6-(4-Bromo­phen­yl)-3-methyl-7H-1,2,4-triazolo[3,4-b][1,3,4]thia­diazine

Fun, H.-K.; Quah, C.K.; Abdel-Aziz, H.A.; Attia, M.I.

doi:10.1107/S1600536812019885

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1681

doi:10.1107/S1600536812019885

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6-(4-Bromophenyl)-3-methyl-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazine

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § Hatem A. Abdel-Aziz ^b and Mohamed I. Attia ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, PO Box 2457, Riyadh 11451, Saudi Arabia
^*Correspondence e-mail: hkfun@usm.my

(Received 30 April 2012; accepted 3 May 2012; online 12 May 2012)

In the title compound, C₁₁H₉BrN₄S, the 1,2,4-triazole ring is essentially planar (r.m.s. deviation = 0.020 Å) and makes a dihedral angle of 29.1 (5)° with the bromobenzene ring. The 3,6-dihydro-1,3,4-thiadiazine ring adopts a twist-boat conformation. In the crystal, molecules are linked by C—H⋯N interactions into sheets lying parallel to the (010) plane. The same N atom accepts two such hydrogen bonds.

Related literature

For general background to and the chemistry and biological activity of the title compound, see: Holla et al. (2001 ); Prasad et al. (1998 ); Dawood et al. (2005 ); Abdel-Aziz et al. (2007 ); Abdel-Wahab et al. (2009 ). For further synthesis details, see: Dickinson & Jacobsen (1975 ). For standard bond-length data, see: Allen et al. (1987 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ). For ring conformations, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₁H₉BrN₄S
M_r = 309.19
Monoclinic, P c
a = 4.0047 (10) Å
b = 13.424 (3) Å
c = 10.938 (3) Å
β = 99.650 (5)°
V = 579.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 3.71 mm⁻¹
T = 100 K
0.46 × 0.10 × 0.03 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.281, T_max = 0.910
5127 measured reflections
2087 independent reflections
1904 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.152
S = 1.04
2087 reflections
149 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 3.33 e Å⁻³
Δρ_min = −0.86 e Å⁻³
Absolute structure: Flack (1983 ), 950 Friedel pairs
Flack parameter: 0.01 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯N3ⁱ	0.97	2.56	3.185 (12)	122
C8—H8B⋯N3ⁱⁱ	0.97	2.31	3.191 (12)	151
Symmetry codes: (i) $[x, -y, z+{\script{1\over 2}}]$ ; (ii) $[x+1, -y, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812019885/hb6774sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812019885/hb6774Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812019885/hb6774Isup3.cml

checkCIF report

Comment top

For the background of the chemistry of 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazine derivatives see: Holla et al. (2001) & Prasad et al. (1998). In continuation of our studies in the chemistry and biological activities of the title compound analogs (Dawood et al., 2005; Abdel-Aziz et al., 2007 & Abdel-Wahab et al., 2009), we reported the synthesis and crystal structure of the title compound.

In the title compound, Fig. 1, the 1,2,4-triazole (N2-N4/C9/C10) is essentially planar (r.m.s. deviation = 0.020 Å) and makes a dihedral angle of 29.1 (5)° with the phenyl ring (C1-C6). The 3,6-dihydro-1,3,4-thiadiazine ring (S1/N1/N2/C7-C9) adopts a twist-boat conformation, with puckering parameters Q = 0.552 (8) Å, Θ = 66.6 (9)° and ϕ = 32.5 (10)° (Cremer & Pople, 1975). Bond lengths (Allen et al., 1987) and angles are within normal ranges.

In the crystal (Fig.2), molecules are linked via C8–H8A···N3 and C8–H8B···N3 bonds (Table 1) into sheets parallel to the (010) plane.

Related literature top

For general background to and the chemistry and biological activity of the title compound, see: Holla et al. (2001); Prasad et al. (1998); Dawood et al. (2005); Abdel-Aziz et al. (2007); Abdel-Wahab et al. (2009). For further synthesis details, see: Dickinson & Jacobsen (1975). For standard bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used in the data collection, see Cosier & Glazer (1986). For ring conformations, see: Cremer & Pople (1975).

Experimental top

The reaction of 4-amino-5-methyl-4H-1,2,4-triazole-3-thiol and 2-bromo-1-phenylethanone afforded the title compound in the form of colourless plates according to the reported method (Dickinson & Jacobsen, 1975).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The crystal structure of the title compound, viewed along the a axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

6-(4-Bromophenyl)-3-methyl-7H-1,2,4- triazolo[3,4-b][1,3,4]thiadiazine top

Crystal data top

C₁₁H₉BrN₄S	F(000) = 308
M_r = 309.19	D_x = 1.771 Mg m⁻³
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 2139 reflections
a = 4.0047 (10) Å	θ = 2.4–27.8°
b = 13.424 (3) Å	µ = 3.71 mm⁻¹
c = 10.938 (3) Å	T = 100 K
β = 99.650 (5)°	Plate, colourless
V = 579.7 (2) Å³	0.46 × 0.10 × 0.03 mm
Z = 2

Data collection top

Bruker SMART APEXII CCD diffractometer	2087 independent reflections
Radiation source: fine-focus sealed tube	1904 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −4→4
T_min = 0.281, T_max = 0.910	k = −15→16
5127 measured reflections	l = −13→12

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)] = 0.057	H-atom parameters constrained
wR(F²) = 0.152	w = 1/[σ²(F_o²) + (0.1109P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2087 reflections	Δρ_max = 3.33 e Å⁻³
149 parameters	Δρ_min = −0.86 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 950 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (2)

Crystal data top

C₁₁H₉BrN₄S	V = 579.7 (2) Å³
M_r = 309.19	Z = 2
Monoclinic, Pc	Mo Kα radiation
a = 4.0047 (10) Å	µ = 3.71 mm⁻¹
b = 13.424 (3) Å	T = 100 K
c = 10.938 (3) Å	0.46 × 0.10 × 0.03 mm
β = 99.650 (5)°

Data collection top

Bruker SMART APEXII CCD diffractometer	2087 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1904 reflections with I > 2σ(I)
T_min = 0.281, T_max = 0.910	R_int = 0.048
5127 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	H-atom parameters constrained
wR(F²) = 0.152	Δρ_max = 3.33 e Å⁻³
S = 1.04	Δρ_min = −0.86 e Å⁻³
2087 reflections	Absolute structure: Flack (1983), 950 Friedel pairs
149 parameters	Absolute structure parameter: 0.01 (2)
2 restraints

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
S1	0.0080 (5)	−0.00421 (15)	0.6539 (3)	0.0264 (5)
Br1	0.93512 (13)	0.44899 (5)	1.15745 (9)	0.0234 (3)
N1	−0.0050 (18)	0.2320 (5)	0.6525 (9)	0.0191 (15)
N2	−0.2131 (19)	0.1740 (6)	0.5631 (6)	0.0203 (16)
N3	−0.420 (2)	0.0529 (5)	0.4417 (8)	0.0308 (18)
N4	−0.5398 (18)	0.1444 (6)	0.3863 (7)	0.0288 (16)
C1	0.406 (2)	0.2109 (6)	0.9745 (7)	0.0188 (15)
H1A	0.3374	0.1478	0.9953	0.023*
C2	0.592 (2)	0.2704 (6)	1.0655 (7)	0.0212 (16)
H2A	0.6494	0.2466	1.1462	0.025*
C3	0.6906 (19)	0.3639 (6)	1.0365 (7)	0.0193 (16)
C4	0.622 (2)	0.3988 (6)	0.9129 (7)	0.0215 (16)
H4A	0.7033	0.4603	0.8919	0.026*
C5	0.4312 (19)	0.3397 (6)	0.8237 (7)	0.0175 (15)
H5A	0.3756	0.3639	0.7432	0.021*
C6	0.319 (2)	0.2450 (7)	0.8506 (8)	0.0194 (18)
C7	0.106 (2)	0.1867 (6)	0.7562 (8)	0.0178 (18)
C8	0.006 (2)	0.0807 (7)	0.7828 (9)	0.0220 (18)
H8A	−0.2194	0.0815	0.8044	0.026*
H8B	0.1608	0.0559	0.8540	0.026*
C9	−0.225 (3)	0.0749 (8)	0.5464 (9)	0.026 (2)
C10	−0.406 (2)	0.2173 (7)	0.4581 (9)	0.0256 (14)
C11	−0.458 (2)	0.3240 (7)	0.4400 (9)	0.0256 (14)
H11A	−0.5670	0.3365	0.3564	0.038*
H11B	−0.2431	0.3574	0.4552	0.038*
H11C	−0.5981	0.3484	0.4966	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0275 (13)	0.0247 (10)	0.0279 (10)	0.0019 (7)	0.0075 (10)	−0.0060 (9)
Br1	0.0201 (4)	0.0356 (4)	0.0131 (4)	−0.0002 (4)	−0.0007 (2)	−0.0050 (4)
N1	0.013 (4)	0.025 (3)	0.018 (3)	0.002 (2)	−0.001 (3)	−0.005 (3)
N2	0.025 (4)	0.028 (4)	0.008 (3)	0.002 (3)	0.002 (3)	0.002 (3)
N3	0.033 (5)	0.038 (4)	0.022 (4)	−0.006 (3)	0.006 (3)	−0.010 (3)
N4	0.025 (4)	0.047 (5)	0.017 (3)	−0.005 (3)	0.009 (3)	−0.007 (3)
C1	0.024 (4)	0.023 (4)	0.009 (4)	−0.001 (3)	0.003 (3)	0.002 (3)
C2	0.020 (4)	0.032 (4)	0.011 (4)	0.007 (3)	0.001 (3)	−0.003 (3)
C3	0.015 (4)	0.029 (4)	0.014 (4)	0.006 (3)	0.004 (3)	0.001 (3)
C4	0.022 (4)	0.026 (4)	0.016 (4)	0.002 (3)	0.003 (3)	0.004 (3)
C5	0.017 (4)	0.027 (4)	0.008 (3)	0.001 (3)	0.002 (3)	0.001 (3)
C6	0.023 (4)	0.029 (4)	0.007 (4)	0.006 (3)	0.003 (3)	0.000 (3)
C7	0.026 (5)	0.013 (4)	0.017 (5)	0.006 (3)	0.009 (4)	0.001 (3)
C8	0.027 (5)	0.018 (4)	0.022 (5)	−0.003 (3)	0.009 (4)	0.001 (3)
C9	0.025 (5)	0.032 (5)	0.020 (5)	−0.003 (3)	0.005 (4)	−0.006 (3)
C10	0.015 (3)	0.048 (4)	0.016 (3)	−0.004 (3)	0.007 (2)	0.000 (3)
C11	0.015 (3)	0.048 (4)	0.016 (3)	−0.004 (3)	0.007 (2)	0.000 (3)

Geometric parameters (Å, º) top

S1—C9	1.737 (11)	C2—H2A	0.9300
S1—C8	1.813 (10)	C3—C4	1.413 (11)
Br1—C3	1.892 (8)	C4—C5	1.384 (11)
N1—C7	1.298 (13)	C4—H4A	0.9300
N1—N2	1.408 (11)	C5—C6	1.395 (13)
N2—C9	1.342 (14)	C5—H5A	0.9300
N2—C10	1.399 (12)	C6—C7	1.454 (12)
N3—C9	1.307 (13)	C7—C8	1.519 (13)
N3—N4	1.417 (11)	C8—H8A	0.9700
N4—C10	1.311 (12)	C8—H8B	0.9700
C1—C2	1.391 (11)	C10—C11	1.455 (14)
C1—C6	1.417 (11)	C11—H11A	0.9600
C1—H1A	0.9300	C11—H11B	0.9600
C2—C3	1.370 (12)	C11—H11C	0.9600

C9—S1—C8	94.0 (4)	C5—C6—C7	120.8 (7)
C7—N1—N2	115.1 (6)	C1—C6—C7	121.7 (8)
C9—N2—C10	107.4 (8)	N1—C7—C6	116.3 (8)
C9—N2—N1	130.2 (8)	N1—C7—C8	122.9 (8)
C10—N2—N1	121.4 (8)	C6—C7—C8	120.7 (8)
C9—N3—N4	106.7 (7)	C7—C8—S1	113.8 (7)
C10—N4—N3	108.5 (7)	C7—C8—H8A	108.8
C2—C1—C6	121.0 (8)	S1—C8—H8A	108.8
C2—C1—H1A	119.5	C7—C8—H8B	108.8
C6—C1—H1A	119.5	S1—C8—H8B	108.8
C3—C2—C1	120.1 (8)	H8A—C8—H8B	107.7
C3—C2—H2A	120.0	N3—C9—N2	110.2 (9)
C1—C2—H2A	120.0	N3—C9—S1	129.0 (8)
C2—C3—C4	120.5 (7)	N2—C9—S1	120.7 (7)
C2—C3—Br1	121.8 (6)	N4—C10—N2	107.1 (9)
C4—C3—Br1	117.7 (6)	N4—C10—C11	128.2 (9)
C5—C4—C3	118.7 (7)	N2—C10—C11	124.6 (8)
C5—C4—H4A	120.6	C10—C11—H11A	109.5
C3—C4—H4A	120.6	C10—C11—H11B	109.5
C4—C5—C6	122.2 (7)	H11A—C11—H11B	109.5
C4—C5—H5A	118.9	C10—C11—H11C	109.5
C6—C5—H5A	118.9	H11A—C11—H11C	109.5
C5—C6—C1	117.4 (8)	H11B—C11—H11C	109.5

C7—N1—N2—C9	−26.3 (14)	C1—C6—C7—C8	−8.3 (13)
C7—N1—N2—C10	166.6 (8)	N1—C7—C8—S1	43.3 (11)
C9—N3—N4—C10	1.6 (11)	C6—C7—C8—S1	−140.3 (7)
C6—C1—C2—C3	0.9 (12)	C9—S1—C8—C7	−48.8 (7)
C1—C2—C3—C4	−3.7 (12)	N4—N3—C9—N2	0.5 (11)
C1—C2—C3—Br1	178.6 (6)	N4—N3—C9—S1	−177.5 (7)
C2—C3—C4—C5	4.8 (12)	C10—N2—C9—N3	−2.2 (12)
Br1—C3—C4—C5	−177.3 (6)	N1—N2—C9—N3	−170.6 (9)
C3—C4—C5—C6	−3.3 (12)	C10—N2—C9—S1	176.0 (7)
C4—C5—C6—C1	0.6 (13)	N1—N2—C9—S1	7.5 (14)
C4—C5—C6—C7	177.0 (7)	C8—S1—C9—N3	−154.5 (10)
C2—C1—C6—C5	0.7 (13)	C8—S1—C9—N2	27.7 (9)
C2—C1—C6—C7	−175.7 (8)	N3—N4—C10—N2	−2.8 (10)
N2—N1—C7—C6	−179.6 (7)	N3—N4—C10—C11	−179.4 (9)
N2—N1—C7—C8	−3.0 (13)	C9—N2—C10—N4	3.1 (10)
C5—C6—C7—N1	−7.9 (13)	N1—N2—C10—N4	172.8 (8)
C1—C6—C7—N1	168.4 (9)	C9—N2—C10—C11	179.8 (9)
C5—C6—C7—C8	175.5 (9)	N1—N2—C10—C11	−10.5 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···N3ⁱ	0.97	2.56	3.185 (12)	122
C8—H8B···N3ⁱⁱ	0.97	2.31	3.191 (12)	151

Symmetry codes: (i) x, −y, z+1/2; (ii) x+1, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₉BrN₄S
M_r	309.19
Crystal system, space group	Monoclinic, Pc
Temperature (K)	100
a, b, c (Å)	4.0047 (10), 13.424 (3), 10.938 (3)
β (°)	99.650 (5)
V (Å³)	579.7 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.71
Crystal size (mm)	0.46 × 0.10 × 0.03

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.281, 0.910
No. of measured, independent and observed [I > 2σ(I)] reflections	5127, 2087, 1904
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.152, 1.04
No. of reflections	2087
No. of parameters	149
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	3.33, −0.86
Absolute structure	Flack (1983), 950 Friedel pairs
Absolute structure parameter	0.01 (2)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···N3ⁱ	0.97	2.56	3.185 (12)	122
C8—H8B···N3ⁱⁱ	0.97	2.31	3.191 (12)	151

Symmetry codes: (i) x, −y, z+1/2; (ii) x+1, −y, z+1/2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009.

Acknowledgements

The authors thank Universiti Sains Malaysia for the Research University Grant (No. 1001/PFIZIK/811160) and the Deanship of Scientific Research and the Research Center, College of Pharmacy, King Saud University.

References

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