阴阳离子穿插的配位聚合物:{[MoS4Cu4(4,4′-bpy)4][MoS4Cu4(4,4′-bpy)2I4·4H2O]}n的合成和晶体结构

徐 艳 , 吴益民

(1.宿迁学院，江苏 宿迁 223800)(2.江苏大学 化学化工学院,江苏 镇江 212013)

阴阳离子穿插的配位聚合物:{[MoS4Cu4(4,4′-bpy)4][MoS4Cu4(4,4′-bpy)2I4·4H2O]}n的合成和晶体结构

徐 艳1, 吴益民2

(1.宿迁学院，江苏 宿迁 223800)(2.江苏大学 化学化工学院,江苏 镇江 212013)

通过一种有效的构建三维 M/S/Cu配位聚合物的方法,成功合成了一个新的基于鞍状单体[MoS4Cu4]的阴阳离子穿插的三维配位聚合物{[MoS4Cu4(4,4′-bpy)4][MoS4Cu4(4,4′-bpy)2I4·4H2O]}n.X射线单晶衍射表明,该晶体属于四方晶系,空间群为I41/acd,a=24.830(3)Å,b=24.830(3)Å,c=28.208(6)Å,α=β=γ=90°.晶体结构分析显示,配位聚合物1由穿插的阳离子[MoS4Cu4(4,4′-bpy)4]2+和阴离子[MoS4Cu4(4,4′-bpy)2I4·4H2O]2-组成的三维钻石状配位聚合物.

配位聚合物; 晶体结构; 钼; 铜

以Mo(W)/Cu/S 簇合物为前驱体进行自组装反应所得含簇配位聚合物不仅具有丰富的化学结构,而且在非线性光学材料、吸附材料、工业催化等方面都有极好的应用前景[1-9].例如,文献[10]报道了具有新颖的空洞结构的三维族合物{[WS4Cu4(4,4’-bpy)4][WS4Cu4I4(4,4’-bpy)2]}∞;文献[11]报道的一个含簇二维聚合物[MoS4Cu6I4(py)4]n不仅具有良好的三阶非线性吸收性质,同时也具有很强的光限制能力.文中将给出一个阴阳离子穿插的配位聚合物{[MoS4Cu4(4,4′-bpy)4][MoS4Cu4(4,4′-bpy)2I4·4H2O]}n的合成及晶体结构.

1 实验

将[NH4]2[MoS4] (1mmol)、CuI (0.3mmol)以及[nBu4N]I (0.2mmol)同时加入到3ml DMF溶液中,搅拌5～10min至溶液变澄清后过滤,然后将滤液移至一细长玻璃管中同时加入少量的DMF作为缓冲层,最后将溶于异丙醇的4,4′-bpy溶液缓缓地注入到玻璃管中,静置扩散,几天后长出黑色的柱状晶体.

选取大小为0.30mm×0.26mm×0.24mm的晶体用于单晶结构分析.晶体衍射数据在Rigaku Mercury CCD衍射仪上收集,采用石墨单色化Mo Kα射线(λ=0.71073Å),以ω扫描方式在2.8°≤θ≤26.0°范围内共收集31056个衍射点,其中独立衍射点4275个.配位聚合物1的晶体学数据见表1,其晶体学信息文件可以从剑桥晶体学数据库获得(fax:+441223336033, e-mail:deposit@ccdc.cam.ac.uk),号码:CCDC 969108.

表1 配位聚合物1的晶体学数据和结构精修数据Table 1 Crystal data and structure refinement for 1

2 结果与讨论

配位聚合物1的非氢原子的坐标和各向同性替换参数见表2,部分键长键角见表3.晶体结构中包含鞍状的五核阳离子建筑块[MoS4Cu4]2+和具有类似结构的阴离子建筑块[MoS4Cu4I4]2-.每一个阳离子建筑块[MoS4Cu4]2+和四对两两平行的4,4′-bpy连接(图1).

在阳离子建筑块[MoS4Cu4]2+中Mo和Cu原子处于同一平面,Mo-Cu的平均键长2.6705(9)Å,Mo-S的平均键长2.2347(15)Å.Cu原子和来自2个4,4′-bpy的N原子及2个S原子配位,Cu-N的键长2.061(5) Å,Cu-S的键长2.2791(17) Å,事实上在配位聚合物1中存在两重穿插的3D阳离子结构(图2).此种结构和已报道的配位聚合物{[WS4Cu4(4,4′-bpy)4][WS4Cu4I4(4,4′-bpy)2]}[10]中的结构相似.

表2 非氢原子的坐标和各向同性替换参数Table 2 Non-hydrogen atom positions and isotropic displacement parameters

表3 部分键长键角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.

图1 阳离子建筑块[MoS4Cu4 (4,4′-bpy)4]2+Fig.1 Building block of cationic [MoS4Cu4 (4,4′-bpy)4]2+

图2 阳离子[MoS4Cu4(4,4′-bpy)4]2+两重穿插Space-filling图Fig.2 Space-filling picture showing the twofold interpenetratingcationic [MoS4Cu4 (4,4′-bpy)4]2+

每一个阴离子建筑块[MoS4Cu4I4]2-和4个4,4′-bpy连接(图3).Cu原子和来自4,4′-bpy的1个N原子、2个S原子和1个I原子配位.Cu-N的键长2.061(5) Å,Cu-S的键长2.2791(17) Å,Cu-I的键长2.061(10)Å,阴离子建筑块同样形成两重穿插的3D阴离子结构(图4).整个分子是一个四重穿插的钻石状结构.

图3 阴离子建筑块[MoS4Cu4I4(4,4′-bpy)2]2-Fig.3 Building block of anionic [MoS4Cu4I4(4,4′-bpy)2]2-

图4 阴离子[MoS4Cu4I4(4,4′-bpy)2]2-两重穿插Space-filling图Fig.4 Space-filling picture showing the twofoldinterpenetrating anionic [MoS4Cu4I4(4,4′-bpy)2]2-

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(责任编辑：顾 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)Å,b=24.830(3)Å,c=28.208(6)Å,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

江苏省高校自然科学研究项目(11KJB450001)

徐 艳(1983—)，女，讲师，研究方向为功能材料.E-mail:xuyan@sqc.edu.cn

O782

A

1673-4807(2014)01-0025-05