BY 4.0 license Open Access Published by De Gruyter (O) October 18, 2021

The crystal structure of 3-amino-5-carboxypyridin-1-ium bromide, C6H7BrN2O2

Chao-Jun Du ORCID logo, De-Long Niu, Zhen-Li Yan, Shi-Li Zheng and Yan Zeng

Abstract

C6H7BrN2O2, triclinic, P 1 (no. 2), a = 7.3026(4) Å, b = 7.4618(4) Å, c = 7.8746(4) Å, α = 81.542(3)°, β = 89.459(3)°, γ = 61.718(3)°, V = 372.86(4) Å3, Z = 2, R gt (F) = 0.0209, wR ref (F 2) = 0.0473, T = 150(2) K.

CCDC no.: 2113910

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.

Table 1:

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]

Table 2:

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].


Corresponding author: Chao-Jun Du, Nanyang Research Institute of Zhengzhou University, Nanyang Institute of Technology, Nanyang, Henan 473000, P. R. China, E-mail:

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: None declared.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2021-09-06
Accepted: 2021-10-05
Published Online: 2021-10-18
Published in Print: 2021-12-20

© 2021 Chao-Jun Du et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 International License.