Two heterometal-organic coordination polymers with chelidamic acid: Syntheses, structures and optical properties

Two heterometal-organic coordination polymers with chelidamic acid ligands, [AgNd(C₇H₃NO₅)₂·3H₂O]_n (1) and 0.75H₃O·[K_0.25Nd(C₇H₃NO₅)₂·3H₂O]·1.75H₂O (2), have been synthesized and characterized by X-ray single-crystal diffraction. The crystal structure of 1 features that chelating units composed of one Nd(III) ion and two tridentate chelating chelidamic acid ligands are connected by the Ag(I) ions to form a one-dimensional chain, further linked by hydrogen bonds into a 3D network. As for 2, discrete independent molecules, made up of Nd(III) and K(I) ions and chelidamic acid ligands, are linked through the hydrogen bonds to form a 1D chain, which are further inter-linked through the complex hydrogen bonds to form a 3D network. The optical properties of 1 and 2 were investigated in terms of fluorescent spectra, which both exhibit good luminescence.     

Four novel Co(II) and Mn(II) coordination polymers with triazolyl derivate: Syntheses, crystal structures and magnetic properties

Four novel coordination polymers, one-dimensional chains [M(PTE)₂(N₃)₂]_n (M = Mn for 1 and Co for 2), and two-dimensional layers [M(PTE)₂(dca)₂]_n (M = Mn for 3 and Co for 4) (PTE = 1-(2,4-difluorophenyl-2-(1H-1,2,4-triazol-1-yl)ethanone, dca = dicyanamide anion, N(CN)₂⁻), have been synthesized under mild ambient conditions and structurally characterized by single crystal X-ray diffraction. In all four crystal structures, the metal atoms adopt octahedral coordination geometry with six nitrogen atoms from two monodentate PTE ligands and four azido (or dca) bridging ligands. The crystal structures of 1 and 2 are isostructural 1-D polymeric chains, alternatively linked by double end-on and double end-to-end azido bridges. However, the bent dca ligands as bidentate μ₂-1,5 bridging ligands interlink the octahedral metal units to lead to 2-D (4,4) grid networks in 3 and 4. Temperature-dependent magnetic measurements in 2-300 K have been performed for these four polymers, and suggest alternative ferro- and antiferromagnetic couplings for end-on and end-to-end azido bridges in 1, and the dominant ferromagnetic coupling in 2, respectively. Both polymers 3 and 4 show weak antiferromagnetic exchanges through the μ₂-1,5-dca bridges. The effects of auxiliary coligands on the structure and the nature of these magnetic exchanges are discussed in the light of the crystal structures in detail.     

Investigation on the coordination modes: Syntheses, characterization and crystal structures of diorganotin (IV) dichloride with 4(5)-imidazoledithiocarboxylic acid

A series of diorganotin (IV) complexes of the types of R₂SnCl(SSCC₃H₃N₂) (R = CH₃1, ⁿBu 2, C₆H₅3 and C₆H₅CH₂4), R₂Sn(SSCC₃H₃N₂)₂ (R = CH₃5, ⁿBu 6, C₆H₅7 and C₆H₅CH₂8) and R₂Sn(SSCC₃H₂N₂) (R = CH₃9, ⁿBu 10, C₆H₅11 and C₆H₅CH₂12) have been obtained by reactions of 4(5)-imidazoledithiocarboxylic acid with diorganotin (IV) dichlorides in the presence of sodium ethoxide. All complexes are characterized by elemental, IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectra analyses. Also, the complexes 1, 7 and 9 are characterized by X-ray crystallography diffraction analyses, which reveal that the complex 1 is monomeric structure with five-coordinate tin (IV) atom, the complex 7 is monomeric structure with six-coordinate tin (IV) atom and the complex 9 is one-dimensional chain with five-coordinate tin (IV) atom.     

Two novel three-dimensional coordination polymers based on metal clusters: Hydrothermal syntheses, crystal structures and luminescence

Two novel coordination polymers with interesting supramolecular architecture, [Zn₂(OH)(BTC)(bix)] (1) and [Cd₂(CDC)₂(bix)₂] (2) (H₃BTC = 1,3,5-benzenetricarboxylic acid, H₂CDC = trans-1,4-cyclohexanedicarboxylic acid and bix = 1,2-bis(imidazol-1-ylmethyl)benzene) have been obtained via hydrothermal reaction and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Complex 1 features a 3D network with one of the scarce (3,8)-connected (4³)₂(4⁶.6¹⁸.8⁴) topology based on the rare CdI₂-type layer constructed from secondary building units (SBUs) of zinc clusters. While 2 exhibits a scarcely reported eight-connected 3⁶.4¹⁶.5⁶ net with dinuclear cadmium clusters as secondary building units. The luminescent properties of 1 and 2 along with the bix ligand in the solid state were investigated.     

Novel cup-like helical coordination polymers: synthesis, crystal structures and thermal properties

By the design of ligand 1,1^′-(1,5-pentamethylene)bis-1H-benzimidazole (pbbm), we have synthesized polymers {[Co(NO₃)(pbbm)₂]NO₃ · 1/2H₂O}_n (1), {[CdCl(pbbm)₂]Cl · CH₃OH}_n (2) and {[Cu(Ac)₂(pbbm)] · CH₃OH}_n (3), and characterized their structures by single crystal X-ray diffraction as well as thermoanalysis. In polymers 1 and 2, one of the anions coordinates to the central ion, the other is located in the environment. Two pbbm ligands coordinate simultaneously to two metal centers generating one-dimensional cup-like helical chains. To our best knowledge, this cup-like structure has never been observed in the reported polymers. In polymer 3, each Cu atom is five-coordinate by two nitrogen atoms from two pbbm ligands, and three oxygen atoms from one monodentate acetate anion and one chelating acetate anion leading to one-dimensional wave-like linear chain. In addition, the DTA and TG results of the three polymers are in agreement with the crystal structures.     

Two cadmium-thiocyanate coordination polymers with organic cations: Synthesis, crystal structures and luminescent properties

Two new inorganic-organic hybrid polymers [ClBzQl]₂[Cd(SCN)_3.5Br_0.5]·0.25H₂O (1) and [ClBzMePy][Cd(SCN)₃] (2) (ClBzQl = 1-(4′-Cl-benzyl)quinolinium cation and ClBzMePy = 1-(4′-Cl-benzyl)-2-methylpyridinium cation) have been synthesized and characterized by IR, UV, elemental analysis and X-ray crystallography. Crystal structure analyses show that two polymers belong to the monoclinic space group P2/n (1) and P2₁/c (2) with a = 18.548(2) Å, b = 9.526(1) Å, c = 20.689(2) Å, β = 94.008(1)°, V = 3646.6(5) Å³ for 1, and a = 11.195(2) Å, b = 16.415(3) Å, c = 10.751(2) Å, β = 102.930(3)°, V = 1925.7(7) Å³ for 2. The Cd atom exhibits a distorted octahedral coordination geometry for 1 and 2. For 1, a pair of 1,1-μ-SCN⁻ anions and a pair of 1,3-μ-SCN⁻ anions are alternately bridge adjacent Cd centers to form infinite polymeric chains. For 2, adjacent Cd atoms are linked by three 1,3-μ-SCN⁻ anions to form infinite [Cd(SCN)₃⁻]_∞ polymeric chains. The luminescent properties of the two polymers in the solid state at room temperature were investigated.     

One-dimensional Zn(II) oligo(phenyleneethynylene)dicarboxylate coordination polymers: Synthesis, crystal structures, thermal and photoluminescent properties

The rigid, π-conjugated dicarboxylic acid 1,4-bis-[2-(4-carboxyphenyl)ethynyl]-2,5-dihexylbenzene {HO₂C[PEP(hexyl)₂EP]CO₂H} has been used to synthesise the new crystalline coordination polymers {Zn(O₂C[PEP(hexyl)₂EP]CO₂)(DMF)₂} (1) and {Zn(O₂C[PEP(hexyl)₂EP]CO₂)(DEF)₂} (2) in N,N-dimethylformamide (DMF) and N,N-diethylformamide (DEF), respectively, under mild conditions. Single-crystal X-ray crystallography revealed that 1 and 2 are isostructural and consist of uncharged zigzag coordination chains in which [Zn(formamide)₂]²⁺ fragments are bridged by (O₂C[PEP(hexyl)₂EP]CO₂)²⁻ ligands. The zigzag chains possess different intra-chain Zn?Zn?Zn angles due to the different volumes of the coordinating formamide molecules and subtle differences in the hydrophobic inter-chain interactions. Upon heating 1 and 2 to 200 °C, removal of the coordinating formamide molecules occurs, yielding the formamide-free compounds 1-DMF and 2-DEF of composition {Zn(O₂C[PEP(hexyl)₂EP]CO₂)}. According to powder X-ray diffraction and FT-IR spectroscopy studies, these materials are not crystalline but still possess partial ordering of intact, yet modified coordination chains in a structural arrangement which appears to be related to the respective parent compounds. Compounds 1, 2, 1-DMF and 2-DEF exhibit blue photoluminescence. The emission maxima of 1-DMF and 2-DEF are red-shifted by ca. 25 nm with respect to λ_max of 1 and 2, respectively.     

Lanthanide(III) coordination polymers from the exo-coordination of Na: Syntheses, structures, luminescence, and decay dynamics

[Na₂[Ln₂(sal)₄(CF₃SO₃)₂(H₂O)₄](CF₃SO₃)₂]_n Ln = Nd (1) and Eu (2) were synthesized from the reaction of salicylaldehyde, lanthanide(III) triflates, and sodium hydroxide. The compounds are iso-structural and possess a 2-D supramolecular network built up from discrete dinuclear Ln(III) units [Ln₂(sal)₄(CF₃SO₃)₂(H₂O)₄] via exo-coordination of Na(CF₃SO₃). The sal ligands display μ₂-O coordination modes involving both the phenolic and carbonyl oxygen atoms while the triflates function as both μ₂ and μ₃ bridges. Each Ln(III) in the network is eight coordinate and in bicapped trigonal prism coordination geometry. Luminescence from [Na₂[Eu₂(sal)₄(CF₃SO₃)₂(H₂O)₄](CF₃SO₃)₂]_n showed temperature dependent sensitized emission with significant quadrupolar contribution and decay dynamical studies followed single exponential kinetics. Together these results indicate that in the presence of Na⁺ ions, sal, and triflate are useful ligands in the construction of Ln(III) coordination polymers with unusual luminescence and structures.     

Hydrothermal synthesis and crystal structures of two lanthanide coordination polymers with novel tetradentate-coordinated perchlorates

Two new 3D lanthanide coordination polymers {[Ln(C₂O₄)(ClO₄)(H₂O)] · Cl}_n [Ln = Pr (1) and Nd (2)] have been synthesized by hydrothermal reactions and characterized by elemental analysis, X-ray single-crystal analyses, IR and Raman spectroscopy. X-ray crystal structure analyses reveal that compounds 1 and 2 are isostructural and crystallized in the space group P2₁/c. A 1D zigzag chains formed by oxalate ligands in μ₂-mode to bridge Ln(III) atoms present in the two complexes and the adjacent zigzag chains were further connected by μ₃-η¹:η¹:η¹:η¹ fashion of into a 3D framework with ordered 1D channels, in which uncoordinated Cl⁻ anions are located as counterions. In addition, the IR and Raman spectrum further confirm the presence of tetradentate-coordinated perchlorates.     

One-dimensional azido-bridged chiral copper(II) coordination polymers: Syntheses, structures and magnetic studies

Two new one-dimensional azido-bridged chiral copper(II) coordination polymers, [(μ-1,1,3-N₃)₂{Cu₂(R-L)₂(N₃)₂}]_n (1) (R-L = R-2-(N-(2-hydroxybutyl)carbaldimino) pyridine) and [(μ-1,1,3-N₃)₂{Cu₂(S-L)₂(N₃)₂}]_n (2) (S-L = S-2-(N-(2-hydroxybutyl)carbaldimino)pyridine) have been synthesized and structurally characterized. Complexes 1 and 2 crystallize in the monoclinic chiral space group P2₁. For 1, with a = 6.9565(17) Å, b = 20.675(5) Å, c = 9.859(2) Å, β = 105.944(5)° and Z = 2. In the case of compound 2, a = 6.9650(17) Å, b = 20.705(5) Å, c = 9.878(2) Å, β = 105.941(4)° and Z = 2. Both complexes consist of one-dimensional chiral structures in which the copper(II) ions with a distorted octahedral geometry are interlinked by the unusual μ-1,1,3 azido ligands. Circular dichroism spectra demonstrate that 1 and 2 are a pair of enantiomers. Their magnetic properties have been studied. Fitting of the susceptibility data for 1 and 2 using the Bleany-Bowers expression derived from the isotropic spin-exchange Hamiltonian H = −2JS₁S₂ leads to the parameters g = 2.21, J = −2.06 cm⁻¹, zJ′ = −0.0309 cm⁻¹ and R = 4.0 × 10⁻⁴.     

Syntheses and characterizations of two lanthanide(III)-copper(II) coordination polymers constructed by pyridine-2,6-dicarboxylic acid

The hydrothermal reaction of La₂O₃ and Pr₂O₃ with pyridine-2,6-dicarboxylic acid (H₂pydc), CuO, and H₂O with a mole ratio of 1:2:4:300 resulted in the formation of two polymeric Cu(II)-Ln(III) complexes, [{Ln₄Cu₂(pydc)₈(H₂O)₈} · 18H₂O]_n (Ln = La (1); Pr (2)). 1 and 2 are isomorphous and crystallize in monoclinic space group C2/c. Complexes 1 and 2 have one-dimensional infinite chains with “∞” shape. The 1D chains are linked by the hydrogen bonds and π?π stacking interactions to form layer structures which are further linked by the hydrogen bonds and π?π stacking interactions to form the three-dimensional (3D) structures with nanoscale porosities. Temperature-dependent magnetic susceptibilities and the thermal stabilities of complexes 1 and 2 were studied.     

Syntheses, structures, and properties of novel one dimensional copper cyanide coordination polymers

Three new one-dimensional copper coordination polymers have been prepared and fully characterized by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and magnetic susceptibility measurements. The structure of [Cu(CN)₂(bpy)] (1) (bpy = 2,2-bipyridyl) (monoclinic P2₁/c, a = 8.9761(7) Å, b = 16.731(1) Å, c = 8.0224(6) Å, β = 114.437(1)°) consists of Cu(II) metal centers coordinated by three cyanide ligands and chelated by one bpy to form the monomers Cu(CN)₃(bpy) with distorted square pyramidal geometry. Each monomer shares two cyanide ligands with two adjacent monomers to form infinite -Cu(II)-CN-Cu(II)-CN-Cu zigzag chains along the c-axis. The one-dimensional structure of [Cu(CN)(bpy)] (2) (hexagonal P3₂, a = 14.4883(6) Å, b = 12.921(1) Å) is built of tetrahedral Cu(CN)₂bpy metal complexes in which Cu(I) metal centers are coordinated by one nitrogen and one carbon from two different CN ligands, and two nitrogens from one bpy. The two CN ligands act as bridging ligands between adjacent monomers to form helical chains along the 3₂ screw axis. The crystal structure of [Cu₂Cl(CN)(bpy)] (3) (orthorhombic Pbca, a = 17.853(2) Å, b = 6.9724 (9) Å, c = 18.7357 (9) Å) consists of two monomers, CuCl₂(CN) and Cu(bpy)(CN) that share a cyanide ligand to form Cu₂Cl₂(CN)(bpy) dimers. The dimers link to each other by sharing Cl ligands leading to the formation of infinite Cu-Cl-Cu chain decorated by the complex Cu(CN)(bpy). Variable-temperature magnetic measurement shows an overall ferromagnetic behavior for compound 1. The magnetic pathway of compound 1 is through the cyanide bridge connecting apical and equatorial positions of adjacent copper (II) ions.     

New yttrium(III) and copper(II) coordination polymers with partially protonated cyclohexane-1,2,3,4,5,6-hexacarboxylato ligands: Synthesis, crystal structures and properties

Two coordination polymers, [Y(H₂O)₄(H₃chhc)]·6H₂O (1) and [Cu₅(H₂O)₁₀(Hchhc)₂]·4H₂O (2) with H₆chhc = cyclohexane-1,2,3,4,5,6-hexacarboxylic acid) represent rare examples of metal complexes with partially protonated cyclohexane-1,2,3,4,5,6-hexacarboxylato ligands. The [Y(H₂O)₄]³⁺ units in 1 are interlinked by the triprotonated (H₃chhc)³⁻ anions in a η⁵μ₄ bridging mode to form 2D (4³)₂(4⁶·6⁶·8³) topological networks, which are stacked along [0 1 0] direction in ···ABAB··· fashion with the lattice H₂O molecules sandwiched between layers. The pentameric [Cu₅(H₂O)₁₀]¹⁰⁺ units in 2 are bridged by monoprotonated (Hchhc)⁵⁻ anions in a η⁸μ₆ fashion to generate a 3D MOF of an unprecendented (4³)(4⁵·6⁷·8³) topology with the lattice H₂O molecules in channels. The temperature-dependent magnetic susceptibility data of 2 could be modeled to a combination of a linear chain of equally-spaced Cu(II) ions (J₁ = 1.86 cm⁻¹) with an isosceles triangular Cu₃ unit (J₂ = 5.86 cm⁻¹).     

Syntheses,structures and properties of three novel coordination polymers with a flexible asymmetrical bridging ligand

Three novel coordination polymers with different structural motifs, [Ag(pmtmb)]_n (1), [Cd(pmtmb)₂(H₂O)]_n (2) and [Cu(pmtmb)₂]_n (3), have been synthesized with a flexible asymmetrical bridging ligand, 4-(2-pyrimidylthiomethyl)benzoic acid (Hpmtmb). X-ray diffraction analyses show that 1 is a 2D layer containing unusual zigzag Ag chains based on mixed ligand-supported and ligand-unsupported Ag–Ag interactions, 2 is a necklace structure that further linked through hydrogen bonding to form a 2D sheet, and 3 is a 3D compact framework full assembled from 1D centipede-like chains via π–π stacking interactions. Interestingly, the ligand pmtmb adopts different configurations and coordination modes in the solid structures of these complexes. Furthermore, three complexes exhibit remarkable thermal stability and the complexes 1 and 2 exhibit intense green and purple luminescence, respectively.     

Syntheses and crystal structures of dimethyltin (IV) derivatives with 2,6-pyridinedicarboxylic acid

A novel cyclic dimethyltin complex [Me₂Sn(2,6-pdc)]₃ (1) (2,6-pdc = 2,6-pyridinedicarboxylate) was synthesized by the reaction of dimethyltin (IV) dichloride and 2,6-pyridinedicarboxylate acid in methanol under solvothermal conditions (150 °C). However, under room temperature (25 °C), we obtained a ladder complex [Me₂Sn(2,6-pdc)]₂(MeOH)₂ (2). Characterization of complexes 1 and 2 was achieved using elemental analysis, IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectra and X-ray diffraction. X-ray data of 1 revealed that it was an unusual cyclic complex with a discrete cyclotrinuclear unit, in which the 12-membered cyclic cavity is almost completely planar. X-ray data of 2 showed that it was a ladder complex, in which a crystallizing methanol molecule is found in each formula unit.     

Syntheses and crystal structures of trimethyltin(IV) coordination polymers based on mixed ligands of 5-nitroisophthalate and 2,2′(4,4′)-bipy or phen

The trimethyltin(IV) polymer [(Me₃Sn)₂(nip) · EtOH]_n (1) of 5-nitroisophthalic acid (H₂nip) and its three derivatives with mixed organic N-donor ligands 2,2′-bipy [(Me₃Sn)₂(nip) · 2H₂O] · [(Me₃Sn)₂(nip) · H₂O] · 2(2,2′-bipy) (2) 4,4′-bipy {[(Me₃Sn)₂(nip)]₂(4,4′-bipy)}_n (3) or phen [(Me₃Sn)₂(nip) · H₂O] · (phen) (4) have been synthesized by the reaction of trimethyltin(IV) chloride and H₂nip when sodium ethoxide was added in the presence of 2,2′-bipy 4,4′-bipy or phen. All complexes 1–4 were characterized by elemental, IR, ¹H, ¹³C, and ¹¹⁹Sn NMR spectroscopy and X-ray crystallography analyses. Crystal, data collection and structure refinement parameters for complexes 1, 2, 3 and 4 are shown in Table 1, Table 2, respectively. The X-ray data showed the geometries of all the tin atoms in complexes 1–4 are trigonal bipyramidal. The X-ray analysis of 1 showed that the structure was a polymeric infinite chain with neighboring triorganotin centers being linked by dicarboxylate ligands and hydrogen bonds were found between adjacent chains. For 2, two different monomers were found, in one monomer, Me₃Sn were coordinated to both carboxyl groups of the ligand and water molecules were coordinated to the two Sn(IV) centers. In the other monomer, water molecules were coordinated to only one Sn center. Co-crystallized2,2′-bipy was found in 2 and a 2D supermolecular structure was formed via O–H⋯O and O–H⋯N (N atoms derived from 2,2′-bipy) hydrogen bonds. In 3 however, a 2D polymeric block was formed due to the inversion center of the 4,4′-bipy. For 4, due to the O–H⋯O and O–H⋯N (N atoms derived from phen) hydrogen bonds and intermolecular Sn⋯O bonds, a 2D polymeric structure was formed.     

Hydroxylation of isophthalic acid in the hydrothermal reaction of Cu-isophthalate system - Syntheses and crystal structures of two coordination polymers

The reaction of isophthalic acid (H₂ip) and copper nitrate under hydrothermal condition produced an in situ synthesized ligand 2-hydroxy isophthalic acid (or 2,6-dicarboxyl phenol, H₃ipO) derived from H₂ip without the presence of N-heterocyclic ligands. The hydroxylation was controlled by the temperature of hydrothermal synthesis. Two coordination polymers, {[Cu₅(OH)₂(ip)(ipO)₂] · (H₂O)}_n (1) and [Cu₃(ipO)₂(H₂O)₂]_n (2) were synthesized and characterized by X-ray crystallography, IR spectra and elemental analyses. Complex 1 was assembled with both the original ligand and the in situ synthesized ligand.     

Syntheses, crystal structures and properties of a series of 3D cadmium coordination polymers with different topologies

Hydrothermal reactions of 2-, 3-, 4-cyanopyridine, NaN₃ with CdCl₂ in basified solvents yielded three coordination polymers [Cd₃(2-pytta)₂(N₃)₄(H₂O)₂]_n (1), [Cd(3-pytta)₂]_n (2), [Cd₃(4-pytta)₂(N₃)₂Cl₂(H₂O)₄]_n (3). A similar reaction of tetrazole as ligand and the CdCl₂ being replaced by CdI₂ resulted in polymer [Cd₂(tta)₃I]_n (4). X-ray single crystal structural analyses revealed that four compounds all show three-dimensional architectures. Complex 1 exhibits rare 3,4,4-connected 3-nodal with (3.9²)₂(3.9⁴.10)(3².9³.10) network in the Schäfli notation, while complex 2 is an anatase net with 3,6-connected (4².6)₂(4⁴.6².8⁸.10) network. Complex 3 is 3,3,4,4-connected 4-nodal network with (4.10²)₂(4².10⁴)(4².6.10².12)₂(4².6)₂ topology, and complex 4 can be simplified as an interesting alpha-Po network. The solid emission spectra of 1, 2, 3 and 4 have also been studied. From the results, it can be found complex 4 exhibits a long triplet lifetime that is unusual in Cd^II complexes.     

Cobalt(II) coordination polymers assembled from polycarboxylate and benzotriazole: Syntheses, structures and physical properties

Hydrothermal reactions of cobalt(II) salt with H₂CAM or H₂SDBA and HBTA in the presence of NaOH afford two interesting coordination polymers, Co₃(CAM)₂(BTA)₂ (1) and Co₃(SDBA)₂(BTA)₂ (2) (H₂CAM = camphoric acid, H₂SDBA = 4,4′-dicarboxybiphenyl sulfone, HBTA = benzotriazole), both of which have been structurally characterized by single-crystal X-ray, elemental analysis, infrared spectroscopy, and thermogravimetric analysis. Complexes 1 and 2 are isostructural and possess two-dimensional covalent network, comprising an unusual linear Co(II) chains of mixed T_d-O_h-T_d geometries. Temperature-dependent magnetic measurements indicate the existence of antiferromagnetic interactions in both 1 and 2.     

Syntheses and crystal structures of di- and trimethyltin (IV) derivatives with phenylphosphonic acid

Three types of methyltin phosphonates, {[(CH₃)₃Sn]₄(O₃PPh)₂}_n (1), {[(CH₃)₃Sn]₂(O₃PPh) · CH₃OH}_n (2) and {[(CH₃)₂SnO₃PPh]₄}_n (3) were synthesized by the reaction of phenylphonic acid with trimethyltin (IV) chloride and dimethyltin (IV) dichloride, respectively. Complexes 1, 2 and 3 were characterized by elemental analysis, IR, NMR (¹H, ¹³C, ³¹P and ¹¹⁹Sn) spectroscopy, TGA and X-ray crystallography diffraction analysis. The X-ray analysis of complex 1 shows that the structure is a polymeric infinite 1D zigzag chain. In complex 2, the oxygen atom of methanol molecule is coordinated to the tin atoms, and a 2D network is generated via O–H?O hydrogen bonds. In complex 3, a novel 2D network containing 12-membered (Sn₃O₆P₃) rings is formed.