6-Chloro-3-[(di­methyl­amino)­methyl­idene]thio­chroman-4-one

Ashraf Y Khan; Nikhath Fathima; Mallikarjun B Kalashetti; Noor Shahina Begum; I M Khazi

doi:10.1107/S1600536813024550

. 2013 Sep 7;69(Pt 10):o1521. doi: 10.1107/S1600536813024550

6-Chloro-3-[(dimethylamino)methylidene]thiochroman-4-one

Ashraf Y Khan ^a, Nikhath Fathima ^b, Mallikarjun B Kalashetti ^a, Noor Shahina Begum ^b, I M Khazi ^a,^*

PMCID: PMC3790392 PMID: 24098211

Abstract

The asymmetric unit of the title compound, C₁₂H₁₂ClNOS, contains three independent molecules, with the thiochroman ring adopting a sofa conformation in each one. The crystal structure features C—H⋯O interactions; one of the O atoms accepts three such bonds. Together, the hydrogen bonds give rise to a molecular tape propagating in [010].

Related literature

For general background and the antifungal activity of thiochromans, see: Wang et al. (2010 ▶); Sosnovskikh (2003 ▶). For the crystal structure of a related compound, see: Butt et al. (1988 ▶).

Experimental

Crystal data

C₁₂H₁₂ClNOS
M _r = 253.74
Monoclinic,
a = 11.0031 (3) Å
b = 12.5937 (3) Å
c = 13.0787 (3) Å
β = 100.255 (2)°
V = 1783.36 (8) Å³
Z = 6
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 296 K
0.18 × 0.16 × 0.16 mm

Data collection

Bruker SMART APEX CCD detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.920, T _max = 0.928
13306 measured reflections
6540 independent reflections
5418 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.087
S = 1.01
6540 reflections
440 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶) and CAMERON (Watkin et al., 1996) ▶; software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813024550/pv2641sup1.cif

e-69-o1521-sup1.cif^{(38.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813024550/pv2641Isup2.hkl

e-69-o1521-Isup2.hkl^{(313.6KB, hkl)}

Click here for additional data file.^{(4.5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813024550/pv2641Isup3.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
C1a—H1a2⋯O1bⁱ	0.97	2.39	3.235 (4)	144
C11a—H11d⋯O1bⁱ	0.96	2.63	3.290 (4)	126
C1b—H1b2⋯O1a	0.97	2.43	3.284 (1)	147
C12a—H12b⋯O1b	0.96	2.59	3.358 (4)	137

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Symmetry code: (i) Inline graphic .

Acknowledgments

IMK is thankful to the University Grants Commission (UGC), India, for financial assistance.

supplementary crystallographic information

1. Comment

Thiochromanones belong to an important class of oxygen containing heterocycles; many of their derivatives have been reported to possess important biological activities including antifungal activity (Wang et al.,2010). They also serve as the starting material for the synthesis of novel heterocyclic systems (Sosnovskikh, 2003).

There are three crystallographically independent molecules (A, B and C) in an asymmetric unit of the title compond (Fig. 1) wherein 6-chloro-thiochroman moiety is substituted with the dimethylaminomethylene group at C2. The dimethylamino group is oriented trans with respect to the oxo group of the thiochroman moiety which is described by the torsion angles N1—C3A—C2A –C4A, N2—C3B—C2B—C4B and N3—C3C—C2C—C4C [172.25 (3), -173.45 (2) and -171.53 (3)°] for the molecules A, B and C, respectively. The thiochroman rings in the three molecules are significantly puckered and adopt sofa conformations. A mean-planes calculation shows that the atoms S1A, S1B and S1C deviate from the mean planes of the remaining ring atoms by 0.7536 (1), -0.7360 (1) and -0.6753 (1) Å, respectively. The bond distances and angles in the three molecules of the title compound agree very well with the corresponding bond distances and angles reported in a closely related compound (Butt et al., 1988).

The crystal structure is stabilized by C—H···O type intermolecular interactions (Tab. 1 & Fig. 2); three such interactions form trifurcated bonds from three donors C1A, C11A and C12A to the same acceptor O1B, linking the molecules in a tape like structure. Whereas, another C—H···O interaction results in a one dimensional chain along the b-axis.

2. Experimental

A mixture of 6-chloro -thiochroman-4-one (0.01 mol) and dimethylformamide-dimethylacetal (DMF-DMA) (2 mL) was heated under reflux for 10 h. The reaction mixture was triturated with ethanol to give a solid product that was collected by filtration and crystallized from ethanol to give the title compound as deep yellow crystals, melting point 379–381 K. Yield 78%.