Self-assembly syntheses and crystal structures of triphenyltin(IV) phenylphosphate: A 1D polymer and a dimer of 24-membered macrocycle

Two novel organotin(IV) complexes of the types [(Ph₃Sn)₄(O₃POPh)₂]_n 1 and [(Ph₃Sn)₆(O₃POPh)₃]₂ 2 have been prepared by treatment of phenylphosphoric acid and the Ph₃SnCl under different conditions. The complexes 1 and 2 were characterized by elemental analysis, IR and NMR (¹H,¹³C,¹¹⁹Sn) spectroscopy and X-ray crystallography diffraction analysis. The structure analyses reveal that complex 1 is an infinite 1D polymer and complex 2 is a dimer which contains two 24-membered macrocycles.     

Syntheses, Characterization and Crystal Structures of Diorganotin(IV) Selenites: 1D Helical Double-Chain Containing Eight-Membered Sn2O4Se2 Inorganic Ring

Three new diorganotin(IV) selenites, [Bu₂Sn(O₂SeC₆H₅OMe)₂]_n (1), [Me₂Sn(O₂SeC₆H₄CHMe₂)₂]_n (2), [Me₂Sn(O₂SeC₆H₄Et)₂]_n (3) have been synthesized and structurally characterized by elemental analysis, FT-IR, NMR (¹H, ¹³C and ¹¹⁹Sn) spectra, TGA, and X-ray crystallography. The X-ray reveals that complexes 1–3 are 1D infinite double-chain polymers. The molecular of complex 1 is further linked by intermolecular C–H···O interactions to form a 2D network polymer. Complex 3 is linked by C–H···O interactions to form a 3D organotin framework.     

Synthesis and Structures of Two Triorganotin(IV) Polymers R3Sn{O2CC6H4[N=C(H)}{C(CH3)CH(CH3)-3-OH]-p} n (R = Me and Ph) Containing a 4-[(2Z)-(3-Hydroxy-1-methyl-2-butenylidene)amino] benzoic Acid Framework

Two new polymeric triorganotin(IV) complexes R₃Sn{O₂CC₆H₄[N=C(H)}{C(CH₃)CH(CH₃)-3-OH]-p} _n ([Me₃Sn(LH)] _n : 1) and ([Ph₃Sn(LH)] _n : 2) containing a 4-[(2Z)-(3-hydroxy-1-methyl-2-butenylidene)amino]benzoate (LH) framework were prepared. Both compounds have been characterized by ¹H, ¹³C, ¹¹⁹Sn NMR, IR and ¹¹⁹Sn Mössbauer spectroscopic techniques in combination with elemental analyses. The crystal structures of complexes 1 and 2 reveal that they exist as polymeric zig-zag chains in which the LH-bridged Sn-atoms adopt a trans-R₃SnO₂ trigonal bipyramidal configuration with R groups in the equatorial positions and the axial sites occupied by an oxygen atom from the carboxylate ligand and the alcoholic oxygen atom of the next carboxylate ligand in the chain. The carboxylate ligands coordinate in the zwitterionic form with the alcoholic proton moved to the nearby nitrogen atom.     

Synthesis and Structural Characterization of Triorganotin(IV) Derivatives with 2,2′-Thiodiglycolic Acid and 3,3′-Thiodipropionic Acid

The synthesis and structural characterization of four novel triorganotin(IV) complexes, {(R₃Sn)₂[C₂H₄S(COO)₂]} _n (R = Me: 1), {(R₃Sn)₄[C₂H₄S(COO)₂]₂} _n (R = nBu: 2), {(R₃Sn)₂[C₄H₈S(COO)₂]} _n (R = Me: 3; nBu: 4) were obtained by the reaction of 2,2′-thiodiglycolic acid, 3,3′-thiodipropionic acid and the corresponding R₃SnCl (R = Me, nBu) with potassium hydroxide in methanol. All the complexes were characterized by elemental analysis, Fourier transform infrared and nuclear magnetic resonance (¹H, ¹³C, ¹¹⁹Sn) spectroscopies, X-ray crystallography and thermogravimetric analyses. The crystal structures show that 1 has 2D network structure in which 2,2′-thiodiglycolic acid acts as a tetradentate ligand coordinating to the trimethyltin(IV) ions. Complexes 2, 3, and 4 are 3D metal-organic framework structures in which the deprotoned acids act as a tetradentate ligand afforded by four oxygen atoms.     

Schiff pentadentate ligands based on an [ON2O2] core displaying structural isomerism and their coordination to dibutyltin moieties

Two tin compounds [Sn(ⁿBu)₂(Lⁿ)], where L¹{O(C₆H₄-2-NC(H)C₆H₄-2′-O)₂}^2 − and L²{O(C₆H₄-2-C(H)NC₆H₄-2′-O)₂}^2 − enclosing five electron donors in an [ON₂O₂] core, were synthesized and structurally characterized by infrared and NMR spectroscopy and by single crystal X-ray crystallographic studies at room temperature. The hepta-coordinate geometry around the Sn centers is achieved through the bonding of two monodentate n-butyl groups and the coordination of the pentadentate Lⁿ ligands, where the [ON₂O₂] core is forming a pentagonal base. The two types of oxygen atoms displayed different bonding situations around the Sn atom. DFT calculations with Gaussian 09 using PBEPBE/6-31G**/SDD level were carried out for both compounds. The topological analysis indicated that bond critical points are present along the SnO_ether direction.     

Syntheses,structures and luminescence of two cadmium entangled coordination polymers based on bis(imidazole) and biscarboxylate ligands

Two entangled coordination polymers [Cd₂(bib)(bdc)₂]_n (1) and [Cd₂(bib)(bda)₂]_n (2) were synthesized by the hydrothermal reaction (bib = 1,4-bis(2-methyl-imidazol-1-yl)butane, bdc = 1,2-benzenedicarboxylate, bda = 1,4-benzenediacetate). 1 exhibits an unusual 6-connected self-catenated 3D network based on Cd₂(COO)₂ dimer with the point symbol of (4⁴·6¹⁰·8). 2 exhibits a 3-fold interpenetrating 3D pcu network based on Cd₂(COO)₂ dimer. The different conformations of bib ligands (the anti–anti–anti conformation in 1 and gauche–anti–gauche conformation in 2) play the key role in the construction of different structures in 1 and 2. The luminescence and thermal stability were investigated.     

Synthesis,crystal structures and urease inhibitory activity of copper(II) complexes with Schiff bases

Two thiocyanate-coordinated Schiff base copper(II) complexes, [CuL¹(NCS)] (1) and [Cu₂(L¹)₂(μ_1,3-NCS)₂]_n (2), where L¹ and L² are the deprotonated forms of 4-bromo-2-[(2-propylaminoethylimino)methyl]phenol (HL¹) and 2-ethoxy-6-[(2-propylaminoethylimino)methyl]phenol (HL²), respectively, have been prepared and structurally characterized. Single crystal X-ray diffraction indicates that 1 is a mononuclear copper(II) complex, while in 2, the adjacent two complex molecules are linked through two phenolate O atoms, forming a dimer. The dimers in 2 are further weakly linked through end-to-end thiocyanate bridges to form a two-dimensional sheet. The Cu atom in 1 is four-coordinate in a square planar geometry, and that in 2 is six-coordinate in an octahedral geometry. Complex 1 shows strong urease inhibitory activity, while complex 2 shows no activity.     

New host–guest supramolecular coordination polymers based on [(Me3Sn)3Fe(CN)6]n with alkali metal iodides and their applications as electrode materials in batteries

The metal iodides reduce partially the host coordination polymer of the type $ ^{ 3}_{\infty } \left[ {\left( {{\text{Me}}_{ 3} {\text{Sn}}} \right)_{ 3} {\text{Fe}}\left( {\text{CN}} \right)_{ 6} } \right] $ , I, to give new host–guest supramolecular coordination polymers (SCP). The physical and chemical characteristics of the new products were studied by elemental analyses, X-ray powder diffraction, IR, UV/Vis, and solid state NMR spectra. The host–guest SCP are [M_x(Me₃Sn)₃Fe_(1–x)^IIIFe _x ^II (CN)₆]_n M = Li⁺·2H₂O, 1; Li⁺, 2; Na⁺, 3; K⁺, 4; Cu⁺, 5, [Li(Me₃Sn)₃Fe^II(CN)₆]_n, 6 and [(LiDEE)_0.9(Me₃Sn)₃Fe _o.1 ^III Fe _o.9 ^II (CN)₆]_n, 7. The stoichiometry and nature of the guest depend on the type of the metal iodide and the reaction conditions. The polymeric nature of these SCP is due to the presence of trigonal bipyramidal configured structure which bridges between the single d-transition metal ions. The host–guest SCP containing the Li ions have been tested as electrodes to construct four different lithium-ion batteries.     

Reactivity of bisthiosemicarbazones with Sn(II) and Sn(IV): The synthesis and structure of an eight-coordinate complex with two bis(thiosemicarbazone) ligands

Reaction of SnCl₂ with the bisthiosemicarbazone ligand ATSMH₂ led to the formation of the octahedral tin(IV) complex [Sn(ATSM)Cl₂] (1) comprising one doubly deprotonated ligand occupying the equatorial positions and two axial chlorides. Reaction with SnI₄ gave [Sn(ATSM)₂] (2), containing two doubly deprotonated ligands giving a distorted dodecahedral geometry. The complexes were characterised by elemental analysis, mass spectrometry, ¹³C and ¹¹⁹Sn CP/MAS NMR and in the case of complex 2 by X-ray diffraction.     

The dimeric and two-dimensional copper(II) complexes constructed from salicylic acid and 4,4′-bipyridine

Two novel complexes, [Cu₂(Hsal)₄(4,4^′-bipyridine)(H₂O)₂(DMF)₂] (1) (H₂sal=salicylic acid) and {[Cu(Hsal)₂(4,4^′-bipyridine)](H₂O)(H₂sal)}_n (2), were synthesized by layered-solution method and structurally characterized. Geometries of copper atoms in both complexes exhibit square pyramidal. Complex 1 is a dimer and hydrogen bonds between water and DMF molecules extend the structure into 1D hydrogen bonding network. Complex 2 consists of two-dimensional square framework structure.     

New Organotin/CuCN/Quinazoline 3D-Supramolecular Coordination Polymers Having Catalytic and Luminescence Activities

The new bimetallic supramolecular coordination polymers (SCP); ³ _∞[Cu(CN)₂·Me₃Sn·qaz], 1 and ³ _∞[Cu₂(CN)₄·(Ph₃Sn)₂·qaz], 2 (qaz?=?quinazoline), are prepared in water/acetonitrile solvent at room temperature. The structure of 1 consists of the anionic Cu(CN)₂ building blocks connected by the Me₃Sn cations to form zigzag chains which are bridged by qaz creating 2D-sheets. The interwoven infinite sheets are arranged in parallel A···A···A fashion developing 3D-network structure via H-bonds, π–π stacking, and Cu–C contacts. The network structure of 2 exhibits two different copper sites forming two Cu(CN)₂ building blocks which are connected by the Ph₃Sn groups constructing elongated corrugated chains. The qaz ligand connects these chains forming 3D-network structure containing the rhombic [Cu₂(μ₃-CN)₂] motif. 1 and 2 are luminescent materials which can be used in applications as molecular sensing systems. Also, the catalytic activity of 1 and 2 was investigated towards the degradation of Metanil Yellow (MY) dye by dilute solution of hydrogen peroxide as oxidant.     

The synthesis and structure of [Sn(NMe2)3Li]∞; an unsolvated polymeric tris(amido)stannate

The reaction of Sn(NMe₂)₂ with LiNMe₂ (1:1 equiv.) gives [Sn(NMe₂)₃Li]_∞ (1). The complex is the simplest tris(amido)stannate to be structurally characterised and the first in which there is no Lewis base solvation of the alkali metal cation; as a result a polymeric structure is obtained in which the stannate anions are involved in bidentate and monodentate coordination of the Li⁺ cations.     

Novel Supramolecular Square Grid-Like Structure: Synthesis and Characterization of [(Me3Sn)2CrO4]

Reactions of K₂Cr₂O₇ and K₂CrO₄ with Me₃SnCl yielded [(Me₃Sn)₂CrO₄] (1) and [(Me₃Sn)₂CrO₄?(Me₃SnOH)] (2), respectively, which were characterized by elemental analysis, ¹H-NMR spectroscopy, and an X-ray diffraction study. Compound 1 shows a novel square grid-like structure consisting of CrO₄ ^2? and Me₃Sn⁺ ions, whereas 2 exhibits a three-dimensional structure composed of CrO₄ ^2?, Me₃Sn⁺, and [(Me₃Sn)₂SnOH]⁺ ions.     

Role of spacers and substituents in the self-assembly process: Syntheses and characterization of two novel thiocyanatocuprates polymers

Two novel cation-induced complexes, {(Phen-dq) [Cu₂(SCN)₄]}_n (1) and {(Phen-dzp) [Cu₂(SCN)₄]}_n (2) [Phen-dq = (C₁₄H₁₂N₂)²⁺, 5,6-dihydropyrazino[1, 2, 3, 4-lmn]-1, 10-phenanthrolinium, Phen-dzp = (C₁₅H₁₄N₂)²⁺, 6,7-dihydro-5H-[1, 4]diazepino[1, 2, 3, 4-lmn][1,10]phenanthroline-4, 8-diium], have been synthesized via the self-assembly reaction in solution. The compound 1 possesses a two-dimensional supramolecular network linked by bridging thiocyanate groups. Complex 2 is also a two-dimensional polymeric architecture with the organic cation Phen-dzp trapped in it. Each Cu(I) atom is coordinated by two N atoms and two S atoms from four NCS groups to form a Cu₂(NCS)₂ rectangular dimer unit. In these two compounds, thanks to the difference from organic cations, the simple modification from Phen-dq to Phen-dzp leads to distinct structures between 1 and 2, and these “planar” cations are effective guests to manipulate the aggregate structure of thiocyanatocuprates.     

An unprecedented 2D isopolymolybdate with (3·4)(3·5·8)(3·4·5·6·8)(3·4·5·6) topology

A novel two-dimensional molybdenum oxide polymer, [Mo₄O₁₃]_n · 2nH₃O, has been prepared under specific hydrothermal conditions and characterized by IR spectroscopy and TG analysis. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a (3, 4, 5, 6)-connected 2D layer structure with (3²·4)(3²·5³·8)(3·4²·5⁴·6·8²)(3⁴·4³·5⁴·6⁴) topology, which is constructed by two parallel molybdenum oxide dimeric chains (Mo₂O₁₀)_n bound together by the dimer of Mo₂O₉ subunits via the sharing of corners. Additionally, the electrochemistry activity of compound 1 is also reported.     

Hydrothermal synthesis of two new zinc coordination polymers with mixed ligands

The hydrothermal reactions of zinc acetate with 1,2,4,5-benzenetetracarboxylic anhydride (btc) and 4,4^′-bipyridine (4,4^′-bpy) for [Zn₂(4,4^′-bpy)(btc)(H₂O)₂]_n·2nH₂O (1) or imidazole (imi) for [Zn₂(imi)₄(btc)(H₂O)₂]_n (2) in the molar ratio of 1:1:1:2000 at 170 °C for five days led to the formation of colorless crystals of 1 and 2. The btc ligand acts as a four-dentate bridging ligand in both compounds to link up zinc atoms into linear chain architectures. In 1, the linear chain subpolymers are further interlinked into a lamellar framework via 4,4^′-bpy ligands. Finally, both 1 and 2 are extended into three-dimensional framework via hydrogen bonding.     

Solvothermal Synthesis and Crystal Structure of a Novel 3D Triorganotin Polymer Containing Polyfunctional Ligand 5-mercapto-1(H)-tetrazoleacetic acid

A novel 3D tri-n-butyltin complex [(n-Bu₃Sn)₂(C₂H₂N₄SCO₂)]_n (1) has been solvothermally synthesized and structurally characterized by elemental analysis, FT-IR, NMR (¹H, ¹³C, and ¹¹⁹Sn) spectra and X-ray crystallography. X-ray data of complex 1 reveals that it is a 3D tri-n-butyltin coordination polymer with a metal-organic framework (MOF) structure , significant N → Sn interactions plays an important role in the construction of this structure.     

Synthesis,characterization and catalytic activity of a new sandwich-type tungstophosphate functionalized by carboxyethyltin

Reaction of the trivacant Keggin-type tungstophosphate (A-α-Na₉PW₉O₃₄⋅ 7H₂O, abbreviated as {PW₉}) with estertin (Cl₃Sn(CH₂)₂COOCH₃) in an acetate buffer solution leads to the formation of a new sandwich-type tungstophosphate functionalized by carboxyethyltin, Na₃K₈[K₃{Sn(CH₂)₂COO}₂(A-α-PW₉O₃₄)₂]·18H₂O (1). The title compound was characterized by single crystal X-ray diffraction, elemental analysis, IR, TG, PXRD, ¹³C, ³¹P and ¹¹⁹Sn NMR. Structural analysis reveals that the basic skeletal structure of 1 is made up of two [Sn(CH₂)₂COO]^2 + groups and three K⁺ ions sandwiched by two A-α-[PW₉O₃₄]^9 − building blocks, which shows the original estertin precursors hydrolyzed into carboxyethyltin. The catalytic activity of 1 has been investigated.     

Novel 3-dimensional sixfold interpenetrating diamondoid networks of copper(I) coordination polymers of polypyridyl ligands – Syntheses,characterization and crystal structures

Two new coordination polymers [Cu(L¹)₂]_n(ClO₄)_n·2nH₂O (1), [Cu(L²)₂]_n(ClO₄)_n·2nH₂O (2) of polydentate imine/pyridyl ligands, L¹ and L² with Cu(I) ion have been synthesized and characterized by single crystal X-ray diffraction studies, elemental analyses, IR′ UV–vis and NMR spectroscopy. They represent 3-dimensional, sixfold interpenetrating diamondoid network structures having large pores of dimension, 35 × 21 Å² in 1 and 38 × 19 Å² in 2, respectively.     

Construction of three Cd(II) coordination polymers based on extended pyridyl-tetrazolyl-bifunctional ligands: Structures and luminescent properties

Reactions of Cd(II) with three new pyridyl-tetrazole-bifunctional ligands, 3-(4-(1H-tetrazol-5-yl)phenyl)pyridine (HL¹), 4-(3-(1H-tetrazol-5-yl)phenyl)pyridine (HL²), and 3-(3-(1H-tetrazol-5-yl)phenyl)pyridine (HL³) resulted in three Cd(II) coordination polymers (CPs), namely, [CdL¹₂]_n (1), [CdL²₂]_n (2), and [CdL³₂(H₂O)]_n (3). Although the geometry of L¹ and L² is quite different, the coordination modes of Cd(II) ion and ligand, as well as the SBUs in compounds 1 and 2 are quite similar, thus give rise to 3D frameworks with same (3,6)-connected ant topology. Compound 3 is a 3D framework composed of 1D helical chains and features as (3,5)-connected tcj topology. The results showed that the topologies are largely dependent on the coordination angle between two coordination groups. The thermal stabilities and luminescent properties of compounds 1–3 have also been studied.