Crystal structure of nylon 12

The crystal structure of nylon 12 prepared by polymerization of dodecalactam has been determined by x-ray diffraction. Nylon 12 fiber exhibits only the γ form as its stable crystal structure. The unit cell of nylon 12 was determined with the aid of the x-ray diffraction pattern of a doubly oriented specimen. The unit cell is monoclinic with a = 9.38 Å, b = 32.2 Å (fiber axis), c = 4.87 Å and β = 121.5° and contains four repeating monomer units. The chain is planar zigzag for the most part but is twisted at the position of amide groups, forming hydrogen bonds between neighboring parallel chains. The chain conformation is similar to that of the γ form of nylon 6 proposed by Arimoto. It was deduced from the calculations that there are two chain conformations statistically coexistent according to the direction of twisting. In each conformation, hydrogen bonds are formed between parallel chains to make pleated sheetlike structures. The sheets are nearly parallel to (200) and in the sheet the directions of the neighboring chains are antiparallel, as is the case with nylon 6.     

Isotactic poly(pentene-1): Polymorphism of form I

The polymorphism of isotactic poly(pentene-1) form I was studied by x-ray diffraction. Upon quenching from the melt at a temperature below 25°C, the films crystallized in a stable monoclinic form, which we have designated as form I (a = 22.4 ± 0.2 Å, b = 6.49 ± 0.05 Å, c = 21.2 ± 0.2 Å, β = 91 ± 1°). For higher quenching temperatures, a metastable form, form I′, appeared, which transforms to the normal modification upon aging (monoclinic, with: a = 24.3 ± 0.2 Å, b = 6.50 ± 0.05 Å, c = 19.3 ± 0.2 Å, β = 96 ± 2°). Both modifications have a 3₁ helical conformation. Limited changes in the packing mode could explain this polymorphism.     

Structural studies of polyethers. IX. Planar zigzag modification of poly(ethylene oxide)

A new crystal modification was found in poly(ethylene oxide) stretched about two-fold after necking at room temperature. An x-ray diffraction analysis indicated that the planar zigzag molecule passes through a triclinic unit cell with parameters α = 4.71 Å, b = 4.44 Å, c (fiber axis) = 7.12 Å, α = 62.8°, β = 93.2°, and γ = 111.4°. The space group is P1 ?C_i¹. Packing of the molecule is very similar to that of monoclinic polyethylene.     

Crystal structure of polysulfonamides

Structures of poly(alkylene-1,3-benzenedisulfonamide)s [? HN(CH₂)_mNH? O₂SC₆H₄SO₂? ]_n (PMm: 2 ≤ m ≤ 6) were studied by x-ray diffraction and infrared spectroscopy. The crystal structure of PB6 is monoclinic, space group C2/m? C_2h³, with a = 7.70 Å, b = 7.76 Å, c (molecular axis) = 14.1 Å, and β = 117°. Two mirror-image molecules repeating with two monomeric units in an identity period 28.2 Å occupy the same lattice site with equal probability. The alkylene chains assume the planar zigzag conformation, which is the structure isomorphous with PB4. An intermolecular hydrogen bond is formed between each NH group and one of the two O = S groups of the corresponding SO₂ unit. The c axis tends to tilt from the fiber axis by an inclination angle of about 3° around the b axis.     

Crystal structure of nylons 2/3/3 and 1,3

The crystal structures of two polyamides, poly(glycyl-β-alanyl-β-alanine) (nylon 2/3/3) and poly(methylene malonamide) (nylon 1,3), have been investigated by x-ray diffraction and electron microscopy. Crystallization of nylon 2/3/3 from a solution in a mixture of water and formic acid yields lamellar single crystals exhibiting a triangular habit. Doughnut-shaped morphologies diffracting as single crystals are obtained in the crystallization of nylon 1,3. A helical structure of the type known as polyglycine II is found for both polyamides. In such a structure, chains are intermolecularly linked by hydrogen bonds giving a hexagonal lattice of a = 4.79 Å. Insufficient data are available to determine precisely the conformation of the chains. We assume a threefold helix having c = 35.2 Å and c = 18.0 Å for nylon 2/3/3 and nylon 1,3 respectively. No sign of the layered structure familiar in polyamides has been detected for these polymers throughout the experiments made in the present study.     

Crystal structure of an alternating copolymer of ethylene and tetrafluoroethylene

The unit cell of an alternating copolymer of ethylene and tetrafluoroethylene was determined by x-ray diffraction. In spite of uncertainties due to irregularities in the chain structure and a low level of crystallinity, a reasonable unit cell and structure was derived which gives a calculated crystalline density of 1.9 g/cm³. The unit cell is believed to be either orthorhombic or monoclinic with the following parameters: a = 9.6 Å, b = 9.25 Å, c = 5.0 Å, (γ = 96°). The molecular conformation is that of the extended zigzag, and the molecular packing appears to be orthorhombic, each molecule having four nearest neighbors with the CH₂ groups of one chain adjacent to the CF₂ groups of the next.     

Structures of three crystal modifications of poly(3,3-dimethyloxacyclobutane)

Three crystal modifications of poly(3,3-dimethyloxacyclobutane) [? CH₂C(CH₃)₂CH₂O? ]_n were found and their structures were analyzed by x-ray diffraction. Modification I is obtained only under tension and disappears on relaxing the tension. From the fiber period of 4.83 Å, the molecular structure seems to be planar zigzag. In modification II, two chains in T₃GT₃? conformation pass through a monoclinic cell with parameters a = 8.93 Å, b = 7.48 Å, c (fiber axis) = 8.35 Å, β = 97.9°, and the space group P2₁/c-C. In modification III, two (T₂G₂)₂ chains pass through an orthorhombic cell with parameters a = 15.60 Å, b = 5.74 Å, c (fiber axis) = 6.51 Å, and the space group, C222₁–D. Molecular conformations of the three crystal modifications correspond to those of polyoxacyclobutane.     

Monohalogenated ferrocenes C5H5FeC5H4X (X = Cl,Br and I) and a second polymorph of C5H5FeC5H4I

The structures of the three title monosubstituted ferrocenes, namely 1‐chloroferrocene, [Fe(C₅H₅)(C₅H₄Cl)], (I), 1‐bromoferrocene, [Fe(C₅H₅)(C₅H₄Br)], (II), and 1‐iodoferrocene, [Fe(C₅H₅)(C₅H₄I)], (III), were determined at 100 K. The chloro‐ and bromoferrocenes are isomorphous crystals. The new triclinic polymorph [space group P, Z = 4, T = 100 K, V = 943.8 (4) ų] of iodoferrocene, (III), and the previously reported monoclinic polymorph of (III) [Laus, Wurst & Schottenberger (2005). Z. Kristallogr. New Cryst. Struct. 220 , 229–230; space group Pc, Z = 4, T = 100 K, V = 924.9 ų] were obtained by crystallization from ethanolic solutions at 253 and 303 K, respectively. All four phases contain two independent molecules in the unit cell. The relative orientations of the cyclopentadienyl (Cp) rings are eclipsed and staggered in the independent molecules of (I) and (II), while (III) demonstrates only an eclipsed conformation. The triclinic and monoclinic polymorphs of (III) contain nonbonded intermolecular I...I contacts, causing different packing modes. In the triclinic form of (III), the molecules are arranged in zigzag tetramers, while in the monoclinic form the molecules are arranged in zigzag chains along the a axis. Crystallographic data for (III), along with the computed lattice energies of the two polymorphs, suggest that the monoclinic form is more stable.     

Structural studies on the polymorphism of nylon 3

The structure and morphology of crystalline nylon 3 [poly(β-alanine)] have been studied by electron microscopy and x-ray diffraction. Two clearly defined forms are detected. Form I appears as spherulites made up of ribbonlike lamellae upon crystallization at high temperature from a solution in phenol–butanediol-1,4. They have monoclinic unit cell with a = 9.60 Å, c = 8.96 Å, and β = 122.5°. The hydrogen-bonded planes run parallel to the long dimension of the crystals. Form II is observed when the samples are prepared from formic acid solution at room temperature. A second type of spherulite with a microfibrillar structure is formed in this case. The isolated crystalline structures obtained from Form II appear to grow along the intersheet direction rather than along the hydrogen bond direction, which constitutes anomalous behaviour. Our results for this second form are consistent with an orthorhombic lattice with a = 9.56 Å and c = 7.56 Å. No clear information is obtained on the b dimension of the unit cell (chain axis) in either case. We assume a value of 4.78 Å, which corresponds to fully extended chains. The two forms coexist in films prepared from a formic acid–water solution as well as in samples recovered immediately after polymerization.     

The crystal structure of 3′-methoxy-5-phenyl-5,10-dihydrophenarsazine,C19H16AsNO

The crystal structure of 3′-methoxy-5-phenyl-5,10-dihydrophenarsazine, C₁₉H₁₆AsNO has been determined by the single crystal x-ray diffraction method. The crystals are monoclinic with a = 15.305(6), b = 5.809(2), c = 17.595(6)Å, β = 92.92(2)°, V = 1562.3(1.0ų, space group P2,/n, Z = 4 and d_calc = 1.485g cm⁻³. An automatic diffractometer with graphite monochromatized MoKα radiation was used to obtain 1480 observed reflection with I > 3σ(I) at 2θ < 50°. Final R = 0.040 and wR = 0.032. The tricyclic ring is folded with the central ring in a flattened boat conformation. The folding angle between the least-squares planes of the two benzo rings is 164.6(2)°. The 3′-methoxyphenyl group is in a boat-axial conformation with respect to the central ring.     

SYNTHESIS OF ONE-AND TWO-DIMENSIONAL ZINC AND CADMIUM COMPLEXES WITH 4, 4′-BIPY

Abstract

The zinc(II) and cadmium(II) complexes [Zn(4, 4′-bipy)(SCN)₂]_∞ 1 and [Cd(4, 4′-bipy)-(SCN)₂]_n 2 have been synthesized and their crystal structures determined by X-ray crystallography. Complex 1 is monoclinic, space group C2/c, with a = 18.076(5), b = 5.190(1), c = 17.315(4)Å; β = 115.54(2), V = 1465.8(8)ų, calculated density 1.530gcm^?3, Z = 4. In this compound, the rod-like ligand 4, 4′-bipy bridges Zn(II) centres, and the NCS groups are terminally coordinated. (N-Zn-N) is 108.5°, resulting in the formation of a zigzag Zn-bipy-Zn chain. These chains are arranged in parallel fashion. The 4, 4′-bipy ligands of adjacent layers are separated by 3.95 (Å). Complex 2 is monoclinic, space group C2/c, a = 11.902(2), b = 11.745(2), c = 10.500(2)Å; β = 109.71(3), V = 1381.8(4)ų calculated density 1.849gcm^?3, Z = 4. In this structure, the cadmium(II) ion is slightly distorted octahedral and the SCN groups act as doubly bridging ligands connecting cadmium atoms to form zigzag chains, separated by 4, 4′-bipy to create two-dimensional planes.     

A Two-coordinate Copper(I) Complex Constructed from Cyanuric acid and 4,4′-bipyridyl: Synthesis, Structure and Photoluminescence

A two-coordinate copper（Ⅰ） complex, Cu2（bipy）（H2L）2 （1） （H3L=cyanuric acid, bipy=4,4＇-bipyridyl）, which exhibits strong photoluminescence, has been synthesized under hydrothermal conditions and structurally characterized by single crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P21/n, with cell parameters： Mr= 539.42, a= 13.4806（5）A↑°, b=4.5234（2） A↑°, c= 15.4952（8）A↑°,β = 105.526（3）°, V=910.39（7）A↑°^3, Z=2 and μ=3.52 mm^ -1. In the structure the two Cu（Ⅰ） ions are bridged by bipy to form a two-coordinate copper（Ⅰ） dimer. The adjacent dimer units are connected by hydrogen bonding interactions, resulting in 1D zigzag chains along the c axis. 1 emits intense yellow light when excited with UV light.     

THE CRYSTAL,MOLECULAR STRUCTURE AND LIGAND BONDING IN TETRAKIS (N,N′-DIMETHYLTHIOUREA) NICKEL (II) BROMIDE DIHYDRATE

Abstract

The crystal structure of tetrakis(N,N′-dimethylthiourea)nickel(II) bromide dihydrate has been determined by three-dimensional x-ray diffraction from 1916 counter-data reflections collected at room temperature.

The structure consists of Ni[SC(NH)₂(CH₃)₂]²⁺ ₄ molecular ions, Br^? ions and waters of hydration. The nickel is located on a center of symmetry and is coordinated to four sulfur atoms in a square planar configuration. The waters of hydration and the bromide ions are involved in hydrogen bonding to the N,N′-dimethylthiourea (dmtu) groups. The orientation of the dmtu groups is such that two bond through the sulfur sp² orbital and the others bond through the π-orbitals of the dmtu group. The Ni-S distances are 2.204 ± 0.002 Å and 2.230 ± 0.002 Å, and the Ni-S-C angles are 106.2 ± 0.2Å and 110.3 ± 0.3°. The dmtu groups are planar except for methyl hydrogens.

The crystals are monoclinic, P2₁/a with a = 13.424 ± 0.002 Å, b = 12.321 ± 0.005 Å, c = 8.460 ± 0.008 Å β = 107.07 ± 0.05°, ρ₀ = 1.67 g cm^?3, ρ_c = 1.66 g cm^?3 and Z = 2. The structure was refined by full-matrix least-squares to a conventional R of 0.0466.     

Molecular conformation of optically active polyesters and their stereocomplexes

Crystal lattices for various polymorphs of poly(α-methly-α-ethyl-β-propiolactone) (PMEPL) are proposed on the basis of combined electron and x-ray diffraction data. Single crystal-like electron diffraction is observed from melt crystallized thin films of isotactic PMEPL and stereocomplex. Melt-crystallized isotactic PMEPL exhibits a monoclinic, pseudo orthorhombic lattice with the unit cell parameter c (4.75 Å) equivalent to the periodicity of the planar zigzag conformation typically obtained by sample elongation. The stereocomplex crystallizes in a distinctly different orthorhombic lattice with c = 7.1 Å, implying a 2₁ helical conformation. In addition, melt-crystallized mixtures of isotactic PMEPL and isotactic poly(α-methyl-α-n-propyl-β-propiolactone) (PMPPL) are examined by solid state ¹³C nuclear magnetic resonance spectroscopy and x-ray diffraction. These techniques reveal that, in such blends, the conformation and crystal structure found for isotactic PMEPL of a given chirality depends on the absolute configuration of the PMPPL present. In samples containing PMEPL and PMPPL of opposite absolute configuration, isotactic PMEPL crystallizes from the melt as a helix, in contrast to its behavior in the pure state, whereas PMPPL adopt the same helical conformation in the blend as when crystallized alone.     

Kristall- und Molekülstruktur von Bis(1,1-diethyl-3-thiobenzoyl-thioureato)nickel(II)

Crystal and Molecular Structure of Bis(1,1-diethyl-3-thiobenzoyl-thioureato)nickel(II). Bis(1, 1-diethyl-3-thiobenzoyl-thioureato)nickel(II) forms two modifications, whose structures have been determined by X-ray structure analysis. The monoclinic modification crystallizes in the space group P2₁/n with a = 13.709, b = 8.571, c = 12.803 Å, β = 68.10° and Z = 2. The triclinic modification crystallizes in the space group I1 with a = 14.406, b = 7.761, c = 11.734 Å, α = 86.10, β = 97.39, γ = 90.18° and Z = 2. The molecular structures of both modifications are nearly identical (packing polymorphism). The coordination is exactly planar, the ligands are arranged in trans position. The average Ni? S bond length is 2.153 Å in the monoclinic form and 2.163 Å in the triclinic form. The chelate rings deviate from planarity.     

Coordination polymer of Ag trifluoroacetate with 2-methylpyrazine: Synthesis and structure of [Ag(CF3CO2)(2-Me-Pyz)]

The [Ag(CF₃CO₂)(2-Me-Pyz)] complex (where 2-Me-Pyz is 2-methylpyrazine) was synthesized and its structure was determined. The crystals are monoclinic, space group P2₁/n, a = 12.440(2) Å, b = 2.605(3) Å, c = 12.646(3) Å, β = 95.95(3)°, V = 1972.3(7) ų, ρ = 2.122 g/cm³, Z = 8. The structure consists of the polymer zigzag chains of [Ag(C₅H₆N₂)] _? ^∞ united into a three-dimensional framework through (CF₃CO₂)^? anions.     

Crystal structure of α-gutta percha: Modification of the constrained least-squares method

The crystal structure of α-gutta percha has been determined by x-ray diffraction. The unit cell parameters are a = 7.98 Å, b = 6.29 Å, c (fiber period) = 8.77 Å, and β = 102.0° (monoclinic). The space group is P2₁/c–C_2h⁵. Two molecular chains of nearly trans-CTS-trans-CTS? conformation pass through a unit cell; C, T, S, and S? being the cis, trans, and two types of skew forms, respectively. The constrainedle astsquares method was modified so that the order of the least squares matrix could be reduced and was applied to the refinement of the crystal structure.     

Isomorphism in the poly(3,3-bis-hydroxymethyloxetane) family and copolymers: Poly (3,3-bis-hydroxymethyloxetane-co-3-methyl-3-hydroxymethyloxetane)

Copolymers of 3,3-bis-hydroxymethyloxetane, BHMO, 3-metyl-3-hydroxymethyloxetane, MHMO, or with 3-ethyl-3-hydroxymethyloxetane, EHMO, monomer units were characterized by x-ray fiber diffraction, differential scanning calorimetry and ¹³C solid-state nuclear magnetic resonance (NMR). The copolymers are statistically random and crystalline throughout the range of compositions. Both P(BHMO) and P(MHMO) appear to crystallize in the same crystal form. The fiber repeat indicates a planar zigzag backbone conformation, c(fiber axis) = 4.77 ± 0.03 Å. Similarities in the x-ray fiber diagrams as well as a linear dependence of T_m with composition of copolymer with no change in fiber diagrams indicates isomorphism, a phenomenon in which the random substitution of MHMO monomeric units into the crystalline lattice of P(BHMO) occurs without hindering crystallization of the resulting copolymer. © 1994 John Wiley & Sons, Inc.     

The synthesis and structure of 5-hydroxy-2-methyl-2-(2-pyridinyl)hexahydro-1,3-pyrimidine

The synthesis and the x-ray structure of 5-hydroxy-2-methyl-(2-pyridinyl)hexahydro-1,3-pyrimidine are reported. The compound was prepared by reaction of 2-acetylpyridine and 1,3-diamino-2-hydroxypropane in a 2:1 molar ratio. The colourless crystals are monoclinic, space group P2₁/c with cell parameters, a = 10.385(5), b = 11.171(5), c = 17.415(6)Å, β = 93.05(37)° for Z = 8. The asymmetric unit of the structure is composed of two independent molecules of the compound which are in the chair form and adopt the same conformation with equatorial -OH and -CH₃ groups and axial pyridine substituents. The packing of the molecule seems to be controlled by two independent hydrogen-bonding sequences.     

Spectroscopic studies and X-ray crystal structures of charge-transfer complexes of 1,4,7-trithiacyclononane with diiodine

1,4,7-Trithiacyclononane ([9]aneS₃) reacts with molecular diiodine in CH₂Cl₂ to form a 1:1 adduct. The formation constant and the thermodynamic parameters of this adduct have been determined by UV-visible spectra of several solutions at the temperatures of 15, 20, 25, 30, and 35°C. The ¹³C NMR spectra show that adducts with higher ligand/diiodine molar ratios are formed. Two neutral charge-transfer molecular compounds having formula 2[9]aneS₃ · 4I₂ ( I ) and [9]aneS₃ · 3I₂ · ( II ) have been obtained as crystals. The crystals of I are triclinic (a = 8.498(2) Å, b = 13.984(4) Å, c = 14.898(6) Å, α = 65.57(2)°, γ = 89.19(2)°, γ = 81.26(2)°, Z = 2, space group P1; R = 0.025) and contain units formed by two [9]aneS₃ molecules connected by a diiodine molecule; one [9]aneS₃ binds two other diiodine molecules, while the second binds only one other diiodine molecule. The crystals of II are monoclinic (a = 13.810(2) Å, b = 9.829(4) Å, c = 16.198(6) Å, β = 113.41(2)°, Z = 4, space group P2₁/c; R = 0.019) and contain molecules of [9]aneS₃ binding three diiodine molecules. FT-Raman spectra in the characteristic v(I–I) region, carried out on the solid adducts, are discussed in comparison with the structural parameters.