Synthesis of a new dibenzo-14-crown-4 lariat ether and structure of its sodium perrhenate complex

A dibenzo-14-crown-4 ether with a novel monooxyacetone sidearm is prepared and its structure with sodium perrhenate is determined. The structure crystallizes in P2₁/c with cell dimensions: a = 8.107(2) Å, b = 28.138(3) Å, c = 10.293(2) Å, and = 104.173(9)°; giving a volume of 2276.6(7) ų. This structure is compared to other sodium complexes of dibenzo-14-crown-4 lariat ethers and is found to be the only one with intramolecular bonding between the sidearm and the cation. Possible reasons for this observation are discussed.     

Crystal structure of [Pb(cis-anti-cis-dicyclohexyl-18-crown-6)(OH2)2][ClO4]2

[Pb(cis-anti-cis-dicyclohexyl-18-crown-6)(OH₂)₂][ClO₄]₂ was crystallized using a slightly modified literature method for the separation of dicyclohexyl-18-crown-6 isomers. It crystallizes in the monoclinic space groupP2₁/n witha=8.415(5),b=20.993(9),c=8.973(5) Å, β=111.56(6)^o, andD _calc=1.84 g/cm³ for Z=2. The Pb²⁺ ion resides on a crystallographic center of inversion and is coordinated to the six crown ether donors and two axial water molecules in a hexagonal bipyramidal geometry. The Pb-O(etheric) distances range from 2.694(4) to 2.743(4) Å while the Pb?OH₂ distance is 2.522(6) Å.     

Synthesis and X-ray crystallographic characterization of [Cd(NO3)2(15-Crown-5)] and [Cd(NO3)2(18-Crown-6)]

Reaction of 15-crown-5 or 18-crown-6 in 3:1 (v/v) CH₃CN:CH₃OH with Cd(NO₃)₂·4H₂O followed by slow evaporation produces [Cd(NO₃)₂(15-crown-5)] or [Cd(NO₃)₂(18-crown-6)]. Crystals of [Cd(NO₃)₂(15-crown-5)] are orthorhombic with space group Pbca and cell parameters a = 13.562(5), b = 15.941(9), and c = 15.011(7) Å at 295 K. [Cd(NO₃)₂(18-crown-6)] crystallizes in the monoclinic space group C2/c with a = 11.235(2), b = 11.196(5), c = 15.385(3) Å, and = 99.89(2)° at 295 K. The metal center in [Cd(NO₃)₂(15-crown-5)] rests atop the macrocyclic donor array with two cis-bound nitrate anions and adopts a distorted tricapped trigonal prismatic geometry. [Cd(NO₃)₂(18-crown-6)] resides on an equatorial two-fold rotation axis with Cd²⁺ coordinated in the 18-crown-6 cavity and the nitrate anions oriented in twisted trans positions.     

Synthesis and crystal structure of a novel 3D supramolecular complex [Na(DC18C6-B)][Ni(mnt)<Subscript>2</Subscript>]

A supramolecular complex [Na(DC18C6-B)][Ni(mnt)₂] (1) (DC18C6-B = cis-anti-cis-dicyclohexyl-18-crown-6, isomer B; mnt = maleonitriledithiolate) has been prepared and characterized by elementary analysis, FT-IR spectroscopy and X-ray single crystal diffraction. It crystallizes in triclinic, space group P1 with crystallographic data: a = 7.974(4) Å, b = 14.343(7) Å, c = 15.559(8) Å, α = 96.230(8)^∘, β = 100.361(8)^∘, γ = 93.849(9)^∘, V = 1733.2(15) ų, Z = 2, D_calcd = 1.408 g/cm³, F(000) = 766, R₁ = 0.0491, wR₂ = 0.1018. The formula unit contains one [Na(DC18C6-B)]⁺ complex cation and one [Ni(mnt)₂]⁻ complex anion, which are constructed into an infinite chain-like structure through Na–N bonds. The resulting chains crisscross on the [Ni(mnt)₂]⁻ complex anions and further assemble into an unusual 3D supramolecular framework via the weak interactions.     

Synthesis and crystal structure of a mixed-ligand lanthanum complex of phenanthroline H-bonded with benzo-15-crown-5

A mixed ligand lanthanum complex H-bonded with a crown ether benzo-15-crown-5 (B15C5), [La(NO₃)₃(H₂O)₂phen]B15C5 (phen = phenanthroline), was synthesized and characterized by elemental analysis, infrared spectrum, and X-ray crystal structure analysis. The crystals of the title compound are monoclinic, P2₁, with a = 18.879(6) Å, b = 20.110(5) Å, c = 19.358(4) Å, V = 6623.4 ų, = 115.68(3)°, Z = 8, D _calc = 1.623 g/cm³. In this complex, two nitrogen atoms from phen and eight oxygen atoms, six from NO₃ ^– and two from H₂O, coordinate to La(III), forming a 10-coordination structural unit. The two H₂O molecules are located in opposite directions of the unit, each H₂O is H-bonded with two O atoms of the B15C5, and each B15C5 molecule is H-bonded with two H₂O molecules on opposite sides, thus an infinite supramolecular chain forms. The title compound has a layered structure, and in each unit cell there exists one 3D channel.     

Synthesis and crystal structure of catena-poly[aqua(cis-syn-cis-dicyclohexyl-18-crown-6) tetra(thiocyanato)barium(II) platinum(II)]: [BaPt(NCS)4(C20H36O6)(H2O)] n

An organic–inorganic hybrid polymeric complex, [BaPt(NCS)₄(C₂₀H₃₆O₆)(H₂O)] _n or [[Ba(DC18C6-A)(H₂O)][Pt(SCN)₄]] _n (1) (DC18C6-A = cis-syn-cis-dicyclohexyl-18-crown-6) has been synthesized by the reaction of cis-syn-cis-dicyclohexyl-18-crown-6 with Ba(SCN)₂, BaCO₃ and H₂PtCl₄, and characterized by elementary analysis, FT-IR spectra and X-ray single-crystal diffraction. It crystallizes as monoclinic, space group P 2₁/n with crystallographic data: a = 14.275(6) ?, b = 13.165(5) ?, c = 18.971(8) ?, β = 106.294(6)°, V = 3422(2) ?³, Z = 4, D _calcd = 1.854 g/cm³, F(000) = 1856, R ₁ = 0.0491, wR ₂ = 0.0709. The asymmetric unit of complex 1 contains one [Ba(DC18C6-A)(H₂O)]²⁺ complex cation and one [Pt(SCN)₄]²⁻ complex anion, which are assembled into an infinite polymeric chain via the bridging SCN groups. The coordinated water molecule gives two different intrachain and interchain hydrogen bonds.     

Crystal structure and electrochemical property of one‐dimensional complex: [K(cis‐syn‐cis‐ dicyclohexyl‐18‐crown‐6)]2[Cu(mnt)2]

One metalorganic complex [K(cis‐syn‐cis‐ dicyclohexyl‐18‐crown‐6)]₂[Cu(mnt)₂] (mnt = maleonitriledithiolate) has been obtained by the reaction of dicyclohexyl‐18‐crown‐6 with K₂mnt and CuCl₂·2H₂O. The title complex has been characterized by elementary analysis, FT‐IR, UV‐Vis spectroscopy and x‐ray single crystal diffraction. The title complex crystallizes in the triclinic space group P1 with crystallographic data: a = 10.870(6) Å, b = 11.536(6) Å, c = 12.904(7) Å, α = 101.541(10)°, β = 110.573(9)°, γ = 99.441(9)°, V = 1435.2(13) ų, Z = 1, D_calcd = 1.350 g/cm³, F(000) = 615, R₁ = 0.0641, wR₂ = 0.1475. It displays one‐dimensional chain‐like structure formed by [K(cis‐syn‐cis‐ dicyclohexyl‐18‐crown‐6)]⁺ complex cations and [Cu(mnt)₂]^2‐ complex anions through N‐K‐N interactions. Its electrochemical behavior has also been studied by the cyclic voltammetry. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

14-Hydroxy-14-phenyldibenzo[a,j]xanthene as a lattice host: crystal and molecular structure of its (1:1) complex with diethyl ether

The title compound 14-hydroxy-14-phenyldibenzo[a,j]xanthene 1 formed a (1:1) complex with diethyl ether. 1,4-Dioxane was also enclathrated, but with a variable stoichiometric ratio. Single crystal X-ray crystallography was used to elucidate the crystal structure of the 1·diethyl ether complex. Crystals are orthorhombic with space group P2₁2₁2₁, a = 8.532(3), b = 15.040(4), c = 18.491(5) Å, V = 2373(1) ų, d_c = 1.256 g/cm³, and Z = 4. Host and guest molecules were found to associate via hydrogen bonds, with the guest molecules residing in undulating channels lined by host molecules.     

The Solid-state Structure of a 4,13-Diaza-18-crown-6 NaI Complex: A Unique Chain-link Assembly

Abstract  Reported within is the crystal structure of 4,13-diaza-18-crown-6 and NaI (P21/c; a = 7.0732(5) ?, b = 15.4058(10) ?, c = 9.9605(6) ?, b = 96.7950(10)°, V = 1077.75(12) ?³, Z = 2). The structure was obtained serendipitously from a crystallization attempt of these two components in the presence of indole. There are two non-equivalent sodium cations, one encapsulated within the diazacrown, and a second cation linking two adjacent diazacrowns and coordinating to both. The sodium cations are also linked through a water bridge. This leads to the formation of infinite 1–D chains in which iodide counterions occupy the space between the chains. This is the first reported example of an unsubstituted 4,13-diaza-18-crown-6 encapsulating Na⁺. The first structure of 4,13-diaza-18-crown-6 and NaI containing two symmetrically inequivalent Na⁺ ions, only one of which is encapsulated by the diazacrown, is reported. Index Abstract  The first structure of 4,13-diaza-18-crown-6 and NaI containing two symmetrically inequivalent Na+ ions, only one of which is encapsulated by the diazacrown, is reported

The X-ray crystal structure of Hg(C6H4OMe-4) (C6F5): an unexpected twist

The X-ray crystal structure of Hg(C₆H₄OMe-4)(C₆F₅) reveals the first example of perpendicular rings in a diarylmercurial complex. Hg(C₆H₄OMe-4) (C₆F₅) crystallizes in monoclinic space group P2₁/c with a = 11.4004(14), b = 7.5683(9), c = 15.0247(18) Å, = 104.849 (2)° with calculated density 2.517 g cm^–3 for Z = 4.     

Synthesis and crystal structure of 1-(4-bromobenzyl)-4-methyl-2,6,7-trioxabicyclo[2.2.2]octane

1-(4-Bromobenzyl)-4-methyl-2,6,7-trioxabicyclo[2.2.2]octane, C₁₃H₁₅BrO₃, has been synthesized from 4-bromophenylacetic acid chloride via the oxetan ester (3-methyl-3-oxetanyl)methyl-2-(4-bromophenyl)acetate. The crystal structure of the title compound has been determined at low temperature (120 K), by X-ray diffraction methods. This compound crystallizes in the monoclinic space group P2₁/n (No. 14), Z = 4, with lattice parametersa = 6.019(5), b = 20.990(5), c = 9.915(2) Å, and = 101.29(1)°.     

Synthesis and crystal structure of [Nd(H2O)2]2(C2O4)3

Some crystals of [Nd(H₂O)₂]₂(C₂O₄)₃ were synthesized hydrothermally by heating at 200°C for 8 days an aqueous suspension of neodymium oxalate decahydrate in presence of terephthallic acid and guanidinium carbonate. They crystallize in the orthorhombic system, space group P2₁2₁2₁, with a = 8.6702(7) Å, b = 9.558(2) Å, and c = 17.009(2) Å. The structure of this complex is built up by two independent neodymium atoms, three bischelating oxalate ligands, and four water molecules forming a rectangle building unit of 6-membered ring, [Ln(H₂O)₂(C₂O₄)]₆. The packing of these units leads to a layer parallel to the plane (001). However, the neodymium atoms of two neighbor layers share an edge of oxalato oxygen atoms thus giving a double-layer. The three dimensionality between these double-layers is insured by hydrogen bonds of water molecules which are bound to the neodymium atoms. There is no zeolitic water molecule. The two neodymium atoms are nine-coordinated. In both cases, the coordination polyhedron can be described as a distorted tricapped trigonal prism.     

Synthesis and crystal structure of a new inorganic – organic complex: (4‐ClC7H6NH3)9[Nd(P6O18)2]·9H2O

Single crystals of (4‐ClC₇H₆NH₃)₉[Nd(P₆O₁₈)₂]·9H₂O were synthesized in aqueous solution. This compound crystallizes in a triclinic P1 unit‐cell, with a = 14.898(6), b = 18.049(7), c = 20.695(6)Å, α = 102.04(3), β = 100.49(3), γ = 98.82(3)°, V = 5245(4) ų and Z = 2. The crystal structure has been solved and refined to R = 0.043 (Rw = 0.061) for 20420 observed reflections. The atomic arrangement of the title compound can be described as infinite layers built by complex of Neodyme [Nd(P₆O₁₈)₂] and nine water molecules. The organic cations are located in the space delimited by the successive inorganic layers. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Two-dimensional crown ether complex. Synthesis and crystal structure of [Na(N15C5)]<Subscript>2</Subscript>[Cu(mnt)<Subscript>2</Subscript>]

A novel crown ether complex [Na(N15C5)]₂[Cu(mnt)₂] (1) (where N15C5 = 2,3-naphtho-15-crown-5 and mnt = maleonitriledithiolate, [C₂S₂(CN)₂]^2–) was synthesized and characterized by elemental analysis, FT-IR spectra, UV-visible spectra and single crystal X-ray diffraction. Structural analysis reveals that the complex 1 consists of two [Na(N15C5)]⁺ complex cations and one [Cu(mnt)₂]^2– complex anion and the complex molecules are assembled into a novel 2D network by Na–N interactions. In the network, there are 34-member macrocycles formed by four sodium ions of complex cations and four complex anions through Na–N bonds. In each macrocycle, – stacking interactions occurred between two parallel naphthylene moieties of N15C5. It is interesting that the 2D network displays an open-capped wave-like sheet viewed along the crystallographic a axis.     

Synthesis and crystal structure of [Tb4(H2O)2](C2O4)2(C5H6O4)4

A terbium complex associating two ligands, oxalate and glutarate, was prepared under hydrothermal conditions at 200°C by treating an aqueous suspension of terbium oxalate decahydrate with glutaric acid and guanidinium carbonate. Its structure was solved by X-ray diffraction on a single crystal. It crystallizes in the monoclinic space group P2₁ with lattice constants, a = 9.514(1) Å, b = 9.0681(8) Å, c = 19.702(2) Å, and = 97.90(1)°. The terbium atoms and the oxalate ligands build dense chains which are connected by one side of the carboxylic group of some glutarate ligands, thus forming a sheet at the c level 0 and 1/2. These sheets are bridged by glutarate groups. The terbium atoms are ninefold coordinate with nine oxygen atoms of the ligands or with one water molecule and eight oxygen atoms of the ligands. Each polyhedron of the terbium atoms share one edge and one face of oxygen atoms with the two neighboring ones. The oxalate ligands are bischelating and bismonodentate. The coordination scheme of glutarate differs: either they are bismonodentate from one side and chelating and monodentate from the other side or they are chelating and monodentate from both sides.     

Crystal structure of [Co(o-SC6H4NH2){P(OMe)3}3]PF6

A cobalt-thiolato-phosphite complex [Co(o-SC₆H₄NH₂){P(OMe)₃}₃]PF₆ has been prepared and characterized by X-ray crystallography. The complex crystallizes in the triclinic space group with a = 10.590(4), b = 11.122(3), c = 13.577(5) Å, = 101.85(1), = 108.50(1), = 101.75(1)°, V = 1420.6(8) ų, and Z = 2. The structure comprises discrete [Co(o-SC₆H₄NH₂){P(OMe)₃}₃]⁺ cations and PF ₆ ^– anions where the metal atom is coordinated in a highly distorted square-pyramidal environment by one chelate o-SC₆H₄NH ₂ ^– (abt) and two P(OMe)₃ ligands in the basal positions, and a third P(OMe)₃ in the axial site with Co–N,, 1.847(5), Co–S, 2.166(2), Co–P, 2.157(2), 2.147(2), and 2.125(2) Å.     

Synthesis and crystal structure of the N4-oxide of an hydroxybenzo[f]quinoxalin-6(5H)-one obtained by oxidative cleavage of beta-lapachone-quinoxaline

The N4-oxide of the 5-(3-hydroxy-3-methylbutyl)-5-hydroxybenzo[f]quinoxalin-6(5H)-one was synthesized from beta-lapachone-quinoxaline by MCPBA oxidation and the crystal structure has been determined (C₁₇H₁₈N₂O₄), Mr=297.3, a=15.880(5), b=16.998(1), c=5.587(2) ?, V=1508.1(5) ?³, D _x=1.31, space group P2₁2₁2, Z=4, S=1.109 and R _obs=0.06. The central ring of the molecule is in a twisted-boat conformation and the molecular packing is done through two intermolecular hydrogen bonds O–H···O [2.072(6)] and [2.177(5) ?], forming columns along the direction parallel to the c-axis.     

Synthesis and crystal structure of a terephthalato-bridged copper(II) complex [Cu2(tpt)(bpy)2(H2O)4] [Cu2(tpt)3 (bpy)2(H2O)2]

A terephthalato-bridged copper(II) complex [Cu₂(tpt)(bpy)₂(H₂O)₄][Cu₂(tpt)₃(bpy)₂ (H₂O)₂] (1) (tpt = terephthalate, bpy =; 2,2'-bipyridine) was synthesized by the reaction of Cu(ClO₄)₂ 6H₂O and terephthalic acid in the presence of 2,2'-bipyridine in H₂O solution. Crystal structure of 1 was determined by X-ray diffraction analysis in the triclinic space group P , with a = 10.7327(10) Å, b = 11.1658(11) Å, c = 17.3768(16) Å, = 108.063(2), = 91.064(2), = 116.721(2), V = 1737.5(3) ų, and Z = 2. Both the anion and the countercation in 1 are copper(II) complexes linked by terephthalate bridges in the bis(monodentate) (syn–anti) mode. The anion and the countercation are also linked by two hydrogen bonds between coordinating water molecules and terephthalate ligand.     

Synthesis and crystal structure of the thiophene-3-acetonitrile complex fac-[Mo(CO)3{NCCH2(C4 H 3S-3)}3]

Reaction of fac-[Mo(CO)₃(NCMe)₃] with three equivalents of NCCH₂(C₄ H ₃S-3) in acetonitrile gives the tris(thiophene-3-acetonitrile) complex, fac-[Mo(CO)₃{NCCH₂(C₄H₃S-3)}₃] (1) in 7% yield. Complex 1 crystallizes out in the orthorhombic space group Pnma with a = 12.714(17), b = 16.41(2), c = 11.304(16) Å, Z = 4. The structure has crystallographic m symmetry and the metal is in an almost perfect octahedral environment, with a facial arrangement of carbonyl and thiophene-3-acetonitrile groups. The thiophene rings are disordered.     

Synthesis of homoleptic lanthanide amides and the crystal structure of [Li(THF)4][Y(NPh2)4]

Anhydrous LnCl₃ reacted with three equivalents of LiNPh₂ in THF to give the unexpected homoleptic lanthanide amides [Li(THF)₄][Ln(NPh₂)₄] (Ln = Sm (1), Y (2)) in high yield. The crystal structure of complex 2 has been determined by X-ray diffraction methods. It crystallizes in the orthorhombic space group Pbcn with a = 17.522(3) Å, b = 16.321(3) Å, c = 19.947(3) Å, V = 5704.4(17) ų, and D _calc = 1.231 mg/m³ for Z = 4. Complex 2 is composed of discrete [Li(THF)₄]⁺ cations and [Y(NPh₂)₄]^– anions, both of which have crystallographically imposed two-fold symmetry. To achieve steric saturation of the metal center, there are interactions between the yttrium atom and one -carbon atom of each amide ligand. The yttrium and lithium atoms both exhibit distorted tetrahedral coordination geometry.