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Synthesis, Crystal Structure and Antitumor Activity of a Ca(II) Coordination Polymer Based on 4-Acetylphenoxyacetate Ligands

Shu-Hua CAO ,  Xi-Shi TAI ,  Chun-Ling XIN

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Citation:  Shu-Hua CAO, Xi-Shi TAI, Chun-Ling XIN. Synthesis, Crystal Structure and Antitumor Activity of a Ca(II) Coordination Polymer Based on 4-Acetylphenoxyacetate Ligands[J]. Chinese Journal of Structural Chemistry, 2021, 40(3): 324-328. doi: 10.14102/j.cnki.0254–5861.2011–2860 shu

Synthesis, Crystal Structure and Antitumor Activity of a Ca(II) Coordination Polymer Based on 4-Acetylphenoxyacetate Ligands

English

  • 1. INTRODUCTION

    The design and synthesis of metal coordination polymers have received considerable attention during the past decades because they show not only structural diversity[1], but also potential widespread applications as functional materials, such as molecular recognition[2], gas storage[3], magnetocaloric effect[4], luminescence[5-7], catalysis[8], magnetic property[9], bioactivity[10], magnetorefrigerant[11], and so on. To our knowledge, many studies on coordination polymers have focused on transition metals in the past years[12-16]. However, few investigations have been done on calcium coordination polymers. In our previous work, some calcium coordination polymers have been synthesized and structurally characterized[17-20]. In order to extend the investigation of novel structures and properties of calcium coordination polymer, in this work, we successfully designed and synthesized a novel 1D Ca(II) coordination polymer, [CaL2(H2O)2]n (HL = 4-acetylphenoxyacetic acid), by 4-acetylphenoxyacetic acid, Ca(ClO4)2·4H2O and NaOH as raw materials. And its antitumor activity against human hepatoma SMMC-7721 cells, human colon carcinoma WiDr cells and human lung adenocarcinoma A549 cells has been investigated. The coordination mode of Ca(II) ion is shown in Fig. 1.

    Figure 1

    Figure 1.  Coordination mode of Ca(II) ion
    DownLoad: Full-Size Img PowerPoint

    2. EXPERIMENTAL

    2.1 Materials and measurements

    4-Acetylphenoxyacetic acid, NaOH, Ca(ClO4)2·4H2O and ethanol solvent were of analytical grade and used directly without further purification. Carbon, hydrogen and nitrogen were determined using an Elementar Vario III EL elemental analyzer. IR spectra were recorded using KBr discs on a Nicolet AVATAR 360 FTIR spectrophotometer (Nicolet Instrument Inc., Madison, WI, USA) (range 4, 000~400 cm–1). Single-crystal X-ray diffraction data of [CaL2(H2O)2]n were collected on a Bruker Smart CCD diffractometer (Bruker, Billerica, MA, USA).

    2.2 Synthesis of [CaL2(H2O)2]n (1)

    4-Acetylphenoxyacetic acid (0.1941 g, 1.0 mmol) and sodium hydrate (0.040 g, 1.0 mmol) were dissolved into 10 mL ethanol solution at room temperature. Then 5 mL of aqueous solution containing 0.1195 g Ca(ClO4)2·4H2O (0.5 mmol) was dropped into the above solution. The mixture was heated at 70 ℃ for 6.5 h with stirring, cooled to room temperature and filtered. Colourless crystals of [CaL2(H2O)2]n were obtained in 25 days by slowly volatilizing the filtrate at room temperature. Anal. Calcd. for C20H22O10Ca: C, 51.90; H, 4.76%. Found: C, 51.65; H, 5.09. IR vmax (cm–1): v (COO–): 1675 cm−1.

    2.3 Antitumor activity

    The culture of tumor cells (Human hepatoma SMMC-7721 cells, human colon carcinoma WiDr cells and human lung adenocarcinoma A549 cells) and the test procedure for the antitumor activity are consistent with the literature[21, 22].

    2.4 Crystal data and structure determination

    A single crystal of 1 (0.12mm × 0.11mm × 0.10mm) was placed on a Bruker SMART APEX CCD X-ray diffractometer equipped with graphite-monochromated MoKα radiation (λ = 0.71073 Å) at 99.99(10) K. 4441 reflections (Rint = 0.0245) were independent for 1. The structure was solved by direct methods using SHELXL-2014/7 program[23]. The OLEX2[24] program was used to refine the structure. The non-hydrogen atoms were refined anisotropically and the hydrogen atoms were generated by theoretical calculations. Crystal data for complex 1: monoclinic system, space group C2/c with a = 24.4894(11), b = 11.3416(5), c = 7.7164(4) Å, β = 94.750(5)º, V = 2135.88(17) Å3, Z = 4, C20H22O10Ca, Mr = 462.45, Dc = 1.438 Mg/m3, F(000) = 968 and μ(MoKα) = 0.348 mm–1. The final R = 0.0319, wR = 0.0753 (w = 1/[σ2(Fo2) + (0.0342P)2 + 1.4584P], where P = (Fo + 2Fc2)/3), S = 1.067. The maximum and minimum peaks are 0.229 and –0.333 e/Å3, respectively.

    3. RESULTS AND DISCUSSION

    3.1 Structural description of [CaL2(H2O)2] n (1)

    Single-crystal X-ray structural analyses show that complex 1 crystallizes in monoclinic space group C2/c. Selected bond distances and bond angles of complex 1 are shown in Table 1. The average distance of the Ca–O bonds is 2.465 Å (ranging from 2.3384(12) to 2.6308(12) Å), which are consistent with those reported[16-21]. And the bond angles of O–Ca–O vary from 50.82(4) to 157.67(4)°.

    Table 1

    Table 1.  Selected Bond Lengths (Å) and Bond Angles (°)
    DownLoad: CSV
    Bond Dist. Bond Dist.
    Ca(1)–O(4) 2.3384(12) Ca(1)–O(5) 2.3828(12)
    Ca(1)–O(4A) 2.6308(12) Ca(1)–O(5A) 2.3827(12)
    Ca(1)–O(4B) 2.6308(12) C(8)–O(4) 1.259(2)
    Ca(1)–O(4C) 2.3384(12) C(4)–O(2) 1.363(2)
    Ca(1)–O(3B) 2.5069(12) C(7)–O(2) 1.427(2)
    Ca(1)–O(3C) 2.5069(12) C(8)–O(3) 1.252(2)
    C(9)–O(1) 1.224(2)
    Angle (°) Angle (°)
    O(4)–Ca(1)–O(4C) 122.51(4) O(4)–Ca(1)–O(3B) 122.51(4)
    O(4)–Ca(1)–O(4B) 72.94(4) O(4A)–Ca(1)–O(3B) 77.99(4)
    O(4A)–Ca(1)–O(4C) 72.94(4) O(4A)–Ca(1)–O(3C) 122.51(4)
    O(4B)–Ca(1)–O(4C) 108.23(5) O(4)–Ca(1)–O(3C) 77.99(4)
    O(4A)–Ca(1)–O(4B) 122.51(4) O(4A)–Ca(1)–O(5A) 78.78(4)
    O(4)–Ca(1)–O(4A) 155.97(6) O(4)–Ca(1)–O(5A) 84.74(4)
    O(4)–Ca(1)–O(5) 78.78(4) O(4B)–Ca(1)–O(3C) 72.78(4)
    O(4A)–Ca(1)–O(5) 84.74(4) O(4B)–Ca(1)–O(3B) 50.82(4)
    O(4C)–Ca(1)–O(3B) 72.78(4) O(3B)–Ca(1)–O(3C) 75.37(5)
    O(4C)–Ca(1)–O(3C) 50.82(4) O(4C)–Ca(1)–O(5A) 83.18(4)
    O(4B)–Ca(1)–O(5) 83.18(4) O(3C)–Ca(1)–O(5A) 102.61(4)
    O(4C)–Ca(1)–O(5) 157.67(4) O(3B)–Ca(1)–O(5) 102.61(4)
    O(4B)–Ca(1)–O(5A) 157.67(4) O(3C)–Ca(1)–O(5) 150.49(4)
    O(3B)–Ca(1)–O(5A) 150.49(4) O(5)–Ca(1)–O(5A) 93.09(6)
    Symmetry transformation: A: 1 – x, y, 1/2 – z; B: 1 – x, 1 – y, 1 – z; C: x, 1 – y, –1/2 + z

    The asymmetric unit of complex 1 is shown in Fig. 2. The fundamental unit of 1 contains one Ca(II) ion, two 4-acetylphenoxyacetate ligands and two coordinated water molecules. Each Ca(II) ion is eight-coordination with six O atoms (O(3B), O(3C), O(4), O(4A), O(4B) and O(4C)) from four 4-acetylphenoxyacetate ligands and two O atoms (O(5) and O(5A)) from two coordinated water molecules, resulting in a distorted triangular dodecahedral geometric configuration. In complex 1, the carboxylate O atoms of 4-acetylphenoxyacetate ligand adopt different coordination modes with Ca(II) ion (Fig. 3): one O atom adopts a bidentate chelating mode to coordinate to different Ca(II) ions, and the other O atom adopts a monodentate chelating mode to coordinate to the Ca(II) ion. The complex forms a one-dimensional (1D) chain structure by the bridging effect of carboxylate O atoms with adjacent Ca(II) ions (Fig. 4). The 3D network structure is also formed by the interactions of 1D chain (Fig. 5). In addition, four uncoordinated water molecules also exist in the crystal structure.

    Figure 2

    Figure 2.  Asymmetric unit of [CaL2(H2O)2]n
    DownLoad: Full-Size Img PowerPoint

    Figure 3

    Figure 3.  Coordination mode of carboxylate O atoms
    DownLoad: Full-Size Img PowerPoint

    Figure 4

    Figure 4.  One-dimension chained structure
    DownLoad: Full-Size Img PowerPoint

    Figure 5

    Figure 5.  3D supramolecular network structure
    DownLoad: Full-Size Img PowerPoint

    3.2. Antitumor activity

    The antitumor activity of 4-acetylphenoxyacetic acid and [CaL2(H2O)2]n was tested against human hepatoma SMMC-7721 cells, human colon carcinoma WiDr cells and human lung adenocarcinoma A549 cells. The data of antitumor activity are given in Table 2. The results show that both 4-acetylphenoxyacetic acid and [CaL2(H2O)2]n exhibit considerable cytotoxicity, but the antitumor effect of [CaL2(H2O)2]n is better than that of 4-acetylphenoxyacetic acid. The antitumor effect of [CaL2(H2O)2]n against WiDr cell is better than that reported[22], while the antitumor effect of [CaL2(H2O)2]n against SMMC-7721 and A549 cells is weaker than that in document[22].

    Table 3

    Table 3.  Antitumor Activity of 4-Acetylphenoxyacetic Acid and [CaL2(H2O)2]n
    DownLoad: CSV
    Compound IC50 (μg/mL)
    SMMC-7721 WiDr A549
    [CaL2(H2O)2]n 12.5 ± 0.2 15.3 ± 0.2 19.2 ± 0.2
    4-Acetylphenoxyacetic acid 15.3 ± 0.2 22.6 ± 0.2 29.1 ± 0.2

    4. CONCLUSION

    In summary, we have synthesized and structurally characterized a new eight-coordinated Ca(II) coordination polymer, [CaL2(H2O)2]n (1). The antitumor activities of 4-acetylphenoxyacetic acid and the Ca(II) coordination polymer have also been tested. The above results provide a good idea for the synthesis of Ca(II) complexes with antitumor activity in the future.


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  • Figure 1  Coordination mode of Ca(II) ion

    下载: 全尺寸图片 幻灯片

    Figure 2  Asymmetric unit of [CaL2(H2O)2]n

    下载: 全尺寸图片 幻灯片

    Figure 3  Coordination mode of carboxylate O atoms

    下载: 全尺寸图片 幻灯片

    Figure 4  One-dimension chained structure

    下载: 全尺寸图片 幻灯片

    Figure 5  3D supramolecular network structure

    下载: 全尺寸图片 幻灯片

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

    Bond Dist. Bond Dist.
    Ca(1)–O(4) 2.3384(12) Ca(1)–O(5) 2.3828(12)
    Ca(1)–O(4A) 2.6308(12) Ca(1)–O(5A) 2.3827(12)
    Ca(1)–O(4B) 2.6308(12) C(8)–O(4) 1.259(2)
    Ca(1)–O(4C) 2.3384(12) C(4)–O(2) 1.363(2)
    Ca(1)–O(3B) 2.5069(12) C(7)–O(2) 1.427(2)
    Ca(1)–O(3C) 2.5069(12) C(8)–O(3) 1.252(2)
    C(9)–O(1) 1.224(2)
    Angle (°) Angle (°)
    O(4)–Ca(1)–O(4C) 122.51(4) O(4)–Ca(1)–O(3B) 122.51(4)
    O(4)–Ca(1)–O(4B) 72.94(4) O(4A)–Ca(1)–O(3B) 77.99(4)
    O(4A)–Ca(1)–O(4C) 72.94(4) O(4A)–Ca(1)–O(3C) 122.51(4)
    O(4B)–Ca(1)–O(4C) 108.23(5) O(4)–Ca(1)–O(3C) 77.99(4)
    O(4A)–Ca(1)–O(4B) 122.51(4) O(4A)–Ca(1)–O(5A) 78.78(4)
    O(4)–Ca(1)–O(4A) 155.97(6) O(4)–Ca(1)–O(5A) 84.74(4)
    O(4)–Ca(1)–O(5) 78.78(4) O(4B)–Ca(1)–O(3C) 72.78(4)
    O(4A)–Ca(1)–O(5) 84.74(4) O(4B)–Ca(1)–O(3B) 50.82(4)
    O(4C)–Ca(1)–O(3B) 72.78(4) O(3B)–Ca(1)–O(3C) 75.37(5)
    O(4C)–Ca(1)–O(3C) 50.82(4) O(4C)–Ca(1)–O(5A) 83.18(4)
    O(4B)–Ca(1)–O(5) 83.18(4) O(3C)–Ca(1)–O(5A) 102.61(4)
    O(4C)–Ca(1)–O(5) 157.67(4) O(3B)–Ca(1)–O(5) 102.61(4)
    O(4B)–Ca(1)–O(5A) 157.67(4) O(3C)–Ca(1)–O(5) 150.49(4)
    O(3B)–Ca(1)–O(5A) 150.49(4) O(5)–Ca(1)–O(5A) 93.09(6)
    Symmetry transformation: A: 1 – x, y, 1/2 – z; B: 1 – x, 1 – y, 1 – z; C: x, 1 – y, –1/2 + z
    下载: 导出CSV

    Table 3.  Antitumor Activity of 4-Acetylphenoxyacetic Acid and [CaL2(H2O)2]n

    Compound IC50 (μg/mL)
    SMMC-7721 WiDr A549
    [CaL2(H2O)2]n 12.5 ± 0.2 15.3 ± 0.2 19.2 ± 0.2
    4-Acetylphenoxyacetic acid 15.3 ± 0.2 22.6 ± 0.2 29.1 ± 0.2
    下载: 导出CSV
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  • 发布日期:  2021-03-01
  • 收稿日期:  2020-04-24
  • 接受日期:  2020-06-29
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