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Synthesis and Theoretical Hirshfeld Analysis of a Supramolecular Heteropolyoxovanadate Architecture
Author(s) -
Grabau Mathias,
Forster Johannes,
Heussner Kirsten,
Streb Carsten
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201001155
Subject(s) - chemistry , supramolecular chemistry , hydrogen bond , crystallography , intermolecular force , crystal structure , ionic bonding , molecule , cluster (spacecraft) , counterion , ion , organic chemistry , computer science , programming language
A supramolecular heteropolyoxovanadate structure has been synthesized and characterized using single‐crystal XRD, powder XRD and a range of spectroscopic methods. The new compound, [ t BuNH(C 2 H 4 OH) 2 ] 4 [H 5 P 1 V 14 O 42 ] · 12H 2 O ( 1 ) was obtained using a one‐pot strategy starting from a simple inorganic vanadium oxide precursor and an amphiphilic cation in acidic aqueous solution. The cluster anion [H 5 P 1 V 14 O 42 ] 4– is based on the well‐known Keggin structure but in addition features two capping vanadyl [V=O] 3+ units. In the crystal lattice, the clusters are arranged in linear 1D chains where neighbouring clusters are directly linked by one hydrogen bond. In addition, the assembly is stabilized by lattice water molecules and organic counterions which aggregate to form hydrophobic cavities with diameters of 0.6 nm. In order to analyze the supramolecular interactions leading to the cluster formation, we have used a combination of traditional structural analysis, theoretical bond valence sum (BVS) calculations and computational Hirshfeld surface analyses which allow the rapid determination of short‐ and long‐range intermolecular contacts. The applicability of the Hirshfeld analysis tool for complex ionic compounds is evaluated and the advantages as well as the limitations of the method are discussed. The combination of these techniques allowed us to assess the dominating intermolecular interactions and showed that the crystal packing is not only controlled by electrostatic interactions, but also by distinctive sets of hydrogen bonds and hydrophobic interactions between adjacent organic counterions.