4-Hydroxy­meth­yl-2-methoxy­phenol

Wang, Q.; Li, S.-P.

doi:10.1107/S1600536809043025

organic compounds

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4-Hydroxymethyl-2-methoxyphenol

Qiang Wang ^a ^* and Suo-Ping Li ^a

^aHenan University, Kaifeng 475004, People's Republic of China
^*Correspondence e-mail: wqwang228@163.com

(Received 19 October 2009; accepted 19 October 2009; online 23 October 2009)

The title compound, C₈H₁₀O₃, is close to planar (r.m.s. deviation = 0.042 Å) apart from the hydroxyl O atom [deviation = 1.285 (1) Å] and an intramolecular O—H⋯O hydrogen bond occurs. In the crystal, intermolecular O—H⋯O links lead to chains propagating in [001].

Related literature

For a related compound used as a food additive, see: Kumar et al. (2004 ); Shaughnessy et al. (2001 ).

Experimental

Crystal data

C₈H₁₀O₃
M_r = 154.16
Monoclinic, P 2₁ /c
a = 9.8476 (6) Å
b = 6.1721 (4) Å
c = 15.4915 (7) Å
β = 126.877 (2)°
V = 753.19 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.29 × 0.11 × 0.07 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.971, T_max = 0.993
3996 measured reflections
1475 independent reflections
1249 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.102
S = 1.05
1475 reflections
102 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2	0.82	2.31	2.6669 (16)	107
O1—H1A⋯O3ⁱ	0.82	1.96	2.7390 (16)	158
O3—H3B⋯O1ⁱⁱ	0.84	2.07	2.8666 (15)	158
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; 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: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809043025/hb5154sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809043025/hb5154Isup2.hkl

checkCIF report

Comment top

4-hydroxy-3-methoxybenzaldehyde is one of the commonly used food additives. In recent years, it was discovered that 4-hydroxy-3-methoxybenzaldehyde has anti-oxidation (Kumar et al., 2004) and inhibition activity of gene mutation (Shaughnessy et al., 2001). But its activity is low. Therefore, preparing derivatives has been an active research area. Herein we report the crystal structure of the title compound (I).

In the structure of the title compound (I) (Fig.1), the S(6) ring of C(1)/C(2)/C(3)/C(4)/C(5)/C(6) in (I) is an aromatic ring. C(1)–O(1) [1.3702 (16) Å], C(6)–O(2)[1.3683 (16) Å], C(8)–O(2)[1.4181 (18) Å], and C(7)–O(3) [1.433 (2) Å] are typical for C–O single bonds.

In the crystal structure, these molecules are linked into infinite one-dimensional network by intermolecular O—H···O hydrogen bonds running along [100] (Fig. 2, Table 1).

Related literature top

For a related compound used as a food additive, see: Kumar et al. (2004); Shaughnessy et al. (2001).

Experimental top

4-Hydroxy-3-methoxybenzaldehyde (3.8 g, 25 mmol) was dissolved in methanol (40 ml) at 283 K. After stirring for 30 min, borohydride (0.94 g, 25 mmol) was added in reaction solution, slowly. After 4 h, the solution was quenched with water (150 ml), vacuum concentrated to remove methanol and the aqueous layer was extracted with chloroform, the combined organic extracts were washed, dried and evaporated under reduced pressure to give the crude product. Then purification by column chromatography and recrystallization from chloroform gave (I) as colourless plates (2.58 g, 67%).

Structure description top

In the crystal structure, these molecules are linked into infinite one-dimensional network by intermolecular O—H···O hydrogen bonds running along [100] (Fig. 2, Table 1).

For a related compound used as a food additive, see: Kumar et al. (2004); Shaughnessy et al. (2001).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I), showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. One-dimensional structure of (I) showing hydrogen bonds as dashed lines.

4-Hydroxymethyl-2-methoxyphenol top

Crystal data top

C₈H₁₀O₃	F(000) = 328
M_r = 154.16	D_x = 1.359 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1768 reflections
a = 9.8476 (6) Å	θ = 2.6–27.6°
b = 6.1721 (4) Å	µ = 0.10 mm⁻¹
c = 15.4915 (7) Å	T = 293 K
β = 126.877 (2)°	Plate, colorless
V = 753.19 (8) Å³	0.29 × 0.11 × 0.07 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1475 independent reflections
Radiation source: fine-focus sealed tube	1249 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ω scans	θ_max = 26.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→8
T_min = 0.971, T_max = 0.993	k = −7→7
3996 measured reflections	l = −17→19

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)] = 0.037	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0462P)² + 0.2254P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1475 reflections	Δρ_max = 0.24 e Å⁻³
102 parameters	Δρ_min = −0.19 e Å⁻³
2 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.043 (6)

Crystal data top

C₈H₁₀O₃	V = 753.19 (8) Å³
M_r = 154.16	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.8476 (6) Å	µ = 0.10 mm⁻¹
b = 6.1721 (4) Å	T = 293 K
c = 15.4915 (7) Å	0.29 × 0.11 × 0.07 mm
β = 126.877 (2)°

Data collection top

Bruker SMART CCD diffractometer	1475 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1249 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.993	R_int = 0.015
3996 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	2 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.05	Δρ_max = 0.24 e Å⁻³
1475 reflections	Δρ_min = −0.19 e Å⁻³
102 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
O1	0.16947 (13)	0.60312 (18)	0.16129 (8)	0.0462 (3)
H1A	0.1727	0.4901	0.1347	0.069*
O2	0.35690 (14)	0.26017 (19)	0.27618 (8)	0.0501 (3)
O3	0.16416 (15)	0.1981 (2)	0.52945 (9)	0.0621 (4)
H3B	0.0675	0.2067	0.4697	0.093*
C1	0.19570 (17)	0.5586 (2)	0.25692 (11)	0.0352 (3)
C2	0.12924 (18)	0.6933 (2)	0.29368 (12)	0.0407 (4)
H2A	0.0704	0.8173	0.2550	0.049*
C3	0.14955 (19)	0.6447 (2)	0.38857 (12)	0.0416 (4)
H3A	0.1034	0.7361	0.4125	0.050*
C4	0.23753 (17)	0.4625 (2)	0.44737 (11)	0.0383 (3)
C5	0.31075 (18)	0.3308 (2)	0.41213 (11)	0.0394 (4)
H5A	0.3734	0.2100	0.4524	0.047*
C6	0.29122 (17)	0.3781 (2)	0.31805 (11)	0.0360 (3)
C7	0.2509 (2)	0.3978 (3)	0.54583 (12)	0.0467 (4)
H7A	0.3696	0.3823	0.6065	0.056*
H7B	0.2026	0.5111	0.5632	0.056*
C8	0.4600 (2)	0.0789 (3)	0.33595 (13)	0.0491 (4)
H8A	0.4997	0.0128	0.2987	0.074*
H8B	0.3948	−0.0242	0.3435	0.074*
H8C	0.5554	0.1256	0.4061	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0591 (7)	0.0473 (6)	0.0406 (6)	0.0118 (5)	0.0344 (5)	0.0107 (5)
O2	0.0624 (7)	0.0559 (7)	0.0461 (6)	0.0249 (5)	0.0400 (6)	0.0144 (5)
O3	0.0635 (7)	0.0802 (9)	0.0413 (6)	−0.0217 (7)	0.0308 (6)	−0.0033 (6)
C1	0.0360 (7)	0.0382 (7)	0.0338 (7)	−0.0010 (6)	0.0223 (6)	0.0021 (6)
C2	0.0446 (8)	0.0359 (8)	0.0413 (8)	0.0057 (6)	0.0256 (7)	0.0033 (6)
C3	0.0467 (8)	0.0412 (8)	0.0434 (8)	0.0016 (6)	0.0304 (7)	−0.0052 (6)
C4	0.0389 (7)	0.0440 (8)	0.0318 (7)	−0.0031 (6)	0.0212 (6)	−0.0040 (6)
C5	0.0399 (7)	0.0428 (8)	0.0339 (7)	0.0070 (6)	0.0212 (6)	0.0056 (6)
C6	0.0348 (7)	0.0403 (8)	0.0360 (7)	0.0029 (6)	0.0228 (6)	0.0008 (6)
C7	0.0542 (9)	0.0532 (10)	0.0374 (8)	−0.0009 (7)	0.0300 (7)	−0.0031 (7)
C8	0.0526 (9)	0.0500 (9)	0.0496 (9)	0.0155 (7)	0.0332 (8)	0.0079 (7)

Geometric parameters (Å, º) top

O1—C1	1.3702 (16)	C3—H3A	0.9300
O1—H1A	0.8200	C4—C5	1.397 (2)
O2—C6	1.3683 (16)	C4—C7	1.5041 (19)
O2—C8	1.4181 (18)	C5—C6	1.3820 (19)
O3—C7	1.433 (2)	C5—H5A	0.9300
O3—H3B	0.8416	C7—H7A	0.9700
C1—C2	1.375 (2)	C7—H7B	0.9700
C1—C6	1.3977 (19)	C8—H8A	0.9600
C2—C3	1.392 (2)	C8—H8B	0.9600
C2—H2A	0.9300	C8—H8C	0.9600
C3—C4	1.378 (2)

C1—O1—H1A	109.5	C4—C5—H5A	119.6
C6—O2—C8	117.84 (11)	O2—C6—C5	125.55 (13)
C7—O3—H3B	107.5	O2—C6—C1	114.85 (12)
O1—C1—C2	119.92 (12)	C5—C6—C1	119.60 (13)
O1—C1—C6	120.39 (12)	O3—C7—C4	111.63 (12)
C2—C1—C6	119.68 (12)	O3—C7—H7A	109.3
C1—C2—C3	120.32 (13)	C4—C7—H7A	109.3
C1—C2—H2A	119.8	O3—C7—H7B	109.3
C3—C2—H2A	119.8	C4—C7—H7B	109.3
C4—C3—C2	120.58 (13)	H7A—C7—H7B	108.0
C4—C3—H3A	119.7	O2—C8—H8A	109.5
C2—C3—H3A	119.7	O2—C8—H8B	109.5
C3—C4—C5	118.93 (13)	H8A—C8—H8B	109.5
C3—C4—C7	121.65 (13)	O2—C8—H8C	109.5
C5—C4—C7	119.38 (13)	H8A—C8—H8C	109.5
C6—C5—C4	120.78 (13)	H8B—C8—H8C	109.5
C6—C5—H5A	119.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.82	2.31	2.6669 (16)	107
O1—H1A···O3ⁱ	0.82	1.96	2.7390 (16)	158
O3—H3B···O1ⁱⁱ	0.84	2.07	2.8666 (15)	158

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

Experimental details

Crystal data
Chemical formula	C₈H₁₀O₃
M_r	154.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.8476 (6), 6.1721 (4), 15.4915 (7)
β (°)	126.877 (2)
V (Å³)	753.19 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.29 × 0.11 × 0.07

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.971, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	3996, 1475, 1249
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.102, 1.05
No. of reflections	1475
No. of parameters	102
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.19

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), 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
O1—H1A···O2	0.82	2.31	2.6669 (16)	107
O1—H1A···O3ⁱ	0.82	1.96	2.7390 (16)	158
O3—H3B···O1ⁱⁱ	0.84	2.07	2.8666 (15)	158

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

References

Bruker (2001). SAINT-Plus, SMART and SADABS. Bruker AXS, Inc., Madison, Wisconsin, USA. Google Scholar
Kumar, S. S., Priyadarsini, K. I. & Sainis, K. B. (2004). J. Agric. Food Chem. 52, 139–145. Web of Science CrossRef PubMed CAS Google Scholar
Shaughnessy, D. T., Setzer, R. W. & DeMarini, D. M. (2001). Mutat. Res. 480–481, 55–69. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2838

https://doi.org/10.1107/S1600536809043025

Open

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