Abstract
C6H7BrN2O2, triclinic,
The asymmetric unit of the title salt 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: | Colorless needle |
| Size: | 0.20 × 0.15 × 0.10 mm |
| Wavelength: | Mo Kα radiation (0.71073 Å) |
| μ: | 5.46 mm−1 |
| Diffractometer, scan mode: | Bruker APEX-II, φ and ω |
| θ max, completeness: | 26.4°, >99% |
| N(hkl)measured, N(hkl)unique, R int: | 7980, 1537, 0.042 |
| Criterion for I obs, N(hkl)gt: | I obs > 2 σ(I obs), 1398 |
| N(param)refined: | 108 |
| Programs: | Bruker [1], Olex2 [2], SHELX [3, 4] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).
| Atom | x | y | z | U iso*/U eq |
|---|---|---|---|---|
| Br1 | 0.73011 (4) | 0.11619 (3) | 0.12488 (3) | 0.02096 (8) |
| C1 | 0.7768 (3) | 0.8168 (3) | 0.7494 (3) | 0.0161 (4) |
| C2 | 0.7724 (3) | 0.6531 (3) | 0.6628 (3) | 0.0137 (4) |
| C3 | 0.8191 (3) | 0.4625 (3) | 0.7575 (3) | 0.0168 (4) |
| H3 | 0.853904 | 0.432947 | 0.877970 | 0.020* |
| C4 | 0.7662 (3) | 0.3524 (3) | 0.5041 (3) | 0.0174 (5) |
| H4 | 0.766441 | 0.245151 | 0.452135 | 0.021* |
| C5 | 0.7164 (3) | 0.5424 (3) | 0.4037 (3) | 0.0149 (4) |
| C6 | 0.7223 (3) | 0.6935 (3) | 0.4880 (3) | 0.0146 (4) |
| H6 | 0.691664 | 0.823974 | 0.424192 | 0.018* |
| H1 | 0.839 (5) | 0.204 (5) | 0.732 (4) | 0.041 (9)* |
| H2 | 0.810 (5) | 0.854 (5) | 0.961 (4) | 0.043 (9)* |
| N1 | 0.8135 (3) | 0.3216 (3) | 0.6730 (2) | 0.0190 (4) |
| N2 | 0.6669 (3) | 0.5749 (3) | 0.2329 (2) | 0.0238 (4) |
| H2A | 0.665895 | 0.476291 | 0.184485 | 0.029* |
| H2B | 0.635612 | 0.694739 | 0.170076 | 0.029* |
| O1 | 0.7418 (3) | 0.9827 (2) | 0.6701 (2) | 0.0240 (4) |
| O2 | 0.8235 (3) | 0.7595 (3) | 0.9161 (2) | 0.0206 (4) |
Source of material
All starting materials were purchased and used as received. Under stirring, 1.38 g of 5-aminopyridine-3-carboxylic acid (10 mmol) was mixed with 10 mL 6 M hydrobromic acid to form a solution. After 15 min, the solution was filtered. Colorless crystals were deposited after about 50 h, yield 65% (based on 5-aminopyridine-3-carboxylic acid).
Experimental details
The structure was solved by direct methods with the SHELXS-2018 program. All H-atoms were positioned with idealized geometry and refined isotropic (U iso (H) = 1.2U eq (C)) and (N) using a riding model with C–H = 0.95 Å and N–H = 0.88 Å of amino group (If the two H atoms of amino group were refined freely, the acceptor of H2A was not found). The H-atoms from O atom and N of pyridine ring were positioned with Q peaks and refined freely with the distance of O2–H2 = 0.795 and N1–H1 = 0.867 Å, respectively.
Comment
Well known as an excellent organic linker, 5-aminopyridine-3-carboxylic acid, that has three different potential coordination groups at the same time, has been exploited to construct metal complexes [5], [6], [7], [8], [9], [10], [11], [12], [13]. Recently, the crystal structure of the corresponding perchlorate salt has been reported [14]. But the crystal structure of its hydrobromide has not been published.
There are two parts in the asymmetric unit: one is the 3-amino-5-carboxypyridin-1-ium cation, and the other is the bromide anion. The nitrogen atom of the pyridine ring is protonated (see the Figure). The distances of C1–O2 and C1–O1 are 1.209 and 1.314 Å, respectively, indicating that the latter is single-bonded. The 3-amino-5-carboxypyridin-1-ium cations are linked by hydrogen bonds N1–H1⃛O1′ and N2–H2B⃛O2″ to form one-dimensional chains, which further are bridged by N2–H2A⃛Br1 and O2–H2⃛Br1′′′ to generate a two-dimensional supramolecular structure. All of the C–C, C–N and C–O bond lengths are similar to the reported 3-amino-5-carboxypyridin-1-ium perchlorate monohydrate [14].
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Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
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Research funding: None declared.
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Conflict of interest statement: The authors declare no conflicts of interest regarding this article.
References
1. Bruker. SAINT (v8.37A); Bruker AXS Inc: Madison, Wisconsin, USA, 2015.Search in Google Scholar
2. Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K., Puschmann, H. The anatomy of a comprehensive constrained, restrained refinement program for the modern computing environment-Olex2 dissected. Acta Crystallogr. 2015, A71, 59–75; https://doi.org/10.1107/s2053273314022207.Search in Google Scholar
3. Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr. 2015, C71, 3–8; https://doi.org/10.1107/s2053229614024218.Search in Google Scholar PubMed PubMed Central
4. Sheldrick, G. Using phases to determine the space group. Acta Crystallogr. 2018, A74, a353; https://doi.org/10.1107/s0108767318096472.Search in Google Scholar
5. Pei, Y., Ge, Z.-W., Liu, P.-W., Chen, J. Structural diversity and solid-state properties of CoII and ZnII coordination complexes with 5-aminonicotinate through metal direction. J. Coord. Chem. 2013, 66, 3305–3313.10.1080/00958972.2013.834334Search in Google Scholar
6. Zhang, C.-L., Qin, L., Zheng, H.-G. Synthesis, crystal structure and optical properties of zinc coordination polymer from 5-aminonicotinic acid ligand. Chin. J. Inorg. Chem. 2014, 30, 800–804.Search in Google Scholar
7. Jiang, Y.-H., Wu, W.-P., Yang, G.-P., Jin, J.-C., Xi, Z.-P., Wang, Y.-Y. Syntheses and structures of three transition metal coordination polymers based on 5-aminonicotinic acid. J. Mol. Struct. 2015, 1091, 25–30; https://doi.org/10.1016/j.molstruc.2015.02.054.Search in Google Scholar
8. Zhou, Y.-Y., Geng, B., Zhang, Z.-W., Bo, Q.-B. Synthesis, structures and photoluminescence of three d10 5-aminonicotinate and 5-aminoisophthalate coordination polymers with bilayer structures. Inorg. Chim. Acta 2016, 444, 150–158; https://doi.org/10.1016/j.ica.2016.02.001.Search in Google Scholar
9. Jiang, T., Lin, C.-C., Liu, X.-J., He, S., Shi, H.-L., Mai, Y.-X. Synthesis, crystal structure and iodine capture of a yttrium(III) coordination polymer with 5-aminonicotinic acid. Chin. J. Struct. Chem. 2017, 36, 1601–1608.Search in Google Scholar
10. Wang, C., Liu, C., Tian, H.-R., Li, L.-J., Sun, Z.-M. Designed cluster assembly of multidimensional titanium coordination polymers: syntheses, crystal structure and properties. Chem. Eur J. 2018, 24, 2952–2961; https://doi.org/10.1002/chem.201705013.Search in Google Scholar PubMed
11. Hou, S.-L., Dong, J., Jiang, X.-L., Jiao, Z.-H., Zhao, B. A noble-metal-free metal-organic framework (MOF) catalyst for the highly efficient conversion of CO2 with propargylic alcohols. Angew. Chem. Int. Ed. 2019, 58, 577–581; https://doi.org/10.1002/anie.201811506.Search in Google Scholar PubMed
12. Lin, M. A bi-functional 3D PbII-organic framework for Knoevenagel condensation reaction and highly selective luminescent sensing of Cr2O. Inorg. Chem. Commun. 2019, 105, 86–92.10.1016/j.inoche.2019.04.042Search in Google Scholar
13. Jin, F. An excellently stable heterovalent copper-organic framework based on Cu4I4 and Cu(COO)2N2 SBUs: the catalytic performance for CO2 cycloaddition reaction and Knoevenagel condensation reaction. Inorg. Chem. Commun. 2020, 116, 107940; https://doi.org/10.1016/j.inoche.2020.107940.Search in Google Scholar
14. Hou, S., Ren, P., Zeng, Y. The crystal structure of 3-amino- 5-carboxypyridin-1-ium perchlorate monohydrate, C6H9ClN2O7. Z. Kristallogr. N. Cryst. Struct. 2021, 236, 727–728; https://doi.org/10.1515/ncrs-2021-0062.Search in Google Scholar
© 2021 Chao-Jun Du et al., published by De Gruyter, Berlin/Boston
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