Dinuclear copper(II) perchlorate complexes with 6-(benzylamino)purine derivatives: Synthesis,X-ray structure,magnetism and antiradical activity

The reactions of Cu(ClO₄)₂·6H₂O with 6-(benzylamino)purine derivatives in a stoichiometric 1:2 metal-to-ligand ratio led to the formation of penta-coordinated dinuclear complexes of the formula [Cu₂(μ-L^1–8)₄(ClO₄)₂](ClO₄)₂·nsolv, where L¹ = 6-(2-fluorobenzylamino)purine (complex 1), L² = 6-(3-fluorobenzylamino)purine (2), L³ = 6-(4-fluorobenzylamino)purine (3), L⁴ = 6-(2-chlorobenzylamino)purine (4), L⁵ = 6-(3-chlorobenzylamino)purine (5), L⁶ = 6-(4-chlorobenzylamino)purine (6), L⁷ = 6-(3-methoxybenzylamino)purine (7) and L⁸ = 6-(4-methoxybenzylamino)purine (8); n = 0–4 and solv = H₂O, EtOH or MeOH. All the complexes have been fully characterized by elemental analysis, FTIR, UV–Vis and EPR spectroscopy, and by magnetic and conductivity measurements. Variable temperature (80–300 K) magnetic susceptibility data of 1–8 showed the presence of a strong antiferromagnetic exchange interaction between two Cu(II) (S = 1/2) atoms with J ranging from −150.0(1) to −160.3(2) cm⁻¹. The compound 6·4EtOH·H₂O was structurally characterized by single crystal X-ray analysis. The Cu?Cu separation has been found to be 2.9092(8) Å. The antiradical activity of the prepared compounds was tested by in vitro SOD-mimic assay with IC₅₀ in the range 8.67–41.45 μM. The results of an in vivo antidiabetic activity assay were inconclusive and the glycaemia in pre-treated animals did not differ significantly from the positive control.     

Fe Spin crossover materials based on dissymmetrical N4 Schiff bases including 2-pyridyl and 2R-imidazol-4-yl rings: Synthesis,crystal structure and magnetic and Mössbauer properties

The synthesis and characterization of new symmetrical Fe^II complexes, [FeL^A(NCS)₂] (1), and [FeL^Bx(NCS)₂] (2–4), are reported (L^A is the tetradentate Schiff base N,N′-bis(1-pyridin-2-ylethylidene)-2,2-dimethylpropane-1,3-diamine, and L^Bx stands for the family of tetradentate Schiff bases N,N′-bis[(2-R-1H-imidazol-4-yl)methylene]-2,2-dimethylpropane-1,3-diamine, with: R = H for L^B1 in 2, R = Me for L^B2 in 3, and R = Ph for L^B3 in 4). Single-crystal X-ray structures have been determined for 1 (low-spin state at 293 K), 2 (high-spin (HS) state at 200 K), and 3 (HS state at 180 K). These complexes remain in the same spin-state over the whole temperature range [80–400 K]. The dissymmetrical tetradentate Schiff base ligands L^Cx, N-[(2-R₂-1H-imidazol-4-yl)methylene]-N′-(1-pyridin-2-ylethylidene)-2,2-R₁-propane-1,3-diamine (R₁ = H, Me; R₂ = H, Me, Ph), containing both pyridine and imidazole rings were obtained as their [FeL^Cx(NCS)₂] complexes, 5–10, through reaction of the isolated aminal type ligands 2-methyl-2-pyridin-2-ylhexahydropyrimidine (R₁ = H, 5–7) or 2,5,5-trimethyl-2-pyridin-2-ylhexahydropyrimidine (R₁ = Me, 8–10) with imidazole-4-carboxaldehyde (R₂ = H: 5, 8), 2-methylimidazole-4-carboxaldehyde (R₂ = Me: 6, 9), and 2-phenyl-imidazole-4-carboxaldehyde (R₂ = Ph: 7, 10) in the presence of iron(II) thiocyanate. Together with the single-crystal X-ray structures of 7 and 9, variable-temperature magnetic susceptibility and Mössbauer studies of 5–10 showed that it is possible to tune the spin crossover properties in the [FeL^Cx(NCS)₂] series by changing the 2-imidazole and/or C2-propylene susbtituent of L^Cx.     

Synthesis and solid-state structural characterisation of Pt(II,IV) bromide complexes containing bidentate organothiomethylpyridine heteroleptic ligands

A convenient synthetic method for the preparation of organothiomethylpyridine ligands 2-(RSCH₂)C₅H₄N (R = Ph (L¹), Me (L²)), 2-MeS–6-Me-C₅H₃N (L³), and 2-MeS–4-Me-C₅H₃N (L⁴) via the initial lithiation of substituted 2-picolines followed by the nucleophilic reaction with a diorganyldisulfide is described. The complexes [PtBr₂L] (L = L¹–L⁴) have been prepared in good to high yields as yellow solids with low solubility in organic solvents. The solid state structures of the complexes have been determined, showing the spatial arrangement of the complexes to depend significantly upon varying substituents within the ligand. The complexes undergo oxidation by bromine to form the tetravalent complexes [PtBr₄(L)] (L = L¹–L⁴). The solid state structures of [PtBr₄(L²)] and [PtBr₄(L₄)] have been determined, and shown to be monomeric with the ligand chelating the platinum centre.     

Infinite chains constructed from flexible bis(benzimidazole)-based ligands

Two neutral ligands, L¹ · 2H₂O and L² · H₂O, and seven complexes, [Cu(pmb)₂(L¹)] (1), [Cu(pmb)₂(L²)] (2), [Cu(Ac)₂(L²)] · 4H₂O (3), [Cu(4-aba)₂(L²)] (4), [Ag(4-ts)(L¹)(H₂O)] (5), [Ag₂(epes)₂(L¹)] · 2H₂O (6), [Ag(1,5-nds)_0.5(L²)] · 0.5C₂H₅OH · H₂O (7) [where L¹ = 1,1′-(1,4-butanediyl)bis(2-methylbenzimidazole); L² = 1,1′-(1,4-butanediyl)bis(2-ethylbenzimidazole), pmb = p-methoxybenzoate anion; Ac = acetate anion; 4-aba = 4-aminobenzoate anion; 4-ts = p-toluenesulfonate anion; epes = N-(2-hydroxyethyl)piperazine-N′-(2-ethanesulfonate) anion; 1,5-nds = 1,5-naphthalenedisulfonate anion], have been synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. The L¹ and L² ligands in compounds 1–7 act as bridging ligands, linking metal ions into chain structures. The chains in compounds 3, 4 and 6 interlace with each other by hydrogen bonds to generate 3D supramolecular structures. In compound 5, π–π interactions between adjacent L¹ ligands hold the chains to a supramolecular layer. In compound 7, the sulfonate anions act as counterions in the framework. The thermal stabilities of 3, 6 and 7, and the luminescent properties for 5–7 in the solid states are also discussed.     

Controlled assembly of zero-, one- and two-dimensional metal-organic frameworks involving in situ ligand synthesis under different reaction pH

Five cadmium(II) metal-organic frameworks, namely [Cd(BIPA)(daf)(H₂O)₃] · 2H₂O (1), Cd₂(BDC)₂(pdon)₂(H₂O)₂ (2), Cd(BIPA)(pdon) (3), Cd(BIPA)(daf) (4) and [Cd₂(BIPA)₂(pdon)₂] · H₂O (5) (H₂BIPA = 5-bromoisophthalic acid, H₂BDC = terephthalic acid, pdon = 1,10-phenanthroline-5,6-dione, daf = 4,5-diaza-fluoren-9-one), have been constructed from cadmium(II) salts with multi-carboxylate ligands and pdon ligands under different reaction pH. The framework structures of these polymeric complexes have been determined by the X-ray single crystal diffraction technique. The differences of the five metal-organic frameworks demonstrate that the reaction pH has an important effect on the structure of these complexes. The thermal analyses of these five complexes have been measured and discussed. Additionally, four complexes show strong fluorescence in the solid state at room temperature.     

Part 1: 1,3-Dipolar addition of activated alkyne towards coordinated azido group in ruthenium(II) complexes containing η-cyclichydrocarbons

The indenyl and pentamethylcyclopentadienyl ruthenium(II) complexes [(η⁵-L₃)Ru(L₂)Cl] (L₃ = C₉H₇, L₂ = dppe (1a), L₂ = dppm (1b); L₃ = C₅Me₅, L₂ = dppe (2a); L₂ = dppm (2b) (where, dppe = Ph₂PCH₂CH₂PPh₂ and dppm = Ph₂PCH₂PPh₂) reacts with NaN₃ to yield the azido complexes [(η⁵-C₉H₇)Ru(L₂)N₃], L₂ = dppe (3a), dppm (3b) and [(η⁵-C₅Me₅)Ru(L₂)N₃], L₂ = dppe (4a), dppm (4b), respectively. The azido complexes undergo [3 + 2] dipolar cycloaddition reaction with dimethylacetylenedicarboxylate to yield triazole complexes [(η⁵-C₉H₇)Ru(L₂)(N₃C₂(CO₂Me)₂)], L₂ = dppe (5a), dppm (5b) and [(η⁵-C₅Me₅)Ru(L₂)(N₃C₂(CO₂Me)₂)], L₂ = dppe (6a), dppm (6b), respectively. The complexes were fully characterized on the basis of microanalyses, FT-IR and NMR spectroscopy. The crystal structures of the starting complex (1a) and representative complexes 5a, 5b and 6a have been established by single X-ray study.     

Synthesis and structural characterisation of five copper(I) and silver(I) complexes with 2-aminopyridine (2-APy), [Cu(μ-Cl)(2-Apy)(PPh3)]2, [Ag(μ-X)(2-Apy)(PPh3)]2 (X = Cl,Br), [Ag(μ-ONO2)(2-Apy)(EPh3)]2 (E = P,As)

Five new copper(I)/silver(I) complexes containing 2-aminopyridine, [Cu(μ-Cl)(2-Apy)(PPh₃)]₂(1), [Ag(μ-Cl)(2-Apy)(PPh₃)]₂(2), [Ag(μ-Br)(2-Apy)PPh₃)]₂(3), [Ag(μ-ONO₂)(2-Apy)(PPh₃)]₂(4), [Ag(μ-ONO₂)(2-Apy)(AsPh₃)]₂(5) have been synthesised for the first time. Complexes 1–5 are obtained by the reactions of MX (MX = CuCl for 1; M = Ag for 2–5; X = Cl, Br for 2–3; X = NO₃ for 4–5) with the monodentate ligands EPh₃ (E = P for 1–4; E = As for 5) and 2-Apy in the molar ratio of 1:1:2 in the mixed solvent of CH₂Cl₂ and MeOH. Complexes 1–5 are characterised by IR and X-ray diffraction. In 1–5, chloride, bromide and nitrate ions bridge two metal atoms to form dinuclear complexes containing the parallelogram cores M₂X₂ (M = Cu, Ag).     

Syntheses,supramolecular structures and properties of six coordination complexes based on 5-sulfosalicylic acid and bipyridyl-like chelates

Six new complexes constructed by 5-sulfosalicylic acid and bipyridyl-like ligands (2,2′-bipy and 1,10-phen), namely [Cu₄(OH)₂(ssal)₂(phen)₄ · 7H₂O] (1), [Cu₄(OH)₂(ssal)₂(bipy)₄ · 2H₂O] (2), [Cd(Hssal)(bipy)] (3), [Cd(HL)₂(phen)₂] (4), [Cr(ssal)(bipy)(H₂O)₂ · 2H₂O] (5) and [Cr(ssal)(phen)₂] (6) (H₃ssal = 5-sulfosalicylic acid, H₂L = p-hydroxybenzenesulfonic acid, bipy = 2,2′-bipy, phen = 1,10-phen) were prepared under hydrothermal conditions and their structures were determined by single-crystal X-ray diffraction. Complexes 1 and 2 are both tetranuclear copper complexes with a stepped topology. In complex 3, a new coordination mode of the Hssal²⁻ group is reported in this work. During the synthetic process of complex 4, in situ decarboxylation of 5-sulfosalicylic acid into p-hydroxybenzenesulfonic acid is involved. Two chromium 5-sulfosalicylates (5 and 6) are reported for the first time. These new complexes display different supramolecular structures by O–H?O, C–H?O hydrogen bonds as well as π?π, C–H?π and O?π interactions. The results of magnetic determination show that ferromagnetic interactions exist in complex 1, however, antiferromagnetic interactions exist in 2.     

Comparative structural study of the complexation behaviour of silver(I), cadmium(II), mercury(II), and palladium(II) with a 17-membered N3O2-donor macrocycle

A comparative investigation of the coordination behaviour of the 17-membered, N₃O₂-donor macrocycle, 1,12,15-triaza-3,4:9,10-dibenzo-5,8-dioxacycloheptadecane, L, with the soft metal ions Ag(I), Cd(II), Hg(II), and Pd(II) is reported. The X-ray structures of 12 complexes have been determined and a range of structural types, including both mononuclear and dinuclear species, shown to occur. In particular cases the effect of anion variation on the resulting structures has been investigated; L reacts with AgX (X = NO₃, ClO₄, PF₆, OTf and CN) to yield related 2:2 (metal:ligand) complexes of types [Ag₂L₂(NO₃)₂] (1), [Ag₂L₂](ClO₄)₂ · 2DMF (2), [Ag₂L₂](PF₆)₂ · 2DMF (3), [Ag₂L₂](OTf)₂ (4) and [Ag₂L₂(μ-CN)][Ag(CN)₂] · H₂O (5). In all five complexes the ether oxygens of each ring are unbound. In 1–4 the macrocycles are present in sandwich-like arrangements that shield the dinuclear silver centres, with each silver bonded to two nitrogen donors from one L and one nitrogen from a second L. A Ag···Ag contact is present between each metal centre such that both centres can be described as showing distorted tetrahedral geometries. In the case of 5 a rare single μ₂-κC:κC symmetrically bridging two-electron-donating cyano bridge links silver ions [Ag···Ag distance, 2.7437(10) Å]; the macrocyclic ligands are orientated away from the dinuclear metal centres. In contrast to the behaviour of silver, reaction of cadmium(II) perchlorate with L resulted in a mononuclear sandwich-like complex of type [CdL₂](ClO₄)₂ · CH₃CN (6). Again, the ether oxygens do not coordinate, with each L binding to the cadmium centre only via its three nitrogen donors in a facial arrangement such that a distorted octahedral coordination geometry is attained. Reaction of L with HgX₂ (X = ClO₄, SCN and I) yielded the monomeric species [HgL(ClO₄)₂] (7), [HgL(SCN)₂]·CH₃CN (8) and [Hg₂L₂](HgI₄)₂ · 2L (9), in which all five donors of L are bound to the respective mercury centres. However, reaction of L with Hg(NO₃)₂ in dichloromethane/methanol gave a mononuclear sandwich-like complex [HgL₂](NO₃)₂ · 2CH₃OH (10) without anion coordination. Reaction of K₂PdCl₄ and Pd(NO₃)₂ with L yielded the 1:1 complexes [PdLCl]Cl · H₂O (11) and [PdL(NO₃)]NO₃ · CH₃OH (12), respectively, in which the metal is bound to three nitrogen donors from L along with the corresponding chloride or nitrate anion. Each palladium adopts a distorted square-planar coordination geometry; once again the ether oxygens are not coordinated.     

New mercury(II) and cadmium(II) complexes with (p-methylbenzoyl)methylene triphenylphosphorane: Synthesis,spectroscopic and structural characterization

Reaction of Ph₃PCHCOC₆H₄Me (L), with HgX₂ and CdCl₂·H₂O in methanol with equimolar ratios give binuclear complexes of the type [MX(μ-X){CH(PPh₃)C(O)C₆H₄Me}]₂ (M = Hg; X = Cl (1), Br (2), I (3), M = Cd; Cl(4)). The bridge-splitting reaction of binuclear complexes [MX(μ-X){CH(PPh₃)C(O)C₆H₄Me}]₂ by dimethyl sulfoxide (DMSO) yields the mononuclear complexes [MX₂{CH(PPh₃)C(O)C₆H₄Me}(OSMe₂)] (M = Hg; X = Cl (5), Br (6), I (7), M = Cd; Cl (8)). The characterization of these complexes was carried out by elemental analysis and FT-IR, ¹H, ³¹P, and ¹³C NMR spectroscopies. C-coordination of ylide and O-coordination of DMSO are demonstrated by single-crystal X-ray analysis of mononuclear complex of [HgBr₂{CH(PPh₃)C(O)C₆H₄Me}(OSMe₂)] (6). Complex 6 is monomeric with tetrahedral geometry around the metal ion.     

Synthesis and spectral studies of cadmium(II) complexes derived from di-2-pyridyl ketone and N-phenylsemicarbazide: First structural report of a cadmium(II) complex of semicarbazone

A new semicarbazone (HL) based on di-2-pyridyl ketone and its three cadmium(II) complexes [CdL(CH₃COO)]₂ · 2CH₃OH (1), Cd(HL)Br₂ (2) and [Cd₂L₂N₃]₂ · H₂O (3) were synthesized and characterized by different physicochemical techniques. The complex, [CdL(CH₃COO)]₂ · 2CH₃OH (1) is having a dimeric structure. In complexes 1 and 3, the ligand moieties are coordinated as monoanionic (L⁻) forms and in complex 2, the ligand is coordinated as neutral (HL) one. The coordination geometry around cadmium(II) in 1 is distorted octahedral, as obtained by X-ray diffraction studies.     

Synthesis and characterization of new oxazoline-based palladacycles with bridging or terminal imidate ligands. Crystal structures of [{Pd(μ-dibromomaleimidate)(Phox)}2], [Pd(dibromomaleimidate)(Phox)(PPh3)] and [Pd(glutarimidate)(Phox)(PPh3)] (Phox = 2-(2-oxazolinyl)phenyl))

The dinuclear hydroxo complex [{Pd(μ-OH)(Phox)}₂] (I) (Phox = 2-(2-oxazolinyl)phenyl) reacts in a 1:2 molar ratio with several imidate ligands to yield new cyclometallated palladium complexes [{Pd(μ-NCO)(Phox)}₂] containing asymmetric imidate –NCO– bridging units. [–NCO– = succinimidate (succ) (1), phtalimidate (phtal) (2), maleimidate (mal) (3), 2,3-dibromomaleimidate (2,3-diBrmal) (4) and glutarimidate (glut) (5)]. The reaction of these complexes with tertiary phosphines provides novel mononuclear N-bonded imidate derivatives of the general formula [Pd(imidate)(Phox)(PR₃)] [R = Ph (a), 4-F–C₆H₄ (b) or CH₂CH₂CN (c)]. The new complexes were characterized by partial elemental analyses and spectroscopic methods (IR, FAB, ¹H, ¹³C and ³¹P). The single-crystal structures of compounds 4, 4a and 5a have been established.     

New triorganotin(IV) complexes of polyfunctional S,N,O-ligands: Supramolecular structures based on π?π and/or C-H?π interactions

A series of new triorganotin(IV) complexes with 4-hydroxy-2-mercapto-6-methylpyrimidine (L¹H₂), 4-hydroxy-2-mercapto-pyrimidine (L²H₂), 2,4(1H,3H)-pyrimidinedithione (L³H₂) (Scheme 1) of the type R₃SnLSnR₃ (R = Me 1, 4, 7; R = Ph 2, 5, 8; R = PhCH₂3, 6, 9) have been synthesized by reactions of triorganotin(IV) chloride and corresponding ligands. All complexes are characterized by elemental analyses, IR spectra and NMR spectra analyses. Among them, complexes 2, 5 and 8 are also characterized by X-ray crystallography diffraction analyses. Significant π?π stacking, C-H?π interactions and intramolecular hydrogen bonds stabilize these structures.     

Self-assembly of di- and triorganotin(IV) complexes: Syntheses, characterization and crystal structures of 1D polymeric chain containing O,O-diethyl or O,O-diisopropyl phosphoric acid ligands

A series of organotin(IV) complexes with O,O-diethyl phosphoric acid (L¹H) and O,O-diisopropyl phosphoric acid (L²H) of the types: [R₃Sn · L]_n (L = L¹, R = Ph 1, R = PhCH₂2, R = Me 3, R = Bu 4; L = L², R = Ph 9, R = PhCH₂10, R = Me 11, R = Bu 12), [R₂Cl Sn · L]_n (L = L¹, R = Me 5, R = Ph 6, R = PhCH₂7, R = Bu 8; L = L², R = Me 13, R = Ph 14, R = PhCH₂15, R = Bu 16), have been synthesized. All complexes were characterized by elemental analysis, TGA, IR and NMR (¹H, ¹³C, ³¹P and ¹¹⁹Sn) spectroscopy analysis. Among them, complexes 1, 2, 3, 5, 8, 9 and 11 have been characterized by X-ray crystallography diffraction analysis. In the crystalline state, the complexes adopt infinite 1D infinite chain structures which are generated by the bidentate bridging phosphonate ligands and the five-coordinated tin centers.     

Synthesis and electrochemical properties of bis(bipyridine)ruthenium(II) complexes bearing pyridinyl- and pyridinylidene ligands induced by cyclometalation of N′-methylated bipyridinium analogs

Ruthenium complexes with bipyridine-analogous quaternized (N,C) bidentate ligands [RuL(bpy)₂](PF₆)₂ (bpy = 2,2′-bipyridine, (1), L = L¹ = N′-methyl-2,4′-bipyridinium; (2), L = L² = N′-methyl-2,3′-bipyridinium) were synthesized and characterized. The structure of complex 2 was determined by the X-ray structure analysis. The ¹³C{¹H} NMR spectroscopic and cyclic voltammetric studies indicate that the coordination modes of these ligands are quite different, that is, the C-coordinated rings of (N,C)-ligands in 1 and 2 are linked to ruthenium(II) with a pyridinium manner and a pyridinylidene one, respectively. The ligand-localized redox potentials of 1 and 2 also revealed the substantial difference in the electron donating ability of both ligands.     

Synthesis,structure, thermal studies on Zn(II), Cd(II) complexes of N-(2-pyridylmethyl)pyridine-2-carbaldimine and N-(2-pyridylmethyl)pyridine-2-methylketimine

The bivalent zinc and cadmium complexes of two Schiff bases N-(2-pyridylmethyl)pyridine-2-carbaldimine (L1), N-(2-pyridylmethyl)pyridine-2-methylketimine (L2), tridentate ligands with an N₃ chromophore and coordinating with two five-membered chelate rings, were synthesized. Complexes [Zn(L1)(NO₃)₂] (1), [Zn(L2)(NO₃)₂] (2), [Cd(L1)(NO₃)₂(H₂O)] (3) and [Cd(L2)(NO₃)₂(CH₃OH)] (4) were characterized by X-ray crystallography. In 1 and 2, Zn(II) has a distorted square-pyramidal geometry where as in 3 and 4, Cd(II) possesses a pseudo-pentagonal-bipyramidal geometry. The following trends in the bond lengths are observed: M–N_im < M–N_py; Zn–N > Zn–O; Cd–N < Cd–O. The final residues from the thermogravimetric analysis are ZnO and CdO, the SEM studies revealed, respectively, their porous and spherical natures. The average activation energy (E) for the loss of pyridine rings obtained from the Friedman fitting of the DSC data, for 1, 2, 3, and 4 are 193.8(2), 114.5(3), 127.1(4), and 63.7(3) kJ mol⁻¹ and their logarithmic pre-exponential factor (A) are 11.22, 5.31, 6.88, and 2.09, respectively.     

Conversion of novel palladacycles into oxopyrrolo[3,4-b]quinolines

The quinolinylcyclopalladated complexes 3a–b were synthesised in good yields (81% and 77%) by the insertion reaction of the prepared dinuclear palladium complexes [Pd(C,N-2-C₉H₄N-CHO-3-R-6)Cl(PPh₃)]₂ [(R = H (2a), R = OMe (2b)] with isonitrile XyNC (Xy = 2,6-Me₂C₆H₃). The cyclopalladated complexes 3a–b were also obtained in low yields (39% and 33.5%) via a one pot oxidative addition reaction of quinoline chloride 1a–b with isonitrile XyNC:Pd(dba)₂ (4:1). The reactions of 3a–b with Tl(TfO) (TfO = triflate, CF₃SO₃) in the presence of H₂O or EtOH causes depalladation reactions of the complexes to provide the corresponding organic compounds 4a–b, 5a–b and 6a–b in yields (41%, 27% and 18–19%). The products were characterized by satisfactory elemental analyses and spectral studies (IR, ¹H, ¹³C and ³¹P NMR). The crystal structures of 2a, 3a and 3b were determined by X-ray diffraction studies.     

Solvothermal syntheses and crystal structures of new Cu(II) complexes with phenylsuccinic acid

Five new Cu(II) complexes [Cu(psa)(phen)] · 3H₂O (1), [Cu(psa)(2bpy)] · 0.5H₂O (2), [Cu(psa)(2bpy)(H₂O)] · 3H₂O (3), [Cu(psa)(4bpy)] · H₂O (4), and [Cu(psa)_0.5(N₃)(2bpy)] (5) (H₂psa = phenylsuccinic acid, phen = 1,10-phenanthroline, 2bpy = 2,2′-bipyridine, and 4bpy = 4,4′-bipyridine) were obtained under solvothermal conditions and characterized by single-crystal X-ray diffraction. Complexes 2 and 3 were formed by one-pot reaction. In complex 2, Cu(II) ion is four-coordinated and locates at a slightly distorted square center. In complex 3, the coordinated water molecule occupies the axial site of Cu(II) ion forming a tetragonal pyramid geometry. Complexes 1 and 3 are of 1D chain structures, and extended into 2D supramolecular network by hydrogen bonds. Complex 2 is of zipper structure, and further assembled into 2D supramolecular network by hydrogen bonds and π–π stacking interactions. Complex 4 is a 3D CdSO₄-like structure with twofold interpenetration, while complex 5 is a dinuclear compound. The different structures of complexes 1–5 can be attributed to using the auxiliary ligands, indicating an important role of the auxiliary ligands in assembly and structure of the title complexes.