Synthesis and characterization of ternary L-histidine complexes. Crystal structure of (2,2′-dipyridyl)-(L-histidinato-N,N′,O)copper(II) perchlorate 1.5 hydrate

A series of ternary complexes of copper(II), cobalt(II) and zinc(II) with L-histidine, 1,10-phenanthroline, 2,2-dipyridyl or imidazole having perchlorate or acetate as counterions were synthesized and characterized by conventional methods and for [Cu(bipy)(L-hist)]ClO₄·1.5H₂O and X-ray crystal structure was determined. The crystals belong to the monoclinic space groupC2 witha=18.843(3),b=10.582(2),c=11.020(2), =115.20(10)°,Z=4,R=0.0535. The structure is consistent of [Cu(bipy)(L-hist)]⁺ cations, perchlorate ions and water molecules. The geometry around copper is trigonal bipyramidal with one N,N,O tridentate L-histidine molecule and one 2,2-dipyridyl ligand, the apical sites are occupied by the -amino nitrogen [Cu–N(71) 1.995(8)] and by N(11) of 2,2-dipyridyl [Cu–N(11) 1.983(7)], the equatorial plane is formed by the N(3) imidazole -nitrogen [Cu–N(3) 2.140(6)], O(82) carboxylic oxygen [Cu–O(82) 2.009(5)] and N(22) [Cu–N(22) 2.010(7)].     

Structure of N,N′,N″-tris(carboxymethyl)-1,3,5-benzenetricarboxamide trihydrate

The title compound, C₁₅H₁₅N₃O₉·3H₂O, crystallizes in the centrosymmetric space group R with a = 13.642(5), b = 13.642(5), c = 18.692(5) Å, D _calc = 1.440 g cm³, and z = 6. An extensive three-dimensional hydrogen bonded network is observed. The network arises from 15 hydrogen bonds per asymmetric unit. Six identical N—H···O hydrogen bonds are formed between two triacid molecules, which results in the face-to-face dimerization of the two triacid molecules. The dimers form extended sheets through hydrogen bond interaction with water molecules. The sheets are held together by hydrogen bonds via the water molecules. The planes of the benzenoid ring are parallel to each other.     

Synthesis and crystal structure of the perchlorate salt of diprotonated N,N′-bis(1-methylimidazole-2-methyl)1,5-diazacyclooctane

The diprotonated perchlorate salt of a new 1,5-diazacyclooctane (DACO) mesocycle functionalized by two imidazole pendants, N,N-bis(1-methylimidazole-2-methyl)-1,5-diazacyclo-octane (C₁₆H₂₈N₆Cl₂O₈), has been synthesized and the structure determined by X-ray diffraction analysis. The title compound crystallizes in the monoclinic system, space group P2₁/c with a = 11.964(2), b = 13.251(3), c = 14.741(3) Å, = 106.00(3)°, Mr = 503.34, V = 2246(1) ų, Z = 4. The crystal structure of the title compound reveals that the DACO ring is also folded up into the chair/boat configuration, which is consistent with the configuration in most of the transition metal complexes of DACO and its derivatives. The two imidazole pendants of the compound are in cis position with a dihedral angle of 16.0(4)°.     

Hydrothermal synthesis of catena(triaqua-(μ-2-croconato-O,O′,O″,O‴)-calcium(II)) calcium croconate trihydrate

The title compound exists as a 1D coordination polymer consisting of alternating calcium cations and croconate anions. Three water molecules complete the 7-coordination sphere of Ca in the form of a pentagonal bipyramid and form hydrogen bonds which link the polymeric chains into layers and also interconnect the layers. The structure has a triclinic space group P–1 with a = 6.642(3)Å, b = 7.793(4)Å, c = 8.854(5) Å, = 106.97(5), = 92.43(4), = 106.98(4)°, V = 415.1(4) ų, and Z = 2.     

The crystal and molecular structure of 14-β-N-pentylaminomorphinone,C22H28N2O3

The crystal and molecular structure of 14--N-pentylaminomorphinone (14--N-PAM), C₂₂H₂₈N₂O₃, has been determined by analysis of single crystal X-ray diffraction data. The compound crystallized at room temperature in the orthorhombic system, space group P2₁2₁2₁ witha=12.4535(8),b=13.7855(8),c=11.710(1) Å,V _c =2010.3(2) ų,Z=4,D _x =1.22 gm/cm³,(Cu K)=6.58 cm^–1, andF(000)=792. The final refinement yieldedR=0.051,R _w =0.059 for 328 variables with 1133 unique observed reflections. The absolute configuration is established via the synthesis from thebaine by the noninvolvement of certain asymmetric centers. The molecule is found to have as its central structure a T shape similar to that found in morphine and codeine. The distinctive feature of the molecule is the 14--N-pentylamino lipophilic side chain. Molecular modeling studies on the alkylamino chain result in the identification of clusters of conformations based on energy and dihedral angle criteria. Selected conformations are compared to 19-propylthevinol (etorphine), another potent analgesic which contains a lipophilic hydroxyalkyl substituent at C19. The enhanced analgesic activity of 14--N-pentylaminomorphinone is postulated to arise from an overall morphine-like contact with the receptor augmented by the interaction of the aliphatic chain with a lipophilic receptor pocket.     

The structure of Wallach's compound. Single-crystal X-ray structure determination oftrans-2,5-bis(trichloromethyl)-N-(1′-hydroxy-2′,2′,2′-trichloroethyl)-4-imino-1,3-dioxolane

The structure of Wallach's compound, C₇H₄O₃NCl₉, prepared in 1874 from concentrated aqueous solutions of potassium cyanide and chloral hydrate, has long been undecided. By single crystal X-ray crystallography it has now been established astrans-2,5-bis(trichloromethyl)-N-(1-hydroxy-2,2,2-trichloroethyl)-4-imino-1,3-dioxolane, confirming the tentative assignment by¹H and¹³C NMR spectrography. The title compound is monoclinic,P2₁/c;a=8.445 (1),b=10.948(1),c=17.923(4) Å;=94.36(1)°;Z=4. The structure was solved by direct methods, from data collected at room temperature on an Enraf-Nonius CAD4 diffractometer, and refined by least squares to a finalR value of 0.041 using 2101 reflections.     

Synthesis,infrared and Mössbauer characterization and X-ray crystal structure of 1,10-phenanthrolinium tetrachloromethoxy phenylantimonate(V)

The compound has been characterized by X-ray crystal structure determination, Mössbauer and i.r. spectroscopy. It crystallizes in the monoclinic space groupP2 ₁ /c (No. 14) witha=24.228(4),b=8.335(2),c=23.975(4) Å,=117.83(3)° andZ=8. Least-squares refinement on 3749 observed reflections gave finalR=0.034 (R _w=0.037). The compound is constituted by [(C₆H₅)SbCl₄OMe]^– anions andphenH⁺cations. The coordination polyhedron about Sb is an octahedron (Sb-Cl 2.416(3), Sb-O 1.962(7) and Sb-C 2.138(9) Å). The whole structure is characterized by two short contacts (O(1)N(2) 2.76(1) O(2)N(4) 2.75(1) Å) involving the methoxy oxygens of the two independent anionic units [(C₆H₅)SbCl₄OMe]^– and two nitrogens of the two independent phenanthrolinium moieties.     

Crystal structure of 1,3-(N,N′-benzamide)-2-methyl-1-pentene

Crystals of the title compound are monoclinic (C20H22N2O2): space groupP2₁/n,a=11.800(3),b=13.820(2),c=11.004(3) Å,=92.74(3)°. The structure was solved by direct methods and refined by block-matrix least-squares procedure to giveR=0.078 andRw=0.076 for 1960 reflections above 3(I). The two amide groups are not coplanar with respect to their benzene rings. An intramolecular N-HO hydrogen bond was found in the molecules which are joined in chains by other strong N-HO hydrogen bonds.     

The reaction of di-2-pyridyl ketone with antimony(III) fluoride. Preparation and crystal structure of difluoro (hydroxodi-2-pyridylmethoxo-NN′O)antimony(III)

The synthesis and the crystal and molecular structure of the difluoro(hydroxodi-2-pyridylmethoxo-NNO) antimony(III) compound determined by single crystal X-ray diffraction analysis are reported. Crystals are orthorhombic, space group Pbcn,a=12.732(2),b=12.165(2),c=15.936(2) Å. Refinement based on 1516 observed reflections led to a finalR value of 0.025 (Rw=0.028). In the crystal the di-2-pyridyl ketone behaves asfacial-(NNO)-terdentate in the Sb coordination, the square pyramid geometry around the metal is completed by the coordination of two fluorine atoms.     

The synthesis and crystal structure of [La(OH2)5(phen)2]Cl3·4H2O·phen

[La(OH₂)₅(phen)₂]Cl₃·4H₂O·phen is centric, Pnna, witha=19.946(7),b=16.458(5),c=12.207(4)Å andD _calc=1.57 g cm^–3 forZ=4. The La(III) ion resides on a crystallographic twofold axis and is coordinated to four nitrogen atoms (from two phen molecules) and five water molecules resulting in a distorted tricapped trigonal prismatic geometry. An uncoordinated phen molecule, two chloride anions, and four uncoordinated water molecules are hydrogen bonded to the coordinated water molecules. The coordinated and uncoordinated phen molecules -stack diagonally through the unit cell.     

The structure of N,N′-bis(2-hydroxyphenyl)butanediamide

The structure of N,N-bis(2-hydroxyphenyl)butanediamide has been determined. The molecule consists of two 2-hydroxyphenyl moieties which are attached (at the 2 position) to the two nitrogens of the butanediamide. The compound C₁₆H₁₆N₂O₄ crystallizes in the monoclinic space group P2₁/c witha=5.576(1),b=4.8853(6),c=25.397(6) Å and =90.58(1)°.     

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.     

Synthesis and crystal structure of N,N′-dicyclohexylimidazolium hexafluorophosphate

N,N-dicyclohexylimidazolium hexafluorophosphate was prepared and its structure was determined by X-ray diffraction. The compound crystallizes in the orthorhombic space group Pbca, with the cell dimensions of a = 14.620(3) Å, b = 15.097(3) Å, c = 16.128(3) Å, V = 3559.4(12) ų, and D _calc. = 1.412 mg/m³ for Z = 8. The structure was solved by direct methods and refined to R value of 0.041. In the solid state, PF₆ ^– anion and imidazolium cation form strong hydrogen bonds, which fix the relative orientation between cations and anions.     

Synthesis and crystal structure of Nd(III)–Zn(II) complex

A novel heteronuclear complex, [NdZn₂L₆(NO ₃)(phen)₂] (HL = -methylacrylic acid, phen = 1,10-phenanthroline), was synthesized and characterized by elemental analysis, infrared absorption spectra (IR) and its molecular structure was also determined by X-ray structure analysis. The title complex contains a discrete trinuclear ZnNdZn molecule bridged by carboxylate groups between Zn and Nd ions and crystallizes in space group P¯1 with the cell dimensions: a = 13.601(3) Å, b = 16.859(2) Å, c = 12.575(2) Å, = 110.09(1), = 112.21(1), = 81.10(2).     

Synthesis and structure of a (4,4′-bipyridine) lanthanide(III) complex with tetraimine (2+2) macrocycle from 2,6-diformyl-4-chlorophenol and 1,3-diamino-2-hydroxypropane

A novel (2+2) macrocyclic Schiff base lanthanide(III) complex [La(H₄L)(NO₃)₃]·(4,4-bipy)·2H₂O has been synthesized by template condensation of 1,3-diamino-2-hydroxypropane and 2,6-diformyl-4-chlorophenol. The compound crystallizes in the orthorhombic space group Pnma with a = 16.400(3), b = 12.985(3), c = 19.118(4) Å, and Z = 4. In the macrocycle, La³⁺ was coordinated by two imino nitrogen atoms, two phenolic oxygen atoms, one pedant alcoholic oxygen atom, and six nitrate oxygen atoms. It is interesting that the neutral lanthanide macrocyle forms a saddlelike supramolecule with 4,4-bipyridine.     

The synthesis and crystal structure of one novel ternary complex of 2,2′-bipyridine N-salicylidenetyrosinatocopper(II)

The crystal structure of copper(II)—salicylidene-aminoacidate Schiff base—nitrogen-donor chelating ligand, [Cu(sal-tyr)(bipy)] (sal-tyr: N-salicylidenetyrosinato; bipy: 2,2-bipyridine) which is obtained by means of one-step synthesis, is presented. It crystallizes in space group P2₁2₁2₁ with a = 9.0356(18) Å, b = 11.992(2) Å, c = 20.618(4) Å. The Cu^II ion is five coordinated by one oxygen atom of carboxylate, the imine nitrogen atom, and the hydroxyl oxygen atom of the salicylidene in the Schiff base anion as well as two nitrogen atoms of bipy, resulting in a seriously distorted square pyramid coordination polyhedron. The phenol group and the apical coordination bond Cu(1)–N(2) are in the same side of the Schiff base chelating plane which could be attributed to the intramolecular C–H s interaction between the H(17) of the bipy and the benzene ring of the phenol. The hydrogen bond between the hydroxyl hydrogen atom of the phenol group and the coordinated oxygen atom of the carboxylate from neighboring molecule is helpful to stabilize the crystal.     

X-ray crystal structure of 2-hydroxy-2′-(1,4-bisoxo-6-hexanol)-1,1′-biphenyl

The X-ray crystal structure of 2-hydroxy-2-(1,4-bisoxo-6-hexanol)-1,1-biphenyl, 3, is presented. This molecule crystallizes in the monoclinic space group P2₁/n (a = 9.440(2), b = 12.679(3), c = 11.679(3) Å = 94.60(2)° V = 1382.5(5) ų; Z = 4). One of the unique features of the X-ray structure of 3 is the intramolecular hydrogen bonding. The hydrogens of the phenolic and hydroxy groups occupies bridging positions via hydrogen bonding to an ether oxygen (O₁) and a phenolic oxygen (O₄), respectively. This hydrogen bonding does not affect the interplanar angle between phenyl rings (49.34°), which is in the range expected for ortho-disubstituted biphenyl compounds. The hydrogen bonding of this type explains why it is difficult to alkylate both phenoxy groups of 2,2-biphenol with tetrahydropyranyl protected 2-(2-chloroethoxy)ethanol.     

5(2′Carboxy)phenylazo barbiturate diaqua copper(II) trihydrate: Characterization and crystal structure

The title compound has been synthesized and characterized by standard spectroscopic techniques and magnetic susceptibility measurements and its structure has been determined by monocrystal X-ray diffraction. The complex crystallizes in the monoclinic space groupP2₁/c in a cell of dimensionsa=11.432(3),b=6.927(2),c=21.289(8)Å,=106.54(4)°,V=1616.1(9)ų,D _c =1.758 Mg m^–3,D(flotation)=1.76 Mg m^–3,M _w =427.8, (CuK)=2.47 mm^–1,F(000)=876. The structure refined to a finalR of 0.041 for 1290 observed independent reflections. The copper atom is coordinated by the nitrogen atom of the azo group next to the phenyl ring, the oxygen atom of one of the carbonyl groups of the barbituric moiety and one of the oxygen atoms of the carboxylate, closing two six-member chelate rings. Two water molecules complete a typical 4+1 square-based pyramidal environment.     

Synthesis and crystal structure of (+)-(2R,3R)-N, N′-bis-trityl-2,3-bis-aziridine

A new C₂ symmetric bis-aziridine derivative was synthesized starting from L-(+)-tartaric acid. The molecular structure of (+)-(2R, 3R)-N, N-bis-trityl-2,3-bis-aziridine 4, was determined by ¹H, ¹³C NMR and elemental analysis and was confirmed by single-crystal X-ray diffraction. Crystal data for 4: C₄₂H₃₆N₂, orthorhombic, space group: P2₁2₁2₁, a = 12.7633(14), b = 14.5661(6), c = 17.4184(14) Å, and Z = 4.     

The electronic nature of the substituents and the structure of 4,4′-dipyridilium dications. The crystal structure of N,N′-di(carbethoxymethyl)-4,4′-dipyridilium diperchlorate

The crystal structure of N,N′-di(carbethoxymethyl)-4,4′-dipyridilium diperchlorate (I) C₁₈H₂₂Cl₂N₂O₁₂ at 293 K is determined by the X-ray diffraction technique. The crystals are monoclinic, a = 5.501(1) Å, b = 26.460(5) Å, c = 8.140(2) Å, β = 100.63(3)°, space group P2₁/n, Z = 2, 2271 reflections measured (2052 reflections unique), R ₁ = 0.062, and wR2 = 0.141 for 1161 reflections with F ≥ 4σ(F). The interaction between the lone-electron pair of the carbonyl oxygen atom of the electron-withdrawing ester group and the π system of the dication manifests itself as the intramolecular O(1)?N contact (2.780 Å). In the absence of charge transfer from the counterion to the dication, this interaction contributes to the stabilization of a planar structure of the dication fragment of the molecule despite the electron-withdrawing nature of the ester groups.