Synthesis and Crystal Structure of Mono-Substituted Ferrocene-Containing Liquid Crystals

Abstract

Ten mono-substituted ferrocene-containing liquid crystals, which containing Schiff base or ester group, were prepared and their mesogenic behaviors were investigated. Two molecular structures were analyzed by X-ray. 4-ferrocenylphenyl 3′-chloro-4′-(2-methylbutyloxy)-benzoate, triclinic crystal system, P1 space group, a=12.035(2)Å, b=14.402(3)Å, c=15.137(3)Å, α =103.07(3)Å, ß = 102.01(3)Å, γ = 96.70(3)Å, Z=4, 8141 independent reflections, R=0.0528, Rw=0.1724. 4-ferrocenylphenyl 3′-chloro-4′-decanyloxybenzoate, triclinic crystal system, P1 space group, a= 11.663(2)Å, b= 11.729(2)Å, c=22.005(4)Å, α=76.10(3)Å, ß =87.56(3)Å, γ = 77.89(3)Å, Z=4, 7935 independent reflections, R=0.0784, Rw=0.2265.     

Crystal Structure of Diethyl 2‐[2,2,2‐ trifluoro‐1‐(indole‐3‐yl)‐ethyl]‐2‐acetamidomalonate

The title compound (C₁₉H₂₁F₃N₂O₅) has been determined from three dimensional X‐ray diffraction data. The crystals are monoclinic, a = 7.626(4)Å, b = 17.515(4)Å, c = 15.066(3)Å, β = 101.02(3)°, V = 1975(1)ų, Z = 4, D_calc = 1.393g cm^‐3, space group P2₁/c. The structure was solved by direct methods and refined by full‐matrix least‐squares method (R = 0.039).     

Synthesis,Crystal Structure and Charge Distribution of InGaZnO4. X‐ray Diffraction Study of 20kb Single Crystal and 50kb Twin by Reticular Merohedry

Synthesis of InGaZnO₄ at 20Kb and 50Kb produced a single crystal and a twinned crystal respectively. The X�ray diffraction crystal structure refinement (R1 = 0.015 and 0.019 respectively) and the Charge Distribution analysis are reported. Space group is R3m; cell parameters in hexagonal axes are a = 3.2990(2)Å, c = 26.1013(25)Å (20kb single crystal) and a = 3.3051(2)Å, c = 26.1029(19)Å (50kb twinned crystal). The cell volume is 246.01(3)ų and 246.94(3)ų respectively. The In is in regular octahedral coordination, whereas Ga/Zn are in trigonal bipyramid co‐ordination. Charge Distribution on cations (2.94 and 2.95 respectively vs. 3.0 for In, and 2.53 vs. 2.5 for Ga/Zn) shows that the structure is well refined. Charge Distribution on oxygens (—1.96 and —2.04 for O1 and O2, vs. —2.0) excludes the presence of valence unbalance effects. A possible structural role of the trigonal bipyramidal coordination is discussed.     

Crystal structures of N1, N5‐dibenzoyltetrahydro‐4‐methyl‐1, 5‐benzodiazepin‐2‐one (DBTBO) and tetrahydro‐4‐methyl‐1, 5‐benzodiazepin‐2‐one (TBO)

Adducing structural analogies between the two fused systems, N1, N5‐Dibenzoyltetrahydro‐4‐methyl‐1,5‐benzodiazepin‐2‐one, C₂₄H₂₀N₂O₃ (DBTBO CCDC 200341) and Tetrahydro‐4‐methyl‐1,5‐benzodiazepin‐2‐one, C₁₀H₁₂ N₂O (TBO CCDC 200342) helps to find the pharmacological differences from the view point of variant hetero atom substitutions in the hetero cycle. Both the diazepines crystallized in identical monoclinic space group P2₁/n with a = 14.1134(1) Å, b = 9.2444(1) Å, c = 16.3812(1) Å; β = 107.11(1)º, V = 2042.7(3) ų for DBTBO and a = 9.3363(7) Å, b = 10.4895(8) Å, c = 9.9852(7) Å, β = 91.314(1)º, V = 977.62(1) ų for TBO, respectively. The two structures were solved by direct methods and refined by full‐matrix least‐squares procedure to final R‐values of R1 = 0.0575(DBTBO) and R1 = 0.0984(TBO). Structural differences include non‐identical boat conformations of these seven‐membered rings and the different non‐bonding interactions in the benzodiazepine pair.     

Synthesis and Structure of 1,4-Diazabutadiene Liquid Crystals

Abstract

Nine 1,4-diazabutadiene compounds, Ar-N=C(R)-C(R)=N-Ar, R=H, Me; Ar=H_2n+1C_nO-C₆H₄, 2,4-(H₉C₄O)(Me)-C₆H₃ were synthesized and their liquid crystal properties were studied through thermal polarizing microscopy. The X-ray single crystal structure of compound 9 (Ar-N=C(H)-C(H)=N-Ar, Ar=2,4-(Me)(H₉C₄O)C₆H₃) was tested. It is a monoclinic crystal system, space group P2₁/C with the unit cell parameters: a=7.0703(3)Å, b=8.6741(4)Å, c=18.3115(8)Å, β =95.392(1)?. V=1114.57(9)ų, z=2, Dc=1.134 Mg/m³, R=0.0490, Rw=0.1237.     

Growth and crystal structure of the layered compound TlGaSe2

The semiconducting compound TlGaSe₂ was grown by solid state reaction technique. The crystal structure of this material was confirmed by single‐crystal X‐ray diffraction. TlGaSe₂ crystallizes in the monoclinic system with space group C2/c (No. 15), Z = 16 and unit cell parameters a = 10.779(2) Å, b = 10.776(1) Å, c = 15.663(5) Å, β = 99.993(6)°. The structural refinement converged to R(F) = 0.0719, R(F²) = 0.0652 and S = 1.17. The structure consists of a three‐dimensional arrangement of distorted TlSe₈ and GaSe₄ polyhedrons. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Morphology of Some Hydrothermally Synthesized Li-Minerals: A-Zeolite, α-Eucryptite, β-Spodumene and β-Eucryptite

The hydrothermal treatment of glass with the composition 2 LiF, Al₂O₃, 3 SiO₂ at 1 kbar in the range of 150 °C to 850 °C gave rise to the formation of A-zeolite with orthorhombic unit cell with å = 10.31 Å/b̊ = 8.18 Å/c̊ = 5.0 Å (space group Pna2₁), α-eucryptite, trigonal, å = 13.4 Å/bº = 13.4/Å/cº = 9.0 Å (space group R 3 ), β-spodumene, pseudocubic/tetragonal, å = 7.53 Å/b̊ = 7.53 Å/c̊ = 9.15 Å (space group P4₃2₁2), β-eucryptite, monoclinic, å = 7.75 Å/b̊ = 5.2 Å/c̊ = 11.16 Å (space group P6₂22). The morphology and development of the mineral phases depend on the temperature of formation.     

An X-ray diffraction refinement of the crystal structure of natural apophyllite

The crystal structure of apophyllite (Andersberg — GDR), with a = 8.966(2), c = = 15.767(1) Å, P4/mnc, z = 2, Q = 2.35 gm · cm⁻³, has been refined (R = 0.035) by least squares with 976 reflections collected with a diffractometer. Apophyllite is a sheet structure with the bringing Si O bond lengths 1.6236 Å, while the non-bridging bond length Si O(3) is 1.5843 Å. The two independent Si O Si angles are 140.09, 140.76 degrees. The mean Si O bond length is 1.6138 Å. As it was not possible to locate unequivocally the H-atoms with the X-ray data, the interpretation of the of water in the structure was based on the charge balance approach of DONNAY and ALLMAN . Assuming that the fluorine ion is bonded to calcium ion (Ca-F = = 2.416 Å) and to H3 atom (F-H3 = 0.9145(1) Å) and water molecule hydrogen bonded to silicate framework. The average bond distances O-H are 0.962(2) Å and angle 105.24(1)°.     

Structural Analysis of Sr<Subscript>3</Subscript>NbFe<Subscript>3</Subscript>Si<Subscript>2</Subscript>O<Subscript>14</Subscript> Single Crystal from the Langasite Family and Finding of Negative Thermal Expansion in the Range of 83–110 K

Iron-containing Sr₃NbFe₃Si₂O₁₄ single crystals from the langasite family, which are interesting for researchers due to their magnetic ordering at T _N = 26 K, have been grown by the floating zone melting method. Accurate X-ray diffraction analysis is performed at 293 and 90.5 K using the data collected on a CCD diffractometer. To compensate for systematic errors, two data sets are collected at each temperature. The structure is refined based on averaged data set: sp. gr. P321, Z = 1, sin θ/λ ≤ 1.35 Å^–1; a = 8.2609(4) Å, c = 5.1313(3) Å at 293 K and a = 8.2344(6) Å, c = 5.1243(6) Å at 90.5 K; the agreement factors are R/wR = 1.18/1.03% and Δρ_min/Δρ_max =–0.57/0.25 e/Å3 for 3583 independent reflections at 293 K and R/wR = 1.18/1.13% and Δρ_min/Δρ_max =–0.54/0.23 e/Å3 for 3638 reflections at 90.5 K. Negative thermal expansion in the direction of the cell c axis is revealed in the range of 83–110 K.     

The crystal and molecular structure of bis(tetramethylammonium) pentachlorooxomolybdate(V)‐acetonitrile(1:1)

The crystal structure of the title compound, C₁₀H₂₇Cl₅MoN₃O was determined by single crystal X‐ray diffraction technique. The crystals are monoclinic, space group C 2/m, with a= 29.075(8) Å, b= 11.843(4) Å, c= 13.252(4) Å, β=117.049(7)°, V = 4064(2) ų, Z=8. The structure was solved by direct methods and refined by least‐squares methods to a final R = 0.0307 for 5095 observed reflections with I>2σ(I). In the pentachlorooxomolybdate anion, the planar chlorines are bent away from the axial oxygen ligand. The Mo‐O bond length is 1.6620(18) Å that indicates significant double bond character. The oxygen trans Mo‐Cl bond is significantly longer than all of the planar Mo‐Cl bonds. These differences can be attributed to a trans influence of the oxygen atom. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Crystal and Molecular Structure of 11,12‐dibromo‐ 7,8—benzo‐1,5‐di(p—tolylsulphonyl)‐1,5‐diazacyclononan

The crystal structure of the title compound, C₂₅H₂₆Br₂N₂O₄S₂ was determined by single crystal X‐ray diffraction technique. The crystals are monoclinic, space group C 2/c, with a=20.7142(2) Å b=11.7910(2) Å, c= 10.6735(3) Å, β=98.549(2)°, V=2577.94(9) ų, Z=4. The structure was solved by direct methods and refined by least‐squares methods to a final R=0.046 for 1866 observed reflections with I>2sigma(I). The title compound, displays disordered geometry around the C1 atom located almost on twofold axis. The nine‐membered heterocylic ring is close to the half‐chair conformation. The dihedral angle between phenyl rings is 34.2(1)°.     

Crystal and molecular structure of 2,6‐bis(4‐chlorophenyl)‐3‐phenylpiperidin‐4‐one

The crystal structure of the title compound is described. The chemical formula of the compound is C₂₃H₁₉Cl₂NO. The compound is found to crystallize in monoclinic system with space group P2₁/c, Z = 4. The unit cell dimensions are a = 15.137(3) Å, b = 8.9171(18) Å, c = 14.779(3) Å, β = 91.461(4)° and V = 1994.2(7) ų, D_calc = 1.320 gcm^‐3. The final R factor is 4.4%. The central piperidone ring of the molecule adopts a slightly distorted chair conformation, the mean torsion angle being 52.3°; the phenyl rings are planar. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal Structure of 6,6′-dimethoxy-2,2′-diphenyl-19-crown-5 Hg(SCN)2

The crystal structure of 6,6′-dimethoxy-2,2′-diphenyl-19-crown-5 Hg(SCN)₂ has been determined from three-dimensional X-ray diffraction data. The compound crystallizes in the triclinic space group P1 (no 2) with unit cell parameters α = 9.712(6) Å, β = 11.137(7) Å, c = 14.768(12) Å, α = 86.04(5), β = 80.36(4), γ = 65.70(4), Z = 2, V= 1435(2) ų. The structure was determined by direct methods which on refinement yielded a final value of R(F) index as 0.068.     

Crystal Structure of 5,6‐Dinitrobenzimidazole.monohydrate

The title compound (C₇H₆N₄O₅) crystallizes in the monoclinic space group P2₁/c with a=8.566(1) Å, b=14.493(3) Å, c=7.583(1) Å, β=87.75(1)°, V=940.7(3) ų, Z=4, D_x=1.597 g.cm^‐3. The structure was solved by direct methods and refined by full‐matrix least‐squares method (R=0.0696). The title compound consists of an imidazole ring with the two NO₂ groups and one water molecule. The short inter‐ molecular N‐H^…N [2.03(5) Å] and O_water‐H^…O [1.98(5) Å] hydrogen bonds are highly effective in holding the molecule in a stable state as a whole.     

Crystal structure of 2‐(3‐amino‐2,4,4‐tricyano‐buta‐1,3‐dienyl)‐ thiophene

The title compound (C₁₁H₆N₄S) crystallizes in the orthorhombic space group Pbca with a = 23.561(4) Å, b = 7.064(1) Å, c = 13.018(3) Å, Z = 8; D_x = 1.387(1) g.cm^‐3 ; R = 0.073 for 1697 observed reflections [F2 ≥ 2σ(F²)]. The interesting feature is disorder in the crystal structure resulting from the existence of two isomeric molecules with interchangable carbon and sulfur positions, occuring at random but with equal probability in the structure.     

Crystal structure and spectroscopic studies of a new organic monohydrogenmonophosphate dihydrate

The crystal synthesis and structure of a new organic monohydrogenmophosphate (3,4‐Cl₂‐CH₂C₆H₃NH₃)₂HPO₄·2H₂O are reported. This compound crystallizes in the monoclinic P2₁/n with a = 9.081(7) Å, b = 6.501(5) Å, c = 35.423(12) Å, β = 91.09(5)°, V = 2090.9(2) ų, and Z = 4. Crystal structure was solved and refined to R = 0.042, using 2543 independent reflections. It can be described by inorganic layers, including the HPO₄^‐ anions and the H₂O molecules, parallel to (a, b) planes and situated at z = 0 and z = 1/2. The interlayer spacing is occupied by the organic molecules which perform different interactions around the 3D network cohesion. A characterization of this compound by solid‐state (¹³C, ³¹P) MAS NMR and IR spectroscopies is also reported. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and structural conformation of N‐substituted 1,4‐dihyropyridine derivatives

N‐(Phenyl)‐3,5‐dicarbethoxy‐2,6‐dimethyl‐4‐(phenyl)‐1,4‐dihydropyridine (A) and N‐(4‐methoxy phenyl)‐‐3,5 dicarbethoxy‐2,6 dimethyl‐4‐(3‐nitro phenyl)‐1,4‐dihydropyridine (B) has been synthesized as per scheme and characterized by the X‐ray diffraction method. The compound A crystallizes in monoclinic space group P21/c with cell parameters a = 9.2770(11)Å, b = 8.6410(5)Å, c = 27.601(3)Å, β = 97.724(3)°, Z = 4. The compound B crystallizes in monoclinic space group P21/c with cell parameters a = 11.229(6), b = 12.746(7)Å, c =17.606(6)Å, β = 104.531(3)°, Z = 4. The structures exhibit both intra and intermolecular hydrogen bonds. Dihydropyridine ring of both the compounds adopt a flat boat conformation. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal and molecular structure of 2-[(4-nitrophenyl)carbonyl]cyclohex-1-ene-1-yl 4-nitrobenzoate

The crystal structure of 2-[(4-nitrophenyl)carbonyl]cyclohex-1-ene-1-yl 4-nitrobenzoate is studied (T = 173 K, R1 = 0.0354 for 2713 observed reflections). This crystal is orthorhombic, a = 7.8367(8) Å, b = 9.6082(10) Å, c = 23.856(3) Å, V = 1796.3(3) ų, space group P2₁2₁2₁, and Z = 4. The molecule has a folded configuration, which is stabilized by π-π interactions between its two parts. A system of intermolecular C-H...O hydrogen bonds (H...O, 2.44–2.67 Å; CHO angles 122°–169°) and intramolecular C-H...O contacts closing five-membered cycles (H...O, 2.42–2.59 Å; CHO angles 96°–102°) are formed in the structure.     

Crystal structure of an ammonium thiocyanate complex of 18–crown–6

The title compound (C₁₃H₃₀N₂O₇S) has been determined from three‐dimensional X‐ray diffraction data. The crystals are monoclinic, a = 22.654(8) Å, b = 8.652(4) Å, c = 23.925(9) Å, β = 123.880(9)°, V = 3893(3) ų, Z = 8, D_calc = 1.192 g/cm³, space group C2/c. The structure was solved by direct methods and refined by full‐matrix least squares method (R = 0.051). The ammonium cation is displaced by 1.08 Å from the mean plane of the ligand causing hydrogen bonding with the macrocyclic O atoms in a perching arrangement. The thiocyanate anion forms an extended hydrogen bonded chain with the cation via the occluded water molecule. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Multicell model of La<Subscript>3</Subscript>Ga<Subscript>5</Subscript>GeO<Subscript>14</Subscript> crystal: A new approach to the description of the short-range order of atoms

The multicell model alternative to the model of mixed atomic sites used now is proposed for a single crystal of La₃Ga₅GeO₁₄ belonging to the langasite family. The multicell consists of four unit cells. In three identical cells of the structure, atoms adapt to the Ge atom occupying one of the two 2d positions on the threefold symmetry axis. In the fourth cell, atoms surround the Ge atom located at the 1a position. The multicell model allows one to study the short-range order of atoms by the methods of classical structure analysis based on Bragg scattering. Four high-resolution data sets measured at 295 and 111.5 K are used in the study. The results are obtained with high relative precision (space group P321, Z = 1; at 295 K a = 8.2020(6) Å and c = 5.1065(6) Å, R/wR = 0.81/0.73% for 3829 unique ref lections; at 111.5 K a = 8.1939(1) Å and c = 5.1022(4) Å, R/wR = 0.85/0.76% for 3880 reflections).