• <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 ?

    兩個由醋酸根和含吡啶基配體構(gòu)筑的Znギ配聚物的合成、晶體結(jié)構(gòu)及其熒光性質(zhì)

    2018-04-10 09:25:52蔣正靜殷竟洲李榮清張載超陸路德
    無機化學學報 2018年4期
    關(guān)鍵詞:吡啶基陸路學報

    蔣正靜 殷竟洲 李榮清 張載超 陸路德

    0 Introduction

    In recent years,coordination polymers have increasingly attracted considerable attention for their structural and topological diversities as well as their potential applications in the fields including luminescence[1-7],gas storage/separation[8-10],magnetic properties[11],catalysis[12-13],drug delivery[14]and precursors for nanoparticles[15],etc.The assembly of coordination polymers can be influenced by some external factors,such as temperature,solvent,reactant concentration,and pH value,etc.,and some internal factors,such as coordination geometries of the central metals,configurations,and nature of the organic ligands[16-17].Among these factors,the choice of the organic ligands is the greatest influence in determining the type and topology of the product.Properties of organic ligands,such as solubility,coordination activity,length,geometry,and relative orientation of the donor groups,play a very important role in dictating polymer framework topology[17].So,it is very important to design the organic ligands or regulate the synthesis conditions.To realize the infinite extension of structure,organic ligands with two or more coordination atoms,such as N,O,and Satoms,are often employed[5,18].Therefore,most coordination polymers are constructed from metal ions and carboxylic acid-or nitrogen-containing ligands.Lewis base coordinated zincギcarboxylate polymers are an important class of coordination polymers,which have been known for many years[19-21].The spherical d10configuration of the Znギcation has associated with it a highly flexible coordination sphere which allows it to adopt multiple geometries to suit the demands of its environment.As a result,Zn is an ideal metal for use in constructing extended coordination networks with ligands that can bridge the metal centers in one or multiple directions.On the other hand,the properties and structures of such materials are easily variable with changes in the counterion present.Anionic carboxylates are highly flexible and versatile O-donor ligands in that a range of substituents may be introduced on the carbonyl carbon to modulate its reactivity and coordination propensity to result in a variety of coordination modes such as monodentate,chelating,bidentate bridging,monoatomic bridging,and chelating bridging[4].Moreover,the choice of the organic ligands is the greatest influence in determining the type and topology of the product.So,the properties and structures of such materials are easily variable with changes in ligand ratio,ligand type and the counterion present.Pyridylcontaining ligand,such as INH or 2-APy,being an interesting N-type of heterocyclic system,has attracted much attention of many researchers[21-23].In earlier efforts,we have used INH ligand with Cuガions to form metal-organic coordination polymers[22-23].As part of our ongoing research in this area,we herein report the synthesis,structures and luminescent properties of two Zincギcoordination polymers constructed by acetate and pyridyl-containing ligands:[Zn(CH3COO)2(INH)]n(1)and[Zn(CH3COO)2(2-APy)]n(2).

    1 Experimental

    1.1 Materials and measurements

    INH(Isonicotinic acid hydrazide;Isoniazid)and 2-APy(2-Aminopyridine)were purchased from Alfa Aesar,UK.All solvents and other chemicals were purchased and use received.Element analyses were performed on a Perkin-Elmer 2400LS elemental analyzer.Powder X-ray diffraction (PXRD)patterns were measured on an ARL/X′PRA powder diffractometer at 40 kV,40 mA using a Cu Kα radiation(λ=0.154 06 nm)in 2θrange of 5°~40°.IR spectra were measured in KBr pellets on a Nicolet AVATAR360 FT-IR spectrometer in the range of 4 000~400 cm-1.Fluorescence spectra were recorded on a Perkin-Elmer LS55 spectrometer.

    1.2 Synthesis of the polymer 1

    Zn(CH3COO)2·2H2O(0.439 g,2 mmol)was dissolved in 10 mL DMF solvent at room temperature.INH(0.274 g,2 mmol)was added to this solution with stirring,during which time white precipitate formed.Then,NH4SCN was added to the reaction mixture until the precipitate dissolved and a colorless solution formed.The colorless solution obtained was filtered and the filtrate was then transfered to two test tubes and carefully layered by i-PrOH.Three weeks later,the products were collected and colorless block crystals of[Zn(CH3COO)2(INH)]nsuitable for X-ray measurements were obtained.Anal.Calcd.for C10H13N3O5Zn(%):C,37.46;H,4.09;N,13.11.Found(%):C,37.22;H,4.20;N,13.28.IR(KBr,cm-1):3 445(m),3 308(m),3 098(m),3 004(m),1 666(s),1 620(s),1 559(vs),1 415(s),1 349(m),1 215(m),1 090(m),1 021(m),693(s),684(m).

    1.3 Synthesis of the polymer 2

    Compound 2 was synthesized by the same procedure as described for 1 except the addition of 2-APy(0.188 g,2 mmol)instead of INH(0.274 g,2 mmol).Colorless block crystals were obtained and collected in the same way as for compound 1.Anal.Calcd for C18H24N4O8Zn2(%):C,38.94;H,4.36;N,10.09.Found(%):C,38.62;H,4.55;N,10.21.IR(KBr,cm-1):3 432(s),3 328(s),3 312(s),1 653(s),1 614(s),1 589(vs),1 557(s),1 501(m),1 444(m),1 396(s),1 332(m),1 058(m),l 002(m),950(m),857(m),768(m),687(m),607(m),478(m),437(m).

    1.4 Powder X-ray diffraction

    The phase purity of the as-synthesized compounds was confirmed by PXRD patterns,which are consistent with the simulated patterns using the Mercury program(version 1.4.2,Cambridge Crystallographic Data Centre,Cambridge,UK)from the singlecrystal X-ray diffraction data.Fig.1(1 and 2)show the PXRD patterns of as-synthesized compounds and the simulated patterns on the basis of single-crystal structures of 1 and 2,respectively.

    Fig.1 Experimental(upper trace)and simulated(lower trace)PXRD patterns of the polymers 1 and 2

    1.5 Determination of crystal structures

    The X-ray diffraction measurement for the two compounds were performed on a Bruker Smart APEXⅡCCD diffractometer equipped with a graphite monochromatized Mo Kα radiation (λ=0.071 073 nm)by using φ-ω scan mode at 296(2)K.The crystal parameters and experimental details of the data collection are summarized in Table 1.Semi-empirical absorption correction was applied to the intensity data using the SADABSprogram[24].The structures were solved by direct methods of SHELXS-97 program and refined by full matrix least-square on F2using the SHELXTL-97 program[25-26].All non-hydrogen atoms were refined with anisotropic thermal parameters,and all hydrogen atoms were included in calculated positions and refined with isotropic thermal parameters riding on those of the parent atoms.

    CCDC:870030,1;1524913,2.

    2 Results and discussion

    2.1 Description of crystal structure

    Single-crystal structure analysis reveals that the polymer 1 crystallizes in the monoclinic system,space group P21/c with 4 asymmetric units in one unit cell,and exhibits a 2D layer network.The structure of the polymer 1 is depicted in Fig.2(1)and Fig.3.Some selected bond lengths and bond angles are listed in Table 2.As depicted in Fig.2,the asymmetric unit contains two acetate anions,an INH ligand and one Znギ ion.In the polymer 1,zincギ is coordinated byfour oxygen atoms from two bridging acetate groups,a non-bridge acetate group and a carbonyl group of INH ligand,a terminal hydrazide nitrogen atom and a pyridine nitrogen atom from two different INH ligands(Fig.3).The coordination geometry of zinc can be described as a distorted octahedral coordination geometry with Zn-N bond lengths ranging 0.215 1(5)~0.2159(4)nmand Zn-Obond lengthsranging0.2069(4)~0.218 0(4)nm,which are comparable to the values in related zincギpolymers[4,21].In the polymer 1,the Zn-N(pyridine nitrogen)bond length is 0.215 1(5)nm,which is similar to the Zn-N (from hydrazide)bond length(0.215 9(4)nm).Also,the Zn-O(from CH3COO-)bond lengths are 0.210 2(3),0.209 0(5),and 0.206 9(4)nm,respectively,which are similar to each other.However,the Zn-O bond(from carbonyl group of INH)length is 0.218 0(4)nm,which is slightly longer.As shown in Fig.3,in the polymer 1,one INH molecule is coordinated to a metal center by an oxygen atom of carbonyl group and a terminal nitrogen atom of the hydrazide,thereby forming a five-membered ring(Zn(1)-O(5)-C(10)-N(2)-N(3)).The pyridine nitrogen of this INH is coordinated to the other metal center.For the polymer 1,the bond angles of O-Zn-N and O-Zn-O (three atoms in the axial direction)are within 163.04(15)°(O(2)iv-Zn(1)-N(3))173.16(16)°(O(1)-Zn(1)-O(3)),which are decreased compared to the bond

    angle of 180°for an ideal octahedron.Additionally,the bond angles of the cis O-Zn-N and O-Zn-O are within 75.47(15)°(O(5)-Zn(1)-N(3))101.47(17)°(N(1)ii-Zn(1)-N(3)),which are different from the bond angle of 90°for an ideal octahedron.These are in accordance with the distorted octahedron configuration.The deviation can be explained by steric effects because the INH acts as a bridge between Znギcenters and the approximation of the metal centers is accompanied by a geometric distortion in the INH molecule[21].In the polymer 1,there are two different types of CH3COO-groups,which are bridging(bidentate bridging)and non-bridging(monodentate)CH3COO-ligands.Two adjacent Znギa(chǎn)toms are bridged by a CH3COO-ligand,forming a 1D chain.The nonbonded Zn…Zn separation within the 1D chain is 0.504 67(11)nm.These 1D chains extend in the c direction.The INH molecules act as bridges to link the Znギ atoms(Zn…Zn separation is 0.914 44(19)nm)of two neighboring 1D chains,which further construct a layer network(Fig.4(1)).

    Table 1 Crystallographic collection and refinement parameters for the title polymers

    Fig.2 Asymmetric units of the title polymers and the labeling scheme used with 30%ellipsoidal probability

    Table 2 Selected bond lengths(nm)and angles(°)for the polymers

    Fig.3 Coordination environment of Znギa(chǎn)tom in the polymer 1 with the ellipsoids drawn

    The polymer 2 crystallizes in the triclinic system,space group P1 with 2 asymmetric units in one unit cell,and exhibits a 1D zig-zag chain.The structure of the polymer 2 is depicted in Fig.2.Some selected bond lengths and bond angles are listed in Table 2.As depicted in Fig.2,the asymmetric unit contains four acetate anions,two 2-APy ligands and two Znギions.In the polymer 2,the Znギ(2)is tetrahedrally surrounded by N(3)of 2-APy,O(7)of the monodentate acetate,O(2),O(5)of the two syn-anti bridging acetate.The Znギ(1)is also tetrahedrally surrounded by N(1)of 2-APy,O(3)of the monodentate acetate,O(1)of the syn-anti bridging acetate and another O of the synanti bridging acetate from the next repeating unit of the polymer.In the polymer 2,the coordination geometry of zinc can be described as a distorted tetrahedral coordination geometry with Zn-N bond lengths ranging 0.202 4(3)~0.203 1(3)nm and Zn-O bond lengths ranging 0.194 5(3)~0.201 3(3)nm,which are comparable to the values in related zincギpolymers[4].However,the Zn-N bond lengths and the Zn-O bond lengths are slightly longer than those of the polymer 1.The nonbonded Zn…Zn separations within the repeating unit and between the repeating units are 0.477 32(20)and 0.461 17(19)nm,and these distances are longer than those of the related reported(0.441 5(1)nm)[4].Another,in the polymer 2,the 2-APy is situated on the opposite side of the growing polymer and thus renders a syndiotactic stereo chemistry,as shown in Fig.4.This structure arise can due to the steric and basic properties of Lewis bases.

    Fig.4 Single 2D coordination sheet for 1 and an 1D zig-zag chain for 2

    Significant hydrogen-bond parameters observed in the polymer 1 and 2 are listed in Table 3.In the crystal lattice of the polymer 1,there exist some week intermolecular and intramolecular interactions,including non-classic C-H…O hydrogen bond.All of the N-terminals are involved in weak hydrogen bonds.The non-bridging CH3COO-ligands are involved in hydrogen bonding,with the hydrazide groups and pyridine ring of neighboring layers,thereby forming a 3Dsupramolecular arrangement.Thebridging CH3COO-ligands are only involved in hydrogen bonding with the N-terminals of the same layer(Fig.5(1)).These week interactions help to stabilize the crystal structure.Also,the polymer 2 is stabilized by some week intermolecular and intramolecular interactions in the crystal lattice(Fig.5(2)).In the crystal lattice of the polymer 2,including intramolecular H-bonding interactions(N(4)-H(4A)…O(2),N(4)-H(4A)…O(3),nonclassic C-H…O)and intermolecular interactions(N(2)-H(2A)…O(7)ii,N(2)-H(2B)…O(4)ii,N(4)-H(4B)…O(8)ii).These interactions exist in the zig-zag chain.The parameters of the H-bonds are listed in Table 3.

    Fig.5 Selected hydrogen bonds for the polymers shown in dashed line

    Table 3 Hydrogen bond parameters for polymers 1 and 2

    2.2 Luminescent properties

    Inorganic-organic hybrid coordination polymers,constructed with d10metal centers and conjugated organic linkers,have received remarkable attention in view of various potential applications,such as in chemical sensors,photochemistry,and so on[5,27-30].The fluorescence properties of the polymer 1 and 2,as well as free ligands INH and 2-APy,have been investigated in the solid state at room temperature,as depicted in Fig.6.Upon excitation at 211 nm,both the microcrystalline free ligand INH and the polymer 1 samples show broad emission bands with the maximum peaks at 369.5 nm for INH,382.6 nm for the polymer 1,respectively(Fig.6(1)).As shown in Fig.6,coordination of the INH ligand with Znギresults in a 13.1 nm red shift of the emission maximum.The emission spectra have broad peaks with maxima at 367.5 nm for polymer 2,and 396.5 nm for 2-APy(λex=250 nm),respectively.Coordination of the free ligand 2-APy with Znギresults in a 29.0 nm blue shift of the emission maximum.These emissions are neither metal-to-ligand charge transfer(MLCT)nor ligand-to-metal charge transfer(LMCT)in nature,since the Zn2+ions are difficult to oxidize or to reduce due to their d10configuration.The emissions of polymers 1,2 may be a mixture of characters of intraligand and ligand-to-ligand charge transition(LLCT).And the observed red or blue shift of the emission maximum between the polymers and the ligands is considered to mainly originate from the influence of the coordination of the ligand to metal atom[27-30].The results indicate that these polymers may be potential candidates of fluorescent materials.

    Fig.6 Solid-state emission spectra of the polymers and the free ligands

    3 Conclusions

    Two zincギcoordination polymers constructed by acetate and pyridyl-containing ligands have been successfully synthesized and structurally characterized.Polymer 1 is a 2D infinite layer framework,and the resulting 2D structure is interconnected by hydrogen-bond interactions to lead to a 3D supramolecular architecture.Polymer 2 is an infinite onedimensional (1D)zig-zag chain.The results of our present research,together with those in the previous study[21-23],demonstrate that the structural diversity in composition and dimensionality of the coordination compounds can be achieved by the adjustments of ligands,metal centers and/or coordinated anions.In addition,the photoluminescence investigation shows that two coordination polymers appear potentially applied as luminescent materials.

    [1]Liu K,Shi W,Cheng P.Coord.Chem.Rev.,2015,289-290:74-122

    [2]Zhou H C,Kitagawa S.Chem.Soc.Rev.,2014,43:5415-5418

    [3]O′Keeffe M,Yaghi O M.Chem.Rev.,2012,112:675-702

    [4]Kumar U,Thomas J,Thirupathi N.Inorg.Chem.,2010,49:62-72

    [5]Zhang X,Hou L,Liu B,et al.Cryst.Growth Des.,2013,13:3177-3187

    [6]Feng X,Ma L F,Liu L,et al.Cryst.Growth Des.,2013,13:4469-4479

    [7]LI Hong-Jin(李紅晉),GAO Zhu-Qing(高竹青),GU Jin-Zhong(顧金忠).Chinese J.Inorg.Chem.(無機化學學報),2014,30(11):2615-2620

    [8]Huang Y M,Zheng X F,Duan J G,et al.Dalton Trans.,2014,43:6811-6818

    [9]Kesanli B,Cui Y,Smith M R,et al.Angew.Chem.Int.Ed.,2005,44:72-75

    [10]Zhang H M,Fu W F,Gan X,et al.Dalton Trans.,2008:6817-6824

    [11]Xie Y B,Gan L,Saudo E C,et al.CrystEngComm,2015,17:4136-4142

    [12]Hong D Y,Hwang Y K,Serre C,et al.Adv.Funct.Mater.,2009,19:1537-1552

    [13]Karmakar A,Rubio G M D M,Silva M F C G,et al.Cryst.Growth Des.,2015,15:4185-4197

    [14]Horcajada P,Chalati T,Serre C,et al.Nat.Mater.,2010,9:172-178

    [15]Kumar U,Thomas J,Nagarajan R,et al.Inorg.Chim.Acta,2011,372:191-199

    [16]Lan Y Q,Jiang H L,Li S L,et al.Inorg.Chem.,2012,51:7484-7491

    [17]Zhao D,Timmons D J,Yuan D,et al.Acc.Chem.Res.,2011,44:123-133

    [18]Hou L,Li D,Shi W J,et al.Inorg.Chem.,2005,44:7825-7832

    [19]Chen S S,Sheng L Q,Zhao Y,et al.Cryst.Growth Des.,2016,16:229-241

    [20]Lee T W,Lau J P K,Wong W T,et al.Polyhedron,2004,23:999-1002

    [21]Freitas M CR,António JM S,Ziolli R L,et al.Polyhedron,2011,30:1922-1926

    [22]Jiang Z J,Zhao P S,Li R Q,et al.J.Chem.Crystallogr.,2013,43:463-470

    [23]JIANG Zheng-Jing(蔣正靜),LU Lu-De(陸路德),WU Xiao-Dong(武曉東),et al.Chinese J.Inorg.Chem.(無機化學學報),2009,25(4):746-750

    [24]Sheldrick G M.SADABS,Program for Empirical Absorption Correction of Area Detector Data,University of G?ttingen,Germany,1996.

    [25]Sheldrick G M.SHELXS-97,Program for X-ray Crystal Structure Solution,University of G?ttingen,Germany,1996.

    [26]Sheldrick G M.SHELXL-97,Program for the Refinement of Crystal Structure,University of G?ttingen,Germany,1996.

    [27]Kreno L E,Leong K,Farha O K,et al.Chem.Rev.,2012,112:1105-1125

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

    [29]Wan X Y,Jiang F L,Chen L,et al.CrystEngComm,2015,17:3829-3837

    [30]Wu G,Wang X F,Okamura T,et al.Inorg.Chem.,2006,45:8523-8532

    猜你喜歡
    吡啶基陸路學報
    從驛庵看宋代嶺南的陸路交通建置
    廣州文博(2020年0期)2020-06-09 05:14:50
    致敬學報40年
    70年滄桑巨變 中國陸路交通的壯麗變奏
    人民交通(2019年16期)2019-12-20 07:04:02
    MEAN-FIELD LIMIT OF BOSE-EINSTEIN CONDENSATES WITH ATTRACTIVE INTERACTIONS IN R2?
    學報簡介
    學報簡介
    一個基于β-[Mo8O26]和5-(3-吡啶基)-四唑橋連的二核鎳配合物構(gòu)筑的無機-有機雜化化合物
    1,3-二吡啶基苯和4,4′-二羧基二苯砜構(gòu)筑的鈷(Ⅱ)配合物合成、結(jié)構(gòu)和性質(zhì)
    2,4-二氨基-6-(2'-吡啶基)均三嗪銅(Ⅱ)配合物的結(jié)構(gòu)、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(gòu)筑的鈷(Ⅱ)配合物的合成、結(jié)構(gòu)、熱穩(wěn)定性及DFT計算
    99精国产麻豆久久婷婷| 成年女人毛片免费观看观看9 | 国产一区二区在线观看av| 日本猛色少妇xxxxx猛交久久| netflix在线观看网站| 曰老女人黄片| 日韩一区二区视频免费看| avwww免费| 黄色视频不卡| 一区在线观看完整版| 亚洲综合色网址| 黄色毛片三级朝国网站| 嫩草影视91久久| 欧美老熟妇乱子伦牲交| 亚洲av国产av综合av卡| 熟女少妇亚洲综合色aaa.| 啦啦啦视频在线资源免费观看| 国产乱来视频区| 久热这里只有精品99| 亚洲欧美精品自产自拍| 少妇人妻久久综合中文| 国产在视频线精品| 国产野战对白在线观看| 叶爱在线成人免费视频播放| 亚洲色图 男人天堂 中文字幕| 国产国语露脸激情在线看| 一边摸一边抽搐一进一出视频| 亚洲国产中文字幕在线视频| a级毛片在线看网站| 日韩精品有码人妻一区| 国产精品 欧美亚洲| 亚洲色图综合在线观看| 老司机在亚洲福利影院| 亚洲美女搞黄在线观看| 国产成人系列免费观看| 日韩,欧美,国产一区二区三区| 国产av精品麻豆| 国产成人精品无人区| 国产精品国产三级专区第一集| 亚洲美女黄色视频免费看| 又大又黄又爽视频免费| 99久久精品国产亚洲精品| 一级片'在线观看视频| 丰满乱子伦码专区| 欧美日韩视频高清一区二区三区二| 丁香六月欧美| 亚洲自偷自拍图片 自拍| 最近2019中文字幕mv第一页| 妹子高潮喷水视频| 老熟女久久久| 精品一品国产午夜福利视频| 亚洲成人国产一区在线观看 | av视频免费观看在线观看| 人人妻人人爽人人添夜夜欢视频| 久久女婷五月综合色啪小说| 成年美女黄网站色视频大全免费| 日韩av在线免费看完整版不卡| 国产 一区精品| 99久久精品国产亚洲精品| 国产精品三级大全| 久久99热这里只频精品6学生| 美女福利国产在线| 在现免费观看毛片| 国产亚洲一区二区精品| 亚洲美女搞黄在线观看| 青春草视频在线免费观看| 男女床上黄色一级片免费看| 伦理电影大哥的女人| 国产女主播在线喷水免费视频网站| 日本一区二区免费在线视频| svipshipincom国产片| 日韩成人av中文字幕在线观看| 高清av免费在线| 大片电影免费在线观看免费| 两性夫妻黄色片| 高清黄色对白视频在线免费看| 久久精品人人爽人人爽视色| 亚洲精品久久成人aⅴ小说| 男女午夜视频在线观看| 熟女av电影| 国产av精品麻豆| 国产欧美日韩综合在线一区二区| 午夜福利网站1000一区二区三区| 电影成人av| 国产成人精品久久二区二区91 | 亚洲av欧美aⅴ国产| 成人免费观看视频高清| 亚洲成人国产一区在线观看 | 电影成人av| 成人国语在线视频| 在线观看免费高清a一片| 国产精品久久久久久久久免| 国产高清国产精品国产三级| 国产精品 国内视频| 日韩大码丰满熟妇| 亚洲国产毛片av蜜桃av| 老司机亚洲免费影院| 久久精品久久精品一区二区三区| 在线观看三级黄色| 欧美精品一区二区大全| 黄频高清免费视频| 成人亚洲欧美一区二区av| 精品人妻在线不人妻| 777久久人妻少妇嫩草av网站| 高清av免费在线| 欧美日韩视频精品一区| 大香蕉久久网| 99久国产av精品国产电影| 黄色怎么调成土黄色| 欧美日韩成人在线一区二区| 精品一区二区三卡| 久久久久久久久免费视频了| 99国产精品免费福利视频| 一级毛片黄色毛片免费观看视频| 国产黄色免费在线视频| 99热网站在线观看| 国产精品一区二区在线不卡| 2021少妇久久久久久久久久久| 飞空精品影院首页| 男女无遮挡免费网站观看| 久久精品人人爽人人爽视色| 只有这里有精品99| 中文字幕色久视频| 国产99久久九九免费精品| 九色亚洲精品在线播放| 波多野结衣av一区二区av| 捣出白浆h1v1| 亚洲一区二区三区欧美精品| xxx大片免费视频| 久久精品国产综合久久久| tube8黄色片| 中文天堂在线官网| 国产av国产精品国产| 男人舔女人的私密视频| 精品福利永久在线观看| 日本爱情动作片www.在线观看| 黑人巨大精品欧美一区二区蜜桃| 天天躁夜夜躁狠狠久久av| 亚洲情色 制服丝袜| 晚上一个人看的免费电影| 大香蕉久久网| 精品午夜福利在线看| 少妇 在线观看| 99国产精品免费福利视频| 少妇人妻 视频| 亚洲四区av| 久久久欧美国产精品| 69精品国产乱码久久久| 99久国产av精品国产电影| 80岁老熟妇乱子伦牲交| av福利片在线| 黄色视频在线播放观看不卡| 亚洲中文av在线| 99久久精品国产亚洲精品| 99久久综合免费| 日韩 亚洲 欧美在线| www.熟女人妻精品国产| 欧美人与性动交α欧美软件| 国产色婷婷99| 亚洲精品aⅴ在线观看| 国产成人啪精品午夜网站| 大片免费播放器 马上看| 亚洲图色成人| 久久久久久免费高清国产稀缺| 国产在线一区二区三区精| 日韩 欧美 亚洲 中文字幕| 免费高清在线观看日韩| 成人黄色视频免费在线看| 国产精品一区二区在线不卡| 国产 精品1| 丁香六月天网| 黑丝袜美女国产一区| 少妇被粗大猛烈的视频| 国产视频首页在线观看| 欧美 亚洲 国产 日韩一| 精品人妻一区二区三区麻豆| 国产一区二区激情短视频 | 大码成人一级视频| 黑人欧美特级aaaaaa片| 欧美日韩精品网址| 精品一品国产午夜福利视频| 女人久久www免费人成看片| 99精品久久久久人妻精品| www.熟女人妻精品国产| 午夜日韩欧美国产| 国产成人欧美| 亚洲男人天堂网一区| 天天躁夜夜躁狠狠久久av| 中文精品一卡2卡3卡4更新| 天天躁日日躁夜夜躁夜夜| 悠悠久久av| 亚洲在久久综合| 超色免费av| 人人澡人人妻人| 国产精品免费视频内射| 一个人免费看片子| 久久精品人人爽人人爽视色| av福利片在线| 久久97久久精品| 黄色 视频免费看| 国产在线视频一区二区| 欧美中文综合在线视频| 精品亚洲成a人片在线观看| 欧美精品人与动牲交sv欧美| 9191精品国产免费久久| 国产av一区二区精品久久| 男女下面插进去视频免费观看| 亚洲欧洲精品一区二区精品久久久 | 久久久久久人妻| 满18在线观看网站| 亚洲国产最新在线播放| 国产欧美亚洲国产| 七月丁香在线播放| 日韩中文字幕欧美一区二区 | 18禁裸乳无遮挡动漫免费视频| 天堂俺去俺来也www色官网| 久久久国产精品麻豆| 操美女的视频在线观看| 国产成人欧美| 超色免费av| 高清欧美精品videossex| 男女床上黄色一级片免费看| 男女高潮啪啪啪动态图| 久久久国产欧美日韩av| 少妇人妻 视频| 国产亚洲av高清不卡| 欧美最新免费一区二区三区| 青春草亚洲视频在线观看| 丝袜喷水一区| 制服诱惑二区| 亚洲欧美激情在线| 国产女主播在线喷水免费视频网站| 高清不卡的av网站| 国产色婷婷99| 女人精品久久久久毛片| 嫩草影视91久久| 日韩一本色道免费dvd| netflix在线观看网站| 欧美激情 高清一区二区三区| tube8黄色片| 一级,二级,三级黄色视频| 日韩欧美精品免费久久| 久久久久久久久久久免费av| 日本av手机在线免费观看| 日韩电影二区| 成年女人毛片免费观看观看9 | 青春草视频在线免费观看| 成人国产麻豆网| 韩国av在线不卡| 国产精品av久久久久免费| 观看美女的网站| 国产xxxxx性猛交| 午夜老司机福利片| 国产欧美日韩一区二区三区在线| 欧美亚洲 丝袜 人妻 在线| 亚洲综合精品二区| 成人亚洲精品一区在线观看| 黄片播放在线免费| 亚洲成人国产一区在线观看 | 一本大道久久a久久精品| 国产av一区二区精品久久| 十分钟在线观看高清视频www| 国产成人欧美| 国产精品无大码| 久久97久久精品| 欧美变态另类bdsm刘玥| 一本色道久久久久久精品综合| 晚上一个人看的免费电影| 老鸭窝网址在线观看| 亚洲欧美清纯卡通| 国产av精品麻豆| 最近中文字幕高清免费大全6| 精品视频人人做人人爽| 色吧在线观看| 精品亚洲乱码少妇综合久久| 午夜老司机福利片| 国产爽快片一区二区三区| 这个男人来自地球电影免费观看 | 亚洲人成电影观看| 亚洲欧美日韩另类电影网站| 日韩人妻精品一区2区三区| 日日爽夜夜爽网站| 熟女av电影| 中国三级夫妇交换| 免费黄网站久久成人精品| 青草久久国产| 下体分泌物呈黄色| 久久女婷五月综合色啪小说| 久久综合国产亚洲精品| 午夜福利,免费看| 国产精品欧美亚洲77777| 免费黄频网站在线观看国产| 国产97色在线日韩免费| 男女午夜视频在线观看| 免费不卡黄色视频| 国产乱人偷精品视频| 99精品久久久久人妻精品| 黄网站色视频无遮挡免费观看| 中文天堂在线官网| 老司机深夜福利视频在线观看 | tube8黄色片| 日韩伦理黄色片| 国产精品国产三级国产专区5o| 男女免费视频国产| 日本欧美国产在线视频| 精品国产乱码久久久久久男人| 久久韩国三级中文字幕| 国产一区二区三区综合在线观看| 久久午夜综合久久蜜桃| 另类亚洲欧美激情| 欧美国产精品一级二级三级| 久久精品aⅴ一区二区三区四区| 久久久久视频综合| 在线观看一区二区三区激情| 久久久久国产一级毛片高清牌| 亚洲精品一区蜜桃| 操美女的视频在线观看| 男女午夜视频在线观看| 亚洲美女视频黄频| 九九爱精品视频在线观看| 国产一区二区三区av在线| 国产精品久久久久成人av| 性高湖久久久久久久久免费观看| 久久人人爽av亚洲精品天堂| 亚洲成av片中文字幕在线观看| 搡老乐熟女国产| 80岁老熟妇乱子伦牲交| 亚洲精品国产色婷婷电影| 国产xxxxx性猛交| 亚洲精品乱久久久久久| 新久久久久国产一级毛片| 精品国产乱码久久久久久小说| 777久久人妻少妇嫩草av网站| av.在线天堂| 一级毛片我不卡| 黄色视频不卡| 亚洲 欧美一区二区三区| 亚洲久久久国产精品| 两个人看的免费小视频| 久久精品国产亚洲av涩爱| 黄片播放在线免费| 日本黄色日本黄色录像| 久久国产亚洲av麻豆专区| 尾随美女入室| 国产成人免费观看mmmm| 精品国产超薄肉色丝袜足j| 国产免费福利视频在线观看| 午夜免费鲁丝| 岛国毛片在线播放| 精品少妇久久久久久888优播| 尾随美女入室| 亚洲精品久久午夜乱码| 伦理电影大哥的女人| 久久 成人 亚洲| www.av在线官网国产| 中国国产av一级| 亚洲精品一二三| 中文字幕色久视频| 一区福利在线观看| xxx大片免费视频| 国产日韩欧美在线精品| 国产激情久久老熟女| 成年动漫av网址| 一边亲一边摸免费视频| 少妇被粗大的猛进出69影院| 丰满迷人的少妇在线观看| 黄片小视频在线播放| 精品第一国产精品| 午夜福利,免费看| 黄片播放在线免费| 国产在线免费精品| 咕卡用的链子| 大话2 男鬼变身卡| 国产精品免费视频内射| 久久精品亚洲av国产电影网| 晚上一个人看的免费电影| 美女主播在线视频| 亚洲精品一区蜜桃| 日韩中文字幕视频在线看片| 国产深夜福利视频在线观看| 中国三级夫妇交换| 国产淫语在线视频| 成人影院久久| 国产一区二区三区综合在线观看| 亚洲成人手机| 久久人妻熟女aⅴ| 亚洲精品日本国产第一区| 纵有疾风起免费观看全集完整版| 少妇 在线观看| 免费人妻精品一区二区三区视频| 飞空精品影院首页| 菩萨蛮人人尽说江南好唐韦庄| 亚洲国产成人一精品久久久| 亚洲伊人久久精品综合| 国产又爽黄色视频| 欧美另类一区| 深夜精品福利| 91精品伊人久久大香线蕉| 波野结衣二区三区在线| 日本欧美国产在线视频| 亚洲精品自拍成人| 国产一级毛片在线| 精品一区二区免费观看| 美女午夜性视频免费| 夫妻午夜视频| 国产不卡av网站在线观看| 9色porny在线观看| 性高湖久久久久久久久免费观看| 夜夜骑夜夜射夜夜干| 最近最新中文字幕大全免费视频 | 精品人妻在线不人妻| 国产高清国产精品国产三级| 国产一区二区三区综合在线观看| 好男人视频免费观看在线| 中文字幕另类日韩欧美亚洲嫩草| 国产 精品1| 欧美亚洲 丝袜 人妻 在线| 999精品在线视频| 国产欧美日韩综合在线一区二区| 日日啪夜夜爽| 美女扒开内裤让男人捅视频| 亚洲国产精品999| 一区二区三区四区激情视频| 美女脱内裤让男人舔精品视频| 色婷婷久久久亚洲欧美| 欧美日韩成人在线一区二区| 精品国产超薄肉色丝袜足j| av福利片在线| 波多野结衣av一区二区av| 熟女少妇亚洲综合色aaa.| 秋霞伦理黄片| 久久久久久久久免费视频了| 人人妻人人澡人人爽人人夜夜| 精品国产国语对白av| 制服丝袜香蕉在线| 国产日韩欧美视频二区| 久久久久精品久久久久真实原创| 欧美精品高潮呻吟av久久| √禁漫天堂资源中文www| 免费看不卡的av| 亚洲情色 制服丝袜| av有码第一页| 老司机亚洲免费影院| 午夜日本视频在线| 中文字幕亚洲精品专区| 久久久久视频综合| 国产一卡二卡三卡精品 | 宅男免费午夜| 国产成人a∨麻豆精品| 黄频高清免费视频| 国产日韩欧美视频二区| 少妇人妻 视频| 午夜影院在线不卡| 多毛熟女@视频| 中文字幕人妻丝袜一区二区 | 日韩人妻精品一区2区三区| 久久精品久久久久久久性| 又大又黄又爽视频免费| 美女午夜性视频免费| 中国国产av一级| 美女高潮到喷水免费观看| 又黄又粗又硬又大视频| 一级,二级,三级黄色视频| 国产一级毛片在线| 亚洲成国产人片在线观看| 丁香六月欧美| 欧美日韩亚洲综合一区二区三区_| 在线 av 中文字幕| 国产精品无大码| 日日啪夜夜爽| 欧美中文综合在线视频| 日韩,欧美,国产一区二区三区| 精品国产国语对白av| 纵有疾风起免费观看全集完整版| 国产精品久久久久久精品古装| 菩萨蛮人人尽说江南好唐韦庄| 青春草视频在线免费观看| 亚洲欧洲精品一区二区精品久久久 | 1024香蕉在线观看| 激情五月婷婷亚洲| 国产不卡av网站在线观看| 久久影院123| 国产免费现黄频在线看| a 毛片基地| 日本午夜av视频| 波多野结衣av一区二区av| 成人影院久久| 夫妻性生交免费视频一级片| 午夜激情av网站| 69精品国产乱码久久久| 免费少妇av软件| 黑人欧美特级aaaaaa片| 欧美日韩亚洲综合一区二区三区_| 国产精品免费视频内射| 人人妻人人澡人人看| av在线老鸭窝| 久久人人爽av亚洲精品天堂| 叶爱在线成人免费视频播放| 在现免费观看毛片| 亚洲av欧美aⅴ国产| 五月天丁香电影| 国产精品香港三级国产av潘金莲 | 亚洲国产精品999| 2018国产大陆天天弄谢| 亚洲国产毛片av蜜桃av| 日韩中文字幕视频在线看片| 无遮挡黄片免费观看| 国产成人欧美在线观看 | 在线免费观看不下载黄p国产| 亚洲国产欧美一区二区综合| 下体分泌物呈黄色| 男女边摸边吃奶| 国产精品国产三级国产专区5o| 国产精品国产三级专区第一集| 麻豆精品久久久久久蜜桃| 香蕉国产在线看| 亚洲精品中文字幕在线视频| 波多野结衣一区麻豆| 中文字幕亚洲精品专区| 亚洲美女视频黄频| 精品人妻一区二区三区麻豆| 亚洲成国产人片在线观看| 国产免费又黄又爽又色| 中文字幕色久视频| 精品国产一区二区三区四区第35| www.精华液| 亚洲成人国产一区在线观看 | 中文字幕精品免费在线观看视频| 精品免费久久久久久久清纯 | 国产av国产精品国产| 国产在线视频一区二区| 久久青草综合色| a级片在线免费高清观看视频| 2018国产大陆天天弄谢| 日韩免费高清中文字幕av| 欧美97在线视频| 亚洲国产中文字幕在线视频| 日韩一区二区视频免费看| svipshipincom国产片| 久久精品国产亚洲av涩爱| av卡一久久| 男女之事视频高清在线观看 | 中国国产av一级| 伦理电影大哥的女人| 国语对白做爰xxxⅹ性视频网站| 纵有疾风起免费观看全集完整版| 秋霞在线观看毛片| 男人操女人黄网站| 欧美 日韩 精品 国产| 欧美日韩一级在线毛片| 男人舔女人的私密视频| 日韩不卡一区二区三区视频在线| 高清在线视频一区二区三区| 成年女人毛片免费观看观看9 | 热re99久久国产66热| 国产av精品麻豆| 五月天丁香电影| 1024视频免费在线观看| 国产老妇伦熟女老妇高清| 亚洲av日韩在线播放| 夜夜骑夜夜射夜夜干| 美女大奶头黄色视频| 黄网站色视频无遮挡免费观看| 两性夫妻黄色片| 国产爽快片一区二区三区| 最近最新中文字幕免费大全7| 免费少妇av软件| 免费不卡黄色视频| 亚洲专区中文字幕在线 | 韩国高清视频一区二区三区| 国产福利在线免费观看视频| 亚洲欧美精品综合一区二区三区| 久久久精品国产亚洲av高清涩受| av在线老鸭窝| 夫妻午夜视频| 久久久久精品人妻al黑| 欧美乱码精品一区二区三区| 天天操日日干夜夜撸| 青春草国产在线视频| 大码成人一级视频| 日韩熟女老妇一区二区性免费视频| 少妇人妻精品综合一区二区| 亚洲一级一片aⅴ在线观看| 欧美日本中文国产一区发布| 亚洲欧美精品综合一区二区三区| 国产97色在线日韩免费| 捣出白浆h1v1| 一级a爱视频在线免费观看| 极品人妻少妇av视频| 人人妻人人爽人人添夜夜欢视频| av不卡在线播放| 视频区图区小说| 亚洲,欧美精品.| 国产片特级美女逼逼视频| 国产一区二区在线观看av| 国产精品二区激情视频| 国产 精品1| 十分钟在线观看高清视频www| 日韩,欧美,国产一区二区三区| 一二三四在线观看免费中文在| 最近最新中文字幕免费大全7| 看免费成人av毛片| 一级黄片播放器| 亚洲av福利一区| 夫妻性生交免费视频一级片| 亚洲精品中文字幕在线视频| 多毛熟女@视频| av.在线天堂| 成年av动漫网址| 黑人欧美特级aaaaaa片| 亚洲av欧美aⅴ国产| 国产野战对白在线观看| 高清不卡的av网站| av在线观看视频网站免费| 国产淫语在线视频|