Self Assembly of three New Copper coordination Polymers Based on N

of 1 were obtained, yield 46% (based on Cu). Anal. Calcd for C9H12CuN2O8S (%): C, 24.38; H, 2.76; N, 6.28; S, 7.33. Found: C, 24.33; H, 2.70; N, 6.30; S, 7.20.2.3.2 Synthesis of [Cu2(L)2]n (2).The procedures were similar to the synthesis of 1 except that the reaction temperature was 120︒C, green block crystals of 2 were obtained with a yield of 23% (based on Cu), Anal. Calcd for C9H8Cu2N2O6S (%): C, 27.12; H, 2.05; N, 7.13; S, 8.06. Found: C, 27.04; H, 2.00; N, 7.01; S, 8.01.2.3.3 Synthesis of [Cu(HL)2]n (3). The procedures were similar to the synthesis of 1 except that the reaction temperature was 90︒C. Yield 55% (based on Cu). Anal. Calcd for C18H18CuN4O12S2 (%): C, 35.47; H, 2.87; N, 9.20; S, 10.45. Found: C, 35.41; H, 2.95; N, 9.18; S, 10.49.2.4 X-ray crystallographyDiffraction intensities were collected on a Bruker Apex CCD area-detector diffractometer (Mo-Ka, r=0.71073 A˚) at 293 K. The structure was solved with direct methods and reEned with a full-matrix least-squares technique with the SHELXTL program package[21]. The hydrogen atoms were placed at calculated positions and refined as riding atoms with isotropic displacement parameters. Crystallographic crystal data and structure processing parameters for 1-3are summarized in Table 1. Selected bond lengths and bond angles for complexe 1-3are listed in table 2, Hydrogen bonds for complexes 1-3 are listed in table 3.3. Results and Discussion3.1. Description of structure3.1.1 Crystal structure of [Cu(L)]·6H2O]n (1).A single-crystal X-ray diffraction study reveals that 1adopts a 3-D coordination polymer which crystallizes in the orthorhombic, space group P212121. The asymmetric unit contains one Cu(II) cation, one ligand and six water molecules.As illustrated in figure 1a, Cu(II) adopts a distorted tetrahedron coordination environment, which is completed by two nitrogen atoms from pyridine (N1A) and sulfamine (N2) of two ligands as well as two oxygen atoms(O1, O4B) from two carboxylates located at the equatorial plane, and one oxygen (O3) from carboxylate at the axial positions. Carboxylic acid using both cis-trans-Bridged bidentate and monodentate coordination of the way. Because of Jahn-Teller effect the bonds, so the Cu-N range from 1.964 (13) to 2.055 (13) Å (Cu(1)–N(2) = 2.1.064 and Cu(1)–N(1)A = 2.055Å), Cu-O bond length range from 1.9066 (11) to 2.422 (1) Å, which similar to the reported bond length[22].Three Cu(II) cations are bridged by one ligand to construct 2-D sheet( figure 1b). Each threeof Cu(II) cations is bridged by two carboxylate groups from two L2- anions in cis-trans-Bridged bidentate mode . The further link by ligand bridging the Cu3 unit with 21 helicity along the c-axisdirection, in which the helical pitch of 9.834 Å is equal to the length of the c-axis (figure 1c). As shown in Figure 1d, the extension of the structure into a 3D framework is accomplished by one ligand bearing two Cu from the different 2D layers along c-axis.3.1.2 Crystal structure of [Cu2(L)2]n (2). A single-crystal X-ray diffraction analysis reveals that crystal 2crystallizes in the monoclinic system, space group P21/c. The asymmetric unit contains two crystallographically independent Cu(II) cations and one ligand. As illustrated in Figure 2a, Cu1(II) cations adopts a distorted tetrahedral coordination environment, which is completed by Cu2(II) cations (Cu(1)–Cu(2)=2.619(13)) and two bridging carboxylate oxygen atoms (O2, O3A) from two different ligands as well as one nitrogen atom (N2) from sulfamine at the axial position. Cu2(II) cations is completed by Cu1(II) cations and bridging carboxylate oxygen atoms (O1, O4) from two different ligands。

Cu1(II) cations is four-coordinated,Cu2(II) cations is three-coordinated. Both carboxylate groups of the ligand adopt cis-cis-Bridged bidentate mode coordinating with two Cu1(II) cations and two Cu2(II) cations. The Cu–Cu bond lengths is 2.619 Å, which is in the normal range[22].Three Cu1–Cu2 units are bridged by one ligand to contruct an 1-D ladder coordination polymer in which Cu–Cu unit take as handraill and pyridine is foodboard in the equatorial direction. From the crystal packing of the coordination polymer, the pyridine are parallel to each other with a centroid-to-centroid distance of 3.4084 Å, which supports the presence of π-πstacking interactions (figure 2b). The non-coordinated sulfamine and sulfonic acid groups participate in N–H···O hydrogen bonds, which defind 3D hydrogen-bonded network and support the supramolecular architecture (figure 2c).3.1.3 Crystal structure of [Cu(HL)2]n (3).A single-crystal X-ray diffraction study reveals that 3 adopts a 1-D coordination polymer which crystallizes in the space group P21/c. The asymmetric unit contains one Cu(II) cation and two ligands. As illustrated in figure 1a, the Cu(II) cation is four-coordinated by two nitrogen atoms from pyridine of two ligands(Cu(1)–N(1) = 2.0140 and Cu(1)–N(1)A = 2.0140Å) and two carboxylate oxygen atoms of two ligands(Cu(1)–O(2)B = 1.9435 and Cu(1)–O(2)C = 1.9435Å). Four coordination sites of Cu(II) are coplanar (N(1)A–Cu(1)–N(1) = 180.00 and O(2)C–Cu(1)–O(2)B = 180.00°) in a perfectly symmetric and form an approximate spuare that Cu(II) cation is located in the center and coordinated atoms are occupied four vertex position of the spuare. The bond lengths and bond angles are in the normalrange[22].Two Cu(II) cations are bridged by one ligand to contruct an 1-D coordination polymer in the equatorial direction(figure 3b). Notably, the presence of sulfonic acid groups and sulfamine leads to the formation of N–H···O and C–H···O hydrogen bonds interactions, which defines a 3D hydrogen-bonded network and, thus, supports the supramolecular architecture (figure 3c).3.2 Powder X-Ray diffractionIn order to check the purity of complex 1, powder X-ray diffraction (XRD) of the as-synthesized sample was measured at room temperature. As shown in Figure 4, the peak positions of experimental patterns are in good agreement with the simulated ones, which clearly indicates good purity of the complex.3.2 Magnetic PropertieThe magnetic property of the complex 1 was investigated over the temperature range 2.0-300.0 K, and the resulting data is shown in Figure 5. For 1, the χm T value at 300 K is 0.51 cm3 mol-1 K, which is much higher than the expected value (0.16 cm3mol-1K ) of two isolated spin-only Cu(II) ions (S=1/2, g =2.0). As T is lowered, χm T decreases continuously to a value of 3.22 cm3mol-1K at 2 K. This behavior in dicatesa dominant antiferromagnetic interaction between the Cu(II) is in correspondence with the Curie-Weiss law in the range of 45-300 K with C = 0.53 cm3mol-1K and θ = -17.43 K.4. ConclusionIn this paper, Cu(NO3)2 ·3H2O, N-[(3-Pyridine)-sulfonyl]aspartate as raw material, in the same ratio material、solvent and pH, under different reaction temperatures , three copper coordination polymers based on N-[(3-Pyridine)-sulfonyl]aspartate ligand were synthesized. Single-crystal X-ray diffraction study reveals that 1 adopts a 3-D coordination polymer which crystallizes in the orthorhombic, space group P212121; 2 crystallizes in the monoclinic system, space group P21/c; 3 adopts a 1-D coordination polymer which crystallizes in the space groupP21/c. A structural comparison of these polymers suggests that different reaction conditions play important role in the construction of resulting architectures for 1-3. It seems more conducive to the synthesis of 3D complexes at high temperature conditions.AcknowledgmentsThe authors acknowledge the financial support from the Scientific Research and Technological Development Project of Guilin (No. 20110330);.The project of Synthesis, Properties of crystal structure and Applied research of 2,4,6 - pyridyl amide(NO. 200807MS090); The project of education department of Guangxi province(NO.YB2014331); Guangxi Natural Science Foundation2014GXNSFAA118035.References[1] Aijaz A., Saudo E.C., Bharadwaj P.K.. Cryst. 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Angew.Chem.,2006, 45, p. 6495.[14] Jiang Y.M., Wang X.J., Ying X.J., et al. Inorg. Chem. Commun., 2006, 9, p. 1063.[15] Hu S., He K.H., Zeng M.H., et al. Inorg. Chem., 2008, 47, p. 5218.[16] Li J.X., Jiang Y.M., Lian B.R. J. Chem. Crystallogr., 2008, 38, p. 711.[17] Zhang S.H., Jiang Y.M., Liu Z.M. J. Coord. Chem., 2008,61, p. 1927.[18] Li J.X., Jiang Y.M., Chen M.J.. J. Coord. Chem., 2008, 61, p. 1765.[19] Qin X.Y., Zhang S.H., Jiang Y.M., et al. J. Coord. Chem., 2009, 62, p. 427.[20] Liang Y.J., Meng X.J., Huang F.P., et al. J. Coord. Chem., 2011, 64, p. 3751.[21] G.M. Sheldrick. SHELXS-97, University of Göttingen,Germany 1997.[22] Abdel-nasser, Alaghaz M. A. J. Mole. Stru., 2014 1072, p. 103.[23] Chowdhuri D.S., Rana A., Bera M., et al. Polyhedron., 2009,28, p. 2131.[24] Deng Z.P., Huo L.H., Li M.S., et al. Cryst. Growth. Des., 2011,11, p. 3090.Figure CaptionsFigure 1. (a) Coordination environment of Cu(II) ions in 1 with hydrogen atoms omitted for clarity with thermal ellipsoids at 50% level.(b) 2-D sheet along the c-axis of ploymer 1. (c) the left- and right-handed helical chains along c-axis. (d) Extended 3D network viewed along the c-axis.Figure 2. (a) Coordination environment of Cu(II) ions in 2 with hydrogen atoms omitted for clarity with thermal ellipsoids at 60% level. (b) 1-D ladder of ploymer 2 and distance of centroid-to-centroid of pyrazine rings. (c) Hydrogen bonds that make up a 3D network polymer.Figure 3. (a) Coordination environment of Cu(II) ions in 3 with hydrogen atoms omitted for clarity with thermal ellipsoids at 50% level. (b) 1-D chain of ploymer 3. (c) Hydrogen bonds that make up a 3D network polymer.Figure 4 XRD pattern of complex 10501001502002503000.0000.0050.0100.0150.0200.0250.0300.0350501001502002503000100200300400500600700χM / (m o l c m -3)T /K0.050.100.150.200.250.300.350.400.45χM T /( c m 3 K m o l -1)1/χM / (m o l c m -3)T /KFigure 5. Temperature dependence of χM , χ M T vs T and χm -1 vs T (inset) for 11.948(5)。