3,8-Dimethyl-4-oxo-3,4-dihydro­quinazoline-6-carbonitrile

Tian, H.-Y.; Bi, J.-C.; Zhang, H.-X.; Zhang, J.

doi:10.1107/S1600536812022088

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1959

doi:10.1107/S1600536812022088

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3,8-Dimethyl-4-oxo-3,4-dihydroquinazoline-6-carbonitrile

Hai-Yan Tian,^a Jian-Cong Bi,^a ^* Hong-Xia Zhang ^a and Juan Zhang ^a

^aKey Laboratory of Green Chemical Engineering and Technology of Colleges of Heilongjiang Province, College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150040, People's Republic of China
^*Correspondence e-mail: bjc@126.com

(Received 23 April 2012; accepted 16 May 2012; online 31 May 2012)

In the title compound, C₁₁H₉N₃O, the quinazoline unit is almost planar, with a mean deviation of 0.006 (1) Å from the least-squares plane defined by the ten constituent atoms. In the crystal, molecules are linked by weak C—H⋯N hydrogen bonds.

Related literature

For the synthesis of the title compound, see: Shapiro et al. (2006 ).

Experimental

Crystal data

C₁₁H₉N₃O
M_r = 199.21
Orthorhombic, P n a 2₁
a = 7.0700 (14) Å
b = 13.441 (3) Å
c = 10.156 (2) Å
V = 965.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.45 × 0.30 × 0.25 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.960, T_max = 0.977
8874 measured reflections
1162 independent reflections
1054 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.095
S = 1.07
1162 reflections
138 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯N1ⁱ	0.93	2.58	3.431 (3)	152
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+1]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (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/S1600536812022088/lx2242sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812022088/lx2242Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812022088/lx2242Isup3.cml

checkCIF report

Comment top

Anthranilic diamide compounds are known as new broad spectrum pesticides, which are developed and produced by E.I.Du Pont Company. The title compound is an important intermediate of this kind of pesticides. Herein, we report the crystal structure of the title compound. The title compound crystallizes as the non-centrosymmetric space group P_na21 in spite of having no asymmetric C atoms.

In the title molecule (Fig. 1), the quinazoline unit is almost planar, with a mean deviation of 0.006 (1) Å from the least-squares plane defined by the ten constituent atoms. In the crystal structure, molecules are connected by weak intermolecular C—H···N hydrogen bonds (Table 1).

Related literature top

For the synthesis of the title compound, see: Shapiro et al. (2006).

Experimental top

The title compound was prepared by the reaction of N-methyl-2-amino-5-cyano-3-methylbenzamide and NaCN in DMSO under reflux conditions (Shapiro et al., 2006). Single crystals suitable for X-ray diffraction were obtained by recrystallization of the title compound from ethyl acetate.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (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 with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius.

3,8-Dimethyl-4-oxo-3,4-dihydroquinazoline-6-carbonitrile top

Crystal data top

C₁₁H₉N₃O	F(000) = 416
M_r = 199.21	D_x = 1.371 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 8275 reflections
a = 7.0700 (14) Å	θ = 3.0–27.5°
b = 13.441 (3) Å	µ = 0.09 mm⁻¹
c = 10.156 (2) Å	T = 293 K
V = 965.1 (3) Å³	Blcok, colorless
Z = 4	0.45 × 0.30 × 0.25 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1162 independent reflections
Radiation source: fine-focus sealed tube	1054 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω scan	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→8
T_min = 0.960, T_max = 0.977	k = −17→17
8874 measured reflections	l = −13→13

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)] = 0.035	Hydrogen site location: difference Fourier map
wR(F²) = 0.095	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0736P)² + 0.0037P] where P = (F_o² + 2F_c²)/3
1162 reflections	(Δ/σ)_max < 0.001
138 parameters	Δρ_max = 0.22 e Å⁻³
1 restraint	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₁H₉N₃O	V = 965.1 (3) Å³
M_r = 199.21	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 7.0700 (14) Å	µ = 0.09 mm⁻¹
b = 13.441 (3) Å	T = 293 K
c = 10.156 (2) Å	0.45 × 0.30 × 0.25 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1162 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1054 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.977	R_int = 0.024
8874 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	1 restraint
wR(F²) = 0.095	H-atom parameters constrained
S = 1.07	Δρ_max = 0.22 e Å⁻³
1162 reflections	Δρ_min = −0.20 e Å⁻³
138 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	0.1413 (2)	0.27920 (15)	−0.02167 (19)	0.0378 (4)
C2	0.1206 (3)	0.37812 (15)	0.02217 (19)	0.0396 (4)
H2	0.1394	0.4300	−0.0370	0.048*
C3	0.0734 (2)	0.39952 (12)	0.1495 (2)	0.0370 (4)
C4	0.0470 (2)	0.31970 (13)	0.23889 (19)	0.0310 (3)
C5	0.0689 (2)	0.22115 (12)	0.19457 (18)	0.0323 (4)
C6	0.1155 (2)	0.20073 (14)	0.06421 (19)	0.0370 (4)
H6	0.1290	0.1354	0.0355	0.044*
C7	0.0396 (2)	0.13796 (13)	0.28618 (19)	0.0359 (4)
C8	−0.0271 (3)	0.26620 (13)	0.44539 (19)	0.0381 (4)
H8	−0.0603	0.2803	0.5320	0.046*
C9	0.1888 (3)	0.25977 (17)	−0.1578 (2)	0.0446 (5)
C10	0.0482 (4)	0.50555 (16)	0.1950 (3)	0.0545 (6)
H10A	0.0682	0.5499	0.1222	0.082*
H10B	0.1382	0.5200	0.2632	0.082*
H10C	−0.0776	0.5143	0.2285	0.082*
C11	−0.0442 (4)	0.09042 (15)	0.5119 (2)	0.0525 (6)
H11A	−0.0593	0.1209	0.5968	0.079*
H11B	0.0612	0.0454	0.5142	0.079*
H11C	−0.1570	0.0544	0.4897	0.079*
N1	0.2256 (3)	0.24416 (16)	−0.2643 (2)	0.0609 (5)
N2	−0.0095 (2)	0.16788 (11)	0.41248 (17)	0.0370 (4)
N3	−0.0021 (2)	0.34132 (12)	0.36812 (16)	0.0375 (4)
O1	0.0553 (2)	0.05017 (10)	0.25774 (18)	0.0547 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0338 (8)	0.0531 (10)	0.0265 (9)	−0.0022 (8)	0.0019 (7)	−0.0016 (8)
C2	0.0431 (9)	0.0448 (9)	0.0309 (9)	−0.0036 (7)	0.0018 (7)	0.0083 (7)
C3	0.0401 (8)	0.0352 (8)	0.0356 (10)	−0.0020 (7)	0.0015 (7)	0.0033 (8)
C4	0.0323 (7)	0.0332 (8)	0.0276 (8)	−0.0002 (6)	0.0006 (6)	−0.0011 (6)
C5	0.0316 (7)	0.0349 (8)	0.0304 (9)	−0.0007 (6)	−0.0001 (6)	−0.0017 (7)
C6	0.0385 (9)	0.0392 (8)	0.0332 (10)	−0.0002 (7)	0.0023 (7)	−0.0057 (7)
C7	0.0402 (8)	0.0340 (8)	0.0335 (9)	−0.0003 (7)	0.0007 (7)	−0.0009 (7)
C8	0.0461 (9)	0.0403 (9)	0.0279 (9)	0.0028 (7)	0.0042 (7)	−0.0013 (7)
C9	0.0431 (10)	0.0586 (12)	0.0321 (11)	−0.0015 (9)	0.0039 (8)	0.0013 (8)
C10	0.0849 (15)	0.0336 (9)	0.0450 (12)	0.0009 (10)	0.0096 (11)	0.0033 (8)
C11	0.0754 (13)	0.0433 (10)	0.0387 (13)	0.0026 (10)	0.0104 (10)	0.0121 (9)
N1	0.0690 (12)	0.0809 (14)	0.0329 (10)	0.0012 (10)	0.0099 (9)	−0.0037 (9)
N2	0.0441 (8)	0.0371 (8)	0.0298 (9)	0.0001 (6)	0.0016 (6)	0.0042 (6)
N3	0.0482 (8)	0.0356 (7)	0.0287 (9)	0.0012 (7)	0.0051 (6)	−0.0023 (6)
O1	0.0816 (11)	0.0328 (6)	0.0498 (10)	0.0011 (7)	0.0053 (8)	−0.0036 (6)

Geometric parameters (Å, º) top

C1—C6	1.381 (3)	C7—N2	1.388 (3)
C1—C2	1.410 (3)	C8—N3	1.291 (2)
C1—C9	1.447 (3)	C8—N2	1.369 (2)
C2—C3	1.366 (3)	C8—H8	0.9300
C2—H2	0.9300	C9—N1	1.132 (3)
C3—C4	1.418 (2)	C10—H10A	0.9600
C3—C10	1.508 (3)	C10—H10B	0.9600
C4—N3	1.388 (2)	C10—H10C	0.9600
C4—C5	1.408 (2)	C11—N2	1.471 (2)
C5—C6	1.392 (3)	C11—H11A	0.9600
C5—C7	1.469 (2)	C11—H11B	0.9600
C6—H6	0.9300	C11—H11C	0.9600
C7—O1	1.220 (2)

C6—C1—C2	120.46 (18)	N3—C8—N2	126.47 (18)
C6—C1—C9	119.78 (19)	N3—C8—H8	116.8
C2—C1—C9	119.76 (19)	N2—C8—H8	116.8
C3—C2—C1	121.54 (17)	N1—C9—C1	179.7 (3)
C3—C2—H2	119.2	C3—C10—H10A	109.5
C1—C2—H2	119.2	C3—C10—H10B	109.5
C2—C3—C4	118.61 (17)	H10A—C10—H10B	109.5
C2—C3—C10	121.16 (18)	C3—C10—H10C	109.5
C4—C3—C10	120.23 (18)	H10A—C10—H10C	109.5
N3—C4—C5	121.79 (16)	H10B—C10—H10C	109.5
N3—C4—C3	118.67 (16)	N2—C11—H11A	109.5
C5—C4—C3	119.54 (16)	N2—C11—H11B	109.5
C6—C5—C4	121.05 (16)	H11A—C11—H11B	109.5
C6—C5—C7	119.06 (15)	N2—C11—H11C	109.5
C4—C5—C7	119.88 (16)	H11A—C11—H11C	109.5
C1—C6—C5	118.80 (16)	H11B—C11—H11C	109.5
C1—C6—H6	120.6	C8—N2—C7	121.87 (16)
C5—C6—H6	120.6	C8—N2—C11	120.03 (18)
O1—C7—N2	121.44 (18)	C7—N2—C11	118.10 (16)
O1—C7—C5	125.00 (19)	C8—N3—C4	116.43 (16)
N2—C7—C5	113.56 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···N1ⁱ	0.93	2.58	3.431 (3)	152

Symmetry code: (i) x−1/2, −y+1/2, z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₉N₃O
M_r	199.21
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	293
a, b, c (Å)	7.0700 (14), 13.441 (3), 10.156 (2)
V (Å³)	965.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.45 × 0.30 × 0.25

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.960, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	8874, 1162, 1054
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.095, 1.07
No. of reflections	1162
No. of parameters	138
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.20

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (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
C8—H8···N1ⁱ	0.93	2.58	3.431 (3)	151.6

Symmetry code: (i) x−1/2, −y+1/2, z+1.

Acknowledgements

The authors thank Harbin University of Science and Technology and Heilongjiang Institute of Science and Technology for supporting this work.

References

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Shapiro, R., Taylor, E. D. & Zimmerman, W. T. (2006). World Patent No. WO2006062978. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar