5-Chloro-2-methyl­sulfonyl-1,2,4-triazolo[1,5-a]quinazoline

Al-Salahi, R.; Al-Omar, M.; Marzouk, M.; Ng, S.W.

doi:10.1107/S1600536812021770

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1809

doi:10.1107/S1600536812021770

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5-Chloro-2-methylsulfonyl-1,2,4-triazolo[1,5-a]quinazoline

Rashad Al-Salahi,^a Mohamed Al-Omar,^a Mohamed Marzouk ^a and Seik Weng Ng ^b,^c ^*

^aDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 10 May 2012; accepted 14 May 2012; online 19 May 2012)

The triazoloquinazole fused-ring system of the title compound, C₁₀H₇ClN₄O₂S, is essentially planar (r.m.s. deviation = 0.009 Å). In the methylsulfonyl substituent, the two S—O bonds are of equal length [1.402 (2) Å]. In the crystal, adjacent molecules interact weakly through Cl⋯N contacts [ca 3.197 (2) Å].

Related literature

For the synthesis of the precursor, see: Al-Salahi & Geffken (2011 ).

Experimental

Crystal data

C₁₀H₇ClN₄O₂S
M_r = 282.71
Monoclinic, P 2₁ /c
a = 12.6386 (3) Å
b = 10.7464 (3) Å
c = 8.6317 (3) Å
β = 102.459 (3)°
V = 1144.74 (6) Å³
Z = 4
Cu Kα radiation
μ = 4.69 mm⁻¹
T = 294 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) T_min = 0.334, T_max = 0.454
10130 measured reflections
2383 independent reflections
2168 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.113
S = 1.03
2383 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.40 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: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812021770/bt5916sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812021770/bt5916Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812021770/bt5916Isup3.cml

checkCIF report

Comment top

In this study, 2-(methylsulfanyl)-[1,2,4]triazolo[1,5-a]quinazolin-5-one (Al-Salahi & Geffken, 2011) was first treated with phosphorus oxychloride to yield the chlorinated compound, whose sulfur linkage was then oxidized by hydrogen peroxide. Chlorination took place at the carbon atom bearing the ketonic oxygen in the title compound (Scheme I). The triazoloquinazole fused-ring system is planar; in the methanesulfonyl substitutent, the two S–O bonds are of equal length (1.402 (2) Å). Adjacent molecules interact weakly through Cl···N contacts (ca. 3.20 Å).

Related literature top

For the synthesis of the precursor, see: Al-Salahi & Geffken (2011).

Experimental top

Under ice-cold conditions, 2-hydrazinobenzoic acid (10 mmol, 1.52 g) was added to a solution of dimethyl N-cyanodithioimidocarbonate (10 mmol, 1.46 g) in ethanol (20 ml). Triethylamine (30 mmol, 3.03 g) was added. The reaction mixture was stirred overnight at room temperature. Concentrated hydrochloric acid was added; the acidified mixture for heated for an hour. The mixture was poured into ice water; the solid that formed was collected and recrystallized from ethanol to give colorless crystals of 2-(methylsulfanyl)-[1,2,4]triazolo[1,5-a]quinazolin-5-one. The procedure was that reported earlier (Al-Salahi & Geffken, 2011).

The above compound (1 mmol, 0.232 g) was heated with phosphorus oxychloride (1 ml) in benzene (10 ml) for 2 h. The solvent was evaporated and the residue was treated with saturated potassium carbonate to give the chlorinated [1,2,4]triazoloquinazoline.

To the boiling mixture of chlorinated [1,2,4]triazoloquinazoline (1 mmol, 0.25 g) in glacial acetic acid (5 ml) was added hydrogen peroxide. Colorless crystals of the oxidized product were obtained when the solution was allowed to cool.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₁₀H₇ClN₄O₂S at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

5-Chloro-2-methylsulfonyl-1,2,4-triazolo[1,5-a]quinazoline top

Crystal data top

C₁₀H₇ClN₄O₂S	F(000) = 576
M_r = 282.71	D_x = 1.640 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 4932 reflections
a = 12.6386 (3) Å	θ = 3.6–76.5°
b = 10.7464 (3) Å	µ = 4.69 mm⁻¹
c = 8.6317 (3) Å	T = 294 K
β = 102.459 (3)°	Prism, colorless
V = 1144.74 (6) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2383 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2168 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.025
Detector resolution: 10.4041 pixels mm^-1	θ_max = 76.7°, θ_min = 3.6°
ω scan	h = −15→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −13→12
T_min = 0.334, T_max = 0.454	l = −10→10
10130 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0707P)² + 0.3878P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2383 reflections	Δρ_max = 0.27 e Å⁻³
165 parameters	Δρ_min = −0.40 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0033 (6)

Crystal data top

C₁₀H₇ClN₄O₂S	V = 1144.74 (6) Å³
M_r = 282.71	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 12.6386 (3) Å	µ = 4.69 mm⁻¹
b = 10.7464 (3) Å	T = 294 K
c = 8.6317 (3) Å	0.30 × 0.25 × 0.20 mm
β = 102.459 (3)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2383 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	2168 reflections with I > 2σ(I)
T_min = 0.334, T_max = 0.454	R_int = 0.025
10130 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.03	Δρ_max = 0.27 e Å⁻³
2383 reflections	Δρ_min = −0.40 e Å⁻³
165 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.45911 (4)	0.43675 (5)	0.75576 (7)	0.05379 (19)
S1	0.88914 (4)	0.86294 (4)	0.54205 (6)	0.04933 (19)
O1	0.82482 (19)	0.94586 (18)	0.4366 (2)	0.0828 (7)
O2	0.9760 (2)	0.8096 (2)	0.4887 (4)	0.1080 (10)
N1	0.58990 (12)	0.60611 (16)	0.6966 (2)	0.0445 (4)
N2	0.74566 (12)	0.56267 (13)	0.59166 (18)	0.0365 (3)
N3	0.82959 (12)	0.62371 (15)	0.55072 (19)	0.0404 (3)
N4	0.71600 (13)	0.75914 (15)	0.6396 (2)	0.0449 (4)
C1	0.57202 (14)	0.48755 (18)	0.6911 (2)	0.0412 (4)
C2	0.63661 (14)	0.39385 (17)	0.6353 (2)	0.0388 (4)
C3	0.61415 (16)	0.26559 (18)	0.6285 (3)	0.0467 (4)
H3A	0.5539	0.2353	0.6620	0.056*
C4	0.68132 (17)	0.18528 (19)	0.5721 (3)	0.0518 (5)
H4	0.6663	0.1005	0.5680	0.062*
C5	0.77164 (17)	0.22883 (19)	0.5209 (3)	0.0498 (5)
H5	0.8158	0.1727	0.4826	0.060*
C6	0.79670 (16)	0.35396 (17)	0.5261 (2)	0.0431 (4)
H6	0.8573	0.3829	0.4924	0.052*
C7	0.72873 (14)	0.43547 (16)	0.5832 (2)	0.0368 (4)
C8	0.67944 (14)	0.64414 (16)	0.6455 (2)	0.0394 (4)
C9	0.80569 (15)	0.74008 (17)	0.5817 (2)	0.0408 (4)
C10	0.9299 (2)	0.9347 (3)	0.7255 (3)	0.0708 (8)
H10A	0.9786	1.0017	0.7171	0.106*
H10B	0.9662	0.8752	0.8018	0.106*
H10C	0.8676	0.9668	0.7591	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0401 (3)	0.0539 (3)	0.0736 (4)	−0.00281 (18)	0.0258 (2)	0.0039 (2)
S1	0.0629 (3)	0.0383 (3)	0.0549 (3)	−0.0106 (2)	0.0306 (2)	−0.00469 (19)
O1	0.1214 (18)	0.0528 (10)	0.0643 (11)	−0.0205 (10)	−0.0021 (11)	0.0108 (8)
O2	0.1003 (16)	0.0681 (13)	0.189 (3)	−0.0195 (11)	0.1040 (18)	−0.0260 (15)
N1	0.0364 (7)	0.0418 (8)	0.0590 (10)	0.0016 (6)	0.0187 (7)	−0.0013 (7)
N2	0.0350 (7)	0.0340 (7)	0.0427 (8)	−0.0004 (5)	0.0135 (6)	−0.0003 (6)
N3	0.0413 (8)	0.0373 (8)	0.0470 (8)	−0.0019 (6)	0.0194 (6)	−0.0006 (6)
N4	0.0438 (8)	0.0358 (8)	0.0602 (10)	0.0010 (6)	0.0224 (7)	−0.0011 (7)
C1	0.0319 (8)	0.0437 (10)	0.0497 (10)	0.0000 (7)	0.0126 (7)	0.0031 (8)
C2	0.0352 (8)	0.0378 (9)	0.0435 (9)	−0.0012 (7)	0.0088 (7)	0.0013 (7)
C3	0.0438 (9)	0.0404 (10)	0.0566 (11)	−0.0060 (8)	0.0124 (8)	0.0012 (8)
C4	0.0567 (12)	0.0351 (10)	0.0645 (13)	−0.0044 (8)	0.0154 (10)	−0.0030 (8)
C5	0.0534 (11)	0.0378 (10)	0.0606 (12)	0.0038 (8)	0.0177 (9)	−0.0055 (8)
C6	0.0418 (9)	0.0392 (9)	0.0512 (10)	0.0004 (7)	0.0165 (8)	−0.0006 (7)
C7	0.0361 (8)	0.0349 (9)	0.0396 (9)	0.0000 (6)	0.0082 (7)	0.0005 (7)
C8	0.0358 (8)	0.0372 (9)	0.0475 (10)	0.0026 (7)	0.0140 (7)	−0.0007 (7)
C9	0.0422 (9)	0.0357 (9)	0.0480 (10)	−0.0018 (7)	0.0176 (8)	−0.0005 (7)
C10	0.0859 (18)	0.0761 (17)	0.0471 (12)	−0.0406 (14)	0.0070 (11)	0.0010 (11)

Geometric parameters (Å, º) top

Cl1—C1	1.7288 (19)	C2—C3	1.406 (3)
S1—O1	1.402 (2)	C2—C7	1.408 (2)
S1—O2	1.402 (2)	C3—C4	1.371 (3)
S1—C10	1.737 (2)	C3—H3A	0.9300
S1—C9	1.7689 (19)	C4—C5	1.391 (3)
N1—C1	1.293 (3)	C4—H4	0.9300
N1—C8	1.363 (2)	C5—C6	1.380 (3)
N2—N3	1.357 (2)	C5—H5	0.9300
N2—C8	1.360 (2)	C6—C7	1.389 (3)
N2—C7	1.383 (2)	C6—H6	0.9300
N3—C9	1.327 (2)	C10—H10A	0.9600
N4—C8	1.324 (2)	C10—H10B	0.9600
N4—C9	1.349 (2)	C10—H10C	0.9600
C1—C2	1.443 (3)

O1—S1—O2	115.62 (17)	C5—C4—H4	119.5
O1—S1—C10	109.07 (14)	C6—C5—C4	121.05 (19)
O2—S1—C10	112.43 (17)	C6—C5—H5	119.5
O1—S1—C9	108.29 (11)	C4—C5—H5	119.5
O2—S1—C9	107.48 (11)	C5—C6—C7	118.07 (18)
C10—S1—C9	103.11 (10)	C5—C6—H6	121.0
C1—N1—C8	115.74 (16)	C7—C6—H6	121.0
N3—N2—C8	110.54 (14)	N2—C7—C6	122.78 (17)
N3—N2—C7	125.77 (15)	N2—C7—C2	115.21 (16)
C8—N2—C7	123.68 (15)	C6—C7—C2	122.01 (17)
C9—N3—N2	100.26 (14)	N4—C8—N2	109.99 (16)
C8—N4—C9	101.57 (15)	N4—C8—N1	127.82 (17)
N1—C1—C2	126.35 (17)	N2—C8—N1	122.18 (16)
N1—C1—Cl1	116.69 (14)	N3—C9—N4	117.62 (16)
C2—C1—Cl1	116.95 (14)	N3—C9—S1	119.54 (14)
C3—C2—C7	118.11 (17)	N4—C9—S1	122.82 (14)
C3—C2—C1	125.06 (17)	S1—C10—H10A	109.5
C7—C2—C1	116.83 (16)	S1—C10—H10B	109.5
C4—C3—C2	119.81 (18)	H10A—C10—H10B	109.5
C4—C3—H3A	120.1	S1—C10—H10C	109.5
C2—C3—H3A	120.1	H10A—C10—H10C	109.5
C3—C4—C5	120.94 (19)	H10B—C10—H10C	109.5
C3—C4—H4	119.5

C8—N2—N3—C9	−0.9 (2)	C3—C2—C7—C6	0.0 (3)
C7—N2—N3—C9	179.96 (17)	C1—C2—C7—C6	−179.65 (17)
C8—N1—C1—C2	−0.6 (3)	C9—N4—C8—N2	−0.5 (2)
C8—N1—C1—Cl1	179.85 (14)	C9—N4—C8—N1	179.41 (19)
N1—C1—C2—C3	−179.0 (2)	N3—N2—C8—N4	0.9 (2)
Cl1—C1—C2—C3	0.5 (3)	C7—N2—C8—N4	−179.93 (17)
N1—C1—C2—C7	0.7 (3)	N3—N2—C8—N1	−178.95 (16)
Cl1—C1—C2—C7	−179.81 (13)	C7—N2—C8—N1	0.2 (3)
C7—C2—C3—C4	0.0 (3)	C1—N1—C8—N4	−179.7 (2)
C1—C2—C3—C4	179.63 (19)	C1—N1—C8—N2	0.2 (3)
C2—C3—C4—C5	−0.2 (3)	N2—N3—C9—N4	0.7 (2)
C3—C4—C5—C6	0.4 (3)	N2—N3—C9—S1	−177.85 (13)
C4—C5—C6—C7	−0.3 (3)	C8—N4—C9—N3	−0.2 (2)
N3—N2—C7—C6	−1.7 (3)	C8—N4—C9—S1	178.32 (15)
C8—N2—C7—C6	179.27 (18)	O1—S1—C9—N3	122.07 (19)
N3—N2—C7—C2	178.86 (16)	O2—S1—C9—N3	−3.5 (2)
C8—N2—C7—C2	−0.1 (3)	C10—S1—C9—N3	−122.44 (19)
C5—C6—C7—N2	−179.21 (19)	O1—S1—C9—N4	−56.4 (2)
C5—C6—C7—C2	0.2 (3)	O2—S1—C9—N4	178.1 (2)
C3—C2—C7—N2	179.43 (17)	C10—S1—C9—N4	59.1 (2)
C1—C2—C7—N2	−0.2 (2)

Experimental details

Crystal data
Chemical formula	C₁₀H₇ClN₄O₂S
M_r	282.71
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	12.6386 (3), 10.7464 (3), 8.6317 (3)
β (°)	102.459 (3)
V (Å³)	1144.74 (6)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	4.69
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.334, 0.454
No. of measured, independent and observed [I > 2σ(I)] reflections	10130, 2383, 2168
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.631

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.113, 1.03
No. of reflections	2383
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.40

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank the Research Center of the College of Pharmacy College and Deanship of Scientific Research of King Saud University, and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.

References

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