Synthesis,structure and cytotoxic activity of binuclear phenyltin(IV) complexes with N,N′‐bis(2‐hydroxybenzyl)‐1,2‐ethanebis(dithiocarbamate) ligand

Two new dinuclear phenyltin(IV) complexes derived from N,N′‐bis(2‐hydroxybenzyl)‐1,2‐ethanebis(dithiocarbamate) ligand, [2‐HOC₆H₄CH₂N(CS₂SnPh₃)CH₂]₂ ( 1 ) and [2‐HOC₆H₄CH₂N(CS₂SnClPh₂)CH₂]₂ ( 2 ) have been synthesized and characterized by elemental analysis, IR and NMR (¹H, ¹³C and ¹¹⁹Sn) spectra. The crystal structures of complexes 1 and 2 were determined by X‐ray single crystal diffraction and show that the dithiocarbamate ligand is coordinated to the tin atom in the anisobidentate manner and the tin atom is five‐coordinated. The coordination geometry of tin atom is best described as an intermediate between trigonal bipyramidal and square pyramidal with τ‐values of 0.63 and 0.53, respectively. Intermolecular hydrogen bonds (O H···S and O H···Cl) in 1 and 2 connect neighboring molecules into a one‐dimensional supramolecular chain with the centrosymmetric cyclic motifs. Complex 1 has potent in vitro cytotoxic activity against two human tumor cell lines, CoLo205 and Bcap37, while complex 2 displays weak cytotoxic activity. Copyright © 2011 John Wiley & Sons, Ltd.     

8‐Chloro‐7‐(2,6‐di­chloro­benzyl)‐1,3‐di­methyl‐7H‐purine‐2,6(1H,3H)‐dione

The title compound, C₁₄H₁₁Cl₃N₄O₂, consists of two planar fragments which are nearly perpendicular to one another. The crystal packing is controlled by intra‐ and intermolecular C—H·O hydrogen bonds, and Cl·phenyl‐ring‐centroid and weak stacking interactions.     

Polysulfonylamine. CLXXVIII Onium‐Salze des Benzol‐1,2‐di(sulfonyl)amins (HZ): Eine zweite Kristallform des Ammonium‐Salzes NH4Z·H2O und Kristallstruktur des Bis(triphenylphosphoranyliden)ammonium‐Salzes [Ph3PNPPh3]Z

Polysulfonylamines. CLXXVIII. Onium Salts of Benzene‐1,2‐di(sulfonyl)amine (HZ): A Second Crystal Form of the Ammonium Salt NH₄Z·H₂O and Crystal Structure of the Bis(triphenylphosphoranylidene)ammonium Salt [Ph₃PNPPh₃]Z A dimorphic form of NH₄Z·H₂O, where Z^? is N‐deprotonated ortho‐benzenedisulfonimide, has been obtained and structurally characterized (previously known form 1A : monoclinic, P2₁/c, Z′ = 1; new polymorph 1B : monoclinic, P2₁/n, Z′ = 1). Both structures are dominated by an abundance of classical hydrogen bonds N⁺–H/O–H···O=S/OH₂, whereby the anionic N^? function does not act as an acceptor. The major difference between the dimorphs arises from the topology of the hydrogen bond network, which is two‐dimensional in 1A , leading to a packing of discrete lamellar layers, but three‐dimensional in 1B . Moreover, the latter network is reinforced by a set of weak C–H··O/N hydrogen bonds, whereas the layered structure of 1A displays only one independent C–H···O bond, providing a link between adjacent layers. The compound [Ph₃PNPPh₃]Z ( 2 , monoclinic, P2₁/c, Z′ = 1) is the first structurally authenticated example of an ionic Z^? derivative in which the cation contains neither metal bonding sites nor strong hydrogen bond donors. This structure exhibits columns of anions, surrounded by four parallel columns of cations, giving a square array. The large cations are associated into a three‐dimensional framework via weak C–H···C(π) interactions and an offset face‐to‐face phenyl interaction, while the anions occupy tunnels in this framework and are extensively bonded to the surrounding cations by C–H···O/N^? hydrogen bonds and C–H···C(π) interactions.     

Two Heteroleptic Zinc(II) Complexes: [Zn(phen)(C9H15O6)2] and [Zn2(phen)2(H2O)2(C10H16O4)2] · 3H2O

Reactions of a freshly prepared Zn(OH)_2‐2x(CO₃)x · yH₂O precipitate, phenanthroline with azelaic and sebacic acid in CH₃OH/H₂O afforded [Zn(phen)(C₉H₁₅O₄)₂] ( 1 ) and [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] · 3H₂O ( 2 ), respectively. They were structurally characterized by X‐ray diffraction methods. Compound 1 consists of complex molecules [Zn(phen)(C₉H₁₅O₄)₂] in which the Zn atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different monodentate hydrogen azelaato groups. Intermolecular C(alkyl)‐H···π interactions and the intermolecular C(aryl)‐H···O and O‐H···O hydrogen bonds are responsible for the supramolecular assembly of the [Zn(phen)(C₉H₁₅O₄)₂] complexes. Compound 2 is built up from crystal H₂O molecules and the centrosymmetric binuclear [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] complex, in which two [Zn(phen)(H₂O)]²⁺ moieties are bridged by two sebacato ligands. Through the intermolecular C(alkyl)‐H···O hydrogen bonds and π‐π stacking interactions, the binuclear complex molecules are assembled into layers, between which the lattice H₂O molecules are sandwiched. Crystal data: ( 1 ) C2/c (no. 15), a = 13.887(2), b = 9.790(2), c = 22.887(3)Å, β = 107.05(1)°, U = 2974.8(8)ų, Z = 4; ( 2 ) P1¯ (no. 2), a = 8.414(1), b = 10.679(1), c = 14.076(2)Å, α = 106.52(1)°, β = 91.56(1)°, γ = 99.09(1)°, U = 1193.9(2)ų, Z = 1.     

Supramolecular solid-state structure,potential energy surfaces and evaluation of antiproliferative effect of 2-benzothiazolylhydrazone derivatives in vitro

The in situ condensation reaction of 2-hydrazinobenzothiazole with salicylaldehyde, 3,4-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2-hydroxy-1-naphthaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde and 6-methoxy-2-naphthaldehyde produced 9 hydrazone Schiff bases (L1–L9, respectively) which were identified and characterized by elemental analysis, IR and NMR spectroscopy. The crystal and molecular structures of four Schiff bases (L1, L7–L9) have been determined by the single-crystal X-ray diffraction method confirming the imino form of L1 and the amino tautomeric form of L7–L9 compounds. Molecular structure analysis also confirmed that reported compounds are E-isomers relative to exo C = N imino bond. The N_hydrazino–H group of amino tautomers forms N_hydrazino–H···N_thiazolyl intermolecular hydrogen bonds shaping molecules into R ₂ ² (8) rings, while imino tautomer of L1 forms C(4) infinite helical chains via N_thiazolyl–H···N_hydrazino type of intermolecular hydrogen bond. The methoxy group (L7–L9) further shaped these primary supramolecular synthons into different supramolecular arrangements via C–H···O, C–H···N and C–H···S intermolecular hydrogen bonds. The role of aryl substituents in the shaping and stabilization of supramolecular architectures of L1, L7–L9 is supported by quantum chemical calculations. Strong antiproliferative effects on tumor cells and cytotoxic effects on fibroblasts are shown for all ligands L1–L9 with exception of L6 and L7 that had no effect on fibroblast cells.     

2,5‐Dichloro‐2,5‐dihydro­thio­phene 1‐oxide: determinaton of the complete stereochemistry

The title five‐membered heterocycle, C₄H₄Cl₂OS, adopts an envelope conformation with the S atom at the tip of the flap. All three ring substituents, viz. the sulfoxide O atom and the two Cl atoms, are cis to each other. The two C atoms α to the sulfoxide group are also bonded to chlorine. The electron‐withdrawing chlorine substituents give rise to weak C—H·O hydrogen bonds with the sulfoxide O atom of a symmetry‐related mol­ecule [H·O = 2.44 (2) and 2.61 (2) Å, C·O = 3.143 (3) and 3.302 (2) Å and C—H·O = 129.9 (19) and 135.1 (19)°]. There is also a possible weak C—H·Cl inter­action. Chains of mol­ecules held together by these weak inter­actions run parallel to the a axis.     

One‐pot Synthesis of a 3,4,5‐Triaryltriazole from the Subsitituted 1,3,4‐Oxadiazole: Crystal Structures Characterization

Two heterocyclic compounds, 2‐(p‐bromophenyl)‐5‐(2‐pyridyl)‐1,3,4‐oxadiazole ( 1 ) and 3‐(p‐bromophenyl)‐4‐phenyl‐5‐(2‐pyridyl)‐1,2,4‐triazole ( 2 ) were successfully synthesized and characterized by UV–vis, FTIR, ¹H NMR, ESI‐MS spectra, elemental analysis, and single crystal X‐ray crystallography. The structural analysis indicates that 1 is almost a planar molecule but 2 not. The crystal structure of 1 is stabilized by two kinds of intermolecular π–π interactions and two types of intermolecular C–H···N hydrogen bonds, whereas 2 by three kinds of C–H···π interactions and three types of intermolecular C–H···N hydrogen bonds. Additional, 2 can be prepared directly from 1 in an aniline solution at 190°C in a yield of 70%.     

Cooperative N–H···N,N–H···O,and O–H···N bonded molecular dimers of two new 3,5-diaryl-1<Emphasis Type="Italic">H</Emphasis>-pyrazoles

Two new 3,5-diaryl-1H-pyrazoles: 3(5)-(4-tert-butylphenyl)-5(3)-(naphthalene-2-yl)-1H-pyrazole (1) and 5-(4-(benzyloxy)phenyl)-3-(furan-2-yl)-1H-pyrazole (2) were synthesized and characterized. Two strong ions peaks [2M]⁺ and [2M + Na]⁺ observed in the ESI–MS spectra are attributed to the dimerization process in solution formed by intermolecular N–H···N hydrogen bonds. The crystal structures have been determined by X-ray crystal structure analysis. Compound 1 exists as a pair of tautomers 1a and 1b, and its dimer [R ₂²(6) motif] is formed by the tautomers 1a and 1b. Compound 2 only exists as a 2a tautomer, and interesting intermolecular N–H···O and O–H···N hydrogen bonds link two pyrazoles and two methanol molecules, leading to the formation of an R ₄⁴(10) dimer motif.     

Synthesis,structure and properties of aquabis(2,4′-bipyridine)di(propionato-O)copper(II)

The title complex has been synthesized and characterized by elemental and thermal analysis, IR and electronic spectroscopy, conductivity studies and X-ray crystallography. In the crystal, the complex has two-fold symmetry and the copper atom adopts square pyramidal coordination. Bond valences for Cu were computed. Cu–O_(propionate) bonds are slightly stronger than the Cu–N bonds, and the Cu–O_(water) bond is distinctly weaker. Molecules are linked by O–H···O hydrogen bonds to form infinite hydrogen-bonded chains along the y axis.     

Polysulfonylamine. CLXVI [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 15 [1] Die isotypen Kristallstrukturen von Ammonium‐ und Caesium‐dimesylamid: Kristallographische Kongruenz zwischen Wasserstoffbrücken N—H···O/N und Metall‐Ligand‐Bindungen Cs—O/N

Polysulfonylamines. CLXVI. Crystal Structures of Metal Di(methanesulfonyl)amides. 15. The Isotypic Crystal Structures of Ammonium and Cesium Dimesylamide: Crystallographic Congruency of Hydrogen Bonds N—H···O/N and Metal‐Ligand Interactions Cs—O/N The ammonium salt NH₄[N(SO₂CH₃)₂] and its previously reported cesium analogue Cs[N(SO₂CH₃)₂] are isostructural (monoclinic, space group P2₁/n, Z = 4, V at —140 °C: 0.761 and 0.832 nm³ respectively). The cesium ion adopts an irregular (O₆N)‐heptacoordination by forming close contacts to one (O, N)‐chelating, one (O, O)‐chelating and three κ¹O‐bonding anions, whereas in the ammonium‐based structure each of the seven Cs—O/N interactions is perfectly mimicked by an N—H···O/N hydrogen‐bond component. To this effect, three N—H donors are engaged in asymmetric three‐centre bonds, the fourth in a moderately strong and approximately linear two‐centre bond. The crystal packings consist of anion monolayers that intercalate planar zigzag rows of cations propagating around symmetry centres (Cs···Cs alternatingly 422.5 and 487.5 pm, Cs···Cs···Cs 135.7°; N···N alternatingly 397.4 and 474.1 pm, N···N···N 136.1°). Each cation row is surrounded by and bonded to four translation‐generated anion stacks, and each anion stack connects two cation rows. The net effect is that the packings display congruent three‐dimensional networks of metal‐ligand bonds or hydrogen bonds, respectively. Moreover, close C—H···O/N interanion contacts consistent with weak hydrogen bonding are observed in both structures.     

The effect of methyl group on the cooperativity between three types of hydrogen bond: O?H···O,C?H···O,and O?H···π

The effect of the methyl group on the cooperativity between three types of hydrogen bond (O H···O, C H···O, and O H···π) in cyclic complex involving an acetylene and two waters has been studied on the basis of high-level ab initio calculations. The total interaction energy of three hydrogen bonds increases as the number of methyl group in the complex increases. The binding distances of O H···π and O H···O hydrogen bonds shorten, while that of C H···O hydrogen bond elongates with increasing methyl group. This indicates that addition of methyl group leads to enhancement of O H···π and O H···O hydrogen bonds, and weakening of C H···O hydrogen bond, as also shown in frequency shift, chemical shifts, charge populations, and stabilization energies of orbital interactions. Although the presence of methyl group has a complicated effect on different type of hydrogen bond, the cooperativity of three hydrogen bonds increases in general with the addition of methyl group. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

[μ‐N,N′‐Bis(2‐amino­ethyl)­oxamidato(2–)]­bis­[(4,5‐di­aza­fluoren‐9‐one)­perchloratocopper(II)] 4,5‐di­aza­fluoren‐9‐one disolvate

The title compound, [Cu₂(C₆H₁₂N₄O₂)(ClO₄)₂(C₁₁H₆N₂O)₂]·2C₁₁H₆N₂O, contains a dinuclear copper(II) complex which lies about a twofold axis at the mid‐point of the C—C bond of the ox­amide ligand that bridges the two Cu^II atoms. The Cu·Cu distance is 5.215 (2) Å and the Cu atoms have distorted octahedral coordination geometry. Intramolecular N—H·O and N—H·N hydrogen bonds and intermolecular C—H·O hydrogen bonds, together with π–π stacking interactions, dominate throughout the crystal structure.     

Synthesis and characterization of copper(II) complexes with 3-methylpicolinic acid. Crystal and molecular structure of bis (3-methylpicolinato- N,O )(4-picoline)copper(II)

Copper(II) complexes of 3-methylpicolinic acid (3-MepicH), namely [Cu(3-Mepic)₂] · 2H₂O (1) and [Cu(3-Mepic)₂(4-pic)] (2) were prepared and characterized by IR spectroscopy and thermal analysis (TGA/DTA). Crystal structure for 2 was determined by X-ray crystal structure analysis. 1 was prepared by reaction of copper(II) sulfate pentahydrate and 3-methylpicolinic acid in aqueous solution, while 2 was prepared by recrystallization of 1 from 4-picoline solution. Structure analysis revealed square-pyramidal copper(II) coordination and N,O-chelating mode of 3-methylpicolinic acid in 2. Copper(II) is coordinated by two 3-Mepic ligands in the basal plane of a square pyramid and by 4-picoline in the apical position. Crystal packing of 2 is dominated by weak intermolecular C–H ··· O hydrogen bonds and π ··· π stacking interactions forming a complex three-dimensional supramolecular architecture.     

Supramolecular hexagonal structure of a segmented liquid crystalline polyester with allyl group as lateral substituent

The molecular structure of the phase—stable at room temperature—for the polymer with formula [ p C₆H₄ COO p C₆H₃(R) p C₆H₃(R) OOC p C₆H₄ O (CH₂)₁₀O ]_x, with R =  CH₂ CHCH₂, is reported. The cell is hexagonal (a = b = 13.43 Å, c = 33.3 Å, γ = 120°), space group P6₃, six chains per unit cell (d_calcd = 1.23 g cm⁻³). The six chains are packed together to give a bundle with the center of mass set at the origin of the unit cell. The allyl groups are placed inside the bundle, thus explaining the unexpected reactivity of the double bonds to give crosslinking when fiber samples are annealed in the solid state. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1601–1607, 1999     

Crystal Structures of [Cu2(bpy)2(H2O)(OH)2(SO4)]·4H2O and [Cu(bpy)(H2O)2]SO4 with bpy = 2, 2′‐Bipyridine

Two sulfato Cu^II complexes [Cu₂(bpy)₂(H₂O)(OH)₂(SO₄)]· 4H₂O ( 1 ) and [Cu(bpy)(H₂O)₂]SO₄ ( 2 ) were synthesized and structurally characterized by single crystal X—ray diffraction. Complex 1 consists of the asymmetric dinuclear [Cu₂(bpy)₂(H₂O)(OH)₂(SO₄)] complex molecules and hydrogen bonded H₂O molecules. Within the dinuclear molecules, the Cu atoms are in square pyramidal geometries, where the equatorial sites are occupied by two N atoms of one bpy ligand and two O atoms of different μ₂—OH groups and the apical position by one aqua ligand or one sulfato group. Through intermolecular O—H···O and C—H···O hydrogen bonds and intermolecular π—π stacking interactions, the dinuclear complex molecules are assembled into layers, between which the hydrogen bonded H₂O molecules are located. The Cu atoms in 2 are octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two H₂O molecules and two sulfato groups with the sulfato O atoms at the trans positions and are bridged by sulfato groups into ¹[Cu(bpy)(H₂O)₂(SO₄)_2/2] chains. Through the interchain π—π stacking interactions and interchain C—H···O hydrogen bonds, the resulting chains are assembled into bi—chains, which are further interlinked into layers by O—H···O hydrogen bonds between adjacent bichains.     

A Co(III) complex with a tridentate amine-imine-oxime ligand from 1,2,3,4-tetrahydroquinazoline: synthesis,crystal structure,spectroscopic and thermal characterization

A cobalt(III) complex [Co(L)₂]Cl · PPO · H₂O (1) (HL = 1-(2-aminobenzylimino)-1-phenyl-propan-2-one oxime, PPO = 1-phenyl-1,2-propanedione-2-oxime) has been synthesized and characterized by elemental analyses, spectral, thermal, magnetic and molar conductance measurements and single crystal X-ray diffraction. It crystallizes in the monoclinic crystal system, space group P2₁/c. Complex 1 consists of one uncoordinated water, one 1-phenyl-1,2-propanedione-2-oxime molecule, one bis[1-(2-aminobenzylimino)-1-phenyl-propan-2-one oxime]cobalt(III) cation and one uncoordinated chloride. The coordination geometry around Co is slightly distorted octahedral, completed with six nitrogens of two L^? ligands. The oxime moieties have E configurations. In the crystal structure, intramolecular O–H···Cl and N–H···O and intermolecular N–H···O, O–H···Cl and N–H···Cl hydrogen bonds link the molecules into chains parallel to the c axis; hydrogen-bonded PPO molecules fill the spaces between the chains and stabilization of the structure.     

(R)‐(6,6′‐Dihydroxybiphenyl‐2,2′‐diyl)bis(diphenylphosphine oxide) methanol solvate

The title compound, C₃₆H₂₈O₄P₂·CH₄O, was synthesized directly from the methoxy analogue. The crystal structure shows that one OH group interacts with an O atom of a phosphine oxide group in an adjacent mol­ecule, while the other OH group complexes with the methanol solvent molecule via intermolecular hydrogen bonds. An O atom of one phosphine oxide group interacts with the hydroxy H atom of methanol via a hydrogen bond. There are intra‐ and intermolecular π–π interactions between the phenyl rings. All these interactions result in the formation of supramolecular chiral parallelogram channels via self‐assembly.     

Synthesis,X‐ray powder structure analysis and biological properties of a mononuclear Cu(II) complex of N‐2‐hydroxyhippuric acid

A mononuclear copper (II) complex of N‐2‐hydroxyhippuric acid (2HHA), [Cu(HA)(H₂O)₂], has been synthesized and characterized by spectroscopic and X‐ray powder diffraction studies. Crystal structure of [Cu(HA)(H₂O)₂] reveals a distorted square‐pyramidal geometry around the metal center. The crystal packing in the complex exhibits a three‐dimensional framework formed by intermolecular O? ; H···O and C? H···O hydrogen bonds. Toxicity and antitumor properties of the complex have been studied in vivo. The complex, capable of depleting glutathione (GSH) at nontoxic doses, may be utilized to sensitize drug‐resistant cells where resistance is due to an elevated level of GSH. Copyright © 2009 John Wiley & Sons, Ltd.     

Structurally characterized dinuclear zinc(II) bis(salamo)‐type tetraoxime complex possessing square pyramidal and trigonal bipyramidal geometries

A novel dinuclear Zn(II) complex with the chemical formula [Zn₂(L)(OCH₃)] has been synthesized by a bis(salamo)‐type tetraoxime ligand based on 3‐bromo‐5‐chlorosalicylicaldehyde, and characterized by elemental analyses, IR, UV–vis, and fluorescent spectra, and single‐crystal X‐ray diffraction analysis. All the Zn(II) atoms are pentacoordinated by N₂O₂ donor atoms from the (L)³⁻ unit and one oxygen atom from one μ₂‐methoxyl group. The Zn(II) (Zn1 and Zn4) atoms have distorted square pyramidal geometries (τ₁ = 0.458, τ₄ = 0.388), whereas the Zn2 and Zn3 atoms adopt trigonal bipyramidal (τ₂ = 0.675, τ₃ = 0.550) geometries. The Zn(II) complex is self‐assembled by intermolecular C H···O interactions to form an infinite three‐dimensional supramolecular structure. Interestingly, the intermolecular C H···π interactions in the Zn(II) complex is involved not in the formation of three‐dimensional structures but rather in the formation of the 0D dimer structure. Meanwhile, the optical properties of the Zn(II) complex were also measured and are discussed.     

A Self-Assembled 3D Hydrogen Bonded Network Constructed from Polyoxovanadate and Protonated Organic Substrate With a Solvent Hydrolysis Reaction

A self-assembled 3D hydrogen bonded network constructed from polyoxovanadate and organic substrate [V₁₀O₂₈][(CH₃)₂NH₂]₄(imidazolium)₂ (1) has been synthesized at room temperature and characterized by elemental analysis, IR and single-crystal X-ray diffraction. The structure of 1 can be regarded as being linked by the dimethylammonium cations of the decavanadate clusters to produce an interesting 3D network with a 4¹²6³ topology. In the resulting network, there exist one-dimensional channels along the a-axis, in which the imidazolium cations filled the channels. These imidazolium cations are involved in intermolecular hydrogen bonds of the types N–H···O and C–H···O, which seem to be main forces to stabilize the holistic structure.