7-Chloro-6,8-dinitro­quinazolin-4(3H)-one acetic acid monosolvate

Yu, Y.

doi:10.1107/S1600536811055735

organic compounds

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Volume 68| Part 2| February 2012| Page o304

doi:10.1107/S1600536811055735

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7-Chloro-6,8-dinitroquinazolin-4(3H)-one acetic acid monosolvate

Yongqiang Yu ^a ^*

^aDepartment of Organic Chemistry, China Pharmaceutical University, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: ypz_99@yahoo.com.cn

(Received 23 December 2011; accepted 26 December 2011; online 7 January 2012)

In the title compound, C₈H₃ClN₄O₅·C₂H₄O₂, both the nitro groups are close to perpendicular [dihedral angles = 67.62 (15) and 86.73 (12)°] to the almost planar quinazoline unit [r.m.s. deviation = 0.014Å]. In the crystal, both the quinazoline and acetic acid molecules form inversion dimers linked by pairs of N—H⋯O and O—H⋯O hydrogen bonds, respectively. R₂²(8) loops arise in each case.

Related literature

For background to the biological properties of quinazoline derivatives, see: Pandeya et al. (1999 ); Tereshima et al. (1995 ); Wolfe et al. (1990 ). For a related structure, see: Srinivasan et al. (2011 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₃ClN₄O₅·C₂H₄O₂
M_r = 330.65
Triclinic, $[P \overline 1]$
a = 7.3041 (12) Å
b = 9.3952 (16) Å
c = 9.6850 (16) Å
α = 83.813 (2)°
β = 88.172 (2)°
γ = 89.033 (2)°
V = 660.35 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 293 K
0.25 × 0.23 × 0.21 mm

Data collection

Rigaku SCXmini diffractometer
4758 measured reflections
2332 independent reflections
1810 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.123
S = 1.05
2332 reflections
200 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O1ⁱ	0.86	1.97	2.827 (3)	173
O6—H100⋯O7ⁱⁱ	0.83	1.86	2.665 (3)	163
Symmetry codes: (i) -x-1, -y+1, -z+1; (ii) -x+2, -y+2, -z+2.

Data collection: CrystalClear (Rigaku, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811055735/hb6577sup1.cif

Supporting information file. DOI: 10.1107/S1600536811055735/hb6577Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536811055735/hb6577Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536811055735/hb6577Isup4.cml

checkCIF report

Related literature top

For background to the biological properties of quinazoline derivatives, see: Pandeya et al. (1999); Tereshima et al. (1995); Wolfe et al. (1990). For a related structure, see: Srinivasan et al. (2011). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

7-Chloro-quinazolin-4(3H)-one(18.0 g, 100 mmol) was added portionwise to a stirred mixture of concentrated sulfuric acid (60 ml) and fuming nitric acid (60 ml) which had been cooled to 273 K. The mixture was stirred at ambient temperature for 1 h and then heated to 373 K for 4 h. Then it was poured into 800 g crush ice. The precipitate was isolated, washed with water and dried. Recrystallization from acetic acid gives 7-chloro-6,8-dinitroquinazolin-4(3H)-one (14.1 g, 52.1%). Yellow blocks were obtained by slow evaporation of an acetic acid solution at room temperature. m.p.:573 K (decomp.) ¹H-NMR (DMSO– d₆, δ (p.p.m.)): 13.2 (1H, brs), 8.89 (1H, s), 8.44 (1H, s), CI—MS (m/e): 271.5 (M+1).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Partial packing view of the title compound, viewed down the c axis.

7-Chloro-6,8-dinitroquinazolin-4(3H)-one acetic acid monosolvate top

Crystal data top

C₈H₃ClN₄O₅·C₂H₄O₂	Z = 2
M_r = 330.65	F(000) = 336
Triclinic, P1	D_x = 1.663 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3041 (12) Å	Cell parameters from 30 reflections
b = 9.3952 (16) Å	θ = 3–25°
c = 9.6850 (16) Å	µ = 0.33 mm⁻¹
α = 83.813 (2)°	T = 293 K
β = 88.172 (2)°	Block, yellow
γ = 89.033 (2)°	0.25 × 0.23 × 0.21 mm
V = 660.35 (19) Å³

Data collection top

Rigaku SCXmini diffractometer	R_int = 0.023
Radiation source: fine-focus sealed tube	θ_max = 25.1°, θ_min = 2.1°
Graphite monochromator	h = −8→8
ω scans	k = −11→11
4758 measured reflections	l = −11→11
2332 independent reflections	3 standard reflections every 150 reflections
1810 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0589P)² + 0.2567P] where P = (F_o² + 2F_c²)/3
2332 reflections	(Δ/σ)_max < 0.001
200 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₈H₃ClN₄O₅·C₂H₄O₂	γ = 89.033 (2)°
M_r = 330.65	V = 660.35 (19) Å³
Triclinic, P1	Z = 2
a = 7.3041 (12) Å	Mo Kα radiation
b = 9.3952 (16) Å	µ = 0.33 mm⁻¹
c = 9.6850 (16) Å	T = 293 K
α = 83.813 (2)°	0.25 × 0.23 × 0.21 mm
β = 88.172 (2)°

Data collection top

Rigaku SCXmini diffractometer	R_int = 0.023
4758 measured reflections	3 standard reflections every 150 reflections
2332 independent reflections	intensity decay: none
1810 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.05	Δρ_max = 0.34 e Å⁻³
2332 reflections	Δρ_min = −0.32 e Å⁻³
200 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
Cl1	0.45451 (9)	0.28014 (8)	0.85154 (7)	0.0573 (3)
C1	−0.0819 (3)	0.4157 (2)	0.6577 (2)	0.0366 (5)
C2	0.0022 (3)	0.5048 (3)	0.7415 (3)	0.0410 (6)
H2	−0.0516	0.5922	0.7573	0.049*
C3	0.1646 (3)	0.4627 (3)	0.8006 (3)	0.0417 (6)
C4	0.2506 (3)	0.3322 (3)	0.7788 (2)	0.0406 (6)
C5	0.1668 (3)	0.2480 (2)	0.6936 (3)	0.0400 (6)
C6	−0.0007 (3)	0.2851 (2)	0.6312 (2)	0.0386 (6)
C7	−0.2288 (3)	0.2322 (3)	0.4948 (3)	0.0474 (6)
H7	−0.2823	0.1714	0.4385	0.057*
C8	−0.2573 (3)	0.4555 (3)	0.5944 (2)	0.0399 (6)
C9	0.6882 (5)	0.8879 (4)	0.7816 (4)	0.0864 (11)
H9A	0.7294	0.9190	0.6883	0.130*
H9B	0.5696	0.9291	0.7990	0.130*
H9C	0.6807	0.7854	0.7936	0.130*
C10	0.8197 (4)	0.9348 (3)	0.8806 (3)	0.0577 (7)
N1	0.2488 (3)	0.5589 (3)	0.8899 (3)	0.0516 (6)
N2	0.2536 (3)	0.1115 (2)	0.6652 (2)	0.0469 (5)
N3	−0.0740 (3)	0.1927 (2)	0.5468 (2)	0.0473 (5)
N4	−0.3205 (3)	0.3552 (2)	0.5155 (2)	0.0424 (5)
H4A	−0.4242	0.3712	0.4768	0.051*
O1	−0.3420 (2)	0.56686 (18)	0.6085 (2)	0.0546 (5)
O2	0.3030 (4)	0.6707 (3)	0.8373 (3)	0.0982 (9)
O3	0.2565 (4)	0.5191 (4)	1.0109 (3)	0.1116 (11)
O4	0.3643 (3)	0.1136 (2)	0.5693 (2)	0.0664 (6)
O5	0.2093 (3)	0.0052 (2)	0.7389 (2)	0.0735 (6)
O6	0.8157 (3)	1.0667 (2)	0.8998 (2)	0.0722 (6)
H100	0.9096	1.0894	0.9368	0.087*
O7	0.9282 (3)	0.8452 (2)	0.9401 (2)	0.0691 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0381 (4)	0.0782 (5)	0.0559 (5)	0.0006 (3)	−0.0151 (3)	−0.0054 (3)
C1	0.0351 (12)	0.0392 (12)	0.0357 (13)	−0.0021 (10)	−0.0042 (10)	−0.0032 (10)
C2	0.0410 (14)	0.0386 (12)	0.0440 (14)	−0.0034 (10)	−0.0038 (11)	−0.0063 (10)
C3	0.0399 (13)	0.0480 (14)	0.0387 (13)	−0.0109 (11)	−0.0032 (11)	−0.0097 (11)
C4	0.0329 (13)	0.0504 (14)	0.0383 (13)	−0.0033 (11)	−0.0033 (11)	−0.0023 (11)
C5	0.0368 (13)	0.0403 (13)	0.0431 (14)	−0.0001 (10)	−0.0039 (11)	−0.0049 (11)
C6	0.0369 (13)	0.0394 (12)	0.0398 (13)	−0.0043 (10)	−0.0034 (11)	−0.0049 (10)
C7	0.0445 (15)	0.0473 (14)	0.0529 (16)	−0.0007 (12)	−0.0117 (13)	−0.0140 (12)
C8	0.0369 (13)	0.0418 (13)	0.0412 (14)	−0.0029 (11)	−0.0079 (11)	−0.0030 (11)
C9	0.092 (3)	0.080 (2)	0.090 (3)	−0.004 (2)	−0.037 (2)	−0.009 (2)
C10	0.0504 (17)	0.0579 (18)	0.0637 (19)	−0.0042 (14)	−0.0068 (14)	0.0007 (14)
N1	0.0443 (13)	0.0635 (15)	0.0504 (15)	−0.0095 (11)	−0.0075 (11)	−0.0179 (12)
N2	0.0406 (12)	0.0462 (13)	0.0546 (14)	0.0049 (10)	−0.0073 (11)	−0.0084 (11)
N3	0.0451 (12)	0.0459 (12)	0.0537 (13)	−0.0001 (10)	−0.0124 (10)	−0.0154 (10)
N4	0.0346 (11)	0.0472 (11)	0.0470 (12)	0.0002 (9)	−0.0135 (9)	−0.0090 (9)
O1	0.0483 (11)	0.0442 (10)	0.0745 (13)	0.0110 (8)	−0.0226 (10)	−0.0169 (9)
O2	0.132 (2)	0.0697 (15)	0.0967 (19)	−0.0419 (15)	−0.0373 (17)	−0.0089 (14)
O3	0.135 (3)	0.154 (3)	0.0519 (15)	−0.075 (2)	−0.0054 (16)	−0.0282 (16)
O4	0.0610 (13)	0.0697 (13)	0.0686 (14)	0.0091 (10)	0.0139 (11)	−0.0138 (11)
O5	0.0827 (16)	0.0466 (11)	0.0875 (16)	0.0069 (10)	0.0103 (13)	0.0048 (11)
O6	0.0634 (13)	0.0667 (14)	0.0885 (16)	0.0045 (10)	−0.0276 (12)	−0.0107 (12)
O7	0.0586 (12)	0.0571 (12)	0.0892 (16)	−0.0049 (10)	−0.0190 (12)	0.0094 (11)

Geometric parameters (Å, º) top

Cl1—C4	1.710 (2)	C8—O1	1.225 (3)
C1—C2	1.390 (3)	C8—N4	1.371 (3)
C1—C6	1.399 (3)	C9—C10	1.482 (4)
C1—C8	1.463 (3)	C9—H9A	0.9600
C2—C3	1.368 (3)	C9—H9B	0.9600
C2—H2	0.9300	C9—H9C	0.9600
C3—C4	1.402 (3)	C10—O7	1.253 (4)
C3—N1	1.471 (3)	C10—O6	1.273 (3)
C4—C5	1.367 (3)	N1—O2	1.186 (3)
C5—C6	1.404 (3)	N1—O3	1.193 (3)
C5—N2	1.470 (3)	N2—O5	1.206 (3)
C6—N3	1.380 (3)	N2—O4	1.210 (3)
C7—N3	1.285 (3)	N4—H4A	0.8600
C7—N4	1.356 (3)	O6—H100	0.8254
C7—H7	0.9300

C2—C1—C6	120.8 (2)	O1—C8—C1	124.6 (2)
C2—C1—C8	121.1 (2)	N4—C8—C1	113.4 (2)
C6—C1—C8	118.0 (2)	C10—C9—H9A	109.5
C3—C2—C1	119.4 (2)	C10—C9—H9B	109.5
C3—C2—H2	120.3	H9A—C9—H9B	109.5
C1—C2—H2	120.3	C10—C9—H9C	109.5
C2—C3—C4	122.0 (2)	H9A—C9—H9C	109.5
C2—C3—N1	118.0 (2)	H9B—C9—H9C	109.5
C4—C3—N1	120.0 (2)	O7—C10—O6	123.4 (3)
C5—C4—C3	117.3 (2)	O7—C10—C9	119.6 (3)
C5—C4—Cl1	120.62 (19)	O6—C10—C9	117.0 (3)
C3—C4—Cl1	122.05 (19)	O2—N1—O3	124.5 (3)
C4—C5—C6	123.1 (2)	O2—N1—C3	117.9 (2)
C4—C5—N2	119.3 (2)	O3—N1—C3	117.5 (3)
C6—C5—N2	117.6 (2)	O5—N2—O4	124.6 (2)
N3—C6—C1	124.0 (2)	O5—N2—C5	117.7 (2)
N3—C6—C5	118.7 (2)	O4—N2—C5	117.7 (2)
C1—C6—C5	117.3 (2)	C7—N3—C6	115.4 (2)
N3—C7—N4	125.3 (2)	C7—N4—C8	123.8 (2)
N3—C7—H7	117.3	C7—N4—H4A	118.1
N4—C7—H7	117.3	C8—N4—H4A	118.1
O1—C8—N4	122.0 (2)	C10—O6—H100	111.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1ⁱ	0.86	1.97	2.827 (3)	173
O6—H100···O7ⁱⁱ	0.83	1.86	2.665 (3)	163

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

Experimental details

Crystal data
Chemical formula	C₈H₃ClN₄O₅·C₂H₄O₂
M_r	330.65
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.3041 (12), 9.3952 (16), 9.6850 (16)
α, β, γ (°)	83.813 (2), 88.172 (2), 89.033 (2)
V (Å³)	660.35 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.25 × 0.23 × 0.21

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4758, 2332, 1810
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.123, 1.05
No. of reflections	2332
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.32

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1ⁱ	0.86	1.97	2.827 (3)	173
O6—H100···O7ⁱⁱ	0.83	1.86	2.665 (3)	163

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

Acknowledgements

The author gratefully acknowledges financial support by the Natural Science Foundation of Jiangsu Province (BK2009293).

References

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