TAI Xi-Shi GUO Hong-Mei GUO Qin-Qin

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Synthesis, Crystal Structure and Antitumor Activity of a Novel Zn(II) Complex with 2-(Nicotinoyloxy)acetic Acid Ligand①

TAI Xi-Shia②GUO Hong-MeibGUO Qian-Qinc

a(261061)b(261061)c(261205)

2-(nicotinoyloxy)acetic acid ligand, Zn(II) complex, synthesis, crystal structure, antitumor activity;

1 INTRODUCTION

The design and synthesis of novel Zn(II) com- plexes with organic ligands containing nitrogen heterocyclic groups or carboxylate groups have received much attention during the past decades[1-3], because Zn(II) complexes show excellent properties in many ways such as antitumor and antibacte- rial[4-7], nonlinear optics[8, 9], luminescence[10-12], ca- talysis[13-15], DNA-binding[16], chemical sensor[17, 18]and so on. In the previous work, we have also repor- ted some metal complexes with ligands containing nitrogen heterocyclic groups or carboxylate groups[19-25]. In this paper, a new Zn(II) complex with 2-(nicotinoyloxy)acetic acid ligand has been synthesized and structurally characterized. The antitumor activities of Zn(II) complex have also been tested.

2 EXPERIMENTAL

2. 1 Materials and measurements

2-(Nicotinoyloxy)acetic acid (A. R.), Zn(OAc)2·2H2O (A. R.) and other chemicals were purchased from Shanghai Chemical Reagent Company. Ele- mental analysis (C, H and N) was performed on anElementar Vario III EL elemental analyzer (Hanau, Germany). The FT-IR spectra were obtained from a Nicolet AVATAR 360 FTIR Spectrophotometer in the range of 4000～400 cm-1. Crystal data of the Zn(II) complex were collected on a Bruker Smart CCD diffractometer (Bruker, Billerica, MA, USA).

2. 2 Synthesis of [ZnL2(H2O)4]·H2O (1)

2-(Nicotinoyloxy)acetic acid (1.0 mmol, 0.1810 g) and NaOH (1.0 mmol, 0.040 g) were dissolved in 15 mL 95% ethanol solution with stirring. Then 5.0 mL water solution containing Zn(OAc)2·2H2O (0.5 mmol, 0.1097 g) was added to the above mixture. The reaction mixture was heated at 60 ℃ for 7 h with stirring and cooled to room temperature. The mixture was filtered, and the block crystals were obtained from filtrate after 25 days. Yield ca. 57%. Anal. Calcd. (%) for C16H24N2O14Zn: C, 35.97; H, 4.50; N, 5.25. Found (%): C, 35.83; H, 4.87; N, 5.41. IR data (KBr, cm-1): 3263, 1711, 1546, 1397, 1146.

2. 3 Crystal data and structure determination

3 RESULTS AND DISCUSSION

3. 1 IR spectroscopy

The 2-(nicotinoyloxy)acetic acid ligand exhibits three strong bands at 1712 cm-1(C=O), 1571 cm–1(C=N) and 1145 cm–1(C–O–C), which appear at 1711 cm–1(C=O), 1545 cm–1(C=N) and 1146 cm–1(C–O–C), respectively in complex 1, suggesting that only the N atom of 2-(nicotinoyloxy)acetic acid ligandcoordinates to the Zn(II) ion[27].

3. 2 Structure description of [ZnL2(H2O)4]·H2O (1)

Fig. 1. Molecular structure of [ZnL2(H2O)4]·H2O.Symmetry code: A: –, –, –

Fig. 2. 3D supramolecular network structure of Zn(II) complex

Table 1. Selected Bond Lengths (?) and Bond Angles (°)

Symmetry code: A: –, –, –

Table 2. Hydrogen Bond Data for the Zn(II) Complex

3. 3 Antitumor activity

The antitumor activities of 2-(nicotino-yloxy)ace- tic acid ligand and its Zn(II) complex were evaluated against human lung adenocarcinomacells, human hepatomacells and human colon carcinomacells by MTT method[30]. The results (Table 3) show that both Zn(II) complex and 2-(nicotinoyloxy)acetic acid ligand have antitumor activities. However, the antitumor effects of Zn(II) complex against human hepatomacells and human colon carcinomacells are better than that of 2-(nicotinoyloxy)acetic acid ligand. The antitumor effect of 2-(nicotinoyloxy)acetic acid ligand against human lung adenocarcinomacells is better than that of Zn(II) complex.

Table 3. Antitumor Activities of the Zn(II) Complex and HL Ligand

4 CONCLUSION

In summary, a new Zn(II) complex with 2-(nico- tinoyloxy)acetic acid ligand has been synthesized and structurally characterized. The Zn(II) complex formed 1D chains by hydrogen bonds, and hydrogen bonding interactions assemble such chains into a 3D network structure. Complex 1 exhibits considerable antitumor activities.

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6 November 2017;

6 March 2018 (CCDC 1568675)

① This work was supported by the National Natural Science Foundation of China (No. 21171132), the Project of Shandong Province Higher Educational Science and Technology Program (J14LC01) and Science Foundation of Weifang

. Tai Xi-Shi, born in 1971, professor, majoring in coordination chemistry. E-mail: taixishi@lzu.edu.cn or taixs@wfu.edu.cn.The first two authors contributed equally to this study

10.14102/j.cnki.0254-5861.2011-1880