Abstract
C6H4BrNO2, orthorhombic, Pna21 (no. 33), a = 14.3975(12) Å, b = 7.5773(7) Å, c = 12.2500(10) Å, β = 90°, V = 1336.4(2) Å3, Z = 8, R gt (F) = 0.0281, wR ref (F 2) = 0.0536, T = 150(2) K.
The asymmetric unit of the title crystal 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 block |
| Size: | 0.25 × 0.15 × 0.10 mm |
| Wavelength: | Mo Kα radiation (0.71073 Å) |
| μ: | 6.08 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: | 15,847, 2696, 0.054 |
| Criterion for I obs, N(hkl)gt: | I obs > 2 σ(I obs), 2341 |
| N(param)refined: | 183 |
| 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 | 0.22803 (4) | 0.52861 (7) | 0.81495 (6) | 0.03716 (14) |
| Br2 | 0.46236 (4) | 0.82636 (10) | 0.14898 (5) | 0.04430 (17) |
| C1 | 0.3262 (4) | 0.5618 (8) | 0.5733 (5) | 0.0336 (14) |
| C2 | 0.3808 (4) | 0.6122 (8) | 0.6736 (5) | 0.0307 (14) |
| C3 | 0.3489 (4) | 0.6082 (8) | 0.7803 (5) | 0.0317 (13) |
| C4 | 0.4073 (4) | 0.6555 (8) | 0.8646 (5) | 0.0349 (14) |
| H4 | 0.385729 | 0.653693 | 0.937917 | 0.042* |
| C5 | 0.4973 (4) | 0.7054 (8) | 0.8414 (5) | 0.0364 (15) |
| H5 | 0.539178 | 0.737623 | 0.897911 | 0.044* |
| C6 | 0.5243 (4) | 0.7069 (8) | 0.7339 (5) | 0.0357 (15) |
| H6 | 0.585833 | 0.743315 | 0.717250 | 0.043* |
| C7 | 0.5299 (4) | 0.8165 (8) | 0.4021 (5) | 0.0333 (13) |
| C8 | 0.6007 (3) | 0.8671 (7) | 0.3169 (5) | 0.0308 (11) |
| C9 | 0.5811 (4) | 0.8806 (8) | 0.2070 (5) | 0.0328 (14) |
| C10 | 0.6498 (4) | 0.9304 (8) | 0.1339 (5) | 0.0372 (14) |
| H10 | 0.637243 | 0.939454 | 0.057940 | 0.045* |
| C11 | 0.7372 (4) | 0.9665 (8) | 0.1751 (5) | 0.0375 (14) |
| H11 | 0.786326 | 1.000954 | 0.127834 | 0.045* |
| C12 | 0.7519 (4) | 0.9514 (8) | 0.2861 (5) | 0.0384 (16) |
| H12 | 0.811946 | 0.977176 | 0.313956 | 0.046* |
| N1 | 0.4685 (3) | 0.6596 (6) | 0.6511 (6) | 0.0326 (9) |
| N2 | 0.6860 (3) | 0.9025 (7) | 0.3558 (4) | 0.0325(11) |
| O1 | 0.2493 (3) | 0.6525 (6) | 0.5614 (4) | 0.0396 (10) |
| H1 | 0.226034 | 0.630712 | 0.500027 | 0.059* |
| O2 | 0.3556 (3) | 0.4546 (6) | 0.5101 (4) | 0.0491 (12) |
| O3 | 0.5656 (3) | 0.7083 (6) | 0.4753 (3) | 0.0361 (10) |
| H3 | 0.525885 | 0.687403 | 0.523783 | 0.054* |
| O4 | 0.4513 (3) | 0.8729 (6) | 0.4024 (4) | 0.0449 (11) |
Source of material
All starting materials were used as received. For the recrystallization 2.01 g (10 mmol) 3-bromopicolinic acid was mixed with 10 mL tetrahydrofuran and 1 mL deionized water under room temperature and was stirred to form a clear solution. The solution was filtered and evaporated naturally. Several days later, colorless block crystals of the title compound were obtained, yield 82% (based on the raw 3-bromopicolinic acid).
Experimental details
The structure was solved by direct methods with the SHELXS-2018 program. All H-atoms from C and N atoms were positioned with idealized geometry and refined isotropic (U iso (H) = 1.2U eq (C)) using a riding model with C–H = 0.95 Å. The H-atoms from O atoms positioned using peaks from the difference Fourier map and refined isotropic with the distance of O1–H1 = 0.84 Å and O3–H3 = 0.84 Å (U iso (H) = 1.5U eq (O)). The distance of Br1 and O4 is 3.034 Å, which indicates a short inter HL⃛A contact between Br1 and O4, resulting an Alert level B for checkcif. But there is no reasonable hydrogen bond. There may be some intermolecular weak interaction between Br1 and O4.
Comment
Among the mono-bromide-substituted picolinic acids, including 4-, 5- and 6-bromide-substituted picolinic acids and their derivatives, only the crystal structures of 4-bromopico-linic acid and methyl 5-bromo-6-methylpicolinate have been reported [5, 6]. Some of their metal complexes [7], [8], [9], [10], [11], [12], [13], [14], [15] and organometal complexes [16], [17], [18], [19], [20], [21], [22] have been also reported elsewhere. To the best of our knowledge, the crystal structures of 3-bromide-substituted picolinic acid has not been reported. Herein we reported the crystal structure of 3-bromopicolinic acid.
The asymmetric unit is made of two 3-bromopicolinic acid molecules, which show a slightly different conformation about the C1–C2 and C7–C8 bond, respectively. All bond lengths of the title compound are comparable with the reported results [5], [6], [7], [8], [9], [10], [11], [12], [13], [14], [15], [16], [17], [18], [19], [20], [21], [22]. There is one dimensional chain generated by hydrogen bonds O1–H1⃛N2 and O3–H3⃛N1.
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Author contributions: The author has 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 author declares no conflicts of interest regarding this article.
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© 2021 Guang Huang, published by De Gruyter, Berlin/Boston
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