4-Hydroxy­meth­yl-2-methoxy­phenol

Abstract

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,

• a = 9.8476 (6) Å

• b = 6.1721 (4) Å

• c = 15.4915 (7) Å

• β = 126.877 (2)°

• V = 753.19 (8) ų

• 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[F ² > 2σ(F ²)] = 0.037

• wR(F ²) = 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

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.

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
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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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%).

Refinement

H atoms were treated as riding, with C—H distances in the range of 0.93–0.97 Å and O—H distances of 0.85 Å, and were refined as riding with U_iso(H)=1.2U_eq(C_methylene and C in phenyl ring) and U_iso(H)=1.5U_eq(O and (C_methyl)).

Figures

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.

Crystal data

C8H10O3	F(000) = 328
Mr = 154.16	Dx = 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

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

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)] = 0.037	H-atom parameters constrained
wR(F2) = 0.102	w = 1/[σ2(Fo2) + (0.0462P)2 + 0.2254P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
1475 reflections	Δρmax = 0.24 e Å−3
102 parameters	Δρmin = −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)

Special details

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
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 (Ų)

	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, °)

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, °)

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.