• <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 ?

    Synthesis, Structures, Luminescence and Catalytic Activity in the Knoevenagel Condensation Reaction of Two Cd(II) Coordination Polymers Based on a Biphenyl-dicarboxylic Acid①

    2022-03-12 07:44:52WUJiangGUJinZhong
    結(jié)構(gòu)化學(xué) 2022年2期

    WU Jiang GU Jin-Zhong

    a (Key Laboratory for Tibet Plateau Phytochemistry of Qinghai Province,School of Pharmacy, Qinghai University for Nationalities, Xining 810007, China)

    b (College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China)

    ABSTRACT Two cadmium(II) coordination polymers, namely [Cd(μ-dda)(H2biim)]n (1) and [Cd(μ4-dda)(py)]n(2) have been constructed hydrothermally using H2dda (H2dda = 4,4?-dihydroxybiphenyl-3,3?-dicarboxylic acid),H2biim (H2biim = 2,2?-biimidazole), py (py = pyridine), and cadmium chloride at 160 °C. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses (TGA), and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that both compounds crystallize in the monoclinic system, space group C2/c. Compound 1 discloses a 1D chain structure. Compound 2 features a 3D framework. The luminescent properties of compounds 1 and 2 were evaluated.Besides, the catalytic activities in the Knoevenagel condensation reaction of two compounds were investigated.Compound 1 exhibits an excellent catalytic activity in the Knoevenagel condensation reaction at room temperature.

    Keywords: coordination polymer, dicarboxylic acid, luminescence, catalytic properties, Knoevenagel condensation reaction; DOI: 10.14102/j.cnki.0254-5861.2011-3250

    1 INTRODUCTION

    Coordination polymers and derived materials have attracted tremendous attention due to their structural and topological diversity as well as their potential applications as functional materials[1-15]. In the last five years, special organic carboxylate ligands have been widely used in synthesizing coordination polymers and derived materials due to strong coordination ability of the carboxyl group and rich coordination modes[5,6,12,16-19]. Among them, biphenylcarboxylic acids have been extensively applied as versatile building blocks towards the assembly of metal-organic architectures[16,20,21].

    The 4,4?-dihydroxybiphenyl-3,3?-dicarboxylic acid (H2dda)is a good bridging ligand for the constructing coordination polymers[22-24], under considering structural semi-rigidity,which has multiple coordinate sites involving four carboxylate oxygen atoms andtwo hydroxyl O atoms.

    Herein, we report the synthesis, crystal structures,luminescence, and catalysis of two Cd(II) coordination polymers with H2dda ligand.

    2 EXPERIMENTAL

    2. 1 General procedures

    All chemicals and solvents were of AR grade and used without further purification. Carbon, hydrogen and nitrogen were determined using an Elementar Vario EL elemental analyzer. IR spectra were recorded using KBr pellets and a Bruker EQUINOX 55 spectrometer. Thermogravimetric analysis (TGA) was performed under N2atmosphere with a heating rate of 10 K/min on a LINSEIS STA PT1600 thermal analyzer. Excitation and emission spectra were recorded on an Edinburgh FLS920 fluorescence spectrometer using the solid samples at room temperature. Powder X-ray diffraction patterns (PXRD) were measured on a Rigaku-Dmax 2400 diffractometer using Cu-Kαradiation (λ= 1.5406 ?); the X-ray tube was operated at 40 kV and 40 mA. The data were collection in the range of 5~45o. Solution1H NMR spectra were recorded on a JNM ECS 400 M spectrometer.

    2. 2 Synthesis of compound 1

    A mixture of CdCl2·H2O (0.040 g, 0.2 mmol), H2dda (0.055 g, 0.2 mmol), H2biim (0.027 g, 0.2 mmol), NaOH (0.016 g,0.4 mmol), and H2O (10 mL) was stirred at room temperature for 15 min, and then sealed in a 25 mL Teflon-lined stainless-steel vessel, and heated at 160 ℃ for 3 days,followed by cooling to room temperature at a rate of 10 ℃/h.Yellow block-shaped crystals of 1 were isolated manually, and washed with distilled water. Yield: 47% (based on H2dda).Anal. Calcd. (%) for C20H14CdN4O6: C, 46.31; H, 2.72; N,10.80. Found (%): C, 46.41; H, 2.71; N, 10.72. IR (KBr, cm-1):1628w, 1553m, 1525w, 1473s, 1414s, 1358w, 1278w, 1250w,1175w, 1155w, 1127w, 1087w, 1039w, 992w, 952w, 920w,860w, 828m, 801w, 757m, 677w, 562w.

    2. 3 Synthesis of compound 2

    Synthesis of 2 was similar to 1 except using py (0.5 mL, 6.3 mmol) instead of NaOH. Colourless block-shaped crystals of 2 were isolated manually, and washed with distilled water.Yield: 50% (based on H2dda). Anal. Calcd. (%) for C19H13CdNO6: C, 49.21; H, 2.83; N, 3.02. Found (%): C,49.45; H, 2.81; N, 3.00. IR (KBr, cm-1): 1628w, 1599w,1539w, 1520m, 1478w, 1450w, 1416s, 1341w, 1294w, 1243m,1220w, 1154w, 1064w, 1036w, 1008w, 952w, 906w, 877w,821m, 745w, 704m, 637w, 554w.

    2. 4 Structure determination

    Two single crystals of the title compounds were mounted on a Bruker CCD diffractometer equipped with a graphitemonochromatic Cu-Kα(λ= 1.54178 ?) radiation using aφ-ωscan mode at 293(2) K. The structures were solved by direct methods with SHELXS-97[25]and refined by full-matrix least-squares techniques onF2with SHELXL-97[26]. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms (except those bound to water molecules)were placed in the calculated positions with fixed isotropic thermal parameters and included in structure factor calculations in the final stage of full-matrix least-squares refinement. Compound 1 crystallizes in monoclinic system,space groupC2/cwitha= 18.4567(4),b= 7.05850(10),c=28.5221(6) ?,V= 3710.03(12) ?3,Z= 8, C20H14CdN4O6,Mr= 518.75,Dc= 1.857 g/cm3,F(000) = 2064, the finalR=0.0231 andwR= 0.0560 for 3440 observed reflections (I>2σ(I)). Compound 2 crystallizes in monoclinic system, space groupC2/cwitha= 18.4249(11),b= 11.6325(5),c=7.7798(4) ?,V= 1604.40(15) ?3,Z= 4, C19H13CdNO6,Mr=463.70,Dc= 1.920 g/cm3,F(000) = 920, the finalR= 0.0273 andwR= 0.0691 for 1491 observed reflections (I> 2σ(I)).The selected important bond parameters are given in Table 1.The hydrogen bonds in crystal packing of compounds 1 and 2 are listed in Tables 2 and 3.

    Table 1. Selected Bond Lengths (?) and Bond Angles (°) for 1 and 2

    Table 2. Geometrical Parameters of Hydrogen Bonds for 1

    Table 3. Geometrical Parameters of Hydrogen Bonds for 2

    2. 5 Catalytic the Knoevenagel condensation reaction of aldehydes

    In a typical test, a suspension of an aromatic aldehyde(0.50 mmol, benzaldehyde as a model substrate),malononitrile (1.0 mmol), and catalyst (typically 2 mol%)in methanol (1.0 mL) was stirred at room temperature.After a desired reaction time, the catalyst was removed by centrifugation, followed by an evaporation of the solvent from the filtrate under reduced pressure to give a crude solid. This was dissolved in CDCl3and analyzed by1H NMR spectroscopy for quantification of the products (Fig. 1). To perform the recycling experiment, the catalyst was isolated by centrifugation, washed with dichloromethane, dried at room temperature, and reused. The subsequent steps were performed as described above.

    Fig. 1. Example of integration in the 1H-NMR spectrum for the determination of the Knoevenagel condensation reaction products (Table 4, Entry)

    3 RESULTS AND DISCUSSION

    3. 1 Crystal structure of 1

    X-ray crystallography analysis reveals that compound 1 crystallizes in the monoclinic system, space groupC2/c. As shown in Fig. 2, the asymmetric unit of 1 bears one crystallographically unique Cd(II) atom (Cd(1)), oneμ-dda2-block, and one H2biim moiety. The tetra-coordinate Cd(1)atom exhibits a distorted tetrahedral {CdN2O2} environment,which is occupied by two carboxylate O donors from two differentμ-dda2-blocks and two N atoms from the H2biim moiety. The Cd-O and Cd-N bond distances are 2.176(2)~2.177(2) and 2.295(2)~2.325(2) ?, respectively; these are within the normal ranges observed in related Cd(II)compounds[12,20,27]. In 1, the dda2-ligand adopts the coordination mode I (Scheme 1) with two COO-groups being monodentate. The H2biim moiety takes the terminal coordination fashion. In the deta4-ligand, a dihedral angle(between two aromatic rings) is 25.17°. Theμ-dda2-blocks connect adjacent Cd atoms to give a 1Dchain (Fig. 3). This 1Dcoordination polymer features double chains built from the 4-connected Cd andμ4-dda2-nodes (Fig. 4). As a result,the chains represent a uninodal 4-connected network with a SP 1-periodic net (4,4)(2,2) topology. The neighboring chains are assembled into a 2Dsheet through the N-H···O hydrogen bonds (Table 2 and Fig. 5).

    Scheme 1. Coordination modes of the dda2- ligands in compounds 1 and 2

    Fig. 2. Coordination environments of the Cd(II) atom in compound 1. The hydrogen atoms are omitted for clarity except in OH and NH groups (Symmetry code: i: -x+2, y+1, -z+1/2)

    Fig. 3. Perspective view of the 1D chain along the c axis

    Fig. 4. Topological representation of a uninodal 4-connected network with a SP 1-periodic net (4,4)(2,2) topology;view along the c axis; 4-linked Cd nodes (green balls), centroids of 4-connected μ4-dda2- nodes (gray)

    Fig. 5. Perspective view of the 2D sheet along the bc plane in 1 (Blue dashed lines present H-bonds)

    3. 2 Crystal structure of 2

    The asymmetric unit of compound 2 contains one crystallographically unique Cd(II) atom (Cd(1) with half occupancy), a half ofμ4-dda2-block, and a half of py moiety.As depicted in Fig. 6, the Cd(1) center is seven-coordinated and displays a distorted pentagonal bipyramidal {CdNO6}geometry. It is taken by six carboxylate O atoms from four individualμ4-dda2-blocks and one N donor from the py ligand. The bond lengths of Cd-O are in the 2.311(2)~2.505(2) ? range, while the Cd-N bond is 2.241(3) ?, being comparable to those found in some reported Cd(II)compounds[20,27,28]. In 2, the dda2-block acts as aμ4-linker(mode II, Scheme 1), in which two carboxylate groups adopt a tridentate mode. Besides, two aromatic rings are coplanar in theμ4-dda2-ligand. Theμ4-dda2-blocks multiply interconnect the neighboring Cd1 centers to generate a 3Dmetal-organic framework (Fig. 7). This structure is assembled from the 4-connected Cd andμ4-dda2-nodes, which are arranged into a binodal 4,4-linked net with a pts [PtS, Cooperite] topology and a point symbol of (42.84) (Fig. 8).

    Fig. 6. Coordination environments of the Cd(II) atom in compound 2. The hydrogen atoms are omitted for clarity except in OH groups(Symmetry codes: i: -x+1/2, -y+1/2, -z+2; ii: x, -y, z+1/2; iii: -x, y, -z+3/2; iv: -x, -y, -z+1)

    Fig. 7. View of 3D metal-organic framework along the ab plane. The py ligands are omitted for clarity

    Fig. 8. Topological representation of a binodal 4,4-connected network with a ptstopology; view along the ab plane; 4-linked Cd nodes (green balls),centroids of 4-connected μ4-dda2- nodes (gray)

    Compounds 1 and 2 were assembled under similar conditions except for the type of auxiliary ligand used(H2biim for 1 and py for 2). The difference in their structures,1Dchain in 1vs. 3Dsheet in 2, indicates that the assembly process is dependent on the type of auxiliary ligand.

    3. 3 Thermal analysis

    To determine the thermal stability of polymers 1 and 2,their thermal behaviors were investigated under nitrogen atmosphere by thermogravimetric analysis (TGA). As shown in Fig. 9, compounds 1 and 2 do not contain solvent of crystallization or H2O ligands and remain stable up to 245 or 274 ℃, followed by a decomposition on further heating. CdO is expected as a final decomposition product of 1 (exptl.25.1%, calcd. 24.8%) and 2 (exptl. 28.0%, calcd. 27.7%).

    Fig. 9. TGA curves of compounds 1 and 2

    3. 4 Luminescent properties

    The excitation and emission spectra of 4,4?-dihydroxybiphenyl-3,3?-dicarboxylic acid (H2dda) and polymers 1 and 2 were measured in the solid state at room temperature (Figs. 10 and 11). The uncoordinated H2dda shows a weak photoluminescence with an emission maximum at 482 nm (λex= 366 nm). In contrast, compounds 1 and 2 display significantly more intense emission bands with the maxima at 455 and 444 nm (λex= 348 nm), respectively. The emissions of compounds 1 and 2 are blue-shifted relative to that of the free H2dda ligand, which can be assigned to the ligand-to-metal charge transfer (LMCT)[27,29]. The luminescence enhancement in the coordination compounds can be attributed to the binding of ligands to the metal centers, which effectively increases the rigidity of the ligand and reduces the loss of energy by radiationless decay[27,28]. The quantum yield and life time were measured (1.36%, 0.1 ms for 1 and 5.88%, 0.3 ms for 2).

    3. 5 Catalytic Knoevenagel condensation reaction

    Given the potential of cadmium(II) coordination compounds to catalyze the organic reactions[30-32], we explored the application of 1 and 2 as heterogeneous catalysts in the Knoevenagel condensation reaction of benzaldehyde as a model substrate to give 2-(phenylmethylene)-propanedinitrile.Typical tests were carried out by reacting a mixture of benzaldehyde, malononitrile, and a Cd catalyst in methanol at room temperature (Scheme 2, Table 4). Such effects as reaction time, catalyst loading, solvent composition, catalyst recycling, and finally substrate scope were investigated.

    Scheme 2. Cd-catalyzed the Knoevenagel condensation reaction of benzaldehyde (model substrate)

    Fig. 10. Solid-state excitation spectra of H2dda, and compounds 1 and 2 at room temperature

    Fig. 11. Solid-state emission spectra of H2dda and compounds 1 and 2 at room temperature

    Table 4. Co-catalyzed Knoevenagel Condensation Reaction of Benzaldehyde with Malononitrile

    Upon using compound 1 as the catalyst (2 mol%), a high conversion of 100% of benzaldehyde into 2-(phenylmethylene)-propanedinitrile was reached after 60 min in methanol at room temperature (Table 4, entry 6).

    The results show that compound 1 is more active than compound 2. Although the relationship between structure and catalytic activity in the present study can not be clearly established, the highest conversation shown by compound 1 may eventually be associated to its 1Dstructure for easily accessible metal centers, together with the presence of the open metal sites[21,30].

    We also compared the activities of catalyst 1 in the reactions of other substituted aromatic aldehydes with malononitrile, and the corresponding yields fall in the range of 55~100% (Table 5). Aryl aldehydes bearing strong electron-withdrawing substituents (e.g., nitro and chloro)exhibited higher reactivities (Table 5, entries 2~5), which may be related to an increase in the electrophilicity of the substrate. Aldehydes containing electron-donating groups(e.g., methyl) showed lower reaction yields (Table 5, entries 6~8), as expected.

    Table 5. Knoevenagel Condensation Reaction of Various Aldehydes with Malononitrile Catalyzed by 1

    To examine the stability of 1 in the catalytic reaction, we tested the recyclability of this heterogeneous catalyst. For this purpose, upon completion of a reaction cycle, we separated the catalyst by centrifugation, washed it with CH2Cl2, and dried it at room temperature before further use. We recycled catalyst 1 repeatedly, and the catalytic system maintained the higher activity over at least five consecutive cycles (the yields are 100, 100, 99, and 98% for the second to fifth runs,respectively). According to the PXRD data (Fig. 12), the structure of 1 is essentially preserved after five catalytic cycles.

    Fig. 12. PXRD patterns for 1: simulated (red), before (black) and after (blue) catalysis

    4 CONCLUSION

    In summary, we have synthesized two Cd(II) coordination polymers based on a dicarboxylate ligand. Compound 1 discloses a 1Dchain structure, and compound 2 features a 3Dframework. The catalytic properties of both compounds were investigated. Compound 1 revealed an excellent catalytic activity in the Knoevenagel condensation reaction at room temperature.

    桃色一区二区三区在线观看| 一个人看的www免费观看视频| 久久精品国产99精品国产亚洲性色| 男插女下体视频免费在线播放| 床上黄色一级片| 999精品在线视频| 免费无遮挡裸体视频| 精品日产1卡2卡| 久久亚洲真实| 国产精品爽爽va在线观看网站| 香蕉av资源在线| 动漫黄色视频在线观看| 欧美乱码精品一区二区三区| 欧美丝袜亚洲另类 | 热99在线观看视频| 婷婷亚洲欧美| 国产在线精品亚洲第一网站| 老司机午夜十八禁免费视频| 亚洲色图 男人天堂 中文字幕| 亚洲黑人精品在线| 亚洲中文av在线| 久久精品国产亚洲av香蕉五月| 嫩草影视91久久| 动漫黄色视频在线观看| 亚洲欧美精品综合一区二区三区| 最新美女视频免费是黄的| 桃色一区二区三区在线观看| 99在线人妻在线中文字幕| 日韩欧美一区二区三区在线观看| 亚洲精品一区av在线观看| 三级男女做爰猛烈吃奶摸视频| 精品久久久久久久人妻蜜臀av| 天堂影院成人在线观看| 国产在线精品亚洲第一网站| 国产熟女xx| 亚洲最大成人中文| 日韩中文字幕欧美一区二区| 老熟妇仑乱视频hdxx| 亚洲中文字幕日韩| 一个人看的www免费观看视频| 搡老熟女国产l中国老女人| 怎么达到女性高潮| 国产精品 欧美亚洲| 老司机午夜福利在线观看视频| 97超级碰碰碰精品色视频在线观看| 国产成人aa在线观看| 后天国语完整版免费观看| 91久久精品国产一区二区成人 | 国语自产精品视频在线第100页| 亚洲中文日韩欧美视频| 欧美一级a爱片免费观看看| aaaaa片日本免费| 一级作爱视频免费观看| 亚洲成av人片免费观看| cao死你这个sao货| 嫩草影院入口| 日本a在线网址| 一进一出好大好爽视频| 国产主播在线观看一区二区| 日韩 欧美 亚洲 中文字幕| ponron亚洲| 欧美又色又爽又黄视频| 久久久久亚洲av毛片大全| 97碰自拍视频| 97碰自拍视频| www.自偷自拍.com| 男人舔女人的私密视频| 国产午夜福利久久久久久| av福利片在线观看| 免费av不卡在线播放| av天堂中文字幕网| 小蜜桃在线观看免费完整版高清| 一级毛片高清免费大全| 免费一级毛片在线播放高清视频| 脱女人内裤的视频| 99精品在免费线老司机午夜| 久久人妻av系列| 91老司机精品| 制服人妻中文乱码| 亚洲精品456在线播放app | 国产精品,欧美在线| 国产一级毛片七仙女欲春2| 一区二区三区激情视频| 一级黄色大片毛片| 国产视频一区二区在线看| 亚洲欧美精品综合一区二区三区| 在线十欧美十亚洲十日本专区| 99国产精品一区二区三区| 日韩国内少妇激情av| 欧美日本视频| 亚洲午夜理论影院| 久久精品亚洲精品国产色婷小说| 在线观看舔阴道视频| 少妇的逼水好多| 99国产精品99久久久久| 亚洲av成人一区二区三| 国产熟女xx| 亚洲自偷自拍图片 自拍| 日韩国内少妇激情av| 欧美绝顶高潮抽搐喷水| 91九色精品人成在线观看| 亚洲av片天天在线观看| 搡老熟女国产l中国老女人| 国产精品乱码一区二三区的特点| 亚洲av五月六月丁香网| 婷婷精品国产亚洲av| 欧美日韩黄片免| 老熟妇仑乱视频hdxx| www.自偷自拍.com| 久久久久亚洲av毛片大全| 无遮挡黄片免费观看| 午夜福利欧美成人| 亚洲成人中文字幕在线播放| 午夜影院日韩av| 草草在线视频免费看| 国产不卡一卡二| 国产高清激情床上av| 香蕉av资源在线| 波多野结衣高清作品| 欧美性猛交黑人性爽| 国产精品精品国产色婷婷| 日韩av在线大香蕉| 精品欧美国产一区二区三| 久久午夜亚洲精品久久| 精品熟女少妇八av免费久了| 久久久国产成人精品二区| 色av中文字幕| 在线播放国产精品三级| 国产又黄又爽又无遮挡在线| 亚洲av中文字字幕乱码综合| 在线国产一区二区在线| 岛国在线观看网站| 夜夜看夜夜爽夜夜摸| 久久久久久人人人人人| 国产精品久久久久久亚洲av鲁大| 久久久国产欧美日韩av| 久久精品夜夜夜夜夜久久蜜豆| 免费av毛片视频| 亚洲熟妇中文字幕五十中出| 天堂√8在线中文| 叶爱在线成人免费视频播放| 亚洲黑人精品在线| 亚洲成av人片免费观看| 性色av乱码一区二区三区2| 国产精品久久久久久精品电影| 久久精品国产清高在天天线| 偷拍熟女少妇极品色| 亚洲人成电影免费在线| 久久国产精品人妻蜜桃| 亚洲专区国产一区二区| av国产免费在线观看| 超碰成人久久| 欧美午夜高清在线| 国产成人精品无人区| 一个人观看的视频www高清免费观看 | 国产精华一区二区三区| 丝袜人妻中文字幕| 最近在线观看免费完整版| 日本撒尿小便嘘嘘汇集6| 91麻豆av在线| 中文在线观看免费www的网站| 看免费av毛片| 国产1区2区3区精品| 搞女人的毛片| 久久精品91蜜桃| www.自偷自拍.com| 久久精品夜夜夜夜夜久久蜜豆| 99精品欧美一区二区三区四区| 亚洲精品国产精品久久久不卡| 一夜夜www| 俺也久久电影网| 三级毛片av免费| 精品99又大又爽又粗少妇毛片 | 亚洲成人久久爱视频| 狂野欧美白嫩少妇大欣赏| 久久久国产成人精品二区| 亚洲精品乱码久久久v下载方式 | 日韩欧美在线二视频| 色综合欧美亚洲国产小说| 亚洲欧洲精品一区二区精品久久久| 啦啦啦韩国在线观看视频| 日韩国内少妇激情av| 午夜福利在线观看免费完整高清在 | 美女高潮的动态| 国产精品久久电影中文字幕| 啦啦啦观看免费观看视频高清| 国产伦在线观看视频一区| 精品福利观看| 精品电影一区二区在线| 久久亚洲精品不卡| АⅤ资源中文在线天堂| 一夜夜www| 热99re8久久精品国产| 国产久久久一区二区三区| 免费一级毛片在线播放高清视频| 看黄色毛片网站| 日本熟妇午夜| 免费在线观看影片大全网站| 91av网一区二区| 精品国产三级普通话版| 综合色av麻豆| 性色avwww在线观看| 热99re8久久精品国产| 成人18禁在线播放| 香蕉久久夜色| 九九在线视频观看精品| 国产真人三级小视频在线观看| 90打野战视频偷拍视频| 亚洲精华国产精华精| 欧美丝袜亚洲另类 | 久久久国产成人精品二区| 精品一区二区三区av网在线观看| 国产精品99久久久久久久久| 熟女电影av网| 美女大奶头视频| 国产私拍福利视频在线观看| 一夜夜www| 18禁黄网站禁片午夜丰满| 精品日产1卡2卡| 成人一区二区视频在线观看| 国产精品99久久99久久久不卡| 国产三级中文精品| 香蕉av资源在线| а√天堂www在线а√下载| 非洲黑人性xxxx精品又粗又长| av女优亚洲男人天堂 | 成人特级黄色片久久久久久久| 久久久久亚洲av毛片大全| 女同久久另类99精品国产91| 老汉色∧v一级毛片| 免费av不卡在线播放| 国产成人系列免费观看| 99在线人妻在线中文字幕| 精品久久久久久久末码| 欧美色欧美亚洲另类二区| 怎么达到女性高潮| 不卡av一区二区三区| 身体一侧抽搐| 久久亚洲精品不卡| a级毛片a级免费在线| 嫁个100分男人电影在线观看| 久久久久国产一级毛片高清牌| 国产精品野战在线观看| 亚洲成人免费电影在线观看| av国产免费在线观看| or卡值多少钱| 香蕉国产在线看| 亚洲第一电影网av| 亚洲一区二区三区不卡视频| 国内少妇人妻偷人精品xxx网站 | av片东京热男人的天堂| 一级毛片女人18水好多| 婷婷精品国产亚洲av| 巨乳人妻的诱惑在线观看| 黄色视频,在线免费观看| 国产淫片久久久久久久久 | 变态另类成人亚洲欧美熟女| 亚洲自拍偷在线| 欧美一区二区国产精品久久精品| 麻豆av在线久日| 成人亚洲精品av一区二区| 欧美乱码精品一区二区三区| 999精品在线视频| 18禁国产床啪视频网站| 偷拍熟女少妇极品色| 国产成人av教育| 一级毛片高清免费大全| 身体一侧抽搐| 亚洲,欧美精品.| 这个男人来自地球电影免费观看| 亚洲avbb在线观看| 欧美乱色亚洲激情| 18禁观看日本| 亚洲18禁久久av| 中国美女看黄片| 亚洲第一电影网av| 亚洲国产高清在线一区二区三| 国产精品av视频在线免费观看| 国产精品精品国产色婷婷| 久99久视频精品免费| 免费在线观看日本一区| 不卡一级毛片| 美女高潮喷水抽搐中文字幕| 国产亚洲精品久久久com| 国产成人av教育| 一级毛片女人18水好多| 亚洲电影在线观看av| 国产精品av视频在线免费观看| 亚洲精华国产精华精| 成人三级做爰电影| 日本熟妇午夜| 嫩草影视91久久| 成年女人永久免费观看视频| 欧美xxxx黑人xx丫x性爽| 欧美日韩亚洲国产一区二区在线观看| 久久精品国产综合久久久| 午夜福利高清视频| 免费高清视频大片| 久久久久国内视频| 国产精品 欧美亚洲| 国产精品一区二区精品视频观看| 97人妻精品一区二区三区麻豆| 午夜亚洲福利在线播放| aaaaa片日本免费| 99久久精品一区二区三区| 亚洲国产高清在线一区二区三| 国产不卡一卡二| 精品免费久久久久久久清纯| 性欧美人与动物交配| 中文字幕av在线有码专区| 18禁观看日本| 国产精品日韩av在线免费观看| 欧美成狂野欧美在线观看| 日韩欧美国产在线观看| 全区人妻精品视频| 亚洲国产看品久久| 国产成人精品久久二区二区91| 国产成人欧美在线观看| 看片在线看免费视频| ponron亚洲| 亚洲国产欧美人成| 国产成人aa在线观看| 国产伦精品一区二区三区四那| 好男人电影高清在线观看| 久久久水蜜桃国产精品网| 在线观看免费午夜福利视频| 国内精品久久久久精免费| 免费在线观看影片大全网站| 国产av不卡久久| 在线观看日韩欧美| 可以在线观看毛片的网站| 大型黄色视频在线免费观看| 亚洲av日韩精品久久久久久密| tocl精华| 成人精品一区二区免费| 国产三级中文精品| 国产精品日韩av在线免费观看| 一进一出抽搐动态| 亚洲第一电影网av| 亚洲中文日韩欧美视频| 好男人电影高清在线观看| 欧美一区二区国产精品久久精品| 国内精品久久久久久久电影| 99久久99久久久精品蜜桃| 亚洲自拍偷在线| 国产成人精品无人区| 法律面前人人平等表现在哪些方面| 国语自产精品视频在线第100页| 久久精品国产清高在天天线| 亚洲成av人片免费观看| 欧美一级a爱片免费观看看| 日韩人妻高清精品专区| 色综合站精品国产| 老司机午夜福利在线观看视频| 日韩精品中文字幕看吧| 少妇丰满av| 免费人成视频x8x8入口观看| 国产在线精品亚洲第一网站| 亚洲专区中文字幕在线| 久久久精品欧美日韩精品| 在线免费观看不下载黄p国产 | 91老司机精品| 成年女人看的毛片在线观看| 国产av不卡久久| 在线看三级毛片| 不卡av一区二区三区| 亚洲欧美日韩无卡精品| 51午夜福利影视在线观看| 99热这里只有精品一区 | 他把我摸到了高潮在线观看| 真人一进一出gif抽搐免费| 麻豆一二三区av精品| 日本五十路高清| 日本 欧美在线| 久久热在线av| 日韩精品青青久久久久久| 一个人免费在线观看电影 | 亚洲欧美日韩无卡精品| 狠狠狠狠99中文字幕| 国产人伦9x9x在线观看| 亚洲国产高清在线一区二区三| 亚洲精品粉嫩美女一区| 久久久久国产一级毛片高清牌| 欧美日韩综合久久久久久 | 999久久久国产精品视频| 日韩欧美免费精品| 国产成人啪精品午夜网站| 九九在线视频观看精品| 亚洲精品国产精品久久久不卡| 两人在一起打扑克的视频| 成人高潮视频无遮挡免费网站| 国产不卡一卡二| 国产亚洲av嫩草精品影院| 精品久久久久久久人妻蜜臀av| 亚洲国产精品999在线| 精品熟女少妇八av免费久了| 亚洲欧美精品综合一区二区三区| 亚洲精品美女久久久久99蜜臀| 99久久综合精品五月天人人| 黄色日韩在线| 97超视频在线观看视频| aaaaa片日本免费| av天堂中文字幕网| 一二三四社区在线视频社区8| 久久久久国内视频| 国产欧美日韩精品一区二区| 五月伊人婷婷丁香| 男人和女人高潮做爰伦理| 窝窝影院91人妻| 午夜影院日韩av| 亚洲精品久久国产高清桃花| 色综合婷婷激情| 中文字幕人成人乱码亚洲影| 男人和女人高潮做爰伦理| 欧美日韩国产亚洲二区| av福利片在线观看| 久久精品综合一区二区三区| 亚洲国产中文字幕在线视频| 日韩欧美 国产精品| 俄罗斯特黄特色一大片| 中文在线观看免费www的网站| 大型黄色视频在线免费观看| 91久久精品国产一区二区成人 | 亚洲色图 男人天堂 中文字幕| 国产精品99久久久久久久久| 1024香蕉在线观看| 一级作爱视频免费观看| 亚洲va日本ⅴa欧美va伊人久久| 深夜精品福利| 国产日本99.免费观看| 久久国产精品影院| 国产av不卡久久| 久久草成人影院| 国产一级毛片七仙女欲春2| 国产精品av久久久久免费| 99久久成人亚洲精品观看| 国产精品综合久久久久久久免费| 欧美日韩乱码在线| 高清在线国产一区| 好男人电影高清在线观看| 夜夜爽天天搞| 亚洲成av人片在线播放无| 欧美午夜高清在线| 两人在一起打扑克的视频| 99视频精品全部免费 在线 | 久久人妻av系列| 国产精品影院久久| 99riav亚洲国产免费| 国产亚洲精品av在线| 久久天堂一区二区三区四区| 国产成人一区二区三区免费视频网站| 婷婷精品国产亚洲av| 我的老师免费观看完整版| www.精华液| 中文字幕av在线有码专区| 免费电影在线观看免费观看| 久久这里只有精品19| 在线十欧美十亚洲十日本专区| 99热只有精品国产| 欧美黄色淫秽网站| 亚洲精品在线美女| 51午夜福利影视在线观看| 欧美大码av| 日本与韩国留学比较| 欧美激情在线99| 亚洲在线自拍视频| 搡老岳熟女国产| 99精品久久久久人妻精品| 特级一级黄色大片| 国产成年人精品一区二区| 91麻豆av在线| 久久久久久人人人人人| 免费大片18禁| 欧美大码av| 日本成人三级电影网站| 极品教师在线免费播放| 国内精品久久久久精免费| 午夜福利18| 久久久国产成人免费| 国产黄片美女视频| 国产精品精品国产色婷婷| 制服人妻中文乱码| 美女免费视频网站| 午夜精品久久久久久毛片777| 国语自产精品视频在线第100页| 九九热线精品视视频播放| 亚洲天堂国产精品一区在线| www.自偷自拍.com| 高清毛片免费观看视频网站| 国产午夜精品论理片| 国产精品九九99| 人妻久久中文字幕网| 久久精品人妻少妇| 亚洲五月天丁香| 国产精品亚洲美女久久久| 国产av不卡久久| 老司机福利观看| 男女午夜视频在线观看| 麻豆成人午夜福利视频| 精品国产亚洲在线| 国模一区二区三区四区视频 | 一二三四社区在线视频社区8| 亚洲第一电影网av| 少妇丰满av| 性欧美人与动物交配| 一进一出抽搐gif免费好疼| 两性夫妻黄色片| 熟女电影av网| 欧美黑人巨大hd| 757午夜福利合集在线观看| or卡值多少钱| 日韩大尺度精品在线看网址| 国产精品久久久久久精品电影| 欧美一级毛片孕妇| 亚洲自拍偷在线| e午夜精品久久久久久久| 日本黄大片高清| 99riav亚洲国产免费| 亚洲人成网站在线播放欧美日韩| 18美女黄网站色大片免费观看| 欧美绝顶高潮抽搐喷水| 国产亚洲欧美在线一区二区| 久久人妻av系列| 男女做爰动态图高潮gif福利片| 中出人妻视频一区二区| 此物有八面人人有两片| 一本一本综合久久| 三级男女做爰猛烈吃奶摸视频| 18禁美女被吸乳视频| netflix在线观看网站| 天堂√8在线中文| 真实男女啪啪啪动态图| 国产不卡一卡二| www国产在线视频色| 国产av在哪里看| 99久久国产精品久久久| 国产一区二区三区视频了| 老鸭窝网址在线观看| 欧美日本视频| 99国产综合亚洲精品| 中文字幕av在线有码专区| 琪琪午夜伦伦电影理论片6080| 精品国内亚洲2022精品成人| 国产精品一及| 国内久久婷婷六月综合欲色啪| 天天躁狠狠躁夜夜躁狠狠躁| 两人在一起打扑克的视频| 国产三级中文精品| 99久久精品国产亚洲精品| 亚洲精品在线观看二区| 午夜激情福利司机影院| 我的老师免费观看完整版| 国模一区二区三区四区视频 | a级毛片a级免费在线| 中文字幕av在线有码专区| 麻豆国产97在线/欧美| 精品国内亚洲2022精品成人| 色综合亚洲欧美另类图片| 亚洲国产精品久久男人天堂| 在线看三级毛片| 亚洲电影在线观看av| 嫩草影院入口| av天堂中文字幕网| 亚洲五月天丁香| 国语自产精品视频在线第100页| 欧美日韩乱码在线| 老司机深夜福利视频在线观看| 叶爱在线成人免费视频播放| 国产精品亚洲美女久久久| 在线观看美女被高潮喷水网站 | 亚洲av成人不卡在线观看播放网| 熟女人妻精品中文字幕| 1000部很黄的大片| 欧美日韩一级在线毛片| 亚洲一区二区三区色噜噜| 久久久色成人| 亚洲专区中文字幕在线| 欧美日韩福利视频一区二区| 免费在线观看影片大全网站| 午夜精品久久久久久毛片777| 国产一区二区三区视频了| 久久性视频一级片| 人妻夜夜爽99麻豆av| 亚洲欧美日韩高清专用| 1000部很黄的大片| 国产成人一区二区三区免费视频网站| 又粗又爽又猛毛片免费看| 精品无人区乱码1区二区| 人人妻,人人澡人人爽秒播| 免费在线观看成人毛片| 久久人人精品亚洲av| 婷婷丁香在线五月| 日韩 欧美 亚洲 中文字幕| 成人三级做爰电影| 男女做爰动态图高潮gif福利片| 伦理电影免费视频| 久久久久久久久久黄片| 精品一区二区三区av网在线观看| 国产av不卡久久| netflix在线观看网站| 一个人免费在线观看电影 | 一个人免费在线观看的高清视频| 91九色精品人成在线观看| 亚洲欧美一区二区三区黑人| 亚洲自偷自拍图片 自拍| 亚洲aⅴ乱码一区二区在线播放| 婷婷亚洲欧美| 久久久久国内视频| 999精品在线视频| 久久这里只有精品19| 天天躁狠狠躁夜夜躁狠狠躁| 美女扒开内裤让男人捅视频| 国产免费av片在线观看野外av| 一本精品99久久精品77| 床上黄色一级片|