supplementary materials


pv2636 scheme

Acta Cryst. (2013). E69, o1094    [ doi:10.1107/S1600536813016073 ]

3-Methyl-2-(3,3,3-trichloro-2-hydroxypropyl)quinazolin-4(3H)-one

F. R. Utayeva, R. Y. Okmanov, N. I. Mukarramov, K. M. Shakhidoyatov and B. Tashkhodjaev

Abstract top

The title molecule, C12H11Cl3N2O2, contains planar quinazolin-4(3H)-one (r.m.s. deviation = 0.0257 Å) and propyl fragments, forming a dihedral angle of 10.4 (2)°. An intramolecular O-H...N hydorgen bond occurs. In the crystal, O-H...O hydrogen bonds link the molecules into an infinite chain running parallel to the b axis.

Comment top

Quinazolin-4(3H)-one and its derivatives are well known to have broad biological activity, such as antibacterial, antifungal, antimicrobial, anticonvulsant and others (Yang et al., 2009). As well as among quinazolin-4(3H)-one derivatives found fungicide, insecticide active compounds for agriculture (Shakhidoyatov, 1988). Reaction of 2,3-dimethylquinazolin-4(3H)-one with chloral hydrate in the of reagent–substrate 1:1.2 ratio resulted in the title compound. The structure of the received product was investigated by X-ray diffraction, 1H NMR, UF and IR methods.

The bond distances and angles in the title compound (Fig. 1) agree very well with the corresponding bond distances and angles reported in closely related compounds (Tashkhodjaev et al., 2001). The molecule has planar quinazolin-4(3H)-one (r.m.s. deviation of 0.0257 Å) and propyl fragment. The angle between planes of quinazolin-4(3H)-one ring and n-propyl fragment is 10.4 (2)°. The sum of bond angles at atom N3 (close to 360°) and bond length indicate sp2 hybridization of atom N3. It indicates that the lone electronic pair of nitrogen atom participate in a conjugation with π-electrons of pyrimidine rings.

In the crystal structure of the title compound is observed a cyclic S(6) intramolecular O2—H···N1 hydrogen bond (Bernstein et al., 1995). Another O2—H···O1C4 hydrogen bond forms an infinite chain along the b-axis (Figure 2 & Table 1).

Related literature top

For the biological properties of quinazolin-4(3H)-one derivatives, see: Yang et al. (2009). For the fungicidal and insecticidal activity and syntheses of quinazolin-4(3H)-one derivatives, see; Shakhidoyatov (1988). For related structures of quinazolin-4(3H)-one derivatives, see; Tashkhodjaev et al. (2001). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

In the pear-shaped flask were placed 2,3-dimethylquinazolin-4(3H)-one (0.348 g, 2 mmol) and chloral hydrate (2,2,2-trichloroethane-1,1-diol) (0.397 g, 2.4 mmol) and heated in an oil bath at 403 K for 6 h (Figure 3). The resulting solid was recrystallized from cyclohexane, yield 0.378 g (59%). The purity of synthesized compound was checked by thin layer chromatography (TLC) on plate Whatman AL Sil G/UV (Germany), viewing box 254 nm. Eluents: benzene/acetone (4:1). Rf 0.65. Colorless crystals, suitable for X-ray (in the form of the prisms and with size 0.23x0.20x0.18 mm) were obtained from ethanol at room temperature, m.p. 423–425 K.

Refinement top

The hydrogen atom of the hydroxyl group were located from a difference Fourier synthesis and were allowed to refine. All other H atoms were placed geometrically (with C—H distances of 0.98 Å for CH; 0.97 Å for CH2; 0.96 Å for CH3; and 0.93 Å for Car) and included in the refinement in a riding motion approximation with Uiso=1.2Ueq(C) [Uiso=1.5Ueq(C,O) for methyl H atoms].

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atom numbering scheme. The displacement ellipsoid are drawn at the 50% probability level. Intramolecular H-bond is shown with dashed lines.
[Figure 2] Fig. 2. A view of the O—H···O hydrogen bonds (dotted lines) in the crystal structure of the title compound.
[Figure 3] Fig. 3. Reaction scheme.
3-Methyl-2-(3,3,3-trichloro-2-hydroxypropyl)quinazolin-4(3H)-one top
Crystal data top
C12H11Cl3N2O2Dx = 1.566 Mg m3
Mr = 321.58Melting point: 423(2) K
Orthorhombic, PbcaCu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ac 2abCell parameters from 1044 reflections
a = 9.3440 (19) Åθ = 3.4–35.8°
b = 11.352 (2) ŵ = 6.09 mm1
c = 25.719 (5) ÅT = 291 K
V = 2728.2 (10) Å3Prizmatic, colorless
Z = 80.23 × 0.20 × 0.18 mm
F(000) = 1312
Data collection top
Oxford Diffraction Xcalibur Ruby
diffractometer
2833 independent reflections
Radiation source: Enhance (Cu) X-ray Source2273 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
Detector resolution: 10.2576 pixels mm-1θmax = 76.4°, θmin = 3.4°
ω scansh = 1011
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
k = 1314
Tmin = 0.284, Tmax = 0.334l = 3231
8631 measured reflections
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0775P)2]
where P = (Fo2 + 2Fc2)/3
2833 reflections(Δ/σ)max < 0.001
177 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.43 e Å3
Crystal data top
C12H11Cl3N2O2V = 2728.2 (10) Å3
Mr = 321.58Z = 8
Orthorhombic, PbcaCu Kα radiation
a = 9.3440 (19) ŵ = 6.09 mm1
b = 11.352 (2) ÅT = 291 K
c = 25.719 (5) Å0.23 × 0.20 × 0.18 mm
Data collection top
Oxford Diffraction Xcalibur Ruby
diffractometer
2833 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
2273 reflections with I > 2σ(I)
Tmin = 0.284, Tmax = 0.334Rint = 0.032
8631 measured reflectionsθmax = 76.4°
Refinement top
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.116Δρmax = 0.34 e Å3
S = 1.03Δρmin = 0.43 e Å3
2833 reflectionsAbsolute structure: ?
177 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. 1H NMR (400 MHz, DMSO): 8.11 (1H, d, J7.9 Hz, H-5), 7.80 (1H, t, J7.9 Hz, H-7), 7.64 (1H, d, J7.9 Hz, H-8), 7.50 (1H, t, J7.9 Hz, H-6), 7.06 (1H, b.d, J4.8 Hz, OH), 4.84 (1H, b.d, J8.6 Hz, CH-10), 3.46 (1H, m, H-9 e), 3.22 (1H, dd, J15.6, J9.2 Hz, H-9a), 3.6 (3H, s, CH3-12).

In the IR spectrum of the title compound were observed absorption bands due to the stretching vibrations of 3401 sm-1 for OH, 2829 sm-1 for CH3, 1657 sm-1 for CO, 1594 sm-1 for CN, 1563 sm-1 for CC– groups. Additionally, at 695 sm-1 was observed p–p valence vibrations of the C—Cl group.

The UV spectrum of title compound in ethanol is characterized by absorption bands at 225, 266, 305 and 316 nm.

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
O10.5628 (2)0.70184 (16)0.27949 (7)0.0607 (5)
N10.27902 (19)0.46334 (15)0.22269 (6)0.0373 (4)
C20.3539 (2)0.53163 (17)0.19344 (7)0.0331 (4)
N30.44671 (19)0.61703 (15)0.21185 (6)0.0375 (4)
C40.4735 (2)0.62977 (19)0.26492 (8)0.0418 (5)
C4A0.3879 (2)0.5557 (2)0.29826 (8)0.0427 (5)
C50.3995 (3)0.5667 (2)0.35264 (9)0.0573 (7)
H5A0.46270.62080.36710.069*
C60.3168 (3)0.4969 (3)0.38393 (9)0.0682 (8)
H6A0.32530.50210.41990.082*
C70.2197 (3)0.4179 (3)0.36200 (10)0.0640 (8)
H7A0.16310.37150.38360.077*
C80.2063 (3)0.4073 (2)0.30879 (9)0.0508 (6)
H8A0.14060.35480.29460.061*
C8A0.2923 (2)0.47628 (19)0.27638 (8)0.0396 (5)
C90.3415 (2)0.52114 (18)0.13538 (7)0.0379 (4)
H9A0.43620.51140.12060.046*
H9B0.30100.59330.12150.046*
C100.2482 (2)0.41768 (17)0.11937 (7)0.0345 (4)
H10A0.15450.42560.13610.041*
C110.2271 (2)0.41360 (18)0.06012 (7)0.0388 (4)
C120.5242 (3)0.6964 (2)0.17710 (9)0.0499 (6)
H12A0.47070.70660.14550.075*
H12B0.61630.66350.16920.075*
H12C0.53650.77140.19380.075*
O20.3064 (2)0.30816 (13)0.13248 (6)0.0496 (4)
Cl10.10438 (8)0.30035 (5)0.04356 (2)0.0569 (2)
Cl20.15423 (7)0.54822 (5)0.03761 (2)0.05238 (19)
Cl30.38904 (8)0.38646 (8)0.02721 (3)0.0712 (2)
H20.326 (3)0.299 (3)0.1623 (13)0.075 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0610 (10)0.0636 (11)0.0576 (10)0.0084 (10)0.0205 (8)0.0186 (8)
N10.0407 (9)0.0369 (9)0.0343 (8)0.0009 (8)0.0039 (7)0.0022 (7)
C20.0328 (9)0.0323 (9)0.0342 (9)0.0032 (8)0.0072 (7)0.0039 (7)
N30.0378 (8)0.0373 (9)0.0372 (8)0.0012 (8)0.0083 (7)0.0037 (7)
C40.0425 (11)0.0428 (11)0.0401 (10)0.0062 (10)0.0121 (9)0.0116 (8)
C4A0.0443 (11)0.0494 (12)0.0345 (10)0.0150 (10)0.0070 (8)0.0056 (8)
C50.0608 (15)0.0744 (17)0.0365 (11)0.0162 (13)0.0099 (11)0.0098 (11)
C60.0766 (18)0.093 (2)0.0348 (11)0.0242 (18)0.0023 (12)0.0001 (13)
C70.0720 (18)0.0722 (17)0.0479 (13)0.0240 (15)0.0159 (13)0.0142 (12)
C80.0552 (14)0.0496 (13)0.0477 (12)0.0098 (11)0.0052 (10)0.0040 (10)
C8A0.0423 (11)0.0411 (10)0.0355 (9)0.0117 (9)0.0026 (8)0.0018 (8)
C90.0425 (10)0.0406 (10)0.0307 (9)0.0041 (9)0.0069 (8)0.0016 (8)
C100.0406 (10)0.0345 (10)0.0285 (8)0.0006 (8)0.0059 (8)0.0008 (7)
C110.0468 (11)0.0369 (10)0.0326 (9)0.0005 (9)0.0060 (8)0.0012 (8)
C120.0498 (13)0.0456 (12)0.0544 (12)0.0112 (11)0.0069 (10)0.0012 (10)
O20.0734 (11)0.0352 (7)0.0403 (8)0.0076 (8)0.0213 (8)0.0016 (6)
Cl10.0771 (4)0.0438 (3)0.0499 (3)0.0108 (3)0.0273 (3)0.0026 (2)
Cl20.0730 (4)0.0420 (3)0.0421 (3)0.0013 (3)0.0189 (3)0.0088 (2)
Cl30.0643 (4)0.0993 (6)0.0499 (3)0.0099 (4)0.0118 (3)0.0174 (3)
Geometric parameters (Å, º) top
O1—C41.227 (3)C8—C8A1.398 (3)
N1—C21.287 (3)C8—H8A0.9300
N1—C8A1.394 (2)C9—C101.520 (3)
C2—N31.384 (3)C9—H9A0.9700
C2—C91.503 (2)C9—H9B0.9700
N3—C41.395 (2)C10—O21.398 (2)
N3—C121.462 (3)C10—C111.537 (3)
C4—C4A1.443 (3)C10—H10A0.9800
C4A—C8A1.388 (3)C11—Cl31.761 (2)
C4A—C51.408 (3)C11—Cl21.770 (2)
C5—C61.369 (4)C11—Cl11.774 (2)
C5—H5A0.9300C12—H12A0.9600
C6—C71.395 (4)C12—H12B0.9600
C6—H6A0.9300C12—H12C0.9600
C7—C81.380 (3)O2—H20.80 (3)
C7—H7A0.9300
C2—N1—C8A117.84 (18)N1—C8A—C8118.7 (2)
N1—C2—N3124.22 (17)C2—C9—C10112.01 (16)
N1—C2—C9119.43 (17)C2—C9—H9A109.2
N3—C2—C9116.35 (17)C10—C9—H9A109.2
C2—N3—C4121.31 (18)C2—C9—H9B109.2
C2—N3—C12122.21 (17)C10—C9—H9B109.2
C4—N3—C12116.47 (18)H9A—C9—H9B107.9
O1—C4—N3119.3 (2)O2—C10—C9113.49 (17)
O1—C4—C4A125.7 (2)O2—C10—C11105.21 (16)
N3—C4—C4A114.95 (18)C9—C10—C11111.45 (16)
C8A—C4A—C5120.6 (2)O2—C10—H10A108.9
C8A—C4A—C4119.60 (19)C9—C10—H10A108.9
C5—C4A—C4119.7 (2)C11—C10—H10A108.9
C6—C5—C4A119.3 (3)C10—C11—Cl3111.79 (15)
C6—C5—H5A120.4C10—C11—Cl2110.34 (14)
C4A—C5—H5A120.4Cl3—C11—Cl2108.92 (12)
C5—C6—C7120.1 (2)C10—C11—Cl1110.05 (14)
C5—C6—H6A119.9Cl3—C11—Cl1108.24 (11)
C7—C6—H6A119.9Cl2—C11—Cl1107.38 (12)
C8—C7—C6121.1 (3)N3—C12—H12A109.5
C8—C7—H7A119.5N3—C12—H12B109.5
C6—C7—H7A119.5H12A—C12—H12B109.5
C7—C8—C8A119.4 (3)N3—C12—H12C109.5
C7—C8—H8A120.3H12A—C12—H12C109.5
C8A—C8—H8A120.3H12B—C12—H12C109.5
C4A—C8A—N1121.8 (2)C10—O2—H2116 (2)
C4A—C8A—C8119.5 (2)
C8A—N1—C2—N30.0 (3)C5—C4A—C8A—N1179.8 (2)
C8A—N1—C2—C9179.45 (18)C4—C4A—C8A—N11.8 (3)
N1—C2—N3—C44.6 (3)C5—C4A—C8A—C80.5 (3)
C9—C2—N3—C4175.97 (19)C4—C4A—C8A—C8178.0 (2)
N1—C2—N3—C12176.9 (2)C2—N1—C8A—C4A3.1 (3)
C9—C2—N3—C122.6 (3)C2—N1—C8A—C8176.62 (19)
C2—N3—C4—O1175.7 (2)C7—C8—C8A—C4A1.2 (3)
C12—N3—C4—O12.9 (3)C7—C8—C8A—N1179.1 (2)
C2—N3—C4—C4A5.5 (3)N1—C2—C9—C105.9 (3)
C12—N3—C4—C4A175.87 (18)N3—C2—C9—C10174.59 (16)
O1—C4—C4A—C8A178.8 (2)C2—C9—C10—O265.8 (2)
N3—C4—C4A—C8A2.5 (3)C2—C9—C10—C11175.64 (17)
O1—C4—C4A—C52.7 (3)O2—C10—C11—Cl358.26 (19)
N3—C4—C4A—C5176.0 (2)C9—C10—C11—Cl365.1 (2)
C8A—C4A—C5—C60.9 (4)O2—C10—C11—Cl2179.63 (14)
C4—C4A—C5—C6179.3 (2)C9—C10—C11—Cl256.2 (2)
C4A—C5—C6—C71.5 (4)O2—C10—C11—Cl162.0 (2)
C5—C6—C7—C80.8 (4)C9—C10—C11—Cl1174.54 (14)
C6—C7—C8—C8A0.5 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.79 (3)2.47 (3)2.924 (2)118 (3)
O2—H2···O1i0.79 (3)2.13 (3)2.842 (2)149 (3)
Symmetry code: (i) x+1, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC12H11Cl3N2O2
Mr321.58
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)291
a, b, c (Å)9.3440 (19), 11.352 (2), 25.719 (5)
V3)2728.2 (10)
Z8
Radiation typeCu Kα
µ (mm1)6.09
Crystal size (mm)0.23 × 0.20 × 0.18
Data collection
DiffractometerOxford Diffraction Xcalibur Ruby
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Tmin, Tmax0.284, 0.334
No. of measured, independent and
observed [I > 2σ(I)] reflections
8631, 2833, 2273
Rint0.032
(sin θ/λ)max1)0.630
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.116, 1.03
No. of reflections2833
No. of parameters177
No. of restraints0
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.34, 0.43

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.79 (3)2.47 (3)2.924 (2)118 (3)
O2—H2···O1i0.79 (3)2.13 (3)2.842 (2)149 (3)
Symmetry code: (i) x+1, y1/2, z+1/2.
Acknowledgements top

We thank the Academy of Sciences of the Republic of Uzbekistan for supporting this study (grant FA-F7-T185).

references
References top

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.

Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.

Shakhidoyatov, Kh. M. (1988). Quinazolin-4-one and their biological activity., edited by M. S. Yunusov, S. R. Tulyaganov & M. M. Yunusov, p. 99. Tashkent: Fan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Tashkhodjaev, B., Turgunov, K. K. & Shakhidoyatov, Kh. M. (2001). J. Struct. Chem. 42, 1040–1043.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.

Yang, X.-H., Chen, X.-B. & Zhou, S.-X. (2009). Acta Cryst. E65, o185–o186.