[(dipicolinate)Fe(II)(OH2)3] | 168288-72-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [(dipicolinate)Fe(II)(OH2)3]
• CAS: 168288-72-0
• 化学式: C₇H₉FeNO₇
• 分子量: 274.998
• InChiKey: NNFOFHMCQAPXEA-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [(dipicolinate)Fe(II)(OH2)3] 在 air 作用下， 以 水 为溶剂， 生成 [(dipicolinate)Fe(III)(H2O)(μ-OH)2Fe(III)(dipicolinate)(OH2)]
  参考文献：
  名称：

  Chemistry of Iron with Dipicolinic Acid. 4. Mixed-Ligand Complexes of Iron(III) and Related Compounds

  摘要：

  The chemistry of iron(III)-2,6-pyridinedicarboxylic (dipicolinic, dipicH(2)) acid complexes with various ligands has been explored. Reaction of [(dipic)Fe-II(OH2)(3)] with bromine water at room temperature led to the binuclear [(dipic)(H2O)Fe-III(mu-OH)(2)Fe-III(OH2)(dipic)] complex in high yield. This dimer reacted with HX to give [(dipic)-(X)Fe-III(OH2)(2)] (X = Br or Cl(1)). Reaction of 1 with 2,4-pentanedione (acacH) yielded [(dipic)(acac)Fe-III-(OH2)] (2), and reaction with 1,10-phenanthroline (phen) gave [(dipic)(Cl)Fe-III(phen)] (3). The reaction of [(dipic)Fe-II(OH2)(3)] with polypyridyl tridentate ligands L did not yield [(dipic)Fe-II(L)] but [Fe(II)L(2)](2+) with [(dipic)(2)Fe-III](-) as counterions. For instance, with L = 2,2':6',2''-terpyridine (tpy), the reaction gave [Fe-II(tpy)(2)][(dipic)(2)-Fe-III](2) (4) and with L = tetrakis(2-pyridyl)pyrazine (tppz) it gave {[Fe-II(tppz)(2)][(dipic)(2)Fe-III](3)}.(H3O) (5) The crystallographic structures of 1-5 have been solved: 1, monoclinic, C2/c, a = 6.015(6) Angstrom, b = 18.74(1) Angstrom, c = 9.81(1) Angstrom, beta = 105.5(6)degrees, V = 1062(2) Angstrom(3), Z = 4; 2 . 0.5C(2)H(5)OH, monoclinic, C2/c, a = 11.510(3) Angstrom, b = 12.734(4) Angstrom, c = 21.819(4) Angstrom, beta = 98.27(2)degrees, V = 3165(7) Angstrom(3), Z = 8; 3 . CH2Cl2, monoclinic, P2(1)/n, a = 9.083-(2) Angstrom, b = 12.899(2) Angstrom, c = 17.490(4) Angstrom, beta = 96.70(8)degrees, V = 2035(2) Angstrom(3), Z = 4; 4 . H2O . 3CH(3)CN, monoclinic, P2(1)/n, a = 8.947(2) Angstrom, b = 37.37(2) Angstrom, c = 18.97(2) Angstrom, beta = 100.07(8)degrees, V = 6243(8) Angstrom(3), Z = 4; 5 . 11H(2)O, monoclinic, C2/c, a = 32.46(3) Angstrom, b = 28.30 Angstrom, c = 27.59(2) Angstrom, beta = 126.34(6)degrees, V = 20417 Angstrom(3) and Z = 8.

  DOI：

  10.1021/ic00125a012
• 作为产物：
  描述：

  吡啶-2,6-二甲酸 、 ammonium iron(II) sulfate hexahydrate 在 NaOH 作用下， 以 水 为溶剂， 以98%的产率得到[(dipicolinate)Fe(II)(OH2)3]
  参考文献：
  名称：

  Chemistry of Iron with Dipicolinic Acid. 1. Mononuclear Complexes of Iron(II) or Iron(III)

  摘要：

  The synthesis, characterization, and properties of dipicolinic acid (dipicH(2)) derivatives are described. Neutralization of hot aqueous concentrated solutions of dipicH(2) showed successive gelifications-liquefaction processes. Isolation of crystalline-phase [(dipicH)(dipicH(2))]Na . 3H(2)O (1) revealed an intricate network of interactions among the acid, the sodium cation, and water molecules. [(dipic)Fe-II(OH2)(3)] (2) was prepared in nearly quantitative yield by reaction of dipic(2-) with an excess of ammonium iron(II) sulfate hexahydrate. 2 reacts with bases (cation(+))OH- to give [(dipic)(2)Fe-II](cation)(2) in high yields (3: cation = NProp(4)(+)). [(dipic)(2)Fe-II](2-) was solvatochromic, due to interactions between the dipic oxygen lone pairs and solvents. Air or bromine water oxidation of 3 yielded quantitatively the iron(III) complexes [(dipic)(2)Fe-III](cation) (4: cation = Na+). The crystal structures of 1-4 have been determined. Comparison of the geometries of 3 and 4 showed that the iron-nitrogen bond lengths are insensitive to iron oxidation states whereas the iron-oxygen distances decrease by 0.15 Angstrom upon iron oxidation. This allowed the calculation of the intervalence band energy in dipic mixed-valence systems. 1 crystallized in the triclinic space group with cell constants a = 6.882(1) Angstrom, b = 11.125(2)Angstrom, c = 11.171(2) Angstrom, alpha = 82.65 (4)degrees, beta = 82.13(4)degrees, gamma = 87.38(6)degrees, V = 844(3) Angstrom(3), and Z = 2. 2 was found in the monoclinic space group P2(1)/c with alpha = 12.410(4) Angstrom, b = 9.314(4) Angstrom, c = 8.746(3) Angstrom, beta = 101.44(4)degrees, V = 990(1) Angstrom(3) and Z = 4. 3 . 7.25H(2)O occurred in the monoclinic space group P2(1)/c with a = 15.320(9) Angstrom, b = 33.83(2) Angstrom, c = 17.24(1) Angstrom, beta = 91.55(4)degrees, V = 8932(9) Angstrom(3), and with Z = 8. 4 . H2O crystallized in the monoclinic space group Cc with a = 14.95(1) Angstrom, b = 12.45(3) Angstrom, c = 8.663(5) Angstrom, beta = 92.99(4)degrees, V = 609(4) Angstrom(3), and Z = 4.

  DOI：

  10.1021/ic00125a009

文献信息

• Chemistry of Iron with Dipicolinic Acid. 2. Bridging Role of Carboxylate Groups in Solid State Structures
  作者：P. Laine、A. Gourdon、J.-P. Launay

  DOI：10.1021/ic00125a010

  日期：1995.10

  This paper reports the syntheses, structures, and properties of iron(II) and dipicolinic acid oligonuclear complexes prepared in slightly acidic medium. Acidification of [(dipic)(2)Fe-II]Na-2 . 2H(2)O or reaction of dipicH(2) (2,6-pyridine dicarboxylic acid) and Mohr's salt (ammonium iron(II) sulfate hexahydrate) at pH 5.3 yielded [(dipic)(2)(dipicH)(2)Fe(II)3(OH2)4].2H2O (1), which consists of two [(dipic)(dipicH)Fe-II] fragments sharing one oxygen atom each with a [Fe-II(OH2)(4)O-2] subunit. Reaction of dipicH(2) and Mohr's salt at pH 6.25 gave the dinuclear species [(dipic)(2)Fe(II)2(OH2)(5)] (2), in which a [(dipic)(2)Fe-II] moiety shares one oxygen atom with a [Fe-II(OH2)(5)O] fragment. When the reaction was conducted at pH 5.85, the reaction gave crystals of [(dipic)(4)(dipicH(2))(2)Fe(II)3(OH2)(6)](NH4)(2) . 4H(2)O (3), which contains, in the unit cell, both the reactants [Fe-II(OH2)(6)](2+) and dipicH(2) and the product [(dipic)(2)Fe-II](2-). At pH 5.65, the reaction yielded crystals of [(dipic)(10)(dipicH)(6)Fe-13(II)(OH2)(24)]. 13H(2)O (4), which contains, in the same unit cell, one trinuclear anionic complex [(dipic)(2)Fe-II]-[Fe-II(OH2)(4)]-[Fe-II(dipic)(2)]}(2-), two doubly protonated cationic dinuclear complexes [(dipicH)Fe-II(dipicH)]-[Fe-II(OH2)(5)]}(2+), two singly protonated cationic dinuclear complexes [(dipicH)Fe-II(dipic)]-[Fe-II(OH2)(5)](+), and two mononuclear anionic complexes [(dipic)(2)Fe-II](2-). The crystal structures for 1-4 have been solved: 1 crystallized in the monoclinic space group P2(1)/n with a = 8.956(3) Angstrom, b = 15.083(7) Angstrom Angstrom, c = 12.504(5) Angstrom, beta = 90.42(8)degrees, V = 1689(1) Angstrom(3), and Z = 2. 2 was found in the triclinic space group P (1) over bar with a = 8.339(2) Angstrom, b = 9.711(2) Angstrom, c = 13.994(4) Angstrom, alpha = 100.75((4)degrees, beta = 101.99(2)degrees, gamma = 97.04(2)degrees, V = 1076(13) Angstrom(3), and Z = 2. 3 crystallized in the triclinic space group P (1) over bar with a = 10.759(2) Angstrom, b = 10.917(3) Angstrom, c = 12.653(3) Angstrom, alpha = 105.62(2)degrees, beta = 96.25(2)degrees, gamma 103.25(2)degrees, V = 1370(11) Angstrom(3), and Z = 1.4 was found in the triclinic space group P (1) over bar with a = 15.700(4) Angstrom, b = 15.811(4) Angstrom, c = 16.558(5) Angstrom, alpha = 85.49(2)degrees, beta = 67.75(2)degrees, gamma = 76.47(3)degrees, V = 3698(15) Angstrom(3), and Z = 1.