7-Chloro-4-oxo-4H-chromene-3-carbaldehyde

Yoshinobu Ishikawa

doi:10.1107/S1600536814014925

. 2014 Jul 2;70(Pt 8):o831. doi: 10.1107/S1600536814014925

7-Chloro-4-oxo-4H-chromene-3-carbaldehyde

Yoshinobu Ishikawa ^a,^*

PMCID: PMC4158550 PMID: 25249886

Abstract

In the title compound, C₁₀H₅ClO₃, a chlorinated 3-formylchromone derivative, all atoms are essentially coplanar (r.m.s. deviation = 0.0592 Å for all non-H atoms), with the largest deviation from the least-squares plane [0.1792 (19) Å] being for the chromone-ring carbonyl O atom. In the crystal, molecules are linked through C—H⋯O hydrogen bonds to form tetrads, which are assembled by stacking interactions [centroid–centroid distance between the pyran rings = 3.823 (3) Å] and van der Waals contacts between the Cl atoms [Cl⋯Cl = 3.4483 (16) Å and C—Cl⋯Cl = 171.73 (7)°] into a three-dimensional architecture.

Keywords: crystal structure

Related literature

For related structures, see: Ishikawa & Motohashi (2013 ▶); Ishikawa (2014a ▶,b ▶). For halogen bonding, see: Auffinger et al. (2004 ▶); Metrangolo et al. (2005 ▶); Wilcken et al. (2013 ▶); Sirimulla et al. (2013 ▶). For halogen–halogen interactions, see: Metrangolo & Resnati (2014 ▶); Mukherjee & Desiraju (2014 ▶).

Experimental

Crystal data

C₁₀H₅ClO₃
M _r = 208.60
Triclinic,
a = 3.823 (2) Å
b = 5.973 (3) Å
c = 18.386 (8) Å
α = 85.99 (4)°
β = 87.74 (4)°
γ = 86.58 (4)°
V = 417.8 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 100 K
0.42 × 0.25 × 0.08 mm

Data collection

Rigaku AFC-7R diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.865, T _max = 0.966
2429 measured reflections
1899 independent reflections
1690 reflections with F ² > 2σ(F ²)
R _int = 0.050
3 standard reflections every 150 reflections intensity decay: −1.1%

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.104
S = 1.10
1899 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: WinAFC Diffractometer Control Software (Rigaku, 1999 ▶); cell refinement: WinAFC Diffractometer Control Software; data reduction: WinAFC Diffractometer Control Software; program(s) used to solve structure: SIR2008 (Burla et al., 2007 ▶); 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/S1600536814014925/tk5323sup1.cif

e-70-0o831-sup1.cif^{(23.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814014925/tk5323Isup2.hkl

e-70-0o831-Isup2.hkl^{(93.5KB, hkl)}

Click here for additional data file.^{(3.3KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814014925/tk5323Isup3.cml

CCDC reference: 1010095

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H4⋯O2ⁱ	0.95	2.34	3.204 (3)	151 (1)
C1—H1⋯O3ⁱⁱ	0.95	2.37	3.209 (3)	148 (1)

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

Acknowledgments

The University of Shizuoka is acknowledged for instrumental support.

supplementary crystallographic information

S1. Structural commentary

Halogen bonding and halogen···halogen interactions have recently attracted much attention in medicinal chemistry, chemical biology, supramolecular chemistry and crystal engineering (Auffinger et al., 2004, Metrangolo et al., 2005, Wilcken et al., 2013, Sirimulla et al., 2013, Mukherjee & Desiraju, 2014, Metrangolo & Resnati, 2014). We have recently reported the crystal structures of a dichlorinated 3-formylchromone derivative 6,8-dichloro-4-oxochromene-3-carbaldehyde (Ishikawa & Motohashi, 2013), and monochlorinated 3-formylchromone derivatives 6-chloro-4-oxo-4H-chromene-3-carbaldehyde (Ishikawa, 2014a) and 8-chloro-4-oxo-4H-chromene-3-carbaldehyde (Ishikawa, 2014b). Halogen bonding between the formyl oxygen atom and the chlorine atom at 8-position and type I halogen···halogen interaction between the chlorine atoms at 6-position are observed in 6,8-dichloro-4-oxochromene-3-carbaldehyde (Fig·2 A). On the other hand, van der Waals contacts between the formyl oxygen atom and the chlorine atom at 6-position in 6-chloro-4-oxo-4H-chromene-3-carbaldehyde (Fig·2 B) and between the formyl oxygen atom and the chlorine atom at 8-position in 8-chloro-4-oxo-4H-chromene-3-carbaldehyde (Fig·2 C) are found. As part of our interest in these types of chemical bonding, we herein report the crystal structure of a monochlorinated 3-formylchromone derivative 7-chloro-4-oxo-4H-chromene-3-carbaldehyde. The objective of this study is to reveal whether a short contact is found for the chlorine atom at 7-position.

The mean deviation of the least-square planes for the non-hydrogen atoms is 0.0592 Å, and the largest deviation is 0.1792 (19) Å for O3.

In the crystal, the molecules are linked through C–H···O hydrogen bonds among the translation-symmetryⁱ and inversion-symmetry equivalents^ii,iii to form tetrads [i: x – 1, y – 1, z, ii: –x, –y, –z + 1, iii: –x + 1, –y + 1, –z + 1], which are assembled by stacking interactions [centroid–centroid distance between the pyran rings = 3.823 (3) Å], as shown in Fig. 1.

Van der Waals contacts between the chlorine atoms of inversion-symmetry equivalents are found [Cl1···Cl1^iv = 3.4483 (16) Å, C6–Cl1···Cl1^iv = 171.73 (7)°, iv: –x + 1, –y + 2, –z + 2], as shown in Fig. 2D. Thus, significant short contact for the chlorine atom at 7-position is not observed. Whereas the characteristic short Cl···O contact is observed in the dichlorinated 3-formylchromone (Fig. 2A), such a short contact is not found in the monochlorinated ones (Fig. 2B, C and D). These findings should be helpful to understand interactions of halogenated ligands with proteins, and thus invaluable for rational drug design.

S2. Synthesis and crystallization

To a solution of 4-chloro-2-hydroxyacetophenone (5.9 mmol) in N,N-dimethylformamide (15 ml) was added dropwise POCl₃ (14.7 mmol) at 0 °C. After the mixture was stirred for 14 h at room temperature, water (50 ml) was added. The precipitates were collected, washed with water, and dried in vacuo (yield: 85%). ¹H NMR (400 MHz, CDCl₃): δ = 7.48 (d, 1H, J = 8.8 Hz), 7.57 (s, 1H), 8.24 (d, 1H, J = 8.8 Hz), 8.52 (s, 1H), 10.37 (s, 1H). DART-MS calcd for [C₁₀H₅Cl₁O₃ + H⁺]: 209.001, found 209.029. Single crystals suitable for X-ray diffraction were obtained from a 1,2-dichloroethane/cyclohexane solution of the title compound at room temperature.

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The C(sp²)-bound hydrogen atoms were placed in geometrical positions [C—H 0.95 Å, U_iso(H) = 1.2U_eq(C)], and refined using a riding model.