| 要約: | A series of novel salts based on aromatic polyamines and 2,3-pyrazinedicarboxylic acid, such as C<sub>10</sub>H<sub>12</sub>N<sub>6</sub>O<sub>5</sub> (<b>1</b>), C<sub>10</sub>H<sub>9</sub>ClN<sub>6</sub>O<sub>4</sub> (<b>2</b>), C<sub>11</sub>H<sub>10</sub>N<sub>8</sub>O<sub>4</sub> (<b>3</b>), and C<sub>14</sub>H<sub>17</sub>N<sub>16</sub>O<sub>5.5</sub> (<b>4</b>) or 3,4-thiophenedicarboxylic acid, such as C<sub>10</sub>H<sub>10</sub>N<sub>4</sub>O<sub>4</sub>S (<b>5</b>), C<sub>10</sub>H<sub>9</sub>ClN<sub>4</sub>O<sub>4</sub>S (<b>6</b>), and C<sub>10</sub>H<sub>10</sub>N<sub>4</sub>O<sub>4</sub>S<sub>2</sub> (<b>7</b>), were synthesized and characterized by single-crystal X-ray diffraction. All compounds crystallize in a monoclinic space group. The structure was subjected to complex Hirshfeld surface analysis, molecular electrostatic potential, enrichment ratio, and energy framework calculations. The influence of different cations on the packing of 3-carboxypyrazine-2-carboxylate and 4-carboxythiophene-3-carboxylate anions in the crystal lattice was studied. O<sup>…</sup>H/H<sup>…</sup>O interactions are the main contributor in all crystals. In addition, in a series of pyrazine-containing structures, N(C)<sup>…</sup>H/H<sup>…</sup>N(C) interactions have relevance, while in a series of thiophene-based compounds, C<sup>…</sup>H/H<sup>…</sup>C and S<sup>…</sup>H(O)/H(O)<sup>…</sup>S. In addition, Cl-based interactions are observed in compound <b>2</b>. According to the enrichment ratio calculations, O<sup>…</sup>H/H<sup>…</sup>O and C<sup>…</sup>C are the most preferable interactions in all structures. The energy frameworks are dominated by the dispersive contribution, only in compound <b>3</b> is the electrostatic term dominant. The analyzed structures reveal intra- and intermolecular recurrent supramolecular synthons. In both series of crystals, the robust H-bonded centrosymmetric dimer <i>R</i><sup>2</sup><sub>2</sub>(8) as homo- or as heterosynthon (in compounds <b>2</b>, <b>3</b>, <b>6</b>, and <b>7</b>) and the intramolecular synthon <i>S</i>(7) generated by O-H<sup>…</sup>O interactions (in compounds <b>2</b>, <b>6</b>, and <b>7</b>) are present. The supramolecular patterns formed by π<sup>…</sup>π (C<sup>…</sup>C) and C-O(Cl,S)<sup>…</sup>C are also noticeable. Notably, a dual synthon linking the supramolecular chain via π<sup>…</sup>π interactions and the homosynthon <i>R</i><sup>2</sup><sub>2</sub>(8) via N-H<sup>…</sup>N interactions is visible in both series of new salts. A library of H-bonding motifs at diverse levels of supramolecular architecture is provided. We extended the analysis of intramolecular H-bonding motifs to similar structures deposited in the Cambridge Structural Database. Another important feature is the existence of an intramolecular O<sup>…</sup>H<sup>…</sup>O bridge between two neighboring carboxylic groups as substituents in anions in compounds <b>3</b> and <b>5</b>. In this context, we performed quantum theory of atoms-in-molecule calculations to reveal more details.
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