CN109232405A - 6-甲基吡啶-2,3-二羧酸镍配合物及其制备方法 - Google Patents

6-甲基吡啶-2,3-二羧酸镍配合物及其制备方法 Download PDF

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CN109232405A
CN109232405A CN201811070171.6A CN201811070171A CN109232405A CN 109232405 A CN109232405 A CN 109232405A CN 201811070171 A CN201811070171 A CN 201811070171A CN 109232405 A CN109232405 A CN 109232405A
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刘峥
梁楚欣
梁秋群
劳洁
吴欢
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/803—Processes of preparation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

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Abstract

本发明公开了一种6‑甲基吡啶‑2,3‑二羧酸镍配合物及其制备方法。该配合物属于单斜晶系，空间群为P21/n，晶胞参数为a=7.83532(16)Å，b=13.2232(3)Å，c=10.0482(2)Å，α=90.00°，β=101.806°，γ=90.00°，V=1019.05(4)Å3，Z=14。所述方法是以6‑甲基吡啶‑2,3‑二羧酸为配体，在无水乙醇、蒸馏水和N,N‑二甲基甲酰胺（DMF）溶液中，与六水合硫酸镍反应，制备6‑甲基吡啶‑2,3‑二羧酸镍配合物。本发明的所述制备方法具有工艺简单、重复性好、绿色环保等优点，成功的合成了6‑甲基吡啶‑2,3‑二羧酸镍配合物，为合成含氮杂环羧酸过渡金属配合物提供了一定的理论依据。

Description

6-甲基吡啶-2,3-二羧酸镍配合物及其制备方法
技术领域
本发明属于金属有机配合物合成技术领域，特别涉及一种6-甲基吡啶-2,3-二羧酸镍配合物及其制备方法。
背景技术
配合物是通过配位键将金属中心离子与有机配体、无机阴离子以及中性配体结合起来而形成结构复杂的分子，凡是含有配位单元的化合物都称作配位化合物。由于配合物的结构复杂多变和性能优异的特点，在光电材料、生物学、磁性材料和催化等领域具有广泛的应用前景，因此设计、合成结构新颖，具有特殊功能的配合物已然成为科研工作者的研究热点。金属离子易于N,S,O,P等含孤对电子原子发生配位，形成具有1D，2D和3D结构的配合物。含氮杂环羧基类配体结合了氮杂环和羧基的特点，其羧酸基团在与金属离子发生配位时，可展现出单齿配位、双齿螯合、不对称螯合、三齿、四齿等多种配位方式，从而能够衍生出构型复杂多样、结构新颖、功能不同的配合物。目前合成配合物常用的方法有：常温溶液法、水热法、溶剂热法、蒸发法、扩散法和电化学法等。
金属离子是影响配合物结构的重要因素，不同的金属离子因为配位数不一样，所形成的配合物的性质也具有不一样。过渡金属配合物在磁性、催化、发光、气体吸附等方面具有广泛的应用。本专利提供了一种以6-甲基吡啶-2,3-二羧酸、过渡金属盐为原料，经溶剂热法，合成化学式为[C8H11NiNO7]n镍配合物的结构及其制备方法。
发明内容
本发明的目的是提供一种6-甲基吡啶-2,3-二羧酸镍配合物及其制备方法。
本发明的思路：利用6-甲基吡啶-2,3-二羧酸为配体和六水合硫酸镍通过溶剂热法获得6-甲基吡啶-2,3-二羧酸镍配合物。
本发明的6-甲基吡啶-2,3-二羧酸镍配合物属于单斜晶系，空间群为P21/n，晶胞参数为α＝90.00°，β＝101.806°，γ＝90.00°， Z＝14。
制备该6-甲基吡啶-2,3-二羧酸镍配合物的具体步骤为：
(1)称量0.25mmol(0.0658g)的NiSO4·6H2O溶于5mL蒸馏水和5mL无水乙醇中，制得硫酸镍溶液。
(2)称量0.1mmol(0.0181g)的6-甲基吡啶-2,3-二羧酸和2mLDMF，加入到25mL的烧杯中，搅拌至溶解，制得6-甲基吡啶-2,3-二羧酸溶液。
(3)将步骤(1)制得的硫酸镍溶液逐滴加入到步骤(2)制得的6-甲基吡啶-2,3-二羧酸溶液中，室温下磁力搅拌30min，用氨水调节pH值至5～7，使溶液澄清，再继续搅拌20min，制得混合溶液。
(4)将步骤(3)制得的混合溶液转入25mL带有聚四氟乙烯瓶的反应釜中，放入烘箱加热至140℃反应72h，然后以5℃/h的速率降温至100℃，再保温12h，关闭烘箱让其在自然状态下冷却至室温后取出反应釜，有淡蓝色块状晶体生成，用丙酮和无水乙醇交替洗涤3次，每次丙酮和无水乙醇的用量均为5mL，然后放入50℃真空干燥箱中，干燥12h，即制得6-甲基吡啶-2,3-二羧酸镍配合物。
本发明的制备方法具有工艺简单、重复性好、绿色环保等优点，成功的合成了6-甲基吡啶-2,3-二羧酸镍配合物，为合成含氮杂环羧酸过渡金属配合物提供了一定的依据。
附图说明
图1是本发明实施例中6-甲基吡啶-2,3-二羧酸镍配合物的晶体结构图。
图2是本发明实施例中6-甲基吡啶-2,3-二羧酸镍配合物的晶体三维堆积图(a方向)。
具体实施方式
实施例：
(1)称量0.25mmol(0.0658g)的NiSO4·6H2O溶于5mL蒸馏水和5mL无水乙醇中，制得硫酸镍溶液。
(2)称量0.1mmol(0.0181g)的6-甲基吡啶-2,3-二羧酸和2mLDMF，加入到25mL的烧杯中，搅拌至溶解，制得6-甲基吡啶-2,3-二羧酸溶液。
(3)将步骤(1)制得的硫酸镍溶液逐滴加入到步骤(2)制得的6-甲基吡啶-2,3-二羧酸溶液中，室温下磁力搅拌30min，用氨水调节pH值至6，使溶液澄清，再继续搅拌20min，制得混合溶液。
(4)将步骤(3)制得的混合溶液转入25mL带有聚四氟乙烯瓶的反应釜中，放入烘箱加热至140℃反应72h，然后以5℃/h的速率降温至100℃，再保温12h，关闭烘箱让其在自然状态下冷却至室温后取出反应釜，有淡蓝色块状晶体生成，用丙酮和无水乙醇交替洗涤3次，每次丙酮的用量为5mL，无水乙醇的用量也为5mL，然后放入50℃真空干燥箱中，干燥12h，得到化学式为[C8H11NiNO7]n镍配合物，即为6-甲基吡啶-2,3-二羧酸镍配合物，产率69％。元素分析理论值(％)：C，32.92；N，4.80；H，3.80；测试值(％)C，32.86；N，4.71；H，3.82。
制得的化学式为[C8H11NiNO7]n镍配合物晶体结构分析：选择尺寸合适的晶体，利用美国Agilent CCD面探单晶衍射仪，温度为293(2)K时，采用Mo-Kα射线以ω扫描方式来收集衍射点。全部晶体数据采用SADABS程序进行Lp因子校正和经验吸收校正，以全矩阵最小二乘法对非氢原子进行修正，氢原子坐标由理论值给出。用Olex2进行结构分析、用Olex2进行结构细化和所有的计算。有关晶体学数据列于表1中，主要键长和键角列于表2中。
表1. 6-甲基吡啶-2,3-二羧酸镍配合物的晶体学数据
表2. 6-甲基吡啶-2,3-二羧酸镍配合物的部分键长和键角(°)
由表1可知，该配合物属于单斜晶系，空间群为P21/n，晶胞参数为 α＝90.00°，β＝101.806°，γ＝90.00°，Z＝14，该配合物基本单元包含一个6-甲基吡啶-2,3-二羧酸阴离子，一个Ni离子以及三个水分子。在该配合物中，中心金属离子Ni分别与一个6-甲基吡啶-2,3-二羧酸配体上羧基的一个氧原子(O4)和来自三个不同水分子中的氧原子(O1A、O2A、O3A)配位。Ni-O键长在之间。该配合物的晶体结构图见图1，a方向堆积图见图2。

Claims (2)

1.一种6-甲基吡啶-2,3-二羧酸镍配合物，其特征在于所述6-甲基吡啶-2,3-二羧酸镍配合物的晶体属于单斜晶系，空间群为P21/n，晶胞参数为a=7.83532(16)Å，b=13.2232(3)Å，c=10.0482(2)Å，α=90.00°，β=101.806°，γ=90.00°，V=1019.05(4) Å3，Z=14。
2.一种如权利要求1所述的6-甲基吡啶-2,3-二羧酸镍配合物的制备方法，其特征在于具体步骤为：
（1）称量0.25mmol的NiSO4·6H2O溶于5mL蒸馏水和5mL无水乙醇中，制得硫酸镍溶液；
（2）称量0.1mmol的6-甲基吡啶-2,3-二羧酸和2mLDMF，加入到25mL的烧杯中，搅拌至溶解，制得6-甲基吡啶-2,3-二羧酸溶液；
（3）将步骤（1）制得的硫酸镍溶液逐滴加入到步骤（2）制得的6-甲基吡啶-2,3-二羧酸溶液中，室温下磁力搅拌30min，用氨水调节pH值至5~7，使溶液澄清，再继续搅拌20min，制得混合溶液；
（4）将步骤（3）制得的混合溶液转入25mL带有聚四氟乙烯瓶的反应釜中，放入烘箱加热至140℃反应72h，然后以5℃/h的速率降温至100℃，再保温12h，关闭烘箱让其在自然状态下冷却至室温后取出反应釜，有淡蓝色块状晶体生成，用丙酮和无水乙醇交替洗涤3次，每次丙酮和无水乙醇的用量均为5mL，然后放入50℃真空干燥箱中，干燥12h，即制得6-甲基吡啶-2,3-二羧酸镍配合物。
CN201811070171.6A 2018-09-13 2018-09-13 6-甲基吡啶-2,3-二羧酸镍配合物及其制备方法 Pending CN109232405A (zh)

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CN112723791A (zh) * 2020-12-29 2021-04-30 江苏恒力化纤股份有限公司 一种聚酯纤维增强沥青混合料及其制备方法
CN112723791B (zh) * 2020-12-29 2022-03-18 江苏恒力化纤股份有限公司 一种聚酯纤维增强沥青混合料及其制备方法

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