Crystal structure of 4-methyl­sulfanyl-2-phenyl­quinazoline

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

doi:10.1107/S1600536814015657

organic compounds

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Volume 70| Part 8| August 2014| Page o871

doi:10.1107/S1600536814015657

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Crystal structure of 4-methylsulfanyl-2-phenylquinazoline

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

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

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 2 July 2014; accepted 4 July 2014; online 23 July 2014)

In the title compound, C₁₅H₁₂N₂S, the methylthioquinazoline group is planar with the methyl C displaced by only 0.116 (3) Å from the plane of the quinazoline moiety. The dihedral angle between the phenyl ring and the quinazoline ring system is 13.95 (5)°. In the crystal, each molecule is linked by π–π stacking between to two adjacent inversion-related molecules. On one side, the inverted quinazoline groups interact with a centroid–centroid distance of 3.7105 (9) Å. On the other side, the quinazoline group interacts with the pyrimidine and phenyl rings of the second neighbour with centroid–centroid distances of 3.5287 (8) and 3.8601 (9) Å, respectively.

Keywords: crystal structure; methylthioquinazoline; π–π stacking.

CCDC reference: 1012164

Related literature

For the synthesis of 4-alkythioqinazolines, see: Leonard & Curtin (1946 ); Hearn et al. (1951 ); Meerwein et al. (1956 ); Blatter & Lukaszewski (1964 ); Segarra et al. (1998 ); Smith et al. (2005a ,b ).

Experimental

Crystal data

C₁₅H₁₂N₂S
M_r = 252.33
Monoclinic, P 2₁ /n
a = 10.1951 (3) Å
b = 7.3545 (2) Å
c = 16.5300 (5) Å
β = 102.860 (3)°
V = 1208.33 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 150 K
0.23 × 0.18 × 0.15 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ) T_min = 0.848, T_max = 1.000
11140 measured reflections
3025 independent reflections
2558 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.097
S = 1.08
3025 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1012164

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814015657/xu5801sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814015657/xu5801Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814015657/xu5801Isup3.cml

checkCIF report

Structural commentary top

In the 4-(methylthio)-2-phenylquinazoline molecule (Fig 1), the angle between the planes through the phenyl and phenylquinazoline ring systems is 13.95 (5)°. The molecules are stacked in the [010] direction with approximately parallel molecular planes. With no strong H-bond donors, one N atom accepts a long C—H···N contact linking molecules along [101]. The second N atom is not involved. 4-Methylthioquinazoline derivatives can be obtained from reaction of the potassium salt of 3H-quinazoline-4-thiones with iodomethane (Leonard & Curtin, 1946; Meerwein et al., 1956). Quinazoline-4-thiones are produced from the corresponding 3H-quinazoline-4-ones using phosphorus pentasulfide (Hearn, et al., 1951), Lawesson's reagent (Segarra et al., 1998) or isothiocyanates (Blatter & Lukaszewski, 1964). In a continuation of our research focused on new synthetic routes towards novel substituted 4-alkylthioquinazoline derivatives (Smith et al., 2005a,b) we have synthesized 4-(methylthio)-2-phenylquinazoline in a high yield (Smith et al., 2005a).

Synthesis and crystallization top

To a solution of 2-phenyl-3H-quinazoline-4-thione (4.81 g, 20.2 mmol) in a 1:1 mixture of MeOH and water (50 ml) containing KOH (3.0 g), was added iodomethane (3.41 g, 24.0 mmol). The reaction mixture was stirred for 20 min at room temperature and the solid obtained was filtered, washed with H₂O (3 × 30 ml), dried and recrystallized from Et₂O to give 4-(methylthio)-2-phenylquinazoline (4.63 g, 18.3 mmol, 91%) as colourless crystals, m.p. 93-94 °C [lit. 94 °C (H₂O); Meerwein et al., 1956). ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.) 8.70-8.66 (m, 2 H, ArH), 8.10-8.03 (m, 2 H, ArH), 7.83 (app. dt, J = 1, 8 Hz, 1 H, H-7), 7.58-7.51 (m, 4 H, ArH), 2.85 (s, 3 H, CH₃). ¹³C NMR (100 MHz, CDCl₃, d, p.p.m.) 171.8 (s, C-2), 159.2 (s, C-4), 149.1 (s, C-8a), 138.5 (s, C-1 of Ph), 133.9 (d, C-7), 131.0 (d, C-4 of Ph), 129.4 (d, C-8), 129.0 (d, C-3/C-5 of Ph), 128.9 (d, C-2/C-6 of Ph), 127.1 (d, C-6), 124.1 (d, C-5), 123.0 (s, C-4a), 13.0 (q, CH₃). EI—MS (m/z, %): 252 (M⁺, 100), 251 (72), 205 (60), 102 (47), 77 (61), 51 (33). CI—MS (m/z, %): 253 (MH⁺, 100), 207 (3). HRMS (CI): Calculated for C₁₅H₁₃N₂S [MH] 253.0794; found, 253.0789.

Refinement top

H atoms were placed in calculated positions with C—H = 0.95 and 0.98 Å and refined in riding mode, U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for aromatic H atoms.

Related literature top

For the synthesis of 4-alkythioqinazolines, see: Leonard & Curtin (1946); Hearn et al. (1951); Meerwein et al. (1956); Blatter & Lukaszewski (1964); Segarra et al. (1998); Smith et al. (2005a,b).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A molecule showing atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Packing diagram.

4-Methylsulfanyl-2-phenylquinazoline top

Crystal data top

C₁₅H₁₂N₂S	F(000) = 528
M_r = 252.33	D_x = 1.387 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.1951 (3) Å	Cell parameters from 2558 reflections
b = 7.3545 (2) Å	θ = 3.1–29.7°
c = 16.5300 (5) Å	µ = 0.25 mm⁻¹
β = 102.860 (3)°	T = 150 K
V = 1208.33 (6) Å³	Block, colourless
Z = 4	0.23 × 0.18 × 0.15 mm

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	3025 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2558 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.030
ω scans	θ_max = 29.7°, θ_min = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	h = −13→12
T_min = 0.848, T_max = 1.000	k = −9→10
11140 measured reflections	l = −17→22

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0323P)² + 0.6772P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3025 reflections	Δρ_max = 0.29 e Å⁻³
164 parameters	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₅H₁₂N₂S	V = 1208.33 (6) Å³
M_r = 252.33	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.1951 (3) Å	µ = 0.25 mm⁻¹
b = 7.3545 (2) Å	T = 150 K
c = 16.5300 (5) Å	0.23 × 0.18 × 0.15 mm
β = 102.860 (3)°

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	3025 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	2558 reflections with I > 2σ(I)
T_min = 0.848, T_max = 1.000	R_int = 0.030
11140 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.08	Δρ_max = 0.29 e Å⁻³
3025 reflections	Δρ_min = −0.34 e Å⁻³
164 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.

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

	x	y	z	U_iso*/U_eq
C1	0.09137 (15)	0.6738 (2)	−0.06125 (9)	0.0182 (3)
C2	0.06916 (15)	0.7676 (2)	0.06700 (9)	0.0189 (3)
C3	−0.07074 (14)	0.8041 (2)	0.03446 (9)	0.0183 (3)
C4	−0.11800 (15)	0.7663 (2)	−0.05066 (9)	0.0196 (3)
C5	−0.16032 (16)	0.8695 (2)	0.08196 (10)	0.0229 (3)
H5	−0.1285	0.8950	0.1393	0.027*
C6	−0.29284 (16)	0.8957 (2)	0.04503 (10)	0.0257 (3)
H6	−0.3531	0.9391	0.0770	0.031*
C7	−0.34049 (16)	0.8591 (2)	−0.03973 (11)	0.0266 (4)
H7	−0.4328	0.8783	−0.0646	0.032*
C8	−0.25564 (15)	0.7960 (2)	−0.08710 (10)	0.0246 (3)
H8	−0.2892	0.7723	−0.1445	0.030*
C9	0.18424 (15)	0.5989 (2)	−0.11089 (9)	0.0188 (3)
C10	0.13360 (15)	0.5219 (2)	−0.18889 (9)	0.0213 (3)
H10	0.0394	0.5222	−0.2116	0.026*
C11	0.22001 (16)	0.4449 (2)	−0.23338 (9)	0.0237 (3)
H11	0.1846	0.3913	−0.2860	0.028*
C12	0.35767 (16)	0.4460 (2)	−0.20139 (10)	0.0253 (3)
H12	0.4166	0.3939	−0.2321	0.030*
C13	0.40914 (16)	0.5234 (2)	−0.12434 (10)	0.0250 (3)
H13	0.5036	0.5249	−0.1025	0.030*
C14	0.32309 (15)	0.5986 (2)	−0.07900 (9)	0.0225 (3)
H14	0.3589	0.6502	−0.0260	0.027*
C15	0.30675 (16)	0.7320 (3)	0.18247 (10)	0.0289 (4)
H15A	0.3070	0.6036	0.1666	0.043*
H15B	0.3564	0.7464	0.2401	0.043*
H15C	0.3498	0.8048	0.1460	0.043*
N1	0.14809 (12)	0.70406 (17)	0.02073 (8)	0.0191 (3)
N2	−0.03494 (12)	0.70111 (17)	−0.09896 (8)	0.0200 (3)
S1	0.13627 (4)	0.80726 (6)	0.17278 (2)	0.02388 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0219 (7)	0.0154 (7)	0.0174 (7)	−0.0014 (5)	0.0049 (6)	0.0015 (6)
C2	0.0237 (7)	0.0172 (7)	0.0156 (7)	−0.0014 (6)	0.0042 (6)	0.0017 (6)
C3	0.0216 (7)	0.0147 (7)	0.0191 (7)	−0.0010 (5)	0.0058 (6)	0.0020 (6)
C4	0.0218 (7)	0.0173 (7)	0.0202 (7)	−0.0011 (6)	0.0055 (6)	0.0014 (6)
C5	0.0282 (8)	0.0212 (8)	0.0208 (8)	0.0013 (6)	0.0088 (6)	0.0005 (6)
C6	0.0254 (8)	0.0229 (8)	0.0316 (9)	0.0035 (6)	0.0126 (7)	−0.0004 (7)
C7	0.0195 (7)	0.0261 (8)	0.0335 (9)	0.0018 (6)	0.0043 (6)	0.0005 (7)
C8	0.0222 (8)	0.0274 (9)	0.0231 (8)	−0.0008 (6)	0.0024 (6)	−0.0016 (7)
C9	0.0232 (7)	0.0161 (7)	0.0176 (7)	0.0008 (6)	0.0059 (6)	0.0026 (6)
C10	0.0229 (7)	0.0216 (8)	0.0195 (7)	−0.0004 (6)	0.0048 (6)	0.0022 (6)
C11	0.0318 (8)	0.0225 (8)	0.0174 (7)	−0.0004 (6)	0.0067 (6)	−0.0011 (6)
C12	0.0300 (8)	0.0234 (8)	0.0256 (8)	0.0037 (6)	0.0131 (7)	0.0006 (7)
C13	0.0226 (8)	0.0258 (9)	0.0274 (8)	0.0019 (6)	0.0071 (6)	0.0017 (7)
C14	0.0252 (8)	0.0230 (8)	0.0188 (7)	0.0001 (6)	0.0039 (6)	−0.0002 (6)
C15	0.0241 (8)	0.0406 (10)	0.0202 (8)	0.0037 (7)	0.0011 (6)	0.0014 (7)
N1	0.0209 (6)	0.0198 (6)	0.0171 (6)	−0.0007 (5)	0.0050 (5)	0.0019 (5)
N2	0.0218 (6)	0.0200 (6)	0.0185 (6)	−0.0005 (5)	0.0051 (5)	−0.0009 (5)
S1	0.0248 (2)	0.0308 (2)	0.0159 (2)	0.00122 (15)	0.00423 (15)	−0.00238 (16)

Geometric parameters (Å, º) top

C1—N2	1.3153 (19)	C8—H8	0.9500
C1—N1	1.3680 (19)	C9—C14	1.396 (2)
C1—C9	1.4897 (19)	C9—C10	1.398 (2)
C2—N1	1.3134 (18)	C10—C11	1.388 (2)
C2—C3	1.433 (2)	C10—H10	0.9500
C2—S1	1.7544 (15)	C11—C12	1.385 (2)
C3—C4	1.410 (2)	C11—H11	0.9500
C3—C5	1.414 (2)	C12—C13	1.387 (2)
C4—N2	1.3730 (18)	C12—H12	0.9500
C4—C8	1.415 (2)	C13—C14	1.389 (2)
C5—C6	1.367 (2)	C13—H13	0.9500
C5—H5	0.9500	C14—H14	0.9500
C6—C7	1.403 (2)	C15—S1	1.7970 (16)
C6—H6	0.9500	C15—H15A	0.9800
C7—C8	1.370 (2)	C15—H15B	0.9800
C7—H7	0.9500	C15—H15C	0.9800

N2—C1—N1	126.73 (13)	C10—C9—C1	120.56 (13)
N2—C1—C9	118.08 (13)	C11—C10—C9	120.43 (14)
N1—C1—C9	115.18 (13)	C11—C10—H10	119.8
N1—C2—C3	122.39 (13)	C9—C10—H10	119.8
N1—C2—S1	119.07 (11)	C12—C11—C10	120.27 (15)
C3—C2—S1	118.54 (11)	C12—C11—H11	119.9
C4—C3—C5	120.11 (14)	C10—C11—H11	119.9
C4—C3—C2	115.34 (13)	C11—C12—C13	119.80 (14)
C5—C3—C2	124.53 (14)	C11—C12—H12	120.1
N2—C4—C3	122.09 (13)	C13—C12—H12	120.1
N2—C4—C8	119.20 (14)	C12—C13—C14	120.23 (15)
C3—C4—C8	118.71 (13)	C12—C13—H13	119.9
C6—C5—C3	119.75 (15)	C14—C13—H13	119.9
C6—C5—H5	120.1	C13—C14—C9	120.38 (14)
C3—C5—H5	120.1	C13—C14—H14	119.8
C5—C6—C7	120.47 (14)	C9—C14—H14	119.8
C5—C6—H6	119.8	S1—C15—H15A	109.5
C7—C6—H6	119.8	S1—C15—H15B	109.5
C8—C7—C6	120.88 (15)	H15A—C15—H15B	109.5
C8—C7—H7	119.6	S1—C15—H15C	109.5
C6—C7—H7	119.6	H15A—C15—H15C	109.5
C7—C8—C4	120.08 (15)	H15B—C15—H15C	109.5
C7—C8—H8	120.0	C2—N1—C1	117.13 (13)
C4—C8—H8	120.0	C1—N2—C4	116.31 (13)
C14—C9—C10	118.88 (13)	C2—S1—C15	101.10 (7)
C14—C9—C1	120.52 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15B···N2ⁱ	0.98	2.67	3.648 (2)	173

Symmetry code: (i) x+1/2, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂N₂S
M_r	252.33
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	10.1951 (3), 7.3545 (2), 16.5300 (5)
β (°)	102.860 (3)
V (Å³)	1208.33 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.23 × 0.18 × 0.15

Data collection
Diffractometer	Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013)
T_min, T_max	0.848, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11140, 3025, 2558
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.698

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.097, 1.08
No. of reflections	3025
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.34

Computer programs: CrysAlis PRO (Agilent, 2013), SHELXTL (Sheldrick, 2008).

Footnotes

‡Additional correspondence author, e-mail: kariukib@cardiff.ac.uk.

Acknowledgements

This project was supported by the Deanship of Scientific Research at Salman bin Abdulaziz University under research project 2013/01/8.

References

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