Molecular structure of (±)-5-benzylamino-endo-tricylo[5.2.1.02,6]dec-4-en-3-one

The crystal and molecular structure of (±)-5-benzylamino-endo-tricyclo[5.2.1.0^2.6]dec-4-en-3-one is described. The X-ray analysis revealed that the reduction of the norbornene double bond is an important process in the irradiation of the used enaminones. The structure was solved by direct methods and refined by least squares methods toR ₁=0.0468 for 2070 reflections (withI>2σ(I). Crystal data: C₁₇H₁₉NO, Orthorhombic, space groupPbcn, a=40.695 (1),b=6.6928 (1),c=10.2378(4)Å,V=2788.44(14)ų,Z=8.     

Red and Blue Compounds Formed from Copper(II) Bromide and the Ligand 7-Isobutyl-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine: Synthesis, Spectroscopy and Single-Crystal Structures

Abstract  

Two newly synthesized coordination compounds copper(II) bromide with the ligand 7-isobutyl-5-methyl[1,2,4]triazolo[1,5-a]pyrimidine (abbreviated as ibmtp) are presented, together with their 3D crystal structure and spectroscopic and magnetic properties. The compounds are CuBr₂(ibmtp)₂ (1) (red crystals) and [CuBr(ibmtp)₄]Br(H₂O)₃ (2) (blue crystals). In (1) the Cu(ii) ion is present in a distorted tetrahedral environment, while in (2) the Cu(ii) ion has a square pyramidal geometry. These crystal structures are also the first ones reported with the ligand ibmtp.     

Dihydrogen Phosphate and Hydrogen Sulphate of 1,4-Dimethyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium: Crystal Structures, Hydrogen Bonding and Infrared Spectra

Abstract  

The crystal structures of the title compounds consist of 1,4-dimethyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium cation [C₈H₁₈N₂]²⁺ and [H₂PO₄]⁻ or [HSO₄]⁻ anions. Both crystal structures are monoclinic, the structure of the dihydrogen phosphate (I) is non-centrosymmetric (P2₁) with a = 6.4090(2) ?, b = 13.6920(5) ?, c = 7.6140(3) ?, β = 94.620(2)°, V = 665.97(4) ?³, Z = 2; whereas the unit cell of the hydrogen sulphate (II) is centrosymmetric (P2₁/c) with a = 13.8460(2) ?, b = 12.6610(2) ?, c = 8.0360(2) ?, β = 99.5800(12)°, V = 1389.10(5) ?³, Z = 4. Both the structures are formed by the different bonding patterns of the anions interlinked by strong and moderate O–H···O hydrogen bonds. While the structure of (I) consists of a two-dimensional network of the hydrogen bonded dihydrogen phosphates, the infinite chains of the hydrogen bonded hydrogen sulphates are the basic building unit of the structure (II). In addition to the dominant electrostatic interaction the divalent cations stabilize themselves in the structures by forming several C–H···O hydrogen bonds to the oxygen atoms of the anions. The IR spectra of both the compounds are strongly affected by the hydrogen bonds whose influence on OH stretching vibrations is analysed by means of the DFT calculations in the solid state.     

Crystal structure of 3-phenyl-7-bromoisoxazolo[4,5-d]pyridazin-4(5H)-one

The crystal and molecular structure of 3-phenyl-7-bromoisoxazolo[4,5-d]-pyridazin-4(5H-one, C₁₁H₆BrN₃O₂, has been determined from two- and three-dimensional X-ray data and refined by Fourier and least-squares methods toR = 0·101 for 1187 observed reflexions. Crystals of 3-phenyl-7-bromoisoxazolo-[4, 5-d]pyridazin-4(5H)-one are monoclinic:a = 7·67,b = 6·84,c = 20·52 Å, = 91·5 °,Z = 4, space groupP2₁/c. The benzene ring makes an angle of 4·5 ° with the plane of the isoxazole ring, and the other part of the molecule is slightly non-planar. The bond distances and angles compare well with those of other similar molecules. Two N-H...O hydrogen bonds join the two molecules related by a centre of symmetry. Close molecular packing is found in layers parallel to (100).     

Synthesis and crystal structure of 1-phenyl-3-methylthio-4-imino-5-allyl-pyrazolo[3,4-d]pyrimidine

The title compound 1-phenyl-3-methylthio-4-imino-5-allyl-pyrazolo[3,4-d]pyrimidine, C₁₅H₁₅N₅S, has been synthesized and characterized by x-ray diffraction: orthorhombic, space group Pbca, with a = 17.3480(9), b = 8.5022(5), c = 19.8132(11) Å. Z = 8, V = 2922.4(3) ų. The compound shows a fully delocalized pyrazolo[3,4-d]pyrimidine system with a sp² hybridization of the N(4) atom.     

Solvothermal Syntheses and Crystal Structures of Neodymium Thiostannates [Nd(dien)3]2[(Sn2S6)Cl2] and [Nd(dien)3]2[(Sn2S6)(SH)2]

Abstract  

Two neodymium thiostannates [Nd(dien)₃]₂[(Sn₂S₆)Cl₂] (1) and [Nd(dien)₃]₂[(Sn₂S₆)(SH)₂] (2) (dien = diethylenetriamine) were synthesized by the reaction of tin and sulfur in the presence of NdCl₃ and Nd₂O₃, respectively under solvothermal conditions. Compounds 1 and 2 crystallize in monoclinic space group P2₁/n. Crystallographic data for 1: a = 11.6722(16), b = 15.119(2), c = 14.1566(19) ?, β = 96.213(3)°, V = 2483.6(6) ?³, Z = 4. For 2: a = 11.7190(14), b = 15.2168(19), c = 14.2209(18) ?, β = 95.775(4)°, V = 2523.1(5) ?³, Z = 4. The nine-coordinate [Nd(trien)₃]³⁺ complex cation formed in situ acts as the counter ion to the [Sn₂S₆]⁴⁻ anion. The [Nd(dien)₃]³⁺, [Sn₂S₆]⁴⁻ and Cl^– (or SH^–) ions form a 3-dimensional network structure through the N–H···S and N–H···Cl hydrogen bonds.     

Synthesis and structural characterization of 5,6,15,16-tetradehydrobenzo[a]phenanthro[9, 10-e]cyclooctene,C24H12

A benzo-phenanthro-fused planar cyclooctatetraene derivative, namely, 5,6,15,16-tetradehydrobenzo[a]phenanthro[9, 10-e]cyclooctene (5) was synthesized in two steps from the known benzo[a]phenanthro[9, 10-e]cyclooctene (6). Compound5 crystallizes in space groupPbam witha=9.828(2),b=19.466(4),c=15.901(3) Å, and Z=8. X-Ray analysis (MoK radiation,R=0.060 for 1233 observed data) has shown that both independent molecules have the same planarC _2v configuration with averaged bond lengths of 1.381(7) and 1.208(7) Å for the phenanthrene C_6a–C_14b bond and the acetylenic CC bond, respectively.¹H and¹³C NMR spectral results of 5 and 5,6,15,16-tetrabromo-5,6,15,16-tetrahydrobenzo[a]phenanthro[9, 10-e]cyclooctene (7) are also presented.     

Neutral Praseodymium(III) Complexes with Tetraselenidoantimonate Ligand: Coligand Influence of Mixed Polyamines on the Coordination Mode of [SbSe4]3? Anion

Abstract  

Mix-coordinated praseodymium(III) complexes concerning the [SbSe₄]³⁻ inorganic ligand, [Pr(en)₂(dien)(η ²-SbSe₄)] (1) and [Pr(en)(trien)(μ-η ¹,η ²-SbSe₄)] _n (2) (en = ethylenediamine, dien = diethylenetriamine, trien = triethylenetetramine), were prepared by solvothermal reactions of Pr₂O₃, Sb and Se in en + dien and en + trien mixed solvents, respectively. They crystallize in the monoclinic space group P2₁/n but with different molecular structures. Crystallographic data for 1: a = 8.610(2), b = 27.722(7), c = 9.294(2) ?, β = 108.987(3)°, V = 2097.7(9) ?³, Z = 4. For 2: a = 14.2987(17), b = 9.0176(9), c = 15.4357(18) ?, β = 100.708(3)°, V = 1955.6(4) ?³, Z = 4. The [SbSe₄]³⁻ anion coordinates to the Pr³⁺ ion in [Pr(en)₂(dien)]³⁺ as a η ²-SbSe₄ chelating ligand, yielding complex 1. It acts as a μ-η ¹,η ²-SbSe₄ bridging ligand to connect the [Pr(en)(trien)]³⁺ ions into the polymer 2. The coordination difference between 1 and 2 is attributed to the coligands of mixed polyamines.     

Synthesis and Crystal Structure of a Novel Heterocycle, 2-Oxa-4,7-Diazabicyclo[3.3.1]Non-3-Ene

Abstract  

The compound 5, containing the novel heterocycle 2-oxa-4,7-diazabicyclo[3.3.1]non-3-ene, has been obtained in a synthetic approach toward oxazoles and 1,3-diazepanes of natural product-like complexity from cyclization and rearrangement of δ-lactam cyanamides. When this procedure was applied to a silyl-protected N-((3S,4S,5S)-4,5-dihydroxy-2-oxopiperidin-3-yl)cyanamide (2b) formation of the novel heterobicyclic scaffold 5 was observed along with the expected oxazole (3b) and diazepane (4b) products. The crystal structures of 5 and diazepane 4b are described. Compound 5 crystallized from methanol in the monoclinic system, P2₁ space group with unit cell parameters a = 15.3402(9), b = 7.2717(4), c = 22.5803(13), β = 106.8620(10) and a cell volume of 2410.5(2) A³.     

Synthesis and Crystal Structures of Copper(II) Complexes Derived from 5-Methoxy-2-[(2-morpholin-4-ylethylimino)methyl]phenolate and (2-Morpholin-4-ylethyl)-(1-pyridin-2-ylethylidene)amine

Abstract  

A pair of copper(II) complexes, [CuL¹(ONO₂)(OH₂)] 1 and [CuBrL²N₃] 2, where L¹ is 5-methoxy-2-[(2-morpholin-4-ylethylimino)methyl]phenolate, and L² is (2-morpholin-4-ylethyl)-(1-pyridin-2-ylethylidene)amine, have been synthesized and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic space group P2₁/c, with a = 10.496(2), b = 19.113(3), c = 8.586(2) ?, β = 105.186(10)°. Complex 2 crystallizes in the monoclinic space group C2/c, with a = 16.606(3), b = 7.357(2), c = 26.043(5) ?, β = 94.996(2)°. The Cu atom in each complex is five-coordinate in a square pyramidal geometry.     

Synthesis and crystal structures of 2-amino-3-cyano-4-(2-chlorophenyl)-1,4-dihydro-2H-pyrano[3, 2-h]quinoline and 2-amino-3-cyano-4-(2-chlorophenyl)-8-(2-chlorobenzylidene)-1,4,5,6,7,8-hexahydrobenzo[b]pyran

The title compounds 2-amino-3-cyano-4-(2-chlorophenyl)-1,4-dihydro-2H-pyrano[3, 2-h]quinoline 1 (C₁₉H₁₂ClN₃O, M _r = 333.77) and 2-amino-3-cyano-4-(2-chlorophenyl)-8-(2-chlorobenzylidene)-1,4,5,6,7,8-hexahydrobenzo[b]pyran 2 were synthesized and crystallized. The crystals of compound 1 are triclinic, space group P-1, a = 7.488(2), b = 9.127(3), c = 12.252(3) Å, = 73.58(2), = 78.38(2)°, = 75.39(2), Z = 2, V = 769.5(4) ų; The compound 2 crystallizes in space group P2₁/n, with cell parameters a = 13.582(2), b = 8.974(1), c = 16.960(2) Å, = 103.34(1)° and D _calc = 1.352 g/cm^–3 for Z = 4. X-ray analysis reveals that atoms C(1)—C(5) and O form a pyran ring in compound 1, which adopts half-chair conformation. In compound 2 the atoms C(12)—C(16) and O form a pyran ring which adopts boat conformation, another six-membered ring (C(8)—C(13)) adopts a half-chair conformation. In addition, there are intermolecular hydrogen bonds in the crystal structures 1 and 2.     

Synthesis and Crystal Structures of Two <Emphasis Type="Italic">N</Emphasis>-Heterocyclic Carbene Adducts of CrCl<Subscript>2</Subscript>

Abstract  

The reactions of CrCl₂ with two N-heterocyclic carbenes (NHC) have afforded the complexes, trans-[CrCl₂(NHC)₂] (NHC = :C{N(C₆H₃Pr₂ⁱ-2,6)C(H)}₂ 1 or :C{N(Prⁱ)C(Me)}₂ 2). The cell parameters of the compounds are 1: P2₁2₁2₁, a = 12.9445(4), b = 20.7364(5), c = 21.2841(6); 2: Pca2₁, a = 21.7583(14), b = 9.9465(8), c = 11.4414(9). The crystal structures of the complexes are the first for NHC adducts of CrCl₂, and both exhibit square planar chromium centers.     

Absolute structure of (11E, 1S, 3S, 4R, 7S, 8R, 14S)-3,7-diiodo-4,8-epoxy-euniolide

3,7-Diiodo-4,8-epoxy-euniolide (2) was synthesized from euniolide (1) by the addition reaction of iodine in the presence of triphenylphosphine in CH₂Cl₂. The absolute structure of 2 was unambiguously determined by a combination of ¹H and ¹³C NMR, HREI mass spectroscopy, and x-ray single crystal analysis as (11E, 1S, 3S, 4R, 7S, 8R, 14S)-3,7-diiodo-4,8-epoxy-cembra-11,15-dien-16,14-olide. X-ray crystallographic data for 2: Orthorhombic P2₁2₁2₁ (#19), a = 10.9688(7), b = 11.3909(8), c = 16.885(1) Å, _calcd = 1.795 g cm^–3, and for Z = 4.     

Synthesis and Characterization of Nickel(II) Complex of 3,14-Dimethyl-2,6,13,17-Tetraazatricyclo[14,4,01.18,07.12]Docosane Containing Pyrazine-2-Carboxylate Ligand

Abstract  

The reaction of [Ni(L)]Cl₂·2H₂O (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^1.18,0^7.12]docosane) with pyrazine-2-carboxylic acid (H-pyc) yields mononuclear nickel(II) complex, [Ni(L)(pyc)₂]·2H₂O (1). This complex has been characterized by X-ray crystallography, electronic absorption and cyclic voltammetry. The crystal structure of 1 exhibits a distorted octahedral geometry with four nitrogen atoms of the macrocycle and two pyrazine-2-carboxylate ligands. It crystallizes in the triclinic system P-1 with a = 9.6643(17), b = 10.116(3), c = 16.99(4) ?, V = 1633(3) ?³, Z = 2. Electronic spectrum of 1 also reveals a high-spin octahedral environment. Cyclic voltammetry of 1 undergoes two waves of a one-electron transfer corresponding to Ni^II/Ni^III and Ni^II/Ni^I processes.     

Synthesis and Crystal Structure of 5-Chloro-3-Methyl-1-Phenyl-1H-Pyrazole-4-Carbaldehyde

Abstract  

The title compound, 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde 2, was prepared in a series of syntheses to produce new pyrazole derivatives, and its crystal structure was determined by X-ray diffraction method. The crystal belongs to monoclinic, space group P2₁/c with unit cell parameters a = 6.7637(4) ?, b = 6.8712(3) ?, c = 22.4188(10) ?, β = 93.8458(14)o, V = 1039.56(9) ?³ and Z = 4. X-Ray reveals that the aldehydic fragment is almost coplanar with the adjacent pyrazole ring, but the two ring planes are inclined at 72.8(1)o. The molecule is linked to its neighbor by two directionally specific C–H···O interactions.     

Synthesis and Crystal Structure of 3-Methyl-4-phenyl-5-(2-pyridyl)-1,2,4-triazole

Abstract  

The title compound, 3-methyl-4-phenyl-5-(2-pyridyl)-1,2,4-triazole was synthesized by reaction of diphenylphosphazoanilide with N-acetyl-N′-(2-pyridoyl)hydrazine. Crystals suitable for X-ray analysis were obtained from a mixed solution of water and ethanol in a one-to-one volume ratio. The crystal is orthorhombic, space group P2₁2₁2₁ with crystallographic parameters: a = 19.414(4) Å, b = 17.172(3) Å, c = 7.4850(15) Å, β = 90.00°, μ = 0.079 mm⁻¹, V = 2495.3(8) Å³, Z = 8, Dc = 1.258 g/cm³, F(000) = 992, T = 295(2) K. The X-ray results showed that in the crystal structure of the title compound, the 1,2,4-triazole, pyridine and benzene rings are not coplanar.     

Crystallographic and conformational analysis of 2-methyl-3-(2-nitro-phenyl)-4-phenyl-[1,2,4]oxadiazolidin-5-one

Molecular and crystal structure of 2-methyl-3-(2-nitro-phenyl)-4-phenyl-[1,2,4]oxadiazolidin-5-one, C₁₅H₁₃N₃O₄, have been determined by single crystal X-ray diffraction study. The title compound is monoclinic, with a = 10.0313(8) Å, b = 9.0372(5) Å, c = 15.5964(14) Å, β = 96.926(7)^∘, Z = 4, D_x = 1.42 g/cm³, μ (Mo-K_α) = 0.105 mm⁻¹, and space group is P 2₁/c. The structure was solved by direct methods and refined to a final R = 0.036 for 1894 reflections with I > 4σ (I). The crystal structure is stabilized by C–H⋅sO type inter-molecular, C–H⋅sN and C–H⋅sO type intra-molecular, π–π stacking and edge to face (C–H⋅s π-ring) interactions. To enlighten conformational flexibility of the title molecule, selected two torsion angles are varied from −180^∘ to +180^∘ in every 10^∘ separetely and then molecular energy profile is calculated and construed.     

Synthesis,Spectroscopic Studies and Structure of 2-[(Benzo[<Emphasis Type="Italic">d</Emphasis>]thiazol-2-ylamino)methyl]phenol

Abstract  

Schiff base (E)-2-[(benzo[d]thiazol-2-ylimino)methyl]phenol (1) has been synthesized from the reaction of 2-hydroxy-benzaldehyde with 2-aminobenzothiazole. The 2-[(benzo[d]thiazol-2-ylamino)methyl]phenol (2) was prepared reduction of the Schiff base 1 with sodium borohydride. The compounds 1 and 2 have been characterized by elemental analysis, FT-IR, ¹H-NMR, ¹³C-NMR and UV–visible spectroscopic techniques. The structure of the compound 2 has also been examined crystallographically. The compound 2 crystallizes in the monoclinic space group P2/c. The unit cell parameters were found as a = 10.017(1), b = 11.725(1), c = 10.341(1) ?, V = 1208.1(1) ?³, D _x = 1.409 g cm⁻³ and Z = 4. The crystal structure was solved by direct methods and refined by the full-matrix least squares method and found as R ₁ = 0.0308 and wR ₂ = 0.0818 for 2032 for the observed reflections [I > 2σ(I)].     

Observation of Strong Antiferromagnetic Exchange Interactions in [1-(4′-methobenzyl)isoquinolinium][Ni(mnt)<Subscript>2</Subscript>]: Crystal Structures,Magnetic Properties

Abstract  

An new ion-pair compound, [CH₃BzQl][Ni(mnt)₂] (1), (CH₃BzQl = 1-(4′-methobenzyl)isoquinolinium and mnt²⁻ = maleonitriledithiolate), has been synthesized, structurally and magnetically characterized. The [Ni(mnt)₂]⁻ anions (A) and [CH₃BzIQl]⁺ cations (C) of 1 alternate to form a mixed columnar stack in the manner of ···ACAC··· along the a-axis, and the neighboring columns connect together to generate a three-dimensional (3D) network structure via intermolecular H-bonding interactions and van der Waals forces. Variable-temperature magnetic susceptibility measurements in the temperature range 2–300 K show that 1 is a spin gap system with strong antiferromagnetic interaction.     

Synthesis and crystal structure of 2-propyl-5-phenyl-1, 4-dioxo-1,2,3,4,5,6,7,8-octahydro-[1,4,2]diazaphosphorino [1,2-a][1,3,2]benzodiazaphosphorine 3-oxide

The synthesis and structure characterization of 2-propyl-5-phenyl-1,4-dioxo-1,2,3,4,5, 6,7,8-octahydro-[1,4,2]diazaphosphorino[1,2-a][1,3,2]benzodiazaphosphorine 3-oxide are described. The title compound has been designed to incorporate proximate carbonyl and phosphoryl groups in a heterocycle fused to benzophosphadiamide heterocycle. Crystal data: C₁₉H₂₀N₃O₃P, Monoclinic, space group P2(1)/c, with a = 9.7585(9) Å, b = 21.4319(19) Å, c = 17.7900(16) Å, β = 100.823(2)°, Z = 8, V = 3654.5(6) ų. The crystal structure shows that the proximate carbonyl and phosphoryl groups are not coplanar, and the [1,4,2]diazaphosphorino moiety prefers the boat conformation.