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Revisiting 2-chloro-4-nitroaniline: analysis of intricate supramolecular ordering of a triclinic polymorph featuring a high Z value and strong second harmonic generation
CrystEngComm ( IF 2.6 ) Pub Date : 2020-07-01 , DOI: 10.1039/d0ce00582g Volodymyr Medviediev 1, 2, 3, 4 , Svitlana Shishkina 5, 6, 7, 8, 9 , A. O. Ribalka 8, 9, 10 , Jan K. Zaręba 4, 11, 12, 13, 14 , Marek Drozd 1, 2, 3, 4 , Marek Daszkiewicz 1, 2, 3, 4
CrystEngComm ( IF 2.6 ) Pub Date : 2020-07-01 , DOI: 10.1039/d0ce00582g Volodymyr Medviediev 1, 2, 3, 4 , Svitlana Shishkina 5, 6, 7, 8, 9 , A. O. Ribalka 8, 9, 10 , Jan K. Zaręba 4, 11, 12, 13, 14 , Marek Drozd 1, 2, 3, 4 , Marek Daszkiewicz 1, 2, 3, 4
Affiliation
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Polymorphism represents an expanding area of crystal engineering and an opportunity for discovery of materials with interesting properties, thus giving new perspectives for “old”, well-known compounds known by chemists for decades. In this work, we revisit 2-chloro-4-nitroaniline (2Cl4na) for which the crystal structure was first determined as early as 1965. Our failed trials to reproduce the original orthorhombic phase of 2Cl4na led to the determination of its new triclinic polymorph. Synthetic screening indicated that 2Cl4na can be obtained from several solvent mixtures as well as by slow cooling of the melted sample. This polymorph crystallizes in the non-centrosymmetric space group P1 with a = 3.7755(2) Å, b = 13.5798(7) Å, c = 28.554(1) Å, α = 89.503(4)°, β = 88.612(4)° and γ = 86.402(4)° lattice parameters and Z = 8. This high number of crystallographically equivalent molecules in the independent part of the unit cell resulted in an unusual supramolecular arrangement of this compound. Energy vector diagrams indicate that the structure of the previously known orthorhombic polymorph is columnar, whereas the triclinic one is quasi-isotropic. Calculations of lattice energies by an ab initio method with periodic boundary conditions showed that the triclinic polymorph is more stable by 0.89 kcal mol−1 in comparison to the orthorhombic one. The cooperative character of weak hydrogen bonds and stacking interactions was suggested as a key governing factor in the crystal growth of needle-like crystals. With the use of the Kurtz–Perry test we also demonstrate that this new polymorphic form of 2Cl4na produces second harmonic generation (SHG) that is 2 times higher than that obtained from potassium dihydrogen phosphate (KDP) upon irradiation with an 800 nm laser beam. Alongside the strong SHG, greenish-yellow two-photon excited fluorescence is also observed.
中文翻译：
回顾2-氯-4-硝基苯胺：分析具有高Z值和强二次谐波的三斜晶型的复杂超分子有序性
多态性代表了晶体工程领域的扩大，并为发现具有有趣特性的材料提供了机会，从而为化学家数十年来所熟知的“古老的”众所周知的化合物提供了新的视角。在这项工作中，我们回顾了早在1965年首次确定晶体结构的2-氯-4-硝基苯胺（2Cl4na）。我们未能成功地复制2Cl4na的原始正交晶相，导致了其新三斜晶型的确定。合成筛选表明，可以从几种溶剂混合物以及通过缓慢冷却熔融样品获得2Cl4na。该多晶型物在a = 3.7755（2）Å，b = 13.5798（7）Å，c的非中心对称空间群P 1中结晶= 28.554（1）Å，α = 89.503（4）°，β = 88.612（4）°和γ = 86.402（4）°晶格参数，Z = 8。晶胞导致该化合物异常的超分子排列。能量向量图表明，先前已知的正交多晶型物的结构是柱状的，而三斜晶型的是准各向同性的。通过具有周期性边界条件的从头算方法的晶格能量计算表明，三斜晶型比0.89 kcal mol -1更稳定与斜方型相比。弱氢键和堆积相互作用的协同特征被认为是针状晶体晶体生长的关键控制因素。通过使用Kurtz-Perry测试，我们还证明了这种新的多晶型2Cl4na在800 nm激光束照射下产生的二次谐波（SHG）比从磷酸二氢钾（KDP）获得的高2倍。除了强烈的SHG，还观察到绿黄色的双光子激发荧光。
更新日期：2020-08-03
中文翻译：
回顾2-氯-4-硝基苯胺：分析具有高Z值和强二次谐波的三斜晶型的复杂超分子有序性
多态性代表了晶体工程领域的扩大，并为发现具有有趣特性的材料提供了机会，从而为化学家数十年来所熟知的“古老的”众所周知的化合物提供了新的视角。在这项工作中，我们回顾了早在1965年首次确定晶体结构的2-氯-4-硝基苯胺（2Cl4na）。我们未能成功地复制2Cl4na的原始正交晶相，导致了其新三斜晶型的确定。合成筛选表明，可以从几种溶剂混合物以及通过缓慢冷却熔融样品获得2Cl4na。该多晶型物在a = 3.7755（2）Å，b = 13.5798（7）Å，c的非中心对称空间群P 1中结晶= 28.554（1）Å，α = 89.503（4）°，β = 88.612（4）°和γ = 86.402（4）°晶格参数，Z = 8。晶胞导致该化合物异常的超分子排列。能量向量图表明，先前已知的正交多晶型物的结构是柱状的，而三斜晶型的是准各向同性的。通过具有周期性边界条件的从头算方法的晶格能量计算表明，三斜晶型比0.89 kcal mol -1更稳定与斜方型相比。弱氢键和堆积相互作用的协同特征被认为是针状晶体晶体生长的关键控制因素。通过使用Kurtz-Perry测试，我们还证明了这种新的多晶型2Cl4na在800 nm激光束照射下产生的二次谐波（SHG）比从磷酸二氢钾（KDP）获得的高2倍。除了强烈的SHG，还观察到绿黄色的双光子激发荧光。
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