X-RAY, FOURIER-TRANSFORM INFRARED, H-1 AND C-13 NUCLEAR-MAGNETIC-RESONANCE, AND PM3 STUDIES OF (N-H...N)+ AND (O-H...O)- INTRAMOLECULAR HYDR OGEN BONDS IN A COMPLEX OF 1,8-BIS(DIMETHYLAMINO)NAPHTHALENE WITH MALEIC-ACID
X-RAY, FOURIER-TRANSFORM INFRARED, H-1 AND C-13 NUCLEAR-MAGNETIC-RESONANCE, AND PM3 STUDIES OF (N-H...N)+ AND (O-H...O)- INTRAMOLECULAR HYDR OGEN BONDS IN A COMPLEX OF 1,8-BIS(DIMETHYLAMINO)NAPHTHALENE WITH MALEIC-ACID
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DOI：
10.1039/ft9938902085
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发表时间：
1993-06-21
期刊：
影响因子：
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通讯作者：
SZAFRAN, M
中科院分区：
文献类型：
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作者：
BARTOSZAK, E;DEGASZAFRAN, Z;SZAFRAN, M
标题化合物的晶体结构经X射线衍射分析确定。质子化1，8-双（二甲氨基）萘阳离子（DMAN+H）中的（NHN）+桥的分子内氢键长度为2.606（3）埃，马来酸氢阴离子（HM-）中的（OHO）-桥的分子内氢键长度为2.401（4）埃。氢键是不对称的，不是严格线性的：NHN为157（3）度，OHO为170（5）度。N-H的几何结构N和0-H研究的阳离子和阴离子的0桥主要由其组成原子的球形排斥作用所控制，在二阶导数光谱中分离了马来酸氢（氘）钾吸收红外光谱中的重叠带。与含有分子间氢键的其他A型酸盐（Δ nu几乎等于20-35 cm-1）相比，马来酸氢离子中的面内模式与骨架模式的强混合导致nu（C=0）带的更大分离（Δ nu几乎等于115 cm-1）。所观察到的溶剂对IR吸收的影响的缺乏表明，在马来酸氢四丁基铵和马来酸氢1，8-双（二甲氨基）萘中的氢键不是极端可极化的。H-1和C-13 NMR化学位移的研究化合物进行了测量，并确定在二维（2D）实验。1H-1 NMR谱显示在约100 nm处有两个窄信号。19.5和18.7ppm，分别归因于OHO和NHN质子。阳离子和阴离子的结构参数也确定了量子力学计算与半经验MNDO-PM 3方法。
The crystal structure of the title compound has been determined by X-ray analysis. The intramolecular hydrogen bond lengths are 2.606(3) angstrom for the (NHN)+ bridge in protonated 1,8-bis(dimethylamino)naphthalene cation (DMAN+H) and 2.401(4) angstrom for the (OHO)- bridge in the hydrogen maleate anion (HM-), The H-bonds are asymmetrical and not strictly linear: NHN, 157(3)-degrees and OHO, 170(5)-degrees. The geometries of the N-H ... N and 0-H ... 0 bridges of the investigated cation and anion are dominated by the spherical repulsions of their constituent atoms.The overlapping bands in the absorbance IR spectra of potassium hydrogen (deuteron) maleate are separated in the second-derivative spectra. The strong mixing of the in-plane modes with skeletal modes in the hydrogen maleate ion causes a larger separation (DELTAnu almost-equal-to 115 cm-1) of the nu(C=0) bands in comparison with those in other type A acid salts containing intermolecular hydrogen bonds (DELTAnu almost-equal-to 20-35 cm-1). The observed lack of solvent effect on the IR absorption suggests that the hydrogen bonds in tetrabutylammonium hydrogen maleate and 1,8-bis(dimethylamino)naphthalene hydrogen maleate are not extremely polarizable. H-1 and C-13 NMR chemical shifts of the investigated compound were measured and identified in two-dimensional (2D) experiments. The H-1 NMR spectra show two narrow signals at ca. 19.5 and 18.7 ppm due to the OHO and NHN protons, respectively. The structural parameters of the cation and anion were also determined by quantum-mechanical calculations with the semiempirical MNDO-PM3 method.