Crystalline products isolated from solutions with commercially available 2,3-bis(2-pyridyl)pyrazine (dpp) as reactant: Detection of a dimerized form of dpp

Abstract

From reaction mixtures of commercially available 2,3-bis(2-pyridyl)pyrazine (dpp) and perchloric acid four different solid products have been isolated and structurally characterized by X-ray crystallography; (dppH 2)(ClO 4) 2·3H 2O ( 1), (dppH 2)(ClO 4) 2 ( 2), (ddppH 2)(ClO 4) 2 ( 3) and (dppH)(ClO 4) ( 4) (dppH is monoprotonated dpp, dppH 2 is the diprotonated dication of dpp, ddppH 2 is the dication 5,5′-bis(2,3-bis(2-pyridyl)pyrazinium), i.e. dimerized dppH). In 1 and 2 the nitrogen atom in both of the pyridyl rings in dpp is protonated. Hydrogen bonding and packing arrangements differ in the two compounds. In 3 a protonated and dimerized form of dpp is found; two 2,3-bis(2-pyridyl)pyrazinium units are connected by a C(sp 2) C(sp 2) bond in the 5-positions of the pyrazine rings, one pyridyl ring in each dpp moiety being protonated at the nitrogen. Strong intra-cation N H⋯N bonds between pyridyl rings are present. In 4 the monomeric dppH moieties display the same type of intramolecular hydrogen bonds as found in 3. Upon reacting dpp with copper(II) salts and oxalate, a dinuclear copper (II) complex, [Cu 2(ddpp)(ox) 2(H 2O) 2] (ddpp = 5,5′-bis(2,3-bis(2-pyridyl)pyrazine)), as well as mononuclear [Cu(dpp)(ox)(H 2O)] have been obtained in the same reaction mixtures. In one of the isolated crystalline products a dimer of dpp is found, as described in the case of compound 3, but no protonation has occurred. The crystal structure determination reveals a dinuclear complex with the neutral ddpp (dimerized dpp) as bridging ligand. Oxalate occurs as a bidentate, terminal ligand; water completes the copper coordination sphere. The dinuclear complex cocrystallizes with a mononuclear Cu-dpp-ox complex; in the mixed crystal two mononuclear units replace one dinuclear unit in 25% of the unit cells, thus the average formula is [Cu 2(ddpp)(ox) 2(H 2O) 2] 0.75[{Cu(dpp)(ox)(H 2O)} 2] 0.25·8H 2O ( 5). The monomeric species also crystallizes in the form of compound 6, [Cu(dpp)(ox)(H 2O)]·2H 2O. In 6 the dpp ligand and oxalate are both chelating to copper in equatorial positions, and [Cu(dpp)(ox)(H 2O)] units are pair-wise connected through weak Cu⋯O (oxalate) interactions (semi-coordination). Geometry optimization through ab initio calculations gave results in good agreement with the experimental molecular geometries of dpp, dppH + and dppH 2 2 + , respectively. An energy minimum was found for the syn conformation of pyridyl rings in the monoprotonated species, conforming to the existence of the intramolecular N H⋯N hydrogen bond. The compounds containing dimerized dpp were minor products (of the order of 1% yield). To determine whether ddpp had been formed in the reaction mixtures, or had been present as a contaminant in the commercially available dpp, an NMR solution study was performed. Samples of dpp, 1, 3, 4 and ddpp (obtained by treating 3 with base) were investigated by 1H (all five compounds) and 13C NMR (the three former compounds) spectroscopy. The results are consistent with the presence of ddpp as a contaminant in commercially available dpp. The study also allowed us to identify the spectral changes involved in going from neutral dpp to the partial ( 4) and fully ( 1) protonated forms.