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, Crystal Structure and Magnetic Properties of Cobalt(II) Complex Involving Imino Nitroxide Radicals

A novel compound [Co(IM2-Py)2(NO3)]?(NO3) (IM2-Py = 2-(2?-pyridyl)-4,4,5,5- tetramethylimidazoline-1-oxyl) has been prepared and structurally characterized by X-ray diffrac- tion method. It crystallizes in orthorhombic, space group P212121 with a = 11.031(2), b = 13.492(3), c = 20.467(4) ?, V = 3046.0(11) ?3, C24H32CoN8O8, Mr = 619.51, Z = 4, Dc = 1.351 g/cm3, μ(MoKα) = 0.620 mm?1, F(000) = 1292, R = 0.0506 and wR = 0.0845 for 3752 observed reflections with I > 2σ(I). X-ray analysis reveals that the crystal structure consists of [Co(IM2- Py)2(NO3)]+ moiety and a NO3 anion. The cobalt(II) ion is six-coordinated with a distorted octahedral geometry. Tempera- ? ture dependence of susceptibility measurements show that there exist an antiferromagnetic inter- action in the compound.

Syntheses and Crystal Structures of Two New Zinc(Ⅱ) Nitroxide Radical Complexes Bridged by Isophthalate

Two novel complexes [Zn（NIT3-py）（ip）]n 1 and [Zn（im3-py）（ip）]n 2 （NIT3-py = 2-（3＇-pyridyl）-4,4,5,5,-tetramethylimidazoline-1-oxyl-3-oxide, im3-py = 2-（3＇-pyridyl）-4,4,5,5-tetramethylimidazoline-1-oxyl, ip = isophthalate） have been synthesized and structurally determined by X-ray diffraction. Crystal data for 1： C32H36N6O8Zn, Mr= 698.04, monoclinic, space group Cc with a = 23.600（3）, b = 10.2073（12）, c = 13.4027（16）A,β = 92.586（2）°, V = 3225.3（7） A^3, Dc= 1.438 g/cm^3, F（000） = 1456,μ（MoKa） = 0.822 mm^-1, Z = 4, the final R = 0.0390 and wR = 0.1032 for 6037 independent reflections with Rint = 0.0214. Crystal data for 2： C32H36N6O6Zn, Mr= 666.04, monoclinic, space group C2/c with a = 24.434（4）, b = 13.543（2）, c = 10.2379（16） A, β = 109.024（2）°, V = 3202.8（9）A3 Dc= 1.381 g/cm^3, F（000） = 1392,μ（MoKa） = 0.820 mm^-1, Z = 4, the final R = 0.0304 and wR = 0.0658 for 2833 independent reflections with Rint = 0.0307. X-ray analysis reveals that both Zn（ Ⅱ ） ions are four-coordinated by two pyridyl-N atoms from nitroxide radicals and two carboxylate oxygen atoms to form distorted tetrahedral geometries. Each isophthalate dianion binds two Zn（ Ⅱ ） ions in a monodentate mode, leading to a I-D chain structure.

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 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 and Crystal Structure of a Novel Complex [Ag(NIT3Py)_3]·(ClO_4)(H_2O)

A novel complex [Ag(NIT3Py)3]?(ClO4)(H2O) has been synthesized and structurally characterized by X-ray diffraction method. It crystallizes in the rhombohedral system, space group R 3 with a = 15.8227(17), b = 15.8227(17), c = 31.445(3) ?, γ = 120°, V = 6817.8(12) ?3, Dc = 1.370 g/cm3, Z = 6, μ = 0.566 mm-1, Mr = 937.18, F(000) = 2916, R = 0.0715, wR = 0.2115 and GOF = 1.086. The structure consists of Ag(NIT3Py)3+ cation moiety, one water molecule and one perchloric ion. The Ag(I) ion is in a trigonal planar coordination environment formed by three nitrogen atoms from three NIT3Py ligand molecules.

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.

Synthesis and Crystal Structure of a Novel Complex [Cu(Phen)_3](ClO_4)_2(btio)(H_2O)

The title compound [Cu(Phen)3](ClO4)2(btio)(H2O), where btio = 2-(4- benzoyloxyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, has been prepared and structurally characterized by X-ray diffraction. It crystallizes in triclinic, space group P?with a = 13.049(4), b = 13.827(5), c = 14.860(5) , a = 71.736(6), b = 77.076(6), g = 87.054(6)? C50H43Cl2CuN8O13, Mr = 1098.36, V = 2481(1) 3, Z = 2, Dc = 1.470 g/cm3, m(MoKa) = 0.622 mm-1, F(000) = 1132, the final R = 0.0639 and wR = 0.1473 for 8705 independent reflections with Rint =0.0285. The title compound is composed of [Cu(Phen)3]2+ moiety , one btio, two perchlorate ions and one water molecule. The copper(II) ion is octahedrally coordinated by three 1,10-phenanthroline ligands. The outer sphere consisting of one btio, two perchlorate ions and one water molecule is combined with the inner by hydrogen bonds and electrostatic interactions.

Synthesis and Crystal Structure of an Imino Nitroxide Complex [Cd(IM2py)_2Cl_2]

The title compound [Cd(IM2py)2Cl2], where IM2py = 2-(2?-pyridinyl)-4,4,5,5-tetra- methylimidazoline-1-oxyl, has been prepared and structurally characterized by X-ray diffraction. It crystallizes in monoclinic, space group C2/c with a = 18.436(6), b = 9.255(3), c = 15.831(5) ? b = 100.274(5)? C24H32CdCl2N6O2, Mr = 619.86, V = 2658.0(14) ?, Z = 4, Dc = 1.549 g/cm3, m(MoKa) = 1.056 mm-1, F(000) = 1264, the final R = 0.0324 and wR = 0.0659 for 2725 independent reflections with Rint = 0.0378. The title complex exists as discrete mononuclear molecules, adopting a distorted octahedral [cis(Cl)-trans(py)] configuration with the cadmium(II) ion being bonded to two bidentate radicals and two chlorine atoms. There exist p???p stacking interactions between the adjacent parallel pyridyl rings of the complex in the ac plane.

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 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 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.

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.

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,Crystal Structure and Magnetic Behavior of a Novel Cd(Ⅱ) Complex with Four Nitroxide Radicals

A novel diamagnetic-metal Cd（Ⅱ） complex with four nitroxide radicals[Cd（IM4Py）4Cl2]（IM4Py=2-（4＇-pyridinyl）-4,4,5,5-tetramethylimidazoline-1-oxyl） was synthesized and characterized by elemental analyses,IR spectra,UV-Vis spectra and X-ray single crystal diffraction.The complex crystallized in triclinic space group P1 with a=0.93285（14） nm,b=1.16827（18） nm,c=1.3660（2） nm,α=112.759（2）°,β=104.524（2）°,γ=92.008（3）°,V= 1.3143（3） nm3,Z=1,Dc=1.335 g/cm3,the final R1=0.0423 and wR2=0.1009.In the title complex,each Cd（Ⅱ） ion adopting a distorted octahedral geometry is coordinated by two Cl-anions and four pyridyl-N atoms from four IM4Py ligands.The magnetic measurements show the weak antiferromagnetic interactions between the nitroxide radicals.

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 Structures and Intermolecular Magnetic Coupling Mechanism of the Mononuclear Radical Complex[1-N-methyl-1,10-phenanthrolium][Ni(dmit)_2]

The mononuclear radical anionic complex [1-N-methyl-1,10-phenanthrolium][Ni（dmit）2]（dmit = 1,3-dithiole-2-thione-4,5-dithiolate） with a new countercation has been prepared and its crystal structure was determined by X-ray crystallography at 298 and 80 K. In the mononuclear radical anionic complex, the nickel ion assumes a slightly distorted square-planar geometry. There are two and three kinds of intermolecular interactions between adjacent mononuclear radical anionic complexes in the crystal at 298 and 80 K, respectively（i.e., Models A and B at 298 K; and Models C, D and E at 80 K）. The variable-temperature magnetic moments indicate a strong antiferromagnetic interaction between the adjacent mononuclear radical anionic complexes, and the theoretical calculations reveal that the stronger antiferromagnetic coupling strength at lower temperature should be contributed to the larger overlap integrals between the short contact atoms. This study is the first to reveal the mechanism of stronger magnetic coupling strength at lower temperature for a mononuclear radical anionic nickel complex with dmit as the ligand.

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.

Syntheses,Crystal Structures and Magnetic Properties of Two Nitrophenyl Substituted Nitronyl Nitroxide Radical-lanthanide Complexes

Syntheses, structures and magnetic properties of two nitrophenyl substituted nitronyl nitroxide radical-lanthanide complexes [Ln（hfac）3（NITmNO2）2] （Ln = Sm（Ⅲ） （1）, Tb（Ⅲ） （2）, hfac = hexafluoroacetylacetonate, NITmNO2 = 2-（3-nitrophenyl）-4,4,5,5-tetramethyl-imidazo- line-1-oxyl-3-oxide） have been described in this paper. X-ray analysis shows that the two complexes have similar mononuclear trispin radical-Ln（Ⅲ）-radical structures, in which the central Ln（Ⅲ） ions are all eight coordinated in D2d dodecahedral （DD） geometry formed by six oxygen atoms from three hfac and two oxygen atoms from nitronyl nitroxide. The magnetic study indicates the antiferromagnetic interaction between Sm（Ⅲ） ion and NITmNO2 in complex 1, while weak ferromagnetic interaction between Tb（Ⅲ） ion and NITmNO2 in complex 2.