Two-dimensional lanthanide coordination polymers with bis(diphenylphosphino)hexane dioxide. The determination of the polymeric structure from twinned crystals

Lanthanide nitrates and bis(diphenylphosphino)hexane dioxide (dpphO₂) formed under solvothermal conditions a series of coordination polymers [Ln(dpphO₂)₂(NO₃)₂](NO₃) (Ln = Pr (1), Nd (2), Sm (3), Dy (4), Lu (5)), featuring two-dimensional network structure of the (4, 4) topology. The compounds [Ln(dpphO₂)₂Cl₂]Cl (Ln = Pr (6), Nd (7), Gd (8)) were obtained from corresponding chlorides. Coordination polymer 7 formed regular single crystals of the orthorhombic Pna₂₁$\mathit{Pna}{2}_1$ space group. The nitrate complexes crystallized in the orthorhombic Aea2 space group, however, the crystals were pseudo-merohedral twins simulating a tetragonal diffraction pattern. Unlike our previously characterized neutral polymers with bis(diphenylphosphino)ethane dioxide, all present coordination networks are cationic, with anions located between or within the two-dimensional layers.     

The solution structures and dynamics and the solid-state structures of substituted cyclopentadienyltitanium(IV) trifluorides

Organotitanium fluorides (C5Me4R)TiF3 (R = H, Me, Et) sublimate with formation of crystalline dimers. From solution, we obtained crystals of dimers and tetramers. The tetramer [{(C5Me5)TiF3}4] irreversibly dissociates in the solid state to dimers (DeltaH = 8.33 kcal mol(-1)). The variable-temperature (1)H and (19)F NMR spectroscopy measurements of the toluene-d(8) solution of [{(C5Me5)TiF3}2] revealed at 202 K one monomeric, two dimeric (with C2h and Cs symmetry), two tetrameric (with D2 and C2v symmetry), and two trimeric (both C2 symmetry) molecules. With the increase in temperature and dilution of the solution, the composition of the solution shifts to the smaller molecules. The thermodynamic and activation parameters for the reversible dissociation of dimers to monomers in the solution are DeltaH = 9.2 kcal mol(-1), DeltaS = 24.2 cal mol(-1) K(-1), DeltaH(double dagger) = 12.2 kcal mol(-1), DeltaS(double dagger) = 9.7 cal mol(-1) K(-1). The dissociation path with a weakly double-bridged transition-state dimer was proposed. The thermodynamic parameters for the reversible dissociation of the C2v tetramer to the dimers in solution are DeltaH = 7.9 kcal mol(-1) and DeltaS = 26.8 cal mol(-1) K(-1). From both tetramers, the D2 molecule is 0.34(5) kcal mol(-1) lower in enthalpy and 6.5(5) cal mol(-1) K(-1) lower in entropy than the C2v molecule. The structures of both trimers were proposed. The low-temperature 19F NMR spectra of the CDCl3 solution of [{(C5Me5)TiF3}2] are consistent with equilibria of a monomer, two dimers (with C2h and Cs symmetry), and a trimer. The vapor pressure osmometric molecular mass determination of CDCl3 solution of [{(C5Me5)TiF3}2] at 302 K is consistent with the equilibrium of the dimer and the monomer.     

Structural features of the modulated BiCu2(P(1-x)V(x))O6 solid solution; 4-D treatment of x = 0.87 compound and magnetic spin-gap to gapless transition in new Cu2+ two-leg ladder systems

The BiCu(2)(P(1-x)V(x))O(6) system shows the appearance of various phenomena that progressively change as a function of the average (P/V)O(4) groups size. Then, from x = 0 to x approximately 0.7, a solid solution exists with respect to the basic orthorhombic unit cell of BiCu(2)PO(6). For greater x values (0.7 < x <0.96), structural modulations with incommensurate q vector that slightly change versus x appear. The 4-D treatment of single-crystal XRD data of the modulated phase corresponding to x = 0.87 at 100 K (orthorhombic, a = 12.379(3)Angstrom, b = 5.2344(9) Angstrom, c = 7.8270(14) Angstrom, q = 0.268(3) b*, super space group: Xbmm(0gamma0) s00, X stands for the nonprimitive centering vector (1/2,0,1/2,1/2), R(obs)(overall) = 5.27%, R(obs)(fundamental) = 4.48%, R(obs)(satellite) = 6.58%) has evidenced strong positional modulated effects within the [BiCu(2)O(2)](3+) ribbons while three XO(4) configurations compete along the x(4) fourth dimension. There is no P/V segregation along x(4) in good agreement with steric-only origins of the modulation. Finally for 0.96 < x <1, two phases coexist, i.e., BiCu(2)VO(6) (X = 1) and a modulated phase of the previous domain.The BiCu(2)VO(6) crystal structure shows a unit cell tripling associated with monoclinic symmetry lowering. The VO(4) orientations between two ribbons proceed with respect to the interribbon distance. Then the full system shows flexible interactions between modulated Bi/M/O-based ribbons and surrounding tetrahedral groups, depending on the average XO(4) size. Furthermore, between two ribbons the Cu(2+) arrangement forms magnetically isolated zigzag copper two-leg ladders. Our preliminary results show a spin-gap behavior likely due to the existence of true S = (1)/(2) Heisenberg two-leg ladders. Modulated compositions are gapless, in good agreement with band-broadening toward a continuum in the magnetic excitation spectrum. The continuous distribution of Cu-Cu distances along the rungs and legs of the ladders should be mainly responsible for this magnetic change.     

Refinement of high pressure single-crystal diffraction data using Jana2006

The refinement of high pressure single-crystal data is difficult as the intensities of the reflections from the sample can be falsified due to effects originating from the components of the diamond anvil cell. A series of procedures were developed and implemented into Jana2006 to allow for an easy identification and handling of the outlying intensities in the structure determination process. The use of these procedures is described on the basis of a working example.     

Synthesis,crystal structure and spectral characteristics of highly fluorescent chalcone-based coumarin in solution and in polymer matrix

A new coumarin chalcone 3-((2E)-3-(2-hydroxyphenyl) prop-2-enoyl)-4-hydroxy-2(H)-chromen-2-one was synthesized using the Claisen Schmidt reaction by the condensation of 3-acetyl-4-hydroxycoumarin and 2-hydroxybenzaldehyde using a mild organic base. This novel compound was characterized by ¹H NMR, FT-IR and UV–vis spectroscopy. Single crystal X-ray diffraction investigation at low temperature (T=120 K) shows that this compound exhibits an intramolecular O3–H…O hydrogen bond, the coumarin ring and the phenyl group are nearly coplanar and the crystal packing is stabilized by intermolecular O3–H…O contacts and π–π stacking interactions. This ortho-hydroxyphenyl-4-hydroxycoumarin chalcone exhibits a strong blue-green emission under visible light excitation at 470 nm. The fluorescence behaviors of this compound doped in poly(methyl methacrylate) (PMMA) were investigated.     

The incommensurate modulation in the Bi2Sr2−xCaxCuO6 superconductor, and its relation to the modulation in Bi2Sr2−xCaxCu2O8

The modulation of the (221) superconducting Bi₂Sr_2−xCa_xCuO₆ phase has been analyzed by X-ray diffraction, using four-dimensional symmetry theory. The pseudo-orthorhombic diffraction pattern is a superposition of two twin related components, such that the main reflections with hkl and hk m superimpose, but the satellite hklm and hk m do not. The latter feature allows separation of the twin intensities. The modulation analysis in superspace group P:Aa:1 shows displacements similar to those observed in the 2212 compound [Y. Gao et al., Science 241 (1988) 954] but with generally larger displacements. In particular, the c-axis displacement amplitude of the Cu atoms is increased to almost 0.5 Å. This and the obliqueness of the q vector (q=0.214a^*+0.61c^*) indicate the absence of a restraining influence exerted by the CuO₂/Sr(Ca)/CuO₂ double layers in the multi-Cu layer phases.     

Cubic octanuclear aluminum fluoride phosphonate

A crystalline complex [Al8F12{(CH3)2C(NH3)PO3}12] (1) was isolated from the supernatant of the hydrothermal reaction of gibbsite Al(OH)3 with 1-amino-1-methyl-ethylphosphonic acid (AIPA) and the HF mineralizer. The single-crystal X-ray diffraction analysis revealed a highly symmetrical cubic Al8F12 core with aluminum atoms at the corners, bridging fluorides spanning all edges, and 12 bidentate bridging phosphonate ligands completing the octahedral coordination sphere of aluminum centers. The stability of the complex in solution was established by electrospray mass spectrometry and the high molecular symmetry (Th) was reflected in the appearance of single resonances in the 1H, 19F, and 31P NMR spectra.