7-Nitro­quinazolin-4(3H)-one

Yong, J.-P.; Yu, G.-P.; Li, J.-M.; Hou, X.-L.; Aisa, H.A.

doi:10.1107/S1600536807062666

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o427

doi:10.1107/S1600536807062666

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7-Nitroquinazolin-4(3H)-one

Jian-Ping Yong,^a,^b Guan-Ping Yu,^a,^b Jiu-Ming Li,^a,^b Xue-Ling Hou ^a and Haji Akber Aisa ^a ^*

^aXinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Science, Urumqi 830011, People's Republic of China, and ^bGraduate School of Chinese Academy of Science, Beijing 100039, People's Republic of China
^*Correspondence e-mail: haji@ms.xjb.ac.cn

(Received 14 November 2007; accepted 23 November 2007; online 11 January 2008)

In the crystal structure of the title compound, C₈H₅N₃O₃, intermolecular N—H⋯O hydrogen bonds link molecules into centrosymmetric dimers. These dimers are, in turn, linked though weak intermolecular C—H⋯O and C—H⋯N hydrogen bonds and π–π stacking interactions, with centroid–centroid distances of 3.678 (3) Å, into a three-dimensional network.

Related literature

For related literature on biological activity, see: Masanori et al. (2003 ); Wolfe et al. (1990 ). For related structures, see: Chadwick & Easton (1983 ); Etter (1983 ).

Experimental

Crystal data

C₈H₅N₃O₃
M_r = 191.15
Monoclinic, P 2₁ /n
a = 5.1063 (10) Å
b = 11.206 (2) Å
c = 13.528 (3) Å
β = 99.19 (3)°
V = 764.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 153 (2) K
0.24 × 0.18 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.969, T_max = 0.979
5749 measured reflections
1340 independent reflections
1215 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.096
S = 1.11
1340 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3ⁱ	0.88	1.98	2.8514 (14)	169
C1—H1B⋯O2ⁱⁱ	0.95	2.54	3.2703 (17)	134
C1—H1B⋯O1ⁱⁱⁱ	0.95	2.55	3.0978 (17)	117
C5—H5A⋯O2^iv	0.95	2.49	3.2846 (16)	142
C7—H7A⋯N1ⁱⁱ	0.95	2.55	3.4402 (18)	155
Symmetry codes: (i) -x+2, -y, -z+1; (ii) -x+1, -y+1, -z+1; (iii) $[x+{\script{3\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[-x-{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXTL (Sheldrick, 2001 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807062666/lh2576sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807062666/lh2576Isup2.hkl

checkCIF report

Comment top

7-Nitro-4(3H)-Quinazolinone (I), is an important intermediate for drugs synthesis and its derivatives show many biological activities including anti-fungal, anti-convulsant (Masanori et al., 2003), anti-bacterial, anti-cancer, anti-inflammatory, and anti-tumor (Wolfe et al., 1990). We report here the crystal structure of (I) (Fig. 1).

In (I) (Fig. 1), all bond lengths and angles are normal and in a good agreement with those reported previously (Chadwick & Easton, 1983; Etter, 1983). Atoms N3 and O3 lie in the 1,2-dihydroquinazoline ring (C1—C8/N1/N2) plane, and the deviations from the least-squares plane through the ring atoms are all smaller than 0.026 (2) Å. The relatively short distances of 3.678 (3)Å between the centroids of 1,2-dihydropyrimidine (C1/C2/C3/C8/N1/N2) and benzene (C3—C8) rings related by (1 + x, y, x) indicates the presence of weak π-π interactions. In the crystal structure, intermolecular N—H···O hydrogen bonds link molecules into centrosymmetric dimers. These dimers, are in turn, linked though weak intermolecular C—H···O and C—H···N hydrogen bonds and π···π stacking interactions into a three-dimensional network.

Related literature top

For related literature on biological activity, see: Masanori et al. (2003); Wolfe et al. (1990). For related structures, see: Chadwick & Easton (1983); Etter (1983).

Experimental top

The title compound was synthesized by the reaction of 4-nitro-2-amino-benezic acid 18.2 g (0.1 mol) and formamidine acetate 10.1 g (0.2 mol) in 100 mL andryous EtOH, refulxing for 6 h. The solid filtrated and washed with 20 ml H₂O, cool 30 ml EtOH and 30 ml e ther, respectively, dried under vacuum to obtain the title compound 15.8 g, yield: 82.8%. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation the solution of 7-Nitro-4(3H)-Quinazolinone in EtOH/acetone/THF (1:1:1 V/V/V) at room temperature over a period of one week.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).

Figures top

	Fig. 1. The molecular structure with displacement ellipsoids drawn at the 35% probability level.
	Fig. 2. The packing of the title compound with hydrogen bonds shown as dashed lines.

7-NitroQuinazolin-4(3H)-one top

Crystal data top

C₈H₅N₃O₃	F(000) = 392
M_r = 191.15	D_x = 1.662 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6207 reflections
a = 5.1063 (10) Å	θ = 6.0–55.0°
b = 11.206 (2) Å	µ = 0.13 mm⁻¹
c = 13.528 (3) Å	T = 153 K
β = 99.19 (3)°	Needle, colorless
V = 764.1 (3) Å³	0.24 × 0.18 × 0.16 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	1340 independent reflections
Radiation source: Rotating Anode	1215 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω Oscillation scans	θ_max = 25.0°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −6→6
T_min = 0.969, T_max = 0.979	k = −13→13
5749 measured reflections	l = −16→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.064P)² + 0.0923P] where P = (F_o² + 2F_c²)/3
1340 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₈H₅N₃O₃	V = 764.1 (3) Å³
M_r = 191.15	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.1063 (10) Å	µ = 0.13 mm⁻¹
b = 11.206 (2) Å	T = 153 K
c = 13.528 (3) Å	0.24 × 0.18 × 0.16 mm
β = 99.19 (3)°

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	1340 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1215 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.979	R_int = 0.021
5749 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.11	Δρ_max = 0.15 e Å⁻³
1340 reflections	Δρ_min = −0.31 e Å⁻³
127 parameters

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) 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) top

	x	y	z	U_iso*/U_eq
O1	−0.37255 (17)	0.37262 (8)	0.24708 (6)	0.0228 (3)
O2	−0.1637 (2)	0.51746 (9)	0.33145 (8)	0.0324 (3)
O3	0.69259 (17)	−0.00398 (7)	0.41669 (6)	0.0203 (3)
N1	0.6334 (2)	0.33230 (10)	0.53066 (8)	0.0214 (3)
N2	0.8443 (2)	0.14538 (9)	0.52489 (7)	0.0183 (3)
H2A	0.9807	0.1015	0.5512	0.022*
C1	0.8209 (2)	0.25752 (11)	0.56195 (9)	0.0206 (3)
H1B	0.9536	0.2827	0.6152	0.025*
C2	0.6655 (2)	0.09785 (11)	0.44863 (8)	0.0163 (3)
C3	0.4471 (2)	0.17821 (10)	0.40975 (8)	0.0160 (3)
C4	0.2491 (2)	0.14293 (11)	0.33110 (9)	0.0188 (3)
H4A	0.2557	0.0658	0.3025	0.023*
C5	0.0451 (2)	0.21960 (11)	0.29509 (9)	0.0194 (3)
H5A	−0.0904	0.1964	0.2421	0.023*
C6	0.0434 (2)	0.33253 (11)	0.33893 (9)	0.0171 (3)
C7	0.2345 (2)	0.37169 (11)	0.41533 (9)	0.0176 (3)
H7A	0.2274	0.4498	0.4421	0.021*
C8	0.4409 (2)	0.29261 (11)	0.45270 (8)	0.0166 (3)
N3	−0.17982 (19)	0.41378 (10)	0.30265 (7)	0.0194 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0179 (5)	0.0261 (6)	0.0224 (5)	−0.0023 (4)	−0.0028 (3)	0.0042 (3)
O2	0.0344 (6)	0.0166 (5)	0.0416 (6)	0.0077 (4)	−0.0086 (4)	−0.0043 (4)
O3	0.0219 (5)	0.0143 (5)	0.0248 (5)	0.0033 (4)	0.0043 (3)	−0.0018 (3)
N1	0.0228 (6)	0.0167 (6)	0.0227 (5)	0.0021 (4)	−0.0023 (4)	−0.0026 (4)
N2	0.0167 (5)	0.0155 (6)	0.0219 (5)	0.0034 (4)	0.0003 (4)	0.0017 (4)
C1	0.0225 (7)	0.0170 (7)	0.0208 (6)	0.0016 (5)	−0.0005 (5)	−0.0008 (4)
C2	0.0170 (6)	0.0146 (7)	0.0183 (6)	−0.0009 (5)	0.0062 (4)	0.0020 (4)
C3	0.0171 (6)	0.0146 (7)	0.0174 (6)	−0.0001 (5)	0.0056 (4)	0.0017 (4)
C4	0.0208 (7)	0.0145 (7)	0.0217 (6)	−0.0011 (5)	0.0049 (5)	−0.0034 (5)
C5	0.0192 (6)	0.0196 (7)	0.0185 (6)	−0.0032 (5)	0.0010 (4)	−0.0011 (5)
C6	0.0165 (6)	0.0156 (6)	0.0195 (6)	0.0014 (5)	0.0036 (4)	0.0033 (5)
C7	0.0201 (7)	0.0127 (6)	0.0199 (6)	0.0010 (5)	0.0033 (5)	−0.0006 (4)
C8	0.0182 (6)	0.0150 (6)	0.0168 (6)	−0.0016 (5)	0.0034 (4)	0.0009 (5)
N3	0.0192 (6)	0.0191 (6)	0.0197 (5)	0.0013 (4)	0.0020 (4)	0.0037 (4)

Geometric parameters (Å, º) top

O1—N3	1.2289 (14)	C3—C4	1.4023 (17)
O2—N3	1.2240 (15)	C3—C8	1.4099 (17)
O3—C2	1.2358 (15)	C4—C5	1.3779 (18)
N1—C1	1.2916 (17)	C4—H4A	0.9500
N1—C8	1.3946 (16)	C5—C6	1.3982 (18)
N2—C1	1.3652 (16)	C5—H5A	0.9500
N2—C2	1.3713 (16)	C6—C7	1.3750 (17)
N2—H2A	0.8800	C6—N3	1.4799 (16)
C1—H1B	0.9500	C7—C8	1.4076 (18)
C2—C3	1.4644 (17)	C7—H7A	0.9500

C1—N1—C8	115.91 (11)	C4—C5—C6	118.03 (11)
C1—N2—C2	123.16 (10)	C4—C5—H5A	121.0
C1—N2—H2A	118.4	C6—C5—H5A	121.0
C2—N2—H2A	118.4	C7—C6—C5	123.78 (11)
N1—C1—N2	125.49 (11)	C7—C6—N3	118.00 (11)
N1—C1—H1B	117.3	C5—C6—N3	118.21 (11)
N2—C1—H1B	117.3	C6—C7—C8	118.02 (11)
O3—C2—N2	121.57 (11)	C6—C7—H7A	121.0
O3—C2—C3	124.30 (11)	C8—C7—H7A	121.0
N2—C2—C3	114.12 (11)	N1—C8—C7	117.89 (11)
C4—C3—C8	120.54 (11)	N1—C8—C3	122.83 (11)
C4—C3—C2	120.97 (11)	C7—C8—C3	119.28 (11)
C8—C3—C2	118.49 (11)	O2—N3—O1	123.89 (10)
C5—C4—C3	120.34 (11)	O2—N3—C6	117.99 (10)
C5—C4—H4A	119.8	O1—N3—C6	118.10 (10)
C3—C4—H4A	119.8

C8—N1—C1—N2	0.28 (19)	N3—C6—C7—C8	177.39 (10)
C2—N2—C1—N1	−0.5 (2)	C1—N1—C8—C7	−179.22 (11)
C1—N2—C2—O3	179.92 (11)	C1—N1—C8—C3	0.03 (18)
C1—N2—C2—C3	0.33 (16)	C6—C7—C8—N1	−179.57 (10)
O3—C2—C3—C4	−0.08 (19)	C6—C7—C8—C3	1.15 (17)
N2—C2—C3—C4	179.50 (10)	C4—C3—C8—N1	−179.68 (11)
O3—C2—C3—C8	−179.62 (10)	C2—C3—C8—N1	−0.14 (17)
N2—C2—C3—C8	−0.04 (16)	C4—C3—C8—C7	−0.44 (18)
C8—C3—C4—C5	−0.31 (18)	C2—C3—C8—C7	179.10 (10)
C2—C3—C4—C5	−179.83 (11)	C7—C6—N3—O2	10.75 (16)
C3—C4—C5—C6	0.30 (18)	C5—C6—N3—O2	−170.57 (11)
C4—C5—C6—C7	0.47 (19)	C7—C6—N3—O1	−167.81 (10)
C4—C5—C6—N3	−178.12 (10)	C5—C6—N3—O1	10.87 (16)
C5—C6—C7—C8	−1.21 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3ⁱ	0.88	1.98	2.8514 (14)	169
C1—H1B···O2ⁱⁱ	0.95	2.54	3.2703 (17)	134
C1—H1B···O1ⁱⁱⁱ	0.95	2.55	3.0978 (17)	117
C5—H5A···O2^iv	0.95	2.49	3.2846 (16)	142
C7—H7A···N1ⁱⁱ	0.95	2.55	3.4402 (18)	155

Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+3/2, −y+1/2, z+1/2; (iv) −x−1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₅N₃O₃
M_r	191.15
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	153
a, b, c (Å)	5.1063 (10), 11.206 (2), 13.528 (3)
β (°)	99.19 (3)
V (Å³)	764.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.24 × 0.18 × 0.16

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.969, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	5749, 1340, 1215
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.096, 1.11
No. of reflections	1340
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.31

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXTL (Sheldrick, 2001).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3ⁱ	0.88	1.98	2.8514 (14)	168.5
C1—H1B···O2ⁱⁱ	0.95	2.54	3.2703 (17)	134.1
C1—H1B···O1ⁱⁱⁱ	0.95	2.55	3.0978 (17)	117.1
C5—H5A···O2^iv	0.95	2.49	3.2846 (16)	141.5
C7—H7A···N1ⁱⁱ	0.95	2.55	3.4402 (18)	155.4

Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+3/2, −y+1/2, z+1/2; (iv) −x−1/2, y−1/2, −z+1/2.

Acknowledgements

This work is financially supported the Foundation of Xinjiang Key Laboratory of Plant Resources and Natural Products Chemistry (No. 2006–6).

References

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