Abstract
C26H24Cl2N6O14, monoclinic, P21/c (no. 14), a = 15.7471(18) Å, b = 14.1486(15) Å, c = 13.7894(15) Å, β = 109.588(3)°, V = 2894.5(6) Å3, Z = 4, Rgt(F) = 0.0744, wRref(F2) = 0.2246, T = 293(2) K.
The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.
Data collection and handling.
| Crystal: | Colourless block |
| Size: | 0.24 × 0.23 × 0.21 mm |
| Wavelength: | Mo Kα radiation (0.71073 Å) |
| μ: | 0.31 mm−1 |
| Diffractometer, scan mode: | CCD, φ and ω |
| θmax, completeness: | 25.0°, >99% |
| N(hkl)measured, N(hkl)unique, Rint: | 18314, 5101, 0.060 |
| Criterion for Iobs, N(hkl)gt: | Iobs > 2 σ(Iobs), 3165 |
| N(param)refined: | 433 |
| Programs: | Olex2 [1], Bruker [2], SHELX [3], Diamond [4] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).
| Atom | x | y | z | Uiso*/Ueq |
|---|---|---|---|---|
| C1 | −0.3160(4) | 0.0886(6) | 0.6687(4) | 0.100(2) |
| H1 | −0.2648 | 0.0786 | 0.6509 | 0.120* |
| C2 | −0.3105(4) | 0.0823(7) | 0.7680(4) | 0.117(3) |
| H2 | −0.2551 | 0.0687 | 0.8175 | 0.140* |
| C3 | −0.3815(5) | 0.0949(6) | 0.7971(5) | 0.097(2) |
| H3 | −0.3763 | 0.0927 | 0.8663 | 0.116* |
| C4 | −0.4704(4) | 0.1178(5) | 0.6211(4) | 0.0808(18) |
| H4 | −0.5268 | 0.1279 | 0.5721 | 0.097* |
| C5 | −0.3977(3) | 0.1098(3) | 0.5920(4) | 0.0546(12) |
| C6 | −0.4711(3) | 0.1253(3) | 0.4040(3) | 0.0522(12) |
| C7 | −0.4978(3) | 0.1364(4) | 0.2154(3) | 0.0531(12) |
| C8 | −0.4524(3) | 0.1265(4) | 0.1447(4) | 0.0689(16) |
| H8 | −0.3901 | 0.1195 | 0.1682 | 0.083* |
| C9 | −0.4985(4) | 0.1271(4) | 0.0415(4) | 0.0683(15) |
| H9 | −0.4675 | 0.1210 | −0.0049 | 0.082* |
| C10 | −0.5932(3) | 0.1370(3) | 0.0047(3) | 0.0534(12) |
| C11 | −0.6375(3) | 0.1462(3) | 0.0751(4) | 0.0553(13) |
| H11 | −0.6999 | 0.1531 | 0.0515 | 0.066* |
| C12 | −0.5915(3) | 0.1455(4) | 0.1797(4) | 0.0581(13) |
| H12 | −0.6227 | 0.1510 | 0.2260 | 0.070* |
| C13 | −0.6400(4) | 0.1389(4) | −0.1062(4) | 0.0580(13) |
| C14 | 0.0123(3) | 0.3871(3) | 0.3999(3) | 0.0452(11) |
| C15 | −0.0603(3) | 0.3625(3) | 0.3133(3) | 0.0545(12) |
| H15 | −0.1108 | 0.3337 | 0.3209 | 0.065* |
| C16 | −0.0574(4) | 0.3809(4) | 0.2163(4) | 0.0606(14) |
| H16 | −0.1055 | 0.3636 | 0.1585 | 0.073* |
| C17 | 0.0157(3) | 0.4244(3) | 0.2046(3) | 0.0545(12) |
| H17 | 0.0180 | 0.4378 | 0.1395 | 0.065* |
| C18 | 0.0857(3) | 0.4299(3) | 0.3849(3) | 0.0489(11) |
| H18 | 0.1358 | 0.4464 | 0.4408 | 0.059* |
| C19 | 0.0743(3) | 0.3810(3) | 0.5899(3) | 0.0449(11) |
| C20 | 0.0991(3) | 0.3575(3) | 0.7761(3) | 0.0456(11) |
| C21 | 0.1923(3) | 0.3687(4) | 0.8142(4) | 0.0576(13) |
| H21 | 0.2247 | 0.3762 | 0.7694 | 0.069* |
| C22 | 0.2358(3) | 0.3685(4) | 0.9190(4) | 0.0612(14) |
| H22 | 0.2980 | 0.3763 | 0.9445 | 0.073* |
| C23 | 0.1896(3) | 0.3571(3) | 0.9872(3) | 0.0467(11) |
| C24 | 0.0976(3) | 0.3458(3) | 0.9497(3) | 0.0487(11) |
| H24 | 0.0658 | 0.3376 | 0.9950 | 0.058* |
| C25 | 0.0524(3) | 0.3467(3) | 0.8447(3) | 0.0502(12) |
| H25 | −0.0099 | 0.3400 | 0.8199 | 0.060* |
| C26 | 0.2370(3) | 0.3570(3) | 1.0999(3) | 0.0514(12) |
| N1 | −0.3973(3) | 0.1159(3) | 0.4926(3) | 0.0594(11) |
| H1A | −0.3454 | 0.1136 | 0.4848 | 0.071* |
| N2 | −0.4443(3) | 0.1353(3) | 0.3199(3) | 0.0670(13) |
| H2A | −0.3873 | 0.1418 | 0.3326 | 0.080* |
| N3 | 0.0476(2) | 0.3563(3) | 0.6713(3) | 0.0492(10) |
| H3A | −0.0073 | 0.3379 | 0.6562 | 0.059* |
| N4 | 0.0076(3) | 0.3677(3) | 0.4969(3) | 0.0519(10) |
| H4A | −0.0425 | 0.3449 | 0.4987 | 0.062* |
| N5 | 0.0835(3) | 0.4471(3) | 0.2884(3) | 0.0523(10) |
| H5 | 0.1293 | 0.4749 | 0.2805 | 0.063* |
| N6 | −0.4615(5) | 0.1109(5) | 0.7239(5) | 0.111(2) |
| H6 | −0.5086 | 0.1172 | 0.7417 | 0.133* |
| O1 | −0.5977(3) | 0.1258(4) | −0.1692(3) | 0.0928(15) |
| O2 | −0.7256(2) | 0.1528(2) | −0.1377(2) | 0.0633(10) |
| H2B | −0.7450 | 0.1527 | −0.2008 | 0.095* |
| O3 | 0.3201(2) | 0.3818(3) | 1.1319(3) | 0.0830(13) |
| H3B | 0.3398 | 0.3795 | 1.1950 | 0.125* |
| O4 | 0.1962(2) | 0.3326(3) | 1.1604(2) | 0.0641(10) |
| O5 | −0.5484(2) | 0.1241(3) | 0.4026(3) | 0.0736(11) |
| O6 | 0.1483(2) | 0.4106(3) | 0.5983(2) | 0.0685(10) |
| O7 | −0.1470(3) | 0.3210(3) | 0.6502(3) | 0.0963(14) |
| O8 | −0.2920(3) | 0.2929(3) | 0.5344(4) | 0.0991(15) |
| O9 | −0.2521(3) | 0.4403(3) | 0.6048(3) | 0.0824(12) |
| O10 | −0.1874(3) | 0.3820(3) | 0.4873(3) | 0.0839(12) |
| O11 | −0.2486(3) | 0.1750(3) | 0.3333(3) | 0.0867(13) |
| O12 | −0.1522(3) | 0.0446(3) | 0.3595(3) | 0.0911(13) |
| O13 | −0.1057(2) | 0.1798(3) | 0.4577(3) | 0.0844(12) |
| O14 | −0.2164(3) | 0.0860(3) | 0.4832(3) | 0.0772(11) |
| Cl1 | −0.18074(8) | 0.12159(8) | 0.40724(8) | 0.0512(4) |
| Cl2 | −0.22089(8) | 0.35742(8) | 0.56956(9) | 0.0512(4) |
Source of material
A solution of pyridine-3-isocyanate (4 mmol) in ethanol (15 mL) was added to a stirred ethanol solution (15 mL) of p-aminobenzoic acid (4 mmol) in a three-necked flask. The reaction mixture was refluxed for 4 h, after that the solution was cooled to room temperature. The white precipitated residue was washed with ethanol and ether 3 times. The white solids (0.1 mmol) were dissolved in 15 mL ethanol. Five drops of HClO4 were added. Single crystals were obtained from an ethanol by slow evaporation at room temperature.
Experimental details
Using Olex2 [1], the structure was solved using Charge Flipping and refined with the ShelXL [3] refinement. All hydrogen atoms were positioned geometrically. The use of a different weighting scheme may reduce the wR2 factor to 15%.
Comment
As a double hydrogen bond donor, ureido derivatives may form double hydrogen bonds to a Y-type hydrogen bond binding site such as AcO− or tetrahedral anions (such as SO42−) [5]. It is more likely that a hydrogen bond may form between ureido and ureido, or between ureido and solvent molecules, etc., which may assemble into supramolecular compounds. This phenomenon has caused extensive attention [6].
In the crystal structure of the title compound, the asymmetric unit consists of two organic cations and two ClO4− anions. The structure of the two independent molecules are slightly different; the dihedral angle of the benzene ring and pyridine ring of one molecule is 172°, and the dihedral angle of the benzene ring and pyridine ring of the other molecule is 161°. The bond lengths and bond angles are in the normal ranges. There are hydrogen bonds between molecules. Carboxy groups within the molecules meet via the hydrogen bonds, such as O2—H2B⋯O4 and O3—H3B⋯O1, resulting into a dimer. By extending the hydrogen bonds between molecules, such as N6—H6⋯O1, N6—H6⋯O3, the dimer form a one-dimensional structure. And by forming a hydrogen bond with ClO−, such as the one-dimensional structure expands into a three-dimensional structure.
Funding source: Guizhou Province – Public Health and Preventive Medicine
Award Identifier / Grant number: 2017[85]
Funding source: Science and Technology Foundation of Guizhou Province
Award Identifier / Grant number: [2019]2792]
Award Identifier / Grant number: [2018]5779–14
Funding statement: This work was supported by the first-class discipline construction project in Guizhou Province – Public Health and Preventive Medicine (NO.2017[85]), Science and Technology Foundation of Guizhou Province (grant number [2019]2792], grant number[2018]5779–14).
References
1. Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H.: OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Crystallogr. 42 (2009) 339–341.10.1107/S0021889808042726Search in Google Scholar
2. Bruker. APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, WI, USA (2012).Search in Google Scholar
3. Sheldrick, G. M.: Crystal structure refinement with SHELXL. Acta Crystallogr. C71 (2015) 3–8.10.1107/S2053229614024218Search in Google Scholar PubMed PubMed Central
4. Brandenburg, K.: DIAMOND. Visual Crystal Structure Information System. Ver. 4.0. Crystal Impact, Bonn, Germany (2015).Search in Google Scholar
5. Wang, L. L.; Lin, Q. F.; Zhang, Y. G.; Liu, Y. X.; Yasin, A.; Zhang, L. T.: Design and synthesis of supramolecular functional monomers bearing urea and norbornene motifs. RSC Adv. 9 (2019) 20058–20064.10.1039/C9RA01852BSearch in Google Scholar
6. Marivel, S.; Arunachalam, M.; Ghosh, P.: Binding of polyatomic anions with protonated ureido-pyridyl ligands. Cryst. Growth Des. 11 (2011) 1642–1650.10.1021/cg101595nSearch in Google Scholar
©2019 Qi-Long Zhang et al., published by De Gruyter, Berlin/Boston
This work is licensed under the Creative Commons Attribution 4.0 Public License.
