3,8-Dimethyl­quinazoline-2,4(1H,3H)-dione

Qin, W.-Y.; Liu, B.; Duan, C.-W.; Yin, Q.-X.

doi:10.1107/S1600536811025232

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1927

doi:10.1107/S1600536811025232

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3,8-Dimethylquinazoline-2,4(1H,3H)-dione

Wei-Yan Qin,^a Bo Liu,^a ^* Cong-Wen Duan ^a and Qing-Xiu Yin ^a

^aKey Laboratory of Green Chemical Technology, College of Heilongjiang Province, School of Chemistry and Environmental Engineering, Harbin University of Science and Technology, Harbin 150040, People's Republic of China
^*Correspondence e-mail: liubo@hrbust.edu.cn

(Received 27 June 2011; accepted 27 June 2011; online 6 July 2011)

In the title compound, C₁₀H₁₀N₂O₂, all non-H atoms are approximately co-planar with an r.m.s. deviation of 0.016 Å. In the crystal, molecules are linked into inversion dimers by pairs of N—H⋯O hydrogen bonds. Chains along [010] are buiilt up by π–π interactions [centroid–centroid distance = 3.602 (1) Å] between the benzene and piperazine rings of adjacent molecules.

Related literature

For the synthesis and background to the title compound, see Feng et al. (2010 ).

Experimental

Crystal data

C₁₀H₁₀N₂O₂
M_r = 190.20
Monoclinic, P 2₁ /c
a = 8.3604 (17) Å
b = 4.8599 (10) Å
c = 22.288 (5) Å
β = 92.09 (3)°
V = 905.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.29 × 0.23 × 0.19 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.972, T_max = 0.981
8373 measured reflections
2085 independent reflections
1497 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.143
S = 1.10
2085 reflections
133 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯O2ⁱ	0.888 (19)	2.011 (19)	2.8931 (17)	171.8 (17)
Symmetry code: (i) -x+1, -y+2, -z+1.

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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811025232/ng5192sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025232/ng5192Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811025232/ng5192Isup3.cml

checkCIF report

Comment top

The title compound is the intermediate of a kind of highly potent and selective insecticide (Feng et al., 2010). Herein, we report the synthesis and crystal structure of the title compound.

In the title compound, C₁₀H₁₀N₂O₂, all non-hydrogen atoms lie on the same plane with the Rms about 0.016 Å, the largest deviation being 0.037 (1) Å for atom O2 (Figure 1).

The isolated title compound molecules are linked by N—H···O hydrogen bonds into dimers (Figure 2, Table 1). Furthermore, the chain structures alone [010] direction are bulit up by /pi-/pi interatcions (center to center distances of 3.602 (1) Å) between the phenyl groups and piperazinyl groups of the adjacent molecules (Figure 3).

Related literature top

For the synthesis and background to the title compound, see Feng et al. (2010).

Experimental top

The title compound was synthesized as the reference method (Feng et al., 2010): To a solution of 2-amino-N,3-dimethylbenzamide (1.64 g, 1.0 mmol) in THF (20 ml), bis(trichloromethyl)-carbonate (1.0 g, 0.33 mmol) was added, and then keep stirring for 2h. After that THF was removed and water (20 ml) was added slowly. The resulting suspension was filtered, and the solids were washed with water (15 ml) and dried (yield 65%). The crystals suitable for X-ray diffraction were obtained by slow evaporation from methanol solution at room temperature for several days.

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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level for non-H atoms.
	Fig. 2. A dimer structure showing the N—H···O hydrogen bonds, no involving H atoms have been omitted for clarity.
	Fig. 3. A partial packing view, showing chain structure forming by π-π interactions along [010] direction, no involving H atoms have been omitted for clarity.

3,8-Dimethylquinazoline-2,4(1H,3H)-dione top

Crystal data top

C₁₀H₁₀N₂O₂	F(000) = 400
M_r = 190.20	D_x = 1.396 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6086 reflections
a = 8.3604 (17) Å	θ = 3.0–27.5°
b = 4.8599 (10) Å	µ = 0.10 mm⁻¹
c = 22.288 (5) Å	T = 295 K
β = 92.09 (3)°	Block, colorless
V = 905.0 (3) Å³	0.29 × 0.23 × 0.19 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	2085 independent reflections
Radiation source: fine-focus sealed tube	1497 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scan	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
T_min = 0.972, T_max = 0.981	k = −6→6
8373 measured reflections	l = −28→28

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0833P)² + 0.0221P] where P = (F_o² + 2F_c²)/3
2085 reflections	(Δ/σ)_max < 0.001
133 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₀H₁₀N₂O₂	V = 905.0 (3) Å³
M_r = 190.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3604 (17) Å	µ = 0.10 mm⁻¹
b = 4.8599 (10) Å	T = 295 K
c = 22.288 (5) Å	0.29 × 0.23 × 0.19 mm
β = 92.09 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2085 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1497 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.981	R_int = 0.030
8373 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.22 e Å⁻³
2085 reflections	Δρ_min = −0.18 e Å⁻³
133 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.36317 (16)	0.6713 (2)	0.37609 (6)	0.0319 (3)
C2	0.47592 (17)	0.4802 (3)	0.35641 (6)	0.0378 (3)
C3	0.43348 (19)	0.3256 (3)	0.30632 (7)	0.0436 (4)
H3	0.5058	0.1965	0.2927	0.052*
C4	0.2866 (2)	0.3552 (3)	0.27525 (7)	0.0459 (4)
H4	0.2625	0.2481	0.2415	0.055*
C5	0.17879 (18)	0.5421 (3)	0.29463 (6)	0.0420 (4)
H5	0.0807	0.5633	0.2741	0.050*
C6	0.21521 (16)	0.7020 (3)	0.34530 (6)	0.0343 (3)
C7	0.09745 (16)	0.8962 (3)	0.36722 (6)	0.0371 (3)
C8	0.29243 (17)	1.0222 (3)	0.44833 (6)	0.0359 (3)
C9	0.03023 (19)	1.2458 (4)	0.44098 (7)	0.0499 (4)
H9A	0.0786	1.3429	0.4745	0.075*
H9B	−0.0632	1.1502	0.4536	0.075*
H9C	0.0002	1.3743	0.4099	0.075*
C10	0.63640 (19)	0.4454 (4)	0.38882 (8)	0.0536 (4)
H10A	0.6956	0.3027	0.3698	0.080*
H10B	0.6206	0.3963	0.4299	0.080*
H10C	0.6950	0.6150	0.3874	0.080*
N1	0.14501 (13)	1.0469 (2)	0.41799 (5)	0.0374 (3)
H1	0.486 (2)	0.829 (3)	0.4482 (8)	0.056 (5)*
N2	0.39514 (14)	0.8334 (2)	0.42650 (5)	0.0368 (3)
O1	−0.03642 (13)	0.9286 (3)	0.34450 (5)	0.0551 (4)
O2	0.32575 (13)	1.1631 (2)	0.49285 (5)	0.0510 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0322 (7)	0.0340 (6)	0.0292 (6)	−0.0020 (5)	−0.0025 (5)	0.0018 (5)
C2	0.0353 (7)	0.0401 (7)	0.0378 (7)	0.0022 (6)	0.0001 (6)	0.0014 (6)
C3	0.0483 (9)	0.0425 (8)	0.0404 (8)	0.0021 (7)	0.0063 (6)	−0.0053 (6)
C4	0.0548 (9)	0.0472 (8)	0.0354 (7)	−0.0065 (7)	−0.0019 (7)	−0.0077 (6)
C5	0.0393 (8)	0.0504 (8)	0.0355 (7)	−0.0073 (7)	−0.0088 (6)	0.0019 (6)
C6	0.0329 (7)	0.0372 (7)	0.0324 (7)	−0.0013 (6)	−0.0040 (5)	0.0042 (5)
C7	0.0321 (7)	0.0425 (7)	0.0361 (7)	−0.0007 (6)	−0.0069 (5)	0.0052 (6)
C8	0.0321 (7)	0.0410 (7)	0.0343 (7)	0.0042 (6)	−0.0046 (5)	−0.0005 (6)
C9	0.0401 (8)	0.0572 (9)	0.0522 (9)	0.0160 (7)	0.0007 (7)	−0.0022 (8)
C10	0.0378 (8)	0.0624 (10)	0.0599 (10)	0.0144 (8)	−0.0063 (7)	−0.0102 (8)
N1	0.0291 (6)	0.0434 (6)	0.0393 (6)	0.0069 (5)	−0.0045 (5)	0.0007 (5)
N2	0.0306 (6)	0.0436 (6)	0.0356 (6)	0.0068 (5)	−0.0081 (5)	−0.0050 (5)
O1	0.0362 (6)	0.0710 (8)	0.0566 (7)	0.0086 (5)	−0.0182 (5)	−0.0021 (6)
O2	0.0438 (6)	0.0614 (7)	0.0467 (6)	0.0140 (5)	−0.0139 (5)	−0.0198 (5)

Geometric parameters (Å, º) top

C1—N2	1.3901 (17)	C7—N1	1.3938 (17)
C1—C6	1.4005 (18)	C8—O2	1.2291 (17)
C1—C2	1.4049 (19)	C8—N2	1.3588 (18)
C2—C3	1.381 (2)	C8—N1	1.3891 (17)
C2—C10	1.5099 (19)	C9—N1	1.4675 (19)
C3—C4	1.395 (2)	C9—H9A	0.9600
C3—H3	0.9300	C9—H9B	0.9600
C4—C5	1.361 (2)	C9—H9C	0.9600
C4—H4	0.9300	C10—H10A	0.9600
C5—C6	1.395 (2)	C10—H10B	0.9600
C5—H5	0.9300	C10—H10C	0.9600
C6—C7	1.461 (2)	N2—H1	0.888 (19)
C7—O1	1.2217 (16)

N2—C1—C6	118.44 (12)	O2—C8—N2	122.52 (12)
N2—C1—C2	121.04 (11)	O2—C8—N1	121.05 (13)
C6—C1—C2	120.52 (12)	N2—C8—N1	116.43 (11)
C3—C2—C1	117.16 (13)	N1—C9—H9A	109.5
C3—C2—C10	121.54 (13)	N1—C9—H9B	109.5
C1—C2—C10	121.29 (12)	H9A—C9—H9B	109.5
C2—C3—C4	122.73 (14)	N1—C9—H9C	109.5
C2—C3—H3	118.6	H9A—C9—H9C	109.5
C4—C3—H3	118.6	H9B—C9—H9C	109.5
C5—C4—C3	119.49 (13)	C2—C10—H10A	109.5
C5—C4—H4	120.3	C2—C10—H10B	109.5
C3—C4—H4	120.3	H10A—C10—H10B	109.5
C4—C5—C6	120.07 (13)	C2—C10—H10C	109.5
C4—C5—H5	120.0	H10A—C10—H10C	109.5
C6—C5—H5	120.0	H10B—C10—H10C	109.5
C5—C6—C1	120.02 (13)	C8—N1—C7	124.86 (11)
C5—C6—C7	120.04 (12)	C8—N1—C9	117.83 (12)
C1—C6—C7	119.92 (12)	C7—N1—C9	117.31 (11)
O1—C7—N1	119.92 (13)	C8—N2—C1	124.52 (11)
O1—C7—C6	124.26 (13)	C8—N2—H1	111.4 (11)
N1—C7—C6	115.81 (11)	C1—N2—H1	124.1 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O2ⁱ	0.888 (19)	2.011 (19)	2.8931 (17)	171.8 (17)

Symmetry code: (i) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₂O₂
M_r	190.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	8.3604 (17), 4.8599 (10), 22.288 (5)
β (°)	92.09 (3)
V (Å³)	905.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.29 × 0.23 × 0.19

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.972, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	8373, 2085, 1497
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.143, 1.10
No. of reflections	2085
No. of parameters	133
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.18

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—H1···O2ⁱ	0.888 (19)	2.011 (19)	2.8931 (17)	171.8 (17)

Symmetry code: (i) −x+1, −y+2, −z+1.

Acknowledgements

The authors thank the National Natural Science Foundation of China (NO: 20272011) and Harbin University of Science and Technology for supporting this work.

References

Feng, Q., Liu, Z.-L., Xiong, L.-X., Wang, M.-Z., Li, Y.-Q. & Li, Z.-M. (2010). J. Agric. Food Chem. 58, 12327–12336. Web of Science CSD CrossRef CAS PubMed Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar