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

Abstract

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,

• a = 4.0047 (10) Å

• b = 13.424 (3) Å

• c = 10.938 (3) Å

• β = 99.650 (5)°

• V = 579.7 (2) ų

• 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[F ² > 2σ(F ²)] = 0.057

• wR(F ²) = 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)

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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812019885/hb6774Isup3.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
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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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).

Refinement

All H atoms were positioned geometrically and refined using a riding model with C–H = 0.93-0.97 Å and U_iso(H) = 1.2 or 1.5 U_eq(C). A rotating-group model was applied for the methyl group. The same U_ij parameters were used for atom pair C10/C11. The highest difference peak is 0.97Å from Br1. The deepest difference hole is 0.89Å from Br1.

Figures

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.

Crystal data

C11H9BrN4S	F(000) = 308
Mr = 309.19	Dx = 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

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

Refinement

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(Fo2) + (0.1109P)2] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
2087 reflections	Δρmax = 3.33 e Å−3
149 parameters	Δρmin = −0.86 e Å−3
2 restraints	Absolute structure: Flack (1983), 950 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.01 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.