Synthesis,characterization, and crystal structure of <Emphasis Type="Italic">N</Emphasis>-<Emphasis Type="Italic">p</Emphasis>-nitrobenzoyl-<Emphasis Type="Italic">N</Emphasis>′-<Emphasis Type="Italic">p</Emphasis>-chlorophenylthiourea

N-p-nitrobenzoyl-N′-p-chlorophenylthiourea was synthesized and characterized by elemental analysis, IR and ¹H NMR etc. Single crystal structure of the title compound was determined on X-ray diffraction instrument. It is confirmed that the title compound crystallizes in monoclinic space group P2(1)/c, with a=8.5985(14) ?, b=12.1537(19) ?, c=14.972(2) ?, β=105.886(2)°, and D _calc=1.482 g/cm³ for Z=4. Intermolecular N–H⋯O H-bonds link pairs of two molecules. H-bonds and π-π stacking are the main non-bonding interactions in the molecular structure.     

Crystal structure of a salt complex between (<Emphasis Type="Italic">S</Emphasis>)-2-(2′-methylbenzyl)succinic acid and (<Emphasis Type="Italic">R</Emphasis>)-1-phenylethylamine

The optically pure 2-(2′-methylbenzyl)succinic acid were obtained by the optical resolution of the racemates with the chiral host 1-phenylethylamine. The structure of the salt complex between (S)-2-(2′-methylbenzyl)succinic acid and (R)-1-phenylethylamine was first elucidated by X-ray analysis: Monoclinic, Space group P2₁ with a=6.0781(12) ?, b=8.8224(18) ?, c=17.675(4) ?, β=97.64(3)°, V=939.4(3) ?³, Z=2, the absolute structure parameter is 0 (9). The crystal structure indicates that the hydrogen bonds are formed between the acetate anions and the protonated amino group. The intermolecular hydrogen bond links the salt complex into a quasi-two-dimentional netlike structure.     

Crystal structure of 1-(2,3:5,6-Di-<Emphasis Type="Italic">O</Emphasis>-isopropylidene-β-D-mannofuranosyl)-1<Emphasis Type="Italic">H</Emphasis>-[1,2,3]triazol-4,5-dicarboxylic acid diethyl ester

The synthesis and X-ray crystal structure of 1-(2,3:5,6-di-O-isopropylidene-β-D-mannofuranosyl)-1H-[1,2,3]triazol-4,5-dicarboxylic acid diethyl ester are reported. It crystallizes in the orthorhombic system with space group P2₁2₁2₁ (No. 19); a=8.6148(5), b=10.4793(6), c=24.6873(15) ? and Z=4. The solid state structure verifies the β-anomeric form of the title compound and provides evidence for the structures of the azide and chloride precursors.     

Synthesis and structure of chiral ligand [(<Emphasis Type="Italic">S</Emphasis>)-1-(((<Emphasis Type="Italic">S</Emphasis>)-1-methylpyrrolidin-2-yl) methyl) pyrrolidin-2-yl] diphenylmethanol

The title compound (C₂₃H₃₀N₂O), a chiral ligand, has been successfully synthesized from a natural proline. FTIR spectrum has been discussed. DFT (B3LYP) method has been used to determine the structure. With the basis set of the 6–311G^* quality, the DFT calculated bond parameters and harmonic vibrations are predicted in very good agreement with experimental data.

Synthesis and crystal structure of 5-allyl-5<Emphasis Type="Italic">H</Emphasis>dibenzo[b,f]azepine

The crystals 5H-dibenzo[b,f]azepine 2 and 5-allyl-5H-dibenzo[b,f]azepine 3 were synthesized and characterized by X-ray crystallography. The compound 3 is a novel synthon for the construction of unusual isoxazoli(ne)dine rings bearing at the 5th position of dibenzo[b,f]azepine moiety. The compound 2 (C₁₄H₁₁N) crystallizes in the orthorhombic space group P2₁2₁2₁ with the parameters a = 6.036(1) Å, b = 8.250(7) Å, c = 20.528(4) Å, Z = 4 and the final R factor is R1 = 0.0544. The compound 3 (C₁₇H₁₅N) crystallizes in the Hexagonal space group P6₁ with the parameters a = 11.043(9) Å, c = 18.575 Å, Z = 6 and the final R factor is R1 = 0.0373.     

Synthesis and crystal structure of the <Emphasis Type="Italic">N</Emphasis>-8-(diphenyl-hydroxy-2-aminomethylpyridine)borane

Reaction of 2-aminomethylpyridine with diphenylborinic acid in a mixture of CHCl₃-diethyl ether gives diphenyl-(2-aminomethylpyridine-N,N)borane, a cyclic adduct that in presence of environmental moisture yields the N-8-(diphenyl-hydroxy-2-aminomethylpyridine)borane. The two compounds were characterized by NMR and infrared spectroscopy. The structure of N-8-(diphenyl-hydroxy-2-aminomethylpyridine)borane was confirmed by X-ray diffraction. This adduct crystallizes in monoclinic P2₁/n space group with unit cell dimensions: a = 13.193(2) (Å), b = 5.913(7) (Å), c = 19.604(2) (Å), = 90.295(3), V = 1529.3(3) ų, Z = 4. The BN distance is 1.645(3) Å and lies in the range of a dative bond. The NH and OH groups are involved in intermolecular hydrogen bonds formation and they add to the stabilization of the acyclic adduct in the solid state.     

Synthesis and crystal structure of 2-anilino-6<Emphasis Type="Italic">H</Emphasis>-5-(1-phenyl-3-methyl-5-pyrazolone-4-ylene)-1,3,4-thiadiazine

A novel pyrazolone derivative 2-anilino-6H-5-(1-phenyl-3-methyl-5-pyrazolone-4-ylene)-1,3,4-thiadiazine (PMCP-PTSC) containing NNS hexa-atomic heterocycle has been obtained and characterized by means of single crystal X-ray diffraction, IR and ¹H NMR spectroscopies. It is interesting that when grown from two different solvents, two different crystalline structures are formed. The monoclinic crystal A belongs to a P2₁/c space group. The unit cell parameters are a = 16.414(4) Å, b = 12.530(3) Å, c = 8.432(1) Å, = 91.75(2) Å, and Z = 4. The triclinic crystal B belongs to a P space group. The unit cell parameters are a = 11.386(2) Å, b = 12.326(2) Å, c = 12.411(3) Å, = 83.07(1)°, = 87.76(2)°, = 86.52(2)°, and Z = 4. The structure analyses show the title compound is the keto-form. Dimers in crystal packing of A and supramolecular one-dimensional (B) concatenate structures were assembled by the intermolecular hydrogen bonds.     

X-ray crystal structures of two polymorphic forms,monoclinic and triclinic,of: 1-[(<Emphasis Type="Italic">E</Emphasis>)-2-(4-bromophenyl)1-diazenyl]-3-({3-[(<Emphasis Type="Italic">E</Emphasis>)-2-(4-bromophenyl)-1-diazenyl]-6-ethylhexahydro-1-pyrimidinyl}methyl)-4-ethylhexahydropyrimidine

1-[(E)-2-(4-bromophenyl)-1-diazenyl]-3-({3-[(E)-2-(4-bromophenyl)-1-diazenyl]-6-ethylhexahydro-1-pyrimidinyl}methyl)-4-ethylhexahydropyrimidine (1) has been synthesized by reaction of a mixture of formaldehyde and 1,3-pentanediamine{DYTEK^®EPdiamine} with p-bromobenzenediazonium chloride. This compound crystallizes in two polymorphic forms 1-α and 1-β whose crystal structures have been determined by single crystal X-ray diffraction analysis. Both polymorphs 1-α and 1-β display crystallographic disorder within the hexahydropyrimidine rings. The molecule of 1 is built up of two equivalent 3-(aryldiazenyl)-6-ethylhexahydro-1-pyrimidinyl groups in the s-trans orientation around the central methylene group (C13). In both structures the triazene moieties adopt the anti configuration around the N=N bonds, displaying significant π-conjugation. The crystal packings are determined only by van der Waals interactions. The crystal structures of 1-α and 1-β are compared with the previously reported structure of the 5,5-dimethylhexahydropyrimidine analogue 3. Compounds 1 and 3 are isomeric with respect to the hexahydropyrimidine moiety. The structures of 1 and 3 are very different in one respect; in 1 the aryldiazenyl-hexahydropyrimidinyl groups are in the s-trans orientation around the central methylene group, whereas in 3 the arrangement of the aryldiazenylhexahydropyrimidinyl groups is the s-cis orientation. Crystal data: 1-α C₂₅H₃₄N₈Br₂, monoclinic, space group P2(1)/c, a = 9.2150(3), b = 19.4059(6), c = 15.4324(5) Å, β = 98.738(1)^°, V = 2727.7(2) ų, for Z = 4; 1-β C₂₅H₃₄N₈Br₂, triclinic, space group P-1, a = 9.6009(3), b = 10.7509(4), c = 14.2169(5) Å, α = 99.830(2), β = 105.973(3), γ = 95.578(1)^°, V = 1373.9(1) ų, for Z = 2.     

Synthesis and crystal structure of mixed-ligand Cu(II) complex of <Emphasis Type="Italic">N</Emphasis>-(1-phenyl-3-methyl-4-benzylidene- 5-pyrazolone) <Emphasis Type="Italic">p</Emphasis>-nitrobezoylhydrazide and pyridine

A new mixed-ligand copper(II) complex, [Cu(PMBP-PNH)Py], (PMBP-PNH = N-(1-phenyl-3-methyl-4-benzylidene-5-pyrazolone) p-nitrobezoylhydrazide; Py = pyridine), has been synthesized by solvothermal method and characterized by elemental analysis, IR spectrum, thermal analysis and single crystal X-ray diffraction: monoclinic, space group Cc with a = 6.0422(8) Å, b = 22.796(3) Å, c = 18.353(3) Å, β = 93.199(3)^∘, Mr = 582.08, V = 2524.0(6) ų, Z = 4. The copper(II) ion in the title complex is in a slightly distorted square-planar arrangement of the ONO donor atoms of primary ligand PMBP-PNH and one N-donor atom in the secondary ligand pyridine.     

4-(<Emphasis Type="Italic">E</Emphasis>)-2-[3-(3-[(<Emphasis Type="Italic">E</Emphasis>)-2-(4-cyanophenyl)-1-diazenyl]hexahydro-1-pyrimidinylmethyl)hexahydro-1-pyrimidinyl]-1diazenylbenzonitrile: X-ray crystal structure

4-(E)-2-[3-(3-[(E)-2-(4-cyanophenyl)-1-diazenyl]hexahydro-1-pyrimidinylmethyl)hexahydro-1-pyrimidinyl]-1-diazenylbenzonitrile (1) has been synthesized by reaction of p-cyanobenzene diazonium chloride with a mixture of formaldehyde and 1,3-propanediamine. The crystal structure has been determined by single crystal X-ray diffraction analysis. The bis-triazene (1) adopts a folded conformation, similar to previously studied ethylenediamine analogues, and there is evidence of -stacking in the crystal packing. The two planar phenyltriazenyl groups are almost parallel, forming an angle of 6.6(1), and display weak intermolecular s interactions between molecules. This result establishes the structure of the product of this diazonium coupling reaction as the 1-(1-hexahydropyimidinylmethyl)hexahydropyrimidine derivative and not the alternate tetraazabicyclo[5.5.1]tridecane derivative. Crystal data: 1C₂₃H₂₆N₁₀, monoclinic, space group P2₁/c, a = 10.717(1) Å, b = 7.749(1) Å, c = 28.252(2) Å, = 97.223(2), V = 2327.5(5) ų, for Z = 4.     

Synthesis and Characterization of the Adducts of Bis(<Emphasis Type="Italic">O</Emphasis>-butyldithiocarbonato)nickel(II) with Substituted Heterocyclic Amines and X-ray Structure of Bis(<Emphasis Type="Italic">O</Emphasis>-butyldithiocarbonato)bis(4-cyanopyridine)nickel(II)

Abstract  

We report the synthesis and study of a new series of the adducts of Bis(O-butyldithiocarbonato)nickel(II) with substituted heterocyclic amines such as amino and cyanopyridines. Analytical results show that the adducts have 1:2 stoichiometry with general formula M(Xan)₂ L ₂ (M = Ni(II), Xan = O-butyldithiocarbonate, L = 2-, 3- and 4-aminopyridines, 3- and 4-cyanopyridines). The complexes have been characterized by analytical, magnetic susceptibility measurements, molar conductivity measurements, IR, electronic spectral data and X-ray diffraction analysis. One of the adducts, bis(O-butyldithiocarbonato)bis(4-cyanopyridine)nickel(II), crystallizes in the monoclinic space group P2₁/c with unit cell parameters : a = 12.546(4), b = 11.495(3), c = 9.351(3) ?, β = 102.73(3)o, Z = 2. Crystal structure was solved by direct methods and refined by full matrix least squares procedures to a final R-value of 0.0299 for 2,788 observed reflections. The packing of layers of molecules is stabilized by weak C–H···N and C–H···π hydrogen bonds.     

Synthesis and crystal structure of 3-chloro-<Emphasis Type="Italic">N</Emphasis>-(2-chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-4-fluorophenyl)-2,2-dimethylpropanamide

The title compound 3-chloro-N-(2-chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-4-fluorophenyl)-2,2-dimethylpropanamide was synthesized by the reaction of 2-(5-amino-4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione with 3-chloro-2,2-dimethylpropanoyl chloride. Its structure was determined by X-ray single crystal diffraction. The crystal belongs to triclinic, space group P-1 with the following crystallographic parameters: a = 9.595(3) Å, b = 12.093(4) Å, c = 18.433(6) Å, α = 83.961(5)^∘, β = 84.819(5)^∘, γ = 67.920(5)^∘, μ = 0.361 mm⁻¹, V = 1967.9(10) ų, Z = 4, Dx = 1.395 mg/m³, F(000) = 856, T = 293(2) K, 1.11^∘ ≤ θ ≤ 25.01^∘. The X-ray results demonstrated that the reaction of 2-(5-amino-4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione with 3-chloro-2,2-dimethylpropanoyl chloride in tetrahydrofuran at room temperature yielded 3-chloro-N-(2-chloro-5-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-4-fluorophenyl)-,2-dimethylpropanamide.     

Synthesis and structure of 7-methyl-5-phenyl-1<Emphasis Type="Italic">H</Emphasis>-pyrazolo[4,3-<Emphasis Type="Italic">e</Emphasis>]tetrazolo[4,5-<Emphasis Type="Italic">b</Emphasis>][1,2,4]triazine<Superscript>(1)</Superscript>

The synthesis of 5-azido-3-methyl-1-phenyl-1H-pyrazolo[4,3-e][1,2,4]triazine 2 and 7-methyl-5-phenyl-1H-pyrazolo[4,3-e]tetrazolo[4,5-b][1,2,4]triazine 3 is described and the crystal and molecular structure of the latter is reported. This compound crystallizes in the monoclinic system, space group P2₁/n, with cell constants a = 11.607(2) Å, b = 7.982(1) Å, c = 13.147(2) Å, = 110.60(1), Z = 4, T = 293 K and D_cal = 1.470 g cm^–3. The structure was solved by direct methods and refined to R value of 0.0368 for 1906 reflections. The X-ray analysis revealed that the linear form of the tetrazolo-fused ring system of 3 exists in the crystal. The molecule as a whole has an almost planar conformation stabilized by the short intramolecular NsH interaction. The molecular packing in the crystal is determined by the van der Waals forces only.Part 26 in 1,2,4-triazines in organic synthesis. For part 25 see Mojzych et al.¹     

Crystal structure of 1,7-dihydroxyxanthone from <Emphasis Type="Italic">Weddellina squamulosa</Emphasis> Tul

1,7-dihydroxyxanthone was isolated from Weddellina squamulosa Tul. (Podostemaceae) and the crystal structure has been determined (C₁₃H₈O₄), Mr = 228.19, a = 4.902(1), b = 13.593(4), c = 14.740(2) Å, space group P2₁2₁2₁, Z = 4, and V = 982.2(4) ų. The 1,7-dihydroxyxanthone molecule is planar with a strong intramolecular H-bond O–HsO [2.607(4) Å]. The molecular packing is done through hydrogen bonds O–HsO [2.786(4) Å], forming channels along the direction parallel to the a-axis.     

2D <Emphasis Type="Italic">s</Emphasis>-<Emphasis Type="Italic">d</Emphasis> Mixed-Metal Coordination Polymer Containing Potassium,Chromium(III) and Dipicolinate Ions: Preparation and Crystal Structure

Abstract  

The reaction of pyridine-2,6-dicarboxylic acid (dipicolinic acid, dipicH₂) with potassium tetraperoxochromate(V) in the mixture of water and ethanol led to the formation of a 2D s-d mixed-metal coordination polymer of {K[Cr(dipic)₂]}_n (1). The compound was characterized by spectroscopic methods (IR, Raman, UV/Vis). Single crystal X-ray diffraction analysis revealed that dipicolinate ligand is coordinated to the chromium(III) ion in an O,N,O′-tridentate fashion, while its uncoordinated and coordinated carboxylate O atoms (with respect to Cr(III) ion) are in turn bound to potassium ions. Therefore, each dipicolinate ligand bridges two potassium ions and a chromium(III) ion between them, giving rise to a 2D coordination network. The coordination of chromium(III) ions is octahedral, while the coordination number of potassium ions is 8. The coordination networks are in turn assembled only by π–π stacking interactions into a 3D structure.     

Synthesis and crystal structure of 1-(4-bromobenzyl)-4-methyl-2,6,7-trioxabicyclo[2.2.2]octane

1-(4-Bromobenzyl)-4-methyl-2,6,7-trioxabicyclo[2.2.2]octane, C₁₃H₁₅BrO₃, has been synthesized from 4-bromophenylacetic acid chloride via the oxetan ester (3-methyl-3-oxetanyl)methyl-2-(4-bromophenyl)acetate. The crystal structure of the title compound has been determined at low temperature (120 K), by X-ray diffraction methods. This compound crystallizes in the monoclinic space group P2₁/n (No. 14), Z = 4, with lattice parametersa = 6.019(5), b = 20.990(5), c = 9.915(2) Å, and = 101.29(1)°.     

Synthesis and X-ray structural analysis of (2<Emphasis Type="Italic">Z</Emphasis>)-3(4-hydroxyphenyl)-2-pyridin-4-ylacrylonitrile and (2<Emphasis Type="Italic">Z</Emphasis>)-3-(3,5-di-<Emphasis Type="Italic">tert</Emphasis>-butyl-4-hydroxyphenyl)2-pyridin-4-ylacrylonitrile

Synthesis and X-ray structural investigations have been carried out for the two title compounds C₁₄H₁₀N₂O (3a) and C₂₂H₂₆N₂O (3b). Compound 3a crystallizes in the monoclinic space group P2₁/c, with a = 3.843(1) Å, b = 24.618(5) Å, c = 11.318(2) Å, = 92.61(3), V = 1069.7(4) Å,³ and Z = 4. Compound 3b crystallizes in the triclinic space group P-1, with a = 9.004(2) Å, b = 9.447(2) Å, c = 11.713(2) Å, = 76.70(3), = 83.12(3), = 82.16(3), V = 956.5(3) Å,³ and Z = 2. Both stilbazole derivatives have Z-geometry about the ethylene bridge which links the heterocyclic and aromatic rings. The molecular skeleton of 3a is slightly non-planar: the dihedral angles between the acrylonitrile linkage and the pyridine ring, and between this linkage and the p-hydroxyphenyl ring are 7.2(2) and 4.1(2), respectively. The molecular skeleton of 3b is less planar: the values of similar dihedral angles are 17.0(2) and 20.8(2), respectively. In the crystal of 3a, the molecules are packed in stacks along the a axis with head-to-head orientation. Intermolecular hydrogen bonds O=H s N and C=H s N link molecules into sheets parallel to (100) plane. In the crystals of 3b, the molecules have a head-to-tail orientation and intermolecular hydrogen bonds O=H s N link the molecules into infinite chains along [01-1] direction.     

Crystallographic and conformational analyses of zwitterionic form of (<Emphasis Type="Italic">E</Emphasis>)-2-methoxy-6-[(2-morpholinoethylimino)methyl]phenolate

The single crystal X-ray diffraction analysis of the title compound, C₁₄H₂₀N₂O₃, reveals that the structure is adapted to its zwitterionic form and centrosymmetric dimers are formed by N⁺–H···O⁻ type ionic weak hydrogen bonds in the crystal structure. The title compound crystallizes in the triclinic space group P−1 with a = 5.9255(13) ?, b = 9.853(3) ?, c = 12.248(3) ?, α = 101.793(19)°, β = 94.941(17)°, γ = 104.36(2)°, Z = 2, D_x = 1.308 g/cm³, μ (Mo-K_α) = 0.092 mm⁻¹. The structure was solved by direct methods and refined to a final R = 0.0371 for 2183 reflections with I > 2σ (I). The crystal structure is stabilized by N⁺–H···O⁻ type intra-molecular hydrogen bonds and N⁺–H···O⁻ type packing interactions referred to as weak hydrogen bonds. To elucidate conformational flexibility of the title molecule, the selected torsion angle is varied from −180° to +180° in every 10° separately and then molecular energy profile is calculated and construed. In addition, charge-population analysis of the crystallographically observed structure confirms its zwitterionic form.     

X-ray diffraction study of (TlInSe<Subscript>2</Subscript>)<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>(TlGaTe<Subscript>2</Subscript>)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> crystal system

The crystallographic and dynamic characteristics of TlInSe₂ and TlGaTe₂ crystals have been studied by X-ray diffraction in the temperature range of 85–320 K. The temperature dependences of the unit-cell parameters a of TlInSe₂ and TlGaTe₂ crystals, as well as their coefficients of thermal expansion along the [100] direction, are determined. The concentration dependences of the unit-cell parameters a and c for (TlInSe₂)_{1 − x} (TlGaTe₂) _x crystals are measured. Anomalies are found in the temperature dependences of the unit-cell parameters a and, correspondingly, the coefficient of thermal expansion, indicating the existence of phase transitions in TlInSe₂ and TlGaTe₂ crystals.     

Synthesis and crystal structure of 3-[2-oxo-2-(4-methyloxyphenylsulfonamidophenyl)ethylidene]-3,4-dihydro-1H-quinoxalin-2-one

3-[2-Oxo-2-(4-methyloxyphenylsulfonamidophenyl)ethylidene]-3,4-dihydro-1H-quinox-alin-2-one (4) was synthesized and characterized by ¹H NMR,¹³C NMR, IR, and single-crystal X-ray diffraction techniques. The crystallographic results show that the composition of the title compound is C₂₃H₁₉N₃O₅S. It belongs to triclinic crystal system and P-1 space group, with a=7.273(6) ?, b=9.092(7) ?, c=15.928(13) ?; α=85.135(11)°, β=78.297(10)°, γ=84.619(11)°, V=1024.4(14) ?³, Z=2, D _c=1.457 mg/m³, μ = 0.201 mm⁻¹, F(000)=468, R=0.0597, wR=0.1438. Supplementary material CCDC-281953 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/retrieving.html or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk.