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• Schiff碱化合物是一类重要的有机配体，易与过渡金属进行有效的配位作用，Schiff碱配合物在催化、生物模拟及医药等领域中具有重要应用价值^[1-3]。在与Schiff碱进行配位作用的过渡金属离子中，汞(Ⅱ)离子具有d¹⁰电子组态，具有不同的配位数，其与有机配体作用过程中能采用不同的配位模式，便于实现结构新颖的超分子组装体构筑，使得汞(Ⅱ)的超分子化学一直是有趣的研究领域^[4-8]。同时，汞是一种剧毒并对环境有害的元素，合理设计有机配体分子与汞进行有效的选择性键合作用，达到混合体系中汞的有效提取与分离一直是富有挑战性的研究课题^[9-10]。据此，本文设计合成了2个含有N、O配位原子的酰腙类Schiff碱有机配体^[11-15]，并分别与氯化汞(HgCl₂)进行配位作用，得到2个汞(Ⅱ)的配位聚合物，在对配合物的晶体结构解析的基础上，进一步考察了它们的热稳定性。

  1   实验部分

  1.1   试剂

  邻氨基苯甲酸甲酯，水合肼(80%，w/w)，3-乙酰吡啶，4-乙酰吡啶，HgCl₂，以及其它所用试剂均为分析纯。

  1.2   测试仪器

  JEOL ECX 400 MHz核磁共振仪(TMS，DMSO-d₆)；Ry-2型熔点仪(温度计未校正)；Bio-Rad型傅立叶红外光谱仪(4 000~400 cm^-1)；Vario EL Ⅱ型元素分析仪(德国)；晶体结构测定采用Bruker Smart Apex CCD单晶衍射仪。

  1.3   配体与配合物合成

  配体及配合物的合成路线：
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      Khavasi H R, Sadegh B M M. Dalton Trans., 2015, 44:5488-5502 doi: 10.1039/C4DT03518F

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      Chang H Q, Jia L, Xu J, et al. Inorg. Chem. Commun., 2015, 57:8-10 doi: 10.1016/j.inoche.2015.04.010

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      李晓静, 吴伟娜, 徐周庆, 等.无机化学学报, 2015, 31(11):2265-2271 LI Xiao-Jing, WU Wei-Na, XU Zhou-Qing, et al. Chinese J. Inorg. Chem., 2015, 31(11):2265-2271

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      黄超, 吴娟, 陈冬梅, 等.无机化学学报, 2015, 31(1):109-113 HUANG Chao, WU Juan, CHEN Dong-Mei, et al. Chinese J. Inorg. Chem., 2015, 31(1):109-113

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      Sheldrick G M. SHELXL-97, Program for X-ray Crystal Structure Solution and Refinement, University of Göttingen, Germany, 1997.

• 

  下载: 全尺寸图片 幻灯片
  

  图 1  (a)配合物1的不对称单元结构; (b)梯状链之间通过π…π堆积作用形成准2D层结构; (c)沿晶体b轴方向观察的准3D结构

  Figure 1  (a) ORTEP view of the asymmetric unit of the complex 1 (probability of ellipsoid is 30%); (b) Layered structure of 1; (c) Part of the quasi 3D structure viewed down the crystallographic b axis

  Hydrogen atoms are not shown, and the hydrogen bonds or π…π interactions are shown as dashed lines; Symmetry codes: ^a1-x, -y, 2-z in (a); ^b2-x, -y, 1-z; ^c1-x, 1-y, 1-z; ^d-1+x, 1+y, z in (b); Cg(1): C1/C2/C3/C4/C5/C6; Cg(2): N4/C13/C12/C11/C10/C14

  下载: 全尺寸图片 幻灯片
  

  图 2  (a)配合物2的不对称单元结构; (b)单股链之间的π…π堆积作用; (c)沿b轴方向观察的准3D结构

  Figure 2  (a) View of the asymmetric unit of the complex 2 (probability of ellipsoid is 30%); (b) π…π interactions between the double-stranded chains; (c) Part of the quasi 3D structure viewed down the crystallographic b axis

  Symmetry codes: ^a3/2-x, -1/2+y, 1/2-z; ^b3/2-x, 1/2+y, 1/2-z in (a); ^c-1/2+x, 1/2-y, -1/2+z; ^d1/2+x, 1/2-y, 1/2+z in (b); ^e1-x, -y, 1-z in (c); Cg(3): N4/C13/C14/C10/C11/C12; Cg(4): C1/C2/C3/C4/C5/C6; Hydrogen atoms are not shown, and the hydrogen bonds or π…π interactions are shown as dashed lines

  下载: 全尺寸图片 幻灯片
  

  图 3  配合物1和2的TG曲线

  Figure 3  TG curves of the complexes 1 and 2

  下载: 全尺寸图片 幻灯片

  表 1  配合物1和2的晶体学及结构修正数据

  Table 1.  Crystal data and structure refinement for complexes 1 and 2

  Complex	1	2
  Empirical formula	C30H36Cl4Hg2N8O4	C14H14Cl2HgN4O
  Formula weight	1 115.65	525.78
  Temperature/K	293(2)	293(2)
  Crystal system	Triclinic	Monoclinic
  Space group	P1	P21/n
  a/nm	0.743 08(3)	0.814 4(2)
  b/nm	1.022 55(4)	1.461 1(4)
  c/nm	1.316 07(6)	1.380 1(3)
  α/(°)	74.859(2)	90
  β/(°)	88.921(2)	93.798(6)
  γ/(°)	69.875(2)	90
  V/nm3	0.903 56(7)	1.638 6(7)
  Z	1	4
  Dc/(g·cm-3)	2.050	2.131
  θ range/(°)	0.966~25.99	0.979~26.00
  Absorption coefficient/mm-1	8.828	9.725
  F(000)	532	992
  Reflections collected	10 086	12 961
  Independent reflections	3 417	3 146
  Observed reflections (I > 2σ(I))	3 084	2 284
  Refinement method	Full-matrix least squares on F2	Full-matrix least squares on F2
  Number of parameters	217	199
  Goodness-of-fit on F2	1.109	1.123
  Final R indices (I > 2σ(I))	R1=0.031 4, wR2=0.079 3	R1=0.033 0, wR2=0.076 0
  R indices (all data)	R1=0.036 7, wR2=0.090 3	R1=0.061 4, wR2=0.099 2
  Final weighting scheme	w=1/[σ2Fo2+(0.036 8P)2+4.235 1P], P=(Fo2+2Fc2)/3	w=1/[σ2Fo2+(0.044 0P)2+0.000 0P], P=(Fo2+2Fc2)/3
  (Δρ)max，（Δρ)min/(e·nm-3)	974, -1 304	1 200, -1 668

  下载: 导出CSV

  表 2  配合物1和2的部分键长和键角

  Table 2.  Selected bond lengths (nm) and bond angles (°) for 1 and 2

  1
  Cl1-Hg1	0.233 27(18)	C12a-Hg1	0.285 74(17)	N4-Hg1	0.222 7(5)
  C12-Hg1	0.254 78(16)
  N4-Hg1-C11	139.87(15)	C11-Hg1-C12	118.74(7)	C11-Hg1-C12a	101.53(7)
  N4-Hg1-C12	100.70(14)	N4-Hg1-C12a	87.32(l4)	C12-Hg1-C12a	86.23(5)
  2
  N4a-Hg1	0.245 5(6)	Cl1-Hg1	0.232 2(2)	Cl2-Hg1	0.233 1(2)
  O1-Hg1	0.248 2(5)
  Cl1-Hg1-C12	158.53(9)	Cl2-Hg1-N4a	94.99(16)	Cl2-Hg1-Ol	99.82(16)
  Cl1-Hg1-N4a	100.41(16)	Cl1-Hg1-O1	97.14(17)	N4a-Hg1-Ol	81.74(19)
  Symmetry codes: a1-x, -y, 2-z for 1; a3/2-x, -1/2+y, 1/2-z for 2

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  表 3  配合物的氢键参数

  Table 3.  Structural parameters of hydrogen bonds for the complexes

  D-H…A	d(D-H)/nm	d(H…A)/nm	d(D…A)/nm	∠DHA/(°)
  1
  N2-H2…O2c	0.086 05	0.244 47	0.303 2(9)	126.04
  O2-H16 …O1d	0.092(11)	0.190(11)	0.275 8(8)	155(9)
  2
  C5-H5 …Cl2e	0.092 95	0.281 44	0.368 8(9)	157.06
  Symmetry codes: c1-x, 1-y, 1-z; d-1+x, 1+y, z for 1; e1-x, -y, 1-z for 2

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