Synthesis,redox properties,and X-ray diffraction structure of 2,3-<Emphasis Type="Italic">bis</Emphasis>(ethylthio)-<Emphasis Type="Italic">N</Emphasis>-(<Emphasis Type="Italic">p</Emphasis>-MeOC<Subscript>6</Subscript>H<Subscript>4</Subscript>)maleimide

Refluxing 2,3-dichloromaleic anhydride with p-anisidine in benzene with water removal gives the condensation product 2,3-dichloro-N-(p-MeOC₆H₄)maleimide (1) 75% yield. This new maleimide compound reacts with added ethanethiol in the presence of Et₃N or DBU to furnish the bidentate sulfide ligand 2,3-bis(ethylthio)-N-(p-MeOC₆H₄)maleimide (2) in 85% yield. Each product has been characterized in solution by IR, NMR, and UV-vis spectroscopies, and the solid-state structure of 2,3-bis(ethylthio)-N-(p-MeOC₆H₄)maleimide was unequivocally established by single-crystal X-ray diffraction analysis. 2,3-bis(Ethylthio)-N-(p-MeOC₆H₄)maleimide crystallizes in the monoclinic space group C2/c, a = 20.035(3)Å, b = 9.188(1)Å, c = 16.887(2)Å, = 93.696(2)°, V = 3102.3(8)ų, Z = 8, and D_calcd = 1.385 mg/m³; R = 0.0268, R_w = 0.0676 for 2025 reflections with I > 2 (I). The nature of the LUMO in 2,3-bis(ethylthio)-N-(p-MeOC₆H₄)maleimide (2) has been determined by extended Hückel molecular orbital calculations, and these data are discussed relative to the cyclic voltammetry results and other structurally relevant compounds prepared in our labs.     

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.     

Synthesis and structural studies of <Emphasis Type="Italic">tris</Emphasis>-2-chlorobenzylamine and <Emphasis Type="Italic">tris</Emphasis>-2-bromobenzylamine

The tris-2-chloro and 2-bromotribenzylamines are prepared from aqueous ammonia and 2-chlorobenzyl chloride and 2-bromobenzyl bromide, respectively, in ethanol. Recrystallization yielded colorless cubes of each product. The crystal structures are each solved in space group P , and are isostructural. The tris-2-chloro compound, 1, has a = 7.4226(5) Å, b = 9.0825(7) Å, c = 14.529(1) Å, = 78.279(1), = 82.389(1), = 84.661(1), and V = 948.41(12) ų with Z = 2, and d_calc = 1.368 Mg/m³. The tris-2-bromo analog, 2, has a = 7.6569(11) Å, b = 9.0922(13) Å, c = 14.614(2) Å, = 79.286(2), = 81.777(2), = 85.401(2), and V = 987.9(2) ų with Z = 2, and d_calc = 1.762 Mg/m³. Lithium–halogen exchange experiments conducted in tetrahydrofuran at –78C using n-butyl lithium revealed that no exchange occurred for the tris-2-chloro compound, but did occur for the tris-2-bromo analog to yield tribenzylamine upon quench and work-up.     

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     

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.     

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.     

Crystal structure analysis of (<Emphasis Type="Italic">N</Emphasis>-methyl piperazino) (phenyl) (dicyclohexylamino) phosphiniminocyclotrithiazene

The title compound (NC₄H₈NCH₃)(C₆H₅)[N(C₆H₁₁)₂]P{—N–S₃N₃ crystallizes in the triclinic crystal system with unit cell dimensions: a = 9.7572(2), b = 10.6845(1), c = 16.9381(3) Å, = 71.75(1), = 80.65(2), = 65.93(1), and Z = 2. The tricoordinated sulfur atom (S1) in the cyclotrithiazene deviates from the mean plane of the other five atoms by 0.716(6) Å, which is the highest among the known phosphiniminocyclotrithiazene structures. In the exocyclic P{—N4–S1 moiety, the two bond distances are short: 1.585(6) and 1.527(6) Å; but the bond angle is large 135.3(4). The S1 displacement is highly correlated with the endocyclic angle at the nitrogen atom (diagonally opposite to S1), but the nature of correlation is bimodal (R = 1.0 + or –1.0) for the cyclic and acyclic substituents (R) in the (R)(C₆H₅)[N(C₆H₁₁)₂]P{—N–S₃N₃ series. On the other hand, the S1–N4 bond distances are negatively correlated (R = –0.94) with the P{—N4–S1 bond angle in the above series.     

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.     

The structure of 2-amino-3-cyano-4-(4-methylphenyl)-6-methoxyl-1,4,9,10-tetrahydrobenzo[<Emphasis Type="Italic">f</Emphasis>]chromene

The X-ray crystal structure of 2-amino-3-cyano-4-(4-methylphenyl)-6-methoxyl-1,4,9,10-tetrahydrobenzo [f]chromene 1, C₂₂H₂₀N₂O₂, is determined. The crystals of compound 1 are triclinic, space group P-1, a = 10.120(1), b = 13.127(1), c = 15.203(2) Å, = 67.841(9), = 80.81(1), = 77.58(1), Z = 4, V = 1819.7(4) ų. It is interesting that all the atoms of the pyran ring are coplanar, which is different from other similar compounds. The structure is stabilized by intermolecular hydrogen bonds.     

Structural Features of <Emphasis Type="Italic">Ortho</Emphasis>-hydroxy Bis-phenols and Their Comparison with <Emphasis Type="Italic">Para</Emphasis>-hydroxy Bis-phenols

Abstract The crystal structures of four bis-phenols are reported to substantiate the fact that the weak interactions play a major role in the crystal packing of bis-phenols. The reaction of 2,4-dimethylphenol with aldehydes such as 2-naphthaldehyde, terephthaldehyde in the presence of trifluoracetic acid gave 2-[bis(2-hydroxy 3,5-dimethylphenyl)methyl]naphthalene (1) and 4-[bis(2-hydroxy 3,5-dimethylphenyl) methyl]benzaldehyde (2), respectively. The 2-[bis-(2-hydroxy 3,5-dimethylphenyl)-methyl]naphthalene (1) crystallizes in orthorhombic, Pbca, a = 11.905(3) ?, b = 18.788(5) ?, c = 18.894(5) ?, 4-[bis(2-hydroxy 3,5-dimethylphenyl)methyl] benzaldehyde (2) in monoclinic, Cc, a = 8.880(3) ?, b = 16.394(7) ?, c = 13.700(5) ?, γ = 104.542(2)°. The reaction of 2-nitrobenzaldehyde with 2,4-dimethylphenol gave 2-benzo[c] isoxazo-3-yl 4,6-dimethylphenol (3) and its crystal parameters are orthorhombic, P2₁2₁2₁, a = 7.737(6) ?, b = 11.885(9) ?, c = 13.336(8) ?. The reaction of 2,6-dimethylphenol with 4-nitrobenzaldehyde and 2-chlorobenzaldehyde gave bis(4-hydroxy 3,5-dimethylphenyl)(4-nitrophenyl)methane (4) and bis(4-hydroxy 3,5-dimethylphenyl)(2-chlorophenyl)methane (5), respectively. The bis(4-hydroxy 3,5dimethylphenyl)(4-nitrophenyl)methane (4) crystallizes in monoclinic, C2/c, a = 25.921(1) ?, b = 12.202(4) ?, c = 15.6084(7) ?, β = 122.172(4)°, and bis(4-hydroxy 3,5-dimethylphenyl) (2-chlorophenyl)methane crystallizes as acetonitrile solvate (5) in triclinic, P-1, a = 12.314(3) ?, b = 14.111(3) ?, c = 15.078(5) ?, α = 98.268(2)°, β = 111.268(2)°, γ = 114.304(1)˚. The unit cell of 5 contains two pairs of crystallographically unsymmetric molecules of bis-phenols. Index abstract The crystal structures of four bis-phenols are reported to substantiate the fact that the weak interactions plays a major role in crystal packing and can induce symmetry non-equivalence among bis-phenols in unit cell of bis-phenols.      

Synthesis and Characterization of <Emphasis Type="Italic">N,N</Emphasis>-di(prop-2-ynyl)-<Emphasis Type="Italic">p</Emphasis>-toluidine

Abstract  

In order to investigate the intramolecular [4 + 2] cycloaddition, we prepared some new tertiary N-(5-substituted-2-furfuryl)-N-prop-2-ynyl-p-toluidines [Hergold-Brundić et al., Acta Cryst C56:e520, 2000; Mance and Jakopčić, Mol Divers 9:229, 2005; Mance, “unpublished results”] by the alkylation of secondary N-(5-substituted-2-furfuryl)-p-toluidines with the propargyl-bromide [Mance and Šindler-Kulyk, Synth Commun 26:923, 1996]. In the course of preparation of N-(5-methoxy-2-furfuryl)-N-prop-2-ynyl-p-toluidine [Mance, “unpublished results”], besides the main product (compound 1) (Scheme 1) we obtained N,N-di(prop-2-ynyl)-p-toluidine (compound 2) as the colourless crystals. The title compound 2, N,N-di(prop-2-ynyl)-p-toluidine, C₁₃H₁₃N, crystallizes in monoclinic C 2/c space group with unit cell parameters: a = 19.5319(9) ?, b = 7.5230(3) ?, c = 15.9000(7) ?, β = 112.554(5)°, V = 2157.64(18) ?³, Z = 8. The crystal structure is dominated by van der Waals forces only. The bond distances around amine N atom correspond to σ dominated bonds (1.467(2), 1.462(2) and 1.419(2) ?). The angles sum around amine N atom is in accord with sp³ hybridization (343°).     

Solid-state structure of a 1:1 adduct of 2-<Emphasis Type="Italic">t</Emphasis>-butylphenol and 3-<Emphasis Type="Italic">t</Emphasis>-butylsalicylaldehyde

The co-crystal structure of 2-t-butylphenol with 3-t-butylsalicylaldehyde (1) was obtained by single-crystal X-ray diffraction. 2-t-Butylphenol was co-crystallized with 1 equivalent of 3-t-butylsalicylaldehyde. The phase crystallizes in the monoclinic system with P2₁/c space group. The unit cell dimensions are a = 12.351(3) Å, b = 15.253(3) Å, c = 10.377(2) Å, β = 97.58(3)^∘, V = 1937.8(7) ų and Z = 4. The structure of the crystal layered by nonpolar group includes strong intramolecular and weak intermolecular hydrogen bonds. The aldehyde oxygen O2 accepts a three-centered bond through intramolecular O1–H1A⋅sO2 and intermolecular O3–H3A⋅sO2 interactions. In addition, the crystal consists of right-handed helical (P) and left-handed helical (M) chains linked by hydrogen bonding.     

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.     

X-ray analysis of sideroxol from <Emphasis Type="Italic">Sideritis leptoclada</Emphasis>

Sideroxol (1), a kaurane diterpene which has the ent-7α,18-dihydroxy-15β,16β-epoxykaurane structure (MW = 320.47, C₂₀H₃₂O₃) was obtained from the acetone extract of Sideritis leptoclada plant as well as from some other Sideritis species. It crystallizes in the orthorhombic space group P2₁, 2₁, 2₁ with a = 10.967(3), b = 24.555(5), c = 6.372(4) Å, Dc = 1.240 g cm⁻³, Z = 4, and refines to R = 0.065 for 721 independent reflections. The skeleton consists of three fused six-membered rings and a five-membered ring with fused epoxide. The six membered rings exhibited slightly distorted chair conformation. In addition to sideroxol, two kaurane and five kaurene diterpenes were isolated from the hexane and acetone extracts of the studied plant.     

Crystal Structure and Conformational Analysis of 4-[(<Emphasis Type="Italic">p</Emphasis>-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-Dimethylamino)Benzylidene]-2-Phenyloxazole-5-One

Abstract  

Molecular and crystal structure of 4-[(p-N,N-dimethylamino)benzylidene]-2-phenyloxazol-5-one, C₁₈H₁₆N₂O₂, have been determined by single crystal X-ray diffraction study. The title compound is monoclinic, with a = 12.1704(23) ?, b = 3.9810(5) ?, c = 30.9603(56) ?, β = 101.176(15)°, Z = 4, D _x = 1.32 g/cm³, μ(Mo Kα) = 0.087 mm⁻¹, and space group is P12₁/c1. The structure was solved by direct methods and refined to a final R = 0.047 for 3166 reflections with I > 2σ(I). The crystal structure is stabilized by C–H⋯O and C–H⋯N type intra-molecular, C–H⋯O type inter-molecular interactions. To enlighten the flexibility and the geometric isomerism (E or Z) of the title compound, the selected torsion angle is varied from −180 to 180° in every 10° separately and molecular energy profile is calculated and analyzed.     

Synthesis,Characterization and Antibacterial Activity of <Emphasis Type="Italic">N</Emphasis>-(<Emphasis Type="Italic">N</Emphasis>-Acetic Acid-yl-Phthalimide-5-yl) Maleamic Acid Dihydrate

Abstract  

The compound N-(N-acetic acid-yl-phthalimide-5-yl) maleamic acid (C₁₄H₁₀N₂O₇, M _r  = 318) was synthesized and its structure was characterized by elemental analysis, ¹H NMR and IR spectra. The single crystal of the title compound (C₁₄H₁₄N₂O₉, M _r  = 354.27) was cultured and its structure was determined by single crystal X-ray diffraction. The crystal belongs to monoclinic system, space group P21/c with a = 14.3859(19), b = 12.5835(18), c = 8.6934(15) ?, β = 102.824(2)°, V = 1534.5(4) ?³, Z = 4, D _c  = 1.534 g cm⁻³, μ(Mo Kα) = 0.131 mm⁻¹, F(000) = 736. The final refinement gave R = 0.0652, wR(F ²) = 0.1239 for 2,703 observed reflections with I > 2σ(I). X-ray diffraction analysis reveals that the asymmetric unit of the title compound contains one N-(N-acetic acid-yl-phthalimide-5-yl) maleamic acid molecule and two water molecules. One of the two water molecules is disordered. The phthalimide group is essentially planar. The crystal structure of the title compound is stabilized by N–H…O and O–H…O hydrogen bonds interactions. The compound N-(N-acetic acid-yl-phthalimide-5-yl) maleamic acid possesses moderate antibacterial activity.     

The Synthesis and Structure of Two Novel <Emphasis Type="Italic">N</Emphasis>-(Benzothiazol-2-yl)benzamides

Abstract  Two novel benzothiazoles 2-chloro-N-(benzothiazol-2-yl)benzamide (1) and 2-chloro-N-(6-cyanobenzothiazol-2-yl)benzamide (2) were obtained in multistep synthesis. They were characterised by means of IR, ¹H- and ¹³C-NMR spectroscopy and also by single-crystal X-ray diffraction. The compound 1 crystallises with triclinic space group P , a = 9.5923(8) ?, b = 9.8583(8) ?, c = 13.8962(10) ?, α = 89.162(6)°, β = 77.741(7)°, γ = 80.064(7)°, V = 1264.5(2) ?³, Z = 4 and compound 2 crystallises as methanol solvate with monoclinic space group P 2₁/n, a = 7.5093(9) ?, b = 13.0211(14) ?, c = 16.032(2) ?, β = 92.717(10)°, V = 1565.9(3) ?³, Z = 4. Both crystal structures consist of discrete dimers connected into a three-dimensional network by intermolecular C–H···O and C–H···X (X = Cl or S) hydrogen bonds and by face-to-face π–π stacking interactions. Index Abstract  The synthesis and structure of two novel N-(benzothiazol-2-yl)benzamides. Irena Ćaleta, Dominik Cinčić, GraceKarminski-Zamola and Branko Kaitner. Hydrogen bonds and π–π interactions in N-(benzothiazol-2-yl)benzamides N-(benzothiazol-2-yl)benzamides.      

Crystal and Molecular Structures of Di-1-Adamantylthiophosphinic Chloride, <Emphasis Type="Italic">P</Emphasis>,<Emphasis Type="Italic">P</Emphasis>-Diphenyl-<Emphasis Type="Italic">N</Emphasis>-Benzyl Phosphinothioic- and Selenoic- Amides

Abstract  Synthesis and X-ray structural determination of three phosphorus compounds are reported. (3b) is monoclinic P2(1)/c with a = 11.852(1), b = 12.825(1), c = 12.445(1) ?, β = 103.693(1)o; (4a) and (4b) are monoclinic P2(1)/n with a = 12.1422(16), b = 9.0860(12), c = 14.845(2) ?, β = 96.498(3)o for (4a), and a = 12.2714(16), b = 9.2812(12), c = 14.800(2) ?, β = 97.176(2)o for (4b). They all exhibit distorted tetrahedral geometry about the P atom. Ph₂P(X)NHC₇H₇ (X=S (4a) and X=Se (4b)) show typical P–S and P–Se double bond distances and P–N single bonds, while P–S bond in 1-Ad₂P(S)Cl (3b) is comparable to P–S single bonded probably due to the largeness of 1-adamantyl groups. Graphical Abstract  Synthesis and X-ray structural determination of 1-Ad₂P(S)Cl (3b), Ph₂P(S)NHC₇H₇ (4a) and Ph₂P(Se)NHC₇H₇ (4b) are reported.      

Crystal structure of <Emphasis Type="Italic">p</Emphasis>-carboxyphenylhydrazone benzoylacetone

The crystal structure of p-carboxyphenylhydrazone benzoylacetone is determined. The crystals are monoclinic, a = 13.614(4) Å, b = 11.388(2) Å, c = 20.029(6) Å, β = 104.82(2)°, V = 2339(9) ų, Z = 8, space group C2/c, and R = 0.038 for 1622 reflections with I > 2σ(I). The crystal is built of C₁₇H₁₄N₂O₄ neutral molecules that are linked by O-H?O hydrogen bonds between the carboxyl groups into centrosymmetric pseudodimers. The effect of carboxylation of the phenylhydrazone fragment and the position of the carboxyl group on the molecular packing in the crystal is determined. The N(1)-H(1N)?O(1) intramolecular hydrogen bond (N-H, 0.94 Å; H?O, 1.87 Å; N?O, 2.59 Å; and the N-H?O angle, 133°) is formed in the molecule.