Crystal structure of 2,2′-diformyl 4,4′-dimethyl 6,6′-[piperazine-1,4-diyl bis-(methylene)]bis phenol

The title compund C₂₂H₂₆N₂O₄,Mr=382.46 crystallizes in the orthorhombic space group P2₁2₁2₁ with =8.867(1)Å,b=13.228(2)Å,c=17.029(3)Å,V=1956.7(2)ų,Z=4, D_cal=1.30 Mgm^–3,F(000)=816, =6.89 cm^–1, (CuK)=1.5418 Å andT=298 K. The structure was solved by direct methods and refined by full-matrix least-squares. The finalR=0.046 for 1995 unique reflections. The phenyl rings are coplanar (oriented at an angle of 6.4(1)^o) and orients at an angle of 112.2(1)^o and 115.7(1)^o, respectively with the piperazine ring. The piperazine ring adopts achair conformation and the substituents at the N-atoms are in an equatiorial position.DCB Contribution No. 823.     

Synthesis, crystal structure, and spectroscopy of (azido-N1)bis(2,2′-bi-imidazoline)copper(II) perchlorate

The compound [Cu(biz)₂(N₃)](ClO₄) (biz = 2,2-bi-imidazoline) has been synthesized and characterized by X-ray crystallography and infrared spectroscopy. In addition, EPR and magnetic measurements have been performed. The compound crystallizes in the monoclinic space group P2₁/c, with a = 9.2716(2), b = 27.6454(4), c = 7.4285(1) Å, = 102.1417(6)°, V = 1861.46(5) ų, and Z = 4. The coordination geometry around the Cu(II) ion is distorted square pyrimidal, with 4 nitrogen atoms of 2 bis-chelating ligand molecules in the basal plane and one nitrogen of the azide molecule in the apical position. The perchlorate ion is noncoordinating. In the infrared the vibrations of the coordinated azide anion are observed at 2050, 1286, and 620 cm^–1, while the vibrations of the free perchlorate anion are observed at 1071, 1035, and 919 cm^–1; Cu—N vibrations are observed at 418 and 336 cm^–1. The molecules are connected in the lattice via relatively strong hydrogen bonding between the N—H groups at the back of the biz ligand and the N1 and N3 atoms of the azide ligand forming layers. No intermolecular magnetic interaction was observed for this compound.     

Hydrogen-bonded dimer of N,N′-(5-n-butyl-5-oxodibenzo[b,d]phosphole-3,7-diyl)bis(benzamide) dimethylformamide solvate

The structure of a large wing-span phosphine, in the oxide form, N,N-(5-n-butyl-5-oxodibenzo[b,d]phosphole-3,7-diyl)bis(benzamide), C₃₀H₂₇N₂O₃P, cocrystallized with dimethylformamide (DMF), C₃H₇NO, is reported. The title compound is crystallized in a triclinic system with cell dimensions of a = 10.295(8) b = 12.743(5) c = 13.239(6) Å, = 108.14(3), = 108.16(5), = 101.20(4)°, and V=1484.4(5) ų, and forms a hydrogen-bonded dimer via two hydrogen bond linkages of the P—O ··· H—N type involving one of the two amide groups.     

Crystal structures of bis(cyanido)bis(N,N′-diethylthiourea-κS) mercury(II) and bis(cyanido)bis(N,N′-dipropylthiourea-κS) mercury(II)

Two mercury(II) complexes containing cyanide and, N,N′-diethylthiourea (detu) and N,N′-dipropylthiourea (dprtu) ligands, [(detu)₂Hg(CN)₂] (1) and [(dprtu)₂Hg(CN)₂] (2), respectively, have been prepared and characterized by X-ray crystallography. In the both complexes Hg atom lies on a 2-fold rotation axis, and is coordinated to the sulfur atoms of two thiourea ligands and to two cyanide carbon atoms. Both have a distorted tetrahedral environment with bond angles about the Hg atoms in the range of 93.41(4)°–146.75(19)°. In the crystal structures symmetry related molecules are linked via N-H-N hydrogen bonds resulting in the formation of a two-dimensional network in 1, while in 2 a double stranded one-dimensional chain is formed.     

Crystal structure and magnetic properties of bis(2,2′-bipyridine) azido copper(II) perchlorate

The title compound has been synthesized and its crystal structure has been solved at room temperature. It crystallizes in the triclinic system, space groupP, witha=7.853(1) Å,b=10.177(1) Å,c=13.651(4) Å,=74.57(1)°,=88.49(1)°, =80.675(4)°, andZ=2. The structure consists of isolated [Cu(bipy)₂N₃]⁺ cations (bipy=2,2-bipyridine) and perchlorate anions. The metallic cation environment has a distorted trigonal-bipyramidal geometry. The EPR spectrum is rhombic, which indicates that the distortion with respect to the perfect trigonal bipyramid is sufficiently pronounced to mixz ²- andx ²–y ²-type orbitals in the ground state. The temperature dependence of the molar magnetic susceptibility has been investigated in the 300-2.2 K temperature range.     

Crystal and molecular structure of aqua(2,2′-bipyridine)bis(betaine)copper(II) perchlorate monohydrate

A new monomeric copper(II) complex with 2,2-bipyridine (bpy) and betaine (bet), [Cu(byy)(bet)₂(H₂O)](ClO₄)₂ · H₂O, has been prepared and characterized by X-ray crystallography. The complex crystallizes in the triclinic space groupP-1 witha=8.859(2),b=11.191(2),c=14.850(3) Å, =91.41(1), =97.19(1), =91.97(1)°,V=1459.2(7) ų, andZ=2. The structure comprises discrete cations [Cu(bpy)(bet)₂(H₂O)]²⁺ in which the metal atom is coordinated in a distorted square-pyramidal environment by two oxygen atoms from a pair of monodentate carboxylato ligands [Cu–O=1.950(2) Å] and two nitrogen atoms of a bidentate bpy ligand [Cu–N=1.997(3)–2.005(3) Å] on the basal plane, and one aqua [Cu–O=2.267(3) Å] ligand at the apical position.     

Structure of lithium (picrate) (2,2′-bipyridyl)

The title compound C₁₆H₁₀N₅O₇Li is triclinic, witha=14.51(1),b=6.90(2),c=9.10(1) Å,=101.5(1),=67.1(2), =105.6°(1),Z=2 and space groupP¯1. Data were measured by photographic methods. The structure was solved by direct methods, and refined by full matrix least-squares. The refinement, based on 1337 reflections, gave the rather highR value of 0.11 because of poor quality data. The complex is dimeric. The coordination around the cation is distorted square-pyramidal. Two coordination sites are occupied by the nitrogen atoms of the bipyridyl ligand, two by the phenolic oxygen and oxygen ofo-nitro group, and the fifth coordination site is occupied by the phenolic oxygen belonging to the symmetry-related molecule (1–x,–y,1–z). Both oxygens act as bridges to form the dimer. The bridging is unsymmetrical, with Li-O (phenolic)=1.84(2) Å and Li¹-O (phenolic)=2.16(2) Å (whereI=1–x,–y, 1–Z).     

Synthesis,Spectral Properties and Structure of New Novel 3,3′-Dibenzoyl-1,1′-(propan-1,3-diyl)-bisthiourea

Abstract  

A new 3,3′-dibenzoyl-1,1′-propan-1,3-diyl)bisthiourea was synthesized by using benzoylisothiocyanate with 1,3-diaminopropane in aprotic solvent. The structure was determinated by means of FT-IR, ¹H-NMR, ¹³C-NMR and mass spectroscopic techniques. The crystal structure of 3,3′-dibenzoyl-1,1′-(propan-1,3-diyl)bisthiourea has also been examined by using X-ray crystallographic techniques and found to be crystallized in the monoclinic space group P2 ₁ /c with the unit cell parameters: a = 5.968(1) ?, b = 19.471(2) ?, c = 16.585(2) ?, β = 98.32(1)°, V = 1907.0(4) ?³, Dx = 1.395 g cm⁻³, and Z = 4 respectively.     

A structural model for a new class of conformationally constrained retinoid: (2Z,4E)-4-[3′,4′-dihydro-1′(2′H)-naphthalene-1′-ylidene]-2-butenoic acid

Racemic (2Z,4E)-4-[3′,4′-dihydro-1′(2′H)-naphthalene-1′-ylidene]-2-butenoic acid (1) is a polyene chain-shortened analog of (9Z)-retinoic acid (3) which uses a tetrahydronaphthyl ring to conformationally constrain the C6-C7 single bond (retinoic acid numbering). The structure of (1) was obtained to determine the effects of the tetrahydronaphthyl ring on the ring to polyene chain conformation as compared to a published crystal structure for (9Z)-retinal (2). The results reveal significant differences between the solid state structures of (1) and (2), particularly for torsion angles about C6, C7 and C8, C9. The title compound crystallizes in the centrosymmetric monoclinic space groupP2₁/n withZ=4. (Cell dimensions:a=10.863(2) Å,b=7.637(2) Å,c=15.781(3) and β=106.11(3)°.) The structure was refined toR=3.88% for those 1132 unique data with |F _o|>6σ(F _o). In the crystal structure, the molecules adopt a hydrogen bonded dimeric structure.     

Synthesis and crystal structure of 1,1′-di(ethylpropionato)-2,2′-biimidazole, a macromolecular precursor

1,1,-Di(ethylpropionato)-2,2-biimidazole, C₁₆H₂₂N₄O₄, crystallizes from ice-cold ethanol in the space group P , with a = 4.6742(9), b = 9.1119(13), c = 10.175(2) Å, = 96.22(1), = 96.29(2), = 97.53(1)°, and Z = 1. The molecule crystallizes with coplanar rings and the substituents assume a trans conformation with a center of inversion between the bridging carbon atoms.     

Synthesis, spectral, and single crystal X-ray structural studies on (2,2′-bipyridyl)bis(dimethyldithiocarbamato) zinc(II) and (1,10-phenanthroline) bis(dimethyldithiocarbamato)zinc(II)

Synthesis, spectral, and single crystal X-ray structural studies on (2,2-bipyridyl)bis (dimethyldithiocarbamato)zinc(II) (1) and (l,10-phenanthroline)bis(dimethyldithiocarbamato)zinc(II) (2) complexes are reported in this paper. The complex (1) crystallizes in the orthorhombic lattice, space group Pcca, a = 18.456(3), b = 6.529(2), and c = 17.092(2) Å. The complex (2) crystallizes in the monoclinic space group C2/c, a = 13.372(2), b = 13.850(2), c = 24.680(3) Å, and = 102.71(4)°. IR spectra of the complexes (1) and (2) show the thioureide (C-N) bands at 1489 and 1510 cm^–1, respectively, which are lower than the value observed for the parent bisdithiocarbamate. Reduction in the thioureide stretching frequency is due to the increase in coordination around the zinc ion and the resultant increase in electron density. Thermal studies indicate that the 1,10-phenanthroline adduct is marginally more stable than the other complex. X-ray crystal structures of the two adducts show them to be octahedrally coordinated and monomeric in nature. The Zn-S distances are longer than those observed in the parent bisdithiocarbamate. The thioureide C-N bond distances in (1) and in (2) indicate the partial double bond character. The most important structural changes as a result of the adduct formation are observed in the Zn-S bond distances and S-Zn-S bond angles, in terms of very significant increases in Zn-S bond distances and reductions in S-Zn-S angles, compared to the parent bisdithiocarbamate. The observed changes are indicative of a strong steric force in operation in the adducts rather than electronic effects.     

Structure of 2,2′-bis(4-cyanatophenyl)isopropylidene

The title compound is monoclinic:a=13.345(3),b=11.393(2),c=10.046(5)Å,=108.48(2)°,Z=4,P2₁/c. The structure was determined by direct methods, using MoK diffractometer data, and refined by full-matrix least squares toR=0.045 for 1463 reflections. The structure shows a central tetrahedral carbon atom surrounded by two methyl and two phenylcyanate groups. The geometry of the cyanate group compares well with that in 4-chloro-3,5-dimethyl-phenyl cyanate, the only example of an organic cyanate in the Cambridge Crystallographic database (V.3). The intermolecular nitrile, C-N, distances were examined for evidence of a possible dimerization interaction; no significant distances were found.     

Structure of 2,2′-anhydro-3′-O-acetyl-2′thio-1-β-D-arabinofuranosylcytosine hydrochloride1

2,2-Anhydro-3-O-acetyl-2-thio-1--D-arabinofuranosylcytosine hydrochloride crystallizes in space group P2₁2₁2₁ witha=10.373(1),b=14.517(2),c=9.496(1) Å. Reflections were measured on a diffractometer and the structure was solved by direct methods. Least-squares refinement converged atR=0.056 andR _w =0.063. The study of this crystal structure showed that the alterations in the geometry of 2,2-anhydro-1--D-arabinofuranosylcytosine when the bridge oxygen is replaced by sulfur are localized in the region of the fused ring. The angle at the bridge atom decreases to nearly 90°, with concomitant enlargements of about 5°–7° in the angles opposite to the bridge atom. Angle C(1)-N(1)-C(6) decreases by 4°. Also, the amount of double bond character in the bond formed by C(2) and the bridge atom decreases. A survey of the conformational features of S,2-cyclonucleosides and comparison with O,2-cyclonucleosidcs showed that their preferred conformations are the same. However, S,2-cyclonucleosides exhibit a wider range of P and values. This correlates with a greater ease of the sulfur containing five-membered ring to pucker as compared to the oxygen-cyclo ring.This paper is part of the authors' dissertation (Vitali, 1986).     

Structure analysis of O,O’-propane-1,3-diyl bis[diphenyl(phosphinothioate)]

A new diphosphine disulphide compound with the formula C₂₇H₂₆O₂|P₂S₂, was synthesized from the reaction between PPh₂SCl and 1,3-propanediol and characterized with different spectroscopic methods. Its structure has also been studied by X-ray diffraction. The compound crystallizes in the triclinic space group $P\bar 1$ . Pentavalent phosphorus atoms in the molecule are in distorted tetrahedral environments.     

Structure of (2,2′-bipyridine)lead(II) saccharinate monohydrate

The structure of (2,2-bipyridine)lead(II) saccharinate monohydrate has been investigated by X-ray diffraction. The compound crystallizes in the monoclinic space group P2 ₁/n with a = 22.903(7), b = 12.608(3), c = 8.682(2) Å, = 96.76(3)°, and Z = 4. The structure consists of Pb²⁺ cations, 2,2-bipyridine ligands, saccharinato anions and water molecules. The Pb²⁺ cation is surrounded by two O atoms and four N atoms. The two saccharinato ions are nonequivalent. The water molecule forms hydrogen bonds of O_W···O_CO [2.810(16) Å] and O_W···O_SO2 [2.893(16) Å] type.     

Crystal and molecular structures of three 2,2′-thio- and 2,2′-sulfonyl-bis(1,3-diarylprop-2-en-1-ones)

The X-ray crystal structures of 2,2-thio- and 2,2-sulfonylbis(1,3-diarylprop-2-en-1-ones) are determined [1: 2,2-thiobis(3-(p-chlorophenyl)-1-phenylprop-2-en-1-one), C₃₀H₂₀Cl₂O₂S, space group C2/c, a = 14.275(3), b = 6.280(1), c = 26.533(5) Å, = 94.55(3)°, Z = 1/2; 2: 2,2-sulfonylbis(1,3-diphenylprop-2-en-1-one), C₃₀H₂₂O₄S, space group P , a = 9.652(1), b = 12.044(1), c = 12.182(1) Å, = 61.985(6), = 77.511(5), = 74.340(6)°, Z = 1; 3: 2,2-sulfonylbis(3-(p-chlorophenyl)-1-phenylprop-2-en-1-one), C₃₀H₂₀Cl₂O₄S, space group P , a = 8.294(1), b = 13.175(2), c = 13.470(1) Å, = 62.870(9), = 83.796(7), = 85.282(8)°, Z = 1]. The C=C double bonds are all clearly defined. The sulfide 1 crystallizes on a crystallographic twofold axis, leading to a symmetric molecular conformation. The sulfones 2 and 3 crystallize on general positions, with different and irregular conformations.     

X-ray crystal structure of cis-{(±)-6,6′-[[1,1′-biphenyl]-2,2′-diylbis(oxy)]bis–dibenzo[d,f][1,3,2]dioxaphosphepin} diiodoplatinum(II)·dichloromethane

Bis(dibenzo[d,f][1,3,2]dixoaphosphepin) ligands are extensively used in catalysts for asymmetric alkene hydroformylation; however, few crystal structures of complexes of these ligands have been reported. In this paper, the synthesis and X-ray crystal structure of cis-{(±)-6,6-[[1,1-biphenyl]-2,2-diylbis(oxy)]bis-dibenzo[d,f][1,3,2]dioxaphosphepin} diiodoplatinum (II)·dichloromethane are presented. This complex crystallizes in the triclinic space group P1¯ with a = 12.0842(2,3) b = 12.6993(15) c = 13.2801(18) Å; = 85.852(10), = 76.723(13), = 72.400(12)°, V = 1890.7(10) ų and Z = 4. The diastereomer that has crystallized has an R*R*R*(S*S*S*) configuration. This X-ray crystal structure supports previous observations that bis(phosphite) ligands with bridging groups derived from 2,2-biphenol can exhibit a wide range of bite angles (>20°).     

The crystal and molecular structure of spiro[1-(S)-Br-3-(S)-H-4-(R)-l-(1′ R,2′ S,5′R)-menthyloxy-5-oxo-6-oxa-bicyclo[3.1.0]hexane-2,3′-(R)-(4′-(R)-diphenylmethoxy-5′-l-(1′ R,2′ S,5′ R)-menthyloxy-butyrolactone)]

Crystal structure of C₄₁H₅₃O₇Br has been determined by single-crystal X-ray diffraction. The compound crystalline in the orthorhombic space group P2₁2₁2₁, with a = 11.264(2), b = 12.058(2), c = 29.337(6) Å, Z = 4. The bond angles of cyclopropane moiety in the molecule are approximate to 60° and agree with theoretic values of the internal angles in a cyclopropane, and two chiral menthyloxy groups are located above and under the whole chiral molecule, respectively. The configuration of the pentacyclic lactone is shown as envelope form.     

Nonpreorganized neutral acyclic anion receptors: Structural investigations of N,N′-diphenyl-1, 3-benzenedisulfonamide and N,N′bis(4-t-butylphenyl)-1, 3-benzenedisulfonamide

The structure of N,N-diphenyl-1,3-benzenedisulfonamide (1) was determined by single crystal X-ray diffraction. It crystallizes in P2₁/n with cell dimensions: a = 11.8390(6) Å, b = 12.3950(10) Å, c = 12.1184(10) Å, = 94.388(6)°, and V = 1773.1(2) ų. Its di-t-butyl derivative, N,N-bis(4-t-butylphenyl)-1,3-benzenedisulfonamide (2), was prepared and structurally characterized as two solvated structures. Both crystallize in P with cell dimensions: 2 CF₃CH₂OH, a = 9.469(2) Å, b = 10.0039(18) Å, c = 16.385(3) Å, = 85.561(16)°, = 83.035(18)°, = 72.459(16), and V = 1467.7(5) ų; 2 ClCH₂CH₂Cl, a = 9.559(2) Å, b = 9.8125(12) Å, c = 17.100(6) Å, = 82.495(19)°, = 83.47(2)°, = 70.100(15), and V = 1491.1(6) ų. The structures exhibit hydrogen-bonding, and are evaluated in terms of preorganization for anion binding.     

Structures of nitrato-(2-hydroxybenzaldehydo) (2,2′-bipyridyl)copper and nitrato-(2-hydroxy-5-nitrobenzaldehydo)(2,2′-bipyridyl)copper

Nitrato-(2-hydroxy-5-nitrobenzaldehydo)(2,2′-bipyridyl)copper (I) and nitrato-(2-hydroxybenzaldehydo)(2,2′-bipyridyl)copper (II) were synthesized and characterized by X-ray diffraction. The coordination polyhedron of the central copper atom in complex I can be described as a distorted tetragonal pyramid whose base is formed by the phenol and carbonyl oxygen atoms of the monodeprotonated 2-hydroxy-5nitrobenzaldehyde molecule and the nitrogen atoms of the 2,2′-bipyridyl ligand and whose apex is occupied by the oxygen atom of the nitrato group. In the crystal structure, complexes I are linked by the acido ligands and the NO₂ groups of the aldehyde molecule into infinite chains. In complex II, the central copper atom is coordinated by 2-hydroxybenzaldehyde, 2,2′-bipyridyl, and the nitrato group, resulting in the formation of centrosymmetric dimers. The coordination polyhedron of the central copper atom can be described as a bipyramid (4 + 1 + 1) with the same base as in complex I. The axial vertices of the bipyramid are occupied by the oxygen atom of the nitrato group and the bridging phenol oxygen atom of the adjacent complex related to the initial complex by a center of symmetry. In the crystal structure, complexes II are hydrogen bonded into infinite chains.