6,8-Di­chloro-4-oxochromene-3-carbalde­hyde

Yoshinobu Ishikawa; Yuya Motohashi

doi:10.1107/S1600536813022228

. 2013 Aug 14;69(Pt 9):o1416. doi: 10.1107/S1600536813022228

6,8-Dichloro-4-oxochromene-3-carbaldehyde

Yoshinobu Ishikawa ^a,^*, Yuya Motohashi ^a

PMCID: PMC3884433 PMID: 24427051

Abstract

The asymmetric unit of the title compound, C₁₀H₄Cl₂O₃, contain two essentially planar independent molecules (mean atomic deviations from the corresponding least-square planes are 0.041 and 0.045 Å for molecules 1 and 2, respectively). In the crystal, molecules are linked through a pair of halogen bonds [Cl⋯O separations are 3.044 (5) and 3.033 (6) Å, C—Cl⋯O angles are 160.4 (3) and 162.8 (3)°, and C=O⋯Cl angles are 138.7 (4) and 139.6 (4)°, respectively, in molecules 1 and 2] and C—H⋯O hydrogen bonds into slightly folded bands [the dihedral angle between the planes of neighboring molecules is 8.6 (2)°] along the c-axis direction.

Related literature

For the biological activity of the title and related compounds, see: Shim et al. (2003 ▶); Kawase et al. (2007 ▶); Dückert et al. (2012 ▶). For related structures, see: Ishikawa et al. (2013a ▶,b ▶). For halogen bonding, see: Auffinger et al. (2004 ▶); Metrangolo et al. (2005 ▶); Wilcken et al. (2013 ▶).

Experimental

Crystal data

C₁₀H₄Cl₂O₃
M _r = 243.05
Triclinic,
a = 8.288 (8) Å
b = 8.325 (7) Å
c = 13.706 (7) Å
α = 96.55 (6)°
β = 92.23 (7)°
γ = 101.98 (7)°
V = 917.2 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 100 K
0.42 × 0.22 × 0.08 mm

Data collection

Rigaku AFC-7R diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.841, T _max = 0.947
5130 measured reflections
4203 independent reflections
2596 reflections with F ² > 2σ(F ²)
R _int = 0.057
3 standard reflections every 150 reflections intensity decay: 4.9%

Refinement

R[F ² > 2σ(F ²)] = 0.076
wR(F ²) = 0.212
S = 1.10
4203 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Data collection: WinAFC (Rigaku, 1999 ▶); cell refinement: WinAFC; data reduction: WinAFC; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku, 2010 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablock(s) General, I. DOI: 10.1107/S1600536813022228/ld2111sup1.cif

e-69-o1416-sup1.cif^{(26.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813022228/ld2111Isup2.hkl

e-69-o1416-Isup2.hkl^{(206KB, hkl)}

Click here for additional data file.^{(3.4KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813022228/ld2111Isup3.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
C4b ⁱ—H2b ⁱ⋯O2a	0.95	2.35	3.246 (8)	157
C4a—H2a⋯O2b ⁱ	0.95	2.35	3.259 (8)	160

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Symmetry code: (i) Inline graphic .

Acknowledgments

We acknowledge the University of Shizuoka for instrumental support.

supplementary crystallographic information

1. Comment

6,8-Dichloro-3-formylchromone shows many biological functions such as protein tyrosine phosphatase inhibitory (Shim et al. 2003), tumor cell-cytotoxic, anti-HIV, anti-Helicobacter pylori, and urease inhibitory activities (Kawase et al. 2007). In addition, it is used as a starting material for the synthesis of biologically relevant molecules (Dückert et al. 2012).

The title compound, C₁₀H₄Cl₂O₃, crystallizes with two independent molecules in the asymmetric unit (Fig. 1). The mean deviations from the least-square planes for all atoms of molecule 1 and 2 are 0.0410 Å and 0.0449 Å, respectively. In addition, the largest deviations of molecule 1 and 2 are 0.1512 (17) Å for Cl1a and -0.0973 Å for H4b, respectively. This means that all atoms of each molecule are essentially coplanar.

In the crystal, the molecules 1 and 2 are linked to each other through intermolecular interactions of the Cl atoms at the 8-position with the O atoms of the formyl groups [Cl2a···O3bⁱ; 3.033 (6) Å, Cl2bⁱ···O3a; 3.044 (5) Å, C7a–Cl2a···O3bⁱ = 160.4 (3)°, C7bⁱ–Cl2bⁱ···O3a =162.8 (3)°, C10a–O3a···Cl2bⁱ = 138.7 (4)°, C10bⁱ–O3bⁱ···Cl2a = 139.6 (4)° (i): -x + 1, -y + 1, -z + 1], and the carbonyl O atoms at the 4-position with the C–H atoms at the 5-position. The short contacts and the geometries involved in the Cl atoms fall into halogen bonding (Auffinger et al. 2004). Due to these halogen and hydrogen bonds, the molecules form wavy bands along c axis, as shown in Fig. 2.

Halogen bonds have been found to occur in organic, inorganic, and biological systems, and have recently attracted much attention in medicinal chemistry, chemical biology, and supramolecular chemistry (Auffinger et al. 2004, Metrangolo et al. 2005, Wilcken et al. 2013). Our analysis suggests that the strong inhibitory activity of the title compound against urease may be attributable to the halogen bond observed in the crystal, because 3-formylchromones without any halogen atom at the 8-position in the literature do not show the urease inhibitory activity (Kawase et al. 2007).

2. Experimental

Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a 2-butanone solution of commercially available 6,8-dichloro-3-formylchromone at room temperature.