Crystal structure of 7-bromo-4-oxo-4H-chromene-3-carbaldehyde

Yoshinobu Ishikawa

doi:10.1107/S1600536814018108

. 2014 Aug 13;70(Pt 9):o996. doi: 10.1107/S1600536814018108

Crystal structure of 7-bromo-4-oxo-4H-chromene-3-carbaldehyde

Yoshinobu Ishikawa ^a,^*

PMCID: PMC4186120 PMID: 25309300

Abstract

In the title compound, C₁₀H₅BrO₃, a brominated 3-formylchromone derivative, all atoms are essentially coplanar (r.m.s. = 0.0631 Å for the non-H atoms), with the largest deviation from the least-squares plane [0.215 (3) Å] being for the formyl O atom. In the crystal, molecules are linked into tapes through C—H⋯O hydrogen bonds and these tapes are assembled by stacking interactions [centroid–centroid distance between the pyran rings = 3.858 (3) Å] to form supramolecular layers that stack along the c axis.

Keywords: crystal structure, chromone, C—H⋯O hydrogen bonding, stacking interaction

Related literature

For related structures, see: 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

C₁₀H₅BrO₃
M _r = 253.05
Monoclinic,
a = 3.8580 (18) Å
b = 6.054 (4) Å
c = 37.268 (13) Å
β = 90.39 (4)°
V = 870.4 (8) Å³
Z = 4
Mo Kα radiation
μ = 4.71 mm⁻¹
T = 100 K
0.45 × 0.20 × 0.10 mm

Data collection

Rigaku AFC-7R diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.339, T _max = 0.624
4817 measured reflections
1980 independent reflections
1710 reflections with F ² > 2σ(F ²)
R _int = 0.024
3 standard reflections every 150 reflections intensity decay: 4.8%

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.109
S = 1.07
1980 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 1.26 e Å⁻³
Δρ_min = −1.73 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/S1600536814018108/tk5337sup1.cif

e-70-0o996-sup1.cif^{(22.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814018108/tk5337Isup2.hkl

e-70-0o996-Isup2.hkl^{(97.5KB, hkl)}

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

Supporting information file. DOI: 10.1107/S1600536814018108/tk5337Isup3.cml

Click here for additional data file.^{(1MB, tif)}

. DOI: 10.1107/S1600536814018108/tk5337fig1.tif

The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are shown as small spheres of arbitrary radius.

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S1600536814018108/tk5337fig2.tif

A packing view of the title compound. C—H⋯O hydrogen bonds are represented by dashed lines.

Click here for additional data file.^{(5.4MB, tif)}

H a H b . DOI: 10.1107/S1600536814018108/tk5337fig3.tif

Sphere models of the crystal structures of 6,8-dibromo-4-oxo-4H-chromene-3-carbaldehyde (top, Ishikawa, 2014a), 6-bromo-4-oxo-4H-chromene-3-carbaldehyde (middle, Ishikawa, 2014b), and the title compound (bottom, this work).

CCDC reference: 1018275

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
C7ⁱ—H4ⁱ⋯O2	0.95	2.30	3.149 (4)	149 (1)
C1ⁱⁱ—H1ⁱⁱ⋯O3	0.95	2.37	3.228 (5)	149 (1)

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

Acknowledgments

The University of Shizuoka is acknowledged for instrument support.

supplementary crystallographic information

S1. Structural commentary

Halogen bonding and halogen···halogen interaction 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 dibrominated 3-formylchromone derivative 6,8-dibromo-4-oxo-4H-chromene-3-carbaldehyde (Ishikawa, 2014a) and a monobrominated 3-formylchromone derivative 6-bromo-4-oxo-4H-chromene-3-carbaldehyde (Ishikawa, 2014b). Halogen bonding between the formyl oxygen atom and the bromine atom at 8-position and type II halogen···halogen interaction between the bromine atoms at 6-position are observed in 6,8-dibromo-4-oxo-4H-chromene-3-carbaldehyde (Fig.3, top). On the other hand, halogen bonding between the formyl oxygen atom and the bromine atom at 6-position is found in 6-bromo-4-oxo-4H-chromene-3-carbaldehyde (Fig.3, middle). As part of our interest in these types of chemical bonding, we herein report the crystal structure of a monobrominated 3-formylchromone derivative 7-bromo-4-oxo-4H-chromene-3-carbaldehyde.

The objective of this study is to reveal whether a short contact is found for the bromine atom at 7-position. The mean deviation of the least-square planes for the non-hydrogen atoms is 0.0631 Å, and the largest deviation is 0.215 (3) Å for the formyl O3 atom (Fig. 1). In the crystal, the molecules are linked through C–H···O hydrogen bonds between the translation-symmetryⁱ and inversion-symmetry equivalents^ii,iii to form tapes [i: x + 1, y + 1, z, ii: –x, –y + 1, –z + 1, iii: –x + 1, –y + 2, –z + 1], which are further assembled by stacking interactions [centroid–centroid distance between the pyran rings of the 4H-chromene units = 3.858 (3) Å], as shown in Fig. 2. A short contact for the bromine atom at 7-position is not observed (Fig. 3, bottom).

S2. Synthesis and crystallization

To a solution of 4-bromo-2-hydroxyacetophenone (4.7 mmol) in N,N-dimethylformamide (15 ml) was added drop-wise POCl₃ (11.6 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: 84%). 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 [C₁₀H₅BrO₃ + H⁺]: 252.950, found 252.981. 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.