張春麗王紅艷鄭和根（宿州學(xué)院化學(xué)化工學(xué)院，宿州　34000）（南京大學(xué)化學(xué)化工學(xué)院，人工微結(jié)構(gòu)科學(xué)與技術(shù)協(xié)同創(chuàng)新中心，南京　0093）

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基于3，5-雙（4-吡啶基）-吡啶的兩個(gè)鈷(Ⅱ)配合物的合成與晶體結(jié)構(gòu)

張春麗1王紅艷1鄭和根＊，2
（1宿州學(xué)院化學(xué)化工學(xué)院，宿州234000）
（2南京大學(xué)化學(xué)化工學(xué)院，人工微結(jié)構(gòu)科學(xué)與技術(shù)協(xié)同創(chuàng)新中心，南京210093）

摘要：用3，5-雙（4-吡啶基）-吡啶（BPYPY）分別與反式-1，4-環(huán)己烷二甲酸（trans-H2chdc）和4，4′-聯(lián)苯醚二甲酸（H2oba）組成混合配體，用溫和的溶劑熱法與Co（NO3）·26H2O合成了2個(gè)配合物［Co（BPYPY）2（H2O）4］·（trans-chdc）·4H2O（1）和｛［Co（BPYPY）（H2O）4］·（oba）｝（2），利用X射線單晶衍射、元素分析對(duì)它們進(jìn)行了表征。結(jié)果顯示，配合物1為單核結(jié)構(gòu)，屬于單斜晶系，P21/n空間群；配位聚合物2是一維鏈通過(guò)O-H…O氫鍵形成的三維超分子結(jié)構(gòu)，屬于正交晶系，Pccn空間群。

關(guān)鍵詞：晶體結(jié)構(gòu)；合成；鈷(Ⅱ)配合物；含氮配體

Crystal engineering of coordination polymers has attractedintensiveattentionduetotheirvariablearchitectures and potential applications in optical materials［1-3］，catalysis［4-5］，gas adsorption［6］，magnetism［7-8］，etc.A large numberofcoordinationpolymers（CPs）ofN containing ligands and carboxylic acids have been reported［9-12］，not only because they can incorporate virtues of different functional groups and it is easier to

國(guó)家自然科學(xué)基金（No.21371092）、安徽高校省級(jí)自然科學(xué)研究重點(diǎn)項(xiàng)目（KJ2015A203）、安徽省自然科學(xué)基金（1408085MB40）和宿州學(xué)院自旋電子與納米材料安徽省重點(diǎn)實(shí)驗(yàn)室開(kāi)放課題（2014YKF51）資助。

＊通信聯(lián)系人。E-mail：zhenghg@nju.edu.cn；會(huì)員登記號(hào)：S060015914M。get architecture controlled by changing one of the above two kinds of ligands，but also due to allowing free rotation oftheimidazoleringtomeetthe requirementofcoordinationgeometriesofmetal ions［13-14］.To date，however，how to rationally design and synthesize the desired architectures and properties is still a great challenge because the formation of CPs may be easily affected by many factors.

Considering that mixed-ligand of N-containing ligands and carboxylic acids offers greater tunability of the structural framework，two carboxylate ligands of trans-1，4-cyclohexanedicarboxylic acid（trans-H2chdc）and 4，4′-oxydibenzoic acid（H2oba）were introduced to reactwith3，5-bis（4-pyridyl）-pyridine（BPYP）of V-shaped flexible polypyridyl ligand and cobalt nitrate. Then two new compounds［Co（BPYPY）2（H2O）4］·（transchdc）·4H2O（1）and｛［Co（BPYPY）（H2O）4］·（oba）｝n（2）were obtained.Further，we described their syntheses and crystal structures in detail.

1　Experimental

1.1Materials and measurement

All the chemicals were commercially purchased andusedwithoutfurtherpurification.Elemental analyses were performed on an Elementar Vario MICRO Elemental Analyzer.Single crystal X-ray diffraction measurements were carried out on a Bruker Smart APEXⅡCCD diffraction.

1.2Synthesis of compounds

［Co（BPYPY）2（H2O）4］·（trans-chdc）·4H2O（1）:A mixture of Co（NO3）2·6H2O（29.1 mg，0.1 mmol），trans-H2chdc（17.2 mg，0.1 mmol）and BPYPY（23.3 mg， 0.1 mmol）were dissolved in 6 mL of H2O/DMF（2∶4，V/V）.The final mixture was placed in a Parr Teflonlined stainless steel vessel（15 mL）and heated at 90 ℃for 3 days.After being cooled to room temperature，orange block crystals were obtained.The yield was ca. 63%based on BPYPY ligand.Anal.Calcd.for C38H48CoN6O12（%）:C，54.30；H，5.72；N，10.00.Found （%）:C，54.27；H，5.74；N，9.88.

｛［Co（BPYPY）（H2O）4］·（oba）｝n（2）:A mixture of Co （NO3）2·6H2O（29.1 mg，0.1 mmol），H2oba （25.8 mg，0.1 mmol）and BPYPY（23.3 mg，0.1 mmol）were dissolved in 6 mL of H2O/DMF（2∶4，V/V）.The final mixture was placed in a Parr Teflon-lined stainless steel vessel（15 mL）and heated at 95℃for 3 days. Orange block crystals were collected.The yield was ca.60%based on BPYPY ligand.Anal.Calcd.for C29H27CoN3O9（%）:C，56.09；H，4.35；N，6.77.Found （%）:C，56.07；H，4.33；N，6.79.

1.3Structure determination of Single Crystals

The regular crystals of compounds 1 and 2 were mounted on a Bruker Smart APEXⅡCCD diffraction （λ=0.071 073 nm）.In all cases，empirical absorption corrections by SADABS were applied to the intensity data［15］.The structures were solved by direct methods，and non-hydrogen atoms were refined anisotropically on F2by the full-matrix least-squares techniques using SHELXL-97 program package［16］.Crystallographic data and structure refinements of compounds 1 and 2 are listed in Table 1.The selected bond lengths and bond angles of compounds are listed in Table 2.

CCDC:1437803，1；1401543，2.

Table 1　Crystallographic data for compounds 1 and 2

Continued Table 1

Table 2　Selected bond lengths（nm）and bond angles（°）of compounds 1 and 2

2　Result and discussion

2.1Crystal structure of compound 1

Compound 1 crystallizes in the monoclinic crystal system with P21/n space group.The asymmetric unit consists of half of a Co atom，one BPYPY ligand，two coordinated water molecules and half of a free transchdc2-，two free water molecules.As shown in Fig.1，each Co(Ⅱ) atom is six coordinated by two nitrogen atoms from two BPYPY ligands and four oxygen atoms from four coordinated water molecules，to form the nuclear of［Co（BPYPY）2（H2O）4］.The bond distances of Co-N are 0.218 06（12）nm.The Co-O（1）bond length is 0.207 40（11）nm，and Co-O（2）bond length is 0.208 54（11）nm.It is noteworthy that［Co（BPYPY）2（H2O）4］cross-link trans-chdc2-by O-H…O hydrogen bonds generating the 2D network（Fig.2）.

2.2Crystal structure of compound 2

Compound 2 crystallizes in the orthorhombic crystal system with the space group of Pccn，and the asymmetric unit consists of half of a Co atom，half of a BPYPY ligand，two coordinated water molecules，half of a free completely deprotonated oba2-ligand. Each Co(Ⅱ)atom is surrounded by two nitrogen atomsfrom two BPYPY ligands，and four oxygen atoms from fourcoordinatedwatermolecules，adoptingan octahedral geometry（Fig.3）.The bond distance of Co-N is 0.216 16（11）nm.The Co-O bond lengths are 0.209 37（11）and 0.213 65（11）nm，respectively.The 1D linear chain with a Co…Co distance of 1.408 49 nm and a Co…Co…Co angle of 180.00°is generated by BPYPY ligands and the Co(Ⅱ) cations.Then，the 1D linear chains are held together via O-H…O interaction to generate an infinite 3D network（Fig.4）.

Fig.1　Coordination environment of the Co(Ⅱ)cation in compound 1

Fig.2　2D network of compound 1

Fig.3　Coordination environment of the Co(Ⅱ)cation in compound 2

Fig.4　3D infinite network of compound 2

3　Conclusions

In summary，by using the V-shaped ligand，3，5-bis（4-pyridyl）-pyridine（BPYPY），and two kinds of dicarboxylates， trans-1，4′-cyclohexanedicarboxylic acid（trans-chdc）and 4，4′-oxydibenzoic acid（H2oba），we have synthesized two new compounds in mild hydrothermal method.Compound 1 has a 2D network generated by hydrogen bond cross-linked［Co（BPYPY）2（H2O）4］and trans-chdc2-.Compound 2 is a 1D chain and further extended via O-H…O interaction to generate infinite 3D supramolecular structure.

References:

［1］Hu Z，Deibert B J，Li J.Chem.Soc.Rev.，2014，43:5815-5840

［2］Zhao X，Wang X，Wang S，et al.Cryst.Growth Des.，2012，12:2736-2739

［3］Liu X G，Wang H，Chen B，et al.Chem.Commun.，2015，51: 1677-1680

［4］Wang L H，Zeng Y，Shen A G，et al.Chem.Commun.，2015，51:2052-2055

［5］Roberts J M，F(xiàn)ini B M，Sarjeant A A，et al.J.Am.Chem Soc.，2012，134:3334-3337

［6］OKeeffe M，Yaghi O M.Chem.Rev.，2012，112:675-702

［7］ZHANGChun-Li（張春麗），QIN Lin（覃玲），YANG Qing-Xian（楊清香），et al.Chinese J.Inorg.Chem.（無(wú)機(jī)化學(xué)學(xué)報(bào)）2013，29（10）:2157-2161

［8］Uemura K，Yamasaki Y，Komagawa Y，et al.Angew.Chem Int.Ed.，2007，46:6662-6665

［9］Qin L，Ju Z M，Wang Z J，et al.Cryst.Growth Des.，2014 14:2742-2746

［10］Qin L，Hu J S，Zhang M D，et al.Chem.Commun.，2012，48 10757-10759

［11］Zhang C L，Qin L，Zheng H G.Inorg.Chem.Commun.，2013 36:192-194

［12］Zhang M D，Di C M，Qin L，et al.Cryst.Growth Des.，2012 12:3957-3963

［13］Zhang C L，Li Y L，Wang T，et al.Chem.Commun.，2015 51:8338-8341

［14］Shi Z Q，Guo Z J，Zheng H G.Chem.Commun.，2015，51 8300-8303

［15］SMART and SAINT，Siemens Analytical X-ray Instrumen Inc.，Madison，WI，1996.

［16］Sheldrick G M.SHELXL-97，Program for the Refinement o Crystal Structure，Universirty of G?ttingen，Germany，1997.

中圖分類號(hào)：O614.81+2

文獻(xiàn)標(biāo)識(shí)碼：A

文章編號(hào)：1001-4861（2016）05-0859-05

DOI：10.11862/CJIC.2016.113

收稿日期：2015-11-23。收修改稿日期：2016-01-30。

Syntheses and Crystal Structures of Two Cobalt(Ⅱ)Compounds Based on 3，5-Bis（4-pyridyl）-pyridine

ZHANH Chun-Li1WANG Hong-Yan1ZHENG He-Gen＊，2
（1School of Chemistry and Chemical Engineering，Suzhou University，Suzhou，Anhui 234000，China）
（2State Key Laboratory of Coordination Chemistry，School of Chemistry and Chemical Engineering，Collaborative Innovation Center of Advanced Microstructures，Nanjing University，Nanjing 210093，China）

Abstract:Two compounds［Co（BPYPY）2（H2O）4］·（trans-chdc）·4H2O（1）and｛［Co（BPYPY）（H2O）4］·（oba）｝n（2）wer synthesized by mild hydrothermal method using two mixed-ligands consisting of 3，5-bis（4-pyridyl）-pyridin （BPYPY），trans-1，4′-cyclohexanedicarboxylic acid（trans-H2chdc），4，4′-oxydibenzoic acid（H2oba）and Co（NO3）2· 6H2O.The complexes were characterized by elemental analysis and their crystal structures were determined by single-crystal X-ray diffraction.Structural analyses show that compound 1 is mononuclear complex，and crystallize in the monoclinic system，space group P21/n；compound 2 is a 1D chain and further extended via O-H…O interaction to generate infinite 3D supramolecular structure，and crystallizes in the orthorhombic system，space group Pccn.CCDC:1437803，1；1401543，2.

Keywords:crystal structure；synthesis；Co(Ⅱ)compound；N-containing ligands