Crystal structure and topology of two new thiosulfates formed with mono- and diprotonated species of 1-methylpiperazine is reported.

In this study, we report the results of continuous rotation electron diffraction studies of single DyPO4·nH2O (rhabdophane) nanocrystals. The diffraction patterns can be fit to a trigonal lattice (P3121) with lattice parameters a = 7.019 (5) and c = 6.417 (5) Å. However, there is also a set of diffuse background scattering features present that are associated with a disordered superstructure that is double these lattice parameters and fits with an arrangement of water mol­ecules present in the structure pore. Pair distribution function (PDF) maps based on the diffuse background allowed the extent of the water correlation to be estimated, with 2–3 nm correlation along the c axis and ∼5 nm along the a/b axis.

K3FeTe2O8(OH)2(H2O)2 was synthesized under hydrothermal conditions from Te(OH)6, FeSO4·7H2O and 85 wt% KOH in a 1:2:6 molar ratio. The crystal structure is built of a triperiodic network. One disordered water molecule per formula unit is located in a channel and can be partially removed by heating. Systematic one-dimensional diffuse scattering indicates a polytypic character, which is best described by application of the order–disorder theory. The major polytype is monoclinic with pseudo-orthorhombic metrics. It is interrupted by fragments of an orthorhombic polytype. The diffraction intensities are analyzed using structure factor calculations.

Organic–inorganic hybrid crystals have diverse functionalities, for example in energy storage and luminescence, due to their versatile structures. The synthesis and structural characterization of a new cobalt–vanadium-containing compound, 2[Co(en)3]3+(V4O13)6−·4H2O (1) is presented. The crystal structure of 1, consisting of [Co(en)3]3+ complexes and chains of corner-sharing (VO4) tetrahedra, was solved by single-crystal X-ray diffraction in the centrosymmetric space group P1. Phase purity of the bulk material was confirmed by infrared spectroscopy, scanning electron microscopy, elemental analysis and powder X-ray diffraction. The volume expansion of 1 was found to be close to 1% in the reported temperature range from 100 to 300 K, with a volume thermal expansion coefficient of 56 (2) × 10−6 K−1. The electronic band gap of 1 is 2.30 (1) eV, and magnetic susceptibility measurements showed that the compound exhibits a weak paramagnetic response down to 1.8 K, probably due to minor CoII impurities (<1%) on the CoIII site.

A new lanthanide coordination polymer, poly[[tri­aqua­bis­(μ4-phthalato)(μ3-pyridine-2,5-di­carboxyl­ato)dipraseodymium] monohydrate], {[Pr2(C7H3NO4)2(C8H4O4)(H2O)3]·H2O}n or {[Pr2(phth)2(pydc)(H2O)3]·H2O}n, (pydc2− = pyridine-2,5-di­carboxyl­ate and phth2− = phthalate) was synthesized and characterized, revealing the structure to be an assembly of di-periodic {Pr2(pydc)(phth)2(H2O)3}n layers. Each layer is built up by edge-sharing {Pr2N2O14} and {Pr2O16} dimers, which are connected through a new coordin­ation mode of pydc2− and phth2−. These layers are stabilized by inter­nal hydrogen bonds and π–π inter­actions. In addition, a three-dimensional supra­molecular framework is built by inter­layer hydrogen-bonding inter­actions involving the non-coordinated water mol­ecule. Thermogravimetric analysis shows that the title compound is thermally stable up to 400°C.

The crystal structure of the title compound {systematic name: (4S,4aS,5aR,12aR)-4,7-bis­(di­methyl­amino)-9-[(2,2-di­methyl­propyl­amino)­meth­yl]-1,10,11,12a-tetra­hydroxy-3,12-dioxo-4a,5,5a,6-tetra­hydro-4H-tetra­cene-2-carb­oxamide dihydrate, C29H40N4O7·2H2O} has been solved and refined using synchrotron X-ray powder diffraction data: it crystallizes in space group R3 with a = 24.34430 (7), c = 14.55212 (4) Å, V = 7468.81 (2) Å3 and Z = 9. Most of the hydrogen bonds are intra­molecular, but two classical N—H⋯O inter­molecular hydrogen bonds (along with probable weak C—H⋯O and C—H⋯N hydrogen bonds) link the mol­ecules into a three-dimensional framework. The framework contains voids, which contain disordered water mol­ecules. Keto–enol tautomerism is apparently important in this mol­ecule, and the exact mol­ecular structure is ambiguous.

This study introduces bis­[hexa­kis­(nitrato-κ2O,O')lanthanum(III)] tris­[hexa­aqua­nickel(II)] hexa­hydrate, [La(NO3)6]2[Ni(H2O)6]3·6H2O, with a structure refined in the hexa­gonal space group Roverline{3}. The salt com­prises [La(NO3)6]3− icosa­hedra and [Ni(H2O)6]2+ octa­hedra, thus forming an intricate network of inter­penetrating honeycomb lattices arranged in layers. This arrangement is stabilized through strong hydrogen bonds. Two successive layers are connected via the second [Ni(H2O)6]2+ octa­hedra, forming sheets which are stacked perpendicular to the c axis and held in the crystal by van der Waals forces. The synthesis of [La(NO3)6]2[Ni(H2O)6]3·6H2O involves dissolving lanthanum(III) and nickel(II) oxides in nitric acid, followed by slow evaporation, yielding green hexa­gonal plate-like crystals.

Crystal formation of penta­sodium nona­deca­cesium tetra­cosa­tungstate(VI) heneikosahydrate, Na5Cs19[W24O84]·21H2O, was successfully achieved by the conversion of [H2W12O42]10− through the addition of excess Cs+. The crystal structure comprising the toroidal isopolyoxidometalate is presented, as well as its Raman spectrum. Na5Cs19(H2O)21W24O84 crystallizes in the rhombohedral space group Roverline{3} with an obverse centering. The title compound represents the addition of a new member to the isopolytungstate family with mixed alkali counter-ions and contains rarely observed five-coordinate tungsten(VI) atoms in the [W24O84]24− anion (site symmetry C3i) arising from the conversion mediated by Cs+ counter-ions.

The title compound, bis­[di­thio­bis­(formamidinium)] hexa­bromido­ruthenium dibromide trihydrate, [(NH2)2CSSC(NH2)2]2[RuBr6]Br2·3H2O, crystallizes in the ortho­rhom­bic system, space group Cmcm, Z = 4. The [RuBr6]2− anionic complex has an octa­hedral structure. The Ru—Br distances fall in the range 2.4779 (4)–2.4890 (4) Å. The S—S and C—S distances are 2.0282 (12) and 1.783 (2) Å, respectively. The H2O mol­ecules, Br− ions, and NH2 groups of the cation are linked by hydrogen bonds. The conformation of the cation is consolidated by intra­molecular O—H⋯Br, O—H⋯O, N—H⋯Br and N—H⋯O hydrogen bonds. The [(NH2)2CSSC(NH2)2]2+ cations form a hydrogen-bonded system involving the Br − ions and the water mol­ecules. Two Br − anions form four hydrogen bonds, each with the NH2 groups of two cations, thus linking the cations into a ring. The rings are connected by water mol­ecules, forming N—H⋯O—H⋯Br hydrogen bonds.

In the title compound, bis­[aqua­(2,2'-bi­pyridine)­fluorido­tin(II)] hexa­fluorido­tin(IV), [SnF(C10H8N2)(H2O)]2[SnF6], an ionic mixed-valent tin(II)–tin(IV) compound, the bivalent tin atom is the center atom of the cation and the tetra­valent tin atom is the center atom of the anion. With respect to the first coordination sphere, the cation is monomeric, with the tin(II) atom having a fourfold seesaw coordination with a fluorine atom in an equatorial position, a water mol­ecule in an axial position and the two nitro­gen atoms of the chelating 2,2'-bi­pyridine ligand in the remaining axial and equatorial positions. The bond lengths and angles of this hypervalent first coordination sphere are described by 2c–2e and 3c–4e bonds, respectively, all of which are based on the orthogonal 5p orbitals of the tin atom. In the second coordination sphere, which is based on an additional, very long tin–fluorine bond that leads to dimerization of the cation, the tin atom is trapezoidal–pyramidally coordinated. The tetra­valent tin atom of the centrosymmetric anion has an octa­hedral coordination. The differences in its tin–fluorine bond lengths are attributed to hydrogen bonding, as the two of the four fluorine atoms are each involved in two hydrogen bonds, linking anions and cations together to form strands.

The present study focuses on the synthesis and structural characterization of a novel dinuclear CuII complex, [tri­chlorido­copper(II)]-μ-chlorido-{bis­[2-hy­droxy-N'-(propan-2-yl­idene)benzohydrazide]copper(II)} monohydrate, [Cu2Cl4(C10H12N2O2)2]·H2O or [Cu(H2L)2(μ-Cl)CuCl3]·H2O [H2L = 2-hy­droxy-N'-(propan-2-yl­idene)benzohydrazide]. The complex crystallizes in the monoclinic space group P21/n with one mol­ecule of water, which forms inter­actions with the ligands. The first copper ion is penta-coordinated to two benzohydrazine-derived ligands via two nitro­gen and two oxygen atoms, and one bridging chloride, which is also coordinated by the second copper ion alongside three terminal chlorines in a distorted tetra­hedral geometry. The arrangement around the first copper ion exhibits a distorted geometry inter­mediate between trigonal bipyramidal and square pyramidal. In the crystal, chains are formed via inter­molecular inter­actions along the a-axis direction, with subsequent layers constructed through hydrogen-bonding inter­actions parallel to the ac plane, and through slipped π–π stacking inter­actions parallel to the ab plane, resulting in a three-dimensional network. The inter­molecular inter­actions in the crystal structure were qu­anti­fied and analysed using Hirshfeld surface analysis. Residual electron density from disordered methanol mol­ecules in the void space could not be reasonably modelled, thus a solvent mask was applied.

The crystal structure of the title compound, hexa­aqua­nickel(II) dichloride–1,4,7,10,13,16-hexa­oxa­cyclo­octa­deca­ne–water (1/2/2), [Ni(H2O)6]Cl2·2C12H24O6·2H2O, is reported. The asymmetric unit contains half of the Ni(OH2)6 moiety with a formula of C12H32ClNi0.50O10 at 105 K and triclinic (P1) symmetry. The [Ni(OH2)6]2+ cation has close to ideal octa­hedral geometry with O—Ni—O bond angles that are within 3° of idealized values. The supra­molecular structure includes hydrogen bonding between the water ligands, 18-crown-6 mol­ecules, Cl− anions, and co-crystallized water solvent. Two crown ether mol­ecules flank the [Ni(OH2)6]2+ mol­ecule at the axial positions in a sandwich-like structure. The relatively symmetric hydrogen-bonding network is enabled by small Cl− counter-ions and likely influences the more idealized octa­hedral geometry of [Ni(OH2)6]2+.

Xylem, in conjunction with its Goulds Water Technology brand, is engaged in regular water well initiatives to provide secure water access to rural areas, striving to increase public awareness of the challenges surrounding lack of water access.

Island H2O Live Water Park plans Glow Foam Party for April 29 at the Kissimmee attraction.

The redetermination of the crystal structure of barium oxidotellurate(IV) monohydrate allowed the localization of the hydrogen atoms that were not determined in the previous study [Nielsen, Hazell & Rasmussen (1971). Acta Chem. Scand. 25, 3037–3042], thus making an unambiguous assignment of the hydrogen-bonding scheme possible. The crystal structure shows a layered arrangement parallel to (001), consisting of edge-sharing [BaO6(H2O)] polyhedra and flanked by isolated [TeO3] trigonal pyramids on the top and bottom. O—H⋯O hydrogen bonds of medium strength link adjacent layers along [001].

The title compound, d-(+)-glucosa­mmonium potassium tetra­thio­cyanato­cobaltate(II) dihydrate, K(C6H14NO5)[Co(NCS)4]·2H2O or (GlcNH)(K)[Co(NCS)4]·2H2O, has been obtained as a side product of an incomplete salt metathesis reaction of d-(+)-glucosa­mine hydro­chloride (GlcN·HCl) and K2[Co(NCS)4]. The asymmetric unit contains a d-(+)-glucos­ammonium cation, a potassium cation, a tetra­iso­thio­cyanato­cobalt(II) complex anion and two water mol­ecules. The water mol­ecules coordinate to the potassium cation, which is further coordinated via three short K+⋯SCN− contacts involving three [Co(NCS)4]2− complex anions and via three O atoms of two d-(+)-glucosa­mmonium cations, leading to an overall eightfold coordination around the potassium cation. Hydrogen-bonding inter­actions between the building blocks consolidate the three-dimensional arrangement.

The title carbonate hydrate, Cs2Mg4(CO3)5·10H2O, was crystallized at room temperature out of aqueous solutions containing caesium bicarbonate and magnesium nitrate. Its monoclinic crystal structure (P21/n) consists of double chains of composition 1∞[Mg(H2O)2/1(CO3)3/3], isolated [Mg(H2O)(CO3)2]2– units, two crystallographically distinct Cs+ ions and a free water mol­ecule. The crystal under investigation was twinned by reticular pseudomerohedry.

Rb0.21(H2O)yWS2, rubidium hydrate di­thio­tungstate, is a new quasi two-dimensional sulfide. Its crystal structure consists of ordered WS2 layers, separated by disordered Rb+ ions and water mol­ecules. All atomic sites are located on mirror planes. The WS2 layers are composed of edge-sharing [WS6] octa­hedra and extend parallel to (001). The presence of structural water was revealed by thermogravimetry, but the position and exact amount could not be determined in the present study. The temperature dependence of the electrical resistance indicates that Rb0.21(H2O)yWS2 is semiconducting between 80–300 K.

The title hydrated salt, tris­[hexa­amminecobalt(III)] tetraoxidorhenate(VII) tetra­kis­[hexa­fluorido­rhenate(IV)] hexa­hydrate, arose unexpectedly due to possible contamination of the K2ReF6 starting material with KReO4. It consists of octa­hedral [Co(NH3)6]3+ cation (Co1 site symmetry 1), tetra­hedral [ReVIIO4]− anions (Re site symmetry 1) and octa­hedral [ReIVF6]2− anions (Re site symmetries 1and overline{3}). The [ReF6]2− octa­hedral anions (mean Re—F = 1.834 Å), [Co(NH3)6]3+ octa­hedral cations (mean Co—N = 1.962 Å), and the [ReO4]− tetra­hedral anion (mean Re—O = 1.719 Å) are slightly distorted. A network of N—H⋯F hydrogen bonds consolidates the structure. The crystal studied was refined as a two-component twin.

The syntheses and crystal structures of three hybrid perovskites, viz. poly[1-methyl­piperizine-1,4-diium [tri-μ-bromido-potassium] hemihydrate], {(C5H14N2)[KBr3]·0.5H2O}n, (I), poly[1-methyl­piperizine-1,4-diium [tri-μ-bromido-rubidium] hemihydrate], {(C5H14N2)[RbBr3]·0.5H2O}n, (II), and poly[1-methyl­piperizine-1,4-diium [tri-μ-bromido-caesium] hemihydrate], {(C5H14N2)[CsBr3]·0.5H2O}n, (III), are described. These isostructural (space group Amm2) phases contain a three-dimensional, corner-sharing network of distorted ABr6 octa­hedra (A = K, Rb, Cs) with the same topology as the classical perovskite structure. The doubly protonated C5H14N22+ cations occupy inter­stices bounded by eight octa­hedra and the water mol­ecules lie in square sites bounded by four octa­hedra. N—H⋯Br, N—H⋯(Br,Br), N—H⋯O and O—H⋯Br hydrogen bonds consolidate the structures.

Highly Brønsted-acidic boron trifluoride monohydrate, a widely used `super acid-catalyst', is a colourless fuming liquid that releases BF3 at room temperature. Com­pared to the liquid com­ponents, i.e. boron trifluoride monohydrate and 1,4-dioxane, their 1:1 adduct, BF3H2O·C4H8O2, is a solid with pronounced thermal stability (m.p. 401–403 K). The crystal structure of the long-time-stable easy-to-handle and weighable com­pound is reported along with new preparative aspects and the results of 1H, 11B, 13C and 19F spectroscopic investigations, particularly documenting its high Brønsted acidity in aceto­nitrile solution. The remarkable stability of solid BF3H2O·C4H8O2 is attributed to the chain structure established by O—H⋯O hydrogen bonds of exceptional strength {O2⋯H1—O1 [O⋯O = 2.534 (3) Å] and O1—H1⋯O3i [2.539 (3) Å] in the concatenating unit >O2⋯H1—O1—H2⋯O3i<}, taking into account the mol­ecular (non-ionic) character of the structural moieties. Indirectly, this structural feature documents the outstanding acidification of the H2O mol­ecule bound to BF3 and reflects the super acid nature of BF3H2O. In detail, the C22(7) zigzag chain system of hydrogen bonding in the title structure is characterized by the double hydrogen-bond donor and double (κO,κO') hydrogen-bond acceptor functionality of the aqua ligand and dioxane molecule, respectively, the almost equal strength of both hydrogen bonds, the approximatety linear arrangement of the dioxane O atoms and the two neighbouring water O atoms. Furthermore, the approximately planar arrangement of B, F and O atoms in sheets perpendicular to the c axis of the ortho­rhom­bic unit cell is a characteristic structural feature.

A peptide biphenyl hybrid compound {systematic name: dimethyl 2,2'-[((2S,2'S)-2,2'-{[(2S,2'S)-1,1'-([1,1'-biphen­yl]-2,2'-dicarbon­yl)bis­(pyrrolidine-1,2-diyl-2-carbon­yl)]bis­(aza­nedi­yl)}bis­(3-phenyl­propano­yl))bis­(aza­nedi­yl)](2S,2'S)-dipropionate hemihydrate}, C50H56N6O10·0.5H2O, was prepared by coupling of [1,1'-biphen­yl]-2,2'-dicarbonyl dichloride, tri­ethyl­amine and the tripeptide Pro–Phe–Ala in CH2Cl2 at 273 K under an N2 atmosphere. In the crystal, the asymmetric unit contains the peptide biphenyl hybrid accompanied by one-half of a water mol­ecule. A C atom of one of the proline rings is disordered between two positions in a 0.746 (11):0.254 (11) ratio. An important structural aspect of peptide compounds is their capacity to self-associate mediated by inter­molecular and intra­molecular hydrogen bonding. This characteristic can be useful in understanding the inter­actions between peptides and biomacromolecular targets, as well as to explain peptide properties.

The title compound, di­aqua­[tris­(2-amino­eth­yl)amine]­nickel(II) hexa­aqua­nickel(II) bis­(sulfate), [Ni(C6H18N4)(H2O)2][Ni(H2O)6](SO4)2 or [Ni(tren)(H2O)2][Ni(H2O)6](SO4)2, consists of two octa­hedral nickel complexes within the same unit cell. These metal complexes are formed from the reaction of [Ni(H2O)6](SO4) and the ligand tris­(2-amino­eth­yl)amine (tren). The crystals of the title compound are purple, different from those of the starting complex [Ni(H2O)6](SO4), which are turquoise. The reaction was performed both in a 1:1 and 1:2 metal–ligand molar ratio, always yielding the co-precipitation of the two types of crystals. The asymmetric unit of the title compound, which crystallizes in the space group Pnma, consists of two half NiII complexes and a sulfate counter-anion. The mononuclear cationic complex [Ni(tren)(H2O)2]2+ comprises an Ni ion, the tren ligand and two water mol­ecules, while the mononuclear complex [Ni(H2O)6]2+ consists of another Ni ion surrounded by six coordinated water mol­ecules. The [Ni(tren)(H2O)2] and [Ni(H2O)6] subunits are connected to the SO42− counter-anions through hydrogen bonding, thus consolidating the crystal structure.

In the title mol­ecular salt, 1,3-dimethyl-2,6-dioxo-2,3,6,7-tetra­hydro-1H-purin-9-ium aqua­tri­chlorido­zincate(II), (C7H9N4O2)[ZnCl3(H2O)], the fused ring system of the cation is close to planar, with the largest deviation from the mean plane being 0.037 (3) Å. In the complex anion, the ZnII cation is coordinated by three chloride ions and one oxygen atom from the water ligand in a distorted tetra­hedral geometry. In the crystal, inversion dimers between pairs of cations linked by pairwise N—H⋯O hydrogen bonds generate R22(10) rings. The anions are linked into dimers by pairs of O—H⋯Cl hydrogen bonds and the respective dimers are linked by O—H⋯O and N—H⋯Cl hydrogen bonds. Together, these generate a three-dimensional supra­molecular network. Hirshfeld surfaces were generated to gain further insight into the packing.

The redetermined structure [for the previous study, see: Godfrey & Waters (1975). Cryst. Struct. Commun. 4, 5–8] of ammonium μ-oxido-μ-[1,5,6-tri­hydroxy­hexane-2,3,4-tris­(olato)]bis­[dioxidomolybdenum(V)] monohydrate, NH4[Mo2(C6H11O6)O5]·H2O, was obtained from an attempt to prepare a glutamic acid complex from the [Co2Mo10H4O38]6− anion. Subsequent study indicated the complex arose from a substantial impurity of mannitol in the glutamic acid sample used. All hydrogen atoms have been located in the present study and the packing displays N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds. A Hirshfeld surface analysis was also performed.

The syntheses and crystal structures of three mol­ecular salts of protonated 3,4-di­amino­benzoic acid, viz. 2-amino-5-carb­oxy­anilinium chloride, C7H9N2O2+·Cl−, (I), 2-amino-5-carb­oxy­anilinium bromide, C7H9N2O2+·Br−, (II), and 2-amino-5-carb­oxy­anilinium nitrate monohydrate, C7H9N2O2+·NO3−·H2O, (III), are described. The cation is protonated at the meta-N atom (with respect to the carb­oxy group) in each case. In the crystal of (I), carb­oxy­lic acid inversion dimers linked by pairwise O—H⋯O hydrogen bonds are seen and each N—H group forms a hydrogen bond to a chloride ion to result in (100) undulating layers of chloride ions bridged by the inversion dimers into a three-dimensional network. The extended structure of (II) features O—H⋯Br, N—H⋯Br and N—H⋯O hydrogen bonds: the last of these generates C(7) chains of cations. Overall, the packing in (II) features undulating (100) sheets of bromide ions alternating with the organic cations. Inter­molecular inter­actions in the crystal of (III) include O—H⋯O, O—H⋯(O,O), N—H⋯O, N—H⋯N and O—H⋯N links. The cations are linked into (001) sheets, and the nitrate ions and water mol­ecules form undulating chains. Taken together, alternating (001) slabs of organic cations plus anions/water mol­ecules result. Hirshfeld surfaces and fingerprint plots were generated to give further insight into the inter­molecular inter­actions in these structures. The crystal used for the data collection of (II) was twinned by rotation about [100] in reciprocal space in a 0.4896 (15):0.5104 (15) ratio.

During investigations of the formation of hydrated magnesium carbonates, a sample of the previously unknown magnesium carbonate hexa­hydrate (MgCO3·6H2O) was synthesized in an aqueous solution at 273.15 K. The crystal structure consists of edge-linked isolated pairs of Mg(CO3)(H2O)4 octa­hedra and noncoordinating water mol­ecules, and exhibits similarities to NiCO3·5.5H2O (hellyerite). The recorded X-ray diffraction pattern and the Raman spectra confirmed the formation of a new phase and its transformation to magnesium carbonate trihydrate (MgCO3·3H2O) at room temperature.

During evaporation of natural and synthetic K–Mg–Cl brines, the formation of almost square plate-like crystals of potassium carnallite (potassium chloride magnesium dichloride hexa­hydrate) was observed. A single-crystal structure analysis revealed a monoclinic cell [a = 9.251 (2), b = 9.516 (2), c = 13.217 (4) Å, β = 90.06 (2)° and space group C2/c]. The structure is isomorphous with other carnallite-type com­pounds, such as NH4Cl·MgCl2·6H2O. Until now, natural and synthetic carnallite, KCl·MgCl2·6H2O, was only known in its ortho­rhom­bic form [a = 16.0780 (3), b = 22.3850 (5), c = 9.5422 (2) Å and space group Pnna].