Crystal structure of 2-ethyl­quinazoline-4(3H)-thione

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

doi:10.1107/S160053681401664X

organic compounds

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doi:10.1107/S160053681401664X

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Crystal structure of 2-ethylquinazoline-4(3H)-thione

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, Wales, 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 13 July 2014; accepted 17 July 2014; online 1 August 2014)

In the title compound, C₁₀H₁₀N₂S, all non-H atoms are almost coplanar [maximum deviation = 0.103 (1) Å]. In the crystal, N—H⋯S interactions form R₂²(8) rings linking pairs of molecules related by inversion. The molecular pairs are stacked along [100]. A herringbone arrangement of pairs in the [010] direction forms layers parallel to (010).

Keywords: crystal structure; N—H⋯S interactions; quinazoline-4(3H)-thione; hydrogen-bonded dimers; herringbone arrangement.

CCDC reference: 1014729

1. Related literature

For the synthesis of quinazoline-4(3H)-thiones, see: Bogert et al. (1903 ); Zoltewicz & Sharpless (1976 ); Segarra et al. (1998 ); El-Hiti (2004 ); Ozturk et al. (2007 ); El-Hiti et al. (2011 ).

2. Experimental

2.1. Crystal data

C₁₀H₁₀N₂S
M_r = 190.26
Orthorhombic, P b c a
a = 5.8231 (3) Å
b = 14.3214 (6) Å
c = 21.7365 (8) Å
V = 1812.71 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 150 K
0.41 × 0.24 × 0.15 mm

2.2. Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014 ) T_min = 0.780, T_max = 1.000
7795 measured reflections
2240 independent reflections
1973 reflections with I > 2σ(I)
R_int = 0.020

2..3. Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.087
S = 1.03
2240 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1ⁱ	0.88	2.53	3.3854 (11)	166
Symmetry code: (i) -x+2, -y+1, -z+1.

Data collection: CrysAlis PRO (Agilent, 2014); 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: 1014729

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S160053681401664X/xu5804sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681401664X/xu5804Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681401664X/xu5804Isup3.cml

checkCIF report

Structural commentary top

The 2-ethyl-3H-quinazoline-4-thione molecule (Fig 1) is almost planer (apart from the ethyl hydrogens) with the ethyl group being twisted from the quinazoline-4-thione plane by 8.7 (2)°. N—H···S interactions form R₂²(8) rings to link pairs of molecules related by inversion. The pairs of molecules are stacked parallel to the a-axis (Fig 2). Adjacent pairs pack in a herring bone arrangement in the [010] direction to form layers parallel to the (010) plane. 2-(Substituted alkyl)-3H-quinazoline-4-thione derivatives can be obtained from double lithiation of 2-alkyl-3H-quinazoline-4-thiones followed by reactions with electrophiles, including alkyl iodides, at low temperature in anhydrous THF (El-Hiti, 2004). Also, 3H-quinazoline-4-thiones are produced from the corresponding 3H-quinazoline-4-ones using phosphorus pentasulfide (Bogert et al., 1903; Ozturk et al., 2007; El-Hiti et al., 2011) or Lawesson's reagent (Segarra et al., 1998). 3H-Quinazoline-4-thiones have also been synthesized in one-step from reaction of 2-aminobenzonitriles and thioamides in the presence of hydrogen bromide in various solvents on a steam bath for 1–4 h (Zoltewicz & Sharpless, 1976).

Synthesis and crystallization top

2-Ethyl-3H-quinazoline-4-thione was obtained in 92% yield from double lithiation of 2-methyl-3H-quinazoline-4-thione with n-butyllithium at 78 ^οC in anhydrous THF under nitrogen followed by reaction with iodomethane (El-Hiti, 2004). Crystallization from methanol gave the title compound as yellow crystals. The NMR and low and high resolution mass spectra for the title compound were consistent with those reported (El-Hiti, 2004).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in calculated positions with C—H = 0.95 and 0.98Å and refined in riding mode, U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2Ueq(C) for aromatic H atoms

Related literature top

For the synthesis of quinazoline-4(3H)-thiones, see: Bogert et al. (1903); Zoltewicz & Sharpless (1976); Segarra et al. (1998); El-Hiti (2004); Ozturk et al. (2007); El-Hiti 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: 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 of the title compound showing atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Crystal structure packing showing N—H···S contacts as dotted lines.

2-Ethylquinazoline-4(3H)-thione top

Crystal data top

C₁₀H₁₀N₂S	D_x = 1.394 Mg m⁻³
M_r = 190.26	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 3617 reflections
a = 5.8231 (3) Å	θ = 3.9–29.3°
b = 14.3214 (6) Å	µ = 0.31 mm⁻¹
c = 21.7365 (8) Å	T = 150 K
V = 1812.71 (14) Å³	Plate, yellow
Z = 8	0.41 × 0.24 × 0.15 mm
F(000) = 800

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	2240 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1973 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.020
ω scans	θ_max = 29.8°, θ_min = 3.0°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −6→7
T_min = 0.780, T_max = 1.000	k = −19→14
7795 measured reflections	l = −23→29

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.087	w = 1/[σ²(F_o²) + (0.0416P)² + 0.7981P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2240 reflections	Δρ_max = 0.30 e Å⁻³
119 parameters	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₀H₁₀N₂S	V = 1812.71 (14) Å³
M_r = 190.26	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 5.8231 (3) Å	µ = 0.31 mm⁻¹
b = 14.3214 (6) Å	T = 150 K
c = 21.7365 (8) Å	0.41 × 0.24 × 0.15 mm

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	2240 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	1973 reflections with I > 2σ(I)
T_min = 0.780, T_max = 1.000	R_int = 0.020
7795 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.03	Δρ_max = 0.30 e Å⁻³
2240 reflections	Δρ_min = −0.25 e Å⁻³
119 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	0.7433 (2)	0.57478 (9)	0.62537 (6)	0.0185 (3)
C2	0.6649 (2)	0.44643 (8)	0.55604 (5)	0.0178 (2)
C3	0.4705 (2)	0.42557 (8)	0.59550 (5)	0.0177 (3)
C4	0.4368 (2)	0.48131 (8)	0.64832 (5)	0.0183 (3)
C5	0.3171 (2)	0.35262 (9)	0.58239 (6)	0.0209 (3)
H5	0.3379	0.3158	0.5465	0.025*
C6	0.1366 (2)	0.33425 (9)	0.62146 (6)	0.0236 (3)
H6	0.0337	0.2845	0.6127	0.028*
C7	0.1046 (2)	0.38917 (9)	0.67440 (6)	0.0240 (3)
H7	−0.0197	0.3760	0.7013	0.029*
C8	0.2513 (2)	0.46175 (9)	0.68761 (6)	0.0218 (3)
H8	0.2272	0.4987	0.7233	0.026*
C9	0.8998 (2)	0.65696 (9)	0.63452 (6)	0.0227 (3)
H9A	0.8734	0.7023	0.6009	0.027*
H9B	1.0609	0.6354	0.6316	0.027*
C10	0.8668 (3)	0.70632 (9)	0.69567 (6)	0.0246 (3)
H10A	0.7058	0.7252	0.7000	0.037*
H10B	0.9652	0.7618	0.6972	0.037*
H10C	0.9080	0.6639	0.7293	0.037*
N1	0.78973 (18)	0.52156 (7)	0.57402 (5)	0.0188 (2)
H1	0.9086	0.5374	0.5513	0.023*
N2	0.57662 (19)	0.55697 (7)	0.66273 (5)	0.0199 (2)
S1	0.73978 (6)	0.38502 (2)	0.49367 (2)	0.02214 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0210 (6)	0.0177 (6)	0.0169 (6)	0.0022 (5)	−0.0006 (4)	−0.0010 (5)
C2	0.0203 (6)	0.0164 (5)	0.0166 (5)	0.0039 (5)	−0.0026 (5)	0.0008 (4)
C3	0.0194 (6)	0.0171 (6)	0.0167 (5)	0.0027 (5)	−0.0019 (5)	0.0020 (4)
C4	0.0197 (6)	0.0178 (6)	0.0172 (5)	0.0019 (5)	−0.0012 (4)	0.0010 (5)
C5	0.0237 (7)	0.0189 (6)	0.0202 (6)	0.0008 (5)	−0.0032 (5)	−0.0006 (5)
C6	0.0238 (7)	0.0212 (6)	0.0258 (6)	−0.0033 (5)	−0.0029 (5)	0.0012 (5)
C7	0.0213 (7)	0.0264 (7)	0.0244 (6)	−0.0013 (5)	0.0028 (5)	0.0038 (5)
C8	0.0242 (7)	0.0226 (6)	0.0186 (6)	0.0015 (5)	0.0016 (5)	0.0002 (5)
C9	0.0238 (7)	0.0208 (6)	0.0233 (6)	−0.0033 (5)	0.0041 (5)	−0.0040 (5)
C10	0.0292 (7)	0.0233 (6)	0.0214 (6)	−0.0047 (5)	0.0001 (5)	−0.0040 (5)
N1	0.0188 (5)	0.0194 (5)	0.0182 (5)	−0.0003 (4)	0.0030 (4)	−0.0024 (4)
N2	0.0220 (6)	0.0191 (5)	0.0187 (5)	−0.0006 (4)	0.0015 (4)	−0.0012 (4)
S1	0.0244 (2)	0.02191 (18)	0.02011 (17)	0.00029 (12)	0.00293 (12)	−0.00599 (12)

Geometric parameters (Å, º) top

C1—N2	1.2908 (16)	C6—C7	1.4061 (19)
C1—N1	1.3784 (16)	C6—H6	0.9500
C1—C9	1.5017 (18)	C7—C8	1.3757 (19)
C2—N1	1.3560 (16)	C7—H7	0.9500
C2—C3	1.4514 (17)	C8—H8	0.9500
C2—S1	1.6737 (12)	C9—C10	1.5177 (17)
C3—C5	1.4038 (18)	C9—H9A	0.9900
C3—C4	1.4119 (16)	C9—H9B	0.9900
C4—N2	1.3910 (16)	C10—H10A	0.9800
C4—C8	1.4054 (18)	C10—H10B	0.9800
C5—C6	1.3766 (19)	C10—H10C	0.9800
C5—H5	0.9500	N1—H1	0.8800

N2—C1—N1	123.21 (12)	C6—C7—H7	119.6
N2—C1—C9	121.86 (11)	C7—C8—C4	120.08 (12)
N1—C1—C9	114.92 (11)	C7—C8—H8	120.0
N1—C2—C3	114.27 (11)	C4—C8—H8	120.0
N1—C2—S1	120.71 (10)	C1—C9—C10	113.84 (11)
C3—C2—S1	125.01 (10)	C1—C9—H9A	108.8
C5—C3—C4	119.83 (12)	C10—C9—H9A	108.8
C5—C3—C2	121.97 (11)	C1—C9—H9B	108.8
C4—C3—C2	118.19 (11)	C10—C9—H9B	108.8
N2—C4—C8	117.93 (11)	H9A—C9—H9B	107.7
N2—C4—C3	122.83 (11)	C9—C10—H10A	109.5
C8—C4—C3	119.22 (12)	C9—C10—H10B	109.5
C6—C5—C3	120.19 (12)	H10A—C10—H10B	109.5
C6—C5—H5	119.9	C9—C10—H10C	109.5
C3—C5—H5	119.9	H10A—C10—H10C	109.5
C5—C6—C7	119.94 (12)	H10B—C10—H10C	109.5
C5—C6—H6	120.0	C2—N1—C1	124.53 (11)
C7—C6—H6	120.0	C2—N1—H1	117.7
C8—C7—C6	120.73 (13)	C1—N1—H1	117.7
C8—C7—H7	119.6	C1—N2—C4	116.89 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.88	2.53	3.3854 (11)	166

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.88	2.53	3.3854 (11)	165.5

Symmetry code: (i) −x+2, −y+1, −z+1.

Footnotes

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

Acknowledgements

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

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 9| September 2014| Page o953

doi:10.1107/S160053681401664X

Open

access