2,4-Dichloro­benzaldehyde

Cabello, R.; Chruszcz, M.; Minor, W.

doi:10.1107/S160053680905435X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o243

doi:10.1107/S160053680905435X

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2,4-Dichlorobenzaldehyde

Ricardo Cabello,^a Maksymilian Chruszcz ^a and Wladek Minor ^a ^*

^aUniversity of Virginia, Department of Molecular Physiology & Biological Physics, 1340 Jefferson Park Avenue, Charlottesville, VA 22908, USA
^*Correspondence e-mail: wladek@iwonka.med.virginia.edu

(Received 4 December 2009; accepted 16 December 2009; online 24 December 2009)

In the crystal structure of the title compound, C₇H₄Cl₂O, the molecules form a network of weak C—H⋯O interactions involving the aldehyde O atom and the ortho-H atom on the benzene ring together with C—H⋯O interactions between the formyl groups. Together, these connect the molecules into (10 $[\overline{1}]$ ) layers, which are stabilized additionally by π–π stacking interactions of the benzene rings [centroid–centroid distance = 3.772 (1) Å]. The aldehyde group is twisted relative to the benzene ring by 7.94 (13)°.

Related literature

For applications of the title compound, see: Katagi (1988 ); Wang et al. (2004 ). For a related structure, see: Gawlicka-Chruszcz et al. (2006 ).

Experimental

Crystal data

C₇H₄Cl₂O
M_r = 175.01
Monoclinic, P 2₁ /n
a = 13.100 (1) Å
b = 3.772 (1) Å
c = 15.332 (1) Å
β = 113.797 (2)°
V = 693.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 100 K
0.40 × 0.10 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (Otwinowski et al., 2003 ) T_min = 0.90, T_max = 0.92
6924 measured reflections
3737 independent reflections
3221 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.114
S = 1.10
3737 reflections
107 parameters
All H-atom parameters refined
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1ⁱ	0.946 (17)	2.533 (17)	3.4289 (11)	158.0 (14)
C6—H6⋯O1ⁱⁱ	0.950 (19)	2.512 (17)	3.2774 (11)	137.8 (12)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+1, -y-1, -z+1.

Data collection: HKL-2000 (Otwinowski & Minor, 1997 ); cell refinement: HKL-2000; data reduction: HKL-2000; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ) and HKL-3000SM (Minor et al., 2006 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and HKL-3000SM; molecular graphics: HKL-3000SM, ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 (Farrugia, 1997 ), Mercury (Macrae et al., 2006 ) and POV-RAY (The POV-RAY Team, 2004 ); software used to prepare material for publication: HKL-3000SM.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680905435X/gk2246sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680905435X/gk2246Isup2.hkl

checkCIF report

Comment top

2,4-Dichlorobenzaldehyde is primarily used in the preparation of dyes, insecticides, herbicides, antiseptics and disinfectants (Wang et al., 2004). It is also used as an intermediate of organic synthesis of fungicide diniconazole (Katagi, 1988).

In the crystal structure of 2,4-dichlorobenzaldehyde (Fig. 1), the aldehyde group is twisted relative to the benzene ring with torsion angles C6—C1—C7—O1 and C2—C1—C7—O1 being -7.94 (13)° and 170.86 (9)°. These torsion angles are significantly smaller in comparison to the corresponding angles in 2,6-dichlorobenzaldehyde (Gawlicka-Chruszcz et al., 2006) which are -27.3° and 152.6° respectively. Significantly bigger twist of the aldehyde group in the case of 2,6-dichlorobenzaldehyde is caused by presence of the chlorine atoms in ortho positions.

The change of the position of chlorine atom causes that interactions in which chlorine atoms are involved in 2,4-dichlorobenzaldehyde and 2,6-dichlorobenzaldehyde differ significantly. In the case of 2,6-dichlorobenzaldehyde Cl2 was involved in weak interaction with hydrogen atom from neighboring benzene ring, while in 2,4-dichlorobenzaldehyde structure such interactions are not observed for any of the chlorine atoms. However, in the case of 2,4-dichlorobenzaldehyde, the chlorine atoms from neighboring molecules form short contacts with Cl1···Cl2 (1/2 + x,1/2 - y,1/2 + z) distance being 3.442Å (Fig. 2).

The weak O···H—C interactions (Table 1) between the aldehyde oxygen and the benzene hydrogen atoms connect molecules to form layers, which are additionally stabilized by stacking of benzene rings (Fig. 2). The oxygen atom from the aldehyde group plays a central role in the formation of weak interactions, and O1···H6—C6 (1 - x,-1 - y,1 - z) and O1···H7—C7 (1,5 - x,-1/2 + y,1.5 - z) distances are 2.51Å and 2.53Å respectively.

Related literature top

For applications of the title compound, see: Katagi (1988); Wang et al. (2004). For a related structure, see: Gawlicka-Chruszcz et al. (2006).

Experimental top

2,4-dichlorobenzaldehyde was purchased from ALDRICH (99% purity, lot 08722CD). The compound was provided in crystalline form.

Computing details top

Data collection: HKL-2000 (Otwinowski & Minor, 1997); cell refinement: HKL-2000 (Otwinowski & Minor, 1997); data reduction: HKL-2000 (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) and HKL-3000SM (Minor et al., 2006); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and HKL-3000SM (Minor et al., 2006); molecular graphics: HKL-3000SM (Minor et al., 2006), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 (Farrugia, 1997), Mercury (Macrae et al., 2006) and POV-RAY (The POV-RAY Team, 2004); software used to prepare material for publication: HKL-3000SM.

Figures top

	Fig. 1. The asymmetric unit of the reported structure. Displacement ellipsoids are drawn at the 50% probability level and hydrogen atoms are drawn as grey spheres of an arbitrary radius.
	Fig. 2. The molecular packing of 2,4-dichlorobenzaldehyde. Weak interactions, in which the oxygen atom participates, are shown as blue, dashed lines.

2,4-Dichlorobenzaldehyde top

Crystal data top

C₇H₄Cl₂O	F(000) = 352
M_r = 175.01	D_x = 1.677 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71074 Å
Hall symbol: -P 2yn	Cell parameters from 31891 reflections
a = 13.100 (1) Å	θ = 1.0–37.8°
b = 3.772 (1) Å	µ = 0.85 mm⁻¹
c = 15.332 (1) Å	T = 100 K
β = 113.797 (2)°	Block, colorless
V = 693.2 (3) Å³	0.40 × 0.10 × 0.10 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	3737 independent reflections
Radiation source: fine-focus sealed tube	3221 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
Detector resolution: 10 pixels mm^-1	θ_max = 37.8°, θ_min = 1.0°
ω scans	h = −22→22
Absorption correction: multi-scan (Otwinowski et al., 2003)	k = −6→6
T_min = 0.90, T_max = 0.92	l = −26→24
6924 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: difference Fourier map
wR(F²) = 0.114	All H-atom parameters refined
S = 1.10	w = 1/[σ²(F_o²) + (0.0708P)² + 0.0197P] where P = (F_o² + 2F_c²)/3
3737 reflections	(Δ/σ)_max = 0.001
107 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₇H₄Cl₂O	V = 693.2 (3) Å³
M_r = 175.01	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.100 (1) Å	µ = 0.85 mm⁻¹
b = 3.772 (1) Å	T = 100 K
c = 15.332 (1) Å	0.40 × 0.10 × 0.10 mm
β = 113.797 (2)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3737 independent reflections
Absorption correction: multi-scan (Otwinowski et al., 2003)	3221 reflections with I > 2σ(I)
T_min = 0.90, T_max = 0.92	R_int = 0.063
6924 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.114	All H-atom parameters refined
S = 1.10	Δρ_max = 0.67 e Å⁻³
3737 reflections	Δρ_min = −0.41 e Å⁻³
107 parameters

Special details top

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 of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl2	0.138241 (15)	0.17792 (6)	0.579292 (15)	0.02422 (7)
Cl1	0.558151 (16)	0.15135 (6)	0.840216 (14)	0.02526 (7)
C1	0.49878 (6)	−0.1166 (2)	0.66074 (6)	0.01968 (13)
C3	0.35318 (6)	0.1385 (2)	0.70157 (6)	0.02006 (14)
C2	0.46410 (6)	0.0484 (2)	0.72565 (5)	0.01980 (13)
C6	0.41880 (6)	−0.1866 (2)	0.56890 (6)	0.02060 (14)
C5	0.30765 (6)	−0.0964 (2)	0.54240 (6)	0.02080 (13)
C4	0.27652 (6)	0.0634 (2)	0.60987 (5)	0.01992 (13)
O1	0.64561 (5)	−0.4059 (2)	0.63526 (5)	0.02975 (14)
C7	0.61622 (6)	−0.2245 (2)	0.68671 (6)	0.02340 (14)
H3	0.3319 (13)	0.260 (4)	0.7450 (12)	0.038 (3)*
H5	0.2576 (13)	−0.150 (4)	0.4813 (13)	0.042 (4)*
H6	0.4423 (13)	−0.293 (5)	0.5239 (12)	0.046 (4)*
H7	0.6686 (14)	−0.131 (4)	0.7449 (13)	0.041 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl2	0.01697 (10)	0.02944 (12)	0.02558 (11)	0.00285 (6)	0.00789 (8)	0.00236 (6)
Cl1	0.02130 (11)	0.02926 (12)	0.02104 (11)	−0.00059 (6)	0.00422 (8)	−0.00518 (6)
C1	0.0165 (3)	0.0207 (3)	0.0213 (3)	−0.0005 (2)	0.0071 (2)	−0.0007 (2)
C3	0.0190 (3)	0.0209 (3)	0.0206 (3)	0.0003 (2)	0.0083 (3)	−0.0003 (2)
C2	0.0182 (3)	0.0203 (3)	0.0195 (3)	−0.0014 (2)	0.0062 (2)	−0.0017 (2)
C6	0.0189 (3)	0.0226 (3)	0.0206 (3)	−0.0002 (2)	0.0082 (2)	−0.0008 (2)
C5	0.0185 (3)	0.0229 (3)	0.0195 (3)	−0.0007 (2)	0.0061 (2)	−0.0008 (2)
C4	0.0168 (3)	0.0209 (3)	0.0215 (3)	0.0001 (2)	0.0071 (2)	0.0016 (2)
O1	0.0214 (3)	0.0378 (3)	0.0304 (3)	0.0045 (2)	0.0108 (2)	−0.0046 (3)
C7	0.0178 (3)	0.0266 (3)	0.0251 (3)	−0.0001 (3)	0.0080 (3)	−0.0013 (3)

Geometric parameters (Å, º) top

Cl2—C4	1.7327 (7)	C3—H3	0.939 (17)
Cl1—C2	1.7343 (8)	C6—C5	1.3869 (11)
C1—C2	1.3961 (11)	C6—H6	0.950 (19)
C1—C6	1.3999 (11)	C5—C4	1.3930 (11)
C1—C7	1.4820 (11)	C5—H5	0.923 (18)
C3—C4	1.3877 (11)	O1—C7	1.2180 (11)
C3—C2	1.3893 (11)	C7—H7	0.946 (17)

C2—C1—C6	118.32 (7)	C1—C6—H6	118.6 (9)
C2—C1—C7	122.14 (7)	C6—C5—C4	118.43 (7)
C6—C1—C7	119.53 (7)	C6—C5—H5	118.4 (10)
C4—C3—C2	118.11 (7)	C4—C5—H5	123.2 (10)
C4—C3—H3	121.2 (10)	C3—C4—C5	122.11 (7)
C2—C3—H3	120.6 (10)	C3—C4—Cl2	118.26 (6)
C3—C2—C1	121.73 (7)	C5—C4—Cl2	119.62 (6)
C3—C2—Cl1	116.99 (6)	O1—C7—C1	123.05 (8)
C1—C2—Cl1	121.28 (6)	O1—C7—H7	121.4 (10)
C5—C6—C1	121.30 (7)	C1—C7—H7	115.5 (10)
C5—C6—H6	120.0 (9)

C4—C3—C2—C1	−0.72 (12)	C1—C6—C5—C4	−0.68 (12)
C4—C3—C2—Cl1	179.11 (6)	C2—C3—C4—C5	−0.19 (12)
C6—C1—C2—C3	0.90 (12)	C2—C3—C4—Cl2	−179.59 (6)
C7—C1—C2—C3	−177.92 (8)	C6—C5—C4—C3	0.88 (12)
C6—C1—C2—Cl1	−178.92 (6)	C6—C5—C4—Cl2	−179.73 (6)
C7—C1—C2—Cl1	2.26 (11)	C2—C1—C7—O1	170.86 (9)
C2—C1—C6—C5	−0.18 (12)	C6—C1—C7—O1	−7.94 (13)
C7—C1—C6—C5	178.67 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.946 (17)	2.533 (17)	3.4289 (11)	158.0 (14)
C6—H6···O1ⁱⁱ	0.950 (19)	2.512 (17)	3.2774 (11)	137.8 (12)

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+1, −y−1, −z+1.

Experimental details

Crystal data
Chemical formula	C₇H₄Cl₂O
M_r	175.01
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	13.100 (1), 3.772 (1), 15.332 (1)
β (°)	113.797 (2)
V (Å³)	693.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.85
Crystal size (mm)	0.40 × 0.10 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (Otwinowski et al., 2003)
T_min, T_max	0.90, 0.92
No. of measured, independent and observed [I > 2σ(I)] reflections	6924, 3737, 3221
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.862

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.114, 1.10
No. of reflections	3737
No. of parameters	107
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.41

Computer programs: HKL-2000 (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008) and HKL-3000SM (Minor et al., 2006), SHELXL97 (Sheldrick, 2008) and HKL-3000SM (Minor et al., 2006), HKL-3000SM (Minor et al., 2006), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 (Farrugia, 1997), Mercury (Macrae et al., 2006) and POV-RAY (The POV-RAY Team, 2004), HKL-3000SM.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.946 (17)	2.533 (17)	3.4289 (11)	158.0 (14)
C6—H6···O1ⁱⁱ	0.950 (19)	2.512 (17)	3.2774 (11)	137.8 (12)

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+1, −y−1, −z+1.

Acknowledgements

This work was supported by contract GI11496 from HKL Research, Inc.

References

Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gawlicka-Chruszcz, A., Zheng, H., Hyacinth, M., Cymborowski, M., Sabat, M. & Minor, W. (2006). Z. Kristallogr. New Cryst. Struct. 221, 545–546. CAS Google Scholar
Katagi, T. (1988). J. Agric. Food Chem. 36, 344–349. CrossRef CAS Web of Science Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Minor, W., Cymborowski, M., Otwinowski, Z. & Chruszcz, M. (2006). Acta Cryst. D62, 859–866. Web of Science CrossRef CAS IUCr Journals Google Scholar
Otwinowski, Z., Borek, D., Majewski, W. & Minor, W. (2003). Acta Cryst. A59, 228–234. Web of Science CrossRef CAS IUCr Journals Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
The POV-RAY Team (2004). POV-RAY. http://www.povray.org/download/ . Google Scholar
Wang, S.-X., Tan, Z.-C., Di, Y.-Y., Xu, F., Zhang, H.-T., Sun, L.-X. & Zhang, T. (2004). J. Chem. Thermodyn. 36, 393–399. Web of Science CrossRef CAS Google Scholar