Synthesis and X-ray structure of 11-N-benzylamido-9,10-dihydro-9,10-ethenoanthracene

As a part of studies on MDR reversing agents, the structure of a benzylamido-9,10-dihydro-9,10-ethenoanthracene is reported: C₂₄ H₁₉ N O; orthorhombic; space group: Pca2₁; a = 9.214(2), b = 18.624(4), c = 10.170(2) Å; 1745.2(6) ų; Z = 4. The three nonplanar rings from the 9,10-dihydro-9,10-ethenoanthracene skeleton of the molecule adopt a boat conformation. The benzamide side-chain is extended (conformation, trans-trans-gauche). The molecules in the crystal are joined by infinite chains of H-bonds N14–H14···O13.     

The triethyl ammonium salt of O,O′-bis(o-tolyl) dithiophosphate [Et3NH]+[(2-MeC6H4O)2PS2]?

The X-ray structure of the triethyl ammonium salt of O,O′-bis(o-tolyl)dithiophosphate, [Et₃NH]⁺[(2-MeC₆H₄O)₂PS₂]⁻, has been determined. Crystal data: Monoclinic, P2₁/c, a = 15.4342(6) Å, b = 10.1913(4) Å, c = 14.0729(6) Å, β = 100.855(1)^∘, V = 2174.0(2) Å⁻³, Z = 4. The immediate environment around phosphorous is distorted tetrahedral with two sulfur and two oxygen atoms in the coordination sphere, with N–H–S bonding involving only one of the sulfur atoms.     

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.     

Nickel(II) complexes with N,N,O-donor Schiff bases. Self-assembly to two-dimensional network via hydrogen bonding

The syntheses, characterization and crystal structures of two mononuclear nickel(II) complexes are described. Reactions of Ni(O₂CCH₃)₂⋅4H₂O with the Schiff bases derived from 2-pyridinecarbaldehyde and ortho-aminophenol (Hpaap) and 2-pyridinecarbaldehyde and ortho-aminobenzoic acid (Hpaab) in methanolic media afford the complexes in good yields. The elemental analysis, magnetic moments, and spectral features of the complexes are consistent with the formulae [Ni(paap)₂]⋅CH₃COOH⋅H₂O and [Ni(paab)₂]⋅2H₂O. Crystal data for [Ni(paap)₂]⋅CH₃COOH⋅H₂O: monoclinic, P2₁/c, a = 9.675(2) Å, b = 17.109(5) Å, c = 14.403(4) Å, β = 92.903(11)^∘, V = 2381.1(11) ų, and Z = 4 and for [Ni(paab)₂]⋅2H₂O: triclinic, P 1, a = 9.834(3) Å, b = 11.319(3) Å, c = 13.130(4) Å, α = 84.68(3), β = 67.54(3), γ = 85.49(2)^∘, V = 1343.4(6) ų, and Z = 2. In each complex, two tridentate monoanionic meridionally spanning ligands form a distorted octahedral N₄O₂ coordination sphere around the metal ion. In [Ni(paap)₂]⋅CH₃COOH⋅H₂O, two metal coordinated phenolate-O atoms are hydrogen bonded to CH₃COOH and H₂O, respectively. Intramolecular C–H⋅ < eqid1 > ⋅O interactions involving the water molecule and the C–H from azomethine and aromatic fragments lead to a two-dimensional network of [Ni(paap)₂]⋅CH₃COOH⋅H₂O in the crystal lattice. An uncoordinated carboxylate O-atom in [Ni(paab)₂]⋅2H₂O is hydrogen bonded to both water molecules. One of the water molecules is again hydrogen bonded to the corresponding symmetry related water molecule forming a dimer. The azomethine groups and the metal coordinated carboxylate-O atoms in [Ni(paab)₂] are involved in intermolecular C–H⋅ < eqid2 > ⋅O interactions forming a chain-like arrangement of the molecules. The water dimers act as bridges between these chains and a two-dimensional network of [Ni(paab)₂]⋅2H₂O is formed.     

Crystal structure,thermal analysis,and IR spectroscopic investigation of bis(2-amino-6-methyl) pyridinium sulfate

Synthesis, crystal structure refinement, phase transitions studied by thermal analysis, and IR spectroscopic investigation of 2C₆H₉N₂ < eqid2 > ⋅SO₄²⁻ are reported. The title compound crystallizes in the monoclinic space group C2/c (no. 15) with a = 10.5068(4) Å, b = 10.2225(5) Å, c = 14.0422(7) Å, and β = 104.489(3)^∘. A crystal packing diagram shows layers built by all the components of the structure and centered by planes z = 1/4 and 3/4. The pyridine substituents stack forming channels parallel to the c direction with dimensions of 4.163(1) Å and 5.148(4) Å. Thermal analysis shows that the anhydrous compound possesses an irreversible weak phase transition.     

C–H⋅<Emphasis Type="Italic">s</Emphasis>O hydrogen bond networks in <Emphasis Type="Italic">E</Emphasis>- and Z-unsaturated esters of C-glycosides

Methyl E(Z)-4,7 anhydro-5-benzamido-6,8-di-O-benzoyl-2,3,5-trideoxy-d-allo-oct-2-enoate have been synthesized like intermediates and isolated as single crystals during the synthesis of pyrazole-related C nucleosides as synthetic product with cytotoxic activity.¹ Crystal structures of E(Z) isomers were determined by X-ray analysis. E isomer crystallizes in the triclinic crystal system, space group P1, a = 5.319(1) Å, b = 10.758(2) Å, c = 12.229(2) Å, α = 72.38(2)^∘, β = 89.97(2)^∘, γ = 87.07(2)^∘, D_x = 1.320 Mgm⁻³ and Z isomer in the orthorhombic crystal system, space group P2₁2₁2₁, a = 5.1297(13) Å, b = 19.667(5) Å, c = 25.871(6) Å, D_x = 1.348 Mgm⁻³. The molecular structure was solved by direct method on the basis of 2609 and 2727 unique reflections recorded at the temperature 293 K (E-isomer) and 173 K (Z-isomer) up to the final R-factor 0.0378 and 0.0435, respectively. C–H⋅sO contact networks were analyzed and the correlation established between the existence of the weak C–H⋅sO hydrogen bonds and the melting point of the single crystals.     

Synthesis,structure and IR characterization of disodium tetra(9,10-dihydro-9-oxo-10-acridineacetato)zincate(II) bis(ethanol) heptahydrate

The synthesis, crystal structure and IR data are reported for Na₂[Zn(CMA)₄]·2EtOH·7H₂O, where CMA^– is the 9,10-dihydro-9-oxo-10-acridinacetate ion. The complex crystallizes in the monoclinic space group P2/n, with cell dimensionsa=17.335(9),b=8.440(5),c=21.875(12) Å, =91.94(5)°,Z=2. The structure was solved by direct methods and refined to a finalR value of 0.0363 for 3022 non-zero reflections. The Zn²⁺ ion occupies twofold axis and is coordinated to four carboxylate ligands, the ZnO₄ tetrahedron is considerably distorted with Zn–O distances of 1.978(3) and 1.961(3)Å. Each Na⁺ cation interacts with two water, one ethanol, and three carboxylate O atoms comprising distorted octahedron. The Zn²⁺ and Na⁺ cations are linked through monooxygen and syn-syn carboxylate bridges forming a trinuclear, mixed-metal cluster. The Zn...Na separation is 3.267(2)Å and Na...Na distance equals 3.520(2)Å. All oxygen bonded H-atoms are utilized in hydrogen bonds. The acridone rings overlap in the crystal with the 3.5 Å interlayer separations. The compound has been characterized by IR spectroscopy.     

Syntheses and crystal structures of two soybean isoflavone derivatives

Two soybean isoflavone derivatives, 7-methoxy-4′-hydroxyisoflavone (1) and 4′, 7-diethoxyl-5-hydroxyisoflavone (2) were synthesized and their crystal structures were determined by single-crystal X-ray diffraction. Two derivatives crystallize in the monoclinic crystal system, space group P2₁/c. The cell dimensions of 1 are a = 8.696(4) Å, b = 11.947(5) Å, c = 12.078(5) Å, β = 93.594(7)^∘, D_c = 1.423 Mg/m³, V = 1252.3(10) ų, Z = 4, and those of 2 are a = 37.672(12) Å, b = 11.228(4) Å, c = 7.582 (3) Å, β = 94.150(6)^∘, D_c = 1.355 Mg/m³, V = 3198.6(18) ų and Z = 8. They have the same isoflavone skeleton which is composed of a benzopyranone moiety and a phenyl moiety. Hydrogen bonding and π < eqid1 > π stacking interactions assemble 1 into supramolecule with a three-dimensional network. And in the crystal structure of 2, hydrogen bonding and C–H ⋅s π stacking interactions lead to the formation of a two-dimensional network.     

Molecular gears: Structures of (9,10-triptyceno) crown ethers

The incorporation of 9,10-triptycene unit in a crown ether is examined from a structural perspective. Insertion of a triptycene group into 18-crown-6 stretches the crown into an ellipse, as seen in structures presented here of 9,10-triptyceno-22-crown-6 and its thallium complex. Symmetric addition of two triptycene groups into 18-crown-6 results in the sterically congested bis(9,10-triptyceno)-26-crown-6, whose crown cavity is filled with the -clouds of two arene groups. The larger bis(9,10-triptyceno)-32-crown-8 is more sterically relaxed. The structures of these bis(triptyceno)crown ether molecules are the first with two triptycene groups simultaneously linked through their 9 and 10 positions, thereby forming a simple molecular gearing mechanism. The compound 9,10-triptyceno-22-crown-6 (1) crystallizes in the orthorhombic space group Pbca with a = 10.7962(7), b = 15.826(3), c = 31.147(5) Å, V = 5321.8(12) ų, and Z = 8; its complex with TlNO₃ (Tl-1) crystallizes in the monoclinic space group P2₁/c with a = 8.1884(14), b = 19.552(2), c = 20.575(4) Å, = 97.062(8)°, V = 3269.2(9) ų, and Z = 4; bis(9,10-triptyceno)-26-crown-6 (2) crystallizes in the triclinic space group P with a = 8.6488(11), b = 10.7718(12), c = 12.3324(12) Å, = 111.58(1), = 100.55(1), = 106.43(1)°, V = 970.3(5) ų, and Z = 1; and bis(9,10-triptyceno)-32-crown-8 (3) crystallizes in the orthorhombic space group Pna2₁ with a = 20.186(3), b = 8.558(2), c = 25.623(2) Å, V = 4426.2(14) ų, and Z = 4.     

Crystal structure of (Ph<Subscript>4</Subscript>P)[Hg(SPh)<Subscript>2</Subscript>Br]: Synthesis,characterization and structural analysis

The complex (Ph₄P)[Hg(SPh)₂Br] has been prepared and the crystal structure has been determined. The complex crystallized in the triclinic space group P with a = 9.607(5), b = 10.120(5), c = 17.071(8) Å, α = 96.00(3), β = 100.36(2), γ = 90.42(3)^∘, V = 1623(2) ų, D_c = 1.71 g cm⁻³, μ = 6.153 cm⁻¹, F(000) = 816 and Z = 2. The anionic complex [Hg(SPh)₂Br]⁻ is the monomer with distorted trigonal planar geometry. It contains relatively strongly bonded two thiolate ligands with a weaker bonding bromide ion. The crystal structure demonstrates a supramolecularity represented by nonconventional Br⋅sH–C(π) hydrogen bonds as well as aryl⋅saryl [C(π)–H⋅sC(π)] interactions. The Ph₄P⁺ cations are forming recognized extended supramolecular motifs of phenyl embraces.     

The crystal and molecular structures of 9,10-dihydro-9, 10-ethano- and etheno-anthracenes

As part of our investigation on histamine receptor antagonists, the structures of two 9-10-dihydroanthracene derivatives are reported: 4: C₂₂H₂₈N₂; hexagonal, P6₁; a = 10.014(1), c = 34.556(7) Å; V = 3001.0(7)ų; and Z = 6; 9:C₁₉H₁₉N: triclinic, P-1; a = 8.427(2), b = 12.806(3), c = 15.292(3) Å, = 70.27(3), = 80.83(3), = 72.98(3)°; V = 1482.0(6) ų; and Z = 4. All non-aromatic rings in both molecules adopt a similar conformation. However, the three six-membered rings in the etheno-anthracene structure adopt a more regular boat form in spite of two sp² carbon bridged atoms.     

Structure and magnetic properties of a dinuclear complex [Cu<Subscript>2</Subscript>(TPA)<Subscript>2</Subscript>(<Emphasis Type="Italic">o-</Emphasis>phth)](ClO<Subscript>4</Subscript>)<Subscript>2</Subscript>

A new dinuclear complex, [Cu₂(TPA)₂(o-phth)](ClO₄)₂ (TPA = tris(2-pyridylmethyl) amine, o-phth = terephthalato dianion), was synthesized and characterized by X-ray crystallography. The unit of dinuclear Cu(II) was bridged by terephthalato dianion. The complex crystallizes in triclinic space group P1, with a = 8.287(3) Å, b = 10.623(4) Å, c = 13.818(5) Å; α = 92.077(7)^∘, β = 94.768(7)^∘, γ = 90.352(6)^∘; V = 1211.4(8) ų; Z = 2; R₁ = 0.0604, wR₂ = 0.1707. In the temperature range 4–300 K, magnetic measurement shows that the exchange interaction of the two metal ions is weak ferromagnetic with J = 1.20 cm⁻¹, g = 1.97.     

Complexation with diol host compounds. Part 3. Molecular inclusion of 4-methylcyclohexanone and 2-methylcyclohexanone by the host,trans-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene

The structures of the 12 molecular complexes oftrans-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with 4-methylcyclohexanone (1) and with 2-methylcyclohexanone (2) have been determined by X-ray crystallography. The crystal data are as follows: Compound (1):P2₂/c,a=8.838(2) Å,b=8.92(1) Å,c=20.879(8)=Å,=98.67(2)°,V=1627(2) ų,Z=2 andR=0.062 for 2201 unique MoK reflections; Compound (2):P¯1,a=8.917(3) Å,b=9.900(2) Å,c=11.250(4) Å,a=68.72(2)°,=64.39(3)°, =74.86(2)°,V=828.1(5) ų,Z=1 andR=0.098 for 2563 unique reflections. Both inclusion compounds exhibit O-HO=C hydrogen bonding interactions. The thermal properties of these compounds have been characterized by DTA and TGA thermograms.     

Synthesis and crystal structure of a binuclear maleatocopper(II) complex with phenanthroline

The title copper(II) complex [Cu₂(C₄H₂O₄)₂(phen)₂]⋅4H₂O (phen = 1,10-phenanthroline) was prepared and its crystal structure was determined by X-ray diffraction method. The crystal belongs to space group C2/c with cell of a = 18.136(5), b = 12.505(5), and c = 14.617(5) Å, β = 103.440(5)^∘ and Z = 4. The Cu(II) atom assumes a square pyramidal coordination geometry with a longer Cu–O3 coordination distance [2.308(3) Å] in the apical direction. The carboxyl O3 atoms from two maleate dianion bridges two Cu(II) atoms to form the binuclear complex with a shorter Cu⋅sCu separation of 3.349(1) Å. The separations of 3.39(1) and 3.41(1) Å between parallel phen rings indicate the existence of aromatic stacking.     

Reactivity of 1,2,4,5-tetracarboxylatebenzene with cobalt(II)

The complexes [Co(H₂O)₆][Co(BTCA)(H₂O)₄]⋅7.2H₂O (1) and [Na₂Co(H₂O)₄(μ-H₂O)₂ (μ-BTCA)] (2) (BTCA = 1,2,4,5-tetracarboxylatebenzene) have been synthesized and characterized by single crystal X-ray diffraction. Compound (1) crystallizes in the triclinic space group P-1 with a = 6.8591(9) Å, b = 9.9691(13) Å, c = 10.9231(11) Å, α = 93.021(2)^∘, β = 104.883(2)^∘, and γ = 103.702^∘ with Z = 1. This compound exhibits a 1-dimensional structure of two alternating layers. A chain of cobalt ions and BTCA constitute one layer. Cobalt complex ions and solvent water molecules occupy the other. Compound (2) crystallizes in the monoclinic space group C 2/m with a = 8.8647(6) Å, b = 10.5247(7) Å, c = 21.2265(14) Å, and β = 92.525(2)^∘, with Z = 2. This compound consists of a 3-dimensional network of cobalt and sodium ions linked by BTCA. The sodium complex moiety is disordered around a center of inversion.     

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.     

X-ray structure of 14-phenyldiquino[3,4 b;4′,3′-e][1,4]thiazine<Superscript>(1)</Superscript>

The title compound 1 (C₂₄H₁₅N₃S) crystallizes in an orthorhombic unit cell, with a = 8.2355(3), b = 19.1499(8), and c = 11.3520(5) Å, Z = 2, and space group Pnma. The pentacyclic ring system is folded mainly along the S–N(2) axis and slightly along the C(3)–C(4) and C(3′)–C(4′) axes. The butterfly folding angle between the two quinoline planes is 48.96(3)^∘ and the angle between the planes of the two halves of the thiazine ring is 43.46(7)^∘. The central thiazine ring is in a boat conformation. The phenyl substituent is unexpectedly in an axial location with respect to the thiazine ring with the C–N⋅ < eqid1 > ⋅S angle of 114.0(1)^∘ and it is perpendicular to the bisecting plane of the pentacyclic ring system.     

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.     

Synthesis and crystal structure of 2-benzoyl-4-methyl phenyl benzoate

The crystal structure of the title compound, C₂₁H₁₆O₃, has been determined. The compound crystallizes in triclinic space group PĪ with cell parameters a = 9.2240(9) Å, b = 9.8050(8) Å, c = 10.1610(11) Å, α = 94.749(6)^∘, β = 112.544(4)^∘, γ = 102.145(6)^∘ and Z = 2. The structure exhibits both intra and intermolecular interactions of the type C–H ⋅s O. The intermolecular interaction between the molecules form centrosymmetric dimers.     

Hydrogen bonding in thiourea: diethyl oxalate complex in 2:1 ratio

The crystal structure of thiourea:diethyl oxalate in 2:1 ratio is the first of its kind where the diethyl oxalate exists as a solid which otherwise is a liquid at room temperature. It crystallizes in triclinic centrosymmetric space group P-1 with the following unit cell dimensions a = 7.1870(7) Å, b = 7.4890(8) Å, c = 8.3637(7) Å, α = 63.783(7)^∘, β = 67.41(1)^∘, γ = 64.933(7)^∘. The R-factor = 0.0386 for 1850 F_o > 4σ (F_o) and 0.0417 for all 2020 data. There is a center of inversion at the center of the C–C bond of diethyl oxalate. This system is stabilized by N–H ⋅s S and N–H ⋅s O hydrogen bonds.