1-(8-Bromo-2-methyl-4-thioxo-3,4,5,6-tetra­hydro-2H-2,6-methano-1,3-benzoxazocin-11-yl)ethanone

G V Palamarchuk; O V Borisov; S S Kovalenko; V P Chernykh; S M Kovalenko; V N Baumer; O V Shishkin

doi:10.1107/S160053680900347X

. 2009 Feb 4;65(Pt 3):o461. doi: 10.1107/S160053680900347X

1-(8-Bromo-2-methyl-4-thioxo-3,4,5,6-tetrahydro-2H-2,6-methano-1,3-benzoxazocin-11-yl)ethanone

G V Palamarchuk ^a,^*, O V Borisov ^b, S S Kovalenko ^b, V P Chernykh ^b, S M Kovalenko ^b, V N Baumer ^a, O V Shishkin ^a

PMCID: PMC2968576 PMID: 21582133

Abstract

In the title compound, C₁₄H₁₄BrNO₂S, there are two similar non-equivalent molecules in the asymmetric unit, displaying three chiral centres each. In the crystal structure, they are linked by intermolecular N—H⋯O hydrogen bonds to form infinite chains, which are in turn connected by weak Br⋯H and S⋯H interactions.

Related literature

For related literature on the applications of thiophene derivatives, see: Zaragoza Dorwald (2000 ▶); Kovalenko & Victorova (2005 ▶). For analogous conformations, see: Bilokin et al. (1988 ▶); Raev et al. (2004 ▶); Biala et al. (2002 ▶); Konovalova et al. (2007 ▶); O’Callaghan et al. (1997 ▶); Zefirov & Zorky (1995 ▶).

Experimental

Crystal data

C₁₄H₁₄BrNO₂S
M _r = 340.23
Triclinic,
a = 8.213 (5) Å
b = 11.625 (7) Å
c = 15.156 (10) Å
α = 98.67 (5)°
β = 99.09 (5)°
γ = 101.81 (5)°
V = 1373.1 (15) Å³
Z = 4
Mo Kα radiation
μ = 3.14 mm⁻¹
T = 293 (2) K
0.6 × 0.1 × 0.05 mm

Data collection

Siemens P3/PC diffractometer
Absorption correction: integration (XPREP; Siemens, 1991 ▶) T _min = 0.611, T _max = 0.855
7869 measured reflections
4773 independent reflections
3383 reflections with I > 2/s(I)
R _int = 0.012
2 standard reflections every 98 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.118
S = 1.03
4773 reflections
348 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: P3 (Siemens, 1991 ▶); cell refinement: P3; data reduction: XDISK and XPREP (Siemens, 1991 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680900347X/bg2221sup1.cif

e-65-0o461-sup1.cif^{(27.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680900347X/bg2221Isup2.hkl

e-65-0o461-Isup2.hkl^{(233.8KB, hkl)}

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
N10A—H10A⋯O14Bⁱ	0.86	2.20	2.981 (4)	150
N10B—H10B⋯O14Aⁱⁱ	0.86	2.15	2.960 (4)	157

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

supplementary crystallographic information

Comment

The fragment of thiophene is a very important pharmacophore part of many biologically active compounds. Thiophene derivatives are used as antitussives (Zaragoza Dorwald, 2000; Kovalenko & Victorova, 2005), antibiotics, anaesthetics, antiparasitics, resolvents, anthelmintic drugs, anticholinergic drugs, antiulcer agents, antihistamines. Investigation of the molecular structure of these compounds may provide useful information for understanding the mechanism of their biological activity. In this paper we report the molecular and crystal structure of the 2-aroyl-3-amino-4-arylsulfonyl-5-arylamino-thiophene. There are two molecules in the asymmetric unit (labelled A and B in Fig. 1), with a similar distribution of chiral centers (C1, C9 and C13). Both molecules have similar geometrical characteristics: the piperidine-2-tione and tetrahydropyran rings adopt a half-chair conformation; deviations of the C1 and C13 atoms of the tetrahydropyrimidine ring from the mean-square planes of the remaining atoms in the ring are -0.46 (1) Å, 0.44 (1) Å and 0.37 (1) Å, -0.51 (1) Å in molecules A and B, respectively. Deviations of the C9 and C13 atoms of the tetrahydropyrane from the mean-square planes of the remaining atoms in the rings are -0.36 (1) Å, 0.44 (1) Å, in both molecules. The two rings are fused in such way that the C16 methyl group and the H atom at the C1 have equatorial orientation (the C7—C8—C9—C16 and C7—C2—C1—H1A torsion angles being -177.2 (3)° and -140.7 (3)° (molecule A) and -175.2 (3)° and -140.0 (3)° (molecule B). The same type of ring fusion have been observed in related compounds (Konovalova et al., 2007; Raev et al., 2004; Bilokin et al., 1988; O'Callaghan et al., 1997; Biala et al., 2002). The C13—C14 bond has an equatorial orientation with regard to the piperidine-2-tione ring (the N10—C9—C13—C14 torsion angle being -176.6 (3)° and -179.8 (3)° (A, B respectively). The acetyl group adopts an orthogonal arrangement relative to the C9—C13 bond (the C9—C13—C14—O14 torsion angle being 92.4 (4)°, -89.8 (4)° (A, B respectively). The main H-bonding interactions are presented in Table 1. Molecules pack as infinite chains of alternating A and B molecules, due to intrachain N—H···O and weak C—H···Br interactions. Neighbouring chains in turn are connected by weak C—H···.S interactions as well as by stacking interactions between phenyl rings with an interplanar distance of 3.37 (1) Å.

Experimental

The title compound was obtained by one-pot synthesis, starting from a mixture of 1 mmol 6-bromocoumarine-3-thioamide and 1.2 mmol of 2,4-pentanedione in 5 ml of methanol containing catalytic amounts of piperidine, which was refluxed for 5 min. Then it was cooled to 500 C and 2 mmol of potassium alkali was added. The reaction mixture was stirred at 500 C for 6 h (monitored by TLC). Then it was cooled to r.t. and diluted with water. Formed precipitate was filtered and washed with water and water–methanol, 1:1.