6 Nitro­quinolin 2(1H) one

organic papers

o2992

9H6N2O3 doi:10.1107/S1600536805025894 Acta Cryst.(2005). E61, o2992–o2993

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

6-Nitroquinolin-2(1

H

)-one

Luiz Everson da Silva,a,b Antonio C. Joussef,aSabine Forob* and Boris Schmidtb

a_{Departamento de Quı´mica–UFSC, 88040-900}

Floriano´polis, SC, Brazil, andb

Clemens–Scho¨pf-Institut fu¨r Organische Chemie und Biochemie, Technische Universita¨t Darmstadt,

Petersenstrasse 22, D-64287 Darmstadt, Germany

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 299 K

Mean(C–C) = 0.004 A˚ Rfactor = 0.055 wRfactor = 0.149

Data-to-parameter ratio = 10.3

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography

Printed in Great Britain – all rights reserved

The title compound, C9H6N2O3, is nearly planar, with maximum deviations from the mean plane of 0.024 (3) A˚ for the C atomparato the ring N atom and 0.048 (2) A˚ for one of the nitro O atoms. Three C—H O and one N—H O intermolecular hydrogen bonds stabilize the crystal structure.

Comment

As part of our ongoing studies on quinoline derivatives as fluorophores, we attempted to prepare, by treatment of 2-chloroquinoline with potassium nitrate and sulfuric acid, the corresponding nitroquinoline derivatives (I) and (II) (Kimber

et al., 2003). However, analytical data from the reaction mixture indicated, besides (I) and (II) as the main products, the presence of another compound whose structure could not be resolved unequivocally by spectroscopic methods. This minor product is the title compound, (III); in order to identify the structure of (III), and hence to help in clarifying the reaction mechanism, its crystal structure was determined by X-ray diffraction.

Four intermolecular hydrogen bonds, viz. one N—H O and three C—H O, form a three-dimensional network (Fig. 2). Details of the hydrogen-bonding geometry are given in Table 1. The title compound is nearly planar, with maximum deviations from the mean plane of 0.024 (3) A˚ for C3 and 0.048 (2) A˚ for O2.

Experimental

The title compound, (III), was obtained as a minor product from a mixture of 2-chloroquinoline, potassium nitrate and sulfuric acid, according to the literature procedure of Kimberet al.(2003). Crystals suitable for X-ray data collection were obtained by recrystallization from dichloromethane–hexane (1:1).

Crystal data

C9H6N2O3

Mr= 190.16 Monoclinic,P2₁=c a= 11.470 (2) A˚

b= 4.8880 (6) A˚

c= 15.065 (2) A˚

= 99.53 (1)

V= 833.0 (2) A˚3

Z= 4

Dx= 1.516 Mg m 3 CuKradiation Cell parameters from 25

reflections

= 6.6–26.7

= 1.00 mm1

T= 299 (2) K Prism, orange 0.180.100.05 mm

Data collection

Nonius CAD-4 diffractometer

!/2scans

Absorption correction: none 1941 measured reflections 1504 independent reflections 892 reflections withI> 2(I)

Rint= 0.069

max= 68.0

h=13!13

k= 0!5

l=18!18 3 standard reflections

frequency: 120 min intensity decay: 1.0%

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.055

wR(F2_{) = 0.149}

S= 1.01 1504 reflections 146 parameters

Only H-atom coordinates refined

w= 1/[2_(F

o2) + (0.0734P)2] whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001

max= 0.29 e A˚ 3 min=0.19 e A˚

3

Extinction correction:SHELXL97

Extinction coefficient: 0.0053 (11)

Table 1

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

C3—H3 O2i

1.04 (3) 2.48 (3) 3.377 (4) 145 (2) C3—H3 O3ii 1.04 (3) 2.50 (3) 3.230 (4) 127 (2) C9—H9 O2i

0.95 (3) 2.53 (3) 3.371 (4) 147 (2) N1—H1N O1iii

0.83 (3) 1.97 (3) 2.794 (3) 175 (3)

Symmetry codes: (i) xþ2;y;zþ1; (ii) x;y1 2;z

1 2; (iii)

xþ1;y2;zþ1.

The H atoms were located in a difference map and refined with

Uiso(H) = 1.2Ueq(parent atom).

Data collection:CAD-4/PC Software (Nonius, 1996); cell refine-ment: CAD-4/PC Software; data reduction: REDU4 (Stoe & Cie, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:PLATON(Spek, 2003); software used to prepare material for publication:SHELXL97.

The authors thank Professor Dr Hartmut Fuess, FG Strukturforschung, FB Material- und Geowissenschaften, Technische Universita¨t Darmstadt, Petersenstrasse 23, 64287 Darmstadt, for diffractometer time.

References

Kimber, M. C., Geue, J. P., Lincoln, S. F., Ward, A. D. & Tiekink, E. R. T. (2003).Aust. J. Chem.56, 39–44.

Nonius (1996).CAD-4/PC Software. Version 2.0. Nonius GmbH, Solingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.

Stoe & Cie (1987).REDU4. Version 6.2c. Stoe & Cie GmbH, Darmstadt, Germany.

Figure 1

The molecular structure of (III), showing the atom labeling and displacement ellipsoids drawn at the 50% probability level.

Figure 2

supporting information

sup-1 Acta Cryst. (2005). E61, o2992–o2993

supporting information

Acta Cryst. (2005). E61, o2992–o2993 [https://doi.org/10.1107/S1600536805025894]

6-Nitroquinolin-2(1

H

)-one

Luiz Everson da Silva, Antonio C. Joussef, Sabine Foro and Boris Schmidt

6-Nitroquinolin-2(1H)-one

Crystal data

C9H6N2O3 Mr = 190.16 Monoclinic, P21/c

Hall symbol: -P 2ybc

a = 11.470 (2) Å

b = 4.8880 (6) Å

c = 15.065 (2) Å

β = 99.53 (1)°

V = 833.0 (2) Å3

Z = 4

F(000) = 392

Dx = 1.516 Mg m−3

Cu Kα radiation, λ = 1.54180 Å

Cell parameters from 25 reflections

θ = 6.6–26.7°

µ = 1.00 mm−1

T = 299 K

Prism, orange

0.18 × 0.10 × 0.05 mm

Data collection

Nonius CAD-4 diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω/2θ scans

1941 measured reflections 1504 independent reflections 892 reflections with I > 2σ(I)

Rint = 0.069

θmax = 68.0°, θmin = 3.9°

h = −13→13

k = 0→5

l = −18→18

3 standard reflections every 120 min intensity decay: 1.0%

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.055} wR(F2_{) = 0.149}

S = 1.01

1504 reflections 146 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: difference Fourier map Only H-atom coordinates refined

w = 1/[σ2_(Fo2_{) + (0.0734P)}2_]

where P = (Fo2 _{+ 2Fc}2_)/3

(Δ/σ)max < 0.001

Δρmax = 0.29 e Å−3

Δρmin = −0.19 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

Special details

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.

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) is used}

only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2

are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

x y z Uiso*/Ueq

C1 0.6288 (3) −0.8802 (6) 0.4297 (2) 0.0474 (7)

C2 0.7255 (3) −0.7901 (7) 0.3868 (2) 0.0542 (8)

H2 0.737 (3) −0.891 (6) 0.332 (2) 0.065*

C3 0.8002 (3) −0.5927 (6) 0.4233 (2) 0.0490 (8)

H3 0.865 (3) −0.522 (7) 0.389 (2) 0.059*

C4 0.7856 (2) −0.4635 (6) 0.50588 (19) 0.0414 (7)

C5 0.6906 (2) −0.5469 (5) 0.54806 (19) 0.0408 (7)

C6 0.6712 (3) −0.4285 (6) 0.6279 (2) 0.0477 (8)

H6 0.611 (3) −0.475 (6) 0.659 (2) 0.057*

C7 0.7479 (3) −0.2273 (6) 0.6680 (2) 0.0469 (8)

H7 0.733 (3) −0.144 (6) 0.720 (2) 0.056*

C8 0.8416 (2) −0.1494 (5) 0.62635 (18) 0.0404 (7)

C9 0.8616 (2) −0.2619 (6) 0.5478 (2) 0.0437 (7)

H9 0.925 (3) −0.205 (6) 0.5181 (19) 0.052*

N1 0.6160 (2) −0.7475 (5) 0.50739 (17) 0.0451 (6)

H1N 0.566 (3) −0.799 (6) 0.538 (2) 0.054*

N2 0.9223 (2) 0.0666 (5) 0.66792 (16) 0.0460 (6)

O1 0.55994 (18) −1.0659 (4) 0.39957 (15) 0.0588 (7)

O2 1.0044 (2) 0.1299 (4) 0.63055 (15) 0.0616 (7)

O3 0.9011 (2) 0.1710 (4) 0.73709 (15) 0.0611 (7)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

C1 0.0494 (17) 0.0431 (17) 0.0507 (18) −0.0013 (15) 0.0110 (14) 0.0024 (14)

C2 0.0585 (19) 0.0518 (18) 0.055 (2) −0.0083 (16) 0.0188 (16) −0.0052 (15)

C3 0.0476 (17) 0.0503 (18) 0.0527 (18) −0.0102 (15) 0.0192 (14) 0.0013 (14)

C4 0.0421 (15) 0.0367 (14) 0.0463 (16) −0.0019 (13) 0.0098 (12) 0.0048 (12)

C5 0.0398 (14) 0.0351 (15) 0.0483 (16) −0.0022 (13) 0.0099 (12) 0.0082 (12)

C6 0.0459 (17) 0.0478 (18) 0.0525 (18) −0.0021 (15) 0.0177 (14) 0.0043 (14)

C7 0.0503 (18) 0.0455 (16) 0.0466 (18) 0.0015 (15) 0.0127 (14) 0.0011 (14)

C8 0.0431 (15) 0.0354 (14) 0.0432 (16) 0.0010 (13) 0.0090 (12) 0.0092 (12)

C9 0.0419 (16) 0.0431 (16) 0.0486 (17) −0.0026 (13) 0.0150 (14) 0.0044 (13)

N1 0.0406 (13) 0.0469 (14) 0.0499 (15) −0.0084 (12) 0.0138 (11) 0.0031 (11)

supporting information

sup-3 Acta Cryst. (2005). E61, o2992–o2993

O2 0.0647 (14) 0.0614 (14) 0.0622 (14) −0.0222 (12) 0.0210 (11) 0.0003 (11)

O3 0.0682 (15) 0.0575 (14) 0.0590 (15) −0.0083 (12) 0.0151 (12) −0.0132 (11)

Geometric parameters (Å, º)

C1—O1 1.239 (3) C6—C7 1.389 (4)

C1—N1 1.366 (4) C6—H6 0.92 (3)

C1—C2 1.442 (4) C7—C8 1.385 (4)

C2—C3 1.347 (4) C7—H7 0.93 (3)

C2—H2 0.99 (3) C8—C9 1.358 (4)

C3—C4 1.429 (4) C8—N2 1.474 (3)

C3—H3 1.04 (3) C9—H9 0.95 (3)

C4—C9 1.396 (4) N1—H1N 0.83 (3)

C4—C5 1.409 (3) N2—O2 1.214 (3)

C5—N1 1.377 (4) N2—O3 1.220 (3)

C5—C6 1.386 (4)

O1—C1—N1 120.6 (3) C7—C6—H6 115 (2)

O1—C1—C2 123.3 (3) C8—C7—C6 118.8 (3)

N1—C1—C2 116.0 (3) C8—C7—H7 122.1 (18)

C3—C2—C1 121.3 (3) C6—C7—H7 119.1 (18)

C3—C2—H2 122.0 (18) C9—C8—C7 122.6 (3)

C1—C2—H2 116.5 (18) C9—C8—N2 118.4 (2)

C2—C3—C4 120.9 (3) C7—C8—N2 119.0 (3)

C2—C3—H3 119.8 (18) C8—C9—C4 119.8 (3)

C4—C3—H3 119.1 (18) C8—C9—H9 122.8 (18)

C9—C4—C5 118.1 (3) C4—C9—H9 117.3 (18)

C9—C4—C3 123.5 (3) C1—N1—C5 124.9 (2)

C5—C4—C3 118.4 (3) C1—N1—H1N 121 (2)

N1—C5—C6 120.4 (3) C5—N1—H1N 114 (2)

N1—C5—C4 118.4 (3) O2—N2—O3 124.7 (3)

C6—C5—C4 121.2 (3) O2—N2—C8 117.8 (2)

C5—C6—C7 119.5 (3) O3—N2—C8 117.5 (2)

C5—C6—H6 125 (2)

O1—C1—C2—C3 −178.1 (3) C6—C7—C8—N2 179.2 (3)

N1—C1—C2—C3 2.0 (5) C7—C8—C9—C4 0.3 (4)

C1—C2—C3—C4 −0.5 (5) N2—C8—C9—C4 −178.9 (2)

C2—C3—C4—C9 178.7 (3) C5—C4—C9—C8 −1.0 (4)

C2—C3—C4—C5 −0.3 (5) C3—C4—C9—C8 −180.0 (3)

C9—C4—C5—N1 −179.4 (2) O1—C1—N1—C5 177.2 (2)

C3—C4—C5—N1 −0.4 (4) C2—C1—N1—C5 −2.8 (4)

C9—C4—C5—C6 1.4 (4) C6—C5—N1—C1 −178.7 (3)

C3—C4—C5—C6 −179.6 (3) C4—C5—N1—C1 2.1 (4)

N1—C5—C6—C7 179.7 (3) C9—C8—N2—O2 −1.3 (4)

C4—C5—C6—C7 −1.1 (5) C7—C8—N2—O2 179.4 (3)

C5—C6—C7—C8 0.4 (4) C9—C8—N2—O3 178.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

C3—H3···O2i _{1.04 (3) 2.48 (3) 3.377 (4) 145 (2)}

C3—H3···O3ii _{1.04 (3) 2.50 (3) 3.230 (4) 127 (2)}

C9—H9···O2i _{0.95 (3) 2.53 (3) 3.371 (4) 147 (2)}

N1—H1N···O1iii _{0.83 (3) 1.97 (3) 2.794 (3) 175 (3)}