Crystal structure of poly(ethylenimine)-hydrogen chloride complex

Linear poly(ethylenimine) was found to form a crystalline complex with hydrogen chloride when poly(ethylenimine) in the state of its anhydrate or hydrates was immersed in concentrated hydrochloric acid or exposed to HCl vapour. The crystal structure of the HCl complex was determined by X-ray diffraction. The crystals are metrically tetragonal with cell constants a = B = 5.06 Å and c (chain axis) = 7.57 Å and the unit cell includes one planar zigzag polymer chain (two monomeric units) and two HCl molecules (the molar ratio is 1:1). The space group of the crystals is, however, not of the tetragonal system: the structure determined can be expressed in terms of any of the following crystal systems and space groups: orthorhombic P222₁, orthorhombic Pcm2₁, orthorhombic Pc2m, and monoclinic P2₁/m (c unique). The Cl···N distance of 3.05 Å strongly indicates that every NH and HCl hydrogen atom participates in hydrogen bondings between nitrogen and chlorine atoms. The HCl complex has a fairly high melting temperature of 265°C, which is about 200°C higher than those of the anhydrate and hydrates.     

Crystal structure of poly(pentamethylene 2,6-naphthalate)

The crystal structure of poly(pentamethylene 2,6-naphthalate) (PPN) was determined by using X-ray diffraction and molecular modeling. The unit cell of PPN was found to be triclinic ( space group) with dimensions of a=0.457 nm, b=0.635 nm, c=2.916 nm, =121.6°, β=90.4°, γ=87.6°, and the calculated crystal density was 1.311 g cm⁻³. The unit cell contains one polymer chain with two repeating units. In the unit cell, the PPN backbone takes gauche/gauche conformation in the middle part of each pentamethylene unit, and two naphthalene rings are in face-to-face arrangement.     

New route for synthesizing Mn-silicalite-1

Mn-silicalite-1 (Mn_5.2Si_90.8O₁₉₂) was synthesized from Mn²⁺ ion-exchanged magadiite. The characteristics of Mn-silicalite-1 were investigated using electron spin resonance, synchrotron X-ray powder diffraction, IR spectroscopy and chemical analysis. The measurements indicate that Mn²⁺ ions replace Si in the silicalite-1 framework. The orthorhombic framework structure of calcined Mn-silicalite-1 has been determined. The space group is Pnma, with a=20.1017(3) Å, b=19.8826(4) Å, c=13.3758(3) Å.     

(CH3CH[NH3]CH2NH3)1/2·ZnPO4, a zincophosphate analogue of aluminosilicate zeolite thomsonite

The synthesis and structure of (CH₃CH[NH₃]CH₂NH₃)_1/2·ZnPO₄, an organically templated zincophosphate (ZnPO) analogue of aluminosilicate zeolite thomsonite (THO), are described. The ZnPO framework is built up from an alternating, vertex-sharing, network of ZnO₄ and PO₄ groups (d_av(Zn–O)=1.944 (8) Å, d_av(P–O)=1.535 (9) Å, θ_av(Zn–O–P)=130.5°) involving distinctive 4=1 secondary building units. The 1,2-diammonium propane cations are highly disordered in the [0 0 1] 8-ring channels. Crystal data: (CH₃CH[NH₃]CH₂NH₃)_1/2·ZnPO₄, M_r=198.42, orthorhombic, space group Pncn (no. 52), a=14.119 (6) Å, b=14.136 (5) Å, c=12.985 (5) Å, V=2591 (3) ų, Z=10, R(F)=0.057, R_w(F)=0.061 (for a twinned crystal).     

Three metal-organic frameworks prepared from mixed solvents of DMF and HAc

Three metal-organic framework compounds [HZn₃(OH)(BTC)₂(2H₂O) (DMF)] · H₂O (MOF-CJ3), [Co₆(BTC)₂(HCOO)₆(DMF)₆] (MOF-CJ4), and [Co₁₈(HCOO)₃₆] · 3H₂O (MOF-CJ5) have been solvothermally synthesized in mixed solvents of DMF and HAc, respectively. These MOFs are characterized by single-crystal X-ray diffraction, X-ray powder diffraction, ICP, TG analyses, IR, and photoluminescence spectroscopy analyses. MOF-CJ3 crystallizes in tetragonal, space group I4cm (No. 108) with a = 20.588(3) Å, b = 20.588(3) Å, c = 17.832(4) Å. Its framework can be described as a 3D decorated (3, 6)-connected net based on the assembly of trigonal prismatic SBUs and triangular links. MOF-CJ4 crystallizes in hexagonal, space group P-3 (No. 147) with a = 13.975(2) Å, b = 13.975(2) Å, c = 8.1650(16) Å. The 2D network of MOF-CJ4 is constructed from [Co₆(R(CO₂)₃)₂(HCO₂)₆(DMF)₆] (R = C₉H₃–) clusters and 1,3,5-benzene-tricarboxylates linkers. MOF-CJ5 crystallizes in triclinic, space group (No. 2) with a = 15.205(3) Å, b = 18.005(4) Å, c = 21.500(4) Å,  = 71.21(3)°, β = 84.47(3)°, γ = 67.15(3)°. MOF-CJ5 has a diamond framework with Co-centered CoCo₄ tetrahedra as nodes. It is noteworthy that the formic ligands in MOF-CJ4 and MOF-CJ5 are generated by the decomposition of DMF under acid conditions and incorporated into these two compounds.     

Characterization of cancrinite synthesized in 1,3-butanediol by Rietveld analysis of powder neutron diffraction data and solid-state Na NMR spectroscopy

The framework structure and extraframework atoms of calcined and dehydrated cancrinite synthesized in 1,3-butanediol are characterized by powder neutron diffraction and ²³Na nuclear magnetic resonance (NMR) spectroscopy. The cancrinite structure is refined in the hexagonal space group P6₃ (No. 173) with lattice parameters a=12.659 Å and c=5.153 Å. Carbonate anions are found occluded in the pores of the cancrinite structure. Although there are two different crystallographic cation sites found by the Rietveld refinement, there are three peaks in the ²³Na magic-angle spinning (MAS) NMR spectrum. These peaks correspond to sodium cations found in site I inside the cancrinite cages, cations in site II inside the cancrinite pore without neighboring carbonates, and cations in site II with neighboring carbonates. Quadrupole coupling constants (QCC) obtained by a simple point-charge model agree well with the simulation of the ²³Na MAS NMR spectra.     

Synthesis, structure and thermal properties of a novel 3D aluminophosphate UiO-26

The synthesis of a novel 3D aluminophosphate is described. The thermal properties of the material were investigated, and the existence of three high-temperature variants was revealed. The crystal structures of the as-synthesized material (UiO-26-as) and the material existing around 250°C (UiO-26-250) were solved from powder X-ray diffraction data. UiO-26-as with the composition [Al₄O(PO₄)₄(H₂O)]²⁻[NH₃(CH₂)₃NH₃]²⁺ crystallizes in the monoclinic space group P2₁/c (no. 14) with a=19.1912(5), b=9.3470(2), c=9.6375(2) Å and β=92.709(2)°. It exhibits a 3D open framework consisting of connections by PO₄ tetrahedra with AlO₄ tetrahedra, AlO₅ trigonal bipyramids and AlO₅(H₂O) octahedra forming two types of layers stacked along [1 0 0] and connected by Al–O–P bondings. The structure possesses a 1D 10-ring channel system running along [0 0 1], in which doubly protonated 1,3-diaminopropane molecules are located. UiO-26-250 with the composition [Al₄O(PO₄)₄]²⁻[NH₃(CH₂)₃NH₃]²⁺ crystallizes in the monoclinic space group P2₁/c with a=19.2491(4), b=9.27497(20), c=9.70189(20) Å and β=93.7929(17)°. The transformation to UiO-26-250 involves removal of the water molecule which originally is coordinated to aluminum. The rest of the structure remains virtually unchanged. The crystal structures of the two other variants existing around 400 (UiO-26-400) and 600°C (UiO-26-600) remain unknown.     

Crystal structures of fully dehydrated fully Sr-exchanged zeolite X and of its ammonia sorption complex

The crystal structures of fully dehydrated Sr₄₆–X [Sr₄₆Si₁₀₀Al₉₂O₃₈₄; a=25.214(7) Å] and of its ammonia sorption complex, Sr₄₆–X·102NH₃ [Sr₄₆Si₁₀₀Al₉₂O₃₈₄·102NH₃; a=25.127(7) Å], have been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd at 21(1)°C. The Sr₄₆–X crystal was prepared by ion exchange in a flowing stream of aqueous 0.05 M Sr(ClO₄)₂ for 5 days followed by dehydration at 360°C and 2×10⁻⁶ Torr for 2 days. To prepare the ammonia sorption complex, another dehydrated Sr₄₆–X crystal was exposed to 230 Torr of zeolitically dried ammonia gas for 1 h followed by evacuation for 12 h at 21(1)°C and 5×10⁻⁴ Torr. The structures were refined to the final error indices, R₁=0.043 and R_w=0.039 with 466 reflections, and R₁=0.049 and R_w=0.044 with 382 reflections, for which I>3σ(I). In dehydrated Sr₄₆–X, all Sr²⁺ ions are located at two crystallographic sites. 16 Sr²⁺ ions are at the centers of the double six-rings, filling that site (site I, Sr–O=2.592(6) Å). The remaining 30 Sr²⁺ ions are in the supercage (site II); each extends 0.56 Å into the supercage from the plane of its three nearest oxygen atoms (Sr–O=2.469(6) Å). In the structure of Sr₄₆–X·102NH₃, the Sr²⁺ ions are located at three crystallographic sites: 12 are found at site I [Sr–O=2.652(10) Å]; four in the sodalite units (site I′) each coordinated to three framework oxygen atoms at 2.654(9) Å and also to three ammonia molecules at 2.76(8) Å. The remaining 30 Sr²⁺ ions lie at site II. Each extends 1.12 Å into the supercage where it coordinates to three framework oxygen atoms at 2.584(7) Å and also to three ammonia molecules at 2.774(24) Å.     

Preparation and crystal structure of RUB-18 modified for synthesis of zeolite RWR by topotactic conversion

The systematic study on the synthetic route of the siliceous zeolite RWR with a small 8-MR straight channel by topotactic conversion of crystalline layered silicate RUB-18 was carried out by using several topotactic precursors obtained from Na-RUB-18. Intermediate layered structures of topotactic precursors were designed by intercalation of amine molecules and acid treatment. Crystal structures of two kinds of TMAOH intercalated RUB-18s (TMA-RUB-18-poly1 and TMA-RUB-18-poly2) and their acidified TMA-RUB-18 were determined by ab initio structure analysis using X-ray powder diffraction data. The layered structure of TMA-RUB-18-poly1 and TMA-RUB-18-poly2 had tetragonal symmetry of space group P4₂/nmc, and the lattice parameters were estimated to be a = 7.4121 Å, c = 22.615 Å for TMA-RUB-18-poly1 and a = 7.3718 Å, c = 29.342 Å for TMA-RUB-18-poly2. Two silicate layers were involved in a unit-cell and TMA⁺ cations were intercalated in the interlayer. The layer stacking sequence was completely different from that of Na-RUB-18. Structure of acidified TMA-RUB-18 had also tetragonal symmetry of space group I4₁/amd and lattice parameters a = 7.4722 Å, c = 37.242 Å with four silica layers. Stacking sequence in acidified TMA-RUB-18 was similar to that of Na-RUB-18 although a large shrinking of interlayer distance (ca. 2.0 Å) was observed. In the acidified TMA-RUB-18, one-dimensional pseudo pore was constructed by semi-circular geometry derived from the framework structure and stabilized by formation of hydrogen bonding between the terminal silanol groups, which faced each other with atomic distance d(O–O) of ca. 2.5 Å. By the dehydration–condensation of silanol groups during careful calcination, zeolite RWR could be successfully prepared from the acidified TMA-RUB-18.     

Synthesis and characterization of phi-type zeolites LZ-276 and LZ-277: faulted members of the ABC-D6R family of zeolites

A new zeolite, LZ-276, was synthesized in an organic (TEAOH) system by varying the crystallization temperature in the procedure used by Jacobs and Martens for the synthesis of zeolite phi. LZ-276 (with SiO₂/Al₂O₃=7.8) is more siliceous than phi. Another silicon-rich zeolite, LZ-277 (SiO₂/Al₂O₃=6.6), was synthesized in a totally inorganic system. The similar chemical and physical properties of LZ-276 and LZ-277 are compared with those of zeolite phi described by Grose and Flanigen, and others. TEM [100] selected area diffraction patterns of LZ-277 can be indexed on a hexagonal unit cell with a=13.8 and c=15 Å. Twin spots and considerable streaking parallel to {00l} indicate mirror faulting along c. High resolution images on selected crystals of LZ-277 show that the most closely spaced mirror faults occur approximately every 18 Å. The bulk X-ray sample of LZ-276 is less faulted. A close match between the experimental synchrotron X-ray powder diffraction pattern of LZ-276 and one simulated by the DIFFaX program (with faulting probability=10%) indicates that the structures of these materials can be described as a chabazite (CHA) topology with faulting along c, the stacking direction in these ABC double six-ring (D6R) materials. The distribution of interior cages, including new larger cages that result from faulting, is presented.     

Cu-3-trz-PMo12的合成、结构及催化氧化碘离子性能

采用水热法合成了一例新的多酸基有机-无机杂化物,通过X射线单晶衍射、傅里叶变换红外光谱（IR）、热分析测试（TG）、X射线衍射分析（XRD）、扫描电子显微镜（SEM）、元素分析对化合物进行了表征。X射线单晶衍射分析结果表明,化合物的结构式为（PMo₁₂O₄₀） ［Cu₆（C₂H₄N₄）₆］（PMo₁₂O₄₀）?H₂O（简称为Cu-3-trz-PMo₁₂）,属于三方晶系,R-3空间群,晶胞参数a=1.756 66（3） nm、b=1.756 66（3） nm、c=2.303 24（6） nm、α=β=90°、γ=120°、V=6.155 2（3） nm³、Z=3、R₁=0.023 8、wR₂=0.059 2。化合物是由6个3-氨基-1,2,4-三氮唑、6个Cu⁺、两个经典的Keggin型［PMo₁₂O₄₀］^3-及一个间隙水分子组成的二聚体,两个这样的二聚体通过氢键交替相连形成次级单元,每个次级单元之间又通过氢键作用进而形成一个三维超分子结构。催化研究表明,该非均相催化剂在催化过氧化氢氧化碘离子中表现出较为优异的催化活性且具有较稳定的可重复性。     

Crystal lattice deformation and the mesophase in poly(ethylene terephthalate) uniaxially drawn by solid-state coextrusion

The development of crystalline and mesophase structure on drawing of poly(ethylene terephthalate) (PET) has been studied. The uniaxial drawing has been done by solid-state coextrusion from 50 to 90°C. The unit-cell parameters of stress-induced crystallites in extrudates have been determined as a function of extrusion draw ratio (EDR) up to 4.4 and at an extrusion temperature (ET) above T_g, at 70 and 90°C. The higher the EDR, the longer the c-axis chain direction, the shorter the a and b axes and the smaller the unit-cell volume. In comparison with the conventional lattice parameters obtained by Bunn and Fisher, the highest elongation of the c axis is near 10%. These features imply that the lattice of stress-induced crystallites is far from the closest packing. Coextrudates made below the T_g of PET differ markedly from those made above T_g. Wide-angle X-ray diffraction (WAXD) patterns of PET extruded at 50°C (below T_g) even at high draw ratio exhibit small and/or imperfect crystallites. They appear much as a mesophase. The distance between macromolecular chains ranges from 3.2 to 5.4 Å. The shortest value in the mesophase approaches the interplanar crystal distance of 3.4 Å for the (100) crystal face, on which the benzene rings lie. The crystalline peak separation of the PET, WAXD curve has been evaluated to obtain absolute crystallinities and the content of mesophase and amorphous phase.     

Synthesis of a new molecular sieve using DABCO-based structure-directing agent

A new 1,4-diazabicyclo[2.2.2]octane (DABCO)-based quaternary ammonium compound is designed, synthesized, and used as structure-directing agent (SDA) for molecular sieve synthesis. Several 1,1′-alkylenedi(4-aza-1-azonia-2,5-dimethylbicyclo[2.2.2]octane) type SDAs are used in all-silica synthesis mixtures. Among the SDAs tested, the use of 1,1′-butylenedi(4-aza-1-azonia-2,5-dimethylbicyclo[2.2.2]octane) gives a new phase (GUS-1), whereas the use of other SDAs gives zeolite beta (^*BEA), ZSM-12 (MTW), and ZSM-5 (MFI). The GUS-1 is indexed in the orthorhombic crystal class with refined lattice constants a=16.4206(4) Å, b=20.0540(4) Å and c=5.0464(1) Å. The crystalline architecture of GUS-1 shows the same [0 0 1] projection of the framework as that of mordenite (MOR), and is characterized by a one-dimensional 12-membered ring channel system that is closely related to the channels of ZSM-12. The GUS-1 is stable to heat upon calcination at 700 °C in air. The calcined material exhibits adsorption capacity that is comparable to typical large-pore one-dimensional microporous silicates. The behavior of the SDA during synthesis is also discussed.     

Highly ordered orthorhombic mesoporous silica films

Mesoporous silica films are made by the spin-coating technique using an ethylene oxide––propylene oxide––ethylene oxide triblock copolymer (Pluronic PE6800) as template. After optimization of the polymer concentration in the silica sol, films are textured and organized over all the thickness. They exhibit an orthorhombic symmetry (a=16.0 nm, b=10.2 nm, c=23.0 nm) with the b-axis perpendicular to the substrate. This results from a body-centered cubic (bcc) micellar structure which is deformed along the [0 1 1]_bcc cubic axis, i.e. perpendicular to the film plane.     

（C5H7N2O2）4（SiMo12O40）的合成、结构及催化氧化碘离子研究

采用常规水溶液法合成了一种新型的有机-无机杂化多金属氧酸盐（C₅H₇N₂O₂）₄（SiMo₁₂O₄₀）（简称SiMo-12）。采用红外光谱（IR）、热重分析（TG）、单晶和粉末X射线衍射（XRD）、元素分析等对SiMo-12进行了表征。以过氧化氢为氧化剂,运用SiMo-12催化碘离子氧化,考察了催化剂用量、氧化剂用量、pH、温度等因素对反应速率的影响。结果表明：该化合物属三斜晶系,P-1空间群,晶胞参数a=1.097 58（4） nm、b=1.144 88（4） nm、c=1.252 66（4） nm、α=64.665（1）°、β=64.804（1）°、γ=83.441（1）°、V=1.282 89（8） nm³、Z=1、R=0.034 0、wR₂=0.079 9。化合物由4个1-咪唑乙酸和一个经典的Keggin型[SiMo₁₂O₄₀]^4-单元组成,有机配体和多金属氧酸阴离子之间通过静电作用、质子转移以及氢键作用沿x轴形成一维链,链与链之间相互平行形成平行于xy面的二维层,层与层之间再通过氢键连接而得到三维网状结构。SiMo-12在催化碘离子氧化中表现出较为优异的催化活性,在c（SiMo-12）=2.0×10^-4 mol/L、c（过氧化氢）=2.0×10^-3 mol/L、pH=1.4、50 ℃条件下反应速率达到2.641 6×10^-5 mol/（L·s）,比未加催化剂时的反应速率提高了1 565倍。     

Spherulitic crystallization in poly(bis(trifluoroethoxy)phosphazene), PBFP

Spherulite formation in poly(bis(trifluoroethoxy)phosphazene) has been investigated from the melt and from solution over a relatively wide crystallization and annealing range. Three polymorphic forms and one mesoform is found in this polymer. Several of these crystal modifications coexist in amounts which depend upon the crystallization conditions. Negatively birefringent spherulites increase in birefringence slightly upon being heated through the thermotropic T(1) transition. This change involves the formation of a chain extended morphology from a chain folded one. Microbeam X-ray analysis made within the spherulite shows that the unit cell [a] direction is along the spherulite radius while the [c] chain direction lies transverse to the spherulite radius. Moreover, below T(1) it has been established that the X-ray long period is invariant with annealing time and temperature, and above T(1) the periodicity disappears, or cannot be recorded. Whenever heating or cooling occurs through T(1), the spherulite birefringence appears to be invariant after initially heating through T(1). However, a substantial volume change (by dilatomery) of 6% occurs through T(1) and this is consistent with a change in crystal structure from a 3D orthorhombic structure below, to a 2D hexagonal form above T(1). From the molten state the transformation occurs rapidly from isotropic to the 2D form of the mesostate, not far below T_m. The 2D hexagonal form reverts to 3D chain extended orthorhombic on cooling below T(1). This stable chain extended morphology also arises whenever PBFP is melted and then cooled below T(1). All transformations from the isotropic melt or the folded chain conformation must pass through the mesophase. All specimens are friable upon cooling below T(1), whereas the solution case spherulitic polymer film is ductile here.     

Conformational and packing energy calculations on the two crystalline modifications of poly (trans-1,4-butadiene)

Conformational and packing energy calculations have been performed on the two crystalline modifications of poly(trans-1,4-butadiene), and the results have been compared with experimental data. The conformational energy calculations predict the chain axis and conformation of the modification that is stable below 76°C, without any a priori assumption. Packing energy calculations on this modification show that the best space group is P2₁/a and the position of the chains is in good agreement with X-ray data. Conformational energy calculations on the modification that is stable above 76°C predict that the lowest energy conformation is a statistical sequence with a random distribution of the three minimum torsion angles around the single bonds adjacent to the double bond, with a trans conformation around the other single bond.     

Structure of a cyclopropane sorption complex of dehydrated fully Mn-exchanged zeolite X

The structure of a cyclopropane sorption complex of dehydrated fully Mn²⁺-exchanged zeolite X, Mn₄₆Si₁₀₀Al₉₂O₃₈₄ · 30C₃H₆ (a=24.690(4) Å), has been determined by single-crystal X-ray diffraction techniques in the cubic space group at 21(1)°C. The crystal was prepared by ion exchange in a flowing stream of 0.05 M aqueous Mn(NO₃)₂ for three days, followed by dehydration at 460°C and 2×10⁻⁶ Torr for two days, and exposure to 100 Torr of cyclopropane gas at 21(1)°C. The structure was determined in this atmosphere and was refined to the final error indices R₁=0.065 and R₂=0.071 with 509 reflections for which I>3σ (I). In this structure, Mn²⁺ ions are located at two crystallographic sites. Sixteen Mn²⁺ ions fill the octahedral site I at the centers of the hexagonal prisms (Mn–O=2.290(9) Å). The remaining 30 Mn²⁺ ions are at site II; each extends 0.41 Å into the supercage (an increase of 0.27 Å upon C₃H₆ sorption as compared to fully dehydrated Mn₄₆Si₁₀₀Al₉₂O₃₈₄) where it coordinates to three trigonally arranged framework oxygens at 2.148(8) Å and complexes weakly and facially to a cyclopropane molecule by a primarily quadrupolar interaction. The carbon atoms of each cyclopropane molecule are equivalent and equidistant from its Mn²⁺ ion (Mn–C=2.95(9) Å). Because of high thermal motion, the C–C bond length is inaccurately determined; the value found, 1.21(8) Å, is too small.     

Crystalline polythiophene film prepared by electrochemical polymerization of thiophene at a nickel electrode

Crystalline polythiophene (Pth) film was first electrochemically deposited onto a nickel substrate from freshly distilled BF₃-diethyl ether (BFEE) solution containing 15 mM thiophene. The crystalline film was studied by the X-ray diffraction technique and it was found to be a monoclinic unit cell with parameters a = 0.624 nm, b = 0.593 nm, c = 0.596 nm, and β = 103.6°. The film obtained from this medium has a compact morphology and great strength. © 1997 Elsevier Science Ltd.     

Energy calculations of the crystal structure of poly(di-methyl silane)

Low energy crystal structures of poly (di-methyl silane), which is known to have a trans backbone conformation, have been investigated. Energy calculations on isolated molecules show that, like its hexyl counterpart, the lowest energy backbone conformation of the molecule is not all-trans but a helix with the backbone bonds rotated 15° away from trans. This corresponds approximately to a 15/7 helix. To determine if the observed trans conformation results from intermolecular interactions, various packing modes of the trans and the 15/7 helix were analysed and their energies compared. Best packing was found for the trans conformation. For the all-trans molecules arranged in an orthorhombic unit cell, the lowest intermolecular energy was found for a = 1.19 and b = 0.78 nm, in good agreement with dimensions found experimentally at room temperature.