The 1,8-Bis(2′-pyridyl)-3,6-dithiaoctane Complex of Rhodium(III)

Abstract  

The tetradentate ligand 1,8-bis(2′-pyridyl)-3,6-dithiaoctane (Pdto) forms a pseudooctahedral structure with rhodium(III). The yellow racemic [Rh(Pdto)Cl₂](CF₃SO₃) compound belongs to the Pbca space group with a = 13.566(15), b = 15.6588(16), c = 21.473(2) ?, and Z = 8. The Rh–S bonds are shorter than is usual, while the pyridine rings are mutually trans and form an interplanar angle of 24°.     

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.     

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).     

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.     

Crystal structure of new complexes of praseodymium(III) nitrate and ytterbium(III) nitrate with 2,2′: 6,2′′-terpyridine

The crystal structure of new complexes of praseodymium(III) and ytterbium(III) (elements from the initial and final parts of the lanthanide series), namely, [Pr(NO₃)₃ (Terpy)((CH₃)₂CO)] (I) and [Yb(NO₃)₂(Terpy)(H₂O)₂]NO₃ · 2H₂O (II), is investigated. The structure of compound I consists of [Pr(NO₃)₃(Terpy)((CH₃)₂CO)] neutral complexes. The coordination number of the praseodymium atom is 10. The coordination polyhedron of the praseodymium atom can be described as a distorted bicapped tetragonal antiprism. The structure of compound II is composed of [Yb(NO₃)₂(Terpy)(H₂O)₂]⁺ cationic complexes, nitrate anions, and molecules of crystallization water. The structural components are joined together via a three-dimensional system of hydrogen bonds. The coordination polyhedron of the ytterbium atom can be represented as a distorted tricapped trigonal prism. The coordination number of the ytterbium atom is 9.     

Synthesis and crystal structure of bis(2,2′-bipyridyl)mononitritozinc(II) perchlorate. An example of a six-coordinate cis-octahedral ZnN4O2 chromophore

The crystal structure of bis(2,2-bipyridyl)mononitritozinc(II) perchlorate, [Zn(bipy)₂ (ONO)][ClO₄] (1) has been determined. The complex is monoclinic, with a = 10.9195(4) Å, b = 12.2320(5) Å, c = 16.5477(8) Å, = 105.6150(10), P2₁/n space group, with final R1 = 0.0657 and wR2 = 0.1630. The complex involves a [Zn(bipy)₂ (ONO)]⁺ cation and a [ClO₄]^– anion. The ZnN₄O₂ chromophore is six-coordinate, with a cis-distortion of the two oxygens of the nitrite, O(1) and O(2), at distances 2.216(5) and 2.197(5) Å from the zinc (Zn– O _mean = 2.206(5) Å, O = 0.019(5) Å) and two out of plane Zn–N bonds, Zn–N(2) and Zn–N(3), at 2.129(4) and 2.135(4) Å (Zn–n _mean/out = 2.132(4) Å, n _2,3 = 0.006(4) Å). The two inplane nitrogens, N(1) and N(4), at distances Zn–N(1) = 2.090(4) and Zn–N(4) = 2.085(4) Å (Zn–n _mean/in = 2.087(4) Å, n _1,4 = 0.005(4) Å) are greater than 2.0 Å, but slightly shorter than the axial bonds. The inplane angles ₁, ₂, and ₃ in 1 have values 150.33(18), 108.98(17), and 99.73(18) respectively. The stereochemistry is cis-distorted octahedral, with an ₃ = 99.37(18), which is lower than ₃ = 103.4(1) observed in [Zn(bipy)₂(ONO)][NO₃] (5). Comparison with the corresponding [Cu(bipy)₂(ONO)][Y] complexes suggested that the cis-distortion of the CuN₄O₂ chromophore in the copper(II) series does not originate in the Jahn–Teller or pseudo-Jahn–Teller effect.     

The crystal structure of 2-amino-5,5′-bis(β-cyanoethyl)-1,2-pyrrolenineN-oxide monohydrate

2-Amino-5,5-di(-cyanoethyl)-1,2-pyrrolenineN-oxide monohydrate, C₁₀H₁₄N₄O·H₂O, crystallizes from MeCN in space group P2₁2₁2₁ witha=7.0007(5),b=8.2998(6),c=20.8418(13) Å,V=1211.0(2) ų,Z=4. The structure was refined toR=0.034 andR _w=0.044 for 2325 observed reflections. The pyrrolenine ring adopts a nearly planar conformation, with maximum deviation from planarity 0.089(2) Å. The N–O distance is 1.345(2) Å. The water molecule bridges two pyrrolenine molecules via hydrogen bonds to theirN-oxide oxygen atoms, and also accepts a hydrogen bond from the NH₂ group of another pyrrolenine molecule.     

Crystal and molecular structure of di-μ-chlorobis[N-(2-hydroxyethyl)salicylideneiminato-N,O,O′ copper(II)] methanol solvate

The structure of the title compound, [Cu₂Cl₂(C₉H₁₀NO₂)₂]·CH₃OH, has been determined from single crystal X-ray diffraction data. The dinuclear units crystallize in the orthorhombic space group P2₁2₁2₁ with 4 formula units in a cell of dimensions:a=9.707(1),b=11.785(2),c=19.843(3)Å. The notable feature of the molecular structure is that it is dimeric with distorted square-pyramidal geometry at each, copper center. The two bridges are formed by C11 and C12 atoms where C11 is equatorial to Cu1 and apical to Cu2 and vice versa for atom C12. The apical Cu1–C12 and Cu2–C11 distances are 2.778(2) and 2.700(2)Å, respectively. The Cu1–Cu2 separation is 3.417(1)Å in the dimers. The geometry of the ligands and hydrogen bonds are discussed.     

Synthesis, crystal structure, and properties of the adduct of bis(O,O′-diisopropyl dithiophosphato)nickel(II) with pyridine [Ni(i-Pr2dtp)2(py)2]

A new adduct bis(pyridine)-bis(O,O-diisopropyl dithiophosphato-S,S)nickel(II), [Ni(i-Pr₂dtp)₂(py)₂] (dtp = dithiophosphate, py = pyridine) has been obtained by re-crystallization from CH₃COCH₃. The crystal and molecular structure of the title complex has been determined by X-ray crystallography. It crystallizes in the monoclinic system, space group P2₁/c, with lattice parameters a = 6.4890(13) Å, b = 16.386(3) Å, c = 14.830(3) Å, = 99.74(3)°, V = 1554.1(5) ų, and Z = 2. The crystal structure consists of discrete molecules of [Ni(i-Pr₂dtp)₂(py)₂], which displays a slightly distorted octahedral geometry for the NiS₄N₂ chromophore. Two O,O-diisopropyl dithiophosphate ions act as bidentate ligands with their S atoms coordinated to Ni atom. Each forms a four-membered chelate ring in the equatorial plane. The N atoms from two pyridine ligands are axially coordinated to the Ni atom. The Ni S bond distances are 2.4492(8) Å and 2.5711(9) Å, and the Ni bond distances are 2.127(3) Å. Thermal analyses show that the thermal decomposition of this adduct is so unstable that loss of two pyridine ligands begins at about 65°C. Electronic and IR spectra data is in agreement with the structural data.     

Preparation and crystal structure of spiro(5,7-dimethoxy-1(1H)oxo-2-benzopyran-3(4H),1′-cyclohexane)

Spiro(5,7-dimethoxy-1(1H)oxo-2-benzopyran-3(4H),1-cyclohexane) (C₁₆H₂₀O₄) was prepared by alkylation of o-lithio 3,5-dimethoxy-N-methyl benzamide with methylene cyclohexane oxide followed by alkaline hydrolysis and its crystal structure was determined by X-ray crystallographic techniques. The compound crystallizes into monoclinic space group P2₁/c with unit cell parameters: a = 11.914(3) Å, b = 9.861(3) Å, c = 12.508(7) Å, = 91.34(3), Z = 4. The structure has been solved by direct methods and refined to R = 0.039 for 1870 observed reflections. The heterocyclic ring adopts distorted sofa conformation while cyclohexane ring assumes a highly symmetric chair conformation. The dihedral angle between the mean planes of isocoumarin nucleus and cyclohexane ring is 105.51(5). Molecules are held together in the crystal by C=H ... O hydrogen bonds.     

The synthesis, characterization, and X-ray crystal structure of trans-bis(1,3-diamino-2-propanolato-N,N′,O)- cobalt(III) perchlorate trihydrate

The crystal structure of [Co(C₃H₉N₂O)₂]ClO₄3H₂O was established by single-crystal X-ray diffraction techniques. The compound crystallized in the monoclinic space group P2₁ with unit cell dimensions a = 6.715(2) Å, b = 12.097(3) Å, c = 9.904(3) Å, = 100.80(3), and z = 2. The final R value for 1359 reflections was 0.039. The 1,3-diamino-2-propanolato ligands are tridentately coordinated to cobalt atoms that have slightly distorted octahedral coordination. The five-membered chelate rings exhibit conformations between pure twist and pure envelope, while the six-membered ring adopts a boat confirmation.     

Spectroscopic studies and crystal structure of (E)-N′-(2-hydroxy-3-methoxybenzylidene)isonicotinohydrazide

The structure of compound has also been examined cyrstallographically. It crystallizes in the monoclinic space group P2₁/c with a = 7.673(1), b = 16.251(2), c = 10.874(1) Å, β = 110.42(1)°, V = 1270.7(3) ų, D _x = 1.418 g cm^?3, R ₁ = 0.0349 and wR ₂ = 0.0935 [I > 2σ(I)], respectively. The title compound has been synthesized from the reaction of isonicotinohydrazide with 2-hydroxy-3-methoxybenzaldehyde. It has been characterized by using elemental analysis, MS, IR, ¹H NMR, ¹³C NMR and UV-Visible spectroscopic techniques.     

Synthesis and crystal structure of α,β-unsaturated ketone: 3,3′-[1,2-ethanediylbis(oxy-2,1-phenylene)]bis[1-(2-pyridyl)-2-propen-1-one]

The title compound, C₃₀H₂₄N₂O₄, 3,3′-[1,2-ethanediyl-bis(oxy-2,1-phenylene)]bis[1-(2-pyridyl)-2-propen-1-one] was synthesized and characterized by elemental analysis, FT-IR spectra, ¹H NMR, and X-ray single-crystal diffraction. In the molecule, the pyridine plane and the adjacent phenyl plane are almost coplanar with the dihedral angle of 3.07°, while the dihedral angle between the mean planes of the two asymmetric units is 67.56°. The crystal packing is stabilized by weak intermolecular C-H...N and C-H...O hydrogen bonds, C-H...π and π...π stacking interactions.     

Synthesis and crystal structure of trans-[PdCl2(EtMeIm)2] (EtMeIm = N-ethyl-N′-methylimidazol-2-ylidene)

The palladium–carbene complex, trans-[Pd(EtMeIm)₂Cl₂] was prepared by carbene transfer via the Ag carbene species. The structure was determined by X-ray crystallography. It crystallizes in the monoclinic unit cell of dimensions of a = 8.0243(9), b = 8.5320(9), c = 11.7473(13) Å, = 100.151(2)° with space group of P2₁/n and Z = 2. The palladium atom is tetracoordinated by two chloride ions and two carbon atoms in a square planar geometry.     

Synthesis and structure of [(nitrito-O,O′) bis(di-2-pyridylamine)copper(II)] nitrite

The synthesis and molecular structure of the title compound, [(nitrito-O,O) (dpa)₂Cu(II)] (NO₂), 1, is reported. Compound 1 crystallized in the orthorhombic space group Pccn with a = 11.397(5) Å, b = 12.256(6) Å, c = 14.876(8) Å, and V = 2077.9(17) ų with Z = 4. The distorted octahedral copper(II) cations are linked through a hydrogen-bonded polymer network. The polymer network is formed through the amine N–H of the cations and hydrogen bonded to the N–HO nitrite anions.     

Phenylmercury(II) dithiophosphates. Crystal structure of (O,O′-diethyldithiophosphate) phenylmercury(II)

The phenylmercury(II) derivatives PhHgS₂P(OR)₂ (R=C₂H₅, C₆H₁₁ and C₆H₅) have been synthesized. (O,O-diethyldithiophosphate) phenylmercury(II), C₁₀H₁₅HgO₂PS₂, crystallizes in the monoclinic space groupP2₁/c (n° 14) witha=7.330(5),b=18.085(2),c=11.552(4)Å,=105.96(5)°,V=1472.3(6)ų,Z=4,D=2.088 g.cm^–3. The mercury atom is coordinated to the phenyl carbon atom and to a ligand sulphur atom in an almost linear arrangement (C-Hg-S angle, 176.0(2)°. The ligand is almost monodentate, its second sulphur atom only being involved in a weak secondary intermolecular bond.IR and Raman studies of the other two compounds suggest the same coordination scheme. Positive ion FAB and¹³C,³¹P and¹⁹⁹Hg NMR spectra are also discussed.     

Synthesis and crystal structure of [Co(phen)(H2O)4](SO4)⋅2(H2O)

The title complex, [Co(phen)(H₂O)₄](SO₄)2(H₂O) (phen = 1,10-phenanthroline) was prepared in aqua tert-butylperoxohydrogen solution. X-ray single crystal structure determination reveals that the complex consists of a phenanthrolinatocobalt(II)tetrahydrate dication, two uncoordinated water molecules and a sulfate anion. It crystallizes in the orthorhombic space group Pbca with a = 8.856(1), b = 18.318(3), c =21.918(5) Å, V = 3555.6(11) ų. The coordination geometry at each cobalt(II) atom is a slightly distorted octahedron.     

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.     

The crystal structures of two reaction products of α-halopyruvamide with nitrogen and sulfur nucleophiles

Two compounds have been prepared during the investigation of the reactivity of -halopyruvamides. The reaction products: 3-(4-chlorophenyl)imidazo[1,2-a]pyridine-2-carboxamide (1) and 7-carbamoyl-5-phenyl-2,3-dihydro[1,3]thiazolo[4,3-b][1,3]thiazol-4-ium chloride (2) were structurally characterized by x-ray crystallography. Compound 1 crystallizes in the orthorhombic space group Pca2₁ with a = 28.813(2), b = 9.369(1), and c = 9.361(1) Å. The structure contains two crystallographically different molecules. Compound 2 crystallizes in the monoclinic space group P2₁/c with the following cell parameters: a = 8.5895(8), b = 22.499(2), c = 7.4133(6) Å, and = 110.204(1)°.     

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.