A new cluster complex, (NH4)6[Mo4Se4(CN)12]·6H2O,containing a tetranuclear mixed‐valence molybdenum core

The title compound, hexa­ammonium tetra‐μ₃‐selenido‐tetra­kis­(tri­cyano­molybdenum) hexahydrate, is isostructural with the Mo/S, W/S and W/Se analogues. The structure contains disordered cyclic hydrogen‐bonded [{(NH₄)(H₂O)}₃]³⁺ cations and [Mo₄Se₄(CN)₁₂]^6? cluster anions with 3m symmetry. The cation assembly consists of alternating ammonium and water mol­ecules linked by N—H?O hydrogen bonds. The anion has a typical cubane cluster structure. The cations and anions are linked together by hydrogen bonds involving the terminal N atoms of the CN groups.     

Picolinamidium squarate and di‐p‐toluidinium squarate dihydrate

The crystal structure determinations of picolinamidium squarate, C₆H₇N₂O⁺·C₄O₄⁻, (I), and di‐p‐toluidinium squarate dihydrate, 2C₇H₁₀N⁺·C₄O₄²⁻·2H₂O, (II), are reported. While salt formation occurs by donation of one H atom from squaric acid to the picolin­amide mol­ecule in (I), in compound (II), each squaric acid mol­ecule donates one H atom to the p‐toluidine N atom of two trans p‐toluidine molecules. In (I), the pyridine ring is coplanar with the squarate monoanion through imposed crystallographic mirror symmetry; in (II), the dihedral angle between the p‐toluidine moiety and the squarate dianion is 70.71 (1)°. In (I), a three‐dimensional structure is formed via van der Waals interactions between parallel planes of mol­ecules, with hydrogen‐bond interactions (N—H⋯O and O—H⋯O) acting within the planes; hydrogen bonds form a three‐dimensional network in (II).     

A capped trigonal prismatic cadmium complex with tetra‐ and tridentate ligands: bis­(tri­ethanol­amine)‐κ3N,O,O′;κ4N,O,O′,O′′‐cadmium(II) squarate monohydrate

In the crystal structure of the title compound, [Cd(C₆H₁₅NO₃)₂](C₄O₄)·H₂O, a supramolecular structure is observed. The asymmetric unit consists of one unit of the cationic Cd complex, one water mol­ecule and two half‐squarate anions, each sitting on a crystallographic inversion center. The different coordinations of the two triethanolamine (TEA) ligands results in an unusual example of coordination number seven for the Cd^II ion. Both TEA ligands coordinate to the Cd^II ion, forming a distorted monocapped trigonal prismatic geometry with approximate C_2v symmetry. One of the TEA ligands acts as an N,O,O′‐tridentate ligand, whereas the other behaves as an N,O,O′,O′′‐tetradentate donor. The anions and cations are linked to one another by hydrogen bonds between hydroxy H atoms of the TEA ligands and squarate O atoms. The crystal structure is stabilized by O—H⋯O hydrogen bonds between the unligated water mol­ecule and a squarate O atom, together with a weak π–ring interaction between the ethyl­ene group of a TEA ligand and a squarate anion.     

catena‐Poly[bis[1‐chloromethyl‐1,4‐diazoniabicyclo[2.2.2]octane] [cadmium(II)‐tri‐μ‐chlorido‐[chloridocadmium(II)]‐di‐μ‐chlorido‐[chloridocadmium(II)]‐tri‐μ‐chlorido] tetrahydrate]

The title compound, {(C₇H₁₅N₂Cl)₂[Cd₃Cl₁₀]·4H₂O}_n, consists of 1‐chloromethyl‐1,4‐diazoniabicyclo[2.2.2]octane dications, one‐dimensional inorganic chains of {[Cd₃Cl₁₀]⁴⁻} anions and uncoordinated water molecules. Each of the two independent Cd^II ions, one with site symmetry 2/m and the other with site symmetry m, is octahedrally coordinated by chloride ions (two with site symmetry m and one with site symmetry 2), giving rise to novel polymeric zigzag chains of corner‐sharing Cd‐centred octahedra parallel to the c axis. The organic cations, bisected by mirror planes that contain the two N atoms, three methylene C atoms and the Cl atom, are ordered. Hydrogen bonds (O—H...Cl and O—H...O) between the water molecules (both with O atoms in a mirror plane) and the chloride anions of neighbouring chloridocadmate chains form a three‐dimensional supramolecular network.     

Hydrogen‐bonding motifs in 4‐carboxy­phenyl­ammonium nitrate and perchlorate monohydrate,and in bis(4‐carboxy­phenyl­ammonium) sulfate

In the title compounds, C₇H₈NO₂⁺·NO₃⁻, (I), C₇H₈NO₂⁺·ClO₄⁻·H₂O, (II), and 2C₇H₈NO₂⁺·SO₄²⁻, (III), the carboxyl planes of the 4‐carboxy­phenyl­ammonium cations are twisted from the aromatic plane. A homonuclear C(8) hydrogen‐bonding motif of 4‐carboxy­phenyl­ammonium cations is observed in both (I) and (II), leading to `head‐to‐tail' layers. The cations in (III) form carboxyl group dimers, making a graph‐set motif of R₂²(8). In all the structures, anions connect the cationic layers and an infinite chain running along the c axis is observed, having the C₂²(6) graph‐set motif. Inter­estingly, in (II), the anions are connected through weak hydrogen bonds involving the water mol­ecules, leading to a graph‐set motif of R₄⁴(12). Alternate hydro­phobic and hydro­philic layers are observed in all three compounds as a result of the column‐like arrangement of the aromatic rings of the cations and the anions. Furthermore, in (I), head‐to‐tail N—H⋯O inter­actions and inter­actions linking the cations and anions form an R₆⁴(16) hydrogen‐bonding motif, resulting in a pseudo‐inversion centre at (, , 0).     

(m‐CH3C6H4NH3)6P6O18

In hexakis(m‐toluidinium) cyclo­hexaphosphate, 6C₇H₁₀N⁺·­P₆O₁₈^6?, the atomic arrangement is typical of a layer structure. Layers including the centrosymmetric P₆O₁₈ ring anions develop around the (100) planes at x = . The hydrogen‐bond distribution is described.     

Structural comparison of three N‐(4‐halogenophenyl)‐N′‐[1‐(2‐pyridyl)ethylidene]hydrazine hydrochlorides

2‐{1‐[(4‐Chloroanilino)methylidene]ethyl}pyridinium chloride methanol solvate, C₁₃H₁₃ClN₃⁺·Cl⁻·CH₃OH, (I), crystallizes as discrete cations and anions, with one molecule of methanol as solvent in the asymmetric unit. The N—C—C—N torsion angle in the cation indicates a cis conformation. The cations are located parallel to the (02) plane and are connected through hydrogen bonds by a methanol solvent molecule and a chloride anion, forming zigzag chains in the direction of the b axis. The crystal structure of 2‐{1‐[(4‐fluoroanilino)methylidene]ethyl}pyridinium chloride, C₁₃H₁₃FN₃⁺·Cl⁻, (II), contains just one anion and one cation in the asymmetric unit but no solvent. In contrast with (I), the N—C—C—N torsion angle in the cation corresponds with a trans conformation. The cations are located parallel to the (100) plane and are connected by hydrogen bonds to the chloride anions, forming zigzag chains in the direction of the b axis. In addition, the crystal packing is stabilized by weak π–π interactions between the pyridinium and benzene rings. The crystal of (II) is a nonmerohedral monoclinic twin which emulates an orthorhombic diffraction pattern. Twinning occurs via a twofold rotation about the c axis and the fractional contribution of the minor twin component refined to 0.324 (3). 2‐{1‐[(4‐Fluoroanilino)methylidene]ethyl}pyridinium chloride methanol disolvate, C₁₃H₁₃FN₃⁺·Cl⁻·2CH₃OH, (III), is a pseudopolymorph of (II). It crystallizes with two anions, two cations and four molecules of methanol in the asymmetric unit. Two symmetry‐equivalent cations are connected by hydrogen bonds to a chloride anion and a methanol solvent molecule, forming a centrosymmetric dimer. A further methanol molecule is hydrogen bonded to each chloride anion. These aggregates are connected by C—H...O contacts to form infinite chains. It is remarkable that the geometric structures of two compounds having two different formula units in their asymmetric units are essentially the same.     

Supra­molecular hydrogen‐bonding networks in bis­(adeninium) phthalate phthalic acid 1.45‐hydrate

In the title compound, 2C₅H₆N₅⁺·C₈H₄O₄²⁻·C₈H₆O₄·1.45H₂O, the asymmetric unit comprises two adeninium cations, two half phthalate anions with crystallographic C₂ symmetry, one neutral phthalic acid mol­ecule, and one fully occupied and one partially occupied site (0.45) for water mol­ecules. The adeninium cations form N—H⋯O hydrogen bonds with the phthalate anions. The cations also form infinite one‐dimensional polymeric ribbons via N—H⋯N inter­actions. In the crystal packing, hydrogen‐bonded columns of cations, anions and phthalate anions extend parallel to the c axis. The water mol­ecules crosslink adjacent columns into hydrogen‐bonded layers.     

l‐Argininamidium bis­(hydrogen­squarate)

Cations and anions of the title compound {systematic name: 1‐[4‐(amino­carbonyl)butyl]guanidinium bis­(hydrogen­squarate)}, C₆H₁₇N₅O²⁺·2C₄HO₄⁻, are connected into a three‐dimensional network by inter­molecular N—H⋯O hydrogen bonds between the l ‐argininamidium ammonium, amide and guanidinium functions and the hydrogensquarate carbonyl O atoms. The independent hydrogensquarate monoanions are linked into dimers by pairs of O—H⋯O′ hydrogen bonds.     

Pseudosymmetry in ammonium [(carboxymethyl)sulfanyl]acetate

The structure of the title compound, NH₄⁺·C₄H₅O₄S⁻, is composed of mono­carboxyl­ate anions of [(carboxymethyl)sulfanyl]acetic acid linked into infinite chains via strong O—H⋯O⁻ hydrogen bonds. The three‐dimensional structure is completed by the ammonium cations, which interlink neighbouring chains via N—H⋯O hydrogen bonds. Solution and refinement in the true space group Pn led to an unambiguous position for the single carboxyl H atom. In the higher symmetry space group P2/n, the carboxylate anion would be located on a twofold axis.     

The supramolecular architecture in 4,4′‐bipyridinium bis(hydrogen oxalate)

The asymmetric unit of the title compound, C₁₀H₁₀N₂²⁺·2C₂HO₄⁻, consists of one half of a 4,4′‐bipyridinium cation, which has inversion symmetry, and a hydrogen oxalate anion, in which an intramolecular hydrogen bond exists. The cations and anions are connected by O—H...O, N—H...O and C—H...O hydrogen bonds, forming a two‐dimensional network, whereas π–π stacking interactions involving the 4,4′‐bipyridinium cations lead to the formation of a three‐dimensional supramolecular structure. An unusual deca‐atomic ring is formed between two hydrogen oxalate anions, which are linked side‐to‐side via O—H...O hydrogen‐bonding interactions.     

2,2′‐Bipyridinium bis(perchlorate)

The title compound, [H₂bipy](ClO₄)₂ or C₁₀H₁₀N₂²⁺·2ClO₄^?, was obtained at the interface between an organic (2,2′‐bi­pyridine in methanol) and an aqueous phase (perchloric acid in water). The compound crystallizes in space group P and comprises discrete diprotonated trans‐bipyridinium cations, [H₂bipy]²⁺, and ClO₄^? anions. The cations and anions are connected through N—H?O and C—H?O hydrogen bonds [distances N?O 2.817 (4) and 2.852 (4) Å, and C?O 3.225 (6)–3.412 (5)Å]. The C—C bond distance between the two rings is 1.452 (5) Å. The bipyridinium cation has a trans conformation and the N—C—C—N torsion angle is 152.0 (3)°.     

Hexakis[3‐(aminocarbonyl)pyridinium] decavanadate(V) dihydrate

The structure of the title compound, (C₆H₇N₂O)₆[V₁₀O₂₈]·2H₂O, at 120 (2) K has monoclinic (C2/c) symmetry. The asymmetric unit consists of one half‐decavanadate anion of C_i symmetry, three cations and one water molecule. Each water molecule is hydrogen bonded to two decavanadate anions, thus forming a one‐dimensional chain of anions. The three‐dimensional supramolecular structure is formed by a network of N—H...O, O—H...O and C—H...O hydrogen bonds, in which the cations, anions and water molecules are involved, and by nonparallel‐displaced π‐stacking interactions between pyridine rings. As a result of hydrogen bonding, the carboxamide groups of the cations are somewhat twisted from the pyridine ring plane.     

Bis(tetraethylammonium) hydrogensulfate dihydrogenphosphate at 292 and 150 K

The title compound, 2C₈H₂₀N⁺·HSO₄⁻·H₂PO₄⁻, was crystallized in a desiccator over P₄O₁₀ from a water solution of stoichiometric amounts of tetraethyl­ammonium hydroxide and sulfuric and phosphoric acids. The compound is deliquescent. The structure contains two symmetry‐independent cations in nearly the same conformation, as well as two symmetry‐independent anions, the central atoms of which are equally occupied by P and S. The anions are interconnected by short O⃛O hydrogen bonds into one‐dimensional chains. The distances and angles between some of the methyl or methyl­ene groups and anionic O atoms indicate the presence of C—H⃛O hydrogen bonds. The structure was determined from data at 292 (2) and 150 (2) K. These room‐ and low‐temperature structures are virtually the same, with the exception of the localization of the H atoms that participate in the symmetry‐restricted O⃛O hydrogen bonds. A differential scanning calorimetry experiment indicated no phase transition below the temperature at which the compound started to decompose (353 K), down to 93 K.     

Lagoden dimethylformamide hemisolvate dihydrate: absolute configuration,dipolar interactions and hydrogen‐bonding interactions

Lagoden (L·3H₂O, where L is Na⁺·C₂₀H₃₃O₆⁻; sodium 3β,16,18‐trihydroxy‐8,13‐epi‐9,13‐epoxylabdan‐15‐oate trihydrate) is widely used as an effective haemostatic agent. It has been crystallized from dimethylformamide (DMF) as sodium 3β,16,18‐trihydroxy‐8,13‐epi‐9,13‐epoxylabdan‐15‐oate dimethylformamide hemisolvate dihydrate, Na⁺·C₂₀H₃₃O₆⁻·0.5C₃H₇NO·2H₂O or L₂·DMF·4H₂O, and the asymmetric unit contains two of the latter formulation. The four symmetry‐independent Na⁺ cations and lagoden anions, one DMF molecule and six of the eight symmetry‐independent water molecules assemble into a one‐dimensional polymeric structure via dipolar and hydrogen‐bonding interactions. The lagoden anions coordinate to the Na⁺ cations via the carboxylate groups and the two primary hydroxy groups, whereas the secondary OH groups are solely involved in hydrogen bonding. Two of the four symmetry‐independent lagoden anions act in a chelating mode, forming seven‐membered chelate rings. The absolute structure, based on anomalous dispersion data collected at 130 K with Cu Kα radiation, confirms an inverted configuration at chiral centres C8 and C13 (labdane numbering) relative to the labdane skeleton.     

2‐Amino‐5‐nitro‐4,6‐dipiperidinopyrimidinium hydrogen­sulfate monohydrate: hydrogen‐bonded sheets containing highly distorted cations

In the title compound, C₁₄H₂₃N₆O₂⁺·HSO₄⁻·H₂O, the pyrimidinium ring of the cation adopts a twist‐boat conformation, induced by steric clashes between adjacent ring substituents; the anions and the water mol­ecules are linked by three O—H⃛O hydrogen bonds [H⃛O = 1.70–1.78 Å, O⃛O = 2.548 (2)–2.761 (2) Å and O—H⃛O = 161–168°] into chains of edge‐fused R(12) rings, which are linked into sheets by the cations, via three N—H⃛O hydrogen bonds [H⃛O = 1.96–2.17 Å, N⃛O = 2.820 (2)–2.935 (2) Å and N—H⃛O = 145–173°].     

Copper(I) π‐Complexes with 2‐Butyne‐1,4‐diol. Synthesis and Crystal Structure of Na[CuCl2(HOCH2C≡CCH2OH)]·2H2O

Crystals of anionic Na[CuCl₂(HOCH₂C≡CCH₂OH)]·2H₂O π‐complex have been synthesized by interaction of 2‐butyne‐1,4‐diol with CuCl in a concentrated aqueous NaCl solution and characterized by X‐ray diffraction at 100 K. The crystals are triclinic: space group , a = 7.142(3), b = 7.703(3), c = 10.425(4) Å, α = 105.60(3), β = 99.49(3), γ = 110.43(3)°, V = 495.9(4) ų, Z = 2, R = 0.0203 for 3496 reflections. The structure is built of discrete [CuCl₂(HOCH₂C≡CCH₂OH)]^? anionic stacks and polymeric cations among the stacks. The Cu^I atom adopts trigonal planar coordination of two Cl^? anions and the C≡C bond of 2‐butyne‐1,4‐diol, Cu–(C≡C) distance is equal to 1.903(3) Å. Na⁺ cations environment is octahedral and consists of O and Cl atoms. The crystal packing is governed by strong hydrogen bonds of O–H···Cl and O–H···O types.     

Tetramethyl­ammonium 2,5‐dinitro­phenolate monohydrate

The crystal structure of the title compound, C₄H₁₂N⁺·C₆H₃N₂O·H₂O, is built up from tetramethyl­ammonium cations, 2,5‐dinitro­phenolate anions and water molecules. The nitro groups are almost coplanar with the aryl ring, which exhibits significant distortion from an ideal hexagonal form. The X‐ray geometry of the tetramethyl­ammonium cation shows slight distortion from the tetrahedral symmetry predicted by molecular orbital calculations. The O—H⋯O hydrogen‐bonded water and 2,5‐dinitro­phenolate units are related by an inversion center and form dimers. The 2,5‐dinitro­phenolate anions, related by an inversion center and translation, are stacked to form a column along the [100] direction.     

Linear hydrogen‐bonded molecular tapes in the cocrystals of squaric acid with 4,4′‐dipyridylacetylene and 1,2‐bis(4‐pyridyl)ethylene

The title compounds, 4,4′‐(ethyne‐1,2‐diyl)­dipyridinium bis(squarate), C₁₂H₁₀N₂²⁺·2C₄HO₄^?, and 4,4′‐(ethene‐1,2‐diyl)­dipyridinium bis­(squarate), C₁₂H₁₂N₂²⁺·2C₄HO₄^?, are isomorphous and crystallize in space group P. The cocrystals contain linear hydrogen‐bonded molecular tape structures along the [120] direction. The squarate monoanions form a ten‐membered dimer linked by two intermolecular O—H?O hydrogen bonds. Each component mol­ecule forms a segregated stack along the c axis. The bond lengths of the squarate monoanion indicate delocalization of the enolate anion.     

Synthesis,Structure, and Luminescent Property of the Templated Borate [C9H14N]·[B5O6(OH)4]

The templated borate, [C₉H₁₄N] · [B₅O₆(OH)₄], was synthesized under hydrothermal conditions. Single crystal X‐ray diffraction techonology reveals that it crystallizes in the triclinic system, space group P$\bar{1}$ (No. 2). The material was also characterized by element analysis, Fourier transform infrared spectroscopy (FTIR), powder X‐ray diffraction (PXRD), thermogravimetric and differential thermal analysis (TG‐DTA), and luminescence spectroscopy. The compound consisted of isolated pentaborate [B₅O₆(OH)₄]^– and N‐butylpyridinium cations [C₉H₁₄N]⁺. The [B₅O₆(OH)₄]^– anions are connected together by hydrogen bonds to form a three‐dimensional framework, in which [C₉H₁₄N]⁺ cations are located in. [C₉H₁₄N] · [B₅O₆(OH)₄] exhibits tunable luminescence emission at 415–458 nm by means of heating treatment from 100 to 300 °C.