陰陽離子穿插的配位聚合物:{[MoS4Cu4(4,4′-bpy)4][MoS4Cu4(4,4′-bpy)2I4·4H2O]}n的合成和晶體結(jié)構(gòu)

徐 艷 , 吳益民

(1.宿遷學院，江蘇 宿遷 223800)(2.江蘇大學 化學化工學院,江蘇 鎮(zhèn)江 212013)

陰陽離子穿插的配位聚合物:{[MoS4Cu4(4,4′-bpy)4][MoS4Cu4(4,4′-bpy)2I4·4H2O]}n的合成和晶體結(jié)構(gòu)

徐 艷1, 吳益民2

(1.宿遷學院，江蘇 宿遷 223800)(2.江蘇大學 化學化工學院,江蘇 鎮(zhèn)江 212013)

通過一種有效的構(gòu)建三維 M/S/Cu配位聚合物的方法,成功合成了一個新的基于鞍狀單體[MoS4Cu4]的陰陽離子穿插的三維配位聚合物{[MoS4Cu4(4,4′-bpy)4][MoS4Cu4(4,4′-bpy)2I4·4H2O]}n.X射線單晶衍射表明,該晶體屬于四方晶系,空間群為I41/acd,a=24.830(3)?,b=24.830(3)?,c=28.208(6)?,α=β=γ=90°.晶體結(jié)構(gòu)分析顯示,配位聚合物1由穿插的陽離子[MoS4Cu4(4,4′-bpy)4]2+和陰離子[MoS4Cu4(4,4′-bpy)2I4·4H2O]2-組成的三維鉆石狀配位聚合物.

配位聚合物; 晶體結(jié)構(gòu); 鉬; 銅

以Mo(W)/Cu/S 簇合物為前驅(qū)體進行自組裝反應所得含簇配位聚合物不僅具有豐富的化學結(jié)構(gòu),而且在非線性光學材料、吸附材料、工業(yè)催化等方面都有極好的應用前景[1-9].例如,文獻[10]報道了具有新穎的空洞結(jié)構(gòu)的三維族合物{[WS4Cu4(4,4’-bpy)4][WS4Cu4I4(4,4’-bpy)2]}∞;文獻[11]報道的一個含簇二維聚合物[MoS4Cu6I4(py)4]n不僅具有良好的三階非線性吸收性質(zhì),同時也具有很強的光限制能力.文中將給出一個陰陽離子穿插的配位聚合物{[MoS4Cu4(4,4′-bpy)4][MoS4Cu4(4,4′-bpy)2I4·4H2O]}n的合成及晶體結(jié)構(gòu).

1 實驗

將[NH4]2[MoS4] (1mmol)、CuI (0.3mmol)以及[nBu4N]I (0.2mmol)同時加入到3ml DMF溶液中,攪拌5～10min至溶液變澄清后過濾,然后將濾液移至一細長玻璃管中同時加入少量的DMF作為緩沖層,最后將溶于異丙醇的4,4′-bpy溶液緩緩地注入到玻璃管中,靜置擴散,幾天后長出黑色的柱狀晶體.

選取大小為0.30mm×0.26mm×0.24mm的晶體用于單晶結(jié)構(gòu)分析.晶體衍射數(shù)據(jù)在Rigaku Mercury CCD衍射儀上收集,采用石墨單色化Mo Kα射線(λ=0.71073?),以ω掃描方式在2.8°≤θ≤26.0°范圍內(nèi)共收集31056個衍射點,其中獨立衍射點4275個.配位聚合物1的晶體學數(shù)據(jù)見表1,其晶體學信息文件可以從劍橋晶體學數(shù)據(jù)庫獲得(fax:+441223336033, e-mail:deposit@ccdc.cam.ac.uk),號碼:CCDC 969108.

表1 配位聚合物1的晶體學數(shù)據(jù)和結(jié)構(gòu)精修數(shù)據(jù)Table 1 Crystal data and structure refinement for 1

2 結(jié)果與討論

配位聚合物1的非氫原子的坐標和各向同性替換參數(shù)見表2,部分鍵長鍵角見表3.晶體結(jié)構(gòu)中包含鞍狀的五核陽離子建筑塊[MoS4Cu4]2+和具有類似結(jié)構(gòu)的陰離子建筑塊[MoS4Cu4I4]2-.每一個陽離子建筑塊[MoS4Cu4]2+和四對兩兩平行的4,4′-bpy連接(圖1).

在陽離子建筑塊[MoS4Cu4]2+中Mo和Cu原子處于同一平面,Mo-Cu的平均鍵長2.6705(9)?,Mo-S的平均鍵長2.2347(15)?.Cu原子和來自2個4,4′-bpy的N原子及2個S原子配位,Cu-N的鍵長2.061(5) ?,Cu-S的鍵長2.2791(17) ?,事實上在配位聚合物1中存在兩重穿插的3D陽離子結(jié)構(gòu)(圖2).此種結(jié)構(gòu)和已報道的配位聚合物{[WS4Cu4(4,4′-bpy)4][WS4Cu4I4(4,4′-bpy)2]}[10]中的結(jié)構(gòu)相似.

表2 非氫原子的坐標和各向同性替換參數(shù)Table 2 Non-hydrogen atom positions and isotropic displacement parameters

表3 部分鍵長鍵角Table 3 Selected bond lengths (angstrom) and angles (degrees) for 1

Symmetry transformations used to generate equivalent atoms:t=-3/4+y,3/4+x,7/4-z,z=-x,3/2-y,z.

圖1 陽離子建筑塊[MoS4Cu4 (4,4′-bpy)4]2+Fig.1 Building block of cationic [MoS4Cu4 (4,4′-bpy)4]2+

圖2 陽離子[MoS4Cu4(4,4′-bpy)4]2+兩重穿插Space-filling圖Fig.2 Space-filling picture showing the twofold interpenetratingcationic [MoS4Cu4 (4,4′-bpy)4]2+

每一個陰離子建筑塊[MoS4Cu4I4]2-和4個4,4′-bpy連接(圖3).Cu原子和來自4,4′-bpy的1個N原子、2個S原子和1個I原子配位.Cu-N的鍵長2.061(5) ?,Cu-S的鍵長2.2791(17) ?,Cu-I的鍵長2.061(10)?,陰離子建筑塊同樣形成兩重穿插的3D陰離子結(jié)構(gòu)(圖4).整個分子是一個四重穿插的鉆石狀結(jié)構(gòu).

圖3 陰離子建筑塊[MoS4Cu4I4(4,4′-bpy)2]2-Fig.3 Building block of anionic [MoS4Cu4I4(4,4′-bpy)2]2-

圖4 陰離子[MoS4Cu4I4(4,4′-bpy)2]2-兩重穿插Space-filling圖Fig.4 Space-filling picture showing the twofoldinterpenetrating anionic [MoS4Cu4I4(4,4′-bpy)2]2-

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(責任編輯：顧 琳)

Synthesis,crystalstructureofinterpenetratingcationicandanioniccoordinationpolymers{[MoS4Cu4(4,4′-bpy)4][MoS4Cu4(4,4′-bpy)2I4·4H2O]}n

Xu Yan1, Wu Yimin2

(1.Suqian College, Suqian Jiangsu 223800, China)(2.School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang Jiangsu 212013, China)

An efficient route to construct three-dimensional (3-D) M/S/Cu nest-cluster-based coordination polymers has been developed. Using this method, we have successfully synthesized new interpenetrating 3-D nest-shaped-cluster [MoS4Cu4]-based coordination polymers, {[MoS4Cu4(4,4′-bpy)4][MoS4Cu4(4,4′-bpy)2I4·4H2O]}n1. The structure of the cluster has been characterized by X-ray diffraction: Tetragonal, space group I41/acd,a=24.830(3)?,b=24.830(3)?,c=28.208(6)?,α=β=γ=90°. The crystallographic analysis of compound 1comprises one quarter of the [MoS4Cu4(4,4′-bpy)4]2+cation and one quarter of the [MoS4Cu4(4,4′-bpy)2I4·4H2O]2-anion which interpenetrate cationic and anionic afford novel 3D diamondoid cluster coordination polymers.

coordination polymer; crystal structure; molybdenum; copper

10.3969/j.issn.1673-4807.2014.01.005

2013-09-17

江蘇省高校自然科學研究項目(11KJB450001)

徐 艷(1983—)，女，講師，研究方向為功能材料.E-mail:xuyan@sqc.edu.cn

O782

A

1673-4807(2014)01-0025-05