Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035714/bi2203sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035714/bi2203Isup2.hkl |
CCDC reference: 631223
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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.
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.
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 π–π 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).
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).
C12H14N4O | F(000) = 976 |
Mr = 230.27 | Dx = 1.290 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2000 reflections |
a = 17.042 (5) Å | θ = 2.2–26.7° |
b = 7.6443 (19) Å | µ = 0.09 mm−1 |
c = 18.228 (5) Å | T = 293 K |
β = 93.36 (2)° | Block, colourless |
V = 2370.5 (11) Å3 | 0.50 × 0.35 × 0.25 mm |
Z = 8 |
Stoe IPDSII diffractometer | 2474 independent reflections |
Radiation source: fine-focus sealed tube | 1991 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
rotation method scans | θmax = 26.7°, θmin = 2.2° |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2005) | h = −21→18 |
Tmin = 0.961, Tmax = 0.985 | k = −9→8 |
5052 measured reflections | l = −23→23 |
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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.178 | H 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 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C12H14N4O | V = 2370.5 (11) Å3 |
Mr = 230.27 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.042 (5) Å | µ = 0.09 mm−1 |
b = 7.6443 (19) Å | T = 293 K |
c = 18.228 (5) Å | 0.50 × 0.35 × 0.25 mm |
β = 93.36 (2)° |
Stoe IPDSII diffractometer | 2474 independent reflections |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2005) | 1991 reflections with I > 2σ(I) |
Tmin = 0.961, Tmax = 0.985 | Rint = 0.030 |
5052 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.178 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.29 e Å−3 |
2474 reflections | Δρmin = −0.31 e Å−3 |
159 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.57814 (17) | 0.4861 (4) | 0.18688 (15) | 0.0808 (8) | |
H1A | 0.5239 | 0.4999 | 0.1974 | 0.097* | |
H1B | 0.5815 | 0.4272 | 0.1407 | 0.097* | |
H1C | 0.6024 | 0.5991 | 0.1844 | 0.097* | |
C2 | 0.68686 (19) | 0.4623 (4) | 0.28983 (16) | 0.0855 (9) | |
H2A | 0.7334 | 0.3937 | 0.2847 | 0.103* | |
H2B | 0.6752 | 0.4672 | 0.3407 | 0.103* | |
H2C | 0.6952 | 0.5786 | 0.2720 | 0.103* | |
C3 | 0.61960 (12) | 0.3805 (3) | 0.24639 (11) | 0.0533 (5) | |
C4 | 0.59540 (11) | 0.0259 (2) | 0.34711 (10) | 0.0434 (4) | |
C5 | 0.71897 (12) | −0.0990 (3) | 0.39858 (15) | 0.0704 (7) | |
H5A | 0.7395 | 0.0170 | 0.4059 | 0.084* | |
H5B | 0.7362 | −0.1454 | 0.3533 | 0.084* | |
H5C | 0.7376 | −0.1726 | 0.4386 | 0.084* | |
C6 | 0.59394 (13) | −0.2015 (3) | 0.44262 (12) | 0.0555 (5) | |
C7 | 0.50876 (12) | −0.1824 (2) | 0.44147 (10) | 0.0480 (5) | |
C8 | 0.46452 (15) | −0.2768 (3) | 0.49027 (11) | 0.0598 (6) | |
H8 | 0.4897 | −0.3527 | 0.5239 | 0.072* | |
C9 | 0.38448 (16) | −0.2584 (3) | 0.48906 (13) | 0.0673 (6) | |
H9 | 0.3552 | −0.3216 | 0.5214 | 0.081* | |
C10 | 0.34776 (14) | −0.1443 (4) | 0.43892 (13) | 0.0672 (6) | |
H10 | 0.2934 | −0.1316 | 0.4381 | 0.081* | |
C11 | 0.38959 (12) | −0.0496 (3) | 0.39044 (11) | 0.0554 (5) | |
H11 | 0.3638 | 0.0260 | 0.3571 | 0.066* | |
C12 | 0.47093 (11) | −0.0679 (2) | 0.39171 (9) | 0.0443 (4) | |
N1 | 0.59441 (9) | 0.2260 (2) | 0.25684 (8) | 0.0483 (4) | |
N2 | 0.63887 (9) | 0.1261 (2) | 0.30930 (9) | 0.0488 (4) | |
N3 | 0.63284 (9) | −0.0931 (2) | 0.39540 (9) | 0.0514 (4) | |
N4 | 0.51535 (9) | 0.0280 (2) | 0.34470 (8) | 0.0451 (4) | |
H4 | 0.4908 (15) | 0.101 (3) | 0.3133 (14) | 0.063 (7)* | |
O1 | 0.63060 (11) | −0.3067 (2) | 0.48180 (12) | 0.0832 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0830 (17) | 0.0804 (17) | 0.0788 (16) | −0.0074 (14) | 0.0020 (13) | 0.0358 (14) |
C2 | 0.0961 (19) | 0.0788 (17) | 0.0796 (16) | −0.0426 (15) | −0.0116 (14) | 0.0101 (14) |
C3 | 0.0534 (11) | 0.0584 (12) | 0.0481 (10) | −0.0081 (9) | 0.0041 (8) | 0.0063 (9) |
C4 | 0.0438 (9) | 0.0413 (9) | 0.0440 (9) | 0.0009 (7) | −0.0077 (7) | −0.0020 (7) |
C5 | 0.0480 (11) | 0.0715 (15) | 0.0892 (17) | 0.0045 (11) | −0.0162 (11) | 0.0151 (13) |
C6 | 0.0647 (13) | 0.0433 (10) | 0.0561 (11) | −0.0018 (9) | −0.0165 (9) | 0.0062 (9) |
C7 | 0.0616 (12) | 0.0397 (9) | 0.0418 (9) | −0.0042 (8) | −0.0056 (8) | −0.0021 (7) |
C8 | 0.0887 (17) | 0.0448 (11) | 0.0452 (10) | −0.0083 (10) | −0.0018 (10) | 0.0017 (8) |
C9 | 0.0794 (16) | 0.0671 (14) | 0.0565 (12) | −0.0175 (12) | 0.0148 (11) | 0.0014 (11) |
C10 | 0.0574 (12) | 0.0794 (16) | 0.0656 (13) | −0.0091 (12) | 0.0103 (10) | 0.0001 (12) |
C11 | 0.0489 (11) | 0.0629 (12) | 0.0539 (11) | −0.0031 (9) | −0.0008 (9) | 0.0018 (9) |
C12 | 0.0516 (10) | 0.0413 (9) | 0.0394 (8) | −0.0058 (8) | −0.0035 (7) | −0.0038 (7) |
N1 | 0.0455 (8) | 0.0533 (9) | 0.0452 (8) | −0.0054 (7) | −0.0049 (6) | 0.0064 (7) |
N2 | 0.0412 (8) | 0.0532 (9) | 0.0511 (9) | −0.0027 (7) | −0.0062 (6) | 0.0053 (7) |
N3 | 0.0453 (9) | 0.0494 (9) | 0.0576 (9) | 0.0033 (7) | −0.0126 (7) | 0.0072 (7) |
N4 | 0.0403 (8) | 0.0495 (9) | 0.0445 (8) | −0.0010 (7) | −0.0073 (6) | 0.0087 (7) |
O1 | 0.0779 (11) | 0.0676 (11) | 0.1006 (13) | 0.0041 (9) | −0.0245 (10) | 0.0375 (10) |
C1—C3 | 1.496 (3) | C6—O1 | 1.223 (2) |
C1—H1A | 0.960 | C6—N3 | 1.391 (3) |
C1—H1B | 0.960 | C6—C7 | 1.458 (3) |
C1—H1C | 0.960 | C7—C12 | 1.391 (3) |
C2—C3 | 1.492 (3) | C7—C8 | 1.399 (3) |
C2—H2A | 0.960 | C8—C9 | 1.370 (4) |
C2—H2B | 0.960 | C8—H8 | 0.930 |
C2—H2C | 0.960 | C9—C10 | 1.386 (4) |
C3—N1 | 1.275 (3) | C9—H9 | 0.930 |
C4—N2 | 1.292 (2) | C10—C11 | 1.373 (3) |
C4—N4 | 1.362 (2) | C10—H10 | 0.930 |
C4—N3 | 1.394 (2) | C11—C12 | 1.392 (3) |
C5—N3 | 1.466 (3) | C11—H11 | 0.930 |
C5—H5A | 0.960 | C12—N4 | 1.386 (2) |
C5—H5B | 0.960 | N1—N2 | 1.410 (2) |
C5—H5C | 0.960 | N4—H4 | 0.89 (3) |
C3—C1—H1A | 109.5 | C12—C7—C8 | 119.5 (2) |
C3—C1—H1B | 109.5 | C12—C7—C6 | 119.69 (18) |
H1A—C1—H1B | 109.5 | C8—C7—C6 | 120.83 (18) |
C3—C1—H1C | 109.5 | C9—C8—C7 | 120.6 (2) |
H1A—C1—H1C | 109.5 | C9—C8—H8 | 119.7 |
H1B—C1—H1C | 109.5 | C7—C8—H8 | 119.7 |
C3—C2—H2A | 109.5 | C8—C9—C10 | 119.1 (2) |
C3—C2—H2B | 109.5 | C8—C9—H9 | 120.5 |
H2A—C2—H2B | 109.5 | C10—C9—H9 | 120.5 |
C3—C2—H2C | 109.5 | C11—C10—C9 | 121.6 (2) |
H2A—C2—H2C | 109.5 | C11—C10—H10 | 119.2 |
H2B—C2—H2C | 109.5 | C9—C10—H10 | 119.2 |
N1—C3—C2 | 124.3 (2) | C10—C11—C12 | 119.3 (2) |
N1—C3—C1 | 117.4 (2) | C10—C11—H11 | 120.3 |
C2—C3—C1 | 118.3 (2) | C12—C11—H11 | 120.3 |
N2—C4—N4 | 125.47 (17) | N4—C12—C7 | 119.13 (17) |
N2—C4—N3 | 117.90 (16) | N4—C12—C11 | 121.06 (17) |
N4—C4—N3 | 116.62 (16) | C7—C12—C11 | 119.81 (18) |
N3—C5—H5A | 109.5 | C3—N1—N2 | 115.55 (16) |
N3—C5—H5B | 109.5 | C4—N2—N1 | 112.38 (15) |
H5A—C5—H5B | 109.5 | C6—N3—C4 | 124.23 (17) |
N3—C5—H5C | 109.5 | C6—N3—C5 | 118.01 (17) |
H5A—C5—H5C | 109.5 | C4—N3—C5 | 117.71 (17) |
H5B—C5—H5C | 109.5 | C4—N4—C12 | 123.79 (16) |
O1—C6—N3 | 120.5 (2) | C4—N4—H4 | 117.5 (16) |
O1—C6—C7 | 123.3 (2) | C12—N4—H4 | 118.5 (16) |
N3—C6—C7 | 116.22 (17) | ||
O1—C6—C7—C12 | −175.7 (2) | C1—C3—N1—N2 | 175.12 (19) |
N3—C6—C7—C12 | 3.7 (3) | N4—C4—N2—N1 | −7.7 (3) |
O1—C6—C7—C8 | 4.9 (3) | N3—C4—N2—N1 | 173.30 (15) |
N3—C6—C7—C8 | −175.71 (17) | C3—N1—N2—C4 | 143.76 (18) |
C12—C7—C8—C9 | 0.5 (3) | O1—C6—N3—C4 | 177.7 (2) |
C6—C7—C8—C9 | 179.9 (2) | C7—C6—N3—C4 | −1.7 (3) |
C7—C8—C9—C10 | −0.2 (3) | O1—C6—N3—C5 | −4.9 (3) |
C8—C9—C10—C11 | 0.1 (4) | C7—C6—N3—C5 | 175.70 (19) |
C9—C10—C11—C12 | −0.2 (3) | N2—C4—N3—C6 | 176.04 (17) |
C8—C7—C12—N4 | 178.54 (16) | N4—C4—N3—C6 | −3.1 (3) |
C6—C7—C12—N4 | −0.9 (3) | N2—C4—N3—C5 | −1.4 (3) |
C8—C7—C12—C11 | −0.6 (3) | N4—C4—N3—C5 | 179.48 (18) |
C6—C7—C12—C11 | 179.92 (18) | N2—C4—N4—C12 | −172.75 (17) |
C10—C11—C12—N4 | −178.67 (19) | N3—C4—N4—C12 | 6.3 (3) |
C10—C11—C12—C7 | 0.5 (3) | C7—C12—N4—C4 | −4.4 (3) |
C2—C3—N1—N2 | −5.4 (3) | C11—C12—N4—C4 | 174.78 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N1i | 0.89 (3) | 2.11 (4) | 2.968 (3) | 164 (4) |
C5—H5c···O1ii | 0.96 | 2.61 | 3.345 (3) | 134 |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+3/2, −y−1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H14N4O |
Mr | 230.27 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 17.042 (5), 7.6443 (19), 18.228 (5) |
β (°) | 93.36 (2) |
V (Å3) | 2370.5 (11) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.50 × 0.35 × 0.25 |
Data collection | |
Diffractometer | Stoe IPDSII |
Absorption correction | Numerical (X-SHAPE; Stoe & Cie, 2005) |
Tmin, Tmax | 0.961, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5052, 2474, 1991 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.633 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.178, 1.07 |
No. of reflections | 2474 |
No. of parameters | 159 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 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).
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N1i | 0.89 (3) | 2.11 (4) | 2.968 (3) | 164 (4) |
C5—H5c···O1ii | 0.96 | 2.61 | 3.345 (3) | 134 |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+3/2, −y−1/2, −z+1. |
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 π–π 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).