Self‐assembly of a luminescent Zn(II) carboxylate with the diamondoid topology

A new coordination polymer [Zn(tdc)(bimb)]_n ( 1 ) (H₂tdc = 3,4‐thiophenedicarboxylic acid, bimb = 1,4‐bis(imidazol‐1ˊ‐yl)butane) has been synthesized under hydrothermal condition. X‐ray single‐crystal diffraction determination reveals that 1 crystallizes in the space group P2₁2₁2₁ of orthorhombic crystal system: a = 10.517(2), b = 10.889(2), c = 15.206(3) Å. This compound features a 3D network which can be rationalized as a 4‐connected diamondoid net. Moreover, thermal and photoluminescent properties for 1 have also been investigated.     

Synthesis,crystal structure and photophysical studies on a ruthenium(II) carbonyl hydrido compound based on 2,2′‐bipyridyl‐5,5′‐dicarboxylic acid (H2bpdc)

A novel complex, namely [Ru^II(PPh₃)(CO)(H)(Hbpdc)]·2MeOH ( 1 ) (H₂bpdc = 2,2′‐bipyridyl‐5,5′‐dicarboxylic acid), has been synthesized from the reaction of H₂bpdc with [Ru^II(PPh₃)₃(CO)(H)₂] in methanol under mild condition and characterized by elemental analysis, IR spectrum, ESI mass spectrometry, and single crystal X‐ray diffraction. The structure shows that the complex crystallizes in the monoclinic space group P2₁/c with unit cell parameters a = 11.8984(13) Å, b = 16.5180(18) Å, c = 25.5322(19) Å, β = 115.302(4)°, V = 4536.6(8) ų, Z = 4. This compound features a 1‐D supramolecular chain constructed via hydrogen bonds. Its photophysical properties have been investigated in MeOH solution and in the solid state at room temperature.     

Crystal structure of aquo (hydroxo) (ethylenediaminetetraacetato) sodium(I) tin(IV), NaSn(OH)(edta)(H2O)

NaSn(OH)(edta)(H₂O) is monoclinic, space groupP2₁/c, witha=9.747(3)Å,b=9.121(3)Å,c=16.430(6)Å, =98.69(4)°, ų, andZ=4. The coordination environment of Sn(IV) is a capped octahedron. Sn–O distances range from 1.990(6)Å to 2.351(7)Å. Na(I) is five coordinated to three different edta molecules. Na–O distances range from 2.283(9)Å to 2.414(7)Å. The edta ligand presents the E, G/R conformation. The crystal structure is composed of sheets parallel to (001): inside a sheet Sn(OH)(edta) molecules are connected to each other by the Na(I) interactions.     

Synthesis,characterization and crystal structure of a novel Ni(II) coordination polymer with dipyrido[3,2‐a:2′,3′‐c]phenazine and 4,4′‐oxy(bisbenzoate)

A novel coordination polymer, [Ni(dppz)(oba)(H₂O)]·0.5H₂O (dppz = dipyrido[3,2‐a:2′,3′‐c]phenazine and oba = 4,4′‐oxy(bisbenzoate)) has been synthesized through hydrothermal method and characterized by IR, and single‐crystal X‐ray diffraction. It crystallizes in monoclinic, space group C2/c with a = 23.163(5), b = 18.211(4), c = 14.460(3) Å, α = γ = 90°, β = 100.45(3)°, V = 5998(2) ų, Z = 2. The structure was solved by direct methods and refined to R = 0.0866 (wR₂ = 0.1836). The compound exhibits interesting one‐dimensional chain structures, which are further stacked through π‐π interactions to form supramolecular double chains. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,characterization and crystal structure of a novel 3‐D copper(II) polymer with bent N‐containing ligand

An exploration of the mixed‐ligand system under hydrothermal condition, has led to the isolation of a 3‐D novel framework {[Cu₂(mp)L₂)(H₂O)₂]·6H₂O}_n ( 1 ) (mp = benzene‐1,2,4,5‐ tetracarboxylate tetraanion, L = 4‐(5‐(pyridin‐4‐yl)‐1,3,4‐thiadiazol‐2yl)pyridine). Single‐crystal X‐ray analyses reveal that it crystallizes in the triclinic space group P‐1, a = 8.807(4) Å, b =11.139(6) Å, c = 11.291(5) Å, α=75.337(7), β = 73.584(5), γ= 66.795(5)°. The Cu^II ions are linked into an extended 2‐D grid net via mp molecules. Further these layers are united together through the bridging L to form a 3‐D structure, which exhibits a new 4‐connected topological network. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal and molecular structure of 1‐allyl‐5‐(4‐methylbenzoyl)‐4‐(4‐methylphenyl)pyrimidine‐2(1H)‐thione

The crystal structure of 1‐allyl‐5‐(4‐methylbenzoyl)‐4‐(4‐methylphenyl)pyrimidine‐2(1H)‐thione (C₂₂H₂₀N₂OS) has been determined from three dimensional single crystal X‐ray diffraction data. The title compound crystallizes in the monoclinic space group P 2₁/c, with a = 10.6674(13), b = 10.1077(7), c = 17.9467(19) Å, β = 98.460(9)°, V = 1914.0(3) ų, D_calc = 1.251 g cm^–3, Z = 4. In the title compound, the allyl group shows positional disorder. Molecules are linked by C‐H···O, C‐H···N and C‐H···S intermolecular interactions forming two‐dimensional network. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of a silver(I) complex with the 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid)

The reaction between freshly precipitated silver oxide Ag₂O and an aqueous solution of tetrabenzenecarboxylic acid H₄L leads to the anhydrous Ag₂H₂L complex. It crystallizes in the space groupP2₁/c, witha=6.457(1),b=8.180(1),c=9.982(1) Å, β=97.83(1)°,V=522.3(1) ?³,Z=2,d=2.976 g cm⁻³. This structure is a three dimensional polymeric network polymer without any silver...silver interaction. The silver environment is a bipyramid trigonal polyhedron with three short bond distances in the equatorial plane (Ag−O=2.255(2), 2.295(2), and 2.499(2) Å) and two longer bond distances in axial positions (Ag−O=2.558(2) and 2.617(2) Å). Thus, the silver polyhedron involves five different ligands. It is noteworthy that the (H₂L₂)²⁻ ligand is located around an inversion centre.     

Synthesis and Structure of Trans‐bis(ethanolamine)bis(saccharinato)mercury(II)

Trans‐bis(ethanolamine)bis(saccharinato)mercury(II), [Hg(ea)₂(sac)₂], where ea and sac denote the ethanolamine molecule and the saccharinate anion, respectively, crystallizes in the triclinic space group P (No. 2) with a = 9.4651 (5), b = 10.4365 (5), c = 11.9314 (6) Å, α = 84.402 (1)° β = 78.313 (1)°, γ = 75.307 (1)°, Z = 2, V = 1115.11 (10) ų. The structure consists of isolated [Hg(ea)₂(sac)₂] units in which the Hg(II) ion is octahedrally coordinated by two nitrogen and two oxygen atoms of two neutral ea ligands, and two nitrogen atoms of two sac ligands. The ea acts as a bidentate N‐ and O‐donor ligand and occupies the trans positions of the equatorial plane of the coordination octahedron forming a fivemembered chelate ring, while sac behaves as a monodentate N‐donor ligand occupying the axial positions. The average Hg‐N_sac and Hg‐N_ea bond distances are 2.739 (3) and 2.114 (7) Å, respectively. The crystal exhibits extensive hydrogen bonds between the hydroxyl and amine hydrogen atoms of the ea ligands and the sulfonyl, carbonyl and amine groups of the sac ligands.     

Synthesis and Crystal Structure of a Novel Self-assembled 2D Coordination Polymer of Chloridobis(imidazolidine-2-thione)thiocyanato dicopper(I)

Abstract  A copper(I) complex, poly(chloridobis(imidazolidine-2-thione)thiocyanato dicopper(I)), [Cu₂(Imt)₂(SCN)Cl] _n (1) (Imt = Imidazolidine-2-thione) has been prepared by the reaction of CuCl₂ with imidazolidine-2-thione and potassium thiocyanate in the ratio of 1:1:2. Compound 1 crystallizes in the monoclinic space group P2₁/a in the form of a coordination polymer, consisting of 2D layers. The solid-state structure is composed of dinuclear units having each copper(I) ion tetrahedrally coordinated. These units aggregate through bridging Imt and thiocyanate leading to a supramolecular 2D-network. Index Abstract  The title complex, poly(chloridobis(imidazolidine-2-thione)thiocyanato dicopper(I)), [Cu₂(Imt)₂(SCN)Cl] _n (Imt = Imidazolidine-2-thione) was prepared by the reaction of CuCl₂ with imidazolidine-2-thione and potassium thiocyanate in the ratio of 1:1:2. The crystal structure consists of dinuclear units having each copper(I) ion tetrahedrally coordinated. These units aggregate through bridging Imt and thiocyanate leading to a supramolecular 2D-network.      

Synthesis and crystallographic characterization of a chiral complex of (R)‐2‐(pyridin‐2‐ylmethylene)amino‐2′‐hydroxy‐1,1′‐binaphthyl(L) with hydrated nickel(II) acetate

A chiral complex of (R)‐2‐((pyridin‐2‐ylmethylene)amino)‐2′‐hydroxy‐1,1′‐binaphthyl ( L ) with hydrated nickel (II) acetate has been synthesized and spectroscopically characterized. The crystal structure of [NiL₂(CH₃OH)(CH₃COO)]CH₃COO·CH₃OH has been determined by single‐crystal X‐ray diffraction. The complex crystallizes in the orthorhombic space group P 2(1) 2(1) 2(1) with cell constants a = 15.1035 (19), b = 17.836 (2), c = 18.730 (2)Å, α = β = γ = 90.00°, Z = 4. The structure was solved by direct methods and refined to R = 0.0346 (wR₂ = 0.0863). The analytical result of the crystal structure indicates that a pair of L ligands chelate to a Ni (II) atom in an asymmetric fashion with one Ni‐N bond being longer than the other, the Ni (II) atom is further coordinated by one methanol molecule and one acetate anion to form a distorted octahedral geometry. In the crystal of the complex, the coordination cation [NiL₂(CH₃OH)(CH₃COO)]⁺, the uncoordinated methanol molecule and uncoordinated acetate anion are further assembled into one‐dimensional chain structure via intermolecular hydrogen bonds along the a‐axis. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and spectroscopic study of Mg13.4(OH)6(HVO4)2(H0.2VO4)6

Single‐crystals of the polar compound magnesium hydrogen vanadate(V), Mg_13.4(OH)₆(HVO₄)₂(H_0.2VO₄)₆, were synthesized hydrothermally. It represents the first hydrogen vanadate(V) among inorganic compounds. Its structure was determined by single‐crystal X‐ray diffraction [space group P 6₃mc, a = 12.9096(2), c = 5.0755(1) Å, V = 732.55(2) ų, Z = 1]. The crystal structure of Mg_13.4(OH)₆(HVO₄)₂(H_0.2VO₄)₆ consists of well separated, vacancy‐interrupted chains of face sharing Mg2O₆ octahedra, with short Mg2—Mg2 distances of 2.537(1) Å, embedded in a porous magnesium vanadate 3D framework having the topology of the zeolite cancrinite. All three hydrogen positions in the structure were confirmed by FTIR spectroscopy. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of bis(4-dimethylaminopyridinium) tribromocuprate(I) and bis(4-dimethylaminopyridinium) tetrabromocuprate(II)

The synthesis and crystal structures of two copper bromide salts of the 4-dimethylaminopyridinium (4DMAP⁺) cation are reported. The Cu(I) salt, (4DMAP)₂CuBr₃, crystallizes in the monoclinic space group C2/c, with a = 11.724(2), b = 11.055(3), c = 15.763(3) Å, = 107.64(3)°, and Z = 4. It contains isolated planar 4DMAP⁺ cations and trigonal planar CuBr₃ ^2– anions. Small distortions from idealized D _3h symmetry are observed for the anion. For the Cu(II) salt, (4DMAP)₂CuBr₄, a triclinic cell is observed with a = 8.2373(2), b = 9.2428(2), c = 14.4391(1) Å, = 93.760(1), = 94.576(1), = 105.249(1)°, and Z = 2. This compound contains discrete planar 4DMAP⁺ cations and flattened tetrahedral CuBr₄ ^2– anions. Small distortions are observed for ideal D _2d symmetry.     

Crystal structure analyses of bis(triphenyl- phosphoranyliden)ammonium bis(pentafluoroethyl) argentate, [Ph3P=N=PPh3][Ag(C2F5)2] and bis[bis(triphenylphosphoranyliden)ammonium] tetrachloro-diargentate, [Ph3P=N=PPh3]2[ClAg(μ-Cl)2AgCl]

Bis(triphenylphosphoranyliden)ammonium bis(pentafluoroethyl)argentate, [Ph₃P=N= PPh₃][Ag(C₂F₅)₂] (1) and bis[bis(triphenylphosphoranyliden)ammonium]tetrachloro-diargentate, [Ph₃P=N=PPh₃]₂[ClAg(μ-Cl)₂AgCl] (2) were crystallized from the reaction mixture of pentafluoroethylsilver(I) and bis(triphenylphosphoranyliden)ammonium chlo-ride. Crystallization of 1 occurs in the centrosymmetric monoclinic space group P2₁/c (No. 14) with a = 17.083(2) Å, b = 11.600(2) Å, c = 19.833(2) Å, β = 109.66(1)°, V = 3700.8(7) ų, Z = 4. 2 crystallizes in the centrosymmetric orthorhombic space group Pbca (No. 61) with a = 19.540(1) Å, b = 15.926(1) Å, c = 20.160(1) Å, V = 6273.6(3) ų, Z = 8.     

Crystal structures of 2-pyrazinecarboxylato silver(I) and ammine 2,3-pyrazinecarboxylato disilver(I)

X-ray analysis has shown that the complexes of silver(I) with the anionic forms of 2-pyrazinecarboxylic and 2,3-pyrazinedicarboxylic acids are three-dimensional network polymers. Ag(C₅H₃O₂N₂) (1) crystallizes in space groupPna2₁ witha=7.028(2),b=11.510(3),c=6.949(2) Å andZ=4. Silver tetrahedral coordination occurs through three ligands: the first one acts as a bidentate chelator (Ag–O=2.539(4), Ag–N=2.334(4)Å), the second one involves one N pyrazine atom (Ag–N=2.196(4)Å) and the third one bonds through one O-carboxylato atom (Ag–O=2.323(4)Å). The dinuclear complex Ag₂(C₆H₂O₄N₂)(NH₃) (2) crystallizes in space groupP2₁/c witha=7.775(2),b=16.455(2),c=7.174(1) Å, -115.21(1)° andZ =4. Each of the two silver atoms shows a trigonal environment. The first silver atom involves two O carboxylic atoms (Ag–O=2.312(4), 2.374(4)Å) and one N pyrazine atom (Ag–N=2.277(3)Å) belonging to three different ligands. The second one involves one O carboxylic atom (Ag–O=2.364(3)Å) and one N pyrazine atom (Ag–N=2.304(4)Å) from the same chelating ligand and one N ammine atom (Ag–N=2.158(5)Å).     

Synthesis,characterization and crystal structure of a 2D Cd(II) complex with a 4,4'‐diazenediyldiphthalic acid ligand

An exploration of the cadmium‐L system under hydrothermal condition, has led to the isolation of a novel framework {[Cd(L)_0.5(H₂O)₃]}_n ( 1 ) (H₄L = 4,4'‐diazenediyldiphthalic acid). Single‐crystal X‐ray analysis reveals that it crystallizes in the triclinic space group P‐1. a = 5.746(3) Å, b =6.526(4) Å, c = 14.701(8) Å, α=92.348(8), β = 99.622(6), γ=106.877(7)°. The Cd^II ions are linked into an extended 2‐D rectangle‐like structure via L ligands, which exhibits an attractive three‐connected honeycomb topological network. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure of (dimethyl sulfoxide‐S){glyoxylic acid thiosemicarbazonato(2–)‐O,N,S }platinum(II)

A crystal of the title complex [Pt(DMSO)(GT)] ( 1a ), where H₂GT = glyoxylic acid thiosemicarbazone, has been characterized by X‐ray crystallography and its structure has been compared with that of the recently described cytotoxic complex [Pt(DMSO)(GT)]·DMSO (1). The crystal of 1a is monoclinic; space group P 2₁/n; unit cell dimensions: a = 7.3270(10), b = 10.313(2), c = 13.706(3) Å, β = 101.92(3)°; V = 1013.3(3) ų; Z = 4. The Pt(II) ion is approximately planar tetragonal coordinated by the carboxylato oxygen, azomethine nitrogen and thiolato sulfur atom of the doubly deprotonated H₂GT molecule, and the sulfur atom of DMSO. The two five membered chelate rings are almost coplanar. In distinct with 1 , the sulfoxide oxygen atom and thiolato sulfur atom are in gauche position. A system of hydrogen bonds of the type N–H···O involving the amino, carboxylato and sulfoxide groups links the complex molecules within the unit cells. The π ‐π stacking pattern between the chelate rings in 1a involves centrosymmetric pairs of complex molecules and differs from that in 1 . (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,characterization and X‐ray crystal structure of guanidinuim (pyridine‐2,6‐dicarboxylato)(pyridine‐2,6‐monocarboxylato) zincate(II) mono pyridine‐2,6‐dicarboxylic acid tetrahydrate

A new complex of Zinc(II) and guanidinium pyridine–2,6–dicarboxylate proton transfer compound, (GnH)₂ (pydc), was synthesized and characterized using IR, ¹H NMR and ¹³C NMR spectroscopy and single crystal X–ray diffraction. The chemical formula and space group of the resulting complex is (GnH)[Zn(pydc)(pydcH)] · (pydcH₂) · 4H₂O, P 1 where the final R value is 0.0310 for 13287 reflections collected. The [Zn(pydc)(pydcH)]^– anions and the (GnH)⁺ counter‐cations form a three‐dimensional solid‐state structure by a variety of noncovalent interactions such as ion pairing, hydrogen bonding and π–π stacking which are going to be discussed. (© 2007 WILEY ‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Interaction in the molten system Rb2O‐P2O5‐TiO2‐NiO. Crystal structure of the langbeinite‐related Rb2Ni0.5Ti1.5(PO4)3

The interaction in the molten system Rb₂O‐P₂O₅‐TiO₂‐NiO was investigated at different molar ratios Rb/P = 0.5‐1.3, fixed Ti/P = 0.15, Ti/Ni = 1.0 at temperature range 1073–953 K. The conditions of formation of complex phosphates RbTi₂(PO₄)₃, Rb₂Ni_0.5Ti_1.5(PO₄)₃ and RbNiPO₄ have been determined. The new phosphate Rb₂Ni_0.5Ti_1.5(PO₄)₃ (space group P2₁3, a = 9.9386(2) Å) has been obtained and investigated by the single crystal X‐ray diffraction and FTIR‐spectroscopy. It has langbeinite‐like structure, that is built up from mixed (Ni/Ti)O₆‐octahedra and РО₄‐tetrahedra. Rubidium atoms are located in closed cavities of 3D‐framework.     

3D Binary copper(I) 3,5-dibutyl-1,2,4-triazolate: Synthesis, Structure and Topology

Abstract  

Binary copper(I) 3,5-dibutyl triazolate has been prepared from 3,5-dibutyl triazole and Cu(NO₃)₂ under hydrothermal condition. This complex crystallizes in tetragonal I4₁/a with a = b = 17.622(3) ?, c = 15.842(3) ? and exhibits a 3D structure of either four-connected lvt or three-connected lvt-a topology.     

Self‐assembly of a cadmium(II) diamondoid net with 2‐fold interpenetrating microporous structure

Assembly of 5‐methoxyisophthalic acid (H₂moip) with cadmium(II) ions in the presence of neutral ancillary 1,3‐bis(4‐pyridyl)propane (bpp) yields a new coordination polymer, [Cd(moip)(bpp)(H₂O)]_n·nH₂O ( 1 ). X‐ray single‐crystal diffraction determination reveals that complex 1 crystallizes in the space group C2/c of monoclinic crystal system: a = 14.545(2), b = 18.749(3), c = 17.359(3) Å, β = 105.480(2)º. Complex 1 is a 4‐connected 3D diamondoid topological framework with a 2‐fold interpenetration. Interestingly, the dense adamantine cages with inherent microporous structure are filled with free water molecules to further stabilize the coordination network.