N-(4,6-Dimethyl­pyrimidin-2-yl)-1,3-benzothia­zol-2-amine

Mohamed, S.K.; Horton, P.N.; El-Remaily, M.A.A.; Abdel-Ghany, H.; Ng, S.W.

doi:10.1107/S1600536811044631

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3131

doi:10.1107/S1600536811044631

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N-(4,6-Dimethylpyrimidin-2-yl)-1,3-benzothiazol-2-amine

Shaaban K. Mohamed,^a Peter N. Horton,^b Mahmoud A. A. El-Remaily,^c Hussam Abdel-Ghany ^c and Seik Weng Ng ^d,^e ^*

^aChemistry and Environmental Division, Manchester Metropolitan University, Manchester M15 6BH, England, ^bSchool of Chemistry, University of Southampton, Southampton SO17 1BJ, England, ^cDepartment of Chemistry, Faculty of Science, Sohag University, Egypt, ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^eChemistry Department, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 17 October 2011; accepted 25 October 2011; online 29 October 2011)

In the title compound, C₁₃H₁₂N₄S, an amino N atom is connected to a 1,3-benzothiazole fused-ring system and a dimethyl-substituted pyrimidine ring, these components being aligned [interplanar dihedral angle = 1.9 (1)°]. The secondary amino N atom forms an intermolecular N—H⋯N hydrogen bond to an N atom of the fused ring of an adjacent molecule, generating a centrosymmetric cyclic hydrogen-bonded dimer [graph set R₂²(8)].

Related literature

For the structure of N-(4,6-dimethylpyrimidin-2-yl)-1H-benzimidazol-2-amine, see: Mohamed et al. (2011 ). For graph-set analysis, see: Etter et al. (1990 ).

Experimental

Crystal data

C₁₃H₁₂N₄S
M_r = 256.34
Monoclinic, P 2₁ /n
a = 6.7608 (2) Å
b = 8.5154 (2) Å
c = 20.6503 (9) Å
β = 97.237 (2)°
V = 1179.39 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 120 K
0.24 × 0.14 × 0.08 mm

Data collection

Bruker–Nonius Roper CCD camera on κ-goniostat diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.940, T_max = 0.980
11943 measured reflections
2704 independent reflections
2100 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.126
S = 1.02
2704 reflections
169 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1ⁱ	0.89 (3)	2.27 (3)	3.142 (2)	168 (2)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; 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/S1600536811044631/zs2156sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811044631/zs2156Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811044631/zs2156Isup3.cml

checkCIF report

Comment top

In an earlier study, we reported the structure of N-(4,6-dimethylpyrimidin-2-yl)-1H-benzimidazol-2-amine (Mohamed et al., 2011). The benzimidazole portion of that molecule was replaced by a benzothiazole unit in the present study, giving the title compound C₁₃H₁₂N₄S (Scheme I). In this molecule, an amino N atom is connected to a benzothiazole fused-ring system and a dimethyl-substituted pyrimidine ring, these being aligned [inter-ring dihedral angle, 1.9 (1)°] (Fig. 1). The amino N atom forms an intermolecular N—H···N hydrogen bond to the N atom of the fused-ring of an adjacent molecule (Table 1) to generate a centrosymmetric cyclic hydrogen-bonded dimer [graph set R</i<>²₂(8) (Etter et al., 1990)].

Related literature top

For the structure of N-(4,6-dimethylpyrimidin-2-yl)-1H-benzimidazol-2-amine, see: Mohamed et al. (2011). For graph-set analysis, see: Etter et al. (1990).

Experimental top

2-(1,3-Benzothiazol-2-yl)guanidine (0.05 mol) was heated in acetylacetone solution (0.10 mol, approx. 10 ml) in the presence of a few drops of acetic acid at 473 K for 1 h. The mixture was cooled and the product was collected and recrystalized from ethanol to give the title compound (m.p. 513 K) in 85% yield.

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); 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. Thermal ellipsoid plot (Barbour, 2001) of C₁₃H₁₂N₄S at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

N-(4,6-Dimethylpyrimidin-2-yl)-1,3-benzothiazol-2-amine top

Crystal data top

C₁₃H₁₂N₄S	F(000) = 536
M_r = 256.34	D_x = 1.444 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 513 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 6.7608 (2) Å	Cell parameters from 2630 reflections
b = 8.5154 (2) Å	θ = 2.9–27.5°
c = 20.6503 (9) Å	µ = 0.26 mm⁻¹
β = 97.237 (2)°	T = 120 K
V = 1179.39 (7) Å³	Block, colorless
Z = 4	0.24 × 0.14 × 0.08 mm

Data collection top

Bruker–Nonius Roper CCD camera on κ-goniostat diffractometer	2704 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	2100 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.1°
ϕ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −11→10
T_min = 0.940, T_max = 0.980	l = −25→26
11943 measured reflections

Refinement top

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0525P)² + 0.7927P] where P = (F_o² + 2F_c²)/3
2704 reflections	(Δ/σ)_max = 0.001
169 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₁₃H₁₂N₄S	V = 1179.39 (7) Å³
M_r = 256.34	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.7608 (2) Å	µ = 0.26 mm⁻¹
b = 8.5154 (2) Å	T = 120 K
c = 20.6503 (9) Å	0.24 × 0.14 × 0.08 mm
β = 97.237 (2)°

Data collection top

Bruker–Nonius Roper CCD camera on κ-goniostat diffractometer	2704 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2100 reflections with I > 2σ(I)
T_min = 0.940, T_max = 0.980	R_int = 0.061
11943 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.29 e Å⁻³
2704 reflections	Δρ_min = −0.46 e Å⁻³
169 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.47670 (7)	0.76071 (6)	0.65817 (3)	0.01754 (17)
N1	0.6118 (2)	0.55355 (17)	0.58054 (8)	0.0158 (4)
N2	0.2981 (2)	0.64918 (19)	0.53944 (9)	0.0170 (4)
H2	0.305 (4)	0.586 (3)	0.5054 (13)	0.034 (7)*
N3	−0.0130 (2)	0.71820 (18)	0.48927 (8)	0.0165 (4)
N4	0.1226 (2)	0.83658 (18)	0.59065 (8)	0.0167 (4)
C1	0.7100 (3)	0.6766 (2)	0.68212 (10)	0.0167 (4)
C2	0.8414 (3)	0.7057 (2)	0.73865 (10)	0.0203 (5)
H2A	0.8097	0.7796	0.7702	0.024*
C3	1.0194 (3)	0.6232 (2)	0.74717 (10)	0.0226 (5)
H3	1.1108	0.6402	0.7854	0.027*
C4	1.0668 (3)	0.5154 (2)	0.70042 (10)	0.0215 (5)
H4	1.1898	0.4602	0.7075	0.026*
C5	0.9374 (3)	0.4875 (2)	0.64396 (10)	0.0184 (4)
H5	0.9708	0.4147	0.6122	0.022*
C6	0.7561 (3)	0.5692 (2)	0.63488 (10)	0.0160 (4)
C7	0.4608 (3)	0.6453 (2)	0.58687 (10)	0.0152 (4)
C8	0.1274 (3)	0.7392 (2)	0.54049 (10)	0.0150 (4)
C9	−0.3381 (3)	0.7869 (2)	0.43244 (11)	0.0201 (4)
H9A	−0.2945	0.7105	0.4017	0.030*
H9B	−0.3627	0.8884	0.4105	0.030*
H9C	−0.4611	0.7497	0.4479	0.030*
C10	−0.1786 (3)	0.8053 (2)	0.48952 (10)	0.0168 (4)
C11	−0.2001 (3)	0.9088 (2)	0.54009 (10)	0.0181 (4)
H11	−0.3180	0.9694	0.5400	0.022*
C12	−0.0455 (3)	0.9217 (2)	0.59088 (10)	0.0168 (4)
C13	−0.0551 (3)	1.0316 (2)	0.64689 (11)	0.0217 (5)
H13A	0.0326	0.9934	0.6851	0.032*
H13B	−0.1924	1.0371	0.6573	0.032*
H13C	−0.0117	1.1364	0.6351	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0175 (3)	0.0186 (3)	0.0166 (3)	0.00010 (19)	0.0027 (2)	−0.00291 (19)
N1	0.0172 (8)	0.0131 (8)	0.0166 (9)	−0.0006 (6)	0.0008 (7)	0.0007 (6)
N2	0.0170 (9)	0.0173 (8)	0.0163 (9)	0.0018 (7)	0.0008 (7)	−0.0029 (7)
N3	0.0158 (8)	0.0159 (8)	0.0181 (9)	−0.0013 (6)	0.0033 (7)	0.0016 (7)
N4	0.0183 (8)	0.0145 (8)	0.0181 (9)	−0.0003 (6)	0.0051 (7)	0.0009 (7)
C1	0.0189 (10)	0.0165 (9)	0.0153 (10)	−0.0022 (8)	0.0040 (8)	0.0017 (8)
C2	0.0241 (11)	0.0222 (10)	0.0152 (11)	−0.0031 (8)	0.0048 (9)	−0.0002 (8)
C3	0.0240 (11)	0.0272 (11)	0.0153 (11)	−0.0037 (9)	−0.0021 (9)	0.0023 (8)
C4	0.0188 (10)	0.0229 (10)	0.0221 (12)	0.0016 (8)	−0.0002 (9)	0.0044 (9)
C5	0.0212 (10)	0.0164 (9)	0.0180 (11)	−0.0012 (8)	0.0038 (8)	0.0005 (8)
C6	0.0179 (10)	0.0145 (9)	0.0153 (10)	−0.0035 (7)	0.0011 (8)	0.0022 (8)
C7	0.0168 (10)	0.0131 (9)	0.0160 (10)	−0.0025 (7)	0.0027 (8)	−0.0001 (7)
C8	0.0160 (9)	0.0129 (9)	0.0167 (11)	−0.0014 (7)	0.0047 (8)	0.0014 (7)
C9	0.0189 (10)	0.0208 (10)	0.0203 (11)	−0.0001 (8)	0.0013 (9)	0.0012 (8)
C10	0.0175 (9)	0.0133 (9)	0.0201 (11)	−0.0017 (7)	0.0044 (8)	0.0042 (8)
C11	0.0164 (10)	0.0166 (9)	0.0222 (11)	0.0021 (8)	0.0060 (8)	0.0039 (8)
C12	0.0199 (10)	0.0131 (9)	0.0184 (11)	−0.0033 (7)	0.0065 (8)	0.0028 (8)
C13	0.0233 (11)	0.0188 (10)	0.0238 (12)	−0.0001 (8)	0.0068 (9)	−0.0030 (8)

Geometric parameters (Å, º) top

S1—C1	1.746 (2)	C3—H3	0.9500
S1—C7	1.762 (2)	C4—C5	1.387 (3)
N1—C7	1.305 (2)	C4—H4	0.9500
N1—C6	1.397 (2)	C5—C6	1.401 (3)
N2—C7	1.378 (2)	C5—H5	0.9500
N2—C8	1.388 (2)	C9—C10	1.502 (3)
N2—H2	0.89 (3)	C9—H9A	0.9800
N3—C8	1.342 (3)	C9—H9B	0.9800
N3—C10	1.343 (2)	C9—H9C	0.9800
N4—C8	1.330 (3)	C10—C11	1.388 (3)
N4—C12	1.349 (3)	C11—C12	1.389 (3)
C1—C6	1.400 (3)	C11—H11	0.9500
C1—C2	1.397 (3)	C12—C13	1.496 (3)
C2—C3	1.385 (3)	C13—H13A	0.9800
C2—H2A	0.9500	C13—H13B	0.9800
C3—C4	1.399 (3)	C13—H13C	0.9800

C1—S1—C7	88.04 (9)	N1—C7—S1	116.81 (14)
C7—N1—C6	109.77 (16)	N2—C7—S1	122.68 (15)
C7—N2—C8	126.35 (18)	N4—C8—N3	127.80 (18)
C7—N2—H2	115.6 (16)	N4—C8—N2	117.28 (17)
C8—N2—H2	118.1 (16)	N3—C8—N2	114.91 (17)
C8—N3—C10	115.50 (17)	C10—C9—H9A	109.5
C8—N4—C12	116.16 (17)	C10—C9—H9B	109.5
C6—C1—C2	121.59 (18)	H9A—C9—H9B	109.5
C6—C1—S1	110.06 (15)	C10—C9—H9C	109.5
C2—C1—S1	128.35 (16)	H9A—C9—H9C	109.5
C3—C2—C1	117.85 (19)	H9B—C9—H9C	109.5
C3—C2—H2A	121.1	N3—C10—C11	121.32 (18)
C1—C2—H2A	121.1	N3—C10—C9	117.08 (18)
C2—C3—C4	121.07 (19)	C11—C10—C9	121.60 (18)
C2—C3—H3	119.5	C10—C11—C12	118.60 (18)
C4—C3—H3	119.5	C10—C11—H11	120.7
C5—C4—C3	121.16 (19)	C12—C11—H11	120.7
C5—C4—H4	119.4	N4—C12—C11	120.60 (18)
C3—C4—H4	119.4	N4—C12—C13	117.25 (18)
C4—C5—C6	118.41 (19)	C11—C12—C13	122.14 (18)
C4—C5—H5	120.8	C12—C13—H13A	109.5
C6—C5—H5	120.8	C12—C13—H13B	109.5
C1—C6—N1	115.32 (17)	H13A—C13—H13B	109.5
C1—C6—C5	119.92 (18)	C12—C13—H13C	109.5
N1—C6—C5	124.76 (18)	H13A—C13—H13C	109.5
N1—C7—N2	120.51 (18)	H13B—C13—H13C	109.5

C7—S1—C1—C6	−0.08 (15)	C8—N2—C7—S1	−0.8 (3)
C7—S1—C1—C2	179.4 (2)	C1—S1—C7—N1	−0.22 (16)
C6—C1—C2—C3	−0.8 (3)	C1—S1—C7—N2	179.59 (17)
S1—C1—C2—C3	179.75 (16)	C12—N4—C8—N3	1.7 (3)
C1—C2—C3—C4	0.6 (3)	C12—N4—C8—N2	−179.41 (16)
C2—C3—C4—C5	0.1 (3)	C10—N3—C8—N4	−0.8 (3)
C3—C4—C5—C6	−0.5 (3)	C10—N3—C8—N2	−179.65 (16)
C2—C1—C6—N1	−179.22 (17)	C7—N2—C8—N4	3.1 (3)
S1—C1—C6—N1	0.3 (2)	C7—N2—C8—N3	−177.90 (17)
C2—C1—C6—C5	0.4 (3)	C8—N3—C10—C11	−0.4 (3)
S1—C1—C6—C5	179.93 (15)	C8—N3—C10—C9	179.09 (17)
C7—N1—C6—C1	−0.5 (2)	N3—C10—C11—C12	0.4 (3)
C7—N1—C6—C5	179.94 (18)	C9—C10—C11—C12	−179.04 (18)
C4—C5—C6—C1	0.3 (3)	C8—N4—C12—C11	−1.6 (3)
C4—C5—C6—N1	179.82 (18)	C8—N4—C12—C13	179.75 (17)
C6—N1—C7—N2	−179.37 (17)	C10—C11—C12—N4	0.6 (3)
C6—N1—C7—S1	0.4 (2)	C10—C11—C12—C13	179.24 (18)
C8—N2—C7—N1	179.05 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1ⁱ	0.89 (3)	2.27 (3)	3.142 (2)	168 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂N₄S
M_r	256.34
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	6.7608 (2), 8.5154 (2), 20.6503 (9)
β (°)	97.237 (2)
V (Å³)	1179.39 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.24 × 0.14 × 0.08

Data collection
Diffractometer	Bruker–Nonius Roper CCD camera on κ-goniostat diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.940, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	11943, 2704, 2100
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.126, 1.02
No. of reflections	2704
No. of parameters	169
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.46

Computer programs: , DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1ⁱ	0.89 (3)	2.27 (3)	3.142 (2)	168 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The use of the EPSRC X-ray crystallographic facilities at the University of Southampton, England, is gratefully acknowledged. We thank Manchester Metropolitan University, Sohag University and the University of Malaya for supporting this study.

References

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