Two Tri-spin Complexes Based on Lanthanide (Ln~Ⅲ =Dy~Ⅲ and Tb~Ⅲ ) and Nitronyl Nitroxide Radicals: Syntheses, Structures and Properties

Two new tri-spin radical-Ln（III）-radical complexes, [Ln（hfac）3（NITPh-Ph）2] （Ln = Dy （1） and Tb （2）, NITPh-Ph = 4＇-biphenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, and hfac = hexafluoroacetylacetonate） have been synthesized and characterized by X-ray diffraction analysis, elemental analysis, IR, Uv-visible and magnetic properties. X-ray analysis reveals that the two complexes are isomorphous and crystallize in the triclinic system, space group P1. For complex 1, a = 12.402（3）, b = 15.414（3）, c = 17.383（3） A, a = 68.61（3）, β = 81.97（3）, y = 79.40（3）°, V = 3031.7（11） A3, Z = 2, Mr = 1401.86, Dc = 1.536 g/cm^3, kt = 1.344 mm^-1, F（000） = 1398, the final GOF = 1.173, R = 0.0670 and wR = 0.1376 for 9035 observed reflections with 1 〉 2a（/）; while for complex 2, a = 12.397（3）, b = 15.391（3）, c = 17.395（4） A, a = 68.62（3）, fl = 81.97（3）, ）, = 79.60（3）°, V = 3030.0（11） A3, Z = 2, Mr = 1398.29, Dc = 1.537 g/cm^3,μ = 1.344 mm-1, F（000） = 1398, the final GOF = 1.130, R = 0.0644 and wR = 0.1382 for 8989 observed reflections with 1 〉 2a（/）. They all consist of the discrete adducts, in which the central Ln（lll） ions are coordinated by six oxygen atoms from three hfacs and two oxygen atoms from nitronyl radicals. The temperature dependency of magnetic susceptibilities for these two complexes is studied, showing that the magnetic interactions are governed by the depopulation of the Ln Stark levels.

A New One-dimensional Dicyanamide Bridged Zinc(II) Complex Containing Nitronyl Nitroxide Radicals:Synthesis,Crystal Structure and Magnetic Properties

A new one-dimensional dicyanamide bridged zinc（Ⅱ） complex containing nitronyl nitroxide radicals [Zn（NO3）（NIT-1′-MeBzIm）（dca）]n·（H2O）n （NIT-1′-MeBzIm = 2-{2′-[（1′-methyl）benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, dca = dicyanamide anion） has been prepared and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in triclinic, space group P^-1, with a = 7.428（3）, b = 9.839（3）, c = 16.708（6） A^°, α = 93.270（4）, β = 101.642（4）,γ= 100.632（4）°, C17.5H21N8O5.5Zn, Mr = 496.79, V = 1169.7（7） A^°^3, Dc = 1.411 g/cm^3, μ（MoKα） - 1.096 mm^-1, Z = 2, F（000） = 512, R = 0.0583 and wR = 0.1663 for 4295 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the zinc（Ⅱ） ion is six-coordinated with a distorted octahedral geometry. These units develop as 1D species where dicyanamide ligands bridge zine（ID ions. In addition, molecules are linked by π-π piling interactions to form 1-D double-chains. Magnetic investigation indicates that the weak intramolecular interactions are antiferromagnetic with J = -0.27 cm^-1, where the spin Hamitonian is defined as H = -2∑ijJijSiS within the complex.

Synthesis,Crystal Structure and Magnetic Properties of an Oxalato-bridged Dinickel(Ⅱ) Complex with Nitronyl Nitroxide Radicals

A new oxalato-bridged dinickel（Ⅱ） complex [Ni2（NIT-MeImz）4（C2O4）]（Ac）2·8H2O has been synthesized and characterized structurally as well as magnetically.It crystallizes in monoclinic,space group C2/c with a=24.608（4）,b=21.399（3）,c=17.992（3）,β=131.680（2）°,V=7076（2）3,C50H86N16Ni2O24,Mr=1412.77,Z=4,Dc=1.326 g/cm3,μ（MoKα）=0.614 mm-1,F（000）=2984,R=0.0751 and wR=0.1791 for 2956 observed reflections with Ⅰ＆gt;2σ（Ⅰ）.X-ray analysis reveals that the crystal structure consists of [Ni2（NIT-MeImz）4（C2O4）]2＋ moiety and two Ac^- anions. Each nickel（H） ion is six-coordinated with a distorted octahedral geometry： two nitrogen atoms and two oxygen atoms from NIT-Melmz together with two other oxygen atoms from the oxalato ion. The 2-D net structure is formed and arranged through intermolecular H-bonding interactions. Magnetic measurements show antiferromagnetic interactions for this complex.

Syntheses, Crystal Structures and Magnetic Properties of a New Nitronyl Nitroxide Radical and Its Cu(Ⅱ) Complex

A new compound （NIT-mNO2 = 4,4,5,5-tetramethylimidazoline-2-yl-（2＇-chlor-5＇- nitrophenyl）-3-oxide-l-oxyl） 1 and its complex （Cu（NIT-mNO2）（hfac）2） 2 have been synthesized and structurally and magnetically characterized. Complex 1 crystallizes in monoclinic, space group P211n with a = 10.6798（9）, b = 11.2705（9）, c = 12.9559（10）A, β = 107.3770（10）°, V = 1488.3（2） A^3, C13H15ClN3O4, Mr = 312.73, Z = 4, Dc = 1.396 g/cm^3, g（MoKa） = 0.276 mm^-1, F（000） = 652, the final R = 0.0606 and wR = 0.1773 for 3405 independent reflections with Rint = 0.0203. The nitronyl nitroxide unit （imidazoline ring） is not coplanar with the phenyl ring with the dihedral angle between them of 55.75°. The compound results in a 1-D zig-zag chain structure by intermolecular H-bond interaction. Compound 2 crystallizes in triclinic, space group Pi with a = 10.3699（10）, b = 10.6286（11）, c = 15.1683（15）A, a = 77.5330（10）, ,β = 773080（10）, y = 87.3420（10）＊, V = 1592.5（3） A^3, C23HITCIFI2N3O8Cu, Mr = 790.39, Z = 2, Dc = 1.648 g/cm^3, μ（MoKa） = 0.888 mm^-1, F（000） = 788, the final R = 0.0793 and wR = 0.2153 for 5794 independent reflections with Rint = 0.0196. The Cu（Ⅱ） ion is located at a center of symmetry, and each Cu（Ⅱ） is surrounded by six oxygen atoms at the vertices of a distorted tetragonal octahedron. Four of the six oxygen atoms belong to two hfac ligands and occupy the equatorial coordination sites, while the other two of NIT-mNO2 act as μ-1,5 bridge between the Cu（Ⅱ） ion, thus forming a 1-D chain structure. The magnetic susceptibility data indicate intermolecular antiferromagnetic interactions between compound 1 and intrachain ferromagnetic behaviors.

Synthesis,Crystal Structure and Magnetic Property of a New Cd(Ⅱ) Complex with Four Nitronyl Nitroxide Radicals

A new Cd（Ⅱ） complex with four nitronyl nitroxide radicals [Cd（NIT4Py）4Cl2]（NIT4Py = 2-（4＇-pyridinyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been synthesized and structurally characterized by X-ray diffraction analysis.It crystallizes in triclinic,space group P1 with a = 7.2441（4）,b = 13.6964（8）,c = 13.7354（8） ,α = 89.8610（10）,β = 77.9180（10）,γ = 87.2250（10）°,V = 1331.01（13） 3,C48H64CdCl2N12O8,Mr = 1120.41,Z = 1,Dc = 1.398 g/cm3,μ（MoKα） = 0.573 mm-1,F（000） = 582,S = 1.043,the final R = 0.0257 and wR = 0.0641 for 4333 observed reflections（I 〉2σ（I））.The title complex exists in the mononuclear-metal structures,in which each Cd（Ⅱ） ion adopts a distorted octahedral geometry and is coordinated by two Cl-anions and four pyridyl-N atoms from four NIT4Py ligands.The magnetic measurements show weak antiferromagnetic interactions between the nitroxide radicals.

One-dimensional lanthanide complexes bridged by nitronyl nitroxide radical ligands with non-chelating nitrogen donors: Structure and magnetic characterization

A series of new lanthanide-radical complexes [{Ln（hfac）3}2（NITPhlM）2] （Ln = Nd （1）, Eu （2）, Tb （3）, Er （4）; hfac = hexafluoroacetylacetonate; NITPhlM = 2-[4-（1-imidazole）phenyl]-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide） have been prepared and characterized. Single crystal X-ray diffraction analyses reveal that these complexes are isostructural with one-dimensional chain structures. These consist in Ln（hfac）3 units bridged by the paramagnetic ligands by the means of coor- dination of their nitronyl nitroxide groups and imidazole rings. Interestingly, each Ln ion is either bound to two nitronyl ni- troxide groups or to two imidazole units, and the different Ln centers alternate along the chain. Magnetic studies show that complex 3 exhibits a single-chain magnet behavior.

Synthesis, Crystal Structure and Magnetic Properties of a New Zn(II)-Nitronyl Nitroxide Complex

A new complex [Zn（NIT-1′-MeBzlm）Cl2（H2O）] （NIT-1′-MeBzlm = 2-{2′-[（1′- methyl）benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been prepared and structurally characterized by X-ray diffraction method. Crystal data： monoclinic, space group P21/n, Z = 4, C15H21Cl2N4O3Zn, Mr = 441.63, a = 7.2225（10）, b = 30.849（4）, c = 8.8758（13）A, β = 103.904（2）°, V = 1919.6（5）A^3, Dc = 1.528 g/cm^3, μ（MoKα） = 1.579 mm^-1, F（000） = 908, R = 0.0436 and wR = 0.1029 for 2456 observed reflections with I〉 2σ（I）. X-ray analysis reveals that the Zn（Ⅱ） ion is four-coordinated with a distorted tetrahedron. There also exist H-bonds, π-π piling interactions and weak intermolecular contacts between the NO groups which form a mutual stagger 3-D network configuration. Magnetic investigation reveals that there exists intermolecular antiferro- and ferromagnetic interactions in the title complex.

Synthesis and Crystal Structure of a New Zn(II) Nitronyl Nitroxide Complex [Zn(NIT4Py)(PDA)(H_2O)_3]

A new Zn（Ⅱ） nitronyl nitroxide complex [Zn（NIT4Py）（PDA）（HzO）3] （NIT4Py = 2-（4＇-pyridyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, H2PDA = pyridine-2,5-dicarboxylic acid） has been synthesized and structurally characterized by X-ray diffraction. It crystallizes in monoclinic, space group P2 1/c with a = 16.881（8）, b = 7.356（4）, c = 18.857（9） A°,β = 108.616（6）°, V = 2219.1 （19）A°^3 ,C 19H25N4O9Zn, Mr = 518.80, Dc = 1.553 g/cm^3, μ（MoKa） = 1.165 mm^-1, F（000） = 1076, Z = 4, the final R = 0.0269 and wR = 0.0715 for 3193 observed reflections with I 〉 2σ（I）. The complex exists as discrete mononuclear molecules and the zinc（Ⅱ） ion is six-coordinated with one radical ligand （NIT4Py）, one bidentate pyridine-2,5-dicarboxylate anion and three water molecules. A three-dimensional network structure is formed through the intermolecular interactions.

Synthesis, Crystal Structure and Optical Properties of a New Nd(III) Nitronyl Nitroxide Complex [Nd(NIT2Py)_2(NO_3)_3]

A new Nd（Ⅲ） nitronyl nitroxide complex [Nd（NIT2Py）2（NO3）3] （NIT2Py = 2-（2＇-pyridyl）-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide） has been synthesized and structurally characterized by X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a = 12.396（4）, b =11.134（4）, c = 23.360（7） A°, β = 98.178（6）°, V= 3191.2（18） A°^3, C24H32N9NdO13, Mr = 798.83, Dc =1.663 g/cm^3, μ（MoKa） = 1.704 mm^-1, F（000） = 1612, Z = 4, the final R = 0.0425 and wR = 0.0957 for 6532 independentreflections with Rint = 0.0642 and 4552 observed reflections （I 〉 2σ（I））. The complex exists as discrete mononuclear molecules and the neodymium（Ⅲ） ion is ten-coordinated with three bidentate nitrate anions and two radical ligands （NIT2Py） via bidentate chelating mode.The optical properties of the complex are discussed.

Synthesis and Crystal Structure of a New One-dimensional Zn(II) Nitronyl Nitroxide Complex Bridged by Pyridine-2,4-dicarboxylate Anion

A new one-dimensional （1-D） Zn（Ⅱ） nitronyl nitroxide complex bridged by pyridine-2,4-dicarboxylate anion, [Zn（NIT4Py）（2,4-PDA）（H2O）2], （NIT4Py = 2-（4′-pyridyl）-4,4,5,5- tetramethylimidazoline-1-oxyl-3-oxide and 2,4-PDA = pyridine-2,4-dicarboxylate anion）, has been synthesized and structurally characterized by X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 16.834（2）, b = 7.4376（10）, c = 18.295（3） A, β = 102.848（2）°, V = 2233.2（5） A^3, C19H23N4O3Zn, Mr = 500.78, Dc = 1.489 g/cm^3,μ（MoKa） = 1.152 mm^-1, F（000） = 1036, Z = 4, the final R = 0.0390 and wR = 0.0915 for 3234 observed reflections. In the complex, each zinc（Ⅱ） ion is six-coordinated by one nitrogen atom of the radical ligand （NIT4Py）, one nitrogen atom and two oxygen atoms of two 2,4-PDA anions and two oxygen atoms of two water molecules. Each 2,4-PDA anion bridges two Zn（Ⅱ） ions via a tridentate mode into a 1-D chain, and these 1-D chains are further linked into a 2-D network via hydrogen-bonding interactions.

Syntheses and Crystal Structures of Zinc(II) and Nickel(II) Complexes Involving Reduced Nitroxide Radicals

Two novel complexes [Zn（Him-thz）2（NO3）]·NO3 1 and [Ni（Him-thz）2（NO3）]·NO3 2 （Him-thz = 2-（2＇-thiazole）-4,4,5,5-teramethyl-dihydro-1H-imidazolyl-1-hydroxy） have been prepared and structurally characterized by X-ray diffraction method. Both complexes crystallize in orthorho- mbic, space group P21 21 2, Z = 2. Crystal data for 1： ZnC20H30N8O8S2, Mr = 640.2, a = 13.1630（14）, b = 10.5149（11）, c = 10.6670（11） A°, V= 1476.4（3）A°^3, Dc = 1.440 g/cm^3, μ（MoKa） = 1.028 mm^-1, F（000） = 664, R = 0.0398 and wR = 0.0901 for 2131 observed reflections with I 〉 2σ（I）. Crystal data for 2： NiC20H30N8O8S2, Mr = 633.36, a = 13.1611（7）, b = 10.4833（6）, c = 10.6928（6） .4,, V = 1475.30（14）A°^3, Dc = 1.426 g/cm^3 ,μ（MoKa） = 0.854 mm^-1, F（000） = 660, R = 0.0281 and wR = 0.0797 for 3099 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the crystal structures consist of [M（Him-thz）2（NO3）]^＋ （M = Zn, Ni） moiety and a NO3^- anion. Both Zinc（Ⅱ） and Nickel（Ⅱ） ions are six-coordinated with distorted octahedral geometries.

Synthesis and Crystal Structure of an Azide Bridged Binuclear Zinc(II) Complex Including the Reduced Derivative of Nitronyl Nitroxide, [Zn(Him2Py)(N_3)_2]_2

The title compound [Zn(Him2Py)(N3)2]2 (Zn2C26H38N18O2, Mr = 765.48) has been prepared and structurally characterized by X-ray diffraction methods. It crystallizes in monoclinic, space group P21/n with a = 10.989(3), b = 11.519(3), c = 13.812(4) ? b = 101.700(5), V = 1711.9(9) ?, Z = 2, Dc = 1.485 g/cm3, m(MoKa) = 1.456 mm～1, F(000) = 792, the final R = 0.0401 and wR = 0.0861 for 2054 observed reflections with I>2s(I). The imino nitroxide 2-(3- methyl-2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxyl (im2Py) was reduced to obtain 2-(3-methyl -2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-ydroxy (Him2Py) coordinating to the zinc (II) ion, around which the coordination geometry is a square-based pyramid with a terminal nitrogen atom located at the apical position. The four basal sites are occupied by two m1,1 nitrogen atoms from two different bridging azide ions and two nitrogen atoms from Him2Py. The units of [Zn(Him2Py)(N3)2]2 were connected as two dimension planes by intermolecular hydrogen bonds.

A Novel Complex of Na(I)-Nitronyl Nitroxide [Na(NIT-1'-MeBzIm)_3]ClO_4: Synthesis and Crystal Structure

A novel complex [Na（NIT-1＇-MeBzIm）3]ClO4 （NIT-1＇-MeBzIm = 2-{2＇-[（1＇- methyl）benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been prepared and structurally characterized by elemental analysis, IR spectra and X-ray diffraction methods. The title complex crystallizes in trigonal, space group P3 and Z = 2. Crystal data： C45H57ClN12NaO10, Mr = 984.47, a = 13.9411（8）, b = 13.9411（8）, c = 14.8622（16） A, γ= 120°, V= 2501.5（3） A^3, Dc = 1.307 g/cm^3, μ（MoKα） = 0.152 mm^-1, F（000） = 1038, R = 0.0637 and wR = 0.1813 for 1957 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the Na（I） ion is six-coordinated with three NIT-1＇-MeBzlm radicals. As we know, three radicals coordinating to the Na（I） ion in the main group by a chelate way is the first example. The Na（I） ion resides in a distorted octahedron with a facial configuration. Meanwhile, the intermolecular weak interactions result in a 2-D double layer conformation where the uncoordinated perchlorate anions are inserted in the packing space and take part in the H-bond interactions, and each complex is connected with six neighboring complexes and three perchlorate anions.

Synthesis,Crystal Structure and Magnetic Properties of a Co(Ⅱ) Complex Containing 2′-(l′-Methyl)benzimidazolyl-substituted Nitronyl Nitroxide

A new complex [Co（NIT-1′-MeBzIm）2Cl2]（NIT-1′-MeBzIm = 2-{2′-[（l′-methyl）-benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been prepared and structurally characterized by X-ray diffraction method.The complex crystallizes in the monoclinic system,space group C2/c,Z = 4.Crystal data：C30H38Cl2CoN8O4,Mr = 704.51,a = 17.074（3）,b = 21.350（3）,c = 11.6962（19）,β = 108.879（2）°,V = 4034.3（11）3,Dc = 1.160 g/cm3,μ（MoKα） = 0.597 mm-1,F（000） = 1468,R = 0.0422 and wR = 0.1141 for 2577 observed reflections with I 2σ（I）.X-ray analysis reveals that the Co（Ⅱ） ion is six-coordinated with a distorted octahedral geometry.Temperature dependence of susceptibility measurements shows the existence of antiferromagnetic interactions between the Co（Ⅱ） ion and the radicals（J =-52.88 cm-1）.

Synthesis and Crystal Structure of a Nitronyl Nitroxide Complex {[Zn(NIT4Py)(fum)(H_2O)_2]·H_2O}_n

The title compound {[Zn（NIT4Py）（fum）（HEO）2]·H2O}n, where NIT4Py = 2-（4＇- pyridinyl）-4,4,5,5-tetra-methylimidazoline-looxyl-3-oxide and fum = fumarate, has been prepared and structurally characterized by X-ray diffraction. It crystallizes in triclinic, space group P1^- with a = 6.9533（9）, b = 9.805（1）, c = 15.248（2） A, α= 94.608（2）, β = 92.328（2）, γ = 105.840（2）°, C16H24N3O9Zn, Mr = 467.75, V = 994.8（2） A^3, Z = 2, Dc = 1.562 g/cm^3,μ（MoKα） = 1.289 mm^-1, F（000） = 486, the final R = 0.0243 and wR = 0.0622 for 3505 independent reflections with Rint = 0.0125. The Zn（II） adopts a distorted five-coordinate triangle bipyramidal geometry. The basic framework structure of the complex is a 1-D chain. The intrachain hydrogen bonds are helpful to stabilize the 1-D chain structure. Furthermore, the chains are connected by O-H…O hydrogen bonds to give a 2-D double-layer network.

Synthesis, Crystal Structure and Magnetic Properties of a Novel Azide-bridged Copper(Ⅱ) Coordination Polymers Containing Nitroxy Nitroxide

A novel azide-bridged copper（Ⅱ） coordination polymer, [Cu3（NITpPy）4（N3）6]n （NITpPy = 4-pyridyl-4,4,5,5-tetramethylimidazline-3-oxide-1-oxyl）, was structurally and magnetically characterized. It crystallizes in the triclinic space group P with a = 7.6932（10）, b = 14.5556（19）, c = 16.122（2） , α = 108.443（2）, β = 95.251（2）, γ = 104.236（2）°, V = 1631.7（4） 3, C48H64Cu3N30O8, Mr = 1379.87, Z = 1, Dc = 1.404 g/cm3, μ（MoKα） = 1.041 mm-1, F（000） = 713, the R = 0.0510 and wR = 0.1185 for 4285 observed reflections with I 2σ（I）. X-ray analysis reveals that the Cu（Ⅱ） ions are linked by nitrogen atom of μ1,1 azido ligands to form a Cu-Cu-Cu unit. The units are linked by μ1,3 azido ligands through a bridging style to form a one-dimensional coordination polymer. The variable-temperature magnetic susceptibility data of the complex show ferromagnetic interactions in the complex.

Synthesis and Crystal Structure of a Novel Co(II)-Nitronyl Complex [Co(IM2-Py)(PCA)(N_3)_2]

The title compound [Co(IM2-Py)(PCA)(N3)2] (IM2-Py = 2-(2?-pyridyl)-4,4,5,5-te- tramethylimidazoline-1-oxyl, PCA = 2-pyridine carboxylic acid) has been prepared and structurally characterized by elemental analysis, IR spectra and X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 13.169(3), b = 11.235(2), c = 15.596(3) ?, β = 104.70(3)o, V = 2232.0(8) ?3, C18H21CoN10O3, Mr = 484.38, Z = 4, Dc = 1.441 g/cm3, μ(MoKα) = 0.811 mm-1, F(000) = 1000, the final R = 0.0563 and wR = 0.1010. The nitronyl nitroxide (NIT2Py) was reduced to IM2-Py, and another NIT2Py oxidated to PCA. The self-redox reaction between the radicals was observed. The cobalt(II) ion is six-coordinated into a distorted octahedral geometry. Meanwhile, the intermolecular hydrogen bonds result in the dimer.

Syntheses,crystal structures and magnetic properties of three lanthanide-nitronyl nitroxide complexes

Three new lanthanide-nitronyl nitroxide radical complexes were successfully synthesized with the formula of [Ln（hfac）3（PyNONIT）2]（Ln=Dy（1）, Tm（2）, Ho（3））. All the complexes were isostructural and crystallized in C2/c space group, in which the central metal ions were eight-coordinated in slightly distorted square antiprism coordination geometries（D4d symmetry）. Magnetic studies indicated the existence of antiferromagnetic interaction in complexes 1–3.

A Cu(II) Complex with IM-MeImz-κ~2 N,O Mode in [Cu(IM-MeImz)_2]·(SCN)_2: Synthesis, Crystal Structure and Magnetic Properties

A new copper（Ⅱ） compound with imino nitroxide radicals [Cu（IM-MeImz）2].（SCN）2 （IM-meImz =2-（5-methylimidazol-4-yl）-4,4,5,5-tetramethyl-2-imidazoline- 1-oxyl） has been synthesized and characterized structurally and magnetically. It crystallizes in monoclinic, space group P21/c with a = 9.3604（7）, b = 10.3012（7）, c = 16.6684（12）A, β = 105.0290（10）^o, V = 1552.25（19）A3, C24H34CUN10O2S2, Mr = 622.27, Z = 2, Dc = 1.331 g/cm^3,μ（MoKα） = 0.876 mm^-1, F（000） = 650, the final R = 0.0374 and wR = 0.1079. X-ray analysis demonstrates that the IM-MeImz ligand is coordinated to the copper（Ⅱ） ion as an unusual didentate chelate with a k-2 N（MeImz）,O（IM） mode in the complex. The square-planar coordination sites at Cu（Ⅱ） are occupied by two 0 and two N atoms from the imino nitroxide radicals. The complex molecules are connected as a onedimensional polymer structure by intermolecular interactions. Magnetic measurements show that there are intramolecular antiferromagnetic interactions between the Cu（Ⅱ） ion and radicals.

Synthesis and Crystal Structure of a 1-D Coordination Polymer {[Cu(NIT4py)_2(ip)]·6H_2O}_n

A new complex { [Cu（NIT4py）2（ip）]·6H2O }, （NIT4py=2-（4＂-pyridinyl）-4,4,5,5-tetra methylimidazoline-1-oxyl-3-oxide and ip = isophthalate dianion） has been synthesized and structurally characterized by X-ray diffraction. It crystallizes in orthorhombic, space group Cmcm with a = 25.161（3）, b =10.045（1）, c = 15.450（2） A°, C32H48N6O14CU, Mr = 804.30, V= 3904.8（8） ,A°^3, Z = 4, De = 1.368 g/cm^3, μ（MoKa） = 0.630 mm^-1, F（000） = 1692, the final R = 0.0326 and wR = 0.0787 for 1843 independent reflections with Rint = 0.0372. Each Cu（Ⅱ） ion is four-coordinated by two carboxylate oxygen atoms and two pyridyl-N atoms from NIT4py radicals to furnish a rhombus geometry. The central Cu（Ⅱ） ion is located at an inversion center and a crystallographic two-fold axis. Each isophthalate dianion binds two Cu（Ⅱ） ions in bis-monodentate mode, leading to a 1-D chain, a＇ these 1-D chains are further linked into a 2-D network via hydrogen-bonding interactions.