Structure of chlorohydroxonitrosyl(terpyridine)ruthenium(II) hexafluorophosphate

The title complex has the NO grouptrans to the hydroxyl ligand and the chloride ion in the plane of the tripyridyl ligand. The Ru−O and Ru−N(O) distances are 1.939(5) ? and 1.764(6) ?, respectively; the Ru−N−O bond angle is 171.7(6)⁰. These values are consistent with previously reported shortening of Ru−O distances whentrans to a linear NO ligand. The space group of the structure isP2₁/c, witha=9.7213(9) ?,b=13.9318(11) ?,c=14.523(4) ?, and β=105.820(13)⁰.     

Crystal and molecular structures of trans-bis(acetonitrile)bis(bipyridine)ruthenium(II) perchlorate and trans-diamminebis(bipyridine)ruthenium(II) perchlorate

The structures of trans-[(MeCN)₂(bpy)₂Ru](ClO₄)₂(I) andtrans-[(NH₃)₂(bpy)₂Ru](ClO₄)₂(II) have been determined by single crystal X-ray diffraction methods. (I) forms monoclinic crystals in the space groupP2₁/c witha=8.399(2),b=10.406(2),c=15.590(3) Å,=93.78(2)° andZ=2 atT=293 K. The final refinement gaveR=0.040 for 2448 reflections withF _o ² >3(F _o ² ). (II) crystallizes in the triclinic space groupP¯1 witha=1.702(1),b=8.439(2),c=10.525(2) Å,=107.56(2),=104.63(1), =100.89(2)° andZ=1 atT=293 K. Refinement using 1878 reflections withF _o ² >3(F _o ² ) produced a finalR value of 0.036. Both of these structures have the ruthenium atom located on a crystallographic inversion center. The bipyridine ligands in both structures are in the bowed conformation as a means of circumventing the steric problems associated with the trans arrangement of the bipyridine ligands. The Ru-N(monodentate) distance is longer for the ammonia complex (2.106(3) Å) than for the acetonitrile complex (2.008(4) Å); there are no significant differences in the distances and angles of the two Ru(bpy)₂ frameworks.     

Structure of dichloroethanolaminecopper(II) and dibromoethanolaminecopper(II)

CuCl₂(NH₂CH₂CH₂OH) is monoclinic, space group C2/c, witha+11.092(2),b+10.012(2),c+6.401(1) Å, =121.71(1)°, andV=604.8(2)ų withZ+4. The structure was refined to a final value ofR+0.27 for 518 unique observed reflections with |F|>3. The ethanolamine and halide ions coordinate to the copper(II) ion forming a pseudoplanar four-coordinate monomeric CuCl₂L² complex (L²+bidentate ligand). The copper ion also interacts with the halides of neighboring complexes through the formation of semi-coordinate Cu-Cl linkages (2.926(1) Å) between oligomers. The copper thus attains a 4+2 elongated octahedral coordination geometry. In this space group, the ligand is statisticallydisordered The Cu-Cl distance is 2.267(1)Å while the Cu-N/O distances are 2.025(2)Å. The dibromide structure is isomorphous with the dichloride structure, with space group C2/c, anda+11.285(2),b+10.218(2),c+6.715(1) Å, =121.65(1)°, andV=659.2(2)ų.     

Mercury complexes with thiacrowns: the crystal structure of bis(1,4,7-trithiacyclodecane) mercury(II) hexafluorophosphate

We report the synthesis, crystal structure, and NMR spectroscopy for the mercury(II) complex with the crown thioether 1,4,7-trithiacyclodecane (10S3) , bis(1,4,7-trithiacyclodecane) mercury(II) hexafluorophosphate (1). The 10S3 ligand coordinates in tridentate fashion and readily forms a distorted bis octahedral complex, an unusual coordination geometry for Hg(II). The crystal structure shows the two 10S3 ligands arranged in a trans or anti fashion around the mercury center, yielding the meso stereoisomer. Bond distances and angles are very comparable to those found in the structure of the perchlorate salt of the complex cation although the hexafluorophosphate salt shows slightly longer and more varied Hg–S distances (2.623(2) , 2.708(2), 2.784(2) Å) with a tetragonal elongation. The ¹⁹⁹Hg¹H NMR spectrum exhibits a single resonance with a chemical shift at –596 ppm consistent with a hexakis(thioether) coordination environment around the mercury center. Crystal data for 1: C2/c, a = 19.184(3) Å, b = 15.235(2) Å, c = 11.3791(15) Å, = 123.358(2)°, V = 2777.9(6) ų, Z = 4.     

Structure of trans-aqua-bis(pyridine)dibenzoatocopper(II)

Crystals oftrans-aqua-bis(pyridine)dibenzoatocopper(II), Cu(NC₅H₅)₂(C₇H₅O₂)₂(H₂O), are monoclinic,P2₁/n, witha=5.9847(10),b=18.874(5),c=19.728(10)A,=92.97(4)°,Z=4, andV=2225.5(13)A³. The full-matrix least-squares refinement used 3030 reflections withI> 2.5(I) and converged toR=0.067. The benzoate ions bond as monodentate ligands in this five-coordinate complex. The copper ion is in a square pyrimidal environment with trans pyridine groups and benzoate ions in a slightly distorted square planar arrangement and a water ligand in the axial position. The Cu-O distance to the water molecule is significantly longer (2.273(4) Å) than the distances to the O atoms of the carboxyl groups (1.934(3) and 1.930(4)Å).     

Structure determination of polytypes (II)

In this part different methods for structure determination of polytypes with diffraction methods are described. These methods are applied to periodic polytypes consisting of one or more sorts of layers and to disordered polytypes consisting of one sort of layers. Furthermore an example for the determination of the structural principle is given.     

Structure of (chloranilato)bis(tri-n-butylphosphine)palladium(II)

(Chloranilato)bis(tri-n-butylphosphine)palladium(II), [Pd(C₆Cl₂O₄){P(C₄H₉)₃}₂] (chloranilic acid=2,5-dichloro-3,6-dihydroxy-p-benzoquinone): FW=718.02,P2₁/c,a=21.729(6),b=17.293(5),c=21.010(9) Å,=112.62(3)°,V=7287.42 ų,Z=8,D _c=1.309mg m^–3, Mo, =0.710730 Å,=0.76 mm^–1,F(000)=3008, finalR=0.087, 2594 observed reflections. Palladium is ligated by a distorted square planar P₂O₂ coordination sphere in the title compound. The two molecules per asymmetric unit differ in the arrangement of phosphine n-butyl chains, yielding two unique metal centers.     

Crystal structure and physical properties of a ruthenium(II) bipyridine dimethylsulfoxide complex

The complex [Ru(bpy)₂(DMSO)C1]PF₆, where bpy is 2,2-bipyridine and DMSO is dimethylsulfoxide, crystallizes in the triclinic space group P1¯ (#2) with a = 8.873 (2), b = 12.805 (4), c = 12.864 (4) Å, = 97.76(3), = 106.45(2), = 107.88(2); Z = 2, and d _calc = 1.75 mg/m³. The coordination geometry is that of a distorted octahedron with a cis –RuN₄SCl arrangement of coordinating atoms. The four Ru—N distances to the bpy ligands are 2.082(5), 2.092(4), 2.044(4), and 2.078(5) Å. The Ru—Cl distance is 2.421(2) Å and the Ru—S distance to DMSO is 2.260(1) Å. The Ru—N bond distance trans to Cl is the shortest; the Ru—N bond distance trans to S is the longest. The complex is oxidized and reduced reversibly at 1.13 and –1.37 V vs. SSCE, respectively. It displays electronic absorptions at 515, 480 (1.5 × 10⁴), 342 (1.5 × 10⁴), 292 (1.2 × 10⁵), and 240 nm (6.2 × 10⁴) and has a broad emission band centered at 607 nm at 77 K in a 4:1 ethanol/methanol glass. The emission lifetime at room temperature is less than the pulse width of the laser, < 20 ns.     

Crystal Structure of Tetraphenylarsonium Diisothiocyanatodichlorocobaltate(II)

Abstract  

Tetraphenylarsonium diisothiocyanatodichlorocobaltate(II) was synthesized by metathetic pathway. It crystallizes in the monoclinic space group C 2/c with unit cell parameters, a = 13.510(4) ?, b = 15.873(5) ?, c = 22.809(7) ?, β = 105.743(6)°, V = 1,618(5) ?³ and Z = 4. X-ray crystal structure analysis reveals that the asymmetric unit contains one {(C₆H₅)₄As}⁺ cation and one half {Co(NCS)₂Cl₂}²⁻ anion, the latter lying on a crystallographic twofold axis. While each {Co(NCS)₂Cl₂}²⁻ anion exhibits hydrogen bonding interactions with eight arsonium cations; CH···π interactions between phenyl rings of arsonium cations is restricted to two such centers in the crystal structure.     

Crystal structure of [bis 1,2-(diphenylphosphino)ethane]-bis(pyridine-2-thiolato)ruthenium(II)

The Ru atom in the title compound, [Ru(dppe)(2-pyS)₂] exists in a distorted octahedral geometry defined by a dppe ligand and two 2-pyS anions which function as bidentate ligands via their N- and S-atoms. Important interatomic parameters are Ru-P2.240(3), 2.256(3); Ru-N 2.131(8), 2.136(8); Ru-S 2.413(3), 2.428(3) Å; P-Ru-P 84.1(1), S-Ru-S 155.0(1) and N-Ru-N 87.5(3)°. Crystals are monoclinic, space groupP2₁/c, with unit cell dimensionsa=10.342(1),b=31.145(6),c=11.107(2) Å,=113.80(1)° andZ=4. The structure was refined to finalR=0.064 for 3057 reflections withI2.5(I).     

Structure of (N-(2-hydroxyphenyl)-salicylaldiminopiperidino) Ni(II) complex

The crystal and molecular structure of the title complex, C₁₈H₁₉N₂O₂Ni, has been determined by direct methods. The compound crystallizes in the monoclinic crystal system witha=22.973(1),b=5.212(1),c=27.076(1)Å, β=106.46(1)°, space groupC2/c,V=3109.1(6)ų, Z=8, andD _x=1.51g cm^?3. The nickel atom is in a slightly distorted square-planar environment of two oxygens [Ni(1)?O(1) 1.824(3) and Ni(1)?O(2) 1.856(3)Å] and two nitrogens [Ni(1)?N(1) 1.849(3) and Ni(1)?N(2) 1.932(3)Å] with O?Ni?N angles between 85.7(1) and 97.1(1)°. The nickel atom is 0.006 Å out of the plane of its ligands.     

Structure of N-(2-thiophenyl)-salicylaldimino-diethylamino nickel(II) complex

N-(2-thiophenyl)-salicylaldimino-diethylamino nickel(II) complex crystallizes in the orthorhombic crystal system witha=19.089(4),b=14.268(7),c=12.091(4) Å, space group Pbca,Z=8, andD _x =1.449 g cm^–3. The central nickel atom is coordinated with S, O, and N atoms. The coordination plane is nearly planar and nearly perpendicular to the diethylamine plane which consist of N(2), C(14), C(15), C(16), and C(17).     

The Crystal and Molecular Structure of the Complex Diaquatetrakis(imidazole)copper(II) Terephthalate Crystal Structure Containing Cu(II) Him and TA

The title compound has been synthesized and its crystals structure determined at room temperature. MW = 536.01, monoclinic, space group C2/c, Z = 4, a = 22.193(5) Å, b = 8.038(2) Å, c = 15.699(4) Å, β = 119.64(2)°. The crystal structure consists of repeated [Cu(Him)₄(H₂O)₂] (Him = imidazole) cations and non-coordinated terephthalato dianions. The copper(II) ion displays an elongated octahedral coordination being linked to the four nitrogen atoms of the four imidazole ligands and to the two oxygen atoms of the two water molecules. The terephthalato dianions are hydrogen bonded to the four water molecules and four imidazole groups.     

Structural confirmation of a template reaction mechanism: Structure of dichloro (2,9-dimethyl-3,10-diphenyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene)cobalt(III) hexafluorophosphate

The structure of the title compound has been investigated by X-ray diffraction methods. The crystals are monoclinic, space groupP2₁/c, with unit cell parameters:a=11.394(3),b=6.381(2),c=17.413(4)Å, and=95.72(2)°. The structure was refined with 2369 unique reflections by a full-matrix least squares procedure givingR andR _w of 3.2 and 4.2%, respectively. The cobalt complex forms a six coordinate distorted octahedral structure with the cobalt atom at a center of symmetry. The macrocyclic ligand presents eighteen of its 28 nonhydrogen atoms in a planar array about the cobalt atom. Only the two central trimethylene carbon atoms and four carbon atoms of each phenyl ring deviate by more than ±0.05 Å from this plane. Thetrans arrangement of substituents on the ligand of the complex confirms the structural assignment previously made based on NMR data and lends support to the proposed template reaction mechanism by which these complexes form.     

Crystal Structure and Energy Optimization of Dichlorobis(ethylanthranilatonicotinamide)Zinc(II)

Abstract  

The title compound, C₃₀H₂₈Cl₂N₄O₆Zn, dichlorobis(ethylanthranilatonicotinamide)zinc(II) crystallized in a triclinic space group, P − 1, with cell parameters a = 7.787(3), b = 13.468(1), c = 15.735(1), α = 110.25(1), β = 95.11(1), γ = 99.32(1) and Z = 2, with the whole molecule being the asymmetric unit. In this compound, zinc is bound to two ethylanthranilatonicotinamide (EAN) ligands and two chloride ligands in a distorted tetrahedral configuration. The nitrogen of the nicotinamide ring participates in bonding with zinc through its lone pair while the anthranilate nitrogen remains free. In one of the two EAN ligands, the anthranilate and nicotinamide groups are nearly co-planar while in the other, the angle between the two is ~35.5°. The complex shows three hydrogen bonds, two being C–H···O bonds and the other being C–H···Cl bond. The amidic N–H groups do not participate in hydrogen bond formation as they are buried in the core structure and are not accessible for other groups for association. Both the C–H···O bonds occur from C–H bonds present on the twisted EAN moiety.     

Crystal structure,physical, and photophysical properties of a ruthenium(II) bipyridine diazafluorenone complex

The complex [Ru(bpy)₂(dafo)](PF₆)₂, where bpy is 2,2-bipyridine and dafo is diazafluorenone crystallizes in the space group P2₁/n witha=9.505(3) Å,b=14.002(4) Å andc=25.783(8) Å. The coordination geometry of the Ru atom is that of a distorted octahedron with a RuN₆ core. The two Ru-N bond distances to the dafo ligand are 2.13(1) and 2.15(1) Å; the four Ru-N bond distances to the bipyridine ligands are 2.03(1), 2.05(1), 2.06(1), and 2.07(1) Å. The three shortest Ru-N distances aretrans to the three longest Ru-N distances. The complex is oxidized and reduced reversibly at 1.41 and –0.65 V vs. SSCE, respectively. It displays absorptions at 438 nm (1.6×10⁴), 285 nm (6.2×10⁴), and 240 nm (4.1×10⁴) and a broad emission centered at 626 nm in water at room temperature. The emission lifetime is 420 ns and the emission quantum yield is 5.3×10^–4.     

Crystal Structure of Tetrakis Imidazole Copper(II) Diadipate Complex

Abstract  The title compound, [Cu(C₃H₄N₂)₄(COO–(CH₂)₄–COOH)₂] is a neutral complex and exist as a monomeric unit. The Cu atom occupies at the center of symmetry (0, 0.5, 0) with a distorted octahedral geometry. Imidazole nitrogens N1 and N6 (Cu1–N1 = 1.993(3) ?; Cu1–N6 = 2.008(3) ?) from two different imidazole group which are symmetrically disposed provides the square base and the long carboxylate oxygens (Cu1–O2 = 2.582(3) ?) from the protonated end of symmetrically oriented dibasic acid at the trans axial position. The adipate monoanion is in weak coordination with the metal center via monodentate fashion. The strong carboxylate-carboxylic acid intermolecular O–H…O interaction between the adjacent molecules is present in this structure as observed in the crystal structure of hexanedioic acid is noteworthy. In addition to the O–H…O H-bonding other molecular interactions such as N–H…O and C–H…O in packing generates a 3-D hydrogen bond network. Graphical Abstract  The title compound tetrakis imidazole Cu(II) diadipate is a neutral complex and exist as a monomeric unit with the metal atom occupies at the center of symmetry. Strong inter and intramolecular H-bonding interactions such as O–H…O, N–H…O and C–H…O in packing generates a 3-D hydrogen bond network.     

The Twinned Crystal Structure of Zinc(II) Acetylacetonate Trimer

Abstract  The crystal structure of the title compound, C₃₀H₄₂O₁₂Zn₃, originally determined from untwinned crystals (Bennett et al. Acta Cryst B 24:904, 1968) has been redetermined from twinned crystals. The effect of the twinning is that additional reflections appear in the diffraction pattern leading to a unit cell with a too long c-axis in which the structure cannot be solved. Thus, for a successful structure solution the correct unit cell has to be found and for refinement the twinning has to be taken into account. The central Zn atom is located on a twofold rotation axis. It is hexacoordinated in a distorted octahedral mode, whereas the coordination geometry of the two terminal Zn atoms is distorted trigonal bipyramidal. Index Abstract  The crystal structure of the title compound, Zinc(II) acetylacetonate trimer, has been redetermined from twinned crystals. For a successful structure solution the correct unit cell had to be found and for refinement the twinning had to be taken into account. The central Zn atom is located on a twofold rotation axis. It is hexacoordinated in a distorted octahedral mode, whereas the coordination geometry of the two terminal Zn atoms is distorted trigonal bipyramidal. An erratum to this article can be found at