Quinazoline-2,4(1H,3H)-dione

Liu, G.

doi:10.1107/S1600536808024240

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1677

doi:10.1107/S1600536808024240

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Quinazoline-2,4(1H,3H)-dione

Ge Liu ^a ^*

^aChifeng University, Chifeng 024000, People's Republic of China
^*Correspondence e-mail: liu_ge2008@163.com

(Received 5 July 2008; accepted 30 July 2008; online 6 August 2008)

In the title compound, C₈H₆N₂O₂, intermolecular N—H⋯O hydrogen bonds involving the amine and carbonyl groups create centrosymmetric dimers between adjacent nearly coplanar molecules. These dimers are further connected by weak N—H⋯O hydrogen bonds, forming a two-dimensional network. Molecules are packed in the crystal structure with adjacent benzene and pyrimidine rings approximately coplanar; the centroid–centroid separation is 3.863 Å and the dihedral angle between the mean planes is 0.64°, indicating the presence of weak intermolecular face-to-face π–π stacking interactions.

Related literature

For background, see: Goto et al. (1993 ); Mohri (2001 ); For further synthetic details, see: Mizuno et al. (2007 ).

Experimental

Crystal data

C₈H₆N₂O₂
M_r = 162.15
Monoclinic, P 2₁ /c
a = 10.891 (2) Å
b = 5.2810 (11) Å
c = 12.701 (3) Å
β = 99.61 (3)°
V = 720.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 (1) K
0.20 × 0.18 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID-S diffractometer
Absorption correction: none
5683 measured reflections
1262 independent reflections
869 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.103
S = 1.06
1262 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O1ⁱ	0.86	2.00	2.854	176
N1—H1A⋯O1ⁱⁱ	0.86	2.13	2.976	168
Symmetry codes: (i) -x, -y+3, -z+1; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); 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/S1600536808024240/bh2183sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024240/bh2183Isup2.hkl

checkCIF report

Comment top

2,4(1H,3H)-Quinazolinedione derivatives are of interest because of their biological activity, and they have been widely used as key structures in medicinal drugs (Goto et al., 1993; Mohri, 2001; Mizuno et al., 2007). We herein report the crystal structure of the title compound (I). In the molecule (Fig. 1), the bond lengths and angles are within normal ranges. Intermolecular N—H···O hydrogen bonds involving amine NH and carbonyl groups O atoms form a two dimensional network (Table 1 and Fig. 2). Weak π–π stacking interactions are also observed in the crystal structure.

Related literature top

For background, see: Goto et al. (1993); Mohri (2001); For further synthetic details, see: Mizuno et al. (2007).

Experimental top

To a 100-ml, 3-necked flask equipped with condenser, were added 2-aminobenzonitrile (5.91 g, 50 mmol) and 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU, 1.50 ml, 10 mmol) under argon, together with a large magnetic stirring bar. Then, CO₂ (1 bar) was charged at 293 K. The mixture was vigorously stirred under CO₂ (1 bar) at 423 K for 4 h. The resulting white solid was then poured into 1 M HCl (100 ml) and washed with t-BuOMe (200 ml) to give pure (I). Single crystals of (I) were obtained from a water solution, at room temperature, by slow evaporation.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); 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 structure of the title compound with 30% displacement probability ellipsoids.
	Fig. 2. Two dimensional sheet formed by hydrogen bonds (dashed lines) in the title compound.

Quinazoline-2,4(1H,3H)-dione top

Crystal data top

C₈H₆N₂O₂	F(000) = 336
M_r = 162.15	D_x = 1.495 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5473 reflections
a = 10.891 (2) Å	θ = 3.3–27.5°
b = 5.2810 (11) Å	µ = 0.11 mm⁻¹
c = 12.701 (3) Å	T = 293 K
β = 99.61 (3)°	Block, colorless
V = 720.2 (3) Å³	0.20 × 0.18 × 0.15 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	869 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.051
Graphite monochromator	θ_max = 25.0°, θ_min = 3.3°
ω scans	h = −12→12
5683 measured reflections	k = −6→6
1262 independent reflections	l = −15→15

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)] = 0.055	H-atom parameters constrained
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.0327P)² + 0.2501P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.004
1262 reflections	Δρ_max = 0.12 e Å⁻³
110 parameters	Δρ_min = −0.12 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.009 (3)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₈H₆N₂O₂	V = 720.2 (3) Å³
M_r = 162.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.891 (2) Å	µ = 0.11 mm⁻¹
b = 5.2810 (11) Å	T = 293 K
c = 12.701 (3) Å	0.20 × 0.18 × 0.15 mm
β = 99.61 (3)°

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	869 reflections with I > 2σ(I)
5683 measured reflections	R_int = 0.051
1262 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.07	Δρ_max = 0.12 e Å⁻³
1262 reflections	Δρ_min = −0.12 e Å⁻³
110 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.2762 (2)	0.9421 (4)	0.57398 (17)	0.0395 (6)
N1	0.11953 (17)	1.0471 (4)	0.67998 (14)	0.0453 (6)
H1A	0.0866	1.0176	0.7357	0.054*
O1	−0.01889 (16)	1.3655 (3)	0.62957 (12)	0.0546 (5)
C2	0.3772 (2)	0.7919 (5)	0.5574 (2)	0.0494 (7)
H2A	0.4148	0.8190	0.4977	0.059*
N2	0.12516 (17)	1.2702 (4)	0.52514 (14)	0.0442 (6)
H2B	0.0924	1.3842	0.4809	0.053*
O2	0.26963 (17)	1.2019 (3)	0.41910 (13)	0.0633 (6)
C3	0.4210 (2)	0.6050 (5)	0.6289 (2)	0.0560 (8)
H3A	0.4884	0.5060	0.6179	0.067*
C4	0.3646 (2)	0.5637 (5)	0.7176 (2)	0.0540 (7)
H4A	0.3943	0.4359	0.7655	0.065*
C5	0.2655 (2)	0.7091 (5)	0.7357 (2)	0.0502 (7)
H5A	0.2287	0.6809	0.7956	0.060*
C6	0.2210 (2)	0.8984 (4)	0.66362 (17)	0.0388 (6)
C7	0.0702 (2)	1.2336 (5)	0.61374 (18)	0.0419 (6)
C8	0.2277 (2)	1.1435 (5)	0.49911 (18)	0.0444 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0414 (14)	0.0406 (14)	0.0384 (13)	−0.0030 (12)	0.0121 (11)	−0.0038 (12)
N1	0.0517 (13)	0.0533 (13)	0.0344 (11)	0.0086 (11)	0.0179 (10)	0.0109 (10)
O1	0.0556 (11)	0.0681 (13)	0.0450 (10)	0.0219 (10)	0.0221 (8)	0.0109 (9)
C2	0.0500 (16)	0.0520 (17)	0.0499 (16)	0.0001 (14)	0.0191 (13)	−0.0075 (14)
N2	0.0538 (13)	0.0474 (13)	0.0346 (11)	0.0079 (10)	0.0169 (10)	0.0077 (10)
O2	0.0853 (14)	0.0669 (13)	0.0469 (10)	0.0062 (11)	0.0380 (10)	0.0071 (10)
C3	0.0486 (16)	0.0527 (17)	0.0670 (19)	0.0098 (14)	0.0107 (15)	−0.0099 (16)
C4	0.0556 (17)	0.0519 (17)	0.0532 (16)	0.0063 (14)	0.0049 (14)	0.0017 (14)
C5	0.0523 (16)	0.0550 (17)	0.0445 (15)	0.0044 (14)	0.0117 (12)	0.0057 (13)
C6	0.0385 (14)	0.0404 (14)	0.0378 (13)	−0.0006 (12)	0.0077 (11)	−0.0037 (12)
C7	0.0456 (15)	0.0482 (15)	0.0336 (13)	0.0018 (13)	0.0118 (12)	0.0019 (12)
C8	0.0547 (17)	0.0442 (15)	0.0379 (14)	−0.0022 (13)	0.0181 (12)	−0.0070 (12)

Geometric parameters (Å, º) top

C1—C6	1.393 (3)	N2—C8	1.389 (3)
C1—C2	1.401 (3)	N2—H2B	0.8600
C1—C8	1.465 (3)	O2—C8	1.221 (3)
N1—C7	1.348 (3)	C3—C4	1.388 (3)
N1—C6	1.399 (3)	C3—H3A	0.9300
N1—H1A	0.8600	C4—C5	1.375 (3)
O1—C7	1.238 (3)	C4—H4A	0.9300
C2—C3	1.372 (3)	C5—C6	1.387 (3)
C2—H2A	0.9300	C5—H5A	0.9300
N2—C7	1.373 (3)

C6—C1—C2	119.1 (2)	C5—C4—C3	120.9 (3)
C6—C1—C8	119.6 (2)	C5—C4—H4A	119.5
C2—C1—C8	121.3 (2)	C3—C4—H4A	119.5
C7—N1—C6	124.0 (2)	C4—C5—C6	119.3 (2)
C7—N1—H1A	118.0	C4—C5—H5A	120.3
C6—N1—H1A	118.0	C6—C5—H5A	120.3
C3—C2—C1	120.2 (2)	C5—C6—C1	120.5 (2)
C3—C2—H2A	119.9	C5—C6—N1	120.3 (2)
C1—C2—H2A	119.9	C1—C6—N1	119.2 (2)
C7—N2—C8	127.2 (2)	O1—C7—N1	123.4 (2)
C7—N2—H2B	116.4	O1—C7—N2	121.0 (2)
C8—N2—H2B	116.4	N1—C7—N2	115.6 (2)
C2—C3—C4	119.9 (2)	O2—C8—N2	120.2 (2)
C2—C3—H3A	120.0	O2—C8—C1	125.4 (2)
C4—C3—H3A	120.0	N2—C8—C1	114.3 (2)

C6—C1—C2—C3	−0.1 (4)	C7—N1—C6—C1	0.0 (3)
C8—C1—C2—C3	179.8 (2)	C6—N1—C7—O1	−179.3 (2)
C1—C2—C3—C4	0.3 (4)	C6—N1—C7—N2	0.9 (3)
C2—C3—C4—C5	−0.5 (4)	C8—N2—C7—O1	177.6 (2)
C3—C4—C5—C6	0.4 (4)	C8—N2—C7—N1	−2.7 (3)
C4—C5—C6—C1	−0.3 (4)	C7—N2—C8—O2	−177.4 (2)
C4—C5—C6—N1	179.4 (2)	C7—N2—C8—C1	3.1 (3)
C2—C1—C6—C5	0.1 (3)	C6—C1—C8—O2	178.7 (2)
C8—C1—C6—C5	−179.9 (2)	C2—C1—C8—O2	−1.3 (4)
C2—C1—C6—N1	−179.6 (2)	C6—C1—C8—N2	−1.8 (3)
C8—C1—C6—N1	0.4 (3)	C2—C1—C8—N2	178.2 (2)
C7—N1—C6—C5	−179.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1ⁱ	0.86	2.00	2.854	176
N1—H1A···O1ⁱⁱ	0.86	2.13	2.976	168

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

Experimental details

Crystal data
Chemical formula	C₈H₆N₂O₂
M_r	162.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.891 (2), 5.2810 (11), 12.701 (3)
β (°)	99.61 (3)
V (Å³)	720.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID-S diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5683, 1262, 869
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.103, 1.07
No. of reflections	1262
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.12

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), 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
N2—H2B···O1ⁱ	0.860	1.995	2.854	176.26
N1—H1A···O1ⁱⁱ	0.860	2.130	2.976	167.91

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

Acknowledgements

The author thanks Chifeng University for supporting this work.

References

Goto, S., Tsuboi, H. & Kagara, K. (1993). Chem. Express, 8, 761–764. CAS Google Scholar
Mizuno, T., Mihara, M., Nakai, T., Iwai, T. & Ito, T. (2007). Synthesis, pp. 2524–2528. Web of Science CrossRef Google Scholar
Mohri, S. J. (2001). Synth. Org. Chem. Jpn, 59, 514–515. CrossRef CAS Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation,Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar