Search

Silicocarnotite, Ca5[(PO4)(SiO4)](PO4), was first described from slag over 140 years ago. In 2013, it was officially recognised as a mineral after being discovered in the larnite–gehlenite hornfels of the pyrometamorphic Hatrurim Complex. This paper describes the composition and structure of V-bearing silicocarnotite, crystals of which were found in a thin paralava vein cutting through the gehlenite hornfels. A network of thin paralava veins a few centimetres thick is widespread in the gehlenite hornfels of the Hatrurim Basin, Negev Desert, Israel. These veins, typically coarse crystalline rock and traditionally referred to as paralava, have a symmetrical structure and do not contain glass. Silicocarnotite in the paralava, whose primary rock-forming minerals are gehlenite, flamite, Ti-bearing andradite, rankinite and pseudowollastonite, was a relatively late-stage high-temperature mineral, crystallising at temperatures above 1100 °C. It formed from the reaction of a Si-rich residual melt with pre-existing fluorapatite. A single-crystal structural study of silicocarnotite (Pnma, a = 6.72970(12) Å, b = 15.5109(3) Å, c = 10.1147(2) Å) suggests that the phenomenon of Ca1 position splitting observed in this mineral is most likely related to the partial ordering of Si and P in the T2O4 tetrahedrons. Raman studies of silicocarnotite with varying vanadium content have shown that phases with V2O5 content of 3–5 wt.% exhibit additional bands at approximately 864 cm−1, corresponding to vibrations of ν1(VO4)3−. [ABSTRACT FROM AUTHOR]

Crystals of karwowskiite, Ca9Mg(Fe2+0.5□0.5)(PO4)7, a new mineral of the merrillite group, were found on an amygdule wall in the central part of an anorthite–tridymite–diopside paralava of the Hatrurim Complex, Daba-Siwaqa, Jordan. The amygdule was filled with a sulfide melt, which after crystallization gave a differentiated nodule, consisting of troilite and pentlandite parts and containing tetrataenite and nickelphosphide inclusions. Karwowskiite crystals are colorless, although sometimes a greenish tint is observed. The mineral has a vitreous luster. The microhardness VHN25 is 365 (12), corresponding to 4 on the Mohs hardness scale. Cleavage is not observed, and fracture is conchoidal. The calculated density is 3.085 g/cm3. Karwowskiite is uniaxial (−): ω = 1.638 (3), ε = 1.622 (3) (λ = 589 nm), and pleochroism is not observed. The composition of karwowskiite is described by the empirical formula: Ca9.00(□0.54Fe2+0.23Mg0.12Na0.04 Sr0.03 Ni0.03K0.01) Σ1.00Mg1.00(PO4)7.02. Karwowskiite is distinct from the known minerals of the merrillite subgroup with the general formula A9XM[TO3(Ø)]7, where A = Ca, Na, Sr, and Y; X = Na, Ca, and □; M = Mg, Fe2+, Fe3+, and Mn; T = P; and Ø = O, in that the X site in it is occupied by Fe2+0.5□0.5. Karwowskiite is trigonal, space group R-3c with a = 10.3375 (2) Å, c = 37.1443 (9) Å, and V = 3437.60 (17) Å3. Karwowskiite crystallizes at temperatures lower than 1100 °C in a thin layer of secondary melt forming on the walls of amygdules and gaseous channels in paralava as a result of contact with heated gases which are by-products of the combustion process. [ABSTRACT FROM AUTHOR]

Reactions between 1,2-di(tetrazol-2-yl)ethane (ebtz), 1,6-di(tetrazol-2-yl)hexane (hbtz) or 1,1′-di(tetrazol-1-yl)methane (1ditz) and Fe(BF4)2 in the presence of adiponitrile (ADN), glutaronitrile (GLN) or suberonitrile (SUN) resulted in the formation of coordination polymers [Fe(μ-ebtz)2(μ-ADN)](BF4)2 (1), [Fe(μ-hbtz)2(μ-ADN)](BF4)2 (2), [Fe(μ-1ditz)2(GLN)2](BF4)2·GLN (3) and [Fe(μ-1ditz)2(μ-SUN)](BF4)2·SUN (4). It was established that the application of dinitriles allows an increase in the dimensionality of the ebtz and hbtz based systems while maintaining the structure of the polymeric units characteristic of previously studied mononitrile based analogues. In 3 and 4, regardless of the type of dinitrile coligand, the motif of 2D polymeric layers constituted by 1ditz molecules remains preserved. However, the dimensionality of 1ditz based networks is governed by the coordination modes of dinitriles. 3, based on a shorter molecule of glutaronitrile, crystallizes as a two-dimensional (2D) coordination polymer. In this compound, dinitriles coordinate monodentately or play the role of guest molecules. The substitution of glutaronitrile with suberonitrile enables the bridging of neighboring polymeric layers, resulting in a 3D network. The intentional selection of bis(tetrazoles) and dinitriles as building blocks has led, as expected, to obtaining systems with the structure of the first coordination sphere consisting of four tetrazole rings and two axially coordinated nitrile molecules. It created the conditions required for the occurrence of thermally induced spin crossover. Magnetic measurements and single crystal X-ray diffraction studies were used for the characterization of the spin crossover properties of 1–4. [ABSTRACT FROM AUTHOR]

Cooling [Fe(bbtr)3](BF4)2 (bbtr=1,4‐di(1,2,3‐triazol‐1‐yl)butane) triggers very slow spin crossover below 80 K (T1/2↓=76 K). The spin crossover (SCO) is accompanied by a hysteresis loop (T1/2↑=89 K). In contrast to isostructural perchlorate analogue [Fe(bbtr)3](ClO4)2 in which spin crossover during cooling is preceded by phase transition at TPT=126 K in tetrafluoroborate phase transition does not occur to the beginning of spin crossover (80 K). Studies of mixed crystals [Fe(bbtr)3](BF4)2(1‐x)(ClO4)2x (0.5≤x≤0.9) showed that a phase transition precedes spin crossover, however, for x≅0.46 intersection of T1/2(x) and TPT(x) dependencies takes place. The application of pressure of 1 GPa shifts the spin crossover in [Fe(bbtr)3](BF4)2 to a temperature above 270 K. High‐pressure studies of neat tetrafluoroborate and perchlorate, as well as mixed crystals [Fe(bbtr)3](BF4)2(1‐x)(ClO4)2x (0.1≤x≤0.9), revealed that at 295 K P1/2 value changes linearly with x indicating similar mechanism of spin crossover under elevated pressure in all systems under investigation. Variable pressure single crystal X‐ray diffraction studies confirmed that in contrast to thermally induced spin crossover undergoing differently in tetrafluoroborate and perchlorate an application of high pressure removes this differentiation leading to a similar mechanism depending at first on start spin crossover and then P‐3→P‐1 phase transition occurs. In this report we have shown that 2D coordination polymer [Fe(bbtr)3](BF4)2 (bbtr=1,4‐di(1,2,3‐triazol‐1‐yl)butane) treated to date as spin crossover silent shows thermally induced spin crossover phenomenon. Spin crossover in tetrafluoroborate is extremely slow. Determination of the spin crossover curve required carrying measurement in the settle mode‐cooling from 85 to 70 K took about 600 h (average velocity of change of temperature ca. 0.0004 K/min). [ABSTRACT FROM AUTHOR]