Crystal Structures and Fluorescence Property of Zn(Ⅱ)/Cd(Ⅱ) Complexes Based on <i>N</i>-((quinolin-8-yl)methylene)acetohydrazide

Citation: XU Zhi-Hong, WU Wei-Na, LIU Shu-Yang, KOU Kai, WANG Yuan. Crystal Structures and Fluorescence Property of Zn(Ⅱ)/Cd(Ⅱ) Complexes Based on N-((quinolin-8-yl)methylene)acetohydrazide[J]. Chinese Journal of Inorganic Chemistry, 2018, 34(2): 375-380. doi: 10.11862/CJIC.2018.032 shu

喹啉-8-甲醛乙酰腙锌/镉配合物的晶体结构及荧光性质

许志红 ^1, ,
吴伟娜 ^{2,
,} ,
刘树阳 ^2, ,
寇凯 ^2, ,
王元 ^{2,
,}

1.
许昌学院化学化工学院, 化学生物传感与检测重点实验室, 许昌 461000
2.
河南理工大学化学化工学院, 河南省煤炭绿色转化重点实验室, 焦作 454000

通讯作者: 吴伟娜, wuwn08@hpu.edu.cn
王元, wangyuan08@hpu.edu.cn

基金项目:
国家自然科学基金 21001040

河南省青年骨干教师项目 2014GGJS-045

国家自然科学基金（No.21001040）、河南省科技厅基础与前沿项目（No.162300410011）和河南省青年骨干教师项目（No.2014GGJS-045）资助

河南省科技厅基础与前沿项目 162300410011

摘要: 合成并通过单晶X射线衍射、元素分析及红外光谱表征了配合物{[Zn（HL）（H₂O）（SO₄）]·H₂O}_n（1），[Cd（HL）Cl₂]（2）和[Cd（HL）I₂]（3）的结构（HL为喹啉-8-甲醛乙酰腙）。单晶衍射结果表明，配合物1中，中心Zn（Ⅱ）离子的配位构型为扭曲的八面体，与来自1个中性三齿配体HL的ONN原子供体，1个水分子和2个μ₂桥联的硫酸根配位，从而形成沿b轴方向的一维链。配合物2和3中Cd（Ⅱ）与1个中性三齿配体HL和2个卤素阴离子（2中为氯离子，3中为碘离子）配位，配位构型为扭曲的四方锥。乙腈溶液中，配合物3与配体HL几乎无荧光发射，而配合物1和2分别在428和408 nm处有强荧光。

关键词:

酰腙
/ 锌配合物
/ 镉配合物
/ 喹啉
/ 荧光

English

Crystal Structures and Fluorescence Property of Zn(Ⅱ)/Cd(Ⅱ) Complexes Based on N-((quinolin-8-yl)methylene)acetohydrazide

XU Zhi-Hong ^1, ,
WU Wei-Na ^{2,
,} ,
LIU Shu-Yang ^2, ,
KOU Kai ^2, ,
WANG Yuan ^{2,
,}

1.
Key Laboratory of Chemo/Biosensing and Detection, School of Chemistry and Chemical Engineering, Xuchang University, Xuchang, Henan 461000, China
2.
College of Chemistry and Chemical Engineering, Henan Key Laboratory of Coal Green Conversion, Henan Polytechnic University, Jiaozuo, Henan 454000, China

Corresponding author: WU Wei-Na, wuwn08@hpu.edu.cn WANG Yuan, wangyuan08@hpu.edu.cn

Received Date: 21 July 2017
Revised Date: 11 November 2017
Available Online: 10 February 2018

Abstract: Three complexes, namely {[Zn(HL)(H₂O)(SO₄)]·H₂O}_n (1), [Cd(HL)Cl₂] (2) and[Cd(HL)I₂] (3) (HL=N-((quinolin-8-yl)methylene)acetohydrazide) have been synthesized and characterized by single crystal X-ray diffraction, elemental analysis and IR spectroscopy. X-ray diffraction analysis results show that in complex 1, the Zn(Ⅱ) ion with a distorted octahedron coordination geometry is six-coordinated, involving one coordinated water molecule, one ONN donor set of an neutral ligand HL, and two O atoms from two independent μ₂-bridged sulfate anions, thus forming one dimension chain-like framework along b axis. However, the coordination geometry of the Cd(Ⅱ) ion in each of complexes 2 and 3 is a distorted square planar geometry with a tridentate acylhydrazone ligand and two halide anions (chloride for 2, while iodide for 3). In CH₃CN solution, the ligand HL and complex 3 exhibit almost none fluorescence emission, whilst complexes 1 and 2 show remarkable peaks at about 428 and 408 nm, respectively.

Key words:

Schiff bases are an important class of ligands in coordination chemistry and have been found extensive application in different fields^[1-2]. As one of the most promising systems, the relevant semicarbazones and thiosemicarbazones involve condensed heterocycle, especially quinoline, have been paid much attention due to their potentially biological activities^[3-6]. However, acylhydrazones, as their structurally analogous, have been paid much less attention^[7-8]. Recently, several quinoline based acylhydrazone chemosensors for the fluorescent detection of metal ions have been reported in the literature, most of which function by coordina-tion reaction with ions^[9-11]. Nevertheless, the crystal structures of corresponding complexes are relatively scarce^[11].

Our previous work also shows that the acylhy-drazone ligand HL (Scheme 1), namely N-((quinolin-8-yl)methylene)acetohydrazide is an excellent fluorescent probe for the detection for Zn(Ⅱ) ions^[11]. Therefore, in this paper, three Zn(Ⅱ) and Cd(Ⅱ) complexes with HL have been synthesized and structural determined by single-crystal X-ray diffraction. In addition, the fluorescence properties of the complexes in CH₃CN solution were investigated.

图Scheme 1 Synthesis route of HL Scheme1. Synthesis route of HL

图选项

下载全尺寸图像

下载幻灯片

1 Experimental

1.1 Materials and measurements

Solvents and starting materials for synthesis were purchased commercially and used as received. Elemental analysis was carried out on an Elemental Vario EL analyzer. The IR spectra (ν=4 000~400 cm^-1) were determined by the KBr pressed disc method on a Bruker V70 FT-IR spectrophotometer. The UV spectra were recorded on a Purkinje General TU-1800 spectrophotometer. Fluorescence spectra were deter-mined on a Varian CARY Eclipse spectrophotometer, in the measurements of emission and excitation spectra the pass width is 5 nm.

1.2 Preparations of complexes 1~3

As shown in Scheme 1, the ligand HL was produced by condensation of 8-formylquinoline and acethydrazide in ethanol at room temperature accor-ding to the literature method^[11]. The complexes 1~3 were generated by reaction of the ligand HL (5 mmol) with equimolar of ZnSO₄, CdCl₂ and CdI₂ in methanol solution (10 mL) at room temperature for 1 h, respe-ctively. Crystals suitable for X-ray diffraction analysis were obtained by evaporating the corresponding reaction solutions at room temperature.

1: Colorless plates. Anal. Calcd. for C₁₂H₁₅N₃O₇SZn (%): C: 35.09; H: 3.68; N: 10.23. Found(%): C: 34.75; H: 3.85; N: 9.94. FT-IR (cm^-1): ν(C=O) 1 655, ν(C=N) 1 592, ν(C=N)_pyrazine 1 560.

2: Colorless blocks. Anal. Calcd. For C₁₂H₁₁N₃O Cl₂Cd(%):C: 36.35; H: 2.80; N: 10.60. Found (%): C: 36.42; H: 3.05; N: 10.37. FT-IR (cm^-1): ν(C=O) 1 654, ν(C=N) 1 590, ν(C=N)_pyrazine 1 558.

3: Colorless blocks. Anal. Calcd. For C₁₂H₁₁N₃OI₂ Cd(%): C: 24.87; H: 1.91; N: 7.25. Found(%): C: 25.00; H: 2.18; N: 7.02. FT-IR (cm^-1): ν(C=O) 1 646, ν(C=N) 1 586, ν(C=N)_pyrazine 1 555.

1.3 X-ray crystallography

The X-ray diffraction measurement for complexes 1~3 were performed on a Bruker SMART APEX Ⅱ CCD diffractometer equipped with a graphite mono-chromatized Mo Kα radiation (λ=0.071 073 nm) by using φ-ω scan mode at 296(2) K. Semi-empirical absorption correction was applied to the intensity data using the SADABS program^[12]. The structures were solved by direct methods and refined by full matrix least-square on F² using the SHELX-97 program^[13]. All non-hydrogen atoms were refined anisotropically. All the H atoms were positioned geometrically and refined using a riding model. Details of the crystal parameters, data collection and refinements for complexes 1~3 are summarized in Table 1.

Table 1. Crystal data and structure refinement for complexes 1~3

表选项

导出Excel

下载全尺寸表图像

	1	2	3
Empirical formula	C₁₂H₁₅N₃O₇SZn	C₁₂H₁₁N₃OCl₂Cd	C₁₂H₁₁N₃OI₂Cd
Formula weight	410.70	396.54	579.44
Size / mm	0.15×0.12×0.06	0.20×0.18×0.16	0.18×0.16×0.15
Crystal system	Monoclinic	Monoclinic	Monoclinic
Space group	P2₁/n	P2₁/c	P2₁/n
a / nm	1.033 9(7)	0.792 90(19)	0.746 79(12)
b / nm	0.664 5(4)	1.523 4(3)	1.659 7(2)
c / nm	2.179 5(14)	1.404 0(3)	1.263 00(12)
β/(°)	93.915(11)	123.322(10)	90.132 0(10)
V/ nm³	1.493 8(16)	1.417 1(5)	1.565 4(3)
Z	4	4	4
D_c / (g·cm^-3)	1.826	1.859	2.459
Unique	2 616	2 495	2 756
R_int	0.072 7	0.021 1	0.022 0
GOF	1.032	1.070	1.053
R indices [I/>2σ(I)]	R₁=0.044 3, wR₂=0.079 5	R₁=0.026 0, wR₂=0.063 5	R₁=0.026 9, wR₂=0.059 7
R indices (all data)	R₁=0.091 6, wR₂=0.092 7	R₁=0.031 4, wR₂=0.066 8	R₁=0.032 7, wR₂=0.062 5

CCDC: 1562151, 1; 1562152, 2; 1562153, 3.

2 Results and discussion

2.1 Crystal structures description

The diamond drawings of complexes 1~3 are shown in Fig. 1. Selected bond distances and angles are listed in Table 2. As shown in Fig. 1a, 1 contains one discrete cationic Zn(Ⅱ) complex and one crystal water molecule in the asymmetric unit. The center Zn(Ⅱ) ion with a distorted octahedron geometry is coordinated by one neutral hydrazone with ONN donor set, one coordinated water molecule and two O atoms from two independent μ₂-bridged sulfate anions, thus forming one dimension chain-like framework along b axis. In addition, in the solid state, the chains were further linked into a 2D supramolecular network by inter-molecular N-H…O and O-H…O hydrogen bonds (Fig. 1d and Table 3).

图1 Diamond drawing of 1~3 (a~c) with 30% thermal ellipsoids; Extended 2D supramolecular structure in complex 1 (d); Chain-like structures in complex 2 (e, along c axis) and 3 (f) formed by hydrogen bonds (shown in dashed line), respectively Figure1. Diamond drawing of 1~3 (a~c) with 30% thermal ellipsoids; Extended 2D supramolecular structure in complex 1 (d); Chain-like structures in complex 2 (e, along c axis) and 3 (f) formed by hydrogen bonds (shown in dashed line), respectively

图选项

下载全尺寸图像

下载幻灯片

Table 2. Selected bond lengths (nm) and angles (°) in complexes 1~3

表选项

导出Excel

下载全尺寸表图像

1
Zn1-N1	0.209 9(4)	Zn1-N2	0.205 9(4)	Zn1-O1	0.2l5 8(3)
Zn1-O2	0.211 4(3)	Zn1-O6	0.200 0(3)	Zn1-O5^ⅰ	0.227 9(3)
O6-Zn1-N2	161.91(14)	N1 -Zn1 -O2	87.73(14)	O6-Zn1-O5^ⅰ	86.08(12)
O6-Zn1-N1	107.02(15)	O6-Zn1 -O1	87.47(14)	N2-Zn1-O5^ⅰ	86.09(13)
N2-Zn1-N1	88.97(15)	N2-Zn1 -O1	76.09(15)	N1-Zn1-O5^ⅰ	87.98(13)
O6-Zn1 -O2	95.30(13)	N1 -Zn1 -O1	164.90(13)	02-Zn1-O5^ⅰ	175.71(12)
N2-Zn1 -O2	93.70(13)	02-Zn1 -O1	95.28(13)	H-Zn1-O5^ⅰ	88.83(12)
2
Cd1-N1	0.235 6(2)	Cd1-N2	0.231 4(2)	Cd1-O1	0.236 0(2)
Cd1-Cl1	0.241 82(11)	Cd1-Cl2	0.244 57(10)
Cl1-Cd1-Cl2	116.27(4)	N2-Cd1-N1	79.00(8)	N2-Cd1-Cl1	117.11(7)
N2-Cd1-Cl2	126.40(7)	N2-Cd1-O1	69.66(8)	N1-Cd1-Cl1	97.34(7)
N1-Cd1-Cl2	98.92(7)	N1-Cd1-O1	147.27(8)	O1-Cd1-Cl1	105.00(6)
O1-Cd1-Cl2	92.37(6)
3
Cd1-N1	0.237 8(4)	Cd1-N2	0.230 8(3)	Cd1-O1	0.238 4(3)
Cd1-I1	0.274 72(7)	Cd1-I2	0.273 21(5)
I2-Cd1-I1	109.208(16)	N2-Cd1-N1	78.88(12)	N2-Cd1-I2	127.43(9)
N2-Cd1-I1	122.37(9)	N2-Cd1-O1	69.29(12)	N1-Cd1-I2	100.14(9)
N1-Cd1-I1	102.92(9)	N1-Cd1-O1	148.15(12)	O1-Cd1-I2	98.28(9)
O1-Cd1-I1	95.17(10)
Symmetry codes: ^ⅰ x, -1+y, z

Table 3. Hydrogen bonds information for complexes 1~3

表选项

导出Excel

下载全尺寸表图像

D-H …A	d(D-H) / nm	d(H …A) / nm	d(D …A) / nm	∠DHA/(°)
1
O6-H6A …O4^ⅰ	0.085	0.191	0.270 9(5)	155.1
N3-H3 …O3^ⅱ	O.O86	0.193	0.274 4(5)	158.2
O6-H6B …O4^ⅲ	0.085	0.189	0.270 1(5)	159.6
O7-H7A …O4	0.085	0.26	0.317 4(6)	125.9
O7-H7B …O3	0.085	0.25	0.297 4(7)	116
2
N3-H3A …Cl2^iv	0.086	0.235	0.318 9(3)	164.3
3
N3-H3A …I1^v	0.086	0.311	0.383 1(4)	142.3
Symmetry codes: ^ⅰ x, -1+y, z; ^ⅱ 1-x, 1-y, -z; ^ⅲ 1.5-x, -0.5+y, 0.5-z; ^ⅳ x, 0.5-y, 0.5+z; ^ⅴ -0.5+x, 1.5-y, -0.5+z

Similarly, the hydrazone HL acts as a neutral tridentate ligand in complexes 2 and 3 (Fig. 1b and 1c). Coordinated by two additional halide anions (chloride for 2, while iodide for 3), the Cd(Ⅱ) ion adopts a distorted square pyramid coordination geometry (τ=0.348 and 0.345 for complex 2 and 3, respectively)^[7]. In the crystal, intermolecular N-H…Cl or N-H…I hydrogen bonds link the complex molecules of 2 or 3 into one dimension chains (Fig. 1e and 1f).

2.2 IR spectra

The FT-IR spectral region for both complexes is more or less similar due to the similar coordination modes of the ligands. The ν(C=O), ν(C=N)_imine and ν(C=N)_quinoline bands are at 1 673, 1 615 and 1 584 cm^-1, respectively. They shift to lower frequency values in the complexes, indicating that the carbonyl O, imine N and quinoline N atoms take part in the coordina-tion^{[7-8, 14-15]}. It is in accordance with the crystal structure study.

2.3 UV spectra

The UV spectra of the ligand HL, complexes 1~3 in CH₃CN solution (c=1×10^-5 mol·L^-1) were measured at room temperature (Fig. 2). The spectra of HL features two main band located around 230 nm (ε=35 288 L·mol^-1·cm^-1) and 320 nm (ε=16 955 L·mol^-1·cm^-1), which could be assigned to characteristic π-π^* transition of quinoline and imine units, respe-ctively^[8]. Both bands have no shift while with absorption intensity change in the spectra of complexes 1~3 (ε₁=34 327, 16 575 L·mol^-1·cm^-1; ε₂=30 131, 14 854 L·mol^-1·cm^-1; ε₃=38 244, 14 870 L·mol^-1·cm^-1). This fact supports the neutral mode of the ligand HL in three complexes^[7].

图2 UV spectra of the ligand HL, complexes 1~3 in CH₃CN solution at room temperature Figure2. UV spectra of the ligand HL, complexes 1~3 in CH₃CN solution at room temperature

图选项

下载全尺寸图像

下载幻灯片

2.4 Fluorescence spectra

The fluorescence spectra of the ligand HL and complexes 1~3 have been studied in CH₃CN solution (c=1×10^-5 mol·L^-1) at room temperature. The free Schiff base ligand HL exhibits almost none fluorescence emission when excited at 320 nm, primarily due to C=N isomerization. However, compl-exes 1 and 2 show remarkable peaks at about 428 and 408 nm under the same tested condition, respectively. Obviously, binding with Zn²⁺/Cd²⁺ inhibits the isome-rization of C=N, thereby increasing the fluorescence intensity through the CHEF mechanism^[9-11]. In addition, it should be noted that complex 3 gives similar emission as the free ligand because of the heavy atom effect of the coordinated iodide anions.

图3 Fluorescence emission spectra of the ligand HL, complexes 1~3 in CH₃CN solution at room temperature Figure3. Fluorescence emission spectra of the ligand HL, complexes 1~3 in CH₃CN solution at room temperature

图选项

下载全尺寸图像

下载幻灯片

1. [1]
  Alagesan L, Bhuvanesh N S P, Dharmaraj N. Dalton Trans., 2013, 42:7210-7223 doi: 10.1039/c3dt50371b
2. [2]
  Ye X P, Zhu T F, Wu W N, et al. Inorg. Chem. Commun., 2014, 47:60-62 doi: 10.1016/j.inoche.2014.07.022
3. [3]
  Bourosh P N, Revenko M D, Stratulat E F, et al. Russ. J. Inorg. Chem., 2014, 59:545-557 doi: 10.1134/S0036023614060059
4. [4]
  Revenko M D, Bourosh P N, Stratulat E F, et al. Russ. J. Inorg. Chem., 2010, 55:1387-1397 doi: 10.1134/S0036023610090093
5. [5]
  毛盼东, 闫玲玲, 王文静, 等.无机化学学报, 2016, 32(3):555-560 doi: 10.11862/CJIC.2016.064MAO Pan-Dong, YAN Ling-Ling, WANG Wen-Jing, et al. Chinese J. Inorg. Chem., 2016, 32(3):555-560 doi: 10.11862/CJIC.2016.064
6. [6]
  毛盼东, 韩学峰, 李珊珊, 等.无机化学学报, 2017, 33(4):692-698 doi: 10.11862/CJIC.2017.067MAO Pan-Dong, HAN Xue-Feng, LI Shan-Shan, et al. Chinese J. Inorg. Chem., 2017, 33(4):692-698 doi: 10.11862/CJIC.2017.067
7. [7]
  李晓静, 吴伟娜, 徐周庆, 等.无机化学学报, 2015, 31(11):2265-2271 http://www.wjhxxb.cn/wjhxxbcn/ch/reader/view_abstract.aspx?file_no=20151123&flag=1LI Xiao-Jing, WU Wei-Na, XU Zhou-Qing, et al. Chinese J. Inorg. Chem., 2015, 31(11):2265-2271 http://www.wjhxxb.cn/wjhxxbcn/ch/reader/view_abstract.aspx?file_no=20151123&flag=1
8. [8]
  常慧琴, 原知则, 赖晓晴, 等.无机化学学报, 2016, 32(11):2058-2062 http://www.wjhxxb.cn/wjhxxbcn/ch/reader/view_abstract.aspx?file_no=20161122&flag=1CHANG Hui-Qin, YUAN Zhi-Ze, LAI Xiao -Qing, et al. Chinese J. Inorg. Chem., 2016, 32(11):2058-2062 http://www.wjhxxb.cn/wjhxxbcn/ch/reader/view_abstract.aspx?file_no=20161122&flag=1
9. [9]
  Liu H, Dong Y, Zhang B, et al. Sens. Actuators B, 2016, 234:616-624 doi: 10.1016/j.snb.2016.04.175
10. [10]
  Ponnuvel K, Kumar M, Padmini V. Sens. Actuators B, 2016, 227:242-247 doi: 10.1016/j.snb.2015.12.017
11. [11]
  Wu W N, Mao P D, Wang Y, et al. Spectrochim. Acta A, 2018, 188:324-331 doi: 10.1016/j.saa.2017.07.020
12. [12]
  Sheldrick G M. SADABS, University of Göttingen, Germany, 1996.
13. [13]
  Sheldrick G M. SHELX-97, Program for the Solution and the Refinement of Crystal Structures, University of Göttingen, Germany, 1997.
14. [14]
  Huang Y Q, Zhao W, Chen J G, et al. Z. Anorg. Allg. Chem., 2012, 638:679-682 doi: 10.1002/zaac.v638.3/4
15. [15]
  Huang Y Q, Wan Y, Chen H Y, et al. New J. Chem., 2016, 40:7587-7595 doi: 10.1039/C6NJ01231K

Scheme 1 Synthesis route of HL

下载: 全尺寸图片幻灯片

Figure 1 Diamond drawing of 1~3 (a~c) with 30% thermal ellipsoids; Extended 2D supramolecular structure in complex 1 (d); Chain-like structures in complex 2 (e, along c axis) and 3 (f) formed by hydrogen bonds (shown in dashed line), respectively

(a~c) H atoms are omitted for clarity; Symmetry codes: ^ⅰ x, -1+y, z; ^ⅱ 1-x, 1-y, -z; ^ⅲ 1.5-x, -0.5+y, 0.5-z; ^ⅳ x, 0.5-y, 0.5+z; ^ⅴ -0.5+x, 1.5-y, -0.5+z

下载: 全尺寸图片幻灯片

Figure 2 UV spectra of the ligand HL, complexes 1~3 in CH₃CN solution at room temperature

下载: 全尺寸图片幻灯片

Figure 3 Fluorescence emission spectra of the ligand HL, complexes 1~3 in CH₃CN solution at room temperature

下载: 全尺寸图片幻灯片

Table 1. Crystal data and structure refinement for complexes 1~3

	1	2	3
Empirical formula	C₁₂H₁₅N₃O₇SZn	C₁₂H₁₁N₃OCl₂Cd	C₁₂H₁₁N₃OI₂Cd
Formula weight	410.70	396.54	579.44
Size / mm	0.15×0.12×0.06	0.20×0.18×0.16	0.18×0.16×0.15
Crystal system	Monoclinic	Monoclinic	Monoclinic
Space group	P2₁/n	P2₁/c	P2₁/n
a / nm	1.033 9(7)	0.792 90(19)	0.746 79(12)
b / nm	0.664 5(4)	1.523 4(3)	1.659 7(2)
c / nm	2.179 5(14)	1.404 0(3)	1.263 00(12)
β/(°)	93.915(11)	123.322(10)	90.132 0(10)
V/ nm³	1.493 8(16)	1.417 1(5)	1.565 4(3)
Z	4	4	4
D_c / (g·cm^-3)	1.826	1.859	2.459
Unique	2 616	2 495	2 756
R_int	0.072 7	0.021 1	0.022 0
GOF	1.032	1.070	1.053
R indices [I/>2σ(I)]	R₁=0.044 3, wR₂=0.079 5	R₁=0.026 0, wR₂=0.063 5	R₁=0.026 9, wR₂=0.059 7
R indices (all data)	R₁=0.091 6, wR₂=0.092 7	R₁=0.031 4, wR₂=0.066 8	R₁=0.032 7, wR₂=0.062 5

下载: 导出CSV

Table 2. Selected bond lengths (nm) and angles (°) in complexes 1~3

1
Zn1-N1	0.209 9(4)	Zn1-N2	0.205 9(4)	Zn1-O1	0.2l5 8(3)
Zn1-O2	0.211 4(3)	Zn1-O6	0.200 0(3)	Zn1-O5^ⅰ	0.227 9(3)
O6-Zn1-N2	161.91(14)	N1 -Zn1 -O2	87.73(14)	O6-Zn1-O5^ⅰ	86.08(12)
O6-Zn1-N1	107.02(15)	O6-Zn1 -O1	87.47(14)	N2-Zn1-O5^ⅰ	86.09(13)
N2-Zn1-N1	88.97(15)	N2-Zn1 -O1	76.09(15)	N1-Zn1-O5^ⅰ	87.98(13)
O6-Zn1 -O2	95.30(13)	N1 -Zn1 -O1	164.90(13)	02-Zn1-O5^ⅰ	175.71(12)
N2-Zn1 -O2	93.70(13)	02-Zn1 -O1	95.28(13)	H-Zn1-O5^ⅰ	88.83(12)
2
Cd1-N1	0.235 6(2)	Cd1-N2	0.231 4(2)	Cd1-O1	0.236 0(2)
Cd1-Cl1	0.241 82(11)	Cd1-Cl2	0.244 57(10)
Cl1-Cd1-Cl2	116.27(4)	N2-Cd1-N1	79.00(8)	N2-Cd1-Cl1	117.11(7)
N2-Cd1-Cl2	126.40(7)	N2-Cd1-O1	69.66(8)	N1-Cd1-Cl1	97.34(7)
N1-Cd1-Cl2	98.92(7)	N1-Cd1-O1	147.27(8)	O1-Cd1-Cl1	105.00(6)
O1-Cd1-Cl2	92.37(6)
3
Cd1-N1	0.237 8(4)	Cd1-N2	0.230 8(3)	Cd1-O1	0.238 4(3)
Cd1-I1	0.274 72(7)	Cd1-I2	0.273 21(5)
I2-Cd1-I1	109.208(16)	N2-Cd1-N1	78.88(12)	N2-Cd1-I2	127.43(9)
N2-Cd1-I1	122.37(9)	N2-Cd1-O1	69.29(12)	N1-Cd1-I2	100.14(9)
N1-Cd1-I1	102.92(9)	N1-Cd1-O1	148.15(12)	O1-Cd1-I2	98.28(9)
O1-Cd1-I1	95.17(10)
Symmetry codes: ^ⅰ x, -1+y, z

下载: 导出CSV

Table 3. Hydrogen bonds information for complexes 1~3

D-H …A	d(D-H) / nm	d(H …A) / nm	d(D …A) / nm	∠DHA/(°)
1
O6-H6A …O4^ⅰ	0.085	0.191	0.270 9(5)	155.1
N3-H3 …O3^ⅱ	O.O86	0.193	0.274 4(5)	158.2
O6-H6B …O4^ⅲ	0.085	0.189	0.270 1(5)	159.6
O7-H7A …O4	0.085	0.26	0.317 4(6)	125.9
O7-H7B …O3	0.085	0.25	0.297 4(7)	116
2
N3-H3A …Cl2^iv	0.086	0.235	0.318 9(3)	164.3
3
N3-H3A …I1^v	0.086	0.311	0.383 1(4)	142.3
Symmetry codes: ^ⅰ x, -1+y, z; ^ⅱ 1-x, 1-y, -z; ^ⅲ 1.5-x, -0.5+y, 0.5-z; ^ⅳ x, 0.5-y, 0.5+z; ^ⅴ -0.5+x, 1.5-y, -0.5+z

下载: 导出CSV

扫一扫看文章

计量

PDF下载量: 3
文章访问数: 1342
HTML全文浏览量: 160

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142