The Crystal Structures of Some 1-Aryl-5-methyl-1,2,3-triazole Derivatives

Abstract  The two 1-aryl-5-methyl-1,2,3-triazole derivatives were prepared by the 1-aryl-5-methyl-1,2,3-triazol-4-carboxylic acids 3. The yielded products 4a–b were confirmed by NMR, MS, IR spectra. We investigated the crystalline structure of compounds 4a and 4b. Compound 4a, C₉H₈BrN₃, Mr = 238.09, crystallizes in the monoclinic space group P2(1)/n with unit cell parameters a = 11.660(2), b = 7.668(2), c = 11.818(2) ?, α = 90.00, β = 116.01(3), γ = 90.00o. V = 949.6(3) ?³, Z = 4, Dx = 1.665 Mg m⁻³. The final R was 0.0477. Compound 4b, C₁₃H₁₁N₃, Mr = 209.25, crystallized in the orthorhombic space group Pbca with unit cell parameters a = 10.373(2) ?, b = 11.691(2) ?, c = 17.579(4) ?, α = 90.00o, β = 90.00o, γ = 90.00o, V = 2131.8(7) ?³, Z = 8, D _m = 1.304 Mg m⁻³. The final R was 0.0565. Index Abstract  The two 1-aryl-5-methyl-1,2,3-triazole derivatives were prepared by the 1-aryl-5-methyl-1,2,3-triazol-4-carboxylic acids 3. The yielded products 4a–b were confirmed by NMR, MS, IR spectra. We investigated the crystalline structure of compounds 4a and 4b. Compound 4a, C9H8BrN3, Mr = 238.09, crystallizes in the monoclinic space group P2(1)/n with unit cell parameters a = 11.660(2), b = 7.668(2), c = 11.818(2)  ?, α = 90.00, β = 116.01(3), γ =90.00o. V = 949.6(3) ?³, Z = 4, Dx = 1.665 Mg m⁻³. The final R was 0.0477. Compound 4b, C13H11N3, Mr = 209.25, crystallized in the orthorhombic space group Pbca with unit cell parameters a = 10.373(2) ?, b = 11.691(2) ?, c = 17.579(4) ?, α = 90.00o, β = 90.00o, γ = 90.00o, V = 2131.8(7) ?³, Z = 8, D _m = 1.304 Mg m⁻³. The final R was 0.0565.      

Tautomeric properties and crystal structure of N-[2-hydroxy-1-naphthylidene]2,5-dichloroaniline

The title compound has been synthesised by the reaction of 2-hydroxy-1-naphthaldehyde with 2,5-dichloroaniline. The compound was characterized by elemental analysis, IR and UV-Visible techniques. The UV-Visible spectra of the Schiff base with OH group in ortho position to the imino group was studied in polar and nonpolar solvents in acidic and basic media. The structure of compound has been examined cyrstallographically. It crystallizes in the orthorhombic space group P2₁2₁2₁ with a = 6.059(1), b = 12.105(2) c = 20.006(2) Å, V = 1467.4(3) ų, D_x = 1.431 g.cm^-3 and Z = 4. The crystal structure was solved by direct methods and refined by full-matrix least squares. Molecule of the title compound N-[2-hydroxy-1-naphthylidene]2,5-dichloroaniline is nearly planar. The molecule contains a strong intramolecular N…H-O hydrogen bond between the imine and hydroxyl group [O1 and N1 = 2.540(4) Å]. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and crystal structure of Schiff base transition metal complex [Co(PMBP-smdtc)2]⋅2H2O

A cobalt(II) complex, [Co(PMBP-smdtc)₂]2H₂O, in which PMBP-smdtc is the l-phenyl-3-methyl-4-benzoyl-5-pyrazolone Schiff base of S-methyldithiocarbazate, has been synthesized and characterized by IR spectrum and single crystal X-ray diffraction. The crystal is monoclinic: space group C2/c, with a = 12.455(2) Å, b = 16.024(2) Å, c = 20.513(3) Å, = 101.18(1)°, V = 4016.3(10) ų, and Z = 4. The cobalt ion is octahedrally coordinated by two tridentate Schiff base ligands with ONS donor atoms. The molecules are bridged together by two water molecules through H-bond along b axis and one-dimensional indented chain structure is formed.     

Crystal Structure of a Non-Conductive Non-Stoichiometric Tetrathiafulvalenium Salt: (TTF)3(BF4)2

Abstract

(TTF)₃(BF₄)₂ crystallizes in the triclinic system, space group P1, a = 8.017(3), b = 8.601(1), c = 11.635(2) Å, α = 108.79(1), β = 100.96(2), γ = 99.09(2)°, Z = 1. The TTF entities are stacked in parallel columns arranged into parallel layers alternating with layers of BF₄ ^? anions. A TTF stack is constituted of (TTF⁺)₂ diads interspersed with TTF° monads; the TTF⁺-TTF⁺ overlap is of the ring-over-ring type while the TTF⁺-TTF⁺ overlap is of the bond-over-ring type. These features explain the low conductivity ([sgrave]_powdcr = 2 × 10^?5 Ω^?l cm^?1) of this apparently non-stoichiometric TTF salt.     

Synthesis and Crystal Structure of <Emphasis Type="Italic">N</Emphasis>′-(6-Chloropyridin-3-formyl)-<Emphasis Type="Italic">N</Emphasis>-<Emphasis Type="Italic">t</Emphasis>-Butyl Urea

Abstract The crystal structure of N′-(6-chloropyridin-3-formyl)-N-t-butyl urea, C₁₁H₁₄ClN₃O₂, has been established, and which belongs to monoclinic crystal system, space group Pn with unit cell dimensions a = 9.335(3) ?, b = 12.715(3) ?, c = 21.813(6) ?, β = 95.417(6)°, V = 2577.6(12) ?³ and Z = 8. An intramolecular N–H···O hydrogen bond forms a six-membered ring in the central part of the molecule. Both two N–H atoms of single unit participate in intermolecular hydrogen bonds and an intramolecular hydrogen bond, respectively. Index Abstract The crystal structure ofN′-(6-chloropyridin-3-formyl)-N-t-butyl urea, C₁₁H₁₄ClN₃O₂, has been established, and which belongs to monoclinic crystal system withZ = 8, space group Pn.      

Reaction of dichloromaleic anhydride with 1,8-diaminonaphthalene: Synthesis and X-ray diffraction structure of 8,9-dichloropyrrolo[1,2-a]perimidin-10-one

The reaction of dichloromaleic anhydride with 1,8-diaminonaphthalene in refluxing toluene or 1,2-dichloroethane produces the new heterocyclic compound 8,9-dichloropyrrolo[1,2-a]perimidin-10-one in low yields. 8,9-Dichloropyrrolo[1,2-a]perimidin-10-one has been isolated by column chromatography and characterized in solution by IR, ¹H NMR, and UV/vis spectroscopies. The solid-state structure was unequivocally established by single-crystal X-ray diffraction analysis. 8,9-Dichloropyrrolo[1,2-a]perimidin-10-one crystallizes in the monoclinic space group P2 ₁/c, a = 7.475(1)Å, b = 10.650(2)Å, c = 14.468(2)Å, = 94.478(2)°, V = 1148.3(3) ų, Z = 4, and d _calc = 1.672 Mg/m³; R = 0.0289, R _w = 0.0762 for 1644 reflections with I > 2(I). The nature of the HOMO and LUMO in 8,9-dichloropyrrolo[1,2-a]perimidin-10-one has been determined by extended Hückel molecular orbital calculations, and these data are discussed relative to the cyclic voltammetric data obtained at a platinum electrode.     

8-Thiatheophylline nitrato silver (I): Spectroscopic characterization and crystal structure

A new metal-theophylline derivative was synthesized from AgNO₃ and 8-thiatheophylline. The thermal stability of the Ag(C₆H₆N₄O₂S)(NO₃) complex was studied by TG and DSC techniques. The silver coordination has been discussed from IR,¹H-NMR and¹³C-NMR spectra. The crystal structure was established by X-ray diffraction. Ag(TTH)(NO₃) crystallizes in space groupP2₁2₁2₁ witha=6.198(1),b=12.576(2),c=13.422(2) Å andZ=4. The structure was refined toR=0.032. This complex reveals interesting features in the coordination mode of the TTH ligand. The sulfur atom and the carbonyl groups are not involved in the coordination. Silver tetrahedral coordination occurs through N7 and N9 of two different TTH ligands (Ag-N7=2.422(3) Å; Ag-N9=2.356(2) Å) and through two oxygen atoms of two different nitrato groups (Ag-O=2.435(4) and 2.518(4) Å) giving a polymeric structure.     

Complexes of azobisindoles with π-organic acceptors

Complexes of azobisindoles with tetracyanoethylene and tetracyanoquinodimethane were studied by UV-Vis, FT-IR, Raman, NMR and X-ray spectroscopies. FT-IR and Raman spectra, as well as X-ray analysis, gave useful information on the participation of various sites to the association, through analysis of CN and N=N vibrational modes, while UV-Vis and NMR spectra were less helpful. The crystal structure of complexes 1-ethyl-2-phenyl-3-(1-ethyl-2-phenyl-3-azoindole)indole/TCNE,3a and 1,2-diphenyl-3-(1,2-diphenyl-3-azoindole)indole/TCNQ,5b are reported. In the two complexes, the distances between donor and acceptor planes range between 3.4 and 3.5 Å; in3a tetracyanoethylene faces the phenyl ring of the indole, while in5b the superposition of tetracyanoquinodimethane with the donor is negligible. Compound3a,P–1,a=9.504(2),b=9.513(3),c=8.941(2) Å, =97.81(4), =103.38(3), =84.14(2)°,Z=2,D _calc=2.55 g cm^–3; compound5b,P–1,a=12.648(3),b=12.205(2),c=7.263(3) Å, =103.69(2), =91.23(3), =110.61(2)°,Z=2,D _calc=2.53 g cm^–3.     

Crystal structure of [RuCl2[N-(2,4,6-trimethyl-benzyl)N-(n-butyl)]-imidazolidin-2-ylidene] and [RuCl2[N-(2,4,6-trimethyl-benzyl)-N-(2-methoxyethyl)]-imidazolidin-2-ylidene]

Two imidazolidin ruthenium complexes, [RuCl₂{[N-(2,4,6-trimethyl-benzyl)-N-(n-butyl)]-imidazolidin-2-ylidene}], 1, and [RuCl₂{[N-(2,4,6-trimethyl-benzyl)-N-(2-methoxyethyl)]-imidazolidin-2-ylidene}], 2, have been synthesised and their crystal structures have been determined from single crystal X-ray diffraction data. Compound 1 is monoclinic, of space group C2/c with a = 18.466(4) Å, b = 14.816(3) Å, c = 15.413(3) Å, β = 118.067(2)^∘, and V = 3720.9(12) ų with Z = 8 for d_calc = 1.536 g/cm³. Compound 2 is monoclinic, of space group P2₁/c with a = 8.1800(5) Å, b = 14.344(8) Å, c = 14.809(9), β = 91.604(10)^∘, and V = 1736.7(18) ų with Z = 4 for d_calc = 1.653 g/cm³. In each complex the ligand functions as an arene and carbene, occupying four coordination sites. The two chlorines in each compound complete a distorted octahedron.     

Tri-(nitrato)-bis-(hexamethylenetetramine)-nona-(aquo) neodymium (III): Synthesis,crystal structure,IR and Raman spectroscopy

This paper reports the structural and spectroscopic properties of tri-(nitrato)-bis-(hexamethylene-tetramine)-nona-(aquo)neodymium (III). The crystals are monoclinic, space groupP2₁/n,Z=4, witha=17.902(4),b=9.335(2),c=18.489(4)Å, B=112.07(2)°. The crystal structure consists of one [Nd(NO₃)₂(H₂O)₆]⁺ cation, two NO ₃ ^– anions coordinated to the neodymium atom, two hexamethylene tetramine molecules, third free NO ₃ ^– anion and three water molecules. The structure was refined to a finalR index 0.039 and weightedR _w 0.039 for 6221 observed reflections. The IR and Raman spectra are fully consistent with the crystallographic results.     

Synthesis and crystal structure of a new composite complex between a hepta-coordinate ytterbium(III) and a heteropoly molybdic anion: [Yb(DMSO)<Subscript>7</Subscript>]H[SiMo<Subscript>12</Subscript>O<Subscript>40</Subscript>] (DMSO = dimethyl sulfoxide)

A new composite complex of the general formula [Yb(DMSO)₇]H[SiMo₁₂O₄₀] has been synthesized from H₄SiMo₁₂O₄₀⋅nH₂O, YbCl₃ and DMSO in mixed solvent of acetonitrile and water and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Singe crystal X-ray structure analysis shows that it belongs to monoclinic system, space group P2₁/c, with a = 11.685(2) Å, b = 14.969(3) Å, c = 35.037(7) Å, β = 98.50(3)^∘, and Z = 4. There is one [Yb(DMSO)₇]³⁺ coordinated cation and one [SiMo₁₂O₄₀]⁴⁻ polyanion in one structure unit. The organic ligands (DMSO) do coordinate directly with ytterbium(III) to form a distorted pentagonal bipyramid complex ion by coordination bond, then combines to the SiMo₁₂O₄₀⁴⁻ anion by static electric force. The results of IR and X-ray diffraction show that there is strong interaction between polyoxometalate and organic donors.     

O-[(Triorganostannyl)methyl] derivatives of 1,2-O-isopropylidene-α-D-xylofuranose

The synthesis, mass, IR and NMR spectra of 3-O-benzyl-1,2-O-isopropylidene-5-O-[(triphenylstannyl)methyl]--D-xylofuranose (9) and 1,2-O-isopropylidene-3-O-(R₃SnCH₂)-5-O-triphenylmethyl--D-xylofuranose (10, R=Bu or Ph) are reported, as is the X-ray structure of10 (R=Ph). Compound10 (R=Ph), crystallizes in the orthorhombic space groupP2₁2₁2₁ (Z=4), witha=11.006(4) Å,b=17.096(6) Å,c=21.164(7) Å. The conformation of the furanose ring in solid10 (R=Ph) is a 8218 mixture of the envelope (E₄) and twist (³T₄) forms: the isopropylidene ring conformation is similarly a mixture of envelope and twist forms, with the former dominant. On dissolution, the furanose ring of10 (R=Ph) undergoes a conformation change, with the³T₂ conformation becoming the major form. The tin center in10 is four-coordinate and has a tetrahedral geometry.     

Crystal structure of hexahydro-cis-(1-H,4a-H)-1-p-bromophenyl-1H,3H-pyrido[1,2-c][1,3]thiazine

The crystal and molecular structure of hexahydro-cis-(1-H,4_a-H)-1-p-bromophenyl-1H,3H-pyrido[1,2-c][1,3]thiazine, (C₁₄H₁₈BrNS), has been determined from three-dimensional diffractometer data. The space group isI4₁/cd and the unit cell has dimensionsa = 22·906(4),b = 22·906(4),c = 10·646(2) Å withZ = 16. The structure has been refined to a residual of 0·065 using least-squares methods on 1235 independent non-zero reflexions.The molecular geometry and conformation of the bicyclic ring is discussed and compared with the related oxazine compound.     

4-(p-Methylthio)phenyl-2,6-diphenyl phosphinine: The first X-ray crystal structure of a λ3-triaryl-phosphabenzene

The new donor functionalized methylthio-phosphabenzene 3 was synthesized by reaction of the corresponding pyrylium salt with P(SiMe₃)₃. This compound was characterized crystallographically, showing eight independent molecules in the asymmetric unit. 3 crystallized in the orthorhombic space group Pna2₁ (no. 33) with cell parameters a=48.3565(8) ?, b=7.64784(7) ?, c=40.8432(4) ?, V=15104.7(3) ?³. This result represents the first crystal structure analysis of a λ³-triaryl-phosphabenzene.     

Crystal structure of 1,2;5,6-di-O-isopropylidene-3-O-(phenylacetyl)-D-glucofuranose

The synthesis and X-ray crystal structure of 1,2;5,6-di-O-isopropylidene-3-O-(phenylacetyl)-D-glucofuranose is reported. It crystallizes in the orthorhombic system with space group P2₁2₁2₁ (No. 19); a = 9.9313(12) Å, b = 10.0657(12) Å, c = 20.343(2) Å, and Z = 4. The solid state structure is discussed in terms of the use of the title compound for further chemistry.     

X-ray mapping in heterocyclic design: 17. Crystal and molecular structures of the “molecule of the month”; and its hydrogenated form

The structures of 2,8-dimethyl-5-[2-(6-methylpyridin-3-yl)ethyl]-2,3,4,4a,5,9b-hexahydro1H-pyrido[4,3-b]indole trihydrobromide (I) (a = 12.865(4) ?, b = 14.281(3) ?, c = 13.553(3) ?, Z = 4, sp. gr. Pna2₁) and 2,8-dimethyl-5-[2-(6-methylpyridin-3-yl)ethyl]-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole dihydrobromide (II) (a = 13.9704(14) ?, b = 14.4447(15) ?, c = 10.7819(12)?, β = 107.58(1)°, Z = 4, sp. gr. P2₁/c) were studied by single-crystal X-ray diffraction. The structures were solved by direct methods and refined by the full-matrix least-squares method with anisotropic displacement parameters to the R factors of 0.0603 and 0.0446, respectively. All Br⁻ anions form hydrogen bonds with protonated nitrogen atoms. The synthesis and physicochemical parameters of these two compounds are reported.     

Stereochemical Assignment of Substituted 2-Aminobicyclo[3.1.0]hexane and 2-Aminobicyclo[5.1.0]octane Derivatives via Single Crystal X-ray Diffraction

Abstract  

Crystals of benzyl (RS,RS,RS)-7-phenylbicyclo[5.1.0]octan-2-ylcarbamate 9 and (RS,RS,RS)-N-[3′-(4″-methylpiperazin-1″-yl)propyl]-N-{5-(4′′′-cyanophenyl)bicyclo[3.1.0]hexan-2-yl}amine dihydrochloride 10·2HCl were synthesised and single crystal X-ray diffraction was used to establish unambiguously the relative configurations within these structures. Compound 9 crystallizes in the orthorhombic space group P2 ₁ 2 ₁ 2 ₁ with cell parameters of a = 6.85340(10) ?, b = 9.8732(2) ?, c = 27.5407(6) ?, V = 1863.54(6) ?³ and Z = 4. In the crystal structure adjacent molecules are linked by N–H···O=C hydrogen bonds. Compound 10·2HCl crystallizes as the corresponding monohydrate in the monoclinic space group P2 ₁/n with cell parameters of a = 7.1540(17) ?, b = 39.763(12) ?, c = 8.163(3) ?, β = 91.062(7)°, V = 2321.7(11) ?³ and Z = 4. In the crystal structure adjacent molecules are linked by a series of hydrogen bonds between the ammonium groups, chloride ions and adventitious water molecules.     

Crystal structure and electrochemical properties of the supramolecular compound [Himi]6[As2Mo18O62]·11H2O

A supramolecular compound, [Himi]₆[As₂Mo₁₈O₆₂]·11H₂O ( 1 ) (imi = imidazole), has been synthesized and characterized by single crystal X‐ray analysis, IR spectra, thermal gravimetric analysis, electrochemical and elemental analysis. The crystals are monoclinic, P 2(1)/n, a = 14.9529(8) Å, b = 20.9521(11) Å, c = 25.2464(13) Å, β = 93.8130(10)°, V = 7892.1(7) ų, Z = 4. X‐ray diffraction indicated that protonated imidazole cation and polyanion were linked together through electrostatic interactions and intermolecular forces (hydrogen bonding). (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The structure of solvate [Cu2(DfH)4(4,4′-Bipy)] · 2DMF

The crystal structure of [Cu₂(DfH)₄(4,4′-Bipy)] · 2DMF prepared by the reaction of copper(II) acetate with diphenylglyoxime (DfH₂) and 4,4′-bipyridine (4,4′-Bipy) was established by X-ray diffraction. The crystals are monoclinic; a = 15.5192(9) Å, b = 16.2427(11) Å, c = 14.0753(7) Å, β = 101.36(3)°, V = 3478.5(5) ų, Z = 2, and sp. gr. P2₁/c. The crystal structure is composed of discrete dinuclear molecules [Cu₂(DfH)₄(4,4′-Bipy)] and dimethylformamide (DMF) molecules. The coordination polyhedron of the Cu atom (the coordination number is 5) is a tetragonal bipyramid formed by the nitrogen atoms of two monodeprotonated bidentate oxime groups and the bidentate bridging 4,4′-Bipy ligand. The DMF molecules occupy the cavities formed by the dinuclear molecules [Cu₂(DfH)₄(4,4′-Bipy)]. The compound was characterized by IR and NMR spectroscopy.