1-Ethyl-3-nitro­quinolin-4(1H)-one

Limbach, D.; Stengelin, E.; Schollmeyer, D.; Detert, H.

doi:10.1107/S2414314616001255

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160125

https://doi.org/10.1107/S2414314616001255

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1-Ethyl-3-nitroquinolin-4(1H)-one

Daniel Limbach,^a Elena Stengelin,^a Dieter Schollmeyer ^a and Heiner Detert ^a ^*

^aUniversity Mainz, Duesbergweg 10-14, 55099 Mainz, Germany
^*Correspondence e-mail: detert@uni-mainz.de

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 18 January 2016; accepted 20 January 2016; online 3 February 2016)

The title compound, C₁₁H₁₀N₂O₃, was obtained as side-product in a project focussing on the synthesis of carbolines. It was prepared from nitroquinolinone, ethanol and phosphoryl chloride. With the exception of the methyl group [C—N—C—C_methyl torsion angle = −96.4 (2)°], the molecule is essentially planar (r.m.s. deviation = 0.033 Å). In the molecular packing, undulating ribbons along the b axis are connected via C—H⋯O hydrogen bonds; an intramolecular C—H⋯O interaction is also noted.

Keywords: crystal structure; quinoline; nitroolefine; eneaminone,.

CCDC reference: 1448516

Structure description

The title compound, C₁₁H₁₀N₂O₃, Fig. 1, was obtained as side-product in a project focussing on the synthesis of carbolines (Dassonneville et al., 2011 ; Letessier & Detert, 2012 ; Letessier et al., 2013 ) and larger heterocycles with azolo-azine fragments (Glang et al., 2014 ; Rieth et al., 2014 ). This compound is one of a series of unexpected side-products in quinoline chemistry (Geffe et al., 2012 ). The chlorination of nitroquinolone (Bachman et al., 1947 ) containing ethanol according to Van Galen (Van Galen et al., 1991 ) yielded the N-ethyl quinolone. A large number of quinolones are used in both human and veterinary medicine (Milata et al., 2000 ). They possess a wide range of biological activities ranging from antibiotic to anticarcinogenic. A carboxyl group in position 3 with a carbonyl group in the 4-position plays an important role in the interaction of a quinoline with DNA-gyrase, the oxo-form can be stabilized by N-alkylation (Langer et al., 2011 ).

Figure 1
Molecular structure of the title compound with atom labelling and displacement ellipsoids drawn at the 50% probability level.

The bicyclic ring system is essentially planar, with the exception of the methyl group, with deviations of 0.03 (2) Å. Similarly, the dihedral angle between the ring and the nitro group is only 4.0 (2)°, being stabilized by an intramolecular hydrogen bond (C2—H2⋯O13; Table 1). Only the methyl group stands nearly orthogonal to the mean plane: the torsion angle C10—C9—N1—C2 amounts to −96.4 (2)°; it acts as a spacer between the molecules. The carbonyl oxygen is the acceptor of a hydrogen bond from C9 (Table 1) whereas the nitro group acts as acceptor for three intermolecular hydrogen bonds (Table 1). The molecules are arranged in undulating ribbons along the b axis, connected via C—H⋯O hydrogen bonds, Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O13	0.95	2.28	2.636 (3)	102
C2—H2⋯O14ⁱ	0.95	2.34	3.239 (2)	159
C9—H9B⋯O14ⁱ	0.99	2.57	3.364 (3)	137
C9—H9B⋯O12ⁱ	0.99	2.37	3.181 (3)	139
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
Part of the molecular packing in a view along the c axis. Hydrogen bonds are shown as dashed lines.

Synthesis and crystallization

The title compound was prepared from freshly recrystallized ethanol containing 4-hydroxy-3-nitroquinoline (2.28 g) (Bachman et al., 1947), phosphorous pentachloride (2.29 g) and phosphoryl chloride (50 ml) (Van Galen et al., 1991). The mixture was heated to reflux for 2 h, phosphoryl chloride was distilled off and the residue mixed with toluene (20 mL) and added to a stirred ice–water mixture. The organic layer was separated, washed with water, dried, filtered and the product crystallized within 3 d. Yield: 559 mg (22%) of an orange–red solid with m.p. = 495 K. Single crystals were obtained by slow evaporation of a saturated solution in chloroform.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₁₀N₂O₃
M_r	218.21
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	193
a, b, c (Å)	5.1565 (6), 12.4881 (9), 15.1083 (12)
V (Å³)	972.90 (15)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.49 × 0.30 × 0.20

Data collection
Diffractometer	Stoe IPDS 2T
No. of measured, independent and observed [I > 2σ(I)] reflections	3974, 2353, 2133
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.664

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.088, 1.05
No. of reflections	2353
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.24
Absolute structure	Flack x determined using 819 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	2.3 (7)
Computer programs: X-AREA (Stoe & Cie, 2011 ), X-RED (Stoe & Cie, 2011), SIR2004 (Burla et al., 2005 ), SHELXL2014 (Sheldrick, 2015 ), PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1448516

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2414314616001255/tk5417sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616001255/tk5417Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616001255/tk5417Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2011); cell refinement: X-AREA (Stoe & Cie, 2011); data reduction: X-RED (Stoe & Cie, 2011); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

1-Ethyl-3-nitroquinolin-4(1H)-one top

Crystal data top

C₁₁H₁₀N₂O₃	D_x = 1.490 Mg m⁻³
M_r = 218.21	Melting point: 495 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
a = 5.1565 (6) Å	Cell parameters from 6181 reflections
b = 12.4881 (9) Å	θ = 2.7–28.3°
c = 15.1083 (12) Å	µ = 0.11 mm⁻¹
V = 972.90 (15) Å³	T = 193 K
Z = 4	Needle, yellow
F(000) = 456	0.49 × 0.30 × 0.20 mm

Data collection top

Stoe IPDS 2T diffractometer	2133 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	R_int = 0.019
Detector resolution: 6.67 pixels mm^-1	θ_max = 28.2°, θ_min = 2.7°
rotation method scans	h = −6→5
3974 measured reflections	k = −16→14
2353 independent reflections	l = −20→16

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.033	w = 1/[σ²(F_o²) + (0.0465P)² + 0.2026P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.088	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.23 e Å⁻³
2353 reflections	Δρ_min = −0.24 e Å⁻³
146 parameters	Absolute structure: Flack x determined using 819 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 2.3 (7)

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
N1	0.2084 (3)	0.47445 (12)	0.65359 (10)	0.0228 (3)
C2	0.3882 (4)	0.47659 (14)	0.71683 (11)	0.0233 (4)
H2	0.4890	0.4140	0.7265	0.028*
C3	0.4353 (4)	0.56468 (15)	0.76878 (12)	0.0232 (4)
C4	0.2937 (4)	0.66408 (14)	0.75900 (11)	0.0222 (3)
C4A	0.0942 (3)	0.65770 (14)	0.68842 (11)	0.0223 (4)
C5	−0.0628 (4)	0.74724 (16)	0.67303 (13)	0.0274 (4)
H5	−0.0392	0.8100	0.7077	0.033*
C6	−0.2510 (4)	0.74565 (17)	0.60848 (14)	0.0318 (4)
H6	−0.3600	0.8061	0.5998	0.038*
C7	−0.2803 (4)	0.65477 (18)	0.55584 (13)	0.0331 (5)
H7	−0.4070	0.6544	0.5102	0.040*
C8	−0.1285 (4)	0.56560 (17)	0.56906 (12)	0.0282 (4)
H8	−0.1498	0.5043	0.5325	0.034*
C8A	0.0581 (4)	0.56545 (15)	0.63672 (11)	0.0228 (4)
C9	0.1748 (4)	0.37471 (15)	0.60113 (12)	0.0272 (4)
H9A	−0.0119	0.3638	0.5888	0.033*
H9B	0.2368	0.3129	0.6363	0.033*
C10	0.3217 (5)	0.37880 (19)	0.51459 (14)	0.0376 (5)
H10A	0.2707	0.3179	0.4776	0.056*
H10B	0.5084	0.3754	0.5264	0.056*
H10C	0.2811	0.4458	0.4837	0.056*
N11	0.6373 (3)	0.55207 (13)	0.83436 (10)	0.0280 (4)
O12	0.6949 (4)	0.62668 (14)	0.88100 (12)	0.0538 (5)
O13	0.7418 (5)	0.46513 (15)	0.84251 (15)	0.0701 (8)
O14	0.3262 (3)	0.74669 (11)	0.80200 (9)	0.0301 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0253 (7)	0.0216 (7)	0.0214 (7)	−0.0007 (6)	0.0009 (6)	−0.0013 (6)
C2	0.0258 (8)	0.0218 (8)	0.0225 (8)	0.0011 (7)	0.0019 (7)	0.0017 (7)
C3	0.0238 (9)	0.0262 (9)	0.0197 (8)	−0.0009 (7)	−0.0004 (6)	0.0013 (7)
C4	0.0232 (8)	0.0229 (8)	0.0205 (7)	−0.0015 (7)	0.0034 (6)	0.0001 (6)
C4A	0.0217 (8)	0.0236 (8)	0.0216 (8)	−0.0013 (6)	0.0035 (6)	0.0024 (7)
C5	0.0279 (9)	0.0256 (9)	0.0287 (9)	0.0023 (8)	0.0041 (7)	0.0022 (8)
C6	0.0280 (9)	0.0338 (10)	0.0337 (10)	0.0061 (8)	0.0015 (8)	0.0093 (8)
C7	0.0267 (10)	0.0441 (12)	0.0285 (9)	0.0002 (8)	−0.0040 (7)	0.0060 (8)
C8	0.0266 (9)	0.0333 (10)	0.0248 (8)	−0.0039 (8)	−0.0007 (7)	0.0005 (7)
C8A	0.0223 (8)	0.0253 (9)	0.0207 (8)	−0.0012 (7)	0.0031 (6)	0.0022 (7)
C9	0.0304 (9)	0.0222 (8)	0.0290 (8)	−0.0040 (8)	0.0002 (8)	−0.0050 (7)
C10	0.0399 (11)	0.0400 (11)	0.0329 (10)	−0.0059 (10)	0.0053 (9)	−0.0130 (9)
N11	0.0314 (9)	0.0289 (8)	0.0237 (7)	0.0013 (7)	−0.0041 (7)	0.0012 (6)
O12	0.0696 (13)	0.0336 (8)	0.0583 (11)	0.0032 (9)	−0.0404 (10)	−0.0085 (8)
O13	0.0946 (17)	0.0451 (10)	0.0708 (13)	0.0360 (11)	−0.0543 (13)	−0.0200 (9)
O14	0.0344 (7)	0.0247 (6)	0.0313 (7)	−0.0001 (6)	−0.0029 (6)	−0.0056 (6)

Geometric parameters (Å, º) top

N1—C2	1.332 (2)	C6—H6	0.9500
N1—C8A	1.399 (2)	C7—C8	1.376 (3)
N1—C9	1.486 (2)	C7—H7	0.9500
C2—C3	1.373 (2)	C8—C8A	1.404 (3)
C2—H2	0.9500	C8—H8	0.9500
C3—N11	1.446 (2)	C9—C10	1.512 (3)
C3—C4	1.448 (2)	C9—H9A	0.9900
C4—O14	1.231 (2)	C9—H9B	0.9900
C4—C4A	1.484 (2)	C10—H10A	0.9800
C4A—C5	1.400 (2)	C10—H10B	0.9800
C4A—C8A	1.404 (2)	C10—H10C	0.9800
C5—C6	1.376 (3)	N11—O12	1.205 (2)
C5—H5	0.9500	N11—O13	1.218 (2)
C6—C7	1.394 (3)

C2—N1—C8A	120.01 (15)	C6—C7—H7	119.5
C2—N1—C9	118.71 (15)	C7—C8—C8A	119.79 (18)
C8A—N1—C9	121.28 (15)	C7—C8—H8	120.1
N1—C2—C3	123.33 (16)	C8A—C8—H8	120.1
N1—C2—H2	118.3	N1—C8A—C8	120.89 (17)
C3—C2—H2	118.3	N1—C8A—C4A	119.45 (15)
C2—C3—N11	115.59 (16)	C8—C8A—C4A	119.65 (17)
C2—C3—C4	122.64 (16)	N1—C9—C10	112.00 (16)
N11—C3—C4	121.77 (16)	N1—C9—H9A	109.2
O14—C4—C3	126.59 (17)	C10—C9—H9A	109.2
O14—C4—C4A	121.26 (17)	N1—C9—H9B	109.2
C3—C4—C4A	112.15 (15)	C10—C9—H9B	109.2
C5—C4A—C8A	119.09 (16)	H9A—C9—H9B	107.9
C5—C4A—C4	118.52 (16)	C9—C10—H10A	109.5
C8A—C4A—C4	122.39 (16)	C9—C10—H10B	109.5
C6—C5—C4A	120.93 (19)	H10A—C10—H10B	109.5
C6—C5—H5	119.5	C9—C10—H10C	109.5
C4A—C5—H5	119.5	H10A—C10—H10C	109.5
C5—C6—C7	119.53 (19)	H10B—C10—H10C	109.5
C5—C6—H6	120.2	O12—N11—O13	121.38 (17)
C7—C6—H6	120.2	O12—N11—C3	119.60 (16)
C8—C7—C6	120.94 (19)	O13—N11—C3	119.00 (16)
C8—C7—H7	119.5

C8A—N1—C2—C3	0.7 (3)	C2—N1—C8A—C8	178.58 (17)
C9—N1—C2—C3	179.78 (16)	C9—N1—C8A—C8	−0.4 (2)
N1—C2—C3—N11	179.74 (16)	C2—N1—C8A—C4A	−1.6 (2)
N1—C2—C3—C4	−0.4 (3)	C9—N1—C8A—C4A	179.37 (16)
C2—C3—C4—O14	−179.06 (18)	C7—C8—C8A—N1	177.65 (18)
N11—C3—C4—O14	0.8 (3)	C7—C8—C8A—C4A	−2.2 (3)
C2—C3—C4—C4A	0.9 (2)	C5—C4A—C8A—N1	−177.91 (16)
N11—C3—C4—C4A	−179.29 (15)	C4—C4A—C8A—N1	2.2 (2)
O14—C4—C4A—C5	−1.7 (3)	C5—C4A—C8A—C8	1.9 (2)
C3—C4—C4A—C5	178.35 (16)	C4—C4A—C8A—C8	−177.99 (16)
O14—C4—C4A—C8A	178.16 (17)	C2—N1—C9—C10	−96.4 (2)
C3—C4—C4A—C8A	−1.8 (2)	C8A—N1—C9—C10	82.6 (2)
C8A—C4A—C5—C6	0.2 (3)	C2—C3—N11—O12	178.05 (19)
C4—C4A—C5—C6	−179.94 (17)	C4—C3—N11—O12	−1.8 (3)
C4A—C5—C6—C7	−2.0 (3)	C2—C3—N11—O13	−3.6 (3)
C5—C6—C7—C8	1.7 (3)	C4—C3—N11—O13	176.6 (2)
C6—C7—C8—C8A	0.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O13	0.95	2.28	2.636 (3)	102
C2—H2···O14ⁱ	0.95	2.34	3.239 (2)	159
C9—H9B···O14ⁱ	0.99	2.57	3.364 (3)	137
C9—H9B···O12ⁱ	0.99	2.37	3.181 (3)	139

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

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