Synthesis and crystal structure of the two-dimensional coordination polymer catena(bis(μ3-iodo)-(μ 2-pyrazine)-di-copper(I))

The two-dimensional coordination polymer [Cu₂ i ₂(pyz)]_n (where pyz = pyrazine) has been synthesized hydrothermally and structurally characterized by single crystal X-ray diffraction analysis. [Cu₂ i ₂(pyz)]_n crystallizes in the space group P with a = 4.1759(4) Å, b = 7.1281(7) Å, c = 8.1279(8) Å, = 109.607(2), = 101.769(2), = 96.676(2), and Z = 1. The sheet-like polymer is characterized by infinite stair step [Cu₂ i ₂]_n double chains connected in two dimensions through bridging pyrazine ligands. The coordination environment about each copper is approximately tetrahedral having three Cu–I bonds and a single Cu–N bond.     

The properties,crystal, and molecular structure of catena-[(μ-acetato-) (μ-phthalazine)silver(I)dihydrate]: {[Ag(μ-O2CCH3) (μ-PHZ) (H2O)2]2}n

The crystal and molecular structure of catena-[(-acetato) (-phthalazine)-silver(I)dihydrate], {[Ag(O₂CCH₃) (C₈H₆N₂)(H₂O)₂]₂}_n, has been determined by single crystal X-ray analysis: the space group is P2₁/n,a=16.150(8) Å,b=3.886(5) Å,c=18.716(9) Å, =96.02(5)°,V=1168 ų. Phthalazine (PHZ) bridges the silver atoms to form {Ag--PHZ]₂ dimeric subunits. These dimeric subunits are planar and stack by bridging acetates to form a polymeric lattice. The acetates also form an asymrnetric chelate ring with the silver atoms which result in a distorted, square pyramidal configuration. The complex is further characterized by its IR and thermal properties.     

Synthesis, spectroscopy, and X-ray structure of the polymer catena-[bis(azido-N)-copper(II)-μ-bis(2-benzimidazolyl)butane]

The title compound, catena-[bis(azido-N)-copper(II)-(bis(2-benzimidazolyl)butane), [Cu(C₁₈H₁₈N₄)(N₃)₂]_n, was obtained from the reaction of the ligand bis(2-benzimidazolyl)butane and Cu(N₃)₂. The x-ray crystal structure is reported. The compound crystallizes in the monoclinic space group P2₁/c with a = 8.2524(10), b = 12.765(5), c = 9.1125(15) Å, = 106.423(12)°, Z = 2. The Cu(II) ions are square-planar coordinated with trans-oriented end-on binding azido ligands. The structure is a polynuclear chain with the benzimidazole bridging at each end. In addition a N_(ligand)-H···N_(azido) H-bridge [N_(ligand)···N_(azido) = 2.994(7) Å] is present, resulting in a pseudo 2-dimensional lattice. The characteristic azido infrared vibrations are found at 2060 and 2077 cm^–1 (_as(N₃)) and 1284 and 1297 cm^–1 ((N₃)).     

Di-μ-sulphido-bis[4-methyl-piperidinedithiocarbamate tin(IV)]: Synthesis,characterization, and crystal and molecular structure

The title compound, C₁₅H₂₆SnN₂S₅Cl₂, was prepared, and characterized by means of X-ray and IR measurements. The crystals are monoclinic, space groupP2₁/n, (non standard setting ofP2₁/c, No. 14) witha=12.330(2),b=11.930(1),c=17.055(2) Å,=106.21(1)° andZ=4.The structure was solved by the heavy-atom method, and least-squares refinement of the structural parameters led to a conventionalR factor of 0.028 for 1284 independent reflections. The structure consists of discrete dimeric units with the metal coordinated to six sulphur atoms. The IR spectrum is consistent with the presence of the sulphur bridge atoms between the two metal ions.     

Synthesis and structural characterization of five new coordination polymer chain structures using a new,Z-shaped ligand, 2,2′-bis-(4-pyridylethynyl)tolane

Using the new ligand, 2,2-bis-(4-pyridylethynyl)tolane we have synthesized five new coordination polymers: HgBr₂[2,2-bis-(4-pyridylethynyl)tolane] (1), HgI₂[2,2-bis-(4-pyridylethynyl)tolane] (2), Ni(acetylacetonate)₂[2,2-bis-(4-pyridylethynyl)tolane] (3), Zn(acetylacetonate)₂[2,2-bis-(4-pyridylethynyl)tolane] (4), and Cu(hexafluoro acetylacetonate)₂[2,2-bis-(4-pyridylethynyl)tolane]CHCl₃ (5). 2,2-Bis-(4-pyridyl ethynyl)tolane is a rigid ligand with a Z-shape that promotes the formation of zig-zag chains. Compounds 1– 5 were characterized by single crystal X-ray diffraction; and compounds 1– 3 were additionally characterized by IR, elemental analysis, and thermogravimetric analysis. Compound 1 crystallizes in the monoclinic space group C2/c with a = 29.761(3) Å, b = 5.0531(5) Å, c = 16.7823(15) Å, = 104.090(2), V = 2447.9(4) ų, Z = 4. Each mercury is bound to two tolane ligands and two bromine anions, resulting in a tetrahedral coordination environment. Compound 2 crystallizes in the monoclinic space group P2/c, with a = 20.3061(17) Å, b = 5.6303(5) Å, c = 24.5459(19) Å, = 110.338(2), V = 2631.4(4) ų, Z = 4. Here also, each mercury is bound to two tolane ligands and two iodine anions in a tetrahedral coordination environment. The ligand orientation differs in compounds 1 and 2 being trans oriented in 1 and cis oriented in 2. Compound 3 crystallizes in the monoclinic space group P2₁/c with a = 14.5947(14) Å, b = 6.3082(6) Å, c = 18.3939(18) Å, = 112.112(2), V = 1568.9(3) ų, Z = 2. Each nickel is bound to two tolane ligands and two bidentate AcAc anions, resulting in an octahedral coordination environment. Compound 4, which is isostructural with 3, also crystallizes in the monoclinic space group P2₁/c with a = 14.6990(9) Å, b = 6.2724(4) Å, c = 18.6433(11) Å, = 112.8610(10), V = 1583.86(17) ų, Z = 2. Compound 5 crystallizes in the triclinic space group P-1 with a = 6.5487(4) Å, b = 11.6471(7) Å, c = 14.3225(9) Å, = 70.1360(10), = 89.3990(10), = 88.7680(10), V = 1027.18(11) ų, Z = 1. Each copper in 5 is bound to two tolane ligands and two bidentate hfAcAc anions, resulting in an octahedral coordination environment identical to that found in 3 and 4.     

Synthesis and crystal structure of a polymeric erbium(III)–sodium(I) coordination complex of picolinic acid N-oxide

A new Er(III)–Na(I) coordination polymer of stoichiometry [NaEr₂L₅(H₂O)₆(NO₃)](NO₃)·3.5H₂O (HL = picolinic acid N-oxide) has been synthesized and characterized by single-crystal X-ray analysis. Crystals are triclinic, P with a = 9.823(2), b = 12.453(2), c = 20.643(4) Å; = 98.49(3), ( = 101.40(3), = 108.69(3)°; V = 2284(1) ų; Z = 2. Of the two independent eight-coordinate erbium(III) ions in this complex, one is surrounded by four bidentate chelating L ligands, and the other by one bidentate chelating L ligand, four aqua ligands and two anti-carboxylate oxygen atoms from two neighboring [ErL₄] units. The sodium(I) ion is in a distorted octahedral environment, being coordinated by a unidentate nitrate anion, three aqua ligands and two anti-carboxylate oxygen atoms from two adjacent [ErL₄] units. The complex is built from zigzag chains of syn-anti carboxylate-bridged erbium(III) moieties directed in the a direction, which are cross-linked pairwise by aqua-bridgeddimericsodium(I) units. The resulting composite polymeric chains are further connected by hydrogen bonds to form a three-dimensional network.     

Bis[aqua(2,5-bis(4-pyridyl)-1,3,4-oxadiazole)thiocyanate] cadmium(II): A three-dimensional framework built from hydrogen bonds and π-π stacking interactions

A three-dimensional (3D) network complex [Cd(L)₂(NCS)₂(H₂O)₂], L being 2,5-bis(4-pyridyl)-1,3,4-oxadiazole, has been synthesized and structurally determined by X-ray diffraction analysis: triclinic, space group P-1 with a = 7.8863(9) Å, b = 8.6287(10) Å, c = 11.4696(12) Å, = 94.346(2)°, = 109.331(2)°, = 94.354(2)°, Mr = 713.04, V = 730.13(14) ų, Z = 1. The crystal structure of the title complex reveals that it is a neutral molecule and the Cd(II) ion is at the center of symmetry. Each Cd(II) is six-coordinated and the CdN₄O₂ coordination sphere can be considered as an octahedron. The most striking feature of this complex resides in the formation of a 3D network through hydrogen bonds and - stacking interactions.     

Structure and spectral properties of (O-Cyclohexyldithiocarbonatio-S,S′) bis(triphesnylphosphine) copper(I) complex

The complex [(C₆H₁₁OCS₂)(PPh₃)₂Cu], was synthesized and characterized using IR, UV, and ¹H NMR. The crystal and molecular structure has been determined by X-ray diffraction. The yellow crystal of the complex is triclinic of space group , with parameters a=10.370(2)Å, b=13.530(3)Å, c=14.640(3)Å, =92.60(3)°, =108.00(3)°, =97.70(3)°, and Z=2. In the complex, the central Cu atom is in a distorted tetrahedral environment and chelated by two phosphorus atoms of the TRIPHOS and two sulfur atoms from the O-cyclohexyldithiocarbonate. The cyclohexane ring adopts a chair conformation. The thermal analytical data indicate that the complex begins to decompose at 101°C and stop at 360°C , leaving CuS. IR, UV, and NMR results supported the crystal structure.     

Crystal and molecular structure of tetraiodo (1,8-di-2-pyridyl-3,6-dithiaoctane-N,S,S′,N′)dimercury(II)

Summary The X-ray crystal structure of the title compound, [Hg₂(C₁₆H₂₀N₂S₂)I₄], has been determined. The crystals are monoclinic (space groupP2₁/c), with cell dimensionsa=15.016(2),b=6.201(3),c=15.273(2) Å,=115.18(1)°;V _o =1287.0(7) ų,M _r =1213.266,Z=4,D _x =6.26mg m^–3, MoK radiation (graphite crystal monochromator, ),(MoK)=336 cm^–1,F(000)=4272, andT=290°K. The final conventionalR factor=0.054, andR _w =0.062 for 2799 observed reflections. The structure was solved by Patterson and Fourier methods and refined by block-diagonal least-squares methods. The coordination around the mercury atoms is approximately tetrahedral, although with considerable distortion, with two iodine atoms and the N and S atoms of one-half of the ligand molecule.     

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.     

Crystal and molecular structure of (3aR,8bS,5′R)3-[(2,5-dihydro-3-methyl-2-oxo-5-furanyl)oxymethylene]-3,3a,4,8b-tetrahydroindeno[1,2-b]furan-2-one

The stereogeometry and absolute configuration of the title compound has been proved by an X-ray diffraction analysis. Crystal data: monoclinic, C2,a=20.2528(4),b=6.7254(2),c=10.6748(2) Å, =94.699(3),Z=4. The crystal structure has been solved by vector search methods and refined toR ₁=0.053 for 2043 observed reflections.     

The crystal and molecular structure of a new polymorph of carbonylhydridotris(triphenylphosphine)rhodium(I) having a Rh-H stretching absorption at 2013 cm−1

A new polymorph of HRh(CO)(PPh₃)₃, with a Rh-H of 2013 cm^–1, has been isolated by crystallization fromtert-butyl methyl ether/tetrahydrofuran. The crystals are monoclinic (space groupP2₁/n), witha=21.48(2) Å,b=14.92(2)Å,c=14.52(1)Å,=107.95(8)°. A finalR value of 0.065 was obtained using 2243 reflections which hadI _net>2.5(I _net). The structure of the new polymorph has a similar coordination geometry to the known polymorph, but a different conformation of one of the phenyl rings.     

Crystal and molecular structure of di-μ-chlorobis [N-(2-hydroxyethyl)salicylideneiminato-N,0,0′ copper(II)] hemihydrate

The structure of the title compound. [Cu₂Cl₂(C₉H₁₀NO₂)₂]·1/2H₂O. has been determined from single crystal X-ray diffraction data. The structure was solved by direct methods. Full-matrix leastsquares refinement of structural parameters led to a conventionalR factor of 0.056 for 3689 intensities above 3σ(l). There are two independent molecules [A andB] of the title compound in the asymmetric unit. These molecules are linked to one water molecule by a system of four hydrogen bonds. The comlexes contain pairs of deformed square-pyramidal copper(II) centers. A tridetate ligand L forms two condensed chelate rings with mean Cu?O_(C?O)+1.900(6), mean Cu?O_(C?OH)+2.004(6) and mean Cu?N-1.930(6)Å. A chloride ions complete the tetrahedral distorted basal plane of each Cu(II) ion forming a square pyramid with the longer fifth apical Cu?Cl bridging bond. The Cu...Cu nonbonding distances in the complexes are 3.445(1)Å for moleculeA and 3.494(1)Å for moleculeB.     

Preparation and Characterization of Bis(μ-1,2-diaminoethane)cobalt(II) Hexavanadate: A Layered Polyoxovanadate Pillared by a Cobalt Coordination Complex

Abstract  The first example of polyoxovanadate layered framework with a cobalt coordination complex as a pillaring unit, Co^II(μ-C₂N₂H₈)₂[V₄^IVV₂^VO₁₄], was readily synthesized under hydrothermal conditions. The structure can be solved and refined in monoclinic P2 ₁ /n with a = 9.143(3) ?, b = 6.5034(11) ?, c = 15.874(4) ?, β = 101.90(2), V = 923.6(4) ?³ and Z = 2. The crystal structure comprises two-dimensional {V₄^IVV₂^VO₁₄}²⁻ layers extending parallel to [101], constructed from tetrahedral {V^VO₄} and square pyramidal {V^IVO₅} building units. Adjacent layers are linked through the octahedral {Co^IIO₂(μ-C₂N₂H₈)₂} pillars, within which the Co^II resides on an inversion center. The structure displays N–H···O and C–H···O hydrogen bonding between the ethylenediamine and vanadium oxide layers. Graphical Abstract  A new polyoxovanadate layered framework pillared with a cobalt coordination complex, Co^II(μ-C₂N₂H₈)₂[V₄^IVV₂^VO₁₄], has been prepared hydrothermally and fully characterized.      

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.     

Supramolecular Organization in Tetra Aqua (μ-8-Hydroxyquinoline-5-sulfonate) Barium (II) and Ag···I Interactions in a Pseudopolymorphic Form of (7-Iodo-8-hydroxyquinoline-5-sulfonate) Silver (I) Monohydrate

Abstract  

The complexes, Ba (HQS) (H₂O)₄ (HQS = 8-hydroxyquinoline-5-sulfonic acid) (1) and Ag (HIQS) (H₂O) (Ferron = 7-iodo-8-hydroxyquinoline-5-sulfonic acid) (2) have been synthesized and characterized by X-ray diffraction analysis and spectroscopic studies. In compound 1, Ba²⁺ ion has a nine-coordinate monocapped antiprismatic geometry. In compound 2, Ag⁺ has distorted tetrahedral coordination and Ag···I interactions generate the supramolecular architectures. The complexes have been characterized by FT-IR and UV–Visible measurements. In both the structures, the inversion-related organic ligands are stacked over one another leading to three-dimensional networks.     

Steroids and related studies,Part 76: Crystal and molecular structure of 4,17a-di(2-hydroxyethyl)-4,17a-diaza-d-homo-5α-androstane (HS461)

The crystal structure of 4,17a-di(2-hydroxyethyl)-4,17a-diaza-d-homo-5-androstane, C₂₂N₂O₂H₄₀ (HS461), the tertiary amine related to HS781, a potential bisquaternary neuromuscular blocking agent, has been determined by direct methods and refined by full-matrix least squares toR=0.0867 for 2049 reflections (R=0.0597), CuK radiation 65°. The space group is P2₁2₁2₁ a=20.295(4),b=7.278(6),c=14.052(4) Å,Z=4. The rings in the modified steroid nucleus are alltrans connected symmetrical chairs. Hydroxyethyl side groups at N(4) and N(17a) both have an equatorial disposition, and the side chains assumetrans conformations.     

Thermolysis of the tetrahedrane cluster PhCCo3(CO)3(μ-CO)Cp2 with the unsaturated diphosphine ligands (Z)-Ph2PCH=CHPPh2 and 4,5-Bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd): Redox properties and molecular structure of PhCCo3(CO)(μ-CO)[(Z)-Ph2PCH=CHPPh2]Cp2

Thermolysis of the tricobalt cluster PhCCo₃(CO)₃(μ-CO)Cp₂ (1) with the diphosphine ligands (Z)-Ph₂PCH=CHPPh₂ and 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) has been examined and found to give the diphosphine-substituted clusters PhCCo₃(CO)[(Z)-Ph₂PCH=CHPPh₂](μ-CO)Cp₂ (2) and PhCCo₃(CO)(bpcd)(μ-CO)Cp₂ (3) in moderate yield. The new compounds 2 and 3 have been isolated and characterized in solution by IR and NMR (¹H and ³¹P) spectroscopies. VT ³¹P NMR data reveal that the chelating diphosphine ligand is fluxional in solution and exhibits a rocking motion between the axial and equatorial sites that renders both phosphorus moieties identical at ambient temperature. The molecular structure of PhCCo₃(CO)[(Z)-Ph₂PCH=CHPPh₂](μ-CO)Cp₂ (2) has been determined by X-ray crystallography. PhCCo₃(CO)[(Z)-Ph₂PCH=CHPPh₂](μ-CO)Cp₂ crystallizes, as the CH₂Cl₂ solvate, in the monoclinic space P2₁/n, a = 16.822(2) Å, b = 10.554(1) Å, c = 23.135(3) Å, β = 100.944(2)^°, V = 4032.4(8) ų, Z = 4, and d _calc = 1.537 Mg/m³; R = 0.0488, R _w = 0.0725 for 9431 reflections with I > 2σ(I). The solid-state structure of cluster 2 establishes the chelating nature of the ancillary (Z)-Ph₂PCH=CHPPh₂ ligand at the unique Co(CO)P₂ center via coordination at an equatorial and an axial site. The redox behavior of clusters 2 and 3 has been explored by cyclic voltammetry and chronocoulometry. Each cluster reveals the presence of two one-electron oxidations of common origin due to the oxidation of a Co–Co bonding orbital. Whereas cluster 2 does not exhibit an accessible reduction process in CH₂Cl₂, a ligand-based one-electron reduction was found for cluster 3 given its low-lying π* LUMO associated with the bpcd ligand. The electrochemical data for clusters 2 and 3 are discussed with respect to the reported redox chemistry for this genre of tricobalt cluster and the bpcd ligand.     

Synthesis and crystal structure of catena-poly[Rh2(OAc)4(C27H15N3)]⋅2CH2CL2, a novel Rh(II) organic/inorganic coordination polymer

A new coordination polymer, catena-poly[Rh₂(OAc)₄(C₂₇H₁₅N₃)]2CH₂Cl₂ 1 has been synthesized by self-assembly from Rh₂(OAc)₄ dimer units and the new ligand, 1,3,5-tris[(2-pyridyl)ethenyl]benzene 2. The compound was characterized by single crystal X-ray diffraction and was found to crystallize in the triclinic space group P-1, with a = 10.8206(9) Å, b = 14.0331(12) Å, c = 15.0901(12) Å, = 113.965(2)°, = 100.250(2)°, = 90.462(2)°, and Z = 2. The one-dimensional polymer contains two crystallographically different Rh-dimer units, both located about crystallographic inversion centers. Each Rh₂(OAc)₄ unit connects in a trans fashion with the potentially tridentate ligand giving an overall 1:1 metal dimer-to-ligand ratio. This arrangement leaves a third nitrogen donor site on the ligand uncoordinated.