Bipy Molecules Research Articles

Crystal and molecular structures of ZnPhen(C2H5OCS2)2 and Zn(2,2′-Bipy)(n-C4H9OCS2)2 mixed-ligand coordination compounds

ZnPhen(EtOCS2)2 (I) and Zn(2,2′-Bipy)(n-BuOCS2)2 (II) mixed-ligand complexes have been synthesized. The structures were solved from X-ray diffraction data (CAD-4 and X8-APEX diffractometers, MoKα radiation, 1879 and 3637 Fhkl, R = 0.0374 and 0.0315). Crystals I are monoclinic with parameters a = 11.678(3) A, b = 19.215(3) A, c = 9.655(1) A; β = 101.23(1)°; V = 2125.0(7) A3; Z = 4, space group P21/c; crystals II are triclinic with parameters a = 8.7875(3) A, b = 11.833(1) A, c = 13.3454(6) A; α = 112.154(2)°, β = 108.503(1)°, γ = 92.787(2)°; V = 1196.2(1) A3; Z = 2, space group 1 \(P\bar 1\). The structures are composed of discrete mononuclear molecules. The polyhedra of the Zn atoms are distorted trigonal bipyramids N2S3 formed by coordination of the N atoms of Phen or 2,2′-Bipy molecules and sulfur atoms of the monodentate and cyclic bidentate xanthogenate ligand. In structures I and II, dimer assemblies are formed by π-π interactions of Phen or 2,2′-Bipy molecules.

Monomers, chains, ladders, and two-dimensional sheets: Structural diversity in six new compounds of Zn(II) with 4,4′-bipyridine

Six new zinc(II)–4,4′-bipyridine coordination polymers with diverse structural topologies are reported. The reaction of one equivalent of zinc(II) perchlorate hexahydrate with three equivalents of 4,4′-bipyridine (bipy) under hydrothermal conditions produces a mixture of [Zn(4,4′-bipy) 2(H 2O) 4](ClO 4) 2 · 2(4,4′-bipy) ( 1), [Zn 3(4,4′-bipy) 4(OAc) 4](ClO 4) 2 · 2(H 2O) ( 2), and [Zn 3(4,4′-bipy) 3(OAc) 4(H 2O) 2](ClO 4) 2 · (H 2O) ( 3) (OAc = acetate), for which single crystals can be isolated. Compound 1 contains sheet-like arrays of discrete monomers co-crystallized with uncoordinated bipy molecules to form extended triangular channels containing counterions. Compounds 2 and 3 consist of acetate-bridged zinc trimers linked by bipy to form three-leg ladders that are isolated in 3 and further linked by bipy into two-dimensional networks in 2. The reaction of one equivalent of zinc(II) perchlorate hexahydrate with 1.5 equivalents of bipy in dimethyl sulfoxide yields single crystals of [Zn(4,4′-bipy)(ClO 4)(H 2O)(OH)] ( 4) and [Zn(4,4′-bipy)(DMSO) 4](ClO 4) 2 ( 5) while crystals of [Zn(4,4′-bipy) 3(DMSO) 2](ClO 4) 2] · 2(4,4′-bipy) · (H 2O) ( 6) are obtained from DMSO with three equivalents of bipy. Compound 4 is a mutually interpenetrated network of hydrogen-bonded, one-dimensional Zn–bipy zig-zag chains and compound 5 exists as isolated, linear chains. Compound 6 also contains linear chains, linked in three-dimensions by π-stacking interactions between bipy ligands and guests.

Crystal Structure of a Flexible Schiff Base Complex of Zn(II) [ZnL(4,4'-bipyridyl)](ClO4), HL = 2-((2-(2-(benzylamino)ethylamino)ethylimino)-methyl)phenol

The crystal structure of [ZnL(4,4′-bipyridyl)2](ClO4) (HL = 2-((2-(2-(benzylamino)ethylamino)ethylimino)methyl)-phenol) was determined by X-ray diffraction method. This complex crystallized in the monoclinic space group P21/c, with, a = 10.536(2), b = 12.172(2), c = 22.219(4)A, β= 99.330(3)°, Z = 4, V = 2811.5(10)A3, and R = 0.0417. Each ZnII ion completed a distorted square pyramidal coordination configuration by three N donor atoms and one phenolic O donor atom from the Schiff base ligand, and one N donor atom from 4,4′-bipy molecule. Hydrogen-bonding dimmers were formed between two adjacent complex molecules by hydrogen bonding between a bipy molecule and a coordinated nitrogen atom of another complex molecule.

β-Cyclodextrin inclusion of europium(III) tris(β-diketonate)-bipyridine

The adduct Eu(NTA) 3 · bipy was prepared by the reaction of Eu(NTA) 3 · 2H 2O with 2,2′-bipyridine in a 1:1 ratio in chloroform [NTA = 1-(2-naphthoyl)-3,3,3-trifluoroacetonate]. Recrystallization of the complex from a chloroform/diethyl ether solvent mixture gave crystals suitable for X-ray diffraction. The structure contained chloroform molecules in partially occupied sites and was found to be different from the two forms previously reported for the same adduct (one unsolvated and the other containing isopropanol molecules). A single eight-coordinate geometry was found for Eu(NTA) 3 · bipy · 0.44CHCl 3, corresponding to a distorted square antiprism, with the bidentate ligands spanning opposite sides of the ‘square’ faces. A 2:1 (host-to-guest) inclusion compound comprising β-cyclodextrin (CD) and Eu(NTA) 3 · bipy was obtained by co-precipitation from a mixed water/ethyl acetate solvent mixture. The formation of a true inclusion complex was supported by powder XRD, thermogravimetric analysis and 13C CP MAS NMR spectroscopy. Photoluminescence spectroscopy indicated the presence of only one low-symmetry environment for the Eu 3+ cations in non-included Eu(NTA) 3 · bipy and the inclusion compound. However, upon encapsulation of the complex in β-CD, some of the Eu 3+ intra-4f 6 5D 0 → 7F 0–4 lines shifted in energy, and the number of Stark components for the 5D 0 → 7F 1–2 transitions increased, indicating a lowering of the symmetry of the Eu 3+ local coordination environment. The room temperature excitation spectrum of the inclusion compound revealed an enhancement of the Eu 3+ sensitized process as a result of encapsulation of the Eu(NTA) 3 · bipy molecules.

Syntheses, structures and properties of two Keggin polyoxometalates [H 5PCo(4,4′-bipy)Mo 11O 39][H 3PMo 12O 40]·3.75(4,4′-bipy)·1.5H 2O and [H 3PMo 12O 40]·2(4,4′-bipy)·1.5H 2O

Two novel Keggin polyoxometalates [H 5PCo(4,4′-bipy)Mo 11O 39][H 3PMo 12O 40]·3.75(4,4′-bipy)·1.5H 2O ( 1) and [H 3PMo 12O 40]·2(4,4′-bipy)·1.5H 2O ( 2) (bipy=bipyridine) were prepared by the hydrothermal method for the first time and characterized by elemental analyses, IR spectra and X-ray single crystal diffraction, showing that compound 1 is a novel organic–inorganic hybrid compound which consists of a cobalt-monosubstituted Keggin polyoxoanion [PCo(4,4′-bpy)Mo 11O 39] 5− with one pendant ligand 4,4′-bipy, a well-known Keggin polyoxoanion [PMo 12O 40] 3−, 4,4′-bipy and lattice water molecules. Additionally, the two different heteropolyoxoanions in 1 with alternating alignment, combined with the discrete organic substrates 4,4′-bipy and water molecules by hydrogen bond interactions to afford a pseudo 3D network structure. While compound 2 is an intermolecular compound between polyoxoanion unit [PMo 12O 40] 3− and organic substrate 4,4′-bipy. Furthermore, both the compounds exhibit strong photoluminescence properties in the solid state at room temperature. The catalytic activities of the two compounds were also determined by the oxidation of benzaldehyde to benzoic acid using H 2O 2 as oxidant in a liquid–solid multiphase system. Meanwhile, the catalytic property of the compound 2 was evaluated by the esterification of MeCO 2H (acetic acid) with n-BuOH ( n-butyl alcohol).

Crystal structures of mixed-ligand complexes [CoPhen{(i-C4H9)2PS2}2], [Co(2,2′-Bipy){(i-C4H9)2PS2}2] and the development of dimer assemblies in them

X-ray diffraction data have been used to determine crystal structures of coordination compounds [CoPhen{ (i-C4H9)2PS2}2] (I) and [Co(2,2′-Bipy){ (i-C4H9)2PS2}2] (II) (X8-APEX diffractometer, MoK α∔ -radiation, 3083 F hkl , R = 0.0647 for I and 5381 F hkl , R = 0.0597 for II). I is triclinic, a = 11.244(1) A, b = 14.892(2) A, c = 21.419(4) A, α = 71.867(4)°, β = 81.553(4)°, γ = 76.777(4)°, V = 3306,9(8) A3; Z = 4, ρcalc = 1.321 g/cm3, space group \(P\bar 1\); II is monoclinic, a = 14.693(2) A; b = 20.868(3) A, c = 11.417(1) A; β = 106.46(5)°; V = 3357.1(7) A3, Z = 4, ρcalc = 1.254 g/cm3, space group P21/c. The structures are built from discrete mononuclear molecules. Coordination polyhedra of Co atoms are distorted octahedra formed by four S atoms of two bi-dentate chelating ligands (i-C4H9)2PS 2 − and two N atoms of two bi-dentate chelating Phen or 2,2′-Bipy molecules. The interaction of the molecules in the structures of I and II has been analyzed. It has been found that the molecules of I and II form dimer ensembles owing to π-π-interactions of Phen or 2,2′-Bipy.

Dimeric ensembles in the crystal structures of mixed-ligand coordination compounds ML(i-Bu2PS2)2 (M = Zn, Cd, Mn, Co, Ni; L = Phen, 2,2′-Bipy)

Single crystals of a mononuclear mixed-ligand complex [Mn(Phen)(i-Bu2PS2)2] were grown and used for X-ray diffraction structural study of the material (diffractometer CAD-4, MoK α -radiation, 1205 F hkl , R = 0.0351). The crystals are monoclinic: a = 15.602(2) A, b = 20.914(3) A, c = 11.419(2) A; β = 111.36(1)°, V = 3470.1(9) A3, Z = 4, ρ(calc) = 1.251 g/cm3, space group P21/c. Coordination polyhedron of Mn is a distorted octahedron N2S4. Molecular and crystal structures of mixed-ligand coordination compounds ML(i-Bu2PS2)2 (M= Zn, Cd, Mn, Co, Ni; L = Phen, 2,2′-Bipy) are considered on the basis of XRD data (automated diffractometers CAD-4 and X8-APEX). The analysis of intermolecular distances in the structures of ten mixed-ligand coordination compounds revealed in nine of them the presence of short contacts made by carbon atoms of the N-heterocycles. These contacts correspond to π-π interactions of Phen or 2,2′-Bipy molecules of two neighboring complexes giving rise to dimeric molecular ensembles.

Hydrothermal Synthesis and Crystal Structure of a Europium(III) Coordination Polymer with 5-Sulfoisophthalate Trivalent Anions and Free 4,4′-Bipyridine Molecules

A novel europium(III) coordination polymer [Eu(Sip)(H2O)5]n · nH2O · 1.5n(Bipy) (I) (Sip is 5-sulfo-isophthalate trivalent anion and Bipy is 4,4′-bipyridine) is hydrothermally synthesized and determined by the single crystal X-ray diffraction method. Polymer I crystallizes in the monoclinic system, space group C2/c with a=30.7515(6) A, b=10.9577(2) A, c=17.5545(4) A, β=112.040(1)°, V=5483.0(2) A3, Z=4, final R 1=0.0253 and wR 2=0.0606. In I, each Eu3+ ion is coordinated by four oxygen atoms from two carboxylate groups of two different Sip anions and five oxygen atoms from five coordinated water molecules to complete a deformed monocap square antiprism. Moreover, each Sip anion acts as a tetradentate ligand to connect two adjacent Eu3+ ions through its two chelating carboxylate groups, resulting in one-dimensional linear chains. In addition, fifteen different kinds of hydrogen-bonding interactions link the chains, lattice water molecules, and free Bipy molecules to engender a complicated hydrogen-bonding network.

The indium–carboxylate chain structure with the rectangular tunnels

A novel metal-organic material, {[In 2(btc) 2(2,2′-bpy) 2] · 4H 2O} n ( 1) (H 3btc = 1,3,5-benzenetricarboxylic acid; 2,2′-bipy = 2,2′-bipyridine), with the one-dimensional double stranded chain framework has been prepared under hydrothermal condition and characterized by single-crystal X-ray diffraction analysis. The structure of polymer 1 is also characteristic of neutral independent rectangular tunnels decorated with 2,2′-bipy molecules. The emission spectrum, IR spectrum and thermogravimetric analysis of 1 are reported.

Syntheses and crystal structures of two structurally diverse cobalt complexes constructed from 5-hydroxyl-1,3-benzenedicarboxylates

Two structurally diverse compounds, {[Co(4,4′-bipy)(H 2O) 4](hmbdc)(H 2O)} n ( 1) and {[Co(4,4′-bipy)(hmbdc)(H 2O) 2](4,4′-bipy)(DMF)} n ( 2) (H 2hmbdc=5-hydroxyl-1,3-benzenedicarboxylic acid, 4,4′-bipy=4,4′-bipyridine), were synthesized using different starting materials and solvents. Compound 1 possesses hydrogen-bonded 3D networks encapsulating 1D covalently bonded infinite [Co(4,4′-bipy)(H 2O) 4] 2+ chain. Compound 2 shows a 2D architecture and free 4,4′-bipy and DMF molecules fill in the channels of the extended 3D hydrogen bonding network as guest molecules.

{[Cu(bipy) 2.5(H 2O)](ClO 4) 2 · (H 2O) · (CH 3OH) 1.5} n (bipy = 4,4′-bipyridine): organic template effect in formation of a novel bilayer coordination polymer with large chiral channels

In the presence of the organic template molecule, 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole, a unique acentric coordination polymer based on linear 4,4′-bipyridine (bipy) bridging ligand, {[Cu(bipy) 2.5(H 2O)](ClO 4) 2 · (H 2O) · (CH 3OH) 1.5} n ( 1), was obtained by the reaction of Cu(II) perchlorate with bipy in H 2O/CH 3OH medium. The bidendate bipy molecules bridge the Cu II centers to form a 2-D bilayer framework with an 8 2 · 10 topology, and the monodendate bipy ligands, locating up and down each 2-D architecture, are involved in significant aromatic stacking interactions with the adjacent 2-D motifs, resulting in a 3-D porous network with large square channels for including the guest solvents and anions.

Three-dimensional porous frameworks constructed by transition metal ions and isoorotic acid

Four new coordination polymers, [M(Hiso)(H 2O) 3] n (M = Co ( 1); M = Ni ( 2)) and {[M 2(Hiso) 2(bipy) 2(H 2O) 4] · 2(bipy)} n (M = Co ( 3); M = Ni ( 4)) (H 2iso = isoorotic acid, bipy = 4,4′-bipyridine), were synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction. The four complexes all comprise 1D chains that are further interlinked via hydrogen bonds, resulting in the formation of 3D frameworks. There are small channels in 1 and 2 and two kinds of larger channels in 3 and 4, in which free bipy molecules residue. In 1 and 2, the Hiso 2− anions act as tridentate ligands to link metal ions; in 3 and 4, the Hiso 2− anions act as bidentate ligands and the metal ions are bridged by bipy.

Crystal structure and magnetic properties of a heteronuclear, gadolinium–zinc carboxylate complex

A novel heteronuclear complex, [Gd2Zn2L10(bipy)(H2O)2]2 (HL = α-methylacrylic acid, bipy = 4,4′-bipyridine), was synthesized and characterized. Its structure, determined by X-ray diffraction, reveals a discrete octanuclear molecule, in which two ZnII ions are linked by a bipy molecule and GdIII ions, and GdIII and ZnII ions are bridged by bidentate α-methylacrylato groups. The complex crystallizes in space group P with Z = 1, a = 13.4504(6), b = 14.9697(5), c = 16.4374(5) Å, α = 64.212(3), β = 89.727(2), γ = 86.241(1)°. The structure was refined to R = 0.0303 for 8925 observed reflections. The temperature dependence of the magnetic susceptibility of the complex shows that a weak intramolecular ferromagnetic interaction exists as well as an intermolecular antiferromagnetic interaction.

Crystal Structures of Molecular Adducts between Uranyl Nitrate and 2,2 : 6 ,2 -Terpyridine or 2,2′-Bipyridyl

Complexes of uranyl nitrate with aromatic molecular ligands : [UO2Terpy(NO3)2] and (H2Terpy)2[UO2(NO3)2(H2O)2](NO3)4 · 4H2O (Terpy 2,2′:6′,2′′-terpyridine), (Hbipy)[UO2(NO3)3] and [(UO2)2(Bipy)2O2(NO3)2] (Bipy—2,2′-bipyridyl) and (HPy)4[(UO2)2(NO3)4(OH)2](NO3)2 (Py—pyridine) were characterized by X-ray diffraction analysis. In all these compounds, the U(VI) atom has the hexagonal bipyramidal environment. The U–O bond lengths in the UO2 2+ have close values. In the equatorial planes, the U–N bond lengths with the Bipy and Terpy ligands are identical, whereas the U–O bond lengths depend on the type of the ligand. The lengths of the equatorial bonds increase in the sequence U–N > U–Onitr > U–Ohydr > U–Operox. The geometric characteristics of the coordinated and solvate Terpy and Bipy molecules are different. The lengths of the N–O bonds in the NO3 – groups depend on the participation of the O atom in the coordination of the central atom, the coordination mode, and the formation of hydrogen bonds.

Mono-cyclopentadienyl complexes of lanthanum: synthesis and characterization of anilido derivatives

Mono-ligand lanthanide complexes utilizing the bulky tris(trimethylsilyl)cyclopentadienyl ligand are reported. Achiral mono-anilido complexes, in which the iodide and anilido groups are trans -disposed, are readily converted to chiral analogues, where the iodide and anilido groups are oriented in a cis fashion, by the addition of a chelating bidentate ligand such as 2,2 ′ -bipyridine. Use of the bulky cyclopentadienyl ligand [η 5 -C 5 H 2 (SiMe 3 ) 3 -1,2,4] − (Cp‴) allows for the isolation of monomeric, mono-ring lanthanide species. As previously reported, (Cp‴)K reacts with LaI 3 (THF) 4 (THF=tetrahydrofuran) in THF/pyridine to form the mono-ring complex (Cp‴)LaI 2 (py) 3 ( 1 ) (py=pyridine); a minor product of this reaction is the bis-ring species (Cp‴) 2 LaI(py) ( 2 ). The solid state structure of 2 reveals a monomeric compound containing a pseudo-tetrahedral metal center exhibiting no unusual intramolecular contacts. Addition of one equiv of KNHAr (Ar=2,6- i Pr 2 C 6 H 3 ) to complex 1 in THF generates the mono-anilido compound (Cp‴)LaI(NHAr)(THF) 2 ( 3 ), which may be converted to the more stable pyridine adduct (Cp‴)LaI(NHAr)(py) 2 ( 4 ) by the addition of pyridine to 3 . An X-ray crystal structure of 3 indicated a trigonal bipyramidal metal center with the anilido group oriented trans to the iodide atom (N1–La1–I1=123.1(3)°). A structural study on the bis-pyridine adduct 4 revealed a similar C s -symmetric structure with a slightly increased N anilido –La–I angle of 132.1(2)°. Addition of KNHAr to the di-iodo bipyridine adduct (Cp‴)LaI 2 (bipy)(py) ( 5 ), in which the two iodide atoms are cis -disposed, yields the mono-anilido complex (Cp‴)LaI(NHAr)(bipy)(py) ( 6 ) (bipy=2,2 ′ -bipyridine); this compound may also be prepared by the addition of bipy to (Cp‴)LaI(NHAr)(py) 2 ( 4 ). An X-ray diffraction study shows that the lanthanum center in 6 is octahedrally coordinated by a Cp‴ ring, an iodide, an anilido group, a pyridine molecule and two nitrogens of a bipy molecule. In this case, the anilido moiety and the iodide ligand are arranged in a cis fashion (N anilido –La–I=111.2(2)°), resulting in a complex with C 1 symmetry. Both (Cp‴)LaI(NHAr)(py) 2 ( 4 ) and (Cp‴)LaI(NHAr)(bipy)(py) ( 6 ) are inactive as catalysts for the hydroamination/cyclization of 2-amino-hex-5-ene.

Modification of binuclear Pt-Tl bonded complexes by attaching bipyridine ligands to the thallium site.

Complex formation of monomeric thallium(III) species with 2,2'-bipyridine (bipy) in dimethyl sulfoxide (dmso) and acetonitrile solutions was studied by means of multinuclear ((1)H, (13)C, and (205)Tl) NMR spectroscopy. For the first time, NMR signals of the individual species [Tl(bipy)(m)(solv)](3+) (m = 1-3) were observed despite intensive ligand and solvent exchange processes. The tris(bipy) complex was crystallized as [Tl(bipy)(3)(dmso)](ClO(4))(3)(dmso)(2) (1), and its crystal structure determined. In this compound, thallium is seven-coordinated; it is bonded to six nitrogen atoms of the three bipy molecules and to an oxygen atom of dmso. Metal-metal bonded binuclear complexes [(NC)(5)Pt-Tl(CN)(n)(solv)](n)(-) (n = 0-3) have been modified by attaching bipy molecules to the thallium atom. A reaction between [(NC)(5)Pt-Tl(dmso)(4)](s) and 2,2'-bipyridine in dimethyl sulfoxide solution results in the formation of a new complex, [(NC)(5)Pt-Tl(bipy)(solv)]. The presence of a direct Pt-Tl bond in the complex is convincingly confirmed by a very strong one-bond (195)Pt-(205)Tl spin-spin coupling ((1)J((195)Pt-(205)Tl) = 64.9 kHz) detected in both (195)Pt and (205)Tl NMR spectra. In solutions containing free cyanide, coordination of CN(-) to the thallium atom occurs, and the complex [(NC)(5)Pt-Tl(bipy)(CN)(solv)](-) ((1)J((195)Pt-(205)Tl) = 50.1 kHz) is formed as well. Two metal-metal bonded compounds containing bipy as a ligand were crystallized and their structures determined by X-ray diffractometry: [(NC)(5)Pt-Tl(bipy)(dmso)(3)] (2) and [(NC)(5)Pt-Tl(bipy)(2)] (3). The Pt-Tl bonding distances in the compounds, 2.6187(7) and 2.6117(5) A, respectively, are among the shortest reported separations between these two metals. The corresponding force constants in the molecules, 1.38 and 1.68 N/cm, respectively, were calculated using Raman stretching frequencies of the Pt-Tl vibrations and are characteristic for a single metal-metal bond. Electronic absorption spectra were recorded for the [(NC)(5)Pt-Tl(bipy)(m)(solv)] compounds, and the optical transition was attributed to the metal-metal bond assigned.

Poly[[[aquamanganese(II)]-mu2-4,4'-bipyridine-mu3-succinato] 4,4'-bipyridine hemisolvate

The polymeric title complex, [[Mn(C(4)H(4)O(4))(C(10)H(8)N(2))(H(2)O)].0.5C(10)H(8)N(2)](n), possesses a three-dimensional open-framework structure, with the solvate 4,4'-bipyridine (bipy) molecules, which lie around centers of inversion, clathrated in the channels of the framework. The Mn(II) center is surrounded by three succinate (succ) ligands, one water molecule and two bipy ligands, and displays a slightly distorted octahedral coordination environment, with cis angles ranging from 84.14 (12) to 96.56 (11) degrees. Each succ dianion coordinates to three Mn(II) atoms, thus acting as a bridging tridentate ligand; in turn, the Mn(II) atoms are bridged by three succ ligands, thus forming a two-dimensional Mn-succ sheet pillared by the bridging bipy ligands. Two hydrogen-bonding interactions, involving the water molecules and the carboxy O atoms of the succ ligands, are present in the crystal structure.

Mono-cyclopentadienyl complexes of lanthanum: synthesis and characterization of anilido derivatives

Use of the bulky cyclopentadienyl ligand [η 5-C 5H 2(SiMe 3) 3-1,2,4] − (Cp‴) allows for the isolation of monomeric, mono-ring lanthanide species. As previously reported, (Cp‴)K reacts with LaI 3(THF) 4 (THF=tetrahydrofuran) in THF/pyridine to form the mono-ring complex (Cp‴)LaI 2(py) 3 ( 1) (py=pyridine); a minor product of this reaction is the bis-ring species (Cp‴) 2LaI(py) ( 2). The solid state structure of 2 reveals a monomeric compound containing a pseudo-tetrahedral metal center exhibiting no unusual intramolecular contacts. Addition of one equiv of KNHAr (Ar=2,6- i Pr 2C 6H 3) to complex 1 in THF generates the mono-anilido compound (Cp‴)LaI(NHAr)(THF) 2 ( 3), which may be converted to the more stable pyridine adduct (Cp‴)LaI(NHAr)(py) 2 ( 4) by the addition of pyridine to 3. An X-ray crystal structure of 3 indicated a trigonal bipyramidal metal center with the anilido group oriented trans to the iodide atom (N1–La1–I1=123.1(3)°). A structural study on the bis-pyridine adduct 4 revealed a similar C s-symmetric structure with a slightly increased N anilido–La–I angle of 132.1(2)°. Addition of KNHAr to the di-iodo bipyridine adduct (Cp‴)LaI 2(bipy)(py) ( 5), in which the two iodide atoms are cis-disposed, yields the mono-anilido complex (Cp‴)LaI(NHAr)(bipy)(py) ( 6) (bipy=2,2 ′-bipyridine); this compound may also be prepared by the addition of bipy to (Cp‴)LaI(NHAr)(py) 2 ( 4). An X-ray diffraction study shows that the lanthanum center in 6 is octahedrally coordinated by a Cp‴ ring, an iodide, an anilido group, a pyridine molecule and two nitrogens of a bipy molecule. In this case, the anilido moiety and the iodide ligand are arranged in a cis fashion (N anilido–La–I=111.2(2)°), resulting in a complex with C 1 symmetry. Both (Cp‴)LaI(NHAr)(py) 2 ( 4) and (Cp‴)LaI(NHAr)(bipy)(py) ( 6) are inactive as catalysts for the hydroamination/cyclization of 2-amino-hex-5-ene.

Synthesis, characterization, and crystal structures of three new divalent metal carboxylate-sulfonates with a layered and one-dimensional structure.

Hydrothermal reactions of 5-sulfoisophthalic acid (HO(3)SC(6)H(3)-1,3-(CO(2)H)(2), H(3)L) with M(II) carbonate (or oxide) and 4,4'-bipyridine (4,4'-bipy) (or 2,2'-bipyridine, 2,2'-bipy) resulted in three new metal carboxylate-sulfonate hybrids, namely, [CdL(H-4,4'-bipy)] (1) and [Cd(3)L(2)(2,2-bipy)(4)(H(2)O)(2)].2H(2)O (2) with layered structures and [ZnL(H-4,4'-bipy)(H(2)O)].2H(2)O (3), whose structure features a one-dimensional double chain. The cadmium(II) ion in complex 1 is seven-coordinated by five carboxylate oxygen atoms and one sulfonate oxygen atom from four ligands and a unidentate 4,4'-bipyridine. The interconnection of the cadmium(II) ions through bridging carboxylate-sulfonate ligands resulted in the formation of a <002> double layer with the bipyridyl rings orientated toward the interlayer space. Complex 2 has a different layered structure. Cd(1) is seven-coordinated by two bidentate chelating carboxylate groups from two ligands, a bidentate chelating 2,2'-bipy and an aqua ligand, and Cd(2) is octahedrally coordinated by two bidentate chelating 2,2'-bipy's, a sulfonate oxygen, and an aqua ligand. The coordination geometry around Cd(3) is similar to that of Cd(1) with the aqua ligand being replaced by an oxygen atom from the sulfonate group. The carboxylate-sulfonate ligand acts as pentadentate ligand, bridging with three cadmium(II) ions. The bridging of cadmium(II) ions through the carboxylate-sulfonate ligands resulted in the formation of <006> and <003> layers; the 2,2'-bipy molecules and [Cd(2)(2,2'-bipy)(2)(H(2)O)] cations are orientated to the interlayer space. Complex 3 features a 1D metal carboxylate-sulfonate double chain along the diagonal of the a- and b-axes. The zinc(II) ion is octahedrally coordinated by four carboxylate O atoms from three ligands, a unidentate 4,4'-bipy, and an aqua ligand. Each pair of zinc(II) ions is bridged by two carboxylate groups from two ligands to form a dimer, and such dimeric units are interconnected by bridging ligands to form a double chain. The sulfonate group of the carboxylate sulfonate ligand remains noncoordinated and forms a number of hydrogen bonds with aqua ligands as well as lattice water molecules.

Hydrothermal Syntheses, Crystal Structures, and Magnetic Properties of Inorganic−Organic Hybrid Vanadium Selenites with Zero- to Three-Dimensional Structures: (1,10-Phenanthroline)2V2SeO7, (2,2‘-Bipyridine)VSeO4, (4,4‘-Bipyridine)V2Se2O8, and (4,4‘-Bipyridine)2V4Se3O15·H2O

A family of inorganic-organic hybrid vanadium selenites with zero-, one-, two-, and three-dimensional structures, (1,10-phen)(2)V(2)SeO(7), (2,2'-bipy)VSeO(4), (4,4'-bipy)V(2)Se(2)O(8), and (4,4'-bipy)(2)V(4)Se(3)O(15).H(2)O (where phen = phenanthroline and bipy = bipyridine), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Different bidentate organodiamine ligands and reactant concentrations were used in the four reaction systems, which are responsible for the variety of structural dimensions of the compounds. (1,10-phen)(2)V(2)SeO(7) crystallizes in a monoclinic system with space group P2(1)/n and cell parameters a = 8.6509(3) A,( )b = 7.8379(2) A, c = 34.0998(13) A, beta = 91.503(2) degrees, and Z = 4. (2,2'-bipy)VSeO(4) crystallizes in a monoclinic system with space group C2/c and cell parameters a = 17.0895(12) A, b = 14.7707(10) A, c = 11.7657(8) A, beta = 131.354(3) degrees, and Z = 8. (4,4'-bipy)V(2)Se(2)O(8) crystallizes in a triclinic system with space group Ponemacr; and cell parameters a = 7.1810(10) A, b = 10.8937(13) A, c = 11.1811(15) A, alpha = 115.455(3) degrees, beta = 107.582(3) degrees, gamma = 91.957(4) degrees, and Z = 2. (4,4'-bipy)(2)V(4)Se(3)O(15).H(2)O crystallizes in a monoclinic system with space group Pc and cell parameters a = 7.9889(9) A, b = 7.8448 A, c = 23.048(3) A, beta = 99.389(4) degrees, and Z = 2. (1,10-phen)(2)V(2)SeO(7) has an isolated structure, (2,2'-bipy)VSeO(4) has a chain structure, (4,4'-bipy)V(2)Se(2)O(8) has a layered structure, and (4,4'-bipy)(2)V(4)Se(3)O(15).H(2)O has a framework structure. The chains are constructed from VO(4)N(2) octahedra and SeO(3) pyramids, laced by organic ligands (2,2'-bipy). The layers consist of vanadium selenite chains [(VO)(2)(SeO(3))(2)]( infinity ), linked by 4,4'-bipy molecules. The framework is composed of vanadium selenite sheets [V(4)Se(3)O(16)]( infinity ), pillared by 4,4'-bipy molecules. All of the compounds are thermally stable to 300 degrees C, and the magnetic susceptibilities confirm the existence of tetravalent V atoms in the antiferromagnetic (4,4'-bipy)V(2)Se(2)O(8) complex and mixed tetravalent and pentavalent V atoms in the paramagnetic complex (4,4'-bipy)(2)V(4)Se(3)O(15).H(2)O.