• <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 ?

    在四氯合鋅離子誘導(dǎo)下反式六元瓜環(huán)與堿金屬離子構(gòu)筑的配位超分子自組裝體

    2016-12-05 05:42:44邱勝超張云黔祝黔江張振琴
    無機化學(xué)學(xué)報 2016年7期
    關(guān)鍵詞:四氯堿金屬南京醫(yī)科大學(xué)

    邱勝超 李 青 張云黔 肖 昕 陶 朱 祝黔江*, 張振琴

    (1貴州大學(xué)化學(xué)與化工學(xué)院,貴州省大環(huán)化學(xué)及超分子化學(xué)重點實驗室,貴陽550025)

    (2南京醫(yī)科大學(xué)藥學(xué)院化學(xué)系,南京210009)

    在四氯合鋅離子誘導(dǎo)下反式六元瓜環(huán)與堿金屬離子構(gòu)筑的配位超分子自組裝體

    邱勝超1李青1張云黔1肖昕1陶朱1祝黔江*,1張振琴*,2

    (1貴州大學(xué)化學(xué)與化工學(xué)院,貴州省大環(huán)化學(xué)及超分子化學(xué)重點實驗室,貴陽550025)

    (2南京醫(yī)科大學(xué)藥學(xué)院化學(xué)系,南京210009)

    在鹽酸介質(zhì)中,通過四氯合鋅離子誘導(dǎo),堿金屬離子能與反式六元瓜環(huán)端口羰基氧原子直接配位構(gòu)筑形成超分子自組裝體。單晶結(jié)構(gòu)表明在HCl介質(zhì)中,四氯合鋅離子形成“蜂巢結(jié)構(gòu)”,而且在[ZnCl4]2-誘導(dǎo)作用下,堿金屬離子和反式六元瓜環(huán)端口羰基氧直接配位形成一維超分子自組裝體而填充在“蜂巢結(jié)構(gòu)”中。

    堿金屬離子;反式六元瓜環(huán);四氯合鋅根離子;超分子自組裝體

    0 Introduction

    An inverted cucurbit[6]uril(i Q[6],Fig.1)was first reported by Isaacs and Kim in 2005[1-2],and since then only a couple of theoretical investigations on their potential properties have been reported[3-4].A low synthetic yield and difficulties in separating i Q[n]s has hindered their investigation.Upon their discovery,it was suggested that i Q[n]s could selectively recognize guests by the shape and dimensions of their cavity[4].Indeed,X-ray crystallographyand1HNMR spectroscopy revealed interesting host-guest interactions between i Q[6]and p-phenylenediaminium in both the solid state and aqueous solution.Two different complexes were observed in the solid state:an inclusion structure and a sandwich structure.In aqueous solution,the i Q [6]host can accommodate the p-phenylenediaminium guest,but the guest favours staying outside the pores of the i Q[6]host,and guest exchange is fast on the NMR time scale[5].

    Fig.1 Structure of the inverted cucurbit[6]uril as viewed from the top(left)and from the side(right)

    We recently developed a convenientmethod for isolating i Q[6]from the normal cucurbit[6]uril(Q[6]) by column chromatography using a Dowex resin[6]. Then we investigated the coordination properties of i Q[6]with variousmetal ions.Obtaining solid crystals of i Q[6]/M+by simplymixing i Q[6]with alkali salts was proved difficult,without the addition of a structure directing agent such as tetrachloride zincate anion ([ZnCl4]2-).However,in thepresenceof[ZnCl4]2-,reaction of alkaline earth cations(AE2+)and the inverted cucurbit[6]uril(i Q[6])yielded linear coordination polymers in which i Q[6]and AE2+cations are directly coordinated to themetal ions.In contrast,in the i Q[6]-Mg2+-[ZnCl4]2-HCl system,there was no direct coordination between i Q[6]and Mg2+or Zn2+,presumably due to the shorter ionic radii preventing direct coordination[6].Recently,we found that the coordination of i Q[6]with Ln3+gave rise to differentinteraction products and isomorphous groups with the heavier lanthanides. The interaction of i Q[6]with lighter lanthanides such as La3+,Ce3+,Pr3+and Nd3+immediately yielded precipitation or single crystal solids,whereas interaction of i Q[6]with Sm3+and Eu3+did notgenerate solidmaterial. Interaction of i Q[6]with heavier lanthanides gave rise to three isomorphous groups with different structure features,with Gd3+,Tb3+,Dy3+and Ho3+forming one group,Er3+,Tm3+and Yb3+forming a separate group, and Lu3+differing from both of these groups[7].

    In the present work,i Q[6]was used as a ligand, and its coordination with alkali cations(M+)in supramolecular assemblieswas investigated in the presence of the structure directing agent[ZnCl4]2-.Single-crystal X-ray diffraction analysis revealed that the i Q[6]-M+-[ZnCl4]2--HCl interaction systems consisted of a supramolecular assembly of i Q[6]/M+complexesand[ZnCl4]2-anions,in which[ZnCl4]2-anions are assembled into a honeycomb-like frameworks via outer surface interactions between i Q[6]s.The linear coordination polymers of i Q[6]hosts coordinated to M+cations(A=Na,K,Rb) fill the poresorchannels in the[ZnCl4]2-framework[8-10].

    1 Experimental

    1.1Reagents and instrument

    All chemicals including alkali metal chlorides (MCl)were of reagent grade and were used without further purification.i Q[6]was prepared as described previously[1].Elemental analysiswas carried out on a EURO EA-3000 elemental analyzer.

    1.2Preparation of titled com pounds

    A similar process was used to prepare crystals forall i Q[6]-M+-[ZnCl4]2--HCl systems.Specifically,MCl (0.15 mmol,M=Na,K,Rb)and ZnCl2(14.79mg,0.12 mmol)were dissolved in 1 mLH2O to prepare solution A,and i Q[6](20 mg,0.015 mmol)was dissolved in 1 mL 6 mol·L-1HCl to prepare solution B.Solution B was then slow ly added to solution A and stirred.X-ray diffraction-quality crystals were obtained by slowly evaporation after 7 days.

    [Na2(H2O)2(i Q[6])]·[ZnCl4]·[Zn(H2O)Cl3](H3O)· 7H2O(1):Anal.Calcd.for C36H59N24O23Na2Zn2Cl7(%):C, 26.68,H,3.67,N,20.74;Found(%):C,26.87,H,3.56, N,21.01.

    {K4(H2O)8[ZnCl4](i Q[6])2}·[ZnCl4]·3[Zn(H2O)Cl3] (H3O)3·22H2O(2):Anal.Calcd.forC72H147N48O60K4Zn5Cl17(%):C,23.18,H,3.97,N,18.02;Found(%):C,23.28, H,3.76,N,18.21.

    [Rb(H2O)(i Q[6])]·[ZnCl4]·[Zn(H2O)Cl3](H3O)2· 16H2O(3):Anal.Calcd.for C36H78N24O32RbZn2Cl7(%): C,23.71,H,4.31,N,18.43;Found(%):C,23.84,H, 4.13,N,18.77.

    1.3X-ray crystallography

    A suitable single crystal(~0.2 mm×0.2 mm×0.1 mm)was embedded in paraffin oil and mounted on a Bruker SMART ApexⅡCCD diffractometer equipped with a graphite-monochromated Mo Kαradiation source (λ=0.071 07 3 nm,μ=0.828mm-1),which was operated in theω-scan mode under a nitrogen stream(-50℃). Datawere corrected for Lorentz and polarization effects using the SAINT program[11],and semi-empirical absorption corrections based on equivalent reflections were applied using the SADABS program[12].The structure was elucidated through directmethods,and full-matrix least-squares refinement of F2values was performed using SHELXS-97[13]and SHELXL-97[14].All nonhydrogen atomswere refined anisotropically,and carbon -bound hydrogen atoms were introduced at calculated positions and treated as riding atoms with an isotropic displacement parameter equal to 1.2 times that of the parent atom.Most of the watermolecules were omitted using the SQUEEZE option of the PLATON program[15]. A total of 8,including 1 protonated watermolecules, 25,including 3 protonated water molecules and 18, including 2 protonated watermoleculeswere squeezed for compounds 1,2,and 3,respectively.Analytical expressions for neutral-atom scattering factors were employed,and anomalous dispersion corrections were incorporated.Details of the crystal parameters,data collection conditions,and refinement parameters for the three compounds are summarized in Table1.

    CCDC:1469246,1;1469247,2;1469248,3.

    Table1 Crystal data and structure refinement details of compounds from i Q[6]-M+-ZnCl2-HCl systems

    Continued Table1

    2 Results and discussion

    Fig.2 Crystal structure of compound 1:(a)Overall view of the supramolecular assembly constructed from i Q[6]/Na+complexes and ZnCl4]2-and[Zn(H2O)Cl3]-anions along the b axis;(b)Zn anion-based honeycomb-like framework;(c)Linear i Q[6]/Na+-based coordination polymer;(d)Interaction of i Q[6]with Zn-based anions;(e)Coordination of i Q[6]with Na cations

    Fig.2shows the structure of compound 1.The supramolecular assembly is based on[ZnCl4]2-and [Zn(H2O)Cl3]-anions in which complexes of i Q[6]and Na+cations(Fig.2a)occupy the pores within the honeycomb-like framework constructed from[ZnCl4]2-and[Zn(H2O)Cl3]-anions(Fig.2b).Each hollow in the honeycomb is occupied by one i Q[6]-Na+-based linear coordination polymer(Fig.2a,2c).Closer inspection of Fig.2a reveals that each i Q[6]molecule interactswith six Zn-based anions(four[ZnCl4]2-anions and two[Zn(H2O)Cl3]-anions)through ion-dipole interactions between Zn-based anions and the electropositive outer surface of i Q[6].The distance between chlorides from [ZnCl4]2-anions and methine or methylene carbons on the outer surface of i Q[6]ranged between 0.342 4 and 0.388 2 nm,and an additional hydrogen bond is present between a coordinated water molecule(O1W)bound to a[Zn(H2O)Cl3]-anion and a portal carbonyl oxygen (O8)of the i Q[6]-Na+complex,with a O1W-O8 distance of 0.270 5 nm(Fig.2d).Each i Q[6]molecule coordinates with four sodium cations,and each i Q[6] portal coordinates two Na1 and Na2 cations.Four carbonyloxygens(O11,O12 to Na1 and O8,O9 to Na2) form the top portal of i Q[6](Fig.2e),and both Na1 and Na2 cations coordinate with water molecules O2W, O3W and a carbonyl oxygen(O1)from a neighboring i Q[6]molecule.Furthermore,four carbonyl oxygens (O1,O2 to Na1 and O1,O6 to Na2)form the bottom portal of the i Q[6](Fig.2e),and again both Na1 and Na2 cations coordinate with water molecules O2W,O3W and a carbonyl oxygen(O1)from another neighboring i Q[6]molecule,with a Na+-portal carbonyl oxygen distanceof0.2286~0.261 7nm,and aNa+-Owaterdistance of 0.237 8~0.243 7 nm.

    Fig.3 Crystal structure of compound 2:(a)Overall view of the supramolecular assembly constructed from i Q[6]/K+complexes and ZnCl4]2-and[Zn(H2O)Cl3]-anions along the b axis;(b)[ZnCl4]2--based honeycomb-like framework;(c)Linear i Q[6]/K+-based coordination polymer;(d)Interaction of an i Q[6]moleculewith Zn-based anions;(e)Coordination of an i Q[6]molecule with K+cations

    Fig.3showsstructureof compound 2.Fig.3a shows a similar supramolecular assembly,comprised of[ZnCl4]2-and[Zn(H2O)Cl3]-anions surrounded with i Q[6]moleculesand K+cationsby non-covalent interaction.Again,the[ZnCl4]2-and[Zn(H2O)Cl3]-anions form a honeycomb-like framework(Fig.3b),and the i Q[6] -K+-based linear coordination polymers occupy the pores in this framework via outer surface interactions with the electropositive surface of Q[n](Fig.3a,c).Five [ZnCl4]2-anionsand three[Zn(H2O)Cl3]-anionssurround each i Q[6]molecule in the assembly,and close inspection reveals detailed interactions that include:(1)an ion-dipole interaction between a[ZnCl4]2-chloride and amethine ormethylene carbon from the outer surface of i Q[6],with a distanceof0.341 2~0.375 5 nm(dashed lines in Fig.3d);(2)an ion-dipole interaction between a[ZnCl4]2-chloride and an electron deficient carbonyl carbon with a distance of 0.327 6~0.336 2 nm(dashed lines in Fig.3d);(3)a hydrogen bond between a water molecule coordinated to the[Zn(H2O)Cl3]-anion or K+cation and a portal carbonyl oxygen or chloride from the [Zn(H2O)Cl3]-anion,with a distance of 0.309 2~0.341 6 nm(dashed lines in Fig.3d).There is an additional interaction between a coordinated K+cation(K4)and a[ZnCl4]2-anion,with K-Cl distances of 0.325 9 and 0.328 9 nm,respectively(Fig.3d).Each i Q[6]in compound 2 is also coordinated to four K+cations(K1 and K2 from one portal,and K3 and K4 from the other portal.K1 coordinates to eight oxygen atoms,two carbonyl oxygens(O1,O2),and six watermolecules (O4W,O5W,O6W,O7W,O10W and O11W);K2 coordinates to seven oxygen atoms,four carbonyloxygens(O3,O4,and O13,O14 from a neighbouring i Q[6]molecule),and three water molecules(O9W, O8W and O7W);K3 coordinates only to three carbonyl oxygens(O7,O12 and O21 from another neighbouring i Q[6]molecule);K4 coordinates only to two carbonyl oxygens(O11 and O21 from another neighbouring i Q[6] molecule).Distances between K+and portal carbonyl oxygens are in the range of 0.232 2~0.321 2 nm,and K+-Owaterdistances are 0.236 2~0.297 4 nm.

    Fig.4 Crystal structure of compound 3:(a)Overall view of the supramolecular assembly constructed from i Q[6]/Rb+complexes and[ZnCl4]2-and[Zn(H2O)Cl3]-anions along the a axis;(b)[ZnCl4]2--based honeycomb-like framework along the a axis; (c)Linear i Q[6]/Rb+-based coordination polymer;(c)Linear i Q[6]/Rb+-based coordination polymer;(d)Interaction of an i Q[6]molecule with Zn-based anions;(e)Coordination of an i Q[6]molecule with Rb+cations

    Compound 3hasasimilarsupramolecularassembly to 1 and 2 described above,in which[ZnCl4]2-and [Zn(H2O)Cl3]-anions form ahoneycomb-like framework, and i Q[6]molecules coordinated with Rb+cations form a linear coordination polymer that is inserted in the cells of the framework(Fig.4a~c).Each i Q[6]molecule is surrounded by three[ZnCl4]2-anions and three [Zn(H2O)Cl3]-anions through ion-dipole interactions between a[ZnCl4]2-chlorideand amethineormethylene carbon on the outer surface of i Q[6],with a distance of0.338 1~0.371 2 nm(Fig.4d).An additionalhydrogen bond is present between watermolecule(O1W)coordinated to the[Zn(H2O)Cl3]-anion and portal carbonyl oxygen(O9),with a distance of 0.268 3 nm(dashed lines in Fig.4d).Each i Q[6]is also coordinated to rubidium cation Rb1 at both portals.Rb1 coordinates to five oxygen atoms(carbonyl oxygensO1,O2 and O10 and O11 from a neighboring i Q[6]),and one water molecule(O2W).The Rb+-portal carbonyl oxygen distance is 0.278 4~0.301 9 nm,and the K+-Owaterdistance is 0.305 6 nm(Fig.4e).

    The crystal structures therefore revealed a similar Zn-based honeycomb-like framework filled with linear i Q[6]/M+-based coordination polymers for all three compounds(Fig.2a,3a,4a).However,closer inspection revealed a slightly different arrangement of the linear i Q[6]/M+-based coordination polymers that led to different porous supramolecular assemblies with different alkali metal ions.With Na+(compound 1),i Q[6]/Na+-based coordination polymers are arranged tightly, with noobvious free space.In contrast,with K+and Rb+(compounds2and 3,respectively),the zigzag-like i Q[6]/ K+and Rb+-based coordination polymersare arranged into different porous assemblies(Fig.5).

    Fig.5 Supramolecular assembly constructed from linear coordination polymers of i Q[6]/Na+(a),i Q[6]/K+(b)and i Q[6]/Rb+(c)

    3 Conclusions

    In the present study,we discovered that iQ[6] forms linear coordination polymers with alkali metal ions(M+)in the presence of[ZnCl4]2-anion structuredirecting agents.The supramolecular assemblies consist of a[ZnCl4]2-based honeycomb-like framework that interacts with the electropositive outer surface of i Q[6]through ion-dipole interactions.The electronegative environment presumably attracts the M+cations to the portals of i Q[6],resulting in their coordination and formation of the 1D coordination polymers.Interestingly,different M+cations resulted in the formation of different supramolecular assemblies with different structural features.In particular the pore size was dependent on the ionic diameter of the cation.The resultant supramolecular assembliesmight give rise to different absorption characteristics,and furtherinvestigation is underway in our laboratory.

    Acknowledgments:Weacknowledge the supportofNational Natural Science Foundation of China(Grant No.21272045, 21561007).

    References:

    [1]Isaacs L,Park SK,Liu SM,etal.J.Am.Chem.Soc.,2005, 127:18000-18001

    [2]Isaacs LD,Liu SM,Kim K,etal.WO Patent,2007014214-A2.2007-02-01.

    [3]PinjariR V,GejjiSP.J.Phys.Chem.A,2009,113:1368-1376

    [4]Raja IA,Gobre V V,Pinjari R V,etal.J.Mol.Model.,2014, 20:1-7

    [5]Zhang D Q,Lin R L,Sun W Q,et al.Org.Biomol.Chem., 2015,13:8330-8334

    [6]Zhang D Q,Sun T,Zhang Y Q,et al.Eur.J.Inorg.Chem., 2015,2:318-323

    [7]Zhang D Q,Zhang Y Q,Xue SF,et al.Polyhedron,2015,99: 147-155

    [8]Ni X L,Xiao X,Cong H,et al.Chem.Soc.Rev.,2013,42: 9480-9508

    [9]NiX L,Xue S F,Tao Z,etal.Coord.Chem.Rev.,2015,287: 89-113

    [10]Ni X L,Xiao X,Cong H,et al.Acc.Chem.Res.,2014,47: 1386-1395

    [11]SAINT,Program for Data Extraction and Reduction,Bruker AXS,Inc.,Madison,WI,2001.

    [12]Sheldrick GM.SADABS,University of G?ttingen,Germany, 1996.

    [13]Sheldrick GM.ActaCrystallogr.Sect.A,2008,A64:112-122

    [14]Sheldrick G M.SHELXL-97,Program for the Solution and Refinement of Crystal Structures,University of G?ttingen, Germany,1997.

    [15]Spek A L.Acta Crystallogr.Sect.A,1990,A46:194-201

    Supramolecular Assemblies Formed by Coordination of AlkaliM etal Ions w ith Inverted Cucurbit[6]uril in the Presence of Tetrachlorozincate

    QIU Sheng-Chao1LIQing1ZHANG Yun-Qian1XIAO Xin1TAO Zhu1ZHUQian-Jiang*,1ZHANG Zhen-Qin*,2
    (1Key Laboratory ofMacrocyclic and Supramolecular Chemistry of Guizhou Province,Guizhou University,Guiyang 550025,China)
    (2School of Pharmacy,Nanjing Medical University,Nanjing 210009,China)

    Coordination in supramolecular assemblies formed in aqueous HCl solution was investigated by reacting alkali cations(M+)and inverted cucurbit[6]uril(i Q[6])in the presence of the structure-directing agent tetrachloride zincate anion([ZnCl4]2-).Single-crystal X-ray diffraction analysis revealed that the i Q[6]-M+-[ZnCl4]2--HCl interaction systems yielded a supramolecular assembly consisting of i Q[6]/M+-based linear coordination polymers residing within the pores of a honeycomb-like framework of[ZnCl4]2-anions.Close inspection revealed that different i Q[6]/M+/[ZnCl4]2--based supramolecular assemblies(M=Na,K,Rb)presented different porous conformations and displayed differentabsorption properties.CCDC:1469246,1;1469247,2;1469248,3.

    alkalinemetal ion;inverted cucurbit[6]uril;tetrachloride zincate anion;supramolecular assemblies

    O614.24+1;O614.112;O614.113;O614.114

    A

    1001-4861(2016)07-1303-08

    10.11862/CJIC.2016.154

    2016-04-19。收修改稿日期:2016-05-26。

    國家自然科學(xué)基金(No.21272045,21561007)資助項目。

    *通信聯(lián)系人。E-mail:gzutao@263.net,zhangzhq@njmu.edu.cn,F(xiàn)ax:+86-851-3620906,Tel:+86-851-3623903

    猜你喜歡
    四氯堿金屬南京醫(yī)科大學(xué)
    南京醫(yī)科大學(xué)國家級基礎(chǔ)醫(yī)學(xué)實驗教學(xué)示范中心
    四氯對苯二甲腈含量分析方法
    地下水中四氯多酚污染治理研究
    南京醫(yī)科大學(xué)附屬江寧醫(yī)院
    相變貯熱材料四氯合鈷酸銨共析物的制備和熱性能
    《堿金屬》疑難問題解析
    有關(guān)堿金屬的計算舉隅
    明辨二甲四氯藥害
    SDS/DTAB/堿金屬氯化鹽復(fù)配囊泡為模板制備PMMA微球
    Detection of prostate cancer using magnetic resonance spectroscopy
    磁共振成像(2015年1期)2015-02-21 05:37:01
    久久久久久伊人网av| 成人一区二区视频在线观看| 亚洲精品色激情综合| 国产高清不卡午夜福利| 日本精品一区二区三区蜜桃| 日本-黄色视频高清免费观看| 老熟妇乱子伦视频在线观看| 伦理电影大哥的女人| 精品久久久久久久人妻蜜臀av| 成人美女网站在线观看视频| 尤物成人国产欧美一区二区三区| 久久久久久久久久久丰满 | 亚洲人与动物交配视频| 日韩高清综合在线| 黄色丝袜av网址大全| 特级一级黄色大片| 国产 一区精品| 变态另类丝袜制服| 成人av在线播放网站| 日韩欧美国产在线观看| 在线天堂最新版资源| 在线观看一区二区三区| 国产精品久久视频播放| 精品久久久久久久久久久久久| 日本熟妇午夜| 久久精品国产自在天天线| 极品教师在线免费播放| 日本黄色片子视频| 欧美日韩国产亚洲二区| 深夜a级毛片| 亚洲精品国产成人久久av| 国产亚洲av嫩草精品影院| 亚洲欧美精品综合久久99| 人人妻人人看人人澡| 国产免费一级a男人的天堂| 久久久久久伊人网av| 欧美成人a在线观看| 99久国产av精品| 国产欧美日韩精品一区二区| 免费在线观看影片大全网站| 美女黄网站色视频| 在现免费观看毛片| av专区在线播放| 国内精品美女久久久久久| 男女做爰动态图高潮gif福利片| 精品免费久久久久久久清纯| 一级黄片播放器| xxxwww97欧美| netflix在线观看网站| 国产精品亚洲美女久久久| 久久久久久九九精品二区国产| 日韩欧美三级三区| 人妻少妇偷人精品九色| 久久久久久久久中文| 我的老师免费观看完整版| 亚洲精品色激情综合| 国产精华一区二区三区| 99热精品在线国产| 人人妻,人人澡人人爽秒播| 久久精品综合一区二区三区| 麻豆av噜噜一区二区三区| 在线播放无遮挡| 午夜免费成人在线视频| 91久久精品国产一区二区成人| 精品午夜福利视频在线观看一区| 亚洲经典国产精华液单| 亚洲综合色惰| 久久久国产成人免费| 日日夜夜操网爽| 伦理电影大哥的女人| 欧美bdsm另类| 嫁个100分男人电影在线观看| av黄色大香蕉| 国产免费一级a男人的天堂| 亚洲内射少妇av| 乱系列少妇在线播放| 日日摸夜夜添夜夜添小说| 老熟妇仑乱视频hdxx| 变态另类丝袜制服| 久久精品国产99精品国产亚洲性色| 欧美绝顶高潮抽搐喷水| 3wmmmm亚洲av在线观看| 国产亚洲精品久久久com| 天堂影院成人在线观看| 男女啪啪激烈高潮av片| 天美传媒精品一区二区| 在线播放国产精品三级| 亚洲第一区二区三区不卡| 欧美黑人欧美精品刺激| 久久久色成人| 在线播放无遮挡| 亚洲成人精品中文字幕电影| 中亚洲国语对白在线视频| 国内久久婷婷六月综合欲色啪| h日本视频在线播放| 国产伦精品一区二区三区视频9| 亚洲精品影视一区二区三区av| 国产大屁股一区二区在线视频| 在线天堂最新版资源| 亚洲av成人av| 两人在一起打扑克的视频| 尾随美女入室| 在线观看一区二区三区| 国产淫片久久久久久久久| 99热精品在线国产| 人人妻人人澡欧美一区二区| 69av精品久久久久久| 亚洲久久久久久中文字幕| 国产精品1区2区在线观看.| 免费av毛片视频| 一边摸一边抽搐一进一小说| 可以在线观看毛片的网站| 亚洲精品亚洲一区二区| 久久久久久久精品吃奶| 天堂网av新在线| 日本成人三级电影网站| 国产一区二区亚洲精品在线观看| 91麻豆av在线| 午夜福利在线观看免费完整高清在 | 久久久国产成人免费| 小蜜桃在线观看免费完整版高清| 国产 一区精品| 亚洲国产精品成人综合色| 国产av一区在线观看免费| 国产极品精品免费视频能看的| 久久人人爽人人爽人人片va| 色视频www国产| 黄色配什么色好看| 亚洲精品色激情综合| 无人区码免费观看不卡| 黄色一级大片看看| 亚洲国产欧洲综合997久久,| 成年女人毛片免费观看观看9| 少妇高潮的动态图| 免费av毛片视频| 好男人在线观看高清免费视频| 国产激情偷乱视频一区二区| 国产精品无大码| 亚洲国产精品成人综合色| 国产色爽女视频免费观看| 国产高潮美女av| 国产精品女同一区二区软件 | 精品乱码久久久久久99久播| 别揉我奶头~嗯~啊~动态视频| 人人妻人人看人人澡| 欧美日韩精品成人综合77777| 性色avwww在线观看| 成人综合一区亚洲| 97人妻精品一区二区三区麻豆| 欧美黑人巨大hd| 日本一本二区三区精品| 最好的美女福利视频网| www.www免费av| 久久久精品大字幕| 欧美又色又爽又黄视频| 99国产精品一区二区蜜桃av| 联通29元200g的流量卡| 欧美日韩精品成人综合77777| 性色avwww在线观看| 亚洲av中文字字幕乱码综合| 国产精品av视频在线免费观看| 春色校园在线视频观看| 日本熟妇午夜| 精品久久久久久久久av| 亚洲图色成人| 亚洲一区二区三区色噜噜| 成人特级av手机在线观看| 国产精品伦人一区二区| 国产高清视频在线播放一区| 欧美在线一区亚洲| 99久久精品一区二区三区| 午夜福利18| 国产精品久久视频播放| 伦精品一区二区三区| 久久99热这里只有精品18| 好男人在线观看高清免费视频| 欧美日韩国产亚洲二区| 天堂√8在线中文| 成人二区视频| 人妻夜夜爽99麻豆av| 观看美女的网站| 在线播放国产精品三级| 国产一区二区三区av在线 | 综合色av麻豆| x7x7x7水蜜桃| 老熟妇乱子伦视频在线观看| 色综合亚洲欧美另类图片| 一级毛片久久久久久久久女| 又黄又爽又刺激的免费视频.| 日韩欧美国产一区二区入口| 亚洲四区av| 亚洲国产日韩欧美精品在线观看| 美女黄网站色视频| 色av中文字幕| 一级黄色大片毛片| 97人妻精品一区二区三区麻豆| 国产精品女同一区二区软件 | 久久人人精品亚洲av| 国产一区二区亚洲精品在线观看| 亚洲成人久久爱视频| a级一级毛片免费在线观看| 日日啪夜夜撸| 听说在线观看完整版免费高清| 非洲黑人性xxxx精品又粗又长| 99热这里只有是精品50| 精品久久久久久久久亚洲 | 大又大粗又爽又黄少妇毛片口| 全区人妻精品视频| 国产蜜桃级精品一区二区三区| 欧美激情在线99| 成人亚洲精品av一区二区| 日韩,欧美,国产一区二区三区 | 国产一区二区在线av高清观看| 日韩欧美精品免费久久| 日韩一区二区视频免费看| 国产精品无大码| 久久国内精品自在自线图片| 亚洲va日本ⅴa欧美va伊人久久| 亚洲av.av天堂| 能在线免费观看的黄片| 久久香蕉精品热| 综合色av麻豆| 国产探花在线观看一区二区| 2021天堂中文幕一二区在线观| 丝袜美腿在线中文| 搡老熟女国产l中国老女人| 丰满的人妻完整版| 久久久久性生活片| 成人特级黄色片久久久久久久| av在线天堂中文字幕| 中文字幕人妻熟人妻熟丝袜美| 欧美又色又爽又黄视频| 午夜精品久久久久久毛片777| 亚洲最大成人中文| 狂野欧美激情性xxxx在线观看| 久久精品国产鲁丝片午夜精品 | 成熟少妇高潮喷水视频| 男人舔奶头视频| 午夜福利在线观看吧| 欧美高清成人免费视频www| 国产私拍福利视频在线观看| 蜜桃久久精品国产亚洲av| 久久久久久九九精品二区国产| 欧美成人a在线观看| 韩国av一区二区三区四区| 深夜精品福利| 色av中文字幕| 人人妻,人人澡人人爽秒播| 久久久久九九精品影院| 欧美绝顶高潮抽搐喷水| 听说在线观看完整版免费高清| 久久久久久久亚洲中文字幕| 成人国产麻豆网| 日韩 亚洲 欧美在线| 国产精品1区2区在线观看.| 黄色视频,在线免费观看| 久久国产精品人妻蜜桃| 日韩欧美一区二区三区在线观看| 一级av片app| 亚洲成人久久性| 一个人观看的视频www高清免费观看| 中文字幕高清在线视频| 国产精品国产三级国产av玫瑰| 干丝袜人妻中文字幕| 午夜福利在线观看免费完整高清在 | 国产三级在线视频| 人妻少妇偷人精品九色| 精品一区二区三区人妻视频| 免费观看的影片在线观看| 日韩国内少妇激情av| 国产黄a三级三级三级人| 亚洲美女搞黄在线观看 | 欧美性猛交╳xxx乱大交人| 真实男女啪啪啪动态图| 91麻豆精品激情在线观看国产| 最新在线观看一区二区三区| av天堂在线播放| 男插女下体视频免费在线播放| 又黄又爽又免费观看的视频| 深爱激情五月婷婷| 黄色欧美视频在线观看| 香蕉av资源在线| 干丝袜人妻中文字幕| ponron亚洲| 97热精品久久久久久| 伦精品一区二区三区| 国产一区二区激情短视频| 99久久成人亚洲精品观看| 色在线成人网| 久久精品国产亚洲网站| 久久热精品热| 免费大片18禁| 国产久久久一区二区三区| 啦啦啦韩国在线观看视频| 少妇高潮的动态图| 免费av毛片视频| 18禁黄网站禁片午夜丰满| 精品福利观看| 我的女老师完整版在线观看| 亚洲人与动物交配视频| 日韩国内少妇激情av| 五月玫瑰六月丁香| 日本黄色片子视频| 身体一侧抽搐| 亚洲一级一片aⅴ在线观看| 成人鲁丝片一二三区免费| av.在线天堂| 中文字幕熟女人妻在线| 国内久久婷婷六月综合欲色啪| 国内精品美女久久久久久| 国产精品女同一区二区软件 | av中文乱码字幕在线| 国产亚洲91精品色在线| 日韩 亚洲 欧美在线| 国产精品乱码一区二三区的特点| 国产主播在线观看一区二区| 亚洲最大成人手机在线| 又黄又爽又刺激的免费视频.| 日韩欧美精品v在线| 日本 欧美在线| 日日夜夜操网爽| 村上凉子中文字幕在线| 精品免费久久久久久久清纯| 国产大屁股一区二区在线视频| 神马国产精品三级电影在线观看| 69av精品久久久久久| 九九爱精品视频在线观看| 国产白丝娇喘喷水9色精品| 国产欧美日韩精品亚洲av| 久久精品国产亚洲网站| 在线观看免费视频日本深夜| 亚洲精品粉嫩美女一区| 成人二区视频| 日本-黄色视频高清免费观看| 舔av片在线| 国产久久久一区二区三区| 99久久久亚洲精品蜜臀av| 男女之事视频高清在线观看| 久久人妻av系列| 村上凉子中文字幕在线| 桃红色精品国产亚洲av| 亚洲无线观看免费| 国产蜜桃级精品一区二区三区| 最后的刺客免费高清国语| 少妇的逼水好多| 亚洲成人中文字幕在线播放| 精品久久久久久久末码| 国产在线精品亚洲第一网站| 99久久中文字幕三级久久日本| 直男gayav资源| 国产高清激情床上av| 婷婷丁香在线五月| 日韩精品青青久久久久久| 午夜精品久久久久久毛片777| 国产一区二区三区视频了| 成人无遮挡网站| 色综合色国产| 嫁个100分男人电影在线观看| 亚洲色图av天堂| 狠狠狠狠99中文字幕| 伦精品一区二区三区| 国产精品女同一区二区软件 | 免费大片18禁| 国产精品乱码一区二三区的特点| 亚洲aⅴ乱码一区二区在线播放| 成人高潮视频无遮挡免费网站| 乱人视频在线观看| 欧美绝顶高潮抽搐喷水| 欧美在线一区亚洲| 在线a可以看的网站| 国产精品久久久久久av不卡| 国产精品亚洲一级av第二区| 嫁个100分男人电影在线观看| 中文亚洲av片在线观看爽| 日本 欧美在线| 亚洲专区国产一区二区| 午夜老司机福利剧场| 成人国产综合亚洲| 欧美黑人巨大hd| 色综合色国产| 日韩高清综合在线| 精品一区二区三区人妻视频| 一进一出抽搐动态| 久久久午夜欧美精品| 亚洲欧美激情综合另类| 日本色播在线视频| 亚洲avbb在线观看| 亚洲av.av天堂| 久久人妻av系列| 深夜精品福利| 午夜视频国产福利| 噜噜噜噜噜久久久久久91| 国产69精品久久久久777片| 老熟妇仑乱视频hdxx| 99riav亚洲国产免费| 久久久久久久久久成人| 色吧在线观看| 99热这里只有是精品在线观看| 欧美最新免费一区二区三区| 极品教师在线免费播放| 午夜精品一区二区三区免费看| 一a级毛片在线观看| 亚洲欧美激情综合另类| 动漫黄色视频在线观看| 久久精品综合一区二区三区| 中文在线观看免费www的网站| 国产精品福利在线免费观看| 能在线免费观看的黄片| 国产熟女欧美一区二区| 亚洲无线在线观看| 午夜福利成人在线免费观看| 国产高清视频在线播放一区| 99国产精品一区二区蜜桃av| 亚洲成av人片在线播放无| 亚洲一级一片aⅴ在线观看| 国产精品永久免费网站| 亚洲一级一片aⅴ在线观看| 男女那种视频在线观看| 久久精品综合一区二区三区| 熟妇人妻久久中文字幕3abv| 色播亚洲综合网| 国产精品98久久久久久宅男小说| 俺也久久电影网| 成年女人看的毛片在线观看| 三级毛片av免费| 日本五十路高清| 欧美3d第一页| 草草在线视频免费看| 久久久久精品国产欧美久久久| 美女高潮喷水抽搐中文字幕| 中文字幕av在线有码专区| 国产精品自产拍在线观看55亚洲| 不卡视频在线观看欧美| 最后的刺客免费高清国语| 久久精品91蜜桃| 久久九九热精品免费| 22中文网久久字幕| 最新在线观看一区二区三区| 国产精品av视频在线免费观看| 久久国产精品人妻蜜桃| 久久久久久国产a免费观看| 亚洲午夜理论影院| 狠狠狠狠99中文字幕| 三级男女做爰猛烈吃奶摸视频| 亚洲四区av| 亚洲 国产 在线| 99热这里只有是精品在线观看| 日韩中字成人| 国产大屁股一区二区在线视频| 男女边吃奶边做爰视频| 亚洲三级黄色毛片| or卡值多少钱| 看十八女毛片水多多多| 国产亚洲精品久久久com| 一进一出抽搐gif免费好疼| 99热6这里只有精品| 国产一区二区三区av在线 | 精品无人区乱码1区二区| 亚洲精品一区av在线观看| 久久草成人影院| 午夜福利欧美成人| 老女人水多毛片| 国产一区二区激情短视频| 亚洲成av人片在线播放无| 一夜夜www| 黄色日韩在线| 最近在线观看免费完整版| 国产男靠女视频免费网站| 精品99又大又爽又粗少妇毛片 | 国产av麻豆久久久久久久| 久久精品影院6| 尾随美女入室| 国模一区二区三区四区视频| 国产乱人视频| 欧美极品一区二区三区四区| 久久久成人免费电影| 亚洲在线自拍视频| 国内毛片毛片毛片毛片毛片| 女同久久另类99精品国产91| 少妇人妻精品综合一区二区 | 伊人久久精品亚洲午夜| 亚洲va在线va天堂va国产| 日本免费一区二区三区高清不卡| 国产精品久久久久久久久免| 美女高潮喷水抽搐中文字幕| 韩国av一区二区三区四区| 嫩草影院入口| 人妻夜夜爽99麻豆av| 欧美日韩黄片免| 日韩欧美精品免费久久| 久久人妻av系列| 窝窝影院91人妻| 精品国产三级普通话版| 婷婷丁香在线五月| 久久人人精品亚洲av| 美女 人体艺术 gogo| 久久热精品热| bbb黄色大片| 此物有八面人人有两片| 三级毛片av免费| 国产三级中文精品| 精品无人区乱码1区二区| 亚洲av中文av极速乱 | 欧美人与善性xxx| 国产伦人伦偷精品视频| 亚洲欧美日韩东京热| 男女之事视频高清在线观看| 不卡视频在线观看欧美| 岛国在线免费视频观看| 伦理电影大哥的女人| 免费搜索国产男女视频| 国产黄片美女视频| 中国美女看黄片| 中文亚洲av片在线观看爽| 毛片女人毛片| 国产午夜福利久久久久久| 亚洲av免费高清在线观看| 国产精品一区二区性色av| 99在线视频只有这里精品首页| 国产女主播在线喷水免费视频网站 | 蜜桃亚洲精品一区二区三区| 日本精品一区二区三区蜜桃| 日韩国内少妇激情av| 国内精品宾馆在线| 搡老岳熟女国产| 午夜久久久久精精品| 国产精品自产拍在线观看55亚洲| 女同久久另类99精品国产91| 欧美色欧美亚洲另类二区| 久久久久久伊人网av| 亚洲精华国产精华液的使用体验 | 简卡轻食公司| 午夜a级毛片| 国产伦精品一区二区三区四那| 欧美在线一区亚洲| 中文字幕av成人在线电影| 亚洲av电影不卡..在线观看| 天堂√8在线中文| 黄色一级大片看看| 日韩 亚洲 欧美在线| 国产精品av视频在线免费观看| 欧美潮喷喷水| 欧美在线一区亚洲| 欧美+亚洲+日韩+国产| 久久精品国产鲁丝片午夜精品 | 亚洲精品一卡2卡三卡4卡5卡| 狂野欧美白嫩少妇大欣赏| 男女做爰动态图高潮gif福利片| 亚洲中文日韩欧美视频| 99riav亚洲国产免费| 亚洲乱码一区二区免费版| 亚洲人成网站高清观看| 超碰av人人做人人爽久久| 国产亚洲精品久久久久久毛片| 很黄的视频免费| 丰满的人妻完整版| 亚洲性久久影院| 男人的好看免费观看在线视频| 人人妻,人人澡人人爽秒播| 国产 一区 欧美 日韩| 一个人免费在线观看电影| 我的老师免费观看完整版| 欧美另类亚洲清纯唯美| 综合色av麻豆| 在线天堂最新版资源| 免费看日本二区| 国产成人福利小说| 久久久久国产精品人妻aⅴ院| 国产美女午夜福利| 男女做爰动态图高潮gif福利片| 91在线观看av| 亚洲av免费高清在线观看| 男人舔女人下体高潮全视频| 日韩一区二区视频免费看| videossex国产| 国产av在哪里看| 久久久精品大字幕| 99久久无色码亚洲精品果冻| 91午夜精品亚洲一区二区三区 | 亚洲狠狠婷婷综合久久图片| 欧美三级亚洲精品| 精品日产1卡2卡| 国产一区二区在线av高清观看| av天堂中文字幕网| 干丝袜人妻中文字幕| 床上黄色一级片| 在线a可以看的网站| 成人二区视频| 国产精品三级大全| 国产熟女欧美一区二区| 特大巨黑吊av在线直播| 国产一区二区激情短视频| 国产视频一区二区在线看| 99久国产av精品| a级毛片免费高清观看在线播放| 日韩中文字幕欧美一区二区| 亚洲av不卡在线观看| 97超视频在线观看视频| 国产精品99久久久久久久久| 精品欧美国产一区二区三| 久久精品久久久久久噜噜老黄 | 久久久久久久精品吃奶| 神马国产精品三级电影在线观看| 亚洲av成人精品一区久久| 夜夜爽天天搞| 精品人妻1区二区| 精品国内亚洲2022精品成人| 中国美女看黄片| 精华霜和精华液先用哪个| 人人妻人人看人人澡| 一本一本综合久久| 男女做爰动态图高潮gif福利片| 伦精品一区二区三区| 日韩 亚洲 欧美在线| 美女高潮喷水抽搐中文字幕|