Crystal structure of 4-meth­oxy­quinazoline

El-Hiti, G.A.; Smith, K.; Hegazy, A.S.; Alshammari, M.B.; Kariuki, B.M.

doi:10.1107/S1600536814025082

organic compounds

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Volume 70| Part 12| December 2014| Page o1279

doi:10.1107/S1600536814025082

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Crystal structure of 4-methoxyquinazoline

Gamal A. El-Hiti,^a ^* Keith Smith,^b Amany S. Hegazy,^b Mohammed B. Alshammari ^c and Benson M. Kariuki ^b ^*

^aCornea Research Chair, Department of Optometry, College of Applied Medical Sciences, King Saud University, PO Box 10219, Riyadh 11433, Saudi Arabia, ^bSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, Wales, and ^cChemistry Department, College of Sciences and Humanities, Salman bin Abdulaziz University, PO Box 83, Al-Kharij 11942, Saudi Arabia
^*Correspondence e-mail: gelhiti@ksu.edu.sa, kariukib@cardiff.ac.uk

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 15 November 2014; accepted 15 November 2014; online 21 November 2014)

The title compound, C₉H₈N₂O, is almost planar, with the C atom of the methoxy group deviating from the mean plane of the quinazoline ring system (r.m.s. deviation = 0.011 Å) by 0.068 (4) Å. In the crystal, molecules form π–π stacks parallel to the b-axis direction [centroid–centroid separation = 3.5140 (18) Å], leading to a herringbone packing arrangement.

Keywords: crystal structure; 4-methoxyquinazoline; quinazoline derivatives; π–π stacks; herringbone packing.

CCDC reference: 1034363

1. Related literature

For the synthesis of quinazoline derivatives, see: Bogert & May (1909 ); Smith et al. (2005 ); Wang et al. (2010 ); Yang et al. (2010 ); Han et al. (2012 ). For the crystal structures of related compounds, see Alshammari et al. (2014 ); Derabli et al. (2013 ); Gao et al. (2012 ); Huang & Tan (2012 ); Jia et al. (2011 ).

2. Experimental

2.1. Crystal data

C₉H₈N₂O
M_r = 160.17
Monoclinic, P 2₁
a = 6.9590 (6) Å
b = 4.0517 (3) Å
c = 13.5858 (12) Å
β = 91.754 (8)°
V = 382.88 (6) Å³
Z = 2
Cu Kα radiation
μ = 0.77 mm⁻¹
T = 150 K
0.57 × 0.12 × 0.08 mm

2.2. Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014 ) T_min = 0.641, T_max = 0.895
2166 measured reflections
1435 independent reflections
1311 reflections with I > 2σ(I)
R_int = 0.040

2.3. Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.159
S = 1.08
1435 reflections
110 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001 ).

Supporting information

CCDC reference: 1034363

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814025082/hb7317sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814025082/hb7317Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814025082/hb7317Isup3.cml

checkCIF report

Structural commentary top

Copper-catalyzed processes offer convenient approaches to various quinazoline derivatives starting from (2-bromophenyl)methylamines, 2-aminobenzylamines or 2-bromobenzonitriles (Wang et al., 2010; Yang et al., 2010; Han et al., 2012). For ring substitution and modification of 4-methoxyquinazolines, see: Smith et al. (2005). 4-Methoxyquinazoline was synthesized in 81% yield from reaction of quinazoline-4(3H)-thione with iodomethane in aqueous methanol containing potassium hydroxide at room temperature for 24 h (Bogert & May, 1909). For the X-ray structures for related compounds, see Alshammari et al. (2014); Derabli et al. (2013); Gao et al. (2012); Huang & Tan (2012); Jia et al. (2011).

The asymmetric unit consists of one molecule of C₉H₈N₂O (Fig. 1). The molecule is almost planar apart from the methyl hydrogen atoms, with C9 deviating from the least squares plane of the quinazoline group by 0.068 (4)Å. The molecules form π-π stacks parallel to the b-axis leading to a herring-bone pattern in the crystal structure (Fig. 2).

Synthesis and crystallization top

To a solution of quinazoline-4(3H)-thione (4.9 g, 30.2 mmol) in a 1:1 mixture of methanol and water (50 ml) containing potassium hydroxide (3.0 g), was added iodomethane (5.7 g, 40.1 mmol) at room temperature. The reaction mixture was stirred for 24 h, then methanol was removed under reduced pressure and the remaining aqueous layer was extracted with diethyl ether (2 × 20 ml). The organic layer was separated, washed with water (2 × 10 ml), dried (MgSO₄), and evaporated under reduced pressure. The residue obtained was purified by column chromatography (silica gel, diethyl ether–hexane, 1:1) to give 4-methoxyquinazoline (3.9 g, 24.4 mmol, 81%) as a white solid. Crystallization from a mixture of ethyl acetate and diethyl ether (1:3 by volume) gave the title compound as colorless needles. mp 34–35°C [lit. 35.4°C; Bogert & May, (1909)]. ¹H NMR (400 MHz, CDCl₃, δ p.p.m.): 8.77 (s, 1 H, H-2), 8.08 (dd, J = 1, 8 Hz, 1 H, H-8), 7.88 (dd, J = 1,8 Hz, 1 H, H-5), 7.76 (app. dt, J = 1, 8 Hz, 1 H, H-7), 7.50 (app. t, J = 8 Hz, 1 H, H-6), 4.13 (s, 3 H, OCH₃). ¹³C NMR (100 MHz, CDCl₃, δ, p.p.m.): 167.4 (s, C-4), 154.6 (d, C-2), 151.1 (s, C-8a), 133.8 (d, C-7), 128.0 (d, C-8), 127.3 (d, C-5), 123.8 (d, C-6), 116.9 (s, C-4a), 54.6 (q, OCH₃). EI–MS (m/z, %): 160 (M⁺, 68), 131 (32), 130 (30), 103 (100), 90 (22), 76 (28), 63 (21). CI–MS (m/z, %): 161 (MH⁺, 100). HRMS (CI): calculated for C₉H₉N₂O [MH] 161.0709; found, 161.0708.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Related literature top

For the synthesis of quinazoline derivatives, see: Bogert & May (1909); Smith et al. (2005); Wang et al. (2010); Yang et al. (2010); Han et al. (2012). For the crystal structures of related compounds, see Alshammari et al. (2014); Derabli et al. (2013); Gao et al. (2012); Huang & Tan (2012); Jia et al. (2011).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001).

Figures top

Fig. 1. The title molecule showing 50% probability displacement ellipsoids.

Fig. 2. Crystal packing viewed down the a axis.

4-Methoxyquinazoline top

Crystal data top

C₉H₈N₂O	F(000) = 168
M_r = 160.17	D_x = 1.389 Mg m⁻³
Monoclinic, P2₁	Cu Kα radiation, λ = 1.54184 Å
a = 6.9590 (6) Å	Cell parameters from 1311 reflections
b = 4.0517 (3) Å	θ = 3.3–67.7°
c = 13.5858 (12) Å	µ = 0.77 mm⁻¹
β = 91.754 (8)°	T = 150 K
V = 382.88 (6) Å³	Needle, colourless
Z = 2	0.57 × 0.12 × 0.08 mm

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	1311 reflections with I > 2σ(I)
ω scans	R_int = 0.040
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014)	θ_max = 74.6°, θ_min = 3.3°
T_min = 0.641, T_max = 0.895	h = −8→8
2166 measured reflections	k = −4→5
1435 independent reflections	l = −11→16

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.054	H-atom parameters constrained
wR(F²) = 0.159	w = 1/[σ²(F_o²) + (0.110P)² + 0.0483P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1435 reflections	Δρ_max = 0.24 e Å⁻³
110 parameters	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₉H₈N₂O	V = 382.88 (6) Å³
M_r = 160.17	Z = 2
Monoclinic, P2₁	Cu Kα radiation
a = 6.9590 (6) Å	µ = 0.77 mm⁻¹
b = 4.0517 (3) Å	T = 150 K
c = 13.5858 (12) Å	0.57 × 0.12 × 0.08 mm
β = 91.754 (8)°

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	1435 independent reflections
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014)	1311 reflections with I > 2σ(I)
T_min = 0.641, T_max = 0.895	R_int = 0.040
2166 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	1 restraint
wR(F²) = 0.159	H-atom parameters constrained
S = 1.08	Δρ_max = 0.24 e Å⁻³
1435 reflections	Δρ_min = −0.23 e Å⁻³
110 parameters

Special details top

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48) Numerical absorption correction based on gaussian integration over a multifaceted crystal model Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	−0.1179 (5)	0.8736 (9)	0.7198 (2)	0.0403 (8)
H1	−0.2391	0.7831	0.7078	0.048*
C2	0.1829 (4)	0.9515 (7)	0.6650 (2)	0.0330 (7)
C3	0.2338 (4)	1.1283 (7)	0.7527 (2)	0.0330 (7)
C4	0.0855 (4)	1.1608 (7)	0.8208 (2)	0.0349 (7)
C5	0.1265 (5)	1.3290 (8)	0.9096 (3)	0.0426 (8)
H5	0.0308	1.3526	0.9554	0.051*
C6	0.3034 (5)	1.4570 (8)	0.9292 (2)	0.0431 (8)
H6	0.3276	1.5675	0.9883	0.052*
C7	0.4520 (5)	1.4246 (10)	0.8608 (3)	0.0411 (7)
H7	0.5731	1.5127	0.8751	0.049*
C8	0.4169 (5)	1.2640 (7)	0.7739 (2)	0.0364 (7)
H8	0.5138	1.2440	0.7287	0.044*
C9	0.2674 (5)	0.7530 (9)	0.5079 (3)	0.0433 (8)
H9A	0.1669	0.8757	0.4745	0.065*
H9B	0.2226	0.5340	0.5215	0.065*
H9C	0.3771	0.7410	0.4669	0.065*
N1	−0.0945 (4)	1.0312 (7)	0.8028 (2)	0.0412 (7)
N2	0.0121 (4)	0.8237 (6)	0.6479 (2)	0.0378 (7)
O1	0.3208 (3)	0.9159 (6)	0.59930 (16)	0.0381 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0293 (13)	0.0351 (16)	0.0562 (19)	−0.0019 (13)	−0.0033 (12)	0.0037 (15)
C2	0.0334 (14)	0.0278 (15)	0.0374 (15)	0.0007 (13)	−0.0059 (11)	0.0054 (12)
C3	0.0310 (14)	0.0268 (14)	0.0408 (15)	0.0051 (11)	−0.0036 (12)	0.0073 (12)
C4	0.0356 (16)	0.0283 (15)	0.0405 (16)	0.0033 (13)	−0.0020 (12)	0.0071 (13)
C5	0.0473 (18)	0.0386 (17)	0.0423 (18)	0.0053 (15)	0.0052 (14)	0.0023 (15)
C6	0.0528 (19)	0.0364 (18)	0.0396 (17)	0.0030 (15)	−0.0075 (14)	−0.0008 (14)
C7	0.0367 (14)	0.0373 (16)	0.0486 (17)	0.0006 (14)	−0.0104 (12)	0.0020 (14)
C8	0.0327 (14)	0.0346 (16)	0.0416 (18)	0.0033 (13)	−0.0051 (12)	0.0057 (14)
C9	0.0445 (17)	0.0437 (18)	0.0414 (17)	0.0051 (16)	−0.0052 (13)	−0.0020 (14)
N1	0.0336 (13)	0.0372 (14)	0.0528 (17)	−0.0001 (11)	0.0023 (11)	0.0013 (13)
N2	0.0346 (13)	0.0336 (14)	0.0446 (14)	−0.0001 (10)	−0.0084 (11)	0.0044 (11)
O1	0.0346 (10)	0.0430 (13)	0.0367 (11)	−0.0004 (11)	−0.0016 (8)	−0.0004 (10)

Geometric parameters (Å, º) top

C1—N1	1.302 (4)	C5—H5	0.9300
C1—N2	1.366 (4)	C6—C7	1.417 (5)
C1—H1	0.9300	C6—H6	0.9300
C2—N2	1.311 (4)	C7—C8	1.363 (5)
C2—O1	1.338 (4)	C7—H7	0.9300
C2—C3	1.425 (4)	C8—H8	0.9300
C3—C8	1.409 (4)	C9—O1	1.445 (4)
C3—C4	1.413 (4)	C9—H9A	0.9600
C4—N1	1.373 (4)	C9—H9B	0.9600
C4—C5	1.407 (5)	C9—H9C	0.9600
C5—C6	1.355 (5)

N1—C1—N2	128.6 (3)	C7—C6—H6	119.6
N1—C1—H1	115.7	C8—C7—C6	119.8 (3)
N2—C1—H1	115.7	C8—C7—H7	120.1
N2—C2—O1	120.3 (3)	C6—C7—H7	120.1
N2—C2—C3	123.2 (3)	C7—C8—C3	120.0 (3)
O1—C2—C3	116.5 (2)	C7—C8—H8	120.0
C8—C3—C4	120.2 (3)	C3—C8—H8	120.0
C8—C3—C2	124.6 (3)	O1—C9—H9A	109.5
C4—C3—C2	115.2 (3)	O1—C9—H9B	109.5
N1—C4—C5	119.8 (3)	H9A—C9—H9B	109.5
N1—C4—C3	121.9 (3)	O1—C9—H9C	109.5
C5—C4—C3	118.2 (3)	H9A—C9—H9C	109.5
C6—C5—C4	120.9 (3)	H9B—C9—H9C	109.5
C6—C5—H5	119.6	C1—N1—C4	115.5 (3)
C4—C5—H5	119.6	C2—N2—C1	115.6 (3)
C5—C6—C7	120.8 (3)	C2—O1—C9	116.9 (2)
C5—C6—H6	119.6

Experimental details

Crystal data
Chemical formula	C₉H₈N₂O
M_r	160.17
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	150
a, b, c (Å)	6.9590 (6), 4.0517 (3), 13.5858 (12)
β (°)	91.754 (8)
V (Å³)	382.88 (6)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.77
Crystal size (mm)	0.57 × 0.12 × 0.08

Data collection
Diffractometer	Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction	Gaussian (CrysAlis PRO; Agilent, 2014)
T_min, T_max	0.641, 0.895
No. of measured, independent and observed [I > 2σ(I)] reflections	2166, 1435, 1311
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.159, 1.08
No. of reflections	1435
No. of parameters	110
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.23

Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS2013 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001).

Acknowledgements

This project was supported by the Deanship of Scientific Research at Salman bin Abdulaziz University under the research project 2013/01/134.

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 12| December 2014| Page o1279

doi:10.1107/S1600536814025082

Open

access