3,5-Dichloro-2-hydroxy­benzaldehyde

Fan, Y.; You, W.; Liu, J.-L.; Qian, H.-F.; Huang, W.

doi:10.1107/S1600536808013901

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1080

doi:10.1107/S1600536808013901

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3,5-Dichloro-2-hydroxybenzaldehyde

Ying Fan,^a Wei You,^a Jian-Lan Liu,^a Hui-Fen Qian ^a ^* and Wei Huang ^b ^*

^aCollege of Sciences, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bState Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: whuang@nju.edu.cn,

(Received 5 May 2008; accepted 9 May 2008; online 14 May 2008)

The title compound, C₇H₄Cl₂O₂, exhibits a layer crystal structure; molecules within each layer are linked by weak C—H⋯O intermolecular hydrogen bonds. There is also an intramolecular O—H⋯O hydrogen bond.

Related literature

For a related compound, see: Fan et al. (2008 ).

Experimental

Crystal data

C₇H₄Cl₂O₂
M_r = 191.00
Monoclinic, P 2₁ /c
a = 8.3359 (16) Å
b = 13.884 (3) Å
c = 7.2341 (14) Å
β = 114.519 (2)°
V = 761.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.79 mm⁻¹
T = 291 (2) K
0.14 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.897, T_max = 0.925
4063 measured reflections
1487 independent reflections
1181 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.097
S = 0.99
1487 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1	0.82	1.92	2.630 (2)	145
C4—H4⋯O1ⁱ	0.93	2.51	3.428 (3)	168
C6—H6⋯O2ⁱⁱ	0.93	2.56	3.394 (3)	149
Symmetry codes: (i) x+1, y, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808013901/at2566sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808013901/at2566Isup2.hkl

checkCIF report

Comment top

We have newly reported the X-ray single-crystal structure of 3,5-dibromo-2-hydroxybenzaldehyde (Fan et al., 2008). In this paper, we report the X-ray single-crystal structure of 3,5-dichloro-2- hydroxybenzaldehyde.

The molecular structure of (I) is illustrated in Fig. 1. The selected bond distances and bond angles are normal. Different from 3,5-dibromo-2-hydroxybenzaldehyde, there is only one crystallographically independent molecule in the asymmetric unit. The molecular geometry of slicylaldehyde unit of (I) is comparable with that of 3,5-dibromo-2-hydroxybenzaldehyde.

In the crystal packing of (I), there are two sets of molecules with the dihedral angle of 6.52 (2) ° and molecules in every layer are linked by intermolecular CO—H···O hydrogen bondings (Fig. 2). A layer packing structure is formed with the mean interlayer separation of 3.428 (2) Å (Fig. 3.). However, no π–π stacking interactions can be observed in (I), which is different from those in 3,5-dibromo-2-hydroxybenzaldehyde.

Related literature top

For a related compound, see: Fan et al. (2008).

Experimental top

The title compound was obtained as received. Single crystals suitable for X-ray diffraction measurement were formed after 6 days in methanol by slow evaporation at room temperature in air. Analysis calculated for C₇H₄O₂Cl₂: C 44.02, H 2.11%. Found: C 44.18, H, 2.24%. FT—IR (KBr pellets, cm^-1): 3066(versus), 2856(s), 1666(versus), 1604(m), 1428(s), 1375(versus), 1276(s), 1208(s), 1171(s), 1103(m), 935(s), 891(versus), 735(s), 703(s), 566(m), and 515(m).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. An ORTEP drawing of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A perspective view of the intralayer intermolecular hydrogen-bond contacts among molecules in the title compound. Hydrogen bonds and Cl···Cl interactions are shown as dashed lines. [Symmetry codes: (i) x+1, y, z; (ii) -x + 1, y+1/2, -z+1/2; (iii) -x+2, y - 1/2, -z + 1/2].
	Fig. 3. A perspective view of the layer packing structure of (I) together with the unit cell.

3,5-Dichloro-2-hydroxybenzaldehyde top

Crystal data top

C₇H₄Cl₂O₂	F(000) = 384
M_r = 191.00	D_x = 1.666 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1691 reflections
a = 8.3359 (16) Å	θ = 2.7–26.8°
b = 13.884 (3) Å	µ = 0.79 mm⁻¹
c = 7.2341 (14) Å	T = 291 K
β = 114.519 (2)°	Block, yellow
V = 761.7 (3) Å³	0.14 × 0.12 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1487 independent reflections
Radiation source: fine-focus sealed tube	1181 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.898, T_max = 0.925	k = −16→16
4063 measured reflections	l = −7→8

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: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0536P)²] where P = (F_o² + 2F_c²)/3
1487 reflections	(Δ/σ)_max < 0.001
101 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₇H₄Cl₂O₂	V = 761.7 (3) Å³
M_r = 191.00	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3359 (16) Å	µ = 0.79 mm⁻¹
b = 13.884 (3) Å	T = 291 K
c = 7.2341 (14) Å	0.14 × 0.12 × 0.10 mm
β = 114.519 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1487 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1181 reflections with I > 2σ(I)
T_min = 0.898, T_max = 0.925	R_int = 0.055
4063 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 0.99	Δρ_max = 0.27 e Å⁻³
1487 reflections	Δρ_min = −0.23 e Å⁻³
101 parameters

Special details top

Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses.

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
C1	0.4748 (2)	0.35190 (14)	0.2605 (3)	0.0419 (5)
C2	0.5509 (2)	0.26110 (14)	0.2721 (3)	0.0383 (4)
C3	0.7213 (2)	0.25643 (14)	0.2822 (3)	0.0379 (4)
C4	0.8119 (2)	0.33830 (13)	0.2774 (3)	0.0422 (5)
H4	0.9261	0.3341	0.2858	0.051*
C5	0.7313 (2)	0.42742 (15)	0.2599 (3)	0.0422 (5)
C6	0.5658 (3)	0.43474 (15)	0.2547 (3)	0.0445 (5)
H6	0.5145	0.4949	0.2474	0.053*
C7	0.2987 (3)	0.35981 (17)	0.2606 (3)	0.0536 (6)
H7	0.2525	0.4210	0.2579	0.064*
Cl1	0.81885 (7)	0.14449 (4)	0.29976 (9)	0.0542 (2)
Cl2	0.84604 (7)	0.52989 (4)	0.24617 (10)	0.0612 (2)
O1	0.21042 (19)	0.29062 (13)	0.2640 (3)	0.0678 (5)
O2	0.46796 (18)	0.17843 (10)	0.2737 (2)	0.0519 (4)
H2	0.3694	0.1904	0.2670	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0364 (10)	0.0424 (12)	0.0505 (11)	0.0021 (8)	0.0216 (9)	0.0031 (9)
C2	0.0405 (10)	0.0354 (11)	0.0423 (10)	−0.0011 (8)	0.0206 (8)	0.0018 (8)
C3	0.0389 (10)	0.0360 (11)	0.0428 (10)	0.0048 (8)	0.0209 (8)	0.0000 (8)
C4	0.0357 (10)	0.0470 (14)	0.0483 (12)	0.0007 (8)	0.0218 (9)	0.0033 (9)
C5	0.0410 (11)	0.0383 (11)	0.0492 (11)	−0.0052 (8)	0.0209 (9)	0.0034 (9)
C6	0.0432 (11)	0.0367 (11)	0.0568 (12)	0.0050 (8)	0.0240 (10)	0.0045 (9)
C7	0.0427 (12)	0.0502 (14)	0.0746 (15)	0.0042 (10)	0.0310 (11)	0.0076 (11)
Cl1	0.0576 (4)	0.0406 (3)	0.0719 (4)	0.0126 (2)	0.0344 (3)	0.0019 (2)
Cl2	0.0515 (3)	0.0438 (4)	0.0914 (5)	−0.0092 (2)	0.0327 (3)	0.0102 (3)
O1	0.0463 (8)	0.0642 (12)	0.1052 (13)	−0.0007 (8)	0.0437 (8)	0.0073 (9)
O2	0.0475 (8)	0.0370 (8)	0.0773 (10)	−0.0056 (6)	0.0319 (8)	0.0020 (7)

Geometric parameters (Å, º) top

C1—C6	1.388 (3)	C4—H4	0.9300
C1—C2	1.398 (3)	C5—C6	1.369 (3)
C1—C7	1.472 (3)	C5—Cl2	1.740 (2)
C2—O2	1.342 (2)	C6—H6	0.9300
C2—C3	1.393 (2)	C7—O1	1.217 (3)
C3—C4	1.373 (3)	C7—H7	0.9300
C3—Cl1	1.7340 (19)	O2—H2	0.8200
C4—C5	1.388 (3)

C6—C1—C2	120.59 (18)	C5—C4—H4	120.3
C6—C1—C7	119.71 (18)	C6—C5—C4	120.85 (18)
C2—C1—C7	119.68 (18)	C6—C5—Cl2	120.63 (16)
O2—C2—C3	118.51 (17)	C4—C5—Cl2	118.52 (14)
O2—C2—C1	123.29 (16)	C5—C6—C1	119.68 (18)
C3—C2—C1	118.20 (17)	C5—C6—H6	120.2
C4—C3—C2	121.30 (17)	C1—C6—H6	120.2
C4—C3—Cl1	119.86 (13)	O1—C7—C1	123.6 (2)
C2—C3—Cl1	118.84 (15)	O1—C7—H7	118.2
C3—C4—C5	119.34 (17)	C1—C7—H7	118.2
C3—C4—H4	120.3	C2—O2—H2	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.82	1.92	2.630 (2)	145
C4—H4···O1ⁱ	0.93	2.51	3.428 (3)	168
C6—H6···O2ⁱⁱ	0.93	2.56	3.394 (3)	149

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

Experimental details

Crystal data
Chemical formula	C₇H₄Cl₂O₂
M_r	191.00
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	8.3359 (16), 13.884 (3), 7.2341 (14)
β (°)	114.519 (2)
V (Å³)	761.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.79
Crystal size (mm)	0.14 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.898, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	4063, 1487, 1181
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.097, 0.99
No. of reflections	1487
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.23

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.82	1.92	2.630 (2)	145.0
C4—H4···O1ⁱ	0.93	2.51	3.428 (3)	168.0
C6—H6···O2ⁱⁱ	0.93	2.56	3.394 (3)	149.0

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

Acknowledgements

WH acknowledges the National Natural Science Foundation of China (No. 20301009) and the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry, for financial support.

References

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fan, Y., You, W., Qian, H.-F., Liu, J.-L. & Huang, W. (2008). Acta Cryst. E64, o799. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar