• <tr id="yyy80"></tr>
  • <sup id="yyy80"></sup>
  • <tfoot id="yyy80"><noscript id="yyy80"></noscript></tfoot>
  • 99热精品在线国产_美女午夜性视频免费_国产精品国产高清国产av_av欧美777_自拍偷自拍亚洲精品老妇_亚洲熟女精品中文字幕_www日本黄色视频网_国产精品野战在线观看 ?

    Syntheses, Structures, and Luminescent Properties of the ZnII and CdII 1-D Chain Polymers Assembled by Salicylhydroxamic Acid①

    2015-03-25 02:35:36GAODnDnGAOQinCHENYnMeiLIHongLIWu
    結(jié)構(gòu)化學(xué) 2015年9期

    GAO Dn-Dn GAO Qin CHEN Yn-Mei LI Y-Hong② LI Wu②

    a (Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources,Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, China)

    b (College of Chemistry, Chemical Engineering and Materials Science,Soochow University, Suzhou 215123, China)

    1 INTRODUCTION

    Hydroxamic acids (HAs) are a valuable class of bioligands and have been extensively employed in chemical biology[1]. They possess high metalchelating affinity and exhibit versatile coordination modes. These properties make hydroxamic acids to be powerful ligands to construct homometallic or heterometallic polynuclear clusters and chain complexes[2-5]. Recent advances in the coordination chemistry of hydroxamic acids reveal that the coordination behaviors of hydroxamic acid can be tuned by the incorporation of different functional groups, e.g., -NMe2[2], -OH[6], -NH2[7], etc., at ortho,meta and (or) para positions of the phenyl ring,generating coordination complexes with fascinating configurations and useful properties.

    Salicylhydroxamic acid (H3shi) is a member of a big family of hydroxamic acids. It shows rich coordination modes[8-18](Scheme 1) due to the extra hydroxyl group at the meta position of phenyl ring.H3shi acted as a polydentate ligand to afford mo-nonuclear complexes with Ru[18], V[14]and Pt[13],generating polynuclear compounds with Cu[10],Mo[11], and V[12]as well as polynuclear heterometallic Mn-Ho and Mn-Dy complexes[10]. To our surprise, no polynuclear coordination complexes of ZnIIand CdIIare reported. As is well known, coordination complexes of ZnIIand CdIIhave attracted a great deal of interest due to their potential applications in fluorescence-emitting materials[19-21], such as light-emitting diodes (LEDs) and organic lightemitting diodes (OLEDs)[22], in biological systems,e.g. cleavage of DNA, RNA and amino acid esters,etc.[23-27], and in organic synthesis[28]. To further explore the coordination chemistry of salicylhydroxamic acid with ZnIIand CdII, we conducted the reaction of salicylhydroxamic acid with Zn(CH3COO)2·2H2O and Cd(CH3COO)2·2H2O,respectively. Two new 1-D polymeric chain complexes with formulas [Zn(H2shi)(CH3COO)]n(1) and[Cd(H2shi)2(H2O)]n(2) were synthesized. Herein, we report the syntheses, structures and luminesient properties of these two complexes.

    Scheme 1. Coordination modes of H3shi

    2 EXPERIMENTAL

    2.1 Materials and physical measurement

    All chemicals were purchased from commercial suppliers and used without further purification. The C, H and N microanalyses were carried out with a Carlo-Erba EA1110 CHNO-S elemental analyzer.FT-IR spectra were recorded from KBr pellets in the range of 400~4000 cm-1on a Nicolet MagNa-IR500 spectrometer. Crystal determination was performed with a Bruker SMART APEX ΙΙ CCDC diffractometer equipped with graphite-monochromatized MoKα radiation (λ = 0.71073 ?). The solid-state luminescence emission/excitation spectra were recorded on a FLS920 fluorescence spectrophotometer equipped with a continuous Xe-900 xenon lamp and a μF900 microsecond flash lamp.Powder X-ray diffraction (PXRD) was recorded on a Rigaku D/Max-2500 diffractometer.

    2.2 Syntheses of the complexes

    2. 2. 1 Synthesis of [Zn(H2shi)(CH3COO)]n(1)

    A mixture of Zn(CH3COO)2·2H2O (0.0216 g,0.10 mmol), H3shi (0.0153 g, 0.10 mmol), and H2O(1.0 mL) was placed in a Pyrex-tube. The tube was heated at 80 ℃ for 6 days. After being cooled to room temperature, pale yellow crystals of the product were afforded. The crystals were collected by filtration, washed with H2O (2 mL) and dried in air. Yield: 40% (based on Zn). Anal. Calcd. (%) for C9H9NO5Zn: C, 39.09; H, 3.28; N, 5.06. Found (%):C, 38.96; H, 3.15; N, 5.01. IR (KBr, cm-1): 3274(s),1612(s), 1551(s), 1481(s), 1367(m), 1250(m),1153(s), 1059(s), 1031(m), 925(s), 812(m), 751(m).

    2.2.2 Synthesis of [Cd(H2Shi)2(H2O)]n(2)

    A mixture of Cd(CH3COO)2·2H2O (0.0207 g,0.10 mmol), H3shi (0.0153 g, 0.10 mmol), and H2O(1.0 mL) was placed in a Pyrex-tube. The tube was heated at 80 ℃ for 7 days. After being cooled to room temperature, pale yellow crystals of the product were afforded. The crystals were collected by filtration, washed with H2O (2 mL) and dried in air. Yield: 56% (based on Cd). Anal. Calcd. (%) for C14H14Cd2N2O7: C, 38.68; H, 3.25; N, 6.44. Found(%): C, 38.76; H, 3.21; N, 6.38. IR (KBr, cm-1):3468(m), 3015(w), 1613(s), 1549(s), 1481(s),1417(s), 1341(s), 1250(s), 1153(s), 1122(s), 1050(s),925(s), 812(m), 751(s), 659(s).

    2.3 X-ray crystal structure determination

    The single crystals of complexes 1 and 2 were determined with MoKα radiation using a Bruker SMART APEX-II CCD diffractometer at 296(2) K for 1 and 293(2) K for 2 using the ω-2θ scan mode.For complex 1, in the range of 2.15≤θ≤28.42o,a total of 13821 reflections were obtained with 2490 unique ones and used in the refinements. For complex 2, in the range of 3.39≤θ≤27.49o, a total of 5355 reflections were obtained with 1573 unique ones and used in the refinements. The structures were solved by direct methods and refined with full-matrix least-squares on F2using SHELXS-97[29]and SHELXL-97[30]. The selected bond lengths and bond angles of complexes 1 and 2 are listed in Table 1.

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

    3 RESULTS AND DISCUSSION

    3.1 Structure descriptions of the complexes

    3. 1. 1 Structure of complex 1

    The crystal structure analysis reveals that 1 crystallizes in the tetragonal crystal system, space group I41/a. The asymmetric unit (Fig. 1) consists of one crystallographically independent ZnIIatom,one H2shi-ligand and one acetate ion. The ZnIIion is penta-coordinated by one carboxyl oxygen atom,one μ2-hydroxamate oxygen atom and one μ1-hydroxamate oxygen atom from two H2shi-ligands,and two oxygen atoms from acetate ions, displaying distorted tetragonal geometry. The adjacent ZnIIions are doubly connected by two oxygen atoms of the acetate ion and one hydroxamate oxygen atom to generate an infinitive 1-D chain structure (Fig. 2).The Zn–O/N bond lengths are in the range of 1.983(2)~2.095(3) ?. The ZnII···ZnIIdistance is 3.6506(7) ?. The H2shi-ligands possess the coordination mode F (Scheme 1).

    Fig. 1. Coordination environment of the Zn ion in 1. Hydrogen atoms have been omitted for clarity.Color scheme: blue, ZnII; red, oxygen; dark blue, nitrogen; yellow, carbon

    Fig. 2. 1-D chain structure of 1. Hydrogen atoms are omitted for clarity.Color scheme: blue, ZnII; red, oxygen; dark blue, nitrogen; yellow, carbon

    3. 1. 2 Structure of complex 2

    The crystal structure analysis reveals that 2 crystallizes in monoclinic, space group P2/c. The crystal structure of 2 (Fig. 3) consists of one CdIIion and two singly deprotonated H2shi-ligands and one coordinated water molecule. The adjacent CdIIions are bridged by the hydroximate oxygen atoms to form a one-dimensional linear chain (Fig. 4).Each CdIIion is bound to seven oxygen atoms (O1,O1A, O3A, O3B, μ2-O1B, μ2-O1C, and O1W)originated from four different H2shi-ligands and one water molecule. Each H2shi-ligand chelates one CdIIion through a μ1-carbonyl oxygen atom and a μ2-hydroxamate oxygen atom (coordination mode F in Scheme 1), with the Cd–O distances ranging from 2.341(2) to 2.432(16) ?. The Cd···Cd distance is 3.7392(6) ?.

    Remarkably, complexes 1 and 2 were prepared by using similar starting materials, but their compositions and structures are totally different, indicating that metal ions play key roles in the construction of coordination polymers.

    Complexes 1 and 2 join a big family of coordination polymers of ZnII/CdII[31-36]. However, the ZnIIand CdII1-D chain complexes supported by the H3shi ligand are never reported.

    Fig. 3. Coordination environment of the Cd ion in 2. Hydrogen atoms have been omitted for clarity.Color scheme: green, CdII; red, oxygen; blue, nitrogen; yellow, carbon

    Fig. 4. 1-D chain structure of 2. Hydrogen atoms are omitted for clarity.Color scheme: green, CdII; red, oxygen; blue, nitrogen; yellow, carbon

    3.2 Powder X-ray diffraction (PXRD)

    In order to check the phase purity of complexes 1 and 2, the powder X-ray diffractions (PXRD) have been measured and compared with those simulated from the single-crystal structure data. As can be seen from Figs. 5 and 6, the experimental PXRD patterns and simulated peaks match well, indicating the purities of the complexes.

    3.3 Luminescent property

    The luminescent properties of the H3shi ligand and complexes 1 and 2 were investigated in the solid state at room temperature (Fig. 7). The H3shi ligand shows photoluminescence emission at 344 nm. Complex 1 shows emission with the maximum peak at 356 nm. Compared with the H3shi ligand,the red-shifted emission of 1 may be ascribed as the intraligand charge transfer (π-π*)[33,37]. The pronounced fluorescence emission of complex 1 reveals its potential application in photoactive materials.

    Fig. 5. Powder XRD patterns of complex 1

    Fig. 6. Powder XRD patterns of complex 2

    Fig. 7. Emission spectra of the H3shi ligand and complex 1 in the solid state at room temperature (Emission slit = 1 nm)

    No emission was observed for complex 2. The water in lattice may prevent an efficient intraligand charge transfer.

    4 CONCLUSION

    In summary, two 1D chain ZnIIand CdIIcomplexes of compositions [Zn(H2shi)(CH3COO)]n(1)and [Cd(H2shi)2(H2O)]n(2) have been prepared under solvothermal conditions. The luminescent properties have been investigated. Complex 1 shows red-shifted luminescence emission. The pronounced fluorescence emission of 1 reveals its potential applications for photoactive materials.

    (1) Codd, R. Traversing the coordination chemistry and chemical biology of hydroxamic acids. Coord. Chem. Rev. 2008, 252, 1387–1408.

    (2) Gaynor, D.; Starikova, Z. A.; Ostrovsky, S.; Haase, W.; Nolan, K. B. Synthesis and structure of a heptanuclear nickel(II) complex uniquely exhibiting four distinct binding modes, two of which are novel, for a hydroxamate ligand. Chem. Commun. 2002, 506–507.

    (3) Jankolovits, J.; Andolina, C. M.; Kampf, J. W.; Raymond, K. N.; Pecoraro, V. L. Assembly of near-infrared luminescent lanthanide host(host-guest)complexes with a metallacrown sandwich motif. Angew. Chem. Int. Ed. 2011, 50, 9660–9664.

    (4) Eltayeb, A. Z.; Nimir, H. I.; Brown, D. A.; Lan, Y.; Anson, C. E.; Powell, A. K. Magnetic and structural studies of novel tetranickel hydroxamates.Inorg. Chim. Acta 2010, 363, 899–904.

    (5) Bai, Y.; Guo, D.; Duan, C. Y.; Dang, D. B.; Pang, K. L.; Meng, Q. J. A three-dimensional porous metal-organic framework [Fe4L6·(DMF)3·(H2O)10]constructed from neutral discrete Fe4L6pyramids (H2L = 1,3-benzodihydroxamix acid). Chem. Commun. 2004, 186–187.

    (6) Gajewska, M.; Luzyanin, K. V.; Guedes da Silva, M. F. C.; Li, Q. S.; Cui, J. R.; Pombeiro, A. J. L. The first tin compounds bearing oximehydroxamate ligands. Eur. J. Inorg. Chem. 2009, 3765–3769.

    (7) Alagha, A. B. M.; Gaynor, D.; Muller-Bunz, H.; Nolan, K. B.; Parthasarathi, L. fac-Tris(4-amino-benzohydroxamato)iron(III) ethanol solvate.Acta Crystallogr., Sect. E 2010, 66, m853–854.

    (8) Lah, M. S.; Pecoraro, V. L. A functional analogy between crown ethers and metallacrowns. Inorg. Chem. 1991, 30, 878–880.

    (9) Zaleski, C. M.; Kampf, J. W.; Mallah, T.; Kirk, M.; Pecoraro, V. L. Assessing the slow magnetic relaxation behavior of LnIII4MnIII6metallacrowns.Inorg. Chem. 2007, 46, 1954–1956. I

    (10) Gibney, B. R.; Kessissoglou, D. P.; Kampf, J. W.; Pecoraro, V. L. Copper(II) 12-metallacrown-4: synthesis, structure, ligand variability, and solution dynamics in the 12-MC-4 structural motif. Inorg. Chem. 1994, 33, 4840–4849.

    (11) Liu, S. C.; Zhu, H. Z.; Zubieta, J. Reactions of polyoxomolybdates with oximes. The crystal and molecular structures of[(C4H9)4N]2[Mo2O5C6H4(O)CHNO2]·CH2Cl2and [(C4H9)4N]2[Mo2O5C6H5CH(O)C(NO)C6H52]. Polyhedron 1989, 8, 2473–2480.

    (12) Si,eT. K.; Chakraborty, S.; Mukherjee, A. K.; Drew, M. G. B.; Bhattacharyy, R. Novel supramolecular network in tri- and mono-nuclear oxovanadium(V)-salicyl-hydroximate: synthesis, structure and catalytic oxidation of hydrocarbons using H2O2as terminal oxidant.. Polyhedron 2008,27, 2233–2242.

    (13) 2Henderson, W.; Evans, C.; Nicholson, B. K.; Fawcett, J. Coordination isomerism in salicylhydroxamate complexes of platinum(II) and palladium(II). Dalton Tran. 2003, 2691–2697.

    (14) Cornman,6C. R.; Colpas, G. J.; Hoeschele, J. D.; Kampf, J.; Pecoraro, V. L. Implications for the spectroscopic assignment of vanadium biomolecules:structural and spectroscopic characterization of monooxovanadium(V) complexes containing catecholate and hydroximate based noninnocent ligands.J. Am. Chem. Soc. 1992, 114, 9925–9933.

    (15) Stemmier, A. J.; Kampf, J. W.; Kirk, M. L.; Pecoraro, V. L. A model for the inhibition of urease by hydroxamates.1J. Am. Chem. Soc. 1995, 117,6368–6369.

    (16) Centore, R.; Tommaso, G. D.; Iuliano, M.; Tuzi, A. An organouranium coordination polymer containing infinite metal oxide chains.5Acta Cryst.2007, C63, m253–m255.

    (17) Tekeste, T.; Vahrenkamp, H. Enzyme inhibitor modeling with TpZn complexes of functional hydroxamates and oximates.5Inorg. Chim. Acta 2007,360, 1523–1528.

    (18) Comiskey, J.; Farkas, E.; Krot-Lacina, K. A.; Pritchard, R. G.; McAuliffe, C. A.; Nolan, K. B. Synthesis, structures and speciation studies of ruthenium(III) hydroxamate/hydroximato complexes. Crystal and molecular structure of hydrated [Ru(H2edta)(2-methoxyphenylhydroxamate)], the first structurally characterised ruthenium(III)-hydroxamate complex. Dalton Tran. 2003, 4243–4249.

    (19) Katsoulakou, E.; Bekiari, V.; Raptopoulou, C. P.; Terzis, A.; Manessi-Zoupa, E.; Powell, A.; Perlepes, S. P. Simultaneous coordination of a ketone by two cadmium(II) ions and conversion to its gem-diolate(-1) form. Inorg. Chem. Commun. 2011, 14, 1057–1060.

    (20) Eom, G. H.; Park, H. M.; Hyun, M. Y.; Jang, S. P.; Kim, C.; Lee, J. H.; Lee, S. J.; Kim, S. J.; Kim, Y. Anion effects on the crystal structures of ZnIIcomplexes containing 2,2?-bipyridine: their photoluminescence and catalytic activities. Polyhedron 2011, 30, 1555–1564.

    (21) Cui, P.; Chen, Z.; Gao, D. L.; Zhao, B.; Shi, W.; Cheng, P. Syntheses, structures, and photoluminescence of a series of three-dimensional CdIIframeworks with a flexible ligand, 1,5-bis(5-tetrazolo)-3-oxapentane. Cryst. Growth & Des. 2010, 10, 4370–4378.

    (22) Wang, R. J.; Deng, L. J.; Fu, M.; Cheng, J. L.; Li, J. Y. Novel ZnIIcomplexes of 2-(2-hydroxyphenyl)benzothiazoles ligands: electroluminescence and application as host materials for phosphorescent organic light-emitting diodes. J. Mater. Chem. 2012, 22, 23454–23460.

    (23) Guha, A.; Chattopadhyay, T.; Paul, N. D.; Mukherjee, M.; Goswami, S.; Mondal, T. K.; Zangrando, E.; Das, D. Radical pathway in catecholase activity with zinc-based model complexes of compartmental ligands. Inorg. Chem. 2012, 51, 8750–8759.

    (24) Panja, A.; Matsuo, T.; Nagao, S.; Hirota, S. DNA cleavage by the photocontrolled cooperation of ZnIIcenters in an azobenzene-linked dizinc complex. Inorg. Chem. 2011, 50, 11437–11445.

    (25) Feng, G. Q.; Natale, D.; Prabaharan, R.; Mareque-Rivas, J. C.; Williams, N. H. Efficient phosphodiester binding and cleavage by a ZnIIcomplex combining hydrogen-bonding interactions and double Lewis acid activation. Angew. Chem., Int. Ed. 2006, 45, 7056–7059.

    (26) Scrimin, P.; Tecilla, P.; Tonellato, U.; Valle, G.; Veronese, A. A zinc(II)-organized molecular receptor as a catalyst for the cleavage of amino acid esters. J. Chem. Soc., Chem. Commun. 1995, 1163–1164.

    (27) Jang, K. J.; Yeo, G. Y.; Cho, T. S.; Eom, G. H.; Kim, C.; Kim, S. K. Real-time detection of DNA cleavage induced by [M(2,2?-dipyridylamine)2(NO3)n]x+(M = Cd, Cu, Ni, Zn, n = 1, 2, x = 0,1): effect of central metal ions. Biophy. Chem. 2010, 148, 138–143.

    (28) Meng, X. R.; Song,Y. L.; Hou, H. W.; Han, H. Y.; Xiao, B.; Fan, Y. T.; Zhu, Y. Hydrothermal syntheses, crystal structures, and characteristics of a series of Cd-btx coordination polymers (btx = 1,4-bis(triazol-1-ylmethyl)benzene). Inorg. Chem. 2004, 43, 3528–3536.

    (29) Sheldrick, G. M. SHELXS-97, Program for Crystal Structure Solution. University of G?ttingen, Germany 1997.

    (30) Sheldrick, G. M. SHELXL-97, Program for the Refinement of Crystal Structures from Diffraction Data. University of G?ttingen, Germany 1997.

    (31) Brown, D. A.; Fitzpatrick, N. J.; Müller-Bunz, H.; Ryan, A. T. Di-, tri-, and tetranuclear zinc hydroxamate complexes as structural models for the inhibition of zinc hydrolases by hydroxamic acids. Inorg. Chem. 2006, 45, 4497–4507.

    (32) Alexiou, M.; Dendrinou-Samara, C.; Raptopoulou, C. P.; Terzis, A.; Kessissoglou, D. P. From monomer zinc-oxamato complexes to tetranuclear inverse 12-membered and octanuclear 12-membered metallacrowns. Inorg. Chem. 2002, 41, 4732–4738.

    (33) Chen, Y. M.; Gao, Q.; Liu, Y. L.; Cao, Y. Y.; Gao, D. D.; Liu, J. N.; Zhao, J. J.; Li, Y. H.; Liu, W.; Li, W. Synthesis, crystal structures and luminescent properties of CdIIand ZnIIcomplexes assembled by 4-aminophenylhydroxamic acid. RSC Adv. 2014, 4, 147–153.

    (34) Chen, W. T.; Yi, X. G.; Wen, J. W. Synthesis, crystal structure and property of (CdCl3)n·nH3O with a one-dimensional infinite chain-like structure.Asian J. Chem. 2014, 26, 1253–1254.

    (35) Chen, W. T.; Hu, R. H.; Yi, X. G.; Wang, Y. F.; Luo, Z. G.; Fu, H. R.; Liu, J.; Chen, H. L. Synthesis, structure, properties and time-dependent density functional theory calculations of cadmium complex. Asian J. Chem. 2014, 26, 4865–4867.

    (36) Chen, W. T.; Hu, R. H.; Luo, Z. G.; Chen, H. L.; Zhang, X.; Liu, J. [N-ethyl-4,4?-bipyridinium][ZnX4] (X = Cl or Br) with N-ethyl-4,4?-bipyridinium generated in situ: syntheses, structures, fluorescence and TDDFT calculations. Chin. J. Struct. Chem. 2014, 33,1141–1146.

    (37) Zheng, S. L.; Yang, J. H.; Yu, X. L.; Chen, X. M.; Wong, W. T. Syntheses, structures, photoluminescence and theoretical studies of d10metal complexes of 2,2?-dihydroxy-[1,1?]binaphthalenyl -3,3?-dicarboxylate. Inorg. Chem. 2004, 43, 830–838.

    操出白浆在线播放| 国产精品免费大片| 久久午夜综合久久蜜桃| 精品少妇一区二区三区视频日本电影| 久久狼人影院| 精品福利永久在线观看| 成人三级做爰电影| 欧美日韩精品网址| 午夜福利一区二区在线看| 欧美日韩亚洲综合一区二区三区_| 美女主播在线视频| 免费在线观看日本一区| 晚上一个人看的免费电影| 久久天堂一区二区三区四区| 亚洲av国产av综合av卡| √禁漫天堂资源中文www| 日本欧美国产在线视频| 国产免费又黄又爽又色| 国产熟女欧美一区二区| 国产成人91sexporn| 日日摸夜夜添夜夜爱| 黄网站色视频无遮挡免费观看| 久热这里只有精品99| 肉色欧美久久久久久久蜜桃| 一本—道久久a久久精品蜜桃钙片| 久久国产亚洲av麻豆专区| 热re99久久精品国产66热6| 亚洲人成网站在线观看播放| 最新的欧美精品一区二区| 大片电影免费在线观看免费| 9热在线视频观看99| 国产又爽黄色视频| 亚洲国产精品一区二区三区在线| 各种免费的搞黄视频| 色播在线永久视频| 好男人视频免费观看在线| 午夜精品国产一区二区电影| 在线天堂中文资源库| 国产精品偷伦视频观看了| 国产亚洲午夜精品一区二区久久| 亚洲专区国产一区二区| 黄片小视频在线播放| 日韩av在线免费看完整版不卡| av网站在线播放免费| 亚洲国产最新在线播放| 十八禁高潮呻吟视频| 久久精品人人爽人人爽视色| 少妇人妻 视频| 久久精品久久精品一区二区三区| 日本五十路高清| 成人亚洲精品一区在线观看| 首页视频小说图片口味搜索 | 亚洲精品美女久久久久99蜜臀 | 欧美+亚洲+日韩+国产| 亚洲精品美女久久av网站| 波多野结衣一区麻豆| 日本av手机在线免费观看| 在线观看www视频免费| 熟女av电影| 亚洲精品日韩在线中文字幕| 午夜免费鲁丝| 亚洲伊人色综图| 国产高清不卡午夜福利| 高清av免费在线| 男人爽女人下面视频在线观看| 丁香六月天网| 久久国产精品大桥未久av| 人体艺术视频欧美日本| 在线av久久热| 久久 成人 亚洲| 欧美日韩精品网址| 在线精品无人区一区二区三| 亚洲色图 男人天堂 中文字幕| 高潮久久久久久久久久久不卡| 欧美日韩黄片免| 深夜精品福利| 18禁黄网站禁片午夜丰满| 国产成人免费无遮挡视频| 伊人久久大香线蕉亚洲五| 视频区欧美日本亚洲| 性少妇av在线| 女性被躁到高潮视频| 国产淫语在线视频| 一级,二级,三级黄色视频| 多毛熟女@视频| 一级a爱视频在线免费观看| 80岁老熟妇乱子伦牲交| 欧美日韩视频精品一区| 91九色精品人成在线观看| 无遮挡黄片免费观看| 少妇裸体淫交视频免费看高清 | 日韩中文字幕视频在线看片| 老司机亚洲免费影院| 男人添女人高潮全过程视频| 欧美亚洲 丝袜 人妻 在线| 青春草亚洲视频在线观看| 狂野欧美激情性bbbbbb| 涩涩av久久男人的天堂| 两性夫妻黄色片| 大香蕉久久网| 女人高潮潮喷娇喘18禁视频| 国产精品麻豆人妻色哟哟久久| 尾随美女入室| 成年美女黄网站色视频大全免费| 后天国语完整版免费观看| 婷婷丁香在线五月| 伦理电影免费视频| 王馨瑶露胸无遮挡在线观看| 一本大道久久a久久精品| 亚洲欧美日韩另类电影网站| 飞空精品影院首页| 精品一区二区三卡| 成年人免费黄色播放视频| 麻豆av在线久日| 国产精品一区二区在线不卡| www.自偷自拍.com| 欧美在线一区亚洲| 亚洲精品av麻豆狂野| 欧美+亚洲+日韩+国产| 肉色欧美久久久久久久蜜桃| 黑人欧美特级aaaaaa片| 91成人精品电影| 成年美女黄网站色视频大全免费| 50天的宝宝边吃奶边哭怎么回事| 91成人精品电影| 亚洲av欧美aⅴ国产| 国产片内射在线| 久久久精品区二区三区| 国产精品av久久久久免费| 一边亲一边摸免费视频| 丰满饥渴人妻一区二区三| 日韩,欧美,国产一区二区三区| 亚洲av成人精品一二三区| av电影中文网址| 日韩电影二区| 亚洲熟女精品中文字幕| 热99国产精品久久久久久7| 久久精品aⅴ一区二区三区四区| 又大又爽又粗| 9191精品国产免费久久| 午夜免费男女啪啪视频观看| 操出白浆在线播放| 一级a爱视频在线免费观看| 深夜精品福利| 精品久久久久久电影网| 丝袜脚勾引网站| 黄片小视频在线播放| 黄色片一级片一级黄色片| 久久精品国产综合久久久| 免费少妇av软件| 丝袜人妻中文字幕| 亚洲 欧美一区二区三区| 一个人免费看片子| 亚洲五月婷婷丁香| 国产成人精品久久二区二区免费| 国产精品国产av在线观看| 成人黄色视频免费在线看| 一级毛片我不卡| 美女中出高潮动态图| 又大又爽又粗| 夜夜骑夜夜射夜夜干| 精品视频人人做人人爽| 欧美日韩福利视频一区二区| 色播在线永久视频| 午夜福利视频精品| 天天躁狠狠躁夜夜躁狠狠躁| 久久精品成人免费网站| 午夜福利视频精品| 久久亚洲国产成人精品v| av福利片在线| 一级a爱视频在线免费观看| 精品人妻熟女毛片av久久网站| 菩萨蛮人人尽说江南好唐韦庄| 在现免费观看毛片| 亚洲中文av在线| 国产亚洲欧美精品永久| 久久久久久久大尺度免费视频| 精品国产一区二区三区久久久樱花| 又粗又硬又长又爽又黄的视频| 麻豆乱淫一区二区| 色网站视频免费| 欧美另类一区| 极品少妇高潮喷水抽搐| 美女大奶头黄色视频| 我的亚洲天堂| 国产成人系列免费观看| 欧美人与性动交α欧美精品济南到| 99久久综合免费| 久久狼人影院| 日韩制服骚丝袜av| 超碰97精品在线观看| 精品国产一区二区三区久久久樱花| www.熟女人妻精品国产| 午夜精品国产一区二区电影| 丝袜人妻中文字幕| 精品久久久精品久久久| 捣出白浆h1v1| 亚洲国产欧美在线一区| 老司机靠b影院| 国产有黄有色有爽视频| 久久99热这里只频精品6学生| 国产成人系列免费观看| 欧美日韩视频精品一区| 亚洲精品一卡2卡三卡4卡5卡 | 国产又爽黄色视频| 午夜老司机福利片| 久久人人爽人人片av| 亚洲人成77777在线视频| 免费av中文字幕在线| 亚洲av综合色区一区| 久久中文字幕一级| 国产99久久九九免费精品| 波多野结衣av一区二区av| 欧美亚洲 丝袜 人妻 在线| 天天躁日日躁夜夜躁夜夜| 国产一卡二卡三卡精品| 首页视频小说图片口味搜索 | 麻豆国产av国片精品| 高清欧美精品videossex| 国产精品二区激情视频| av网站在线播放免费| 国产高清视频在线播放一区 | 七月丁香在线播放| 久久久久久人人人人人| 日韩av在线免费看完整版不卡| 大片免费播放器 马上看| av视频免费观看在线观看| 日本wwww免费看| 99热全是精品| 久久99一区二区三区| 亚洲,一卡二卡三卡| 久久亚洲精品不卡| 99热网站在线观看| 久久久精品区二区三区| 国产精品 国内视频| 中文字幕高清在线视频| 久久精品国产亚洲av涩爱| av又黄又爽大尺度在线免费看| 飞空精品影院首页| 免费高清在线观看视频在线观看| 9热在线视频观看99| 免费高清在线观看日韩| av在线播放精品| 精品视频人人做人人爽| 久久久久久亚洲精品国产蜜桃av| 久久久久久久国产电影| 成人黄色视频免费在线看| 曰老女人黄片| 国产伦人伦偷精品视频| 日日摸夜夜添夜夜爱| 欧美变态另类bdsm刘玥| 极品人妻少妇av视频| 日韩中文字幕欧美一区二区 | 国产精品久久久久成人av| 国产欧美日韩精品亚洲av| 国产成人啪精品午夜网站| 自线自在国产av| 只有这里有精品99| 亚洲一区中文字幕在线| 国产av精品麻豆| 制服人妻中文乱码| 精品人妻在线不人妻| 日本wwww免费看| 一区二区三区激情视频| av网站免费在线观看视频| 国产免费一区二区三区四区乱码| 黄色一级大片看看| 久久青草综合色| 精品一区二区三卡| 18在线观看网站| 美女扒开内裤让男人捅视频| 久久精品人人爽人人爽视色| 亚洲一码二码三码区别大吗| 亚洲精品乱久久久久久| a级毛片黄视频| 日韩电影二区| 日韩av在线免费看完整版不卡| 久久热在线av| 每晚都被弄得嗷嗷叫到高潮| 在线天堂中文资源库| 人人妻人人澡人人看| 国产成人a∨麻豆精品| 黄色 视频免费看| 国产欧美日韩精品亚洲av| 久久性视频一级片| 一区二区三区四区激情视频| 国产一级毛片在线| 日韩熟女老妇一区二区性免费视频| 女人精品久久久久毛片| 老司机在亚洲福利影院| 亚洲精品一二三| 欧美精品一区二区免费开放| 精品少妇久久久久久888优播| 黄色 视频免费看| 在线天堂中文资源库| 亚洲免费av在线视频| 99久久99久久久精品蜜桃| av天堂在线播放| 中文字幕另类日韩欧美亚洲嫩草| av网站在线播放免费| 久久国产精品影院| 一个人免费看片子| 欧美激情极品国产一区二区三区| 大香蕉久久成人网| 色综合欧美亚洲国产小说| 九色亚洲精品在线播放| 赤兔流量卡办理| 国产成人影院久久av| 真人做人爱边吃奶动态| 国产精品麻豆人妻色哟哟久久| 国产男女超爽视频在线观看| 国产精品亚洲av一区麻豆| 免费在线观看视频国产中文字幕亚洲 | 久久亚洲精品不卡| 男女之事视频高清在线观看 | 国产精品熟女久久久久浪| 在线观看免费视频网站a站| 国产黄色免费在线视频| 脱女人内裤的视频| 午夜福利视频在线观看免费| 又大又爽又粗| 91精品国产国语对白视频| 国产真人三级小视频在线观看| 国产成人精品久久久久久| 亚洲精品国产一区二区精华液| 久久国产精品影院| 精品人妻熟女毛片av久久网站| 国产一区二区在线观看av| 丝袜脚勾引网站| 欧美日本中文国产一区发布| 日本vs欧美在线观看视频| 国产精品熟女久久久久浪| 欧美激情 高清一区二区三区| 国产欧美日韩综合在线一区二区| 久久99热这里只频精品6学生| 十八禁高潮呻吟视频| 波多野结衣一区麻豆| 国产亚洲av高清不卡| 黄频高清免费视频| 我的亚洲天堂| 国产精品麻豆人妻色哟哟久久| 天天操日日干夜夜撸| 久久热在线av| 久久天堂一区二区三区四区| 欧美精品av麻豆av| 天天躁狠狠躁夜夜躁狠狠躁| 两性夫妻黄色片| 夜夜骑夜夜射夜夜干| 国产精品国产av在线观看| 亚洲精品乱久久久久久| 精品亚洲乱码少妇综合久久| 亚洲欧美成人综合另类久久久| 欧美日韩黄片免| 在线观看免费日韩欧美大片| 国产亚洲av高清不卡| 免费看十八禁软件| 黄网站色视频无遮挡免费观看| 人成视频在线观看免费观看| 中文乱码字字幕精品一区二区三区| 大话2 男鬼变身卡| 2021少妇久久久久久久久久久| 一级毛片黄色毛片免费观看视频| 午夜91福利影院| 啦啦啦 在线观看视频| 精品少妇久久久久久888优播| 高清视频免费观看一区二区| 久久久久久久久免费视频了| 捣出白浆h1v1| 亚洲中文日韩欧美视频| www.999成人在线观看| 免费久久久久久久精品成人欧美视频| 久久精品久久久久久久性| 色94色欧美一区二区| 日韩一卡2卡3卡4卡2021年| 国产黄色视频一区二区在线观看| av视频免费观看在线观看| 精品一区二区三区四区五区乱码 | 免费在线观看影片大全网站 | 操美女的视频在线观看| 天天躁狠狠躁夜夜躁狠狠躁| 亚洲国产欧美在线一区| 国产av一区二区精品久久| 日本猛色少妇xxxxx猛交久久| 国产真人三级小视频在线观看| 777米奇影视久久| 精品一区二区三卡| 欧美少妇被猛烈插入视频| 国产精品久久久av美女十八| 一区在线观看完整版| 久久久国产精品麻豆| 国产黄频视频在线观看| svipshipincom国产片| 黄色 视频免费看| 成在线人永久免费视频| 日韩大片免费观看网站| 少妇 在线观看| 亚洲成av片中文字幕在线观看| 操出白浆在线播放| 超碰成人久久| 国产淫语在线视频| 天天躁夜夜躁狠狠久久av| 国产成人a∨麻豆精品| tube8黄色片| 色精品久久人妻99蜜桃| 亚洲精品av麻豆狂野| 欧美日韩亚洲高清精品| 成人亚洲精品一区在线观看| 国产亚洲欧美精品永久| 久久久久久久大尺度免费视频| 视频在线观看一区二区三区| 我要看黄色一级片免费的| 大香蕉久久网| 国产一区二区 视频在线| 精品亚洲成a人片在线观看| 视频在线观看一区二区三区| 亚洲午夜精品一区,二区,三区| 黄色视频不卡| 可以免费在线观看a视频的电影网站| 亚洲欧美精品综合一区二区三区| 国产成人精品在线电影| 国产高清国产精品国产三级| 欧美日本中文国产一区发布| 亚洲国产欧美网| 久久人妻福利社区极品人妻图片 | 国产又色又爽无遮挡免| 国产一区二区在线观看av| 电影成人av| 天堂8中文在线网| 亚洲成人免费av在线播放| 免费看十八禁软件| 9191精品国产免费久久| 国产野战对白在线观看| 日韩av不卡免费在线播放| 日日摸夜夜添夜夜爱| 免费看不卡的av| 婷婷色综合大香蕉| 下体分泌物呈黄色| 你懂的网址亚洲精品在线观看| 久久国产亚洲av麻豆专区| 99精国产麻豆久久婷婷| 欧美性长视频在线观看| 最新的欧美精品一区二区| 亚洲精品国产区一区二| 99热网站在线观看| 久久亚洲精品不卡| 免费在线观看日本一区| 国产熟女欧美一区二区| 一级黄色大片毛片| 欧美成狂野欧美在线观看| 麻豆乱淫一区二区| 亚洲一区二区三区欧美精品| 中文乱码字字幕精品一区二区三区| 亚洲中文av在线| 国产成人啪精品午夜网站| 久久人人97超碰香蕉20202| 日韩av在线免费看完整版不卡| 大话2 男鬼变身卡| 高清不卡的av网站| 精品人妻在线不人妻| 日本色播在线视频| 精品福利观看| 亚洲av日韩在线播放| 亚洲精品国产av成人精品| 国产熟女欧美一区二区| 国语对白做爰xxxⅹ性视频网站| 久久女婷五月综合色啪小说| 啦啦啦在线免费观看视频4| 亚洲男人天堂网一区| 我的亚洲天堂| 国产欧美日韩精品亚洲av| 高潮久久久久久久久久久不卡| 亚洲成人国产一区在线观看 | 老熟女久久久| 操出白浆在线播放| 999精品在线视频| 久久精品成人免费网站| 五月天丁香电影| 欧美激情高清一区二区三区| 午夜福利视频精品| 国产精品.久久久| 国产成人免费无遮挡视频| 欧美激情极品国产一区二区三区| 50天的宝宝边吃奶边哭怎么回事| 国产精品二区激情视频| 搡老乐熟女国产| 久久久精品免费免费高清| 亚洲美女黄色视频免费看| 亚洲欧美激情在线| 1024视频免费在线观看| 亚洲欧美一区二区三区国产| 老鸭窝网址在线观看| 丝袜脚勾引网站| 在线看a的网站| 高清欧美精品videossex| 久久女婷五月综合色啪小说| 久久精品久久精品一区二区三区| 欧美黑人欧美精品刺激| 久久影院123| 午夜福利,免费看| 看免费av毛片| 波多野结衣av一区二区av| 色婷婷av一区二区三区视频| 91字幕亚洲| 在线观看免费午夜福利视频| 欧美 日韩 精品 国产| 久9热在线精品视频| 亚洲精品国产区一区二| 精品熟女少妇八av免费久了| 欧美日韩亚洲高清精品| 国产成人影院久久av| 欧美精品啪啪一区二区三区 | 国产野战对白在线观看| 日韩制服骚丝袜av| 三上悠亚av全集在线观看| 交换朋友夫妻互换小说| 日韩 亚洲 欧美在线| a级毛片在线看网站| 久久国产精品影院| 肉色欧美久久久久久久蜜桃| 五月天丁香电影| 高清黄色对白视频在线免费看| 一边摸一边抽搐一进一出视频| 男女免费视频国产| 丝袜脚勾引网站| 人成视频在线观看免费观看| 国语对白做爰xxxⅹ性视频网站| 热99久久久久精品小说推荐| 制服人妻中文乱码| 91麻豆精品激情在线观看国产 | 五月开心婷婷网| 精品一区二区三区av网在线观看 | 国产一区二区三区av在线| 国产精品免费视频内射| 在线观看免费日韩欧美大片| 一级a爱视频在线免费观看| 永久免费av网站大全| 黄色视频在线播放观看不卡| 1024视频免费在线观看| 午夜激情av网站| 亚洲九九香蕉| 男人爽女人下面视频在线观看| 少妇裸体淫交视频免费看高清 | 另类精品久久| 电影成人av| 国产黄色视频一区二区在线观看| 1024视频免费在线观看| 777久久人妻少妇嫩草av网站| 久久人妻熟女aⅴ| a 毛片基地| 免费看十八禁软件| 亚洲熟女毛片儿| 伊人亚洲综合成人网| 婷婷色综合www| 亚洲黑人精品在线| 一二三四在线观看免费中文在| 久久精品成人免费网站| 又紧又爽又黄一区二区| 嫁个100分男人电影在线观看 | 视频在线观看一区二区三区| 麻豆乱淫一区二区| 亚洲国产精品一区二区三区在线| 欧美 亚洲 国产 日韩一| 国产精品久久久久久人妻精品电影 | 婷婷色综合www| 波野结衣二区三区在线| 精品少妇内射三级| 大话2 男鬼变身卡| 精品福利观看| 日韩av在线免费看完整版不卡| 国产日韩欧美视频二区| 最黄视频免费看| 无遮挡黄片免费观看| 欧美中文综合在线视频| 国产精品久久久人人做人人爽| 伦理电影免费视频| 亚洲国产日韩一区二区| 99九九在线精品视频| av网站免费在线观看视频| 又紧又爽又黄一区二区| 国产精品成人在线| 亚洲精品一区蜜桃| 免费久久久久久久精品成人欧美视频| 国产成人一区二区在线| netflix在线观看网站| 精品免费久久久久久久清纯 | tube8黄色片| 亚洲国产欧美在线一区| 超碰97精品在线观看| 亚洲一卡2卡3卡4卡5卡精品中文| 亚洲国产欧美日韩在线播放| 欧美成狂野欧美在线观看| 亚洲精品一区蜜桃| 成年女人毛片免费观看观看9 | 免费看av在线观看网站| 中文字幕人妻熟女乱码| 少妇精品久久久久久久| 男女高潮啪啪啪动态图| 一二三四社区在线视频社区8| 天堂8中文在线网| 看十八女毛片水多多多| 中文乱码字字幕精品一区二区三区| 亚洲精品自拍成人| 欧美亚洲日本最大视频资源| 日本wwww免费看| 欧美97在线视频| 中国国产av一级| 国产在线免费精品| 一本久久精品| 天天操日日干夜夜撸| 国产精品一二三区在线看| 色婷婷av一区二区三区视频| 国产精品久久久av美女十八| 制服人妻中文乱码| 岛国毛片在线播放| 不卡av一区二区三区|