Synthesis,Structures and Magnetic Properties of Two Binuclear Cobalt(II) Complexes Bridged by Bis(p‐nitrophenyl) Phosphate or Diphenylphosphinate Ion

Two new binuclear cobalt(II) complexes, [Co₂ L¹ (μ₂‐DPP)]²⁺ ( 1 ) (H L¹ = N, N, N′, N′‐ tetrakis (2‐benzimidazolylmethyl)‐2‐hydroxyl ‐1,3‐diaminopropane; DPP = diphenylphosphinate) and [Co₂ L² (μ₂‐BNPP)₂]⁺ ( 2 ) (H L² = 2,6‐bis‐[N,N‐di(2‐ pyridylmethyl)aminomethyl]‐4‐methylphenol, BNPP = bis(4‐nitrophenyl)phosphate) have been synthesized and their crystal structures and magnetic properties are shown. In 1 , each Co^II atom has a distorted trigonal bipyramidal coordination sphere with a N₃O₂ donor set and the central two Co^II atoms are bridged by one alkoxo‐O atom and one μ₂‐DPP ion with the Co1‐Co2 separation of 3.542Å. In 2 , each Co^II atom has a pseudo octahedral environment with a N₃O₃ donor set and the central two Co^II atoms are bridged by a phenolic oxygen atom of L² and two μ₂‐BNPP ions with the Co1‐Co2 separation of 3.667Å. Susceptibility data of 1 and 2 indicate intramolecular antiferromagnetic coupling of the high‐spin Co^II atoms.     

Syntheses,Structures, and Polymorphism of β‐Diketonato Complexes – Co(thd)3

Oxidation of Co(thd)₂ dissolved in different solvents has been investigated in air and oxygen atmosphere. In oxygen atmosphere and at the boiling point of the solvents this treatment leads to oxidation of Co^II to Co^III, but also to degradation of some of the thd ligands and formation of a new mixed‐ligand complex. Three pure‐cultivated crystalline Co(thd)₃ phases are reported: 1 (room‐temperature phase), 2 (low‐temperature phase), and 3 (metastable phase) and in addition there exists an amorphous Co(thd)₃ phase ( 4 ) with approximate composition Co(thd)₃·xH(thd); x = 0.06. Reaction of metal(II) oxides (MO, M = Mn, Fe, and Co) with H(thd) under air or O₂ atmosphere is an easy direct route to M(thd)₃ complexes. Structure determinations are reported for Co(thd)₃ ( 1 – 3 ) based on single‐crystal X‐ray diffraction data. Modification 1 crystallizes in space group with a = b = 18.8100(10), c = 18.815(2) Å at 295 K; R(wR2) = 0.180, modification 2 in space group C2/c with a = 28.007(12), b = 18.482(8), c = 21.356(9) Å, β = 97.999(5)° at 100 K; R(wR2) =0.211, and modification 3 in space group Pnma with a = 19.2394(15), b = 18.8795(15), c = 10.7808(8) Å at 100 K; R(wR2) = 0.193. The molecular structures of 1 – 3 all comprise a central Co atom octahedrally co‐ordinated by the ketonato O atoms of three thd ligands. The transformation between modifications 1 and 2 is of a fully reversible second‐order character. Modifications 1 and 3 are, on the other hand, related by a quasi‐reversible cycle. Heat treatment (specifically sublimation) of 1 leads to 3 whereas re‐crystallization or prolonged storage at room temperature is required to regenerate 1 . Co(thd)₃ has sufficient thermal stability to permit sublimation without degradation. The various forms of Co(thd)₃ are all diamagnetic, viz. a confirmation of the Co^III valence state.     

On the Oxidation of Octamethylenetetrathiafulvalene by CuBr2 – Synthesis,Crystal Structure and Magnetic Properties of (OMTTF)2[Cu4Br10]

The reaction of octamethylenetetrathiafulvalene (OMTTF) with excess CuBr₂ in tetrahydrofurane/acetonitrile yields black (OMTTF)₂[Cu₄Br₁₀] ( 1 ). The crystal structure determination shows the presence of OMTTF cations and tetranuclear bromidocuprate anions. The novel anion consists of four edge and corner sharing CuBr₄ tetrahedra, which are connected to a ring. The assignment of the ionic charges and oxidation states for the copper atoms is supported by the magnetic properties. 1 is antiferromagnetic with T_N ≈ 30 K. The magnetic moment reaches 2.54 B.M., which indicates, together with the Curie–Weiss constant of –35 K, a coupling of the paramagnetic spins over the whole temperature region. The ionic charges of the salt‐like compound 1 are therefore (OMTTF²⁺)₂[(Cu⁺)₂(Cu²⁺)₂Br₁₀]^4–. The antiferromagnetism is explained by the coupling of the spins of two Cu²⁺ ions in the anion with an exchange constant of J = –18 cm^–1. The Cu^I and Cu^II atoms are clearly distinguishable in the mixed valent anion. The OMTTF cation is not planar but exhibits an interplanar angle between the two central C₃S₂ ring moieties of 15.3°, which is in accordance to the dicationic oxidation state.     

Synthesis,Crystal Structures,and Magnetic Properties of Two Tetrahedral MnIIMnIII3 Complexes

Two tetranuclear manganese complexes, [NaMn^IIMn₃^III(μ₄‐O^2–)(HL)₃(SCN)₄] ( 1 ) and [NaMn^IIMn₃^III(μ₄‐O^2–)(HL)₃Cl₄][NaMn^IIMn₃^III(μ₄‐O^2–)(HL)₃Cl₃(H₂O)]ClO₄ · 3.5H₂O ( 2 ) were obtained from the reaction of manganese perchlorate with a quadridentate Schiff base ligand, 3‐(2‐hydroxybenzylideneamino)propane‐1, 2‐diol (H₃L) derived from condensation of 2‐hydroxybenzaldehyde with 3‐amino‐1, 2‐propanediol, as well as the coligand KSCN or NaCl under basic conditions. Single‐crystal X‐ray studies reveal that those two complexes all have a mixed‐valent tetrahedral core, which contains an apical Mn^II ion and three basal Mn^III ions situated in the [Mn₃(μ₄‐O^2–)]⁷⁺ equilateral triangle plane. Fitting of the magnetic susceptibility data to the theoretical χ_mT vs. T expression, revealed that the presence of only antiferromagnetic interactions between the central metal atoms in 1 , while both antiferromagnetic and ferromagnetic interactions are present in 2 .     

两个半夹心型聚吡唑硼酸盐羧酸钴配合物的合成、结构及催化活性

设计合成了2个结构新颖的半夹心单核聚吡唑硼酸盐羧酸配合物Tp^*Co(Hglu)(CH₃OH)(1)和Tp^*Co(Hsub)(H₂O)(2)[Tp^*=三聚(3,5-二甲基吡唑)硼酸根, H₂glu=戊二酸, H₂sub=辛二酸], 并通过元素分析、 红外光谱、 紫外-可见光谱和X射线单晶结构分析对标题配合物进行了表征. 结构分析表明, 在配合物1和2中, 配体Tp^*都是三齿配位, 配位模式相同; 戊二酸和辛二酸都以μ₁-η¹-η¹的端基配位模式与金属相连. 此外, 还对配合物的热稳定性进行了详细分析, 并初步探讨了配合物催化氧化环己烷的催化活性.     

Synthesis,Characterization, and Magnetic Properties of Novel Cobalt(II) and Copper(II) Complexes with 5‐(Isonicotinamido)isophthalate Ligand

Two new complexes, {[Co(INAIP) · H₂O] · 2H₂O}_n ( 1 ), and {[Cu(INAIP)] · H₂O}_n ( 2 ) [H₂INAIP = 5‐(isonicotinamido)isophthalic acid] were synthesized under hydrothermal conditions, and characterized by single‐crystal X‐ray structure determination, thermogravimetric analysis, X‐ray powder diffraction, and magnetic studies. In complex 1 both Co^II atoms and INAIP^2– ligands act as four‐connected node, whereas in 2 both Cu^II atoms and INAIP^2– ligands act as three‐connected node.     

Synthesis,Structure, and Spectroscopic Properties of Copper(II) and Nickel(II) Complexes Containing the 1, 4, 7‐Triisopropyl‐1, 4, 7‐triazacyclononane Ligand

Three new complexes [CuL(N₃)₂] ( 1 ), [CuL(SCN)₂] ( 2 ), and [NiL(SCN)₂] ( 3 ) (L = 1, 4, 7‐triisopropyl‐1, 4, 7‐triazacyclononane, [—NR—C₂H₄—NR—C₂H₄—NR—C₂H₄—], R = i‐Pr) have been synthesized and structurally characterized. The three complexes all crystallize in the monoclinic space group P2₁/n, with the unit cell parameters a = 9.100(5), b = 19.492(11), c = 11.646(6)Å, β = 94.526(9)° for 1 , a = 10.148(3), b = 13.611(5), c = 15.777(6)Å, β = 95.412(6)° for 2 and a = 9.270(7), b = 16.629(14), c = 14.886(12)Å, β = 101.217(15)° for 3 . The central copper(II) and nickel(II) ions are coordinated to five nitrogen atoms, three of which from the L and two from N₃^— or SCN^—, forming a slightly distorted square pyramidal geometry. Moreover, elemental analysis, IR, UV‐vis and ESR spectra of complexes 1 ‐ 3 were also determined.     

Synthesis,Structures, and Properties of Four Novel Coordination Compounds based on a Flexible Tetrakis(imidazol‐1‐ylmethyl)methane Ligand

Four coordination polymers, namely, [Zn₂(TIYM)(2,6‐PYDC)₂]_n · n(CH₃OH) · 3n(H₂O) ( 1 ), [Cu(TIYM)(2,6‐PYDC)]_n · 3n(H₂O) ( 2 ), [Co(TIYM)(2,6‐PYDC)]_n · n(CH₃OH) · 3n(H₂O) ( 3 ), and [Cd₂(TIYM)(2,6‐PYDC)₂(H₂O)]_n · n(H₂O) ( 4 ) with the flexible N‐containing ligand [tetrakis(imidazol‐1‐ylmethyl)methane (TIYM)] and the N‐containing dicarboxylic acid [2,6‐pyridinedicarboxylic acid (2,6‐PYDC)] were prepared. Compounds 1 – 4 show various structures because of different N–C_center–N angles (θ) of TIYM ligands and changing coordination modes of 2,6‐PYDC. Compounds 1 , 2 , and 3 display a similar 1D ladder‐like chain, whereas 4 gives a 1D quad‐core lifting platform shaped belt. The structural diversities in 1 – 4 suggest that the multiple coordination modes or the different freely twist angles of ligands and the presence of different metal atoms play important roles in the resulting structures of the coordination polymers. Furthermore, the solid‐state luminescence properties of 1 and 4 , and the magnetic properties of 3 were investigated.     

Synthesis,Structure, Antibacterial and Spectroscopic Properties of a Zinc(II) Complex with the Ligand 4‐Heptanoyl‐pyrazol‐5‐one

The long‐chain ligand, 1‐phenyl‐3‐methyl‐4‐heptanoyl‐pyrazol‐5‐one (HL) and its zinc(II) complex ZnL₂ were synthesized. The structure and the properties of ZnL₂ were characterized by elemental analysis, IR spectroscopy, X‐ray diffraction, and thermogravimetric analysis. The zinc ion is five‐coordinated in a square‐pyramidal environment by four oxygen atoms of the HL ligands in the equatorial plane and one water molecule in the axial position. The water molecule is directly bonded to Zn²⁺ and involved in intermolecular hydrogen bonding network. The complex and its corresponding ligand were screened in vitro against some strains of the human pathogenic bacteria. The metal complex exhibits higher antibacterial activity than its corresponding ligand. The complex exhibits purple effect emission as the result of fluorescence from the intraligand emission excited state.     

Synthesis,Structures and Spectroscopic Properties of Platinum(II), Palladium(II) and Copper(I) Halide Complexes with Pyrimidine‐phosphine Ligand

The reactions of pyrimidine‐phosphine ligand N‐[(diphenylphosphino)methyl]‐2‐pyrimidinamine ( L ) with various metal salts of Pt^II, Pd^II and Cu^I provide three new halide metal complexes, Pt₂Cl₄(μ‐L)₂·2CH₂Cl₂ ( 1 ), Pd₂Cl₄(μ‐L)₂ ( 2 ), and [Cu₂(μ‐I)₂L₂]_n ( 3 ). Single crystal X‐ray diffraction studies show that complexes 1 and 2 display a similar bimetallic twelve‐membered ring structure, while complex 3 consists of one‐dimensional polymeric chains, which are further connected into a 2‐D supramolecular framework through hydrogen bonds. In the binuclear complexes 1 and 2 , the ligand L serves as a bridge with the N and P as coordination atoms, but in the polymeric complex 3 , both bridging and chelating modes are adopted by the ligand. The spectroscopic properties of complexes 1 ‐ 3 as well as L have been investigated, in which complex 3 exhibits intense photoluminescence originating from intraligand charge transfer (ILCT) π→π* and metal‐to‐ligand charge‐transfer (MLCT) excited states both in acetonitrile solution and solid state, respectively.     

Synthesis,Structure, and Catalytic Behavior of Ytterbium Complexes Derived from a Linked Bis(β‐ketoiminato) Ligand

Ytterbium complexes supported by a linked bis(β‐ketoiminato) ligand, N,N′‐ethylenebis(benzoylacetoimine) (H₂L), were synthesized and their catalytic behavior was explored. The reaction of YbCl₃ with 1 equiv. of LLi₂ afforded the mononuclear ytterbium chloride LYbCl(THF)₂ ( 1 ) in high yield. Complex 1 can be used as starting material to prepare β‐ketoiminate‐ytterbium derivatives. Treatment of complex 1 with NaN(SiMe₃)₂ produced the dimeric ytterbium amide {LYb[N(SiMe₃)₂]}₂ ( 2 ), while the similar reaction of complex 1 with NaOAr (ArO = 2, 6‐tBu‐4‐MeC₆H₂O) led to the mononuclear ytterbium aryloxide LYbOAr(THF) ( 3 ). The three complexes were well detected by elemental analysis and single‐crystal X‐ray analysis. It was found that complexes 2 and 3 can initiate the ring‐opening polymerization of ?‐caprolactone with moderate activity.     

镧系四元混配化合物[Ln(BA)2(NO3)(phen)]2的合成、晶体结构和波谱研究

在酸性介质、含水溶剂中合成了四元混配化合物[Ln(BA)₂(NO₃)(phen)]₂(BA=苯甲酸根;Ln=La,Ce,Pr,Nd,Sm,Eu,Dy,Gd,Tb,Er),用元素分析、IR、DTA-TG等方法对配合物进行了表征.研究了配合物的顺磁性能和荧光性能.镨配合物的单晶衍射结果表明,配合物属三斜晶系,双核,Pr³⁺的配位数为9,4个BA呈二种配位方式,丰富了四元配合物的结构表现形式.     

Syntheses,Structures, and Properties of Copper(II), Cobalt(II), and Cadmium(II) Complexes with Flexible Multicarboxylate Ligand

Three new coordination polymers, namely, [CuL_0.5] ( 1 ), [Co(H₂L)(H₂O)₂][H₂O] ( 2 ), and [(CdCl)_0.5Cd_0.25(H₂L)_0.5] ( 3 ) were synthesized under hydrothermal conditions from the corresponding Cu^II, Co^II, and Cd^II salts with a multidentate ligand of 2,2′,2′′,2′′′‐[2,3,5,6‐tetramethyl‐1,4‐phenylenebis(methylenenitrilo)]tetraacetic acid (H₄L). The complexes were characterized by single‐crystal X‐ray diffraction, IR, thermogravimetric, and elemental analyses. Complex 1 crystallizes in the orthorhombic space group Pbca and has a three‐dimensional architecture with infinite two‐dimensional networks linked together by weak Cu–O interactions. Complex 2 crystallizes in the monoclinic space group P2(1) and displays a 2D network. Complex 3 crystallizes in the tetragonal space group P4(2)/ncm and exhibits an infinite 3D architecture that has unusual [Cd₂(CO₂)₄Cl₂] dinuclear paddle‐wheel units and [Cd(CO₂)₄] dodecahedron units. The results showed that the coordination arrangement of central metal atoms and the conformation and coordination mode of organic ligands play an important role in determining the structure of the complexes. The luminescence property of complex 3 was studied in the solid state at room temperature.     

The Building Block [FeIII(pzphen)(CN)4]– and its Lanthanide Complexes: Synthesis,Crystal Structure,and Magnetic Properties

The cyanide building block [Fe^III(pzphen)(CN)₄]^– and its four lanthanide complexes [{Fe^III(pzphen)(CN)₄}₂Ln^III(H₂O)₅(DMF)₃] · (NO₃) · 2(H₂O) · (CH₃CN) [Ln = Nd ( 1 ), Sm ( 2 ), DMF = dimethyl formamide] and [{Fe^III(pzphen)(CN)₄}₂Ln^III(NO₃)(H₂O)₂(DMF)₂](CH₃CN) [Ln = Gd ( 3 ), Dy ( 4 )] were synthesized and structurally characterized by single‐crystal X‐ray diffraction. Compounds 1 and 2 are ionic salts with two [Fe^III(pzphen)(CN)₄]^– cations and one Ln^III ion, but compounds 3 and 4 are cyano‐bridged Fe^III‐Ln^III heterometallic 3d‐4f complexes exhibiting a trinuclear structure in the same conditions. Magnetic studies show that compound 3 is antiferromagnetic between the central Fe^III and Gd^III atoms. Furthermore, the trinuclear cyano‐bridged Fe^III₂Dy^III compound 4 displays no single‐molecular magnets (SMMs) behavior by the alternating current magnetic susceptibility measurements.     

Synthesis,Crystal Structure,and Properties of a Cadmium(II) Complex with the Flexible Ligand (1′H‐[2, 2′]Biimidazoly‐1‐yl)‐acetic Acid

A novel coordination polymer {[Cd(BDAC)]₂ · H₂O}_n ( 1 ) [HBDAC = (1′H‐[2, 2′]biimidazoly‐1‐yl)‐acetic acid] was synthesized under hydrothermal conditions and characterized by elemental analysis and single‐crystal X‐ray diffraction. Complex 1 crystallizes in the acentric orthorhombic space group Ccc2. The Cd1 atoms and BDAC^2– ligands construct [Cd1(BDAC)] rhomboid grid (4, 4)‐topology layer motifs, whereas the Cd2 atoms and BDAC^2– ligands form [Cd2(BDAC)] 1D coordination polymer ribbons. Furthermore, adjacent lay motifs are linked into 3D net structures by 1D coordination polymer ribbons with 4‐connected 3D trinodal {4²8²10²}{4⁴6²}{4³6²8}₂ topology. The measurement of electric hysteresis loops indicated that complex 1 displays a ferroelectric characteristic.     

Synthesis,Structure, and Magnetic Properties of a Mn4 Cluster derived from Benzimidazole‐Alcohol Ligands

The synthesis, crystal structure, and magnetic properties of a [Mn^III₃Mn^II(μ₃‐O)(mbp)₃(OAc)₃] · 4H₂O ( 1 ) [H₂mbp = 2‐(1H‐benzimidazol‐2‐yl)‐2‐ methylpropane‐1,3‐diol] cluster are reported herein. Mn ions in compound 1 have a tetrahedron topology. Solid‐state direct current and alternating current magnetic susceptibility measurements on compound 1 reveal a ground state with S_T = 7/2 as well as the probable single‐molecule magnetic behavior.     

Syntheses,Crystal Structures,and Properties of Metal(II) Coordination Polymers based on Flexible Ligand 1,3‐Bis(4‐phenoxy)benzenedicarboxylic Acid and Bis(benzimidazole)

Three new coordination polymers, [Zn(PBDC)(bbbm)_0.5]_n ( 1 ), [Co(PBDC)(bbbm)]_n ( 2 ), and [Cd(PBDC)(bbbm)]_n ( 3 ) were prepared via hydrothermal reactions of different metal(II) nitrates with flexible 1,3‐bis(4‐phenoxy)benzenedicarboxylic acid (H₂L) and 1,1‐(1,4‐butanediyl)bis(benzimidazole) ligand. All these complexes were fully characterized by elemental analysis, FT‐IR, thermogravimetric analysis (TGA), powder X‐ray diffraction, and single‐crystal X‐ray diffraction. Structure analyses revealed that complex 1 has a 2D→2D twofold interpenetrating framework simplified by a 4‐connected sql net with point symbol (4⁴.6²), whereas complexes 2 and 3 are isostructural and exhibit a 2D→2D twofold interpenetrating framework rationalized as a three‐connected hcb net with point symbol (6³). Complexes 1 – 3 further expand to 3D supramolecular structures through non‐covalent C–H ··· O interactions. Additionally, the luminescent and magnetic properties of some of these complexes were studied. Complex 3 presents ideal photoluminescent behavior, whereas complex 2 shows antiferromagnetic coupling between the central Co^II ions, suggesting its latent application in magnetic material.     

Structure and Magnetic Properties of Mononuclear Copper(II) Complexes with 2,2‐Bipyrimidine, 2,3‐Bis(2‐pyridyl)pyrazine,and 4‐Terpyridone Based Ligands

Four new complexes of [Cu(bpm)(ox)(H₂O)] ( 1 ), [Cu(tpd)(dca)(H₂O)] ( 2 ), [Cu(bppz)(N₃)₂] ( 3 ), and [Cu(bpm)₂(μ_1,3‐N₃)(N₃)] ( 4 ) (bpm = 2,2′‐bipyrimidine, bppz = 2,3‐bis(2‐pyridyl)pyrazine, tpd = 4‐terpyridone, dca = dicyanamide, ox = oxalate) have been prepared and characterized by X‐ray single‐crystal analysis and variable‐temperature magnetic measurements. Compounds 1–4 are essentially mononuclear Cu(II) complexes. However, in complex 1 , Cu(II) it was found that intermolecular hydrogen bonding through between H₂O and ox formed 1‐D chain structure. In complex 2 it was found that the hydrogen bonding between H₂O and tpd of the next molecule led to for a binuclear Cu(II) complex. In complex 3 , two nitrogen atoms, one of the pyridyl group of bppz and one of N₃^? ligands, are weakly coordinated to neighbor Cu(II) ion thus leading to formation of a 1‐D chain structure. In complex 4 , one nitrogen atom of terminated N₃^? is weakly coordinated to the neighbor Cu(II) site to form a 1‐D polymeric structure. The magnetic susceptibility measurements indicate that complex 1 and 4 exhibit a weak antiferromagnetic interaction whereas a ferromagnetic coupling has been established for complexes 2 and 3 .     

Synthesis,Spectral, Thermal Studies of Co(II), Ni(II), Cu(II) and Zn(II)‐arginato Complexes. Crystal Structure of Monoaquabis(arginato‐κO,κN)copper(II). [Cu(arg)2(H2O)].NaNO3

Transition metal complexes of arginine (using Co(II), Ni(II), Cu(II) and Zn(II) cations separately) were synthesized and characterized by FTIR, TG/DTA‐DrTG, UV‐Vis spectroscopy and elemental analysis methods. Cu(II)‐Arg complex crystals was found suitable for x‐ray diffraction studies. It was contained, one mole Cu^II and Na⁺ ions, two arginate ligands, one coordinated aqua ligand and one solvent NO₃^? group in the asymmetric unit. The principle coordination sites of metal atom have been occupied by two N atoms of arginate ligands, two carboxylate O atoms, while the apical site was occupied by one O atom for Cu^II cation and two O atoms for Co^II, Ni^II, Zn^II atoms of aqua ligands. Although Cu^II ion adopts a square pyramidal geometry of the structure. Co^II, Ni^II, Zn^II cations have octahedral due to coordination number of these metals. Neighbouring chains were linked together to form a three‐dimensional network via hydrogen‐bonding between coordinated water molecule, amino atoms and O atoms of the bridging carboxylate groups. Cu^II complex was crystallized in the monoclinic space group P2₁, a = 8.4407(5) Å, b = 12.0976(5) Å, c = 10.2448(6) Å, V = 1041.03(10) ų, Z = 2. Structures of the other metal complexes were similar to CuII complex, because of their spectroscopic studies have in agreement with each other. Copper complex has shown DNA like helix chain structure. Lastly, anti‐bacterial, anti‐microbial and anti‐fungal biological activities of complexes were investigated.     

Synthesis,Crystal Structures,and Magnetic Properties of Two Copper(II) Radical Heterospin Complexes

Two heterospin complexes [Cu(NIT3Py)(cda)H₂O] · H₂O ( 1 ) and [Cu(NIT2Py)(cda)H₂O] · H₂O · CH₃OH ( 2 ) with Cu^II ions and pyridyl‐substituted nitronyl nitroxide radicals (NITxPy = 2‐(x′‐pyridyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide, x = 3, 2; H₂cda = 4‐hydroxy‐pyridine‐2,6‐dicarboxylic acid) were synthesized and characterized structurally and magnetically. The single crystal structures show that the two complexes are both two‐spin complexes, in which the different radicals make the two complexes have different hydrogen bonding interactions to form 2D and 1D supramolecular network for complexes 1 and 2 , respectively. The magnetic measurements indicate that complexes 1 and 2 both exhibit antiferromagnetic interactions between Cu^II and radicals.