectroscopic features of ligands and complexes are investigated. Keywords:Thiophosphoryl,Mercury(II), Crystal structure, Coordination polymer References [1] O. V. Moroz, V. A. Trush, I. S. Konovalova, O. V. Shishkin, Y. S. Moroz, S. Demeshko, V. M. Amirkhanov, Polyhedron, 2009, 28, 1331–1335. [2] J. R. Dilworth, N. Wheatley, Coordination Chemistry Review, 2000, 199, 89-158. [3] C. R. Groom& F. H. Allen, Angew. Chem. Int.Ed.,2014,53, 662–671.

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