Two Novel Mercury(II) and Copper(II) Complexes Based on (5-Chloro-quinolin-8-yloxy)acetic Acid

Teng ZHAO Yu-Hong WANG Rui-Feng SONG

Citation:  ZHAO Teng, WANG Yu-Hong, SONG Rui-Feng. Two Novel Mercury(II) and Copper(II) Complexes Based on (5-Chloro-quinolin-8-yloxy)acetic Acid[J]. Chinese Journal of Structural Chemistry, 2016, 35(7): 1137-1144. doi: 10.14102/j.cnki.0254-5861.2011-1034 shu

Two Novel Mercury(II) and Copper(II) Complexes Based on (5-Chloro-quinolin-8-yloxy)acetic Acid

English

  • 

    1   INTRODUCTION

    In the past several years, luminescent complexes with nitrogen-containing ligands have attracted much attention due to their good performance in electroluminescent devices and sensor technologies[1-5]. Recently, Hg (II) and Cu (II) complexes with nitrogen-containing ligands have begun to receive attention[6-15]. On one hand, some Hg (II) and Cu (II) complexes of nitrogen-containing ligands exhibit efficient luminescent properties which show that this new class of luminescent metal compounds may be potential applications in optoelectronic devices[6-12]. On the other hand, the design and synthesis of efficient luminescent chelating Hg (II) complexes is also of importance for the detection of Hg (II), as mercury presents one of the most hazardous and toxic pollutants that impact on the environment and biological systems[13-15]. Therefore, the synthesis of new Hg (II) and Cu (II) complexes with nitrogen-containing ligands is of great significance. Quinoline derivatives are well known nitrogen-containing ligands, and their complexes have been intensively studied due to their intriguing diversity and potential applications as functional materials[16-21]. 8-Quinolinyloxyacetic acid and their derivatives exhibit a rich structural variety, and reports on the complexes with such as quinolin-8-yloxy acetic acid and (5-chloro-quinolin-8-yloxy) acetic acid ligands have increased in recent years[22-30]. The carboxylate groups exhibit diverse coordination modes in these complexes due to deprotonation. As a continuation of our work[23, 24, 27-30], HgII and CuII complexes of (5-chloro-quinolin-8-yloxy) acetic acid were prepared. Interestingly, when (5-chloro-quinolin-8- yloxy) acetic acid reacted respectively with HgII and CuII ions by the synthesis method of PbII complex[29], the complexes of deprotonation ligand are not be prepared. Unexpectedly, complexes HgII (1) and CuII (2) of the ester product were obtained. In this paper, we report here the crystal structures and luminescent properties of 1 and 2.

    2   EXPERIMENTAL

    2.1   Materials and general methods

    All reagents for syntheses and analyses were of analytical grade. (5-Chloro-quinolin-8-yloxy) acetic acid ligand was prepared by reported procedures[29]. Complexes 1 and 2 were prepared by solvothermal method. FT-IR spectra (KBr pellet) were taken on a FT-IR 170 SX (Nicolet) spectrometer in the 4000~ 400 cm-1 region. Elemental analysis (C, H and N) was carried out on a Perkin-Elmer 240C analytical instrument. X-ray powder diffraction (XRPD) was recorded on a Rigaku D/Max-3C diffractometer at 40 kV, 30 mA for a Cu-target tube and a graphitemonochromator. Thermal analysis (TGA) of the complexes was performed with a SDT 2960 thermoanalyzer at a heating rate of 10 ℃/min from 30 to 800 ℃ under a 50.0 mL/min nitrogen gas flow. UV-Vis-NIR spectra were measured with a Shimadzu UV-3150 spectrometer at room temperature. Solid fluorescence spectra were determined on an Eclipse Cary fluorescence spectrometer.

    2.2   Syntheses

    HgLBr2 (1) In a thick Pyrex tube with the length of 15 cm and inner diameter of 1 cm, (5-chloro-quinolin-8-yl-oxy) acetic acid (0.0238 g, 0.1 mmol), methanol (4 mL), triethylamine (10.1 mg, 0.1 mmol) and HgBr2(36.0 mg, 0.1 mmol) were placed successively. The mixture was heated at 120 ℃ for 3 days. After cooling at a rate of 5 ℃/h to ambient, colorless block crystals were collected. The product was washed with anhydrous ethanol and dried at room temperature, obtaining 65.3% yield based on (5-chloro-quinolin-8-yloxy) acetic acid. IR (KBr pellet, cm-1): 2957w, 2915w, 2839w, 1744vs, 1592m, 1502m, 1366s, 1222s, 1109m, 865m, 796s, 807m. Analysis found (%): C, 23.57; H, 1.66; N, 2.30. Calcd. (%) for C12H10Br2ClHgNO3: C, 23.53; H, 1.63; N, 2.29.

    CuL2Cl2 (2) A green block crystal of 2 suitable for X-ray analysis was obtained by a similar method described for 1. Yield: 59%. IR (KBr pellet, cm-1): 2960w, 2913w, 2841w, 1739vs, 1597m, 1502m, 1373s, 1231s, 1047m. Anal. found: C, 44.33; H, 3.35; N, 4.41. Calcd. for C24H20Cl4CuN2O6: C, 45.20; H, 3.16; N, 4.39.

    2.3   Structure determination

    The crystals (0.28mm × 0.12mm × 0.06mm for 1 and 0.50mm × 0.20mm × 0.20mm for 2) were mounted on a glass fiber in a random orientation. All measurements were made on a Bruker APEX-II CCD with graphite-monochromated MoKα radiation (λ = 0.71070 Å). The data were collected at 223(2) K in the ranges of 3.03≤θ≤27.49° for 1 and 3.0 ≤ θ ≤ 27.50° for 2. A total of 6953 reflections for 1 and 11669 for 2 were collected with 3388 unique ones (Rint = 0.0453) for 1 and 5717 (Rint = 0.0312) for 2, of which 2615 with I > 2σ(I) for 1 and 4174 for 2 were observed and used in the succeeding refinements. Their intensity data were corrected for Lp factors and empirical absorption. The structures were solved by direct methods and expanded by using difference Fourier techniques with SHELXS-97[31]. All of the non-hydrogen atoms were located with successive difference Fourier syntheses and refined by full-matrix least-squares methods on F2 with anisotropic thermal parameters[32]. H atoms were added geometrically and refined as riding. The final refinement gave R = 0.0351 for 1 / 0.0408 for 2 and wR = 0.0504 for 1 / 0.0922 for 2 (For 1, w = 1/[σ2(Fo)2 + (0.0013P)2 + 0.0000P], where P = (Fc 2 + 2Fc 2)/3, (Δ/σ) max = 0.001, S = 0.946, (Δρ) max = 1.197 and (Δρ) min = -1.295 e/Å3; For 2, w = 1/[σ2(Fo)2 + (0.0420P)2 + 0.0000P], where P = (Fo 2 + 2Fc 2)/3, (Δ/σ) max = 0.001, S = 1.018, (Δρ) max = 0.465 and (Δρ) min = -0.414 e/Å3). Selected bond lengths and bond angles are listed in Table 1.

    Table 1.  Selected Bond Lengths (Å) and Bond Angles (°)
    1BondDist.BondDist.BondDist.Hg(1)-Br(1)2.4381(6)Hg(1)-Br(2)2.4301(7)Hg(1)-N(1)2.570(6)Angle(°)Angle(°)Angle(°)Br(2)-Hg(1)-Br(1)163.47(3)Br(2)-Hg(1)-N(1)101.94(10)Br(1)-Hg(1)-N(1)92.15(10)2BondDist.BondDist.BondDist.Cu(1)-N(1)2.038(2)Cu(1)-N(2)2.060(2)Cu(1)-O(1)2.4308(19)Angle(°)Angle(°)Angle(°)N(1)-Cu(1)-N(2)89.34(8)Cl(4)-Cu(1)-O(1)103.39(5)N(1)-Cu(1)-Cl(4)89.49(6)Cl(3)-Cu(1)-O(1)87.72(4)N(2)-Cu(1)-O(4)71.24(7)Cl(3)-Cu(1)-O(4)92.64(5)
    Cu(1)-Cl(4)2.2530(8)Cu(1)-Cl(3)2.2679(7)Cu(1)-O(4)2.4313(19)
    N(2)-Cu(1)-Cl(4)158.81(6)N(1)-Cu(1)-O(4)106.69(8)N(1)-Cu(1)-Cl(3)159.61(6)
    N(2)-Cu(1)-Cl(3)90.85(6)Cl(4)-Cu(1)-O(4)88.87(5)Cl(4)-Cu(1)-Cl(3)97.49(3)
    N(1)-Cu(1)-O(1)72.01(7)O(1)-Cu(1)-O(4)167.58(6)N(2)-Cu(1)-O(1)96.34(8)
    Table 1.  Selected Bond Lengths (Å) and Bond Angles (°)

    3   RESULTS AND DISCUSSION

    3.1   Crystal structures

    Complex 1 is a mononuclear compound consisting of one HgII ion, two Br anions and one L ligand (Fig. 1). The HgII centre has a distorted trigonal planar geometry comprised of two Br atoms and one quinoline N atom of the L ligand. The Hg-N bond length is 2.570(6) Å and the Hg-Br bond lengths are 2.4381(6) and 2.4301(7) Å. The angles around the Hg atom are 92.15(10), 101.94(10) and 163.47(3)°, respectively. Weak Hg…O interactions with distances of 2.766(1) and 2.849(1) Å are observed. If these are considered to be chemically significant interactions, a grossly distorted trigonal biyramid coordination about Hg is thus resulted (Fig. 1). The centroid-centroid separation (3.656(1) Å) between the pyridine moieties of the quinoline rings of centrosymmetrically related complex molecules indicate the presence of intermolecular face-to-face π-π stacking interactions (Fig. 2)[33]. Intermolecular C-H…π stacking interactions are also observed between methyl hydrogen atom H (12B) from one ligand and the centroid of the quinoline ring of the adjacent ligand, with a separation of 2.859(1) Å (Fig. 2)[34]. Intermolecular C-H…Br hydrogen bonds also exist in the H (3A) atoms of quinoline rings and the boromide atoms Br (2) (symmetry code: 1-x, -y, 1-z) of adjacent complex molecule as well as the methylene hydrogen atoms H (10B) and the boromide atoms Br (1) (symmetry code: -x, -y, 2-z) of adjacent complex molecule, as shown in Fig. 2 and Table 2[35]. Furthermore, the quasi one-dimensional chains are assembled by these intermolecular π-π, C-H…π interactions and intermolecular C-H…Br hydrogen bonds (Fig. 2).

    Figure 1.  Molecular structure of complex 1 with atomic numbering scheme (50% probability displacement ellipsoids)
    Figure 2.  Quasi the one-dimensional chain through intermolecular π-π, C-H…π stacking interaction and C-H…Br hydrogen bonds
    Table 2.  Hydrogen Bond Lengths (Å) and Bond Angles (°)
    D-H…Ad(D-H)d(H…A)d(D…A)∠D-H…A
    C(3)-H(3A)…Br(2)i0.932.9953.845(10)153
    C(10)-H(10B)… Br(1)ii0.972.9883.922(10)162
    C(19)-H(19)…Cl(3)iii0.942.713.641(3)174
    C(22)-H(22B)…Cl(3)iii0.982.653.574(3)157
    C(10)-H(10B)…Cl(4)iv0.982.823.414(2)120
    Symmetry codes: (i) 1-x, -y, 1-z; (ii) -x, -y, 2-z; (iii) 1-x, 1-y, 1-z; (iv) 2-x, 1-y, -z
    Table 2.  Hydrogen Bond Lengths (Å) and Bond Angles (°)

    Complex 2 is a neutral mononuclear complex consisting of one copper (II) ion, two Cl anions and two L ligands (Fig. 3). Each CuII center has a distorted octahedral geometry (Table 1) comprised of two chloride ions, two quinoline N atoms and two O atoms of two L ligands. The coordination basal plane is defined by N (1), N (2), Cl (3) and Cl (4), and the apical position is occupied by O (1) and O (4). Atoms N (1), N (2), Cl (3) and Cl (4) show deviations of -0.4153(1), 0.4065(1), -0.3363(1) and 0.3452(1)°, respectively from their leastsquares mean plane. Intermolecular C-H…Cl hydrogen bonds exist in the quinoline rings H (19) atoms, the methylene hydrogen atoms H (22B) and the chloride atoms Cl (3) (symmetry code: 1-x, 1-y, 1-z) of one adjacent complex molecule as well as the methylene hydrogen atoms H (10B) and the chloride atoms Cl (4) (symmetry code: 2-x, 1-y, -z) of another adjacent complex molecule, as shown in Fig. 4 and Table 2[35]. Then, the quasi one-dimensional chains are assembled by intermolecular C-H…Cl hydrogen bonds (Fig. 4).

    Figure 3.  Molecular structure of complex 2 with atomic numbering scheme (50% probability displacement ellipsoids)
    Figure 4.  Quasi the one-dimensional chain through intermolecular C-H…Cl hydrogen bonds (Other hydrogen atoms are omitted for clarity)

    The structural differences between 1 and 2 exhibit the influences of different metal ions, and may mainly attribute to the differences of their coordination abilities. The atomic radius of Hg is greater than that of Cu, resulting in trigonal planar geometry of HgII centre and octahedron geometry of CuII centre. However, compared with complex [C11H7Cl2NO3Pb][29], no (5-chloro-quinolin-8-yloxy) acetate exists in complexes 1 and 2 while ligand L is formed in 1 and 2. This shows triethylamine does not have the effect of neutralizing protons of (5-chloro-quinolin-8-yloxy) acetic acid. So, it indicates HgII and CuII ions may play a catalytic role in the formation of L.

    3.2   XRPD results and thermal analysis

    In order to confirm whether the crystal structures are truly representative of the bulk materials, X-ray powder diffraction experiments have been carried out for 1 and 2. The XRPD experimental and computer simulated patterns of the corresponding complexes are shown in Figs. 5 and 6. Their peaks are in good agreement with those calculated from X-ray single-crystal diffraction data, indicating the phase purity of the as-synthesized sample.

    Figure 5.  Experimental and simulated power X-ray diffraction patterns of compound 1
    Figure 6.  Experimental and simulated power X-ray diffraction patterns of compound 2

    Thermal decomposition behaviors of complexes 1 and 2 have been studied by TG in the nitrogen atmosphere. The TG curves of 1 and 2 are illustrated in Fig. 7. Complex 1 occurs in two distinct decomposition stages. It is thermally stable up to 155 ℃ and the first mass loss takes place between 155 and 316 ℃. The experimental mass loss of 68.54% corresponds to the elimination of ligand L and Br anions. The weight loss of 68.54% is close to that calculated (67.23%) for the formula. The second stage in the range of 316 ~ 598 ℃ is complete evaporation of the residual metallic mercury with a mass loss 31.46% (theoretical value 32.77%). So, no remaining residue is observed. The thermal decomposition process of 2 has two steps. It is thermally stable up to 235 ℃. The first weight loss appears at 235~377 ℃, with the weight loss of 34.10% corresponding to the removal of CH2COOCH3 and coordinated Cl anion and close to that calculated (34.05%). The second weight loss (54.78%) from 377 to 622 ℃ is attributed to the elimination of residue ligands (56.00%). Because of the nitrogen atmosphere, the remaining residue is metallic copper (11.12%), which is consistent with the theoretical value of 9.95%.

    Figure 7.  TG curves of complexes 1 and 2

    3.3   Solid fluorescence spectra and optical property of complexes 1 and 2

    Solid fluorescence behaviors of complexes 1 and 2 were determined by 350 nm excitation wavelengths at room temperature (Fig. 8). Complexes 1 and 2 exhibit respectively narrow fluorescence emission at 406 and 410 nm, which are similar to that of complex [C11H7Cl2NO3Pb][29] with a fluorescence emission at 407 nm. Thus, compared with the ligand, the emission peak of the complex may be attributed to the ligand-to-metal charge transfer transition.

    Figure 8.  Fluorescence spectra of complexes 1 and 2

    UV-VIS-NIR diffuse reflectance spectra of 1 were determined at room temperature. The absorption (α/S) data were calculated by the Kubelka- Munk function, α/S = (1 - R)2/2R[36]. The optical band gaps (Eonset) are obtained by the extrapolation of linear portion of the absorption edges. The optical bandgap of 3.2 eV is estimated approximately in complex 1 (Fig. 9), which indicates that it maybe has potential semiconductor property.

    Figure 9.  Solid-state optical absorption spectra of complex 1
    1. [1]

      Baldo M. A., Lamansky S., Burrows P. E., Thompson M. E., Forrest S. R.. Very high-efficiency green organic light-emitting devices based on electro-phosphorescence[J]. Applied. Physics. Letters, 1999, 75:  4-6. doi: 10.1063/1.124258

    2. [2]

      Xia H., Zhang C. B., Liu X. D., Qiu S., Lu P., Shen F. Z., Zhang J. Y., Ma Y. G.. Ruthenium(II) complex as phosphorescent dopant for highly efficient red polymers light-emitting diodes[J]. J. Phys. Chem. B, 2004, 108:  3185-3190. doi: 10.1021/jp0369645

    3. [3]

      Tu ng, Y. L., Lee S. W., Chi Y., Chen L. S., Shu C. F., Wu F. I., Carty A. J., Chou P. T., Peng S. M., Lee G. H.. Organic light-emitting diodes based on charge-neutral RuII phosphorescent emitters[J]. Advanced. Materials, 2005, 17:  1059-1064. doi: 10.1002/(ISSN)1521-4095

    4. [4]

      Yu G., Yin S. Y., Liu Y. Q., Shuai Z. G., Zhu D. B.. Structures, electronic states, and electroluminescent properties of a zinc(II) 2-(2-hydroxyphenyl)benzothiazolate complex[J]. J. Am. Chem. Soc., 2003, 125:  14816-14824. doi: 10.1021/ja0371505

    5. [5]

      Aragoni , M. G., Ar ca, M , Demartin , F , Devillanova , F. A., Isaia F., Garau A., Lippolis V., Jalali F., Papke U., Shamsipur M., Tei L., Yari A., Verani G.. Fluorometric chemosensors[J]. Interaction of toxic heavy metal ions PbII, CdII, and HgII with novel mixed-donor phenanthroline-containing macrocycles: spectrofluorometric, conductometric, and crystallographic studies. Inorg. Chem., 2002, 41:  6623-6632.

    6. [6]

      Fan R. Q., Yang Y. L., Yin Y. B., Hasi W. L. J., Mu Y.. Syntheses and structures of blue-luminescent mercury(II) complexes with 2,6-bis(imino)pyridyl ligands[J]. Inorg. Chem., 2009, 48:  6034-6043. doi: 10.1021/ic900339u

    7. [7]

      L iu, Q. X., Y ao, Z. Q., Zh ao, X. J., Zh ao, Z. X., Wa ng, X. G.. NHC metal (silver, mercury, and nickel) complexes based on quinoxaline-dibenzimidazolium salts: synthesis, structural studies and fluorescent chemosensors for Cu2+ by charge transfer[J]. Organometallics, 2013, 32:  3493-3501. doi: 10.1021/om400277z

    8. [8]

      Yang Y. M., Zhao Q., Feng W., Li F. Y.. Luminescent chemodosimeters for bioimaging[J]. Chem. Rev., 2013, 113:  192-270. doi: 10.1021/cr2004103

    9. [9]

      YamV. W. W., Pui Y. L., Cheug K. K.. Synthesis, structure, luminescence, and electrochemical properties of polynuclear mercury(II) chalcogenolate complexes[J]. J. Chem. Soc. Dalton. Trans., 2000, :  3658-3662.

    10. [10]

      Kunkely H., Vogler A.. Photoluminescence of 8-quinolinolatomethylmercury(II). J. Photochem. and Photobio[J]. A: Chem., 2001, 144:  69-72.

    11. [11]

      David G. C., Elena L. T., Mendiola M. A.. A fluorescent dissymmetric thiosemicarbazone ligand containing a hydrazonequinoline arm and its complexes with cadmium and mercury[J]. Eur. J. Inorg. Chem., 2013, :  80-90.

    12. [12]

      Jassal A. K., Sharma S., Hundal G., Hundal M. S.. Structural diversity, thermal studies, and luminescent properties of metal complexes of dinitrobenzoates: a single crystal to single crystal transformation from dimeric to polymeric complex of copper(II). Cryst[J]. Growth. Des., 2015, 15:  79-93. doi: 10.1021/cg500883w

    13. [13]

      Sazanovich I. V., Kirmaier C., Hindin E., Yu L. H., Bocian D. F., Lindsey J. S., Holten D.. Structural control of the excited-state dynamics of bis(dipyrrinato)zinc complexes: self-assembling chromophores for light-harvesting architectures[J]. J. Am. Chem. Soc., 2004, 126:  2664-2665. doi: 10.1021/ja038763k

    14. [14]

      Y u, Y , L in, L. R., Ya ng, K. B., Zhong , X , Huang , R. B., Zheng , L. S.. p-Dimethylaminobenzaldehyde thiosemicarbazone: a simple novel selective and sensitive fluorescent sensor for mercury(II) in aqueous solution[J]. Talanta, 2006, 69:  103-106. doi: 10.1016/j.talanta.2005.09.015

    15. [15]

      Li X. H., Gao X. G., Shi W., Ma H. M.. Design strategies for water-soluble small molecular chromogenic and fluorogenic probes[J]. Chem. Rev., 2014, 114:  590-659. doi: 10.1021/cr300508p

    16. [16]

      Tang C. W., Vanslyke S. A.. Organic electroluminescent diodes[J]. Applied. Physics. Letters, 1987, 51:  913-915. doi: 10.1063/1.98799

    17. [17]

      Hanson S. K., Baker R. T., Gordon J. C., Scott B. L., Silks L. A., Thorn D. L.. Mechanism of alcohol oxidation by dipicolinate vanadium(V): unexpected role of pyridine[J]. J. Am. Chem. Soc., 2010, 132:  17804-17816. doi: 10.1021/ja105739k

    18. [18]

      Tong L. P., Wang Y., Duan L. L., Xu Y. H., Cheng X., Fischer A., Ahlquist M. S. G., Sun L. C.. Water oxidation catalysis: influence of anionic ligands upon the redox properties and catalytic performance of mononuclear ruthenium complexes[J]. Inorg. Chem., 2012, 51:  3388-3398. doi: 10.1021/ic201348u

    19. [19]

      Moberg C., Muhammed M., Svensson G., Weber M.. Novel quinaldic acids for selective chelation of cadmium(II). X-ray crystal structure of [Cd(C18H12NO4)2](Me2SO)·2H2O. J. Chem[J]. Soc. Chem. Commun., 1988, 12:  810-812.

    20. [20]

      Deun R. V., Fias P., Nockemann P., Schepers A., Parac-Vogt T. N., Hecke K. V., Meervelt L. V., Binnemans K.. Rare-earth quinolinates: infrared-emitting molecular materials with a rich structural chemistry[J]. Inorg. Chem., 2004, 43:  8461-8469. doi: 10.1021/ic048736a

    21. [21]

      Middleton A. J., Marshall W. J., Radu N. S.. Elucidation of the structure of a highly efficient blue electroluminescent material[J]. J. Am. Chem. Soc., 2003, 125:  880-881. doi: 10.1021/ja027323a

    22. [22]

      Kumar D. V. G., Chen W., Weng N. S., Mak T. C. W.. Triphenyltin(IV) 8-quinolyloxyacetate hydrate, [Ph3SnO2CCH2(8-C9H6NO)·H2O]n, an organotin ester derivative built of hydrogen-bonded helical chains[J]. J. Organomet. Chem., 1987, 322:  33-47. doi: 10.1016/0022-328X(87)85021-0

    23. [23]

      Wang Y. H., Song R. F., Zhang F. Y.. Carboxylate-bridged helical-chain Cu(II) complex and zig-zag chain Ni(II) and Co(II) complexes from 8-quinolinyloxyacetate[J]. J. Mol. Struct., 2005, 752:  104-109. doi: 10.1016/j.molstruc.2005.05.031

    24. [24]

      Wang Y. H., Zhao K. Y., Du J.. Synthesis and crystal structure of dinuclear Cd(Ⅱ) complex with 8-quinolinyloxyacetate[J]. Chin. J. Inorg. Chem., 2005, 21:  511-514.

    25. [25]

      Cheng X. N., Zhang W. X., Chen X. M.. Single-crystal-to-single-crystal transformation from ferromagnetic discrete molecules to a spin-canting antiferromagnetic layer[J]. J. Am. Chem. Soc., 2007, 129:  15738-15739. doi: 10.1021/ja074962i

    26. [26]

      Fan J., Wang Z. H., Yin X., Zhang W. G., Huang Z. F., Zeng R. H.. Controlled synthesis, structures and properties of one-, two-, and three-dimensional lanthanide coordination polymers based on (8-quinolyloxy)acetate[J]. CrystEngComm., 2010, 12:  216-225. doi: 10.1039/B910219A

    27. [27]

      Song R. F., Yang J., Qiu J. X., Wang Y. H.. Solvothermal synthesis and crystal structure of a 1D helical-chain cobalt(II) complex containing (quinolin-8-yloxy)acetate[J]. Chin. J. Struct. Chem., 2011, 30:  1085-1090.

    28. [28]

      Wang Y. H., Song R. F., Xu X. W.. A novel chain lead(II) coordination polymer [Pb(QOA)2]n based on 8-quinolinic acid ligand: synthesis, crystal structure and properties[J]. Chin.J. Inorg. Chem., 2014, 30:  1250-1254.

    29. [29]

      Li J., Wang Y. H., Song R. F.. A novel two-dimensional lead(II) coordination polymer based on dinuclear lead(II) unit containing (5-chloro-quinolin-8-yloxy) acetate[J]. Chin. J. Struct. Chem., 2014, 33:  1488-1494.

    30. [30]

      Wang Y. H., Yang J., Zhong Q., Song R. F.. A two-dimensional lead(II) coordination polymer based on rectangular hexanuclear lead(II): synthesis, crystal structure and properties[J]. Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 2015, 45:  725-729. doi: 10.1080/15533174.2013.843553

    31. [31]

      Sheldrick, G. M. SHELXS-97, Program for X-ray Crystal Structure Solution. Göttingen University, Germany 1997.

    32. [32]

      Sheldrick, G. M. SHELXL-97, Program for X-ray Crystal Structure Refinement. Göttingen University, Germany 1997.

    33. [33]

      Janiak C.. A critical account on π-π stacking in metal complexes with aromatic nitrogen-containing ligands[J]. J. Chem. Soc. Dalton Trans., 2000, :  3885-3896.

    34. [34]

      Russell V., Scudder M., Dance I.. The crystal supramolecularity of metal phenanthroline complexes[J]. J. Chem. Soc., Dalton Trans., 2001, :  789-799.

    35. [35]

      Van den Berg J. A., Seddon K. R.. Critical evaluation of C-H···X hydrogen bonding in the crystalline state[J]. Crystal Growth Des., 2003, 3:  643-661. doi: 10.1021/cg034083h

    36. [36]

      Wendlandt, W. W.; Hecht, H. G. Reflectance Spectroscopy. Interscience Publishers, New York 1966.

  • Figure 1  Molecular structure of complex 1 with atomic numbering scheme (50% probability displacement ellipsoids)

    Figure 2  Quasi the one-dimensional chain through intermolecular π-π, C-H…π stacking interaction and C-H…Br hydrogen bonds

    Figure 3  Molecular structure of complex 2 with atomic numbering scheme (50% probability displacement ellipsoids)

    Figure 4  Quasi the one-dimensional chain through intermolecular C-H…Cl hydrogen bonds (Other hydrogen atoms are omitted for clarity)

    Figure 5  Experimental and simulated power X-ray diffraction patterns of compound 1

    Figure 6  Experimental and simulated power X-ray diffraction patterns of compound 2

    Figure 7  TG curves of complexes 1 and 2

    Figure 8  Fluorescence spectra of complexes 1 and 2

    Figure 9  Solid-state optical absorption spectra of complex 1

    Table 1.  Selected Bond Lengths (Å) and Bond Angles (°)

    1BondDist.BondDist.BondDist.Hg(1)-Br(1)2.4381(6)Hg(1)-Br(2)2.4301(7)Hg(1)-N(1)2.570(6)Angle(°)Angle(°)Angle(°)Br(2)-Hg(1)-Br(1)163.47(3)Br(2)-Hg(1)-N(1)101.94(10)Br(1)-Hg(1)-N(1)92.15(10)2BondDist.BondDist.BondDist.Cu(1)-N(1)2.038(2)Cu(1)-N(2)2.060(2)Cu(1)-O(1)2.4308(19)Angle(°)Angle(°)Angle(°)N(1)-Cu(1)-N(2)89.34(8)Cl(4)-Cu(1)-O(1)103.39(5)N(1)-Cu(1)-Cl(4)89.49(6)Cl(3)-Cu(1)-O(1)87.72(4)N(2)-Cu(1)-O(4)71.24(7)Cl(3)-Cu(1)-O(4)92.64(5)
    Cu(1)-Cl(4)2.2530(8)Cu(1)-Cl(3)2.2679(7)Cu(1)-O(4)2.4313(19)
    N(2)-Cu(1)-Cl(4)158.81(6)N(1)-Cu(1)-O(4)106.69(8)N(1)-Cu(1)-Cl(3)159.61(6)
    N(2)-Cu(1)-Cl(3)90.85(6)Cl(4)-Cu(1)-O(4)88.87(5)Cl(4)-Cu(1)-Cl(3)97.49(3)
    N(1)-Cu(1)-O(1)72.01(7)O(1)-Cu(1)-O(4)167.58(6)N(2)-Cu(1)-O(1)96.34(8)
    下载: 导出CSV

    Table 2.  Hydrogen Bond Lengths (Å) and Bond Angles (°)

    D-H…Ad(D-H)d(H…A)d(D…A)∠D-H…A
    C(3)-H(3A)…Br(2)i0.932.9953.845(10)153
    C(10)-H(10B)… Br(1)ii0.972.9883.922(10)162
    C(19)-H(19)…Cl(3)iii0.942.713.641(3)174
    C(22)-H(22B)…Cl(3)iii0.982.653.574(3)157
    C(10)-H(10B)…Cl(4)iv0.982.823.414(2)120
    Symmetry codes: (i) 1-x, -y, 1-z; (ii) -x, -y, 2-z; (iii) 1-x, 1-y, 1-z; (iv) 2-x, 1-y, -z
    下载: 导出CSV
  • 加载中
计量
  • PDF下载量:  2
  • 文章访问数:  1704
  • HTML全文浏览量:  40
文章相关
  • 收稿日期:  2015-10-31
  • 接受日期:  2015-12-31
通讯作者: 陈斌, bchen63@163.com
  • 1. 

    沈阳化工大学材料科学与工程学院 沈阳 110142

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索

/

返回文章