• <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 ?

    基于一種柔性和角型有機芳香多酸配體的兩種3D配位聚合物的合成、結構和熒光性

    2017-09-12 08:59:35李付安徐伏楊維春
    無機化學學報 2017年9期
    關鍵詞:間苯二甲酸吡啶基楊維

    李付安徐伏楊維春

    基于一種柔性和角型有機芳香多酸配體的兩種3D配位聚合物的合成、結構和熒光性

    李付安*徐伏楊維春

    (平頂山學院化學與環(huán)境工程學院,平頂山467000)

    通過水熱合成的方法制得具有三維超分子結構的2種配位聚合物{[Zn(L)(bpa)0.5(H2O)2]·2.25H2O}n(1)和{[Cd(L)(H2O)]·2H2O}n(2),其中,H3LCl為氯化5-(4-羥基吡啶基甲基)間苯二甲酸,bpa為1,2-二(4-吡啶基)乙烷。這2種化合物的結構通過單晶X射線衍射、紅外光譜(IR)、元素分析、熱重分析(TG)等方法進行了表征。結構解析表明:化合物1是一種梯型鏈式結構,并通過鏈間氫鍵作用延伸成了3D超分子網絡;化合物2為含有大量一維隧道空腔的2D配位網絡。此外,研究了這2種化合物的熒光性質。

    氯化5-(4-羥基吡啶基甲基)間苯二甲酸;1,2-二(4-吡啶基)乙烷;鋅;鎘

    In recent years,the complexes based on organic aromaticcarboxylateligandshavebecomean interesting research area due to their pluridentated and excellent coordinated ability[1-4]as well as their charming architectures and potential applications in adsorption,catalysis,and luminescence,and so on[5-6]. Among the reported compounds,the coordination polymers from flexible or angular organic aromatic multi-carboxylate ligands are especially interesting because they can adopt a variety of coordination modes resulting in diverse multidimensional architectures[7-10].Up to now,many aromatic carboxylate ligands with flexible or angular structures have been synthesized and reported.For example,Li et al.havereported a series of metal-organic frameworks based on flexible ligand 4-carboxy-1-(3,5-dicarboxy-benzyl) pyridinium chloride[11];Sun et al.have synthesized a flexible and angular ligands 5-(imidazol-1-ylmethyl) isophthalic acid,and report a series of coordination polymers with novel networks[12-13];Zang et al.have investigated a series of angular carboxylate ligands, 3,5-bis(imidazol-1-ylmethyl)benzoic acid hydrochloride[14],2,3,2′,3′-thiaphthalic acid[15],1-(pyridin-4-ylthio)benzene-2,4-dioic acid[16].Recently,we have also synthesized a versatile ligand,H3LCl(5-(4-hydroxypyridinium-1-ylmethyl)isophthalic acid chloride),and its corresponding coordination polymers have been reported[17].To continue our effort in this area,two coordination polymers,{[Zn(L)(bpa)0.5(H2O)2]·2.25H2O}n(1)and{[Cd(L)(H2O)]·2H2O}n(2),with novel networks from H2L ligand have been hydrothermally synthesized and structurally characterized by X-ray diffraction analyses and further characterized by infrared spectra (IR),elemental analyses and thermogravimetric(TG) analyses.

    Scheme 1Coordination mode of the ligand H3LCl found in compounds 1(a)and in 2(b)

    1 Experimental

    1.1 Materials and physical measurement

    H3LClwassynthesizedaccordingtotheliterature[17], and other starting materials were of reagent quality and obtained from commercial sources without further purification.Elemental analysis for C,H and N was performed on a Perkin-Elmer 240 elemental analyzer. The FT-IR spectra were recorded from KBr pellets in the range from 4 000 to 400 cm-1on a Nicolet NEXUS 470-FTIRspectrometer.Thermalanalysiswas performed on a SDT 2960 thermal analyzer from room temperature to 800℃with a heating rate of 10℃· min-1under nitrogen flow.Powder X-ray diffraction (PXRD)for compounds 1 and 2 were measured at 293 K on a Rigaku D/max-3B diffractometer equipped with Cu Kα(λ=0.154 06 nm)radiation(45 kV,200 mA). The crushed single crystalline powder samples were prepared by crushing the crystals and the 2θ scanning angle range was from 5°to 50°.Luminescence spectra for the solid samples were recorded on a Hitachi 850 fluorescence spectrophotometer.

    1.2 Synthesis

    1.2.1 Synthesis of{[Zn(L)(bpa)0.5(H2O)2]·2.25H2O}n(1)

    Compound 1 was synthesized hydrothermally in a 25 mL Teflon-lined autoclave by heating a mixture of bpa(0.009 1 g,0.05 mmol),Zn(OAc)·2H2O(0.022 g, 0.1 mmol),H3LCl(0.015 4 g,0.05 mmol),and LiOH (0.004 2 g,0.1 mmol)at 160℃in 6 mL H2O for three days.Colorless block-wise crystals of 1 were obtained in 80%yield based on H2L.Anal.Calcd.for C20H23.5N2O9.25Zn(%):C 47.54,H 4.69,N 5.54;Found (%):C 47.51,H 4.73,N 5.50.IR(KBr,cm-1):3 388 (m,br),3 120(m),1 640(s),1 620(s),1 582(s),1 556 (s),1 361(s),1 239(w),1 226(w),1 193(m),1 029(w), 847(w),774(w),729(w).

    1.2.2 Synthesis of{[Cd(L)(H2O)]·2H2O}n(2)

    A mixture of Cd(OAc)2·2H2O(0.026 g,0.1 mmol), H2L(0.016 8 g,0.05 mmol),LiOH(0.004 2 g,0.1 mmol),and H2O(6 mL)was placed in a 25 mL Teflon -lined stainless steel vessel,and heated at 160℃for three days.After the mixture was slowly cooled to room temperature,colorless crystals of 2 were obtained in 76%yield based on H2L.Anal.Calcd.for C14H15NO8Cd (%):C 38.42,H 3.45,N 3.30;Found(%):C 38.39,H 3.51,N 3.20.IR(KBr,cm-1):3 410(s,br),3 045(m), 1647(s),1 619(s),1 563(m),1 524(s),1 447(w),1 340(s), 1 293(w),1 187(m),1 049(w),1 028(w),856(s),774(s), 726(w).

    1.3 Crystallographic data collection and structure determination

    Single-crystal X-ray diffraction data of compounds 1 and 2 were collected on a Bruker SMART APEX CCD diffractometer[18]equipped with graphite monochromatized Mo Kα radiation(λ=0.071 073 nm) at room temperature using the φ-ω scan technique. Empirical absorption corrections were applied to the intensities using the SADABS program[19].The struct-ures were solved with direct methods using the program SHELXS-97[20]and refined anisotropically with the program SHELXL-97[21]using full matrix leastsquares procedures.All non-hydrogen atoms were refined anisotropically.The hydrogen atoms of the coordinationwatermolecules,andligandswere included in the structure factor calculation at idealized positionsbyusingaridingmodelandrefined isotropically.The hydrogen atoms of the solvent water molecules were located from the difference Fourier maps,then restrained at fixed positions and refined isotropically.Analytical expressions of neutral atom scatteringfactorswereemployed,andanomalous dispersion corrections were incorporated.The crystallographic data for 1 and 2 are summarized in Table 1. Selected bond lengths and angles are given in Table 2.

    CCDC:908522,1;908526,2.

    Table1 Crystal data and structure refinement for compounds 1 and 2

    Table2 Selected bond lengths(nm)and bond angles(°)for compounds 1 and 2

    Symmetry codes:ix+1,y,z for 1;ix,1+y,z;ii2-x,1-y,1-z;iii3-x,1-y,-z for 2.

    2 Results and discussion

    2.1 Crystal structure of{[Zn(L)(bpa)0.5(H2O)2]· 2.25H2O}n(1)

    The compound 1 crystallizes in the monoclinic system with space group P1.Its asymmetric unit consists of one Zncenter,half of a bpa ligand,one L2-anion,two coordinated water molecules,and three free water molecules with the total site occupancies of 2.25(Fig.1a).The Zncenter is five-coordinated by two carboxylic oxygen atoms(O1,O4i)from two different L2-ligands,two oxygen atoms(O1W,O2W)from two water molecules and one nitrogen atom(N2)from one bpa ligand.The coordination geometry of Zn1 atom is a distorted trigonal bipyramidal with two water oxygen atoms(O1W and O2W)at the axial position(Fig.1a). The Zn1-O bond lengths range from 0.195 2(2)to 0.229 1(2)nm,andthe Zn1-N bond distance is 0.205 5(2)nm.The L2-anion bridges two Znatoms with both two carboxylic groups in μ2-η1∶η1modes (Scheme 1a).In this way,L2-anions link neighboring Zn1 atoms to yield an infinite 1D(Zn-L)nchain.Such (Zn-L)nchains are further bridged by bpa molecules into an infinite 1D ladder-like chain(Fig.1b).Such chainsarefurtherunitedtogetherbynumerous hydrogen bonds involving the coordinated waters, lattice waters and carboxyl oxygen atoms to generate a 3D supramolecular architecture(Fig.1c).According to graph set analysisnomenclature[22],the hydrogen motifs within the water cluster can be assigned to be R42(8)and R66(16),respectively(Fig.1d,Table 3).

    Fig.1 (a)Metal coordination and atom labeling in compound 1 with thermal ellipsoids at 50%probability level; (b)1D ladder-like chain;(c)View of 3D supramolecular framework of 1 via hydrogen bonds(the dashed lines represent the hydrogen bonds);(d)Hydrogen bonds in compound 1

    2.2 Crystalstructureof{[Cd(L)(H2O)]·2H2O}n(2) Compound 2 crystallizes in the triclinic space group P1.The asymmetric unit contains one Cdcenter,one L2-anion,one coordinated water molecule, and two lattice water molecules.The Cd1 is sevencoordinated in a pentagonal bipyramidal geometry.As shown in Fig.2a,five carboxylate oxygen atoms(O1, O2,O3i,O4i,and O3iii)from three distinct L2-anions form the equatorial plane;O5ii(HO-L2)and O1W (H2O)occupy the axial positions.The bond length of Cd1-O is in the range of 0.227 4(3)~0.239 8(2)nm. Each L2-ligand bridges fourcrystallographically identical Cd1 ions with one of the carboxylate groups in a μ2-η1∶η1mode,while the other in a μ3-η1∶η2coordinationmodeandthehydroxylgroupin monodentate coordination mode(Scheme 1b).Thus, two cadmium ions are first linked by two L2-anions via the carboxylate groups and monodentate hydroxyl group to generate a[Cd2(L)2]metallamacrocycle with the Cd-Cd distance being 1.129 1 nm(Fig.2b).Each metallamacrocycle links two distinct metallamacrocycle together to form the tube(Fig.2c).The carboxylate groups in μ3-η1∶η2coordination mode further participate in the coordination with Cd1 ions of the tube.Thus, the tubes are connected together to give rise to a 2D layer with tubular channels(Fig.2d).Furthermore,the 2D layers are further extended into 3D supramolecular architecture via hydrogen-bonding interactions(Fig.2e, Table 3).

    Fig.2 (a)Metal coordination and atom labeling in compound 2;(b)Dinuclear metallamacrocycle unit; (c)Side view of the tubular structure;(d)Tubular channels perpendicular to the ab plane of 2; (e)Three dimensional supramolecular structure of 2

    Table3 Geometrical parameters of hydrogen bonds in compounds 1~2

    2.3 Thermal analyses and PXRD analyses

    Thermal gravimetric analysis(TGA)was used to characterize the thermal stability of compounds,and the TGA of compounds 1~2 were carried out in nitrogen atmosphere(Fig.3).For compound 1,the weight loss of 14.99%from 30 to 117℃is assigned to the loss of two coordinated and 2.25 lattice water molecules (Calcd.15.15%).There is no further weight loss from 117 to 362℃,After 362℃,the organic components start to decompose.In the TG curve of compound 2, the weight loss in the range of 30~209℃(Obsd. 11.53%,Calcd.12.35%)can be attributed to the removal of two lattice and one coordinated water molecules.The further weight losses represented the decomposition of the compound 2.

    The synthesized products of 1~2 havebeen characterized by powder X-ray diffraction(PXRD).As shown in Fig.4,the experimental PXRD patterns correspond well with the results simulated from thesingle crystal data,indicating the high purity of the synthesized samples and single phases of compounds 1~2.

    Fig.3 TG curves for compounds 1 and 2

    Fig.4 Simulated and experimental PXRD patterns for compounds 1(a)and 2(b)

    2.4 Photochemical properties

    The solid-state photo-luminescent properties of the free H3LCl ligand,coordination polymers 1 and 2 have been investigated in the solid state at room temperature.The emission spectra of these compounds are shown in Fig.5.An intense band is observed at 412 nm(λex=317 nm)for H2L.Compared to the H3LCl ligand,compound 1 results in red shift of 13 nm(425 nm,λex=364 nm).The shift of the emission maximum between 1 and H3LCl is considered to mainly originate from the influence of the coordination of the ligand to metal atom[23-24].The compound 2 has same emission peak of 412 nm(λex=315 nm)with the free H2L,which indicates that it may originate from metal-perturbed intraligand charge transfers[25-27].

    Fig.5 Solid-state emission spectra of free H2L and compounds 1 and 2 at room temperature

    3 Conclusions

    We have reported the syntheses,crystal structures and properties of two coordination polymers,{[Zn(L) (bpa)0.5(H2O)2]·2.25H2O}n(1)and{[Cd(L)(H2O)]·2H2O}n(2)with different structure derived from 5-(4-hydroxypyridinium-1-ylmethyl)isophthalicacidchloride ligand.Both compound 1 and 2 have a 3D supramoleculararchitectureextendedbyhydrogen-bonding interactions,but the 3D network of compound 1 is constructed by an infinite 1D ladder-like chain,and that of compound 2 is formed by a 2D layer structure with tubular channels.In addition,the coordination modes of carboxylate groups in two compounds are different:μ2-η1∶η1mode for compound 1,μ3-η1∶η2mode for 2.Compared to the compounds based on the present ligand and reported in the literature[17],they have not only different structure,but also different coordination modes,which indicate that H3LCl ligand is a favorable and fashionable building block for compounds with abundant structural features and useful properties. Subsequent studies will focuse on the structures and properties of the novel functional coordination polymers constructed by the present ligand with a wide range of rareearthmetals.Furtherinvestigationsonthis domain are underway.

    [1]Cao L H,Zang S Q,Li J B.Z.Anorg.Allg.Chem.,2011, 637:1427-1431

    [2]Zhu H F,Fan J,Okamura T A,et al.Inorg.Chem.,2006,45 (10):3941-3948

    [3]Zhang L P,Ma J F,Yang J,et al.Cryst.Growth Des.,2009, 9(11):4660-4673

    [4]QIAO Yu(喬宇),WEI Bing(尉兵),WANG Lu-Yao(王璐瑤), et al.Chinese J.Inorg.Chem.(無機化學學報),2016,32(7): 1261-1266

    [5]Dong X Y,Zhang M,Pei R B,et al.Angew.Chem.Int.Ed., 2016,55:2073-2077

    [6]Pan C,Nan J P,Dong X L,et al.J.Am.Chem.Soc.,2011, 133(32):12330-12333

    [7]Han L,Valle H,Bu X H.Inorg.Chem.,2007,46:1511-1513

    [8]Qi Y,Luo F,Batten S R,et al.Cryst.Growth Des.,2008,8: 2806-2813

    [9]Hu Y W,Li G H,Liu X M,et al.CrystEngComm,2008,10: 888-893

    [10]Li S L,Lan Y Q,Qin J S,et al.Cryst.Growth Des.,2009,9: 4142-4146

    [11]Li H Y,Cao L H,Wei Y L,et al.CrystEngComm,2015,17: 6297-6307

    [12]Kuai H W,Fan J,Liu Q,et al.CrystEngComm,2012,14: 3708-3716

    [13]Kuai H W,Hou C,Sun W Y.Polyhedron,2013,52:1268-1275

    [14]Ji C,Li B,Ma M L,et al.CrystEngComm,2012,14:3951-3958

    [15]Li J B,Dong X Y,Cao L H,et al.CrystEngComm,2012,14: 4444-4453

    [16]Zang S Q,Cao L H,Liang R,et al.Cryst.Growth Des.,2012,12:1830-1837

    [17]LI Fu-An(李付安),XU Fu(徐伏),YANG Wei-Chun(楊維春),et al.Chinese J.Inorg.Chem.(無機化學學報),2016,32 (9):1683-1691

    [18]SMART and SAINT,Area Detector Control and Integration Software,Siemens Analytical X-Ray Systems,Inc.,Madison, WI,1996.

    [19]Sheldrick G M.SADABS 2.05,University of G?ttingen, Germany,1997.

    [20]Sheldrick G M.SHELXS-97,Program for the Solution of Crystal Structures,University of G?ttingen,1997.

    [21]Sheldrick G M.Acta Crystallogr.Sect.A,2008,A64:112

    [22]Bernstein J,Davis R E,Shimoni L,et al.Angew.Chem.Int. Ed.,1995,34:1555-1573

    [23]Chang Z,Zhang A S,Hu T L,et al.Cryst.Growth Des., 2009,9:4840-4846

    [24]Guo J,Ma J F,Liu B,et al.Cryst.Growth Des.,2011,11: 3609-3621

    [25]Zheng S L,Yang J H,Yu X L,et al.Inorg.Chem.,2004,43: 830-838

    [26]Fang S M,Zhang Q,Hu M,et al.Cryst.Growth Des.,2010, 10:4773-4785

    [27]Su Z,Fan J,Chen M,et al.Cryst.Growth Des.,2011,11: 1159-1169

    Syntheses,Structures and Photoluminescent Properties of Two 3D Coordination Polymers Based on a Flexible and Angular Organic Aromatic Multi-carboxylate Ligand

    LI Fu-An*XU FuYANG Wei-Chun
    (College of Chemistry and Environmental Engineering,Pingdingshan University,Pingdingshan,Henan 467000,China)

    Two coordination polymers with 3D supramolecular network,{[Zn(L)(bpa)0.5(H2O)2]·2.25H2O}n(1)and {[Cd(L)(H2O)]·2H2O}n(2)(H3LCl=5-(4-hydroxypyridinium-1-ylmethyl)isophthalic acid chloride,bpa=1,2-bis(4-pyridyl)ethane)were hydrothermally synthesized and structurally characterized by X-ray diffraction analyses and further characterized by infrared spectra(IR),elemental analyses,and thermogravimetric(TG)analyses. Compound 1 exhibits a ladder-like chain structure,and such chains are further united together to generate a 3D supramolecular structure through the hydrogen bonding interactions.Compound 2 possesses a 2D coordination network with a 1D channel that run parallel to the coordination layers.Meanwhile,their luminescent properties have also been investigated in detail.CCDC:908522,1;908526,2.

    5-(4-hydroxypyridinium-1-ylmethyl)isophthalic acid chloride;1,2-bis(4-pyridyl)ethane;zinc;cadmium

    O614.24+1;O614.24+2

    A

    1001-4861(2017)09-1631-08

    10.11862/CJIC.2017.190

    2017-03-14。收修改稿日期:2017-05-26。

    河南省高等學校重點科研項目(No.15A150068)和平頂山學院應用化學重點實驗室(No.201201)資助。*

    。E-mail:lifuanpds@163.com

    猜你喜歡
    間苯二甲酸吡啶基楊維
    間苯二甲酸二烯丙酯合成方法
    An Exploration of Self—Concept, Parent Education, Parent and Student Attitudes Towards School, Study Habits and Achievement of Students
    素質教育(2015年3期)2015-10-21 19:42:04
    An Exploration of Self—Concept, Parent Education, Parent and Student Attitudes Towards School, Study Habits and Achievement of Students
    素質教育(2014年3期)2014-10-21 19:44:56
    楊維松的詩
    基于5,5'-亞甲基二間苯二甲酸及1,2-雙(咪唑基-1-甲基)苯的Zn2+、Co2+配位聚合物的合成及晶體結構
    一個基于β-[Mo8O26]和5-(3-吡啶基)-四唑橋連的二核鎳配合物構筑的無機-有機雜化化合物
    5-4-(1H-四唑基)苯氧基-間苯二甲酸構筑的鎘配位聚合物的合成、晶體結構及熒光性質
    1,3-二吡啶基苯和4,4′-二羧基二苯砜構筑的鈷(Ⅱ)配合物合成、結構和性質
    2,4-二氨基-6-(2'-吡啶基)均三嗪銅(Ⅱ)配合物的結構、抗菌活性及DNA作用
    以二羧酸二苯甲醚和吡啶基三唑為配體構筑的鈷(Ⅱ)配合物的合成、結構、熱穩(wěn)定性及DFT計算
    午夜福利18| 3wmmmm亚洲av在线观看| 国产午夜福利久久久久久| 久久久久国产精品人妻aⅴ院| 怎么达到女性高潮| 直男gayav资源| 国产v大片淫在线免费观看| 欧美色视频一区免费| 男插女下体视频免费在线播放| 成年女人永久免费观看视频| 久久中文看片网| 亚洲片人在线观看| 此物有八面人人有两片| 12—13女人毛片做爰片一| 国产精品亚洲一级av第二区| 特级一级黄色大片| 99久久99久久久精品蜜桃| 淫妇啪啪啪对白视频| 精品久久久久久久久久久久久| 久久精品国产99精品国产亚洲性色| 午夜激情福利司机影院| 亚洲欧美清纯卡通| 一区二区三区免费毛片| 国产精品自产拍在线观看55亚洲| 国产精品三级大全| 琪琪午夜伦伦电影理论片6080| 黄片小视频在线播放| 精品一区二区免费观看| 成人三级黄色视频| 2021天堂中文幕一二区在线观| 午夜福利在线观看免费完整高清在 | 俄罗斯特黄特色一大片| 少妇的逼好多水| 亚洲,欧美精品.| 琪琪午夜伦伦电影理论片6080| 欧美三级亚洲精品| 欧美不卡视频在线免费观看| 看黄色毛片网站| a级一级毛片免费在线观看| av在线老鸭窝| 久久国产精品人妻蜜桃| 久久久久精品国产欧美久久久| 老司机福利观看| 国产精品伦人一区二区| 蜜桃亚洲精品一区二区三区| 老司机午夜十八禁免费视频| 51国产日韩欧美| 在现免费观看毛片| 国产精华一区二区三区| 欧美成人一区二区免费高清观看| or卡值多少钱| 亚洲熟妇熟女久久| 亚洲内射少妇av| 亚洲国产欧洲综合997久久,| 国产欧美日韩一区二区三| 国产高清激情床上av| 男人舔女人下体高潮全视频| 国产一区二区在线观看日韩| 深夜a级毛片| 日韩中字成人| 亚洲欧美日韩无卡精品| 亚洲欧美日韩无卡精品| 国产真实伦视频高清在线观看 | 亚洲最大成人中文| 欧美+日韩+精品| 91狼人影院| 国产伦在线观看视频一区| 国产精品不卡视频一区二区 | 国产主播在线观看一区二区| 少妇人妻一区二区三区视频| 免费看a级黄色片| 亚洲精品亚洲一区二区| 嫩草影视91久久| 欧美日本亚洲视频在线播放| 国产午夜精品久久久久久一区二区三区 | 麻豆成人av在线观看| 三级男女做爰猛烈吃奶摸视频| 国产精品1区2区在线观看.| 国产黄片美女视频| 又黄又爽又免费观看的视频| 精品福利观看| 日本成人三级电影网站| 国产亚洲精品久久久久久毛片| 麻豆成人av在线观看| 九九在线视频观看精品| 久久精品91蜜桃| 精品一区二区三区视频在线观看免费| 亚洲成人久久性| 成人毛片a级毛片在线播放| 麻豆久久精品国产亚洲av| 悠悠久久av| 日韩免费av在线播放| 国产精品影院久久| 久久久久亚洲av毛片大全| 亚洲美女黄片视频| 91av网一区二区| 久久99热这里只有精品18| 热99在线观看视频| 国产精品av视频在线免费观看| 欧美午夜高清在线| 亚洲av美国av| 亚洲精品粉嫩美女一区| 亚洲av电影在线进入| 99国产综合亚洲精品| а√天堂www在线а√下载| 丝袜美腿在线中文| 老鸭窝网址在线观看| 午夜福利视频1000在线观看| 简卡轻食公司| 很黄的视频免费| 成人亚洲精品av一区二区| 尤物成人国产欧美一区二区三区| 亚洲av成人精品一区久久| 欧美一级a爱片免费观看看| 波多野结衣巨乳人妻| 757午夜福利合集在线观看| 欧美不卡视频在线免费观看| 中文亚洲av片在线观看爽| 精品国产亚洲在线| 国产爱豆传媒在线观看| 日本与韩国留学比较| 一级a爱片免费观看的视频| 草草在线视频免费看| 丰满人妻一区二区三区视频av| 免费高清视频大片| 亚洲狠狠婷婷综合久久图片| 日本免费a在线| 老鸭窝网址在线观看| 最近在线观看免费完整版| 国产中年淑女户外野战色| 又爽又黄无遮挡网站| 色尼玛亚洲综合影院| 国产精品不卡视频一区二区 | 亚洲国产精品999在线| 3wmmmm亚洲av在线观看| 日韩欧美一区二区三区在线观看| www.999成人在线观看| 久久久久久久午夜电影| 欧美性猛交╳xxx乱大交人| 成人午夜高清在线视频| 97热精品久久久久久| 欧美乱妇无乱码| 国产视频内射| 内地一区二区视频在线| 夜夜躁狠狠躁天天躁| 9191精品国产免费久久| 婷婷亚洲欧美| 国产午夜福利久久久久久| 此物有八面人人有两片| 国产一区二区在线观看日韩| 精品乱码久久久久久99久播| 亚洲国产欧美人成| 少妇裸体淫交视频免费看高清| 色播亚洲综合网| 男人和女人高潮做爰伦理| 国产亚洲欧美98| 精品人妻一区二区三区麻豆 | 色哟哟哟哟哟哟| 97碰自拍视频| 国产精品av视频在线免费观看| 欧美精品国产亚洲| 久久精品综合一区二区三区| 性色av乱码一区二区三区2| 亚洲精品久久国产高清桃花| 一进一出抽搐动态| 亚洲avbb在线观看| 99精品在免费线老司机午夜| 国产伦一二天堂av在线观看| 小说图片视频综合网站| 神马国产精品三级电影在线观看| 国产午夜精品久久久久久一区二区三区 | 国产午夜精品久久久久久一区二区三区 | 97碰自拍视频| 亚洲成人中文字幕在线播放| 丰满的人妻完整版| 色综合站精品国产| 亚洲精华国产精华精| 免费在线观看成人毛片| 亚洲男人的天堂狠狠| 免费人成在线观看视频色| 亚洲最大成人中文| 欧美三级亚洲精品| 男女下面进入的视频免费午夜| 一二三四社区在线视频社区8| 亚洲aⅴ乱码一区二区在线播放| 精品欧美国产一区二区三| 麻豆av噜噜一区二区三区| 亚洲不卡免费看| 在线播放无遮挡| 在线天堂最新版资源| 神马国产精品三级电影在线观看| 国产精品一及| 免费观看人在逋| 成年人黄色毛片网站| 国产单亲对白刺激| 啦啦啦观看免费观看视频高清| 亚洲无线观看免费| 欧美三级亚洲精品| www日本黄色视频网| 麻豆国产97在线/欧美| 色精品久久人妻99蜜桃| 欧美xxxx性猛交bbbb| 欧美极品一区二区三区四区| 免费一级毛片在线播放高清视频| 亚洲色图av天堂| 中文字幕av成人在线电影| 男女下面进入的视频免费午夜| 久久精品综合一区二区三区| 午夜福利在线观看吧| 久久久久性生活片| 男女那种视频在线观看| 欧美日韩瑟瑟在线播放| 国产高潮美女av| 婷婷六月久久综合丁香| 亚洲狠狠婷婷综合久久图片| 一本久久中文字幕| 久久草成人影院| 免费人成在线观看视频色| 免费av不卡在线播放| 久久人人精品亚洲av| 天堂√8在线中文| 久久6这里有精品| 国产精品美女特级片免费视频播放器| 久久久久精品国产欧美久久久| 日韩欧美在线乱码| 999久久久精品免费观看国产| avwww免费| 亚洲av电影在线进入| 午夜精品在线福利| 亚洲人成网站在线播| 看片在线看免费视频| 在线a可以看的网站| 91av网一区二区| 色综合站精品国产| 亚洲欧美日韩高清专用| 国产日本99.免费观看| 国产探花在线观看一区二区| 亚洲精品一卡2卡三卡4卡5卡| 婷婷精品国产亚洲av在线| 十八禁网站免费在线| 蜜桃久久精品国产亚洲av| 亚洲国产日韩欧美精品在线观看| 国产白丝娇喘喷水9色精品| 日本黄大片高清| 一a级毛片在线观看| 舔av片在线| 精品人妻熟女av久视频| 天堂影院成人在线观看| 黄色配什么色好看| 亚洲乱码一区二区免费版| 麻豆国产97在线/欧美| 久久午夜亚洲精品久久| 中文字幕人妻熟人妻熟丝袜美| 国产白丝娇喘喷水9色精品| 精品久久久久久,| 噜噜噜噜噜久久久久久91| 国产淫片久久久久久久久 | 久久久久久久久中文| 亚洲一区二区三区色噜噜| 日本精品一区二区三区蜜桃| 嫩草影院入口| 亚洲精品456在线播放app | 看免费av毛片| 国产午夜福利久久久久久| 国产私拍福利视频在线观看| 一区二区三区四区激情视频 | 在线免费观看不下载黄p国产 | 亚洲人成网站高清观看| 白带黄色成豆腐渣| 久久国产乱子免费精品| 亚洲av一区综合| 免费在线观看成人毛片| 欧美最黄视频在线播放免费| 国产极品精品免费视频能看的| www.色视频.com| 精品久久久久久久末码| 一卡2卡三卡四卡精品乱码亚洲| 国产成+人综合+亚洲专区| 99久久久亚洲精品蜜臀av| 国产私拍福利视频在线观看| 久久亚洲真实| 亚洲不卡免费看| 亚洲经典国产精华液单 | 少妇人妻精品综合一区二区 | 香蕉av资源在线| 久久中文看片网| 午夜亚洲福利在线播放| 欧美在线一区亚洲| 久久久久性生活片| 日韩欧美在线乱码| 嫩草影视91久久| 床上黄色一级片| 真人一进一出gif抽搐免费| 观看免费一级毛片| 又紧又爽又黄一区二区| 国产高清激情床上av| 免费人成视频x8x8入口观看| 久久草成人影院| 搞女人的毛片| 日韩成人在线观看一区二区三区| 中文字幕熟女人妻在线| 国产中年淑女户外野战色| 午夜视频国产福利| 在线观看av片永久免费下载| 久久精品影院6| 国产亚洲精品久久久com| 日本一本二区三区精品| 亚洲精品在线美女| 男女做爰动态图高潮gif福利片| 69av精品久久久久久| 精品99又大又爽又粗少妇毛片 | 人人妻人人看人人澡| 成人国产一区最新在线观看| 琪琪午夜伦伦电影理论片6080| 好男人在线观看高清免费视频| 又黄又爽又刺激的免费视频.| 久久精品91蜜桃| 亚洲精品色激情综合| 青草久久国产| av在线老鸭窝| 亚洲 欧美 日韩 在线 免费| 亚洲精品色激情综合| 国产亚洲av嫩草精品影院| 十八禁国产超污无遮挡网站| 久久精品91蜜桃| 88av欧美| 欧美乱妇无乱码| 怎么达到女性高潮| 国产爱豆传媒在线观看| 丰满乱子伦码专区| 成人性生交大片免费视频hd| 欧美最黄视频在线播放免费| 我的老师免费观看完整版| 国产精品三级大全| x7x7x7水蜜桃| 搡老熟女国产l中国老女人| av中文乱码字幕在线| 18禁在线播放成人免费| 女人被狂操c到高潮| 成人高潮视频无遮挡免费网站| 国产不卡一卡二| 欧美成人a在线观看| 最近最新中文字幕大全电影3| 永久网站在线| 床上黄色一级片| 三级毛片av免费| 在线观看舔阴道视频| 村上凉子中文字幕在线| 我要搜黄色片| 久久草成人影院| 伦理电影大哥的女人| 97超视频在线观看视频| 日韩有码中文字幕| 99久久精品一区二区三区| 久久天躁狠狠躁夜夜2o2o| 乱码一卡2卡4卡精品| 久久精品91蜜桃| 国产成人福利小说| 精品无人区乱码1区二区| 欧美乱色亚洲激情| 午夜a级毛片| 午夜免费激情av| 国内精品久久久久精免费| 国内少妇人妻偷人精品xxx网站| 90打野战视频偷拍视频| 首页视频小说图片口味搜索| 成人高潮视频无遮挡免费网站| 国产伦精品一区二区三区视频9| 嫁个100分男人电影在线观看| 免费在线观看日本一区| 久久精品人妻少妇| 少妇裸体淫交视频免费看高清| 欧洲精品卡2卡3卡4卡5卡区| 国产精品久久久久久久电影| 精品久久久久久久久av| 欧美色欧美亚洲另类二区| 欧美不卡视频在线免费观看| 国产精品一及| 精品人妻熟女av久视频| 欧美日本视频| 精华霜和精华液先用哪个| 啪啪无遮挡十八禁网站| 久久久久久久亚洲中文字幕 | 男插女下体视频免费在线播放| 日本一本二区三区精品| 久久人人精品亚洲av| 国产高清有码在线观看视频| 久久国产精品人妻蜜桃| 男人舔奶头视频| 嫩草影院新地址| 欧美国产日韩亚洲一区| 成人毛片a级毛片在线播放| 国产精品女同一区二区软件 | 成人鲁丝片一二三区免费| 国产精品一区二区三区四区免费观看 | 久久午夜亚洲精品久久| 欧美潮喷喷水| 精品人妻1区二区| 日日干狠狠操夜夜爽| 久久精品国产亚洲av天美| 成年女人看的毛片在线观看| 国产一区二区亚洲精品在线观看| 国产亚洲欧美98| 国产精品一区二区三区四区免费观看 | 成人午夜高清在线视频| 中文字幕人妻熟人妻熟丝袜美| 日韩人妻高清精品专区| 欧美激情在线99| 午夜精品一区二区三区免费看| 亚洲美女黄片视频| 性色avwww在线观看| 可以在线观看毛片的网站| av在线观看视频网站免费| 久久久久九九精品影院| 真人做人爱边吃奶动态| 亚洲自拍偷在线| 最近在线观看免费完整版| 91狼人影院| 91麻豆精品激情在线观看国产| 热99re8久久精品国产| 亚洲欧美日韩东京热| 色综合亚洲欧美另类图片| 麻豆成人午夜福利视频| 国产探花极品一区二区| 亚洲精品色激情综合| 免费在线观看亚洲国产| 亚洲av二区三区四区| 精品久久久久久久久av| 特大巨黑吊av在线直播| 亚洲国产高清在线一区二区三| 国产一区二区激情短视频| 一级av片app| 亚洲精品在线美女| 九九热线精品视视频播放| 尤物成人国产欧美一区二区三区| 国内少妇人妻偷人精品xxx网站| 国产精品自产拍在线观看55亚洲| 日本三级黄在线观看| 又粗又爽又猛毛片免费看| 色播亚洲综合网| 真人做人爱边吃奶动态| 男女做爰动态图高潮gif福利片| 国产成人aa在线观看| 国产精品98久久久久久宅男小说| АⅤ资源中文在线天堂| 色综合欧美亚洲国产小说| 十八禁网站免费在线| 少妇人妻精品综合一区二区 | 国产单亲对白刺激| 动漫黄色视频在线观看| 免费观看人在逋| 亚洲欧美日韩高清在线视频| 免费看a级黄色片| 美女cb高潮喷水在线观看| 在线观看舔阴道视频| 精品一区二区免费观看| x7x7x7水蜜桃| 一区二区三区激情视频| 国内毛片毛片毛片毛片毛片| 精品久久久久久久久久久久久| 国产精品久久久久久亚洲av鲁大| 一边摸一边抽搐一进一小说| 9191精品国产免费久久| 国产精品久久久久久精品电影| aaaaa片日本免费| 中文亚洲av片在线观看爽| 观看美女的网站| 欧美最黄视频在线播放免费| 婷婷色综合大香蕉| 亚洲人成电影免费在线| 小说图片视频综合网站| 在线观看美女被高潮喷水网站 | 一级黄色大片毛片| 极品教师在线免费播放| av在线老鸭窝| 少妇被粗大猛烈的视频| 国产人妻一区二区三区在| 精品福利观看| 亚洲av成人不卡在线观看播放网| 成人av在线播放网站| 国产高清视频在线播放一区| 性色avwww在线观看| 国产成+人综合+亚洲专区| 久久人人爽人人爽人人片va | 搡老熟女国产l中国老女人| 丰满人妻一区二区三区视频av| 夜夜夜夜夜久久久久| 每晚都被弄得嗷嗷叫到高潮| 免费人成视频x8x8入口观看| 日日摸夜夜添夜夜添av毛片 | 亚洲激情在线av| 美女 人体艺术 gogo| 精品国产亚洲在线| 日本免费a在线| 小蜜桃在线观看免费完整版高清| www.色视频.com| 成熟少妇高潮喷水视频| 久久久久久九九精品二区国产| 99riav亚洲国产免费| 国产精品一区二区三区四区免费观看 | 欧美黑人巨大hd| 成人永久免费在线观看视频| 亚洲精品粉嫩美女一区| 国产又黄又爽又无遮挡在线| 精品久久久久久久久亚洲 | 久久午夜亚洲精品久久| 国产精品1区2区在线观看.| 免费观看人在逋| 小蜜桃在线观看免费完整版高清| www.色视频.com| 成人亚洲精品av一区二区| 国产爱豆传媒在线观看| 欧美成狂野欧美在线观看| 白带黄色成豆腐渣| 99国产综合亚洲精品| 精品久久久久久久人妻蜜臀av| 色吧在线观看| 亚洲精品乱码久久久v下载方式| 无遮挡黄片免费观看| 国产成人aa在线观看| 欧美三级亚洲精品| 性插视频无遮挡在线免费观看| 日日摸夜夜添夜夜添av毛片 | 宅男免费午夜| 亚洲av不卡在线观看| 午夜福利18| 国产视频内射| 国产乱人视频| 高清毛片免费观看视频网站| 亚洲av二区三区四区| 亚洲aⅴ乱码一区二区在线播放| 搡老熟女国产l中国老女人| 国产精品一区二区三区四区久久| 高清在线国产一区| 少妇丰满av| 首页视频小说图片口味搜索| 亚洲av成人不卡在线观看播放网| 国产欧美日韩一区二区精品| 国产老妇女一区| 亚洲五月天丁香| 欧美绝顶高潮抽搐喷水| or卡值多少钱| 中文字幕高清在线视频| 国产国拍精品亚洲av在线观看| 级片在线观看| 国产主播在线观看一区二区| 亚洲第一欧美日韩一区二区三区| 日韩精品青青久久久久久| 简卡轻食公司| 精品一区二区三区人妻视频| 嫁个100分男人电影在线观看| 黄色日韩在线| 亚洲黑人精品在线| 欧美日韩瑟瑟在线播放| 国产高清有码在线观看视频| 18+在线观看网站| 一个人免费在线观看的高清视频| 99精品在免费线老司机午夜| 88av欧美| 久久久久久久亚洲中文字幕 | 亚洲精品456在线播放app | 久久人人精品亚洲av| 在线免费观看不下载黄p国产 | 日本免费一区二区三区高清不卡| 好男人在线观看高清免费视频| 亚洲 欧美 日韩 在线 免费| 欧美成人一区二区免费高清观看| 变态另类成人亚洲欧美熟女| 中国美女看黄片| 在线观看免费视频日本深夜| 亚洲精品久久国产高清桃花| 在线观看66精品国产| 欧美黑人巨大hd| 国产白丝娇喘喷水9色精品| 狠狠狠狠99中文字幕| 少妇熟女aⅴ在线视频| 欧美成人性av电影在线观看| 亚洲欧美日韩东京热| 91久久精品国产一区二区成人| 国产精品一区二区三区四区免费观看 | 99热6这里只有精品| 婷婷精品国产亚洲av在线| 国内精品久久久久久久电影| 日本五十路高清| 欧美3d第一页| 精品久久久久久,| 一级av片app| 欧美在线黄色| 丰满人妻熟妇乱又伦精品不卡| 一进一出好大好爽视频| 尤物成人国产欧美一区二区三区| 久久久久久久久大av| 国产aⅴ精品一区二区三区波| 亚洲av免费在线观看| 亚洲欧美日韩高清在线视频| www.999成人在线观看| 日韩大尺度精品在线看网址| 五月玫瑰六月丁香| 啦啦啦观看免费观看视频高清| 国产欧美日韩精品亚洲av| 可以在线观看毛片的网站| 成年女人永久免费观看视频| 成人精品一区二区免费| or卡值多少钱| 日本熟妇午夜| 久久天躁狠狠躁夜夜2o2o| 国产亚洲精品久久久久久毛片| 日本一二三区视频观看| 亚洲第一区二区三区不卡| 亚洲欧美日韩高清专用| 国产精品综合久久久久久久免费| 国产麻豆成人av免费视频| 国产精品影院久久| 亚洲成a人片在线一区二区| 国产午夜精品久久久久久一区二区三区 |