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

Abstract

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 R ₂ ²(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,

• a = 6.7608 (2) Å

• b = 8.5154 (2) Å

• c = 20.6503 (9) Å

• β = 97.237 (2)°

• V = 1179.39 (7) ų

• 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[F ² > 2σ(F ²)] = 0.048

• wR(F ²) = 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

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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811044631/zs2156Isup3.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
N2—H2⋯N1i	0.89 (3)	2.27 (3)	3.142 (2)	168 (2)

Symmetry code: (i) .

supplementary crystallographic information

Comment

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)].

Experimental

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.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H, 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2 to 1.5U_eq(C). The amino H-atom was located in a difference Fourier map, and was freely refined. The reflections (-1 2 3) and (0 1 2) were omitted because to bad agreement.

Figures

Fig. 1.

Thermal ellipsoid plot (Barbour, 2001) of C13H12N4S at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C13H12N4S	F(000) = 536
Mr = 256.34	Dx = 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

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	Rint = 0.061
Detector resolution: 9.091 pixels mm-1	θmax = 27.6°, θmin = 3.1°
φ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −11→10
Tmin = 0.940, Tmax = 0.980	l = −25→26
11943 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)] = 0.048	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(Fo2) + (0.0525P)2 + 0.7927P] where P = (Fo2 + 2Fc2)/3
2704 reflections	(Δ/σ)max = 0.001
169 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.46 e Å−3

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

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) −x+1, −y+1, −z+1.