The synthesis and crystal structure of bis-[3,3-diethyl-1-(phenyl-imino-κN)thio-urea-κS]silver hexa-fluorido-phosphate.

Vincent M Groner,James G Moberly,Kristopher V Waynant,Garrett E Larson,Mark F Roll,Yuwei Kan

doi:10.1107/s2056989019011824

Abstract

The structure of the title complex, [Ag(C11H15N3S)2]PF6, has monoclinic (P21/c) symmetry, and the silver atom has a distorted square-planar geometry. The coordination complex crystallized from mixing silver hexa-fluorido-phosphate with a concentrated tetra-hydro-furan solution of N,N-di-ethyl-phenyl-azo-thio-formamide [ATF; systematic name: 3,3-diethyl-1-(phenyl-imino)-thio-urea] under ambient conditions. The resultant coordination complex exhibits a 2:1 ligand-to-metal ratio, with the silver(I) atom having a fourfold AgN2S2 coordination sphere, with a single PF6 counter-ion. In the crystal, however, one sulfur atom from an ATF ligand of a neighboring complex coordinates to the silver atom, with a bond distance of 2.9884 (14) Å. This creates a polymeric zigzag chain propagating along the c-axis direction. The chains are linked by C-H⋯F hydrogen bonds, forming slabs parallel to the ac plane.

Highlights

The redox-active azothioformamide (ATF) ligand class was identified as a metal coordinative species over 40 years ago (Bechgaard, 1974, 1977)
Further investigations found that ATF ligands were capable of removing similar late transition metal (Cu or Pd) nanoparticles and catalysts from polymeric materials (Nielsen et al, 2005, 2006)
The investigation of monovalent metals led to this report describing the coordination complex formed when the N,N-diethylphenylazothioformamide (ATF) ligand is treated with an Ag(I) species containing the non-coordinative counter-ion hexafluoridophosphate in concentrated THF solution

Summary

DÁ Á ÁA

D—HÁ Á ÁA 167 158 164 and two N—Ag bonds, the N4—Ag1 bond is lengthened in comparison with previously mentioned complexes (Johnson et al, 2017). This lengthening has influenced the packing structure of the crystal to allow for an adjacent ATF ligand to interact with the silver atom at a bond distance Ag1Á Á ÁS2i of 2.9884 (14) A , producing a polymeric zigzag chain (Fig. 2 and Table 1). Sulfur atom S1 is involved in an intramolecular C—HÁ Á ÁS hydrogen bond (Fig. 1 and Table 2). CSD = Cambridge Structural Database (Groom et al, 2016); DSP = distorted square-planar; DT = distorted tetrahedral

CuIIc PdIIc PtIIc NiIIc

No of parameters

Bruker SMART APEXII area detector diffractometer

Findings

Special details