A pseudo‐merohedrally twinned rare‐earth sulfate: K6[Ce(HSO4)2(SO4)4]·H2O,a novel structure type

A novel structure type of an acidic rare‐earth sulfate, hexa­potassium cerium dihydrogensulfate tetra­sulfate monohydrate, is reported. The crystal is twinned, mimicking tetra­gonal symmetry. The Ce^IV atom is nine‐coordinate, connecting to one corner‐sharing and four edge‐sharing sulfate groups. One of the potassium ions is disordered over two general positions. The compound is unique as it contains rare‐earth monomers, [Ce(HSO₄)(SO₄)₄]⁵⁻. The structure is composed of these monomers, water mol­ecules, discrete hydrogensulfate ions and potassium ions held together by ionic inter­actions. There are two types of alternating layers in the structure, with compositions [K₄Ce(HSO₄)(SO₄)₄]⁻ and [K₂(HSO₄)(H₂O)]⁺.     

(NH4)3[VO2(SO4)2(H2O)2]·1.5H2O

The title compound, tri­ammonium cis‐di­aqua‐cis‐dioxo‐trans‐disulfatovanadate 1.5‐hydrate, was obtained by oxidizing V^IV to V^V in a 2 M sulfuric acid solution of vanadyl­ sulfate and adding ammonium sulfate. Here, the V atom is sandwiched by two sulfate groups by corner‐sharing to form a discrete [VO₂(SO₄)₂(OH₂)₂]^3? anion. The water mol­ecules occupy cis positions in the equatorial plane of the vanadium octahedron.     

A uranyl sulfate cluster in Na10[(UO2)(SO4)4](SO4)2·3H2O

Decasodium uranyl hexa­sulfate trihydrate, Na₁₀[(UO₂)(SO₄)₄](SO₄)₂·3H₂O, contains an unusual uranyl sulfate cluster with the composition [(UO₂)(SO₄)₄]^6?. The cluster is composed of a uranyl pentagonal bipyramid and four sulfate tetrahedra. Three sulfate tetrahedra are linked to the uranyl pentagonal bipyramid by the sharing of vertices, and the other shares an equatorial edge of the uranyl pentagonal bipyramid. The uranyl sulfate clusters occur in layers parallel to (010). The structure also contains two isolated symmetrically distinct sulfate tetrahedra, which also occur in layers parallel to (010). The uranyl sulfate clusters and isolated sulfate tetrahedra are linked through bonds to Na⁺ cations, and by hydrogen bonding involving the water molecules.     

Single‐crystal neutron‐diffraction study of 3.4% Zn‐doped (ND4)2[Cu(D2O)6](SO4)2 at 20 K

Doping the perdeuterated ammonium copper Tutton salt (ND₄)₂[Cu(D₂O)₆](SO₄)₂ [perdeuterated diammonium hexa­aqua­copper(II) bis­(sulfate)] with Zn leads to a change in the structure from dimorph A (low density) to dimorph B (high density). This change, which accompanies a switch in the direction of the Jahn–Teller distortion, had previously been observed to occur with substitution of Zn²⁺ at the Cu²⁺ site of between 1.3 (A) and 3.4% (B). In this study, the single‐crystal neutron‐diffraction analysis of (ND₄)₂[(Cu/Zn)(D₂O)₆](SO₄)₂ at 20 K, with 3.4% Zn doping and a deuterium substitution of 85% on the H‐atom sites, reveals that the structure is entirely of type B, with the Cu/Zn site at an inversion centre and with no evidence of disorder or unusual atomic displacement parameters that might occur near a phase transition boundary.     

(H3O)Nd(SO4)2

The crystal structure of oxonium neodymium bis(sulfate), (H₃O)Nd(SO₄)₂, shows a two‐dimensional layered framework assembled from SO₄ tetrahedra and NdO₉ tricapped trigonal prisms. One independent sulfate group makes four S—O—Nd linkages, while the other makes five such connections to generate an unprecedented anhydrous anionic [Nd(SO₄)₂]⁻ layer. To achieve charge balance, H₃O⁺ cations are inserted between adjacent layers where they participate in hydrogen‐bonding interactions with the sulfate O atoms of adjacent layers.     

Bis­(melaminium) sulfate dihydrate

The crystals of a new melaminium salt, bis(2,4,6-tri­amino-1,3,5-triazin-1-ium) sulfate dihydrate, 2C₃H₇N₆⁺·SO₄²⁻·2H₂O, are built up from monoprotonated melaminium(1+) residues, sulfate(2−) anions and water mol­ecules. The SO₄²⁻ ion has a slightly distorted tetrahedral geometry. The melaminium residues are interconnected by N—H⋯N hydrogen bonds, forming chains. The chains of melaminium residues develop a three-dimensional network through multiple donor–acceptor hydrogen-bond interactions with sulfate anions and water mol­ecules.     

Hemi(piperazinediium) hexaaqua­aluminium(III) bis­(sulfate) tetrahydrate: a new double aluminium sulfate salt

Piperazinium aluminium sulfate decahydrate, (C₄H₁₂N₂)_0.5[Al(H₂O)₆](SO₄)₂·4H₂O, exhibits a crystal structure built from isolated [Al(H₂O)₆]³⁺, SO₄²⁻, C₄H₁₂N₂²⁺ and H₂O units connected by a complex hydrogen‐bond network. The title compound shows strong similarities to many double alumin­ium sulfates, such as alums and Tutton's salts. However, since its structure is not derived directly from that of these compounds, it is assumed to be a new structure type.     

Pt2(HSO4)2(SO4)2, the First Binary Sulfate of Platinum

Red single crystals of Pt₂(HSO₄)₂(SO₄)₂ were obtained by the reaction of elemental platinum with conc. sulfuric acid at 350 °C in sealed glass ampoules. The crystal structure (monoclinic, P2₁/c, Z = 2, a = 868.6(2), b = 826.2(1), c = 921.8(2) pm, β=116.32(1)°, R_all = 0.0348) shows dumbbell shaped Pt₂⁶⁺ cations which are coordinated by four SO₄^2— and two HSO₄^— ions. Each of the sulfate ions is attached to another Pt₂⁶⁺ ion yielding layers according to equation/tex2gif-stack-1.gif[Pt₂(SO₄)_4/2(HSO₄)_2/1]. The layers are connected by hydrogen bonds with the OH group of the hydrogensulfate ion as donor and the non‐bonding oxygen atom of the sulfate ion as acceptor.     

Two 2,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazo­le–metal complexes (M = Cu and Ni)

The reaction of the diazine ligand 3,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazole (pod, C₁₂H₈N₄O), with Cu(CF₃SO₃)₂ or Ni(ClO₄)₂ afforded the title complexes di­aqua­bis­[3,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazole‐N²,N³]copper(II) bis­(tri­fluoro­methane­sul­fon­ate), [Cu(pod)₂(H₂O)₂](CF₃SO₃)₂, and di­aqua­bis­[3,5‐bis(2‐pyridinyl)‐1,3,4‐oxa­diazo­le‐N²,N³]­nickel(II) diperchlorate, [Ni(pod)₂(H₂O)₂](ClO₄)₂. Both complexes present a crystallographically centrosymmetric mononuclear cation structure which consists of a six‐coordinated Cu^II or Ni^II ion with two pod mol­ecules acting as bidentate ligands and two axially coordinated water mol­ecules.     

Two thiourea‐containing gold(I) complexes

The crystal structures of two salts of bis­(thio­urea)­gold(I) complexes, namely bis­(thio­urea‐κS)­gold(I) chloride, [Au(CH₄N₂S)₂]Cl, (I), and bis­[bis­(thio­urea‐κS)­gold(I)] sulfate, [Au(CH₄N₂S)₂]₂SO₄, (II), have been determined. The chloride salt, (I), is isomorphous with the corresponding bromide salt, although there are differences in the bonding. The Au^I ion is located on an inversion centre and coordinated by two symmetry‐related thio­urea ligands through the lone pairs on their S atoms [Au—S 2.278 (2) Å and Au—S—C 105.3 (2)°]. The sulfate salt, (II), crystallizes with four independent [Au(CH₄N₂S)₂]⁺ cations per asymmetric unit, all with nearly linear S—Au—S bonding. The cations in (II) have similar conformations to that found for (I). The Au—S distances range from 2.276 (3) to 2.287 (3) Å and the Au—S—C angles from 173.5 (1) to 177.7 (1)°. These data are relevant in interpreting different electrochemical processes where gold–thio­urea species are formed.     

Synthese und Kristallstruktur von CsAu(SO4)2

Synthesis and Crystal Structure of CsAu(SO₄)₂ Light yellow single crystals of CsAu(SO₄)₂ were obtained upon evaporation of a solution of Au(OH)₃ and Cs₂SO₄ in sulfuric acid (96 % H₂SO₄). In the crystal structure (monoclinic, P2₁/c, Z = 4, a = 1029.7(2), b = 893.4(2), c = 901.0(1) pm, β = 111.08(1)°) Au³⁺ is in square planar coordination of oxygen atoms which belong to four SO₄^— ions. According to [Au(SO₄)_4/2]^— puckered layers are formed which are connected by the Cs⁺ ions. The latter are surrounded by five chelating and three monodentate sulfate groups leading to a CN of 13.     

Syntheses and Structures of Na2Mg3(OH)2(SO4)3·4H2O and K2Mg3(OH)2(SO4)3·2H2O

The crystal structures of Na₂Mg₃(OH)₂(SO₄)₃ · 4H₂O and K₂Mg₃(OH)₂(SO₄)₃ · 2H₂O, were determined from conventional laboratory X‐ray powder diffraction data. Synthesis and crystal growth were made by mixing alkali metal sulfate, magnesium sulfate hydrate, and magnesium oxide with small amounts of water followed by heating at 150 °C. The compounds crystallize in space group Cmc2₁ (No. 36) with lattice parameters of a = 19.7351(3), b = 7.2228(2), c = 10.0285(2) Å for the sodium and a = 17.9427(2), b = 7.5184(1), c = 9.7945(1) Å for the potassium sample. The crystal structure consists of a linked MgO₆–SO₄ layered network, where the space between the layers is filled with either potassium (K⁺) or Na⁺‐2H₂O units. The potassium‐bearing structure is isostructural to K₂Co₃(OH)₂(SO₄)₃ · 2(H₂O). The sodium compound has a similar crystal structure, where the bigger potassium ion is replaced by sodium ions and twice as many water molecules. Geometry optimization of the hydrogen positions were made with an empirical energy code.     

l‐Kynureninium sulfate dihydrate

In the structure of the title compound, 2‐(3‐ammonio‐3‐carboxy­propanoyl)‐1‐anilinium sulfate dihydrate, C₁₀H₁₄N₂O₃²⁺·SO₄^2?·2H₂O, the two amino groups are proton­ated. The mol­ecule has a trans planar zigzag carbon‐skeletal conformation elongated nearly in the benzene ring plane. The two amino and the carboxyl groups are located on the same side of the mol­ecule. The crystal structure is stabilized by intermolecular hydrogen bonds involving the water mol­ecules and the sulfate ion.     

New Structure Type among Octahydrated Rare‐Earth Sulfates, β‐Ce2(SO4)3·8H2O,and a new Ce2(SO4)3·4H2O Polymorph

Syntheses, crystal structures and thermal behavior of two new hydrated cerium(III) sulfates are reported, Ce₂(SO₄)₃·4H₂O ( I ) and β‐Ce₂(SO₄)₃·8H₂O ( II ), both forming three‐dimensional networks. Compound I crystallizes in the space group P2₁/n. There are two non‐equivalent cerium atoms in the structure of I , one nine‐ and one ten‐fold coordinated to oxygen atoms. The cerium polyhedra are edge sharing, forming helically propagating chains, held together by sulfate groups. The structure is compact, all the sulfate groups are edge‐sharing with cerium polyhedra and one third of the oxygen atoms, belonging to sulfate groups, are in the S–Oμ₃–Ce₂ bonding mode. Compound II constitutes a new structure type among the octahydrated rare‐earth sulfates which belongs to the space group Pn. Each cerium atom is in contact with nine oxygen atoms, these belong to four water molecules, three corner sharing and one edge sharing sulfate groups. The crystal structure is built up by layers of [Ce(H₂O)₄(SO₄)]_nⁿ⁺ held together by doubly edge sharing sulfate groups. The dehydration of II is a three step process, forming Ce₂(SO₄)₃·5H₂O, Ce₂(SO₄)₃·4H₂O and Ce₂(SO₄)₃, respectively. During the oxidative decomposition of the anhydrous form, Ce₂(SO₄)₃, into the final product CeO₂, small amount of CeO(SO₄) as an intermediate species was detected.     

The Upper Limit of Luminol's Amphiprotism: The Crystal Structure of 5-Ammonium-2-hydro-1,4-phthalzinediol Sulfate(IV)

Luminol is chemically sufficiently stable to be diprotonated at high proton concentrations as provided by concentrated sulfuric acid. The luminol dication (5-ammonium-2-hydro-1,4-phthalzinediol) sulfate was isolated as macroscopic single crystals and its structure was determined and refined from single-crystal X-ray data collected at 173 K [cell parameters: a = 8.3994(17) Å, b = 6.9985(14) Å, c = 17.486(4) Å, β = 90.85(3)°, V = 1027.8(4) ų, space group P2₁/c]. The structure is comprised of layers stacked along the b axis. Intralayer interactions are accomplished by strong hydrogen bonds of three luminol dications to one central [SO₄]^2– ion. Interlayer interactions are formed by weak hydrogen bonds of one luminol dication to two [SO₄]^2– ions in the adjacent layers, respectively, and alternating sandwich and parallel-displaced π-π-stacking of the 1-hydropyridazine-3,6-diol moieties of luminol dications in adjacent layers, respectively.     

(BETS)2[Fe(tdas)2]2: a new metal in the molecular conductor family

The structure of bis­[4,5‐ethyl­enedi­thio‐2‐(4,5‐ethyl­enedi­thio‐1,3‐diselena­cyclo­pent‐4‐en‐2‐yl­idene)‐1,3‐diselena­cyclo­pent‐4‐enium] bis(μ‐1,2,5‐thia­diazo­le‐3,4‐di­thiol­ato‐κ³S⁴,S⁵:S⁴)bis[(1,2,5‐thia­diazo­le‐3,4‐di­thiol­ato‐κ²S⁴,S⁵)­iron(III)], (BETS)₂[Fe(tdas)₂]₂ [BETS is alternatively called bis­(ethyl­enedi­thio)­tetraselenafulvalenium] or (C₁₀H₈S₄Se₄)₂[{Fe(C₂N₂S₃)₂}₂], consists of segregated columns of dimers of BETS and columns of dimers of [Fe(tdas)₂]. Each dimer displays inversion symmetry. Numerous chalcogen–chalcogen contacts are observed within and between the columns, producing a network of interactions responsible for the metal‐like behaviour of the compound.     

Li+ cation coordination in [Li2(CF3SO3)2(diglyme)] and [Li3(C2F3O2)3(diglyme)]

The title compounds, poly­[[[bis(2‐methoxy­ethyl) ether]­lithium(I)]‐di‐μ₃‐tri­fluoro­methanesulfonato‐lithium(I)], [Li₂(CF₃SO₃)₂(C₆H₁₄O₃)]_n, and poly­[[[bis(2‐methoxy­ethyl) ether]­lithium(I)]‐di‐μ₃‐tri­fluoro­acetato‐dilithium(I)‐μ₃‐tri­fluoro­acetato], [Li₃(C₂F₃O₂)₃(C₆H₁₄O₃)]_n, consist of one‐dimensional polymer chains. Both structures contain five‐coordinate Li⁺ cations coordinated by a tridentate diglyme [bis(2‐methoxy­ethyl) ether] mol­ecule and two O atoms, each from separate anions. In both structures, the [Li(diglyme)X₂]^? (X is CF₃SO₃ or CF₃CO₂) fragments are further connected by other Li⁺ cations and anions, creating one‐dimensional chains. These connecting Li⁺ cations are coordinated by four separate anions in both compounds. The CF₃SO₃^? and CF₃CO₂^? anions, however, adopt different forms of cation coordination, resulting in differences in the connectivity of the structures and solvate stoichiometries.     

Dy2(SO3)2(SO4)(H2O)2: the first lanthanide mixed sulfate–sulfite inorganic compound

The first lanthanide mixed sulfate–sulfite inorganic coordination polymer, poly[diaqua‐μ₄‐sulfato‐di‐μ₄‐sulfito‐didysprosium(III)], [Dy₂(SO₃)₂(SO₄)(H₂O)₂]_n, has been obtained, in which both sulfate and sulfite groups originate from the disproportionation of S₂O₃²⁻ under hydrothermal and weakly acidic conditions. The crystal structure of the title compound exhibits a three‐dimensional framework. The Dy^III ion is surrounded by eight O atoms from one water molecule and two sulfate and five sulfite groups. These DyO₈ polyhedra have two shared edges and form an infinite zigzag Dy—O chain. In the bc plane, neighbouring chains are integrated through SO₃ trigonal pyramids, forming a two‐dimensional sheet. Along the a‐axial direction, the sulfate group, with the central S atom lying on a twofold axis, links adjacent two‐dimensional sheets via two S—O—Dy connections, thus generating the three‐dimensional framework.     

An unusual P312 framework for the Ni(4,4′‐bipyridine)(H2O)4 chain

catena‐Poly[[[tetra­aqua­nickel(II)]‐μ‐4,4′‐bipyridine‐κ²N:N′] thio­sulfate dihydrate], {[Ni(C₁₀H₈N₂)(H₂O)₄]S₂O₃·2H₂O}_n, (I), and catena‐poly[[[tetra­aqua­nickel(II)]‐μ‐4,4′‐bipyridine‐κ²N:N′] sulfate methanol solvate monohydrate], {[Ni(C₁₀H₈N₂)(H₂O)₄]SO₄·CH₄O·H₂O}_n, (II), are built up of {[Ni(4,4′‐bipy)(H₂O)₄]²⁺}_n chains (4,4′‐bipy is 4,4′‐bipyridine) inter­woven in an unusual P3₁ fashion. Voids are filled by the corresponding counter‐anions and solvate mol­ecules, defining a complex three‐dimensional network surrounding them. In both structures, the cationic chains evolve around a set of twofold axes passing through the Ni^II ions and bis­ecting the aromatic amines through their N (and their opposite C) atoms.     

Hydro­gen bonding in calcium–tri­fluoro­methane­sulfonate–1,3‐di‐4‐pyridyl­urea–methanol (1/2/2/4)

The structure of the supramolecular complex calcium–tri­fluoro­methane­sulfonate–1,3‐di‐4‐pyridyl­urea–methanol (1/2/2/4), Ca²⁺·2CF₃SO₃⁻·2C₁₁H₁₀N₄O·4CH₄O, is presented. The Ca²⁺ ion lies on an inversion centre and is octahedrally coordinated by four methanol mol­ecules and two tri­fluoro­methane­sulfonate counter‐ions. The molecular packing is dominated by hydrogen‐bonded sheets in the (110) plane which contain R(32) rings; in these rings, significant π–π interactions are observed between inversion‐related 1,3‐di‐4‐pyridyl­urea mol­ecules.