Geminal and vicinal bis­(tri­fluoro­methane­sulfonate) esters are highly reactive alkyl­ene synthons used as potent electrophiles in the macrocyclization of imid­azoles and the transformation of bypyridines to diquat derivatives via nucleophilic substitution reactions. Herein we report the crystal structures of methyl­ene (C3H2F6O6S2) and ethyl­ene bis­(tri­fluoro­methane­sulfonate) (C4H4F6O6S2), the first examples of a geminal and vicinal bis­(tri­fluoro­methane­sulfonate) ester characterized by single-crystal X-ray diffraction (SC-XRD). With melting points slightly below ambient temperature, both reported bis­(tri­fluoro­methane­sulfonate)s are air- and moisture-sensitive oils and were crys­tallized at 277 K to afford two-com­ponent non-merohedrally twinned crystals. The dominant inter­actions present in both com­pounds are non-classical C—H⋯O hydrogen bonds and inter­molecular C—F⋯F—C inter­actions between tri­fluoro­methyl groups. Mol­ecular electrostatic potential (MEP) cal­culations by DFT-D3 helped to qu­antify the polarity between O⋯H and F⋯F contacts to rationalize the self-sorting of both bis­(tri­fluoro­methane­sulfonate) esters in polar (non-fluorous) and non-polar (fluorous) domains within the crystal structure.

Mevalonate kinase is central to the isoprenoid biosynthesis pathway. Here, high-resolution X-ray crystal structures of two mevalonate kinases are presented: a eukaryotic protein from Ramazzottius varieornatus and an archaeal protein from Methanococcoides burtonii. Both enzymes possess the highly conserved motifs of the GHMP enzyme superfamily, with notable differences between the two enzymes in the N-terminal part of the structures. Biochemical characterization of the two enzymes revealed major differences in their sensitivity to geranyl pyrophosphate and farnesyl pyrophosphate, and in their thermal stabilities. This work adds to the understanding of the structural basis of enzyme inhibition and thermostability in mevalonate kinases.

The reaction between the (R,S)-fixolide 4-methyl­thio­semicarbazone and PdII chloride yielded the title compound, [Pd(C20H30N3S)2]·C2H6O {common name: trans-bis­[(R,S)-fixolide 4-methyl­thio­semicarbazonato-κ2N2S]palladium(II) ethanol monosolvate}. The asymmetric unit of the title compound consists of one bis-thio­semicarbazonato PdII complex and one ethanol solvent mol­ecule. The thio­semicarbazononato ligands act as metal chelators with a trans configuration in a distorted square-planar geometry. A C—H⋯S intra­molecular inter­action, with graph-set motif S(6), is observed and the coordination sphere resembles a hydrogen-bonded macrocyclic environment. Additionally, one C—H⋯Pd anagostic inter­action can be suggested. Each ligand is disordered over the aliphatic ring, which adopts a half-chair conformation, and two methyl groups [s.o.f. = 0.624 (2):0.376 (2)]. The disorder includes the chiral carbon atoms and, remarkably, one ligand has the (R)-isomer with the highest s.o.f. value atoms, while the other one shows the opposite, the atoms with the highest s.o.f. value are associated with the (S)-isomer. The N—N—C(=S)—N fragments of the ligands are approximately planar, with the maximum deviations from the mean plane through the selected atoms being 0.0567 (1) and −0.0307 (8) Å (r.m.s.d. = 0.0403 and 0.0269 Å) and the dihedral angle with the respective aromatic rings amount to 46.68 (5) and 50.66 (4)°. In the crystal, the complexes are linked via pairs of N—H⋯S inter­actions, with graph-set motif R22(8), into centrosymmetric dimers. The dimers are further connected by centrosymmetric pairs of ethanol mol­ecules, building mono-periodic hydrogen-bonded ribbons along [011]. The Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are [atoms with highest/lowest s.o.f.s considered separately]: H⋯H (81.6/82.0%), H⋯C/C⋯H (6.5/6.4%), H⋯N/N⋯H (5.2/5.0%) and H⋯S/S⋯H (5.0/4.9%).

In the structure of the title compound, C19H19N3O5S·C4H8O2, the two independent dioxane mol­ecules each display inversion symmetry. The pyrazole ring is approximately parallel to the aromatic ring of the oxy-ethanone group and approximately perpendicular to the tolyl ring of the sulfonyl substituent. An extensive system of classical and `weak' hydrogen bonds connects the residues to form a layer structure parallel to (201), within which dimeric subunits are conspicuous; neighbouring layers are connected by classical hydrogen bonds to dioxanes and by `weak' hydrogen bonds from Htol­yl donors.

The reaction of the Schiff base 2-[1-(pyridin-2-yl)ethyl­idene­amino]­ethanol (HL), which is formed by reaction of 2-amino­ethanol and 2-acetyl­pyridine with CuBr2 in ethanol results in the isolation of the new polymeric complex poly[hexa-μ-bromido-bis­{2-[1-(pyridin-2-yl)ethyl­idene­amino]­ethano­lato}tetra­copper(II)], [Cu4Br6(C9H11N2O)2]n or [Cu4Br6L2]n. The asymmetric unit of the crystal structure of the polymeric [Cu4Br6L2]n complex is composed by four copper (II) cations, two monodeprotonated mol­ecules of the ligand, and six bromide anions, which act as bridges. The ligand mol­ecules act in a tridentate fashion through their azomethine nitro­gen atoms, their pyridine nitro­gen atoms, and their alcoholate O atoms. The crystal structure shows two types of geometries in the coordination polyhedrons around Cu2+ ions. Two copper cations are situated in a square-based pyramidal environment, while the two other copper cations adopt a tetra­hedral geometry. Bromides anions acting as bridges between two metal ions connect the units, resulting in a tetra­nuclear polymer compound.

The title compound, N1,N2-di­methyl­ethane­dihydrazide, C4H10N4O2, was obtained by the methyl­ation of oxalyl dihydrazide protected with phthalimide. The mol­ecule is essentially non-planar with a dihedral angle between the two planar hydrazide fragments of 86.5 (2)°. This geometry contributes to the formation of a multi-contact three-dimensional supra­molecular network via C—H⋯O, N—H⋯O and N—H⋯N hydrogen bonds.

We report the synthesis and structural characterization of three crystalline borylated ortho-silylaryl tri­fluoro­methane­sulfonates: 5-(4,4,5,5-tetra­methyl-1,3,2-dioxaborolan-2-yl)-2-(tri­methyl­sil­yl)phenyl tri­fluoro­methane­sulfonate, C16H24BF3O5SSi (1a), 4-(4,4,5,5-tetra­methyl-1,3,2-dioxaborolan-2-yl)-2-(tri­methyl­sil­yl)phenyl tri­fluoro­methane­sulfonate, C16H24BF3O5SSi (1b), and 2-methyl-4-(4,4,5,5-tetra­methyl-1,3,2-dioxaborolan-2-yl)-6-(tri­methyl­silyl)phen­yl tri­fluoro­methane­sulfonate, C17H26BF3O5SSi (2), which are versatile aryne precursors. For all three compounds, the heteroatom substituents are almost coplanar with the central aromatic moiety. C—heteroatom bonding metrics are unexceptional and fall withing the typical range of C—B, C—Si, and C—O single bonds. Despite numerous electronegative sites, only weak inter­molecular inter­actions are observed in the solid state.

The title compound, C27H20N4O3S, crystallizes in the monoclinic system, space group P21/n, with Z = 4. The global shape of the mol­ecule is determined by the orientation of the substituents on the central 4H-1,2,4-triazole ring. The nitro­phenyl ring, phenyl ring, and naphthalene ring system are oriented at dihedral angles of 82.95 (17), 77.14 (18) and 89.46 (15)°, respectively, with respect to the triazole ring. The crystal packing features chain formation in the b-axis direction by S⋯O inter­actions. A Hirshfeld surface analysis indicates that the highest contributions to surface contacts arise from contacts in which H atoms are involved.

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 asymmetric unit of the title compound, 2C31H28N2O4S·C2H6O, contains a parent mol­ecule and a half mol­ecule of ethanol solvent. The main compound stabilizes its mol­ecular conformation by forming a ring with an R12(7) motif with the ethanol solvent mol­ecule. In the crystal, mol­ecules are connected by C—H⋯O and O—H⋯O hydrogen bonds, forming a three-dimensional network. In addition, C—H⋯π inter­actions also strengthen the mol­ecular packing.

Reaction of Co(NCS)2 with 4-methyl­pyridine N-oxide in methanol leads to the formation of crystals of the title compound, [Co2(NCS)4(C6H7NO)4(CH4O)2] or Co2(NCS)4(4-methyl­pyridine N-oxide)4(methanol)2. The asymmetric unit consist of one CoII cation, two thio­cyanate anions, two 4-methyl­pyridine N-oxide coligands and one methanol mol­ecule in general positions. The H atoms of one of the methyl groups are disordered and were refined using a split model. The CoII cations octa­hedrally coordinate two terminal N-bonded thio­cyanate anions, three 4-methyl­pyridine N-oxide coligands and one methanol mol­ecule. Each two CoII cations are linked by pairs of μ-1,1(O,O)-bridging 4-methyl­pyridine N-oxide coligands into dinuclear units that are located on centers of inversion. Powder X-ray diffraction (PXRD) investigations prove that the title compound is contaminated with a small amount of Co(NCS)2(4-meth­yl­pyridine N-oxide)3. Thermogravimetric investigations reveal that the methanol mol­ecules are removed in the beginning, leading to a compound with the composition Co(NCS)2(4-methyl­pyridine N-oxide), which has been reported in the literature and which is of poor crystallinity.

Two 2,4,6-tri­methyl­aniline-based trifuloro­methane­sulfonate (tri­fluoro­methane­sulfonate) salts were synthesized and characterized by single-crystal X-ray diffraction. N,2,4,6-Tetra­methyl­anilinium tri­fluoro­methane­sulfonate, [C10H14NH2+][CF3O3S−] (1), was synthesized via methyl­ation of 2,4,6-tri­methyl­aniline. N-Iso­propyl­idene-N,2,4,6-tetra­methyl­anilinium tri­fluoro­meth­ane­sulfonate, [C13H20N+][CF3O3S−] (2), was synthesized in a two-step reaction where the imine, N-iso­propyl­idene-2,4,6-tri­methyl­aniline, was first prepared via a dehydration reaction to form the Schiff base, followed by methyl­ation using methyl tri­fluoro­methane­sulfonate to form the iminium ion. In compound 1, both hydrogen bonding and π–π inter­actions form the main inter­molecular inter­actions. The primary inter­action is a strong N—H⋯O hydrogen bond with the oxygen atoms of the tri­fluoro­methane­sulfonate anions bonded to the hydrogen atoms of the ammonium nitro­gen atom to generate a one-dimensional chain. The [C10H14NH2+] cations form dimers where the benzene rings form a π–π inter­action with a parallel-displaced geometry. The separation distance between the calculated centroids of the benzene rings is 3.9129 (8) Å, and the inter­planar spacing and ring slippage between the dimers are 3.5156 (5) and 1.718 Å, respectively. For 2, the [C13H20N+] cations also form dimers as in 1, but with the benzene rings highly slipped. The distance between the calculated centroids of the benzene rings is 4.8937 (8) Å, and inter­planar spacing and ring slippage are 3.3646 (5) and 3.553 Å, respectively. The major inter­molecular inter­actions in 2 are instead a series of weaker C—H⋯O hydrogen bonds [C⋯O distances of 3.1723 (17), 3.3789 (18), and 3.3789 (18) Å], an inter­action virtually absent in the structure of 1. Fluorine atoms are not involved in strong directional inter­actions in either structure.

The title compound, C12H10N2O3, was obtained by the de­acetyl­ation reaction of 1-(6-amino-5-nitro­naphthalen-2-yl)ethanone in a concentrated sulfuric acid methanol solution. The mol­ecule comprises a naphthalene ring system bearing an acetyl group (C-3), an amino group (C-7), and a nitro group (C-8). In the crystal, the mol­ecules are assembled into a two-dimensional network by N⋯H/H⋯N and O⋯H/H⋯O hydrogen-bonding inter­actions. n–π and π–π stacking inter­actions are the dominant inter­actions in the three-dimensional crystal packing. Hirshfeld surface analysis indicates that the most important contributions are from O⋯H/H⋯O (34.9%), H⋯H (33.7%), and C⋯H/H⋯C (11.0%) contacts. The energies of the frontier mol­ecular orbitals were computed using density functional theory (DFT) calculations at the B3LYP-D3BJ/def2-TZVP level of theory and the LUMO–HOMO energy gap of the mol­ecule is 3.765 eV.

The few examples of structures containing the 2-chloro-N,N-di­methyl­ethan-1-aminium or 3-chloro-N,N-di­methyl­propan-1-aminium cations show a compet­ition between gauche and anti conformations for the chloro­alkyl chain. To explore further the conformational landscape of these cations, and their possible use as mol­ecular switches, the title salts, (C4H11ClN)2[CoCl4] and (C4H11ClN)2[ZnCl4], were prepared and structurally characterized. Details of both structures are in close agreement. The inorganic complex exhibits a slightly flattened tetra­hedral geometry that likely arises from bifurcated N—H hydrogen bonds from the organic cations. The alkyl chain of the cation is disordered between gauche and anti conformations with the gauche conformation occupancy refined to 0.707 (2) for the cobaltate. The gauche conformation places the terminal Cl atom at a tetra­hedral face of the inorganic complex with a contact distance of 3.7576 (9) Å to the Co2+ center. The anti conformation places the terminal Cl atom at a contact distance to a neighboring anti conformation terminal Cl atom that is ∼1 Å less than the sum of the van der Waals radii. Thus, if the anti conformation is present at a site, then the nearest neighbor must be gauche. DFT geometry optimizations indicate the gauche conformation is more stable in vacuo by 0.226 eV, which reduces to 0.0584 eV when calculated in a uniform dielectric. DFT geometry optimizations for the unprotonated mol­ecule indicate the anti conformation is stabilized by 0.0428 eV in vacuo, with no strongly preferred conformation in uniform dielectric, to provide support to the notion that this cation could function as a mol­ecular switch via deprotonation.

The title mol­ecule, C18H26O4, consists of two symmetrical halves related by the inversion centre at the mid-point of the central –C—C– bond. The hexene ring adopts an envelope conformation. In the crystal, the mol­ecules are connected into dimers by C—H⋯O hydrogen bonds with R22(8) ring motifs, forming zigzag ribbons along the b-axis direction. According to a Hirshfeld surface analysis, H⋯H (68.2%) and O⋯H/H⋯O (25.9%) inter­actions are the most significant contributors to the crystal packing. The contribution of some disordered solvent to the scattering was removed using the SQUEEZE routine [Spek (2015). Acta Cryst. C71, 9–18] in PLATON. The solvent contribution was not included in the reported mol­ecular weight and density.

The synthesis, crystallization and characterization of a tri­fluoro­methane­sulfonate salt of 5,10,15,20-tetra­kis­(1-benzyl­pyridin-1-ium-4-yl)-21H,23H-por­phy­rin, C68H54N84+·4CF3SO3−·4H2O, 1·OTf, are reported in this work. The reaction between 5,10,15,20-tetra­kis­(pyridin-4-yl)-21H,23H-porphyrin and benzyl bromide in the presence of 0.1 equiv. of Ca(OH)2 in CH3CN under reflux with an N2 atmosphere and subsequent treatment with silver tri­fluoro­methane­sulfonate (AgOTf) salt produced a red–brown solution. This reaction mixture was filtered and the solvent was allowed to evaporate at room temperature for 3 d to give 1·OTf. Crystal structure determination by single-crystal X-ray diffraction (SCXD) revealed that 1·OTf crystallizes in the space group P21/c. The asymmetric unit contains half a porphyrin mol­ecule, two tri­fluoro­methane­sulfonate anions and two water mol­ecules of crystallization. The macrocycle of tetra­pyrrole moieties is planar and unexpectedly it has coordinated CaII ions in occupational disorder. This CaII ion has only 10% occupancy (C72H61.80Ca0.10F12N8O16S4). The pyridinium rings bonded to methyl­ene groups from porphyrin are located in two different arrangements in almost orthogonal positions between the plane formed by the porphyrin and the pyridinium rings. The crystal structure features cation⋯π inter­actions between the CaII atom and the π-system of the phenyl ring of neighboring mol­ecules. Both tri­fluoro­methane­sulfonate anions are found at the periphery of 1, forming hydrogen bonds with water mol­ecules.

In the title complex, [U(C10H7N3O3)O2(CH3OH)]n, the UVI cation has a typical penta­gonal–bipyramidal environment with the equatorial plane defined by one N and two O atoms of one doubly deprotonated 2-[5-(2-hy­droxy­phen­yl)-1H-1,2,4-triazol-3-yl]acetic acid ligand, a carboxyl­ate O atom of the symmetry-related ligand and the O atom of the methanol mol­ecule [U—N/Oeq 2.256 (4)–2.504 (5) Å]. The axial positions are occupied by two oxide O atoms. The equatorial atoms are almost coplanar, with the largest deviation from the mean plane being 0.121 Å for one of the O atoms. The benzene and triazole rings of the tetra­dentate chelating–bridging ligand are twisted by approximately 21.6 (2)° with respect to each other. The carboxyl­ate group of the ligand bridges two uranyl cations, forming a neutral zigzag chain reinforced by a strong O—H⋯O hydrogen bond. In the crystal, adjacent chains are linked into two-dimensional sheets parallel to the ac plane by C/N—H⋯N/O hydrogen bonding and π–π inter­actions. Further weak C—H⋯O contacts consolidate the three-dimensional supra­molecular architecture. In the solid state, the compound shows a broad medium intensity LMCT transition centred around 463 nm, which is responsible for its red colour.

Two new [1-(phenyl­sulfon­yl)-1H-indol-2-yl]methanamine derivatives, namely, N-(3-meth­oxy­phen­yl)-N-{[1-(phenyl­sulfon­yl)-1H-indol-2-yl]meth­yl}acetamide, C24H22N2O4S, (I), and N-(2,5-di­meth­oxy­phen­yl)-N-{[1-(phenyl­sulfon­yl)-1H-indol-2-yl]meth­yl}benzene­sulfonamide, C29H26N2O6S2, (II), reveal a nearly orthogonal orientation of their indole ring systems and sulfonyl-bound phenyl rings. The sulfonyl moieties adopt the anti-periplanar conformation. For both compounds, the crystal packing is dominated by C—H⋯O bonding [C⋯O = 3.312 (4)–3.788 (8) Å], with the structure of II exhibiting a larger number, but weaker bonds of this type. Slipped π–π inter­actions of anti­parallel indole systems are specific for I, whereas the structure of II delivers two kinds of C—H⋯π inter­actions at both axial sides of the indole moiety. These findings agree with the results of Hirshfeld surface analysis. The primary contributions to the surface areas are associated with the contacts involving H atoms. Although II manifests a larger fraction of the O⋯H/H⋯O contacts (25.8 versus 22.4%), most of them are relatively distal and agree with the corresponding van der Waals separations.

In the structure of the title salt, {[Ba(μ3-C3H2N3O2)2(μ-H2O)(H2O)]·H2O}n, the barium ion and all three oxygen atoms of the water mol­ecules reside on a mirror plane. The hydrogen atoms of the bridging water and the solvate water mol­ecules are arranged across a mirror plane whereas all atoms of the monodentate aqua ligand are situated on this mirror plane. The distorted ninefold coord­ination of the Ba ions is completed with four nitroso-, two carbonyl- and three aqua-O atoms at the distances of 2.763 (3)–2.961 (4) Å and it is best described as tricapped trigonal prism. The three-dimensional framework structure is formed by face-sharing of the trigonal prisms, via μ-nitroso- and μ-aqua-O atoms, and also by the bridging coordination of the anions via carbonyl-O atoms occupying two out of the three cap positions. The solvate water mol­ecules populate the crystal channels and facilitate a set of four directional hydrogen bonds. The principal Ba–carbamoyl­cyano­nitro­somethanido linkage reveals a rare example of the inherently polar binodal six- and three-coordinated bipartite topology (three-letter notation sit). It suggests that small resonance-stabilized cyano­nitroso anions can be utilized as bridging ligands for the supra­molecular synthesis of MOF solids. Such an outcome may be anti­cipated for a broader range of hard Lewis acidic alkaline earth metal ions, which perfectly match the coordination preferences of highly nucleophilic nitroso-O atoms. Thermal analysis reveals two-stage dehydration of the title compound (383 and 473 K) followed by decomposition with release of CO2, HCN and H2O at 558 K.

The mol­ecular structure of the tripodal carbamoyl­methyl­phosphine oxide compound diethyl {[(5-[2-(di­eth­oxy­phosphor­yl)acetamido]-3-{2-[2-(di­eth­oxy­phos­phor­yl)acetamido]­eth­yl}pent­yl)carbamo­yl]meth­yl}phospho­nate, C25H52N3O12P3, features six intra­molecular hydrogen-bonding inter­actions. The phospho­nate groups have key bond lengths ranging from 1.4696 (12) to 1.4729 (12) Å (P=O), 1.5681 (11) to 1.5811 (12) Å (P—O) and 1.7881 (16) to 1.7936 (16) Å (P—C). Each amide group adopts a nearly perfect trans geometry, and the geometry around each phophorus atom resembles a slightly distorted tetra­hedron.

The mol­ecule of the title compound, [Ni(C5H7O2)2(C8H9N3)(H2O)]·C2H5OH, has triclinic (Poverline{1}) symmetry. This compound is of inter­est for its anti­microbial properties. The asymmetric unit comprises two independent complex mol­ecules, which are linked by N—H⋯O and O—H⋯O hydrogen bonds along [111]. Hirshfeld surface analysis indicates that 71.7% of inter­mol­ecular inter­actions come from H⋯H contacts, 17.7% from C⋯H/H⋯C contacts and 7.6% from O⋯H/H⋯O contacts, with the remaining contribution coming from N⋯H/H⋯N, C⋯N/N⋯C, C⋯C and O⋯O contacts.

Reaction of 4-methyl­pyridine N-oxide and Co(NCS)2 in ethanol as solvent accidentally leads to the formation of single crystals of Co(NCS)2(4-methyl­pyridine N-oxide)(ethanol) or [Co(NCS)2(C6H7NO)(C2H6O)]n. The asymmetric unit of the title compound consists of one CoII cation, two crystallographically independent thio­cyanate anions, one 4-methyl­pyridine N-oxide coligand and one ethanol mol­ecule on general positions. The cobalt cations are sixfold coordinated by one terminal and two bridging thio­cyanate anions, two bridging 4-methyl­pyridine N-oxide coligands and one ethanol mol­ecule, with a slightly distorted octa­hedral geometry. The cobalt cations are linked by single μ-1,3(N,S)-bridging thio­cyanate anions into corrugated chains, that are further connected into layers by pairs of μ-1,1(O,O)-bridging 4-methyl­pyridine N-oxide coligands. The layers are parallel to the bc plane and are separated by the methyl groups of the 4-methyl­pyridine N-oxide coligands. Within the layers, intra­layer hydrogen bonding is observed.

The title compound, [Cd(C14H16N3S)Cl] or [CdLCl] (1), where LH = 2-[bis­(pyridin-2-ylmeth­yl)amino]­ethane-1-thiol, was prepared and structurally characterized. The Cd2+ complex crystallizes in P21/c with a distorted trigonal–bipyramidal metal coordination geometry. Supra­molecular inter­actions in 1 include parallel offset face-to-face inter­actions between inversion-related pyridyl rings and potential hydrogen bonds with chlorine or sulfur as the acceptor. Additional cooperative pyrid­yl–pyridyl inter­actions with roughly 45° tilt angles and centroid–centroid distances of less than 5.5 Å likely also contribute to the overall solid-state stability. Hirshfeld surface analysis indicates that H⋯H (51.2%), Cl⋯H/H⋯Cl (13.9%), C⋯H/H⋯C (12.3%) and S⋯H/H⋯S (11.8%) inter­actions are dominant in the solid state.

Reaction of copper(I)chloride with 2,3-di­methyl­pyrazine in ethanol leads to the formation of the title compound, poly[[μ-chlorido-μ-(2,3-di­methyl­pyrazine)-copper(I)] ethanol hemisolvate], {[CuCl(C6H8N2)]·0.5C2H5OH}n or CuCl(2,3-di­methyl­pyrazine) ethanol hemisolvate. Its asymmetric unit consists of two crystallographically independent copper cations, two chloride anions and two 2,3-di­methyl­pyrazine ligands as well as one ethanol solvate mol­ecule in general positions. The ethanol mol­ecule is disordered and was refined using a split model. The methyl H atoms of the 2,3-di­methyl­pyrazine ligands are also disordered and were refined in two orientations rotated by 60° relative to each other. In the crystal structure, each copper cation is tetra­hedrally coordinated by two N atoms of two bridging 2,3-di­methyl­pyrazine ligands and two μ-1,1-bridg­ing chloride anions. Each of the two copper cations are linked by pairs of bridging chloride anions into dinuclear units that are further linked into layers via bridging 2,3-di­methyl­pyrazine coligands. These layers are stacked in such a way that channels are formed in which the disordered solvent mol­ecules are located. The topology of this network is completely different from that observed in the two polymorphic modifications of CuCl(2,3-di­methyl­pyrazine) reported in the literature [Jess & Näther (2006). Inorg. Chem. 45, 7446–7454]. Powder X-ray diffraction measurements reveal that the title compound is unstable and transforms immediately into an unknown crystalline phase.

The title compound, catena-poly[[tri­aqua­sodium]-di-μ-aqua-[tri­aqua­sodium]-μ-(ethane-1,2-di­yl)bis­[(3-meth­oxy­prop­yl)phosphinodi­thiol­ato]], [Na2(C10H22O2P2S4)(H2O)8]n, crystallizes in the triclinic space group P1. The dianionic [CH3O(CH2)3P(=S)(S—)CH2CH2P(=S)(S—)(CH2)3OCH3]2− ligand fragments are joined by a dicationic [Na2(H2O)8]2+ cluster that includes the oxygen of the meth­oxy­propyl unit of the ligand to form infinite chains.

The unit cell of the title compound, [Ni(C16H10ClN6)2]·2CH3OH, consists of a neutral complex and two methanol mol­ecules. In the complex, the two tridentate 2-(3-(4-chloro­phen­yl)-1H-1,2,4-triazol-5-yl)-6-(1H-pyrazol-1-yl)pyridine ligands coordinate to the central NiII ion through the N atoms of the pyrazole, pyridine and triazole groups, forming a pseudo­octa­hedral coordination sphere. Neighbouring tapered mol­ecules are linked through weak C—H(pz)⋯π(ph) inter­actions into monoperiodic chains, which are further linked through weak C—H⋯N/C inter­actions into diperiodic layers. The inter­molecular contacts were qu­anti­fied using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing the relative contributions of the contacts to the crystal packing to be H⋯H 32.8%, C⋯H/H⋯C 27.5%, N⋯H/H⋯N 15.1%, and Cl⋯H/H⋯Cl 14.0%. The average Ni—N bond distance is 2.095 Å. Energy framework analysis at the HF/3–21 G theory level was performed to qu­antify the inter­action energies in the crystal structure.

A new uranium metal–organic complex salt, [U(C10H9O2)2O2(C2H6O)], with benzoyl acetone, namely, bis­(benzoyl­acetonato)(ethanol)dioxidouranium(VI), was synthesized. The compound has monoclinic P21/n symmetry. The geometry of the seven-coordinate U atom is penta­gonal bipyramidal, with the uranyl oxygen atoms in apical positions. In the complex, the ligands bind to the metal through oxygen atoms. Additional weak O—H⋯O contacts between the cations and anions consolidate the three-dimensional arrangement of the structure. On the Hirshfeld surface, the largest contributions come from the short contacts such as van der Waals forces, including H⋯H, O⋯H and C⋯H. Inter­actions including C⋯C and O⋯C contacts were also observed; however, their contribution to the overall cohesion of the crystal structure is minor. A packing analysis was performed to check the strength of the crystal packing.

In this work, we showed that the use of ethanol to increase image contrast when imaging cardiac tissue with synchrotron X-ray phase-contrast imaging (X-PCI) leads to heterogeneous tissue shrinkage, which has an impact on the 3D organization of the myocardium.

The Lufthansa Group has teamed up with

File: Queen's Freddie Mercury has his mustache groomed.
; Credit: Steve Wood/Express/Getty Images

The new Queen compilation "Queen Forever" includes three previously unreleased tracks, but the one that has people talking is a collaboration between two legends: Freddie Mercury and Michael Jackson.

The new song, "There Must Be More to Life Than This," was an unfinished track recorded during studio sessions for the 1981 Queen album "Hot Space," according to a press release on the new compilation. Queen also looked at the song for 1984's "The Works," but still don't go with it — the song finally landed, sans Jackson, on 1985's Mercury solo album "Mr. Bad Guy."

Listen to the new version of the song here:

Michael Jackson/Queen Soundcloud

Listen to the originally recorded version of the Queen/Jackson collaboration below:

Michael Jackson/Queen collabo

The new version was produced by William Orbit, who also did a remix of the song.

"Hearing Michael Jackson's vocals was stirring. So vivid, so cool, and poignant, it was like he was in the studio singing live. With Freddie's vocal solo on the mixing desk, my appreciation for his gift was taken to an even higher level," Orbit said in a press release.

The song is a call for peace, talking human rights in a general way. It almost didn't end up on the album — Queen's Brian May said that working with the Jackson family and Jackson's estate was like "wading through glue," according to Philly.com, but the track ended up making the cut.

The album also includes unreleased song "Let Me In Your Heart Again" and a new version of a song Mercury released solo, an acoustic take on "Love Kills." "Let Me In Your Heart Again" was previously recorded and released by May's wife Anita Dobson.

"Freddie sounds as fresh as yesterday," May said at a press conference while the new compilation was in the works.

Listen to Mercury's solo version of "There Must Be More to Life Than This" below:

There Must Be More To Life Than This, solo

Listen to Anita Dobson's version of "Let Me In (Your Heart Again)" below:

Anita Dobson track

Full Text:

The Maya of Central America are thought to have been a kinder, gentler civilization, especially compared to the Aztecs of Mexico. At the peak of Mayan culture some 1,500 years ago, warfare seemed ritualistic, designed to extort ransom for captive royalty or to subjugate rival dynasties, with limited impact on the surrounding population. Only later, archeologists thought, did increasing drought and climate change lead to total warfare -- cities and dynasties were wiped off the map in so-called termination events -- and the collapse of the lowland Maya civilization around 1,000 A.D. (or C.E., current era). New evidence unearthed by National Science Foundation-funded researchers call all this into question, suggesting that the Maya engaged in scorched-earth military campaigns -- a strategy that aims to destroy anything of use, including cropland -- even at the height of their civilization, a time of prosperity and artistic sophistication. The finding also indicates that this increase in warfare, possibly associated with climate change and resource scarcity, was not the cause of the disintegration of the lowland Maya civilization.

Image credit: Francisco Estrada-Belli/Tulane

; Credit: /Rose Wong for NPR/KHN

Claire Lang-Ree was in a lab coat taking a college chemistry class remotely in the kitchen of her Colorado Springs, Colo., home, when a profound pain twisted into her lower abdomen. She called her mom, Jen Lang-Ree, a nurse practitioner who worried it was appendicitis and found a nearby hospital in the family's health insurance network.

After a long wait in the emergency room of Penrose Hospital, Claire received morphine and an anti-nausea medication delivered through an IV. She also underwent a CT scan of her abdomen and a series of tests.

Hospital staffers ruled out appendicitis and surmised Claire was suffering from a ruptured ovarian cyst, which can be a harmless part of the menstrual cycle but can also be problematic and painful. After a few days — and a chemistry exam taken through gritted teeth — the pain went away.

Then the bill came.

Patient: Claire Lang-Ree, a 21-year-old Stanford University student who was living in Colorado for a few months while taking classes remotely. She's insured by Anthem Blue Cross through her mom's work as a pediatric nurse practitioner in Northern California.

Total Bill: $18,735.93, including two $722.50 fees for a nurse to "push" drugs into her IV, a process that takes seconds. Anthem's negotiated charges were $6,999 for the total treatment. Anthem paid $5,578.30, and the Lang-Rees owed $1,270.45 to the hospital, plus additional bills for radiologists and other care. (Claire also anted up a $150 copay at the ER.)

Service Provider: Penrose Hospital in Colorado Springs, part of the regional health care network Centura Health.

What Gives: As hospitals disaggregate charges for services once included in an ER visit, a hospitalization or a surgical procedure, there has been a proliferation of newfangled fees to increase billing. In the health field, this is called "unbundling." It's analogous to the airlines now charging extra for each checked bag or for an exit row seat. Over time, in the medical industry, this has led to separate fees for ever-smaller components of care. A charge to put medicine into a patient's IV line — a "push fee" — is one of them.

Though the biggest charge on Claire's bill, $9,885.73, was for a CT scan, in many ways Claire and her mom found the push fees most galling. (Note to readers: Scans are frequently many times more expensive when ordered in an ER than in other settings.)

"That was so ridiculous," says Claire, who adds she had previously taken the anti-nausea drug they gave her; it's available in tablet form for the price of a cup of coffee, no IV necessary. "It works really well. Why wasn't that an option?"

In Colorado, the average charge for the code corresponding to Claire's first IV push has nearly tripled since 2014, and the dollars hospitals actually get for the procedure has doubled. In Colorado Springs specifically, the cost for IV pushes rose even more sharply than it did statewide.

A typical nurse in Colorado Springs makes about $35 an hour. At that rate, it would take nearly 21 hours to earn the amount of money Penrose charged for a push of plunger that likely took seconds or at most minutes.

The hospital's charge for just one "IV push" was more than Claire's portion of the monthly rent in the home she shared with roommates. In the end, Anthem did not pay the push fees in its negotiated payment. But claims data shows that in 2020 Penrose typically received upward of $1,000 for the first IV push. And patients who didn't have an insurer to dismiss such charges would be stuck with them. Colorado hospitals on average received $723 for the same code, according to the claims database.

"It's insane the variation that we see in prices, and there's no rhyme or reason," says Cari Frank with the Center for Improving Value in Health Care, a Colorado nonprofit that runs a statewide health care claims database. "It's just that they've been able to negotiate those prices with the insurance company and the insurance company has decided to pay it."

To put the total cost in context, Penrose initially charged more money for Claire's visit than the typical Colorado hospital would have charged for helping someone give birth, according to data published by the Colorado Division of Insurance.

Even with the negotiated rate, "it was only $1,000 less than an average payment for having a baby," Frank says.

In an email statement, Centura said it "conducted a thorough review and determined all charges were accurate" and went on to explain that "an Emergency Room (ER) must be prepared for anything and everything that comes through the doors," requiring highly trained staff, plus equipment and supplies. "All of this adds up to large operating costs and can translate into patient responsibility."

As researchers have found, little stands in the way of hospitals charging through the roof, especially in a place like an emergency room, where a patient has few choices. A report from National Nurses United found that hospital markups have more than doubled since 1999, according to data from the United States Bureau of Labor Statistics. In an email, Anthem called the trend of increasing hospital prices "alarming" and "unsustainable."

But Ge Bai, an associate professor of accounting and health policy at Johns Hopkins University, says when patients see big bills it isn't only the hospital's doing — a lot depends on the insurer, too. For one, the negotiated price depends on the negotiating power of the payer, in this case, Anthem.

"Most insurance companies don't have comparable negotiating or bargaining power with the hospital," said Bai. Prices in a state like Michigan, where Bai said the UAW union covers a big proportion of Michigan patients, will look very different from those in Colorado.

Also, insurers are not the wallet defenders patients might assume them to be.

"In many cases, insurance companies don't negotiate as aggressively as they can, because they earn profit from the percentage of the claims," she says. The more expensive the actual payment is, the more money they get to extract.

Though Anthem negotiated away the push fees, it paid the hospital 30% more than the average Level IV emergency department visit in Colorado that year, and it paid quadruple what Medicare would allow for her CT scan.

Resolution: Claire and her mom decided to fight the bill, writing letters to the hospital and searching for information on what the procedures should have cost. The cost of the IV pushes and CT scan infuriated them — the hospital wanted more than double for a CT than what top-rated hospitals typically charged in 2019.

But the threat of collections wore them out and ultimately they paid their assigned share of the bill — $1,420.45, which was mostly coinsurance.

"Eventually it got to the point where I was like, 'I don't really want to go to collections, because this might ruin my credit score,'" says Claire, who didn't want to graduate from college with dinged credit.

Bai and Frank say the state of Maryland can provide a useful benchmark for medical bills, since it sets the prices that hospitals can charge for each procedure. Data provided by the Maryland Health Care Commission shows that Anthem and Claire paid seven times what she likely would have paid for the CT scan there, and nearly 10 times what they likely would have paid for the emergency department Level IV visit. In Maryland, intravenous pushes typically cost about $200 apiece in 2019. A typical Maryland hospital would have received only about $1,350 from a visit like Claire's, and the Lang-Rees would have been on the hook for about $270.

Claire's pain has come back a few times, but never as bad as that night in Colorado. She has avoided reentering an emergency room since then. After visiting multiple specialists back home in California, she learned she might have had a condition called ovarian torsion.

The Takeaway: Even at an in-network facility and with good insurance, patients can get hurt financially by visiting the ER. A few helpful documents can help guide the way to fighting such charges. The first is an itemized bill.

"I just think it's wrong in the U.S. to charge so much," says Jen Lang-Ree. "It's just a little side passion of mine to look at those and make sure I'm not being scammed."

Bai, of Johns Hopkins, suggests asking for an itemized explanation of benefits from the insurance company, too. That will show what the hospital actually received for each procedure.

Find out if the hospital massively overcharged. The Medicare price lookup tool can be useful for getting a benchmark. And publicly available data on health claims in Colorado and at least 17 other states can help, too.

Vincent Plymell with the Colorado Division of Insurance encourages patients to reach out if something on a bill looks sketchy. "Even if it's not a plan we regulate," he wrote in an email, departments such as his "can always arm the consumer with info."

Finally, make scrutinizing such charges fun. Claire and Jen made bill-fighting their mother-daughter hobby for the winter. They recommend pretzel chips and cocktails to boost the mood.

Bill of the Month is a crowdsourced investigation by KHN and NPR that dissects and explains medical bills. Do you have an interesting medical bill you want to share with us? Tell us about it!

This content is from Southern California Public Radio. View the original story at SCPR.org.

People rest while riding a Los Angeles Metro Rail train amid the coronavirus pandemic on April 1, 2020 in Los Angeles, California.; Credit: Mario Tama/Getty Images

Despite the racial reckoning going on in America right now, and despite the fact that attitudes towards race, inclusion and representation are different now than they were 30 years ago, new research from UC Berkeley shows that a large majority of American metro areas are more segregated now than they were in 1990. The new report from Berkeley’s Institute covers a number of topic areas, but among the key findings were from the national segregation report component of the project, which found Los Angeles to be the sixth-most segregated metro area with more than 200,000 people.

Today on AirTalk, we’ll talk with the lead researcher on the new report and a local historian to talk about how we see the findings of the report play out in Southern California.

Guests:

Stephen Menendian, assistant director and director of research at the Othering & Belonging Institute at UC Berkeley, which works to identify and eliminate the barriers to an inclusive, just, and sustainable society in order to create transformative change; he tweets @SMenendian

Eric Avila, professor of history, urban planning, and Chicano/a studies at UCLA

This content is from Southern California Public Radio. View the original story at SCPR.org.

A voter marks his ballot at a polling place on Nov. 3, 2020, in Richland, Iowa. A new poll finds ensuring access to voting is more important than tamping down voter fraud for most Americans.; Credit: Mario Tama/Getty Images

A majority of Americans believes ensuring access to voting is more important than rooting out fraud, the latest NPR/PBS NewsHour/Marist survey finds.

At the same time, there was broad agreement that people should have to show identification when they go to the polls.

Two-thirds of Americans also believe democracy is "under threat," but likely for very different reasons.

"For Democrats, Jan. 6 undoubtedly looms large," said Lee Miringoff, director of the Marist Institute for Public Opinion, referring to the violence and insurrection at the Capitol, "while, for Republicans, it's more likely about Trump and his claims of a rigged election."

Voting access vs. fraud

By a 56%-41% margin, survey respondents said making sure that everyone who wants to vote can do so is a bigger concern than making sure that no one who is ineligible votes.

But there were wide differences by political party and by race.

Among Democrats, almost 9 in 10 said access was more important, but almost three-quarters of Republicans said it was making sure no one votes who isn't eligible.

By race, a slim majority of whites said ensuring everyone who wants to vote can was most important, but almost two-thirds of nonwhites said so.

Photo ID is popular

Nearly 8 in 10 Americans said they believe voters should be required to show government-issued photo identification whenever they vote.

Majorities of Democrats, Republicans, independents, whites and nonwhites all said so. Democrats were far lower, though, with 57% believing photo ID should be required.

Biden holding steady

President Biden gets a 50% job approval rating, largely unchanged from last month. There is a sharp partisan divide with 9 in 10 Democrats approving, and more than 8 in 10 Republicans disapproving.

Biden continues to get his highest ratings when it comes to his handling of the coronavirus pandemic, and his economic approval is holding steady. But Americans have less confidence in his handling of foreign policy, especially immigration. His approval on immigration ticked up slightly from March when it was last measured in the poll.

By a 50%-43% margin, respondents said Biden had strengthened America's role on the world stage.

Americans are split about whether the country is headed in the right direction or not — 49% said it wasn't, 47% said it was. It's an improvement, however, from right after the Jan. 6 insurrection when three-quarters said the country was on the wrong track.

The tone has gotten worse in Washington since Biden was elected, 41% said, but that's better than the two-thirds who said so consistently during the Trump years.

Methodology: The poll of 1,115 U.S. adults was conducted using live telephone interviewers from June 22-29. Survey questions were available in English or Spanish. The full sample has a margin of error of plus or minus 3.7 percentage points with larger margins of error for smaller group subsets.

This content is from Southern California Public Radio. View the original story at SCPR.org.

Hercules Metals Corp. (BADEF:OTCMKTS; BIG:TSXV) has announced advancements in its exploration efforts at the western Idaho Leviathan porphyry copper system. Read more about the significant shallow mineralization discoveries and new target areas that could indicate further resource potential.

Full Text:

Earth's magnetic field seems steady and true -- reliable enough to navigate by. Yet, largely hidden from daily life, the field drifts, waxes and wanes. The magnetic North Pole is currently shifting toward Siberia, forcing the Global Positioning System that underlies modern navigation to update its software sooner than expected. Every several hundred thousand years, the magnetic field dramatically shifts and reverses its polarity. Magnetic north flips to the geographic South Pole and, eventually, back again. This reversal has happened countless times over Earth's history, but scientists' understanding of why and how the field reverses is limited. The researchers find that the most recent field reversal 770,000 years ago took at least 22,000 years to complete, several times longer than previously thought. The results call into question controversial findings that some reversals could occur within a human lifetime.

Image credit: Brad Singer

Darkly colored, carotene-rich fruits and vegetables -- such as carrots, sweet potatoes, and broccoli -- provide the body with half as much vitamin A as previously thought.

The National Research Council today released its assessment of U.S. doctoral programs, which includes data on over 5,000 programs in 62 fields at 212 universities nationwide.

As of today all PDF versions of books published by the National Academies Press will be downloadable to anyone free of charge. This includes a current catalog of more than 4,000 books plus future reports produced by the Press.

On average, Americans die sooner and experience higher rates of disease and injury than people in other high-income countries, says a new report from the National Research Council and Institute of Medicine.

The National Academy of Medicine (NAM) today announced that more than 130 organizations across the U.S. -- including associations, hospital and medical systems, universities, and professional societies -- have joined NAM in declaring their commitment to reducing burnout and promoting well-being among clinicians.

The U.S. should take bold steps to improve measurement, monitoring, and inventories of methane emissions caused by human activities, says a new report from the National Academies of Sciences, Engineering, and Medicine.

The National Academy of Medicine (NAM) announced today that more than 100 organizations across the U.S. — including community organizations, hospital and medical systems, academia, nonprofits, and health professional societies — have joined NAM in declaring their commitment to reversing national trends in opioid misuse and overdose.

Sethuraman “Panch” Panchanathan, executive vice president and chief research and innovation officer at Arizona State University (ASU), and ASU’s named representative to the National Academies’ Government-University-Industry-Research Roundtable (GUIRR), has been nominated by President Trump to serve as the next director of the National Science Foundation.

This summer, as COVID-19 continued its spread across the U.S., the National Academies brought together engineers, virologists, public health experts, and others for a meeting to dive into the rapidly evolving science of COVID-19 airborne transmission.

The average time it takes attackers to weaponize a vulnerability, either before or after a patch is released, shrank from 63 days in 2018-2019 to just five days last year

Newly published research by Indiana University scientists finds that low relative humidity in the atmosphere is a significant, growing and often under-appreciated cause of plant stress in hot, dry weather conditions.

read more

The Garden is closed today for the Thanksgiving holiday.

According to Ireland's Central Statistics Office (CSO), data centers consumed 21 percent of all metered electricity consumption in 2023, up from five percent in 2015 and 18 percent in 2022.

Around 95 per cent of the existing capacity is in six cities with Mumbai and Chennai leading the race, Icra said.