Cobalt(II) Complexes with N‐Thioacylamidophosphates and 2,2′‐Bipyridyl and 1,10‐Phenathroline. Crystal Structures,Solution 1H NMR Spectral and Magnetic Properties

Structure and magnetic properties of N‐diisopropoxyphosphorylthiobenzamide PhC(S)‐N(H)‐P(O)(OiPr)₂ ( HL^I ) and N‐diisopropoxyphosphoryl‐N′‐phenylthiocarbamide PhN(H)‐C(S)‐N(H)‐P(O)(OiPr)₂ ( HL^II ) complexes with the Co^II cation of formulas [Co{PhC(S)‐N‐P(O)(OiPr)₂}₂] ( 1 ), [Co{PhN(H)‐C(S)‐N‐P(O)(OiPr)₂}₂] ( 2 ), [Co{PhC(S)‐N(H)‐P(O)(OiPr)₂}₂{PhC(S)‐N‐P(O)(OiPr)₂}₂] ( 1a ) and [Co{PhC(S)‐N‐P(O)(OiPr)₂}₂}(2,2′‐bipy)] ( 3 ), [Co{PhC(S)‐N‐P(O)(OiPr)₂}₂(1,10‐phen)] ( 4 ), [Co{PhN(H)‐C(S)‐N‐P(O)(OiPr)₂}₂(2,2′‐bipy)] ( 5 ), [Co{PhN(H)‐C(S)‐N‐P(O)(OiPr)₂}₂(1,10‐phen)] ( 6 ) were investigated. Paramagnetic shifts in the ¹H NMR spectrum were observed for high‐spin Co^II complexes with HL^I,II , incorporating the S‐C‐N‐P‐O chelate moiety and two aromatic chelate ligands. Investigation of the thermal dependence of the magnetic susceptibility has shown that the extended materials 1‐2 and 6 show ferromagnetic exchange between distorted tetrahedral ( 1 , 2 ) or octahedral ( 1a , 6 ) metal atoms whereas 3 and 5 show antiferromagnetic properties. Compound 4 behaves as a spin‐canted ferromagnet, an antiferromagnetic ordering taking place below a critical temperature, T_c = 115 K. Complexes 1 and 1a were investigated by single crystal X‐ray diffraction. The cobalt(II) atom in complex 1 resides a distorted tetrahedral O₂S₂ environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. Complex 1a has a tetragonal‐bipyramidal structure, Co(O^ax)₂(O^eq)₂(S^eq)₂, and two neutral ligand molecules are coordinated in the axial positions through the oxygen atoms of the P=O groups. The base of the bipyramid is formed by two anionic ligands in the typical 1,5‐O,S coordination mode. The ligands are in a trans configuration.     

Crystal Structure of a Trinuclear Titanium(IV) Complex with (rac)‐3,3′‐Bis(methoxymethyl)‐BINOLate

Reaction of (rac)‐3,3′‐bis(methoxymethyl)‐BINOL [H₂(CH₃OCH₂)₂BINO] with excess Ti(OⁱPr)₄ and one equivalent of H₂O in CH₂Cl₂ affords a trinuclear titanium(IV) complex [{(CH₃OCH₂)₂BINO}Ti₃(μ₃‐O)(OiPr)₆(μ₂‐OiPr)₂]. By dissolving it in dichloromethane and hexane and cooling to 0 °C, plate‐like pale yellow single crystals (monoclinic, P2₁/n, a = 12.605(3), b = 21.994(5), c = 19.090(4) Å, β = 92.764(8)°, V = 5286.2(19) ų, T = 293(2) K) were obtained. Each oxygen atom at 2 or 2′ position of the (CH₃OCH₂)₂BINO ligand bonds to only one titanium atom. There is no interaction between the third Ti atom and the two oxygen atoms of 3,3′‐bis(methoxymethyl)‐BINOLate.     

How Does Substitutional Doping Affect Visible Light Absorption in a Series of Homodisperse Ti11 Polyoxotitanate Nanoparticles?

Homodisperse doped polyoxotitanate nanoclusters with formulae Ti₁₁(MX)O₁₄(OiPr)₁₇ (M=Mn, Fe or Co; X=Cl, Br or I, OiPr=isopropoxide) display strongly dopant‐dependent properties. Spectroscopic solution and reflectance measurements backed up by density of states and time‐dependent DFT calculations based on the determined structures, show the prominent effect of FeX substitution by decreasing the HOMO–LUMO gap of the particles. The effect is attributed to the presence of an occupied Fe β orbital halfway up the bandgap, leading to long‐wavelength absorption with electron transfer to the titanium atoms of the cluster. Whereas the light absorption varies significantly with variation of the transition metal dopant, its dependency on the nature of the halogen atom or the change in dipole moment across the series is minor.     

Rapid ring‐opening polymerization of 1,4‐dioxan‐2‐one initiated by titanium alkoxides

Ring‐opening polymerization of 1,4‐dioxan‐2‐one in bulk was initiated by three titanium alkoxides, titanium dichlorodiisopropoxide (TiCl₂(OiPr)₂), titanium chlorotriisopropoxide (TiCl(OiPr)₃), and titanium tetraisopropoxide (Ti(OiPr)₄). The results indicate that the polymerization rate increased with number of OiPr groups in the initiator. High conversion of monomer (90%) and high molecular weight (11.9 × 10⁴ g/mol) of resulting polymer can be achieved in only 5 min at 60 °C with Ti(OiPr)₄ as an initiator. Analysis on nuclear magnetic resonance (NMR) spectra suggests the initiating sites for TiCl₂(OiPr)₂, TiCl(OiPr)₃, and Ti(OiPr)₄ to be 1.9, 2.6, and 3.8, respectively. Coordination‐insertion mechanism for the polymerization via cleavage of the acyl–oxygen bonds of the monomer was proved by NMR investigation. Kinetic studies indicate that polymerization initiated by Ti(OiPr)₄ followed a first‐order kinetics, with an apparent activation energy of 33.7 kJ/mol. It is noteworthy that this value is significantly lower than earlier reported values with other catalysts, namely La(OiPr)₃ (50.5 kJ/mol) and Sn(Oct)₂ (71.8 kJ/mol), which makes it an attractive catalyst for reactive extrusion polymerization. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Influence of the lead carboxylate on the molecular composition of its solutions with zirconium and titanium isopropoxides or n-butoxides: 2-ethylhexanoate vs acetate, a way to stabilize the first Pb-Zr carboxylatoalkoxides of 1:1 stoichiometry

The reactions between titanium or zirconium alkoxides namely Ti(OR)₄ (R = ⁱ Pr, ⁿ Bu) or Zr₂(O ⁱ Pr)₈(HO ⁱ Pr)₂, Zr(O ⁿ Bu)₄ respectively and lead 2-ethylhexanoate Pb(O₂CC₇H₁₅)₂ were investigated at room temperature (rt) and by heating. The various compounds were characterized by elemental analysis, FT-IR, ¹H and ²⁰⁷Pb NMR. The mixed-metal species obtained at rt were adducts Pb₄Zr₄(μ-O₂CR′)₈(OR)₁₆(OHR)₂ 1 and Pb₂Ti₄(μ-O₂CR′)₄(OR)₁₆ 2 (R′=CHCHEt(CH₂)₂Me, R = ⁱ Pr) independently of the stoichiometry used. The structures of 1 and 2 are based on triangular M₂Pb cores (M = Zr, Ti). with 6-coordinate transition metals -as required for perovskites- and 6- or 7-coordinate lead atoms. Similar observations were made with n-butoxides. Thermal and hydrolytic condensation reactions were investigated. Thermal condensation was more difficult for the n-butoxide derivatives than for the isopropoxide ones. Powders derived from the hydrolysis of the Single Source Precursor 1 in various conditions were characterized by TGA, XRD and SEM for the PZ ceramic.     

[Pd8(CH3COO)8(NO)8]: solution from X‐ray powder diffraction data

The water‐insoluble title compound, octakis(μ‐acetato‐κ²O:O)­octakis(μ‐nitro­so‐κ²N:O)­octapalladium(II), [Pd₈(CH₃COO)₈(NO)₈], was precipitated as a yellow powder from a solution of palladium nitrate in nitric acid by adding acetic acid. Ab initio crystal structure determination was carried out using X‐ray powder diffraction techniques. Patterson and Fourier syntheses were used for atom locations, and the Rietveld technique was used for the final structure refinement. The crystal structure is of a molecular type. The skeleton of the [Pd₈(CH₃COO)₈(NO)₈] mol­ecule is con­structed as a tetragonal prism with Pd atoms at the vertices. The eight NO⁻ groups are in bridging positions along the horizontal edges of the prism. The N and O atoms of each nitro­so group coordinate two different Pd atoms. The vertical edges present Pd⋯Pd contacts with a short distance of 2.865 (1) Å. These Pd atoms are bridged by a pair of acetate groups in a cis orientation with respect to each other. The complex has crystallographically imposed 4/m symmetry; all C atoms of the acetate groups are on mirror planes. The unique Pd atom lies in a general position and has square‐planar coordination, consisting of three O and one N atom.     

Dinuclear Complexes of Copper(I) with Crown Ether‐containing N‐Thiophosphorylated Bis‐thioureas and 2,2′‐Bipyridine or 1,10‐Phenanthroline: Synthesis,Characterization, and Picrate Extraction Properties

Reaction of O,O′‐diisopropylthiophosphoric acid isothiocyanate (iPrO)₂P(S)NCS with 1,10‐diaza‐18‐crown‐6, 1,7‐diaza‐18‐crown‐6, or 1,7‐diaza‐15‐crown‐5 leads to the N‐thiophosphorylated bis‐thioureas N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 ( H₂L^I ), N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐18‐crown‐6 ( H₂L^II ) and N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐15‐crown‐5 ( H₂L^III ). Reaction of the potassium salts of H₂L^I–III with a mixture of CuI and 2,2′‐bipyridine ( bpy ) or 1,10‐phenanthroline ( phen ) in aqueous EtOH/CH₂Cl₂ leads to the dinuclear complexes [Cu₂(bpy)₂L^I–III] and [Cu₂(phen)₂L^I–III] . The structures of these compounds were investigated by ¹H, ³¹P{¹H} NMR spectroscopy, and elemental analysis. The crystal structures of H₂L^I and [Cu₂(phen)₂L^I] were determined by single‐crystal X‐ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(=CMe₂)CH₂P(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(S)NHP(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 towards the picrate salts LiPic, NaPic, KPic. and NH₄Pic were also studied.     

Coordination Mode of the Nickel(II) Cation with N‐Diisopropoxyphosphinyl‐p‐bromothiobenzamide

Reaction of the potassium salt of N‐diisopropoxyphosphinyl‐p‐bromothiobenzamide p‐BrC₆H₄C(S)NHP(O)(OiPr)₂ ( HL ) with Ni(NO₃)₂ in aqueous EtOH leads to complex of formula [Ni(HL‐O)₂(L‐O,S)₂] ( 1 ). The structure of 1 was investigated by single crystal X‐ray diffraction analysis, IR, ¹H and ³¹P{¹H} NMR spectroscopy, MALDI and microanalysis. The nickel(II) ion in 1 has a tetragonal‐bipyramidal environment, (O^ax)₂(O^eq)₂(S^eq)₂, with two neutral ligand molecules coordinated in axial positions through the oxygen atoms of the P=O groups. The equatorial plane of bipyramide is formed by two anionic ligands involving 1,5‐O,S‐coordination mode. The chelating ligands are bound in trans configuration.     

Structural Characterization of (Arylimido)vanadium(V) Compounds with 2,6‐Difluorophenoxide Ligand

The (arylimido)vanadium(V) compound, [(p‐MeOC₆H₄N)V(OiPr)₃] was demonstrated to undergo ligand exchange reaction with one or two equivalents of 2,6‐difluorophenol, affording the (arylimido)vanadium(V) compounds, [(p‐MeOC₆H₄N)V(OiPr)₂(O‐2,6‐F₂Ph)] and [(p‐MeOC₆H₄N)V(OiPr)(O‐2,6‐F₂Ph)₂]. Their X‐ray crystallographic analyses elucidated the μ‐isopropoxido‐bridged dimeric structures, wherein each vanadium atom has a trigonal‐bipyramidal arrangement with the imido and bridging isopropoxide ligands in the apical positions. The isopropoxide ligand was selectively employed as a bridging ligand between two central vanadium atoms. On the other hand, the reaction of the (arylimido)vanadium(V) compound, [(p‐MeOC₆H₄N)VCl₃] and three equivalents of lithium 2,6‐difluorophenoxide gave the (arylimido)vanadium(V) compound, [(p‐MeOC₆H₄N)V(O‐2,6‐F₂Ph)₃]. In the crystal packing, the thus‐obtained compound showed a distorted trigonal‐bipyramidal environment at the vanadium atoms with the μ‐phenoxido‐bridged dimeric structure, wherein the 2,6‐difluorophenoxide ligand was found to serve as a bridging ligand.     

Reactions of chlorotitanium tri-iso-propoxide with methanol and tributylamine

Reactions of TiCl(OⁱPr)₃ with methanol or tributylamine in heptane resulted in the formation of crystalline Ti₄Cl₂(μ₃-OMe)₂(μ₂-OMe)₄(OⁱPr)₈ and [Bu₃NH][Ti₂Cl₃(OⁱPr)₆], respectively. The solid state structures of both compounds are described.     

Cross‐linking of poly(methyl methacrylate) by oxozirconate and oxotitanate clusters

Radical polymerization of methyl methacrylate with 0.5‐2 mol% of the (meth)acrylate‐substituted oxozirconium and oxotitanium clusters Zr₆(OH)₄O₄(OMc)₁₂ (OMc = methacrylate), Zr₄O₂(OMc)₁₂, Ti₆O₄(OEt)₈(OMc)₈ and Ti₄O₂(OPrⁱ)₆(OAcr)₆ (OAcr = acrylate) results in an efficient cross‐linking of the organic polymers. The obtained inorganic‐organic hybrid polymers exhibit a higher thermal stability due to inhibited depolymerization reactions. Contrary to undoped poly(methyl methacrylate), the cluster cross‐linked polymers are insoluble but swell in organic solvents. The solvent uptake upon swelling decreases with an increasing amount of polymerized cluster. The impedance spectra of PMMA doped with various proportions of Zr₄O₂(OMc)₁₂ show that the capacitance of the polymers decreases with an increasing proportion of the cluster. The polymer doped with 2 mol% of Zr₄O₂(OMc)₁₂ shows an increase in conductivity to 0.9·10⁻⁷ S·cm⁻¹ at 74°C.     

Gallium and Indium Alkoxides with Hydride,Cyclopentadienediide and Copper(I) tert‐Butoxide as further Components

Gallium hydride stabilized by the base quinonuclidine reacts with acetone under addition of the Ga‐H function to the carbon–oxygen double bond yielding (HGa)₅(OiPr)₈O ( 1 ) as isolable compound. (HGa)₅(OiPr)₈O may be formally split in to four entities of HGa(OiPr)₂ and one entity HGaO. The inner atomic skeleton of 1 is a novel Ga₅O₉ heterocluster with gallium atoms occupying the corners of a distorted trigonal bi‐pyramid, an oxygen atom in the center and the remaining alcoholate oxygen atoms bridging eight of the nine edges of the bi‐pyramid (X‐ray diffraction analysis). Potassium indium alkoxide KIn(OtBu)₄ has been used to synthesize several new compounds like In₄(OtBu)₈(C₅H₄)₂ ( 2 ), (py)₂CuIn(OtBu)₄ ( 3 ), and [CuIn(OtBu)₄]₂ ( 4 ) by reaction with TiCl₂cp₂ ( 2 ) and CuCl ( 3 , 4 ). All compounds were characterized by spectroscopic means and by X‐ray structure analyses revealing novel polycyclic structures.     

Living cationic isomerization polymerization of β-pinene. III. Synthesis of end-functionalized polymers and graft copolymers

α-End-functionalized polymers and macromonomers of β-pinene were synthesized by living cationic isomerization polymerization in CH₂Cl₂ at −40°C initiated with the HCl adducts [ 1; CH₃CH(OCH₂CH₂X)Cl; X = chloride ( 1a ), acetate ( 1b ), and methacrylate ( 1c )] of vinyl ethers carrying pendant substituents X that serve as terminal functionalities. In conjunction with TiCl₃(OiPr) and nBu₄NCl, these functionalized initiators led to living β-pinene polymerization where the carbon–chlorine bond of 1 was activated by TiCl₃(OiPr). Similarly, end-functionalized poly(p-methylstyrene)-block-poly(β-pinene) were also obtained. ¹H-NMR analysis showed that the polymers possess controlled molecular weights (DP _n = [M]₀/[ 1 ]₀) and number-average end functionalities close to unity. The end-functionalized methacrylate-capped macromonomers form 1c were radically copolymerized with methyl methacrylate (MMA) to give graft copolymers carrying poly(β-pinene) or poly(p-methylstyrene)-block-poly(β-pinene) as graft chains attached to a PMMA backbone. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1423–1430, 1997     

Poly[μ8‐4,4′‐bipyridine‐2,2′,6,6′‐tetracarboxylato‐dilead(II)]

The Pb^II cation in the title compound, [Pb₂(C₁₄H₄N₂O₈)]_n, is seven‐coordinated by one N atom and six O atoms from four 4,4′‐bipyridine‐2,2′,6,6′‐tetracarboxylate (BPTCA⁴⁻) ligands. The geometric centre of the BPTCA⁴⁻ anion lies on an inversion centre. Each pyridine‐2,6‐dicarboxylate moiety of the BPTCA⁴⁻ ligand links four Pb^II cations via its pyridyl N atom and two carboxylate groups to form two‐dimensional sheets. The centrosymmetric BPTCA⁴⁻ ligand then acts as a linker between the sheets, which results in a three‐dimensional metal–organic framework.     

Poly[bis(μ‐benzene‐1,4‐dicarboxylato)bis[μ‐6‐(4‐pyridyl)‐5H‐imidazolo[4,5‐f][1,10]phenanthroline]dilead(II)]: an interpenetrating α‐Po net

The asymmetric unit of the title compound, [Pb₂(C₈H₄O₄)₂(C₁₈H₁₁N₅)₂]_n, contains two Pb^II atoms, two benzene‐1,4‐dicarboxylate (1,4‐bdc) dianions and two 6‐(4‐pyridyl)‐5H‐imidazolo[4,5‐f][1,10]phenanthroline (L) ligands. Each Pb^II atom is eight‐coordinated by three N atoms from two different L ligands and five carboxylate O atoms from three different 1,4‐bdc dianions. The two 1,4‐bdc dianions (1,4‐bdc₁ and 1,4‐bdc₂) show different coordination modes. Each 1,4‐bdc₁ coordinates to two Pb^II atoms in a chelating bis‐bidentate mode. Each carboxylate group of the 1,4‐bdc₂ anion connects two Pb^II atoms in a chelating–bridging tridentate mode to form a dinuclear unit. Neighbouring dinuclear units are connected together by the aromatic backbone of the 1,4‐bdc dianions and the L ligands into a three‐dimensional six‐connected α‐polonium framework. The most striking feature is that two identical three‐dimensional single α‐polonium nets are interlocked with each other, thus leading directly to the formation of a twofold interpenetrated three‐dimensional α‐polonium architecture. The framework is held together in part by strong N—H...O hydrogen bonds between the imidazole NH groups of the L ligands and the carboxylate O atoms of 1,4‐bdc dianions within different α‐polonium nets.     

A one‐dimensional mixed‐anion lead(II) coordination polymer: catena‐poly[[(1,10‐phenanthroline)lead(II)]‐μ‐benzoato‐μ‐nitrato‐[(1,10‐phenanthroline)lead(II)]‐di‐μ‐benzoato]

In the title polymeric compound, [Pb₂(C₇H₅O₂)₃(NO₃)(C₁₂H₈N₂)₂]_n, both independent Pb atoms adopt an eight‐coordinate geometry formed by one nitrate, three benzoate and one 1,10‐phenanthroline ligand. The one‐dimensional polymer consists of dimeric [Pb₂(C₇H₅O₂)₃(NO₃)(C₁₂H₈N₂)₂] units, in which all nitrate and benzoate ligands act in a bridging–chelating coordination mode.     

Assembly of a Wheel‐Like Eu24Ti8 Cluster under the Guidance of High‐Resolution Electrospray Ionization Mass Spectrometry

A building blocks strategy is an effective approach for constructing the large molecular systems. Herein, we demonstrate that high‐resolution electro‐spray ionization mass spectrometry (HRESI‐MS) provides an effective chance to insight the assemble process of the building blocks and guides the construction of high‐nuclearity metal clusters on the basis of the reaction of Ti(OⁱPr)₄, Eu(acac)₃, and salicylic acid. The time‐dependent HRESI‐MS indicates that not only a Eu₃Ti building block can be formed, but that it can further assemble into a Eu₂₄Ti₈ compound. Temperature‐dependent HRESI‐MS reveals that increase of the reaction temperature favors the formation and crystallization of the stable Eu₂₄Ti₈ structure. Single‐crystal structural analysis demonstrates that the Eu₂₄Ti₈ has a wheel‐like structure with diameter of ca. 4.1 nm and is the highest nuclearity lanthanide‐titanium oxo cluster reported to date.     

The Features of Interaction of Bis(4, 6‐di‐tert‐butyl‐N‐(2, 6‐diisopropylphenyl)‐o‐amidophenolato)tin(IV) with Bromine and Iodine

The oxidation of tin(IV) bis‐amidophenolate (APiPr)₂Sn · THF ( I ) by bromine and iodine leads to the formation of monoradical mixed‐ligand complexes (APiPr)(ISQiPr)SnBr · THF ( II ) and (APiPr)(ISQiPr)SnI · THF ( III ) or diradical complexes (ISQiPr)₂SnBr₂ ( IV ) and (ISQiPr)₂SnI₂ ( V ), respectively [APiPr = dianion 4, 6‐di‐tert‐butyl‐N‐(2, 6‐diisopropylphenyl)‐o‐amidophenolate; ISQiPr = radical‐anion 4, 6‐di‐tert‐butyl‐N‐(2, 6‐diisopropylphenyl)‐o‐iminobenzosemiquinone], depending on the molar ratio of reagents (2:1 or 1:1). According to EPR data for compounds II and III , the unpaired electron is delocalized between both organic ligands. The EPR spectrum of IV in toluene matrix at 130 K is typical for diradical species with S = 1 with parameters D = 530 G, E = 105 G. The mixed‐ligand complexes II and III are unstable and undergo to symmetrization leading to formation of IV or V . The molecular structures of IV and V are determined by X‐ray analysis.     

Poly[[tetra‐μ3‐acetato‐hexa‐μ2‐acetato‐diaqua‐μ2‐oxalato‐tetrapraseodymium(III)] dihydrate]

The title complex, {[Pr₄(C₂H₃O₂)₁₀(C₂O₄)(H₂O)₂]·2H₂O}_n, was synthesized under hydrothermal conditions from praseodymium acetate and the ionic liquid 1‐butyl‐3‐methylimidazolium chloride via an in situ oxalate‐ligand synthesis. The compound is a two‐dimensional polymer and in the structure presents tightly bound planes parallel to (100), which are in turn linked into a three‐dimensional network by hydrogen bonds involving both coordinated and solvent water molecules. The oxalate anion lies across an inversion centre and acts as a bridge between pairs of Pr atoms within a tetranuclear segment of the polymer.     

Two two‐dimensional MnII and NaI coordination polymers constructed by the flexible benzene‐1,4‐dioxy­acetate ligand

Two new two‐dimensional coordination polymers, poly­[[[aqua(2,2′‐bi­pyridine‐κ²N,N′)manganese(II)]‐μ₃‐p‐phenyl­enebis­(oxy­acet­ato)‐κ³O:O′:O′′] dihydrate], {[Mn(C₁₀H₈O₆)(C₁₀H₈N₂)(H₂O)]·2H₂O}_n, (I), and poly­[[di‐μ‐aqua‐bis­[aqua­sodium(I)]]‐μ₄‐p‐phenyl­enebis­(oxy­acetato)‐κO:O′,O′′:O′′′,O′′′′:O′′′′′], [Na₂(C₁₀H₈O₆)(H₂O)₄]_n, (II), have been synthesized and characterized by X‐ray single‐crystal diffraction. In (I), there are two 1,4‐BDOA²⁻ [p‐phenyl­enebis­(oxy­acetate) or, more commonly, benzene‐1,4‐dioxy­acetate] ligands, each lying about inversion centres, while in (II), there is one such ligand and it also has crystallographically imposed inversion symmetry. In (I), each Mn^II atom displays an octahedral MnN₂O₄ configuration, defined by three carboxyl O atoms of different 1,4‐BDOA²⁻ groups, two N atoms of one 2,2′‐bi­pyridine ligand and one water mol­ecule. In (II), each Na^I atom is octahedrally coordinated by one ether O atom, two carboxyl O atoms of different 1,4‐BDOA²⁻ ligands and three water mol­ecules. The metal ions in complexes (I) and (II) are bridged by 1,4‐BDOA²⁻ groups into two‐dimensional layer structures. Furthermore, three‐dimensional supramolecular networks are constructed via hydrogen bonds in (I) and (II), and by additional π–π stacking interactions in (I).