Cu^I-catalyzed cycloaddition (CA) of the ketonitrones, Ph₂C═N⁺(R′)O^– (R′ = Me, CH₂Ph), to the disubstituted cyanamides, NCNR₂ (R = Me₂, Et₂, (CH₂)₄, (CH₂)₅, (CH₂)₄O, C₉H₁₀, (CH₂Ph)₂, Ph(Me)), gives the corresponding 5-amino-substituted 2,3-dihydro-1,2,4-oxadiazoles (15 examples) in good to moderate yields. The reaction proceeds under mild conditions (CH₂Cl₂, RT or 45 °C) and requires 10 mol % of [Cu(NCMe)₄](BF₄) as the catalyst. The somewhat reduced yields are due to the individual properties of 2,3-dihydro-1,2,4-oxadiazoles, which easily undergo ring opening via N—O bond splitting. Results of density functional theory calculations reveal that the CA of ketonitrones to Cu^I-bound cyanamides is a concerted process, and the copper-catalyzed reaction is controlled by the predominant contribution of the HOMO_dipole–LUMO_{dipolarophile} interaction (group I by Sustmann’s classification). The metal-involving process is much more asynchronous and profitable from both kinetic and thermodynamic viewpoints than the hypothetical metal-free reaction.

The crystal structure of dmisteinbergite has been determined using crystals from the type locality in Kopeisk city, Chelyabinsk area, Southern Urals, Russia. The mineral is trigonal, with the following structure: P312, a = 5.1123(2), c = 14.7420(7) Å, V = 333.67(3) ų, R₁ = 0.045, for 762 unique observed reflections. The most intense bands of the Raman spectra at 327s, 439s, 892s, and 912s cm ⁻¹ correspond to different types of tetrahedral stretching vibrations: Si–O, Al–O, O–Si–O, and O–Al–O. The weak bands at 487w, 503w, and 801w cm⁻¹ can be attributed to the valence and deformation modes of Si–O and Al–O bond vibrations in tetrahedra. The weak bands in the range of 70–200 cm⁻¹ can be attributed to Ca–O bond vibrations or lattice modes. The crystal structure of dmisteinbergite is based upon double layers of six-membered rings of corner-sharing AlO₄ and SiO₄ tetrahedra. The obtained model shows an ordering of Al and Si over four distinct crystallographic sites with tetrahedral coordination, which is evident from the average <T–O> bond lengths (T = Al, Si), equal to 1.666, 1.713, 1.611, and 1.748 Å for T1, T2, T3, and T4, respectively. One of the oxygen sites (O4) is split, suggesting the existence of two possible conformations of the [Al₂Si₂O₈]²⁻ layers, with different systems of ditrigonal distortions in the adjacent single layers. The observed disorder has a direct influence upon the geometry of the interlayer space and the coordination of the Ca2 site. Whereas the coordination of the Ca1 site is not influenced by the disorder and is trigonal antiprismatic (distorted octahedral), the coordination environment of the Ca2 site includes disordered O atoms and is either trigonal prismatic or trigonal antiprismatic. The observed structural features suggest the possible existence of different varieties of dmisteinbergite that may differ in: (i) degree of disorder of the Al/Si tetrahedral sites, with completely disordered structure having the P6₃/mcm symmetry; (ii) degree of disorder of the O sites, which may have a direct influence on the coordination features of the Ca²⁺ cations; (iii) polytypic variations (different stacking sequences and layer shifts). The formation of dmisteinbergite is usually associated with metastable crystallization in both natural and synthetic systems, indicating the kinetic nature of this phase. Information-based complexity calculations indicate that the crystal structures of metastable CaAl₂Si₂O₈ polymorphs dmisteinbergite and svyatoslavite are structurally and topologically simpler than that of their stable counterpart, anorthite, which is in good agreement with Goldsmith’s simplexity principle and similar previous observations.

This work is part of a project focused on the Somma–Vesuvius volcano and aimed at identifying Cu minerals related to mineralizing processes associated with magmatic activity in an active magmatic-hydrothermal system. A mineralogical survey was carried out on a set of samples represented by sublimates and fumarolic products from the collection of the Mineralogical Museum of the University of Naples Federico II (Italy). These samples are mainly related to most recent eruptive episodes of Vesuvius activity, from 1631 onward. Copper-bearing minerals were characterized, as well as associated minerals, by X-ray diffraction (XRD) scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS). An investigation on the structural complexity of Cu-mineral assemblages with different temperature formations was also carried out using the TOPOS software package. The main copper phases are sulfates, followed by vanadates, hydroxyhalides, oxides, carbonates, silicates and finally, phosphates. New mineral occurrences for Vesuvius, both Cu-bearing and Cu-free, are described. Nevertheless, the fumarolic/alteration minerals at Vesuvius cannot be considered of economic relevance as a copper reservoir, this type of mineralizations are significant for copper crystal chemistry and for the knowledge of the mineralogical variants. The obtained datasets can be of interest for the knowledge of volcanic byproducts of copper ore deposits (i.e., porphyry copper systems) and of (base) metal segregation processes.