2-hydroxy-5-nitrophenyl-(2-pyridyl)methaneimine | 29644-92-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 2-hydroxy-5-nitrophenyl-(2-pyridyl)methaneimine
• 英文别名: 4-nitro-2-pyridin-2-ylmethyleneamino-phenol；Picolinaldehyd-2-hydroxy-5-nitroanil；4-Nitro-2-(pyridin-2-ylmethylideneamino)phenol
• CAS: 29644-92-6
• 化学式: C₁₂H₉N₃O₃
• 分子量: 243.222
• InChiKey: OXDZBSPFBVPRHP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  91.3
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-hydroxy-5-nitrophenyl-(2-pyridyl)methaneimine 、 iron(II) tetrafluoroborate hexahydrate 在 三乙胺 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以61%的产率得到Fe^II(pap-5NO₂)₂
  参考文献：
  名称：

  Fe^II(pap-5NO₂)₂and Fe^II(qsal-5NO₂)₂Schiff-Base Spin-Crossover Complexes: A Rare Example with Photomagnetism and Room-Temperature Bistability

  摘要：

  We focus here on the properties of Fe complexes formed with Schiff bases involved in the chemistry of FeIII spin-transition archetypes. The neutral Fe(pap-5NO(2))(2) (1) and Fe(qsal-5NO(2))(2).Solv (2 and 2.Solv) compounds (Solv = 2H(2)O) derive from the reaction of FeII salts with the condensation products of pyridine-2-carbaldehyde with 2-hydroxy-5-nitroaniline (Hpap-5NO(2)) or 5-nitrosalicylaldehyde with quinolin-8-amine (Hqsal-5NO(2)), respectively. While the Fe(qsal-5NO(2))(2).Solv solid is essentially low spin (S = 0) and requires temperatures above 300 K to undergo a S = 0 <-> S = 2 spin-state switching, the Fe(pap-5NO(2))(2) one presents a strongly cooperative first-order transition (T-down arrow = 291 K, T? = 308 K) centered at room temperature associated with a photomagnetic effect at 10 K (TLIESST = 58 K). The investigation of these magnetic behaviors was conducted with single-crystal X-ray diffraction (1, 100 and 320 K; 2, 100 K), Mossbauer, IR, UVvis (1 and 2.Solv), and differential scanning calorimetry (1) measurements. The Mossbauer analysis supports a description of these compounds as FeII Schiff-base complexes and the occurrence of a metal-centered spin crossover process. In comparison with FeIII analogues, it appears that an expanded coordination sphere stabilizes the valence 2+ state of the Fe ion in both complexes. Strong hydrogen-bonding interactions that implicate the phenolato group bound to FeII promote the required extra-stabilization of the S = 2 state and thus determines the spin transition of 1 centered at room temperature. In the lattice, the hydrogen-bonded sites form infinite chains interconnected via a three-dimensional network of intermolecular van der Waals contacts and pp interactions. Therefore, the spin transition of 1 involves the synergetic influence of electrostatic and elastic interactions, which cause the enhancement of cooperativity and result in the bistability at room temperature.

  DOI：

  10.1021/ic5027043
• 作为产物：
  描述：

  吡啶-2-甲醛 、 2-氨基-4-硝基苯酚 以 甲苯 为溶剂， 反应 8.0h， 生成 2-hydroxy-5-nitrophenyl-(2-pyridyl)methaneimine
  参考文献：
  名称：

  Dinuclear heptacoordinate dibutyltin (IV) complexes derived from Schiff bases and dicarboxylates: Synthesis, cytotoxicity, and antioxidant activity

  摘要：

  The synthesis of dinuclear dibutyltin (IV) complexes 1a-4d, prepared in one pot by the reaction of 2-amino-4-R-phenol (R = H, Me, Cl, NO2), 2-pyridinecarboxaldehyde, dicarboxylic (2,5-pyridinedicarboxylic, terephthalic, isophthalic, and oxalic) acids and dibutyltin oxides, is described. The complexes were characterized using IR, MS and H-1, C-13 and Sn-119 NMR techniques. The molecular structures of complexes 1a, 1c and 4c were established using X-Ray diffraction, and these complexes exhibited a distorted pentagonal-bipyramidal (BPT) geometry in which the equatorial plane consisted of three oxygen atoms and two nitrogen atoms, and the butyl groups occupied the axial positions. The cytotoxicity of the terephthalic acid derivatives 1a-d in HCT-15 colon cancer, MCF7 breast cancer and PC3 prostate cancer cell lines was investigated in vitro. The antioxidant activity of these complexes was also measured using the DPPH (1,1-diphenyl-2-picrylhydrazyl) assay. (C) 2013 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2013.03.038

文献信息

• Penta- and heptacoordinated tin(IV) compounds derived from pyridine Schiff bases and 2-pyridine carboxylate: Synthesis and structural characterization
  作者：Alejandro Ramírez-Jiménez、Elizabeth Gómez、Simón Hernández

  DOI：10.1016/j.jorganchem.2009.04.035

  日期：2009.8

  The synthesis of the Sn(IV)-complexed, Schiff base derivatives 1a–1l, prepared in one pot by the reaction of 2-amino-4-R-phenol (R = H, Me, Cl, NO2), 2-pyridinecarboxaldehyde, 2-picolinic acid and dimethyl-, dibutyl-, and diphenyltin oxides, is described. The complexes were characterized by IR, MS, 1H, 13C, 119Sn NMR. Suitable crystals of 1e and 1h enabled us to use X-ray diffraction to determine their

  一锅中通过2-氨基-4-R-苯酚（R = H，Me，Cl，NO 2），2-的反应制备的Sn（IV）络合Schiff碱衍生物1a - 1l的合成描述了吡啶甲醛，2-吡啶甲酸和二甲基-，二丁基-和二苯基锡的氧化物。通过IR，MS，1 H，13 C，119 Sn NMR对络合物进行表征。合适的1e和1 h晶体使我们能够使用X射线衍射来确定其分子结构，这些分子表现出五边形-双锥体的几何形状，其中丁基占据轴向位置，而氮和氧原子占据赤道位置。席夫碱的反应2与二丁基氧化锡导致五配复杂，2H，通过添加甲醇到C N键。2-氨基-4-硝基苯酚，二丁基氧化锡和2-吡啶甲醛的反应发生了不寻常的还原-氧化反应，生成了相应的胺3h和酰胺4h锡（IV）衍生物。两种结构都是通过X射线晶体学确定的，并呈现出扭曲的双锥三角（BPT）几何形状。
• Dinuclear heptacoordinate dibutyltin (IV) complexes derived from Schiff bases and dicarboxylates: Synthesis, cytotoxicity, and antioxidant activity
  作者：Alejandro Ramírez-Jiménez、Rolando Luna-García、Armando Cortés-Lozada、Simón Hernández、Teresa Ramírez-Apan、Antonio Nieto-Camacho、Elizabeth Gómez

  DOI：10.1016/j.jorganchem.2013.03.038

  日期：2013.8

  The synthesis of dinuclear dibutyltin (IV) complexes 1a-4d, prepared in one pot by the reaction of 2-amino-4-R-phenol (R = H, Me, Cl, NO2), 2-pyridinecarboxaldehyde, dicarboxylic (2,5-pyridinedicarboxylic, terephthalic, isophthalic, and oxalic) acids and dibutyltin oxides, is described. The complexes were characterized using IR, MS and H-1, C-13 and Sn-119 NMR techniques. The molecular structures of complexes 1a, 1c and 4c were established using X-Ray diffraction, and these complexes exhibited a distorted pentagonal-bipyramidal (BPT) geometry in which the equatorial plane consisted of three oxygen atoms and two nitrogen atoms, and the butyl groups occupied the axial positions. The cytotoxicity of the terephthalic acid derivatives 1a-d in HCT-15 colon cancer, MCF7 breast cancer and PC3 prostate cancer cell lines was investigated in vitro. The antioxidant activity of these complexes was also measured using the DPPH (1,1-diphenyl-2-picrylhydrazyl) assay. (C) 2013 Elsevier B. V. All rights reserved.
• Fe^II(pap-5NO₂)₂and Fe^II(qsal-5NO₂)₂Schiff-Base Spin-Crossover Complexes: A Rare Example with Photomagnetism and Room-Temperature Bistability
  作者：Olga Iasco、Eric Rivière、Régis Guillot、Marylise Buron-Le Cointe、Jean-François Meunier、Azzedine Bousseksou、Marie-Laure Boillot

  DOI：10.1021/ic5027043

  日期：2015.2.16

  We focus here on the properties of Fe complexes formed with Schiff bases involved in the chemistry of FeIII spin-transition archetypes. The neutral Fe(pap-5NO(2))(2) (1) and Fe(qsal-5NO(2))(2).Solv (2 and 2.Solv) compounds (Solv = 2H(2)O) derive from the reaction of FeII salts with the condensation products of pyridine-2-carbaldehyde with 2-hydroxy-5-nitroaniline (Hpap-5NO(2)) or 5-nitrosalicylaldehyde with quinolin-8-amine (Hqsal-5NO(2)), respectively. While the Fe(qsal-5NO(2))(2).Solv solid is essentially low spin (S = 0) and requires temperatures above 300 K to undergo a S = 0 <-> S = 2 spin-state switching, the Fe(pap-5NO(2))(2) one presents a strongly cooperative first-order transition (T-down arrow = 291 K, T? = 308 K) centered at room temperature associated with a photomagnetic effect at 10 K (TLIESST = 58 K). The investigation of these magnetic behaviors was conducted with single-crystal X-ray diffraction (1, 100 and 320 K; 2, 100 K), Mossbauer, IR, UVvis (1 and 2.Solv), and differential scanning calorimetry (1) measurements. The Mossbauer analysis supports a description of these compounds as FeII Schiff-base complexes and the occurrence of a metal-centered spin crossover process. In comparison with FeIII analogues, it appears that an expanded coordination sphere stabilizes the valence 2+ state of the Fe ion in both complexes. Strong hydrogen-bonding interactions that implicate the phenolato group bound to FeII promote the required extra-stabilization of the S = 2 state and thus determines the spin transition of 1 centered at room temperature. In the lattice, the hydrogen-bonded sites form infinite chains interconnected via a three-dimensional network of intermolecular van der Waals contacts and pp interactions. Therefore, the spin transition of 1 involves the synergetic influence of electrostatic and elastic interactions, which cause the enhancement of cooperativity and result in the bistability at room temperature.