5-(5-Chloro-2-hy­droxy­benzo­yl)-1-methyl-3-nitro­pyridin-2(1H)-one

Bargavi, S.; Poomathi, N.; Maheswari, N.U.; Lakshmi, S.

doi:10.1107/S2414314617013451

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 10| October 2017| x171345

https://doi.org/10.1107/S2414314617013451

Open

access

5-(5-Chloro-2-hydroxybenzoyl)-1-methyl-3-nitropyridin-2(1H)-one

Srinivasan Bargavi,^a Nataraj Poomathi,^b Narayanan Uma Maheswari ^b and Srinivasakannan Lakshmi ^a ^*

^aDepartment of Physics, S.D.N.B. Vaishnav College for Women, Chromepet, Chennai 600 044, India, and ^bOrganic Chemistry Division, CSIR Central Leather Research Institute, Chennai 600 020, India
^*Correspondence e-mail: lakssdnbvc@gmail.com

Edited by K. Fejfarova, Institute of Biotechnology CAS, Czech Republic (Received 13 September 2017; accepted 20 September 2017; online 6 October 2017)

In the title compound, C₁₃H₉ClN₂O₅, the dihedral angle between the planes of the benzene and pyridine rings is 55.30 (13)°. The nitro group is tilted by 38.21 (10)° with respect to the mean plane of the pyridine ring. In the crystal, molecules are linked by O—H⋯O and C—H⋯O hydrogen bonds, forming a three-dimensional framework. The crystal packing is further stabilized by π–π stacking interactions [intercentroid distance = 3.5877 (17) Å].

Keywords: crystal structure; nitropyridine; hydrogen bonding; framework; π–π interactions.

CCDC reference: 1575441

Structure description

The pyridine moiety has profound importance in the fields of chemistry and biology (Ghosh et al., 2014 ). Compounds that contain pyridine and its derivatives have occupied a central role in the development of coordination chemistry and biochemistry (Rajeswar et al., 2014 ). Heterocycles are important molecular building blocks that are involved in the structural composition of crucial chemicals for humans, including pharmaceuticals, natural resources, veterinary, agricultural products, analytical reagents and dyes (Göktaş et al., 2014 ). In drug discovery, pyridine has been used as a bioisosteric replacement of the benzene ring (Ajit Kumar et al., 2011 ). Pyridine derivatives of different heterocyclic nuclei have shown important pharmacological properties such as anticancer (Abbas et al., 2015 ), antimicrobial (Hussein et al., 2014 ), antibacterial (Rani et al., 2012 ), antimycobacterial (Banfi et al., 2001 ) and antioxidant activities (Fadda et al., 2012 ).

In the title compound (Fig. 1), the dihedral angle between the benzene (C1–C6) and pyridine (N1/C8–C12) rings is 55.30 (13)°. The nitro group is tilted by 38.21 (10)° with respect to the mean plane of the pyridine ring. The chlorine atom Cl1 deviates from the plane of the benzene ring by 0.009 (1) Å. The Cl1—C2—C3—C4 torsion angle of 179.7 (2)° indicates that the chlorine atom Cl1 is not quite coplanar with the phenol ring.

Figure 1
The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

In the crystal, molecules are linked by O1—H1⋯O4 and O1—H1⋯O5 hydrogen bonds (Table 1), forming chains, which are further linked by C1—H1A⋯O4 and C12—H12⋯O2 hydrogen bonds, forming a two-dimensional network parallel to (100) (Fig. 2). The crystal packing also features π–π stacking interactions [Cg1⋯Cg2ⁱ = 3.5877 (17) Å, interplanar distance = 3.3360 (11) Å, Cg1 and Cg2 are the centroids of rings N1/C8–C12 and C1–C6, respectively; symmetry code: (i) 2 − x, −y, − $[{1\over 2}]$ + z].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4ⁱ	0.82	2.40	2.774 (3)	109
O1—H1⋯O5ⁱ	0.82	2.05	2.820 (3)	157
C1—H1A⋯O4ⁱⁱ	0.93	2.49	3.412 (3)	169
C12—H12⋯O2ⁱⁱⁱ	0.93	2.56	3.111 (4)	118
Symmetry codes: (i) $[-x+{\script{5\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z]$ ; (iii) $[-x+2, -y, z-{\script{1\over 2}}]$ .

Figure 2
Hydrogen-bonding network, viewed along the a axis. Hydrogen bonds (see Table 1

) are shown as dashed lines.

Synthesis and crystallization

A mixture of 6-chloro-3-formylchromone (1 mmol), (Z)-N-methyl-1-(methylthio)-2-nitroethenamine (1 mmol), and indium trifluoromethanesulfonate (0.020 mmol) in ethanol (3 ml) were charged in a 25 ml round-bottomed flask and the mixture was heated at reflux. The resulting solution was stirred for 1h. The consumption of the starting material was monitored by TLC. After completion of the reaction, the product was filtered, washed with ethanol, dried under vacuum and the pure product obtained in good yield (88%). The purified compound was recrystallized from ethanol and DMSO-d₆ by using the slow evaporation method_.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₉ClN₂O₅
M_r	308.67
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	296
a, b, c (Å)	11.1491 (4), 15.0153 (6), 7.7045 (3)
V (Å³)	1289.79 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.32
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.908, 0.938
No. of measured, independent and observed [I > 2σ(I)] reflections	4752, 1705, 1614
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.070, 1.06
No. of reflections	1705
No. of parameters	191
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.21
Absolute structure	Flack (1983 ), 481 Friedel pairs
Absolute structure parameter	0.59 (3)
Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1575441

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617013451/ff4020sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617013451/ff4020Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617013451/ff4020Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

5-(5-Chloro-2-hydroxybenzoyl)-1-methyl-3-nitropyridin-2(1H)-one top

Crystal data top

C₁₃H₉ClN₂O₅	D_x = 1.590 Mg m⁻³
M_r = 308.67	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 1614 reflections
a = 11.1491 (4) Å	θ = 2.3–25.0°
b = 15.0153 (6) Å	µ = 0.32 mm⁻¹
c = 7.7045 (3) Å	T = 296 K
V = 1289.79 (9) Å³	Block, colourless
Z = 4	0.30 × 0.25 × 0.20 mm
F(000) = 632

Data collection top

Bruker Kappa APEXII CCD diffractometer	1614 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.015
ω and φ scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→12
T_min = 0.908, T_max = 0.938	k = −17→10
4752 measured reflections	l = −5→9
1705 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.026	H-atom parameters constrained
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0449P)² + 0.1924P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1705 reflections	Δρ_max = 0.12 e Å⁻³
191 parameters	Δρ_min = −0.21 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 481 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.59 (3)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.63594 (6)	0.15295 (6)	0.00210 (13)	0.0547 (3)
C9	1.0658 (2)	−0.18373 (17)	0.2334 (4)	0.0292 (6)
H9	1.0034	−0.2146	0.2864	0.035*
O5	1.35111 (14)	−0.22295 (12)	0.0251 (3)	0.0389 (5)
C8	1.0640 (2)	−0.09006 (17)	0.2281 (4)	0.0262 (5)
N1	1.25635 (18)	−0.09334 (14)	0.0949 (3)	0.0290 (5)
C12	1.1613 (2)	−0.04804 (17)	0.1581 (4)	0.0278 (5)
H12	1.1621	0.0138	0.1538	0.033*
O4	1.1848 (2)	−0.36386 (13)	0.0251 (4)	0.0543 (6)
C13	1.3620 (2)	−0.04375 (19)	0.0311 (5)	0.0442 (8)
H13A	1.3441	0.0188	0.0289	0.066*
H13B	1.3816	−0.0635	−0.0839	0.066*
H13C	1.4288	−0.0543	0.1069	0.066*
O2	0.87647 (16)	−0.08953 (12)	0.3612 (3)	0.0433 (5)
C11	1.2624 (2)	−0.18667 (17)	0.0867 (3)	0.0294 (6)
O1	1.09214 (16)	0.11145 (13)	0.3731 (3)	0.0415 (5)
H1	1.1227	0.1599	0.3941	0.062*
N2	1.14859 (19)	−0.32526 (15)	0.1549 (4)	0.0371 (6)
C2	0.7722 (2)	0.1431 (2)	0.1122 (4)	0.0360 (7)
C4	0.9437 (3)	0.20821 (18)	0.2460 (4)	0.0382 (7)
H4	0.9867	0.2584	0.2792	0.046*
C6	0.9226 (2)	0.04896 (16)	0.2385 (3)	0.0277 (6)
C7	0.9520 (2)	−0.04566 (17)	0.2865 (4)	0.0278 (6)
C10	1.1577 (2)	−0.22868 (16)	0.1617 (4)	0.0288 (6)
O3	1.0998 (2)	−0.36325 (13)	0.2761 (4)	0.0542 (6)
C1	0.8133 (2)	0.05953 (17)	0.1519 (4)	0.0308 (6)
H1A	0.7685	0.0098	0.1212	0.037*
C5	0.9880 (2)	0.12375 (17)	0.2852 (4)	0.0310 (6)
C3	0.8360 (3)	0.21806 (18)	0.1579 (4)	0.0416 (7)
H3	0.8073	0.2744	0.1301	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0456 (4)	0.0718 (5)	0.0467 (5)	0.0250 (4)	−0.0078 (4)	0.0019 (5)
C9	0.0263 (11)	0.0288 (13)	0.0325 (14)	−0.0007 (11)	−0.0017 (12)	−0.0002 (13)
O5	0.0297 (10)	0.0354 (10)	0.0517 (14)	0.0080 (7)	0.0065 (10)	−0.0029 (11)
C8	0.0268 (11)	0.0255 (13)	0.0264 (13)	0.0030 (10)	−0.0027 (11)	0.0012 (12)
N1	0.0252 (10)	0.0286 (11)	0.0332 (12)	0.0016 (9)	0.0005 (9)	0.0046 (10)
C12	0.0295 (12)	0.0246 (12)	0.0294 (13)	0.0036 (10)	−0.0054 (11)	0.0014 (12)
O4	0.0604 (13)	0.0333 (11)	0.0693 (18)	0.0061 (9)	0.0146 (14)	−0.0093 (13)
C13	0.0318 (13)	0.0399 (16)	0.061 (2)	−0.0034 (11)	0.0084 (14)	0.0076 (18)
O2	0.0364 (10)	0.0330 (11)	0.0604 (14)	0.0012 (8)	0.0142 (10)	0.0032 (11)
C11	0.0273 (13)	0.0304 (13)	0.0305 (13)	0.0042 (11)	−0.0046 (11)	0.0007 (12)
O1	0.0362 (10)	0.0371 (10)	0.0513 (13)	−0.0051 (9)	−0.0084 (10)	−0.0106 (11)
N2	0.0312 (12)	0.0285 (12)	0.0515 (16)	0.0056 (10)	0.0002 (12)	0.0020 (13)
C2	0.0367 (15)	0.0445 (16)	0.0266 (15)	0.0128 (13)	0.0022 (12)	−0.0006 (12)
C4	0.0492 (16)	0.0279 (13)	0.0376 (17)	−0.0043 (12)	0.0070 (14)	−0.0041 (13)
C6	0.0274 (12)	0.0277 (13)	0.0281 (14)	0.0033 (10)	0.0037 (11)	−0.0027 (12)
C7	0.0273 (12)	0.0266 (12)	0.0294 (14)	−0.0022 (10)	−0.0009 (11)	−0.0044 (11)
C10	0.0300 (13)	0.0244 (13)	0.0320 (14)	0.0026 (10)	−0.0028 (11)	0.0026 (12)
O3	0.0534 (13)	0.0370 (11)	0.0720 (17)	0.0006 (10)	0.0165 (13)	0.0192 (12)
C1	0.0298 (13)	0.0302 (14)	0.0322 (14)	0.0040 (11)	0.0024 (12)	−0.0061 (12)
C5	0.0308 (13)	0.0328 (14)	0.0295 (14)	−0.0021 (11)	0.0056 (12)	−0.0050 (12)
C3	0.0569 (18)	0.0295 (15)	0.0383 (16)	0.0105 (13)	0.0091 (15)	0.0011 (14)

Geometric parameters (Å, º) top

Cl1—C2	1.746 (3)	C11—C10	1.447 (4)
C9—C10	1.346 (4)	O1—C5	1.357 (3)
C9—C8	1.407 (4)	O1—H1	0.8200
C9—H9	0.9300	N2—O3	1.222 (4)
O5—C11	1.225 (3)	N2—C10	1.455 (3)
C8—C12	1.366 (3)	C2—C1	1.371 (4)
C8—C7	1.485 (3)	C2—C3	1.377 (4)
N1—C12	1.350 (3)	C4—C3	1.387 (4)
N1—C11	1.404 (3)	C4—C5	1.394 (4)
N1—C13	1.477 (3)	C4—H4	0.9300
C12—H12	0.9300	C6—C5	1.386 (4)
O4—N2	1.224 (3)	C6—C1	1.398 (4)
C13—H13A	0.9600	C6—C7	1.504 (3)
C13—H13B	0.9600	C1—H1A	0.9300
C13—H13C	0.9600	C3—H3	0.9300
O2—C7	1.214 (3)

C10—C9—C8	120.0 (2)	C1—C2—C3	121.2 (3)
C10—C9—H9	120.0	C1—C2—Cl1	118.5 (2)
C8—C9—H9	120.0	C3—C2—Cl1	120.3 (2)
C12—C8—C9	117.5 (2)	C3—C4—C5	120.6 (3)
C12—C8—C7	125.4 (2)	C3—C4—H4	119.7
C9—C8—C7	116.9 (2)	C5—C4—H4	119.7
C12—N1—C11	123.8 (2)	C5—C6—C1	119.3 (2)
C12—N1—C13	119.5 (2)	C5—C6—C7	126.0 (2)
C11—N1—C13	116.7 (2)	C1—C6—C7	114.5 (2)
N1—C12—C8	122.2 (2)	O2—C7—C8	118.9 (2)
N1—C12—H12	118.9	O2—C7—C6	118.6 (2)
C8—C12—H12	118.9	C8—C7—C6	122.1 (2)
N1—C13—H13A	109.5	C9—C10—C11	124.0 (2)
N1—C13—H13B	109.5	C9—C10—N2	117.5 (2)
H13A—C13—H13B	109.5	C11—C10—N2	118.5 (2)
N1—C13—H13C	109.5	C2—C1—C6	120.1 (2)
H13A—C13—H13C	109.5	C2—C1—H1A	119.9
H13B—C13—H13C	109.5	C6—C1—H1A	119.9
O5—C11—N1	120.0 (2)	O1—C5—C6	118.0 (2)
O5—C11—C10	127.7 (2)	O1—C5—C4	122.3 (2)
N1—C11—C10	112.2 (2)	C6—C5—C4	119.6 (3)
C5—O1—H1	109.5	C2—C3—C4	119.0 (2)
O3—N2—O4	123.4 (2)	C2—C3—H3	120.5
O3—N2—C10	118.0 (3)	C4—C3—H3	120.5
O4—N2—C10	118.6 (3)

C10—C9—C8—C12	−3.9 (4)	N1—C11—C10—C9	−0.9 (4)
C10—C9—C8—C7	171.3 (3)	O5—C11—C10—N2	−4.9 (4)
C11—N1—C12—C8	3.3 (4)	N1—C11—C10—N2	177.1 (2)
C13—N1—C12—C8	−176.1 (3)	O3—N2—C10—C9	−35.8 (4)
C9—C8—C12—N1	0.3 (4)	O4—N2—C10—C9	140.7 (3)
C7—C8—C12—N1	−174.6 (2)	O3—N2—C10—C11	146.1 (3)
C12—N1—C11—O5	178.9 (3)	O4—N2—C10—C11	−37.4 (4)
C13—N1—C11—O5	−1.6 (3)	C3—C2—C1—C6	−0.8 (4)
C12—N1—C11—C10	−2.9 (3)	Cl1—C2—C1—C6	179.4 (2)
C13—N1—C11—C10	176.6 (2)	C5—C6—C1—C2	0.7 (4)
C12—C8—C7—O2	−173.3 (3)	C7—C6—C1—C2	175.3 (2)
C9—C8—C7—O2	11.9 (4)	C1—C6—C5—O1	178.3 (2)
C12—C8—C7—C6	13.9 (4)	C7—C6—C5—O1	4.4 (4)
C9—C8—C7—C6	−160.9 (2)	C1—C6—C5—C4	0.3 (4)
C5—C6—C7—O2	124.2 (3)	C7—C6—C5—C4	−173.6 (2)
C1—C6—C7—O2	−49.9 (3)	C3—C4—C5—O1	−179.1 (3)
C5—C6—C7—C8	−62.9 (4)	C3—C4—C5—C6	−1.2 (4)
C1—C6—C7—C8	122.9 (3)	C1—C2—C3—C4	−0.1 (4)
C8—C9—C10—C11	4.3 (4)	Cl1—C2—C3—C4	179.7 (2)
C8—C9—C10—N2	−173.7 (2)	C5—C4—C3—C2	1.1 (4)
O5—C11—C10—C9	177.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱ	0.82	2.40	2.774 (3)	109
O1—H1···O5ⁱ	0.82	2.05	2.820 (3)	157
C1—H1A···O4ⁱⁱ	0.93	2.49	3.412 (3)	169
C12—H12···O2ⁱⁱⁱ	0.93	2.56	3.111 (4)	118

Symmetry codes: (i) −x+5/2, y+1/2, z+1/2; (ii) x−1/2, −y−1/2, z; (iii) −x+2, −y, z−1/2.

Acknowledgements

The authors thank the Department of Chemistry, IIT, Chennai, for the data collection.

References

Abbas, I., Gomha, S., Elaasser, M. & Bauomi, M. (2015). Turk. J. Chem. 39, 334–346. Web of Science CrossRef CAS Google Scholar
Ajit Kumar, C. & Pandeya, S. N. (2011). Int. J. Res. Ayurveda. Pharm. 2, 1763–1767. Google Scholar
Banfi, E., Mamolo, M. G., Zampieri, D., Vio, L. & Bragadin, C. M. (2001). J. Antimicrob. Chemother. 48, 705–707. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2008). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fadda, A. A., Sanad, M. & Abd El-Galil, I. (2012). Int. J. Modern Org. Chem. 1, 136–149. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Ghosh, P. S., Manna, K., Banik, U., Das, M. & Sarkar, P. (2014). Int. J. Pharm. Pharm. Sci. 6, 39–42. Google Scholar
Göktaş, F., Cesur, N., Şatana, D. & Uzun, M. (2014). Turk. J. Chem. 38, 581–591. Google Scholar
Hussein, A. M., El-Adasy, A. A., Hafi, I. A., Ishak, E. A., Gawish, E. H. & El-Gaby, M. A. (2014). J. App. Pharm. 6, 296–307. CAS Google Scholar
Rajeswar, V. R., Dharmale, M. K. & Pingalkar, S. R. (2014). Int. J. Curr. Res. Chem. Pharma. Sci. 1, 40–50. Google Scholar
Rani, E. S., Parameshwar, R., Babu, V. H., Ranganath, Y. S., Kumar, B. N. & Kumar, G. A. (2012). Int. J. Pharm. Pharm. Sci. 4, 424–427. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.