Crystal structure of 6,7-di-chloro-4-oxo-4H-chromene-3-carbaldehyde.

In the title compound, C10H4Cl2O3, a dichlorinated 3-formyl-chromone, the non-H atoms of the 4H-chromene ring are essentially coplanar (r.m.s. = 0.0188 Å), with the largest deviation from the least-squares plane [0.043 (2) Å] being for the pyran C=O C atom. The α,β-unsaturated carbonyl O atom deviates from the least-square plane by 0.124 (2) Å. The dihedral angle between the chromone and formyl least-square planes is 6.76 (3)°. In the crystal, mol-ecules are linked through C-H⋯O hydrogen bonds between the translation-symmetry and inversion-symmetry equivalents to form tetrads, which are further assembled by stacking inter-actions [centroid-centroid distance between the benzene rings = 3.769 (2) Å]. van der Waals contacts are found between the Cl atoms at the 6-position and the Cl atoms at 7-position of the glide-reflection-symmetry equivalents [Cl⋯Cl = 3.4785 (16) Å, C-Cl⋯Cl = 160.23 (7)° and Cl⋯Cl-C = 122.59 (7)°].

Related literature

For related structures, see: Ishikawa & Motohashi (2013 ▸); Ishikawa (2014a ▸,b ▸, 2015 ▸). For halogen bonding and halogen⋯halogen interactions, see: Auffinger et al. (2004 ▸); Metrangolo et al. (2005 ▸); Metrangolo & Resnati (2014 ▸); Mukherjee & Desiraju (2014 ▸); Wilcken et al. (2013 ▸); Sirimulla et al. (2013 ▸); Persch et al. (2015 ▸).

Experimental

Crystal data

C10H4Cl2O3

M = 243.05

Monoclinic,

a = 3.7695 (13) Å

b = 6.1465 (16) Å

c = 39.431 (13) Å

β = 90.72 (3)°

V = 913.5 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.69 mm−1

T = 140 K

0.30 × 0.25 × 0.10 mm

Data collection

Rigaku AFC–7R diffractometer

Absorption correction: ψ scan (North et al., 1968 ▸) T min = 0.574, T max = 0.934

5075 measured reflections

2089 independent reflections

1747 reflections with F 2 > 2.0σ(F 2)

R int = 0.052

3 standard reflections every 150 reflections intensity decay: 0.6%

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.098

S = 1.04

2089 reflections

136 parameters

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.36 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: SIR2011 (Burla et al., 2012 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: CrystalStructure (Rigaku, 2015 ▸); software used to prepare material for publication: CrystalStructure.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015014644/zl2636sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014644/zl2636Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015014644/zl2636Isup3.cml

Click here for additional data file.

a H a b H b c d H e . DOI: 10.1107/S2056989015014644/zl2636fig1.tif

Sphere models of the crystal structures of (a) 6-chloro-4-oxo-4H-chromene-3-carbaldehyde (Ishikawa, 2014a), (b) 7-chloro-4-oxo-4H-chromene-3-carbaldehyde (Ishikawa, 2014b), (c) 6,8-di­chloro-4-oxochromene-3-carbaldehyde (Ishikawa & Motohashi, 2013), (d) 7,8-di­chloro-4-oxo-4H-chromene-3-carbaldehyde (Ishikawa, 2015) and (e) the title compound (this work).

Click here for additional data file.

. DOI: 10.1107/S2056989015014644/zl2636fig2.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.

. DOI: 10.1107/S2056989015014644/zl2636fig3.tif

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

CCDC reference: 1416757

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

C10H4Cl2O3	F(000) = 488.00
Mr = 243.05	Dx = 1.767 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
a = 3.7695 (13) Å	Cell parameters from 25 reflections
b = 6.1465 (16) Å	θ = 15.2–17.2°
c = 39.431 (13) Å	µ = 0.69 mm−1
β = 90.72 (3)°	T = 140 K
V = 913.5 (5) Å3	Plate, yellow
Z = 4	0.30 × 0.25 × 0.10 mm

Rigaku AFC–7R diffractometer	Rint = 0.052
ω scans	θmax = 27.8°, θmin = 3.1°
Absorption correction: ψ scan (North et al., 1968)	h = −4→2
Tmin = 0.574, Tmax = 0.934	k = −7→7
5075 measured reflections	l = −50→50
2089 independent reflections	3 standard reflections every 150 reflections
1747 reflections with F2 > 2.0σ(F2)	intensity decay: 0.6%

Refinement on F2	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0487P)2 + 0.5553P] where P = (Fo2 + 2Fc2)/3
2089 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.36 e Å−3
Primary atom site location: structure-invariant direct methods

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

	x	y	z	Uiso*/Ueq
Cl1	0.55004 (14)	0.47912 (8)	0.27821 (2)	0.02586 (15)
Cl2	0.92228 (14)	0.92474 (8)	0.29767 (2)	0.02698 (15)
O1	0.8830 (4)	0.6908 (2)	0.41933 (3)	0.0230 (3)
O2	0.3678 (4)	0.1171 (2)	0.40111 (3)	0.0274 (3)
O3	0.7039 (5)	0.2474 (3)	0.49732 (4)	0.0373 (4)
C1	0.8118 (6)	0.5474 (3)	0.44408 (5)	0.0224 (4)
H1	0.8796	0.5864	0.4666	0.027*
C2	0.6523 (5)	0.3530 (3)	0.43968 (4)	0.0208 (4)
C3	0.5328 (5)	0.2856 (3)	0.40621 (5)	0.0199 (4)
C4	0.5555 (5)	0.3935 (3)	0.34486 (4)	0.0192 (4)
H2	0.4430	0.2604	0.3389	0.023*
C5	0.6442 (5)	0.5401 (3)	0.31980 (5)	0.0197 (4)
C6	0.8083 (5)	0.7381 (3)	0.32843 (4)	0.0189 (4)
C7	0.8846 (5)	0.7862 (3)	0.36175 (5)	0.0199 (4)
H3	0.9962	0.9196	0.3678	0.024*
C8	0.6295 (5)	0.4389 (3)	0.37891 (4)	0.0180 (4)
C9	0.7948 (5)	0.6354 (3)	0.38648 (4)	0.0188 (4)
C10	0.5952 (6)	0.2085 (3)	0.46908 (5)	0.0278 (5)
H4	0.4657	0.0777	0.4655	0.033*

	U11	U22	U33	U12	U13	U23
Cl1	0.0352 (3)	0.0278 (3)	0.0144 (2)	−0.0004 (2)	−0.00603 (19)	−0.00328 (17)
Cl2	0.0343 (3)	0.0257 (3)	0.0209 (2)	−0.0016 (2)	−0.0012 (2)	0.00378 (18)
O1	0.0335 (8)	0.0206 (7)	0.0148 (6)	−0.0087 (6)	−0.0050 (5)	−0.0014 (5)
O2	0.0360 (9)	0.0226 (7)	0.0234 (7)	−0.0121 (6)	−0.0061 (6)	−0.0005 (6)
O3	0.0558 (11)	0.0357 (9)	0.0200 (7)	−0.0143 (8)	−0.0102 (7)	0.0052 (6)
C1	0.0285 (11)	0.0233 (9)	0.0153 (8)	−0.0030 (8)	−0.0021 (7)	−0.0011 (7)
C2	0.0253 (10)	0.0205 (9)	0.0166 (9)	−0.0041 (8)	−0.0024 (7)	−0.0002 (7)
C3	0.0229 (10)	0.0192 (9)	0.0175 (9)	−0.0013 (7)	−0.0018 (7)	−0.0019 (7)
C4	0.0224 (10)	0.0177 (8)	0.0174 (8)	−0.0008 (7)	−0.0033 (7)	−0.0037 (7)
C5	0.0223 (9)	0.0217 (9)	0.0149 (8)	0.0018 (7)	−0.0029 (7)	−0.0034 (7)
C6	0.0219 (10)	0.0186 (9)	0.0161 (8)	0.0004 (7)	−0.0016 (7)	0.0021 (7)
C7	0.0222 (10)	0.0175 (8)	0.0197 (9)	−0.0029 (7)	−0.0023 (7)	−0.0020 (7)
C8	0.0209 (9)	0.0170 (8)	0.0161 (8)	−0.0013 (7)	−0.0029 (7)	−0.0017 (6)
C9	0.0225 (9)	0.0193 (8)	0.0146 (8)	−0.0012 (7)	−0.0035 (7)	−0.0034 (7)
C10	0.0370 (12)	0.0265 (10)	0.0199 (9)	−0.0081 (9)	−0.0032 (8)	0.0023 (8)

Cl1—C5	1.7148 (19)	C3—C8	1.480 (3)
Cl2—C6	1.7275 (19)	C4—C5	1.381 (3)
O1—C1	1.344 (2)	C4—C8	1.396 (2)
O1—C9	1.376 (2)	C4—H2	0.9500
O2—C3	1.223 (2)	C5—C6	1.405 (3)
O3—C10	1.206 (2)	C6—C7	1.374 (2)
C1—C2	1.348 (3)	C7—C9	1.391 (3)
C1—H1	0.9500	C7—H3	0.9500
C2—C3	1.450 (2)	C8—C9	1.390 (3)
C2—C10	1.478 (3)	C10—H4	0.9500
C1—O1—C9	118.23 (15)	C7—C6—C5	120.28 (17)
O1—C1—C2	125.47 (16)	C7—C6—Cl2	118.54 (15)
O1—C1—H1	117.3	C5—C6—Cl2	121.18 (14)
C2—C1—H1	117.3	C6—C7—C9	118.52 (17)
C1—C2—C3	120.25 (17)	C6—C7—H3	120.7
C1—C2—C10	120.05 (17)	C9—C7—H3	120.7
C3—C2—C10	119.69 (17)	C9—C8—C4	117.65 (17)
O2—C3—C2	122.92 (17)	C9—C8—C3	120.72 (16)
O2—C3—C8	123.27 (16)	C4—C8—C3	121.63 (16)
C2—C3—C8	113.81 (16)	O1—C9—C8	121.32 (16)
C5—C4—C8	120.70 (17)	O1—C9—C7	115.91 (16)
C5—C4—H2	119.7	C8—C9—C7	122.76 (16)
C8—C4—H2	119.7	O3—C10—C2	123.64 (19)
C4—C5—C6	120.10 (16)	O3—C10—H4	118.2
C4—C5—Cl1	119.51 (14)	C2—C10—H4	118.2
C6—C5—Cl1	120.40 (15)
C9—O1—C1—C2	−1.5 (3)	C5—C4—C8—C3	179.21 (18)
O1—C1—C2—C3	−1.7 (3)	O2—C3—C8—C9	175.37 (19)
O1—C1—C2—C10	178.9 (2)	C2—C3—C8—C9	−4.8 (3)
C1—C2—C3—O2	−175.48 (19)	O2—C3—C8—C4	−3.9 (3)
C10—C2—C3—O2	3.9 (3)	C2—C3—C8—C4	175.93 (17)
C1—C2—C3—C8	4.7 (3)	C1—O1—C9—C8	1.4 (3)
C10—C2—C3—C8	−175.96 (18)	C1—O1—C9—C7	−177.98 (17)
C8—C4—C5—C6	−0.5 (3)	C4—C8—C9—O1	−178.76 (17)
C8—C4—C5—Cl1	179.93 (15)	C3—C8—C9—O1	1.9 (3)
C4—C5—C6—C7	0.6 (3)	C4—C8—C9—C7	0.6 (3)
Cl1—C5—C6—C7	−179.76 (15)	C3—C8—C9—C7	−178.76 (18)
C4—C5—C6—Cl2	−179.99 (15)	C6—C7—C9—O1	178.95 (17)
Cl1—C5—C6—Cl2	−0.4 (2)	C6—C7—C9—C8	−0.4 (3)
C5—C6—C7—C9	−0.2 (3)	C1—C2—C10—O3	−4.9 (4)
Cl2—C6—C7—C9	−179.59 (15)	C3—C2—C10—O3	175.8 (2)
C5—C4—C8—C9	−0.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3i	0.95	2.34	3.187 (3)	148 (1)
C7—H3···O2ii	0.95	2.26	3.129 (2)	151 (1)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C1H1O3i	0.95	2.34	3.187(3)	148(1)
C7H3O2ii	0.95	2.26	3.129(2)	151(1)

Symmetry codes: (i) ; (ii) .