Coordination geometry of chromium(VI) species. The first example of cis-bridging chromate ions in helically structured catena(m-CrO4-O,O0)[Ni(HIm)3H2O]

Nickel(II) chromate complex with imidazole (HIm) was isolated from the [Ni2C–HIm–CrO4 2K] system in various experimental conditions, i.e. reagent molar ratios and nickel(II) salts. The catena(m-CrO4-O,O0)[Ni(HIm)3H2O] (1) crystallizes in monoclinic crystal system—space group P21/n with cell parameters: aZ11.784(2), bZ8.899(2), cZ13.934(3) (A° ), bZ95.19(3) (8). The unit cell contains two independent helixes, left- and right-handed, stabilized by intrahelical and interhelical hydrogen bonds (HB) and p–p interactions. The cis coordination of the CrO4 2K anions and the HB systems appeared to be the main determinants of the helical architecture. To the best of our knowledge the cischromate coordination was observed for the first time. The cis coordination causes the distortion of the nickel octahedron, which was analysed by 4 K single crystal electronic spectra with D4h symmetry approximation (gaussian resolution and crystal field parameters). This symmetry was also confirmed with the polarised electronic spectra. The magnetic properties of the complex suggest the occurrence of weak intrachain antiferromagnetic interactions between the magnetic NiII center. The computational DFT studies of complex 1 assuming three possible isomers mer[(HIm)3]–cis[(CrO4 2K)2], mer–trans and fac–cis suggested that the main contribution to the stability of 1 might have interhelical and intrahelical hydrogen bonds. q 2004 Elsevier B.V. All rights reserved