基于3,5-双(4-吡啶基)-吡啶的两个钴(ⅱ)配合物的合成与晶体结构-张春丽.pdf

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1、第32卷第5期2016年5月无 机 化 学 学 报CHINESE JOURNAL OF INORGANIC CHEMISTRYV0132 No5859863基于3,5双(4吡啶基)吡啶的两个钴()配合物的合成与晶体结构张春丽1王红艳1郑和根2f1宿州学院化学化工学院，宿州 234000)(2南京大学化学化工学院，人工微结构科学与技术协同创新中心，南京 210093)摘要：用3,5一双(4吡啶基)一吡啶(BPYPY)分别与反式一1，4一环己烷二甲(transH2ehdc)和4，4一联苯醚二甲酸(H20ba)组成混合配体用温和的溶剂热法与Co(NO，)：6H：0合成了2+配物Co(BPYPY)2(

2、H20)4】(transchdc)4H20(1)和Co(BPYPY)(HzO)4(oba)。(2)，利用X射线单晶衍射、元素分析对它们进行了表征。结果显示，配合物1为单核结构，属于单斜晶系，P2n空间群；配位聚合物2是一维链通过0H0氢键形成的三维超分子结构，属于正交晶系，Pccn空间群。关键词：晶体结构；合成；钴()配合物；含氮配体中图分类号：061481+2 文献标识码：A 文章编号：1001-4861(2016)05085905DoI：1011862CJIC2016113Syntheses and Crystal Structures of Two Cobal3,5-Bis(4一pyri

3、dyl)-pyridineCompounds Based onZHANH ChunLil WANG Hong-Yanl ZHENG HeGen+。(1School of Chem蠡try and Chemical Engineering,Suzhou University,Suzhou，A nhui 234000，China)(St越e Key Laboratory of Coordination Chem蠡try,School of Chem厶try and Chemical E嚼neering,Collaborative Innovation CenterofAdvanced Micros

4、tructures，Nanjing University,Nanjing 210093，China)Abstract：Two compoundsCo(BPYPY)2(H20)4(tra瑚一chdc)4H20(1)andCo(BPYPY)(H20)4(oba)】。(2) Weresynthesized by mild hydrothermal method using two mixedligands consisting of 3,5-bis(4-pyridyl)-pyridine(BPYPY)，trans一1，4一cyclohexanedicarboxylic acid(trat“-H2ch

5、dc)，4,4oxydibenzoic acid(H20ba)and Co(N03)2。6H，0The complexes were characterized by elemental analysis and their crystal structures were determined bysinglecrystal Xray diffractionStructural analyses show that compound 1 is mononuclear complex，and crystallizesin the monoclinic system，space group P21

6、n；compound 2 is a 1D chain and further extended via OHOinteraction to generate infinite 3D supramolecular structure，and crystallizes in the orthorhombic system，spacegroup PccnCCDC：1437803，1；1401543，2Keywords：crystal structure；synthesis；Co(n)compound；Ncontaining ligandsCrystal engineering of coordina

7、tion polymers hasattracted intensive attention due to their variable architectures and potential applications in optical materialscatalysist*习，gas adsorption【6】，magnetisml7s1，etcA largenumber of coordination polymers (CPs)of N-containing ligands and carboxylic acids have beenreported9-12not only bec

8、ause they can incorporatevirtues of different functional groups and it is easier to收稿日期：201511-23。收修改稿日期：20160l一30。国家自然科学基金(No21371092)、安徽高校省级自然科学研究重点项目(KJ2015A203)、安徽省自然科学基金(1408085MB40)和宿州学院自旋电子与纳米材料安徽省重点实验室开放课题(2014YKF51)资助。通信联系人。E-mail：zhenghgnjueducn；会员登记号：S060015914M。万方数据860 无机化学学报 第32卷get arc

9、hitecture controlled by changing one of theabove two kinds of ligands，but also due to allowingfree rotation of the imidazole ring to meet therequirement of coordination geometries of metalions【1To datehoweverhow to rationally design andsynthesize the desired architectures and properties isstill a gr

10、eat challenge because the formation of CPs maybe easily affected by many factorsConsidering that mixed-ligand of Ncontainingligands and carboxylic acids offers greater tunabilityof the structural framework，two carboxylate ligands oftrans1，4一cyclohexanedicarboxylic acid(trans-Hachdc)and 4,4-oxydibenz

11、oic acid(Haoba)were introduced toreact with 3,5一bis(4-pyridyl)一pyridine(BPYP)of V-shaped flexible polypyridyl ligand and cobalt nitrateThen two new compoundsCo(BPYPY)R(H20)4(trans-chdc)4HzO(1)andCo(BPYPY)(H20)4(oba)。(2)were obtainedFurther，we described their synthesesand crystal structures in detail

12、1 Experimental11 Materials and measurementA1l the chemicals were commercially purchasedand used without further purificationElementalanalyses were performed on an Elementar VarioMICRO Elemental AnalyzerSingle crystal Xraydiffraction measurements were carried out on a BrukerSmart APEXCCD diffraction1

13、2 Synthesis of compoundsCo(BPYPY)2(H20)4(trans-chdc)4H20 (1)： Amixture of Co(N03)26H20(291 mg，01 mm01)，tra帆sH2chdc(172 mg，01 mm01)and BPYPY(233 mg，01 mm01)were dissolved in 6 mL of H20DMF f2：4yThe final mixture was placed in a Parr Teflonlined stainless steel vessel f 1 5 mLl and heated at 90for 3 d

14、aysAfter being cooled to room temperatureorange block crystals were obtainedThe yield was ca63based on BPYPY 1igandAnalCalcdforCssH4sCoN6012()：C，5430；H，572；N，1000Found()：C，5427；H，574；N，988Co(BPYPY)(HzO)4(oba)。(2)：A mixture of Co(N03)26H20(291 mg，01 mm01)，H20ba(258 mg，01 mm01)and BPYPY (233 mg，01 mm0

15、1)weredissolved in 6 mL of H，0DMF f2：4vv)The finalmixture was placed in a Parr Teflonlined stainlesssteel vessel f15 mE)and heated at 95 oC for 3 daysOrange block crystals were collectedThe yield wasca,60based on BPYPY ligandAnalCalcdforC29H27CoN309()：C，5609；H，435；N，677Found()：C，5607；H，433；N，67913 S

16、tructure determination of Single CrystalsThe regular crystals of compounds 1 and 2 weremounted on a Bruker Smart APEX II CCD diffraction似=007 1 073 nm)In all cases，empirical absorptioncorrections by SADABS were applied to the intensitydata旧The structures were solved by direct methods，and non-hydroge

17、n atoms were refined anisotropicallyon F2 by the fullmatrix leastsquares techniques usingSHELXL97 program package【l卿Crystallographic dataand structure refinements of compounds 1 and 2 arelisted in Table 1The selected bond lengths and bondangles of compounds are listed in Table 2CCDC：1437803。1；140154

18、3，2Table 1 Crystallographic data for compounds 1 and 2Compound 1 2万方数据第5期 张春丽等：基于3,5双(4一吡啶基)吡啶的两个钴()配合物的合成与晶体结构861Continued Table lZ 2 4Dc(gcm一3) 1410 1548Sizemm 028x026x022 030x028x026肛mm一1 0504 0708凡0001 882 1284，(。) 271，3067 265，2756Goodness of fit on F2 1033 1058Reflections collected 13 752 13 7

19、59Independent reflections假，。)4 892(0021 1) 3048(0017 7)R1，wR2，2口0033 7，0086 8 0030 7，0084 9R】，wR2(all data) 0045 2，0093 8 O035 7，O088 5(却)。，(却)。(enm一，413，-298 272，一349Table 2 Selected bond lengths(nm)and bond angles(。)of compounds 1 and 2Compound 1Co(1)一O(1) 0207 40(1 1) Co(1)-N(1)0218 06(12) Co(1)一

20、0(2) 0208 54(1 1)0(1)一Co(1)一0(1)#10(1)-Co(1)一0(2)#lO(1)一Co(1)一N(1)#lN(1)一Co(1)一0(2)1 8000(719139(5)8754(5)8896(4)O(1)一Co(1)一0(2)0(2)一Co(1)-O(2)引0(1)Co(1)一N(1)0(2)lCo(1)一N(1)8861(5)1 8000(8)9246(5)9104(4)0(1)#lCo(1)一0(2)0(2)一Co(I)一N(I)#1O(1)#1-Co(I)-N(I)N(1)#1-Co(1)-N(I)9139(5)9104f418754(5)18000(16)

21、Compound 2Co(1)一N(1) 0216 16(1 I) Co(1)-o(1) 0209 37(1 1) Co(I)一0(2)0213 65(1 1)O(2)一Co(1)一N0)8977(4) 0(1)一Co(1)一0(2)#2 9338(4) 0(2)一Co(I)一0(2)#2 180O(1)#2一Co(1)一O(1) 180 00)一Co(1)一0(2)8662(4) N(1)#2一Co(1)N(1) 18000(3)0(1)一Co(1)一N(1)871 1(4) 0(2)2一Co(1)一N(1) 9023(4) 0(1)#2-Co(1)-N(I) 9289(4)Symmetry

22、 codes：#1：1+1，-y+l，一for l；#2：叫+l，-y，-z+1 for 22 Result and discussion21 Crystal structure of compound 1Compound 1 crystallizes in the monoclinic crystalsystem with P2ln space groupThe asymmetric unitconsists of half of a Co atom，one BPYPY ligand，twocoordinated water molecules and half of a free tran

23、schdcntwo free water moleculesAs shown in Fig1，each Co(II)atom iS six coordinated by two nitrogenatoms from two BPYPY ligands and four oxygen atomsfrom four coordinated water molecules，to form thenuclear of【Co(BPYPY)2(H20)4The bond distancesof Co-N are 0218 06(12)nmThe Coo(1)bondlength is 0207 40(1

24、1)am，and Co一0(2)bond length is0208 54(1 1)nmIt is noteworthy thatCo(BPYPY)2(H20)4crosslink trarts-chdc2。by OHO hydrogenbonds generating the 2D network(Fig2)22 Crystal structure of compound 2Compound 2 crystallizes in the orthorhombiccrystal system with the space group of Pccn，and theasymmetric unit

25、consists of half of a Co atom，half ofa BPYPY ligand，two coordinated water molecules，half of a free completely deprotonated oba2。ligandEach Co(II)atom iS surrounded by two nitrogen atoms万方数据862 无机化学学报 第32卷C60 吣。 川。7急z一Thermal ellipsoids were drawn at the 30level，and the hydrogen atoms were omitted fo

26、r clarity；Symmetry codes：#l：-x+1，一”1，1Fig1 Coordination environment of the Co(H)cation in compound 1口日Fig2 2D network of compound 1All hydrogen atoms were omitted for clarity；Symmetry codes：#2：x+1-y-z+lFig3 Coordination environment of the Co(H)cation in compound 2from two BPYPY ligands，and four oxyg

27、en atoms fromfour coordinated water molecules，adopting anoctahedral geometry(Fig3)The bond distance of Co-N is 0216 16(1 11 nmThe CoO bond lengths are0209 37(1 1)and 0213 65(1 1)nm，respectivelyThe1D linear chain with a CoCo distance of 1408 49nm and a CoCoCo angle of 18000。is generatedby BPYPY ligan

28、ds and the Co(11)cationsThen，the1 D linear chains are held together via O-HOinteraction to generate an infinite 3D network(Fig4)。等o_一。一一一一躐g一一馥一一r。：万方数据第5期 张春丽等：基于3,5一双(4吡啶基)吡啶的两个钴()配合物的合成与晶体结构 8633 ConclusionsThe 0一H0 hydrogen bonds are shown as dashed linesFig4 3D infinite network of compound 2In

29、summary，by using the Vshaped ligand，3，5一bis(4一pyridyl)一pyridine(BPYPY)，and two kinds ofdicarboxylates，trans-1，47一cyclohexanedicarboxylicacid(transchdc)and 4,4-oxydibenzoic acid(H20ba)，we have synthesized two new compounds in mildhydrothermal methodCompound 1 has a 2D networkgenerated by hydrogen bon

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