2-Methyl­sulfanyl-9H-1,3,4-thia­diazolo[2,3-b]quinazolin-9-one

Abstract

In the title compound, C₁₀H₇N₃OS₂, the 16 non-H atoms are almost planar (r.m.s. deviation = 0.037 Å) and the S-bound methyl group is syn to the ketone O atom. In the crystal, centrosymmetrically related mol­ecules are connected by pairs of C—H⋯O inter­actions between the ketone O and methyl H atoms. The dimeric aggregates are connected into a linear supra­molecular chain along the b axis via π–π inter­actions occurring between the five-membered and benzene rings [centroid–centroid distance = 3.6123 (9) Å]. The chains assemble into layers in the bc plane via S⋯S inter­actions involving the endocyclic S atoms [S⋯S = 3.4607 (6) and 3.4792 (6) Å].

Related literature  

For recent studies on the synthesis and biological properties of quinazoline-4(3H)-one derivatives, see: El-Azab & ElTahir (2012 ▶); El-Azab et al. (2011 ▶). For the synthesis and anti-microbial activity of the title compound, see: El-Azab (2007 ▶).

Experimental  

Crystal data  

• C₁₀H₇N₃OS₂

• M _r = 249.31

• Monoclinic,

• a = 11.8193 (4) Å

• b = 4.9841 (2) Å

• c = 17.4985 (6) Å

• β = 91.453 (3)°

• V = 1030.48 (6) ų

• Z = 4

• Cu Kα radiation

• μ = 4.53 mm⁻¹

• T = 100 K

• 0.30 × 0.10 × 0.03 mm

Data collection  

• Agilent SuperNova Dual diffractometer with an Atlas detector

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.344, T _max = 0.876

• 3781 measured reflections

• 2110 independent reflections

• 1937 reflections with I > 2σ(I)

• R _int = 0.018

Refinement  

• R[F ² > 2σ(F ²)] = 0.029

• wR(F ²) = 0.082

• S = 1.09

• 2110 reflections

• 145 parameters

• H-atom parameters constrained

• Δρ_max = 0.36 e Å⁻³

• Δρ_min = −0.27 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812026189/hb6843Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯O1i	0.98	2.32	3.170 (2)	145

Symmetry code: (i) .

supplementary crystallographic information

Comment

Quinazoline-4(3H)-one derivatives attract interest owing to their putative biological activity (El-Azab & ElTahir, 2012; El-Azab et al., 2011). The title compound, 2-(methylthio)-5H-[1,3,4]thiadiazolo[2,3-b]quinazolin-5-one (I), has been synthesized previously and evaluated for its anti-microbial activity (El-Azab, 2007). Herein, we describe its crystal structure determination.

The 16 non-hydrogen atoms in (I), Fig. 1, are planar with the r.m.s. deviation being 0.037 Å. The maximum deviations from the least-squares plane are 0.068 (1) Å for the ketone-O1 atom and -0.065 (2) Å for the methyl-C10 atom. The S-bound methyl group is syn to the ketone-O1 atom.

In the crystal packing, centrosymmetrically related molecules are connected by C—H···O interactions between the ketone-O and methyl-H atoms, Table 1, via a 16-membered {···HCSCN₂CO}₂ synthon, Fig. 2. The dimeric aggregates are connected into a linear supramolecular chain along the b axis viaπ—π interactions occurring between the five-membered and benzene rings [inter-centroid distance = 3.6123 (9) Å, angle of inclination = 2.09 (7)° for symmetry operation: x, 1 + y, z]. The chains assemble into layers in the bc plane via S···S interactions involving the endocyclic-S1 atoms whereby each S1 atom forms two such interactions [S1···S1ⁱ = 3.4607 (6) Å for symmetry operation i: 2 - x,2 - y,1 - z; and S1···S1ⁱⁱ = 3.4792 (6) Å for ii: 2 - x, 1 - y, 1 - z]. Layers stack along the a axis without specific interactions between them, Fig. 3.

Experimental

A mixture of 2-mercapto-5H-[1,3,4]thiadiazolo[2,3-b]quinazolin-5-one (470 mg, 2 mmol) and methyliodide (2.1 mmol) in acetone (10 ml) containing anhydrous potassium carbonate (300 mg) was stirred at room temperature for 12 h. The reaction mixture was filtered, the solvent removed under reduced pressure and the solid obtained was dried and recrystallized from ethanol. Yield 88%. ¹H NMR (CDCl₃): δ 8.42 (d, 1H, J = 7.5 Hz), 7.79 (t, 1H, J = 7.0 Hz), 7.63 (d, 1H, J = 8.0 Hz), 7.49 (t, 1H, J = 7.0 Hz), 2.84 (s, 3H) p.p.m.. ¹³C NMR (CDCl₃): δ = 15.3, 118.9, 126.2, 127.6, 134.8, 147.2, 156.2, 157.1, 158.5 p.p.m..

Refinement

Carbon-bound H-atoms were placed in calculated positions [C—H = 0.95 to 0.98 Å, U_iso(H) = 1.2–1.5U_eq(C)] and were included in the refinement in the riding model approximation.

Figures

Fig. 1.

The molecular structure of (I) showing displacement ellipsoids at the 50% probability level.

Fig. 2.

A view of the linear supramolecular chain along the b axis in (I). The C—H···O and π—π interactions are shown as orange and purple dashed lines respectively.

Fig. 3.

A view in projection down the b axis of the unit-cell contents for (I). The C—H···O, π—π and S···S interactions are shown as orange, purple and blue dashed lines respectively.

Crystal data

C10H7N3OS2	F(000) = 512
Mr = 249.31	Dx = 1.607 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 2166 reflections
a = 11.8193 (4) Å	θ = 3.7–76.5°
b = 4.9841 (2) Å	µ = 4.53 mm−1
c = 17.4985 (6) Å	T = 100 K
β = 91.453 (3)°	Prism, colourless
V = 1030.48 (6) Å3	0.30 × 0.10 × 0.03 mm
Z = 4

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector	2110 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1937 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.018
Detector resolution: 10.4041 pixels mm-1	θmax = 76.7°, θmin = 3.7°
ω scan	h = −12→14
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −5→6
Tmin = 0.344, Tmax = 0.876	l = −15→21
3781 measured reflections

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0457P)2 + 0.3686P] where P = (Fo2 + 2Fc2)/3
2110 reflections	(Δ/σ)max = 0.001
145 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.90968 (3)	0.75129 (8)	0.46619 (2)	0.01702 (12)
S2	0.76245 (3)	1.12015 (8)	0.55613 (2)	0.01660 (12)
N1	0.90012 (11)	0.3645 (3)	0.35873 (8)	0.0160 (3)
N2	0.72981 (11)	0.5607 (3)	0.40394 (7)	0.0145 (3)
N3	0.68915 (11)	0.7516 (3)	0.45394 (7)	0.0160 (3)
O1	0.55197 (9)	0.4218 (3)	0.36566 (7)	0.0217 (3)
C1	0.65417 (13)	0.4007 (3)	0.36022 (9)	0.0159 (3)
C2	0.71312 (13)	0.2152 (3)	0.31034 (9)	0.0153 (3)
C3	0.64945 (13)	0.0467 (4)	0.26154 (9)	0.0183 (3)
H3	0.5691	0.0533	0.2616	0.022*
C4	0.70332 (14)	−0.1282 (4)	0.21351 (9)	0.0196 (3)
H4	0.6602	−0.2429	0.1806	0.024*
C5	0.82196 (14)	−0.1368 (3)	0.21325 (9)	0.0192 (3)
H5	0.8589	−0.2560	0.1796	0.023*
C6	0.88539 (13)	0.0261 (3)	0.26135 (9)	0.0179 (3)
H6	0.9657	0.0173	0.2609	0.021*
C7	0.83228 (13)	0.2050 (3)	0.31091 (9)	0.0149 (3)
C8	0.84595 (12)	0.5289 (3)	0.40102 (8)	0.0149 (3)
C9	0.77423 (13)	0.8644 (3)	0.48930 (9)	0.0152 (3)
C10	0.61018 (14)	1.1556 (4)	0.55743 (10)	0.0211 (3)
H10A	0.5903	1.2965	0.5938	0.032*
H10B	0.5762	0.9854	0.5730	0.032*
H10C	0.5815	1.2041	0.5062	0.032*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.01263 (19)	0.0180 (2)	0.0204 (2)	−0.00013 (13)	−0.00028 (14)	−0.00389 (14)
S2	0.0170 (2)	0.0176 (2)	0.0151 (2)	0.00105 (14)	−0.00022 (14)	−0.00248 (14)
N1	0.0136 (6)	0.0176 (7)	0.0167 (6)	0.0001 (5)	0.0003 (5)	−0.0019 (5)
N2	0.0124 (6)	0.0179 (7)	0.0133 (6)	0.0031 (5)	0.0007 (5)	−0.0011 (5)
N3	0.0161 (6)	0.0180 (7)	0.0139 (6)	0.0031 (5)	0.0001 (5)	−0.0018 (5)
O1	0.0118 (5)	0.0294 (7)	0.0239 (6)	0.0024 (5)	−0.0007 (4)	−0.0067 (5)
C1	0.0148 (7)	0.0191 (7)	0.0138 (7)	0.0014 (6)	−0.0011 (6)	−0.0006 (6)
C2	0.0151 (7)	0.0176 (7)	0.0131 (7)	0.0011 (6)	−0.0001 (5)	0.0006 (6)
C3	0.0146 (7)	0.0227 (8)	0.0176 (7)	0.0013 (7)	−0.0018 (6)	−0.0009 (6)
C4	0.0190 (8)	0.0219 (8)	0.0177 (8)	0.0007 (6)	−0.0041 (6)	−0.0031 (6)
C5	0.0204 (8)	0.0207 (8)	0.0166 (7)	0.0037 (6)	0.0012 (6)	−0.0032 (6)
C6	0.0135 (7)	0.0206 (8)	0.0195 (7)	0.0022 (6)	0.0013 (6)	−0.0013 (6)
C7	0.0149 (7)	0.0160 (7)	0.0139 (7)	−0.0004 (6)	0.0001 (5)	0.0017 (6)
C8	0.0127 (7)	0.0159 (7)	0.0160 (7)	−0.0008 (6)	−0.0005 (5)	0.0023 (6)
C9	0.0155 (7)	0.0160 (7)	0.0141 (7)	0.0019 (6)	0.0005 (5)	0.0014 (6)
C10	0.0178 (7)	0.0261 (9)	0.0194 (8)	0.0048 (7)	0.0015 (6)	−0.0032 (7)

Geometric parameters (Å, º)

S1—C8	1.7473 (16)	C2—C7	1.409 (2)
S1—C9	1.7542 (16)	C3—C4	1.378 (2)
S2—C9	1.7378 (16)	C3—H3	0.9500
S2—C10	1.8091 (17)	C4—C5	1.403 (2)
N1—C8	1.286 (2)	C4—H4	0.9500
N1—C7	1.393 (2)	C5—C6	1.378 (2)
N2—C8	1.3840 (18)	C5—H5	0.9500
N2—N3	1.3866 (18)	C6—C7	1.403 (2)
N2—C1	1.409 (2)	C6—H6	0.9500
N3—C9	1.296 (2)	C10—H10A	0.9800
O1—C1	1.2186 (19)	C10—H10B	0.9800
C1—C2	1.461 (2)	C10—H10C	0.9800
C2—C3	1.403 (2)
C8—S1—C9	88.48 (7)	C6—C5—H5	119.7
C9—S2—C10	100.19 (8)	C4—C5—H5	119.7
C8—N1—C7	114.96 (13)	C5—C6—C7	120.47 (14)
C8—N2—N3	117.51 (13)	C5—C6—H6	119.8
C8—N2—C1	122.09 (13)	C7—C6—H6	119.8
N3—N2—C1	120.37 (12)	N1—C7—C6	118.30 (14)
C9—N3—N2	108.78 (13)	N1—C7—C2	122.93 (14)
O1—C1—N2	121.69 (14)	C6—C7—C2	118.77 (14)
O1—C1—C2	126.16 (15)	N1—C8—N2	127.10 (14)
N2—C1—C2	112.15 (13)	N1—C8—S1	124.55 (12)
C3—C2—C7	120.23 (14)	N2—C8—S1	108.35 (11)
C3—C2—C1	119.08 (14)	N3—C9—S2	124.42 (12)
C7—C2—C1	120.69 (14)	N3—C9—S1	116.88 (12)
C4—C3—C2	120.06 (15)	S2—C9—S1	118.69 (9)
C4—C3—H3	120.0	S2—C10—H10A	109.5
C2—C3—H3	120.0	S2—C10—H10B	109.5
C3—C4—C5	119.90 (15)	H10A—C10—H10B	109.5
C3—C4—H4	120.0	S2—C10—H10C	109.5
C5—C4—H4	120.0	H10A—C10—H10C	109.5
C6—C5—C4	120.56 (15)	H10B—C10—H10C	109.5
C8—N2—N3—C9	−0.24 (19)	C3—C2—C7—N1	−179.16 (15)
C1—N2—N3—C9	177.60 (13)	C1—C2—C7—N1	0.9 (2)
C8—N2—C1—O1	176.66 (15)	C3—C2—C7—C6	0.7 (2)
N3—N2—C1—O1	−1.1 (2)	C1—C2—C7—C6	−179.20 (15)
C8—N2—C1—C2	−3.1 (2)	C7—N1—C8—N2	0.4 (2)
N3—N2—C1—C2	179.13 (13)	C7—N1—C8—S1	179.87 (11)
O1—C1—C2—C3	1.9 (3)	N3—N2—C8—N1	−179.87 (15)
N2—C1—C2—C3	−178.30 (14)	C1—N2—C8—N1	2.3 (2)
O1—C1—C2—C7	−178.17 (16)	N3—N2—C8—S1	0.61 (17)
N2—C1—C2—C7	1.6 (2)	C1—N2—C8—S1	−177.18 (12)
C7—C2—C3—C4	−0.5 (2)	C9—S1—C8—N1	179.88 (15)
C1—C2—C3—C4	179.44 (15)	C9—S1—C8—N2	−0.59 (11)
C2—C3—C4—C5	−0.3 (3)	N2—N3—C9—S2	178.77 (11)
C3—C4—C5—C6	0.8 (3)	N2—N3—C9—S1	−0.27 (17)
C4—C5—C6—C7	−0.5 (3)	C10—S2—C9—N3	0.76 (16)
C8—N1—C7—C6	178.13 (15)	C10—S2—C9—S1	179.79 (10)
C8—N1—C7—C2	−2.0 (2)	C8—S1—C9—N3	0.53 (13)
C5—C6—C7—N1	179.67 (15)	C8—S1—C9—S2	−178.57 (10)
C5—C6—C7—C2	−0.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O1i	0.98	2.32	3.170 (2)	145

Symmetry code: (i) −x+1, −y+2, −z+1.