(N,N′-Diethylthiourea-κS)tris(triphenylphosphane-κP)silver(I) acetate methanol monosolvate

Abstract

In the mononuclear title complex, [Ag(C5H12N2S)(C18H15P)3](CH3COO)·CH3OH, the AgI ion is in a distorted tetra­hedral coordination geometry formed by three P atoms from three tri­phenyl­phosphane ligands and one S atom from an N,N′-di­ethyl­thio­urea ligand. In the crystal, the acetate anion is connected to the complex mol­ecule via a pair of N—H⋯O hydrogen bonds [graph-set motif R 2 2(8)] and the solvent methanol mol­ecule is connected to the anion via an O—H⋯O hydrogen bond. This aggregate is further connected through a weak C—H⋯O hydrogen bond, forming a chain along [100]. In addition, sixfold phenyl embraces with inter­molecular distances of 6.6463 (13)–6.667 (2) Å are arranged in a chain along [001]. The combination of hydrogen bonding and phen­yl⋯phenyl inter­actions leads to the formation of a two-dimensional network parallel to (010).

Crystal structure of (1,3-dimethylthiourea-κS)tris(triphenylphosphane-κP)silver(I) acetate

“…For potential applications of silver(I) complexes, see: Isab et al (2010); Ferrari et al (2007). The observed bond lengths distribution is in good agreement with related structures, such as [Ag 2 Cl 2 (-S-HL) 2 (PPh 3 ) 2 ] (HL = 2-benzoylpyridine thiosemicarbazone; Lobana et al, 2008) and [Ag(C 5 H 12 N 2 S)(C 18 H 15 P) 3 ](CH 3 -COO)ÁCH 3 OH (Wattanakanjana et al, 2014). For graph-set analysis, see: Etter et al (1990 Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008) and SHELXLE (Hü bschle et al, 2011); molecular graphics: Mercury (Macrae et al, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).…”

Controlling Molecular Organization by Using Phenyl Embraces of Multiple Trityl Groups

“…In addition, functional groups able to participate in embraces, such as trityl, can be attached in straightforward ways to various molecular cores, without substantially changing the intrinsic properties of the core or introducing sites of high chemical reactivity. Previous studies have revealed many examples of sixfold embraces in the structures of compounds with trityl groups and their analogues. − However, a close examination of this body of work shows that only a small fraction of eligible compounds actually incorporate sixfold embraces. This low percentage suggests that sixfold embraces cannot easily override competing aromatic interactions and cannot therefore play a predictably dominant role in directing molecular association.…”

“…Appealing candidates include triphenylmethyl (trityl) groups and their analogues, which engage in characteristic aromatic interactions known as sixfold phenyl embraces, as well as related patterns of association (Figure ). The current understanding of these motifs is based in part on the extensive studies published by Dance, Scudder, and collaborators during the period 1995–2002; − however, the basic sixfold embrace was noted earlier, − and simple examples of the motif have been observed by many other researchers. − …”

“…The net stabilization attributed to the cyclic concerted edge-to-face interaction of six phenyl rings is approximately 8–11 kcal mol –1 , − making the sixfold embrace of trityl groups and analogues similar in energy to strong hydrogen bonds. In such embraces, the tetrahedral centers are normally separated by 5.7–7.0 Å. − ,− If a trityl group is treated as a hemisphere with the tetrahedral carbon atom at its center, then its van der Waals radius is approximately 6.1 Å. As a result, the characteristic center-center distance in a sixfold embrace denotes a significant degree of interpenetration of the two hemispheres.…”