Crystal structure of 4-methyl­sulfanyl-2-phenyl­quinazoline

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 [pi]-[pi] 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.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.039
• wR factor = 0.097
• Data-to-parameter ratio = 18.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H15B   ..  N2      ..       2.67 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.363 Check
PLAT934_ALERT_3_C Number of (Iobs-Icalc)/SigmaW > 10 Outliers ....          1 Check

Alert level G
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          3 Why ?
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        405 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   2 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Structural commentary

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).

S2. Synthesis and crystallization

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.

S3. Refinement

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

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

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

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

4-Methylsulfanyl-2-phenylquinazoline

Crystal data

C15H12N2S	F(000) = 528
Mr = 252.33	Dx = 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) Å^3	Block, colourless
Z = 4	0.23 × 0.18 × 0.15 mm

Data collection

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	Rint = 0.030
ω scans	θmax = 29.7°, θmin = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	h = −13→12
Tmin = 0.848, Tmax = 1.000	k = −9→10
11140 measured reflections	l = −17→22

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0323P)^2 + 0.6772P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
3025 reflections	Δρmax = 0.29 e Å^−3
164 parameters	Δρmin = −0.34 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15B···N2^i	0.98	2.67	3.648 (2)	173

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