Crystal structure of cyclo-bis-(μ4-2,2-di-allyl-malonato-κ(6) O (1),O (3):O (3):O (1'),O (3'):O (1'))tetra-kis-(triphenyl-phosphane-κP)tetra-silver(I).

Peter Frenzel,Dieter Schaarschmidt,Alexander Jakob,Tobias Rüffer,Heinrich Lang

doi:10.1107/s1600536814019394

Peter Frenzel, Dieter Schaarschmidt + Show 3 more

Open Access

https://doi.org/10.1107/s1600536814019394

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Abstract

In the tetra-nuclear mol-ecule of the title compound, [Ag4(C9H10O4)2(C18H15P)4], the Ag(I) ion is coordinated by one P and three O atoms in a considerably distorted tetra-hedral environment. The two 2,2-di-allyl-malonate anions bridge four Ag(I) ions in a μ4-(κ(6) O (1),O (3):O (3):O (1'),O (3'):O (1')) mode, setting up an Ag4O8P4 core (point group symmetry -4..) of corner-sharing tetra-hedra. The shortest intra-molecular Ag⋯Ag distance of 3.9510 (3) Å reveals that no direct d (10)⋯d (10) inter-actions are present. Four weak intra-molecular C-H⋯O hydrogen bonds are observed in the crystal structure of the title compound, which most likely stabilize the tetra-nuclear silver core.

Highlights

In the tetranuclear molecule of the title compound, [Ag4(C9H10O4)2(C18H15P)4], the AgI ion is coordinated by one P and three O atoms in a considerably distorted tetrahedral environment
Four weak intramolecular C—H O hydrogen bonds are observed in the crystal structure of the title compound, which most likely stabilize the tetranuclear silver core
In the case of silver, this can be realized by the use of phosphanes as a Lewis base; the concomitant increase of the molecular weight of the transition metal complex may decrease its vapour pressure

Summary

Chemical context

Silver(I) carboxylates of general type [AgO2CR]n (n is the degree of aggregation) are of interest due to their versatile structures in the solid state and in solution, their synthetic methodologies and their manifold reaction behavior (see, for example: Schliebe et al, 2013; Jahn et al, 2010; Wang et al., 2008; Fernández et al, 2007; Olson et al, 2006; Szymańska et al, 2007). In the case of silver, this can be realized by the use of phosphanes as a Lewis base; the concomitant increase of the molecular weight of the transition metal complex may decrease its vapour pressure. In the context of this approach, the title compound [{(Ph3P)Ag}4{(O2C)2C(CH2CH CH2)2}2], (I), was obtained by the reaction of the silver salt of 2,2-diallylmalonic acid with triphenylphosphane

Structural commentary

Supramolecular features

Database survey

Synthesis and crystallization