organic compounds
Ethyl 4-oxo-1,4-dihydropyridine-3-carboxylate
aSchool of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan, Hubei 430205, People's Republic of China
*Correspondence e-mail: longsihui@yahoo.com
The title compound, C8H9NO3, likely generated through hydrolysis and esterification of 3′-carboxy-3-methyl-(1,4′-bipyridin)-1-ium chloride by ethanol, which contained water, has a nearly planar conformation. The is sustained by one-dimensional chains along the a-axis direction based on bifurcated N—H⋯(O,O) hydrogen bonds between the NH group of the 4-oxo-1,4-dihydropyridine ring and the two carbonyl O atoms.
Keywords: crystal structure; bifurcated hydrogen bonds.
CCDC reference: 2086773
Structure description
The title compound (Fig. 1) was first synthesized by Ross (1966). It may be a potential inhibitor of the glycolytic process by which many cancer cells derive an appreciable proportion of their energy requirement (Ross, 1966). Balogh et al. (1980) demonstrated that the compound exhibited antimicrobial activity. In our study, the compound was obtained serendipitously during an attempt to grow single crystals of 3′-carboxy-3-methyl-(1,4′-bipyridin)-1-ium chloride in ethanol. The compound has a nearly planar conformation, as evidenced by the dihedral angle between the 4-oxo-1,4-dihydropyridine ring and the ester moiety [2.3 (2)°]. In the crystal, the molecules form chains propagating parallel to the a-axis through bifurcated hydrogen bonds between the NH group and the two carbonyl oxygen atoms. The hydrogen bond parameters for NH⋯O=C (ring) are: 1.96 (2) Å for bond length, and 134.9 (17)° for the bond angle. The corresponding parameters for NH⋯O=C (ester) are 2.15 (2) Å and 139.6 (17)° (Fig. 2, Table 1).
Synthesis and crystallization
The title compound was obtained during an attempt to grow single crystals of 3′-carboxy-3-methyl-(1,4′-bipyridin)-1-ium chloride by slow evaporation of an ethanolic solution. 3′-Carboxy-3-methyl-(1,4′-bipyridin)-1-ium chloride was dissolved in bulk ethanol at 343 K, and then the resulting solution was left in a refrigerator. Colorless plate-shaped crystals (Fig. 3) were harvested after several days. by single-crystal X-ray diffraction revealed the identity of the crystals to be ethyl 4-oxo-1,4-dihydropyridine-3-carboxylate. Hydrolysis and esterification of 3′-carboxy-3-methyl-[1,4′-bipyridin]-1-ium chloride may have led to the title compound (Fig. 4).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 2086773
https://doi.org/10.1107/S2414314621005551/pk4034sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621005551/pk4034Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314621005551/pk4034Isup3.cml
Data collection: CrysAlis PRO (Rigaku OD, 2020); cell
CrysAlis PRO (Rigaku OD, 2020); data reduction: CrysAlis PRO (Rigaku OD, 2020); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C8H9NO3 | F(000) = 352 |
Mr = 167.16 | Dx = 1.313 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
a = 6.4973 (2) Å | Cell parameters from 3630 reflections |
b = 11.5323 (5) Å | θ = 6.8–76.4° |
c = 11.2908 (5) Å | µ = 0.86 mm−1 |
β = 91.500 (4)° | T = 293 K |
V = 845.72 (6) Å3 | Needle, clear light colourless |
Z = 4 | 0.07 × 0.03 × 0.02 mm |
Rigaku Oxford Diffraction, Synergy Custom system, HyPix diffractometer | 1693 independent reflections |
Radiation source: Rotating-anode X-ray tube, Rigaku (Cu) X-ray Source | 1456 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.022 |
Detector resolution: 10.0000 pixels mm-1 | θmax = 77.4°, θmin = 6.8° |
ω scans | h = −8→7 |
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020) | k = −14→5 |
Tmin = 0.311, Tmax = 1.000 | l = −13→14 |
5379 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.129 | w = 1/[σ2(Fo2) + (0.0674P)2 + 0.1472P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
1693 reflections | Δρmax = 0.21 e Å−3 |
114 parameters | Δρmin = −0.22 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.52166 (14) | 0.40585 (10) | 0.20366 (11) | 0.0600 (4) | |
O2 | 0.57531 (15) | 0.62403 (10) | 0.09977 (11) | 0.0584 (4) | |
O3 | 0.28325 (16) | 0.71651 (9) | 0.05152 (11) | 0.0555 (3) | |
N1 | −0.08871 (17) | 0.47182 (12) | 0.17157 (11) | 0.0471 (3) | |
C1 | 0.25305 (18) | 0.53513 (12) | 0.14051 (12) | 0.0388 (3) | |
C2 | 0.33512 (19) | 0.42840 (13) | 0.19022 (13) | 0.0436 (4) | |
C3 | 0.1821 (2) | 0.34638 (14) | 0.22568 (15) | 0.0538 (4) | |
H3 | 0.224295 | 0.274979 | 0.255937 | 0.065* | |
C4 | −0.0203 (2) | 0.36993 (15) | 0.21635 (15) | 0.0517 (4) | |
H4 | −0.114786 | 0.315080 | 0.241186 | 0.062* | |
C5 | 0.04315 (19) | 0.55121 (13) | 0.13385 (13) | 0.0421 (3) | |
H5 | −0.008399 | 0.619967 | 0.101877 | 0.051* | |
C6 | 0.3901 (2) | 0.62675 (12) | 0.09660 (13) | 0.0421 (3) | |
C7 | 0.3996 (3) | 0.81144 (16) | 0.00264 (19) | 0.0663 (5) | |
H7A | 0.470155 | 0.786241 | −0.067519 | 0.080* | |
H7B | 0.501453 | 0.839160 | 0.060290 | 0.080* | |
C8 | 0.2495 (4) | 0.90531 (19) | −0.0281 (2) | 0.0899 (7) | |
H8A | 0.317924 | 0.965688 | −0.070384 | 0.135* | |
H8B | 0.194250 | 0.936516 | 0.043203 | 0.135* | |
H8C | 0.139659 | 0.874119 | −0.076909 | 0.135* | |
H1 | −0.224 (3) | 0.4880 (17) | 0.1645 (17) | 0.071 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0234 (5) | 0.0609 (7) | 0.0956 (9) | 0.0027 (4) | 0.0007 (5) | 0.0191 (6) |
O2 | 0.0296 (5) | 0.0541 (7) | 0.0918 (9) | −0.0041 (4) | 0.0038 (5) | 0.0110 (6) |
O3 | 0.0411 (6) | 0.0456 (6) | 0.0799 (8) | 0.0017 (4) | 0.0029 (5) | 0.0130 (5) |
N1 | 0.0211 (5) | 0.0596 (8) | 0.0608 (7) | −0.0002 (5) | 0.0018 (5) | 0.0002 (6) |
C1 | 0.0255 (6) | 0.0448 (8) | 0.0460 (7) | 0.0000 (5) | 0.0022 (5) | −0.0028 (6) |
C2 | 0.0241 (6) | 0.0512 (8) | 0.0555 (8) | −0.0001 (5) | 0.0018 (5) | 0.0018 (6) |
C3 | 0.0321 (7) | 0.0519 (9) | 0.0774 (11) | −0.0012 (6) | 0.0020 (7) | 0.0147 (8) |
C4 | 0.0288 (7) | 0.0588 (9) | 0.0678 (10) | −0.0075 (6) | 0.0045 (6) | 0.0075 (7) |
C5 | 0.0279 (6) | 0.0467 (8) | 0.0517 (8) | 0.0028 (5) | 0.0006 (5) | −0.0024 (6) |
C6 | 0.0307 (6) | 0.0423 (7) | 0.0532 (8) | 0.0010 (5) | 0.0016 (5) | −0.0022 (6) |
C7 | 0.0674 (11) | 0.0478 (9) | 0.0842 (12) | −0.0088 (8) | 0.0079 (9) | 0.0110 (8) |
C8 | 0.1063 (19) | 0.0616 (13) | 0.1014 (17) | 0.0040 (11) | −0.0053 (14) | 0.0288 (11) |
O1—C2 | 1.2450 (16) | C1—C2 | 1.449 (2) |
O2—C6 | 1.2032 (16) | C1—C5 | 1.3765 (17) |
O3—C6 | 1.3395 (17) | C1—C6 | 1.4760 (19) |
O3—C7 | 1.448 (2) | C2—C3 | 1.437 (2) |
N1—C4 | 1.350 (2) | C3—C4 | 1.344 (2) |
N1—C5 | 1.3314 (19) | C7—C8 | 1.492 (3) |
C6—O3—C7 | 117.28 (12) | C4—C3—C2 | 121.85 (15) |
C5—N1—C4 | 120.66 (12) | C3—C4—N1 | 121.15 (14) |
C2—C1—C6 | 121.28 (11) | N1—C5—C1 | 122.33 (13) |
C5—C1—C2 | 119.33 (12) | O2—C6—O3 | 122.66 (13) |
C5—C1—C6 | 119.40 (12) | O2—C6—C1 | 125.66 (13) |
O1—C2—C1 | 124.89 (13) | O3—C6—C1 | 111.68 (11) |
O1—C2—C3 | 120.46 (14) | O3—C7—C8 | 107.00 (16) |
C3—C2—C1 | 114.65 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.90 (2) | 1.96 (2) | 2.6771 (15) | 134.9 (17) |
N1—H1···O2i | 0.90 (2) | 2.15 (2) | 2.9002 (17) | 139.6 (17) |
Symmetry code: (i) x−1, y, z. |
Funding information
The authors thank the Natural Science Foundation of Hubei Province for financial support (2014CFB787).
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