Aurihydrargyrumite, a Natural Au6Hg5 Phase from Japan

Aurihydrargyrumite, a natural Au6Hg5 phase, was found in Iyoki, Uchiko, Ehime Prefecture, Shikoku Island, Japan. Aurihydrargyrumite with a metallic silver luster occurs as a submicron- to 2 μm-thick layer on the outermost surface of the placer gold. A prismatic face may be formed by {001} and {100} or {110}. The streak is also silver white and its Mohs hardness value is ca. 2.5. Its tenacity is ductile and malleable, and its density, as calculated based on the empirical formula and powder unit-cell data, is 16.86 g·cm−3. The empirical formula of aurihydrargyrumite, on the basis of 11 Au + Hg, is Au5.95Hg5.05. Aurihydrargyrumite is hexagonal, P63/mcm, with the lattice parameters a = 6.9960(10) Å, c = 10.154(2) Å and V = 430.40(15) Å3, which is identical with the synthetic Au6Hg5 phase. The seven strongest lines in the powder X-ray diffraction (XRD) pattern [d in Å(I/I0)(hkl)] were 2.877(29)(112), 2.434(42)(113), 2.337(100)(104), 2.234(87)(211), 1.401(39)(314), 1.301(41)(404), and 1.225(65)(217). Aurihydrargyrumite forms through the weathering of mercury-bearing placer gold by involvement of self-electrorefining. This new mineral has been approved by the IMA-CNMNC (2017-003) and it is named for its composition, being a natural amalgam of gold (Latin: aurum) and mercury (Latin: hydrargyrum).

Synthesis of Lanthanoid Complexes from Ln2O3 and Diatrizoic Acid

We present a pathway to synthesize diatrizoate lanthanoid complexes directly from Ln2O3 and diatrizoic acid (DTAH=3,5-diacetamido-2,4,6-triiodobenzoic acid) at room temperature yielding [Ln(H2O)8][DTA]3 in moderate (for the heavier lanthanoids) to good (for the lighter lanthanoids) yields. Compounds were recrystallized from DMSO or water and their X-ray crystal structures were obtained. The complexes have metal centres solely coordinated by solvent molecules with no direct interaction between the metal centre and the DTA anion. The compounds crystallized from DMSO have the formulation [Ln(DMSO)4(H2O)4][DTA]3.DMSO (Ln=La, Nd, Sm, Eu, Dy; only unit cell data were confirmed for Ln=Nd, Sm) whereas the compound crystallized from water has the formulation [Dy(H2O)8][DTA]3.7H2O.

(4,4′-Dimethoxy-2,2′-bipyridine-κ2N,N′)bis[2-(pyridin-2-yl)phenyl-κC1]iridium(III) hexafluoridophosphate unknown solvate

The asymmetric unit of the title complex, [Ir(C11H8N)2(C12H12N2O2)]PF6, comprises a [Ir(ppy)2(diMeO-bpy)]+cation (Hppy = 2-phenylpyridine and diMeO-bpy = 4,4′-dimethoxy-2,2′-bipyridine) and a PF6−anion. The IrIIIatom is coordinated by two anionic ppy−ligands, each coordinating in aC^Ncyclometalated mode, and one neutral diMeO-bpy ligand, leading to a distorted octahedral geometry defined by acis-C2N4donor set. Intermolecular C—F...H contacts lead to a three-dimensional architecture that define columns parallel toa. Unknown disordered solvent molecules reside in these columns with the electron density being treated with SQUEEZE [Spek (2015).Acta Cryst. C71, 9–18]. The unit-cell data do not reflect the presence of the unresolved solvent.

(5-Methylpyrazine-2-carboxylato-κ2N1,O)bis[2-(4-methylpyridin-2-yl-κN)-3,5-bis(trifluoromethyl)phenyl-κC1]iridium(III) chloroform hemisolvate

In the title complex, [Ir(C14H8F6N)2(C6H5N2O2)]·0.5CHCl3, the IrIIIatom adopts a distorted octahedral geometry, being coordinated by three N atoms (arranged meridionally), two C atoms and one O atom of three bidentate ligands. The complex molecules pack with no specific intermolecular interactions between them. TheSQUEEZEprocedure inPLATON[Spek (2009).Acta Cryst.D65, 148–155] was used to model a disordered chloroform solvent molecule; the calculated unit-cell data allow for the presence of half of this molecule in the asymmetric unit.

1,3,5-Tris(4-methoxyphenyl)-1,3,5-triazinane-2,4,6-trione

The complete molecule of the title compound, C24H21N3O6, is generated by the application of threefold rotation symmetry about an axis perpendicular to the central ring. The molecule exhibits a propeller-like shape. The dihedral angle between each benzene ring and the heterocyclic ring is 74.0 (1)°. The molecules pack with no specific intermolecular interactions between them. TheSQUEEZEprocedure inPLATON[Spek (2009).Acta Cryst.D65, 148–155] was used to model disordered solvent molecules, presumed to be acetone; the calculated unit-cell data do not take into account the presence of these.

Demicheleite-(I), BiSI, a new mineral from La Fossa Crater, Vulcano, Aeolian Islands, Italy

Demicheleite-(I), ideally BiSI, is the iodine-dominant analogue of demicheleite-(Br) and demicheleite-(Cl). It was found in an active medium-temperature intracrateric fumarole at La Fossa crater, Vulcano Island, Aeolian archipelago, Sicily, Italy. The mineral is the first bismuth sulphoiodide so far discovered in a wholly natural environment, and corresponds to the already known synthetic compound. It occurs as acicular to stout, translucent crystals up to 0.25 mm long in an altered pyroclastic breccia, together with demicheleite-(Br), bismoclite, bismuthinite, godovikovite, panichiite, aiolosite, brontesite, adranosite and other new phases under study. The colour is dark red to black, the lustre submetallic. The unit cell is orthorhombic, space group Pnam, with a = 8.4501(7) Å, b = 10.1470(9) Å , c = 4.1389(4) Å , V = 354.88(4) Å3, and Z = 4. The crystal habit is prismatic, with the main forms {110} and {111} inferred from analogy with demicheleite-(Br). Twinning was not observed. The strongest 6 lines in the X-ray powder diffraction pattern [dobs.(Å) (I/I0) (hkl)] are: 6.490 (100) (110); 4.346 (94) (120); 3.896 (90) (210); 2.709 (60) (310); 2.161 (38) (330); 3.243 (22) (220). The chemical analysis obtained by WDS electron microprobe gave: Bi 58.32, S 9.43, I 23.69, Br 5.66, Cl 1.01, totalling 98.11 wt.%, corresponding to an empirical formula (based on 3 a.p.f.u.) of: Bi0.97S1.03(I0.65Br0.25Cl0.10)Σ1.00. The unit-cell data are close to those of the synthetic compound, whose crystal structure is already known. The calculated density is 6.411 g cm–3.

Enumeration of four-connected three-dimensional nets. III. Conversion of edges of three-connected two-dimensional nets into saw chains

A three-repeat saw (s) chain has each vertical edge separated by a tooth composed of two tilted edges zig and zag. Some horizontal (h) edges from a parallel stack of three-connected two-dimensional (2D) nets can be converted into an s chain. Each resulting four-connected vertex in the three-dimensional (3D) net may be part of either one, two or three s chains. The first type of (h,s)* 3D net is related by a sigma-type mirror plane to a (h,z)* net listed in paper II [Han & Smith (1998). Acta Cryst. A55, 342–359]. The second type does not have an (h,z)* relative. Using the same three-connected 2D nets as in paper II, 174 four-connected 3D nets were selected from the first two types, including six in known structures: `nepheline hydrate' (International Zeolite Association Structure Commission code JBW), AlPO4-12-TAMU (ATT), offretite (OFF), Linde Type L (LTL), SUZ-4 (SZF) and ZSM-10 (ZST). The third type with three back-to-back s chains is represented by edingtonite (EDI), and systematic enumeration is in progress. The geometrical and topological properties of the 3D nets are given. Idealized unit-cell data and atomic coordinates for tetrahedral bonding were obtained for 40 selected 3D nets by distance-least-squares (DLS) refinement.

Compositional segregation and solid solution in the lead-dominant alunite-type minerals from Broken Hill, N.S.W.

A study of the composition and unit cell data of a suite of lead-rich minerals of the alunite-jarosite group from the oxidized zone of the ore body at Broken Hill, New South Wales, Australia, has revealed almost complete XO4 (X = As, P, S) solid solution in these minerals at this deposit. The species in the group noted are hidalgoite, hinsdalite, beudantite, segnitite and plumbogummite. These minerals at Broken Hill exhibit a number of growth textures, including oscillatory zoning, colloform banding and replacements. Zoning in these minerals is due to the segregation of Al- and Fe-rich members, and compositions indicate a strong coupling of Fe3+ with and Al with

Kristallchemische Analyse der Stereochemie des Kations und Anions in Bis(triphenylphosphin)iminium-di(phthalocyaninato)metallaten der Selenen Erden, (PNP)[Ln(Pc2-)2]•xH2O (Ln = La, Gd, Tm; x ≤ 0,5) / Crystalchemical analysis of the stereochemistry of the cations and anions in bis(triphenylphosphine)iminium di(phthalocyaninato)metalates of the rare earth elements, (PNP)[Ln(Pc2-)2]•xH2O (Ln = La, Gd, Tm; x ≤ 0,5)

Of the isostructural series of monoclinic (PNP)[Ln(Pc)2]• xH2O compounds (Ln = La ••• Tm) the crystal structures of the complex salts of tervalent La (1), Gd (2) and Tm (3) have been determined by single crystal X-ray diffraction analysis. Unit cell data for 2: space group P21/c; a = 15.172(8), b = 20.826(2), c = 25.876(3) Å, β = 95.19(3)°, V - 8143(4) Å3, Z = 4; 1 and 3 are isostructural with 2. The lanthanide ion occupies the center of a nearly ideal square antiprism, although the two staggered phthalocyanine rings are severely distorted in an unsymmetrical funnel-shaped fashion due to electronic, steric, and packing influences in the crystal lattice. Steric effects dictate also the geometry of the PNP cation, which adopts a hybrid conformation whose structural characteristics are between the common linear and bent conformers with medium short P-N distances (1.562 Å) and large P-N-P angles in the range 165.6° (1) > 158.3° (2) > 156.1° (3). The strong IR bands at ca. 1375 cm-1 assigned to the asym. (P-N) stretch are diagnostic for this hybrid conformation. The presence of water of crystallization in the periphery of the diphthalocyanine anion is confirmed. The shortest contact distance is observed to one of the bridging nitrogen atoms of the Pc2- ligand (3.02 Å) indicating a weak (HO-H•••N) hydrogen bond