2-(Adamantan-1-yl)-N-(6-meth­oxy-1,3-benzo­thia­zol-2-yl)acetamide

Alexander S Bunev; Prokofij V Sklyuev; Gennady I Ostapenko; Petr P Purygin; Victor N Khrustalev

doi:10.1107/S1600536813023313

. 2013 Aug 23;69(Pt 9):o1472. doi: 10.1107/S1600536813023313

2-(Adamantan-1-yl)-N-(6-methoxy-1,3-benzothiazol-2-yl)acetamide

Alexander S Bunev ^a,^*, Prokofij V Sklyuev ^a, Gennady I Ostapenko ^a, Petr P Purygin ^b, Victor N Khrustalev ^c

PMCID: PMC3884489 PMID: 24427094

Abstract

The asymmetric unit of the title compound, C₂₀H₂₄N₂O₂S, contains two independent molecules having very similar geometries. The main N-(6-methoxy-1,3-benzothiazol-2-yl)acetamide moiety adopts an almost planar structure (r.m.s. deviations of 0.091 and 0.051 Å for the two independent molecules). The adamantyl substituent occupies the gauche position relative to the C—N bond of the acetamide moiety [the corresponding N–C–C–C dihedral angles are −100.3 (3) and −96.5 (3)° for the two independent molecules]. In the crystal, the two independent molecules form a dimer via a pair of N—H⋯N hydrogen bonds. The dimers are further linked by C—H⋯O hydrogen bonds and attractive S⋯S [3.622 (2) Å] interactions into ribbons along [100].

Related literature

For properties of benzothiazoles as building blocks in organic synthesis, see: Gupta & Rawat (2010 ▶); Facchinetti et al. (2012 ▶); Sareen et al. (2012 ▶); Radatz et al. (2013 ▶). For syntheses and properties of 2-substituted benzothiazoles, see: Hussein et al. (2012 ▶); Ugale et al. (2012 ▶); Yoo et al. (2012 ▶); Zhu et al. (2012 ▶); Bhardwaj et al. (2013 ▶); Patel et al. (2013 ▶). graphic file with name e-69-o1472-scheme1.jpg

Experimental

Crystal data

C₂₀H₂₄N₂O₂S
M _r = 356.48
Triclinic,
a = 11.0114 (13) Å
b = 13.6647 (18) Å
c = 13.9230 (18) Å
α = 61.554 (3)°
β = 80.252 (3)°
γ = 89.782 (4)°
V = 1808.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 100 K
0.20 × 0.15 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.962, T _max = 0.981
17897 measured reflections
7124 independent reflections
4424 reflections with I > 2σ(I)
R _int = 0.071

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.115
S = 0.91
7124 reflections
459 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813023313/rk2412sup1.cif

e-69-o1472-sup1.cif^{(45KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813023313/rk2412Isup2.hkl

e-69-o1472-Isup2.hkl^{(348.6KB, hkl)}

Click here for additional data file.^{(7.2KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813023313/rk2412Isup3.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—H2N⋯N3	0.87 (3)	2.13 (3)	2.995 (3)	169 (2)
N4—H4N⋯N1	0.78 (3)	2.30 (3)	3.077 (3)	174 (2)
C6—H6⋯O3ⁱ	0.95	2.58	3.452 (3)	153
C26—H26⋯O1ⁱⁱ	0.95	2.45	3.392 (3)	174

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors are grateful to the Ministry of Education and Science of the Russian Federation (State program No. 3.1168.2011).

supplementary crystallographic information

1. Comment

Benzothiazoles are important and versatile building blocks in organic synthesis, in particular, for production of various biologically active compounds in medicinal and industrial fields (Gupta & Rawat, 2010; Facchinetti et al., 2012; Sareen et al., 2012; Radatz et al., 2013). Notably, among all benzothiazole derivatives, 2-substituted benzothiazoles are of special interest due to their multiple applications as medicinal agents, agrochemicals, materials for chemical sensors etc. (Hussein et al., 2012; Ugale et al., 2012; Yoo et al., 2012; Zhu et al., 2012; Bhardwaj et al., 2013; Patel et al., 2013).

In this work, a 2-(1-adamantyl)-N-(6-methoxy-1,3-benzothiazol-2-yl)acetamide, C₂₀H₂₄N₂O₂S, (I) was prepared by the reaction of 1-(1-adamantylacetyl)-1H-imidazole with 6-methoxy-1,3-benzothiazol-2-amine (Fig. 1) and its structure was unambiguously established by the X-ray diffraction study.

Compound I crystallizes in the triclinic P1 space group with two crystallographically independent molecules forming an H-bonded dimer by the two classical intermolecular N–H···N hydrogen bonds (Table 1, Fig. 2). The geometries of these two independent molecules are very similar. The main N-(6-oxy-1,3-benzothiazol-2-yl)acetamide fragment adopts almost planar structure determined by the long chain of conjugated bonds. The adamantyl substituent occupies the gauche position in relative to the C–N bond of the acetamide moiety (the corresponding N–C–C–C dihedral angles are -100.3 (3)° and -96.5 (3)° for the two independent molecules, respectively).

In the crystal, the H-bonded dimers of I are linked by the intermolecular C6–H6···O3ⁱ and C26–H26···O1ⁱⁱ non-classical hydrogen bonds (Table 1) as well as attractive S1···S2ⁱ (3.622 (2)Å) interactions into ribbons toward [100] (Fig. 3). Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z.

2. Experimental

A mixture 1-(1-adamantylacetyl)-1H-imidazole (1.06 g, 4.3 mmol) and 6-methoxy-1,3-benzothiazol-2-amine (0.9 g, 4.9 mmol) in CHCl₃ (50 ml) were refluxed for 6 h. The precipitate was filtered, and then reaction mixture was concentrated in vacuo. The residue crystallized from 80% EtOH. Yield is 22%. The single crystals of the product I was obtained by slow crystallization from EtOH. M.p. = 485-486 K. IR (KBr), ν/cm^-1: 3178, 2903, 2848, 1668, 1604, 1472, 1267, 1062, 827. ¹H NMR (500 MHz, DMSO-d₆, 304 K): δ = 1.52-1.49 (m, 6H), 1.66-1.63 (m, 6H), 1.96-1.93 (m, 3H), 2.63-2.61(m, 2H), 3.76 (s, 3H), 7.03-7.01 (m, 1H), 7.35-7.34 (m, 1H), 7.73 (dd, 1H, J = 8.87). Anal. Calcd for C₂₀H₂₄N₂O₂S: C, 67.38; H, 6.79. Found: C,67.32; H, 6.82.