3-Chloro­meth­yl-2-hy­droxy­benzaldehyde

Fu, W.-W.

doi:10.1107/S1600536812038421

organic compounds

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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Page o2928

https://doi.org/10.1107/S1600536812038421

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3-Chloromethyl-2-hydroxybenzaldehyde

Wei-Wei Fu ^a ^*

^aKey Laboratory of Functional Organometallic Materials of General Colleges and Universities in Hunan Province, Department of Chemistry and Materials Science, Hengyang Normal University, Hengyang 421008, People's Republic of China
^*Correspondence e-mail: w.w.fu@hotmail.com

(Received 9 August 2012; accepted 7 September 2012; online 15 September 2012)

In the title compound, C₈H₇ClO₂, the hydroxyl and aldehyde groups are co-planar with the benzene ring [maximum deviation 0.018 (3) Å], and the Cl—C—C plane is almost perpendicular to the benzene ring [dihedral angle 83.7 (2)°]. An intramolecular O—H⋯O hydrogen bond occurs between the hydroxyl and aldehyde groups.

Related literature

For related structures, see: Zondervan et al. (1997 ); Tang et al. (2010 ). For the synthesis, see: Song & Liu (2004 ).

Experimental

Crystal data

C₈H₇ClO₂
M_r = 170.59
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.483 (6) Å
b = 12.521 (18) Å
c = 13.71 (2) Å
V = 769.6 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 293 K
0.30 × 0.23 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.88, T_max = 0.92
3730 measured reflections
1369 independent reflections
1075 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.133
S = 0.98
1369 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.32 e Å⁻³
Absolute structure: Flack (1983 ), 6571 Friedel pairs
Flack parameter: −0.06 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.82	1.91	2.628 (5)	146

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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 I, global. DOI: https://doi.org/10.1107/S1600536812038421/xu5608sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812038421/xu5608Isup2.hkl

checkCIF report

Comment top

5-(Chloromethyl)-2-hydroxybenzaldehyde are well investigated just as it can be a precusor to an inhibitor-schiff bases for metal. However, just as we synthesize 5-(chloromethyl)-2-hydroxybenzaldehyde following one mehtod(Song & Liu, 2004) an unexpected byprodut 3-(chloromethyl)-2-hydroxybenzaldehyde was found and its cystal structure was determined.

Related literature top

For related structures, see: Zondervan et al. (1997); Tang et al. (2010). For the synthesis, see: Song & Liu (2004).

Experimental top

Following a reference (Song et al. 2004), salicylaldehyde (30.5 g), paraformaldehyde (13.5 g) and conc. HCl (150 ml) were mixed and stirred at room temperature for 48 h. The precipitated benzylchloride derivatives which mostly are 5-(chloromethyl)-2-hydroxybenzaldehyde were filtered off then washed with 0.5% NaHCO₃ solution and water slightly. These humid precipitate were then dried in vac. for about 3 months. There are block colorless crystals appeared on the surface of precipitate.

Structure description top

For related structures, see: Zondervan et al. (1997); Tang et al. (2010). For the synthesis, see: Song & Liu (2004).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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. The molecular structure of title compound, with atom labels and 30% probability displacement ellipsoids for all atoms.
	Fig. 2. The cell packing diagram of title compound, viewed down the a axis.

3-Chloromethyl-2-hydroxybenzaldehyde top

Crystal data top

C₈H₇ClO₂	F(000) = 352
M_r = 170.59	D_x = 1.472 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1369 reflections
a = 4.483 (6) Å	θ = 2.2–25.0°
b = 12.521 (18) Å	µ = 0.44 mm⁻¹
c = 13.71 (2) Å	T = 293 K
V = 769.6 (19) Å³	Block, colorless
Z = 4	0.30 × 0.23 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	1369 independent reflections
Radiation source: fine-focus sealed tube	1075 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ω scan	θ_max = 25.2°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −5→5
T_min = 0.88, T_max = 0.92	k = −15→14
3730 measured reflections	l = −16→16

Refinement top

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)] = 0.033	H-atom parameters constrained
wR(F²) = 0.133	w = 1/[σ²(F_o²) + (0.P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max < 0.001
1369 reflections	Δρ_max = 0.31 e Å⁻³
101 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 6571 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.06 (13)

Crystal data top

C₈H₇ClO₂	V = 769.6 (19) Å³
M_r = 170.59	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.483 (6) Å	µ = 0.44 mm⁻¹
b = 12.521 (18) Å	T = 293 K
c = 13.71 (2) Å	0.30 × 0.23 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	1369 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1075 reflections with I > 2σ(I)
T_min = 0.88, T_max = 0.92	R_int = 0.052
3730 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.133	Δρ_max = 0.31 e Å⁻³
S = 0.98	Δρ_min = −0.32 e Å⁻³
1369 reflections	Absolute structure: Flack (1983), 6571 Friedel pairs
101 parameters	Absolute structure parameter: −0.06 (13)
0 restraints

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
Cl1	0.5383 (2)	0.21212 (5)	0.21927 (5)	0.0606 (3)
O1	0.3758 (7)	−0.05428 (14)	0.16474 (16)	0.0558 (7)
H1	0.2636	−0.1057	0.1598	0.084*
O2	0.0222 (7)	−0.18989 (15)	0.07502 (19)	0.0640 (7)
C11	0.6216 (8)	0.07288 (19)	0.0685 (2)	0.0440 (7)
C12	0.4289 (7)	−0.01314 (17)	0.0756 (2)	0.0384 (7)
C13	0.2937 (8)	−0.05626 (17)	−0.0076 (2)	0.0403 (7)
C14	0.3593 (9)	−0.0101 (2)	−0.0985 (2)	0.0509 (9)
H14A	0.2719	−0.0378	−0.1546	0.061*
C15	0.5488 (10)	0.0745 (2)	−0.1057 (2)	0.0560 (9)
H15A	0.5907	0.1043	−0.1663	0.067*
C16	0.6779 (9)	0.1157 (2)	−0.0228 (3)	0.0507 (8)
H16A	0.8062	0.1738	−0.0282	0.061*
C17	0.7744 (9)	0.1173 (3)	0.1567 (3)	0.0572 (9)
H17A	0.9581	0.1522	0.1371	0.069*
H17B	0.8252	0.0594	0.2007	0.069*
C18	0.0905 (9)	−0.14473 (19)	−0.0012 (2)	0.0504 (9)
H18A	0.0050	−0.1695	−0.0587	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0771 (7)	0.0537 (4)	0.0510 (5)	−0.0025 (4)	−0.0076 (4)	−0.0126 (3)
O1	0.078 (2)	0.0496 (10)	0.0400 (12)	−0.0038 (11)	−0.0019 (12)	0.0056 (7)
O2	0.074 (2)	0.0533 (9)	0.0649 (15)	−0.0091 (11)	0.0058 (15)	0.0042 (9)
C11	0.045 (2)	0.0425 (11)	0.0443 (16)	0.0089 (12)	−0.0040 (13)	−0.0039 (10)
C12	0.0424 (18)	0.0371 (9)	0.0358 (13)	0.0089 (11)	0.0027 (14)	0.0003 (9)
C13	0.042 (2)	0.0386 (10)	0.0398 (16)	0.0085 (12)	−0.0002 (13)	−0.0032 (9)
C14	0.067 (3)	0.0507 (12)	0.0353 (15)	0.0082 (14)	−0.0039 (16)	−0.0031 (10)
C15	0.067 (3)	0.0583 (14)	0.0427 (17)	0.0024 (16)	0.0070 (17)	0.0048 (11)
C16	0.050 (2)	0.0474 (12)	0.055 (2)	−0.0035 (14)	0.0055 (17)	0.0036 (12)
C17	0.054 (2)	0.0597 (14)	0.058 (2)	0.0024 (15)	−0.0145 (17)	−0.0069 (14)
C18	0.053 (2)	0.0412 (11)	0.057 (2)	0.0004 (12)	0.0011 (17)	−0.0076 (11)

Geometric parameters (Å, º) top

Cl1—C17	1.808 (4)	C13—C18	1.437 (4)
O1—C12	1.348 (4)	C14—C15	1.362 (5)
O1—H1	0.8200	C14—H14A	0.9300
O2—C18	1.227 (4)	C15—C16	1.376 (5)
C11—C12	1.384 (4)	C15—H15A	0.9300
C11—C16	1.386 (5)	C16—H16A	0.9300
C11—C17	1.496 (5)	C17—H17A	0.9700
C12—C13	1.400 (4)	C17—H17B	0.9700
C13—C14	1.404 (4)	C18—H18A	0.9300

C12—O1—H1	109.5	C14—C15—H15A	120.2
C12—C11—C16	118.6 (3)	C16—C15—H15A	120.2
C12—C11—C17	121.2 (3)	C15—C16—C11	121.7 (3)
C16—C11—C17	120.2 (3)	C15—C16—H16A	119.2
O1—C12—C11	118.1 (3)	C11—C16—H16A	119.2
O1—C12—C13	121.0 (3)	C11—C17—Cl1	111.1 (3)
C11—C12—C13	120.9 (3)	C11—C17—H17A	109.4
C12—C13—C14	118.2 (3)	Cl1—C17—H17A	109.4
C12—C13—C18	121.5 (3)	C11—C17—H17B	109.4
C14—C13—C18	120.3 (3)	Cl1—C17—H17B	109.4
C15—C14—C13	121.0 (3)	H17A—C17—H17B	108.0
C15—C14—H14A	119.5	O2—C18—C13	124.5 (3)
C13—C14—H14A	119.5	O2—C18—H18A	117.8
C14—C15—C16	119.6 (3)	C13—C18—H18A	117.8

C16—C11—C12—O1	180.0 (3)	C18—C13—C14—C15	179.3 (3)
C17—C11—C12—O1	1.8 (4)	C13—C14—C15—C16	−0.1 (5)
C16—C11—C12—C13	0.1 (4)	C14—C15—C16—C11	0.4 (5)
C17—C11—C12—C13	−178.1 (3)	C12—C11—C16—C15	−0.4 (5)
O1—C12—C13—C14	−179.7 (3)	C17—C11—C16—C15	177.8 (3)
C11—C12—C13—C14	0.2 (4)	C12—C11—C17—Cl1	−84.7 (3)
O1—C12—C13—C18	0.9 (4)	C16—C11—C17—Cl1	97.2 (4)
C11—C12—C13—C18	−179.3 (3)	C12—C13—C18—O2	−0.9 (5)
C12—C13—C14—C15	−0.2 (5)	C14—C13—C18—O2	179.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	1.91	2.628 (5)	146

Experimental details

Crystal data
Chemical formula	C₈H₇ClO₂
M_r	170.59
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	4.483 (6), 12.521 (18), 13.71 (2)
V (Å³)	769.6 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.44
Crystal size (mm)	0.30 × 0.23 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.88, 0.92
No. of measured, independent and observed [I > 2σ(I)] reflections	3730, 1369, 1075
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.133, 0.98
No. of reflections	1369
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.32
Absolute structure	Flack (1983), 6571 Friedel pairs
Absolute structure parameter	−0.06 (13)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	1.91	2.628 (5)	146

Acknowledgements

The author thanks the doctoral startup foundation of Hengyang Normal University (09B02) and the foundation of Hengyang Bureau of Science and Technology (2011 K J21) for financial support. He also thanks Dr L.-S. Wang for help with the structure determination.

References

Bruker (2001). SADABS. Bruker AXS Ins. Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Ins. Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Song, S.-H. & Liu, S.-Z. (2004). J. Henan Normal Univ. (Nat. Sci.), 32, 101–103. CAS Google Scholar
Tang, B., Chen, G., Song, X., Cen, C. & Han, C. (2010). Acta Cryst. E66, o1912. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zondervan, V., van den Beuken, E. K., Kooijman, H., Spek, A. L. & Feringa, B. L. (1997). Tetrahedron Lett. 38, 3111–3114. CSD CrossRef CAS Web of Science Google Scholar