3,5-Dichloro-2-hydroxy­benzaldehyde

Abstract

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,

• a = 8.3359 (16) Å

• b = 13.884 (3) Å

• c = 7.2341 (14) Å

• β = 114.519 (2)°

• V = 761.7 (3) ų

• 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[F ² > 2σ(F ²)] = 0.036

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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).

Refinement

The H atoms were placed in geometrically idealized positions (C—H = 0.93 Å and O—H = 0.82 Å) and refined as riding atoms, with U_iso(H) = 1.2U_eq(C) and U_iso(H) = 1.5U_eq(O).

Figures

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.

Crystal data

C7H4Cl2O2	F000 = 384
Mr = 191.00	Dx = 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 = 2.7–26.8º
b = 13.884 (3) Å	µ = 0.79 mm−1
c = 7.2341 (14) Å	T = 291 (2) K
β = 114.519 (2)º	Block, yellow
V = 761.7 (3) Å3	0.14 × 0.12 × 0.10 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	1487 independent reflections
Radiation source: fine-focus sealed tube	1181 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.055
T = 291(2) K	θmax = 26.0º
φ and ω scans	θmin = 2.7º
Absorption correction: multi-scan(SADABS; Bruker, 2000)	h = −10→10
Tmin = 0.898, Tmax = 0.925	k = −16→16
4063 measured reflections	l = −7→8

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036	H-atom parameters constrained
wR(F2) = 0.097	w = 1/[σ2(Fo2) + (0.0536P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99	(Δ/σ)max < 0.001
1487 reflections	Δρmax = 0.27 e Å−3
101 parameters	Δρmin = −0.23 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.