Dynamics of the intermolecular hydrogen bonds in the polymorphs of paracetamol in relation to crystal packing and conformational transitions: a variable-temperature polarized Raman spectroscopy study

The properties of the intermolecular hydrogen bonds in the monoclinic (Form I) and the orthorhombic (Form II) polymorphs of paracetamol, C(8)H(9)NO(2), have been studied by single crystal polarized Raman spectroscopy (40 to 3700 cm(-1)) in a wide temperature range (5 K < T < 300 K) in relation to the dynamics of methyl-groups of the two forms. A detailed analysis of the temperature dependence of the wavenumbers, bandwidths and integral intensities of the spectral bands has revealed an essential difference between the two polymorphs in the strength and ordering of OH···O and NH···O hydrogen bonds. The compression of intermolecular hydrogen bonds is interrelated with crystal packing and the dynamics of methyl-groups. On structural compression of the orthorhombic polymorph on cooling, a compromise is to be sought between the shortening of OH···O and NH···O bonds, attractive CH···O and repulsive CH···H contacts in the crystal structure. As a result of a steric conflict at temperatures below 100 K, N-H···O hydrogen bonds become significantly disordered, and an extended intramolecular transition from the conformation "staggered" with respect to the C=O bond to the one "staggered" with respect to the NH bond is observed. In most of the studied crystals this transition was only about 60% complete even at 5 K, but in some of the crystals the orientation of all the methyl-groups became staggered with respect to the NH bond at low temperatures. This complete transition was coupled to a sharp shortening of the OH···O and NH···O hydrogen bonds at <100 K, the appearance of new additional positions of the protons in these H-bonds, and a slight strengthening of the C-HO bonds formed by methyl-groups. The same conformational transition has been observed also in the monoclinic polymorph at T < 80 K. The crystal packing in Form I prevents the O-H···O hydrogen bonds from adopting the optimum geometry, and they are significantly disordered at all the temperatures, especially at ≤200 K. The packing of molecules in Form I is also not favourable to form C-H···O hydrogen bonds involving methyl-groups. One can conclude from the comparison of diffraction and spectroscopic data that the higher stability of Form I results not from a larger strength of individual OH···O and NH···O hydrogen bonds, but is a cumulative effect: all the hydrogen bonds together stabilize the structure of the monoclinic polymorph more than that of the orthorhombic polymorph.     

Order-disorder antiferroelectric phase transition in a hybrid inorganic-organic framework with the perovskite architecture

[(CH3)2NH2]Zn(HCOO)3, 1, adopts a structure that is analogous to that of a traditional perovskite, ABX3, with A = [(CH3)2NH2], B = Zn, and X = HCOO. The hydrogen atoms of the dimethyl ammonium cation, which hydrogen bond to oxygen atoms of the formate framework, are disordered at room temperature. X-ray powder diffraction, dielectric constant, and specific heat data show that 1 undergoes an order-disorder phase transition on cooling below 156 K. We present evidence that this is a classical paraelectric to antiferroelectric phase transition that is driven by ordering of the hydrogen atoms. This sort of electrical ordering associated with order-disorder phase transition is unprecedented in hybrid frameworks and opens up an exciting new direction in rational synthetic strategies to create extended hybrid networks for applications in ferroic-related fields.     

Disproportionation of pyrazine in NH+...N hydrogen-bonded complexes: new materials of exceptional dielectric response

Centrosymmetric pyrazinium NH+...N bonded complexes allow their dielectric properties to be analyzed separately from the bulk ferroelectric polarization observed in the noncentrosymmetric DABCO monosalts. The method of dielectric permittivity measurements has been employed for monitoring polarization fluctuations generated by proton transfers in the NH+...N bonded linear polycations. The revealed dielectric response of [C4H5N2]+BF4- and [C4H5N2]+ClO4- cannot be reconciled with the centrosymmetric symmetry of their structures, but suggests formation of polar defects or nanoregions. Unique transformations of the pyrazine [C4H5N2]+BF4- complex between linear NH+...N hydrogen-bonded polycationic aggregates antiparallel in phase gamma, perpendicular chains in phase beta, and with NH+...N bonds broken in phase alpha have been observed. The [C4H5N2]+ClO4- and [C4H5N2]+BF4- complexes as grown at 290 K are isostructural in orthorhombic phase , space group Pbcm, with linear polycationic chains arranged antiparallel. On heating, the tetrafluoroborate and perchlorate salts each undergoes two first-order phase transitions at similar temperatures about 340-360 K, while on cooling only one phase transition has been observed. An extremely unique sequence of two phase transitions subsequently lowering the symmetry of the [C4H5N2]+BF4- crystal when temperature is increased has been evidenced: the orthorhombic phase heated above 343 K transforms into the monoclinic C2/c-symmetric phase beta, in which the NH+...N bonded linear chains assume perpendicular arrangement; and at about 353-357 K the anions and cations adopt a typical ionic-crystal packing without homonuclear NH+...N hydrogen bonds in a still lower-symmetry monoclinic P21/n-symmetric structure. The exceptional perpendicular arrangement of the linear NH+...N bonded chains in phase beta constitutes a unique system where polarization of small regions can assume various orientations within a plane, depending on the H+ sites. No phase transitions or anomalous dielectric response were observed in the NH+...O bonded [C4H5N2]+NO3- complex. The unprecedented structure-property relations of the pyrazinium complexes fully confirm the role of the NH+...N bond transformations for the dielectric response of analogous DABCO ferroelectrics.     

Magnetostructural relationship in the spin-crossover complex t-{Fe(abpt)2[N(CN)2]2}: polymorphism and disorder phenomenon

t-{Fe(abpt)(2)[N(CN)(2)](2)} [abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole] is an intriguing spin-crossover system that crystallizes in two polymorphs. Polymorph A is paramagnetic; its crystal structure consists of a single molecule located at the center of inversion symmetry. Polymorph B, on the other hand, exhibits a rather complicated two-step-like spin transition; its crystal structure consists of two symmetry-independent molecules. The crystal structure of polymorph B has been derived in the different spin states: above the high-temperature step (300 K), between the two steps (90 K), below the incomplete low-temperature step (50 K), in the light-induced metastable state (15 K), in the thermally quenched metastable state (15 K), and after relaxation from the quenched state (15 K). The correlation between the structure and magnetic properties is precisely established, allowing the complicated magnetic behavior of polymorph B to be well understood. A unique order-disorder phase transition, resulting in a modulation of the metastable state structures, is detected for the first time on such spin-transition compounds. The modulation of the structure originates from a particular ordering of the dicyanamide ligand at one of the two Fe sites.     

Design of a magnetic bistability molecular system constructed by H-bonding and pi...pi-stacking interactions

Crystal structures and magnetic properties were determined for two novel polymorphs of the complex [H2DABCO][Ni(mnt)2] [(H2DABCO)2+ = diprotonated 1,4-diazabicyclo[2.2.2]octane; mnt2- = maleonitriledithiolate]. For each polymorph, anions form a layered structure in which two kinds of dimers were observed. The adjacent anionic sheets are held together by cations via H-bonding interactions between protons of cations and CN groups of anions. Two polymorphs possess spin bistability; namely, upon cooling, a magnetic transition happens at around 120 K with about 1 K hysteresis on heating for the alpha phase and at 112 K with about 10 K hysteresis for the beta phase. Above the transition, the magnetic behaviors of two polymorphs can be approximately interpreted by a singlet-triplet model of an antiferromagnetically coupled S = 1/2 dimer, which is supported by the crystal structures and spin dimer analyses based on extended Hückel molecular orbital calculations.     

Synthesis, DTA, IR and Raman spectra of penthylenediammonium hexachlorostannate NH3(CH2)5NH3SnCl6.

The Raman and IR spectra of NH3(CH2)5NH3SnCl6 have been measured at ambient temperature. It is shown that the cations in the compound assume a symmetry lower than C2v. Combination bands observed in the 2100-1800 cm(-1) region in the IR spectrum of NH3(CH2)5NH3SnCl6 indicate that the compound contains the C-NH3 grouping, the bands are discussed and their assignment are suggested. No evidence of existence of hydrogen bonding is found from the infrared spectrum in the region of 2800-3200 cm(-1); anions and cations are found not connected by hydrogen bonding and are therfore isolated. The Raman spectrum of anions can be interpreted in terms of disordered groups, not clearly showing the predicted splitting of bands.     

M(3-x)(NH4)(x)CrO8 (M = Na, K, Rb, Cs): a new family of Cr5+-based magnetic ferroelectrics

Upon consideration of the hydrogen-bonding properties of the NH(4)(+) cation, we synthesized a new class of compounds, M(3-x)(NH(4))(x)CrO(8) (M = Na, K, Rb, Cs). These magnetic compounds with the simple 3d(1) ground state become ferroelectric. X-ray studies confirmed that the phase transition involves a symmetry change from I42m to Cmc2(1) to P1. The transition temperature depends linearly on the composition variable x. The transitions are of the order-disorder type, with N-H···O bonding playing the central role in the mechanism. Extension of this idea to the introduction of ferroelectricity in several other classes of materials is suggested.     

Effect of High Pressure on the Polymorphs of Paracetamol

Effect of hydrostatic pressure on the two (I – monoclinic and II – orthorhombic) polymorphs of paracetamol was studied by X-ray diffraction in the diamond anvil cell at pressures up to 4.5 GPa (for the monoclinic form) and up to 5.5 GPa (for the orthorhombic form). The two groups of phenomena were studied: (i) the anisotropic structural distortion of the same polymorph, (ii) transitions between the polymorphs induced by pressure. The anisotropy of structural distortion of polymorphs I and II was well reproducible from sample to sample, also from powder samples to single crystals. The bulk compressibility of the two forms was shown to be practically the same. However, a noticeable qualitative difference in the anisotropy of structural distortion was observed: with increasing pressure the structure of polymorph II contracted in all the directions showing isotropic compression in the planes of hydrogen-bonded molecular layers, whereas the layers in the structure of the polymorph I expanded in some directions. Maximum compression in both polymorphs I and II was observed in the directions normal to the molecular layers. The transitions between the polymorphs induced by pressure were poorly reproducible and depended strongly on the sample and on the procedure of increasing/decreasing pressure. No phase transitions were induced in the single crystals of the monoclinic polymorph at pressures at least up to 4GPa, although a partial transformation of polymorph I into polymorph II was observed at increased pressure in powder samples. Polymorph II transformed partly into the polymorph I during grinding. The transformation could be hindered if grinding was carried out in CCl₄. This revised version was published online in August 2006 with corrections to the Cover Date.     

Self-Assemblies of Extended Hydrogen-Bonded Arrays Using 1,4-Butanebisphosphonic Acid as a Versatile Building Block

Two organic salts of 1,4-butanebisphosphonic acid, bis(ethylenediammonium) butanebisphosphonate hydrate ( 1 ) and bis(hexamethylenediammonium) butanebisphosphonate hydrate ( 2 ), have been structurally characterized using single-crystal x-ray diffraction analyses. Compound 1 exhibits a H-bonded pillared bilayered structure, in which etheylenediammonium cation acts as a spacer between the anions resulting in the formation of two types of cavities. The larger cavity is filled by four water molecules though having hydrophobic character. Thus, the material behaves as a nanoporous organic solid. Compound 2 shows a multidimensional hydrogen bonding networks: one-dimensional arrays parallel to the b axis and two-dimensional sheets parallel to the ab plane. The N--H·;·;·;O--P hydrogen bonds, forming H-bonded supramolecular networks, are regarded to be strong and directional hydrogen bonds.     

Free energy of the solid C60 fullerene orientational order-disorder transition

The free energies of the orientationally ordered crystal phase of C60 at low temperatures and the disordered crystal phase at high temperatures are calculated to an accuracy of +/-0.05 kJ/mol using the expanded ensemble Monte Carlo method with the potential model of Sprik et al. [J. Phys. Chem. 96, 2027 (1992)]. The order-disorder transition temperature at zero pressure is determined directly from these free energies, and is found to be consistent with the abrupt changes in configurational energy and unit cell size also found in simulation. A modification of the potential results in predictions of the transition temperature of 257 K and the entropy change of 18.1 J/mol K at this transition, which are in good agreement with the experimental values of 260 K and 19 J/mol K, respectively. The orientational distinguishability in the ordered phase and the indistinguishability in the disordered phase lead to a contribution to the entropy difference of k ln 60, with 60 being the symmetry number of C60. This quantum mechanical correction is important for the accurate prediction of the phase transition properties of the C60 crystals.     

The first polymorph, κ″-(ET)2Cu[N(CN)2]Cl, in the family of κ-(ET)2Cu[N(CN)2]X (X=Cl, Br, I) radical cation salts

The first polymorph, κ″-(ET)₂Cu[N(CN)₂]Cl, of the well known Mott insulator κ-(ET)₂Cu[N(CN)₂]Cl has been prepared and its crystal and electronic structures have been examined. The polymorph has monoclinic symmetry in contrast with the orthorhombic one of the isostructural κ-salts of the family (ET)₂Cu[N(CN)₂]X (X=Cl, Br, I). The monoclinic phase exhibits a layered structure in which the conducting layers are packed in a κ-type arrangement and the anion sheets consist of polymeric zigzag chains formed by Cu[N(CN)₂]Cl units. The main structural differences with the orthorhombic κ-salts are that the anion sheets are disordered and the ET molecules are less planar. The new polymorph shows metallic type resistivity down to 4.2 K.     

Giant dielectric anisotropy and relaxor ferroelectricity induced by proton transfers in NH+...N-bonded supramolecular aggregates

A huge dielectric effect has been observed in a pure and water-soluble hydrogen-bonded organic crystal, 1,4-diazabicyclo[2.2.2]octane hydroiodide [C6H13N2]+.I(-) (dabcoHI). In this structure, the dabco cations are NH+...N bonded into linear aggregates, where the protons are disordered at two nitrogen atoms and the crystal acquires the symmetry of space group P6m2. This nonpolar crystal exhibits a barely temperature-dependent dielectric constant exceeding 1000 at ambient conditions. The dielectric response is extremely anisotropic, more than 2 orders of magnitude higher along the linear hydrogen bonded chains than in perpendicular directions. The physics underlying this effect originates from proton transfers in the NH+...N bonds, leading to disproportionation defects and formation of polar nanodomains, which, on the macroscopic scale, results in one-dimensional relaxor ferroelectricity. Such properties are unprecedented for the materials with hydrogen bonds highly polarizable due to proton disorder. The proton disordering in dabcoHI is analogous to this in H2O ice, where the hydrogen bonds remain disordered until the lowest temperature.     

Phase behavior and structure in mesogen containing polyurethanes

The mesophase to crystal phase transition observed upon heating the monotropic liquid crystal polyurethane (2,6-LCPU-6), based on the mesogenic biphenol 4,4′-bis(6-hydroxyhexoxy)biphenyl (BHHBP) and 2,6-toluenediisocyanate (2,6-TDI), has been investigated by differential scanning calorimetry (DSC), wide angle x-ray scattering (WAXS) and infrared (IR) spectroscopy. Hexafluoroisopropanol (HFIP) fast solvent-evaporation casting resulted in 2,6-LCPU-6 thin films with a glassy mesophase morphology. The mesophase to crystal exothermic transition has been observed by DSC between 130 and 140°C, depending on sample preparation. It is accompanied by a substantial increase of H-bonding between urethane C=O and N-H, as observed by IR. Curve fitting analysis of the conformationally sensitive amide I region revealed three bands; ordered H-bonded carbonyl groups, disordered H-bonded carbonyl groups, and “free” carbonyl groups. The prime feature of the 130°C transition is the substantial increase of ordered H-bonded carbonyl groups at the expense of disordered H-bonded carbonyl groups. Crystal melting occurs between 180 and 210°C and is accompanied by the complete disappearance of the ordered H-bonded peak along with substantial changes in the frequency and width at half-height of the disordered H-bonded peak     

Structural phase transition of magnetic [Ni(dmit)2]- salts induced by supramolecular cation structures of (M+)([12]crown-4)2

Sandwich-type supramolecular cation structures of (M(+))([12]crown-4)(2) complexes (M(+) = Li(+), Na(+), K(+), and Rb(+)) were introduced as countercations to the [Ni(dmit)(2)](-) anion, which bears an S = (1)/(2) spin, to form novel magnetic crystals (dmit(2-) = 2-thione-1,3-dithiole-4,5-dithiolate). The zigzag arrangement of Li(+)([12]crown-4)(2) cations in Li(+)([12]crown-4)(2)[Ni(dmit)(2)](-) salt induced weak intermolecular interactions of [Ni(dmit)(2)](-) dimers, whose magnetic spins were isolated from each other. The molecular arrangements of cations and anions in M(+)([12]crown-4)(2)[Ni(dmit)(2)](-) salts (M(+) = Na(+), K(+), and Rb(+)) were isostructural to each other. In the case of Na(+)([12]crown-4)(2)[Ni(dmit)(2)](-), the space group C2/m changed to C2/c with a lowering in temperature from 298 to 100 K. This structural change occurred at 222.5 K as a first-order phase transition. The space group C2/m (T = 298 K) in the salt K(+)([12]crown-4)(2)[Ni(dmit)(2)](-) also changed to C2/c (T = 100 K), which transition occurred at 270 K. Crystal structural analyses at 298 and 100 K revealed changes in both supramolecular cation conformation and [Ni(dmit)(2)](-) anion arrangements. The transition from C2/m to C2/c crystals generated a dipole moment in the Na(+)([12]crown-4)(2) and K(+)([12]crown-4)(2) structures, which were reconstructed to cancel the net dipole moment of the C2/c crystals. These cation transformations led to changes in intermolecular interactions between the [Ni(dmit)(2)](-) anions via structural rearrangements. The crystal structure of C2/c was stabilized in Rb(+)([12]crown-4)(2)[Ni(dmit)(2)](-) at 298 K. The [Ni(dmit)(2)](-) configuration in these salts with the C2/c space group was a one-dimensional uniform chain, which showed the temperature-dependent magnetic susceptibility of a one-dimensional linear Heisenberg antiferromagnetic chain.     

First principles molecular dynamics study of filled ice hydrogen hydrate

We investigated structural changes, phase diagram, and vibrational properties of hydrogen hydrate in filled-ice phase C(2) by using first principles molecular dynamics simulation. It was found that the experimentally reported "cubic" structure is unstable at low temperature and∕or high pressure: The "cubic" structure reflects the symmetry at high (room) temperature where the hydrogen bond network is disordered and the hydrogen molecules are orientationally disordered due to thermal rotation. In this sense, the "cubic" symmetry would definitely be lowered at low temperature where the hydrogen bond network and the hydrogen molecules are expected to be ordered. At room temperature and below 30 GPa, it is the thermal effects that play an essential role in stabilizing the structure in "cubic" symmetry. Above 60 GPa, the hydrogen bonds in the framework would be symmetrized and the hydrogen bond order-disorder transition would disappear. These results also suggest the phase behavior of other filled-ice hydrates. In the case of rare gas hydrate, there would be no guest molecules' rotation-nonrotation transition since the guest molecules keep their spherical symmetry at any temperature. On the contrary methane hydrate MH-III would show complex transitions due to the lower symmetry of the guest molecule. These results would encourage further experimental studies, especially nuclear magnetic resonance spectroscopy and neutron scattering, on the phases of filled-ice hydrates at high pressures and∕or low temperatures.     

Deuteration triggered downward shift of dielectric phase transition temperature in a hydrogen-bonded molecular crystal

Deuteration of hydrogen-bonded phase transition crystals can increase the transition temperatures due to the isotope effect. But rare examples show the opposite trend that originates from the structural changes of the hydrogen bond, known as the geometric H/D isotope effect. Herein, we report an organic crystal, diethylammonium hydrogen 1,4-terephthalate, exhibits a reversible structural phase transition and dielectric switching. Structural study shows the cations reside in channels formed by on...     

Supramolecular H-bonded assemblies of redox-active metallodendrimers and positive and unusual dendritic effects on the recognition of H2PO4-

The DSM polyamine dendrimers dend-DAB-(NH2)x of generations 1 (x = 4) to 4 (x = 32) form H-bonded dendritic assemblies with the phenol AB3 units p-HOC6H4C(CH2CHCH2)3 and p-HOC6H4C{(CH2)3SiCH2NHCOFc}3 (Fc = ferrocenyl), as shown by the shifts of the NH2 and OH signals giving a concentration-dependent common signal between 2.4 and 4.1 ppm in CDCl3. The supramolecular dendrimers efficiently recognize H2PO4- anions with positive and unusual dendritic effects upon electrochemical titration involving half-stoichiometry for G1, a sudden cyclovoltammetry wave change at the equivalent point, and a dramatic intensity decrease of the new wave.     

Nature of weak inter-and intramolecular interactions in crystals 7. Stability of homochiral supramolecular organization of dications in crystals of 1,3-dialkyl-4,5-bis(3-guanidinioamino)imidazolidin-2-one salts

The geometries and peculiarities of the electronic structure of chiral 1,3-dialkyl-4,5-bis(3-guanidinioamino)imidazolidin-2-one dications (C ₂ symmetry) and their associates in salts containing chloride and nitrate anions were studied by X-ray diffraction analysis and quantum chemistry methods. Homochiral H-bonded cation chains are stable supramolecular fragments; however, their presence in the crystal structures does not provide spontaneous resolution of racemates upon crystallization. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 387–395, March, 2006.     

Raman and X-ray investigations of ferroelectric phase transition in NH4HSO4

Temperature-dependent Raman spectroscopy and X-ray diffraction studies have been carried out on NH(4)HSO(4) single crystals in the temperature range 77-298 K. Two structural transitions driven by the molecular ordering and change in crystal symmetries are observed below 263 and 143 K. These phase transitions are marked by the anomalies in the temperature dependence of wavenumber and fwhm of several internal vibrational modes. The Raman spectra and X-ray data enable us to understand the nature of the molecular ordering resulting in the ferroelectric phase below 263 K, sandwiched between two nonferroelectric phases. The crystal structure of the ferroelectric phase is determined correctly as Pc, which has been earlier solved in Ba symmetry. The temperature dependent Raman and X-ray results suggest that the disorder to order transition leading to lower symmetry below 263 K is driven by the change in HSO(4)(-) ions and that below 143 K is driven by the change in both HSO(4)(-) and NH(4)(+) ions.     

A Coformer Approach for Supramolecular Polymerization at High Concentrations

Insolubility of functional molecules caused by polymorphism sometimes poses limitations for their solution-based processing. Such a situation can also occur in the preparation processes of supramolecular polymers formed in a solution. An effective strategy to address this issue is to prepare amorphous solid states by introducing a “coformer” molecule capable of inhibiting the formation of an insoluble polymorph through co-aggregation. Herein, inspired by the coformer approach, we demonstrated a solubility enhancement of a barbiturate π-conjugated compound that can supramolecularly polymerize through six-membered hydrogen-bonded rosettes. Our newly synthesized supramolecular coformer molecule features a sterically demanding methyl group in the π-conjugated unit of the parent molecule. Although the parent molecule exhibits low solubility in nonpolar solvents due to the formation of a crystalline polymorph comprising a tape-like hydrogen-bonded array prior to the supramolecular polymerization, mixing with the coformer compound enhanced the solubility by inhibiting mesoscopic organization of the tapes. The two monomers were then co-polymerized into desired helicoidal supramolecular polymers through the formation of heteromeric rosettes.