The new mineral paramarkeyite (IMA2021-024), Ca2(UO2)(CO3)3⋅5H2O, was found in the Markey mine, San Juan County, Utah, USA, where it occurs as a secondary phase on gypsum-coated asphaltum in association with andersonite, calcite, gypsum and natromarkeyite. Paramarkeyite crystals are transparent, pale green-yellow, striated tablets, up to 0.11 mm across. The mineral has white streak and vitreous lustre. It exhibits moderate bluish-white fluorescence (405 nm laser). It is very brittle with irregular, curved fracture and a Mohs hardness of 2½. It has an excellent {100} cleavage and probably two good cleavages on {010} and {001}. The measured density is 2.91(2) g cm–3. Optically, the mineral is biaxial (–) with α = 1.550(2), β = 1.556(2), γ = 1.558(2) (white light); 2V = 60(2)°; strong r > v dispersion; orientation: Y = b; nonpleochroic. The Raman spectrum exhibits bands consistent with UO22+, CO32– and O–H. Electron microprobe analysis provided the empirical formula (Ca1.83Na0.20Sr0.03)Σ2.05(UO2)(CO3)3⋅5H2O (+0.07 H). Paramarkeyite is monoclinic, P21/n, a = 17.9507(7), b = 18.1030(8), c = 18.3688(13) Å, β = 108.029(8)°, V = 5676.1(6) Å3 and Z = 16. The structure of paramarkeyite (R1 = 0.0647 for 6657 I > 2σI) contains uranyl tricarbonate clusters that are linked by Ca–O polyhedra to form heteropolyhedral layers. The structure of paramarkeyite is very similar to those of markeyite, natromarkeyite and pseudomarkeyite.

Jeankempite, Ca5(AsO4)2(AsO3OH)2(H2O)7, is a new mineral species (IMA2018-090) discovered amongst coatings of arsenate minerals on oxidised copper arsenides from the Mohawk No. 2 mine, Mohawk, Keweenaw County, Michigan, USA. The new mineral occurs as lamellar bundles of colourless to white plates up to 1 mm wide and is visually indistinguishable from guérinite, with which it forms intergrowths. Jeankempite is transparent to translucent with a waxy lustre and white streak, is non-fluorescent under longwave and shortwave ultraviolet illumination, has a Mohs hardness of ~1.5 and brittle tenacity with uneven fracture. Crystals are flattened on {01$\bar{1}$} and exhibit perfect cleavage on {01$\bar{1}$}. Optically, jeankempite is biaxial (+), α = 1.601(2), β = 1.607(2), γ = 1.619(2) (white light); 2Vmeas. = 72(2)° and 2Vcalc. = 71.0°. The empirical formula is (Ca4.97Na0.013Mg0.017)(As3.99S0.01)4O23H16, based on 23 O and 16 H atoms per formula unit. Thermogravimetric analysis indicates that jeankempite undergoes four weight losses totalling 16.82%, close to the expected loss of 16.30%, corresponding to eight H2O. Jeankempite is triclinic, P$\bar{1}$, a = 6.710(6), b = 14.901(14), c = 15.940(15) Å, α = 73.583(12)°, β = 81.984(12)°, γ = 82.754(12)°, V = 1507(2) Å3 and Z = 3. The final structure was refined to R1 = 0.0591 for 2781 reflections with Iobs > 3σI. The crystal structure of jeankempite is built from a network of edge- and vertex-sharing CaO6, CaO7 and AsO4 polyhedra, and we hypothesise that the new mineral has formed due to a topotactic reaction brought on by dehydration of preexisting guérinite.

The new minerals natromarkeyite, Na2Ca8(UO2)4(CO3)13(H2O)24⋅3H2O (IMA2018-152) and pseudomarkeyite, Ca8(UO2)4(CO3)12(H2O)18⋅3H2O (IMA2018-114) were found in the Markey mine, San Juan County, Utah, USA, where they occur as secondary phases on asphaltum. Natromarkeyite properties are: untwinned blades and tablets to 0.2 mm, pale yellow green colour; transparent; white streak; bright bluish white fluorescence (405 nm laser); vitreous to pearly lustre; brittle; Mohs hardness 1½ to 2; irregular fracture; three cleavages ({001} perfect, {100} and {010} good); density = 2.70(2) g cm–3; biaxial (–) with α = 1.528(2), β = 1.532(2) and γ = 1.533(2); and pleochroism is X = pale green yellow, Y ≈ Z = light green yellow. Pseudomarkeyite properties are: twinned tapering blades and tablets to 1 mm; pale green yellow colour; transparent; white streak; bright bluish white fluorescence (405 nm laser); vitreous to pearly lustre; brittle; Mohs hardness ≈ 1; stepped fracture; three cleavages ({10$\bar{1}$} very easy, {010} good, {100} fair); density = 2.88(2) g cm–3; biaxial (–) with α = 1.549(2), β = 1.553(2) and γ = 1.557(2); and it is nonpleochroic. The Raman spectra of markeyite, natromarkeyite and pseudomarkeyite are very similar and exhibit bands consistent with UO22+, CO32– and O–H. Electron microprobe analyses provided the empirical formula Na2.01Ca7.97Mg0.03Cu2+0.05(UO2)4(CO3)13(H2O)24⋅3H2O (–0.11 H) for natromarkeyite and Ca7.95(UO2)4(CO3)12(H2O)18⋅3H2O (+0.10 H) for pseudomarkeyite. Natromarkeyite is orthorhombic, Pmmn, a = 17.8820(13), b = 18.3030(4), c = 10.2249(3) Å, V = 3336.6(3) Å3 and Z = 2. Pseudomarkeyite is monoclinic, P21/m, a = 17.531(3), b = 18.555(3), c = 9.130(3) Å, β = 103.95(3)°, V = 2882.3(13) Å3 and Z = 2. The structures of natromarkeyite (R1 = 0.0202 for 2898 I > 2σI) and pseudomarkeyite (R1 = 0.0787 for 2106 I > 2σI) contain uranyl tricarbonate clusters that are linked by (Ca/Na)–O polyhedra forming thick corrugated heteropolyhedral layers. Natromarkeyite is isostructural with markeyite; pseudomarkeyite has a very similar structure.

The crystal structure of szenicsite, Cu3MoO4(OH)4, orthorhombic, a = 8.5201(8), b = 12.545(1), c = 6.0794(6) Å, V = 649.8(2) Å3, space group Pnnm, Z = 4, has been solved by direct methods and refined by least-squares techniques to an agreement index (R) of 3.34% and a goodness-of-fit (S) of 1.11 for 686 unique observed [|F| ⩾ 4σF] reflections collected using graphite-monochromated Mo-Kα X-radiation and a CCD area detector. The structure contains three unique Cu2+ positions that are each coordinated by six anions in distorted octahedral arrangements; the distortions of the octahedra are due to the Jahn-Teller effect associated with a d9 metal in an octahedral ligand-field. The single unique Mo6+ position is tetrahedrally coordinated by four O2− anions. The Cu2+ϕ6 (ϕ: unspecified ligand) octahedra share trans edges to form rutile-like chains, three of which join by the sharing of octahedral edges to form triple chains that are parallel to [001]. The MoO4 tetrahedra are linked to either side of the triple chain of Cu2+ϕ6 octahedra by the sharing of two vertices per tetrahedron, and the resulting chains are cross-linked through tetrahedral-octahedral vertex sharing to form a framework structure. The structure of szenicsite is closely related to that of antlerite, Cu3SO4(OH)4, which contains similar triple chains of edge-sharing Cu2+ϕ6 octahedra.

Redcanyonite (IMA2016-082), (NH4)2Mn[(UO2)4O4(SO4)2](H2O)4, occurs underground in the Blue Lizard mine, Red Canyon, White Canyon district, San Juan County, Utah, USA. It occurs with natrozippeite, brochantite, devilline, posnjakite, johannite, gypsum, bobcookite, pickeringite, pentahydrite and the NH4-analogue of zippeite: ammoniozippeite. Redcanyonite occurs as radial aggregates of red–orange needles and blades individually reaching up to 0.2 mm long, with aggregates measuring up to 1 mm in diameter. Crystals are flattened on {010} and elongated along [100], exhibit perfect cleavage on {010}, and exhibit the forms {010}, {001}, {101} and {10$\bar{1}$}. Twinning is ubiquitous, by 180° rotation on [100]. Redcanyonite is translucent with a pale orange streak, is non-fluorescent, has a Mohs hardness of 2, and has brittle tenacity with uneven fracture. Optically, redcanyonite is biaxial (+), α = 1.725(3), β = 1.755(3), γ = 1.850(5) (white light); 2V (meas.) = 60(2)°, 2V (calc.) = 61.3°; and dispersion is r < v, very strong. Pleochroism is: X = orange, Y = yellow and Z = orange; Y << X < Z. The optical orientation is X = b, Y ≈ c*, Z ≈ a. The empirical formula is (NH4)2.02(Mn0.49Cu0.09Zn0.06)Σ0.64H+0.72[(UO2)4O4(S0.99P0.01O4)2](H2O)4, based on 4 U and 24 O apfu. Redcanyonite is monoclinic, C2/m, a = 8.6572(17), b = 14.155(3), c = 8.8430(19) Å, β = 104.117(18)°, V = 1050.9(4) Å3 and Z = 2. The structure was refined to R1 = 0.0382 for 1079 reflections with Iobs > 3σI. Uranyl oxo-sulfate sheets in redcanyonite adopt the well-known zippeite topology, which consists of zigzag chains of uranyl pentagonal bipyramids linked by sulfate tetrahedra to form sheets. The sheets are linked to each other through bonds to interlayer NH4+ groups and octahedrally coordinated Mn2+, and by hydrogen bonds from H2O groups. Redcanyonite is named for Red Canyon in southeast Utah, USA.

Leószilárdite (IMA2015-128), Na6Mg(UO2)2(CO3)6·6H2O, was found in the Markey Mine, Red Canyon, White Canyon District, San Juan County, Utah, USA, in areas with abundant andersonite, natrozippeite, gypsum, anhydrite, and probable hydromagnesite along with other secondary uranium minerals bayleyite, čejkaite and johannite. The new mineral occurs as aggregates of pale yellow bladed crystals flattened on ﹛001﹜ and elongated along [010], individually reaching up to 0.2 mmlong. More commonly it occurs as pale yellow pearlescent masses to 2 mm consisting of very small plates. Leószilárdite fluoresces green under both longwave and shortwave ultraviolet light, and is translucent with a white streak, hardness of 2 (Mohs), and brittle tenacity with uneven fracture. The new mineral is readily soluble in room temperature H2O. Crystals have perfect cleavage along ﹛001﹜, and exhibit the forms ﹛110﹜,﹛001﹜,﹛100﹜,﹛101﹜ and ﹛101﹜. Optically, leószilárdite is biaxial (-), α= 1.504(1), β= 1.597(1), γ= 1.628(1) (white light); 2V (meas.) = 57(1)°, 2V (calc.) = 57.1°; dispersion r > v, slight. Pleochroism: X= colourless, Y and Z= light yellow; X<Y ≈ Z The average of six wavelength dispersive spectroscopic analyses provided Na2O 14.54, MgO 3.05, UO3 47.95, CO2 22.13, H2O 9.51, total 97.18 wt.%. The empirical formula is Na5.60Mg0.90U2O28C6H12.60, based on 28 O apfu. Leószilárdite is monoclinic, C2/m, a = 11.6093(21), b = 6.7843(13), c = 15.1058(28) Å, β = 91.378(3)°, V= 1189.4(4) Å3 and Z = 2. The crystal structure (R1 = 0.0387 for 1394 reflections with Iobs > 4σI), consists of uranyl tricarbonate anion clusters [(UO2)(CO3)3]4- held together in part by irregular chains of NaO5(H2O) polyhedra sub parallel to [010]. Individual uranyl tricarbonate clusters are also linked together by three-octahedron units consisting of two Na-centred octahedra that share the opposite faces of a Mg-centred octahedron at the centre (Na–Mg–Na), and have the composition Na2MgO12(H2O)4. The name of the new mineral honours the Hungarian-American physicist, inventor and biologist Dr. Leó Szilárd (1898–1964).

U60 ([UO2(O2)(OH)]60 60− in water) is a uranyl peroxide nanocluster with a fullerene topology and O h symmetry. U60 clusters can exist in crystalline solids or in liquids; however, little is known of their behavior at high pressures. We compressed the U60-bearing material: Li68K12(OH)20[UO2(O2)(OH)]60(H2O)310 ( $Fm\bar 3$ ; a = 37.884 Å) in a diamond anvil cell to determine its response to increasing pressure. Three length scales and corresponding structural features contribute to the compression response: uranyl peroxide bonds (<0.5 nm), isolated single nanoclusters (2.5 nm), and the long-range periodicity of nanoclusters within the solid (>3.7 nm). Li68K12(OH)20[UO2(O2)(OH)]60(H2O)310 transformed to a tetragonal structure below 2 GPa and irreversibly amorphized between 9.6 and 13 GPa. The bulk modulus of the tetragonal U60-bearing material was 25 ± 2 GPa. The pressure-induced amorphous phase contained intact U60 clusters, which were preserved beyond the loss of long-range periodicity. The persistence of U60 clusters at high pressure may have been enhanced by the interaction between U60 nanoclusters and the alcohol pressure medium. Once formed, U60 nanoclusters persist regardless of their associated long-range ordering—in crystals, amorphous solids, or solutions.

An X-ray powder-diffraction pattern for boracite, Mg3B7O13Cl, is reported. Boracite is orthorhombic, space group Pca21, and the refined unit-cell parameters are a=8.557(6), b=8.553(8), c= 12.09(1) Å. X-ray powder-diffraction patterns have been calculated for the boracite-group minerals boracite, ericaite, trembathite and congolite. The calculated pattern for boracite is in good agreement with the observed pattern reported here, but the PDF entry (5-710) for boracite is missing several intense peaks. The calculated pattern for ericaite is in poor agreement with the PDF entry (29-697) for ericaite, and PDF 29-697 is for congolite, not ericaite. The calculated powder patterns presented here for these four minerals will facilitate their identification via X-ray powder diffraction. © 1995 International Centre for Diffraction Data.

The crystal structure of monoclinic CuF2 has been refined by the Rietveld method from X-ray powder diffraction data. The structure is monoclinic, space group P21/n, a = 3.2973(2), b = 4.5624(3), c = 4.6157(3) Å, β = 83.293(3)°, V = 68.96(2) Å3, with Cu+2 at (0,0,0) and F−1 at (−0.04176(68), 0.29410(35), 0.29410(35)). Final RB = 0.97%, RP = 1.99%, Rwp = 2.32%, RWP(expected) = 1.46%. The structure has a rutile-type arrangement, but with a monoclinic distortion that produces a highly distorted octahedral coordination around the Cu2+ ion with equatorial and apical Cu-F distances of 1.92 and 2.32 Å respectively.

The crystal structure of α-CoSO4 has been refined by the Rietveld method from X-ray powder diffraction data. The structure is orthorhombic, space group Pnma, a = 8.6127(4), b = 6.7058(3), c = 4.7399(2) Å, V = 273.75(3) Å3. Final RB = 2.41%, RP = 5.24%, RWP=6.66%, RWP (expected) =5.74% (WP =weighted profile). The structure consists of edge-sharing octahedral chains parallel to [010] interconnected by SO4 tetrahedra.

By contracting with the Parr Instrument Company and Bruker Optical Systems, we have developed a system for continuous monitoring of hydrothermal and room temperature reactions by Raman spectroscopy. Using the uranyl peroxide cage cluster {[UO2(O2)(OH)]16[UO2(OM)2]4}24- (denoted {U20R}) and a coordination polymer made from uranyl ions and 4,4’-biphenyldicarboxylate as model systems, we demonstrate the spectroscopically observable changes associated with reaction progress and crystallization.

Actinide solid-state and coordination chemistry has advanced through unexpected results that have further revealed the complex nature of the 5f elements. Nanoscale control of actinide materials is emerging, as shown by the creation of a considerable range of cluster and tubular topologies. Departures from established structural trends for actinyl ions are provided by cation-cation interactions in which an O atom of one actinyl ion is an equatorial ligand of a bipyramid of another actinyl ion. The solid-state structural complexity of actinide materials has been further demonstrated by open framework materials with interesting properties. The U(VI) tetraoxide core has been added to this cation's repertoire of coordination possibilities. The emergence of pentavalent uranium solid-state and coordination chemistry has resulted from the prudent selection of ligands. Finally, analogues of the uranyl ion have challenged our understanding of this normally unreactive functional group.