A new organic–inorganic hybrid salt [L]2[MnCl4] (I) where L + is the 2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridinium cation, is built of discrete organic cations and tetrachloridomanganate(II) anions. The L + cation was formed in situ in the oxidative cyclocondensation of 2-pyridinecarbaldehyde and CH3NH2·HCl in methanol. The structure was refined as a two-component twin using PLATON (Spek, 2020) to de-twin the data. The twin law (−1 0 0 0 − 1 0 0.5 0 1) was applied in the refinement where the twin component fraction refined to 0.155 (1). The compound crystallizes in the space group P21/c with two crystallographically non-equivalent cations in the asymmetric unit, which possess similar structural conformations. The fused pyridinium and imidazolium rings of the cations are virtually coplanar [dihedral angles are 0.89 (18) and 0.78 (17)°]; the pendant pyridyl rings are twisted by 36.83 (14) and 36.14 (13)° with respect to the planes of the remaining atoms of the cations. The tetrahedral MnCl4 2– anion is slightly distorted with the Mn—Cl distances falling in the range 2.3469 (10)–2.3941 (9) Å. The distortion value of 0.044 relative to the ideal tetrahedron was obtained by continuous shape measurement (CShM) analysis. In the crystal, the cations and anions form separate stacks propagating along the a-axis direction. The organic cations display weak π–π stacking. The anions, which are stacked identically one above the other, demonstrate loose packing; the minimum Mn...Mn separation in the cation stack is approximately 7.49 Å. The investigation of the fluorescent properties of a powdered sample of (I) showed no emission. X-band EPR data for (I) at 293 and 77 K revealed broad fine structure signals, indicating moderate zero-field splitting.

中文翻译：

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咪唑并[1,5-a]吡啶基杂化盐(C13H12N3)2[MnCl4]的晶体结构


一种新型有机-无机杂化盐 [L]2[MnCl4] (I)，其中 L+ 是 2-甲基-3-(吡啶-2-基)咪唑并[1,5-a]吡啶鎓阳离子，由离散的有机盐构成阳离子和四氯化锰(II) 阴离子。 L+阳离子是在2-吡啶甲醛和CH3NH2·HCl在甲醇中氧化环缩合反应中原位形成的。使用 PLATON（Spek，2020）对数据进行解孪，将该结构细化为双组件孪生。细化中应用孪晶定律 (−1 0 0 0 − 1 0 0.5 0 1)，其中孪晶组分分数细化至 0.155 (1)。该化合物在空间群 P21/c 中结晶，不对称单元中具有两个晶体学上不等价的阳离子，它们具有相似的结构构象。阳离子的稠合吡啶鎓环和咪唑鎓环实际上是共面的[二面角为0.89(18)°和0.78(17)°]；吡啶基侧环相对于其余阳离子原子的平面扭转 36.83 (14) 和 36.14 (13)°。四面体 MnCl42- 阴离子稍微扭曲，Mn-Cl 距离落在 2.3469 (10)–2.3941 (9) Å 范围内。通过连续形状测量（CShM）分析得到相对于理想四面体的畸变值为0.044。在晶体中，阳离子和阴离子形成沿a轴方向传播的单独的堆叠。有机阳离子表现出弱的π-π堆积。阴离子彼此堆叠相同，表现出松散堆积；阳离子堆中的最小 Mn...Mn 间距约为 7.49 Å。 (I)的粉末样品的荧光特性的研究表明没有发射。 (I) 在 293 和 77 K 的 X 波段 EPR 数据揭示了广泛的精细结构信号，表明中等的零场分裂。