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In the title compound, C12H14N4O, inter­molecular N—H...N hydrogen bonds link the mol­ecules into pairs around twofold rotation axes. C—H...O hydrogen bonds and π–π stacking inter­actions with a distance of 3.5555 (15) Å are observed between the pairs.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035714/bi2203sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035714/bi2203Isup2.hkl
Contains datablock I

CCDC reference: 631223

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.061
  • wR factor = 0.178
  • Data-to-parameter ratio = 15.6

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C3 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C1 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C2 PLAT413_ALERT_2_C Short Inter XH3 .. XHn H1A .. H1A .. 2.13 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H5C .. O1 .. 2.61 Ang.
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

N-heterocycles are of considerable importance in view of their presence in several biological systems. Quinazoline and its derivatives have a wide range of biological activity, and are potential drugs for various disorders. They have been found to be anti-cancer, anti-inflammatory and anti-hypertensive agents (Seijas et al., 2000; Rewcastle et al., 1995). In this direction, many multidentate N-heterocycles and their complexes have been prepared and characterized.

The molecular structure and unit-cell contents of the title compound are shown in Figures 1 and 2, respectively. The bond lengths and angles agree well with values reported in the literature for some analogous structures containing quinazoline or pyrimidine rings (Djinović et al., 1990). Both the benzene and pyrimidine rings of the quinazoline group adopt almost planar conformations. The average value of the endocyclic bond angles for the pyrimidine ring and benzene ring are very close to 120°.

Intermolecular N—H···N hydrogen bonds (Table 1) link the molecules into pairs around 2-fold rotation axes. Molecules in adjacent pairs adopt centrosymmetric orientations with ππ stacking interactions between symmetry-related benzene and pyrimidine rings (Figure 3). The centroid-centroid distance between the N3/C4/N4/C12/C7/C8 and C7/C8/C9/C10/C11/C12 rings is 3.5555 (15) Å [symmetry code: -x, -y, 1 - z]. C—H···O interactions are also observed between molecules (Table 1).

Related literature top

For related literature, see: Djinović et al. (1990); Rewcastle et al. (1995); Seijas et al. (2000); Rajnikant et al. (2001); Tulyasheva et al. (2005); Naveen et al. (2006).

Experimental top

2-Aminobenzoic acid (2.74 g, 20 mmol) and methyl iso-thiocyanomethane (1.46 g, 20 mmol) were refluxed for 2 h in 50 ml acetic acid, yielding a pale yellow precipitate, which was filtered and dried. The resulting powder (1.92 g) was dissolved in 50 ml butanol, and hydrazine (2.5 ml) was added. The mixture was refluxed for 4–5 h, and the title compound was obtained as a white powder. After filtration, the powder was dissolved in acetone (30 ml) and colourless crystals were obtained after a few days standing at room temperature.

Refinement top

H atoms bound to C atoms were placed geometrically and allowed to ride during refinement with C—H = 0.93 or 0.96 Å and with Uiso(H) = 1.2 or 1.5Ueq(C). Atom H4 was located in a difference Fourier map and refined isotropically without restraint.

Structure description top

N-heterocycles are of considerable importance in view of their presence in several biological systems. Quinazoline and its derivatives have a wide range of biological activity, and are potential drugs for various disorders. They have been found to be anti-cancer, anti-inflammatory and anti-hypertensive agents (Seijas et al., 2000; Rewcastle et al., 1995). In this direction, many multidentate N-heterocycles and their complexes have been prepared and characterized.

The molecular structure and unit-cell contents of the title compound are shown in Figures 1 and 2, respectively. The bond lengths and angles agree well with values reported in the literature for some analogous structures containing quinazoline or pyrimidine rings (Djinović et al., 1990). Both the benzene and pyrimidine rings of the quinazoline group adopt almost planar conformations. The average value of the endocyclic bond angles for the pyrimidine ring and benzene ring are very close to 120°.

Intermolecular N—H···N hydrogen bonds (Table 1) link the molecules into pairs around 2-fold rotation axes. Molecules in adjacent pairs adopt centrosymmetric orientations with ππ stacking interactions between symmetry-related benzene and pyrimidine rings (Figure 3). The centroid-centroid distance between the N3/C4/N4/C12/C7/C8 and C7/C8/C9/C10/C11/C12 rings is 3.5555 (15) Å [symmetry code: -x, -y, 1 - z]. C—H···O interactions are also observed between molecules (Table 1).

For related literature, see: Djinović et al. (1990); Rewcastle et al. (1995); Seijas et al. (2000); Rajnikant et al. (2001); Tulyasheva et al. (2005); Naveen et al. (2006).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level for non-H atoms.
[Figure 2] Fig. 2. Unit-cell contents of the title compound. Hydrogen bonds are shown by dashed lines.
[Figure 3] Fig. 3. A view of the ππ stacking interactions between two parallel rings. The centroid-centroid distance between the N3/C4/N4/C12/C7/C8 and C7/C8/C9/C10/C11/C12 rings is 3.5555 (15) Å [symmetry code: -x, -y, 1 - z).
2-(Isopropylidenehydrazono)-3-methyl-2,3-dihydroquinazoline-4(1H)-one top
Crystal data top
C12H14N4OF(000) = 976
Mr = 230.27Dx = 1.290 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2000 reflections
a = 17.042 (5) Åθ = 2.2–26.7°
b = 7.6443 (19) ŵ = 0.09 mm1
c = 18.228 (5) ÅT = 293 K
β = 93.36 (2)°Block, colourless
V = 2370.5 (11) Å30.50 × 0.35 × 0.25 mm
Z = 8
Data collection top
Stoe IPDSII
diffractometer
2474 independent reflections
Radiation source: fine-focus sealed tube1991 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
rotation method scansθmax = 26.7°, θmin = 2.2°
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 2005)
h = 2118
Tmin = 0.961, Tmax = 0.985k = 98
5052 measured reflectionsl = 2323
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.178H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0919P)2 + 1.3884P]
where P = (Fo2 + 2Fc2)/3
2474 reflections(Δ/σ)max = 0.029
159 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
C12H14N4OV = 2370.5 (11) Å3
Mr = 230.27Z = 8
Monoclinic, C2/cMo Kα radiation
a = 17.042 (5) ŵ = 0.09 mm1
b = 7.6443 (19) ÅT = 293 K
c = 18.228 (5) Å0.50 × 0.35 × 0.25 mm
β = 93.36 (2)°
Data collection top
Stoe IPDSII
diffractometer
2474 independent reflections
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 2005)
1991 reflections with I > 2σ(I)
Tmin = 0.961, Tmax = 0.985Rint = 0.030
5052 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0610 restraints
wR(F2) = 0.178H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.29 e Å3
2474 reflectionsΔρmin = 0.31 e Å3
159 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
xyzUiso*/Ueq
C10.57814 (17)0.4861 (4)0.18688 (15)0.0808 (8)
H1A0.52390.49990.19740.097*
H1B0.58150.42720.14070.097*
H1C0.60240.59910.18440.097*
C20.68686 (19)0.4623 (4)0.28983 (16)0.0855 (9)
H2A0.73340.39370.28470.103*
H2B0.67520.46720.34070.103*
H2C0.69520.57860.27200.103*
C30.61960 (12)0.3805 (3)0.24639 (11)0.0533 (5)
C40.59540 (11)0.0259 (2)0.34711 (10)0.0434 (4)
C50.71897 (12)0.0990 (3)0.39858 (15)0.0704 (7)
H5A0.73950.01700.40590.084*
H5B0.73620.14540.35330.084*
H5C0.73760.17260.43860.084*
C60.59394 (13)0.2015 (3)0.44262 (12)0.0555 (5)
C70.50876 (12)0.1824 (2)0.44147 (10)0.0480 (5)
C80.46452 (15)0.2768 (3)0.49027 (11)0.0598 (6)
H80.48970.35270.52390.072*
C90.38448 (16)0.2584 (3)0.48906 (13)0.0673 (6)
H90.35520.32160.52140.081*
C100.34776 (14)0.1443 (4)0.43892 (13)0.0672 (6)
H100.29340.13160.43810.081*
C110.38959 (12)0.0496 (3)0.39044 (11)0.0554 (5)
H110.36380.02600.35710.066*
C120.47093 (11)0.0679 (2)0.39171 (9)0.0443 (4)
N10.59441 (9)0.2260 (2)0.25684 (8)0.0483 (4)
N20.63887 (9)0.1261 (2)0.30930 (9)0.0488 (4)
N30.63284 (9)0.0931 (2)0.39540 (9)0.0514 (4)
N40.51535 (9)0.0280 (2)0.34470 (8)0.0451 (4)
H40.4908 (15)0.101 (3)0.3133 (14)0.063 (7)*
O10.63060 (11)0.3067 (2)0.48180 (12)0.0832 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0830 (17)0.0804 (17)0.0788 (16)0.0074 (14)0.0020 (13)0.0358 (14)
C20.0961 (19)0.0788 (17)0.0796 (16)0.0426 (15)0.0116 (14)0.0101 (14)
C30.0534 (11)0.0584 (12)0.0481 (10)0.0081 (9)0.0041 (8)0.0063 (9)
C40.0438 (9)0.0413 (9)0.0440 (9)0.0009 (7)0.0077 (7)0.0020 (7)
C50.0480 (11)0.0715 (15)0.0892 (17)0.0045 (11)0.0162 (11)0.0151 (13)
C60.0647 (13)0.0433 (10)0.0561 (11)0.0018 (9)0.0165 (9)0.0062 (9)
C70.0616 (12)0.0397 (9)0.0418 (9)0.0042 (8)0.0056 (8)0.0021 (7)
C80.0887 (17)0.0448 (11)0.0452 (10)0.0083 (10)0.0018 (10)0.0017 (8)
C90.0794 (16)0.0671 (14)0.0565 (12)0.0175 (12)0.0148 (11)0.0014 (11)
C100.0574 (12)0.0794 (16)0.0656 (13)0.0091 (12)0.0103 (10)0.0001 (12)
C110.0489 (11)0.0629 (12)0.0539 (11)0.0031 (9)0.0008 (9)0.0018 (9)
C120.0516 (10)0.0413 (9)0.0394 (8)0.0058 (8)0.0035 (7)0.0038 (7)
N10.0455 (8)0.0533 (9)0.0452 (8)0.0054 (7)0.0049 (6)0.0064 (7)
N20.0412 (8)0.0532 (9)0.0511 (9)0.0027 (7)0.0062 (6)0.0053 (7)
N30.0453 (9)0.0494 (9)0.0576 (9)0.0033 (7)0.0126 (7)0.0072 (7)
N40.0403 (8)0.0495 (9)0.0445 (8)0.0010 (7)0.0073 (6)0.0087 (7)
O10.0779 (11)0.0676 (11)0.1006 (13)0.0041 (9)0.0245 (10)0.0375 (10)
Geometric parameters (Å, º) top
C1—C31.496 (3)C6—O11.223 (2)
C1—H1A0.960C6—N31.391 (3)
C1—H1B0.960C6—C71.458 (3)
C1—H1C0.960C7—C121.391 (3)
C2—C31.492 (3)C7—C81.399 (3)
C2—H2A0.960C8—C91.370 (4)
C2—H2B0.960C8—H80.930
C2—H2C0.960C9—C101.386 (4)
C3—N11.275 (3)C9—H90.930
C4—N21.292 (2)C10—C111.373 (3)
C4—N41.362 (2)C10—H100.930
C4—N31.394 (2)C11—C121.392 (3)
C5—N31.466 (3)C11—H110.930
C5—H5A0.960C12—N41.386 (2)
C5—H5B0.960N1—N21.410 (2)
C5—H5C0.960N4—H40.89 (3)
C3—C1—H1A109.5C12—C7—C8119.5 (2)
C3—C1—H1B109.5C12—C7—C6119.69 (18)
H1A—C1—H1B109.5C8—C7—C6120.83 (18)
C3—C1—H1C109.5C9—C8—C7120.6 (2)
H1A—C1—H1C109.5C9—C8—H8119.7
H1B—C1—H1C109.5C7—C8—H8119.7
C3—C2—H2A109.5C8—C9—C10119.1 (2)
C3—C2—H2B109.5C8—C9—H9120.5
H2A—C2—H2B109.5C10—C9—H9120.5
C3—C2—H2C109.5C11—C10—C9121.6 (2)
H2A—C2—H2C109.5C11—C10—H10119.2
H2B—C2—H2C109.5C9—C10—H10119.2
N1—C3—C2124.3 (2)C10—C11—C12119.3 (2)
N1—C3—C1117.4 (2)C10—C11—H11120.3
C2—C3—C1118.3 (2)C12—C11—H11120.3
N2—C4—N4125.47 (17)N4—C12—C7119.13 (17)
N2—C4—N3117.90 (16)N4—C12—C11121.06 (17)
N4—C4—N3116.62 (16)C7—C12—C11119.81 (18)
N3—C5—H5A109.5C3—N1—N2115.55 (16)
N3—C5—H5B109.5C4—N2—N1112.38 (15)
H5A—C5—H5B109.5C6—N3—C4124.23 (17)
N3—C5—H5C109.5C6—N3—C5118.01 (17)
H5A—C5—H5C109.5C4—N3—C5117.71 (17)
H5B—C5—H5C109.5C4—N4—C12123.79 (16)
O1—C6—N3120.5 (2)C4—N4—H4117.5 (16)
O1—C6—C7123.3 (2)C12—N4—H4118.5 (16)
N3—C6—C7116.22 (17)
O1—C6—C7—C12175.7 (2)C1—C3—N1—N2175.12 (19)
N3—C6—C7—C123.7 (3)N4—C4—N2—N17.7 (3)
O1—C6—C7—C84.9 (3)N3—C4—N2—N1173.30 (15)
N3—C6—C7—C8175.71 (17)C3—N1—N2—C4143.76 (18)
C12—C7—C8—C90.5 (3)O1—C6—N3—C4177.7 (2)
C6—C7—C8—C9179.9 (2)C7—C6—N3—C41.7 (3)
C7—C8—C9—C100.2 (3)O1—C6—N3—C54.9 (3)
C8—C9—C10—C110.1 (4)C7—C6—N3—C5175.70 (19)
C9—C10—C11—C120.2 (3)N2—C4—N3—C6176.04 (17)
C8—C7—C12—N4178.54 (16)N4—C4—N3—C63.1 (3)
C6—C7—C12—N40.9 (3)N2—C4—N3—C51.4 (3)
C8—C7—C12—C110.6 (3)N4—C4—N3—C5179.48 (18)
C6—C7—C12—C11179.92 (18)N2—C4—N4—C12172.75 (17)
C10—C11—C12—N4178.67 (19)N3—C4—N4—C126.3 (3)
C10—C11—C12—C70.5 (3)C7—C12—N4—C44.4 (3)
C2—C3—N1—N25.4 (3)C11—C12—N4—C4174.78 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N1i0.89 (3)2.11 (4)2.968 (3)164 (4)
C5—H5c···O1ii0.962.613.345 (3)134
Symmetry codes: (i) x+1, y, z+1/2; (ii) x+3/2, y1/2, z+1.

Experimental details

Crystal data
Chemical formulaC12H14N4O
Mr230.27
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)17.042 (5), 7.6443 (19), 18.228 (5)
β (°) 93.36 (2)
V3)2370.5 (11)
Z8
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.50 × 0.35 × 0.25
Data collection
DiffractometerStoe IPDSII
Absorption correctionNumerical
(X-SHAPE; Stoe & Cie, 2005)
Tmin, Tmax0.961, 0.985
No. of measured, independent and
observed [I > 2σ(I)] reflections
5052, 2474, 1991
Rint0.030
(sin θ/λ)max1)0.633
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.061, 0.178, 1.07
No. of reflections2474
No. of parameters159
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.29, 0.31

Computer programs: X-AREA (Stoe & Cie, 2005), X-AREA, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N1i0.89 (3)2.11 (4)2.968 (3)164 (4)
C5—H5c···O1ii0.962.613.345 (3)134
Symmetry codes: (i) x+1, y, z+1/2; (ii) x+3/2, y1/2, z+1.
 

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