Compounds based on new cyanide cluster anions [{Mo6I8}(CN)6]2–, trans-[{Mo6I8}(CN)4(MeO)2]2– and trans-[{W6I8}(CN)2(MeO)4]2− were synthesized using mechanochemical or solvothermal synthesis. The crystal and electronic structures as well as spectroscopic properties of the anions were investigated. It was found that the new compounds exhibit red luminescence upon excitation by UV light in the solid state and solutions, as other cluster complexes based on {Mo6I8}4+ and {W6I8}4+ cores do. The compounds can be recrystallized from aqueous methanol solutions; besides this, it was shown using NMR and UV-Vis spectroscopy that anions did not undergo hydrolysis in the solutions for a long time. These facts indicate that hydrolytic stabilization of {Mo6I8} and {W6I8} cluster cores can be achieved by coordination of cyanide ligands.

Two new mixed-valence tungsten cluster anions with bitetrahedral cores, {W6(μ4-O)2(μ3-CCN)4} and {W6(μ4-O)2(μ3-As)4} were synthesized from WO3.

Supporting information: this article has supporting information at journals.iucr.org/cThe first example of the stereoselective synthesis and crystal structure of a spirobicycloquinazolinone based on (-)-fenchone and anthranilamideThe possibility of a single-stage solvent-free stereoselective synthesis of a spirocyclic compound from the natural bicyclic monoterpenoid (À)-fenchone and anthranilamide has been shown for the first time. The molecular and crystal structure of (1R,2S,4S)-1,3,3-trimethyl-1 0 H-spiro[bicyclo[2.2.1]heptane-2,2 0quinazolin]-4 0 (3 0 H)-one, C 17 H 22 N 2 O, was established by X-ray diffraction though the chirality was assumed via the known reactant connectivity and 1 H and 13 C NMR spectroscopy. It has shown that in the molecule, for steric reasons, there is an elongation of the Me 2 C-C(N)N bond to 1.603 (5) Å . The formation of dimers via N-HÁ Á ÁO C hydrogen bonds with an interaction energy of 93.30 kJ mol À1 and through cavities (33.7% of the unit-cell volume) was established in the packing of the molecules. There are no -stacking interactions in the structure. research papers Acta Cryst. (2019). C75, 1675-1680 Chernyshov et al. A spirobicycloquinazolinone based on (À)-fenchone 1679