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Ambient‐pressure trigonal phase α of selenourea SeC(NH2)2 is noncentrosymmetric, with high Z′ = 9. Under high pressure it undergoes several intriguing transformations, depending on the pressure‐transmitting medium and the compression or recrystallization process. In glycerine or oil, α‐SeC(NH2)2 transforms into phase β at 0.21 GPa; however in water, phase α initially increases its volume and can be compressed to 0.30 GPa due to the formation of α‐SeC(NH2)2·xH2O. The single crystals of α‐SeC(NH2)2 and of its partial hydrate α‐SeC(NH2)2·xH2O are shattered by pressure‐induced transitions. Single crystals of phase β‐SeC(NH2)2 were in situ grown in a diamond‐anvil cell and studied by X‐ray diffraction. The monoclinic phase β is centrosymmetric, with Z′ = 2. It is stable to 3.20 GPa at least, but it cannot be recovered at ambient conditions due to strongly strained NH...Se hydrogen bonds. No hydrogen‐bonding motifs present in the urea structures have been found in selenourea phases α and β. [ABSTRACT FROM AUTHOR]

High‐nitrogen‐content compounds 6‐azido‐1,2,4‐triazolo[4,3‐b]pyridazine (C5H3N7) and its 3‐methyl derivative (C6H5N7) have been in situ crystallized in a diamond‐anvil cell and their structures determined by single‐crystal X‐ray diffraction. Under ambient and high‐pressure conditions the crystallizations yield the same phases: the C5H3N7 anhydrate and C6H5N7 hydrated clathrate. In both the structures there are clearly distinguished regions of short CH...N and N...N intermolecular contacts, the latter involving exclusively the azide groups. High pressure initially increases the contents of water in the channel pores of the clathrate. [ABSTRACT FROM AUTHOR]

High-pressure (HP) structural and magnetic properties of a magnetic coordination polymer {[NiII(pyrazole)4]2[NbIV(CN)8]·4H2O}n (Ni2Nb) are presented, discussed and compared with its two previously reported analogs {[MnII(pyrazole)4]2[NbIV(CN)8]·4H2O}n (Mn2Nb) and {[FeII(pyrazole)4]2[NbIV(CN)8]·4H2O}n (Fe2Nb). Ni2Nb shows a significant decrease of the long-range ferromagnetic ordering under high pressure when compared to Mn2Nb, where the pressure enhances the Tc (magnetic ordering temperature), or to Fe2Nb exhibiting a pressure-induced spin crossover. The different HP magnetic responses of the three compounds were rationalized and correlated with the structural models as determined by single-crystal X-ray diffraction. [ABSTRACT FROM AUTHOR]

Distortions of the directional requirements in halogen…halogen contacts between hexachloroethane (HCE), C2Cl6, molecules lead to a loose crystal under ambient conditions. Single-crystal X-ray diffraction shows that the orthorhombic HCE phase of space group Pnma, with the molecules in the staggered conformation, extends at least from 85 to 305 K and from 0.1 MPa to 5.42 GPa. At ambient pressure, all intermolecular distances are longer than the sum of van der Waals radii, reached only at the pressure of ca. 1.2 GPa. [ABSTRACT FROM AUTHOR]

Abstract: X‐ray diffraction structure of two new bis [1‐methyl‐3‐(methoxycarbonylmethyl) benzimidazolium]2+ [CuBr4]2− and [ZnBr4]2− compounds has been determined. Zn‐crystal is monoclinic with perfect Td symmetry of the ZnBr4 tetrahedron, whereas the Cu‐compound is orthorhombic with D2d symmetry of CuBr4 tetrahedron. The difference in these structures is described as due to the static Jahn‐Teller effect. Vibrational spectroscopy (1800–3200 cm−1) identified hydrogen bond network. NIR‐UV‐Vis spectra (5000–50000 cm−1) are dominated by ligand‐to‐metal bands with d‐d transition contribution. EPR results (Q‐band) analyzed in terms of the MO‐theory showed a very strong delocalization of unpaired electron density on ligands accompanied by the Cu(II) 4pz orbital contribution. This effect is partially compensated by charge transfer transitions to the EPR g‐factor. [ABSTRACT FROM AUTHOR]

In pentachloroethane, C2HCl5, high pressure initially strongly compresses the C–H…Cl bonds in phase I; however, in phase II which is stable above 0.62 GPa the role of hydrogen bonds is diminished and molecular aggregation is dominated by halogen bonds Cl…Cl. Both phases have been determined by X-ray diffraction and the phase diagram of C2HCl5 has been outlined. The transition between phases I and II retains some relation between their structures and reduces the symmetry from class mmm (space group Pnma) to 2/m (space group P21/n11). The discontinuous transition, with the shear strain exceeding 21°, is so strong that its progress can be visually observed even for powdered samples. The single-crystal growth suggests a surface-roughening transition, as phase I grows in the form of dendrites combining into oval plates, while phase II forms prisms with sharp edges. [ABSTRACT FROM AUTHOR]

Hydroxypyridazinone and pyrroledione rings condensation in the reactions of hydrazine hydrate with citraconic, 2,3-dimethylmaleic, succinic and cis-cyclohexanedicarboxylic anhydrides have been conducted in the HCl aqueous solution. The pyridazine-ring condensation yields products unexpected for these conditions. They have been identified by 1 H/ 13 C NMR and X-ray diffraction. The course of the reaction toward the five- and six-membered ring condensation strongly depends on methyl and other substituents in the anhydrides and in hydrazine. The obtained products indicate that the ring condensation is controlled by the molecular strains and steric hindrances between the substituents in anhydrides and pyridazinone products. The condensation of cyclic anhydrides with hydrazines has been reduced to one-step reaction and its yield significantly increased. [ABSTRACT FROM AUTHOR]

The structure of bis(4-trimethylammoniumbenzoate) hydroiodide hydrate 1 has been studied by X-ray diffraction, B3LYP/6–311G(d,p) calculations, FTIR, Raman and NMR spectroscopic techniques. The crystal is polar in monoclinic space group Cc. Two 4-trimethylammoniumbenzoate moieties are joined by a short and asymmetric hydrogen bond of 2.45(2) Å. Water molecules are gradually released from the structure, causing shifts in the position of iodine anions, which induces their disorder. The water molecule interacts with 4-trimethylammoniumbenzoate moiety and iodide anion via two O(3)–H(1)⋯O(1) and O(3)–H(2)⋯I(1) hydrogen bonds of lengths 2.70(3) and 3.51(1) Å. Hydrogen bonds in theoretically predicted structures of 2 and 3 (in vacuum), and 4 , 5 (in DMSO) optimized by the B3LYP/6-311G(d,p) approach are slightly longer than in crystal 1 . The FTIR spectrum of 1 shows a broad and intense absorption in the 1500–400 cm −1 region, typical of short hydrogen bonds assigned to the ν as (OHO) + γ (OHO) vibrations. The correlations between the experimental 13 C and 1 H chemical shifts ( δ exp ) of the investigated compound in DMSO and the GIAO/B3LYP/6-311G(d,p) magnetic isotropic shielding constants ( σ calc ) calculated by using the screening solvation model (COSMO) are linear, δ exp = a + b σ calc , and they well reproduce the experimental chemical shifts. [ABSTRACT FROM AUTHOR]

1,4-Dibromobenzene melts at a considerably higher temperature than the 1,2- and 1,3-isomers. This melting-point difference is consistent with the molecular symmetry, as described by Carnelley's rule, and with the frequency of Br...Br halogen bonds. The lowest melting point of 1,3-dibromobenzene correlates with its two symmetry-independent molecules, indicating their inability to pack closely. Single crystals of 1,2- and 1,3-dibromobenzene have been grown under isochoric conditions in a diamond-anvil cell and at isobaric conditions in a glass capillary. Their structures have been determined in situ by X-ray diffraction. At 295 K 1,2-dibromobenzene crystallizes at 0.2 GPa as orthorhombic, space group Pbca, Z′ = 1, and 1,3-dibromobenzene at 0.3 GPa as orthorhombic, space group P212121, Z′ = 2. The same crystal phases are formed at ambient pressure by freezing these liquids below 256.15 and 248.45 K, respectively. The third isomer, 1,4-dibromobenzene, is a solid at room temperature and crystallizes as monoclinic, space group P21/ a. Striking relations between the structures and melting points of the corresponding dibromobenzene and dichlorobenzene isomers have been discussed. [ABSTRACT FROM AUTHOR]

The 1:2 complex of 1,4-dimethylpiperazine mono-betaine (MBPZ) with squaric acid (H2SQ) has been characterised by single-crystal X-ray analysis, FTIR and NMR spectroscopies, and by DFT calculations. The crystals are monoclinic, space groupP21/c. Two MBPZ cations and four hydrogen squarate anions (HSQ− ) are linked by strong O(1)–H…O(13) (2.525(4) Å), O(14)–H…O(21) (2.511(4) Å) and N(4)–H…O(23) (2.607(3) Å) hydrogen bonds into a cyclamer. In turn, the cyclamers are linked into a helixthrough two O(24)–H…O(11) hydrogen bonds of 2.516(4) Å. The piperazinium ring has a chair conformation with N(4)–CH3and N(1)–CH2COOH substituents in the equatorial positions, and N(1)–CH3in the axial position. The FTIR spectrum is consistent with the crystal data. Two models of the 1:2 complex of MBPZ with H2SQ have been optimised at the B3LYP/6-311++G(d,p) level of theory and have been used to calculate harmonic IR frequencies. One of the models (2) is dominated by electrostatic attraction between NH(4)+and HSQ− , whereas in the other (3) squaric acid interacts with a zwitterionic MBPZ through the O–H…O and O–H…N hydrogen bonds. [ABSTRACT FROM PUBLISHER]

Two phase transitions in compressed benzimidazole polymorphsreveala remarkable interplay of the H-site in NH···N hydrogen-bondedaggregates and the crystal structure. The ambient-pressure polar polymorphα, space group Pna21, at p1= 0.26 GPa transforms into centrosymmetricphase β, space group Pccn, and above p2= 2.26 GPa into another centrosymmetric polymorphγ, space group Pbca. Single crystals of formsα, β, and γ have been in situgrownin isothermal and isochoric conditions in a diamond-anvil cell, andtheir structures were determined by X-ray diffraction. Both at p1and p2the H-bonddistance N···N increases in the higher-pressure phase.However, the H-atom always assumes the site for which the H···Ndistance in the homoconjugated NH···N bond is shorter. [ABSTRACT FROM AUTHOR]

Abstract: The location of H-atoms sites in carboxylic-acid dimers has been related to the crystal environment. It has been shown that the H-sites are coupled to the orientation of carboxylic-acid groups. Consequently, the H-bonds can be strained and the H-atoms destabilized and disordered by the symmetric crystal environment of symmetric molecules. The coupling results in the O⋯O distance contraction by about 0.015Å in carboxylic acids with disordered H-atoms, this magnitude calculated from H-bonds strain being consistent with that observed in crystal structures. This strain analysis provides an easy method of locating the H-atoms in hydrogen bonds between carboxyl groups, verifying experimental data determined by X-ray diffraction, calculating the magnitudes of O⋯O distance contraction and molecular reorientations induced by the H-atoms disordering structural effects, and predicting properties related to the H-atom dynamics. The survey of carboxylic-acid structures corroborates the effects of the molecular environment on the H-sites and hydrogen-bond dimensions. [Copyright &y& Elsevier]

The synthesis of 6-chloro-3-chloromethyl-1,2,4-triazolo[4,3-b]pyridazine and its vicarious nucleophilic substitution products are described and characterized by spectroscopic methods and X-ray diffraction. The lipophilicities of the title compound, its acetate, and the derived 3-methyl tetrazolopyridazine have been measured and correlated with the chlorine substitution. The title compound co-crystallizes with acetic acid in the structure of the same symmetry and very similar layered arrangement as the crystals of its acetoxymethyl analog, despite the considerably different substituents and intermolecular contacts. The details of the intermolecular interactions are discussed. [ABSTRACT FROM AUTHOR]

A series of 1,2-dihalotetrafluoroethanes X(CF2)2X (X = Br, I) has been in-situpressure crystallized in a diamond-anvil cell (DAC), their structures determined by single crystal X-ray diffraction and rationalized by weak intermolecular interactions. For isoelectronic and isostructural 1,2-dibromotetrafluoroethane (BrCF2CF2Br), 1,2-diiodotetrafluoroethane (ICF2CF2I) and 1-bromo-2-iodotetrafluoroethane (BrCF2CF2I), the crystals are monoclinic, space group P21/n, with the midpoint of the C–C bond located at the centre of inversion. The freezing pressures of these compounds have been determined to be 0.80 GPa, 0.30(5) GPa and 0.10(5) GPa for BrCF2CF2Br, BrCF2CF2I and CF2ICF2I, respectively. In the structure of ICF2CF2I, the –CF2–CF2– moiety is orientationally disordered at 0.16 GPa, but it becomes ordered at 0.86 GPa; in the BrCF2CF2I crystal the Br and I atoms are substitutionally disordered; and the BrCF2CF2Br structure is completely ordered. The formation of isostructural crystals by these compounds and different types of molecular disorder can be rationalized by the intermolecular interactions at varied thermodynamical conditions. The phenomenon of “self-healing” has been observed, in which crystal defects, formed during initial crystallization in the DAC, repaired themselves during the annealing process, which greatly facilitates the formation of single crystals. Pressure considerably affects the crystal morphology of ICF2CF2I, where the elimination of –CF2–CF2– disorder coincides with the appearance of dendritic forms of the crystal phases. [ABSTRACT FROM AUTHOR]

Abstract: Intermolecular interactions and the role of fluorine substitution have been investigated for a halogenated-ethane anesthetic. 2-Bromo-2-chloro-1,1,1-trifluoroethane, BrClCHCF3 (Halothane), has been in situ pressure frozen in a diamond anvil cell and its structure determined by single-crystal X-ray diffraction at 1.85(5)GPa/296K. Crystal is triclinic, space group . In this racemic structure the enantiomorphic molecules are substitutionally disordered at the same general positions in that way that bromine and chlorine atoms occupy the same site at the 50:50 ratio. Despite the fact that only the Br and Cl atoms are disordered, the crystal packing is dominated by halogen⋯halogen and halogen⋯hydrogen interactions. This X-ray diffraction study provides structural explanation of considerably increased vapor pressure of Halothane compared to its hydrogenated analogue. [Copyright &y& Elsevier]

Trimethyl(trifluoromethyl)silane, (CH3)3SiCF3, has been in situ pressure frozen in a diamond anvil cell and its structure determined at 0.90(5) GPa/296 K by single-crystal X-ray diffraction. The crystal is monoclinic, space group P21/m, with the molecules lying on crystallographic mirror planes. The CH3 and CF3 groups assume the fully staggered conformation. The 14-fold coordination scheme of the molecules is similar to those in (CH3)3SiCl polymorphs, but different from that in crystalline tetramethylsilane, (CH3)4Si (TMS). The longest Si—C bond length of 1.943(12) Å observed in the crystal structure has been documented. The shortest intermolecular contacts in the structure of pressure-frozen CF3Si(CH3)3 are observed between the hydrogen atoms, and those involving fluorine atoms are longer than sums of van der Waals’ radii. These structural features explain the facile cleavage of Si—CF3 bond for CF3 group transfer in organic reactions. [Copyright &y& Elsevier]

Abstract: The structure of 4-hydroxy-1-methylpiperidinium perchlorate has been characterized by X-ray diffraction, FTIR, Raman and NMR spectroscopies, and by DFT calculations. The crystals belong to orthorhombic Pbca group. The piperidine ring has a chair conformation with the hydroxyl and methyl groups in the equatorial positions. The hydroxyl group interacts by bifurcated O–H···O hydrogen bonds with the ClO4 − anion of 2.905(5) and 3.045(5)Å. Two optimized structures of the title compound have been calculated by the B3LYP/6–31G(d,p) approach. In one of them the anion is involved in the N+–H···O hydrogen bonds of 2.629Å, while in the other the anion interacts electrostatically with the N+ atom of the 4-hydroxy-1-methylpiperidinium cation. In aqueous solution two 4-hydroxy-1-methylpiperidinium perchlorates are in the conformational equilibrium. Their conformations are discussed on the basis of the NMR spectra. The solid state FTIR spectrum is consistent with the X-ray data. [Copyright &y& Elsevier]

Rocksalt-type (Pb,Cd)Te belongs to IV–VI semiconductors exhibiting thermoelectric properties. With the aim of understanding of the influence of Cd substitution in PbTe on thermostructural and elastic properties, we studied PbTe and Pb0.884Cd0.116Te (i) at low temperatures (15 to 300 K) and (ii) at high pressures within the stability range of NaCl-type PbTe (up to 4.5 GPa). For crystal structure studies, powder and single crystal X-ray diffraction methods were used. Modeling of the data included the second-order Grüneisen approximation of the unit-cell-volume variation, V(T), the Debye expression describing the mean square atomic displacements (MSDs), 2>(T), and Birch–Murnaghan equation of state (BMEOS). The fitting of the temperature-dependent diffraction data provided model variations of lattice parameter, the thermal expansion coefficient, and MSDs with temperature. A comparison of the MSD runs simulated for the PbTe and mixed (Pb,Cd)Te crystal leads to the confirmation of recent findings that the cation displacements are little affected by Cd substitution at the Pb site; whereas the Te displacements are markedly higher for the mixed crystal. Moreover, information about static disorder caused by Cd substitution is obtained. The calculations provided two independent ways to determine the values of the overall Debye temperature, θD. The resulting values differ only marginally, by no more than 1 K for PbTe and 7 K for Pb0.884Cd0.116Te crystals. The θD values for the cationic and anionic sublattices were determined. The Grüneisen parameter is found to be nearly independent of temperature. The variations of unit-cell size with rising pressure (the NaCl structure of Pb0.884Cd0.116Te sample was conserved), modeled with the BMEOS, provided the dependencies of the bulk modulus, K, on pressure for both crystals. The K0 value is 45.6(2.5) GPa for PbTe, whereas that for Pb0.884Cd0.116Te is significantly reduced, 33.5(2.8) GPa, showing that the lattice with fractional Cd substitution is less stiff than that of pure PbTe. The obtained experimental values of θD and K0 for Pb0.884Cd0.116Te are in line with the trends described in recently reported theoretical study for (Pb,Cd)Te mixed crystals. [ABSTRACT FROM AUTHOR]

The method of exhaustive methylation has been applied for investigating tautomeric stability and its temperature variation of 6-hydroxy-5-methyl-3-pyridazinone (1) and its N-phenyl derivative (2)—two model compounds chosen for studying tautomeric transformations of pyridazine medicinal drugs, either in the process of their production, or then their activity in the living tissue. The resulting N-methylated and O-methylated products were separated, and characterized by 1H NMR and X-ray diffraction. The methylation of 1 and 2 in the dimethyl sulfate as well as in its aqueous solution leads predominantly to the O-methylated forms, but the rising temperature favours the N-methylation. [Copyright &y& Elsevier]

A novel anhydrous 1:1 and 2:1 complexes of quinoline betaine (QB) with perchloric acid have been prepared and their structures determined by X-ray diffraction. The 1:1 complex betaine is protonated and the carboxylate group forms a hydrogen bond with the ClO4 ion: O⋯O distance is 2.820(3) A˚. In the 2:1 complex, the carboxylate group of a pair of QB molecules are bridged by a proton to form dimeric cation in non-planar configuration, [(QB)2H]+, featuring a very strong hydrogen bond of the length 2.453(3) A˚. The FTIR spectrum of the 1:1 complex shows a strong absorption at ca. 3100 cm−1 due to the νOH vibration. Broad and intense absorption in the 1500–400 cm−1 region in the spectrum of the 2:1 complex is typical for the very short hydrogen bonds. B3LYP calculations predict slightly shorter hydrogen bonds with different orientation of the ring vs. COOH group than these observed in crystals. [Copyright &y& Elsevier]

Reports on the third polymorph (MH3) of maleic hydrazide, studied by X-ray diffraction and shown to be monoclinic, space group P2[sub 1]/n. Finding that the polymorph MH3 is the prevailing form along with the rare triclinic polymorph MH1; Accommodation of the supramolecular conformations to the requirements of close pacing of the aggregates in crystal lattices.

The half-chair conformation of the dynamically disordered molecular ring of 2-methyl-1-3-cyclohexanedione. C7H10O2 transforms to a sofa below Tc = 244K, when the crystal undergoes a continuous phase transition induced by the onset of halting large-amplitude vibration of methylene groups C(4)H2. The temperature dependence of the crystal structure has been investigated by X-ray diffraction. The Ibam symmetry of the crystal reduces below T.. to space group Pccn. the mechanism of the phase transition and of the conversion of the ring conformation is discussed. [ABSTRACT FROM AUTHOR]

Highly favoured N–HO bonded honeycomb layers in guanidinium nitrate, C(NH2)3+NO3−, have been destabilized by a pressure of 0.6 GPa, and the novel motif of 3-dimensional N–HO bonded aggregation in high-pressure phase IV determined for in situgrown single-crystal by X-ray diffraction. The mechanism of the transition involves the collapse of voids present in phases I, II and III. In the P/T phase diagram a large hysteresis of the phase IV boundaries is caused by the strongly reconstructive character of the transition and pressure dependent H-accepting capacity of oxygen atoms. [ABSTRACT FROM AUTHOR]

A novel and unique crystalline three-component complex was formed of 2-(1-piperidine)ethanol, p -hydroxybenzoic acid and water at the ratio 1:1:1. Its structure has been determined by single-crystal X-ray diffraction. This is an example of a hydrogen-bonded interaction between amino alcohol and benzoic acid molecules. Water acts as a bridge between molecules. The molecules are linked through medium-strong OH⋯O hydrogen bonds from 2.665(6) to 2.813(6) Å and NH⋯O one 2.744(5) Å in length. The molecular structure of 2-(1-piperidinium)ethanol p -hydroxybenzoate hydrate has been characterized by FTIR and Raman spectra and optimized at the B3LYP/6−311++G(d,p) level of theory. The potential energy distributions (PED) have been used to assign the vibrational spectra. Charge delocalization was analyzed using the natural bond orbital (NBO) methods. [ABSTRACT FROM AUTHOR]

The structures of a series of the simplest aliphatic amines determined at high pressure by single crystal X-ray diffraction reveal systematic structure property relations involving intermolecular interactions and molecular symmetries. Five new polymorphs have been found: one of methylamine (phase II, space group Fdd2), two of dimethylamine (phase I, space group C2/c and phase II, P21/c), and two of trimethylamine (phase II, space group P21/n and phase III, P21/m). The methylamine and dimethylamine molecules are arranged according to the NH...N hydrogen bonds. The phase diagrams of methylamines have been outlined up to 6 GPa. [ABSTRACT FROM AUTHOR]

The 1:1 complex of piperidine-4-carboxylic acid (isonipecotic acid, P4C) with 2,6-dichloro-4-nitrophenol (DCNP), has been investigated by single-crystal X-ray analysis, Raman and FTIR spectroscopy and theoretical calculations. The hydrogen-bonded-ion-pair complex is observed in the crystalline state with the O⋯H⋯OOC hydrogen bond of 2.453(16) Å. FTIR spectrum shows a broad absorption in the 1600–400 cm −1 region characteristic of very short OHO hydrogen bond, broken by the Evans holes. The complexes are joined through N H⋯O into a H-bonding network. The N H⋯O mode appears as a broad band in the range of 3100–2000 cm −1 . In the structure optimized at the B3LYP/6–311 + +G(d,p) level of theory the proton is transferred from DCNP to P4C, and molecules are joined through the O⋯HOOC hydrogen bond of 2.640 Å. The experimental and theoretical infrared spectra are discussed. Detail interpretation of the vibrational spectra has been carried out with the use of computed Potential Energy Distribution (PED). [ABSTRACT FROM AUTHOR]

( R / S )-Piperidine-3-carboxylic acid (P3C, nipecotic acid) forms a stable 1:1 hydrogen-bonded complex with 2,6-dichloro-4-nitrophenol (DCNP). Both, in crystal and in the optimized theoretically structure by the B3LYP/6-311 + +G(d,p) approach the proton is transferred from DCNP to P3C. The ( R ) and ( S )-stereoisomersic complexes of piperidinium-3-carboxylic acid 2,6-dichloro-4-nitrophenolate, P3C + H·DCNP − , aggregate into centrosymmetric cyclic dimers through the COOH⋯O − and N + H⋯ONO hydrogen bonds of 2.57(1) and 3.06(1) Å, respectively, which in turn are linked into a ladder-type cyclamer through the C H⋯Cl hydrogen bonds of 3.71(1) Å. The title compound is characterized by single-crystal X-ray analysis, Raman and FTIR spectroscopies. The structures of the complexes of the ratio 1:1 (monomer), 2:2 (dimer) and 4:4 (cyclamer) of P3C + H·DCNP − units are optimized by the B3LYP/6-311 + + G(d,p) approach and compared with the solid-state experimental structure. Detail interpretation of the vibrational spectra has been carried out by computing Potential Energy Distribution (PED). Charge delocalization has been analyzed using the Natural Bond Orbital (NBO) method. [ABSTRACT FROM AUTHOR]

• Structure of 8 - hydroxyquinoline betaine monohydrate was solved by X-ray. • The one proton of disordered water molecules is shared between two half-occupied sides. • Three broad bands classify the FTIR spectrum as the ABC type. • PED are used to assign the bands in the vibrational spectrum. • Hirshfeld surface, Mulliken atomic charges, MEP, HOMO-LUMO were computed. • The assignment of 1H and 13C resonance signals are based on the 2D measurements. Molecular structure and properties of 8-hydroxyquinoline betaine monohydrate (1-carboxymethyl-8-hydroxyquinolinium inert salt monohydrate) were studied by X-ray diffraction, DFT calculations, FTIR and NMR spectra. In the crystals, 8-hydroxyquinoline betaine and water are bonded by an intermolecular and asymmetric COO···H 2 O hydrogen bond of 2.782(3) Å. The water molecules are disordered so that one of the proton is shared between two half occupied sites. The hydroxyl group of quinoline is bonded to the neighboring molecule by the O−H···OOC hydrogen bond of 2.571(3) Å. The molecular geometry, Hirshfeld surface, Mulliken atomic charge distribution, molecular electrostatic potential, frontier molecular orbitals, vibrational wavenumbers, magnetic isotropic shielding constants were determined using the density functional theory (DFT/B3LYP) with 6–311++G(d,p) basis set. The FTIR spectrum shows a characteristic ABC structure, typical of medium-short hydrogen bonds. The potential energy distribution (PED) was used to assign the bands in the vibrational spectrum. 1H and 13C NMR spectra were analyzed. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract: The ionophoric antibiotic lasalocid acid has been converted to a novel 6-bromohexyl ester (LASBR) and its structure has been determined in the crystal by X-ray diffraction and in solution by NMR and FT-IR methods. In the crystal two symmetry-independent LASBR molecules are present. The structure of LASBR in solution is slightly different because the strongest intramolecular C(1)Hogen bond in the pseudo-aromatic ring becomes partially broken and a new hydrogen bond between O(4)H and carbonyl group C(13)ed. LASBR forms complexes with Li+, Na+ and K+ cations of exclusively 1:1 stoichiometry. The structures of complexes have been studied and visualized using semi-empirical calculation based on results of spectrometric and spectroscopic investigation. It is demonstrated that in contrast to lasalocid acid the novel ester forms preferential complexes with Li+ cation. [Copyright &y& Elsevier]

Abstract: 4-Nitrophenyl[bis(benzylthio)]methane was synthesized and used in structural study by X-ray diffraction combined with NMR and spectrophotometric method. In the crystal structure the molecule assumes the conformation where the acidic H-atom is difficult to access due to sterical hindrances of three surrounding phenyls. The acidic properties of 4-nitrophenyl[bis(benzylthio)]methane have been compared and discussed with the analogous disulfonyl carbon acid 4-nitrophenyl[bis(benzylsulfonyl)]methane. [Copyright &y& Elsevier]

Abstract: Intermolecular interactions in a synthesized C-acid, 4-nitrophenyl[bis(ethylsulfonyl)]methane have been analysed and its structure determined by X-ray diffraction. The molecular packing in the crystal is governed by CH…O. The dimensions of the hydrogen bonds and the shortest non-bonded distances are also determined. The possible implications in the formation of the hydrogen bonded complexes with the strong organic bases are also discussed. [Copyright &y& Elsevier]

Abstract: The 2:2 hydrogen-bonded complex between Kemp’s triacid (KTA) and 1,1,3,3-tetramethylguanidine (TMG) has been synthesised and studied by X-ray diffraction and by FT-IR spectroscopy. Cocrystals of KTA–TMG belong to the monoclinic system and crystallize in the space group is P2 1 with a =10.5017(3)Å, b =7.9504(3)Å, c =11.8910(4)Å, β =104.004(4)° and Z =2. The ring of the KTA monoanion molecule exhibits a chair conformation with all three carboxylic groups in the axial positions and all three methyl groups in the equatorial positions. In the crystal of the complex, cooperative systems involving inter- and intra-molecular hydrogen bonds are formed. In the solid state two protonated TMG molecules and two deprotonated KTA molecules form a dimer in which three-dimensional hydrogen-bonded networks are found. [Copyright &y& Elsevier]

Abstract: Crystal structure of monensin A rubidium salt dihydrate, [Rb(C36H61O11)·2H2O], has been studied by X-ray diffraction, FT-IR spectroscopy and PM5 semiempirical methods. The crystal space group is P212121 with a =12.6153(7), b =16.4841(10), c =19.4840(12) and Z =4. The Rb–O bond lengths are between 2.788(7) and 2.901(6)Å. The carboxyl group of monensin A is deprotonated and engaged in two intramolecular O(11)–H···O(1) of 2.52(1)Å and O(10)–H···O(2) of 2.60(1)Å hydrogen bonds with hydroxyl groups, accompanied with formation of a pseudo-cyclic structure. This structure is stabilised by the coordination of the Rb+ cation by oxygen atoms. Two water molecules are involved in the weak intermolecular hydrogen bond between the different species forming a supramolecule. The IR spectrum of the crystal is consistent with the results obtained by the X-ray study and provides spectroscopic evidence for the complex formation. The calculated structure and the structural parameters of the monensin A rubidium salt are comparable with those determined by the X-ray study. [Copyright &y& Elsevier]

Abstract: The 2:2 hydrogen-bonded cocrystals between Kemp’s triacid (KTA) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) have been prepared and characterized by X-ray diffraction and FT-IR spectroscopy. Cocrystals of KTA–TBD (2:2) belong to the monoclinic system and its space group is P21/n with a =12.3016(7)Å, b =11.8130(6)Å, c =14.3279(7)Å, β =101.15(1)° and Z =4. The KTA mono anion ring has a chair conformation with all three carboxylic groups in the axial positions and all three CH3 groups in the equatorial positions. In the crystal of the complex the cooperative systems involving inter- and intra-molecular hydrogen bonds are formed. In the solid state two protonated TBD molecules and two deprotonated KTA molecules form a dimer in which three-dimensional hydrogen-bonded networks have been found. The nature of these hydrogen bonds is well reflected by the proton vibrations in the FT-IR spectra of the crystal studied. The negative ion mode ESI-MS spectrum of the cocrystal indicated the existence of a KTA monoanion. The fragmentation pathways of this anion are discussed. [Copyright &y& Elsevier]

Abstract: 2-Hydroxymethyl-pyridine with phenacyl bromide gives 3-hydroxy-3-phenyl-pyrido[2,1-c][1,4]dihydrooxazinium bromide (1). Its structure in crystal was determined by X-ray diffraction and confirmed by FTIR spectra and B3LYP calculations. In DMSO and D2O solutions, this compound exists in equilibrium mixtures with N-phenacyl-2-hydroxymethyl-pyridinium bromide (2). The equilibrium mixture was proved by FTIR, 1H, 13C and 15N NMR spectra. Correlations between the experimental 1H and 13C NMR chemical shifts for 1 and 2 and GIAO/B3LYP/6-31G(d,p) calculated magnetic isotropic shielding tensors (σ), δ exp=a+bσ cal, are reported. A good linear relationship between the experimental and calculated data was obtained only for carbons. [Copyright &y& Elsevier]

Abstract: Azido-tetrazolo tautomeric conversions have been investigated by NMR, X-ray and semiempirical calculations in a series of new 7(8)-methylated azolopyridazines. The transannular effects of the triazole- and tetrazole-ring fusion with pyridazine have been compared, and the thermodynamic equilibrium of the 7- to 8-methyl conversions of the 6-azido-7(8)-methyltetrazolopyridazines monitored in the function of temperature by 1H NMR shifts of the pyridazine hydrogens. General rules governing the azido-tetrazolo conversions in azolopyridazines have been formulated and based on the molecular structure and strains induced in the pyridazine ring by its substituents. [Copyright &y& Elsevier]

Crystals of the Schiff base derivative of gossypol with 3,6,9-trioxa-decylamine were examined using X-ray diffraction, FT-IR and CPMAS spectroscopy. The Schiff base crystallizes as a racemate in the space group C2/c with a=24.390(5), b=12.026(2), c=14.810(3) A˚, β=102.78(3)°, and Z=4. The results of the FT-IR, and CPMAS study of the crystals are in agreement with the X-ray data. The FT-IR spectrum of the crystals shows that the OH groups at position 1,1′ and 6,6′ as well as the N16–H proton are involved in weak intermolecular and intramolecular hydrogen bonds, respectively. The FTIR and CP-MAS spectral behaviour is in agreement with the crystallographic results demonstrating the existence of the enamine-enamine tautomeric form of the Schiff base studied. [Copyright &y& Elsevier]

Abstract 2-(Quinuclidinium)-alkanocarboxylates co-crystallize with 2,6-dichloro-4-nitrophenol at the ratios 1:1 and 1:2 depending on the alkyl-chain lengths. The obtained complexes have been characterized by single-crystal X-ray diffraction, UV–vis, FTIR and NMR spectroscopy. The compounds 2-(quinuclidinium)-acetate and 2-(quinuclidinium)-propionate form complexes with 2,6-dichloro-4-nitrophenol at the stoichiometric ratio 1:2, while 2-(quinuclidinium)-butyrate and 2-(quinuclidinium)-valerate at ratio 1:1. Three crystal structures of compounds of these series were determined, but no single crystals of sufficient quality could be obtained of the 2-(quinuclidinium)-butyrate complex. The B3LYP/6-311++G(d,p) approach has been used to determine structures of their isolated molecules and to interpret the IR and UV–vis spectra. Diagrams of the HOMO and LUMO of molecules have been obtained. Graphical abstract Image 1 Highlights • Quiniclidinium-alkanocarboxylates form H B complexes with 2,6-dichloro-4-nitrophenol. • Lower homologues form molecular complexes at the 1:2 ratio. • Longer homologues form proton transfer 1:1 complexes. • Molecular structures were solved by X-ray diffraction and optimized by DFT methods. • UV–vis, FTIR and NMR spectra were measured. [ABSTRACT FROM AUTHOR]

The structures of 1,3-bis(3-hydroxymethylpyridinium)propane dibromide ( 1 ), 1,3-bis(3-hydroxymethylpyridinium)propane tetrabromozincate ( 2 ) and 1,3-bis(3-hydroxymethylpyridinium)propane tetrabromocuprate ( 3 ) have been studied by X-ray diffraction, DFT, FTIR, NMR and UV–vis methods. The crystal structures of three analogous compounds are significantly different: 1 is orthorhombic, space group Fdd 2, Z = 8, 2 is triclinic, space group P 1 ¯ , Z = 2 and 3 is monoclinic, space group C 2 /c , Z = 8. The bispyridinium dication in 1 lies on the special position on the 2-fold axis. Each 3-hydroxymethyl group forms an OH⋯Br hydrogen bond, and the dications combine into three-dimensional networks through numerous CH⋯Br bonds. The IR spectra of the dibromide of 1,3-bis(3-hydroxymethylpyridinium)propane ( 1 ) and its tetrabromometallates ( 2 and 3 ) were compared and their interpretation was confirmed by calculated spectra. UV–vis spectra for tetrabromocuprate salt ( 3 ) showed significant differences between solid-phase and water solution. [ABSTRACT FROM AUTHOR]

The complex of 2-(hydroxymethyl)-1-methyl-piperidine [2-(1-methyl-piperidine)-methanol] (MPMe) and p -hydroxybenzoic acid (HBA) crystallizes as a hydrate. HBA interacts through the OH···O and NH···O hydrogen bonds with MPMe. The water mediated hydrogen-bonded bridge molecules MPMe and HBA. The structure of 2-(hydroxymethyl)-1-methyl-piperidinium p -hydroxybenzoate hydrate has been characterized by X-ray diffraction, FTIR and NMR spectroscopy and optimized at the B3LYP/6-311++G(d,p) level of theory. The potential energy distributions, PED, have been used to assign the vibrational spectra. The GIAO/B3LYP/6-311++G(d,p) calculated magnetic isotropic shielding constants have been used to interpret the chemical shifts in the 1 H and 13 C NMR spectra. [ABSTRACT FROM AUTHOR]

The molecular structure of 1,2-di(3-hydroxymethylpyridinium)ethane dibromide ( 1 ) has been characterized by X-ray diffraction, B3LYP/6-311++G(d,p) calculations, FTIR, Raman and NMR spectra. The crystals are monoclinic, space group C2/c . 1,2-Di(3-hydroxymethylpyridinium)ethane dication and hydrogen-bonded bromide anions in crystals are located at the inversion center. The both CH 2 OH groups are engaged in two equal length hydrogen bonds with bromide anions. Two structures ( 2 ) and ( 3 ) were optimized at the B3LYP/6-311++G(d,p) level of theory. The optimized complex ( 2) resembles the crystal structure, while complex ( 3 ) is preferred energetically. The O⋯Br − hydrogen bonds distances are: 3.289(2) Å in crystals ( 1 ), but in the optimized structures ( 2 ) and ( 3 ) they are 3.303 Å and 3.461 Å, respectively. The investigated complex is additionally stabilized by the N + ⋯Br − electrostatic attractions. The potential energy distributions (PED) were used for the assignments of IR and Raman frequencies in the experimental and calculated spectra of the title compound. The FTIR spectrum of ( 1 ) is consistent with the X-ray results. Interpretation of the 1 H and 13 C NMR spectra in DMSO- d 6 has been based on 2D experiments. The calculated GIAO/B3LYP/6-311++G(d,p) magnetic shielding constants have been used to predict 1 H and 13 C chemical shifts for the optimized structures of ( 2 ) and ( 3 ). [ABSTRACT FROM AUTHOR]

The structure of the complex of dimethylphenyl betaine (DMPB) with dichloroacetic acid (DCA) ( 1 ) has been investigated by X-ray diffraction, FTIR and Raman spectroscopy, and B3LYP/6-311 + + G(d,p) calculations. The crystal is monoclinic, space group P 2 1 . The acid is connected with betaine through the O H⋯O hydrogen bond of 2.480(2) Å. In the optimized structure the short, asymmetric O⋯O distance is 2.491 Å. FTIR spectrum shows a broad absorption in the 1500–400 cm −1 region characteristic of very short O H⋯O hydrogen bond caused by Fermi resonance between νOH and overtones of δOH and γOH. In the Raman spectrum this broad absorption is not observed. The potential energy distributions (PED) were used for the assignments of IR and Raman frequencies in the experimental and calculated spectra. The FTIR and Raman spectra of the crystal complex are consistent with the X-ray results. [ABSTRACT FROM AUTHOR]

The 1:2 complex ( 1 ) of dimethylphenyl betaine (DMPB) with two molecules of 2,6-dichloro-4-nitro-phenol (DCNP) was prepared and characterized by X-ray diffraction, B3LYP/6-311++G(d,p) and B3LYP-D3/6-311++G(d,p)calculations, FTIR and NMR spectroscopies. The crystal is monoclinic, space group P 2 1 / c with Z = 4. The protons at the oxygen atoms of phenols are bonded to each oxygen atoms of the DMPB carboxylate group by two nonequivalent H-bonds with the O H⋯O distances of 2.473(5) and 2.688(4) Å. Both H-bonds in the optimized structures 2 (in vacuum), 3 (in DMSO solution) and dispersion-correlated functional (D3) 4 (in vacuum) are comparable and are slightly shorter than O(6) H(O6)⋯O(2) in the crystal. The FTIR spectrum of 1 shows a broad absorption in the 3400–2000 cm −1 region corresponding to a longer hydrogen bond and a broad absorption in the 1800–500 cm −1 region caused by the shorter H-bond. The relations between the experimental 13 C and 1 H chemical shifts ( δ exp ) of the investigated compound 1 in DMSO solution and GIAO/B3LYP/6-311++G(d,p) magnetic isotropic shielding constants ( σ calc ) obtained by using the screening solvation model (COSMO) for 3 are linear and reproduce well the experimental chemical shifts described by the equation: δ exp = a + b σ calc . [ABSTRACT FROM AUTHOR]

Exceptionallyrich diagram of ten phases, I–X, has beenrevealed for ferroelectric 1,4-diazabicyclo[2.2.2]octane perchlorate,[C6H13N2]+ClO4–, dabcoHClO4. Pressure- and temperature-induced transformations of thisNH+···N hydrogen bonded structure have beencharacterized by single-crystal X-ray diffraction, calorimetric, anddielectric measurements. At high pressure the single crystals werein situ grown in a diamond-anvil cell at isochoric conditions. Thereare nine phases of dabcoHClO4between 400 and 11 K at ambientpressure, whereas phase X is formed at 1.5 GPa and 296 K. Tetragonalphase I space group P4/mmmtransformsto orthorhombic phases II (Pm21n), III (Pc21n), IV (Pc2a), and V (orthorhombic-modulated)on decreasing temperature. Phase II is stable up to 0.22 GPa, at 0.6GPa phase III is formed, and above 1.50 GPa a new phase X (Pc21a) has been obtained. Atnormal conditions dabcoHClO4is isostructural with theferroelectric crystal of dabcoHBF4; however, their phasediagrams are very different. Above 1.8 GPa dabcoHClO4cocrystallizeswith solvate molecules. [ABSTRACT FROM AUTHOR]

Abstract: A complex between a new N-phenylamide of monensin A (M-AM1) and sodium chloride has been synthesised and studied by X-ray diffraction and FT-IR spectroscopy. The crystal structure of the complex between M-AM1 and sodium chloride with acetonitrile was examined using X-ray diffraction and discussed in detail. Its structure is stabilised by coordination of the Na+ cation with oxygen atoms. The Na–O bond lengths are between 2.382(2) and 2.562(2)Å. The chloride anion is involved in a weak intermolecular hydrogen bond between different species forming a supramolecule. The ESI-MS spectra indicate that the amide forms stable complexes of exclusively 1:1 stoichiometry with Na+ cations. The FT-IR spectrum of the crystal is consistent with the results obtained by the X-ray study and provides spectroscopic evidence for the complex formation. Due to its specific structural properties N-phenylamide of monensin A efficiently binds sodium chloride. The result of the PM5 semiempirical calculation is in agreement with the spectroscopic data and allows visualisation of the structure of the M-AM1–Na+ complex. The new amide of monensin A has been additionally tested in view of its antimicrobial properties. It shows great activity towards some strains of Gram-positive bacteria (MIC=6.25–12.5μg/ml). [Copyright &y& Elsevier]

Abstract: The crystal structure of the 1:1 complex of lasalocid acid with 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) has been studied by X-ray diffraction, FT-IR spectroscopy and 1H NMR. The crystal space group is P212121 with a =11.401(2)Å, b =13.393(3)Å, c =30.063(6)Å and Z =4. In the crystal of the complex a cooperative system involving inter and intramolecular hydrogen bonds is formed. The protonated TBD and two ends of the lasalocid acid anion are hydrogen bonded. These NH⋯O hydrogen bonds are, with a length of 2.907(9) and 2.930(8)Å, relatively long. In the crystal structure the oxygen atoms of the carboxylate group are involved in three intramolecular hydrogen bonds of different length: O(4)O(1) of 2.848(7)Å, O(8)O(1) of 2.938(6)Å and O(3) O(2) of 2.460(8)Å. In chloroform and acetonitrile solutions the crystal structure of the 1:1 complex is only partially preserved, and additionally a new structure, in which the ketone carbonyl group is hydrogen bonded, is formed. The structures have been modeled using the semiempirical PM5 method. [Copyright &y& Elsevier]

• 5-(Quinolinium)-valeric acid bromide hydrates form centrosymmetric and asymmetric dimers. • Water is a bridge between 5-(quinolinium)-valeric acid cations and bromide anions. • The DFT calculations were used to optimize isolated structures of monomer and dimer. • PED are used to assign the bands in the vibrational spectrum. • The NBO, MEP and QTAIM methods were used to characterize the optimized structures. The molecular structure and properties of 5-(quinolinium)-valeric acid bromide monohydrate are characterized by X-ray diffraction, B3LYP/6–311++G(d,p) calculations, FTIR and NMR spectra. Two molecules of this compound are hydrogen bonded through two water molecules and two bromide anions into centrosymmetric dimers, which are arranged in a strongly anisotropic layered structure. The structures of monomer and dimer of the title complex are optimized at the B3LYP/6–311++G(d,p) level of theory. The conformations of the valeric acid unit in the crystalline monohydrate and in isolated molecules (monohydrates and anhydrous forms) are compared. The experimental and theoretical infrared spectra are discussed. The FTIR spectrum shows an absorption in the 3500–2700 cm−1 region attributed to the νCOOH···OH 2 and νBr−···H 2 O. The potential energy distributions (PED) are used to assign bands in the IR spectrum of the monomer. The 1H and 13C NMR chemical shifts are assigned by two-dimensional techniques, COSY, HSQC and HMBC. Charge delocalization is analyzed using the natural bond orbital (NBO) method and it is shown in molecular electrostatic potential (MEP) maps. The bent conformations of the computed structures are characterized by the QTAIM method. Image, graphical abstract [ABSTRACT FROM AUTHOR]

N- Methylpyrrolidine betaine (N- carboxymethyl- N- methyl-pyrrolidinium, inner salt, MPRB) cocrystallizes with p -hydroxybenzoic acid (HBA) at the 1:1 ratio. The complex is characterized by single-crystal X-ray diffraction, FTIR and NMR spectra. The pyrrolidinium ring adopts an envelope conformation with the methyl group in axial and the carboxymethyl substituent in the equatorial positions. In the cocrystal the COO⋯HO and COO⋯HOOC hydrogen bonds are of 2.574 (4) and 2.586 (4) Å, respectively. The molecular geometry, Hirshfeld surface, natural bond orbitals (NBO), molecular electrostatic potential (MEP), vibrational wavenumbers, magnetic isotropic shielding constants were performed using the density functional theory (DFT/B3LYP) with 6–311++G (d,p) basis set. The molecular structures of isolated 1:1 and 1:2 complexes were optimized. The potential energy distribution (PED) of the IR vibrational modes were used to assign the bands in the IR spectrum. Diagrams of the HOMO and LUMO of components and complex are presented. Theoretical and experimental results are in a good agreement. Image 1 • The 1:1 complex of N-methylpyrrolidine betaine with p -hydroxybenzoic acid was prepared. • Structure of complexes were characterized by X-ray diffraction, FTIR and NMR spectra. • The structures of 1:1 and 1:2 complexes were optimized by the B3LYP/6-311++G(d,p) approach. • The molecules are linked through the OH∙∙∙OOC and COOH∙∙∙OOC hydrogen-bonds. • The IR and NMR experimental and computed spectra were discussed. [ABSTRACT FROM AUTHOR]