2-Hy­droxy-3-meth­oxy­methyl-5-methyl­benzaldehyde

Gunasekaran, B.; Jayamani, A.; Sengottuvelan, N.; Chakkaravarthi, G.

doi:10.1107/S1600536813002845

organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page o317

doi:10.1107/S1600536813002845

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2-Hydroxy-3-methoxymethyl-5-methylbenzaldehyde

B. Gunasekaran,^a A. Jayamani,^b N. Sengottuvelan ^b and G. Chakkaravarthi ^c ^*

^aDepartment of Physics & Nano Technology, SRM University, SRM Nagar, Kattankulathur, Kancheepuram Dist, Chennai 603 203 Tamil Nadu, India, ^bDepartment of Chemistry, DDE, Alagappa University, Karaikudi 630 003, India, and ^cDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: chakkaravarthi_2005@yahoo.com

(Received 27 January 2013; accepted 28 January 2013; online 31 January 2013)

In the title molecule, C₁₀H₁₂O₃, all non-H atoms lie in a common plane (r.m.s deviation = 0.010 Å). The molecular conformation is stabilized by an intramolecular O—H⋯O hydrogen bond.

Related literature

For the biological activity of methylbenzene derivatives, see: Anbarasan et al. (2011 ); Chan & Daniels (2007 ). For related structures see: Wang et al. (2011 ); Kılıç et al. (2009 ); For graph-set notation of hydrogen bonds, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₀H₁₂O₃
M_r = 180.20
Monoclinic, P 2₁ /c
a = 13.899 (3) Å
b = 8.9184 (19) Å
c = 7.5043 (16) Å
β = 94.098 (6)°
V = 927.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.30 × 0.24 × 0.20 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.972, T_max = 0.981
10089 measured reflections
2329 independent reflections
1213 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.181
S = 1.03
2329 reflections
121 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.22 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	1.91	2.628 (3)	146

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813002845/bt6886sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813002845/bt6886Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813002845/bt6886Isup3.cml

checkCIF report

Comment top

In recent days methylbenzene (toluene) and substituted methylbenzene have become very important on account of their wide range of applications in medicine and industry (Anbarasan et al., 2011). For example 3-chloro-2-methylbenzene-1-sulfonylchloride shows the biological activity of hydroxysteriod dehydrogenase inhibitors (Chan & Daniels, 2007).

The geometric parameters of the compound (I), (Fig. 1) agree well with those of a reported similar structure (Wang et al., 2011; Kılıç et al., 2009) The molecular structure is stabilized by an intramolecular O-H..O interaction generating a six-membered ring S(6) graph-set motif (Bernstein et al., 1995).

Related literature top

For the biological activity of methylbenzene derivatives, see: Anbarasan et al. (2011); Chan & Daniels (2007). For related structures see: Wang et al. (2011); Kılıç et al. (2009); For graph-set notation of hydrogen bonds, see: Bernstein et al. (1995);

Experimental top

To a methanolic solution of 2-hydroxy-5-methyl-1,3-benzenedicarboxaldehyde (1g, 6mmol) decarborane (0.37, 3 mmol) was added slowly with constant stirring at room temperature in nitrogen atmosphere for 24 hours. A pale yellow solution formed after 24h and was concentrated to get the crude product. The crude product was washed well with methanol and dried in vacuum. The product was recrystallized in chloroform to get pale yellow coloured crystals suitable for single crystal XRD. yield 0.96g, 80% .

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.

2-Hydroxy-3-methoxymethyl-5-methylbenzaldehyde top

Crystal data top

C₁₀H₁₂O₃	F(000) = 384
M_r = 180.20	D_x = 1.290 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3221 reflections
a = 13.899 (3) Å	θ = 2.7–24.8°
b = 8.9184 (19) Å	µ = 0.10 mm⁻¹
c = 7.5043 (16) Å	T = 295 K
β = 94.098 (6)°	Block, yellow
V = 927.8 (3) Å³	0.30 × 0.24 × 0.20 mm
Z = 4

Data collection top

Bruker Kappa APEXII diffractometer	2329 independent reflections
Radiation source: fine-focus sealed tube	1213 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ω and ϕ scans	θ_max = 28.7°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→18
T_min = 0.972, T_max = 0.981	k = −11→12
10089 measured reflections	l = −9→9

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.181	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0625P)² + 0.4641P] where P = (F_o² + 2F_c²)/3
2329 reflections	(Δ/σ)_max < 0.001
121 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₀H₁₂O₃	V = 927.8 (3) Å³
M_r = 180.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.899 (3) Å	µ = 0.10 mm⁻¹
b = 8.9184 (19) Å	T = 295 K
c = 7.5043 (16) Å	0.30 × 0.24 × 0.20 mm
β = 94.098 (6)°

Data collection top

Bruker Kappa APEXII diffractometer	2329 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1213 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.981	R_int = 0.050
10089 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.181	H-atom parameters constrained
S = 1.03	Δρ_max = 0.24 e Å⁻³
2329 reflections	Δρ_min = −0.22 e Å⁻³
121 parameters

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

	x	y	z	U_iso*/U_eq
C8	0.92734 (18)	1.0908 (3)	0.1482 (4)	0.0617 (7)
H8	0.9842	1.1345	0.1959	0.074*
C1	0.85176 (16)	1.1898 (2)	0.0792 (3)	0.0459 (6)
C6	0.86550 (16)	1.3446 (3)	0.0868 (3)	0.0497 (6)
H6	0.9241	1.3825	0.1349	0.060*
C5	0.79476 (17)	1.4420 (2)	0.0250 (3)	0.0479 (6)
C4	0.70806 (16)	1.3801 (2)	−0.0467 (3)	0.0457 (6)
H4	0.6595	1.4449	−0.0906	0.055*
C3	0.69089 (16)	1.2288 (2)	−0.0558 (3)	0.0426 (5)
C2	0.76424 (16)	1.1324 (2)	0.0081 (3)	0.0438 (5)
C9	0.59741 (17)	1.1631 (3)	−0.1290 (3)	0.0536 (6)
H9A	0.6088	1.0965	−0.2275	0.064*
H9B	0.5690	1.1049	−0.0370	0.064*
C10	0.4451 (2)	1.2195 (3)	−0.2637 (4)	0.0741 (9)
H10A	0.4569	1.1579	−0.3648	0.111*
H10B	0.4030	1.3006	−0.3012	0.111*
H10C	0.4155	1.1602	−0.1759	0.111*
C7	0.8079 (2)	1.6091 (3)	0.0330 (4)	0.0687 (8)
H7A	0.7929	1.6451	0.1483	0.103*
H7B	0.7657	1.6556	−0.0576	0.103*
H7C	0.8736	1.6336	0.0132	0.103*
O1	0.92264 (14)	0.9535 (2)	0.1490 (3)	0.0772 (6)
O2	0.74664 (13)	0.98329 (17)	0.0006 (3)	0.0618 (5)
H2	0.7946	0.9376	0.0410	0.093*
O3	0.53348 (12)	1.27783 (19)	−0.1888 (3)	0.0638 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C8	0.0507 (15)	0.0628 (17)	0.0718 (19)	0.0088 (12)	0.0061 (12)	0.0047 (13)
C1	0.0469 (13)	0.0412 (12)	0.0500 (14)	0.0053 (10)	0.0060 (10)	0.0027 (9)
C6	0.0463 (13)	0.0475 (14)	0.0549 (15)	−0.0047 (10)	0.0020 (10)	−0.0034 (11)
C5	0.0530 (14)	0.0374 (11)	0.0532 (14)	−0.0033 (10)	0.0039 (10)	−0.0027 (10)
C4	0.0475 (13)	0.0361 (11)	0.0535 (14)	0.0042 (9)	0.0028 (10)	0.0029 (10)
C3	0.0475 (12)	0.0357 (11)	0.0449 (13)	−0.0051 (9)	0.0059 (9)	0.0007 (9)
C2	0.0515 (13)	0.0319 (11)	0.0487 (13)	−0.0005 (9)	0.0086 (10)	0.0017 (9)
C9	0.0560 (14)	0.0406 (12)	0.0638 (16)	−0.0052 (11)	0.0027 (12)	0.0040 (11)
C10	0.0586 (17)	0.0758 (19)	0.085 (2)	−0.0147 (14)	−0.0139 (14)	0.0095 (16)
C7	0.0728 (18)	0.0374 (13)	0.095 (2)	−0.0071 (12)	−0.0003 (15)	−0.0078 (13)
O1	0.0704 (13)	0.0538 (12)	0.1080 (18)	0.0216 (9)	0.0109 (11)	0.0142 (11)
O2	0.0665 (12)	0.0333 (9)	0.0858 (14)	0.0009 (7)	0.0063 (10)	0.0045 (8)
O3	0.0500 (10)	0.0528 (10)	0.0858 (13)	−0.0075 (8)	−0.0136 (9)	0.0087 (9)

Geometric parameters (Å, º) top

C8—O1	1.227 (3)	C2—O2	1.352 (2)
C8—C1	1.440 (3)	C9—O3	1.407 (3)
C8—H8	0.9300	C9—H9A	0.9700
C1—C2	1.391 (3)	C9—H9B	0.9700
C1—C6	1.394 (3)	C10—O3	1.413 (3)
C6—C5	1.368 (3)	C10—H10A	0.9600
C6—H6	0.9300	C10—H10B	0.9600
C5—C4	1.398 (3)	C10—H10C	0.9600
C5—C7	1.503 (3)	C7—H7A	0.9600
C4—C3	1.372 (3)	C7—H7B	0.9600
C4—H4	0.9300	C7—H7C	0.9600
C3—C2	1.392 (3)	O2—H2	0.8200
C3—C9	1.494 (3)

O1—C8—C1	125.2 (3)	O3—C9—C3	110.18 (18)
O1—C8—H8	117.4	O3—C9—H9A	109.6
C1—C8—H8	117.4	C3—C9—H9A	109.6
C2—C1—C6	119.6 (2)	O3—C9—H9B	109.6
C2—C1—C8	120.5 (2)	C3—C9—H9B	109.6
C6—C1—C8	119.9 (2)	H9A—C9—H9B	108.1
C5—C6—C1	121.5 (2)	O3—C10—H10A	109.5
C5—C6—H6	119.3	O3—C10—H10B	109.5
C1—C6—H6	119.3	H10A—C10—H10B	109.5
C6—C5—C4	117.3 (2)	O3—C10—H10C	109.5
C6—C5—C7	122.3 (2)	H10A—C10—H10C	109.5
C4—C5—C7	120.4 (2)	H10B—C10—H10C	109.5
C3—C4—C5	123.3 (2)	C5—C7—H7A	109.5
C3—C4—H4	118.3	C5—C7—H7B	109.5
C5—C4—H4	118.3	H7A—C7—H7B	109.5
C4—C3—C2	118.0 (2)	C5—C7—H7C	109.5
C4—C3—C9	123.2 (2)	H7A—C7—H7C	109.5
C2—C3—C9	118.74 (19)	H7B—C7—H7C	109.5
O2—C2—C1	121.9 (2)	C2—O2—H2	109.5
O2—C2—C3	117.8 (2)	C9—O3—C10	111.7 (2)
C1—C2—C3	120.25 (19)

O1—C8—C1—C2	0.9 (4)	C8—C1—C2—O2	−0.1 (3)
O1—C8—C1—C6	179.6 (2)	C6—C1—C2—C3	0.2 (3)
C2—C1—C6—C5	−0.3 (3)	C8—C1—C2—C3	179.0 (2)
C8—C1—C6—C5	−179.0 (2)	C4—C3—C2—O2	179.3 (2)
C1—C6—C5—C4	−0.2 (3)	C9—C3—C2—O2	−0.1 (3)
C1—C6—C5—C7	179.6 (2)	C4—C3—C2—C1	0.2 (3)
C6—C5—C4—C3	0.7 (3)	C9—C3—C2—C1	−179.2 (2)
C7—C5—C4—C3	−179.1 (2)	C4—C3—C9—O3	1.4 (3)
C5—C4—C3—C2	−0.8 (3)	C2—C3—C9—O3	−179.2 (2)
C5—C4—C3—C9	178.7 (2)	C3—C9—O3—C10	178.3 (2)
C6—C1—C2—O2	−178.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.82	1.91	2.628 (3)	146
C4—H4···O3	0.93	2.38	2.736 (3)	103

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂O₃
M_r	180.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	13.899 (3), 8.9184 (19), 7.5043 (16)
β (°)	94.098 (6)
V (Å³)	927.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.24 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.972, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	10089, 2329, 1213
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.181, 1.03
No. of reflections	2329
No. of parameters	121
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.22

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.82	1.91	2.628 (3)	146

Acknowledgements

The authors wish to acknowledge the SAIF, IIT, Madras for the data collection.

References

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