1,3-Benzodioxol-5-ylmethanol

The title compound, C₈H₈O₃, is an acid-protecting group used in the synthesis of peptides and as an accelerator in polymerization reactions. Its oxidation product, piperonal (heliotropine), is used in the flavouring and perfume industries. All the non-H atoms, except the O atom of the hydroxyl group, are coplanar (r.m.s. deviation 0.028 Å). The crystal packing is stabilized by an O—H...O hydrogen bond.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C)= 0.002 Å
• R factor = 0.033
• wR factor = 0.087
• Data-to-parameter ratio = 12.8

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S1. Comment

The title compound, (I), is an acid-protecting group used in the synthesis of peptides (Stewart, 1971) and as an accelerator in polymerization reactions (Ortiz et al., 2005). Its oxidation product, piperonal (heliotropine) is used in the flavouring and perfume industry.

A perspective view of (I) is shown in Fig. 1. Bond lengths and angles can be regarded as normal [Cambridge Structural Database, Version 5.28, November 2006,

updated January 2007 (Allen, 2002); Mogul, Version 1.1 (Bruno et al., 2004)]. All the non-H atoms of the molecule, except the hydroxyl O atom, lie in a common plane (r.m.s. deviation 0.028 Å). The hydroxyl O atom deviates by

0.529 (1) Å from this plane.

The crystal packing is stabilized by an O—H···O hydrogen bond (Table 1 and Fig. 2).

Related literature

For related structures, see: Viladomat et al. (1998); Nagaraj et al. (2005); Sonar et al. (2006); Harrison et al. (2006).

For related literature, see: Allen (2002); Bruno et al. (2004); Ortiz et al. (2005); Stewart (1971).

S2. Experimental

The title compound was obtained as a gift sample from Arvee Chem Pharma, Mysore, India. X-ray quality crystals of (I) were obtained from a solution in acetonitrile after slow evaporation (m.p. 329 K).

S3. Refinement

H atoms were found in a difference map, but those bonded to C atoms were relocated in idealized locations and refined using a riding model, with C_aromatic—H = 0.95 Å or C_methylene—H = 0.99 Å and with U_iso(H) = 1.2U_eq(C). The hydroxyl H atom was refined freely.

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 and PLATON.

Figures

	Fig. 1. A perspective view of (I), with displacement ellipsoids drawn at the 50% probability level (arbitrary spheres for H atoms).
	Fig. 2. A packing diagram for (I). Hydrogen bonds are shown as dashed lines.

1,3-Benzodioxol-5-ylmethanol

Crystal data

C8H8O3	F(000) = 320
Mr = 152.14	Dx = 1.399 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3407 reflections
a = 13.544 (2) Å	θ = 3.7–25.6°
b = 4.6718 (4) Å	µ = 0.11 mm^−1
c = 12.6416 (19) Å	T = 173 K
β = 115.437 (11)°	Block, colourless
V = 722.35 (18) Å^3	0.42 × 0.38 × 0.37 mm
Z = 4

Data collection

Stoe IPDSII two-circle diffractometer	1221 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 25.6°, θmin = 3.6°
ω scans	h = −16→14
3862 measured reflections	k = −5→5
1342 independent reflections	l = −15→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0466P)^2 + 0.1849P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
1342 reflections	Δρmax = 0.19 e Å^−3
105 parameters	Δρmin = −0.13 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.038 (5)

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	0.05317 (7)	0.13672 (19)	0.29543 (7)	0.0307 (3)
H1	0.0202 (16)	0.309 (5)	0.2709 (16)	0.064 (5)*
O2	0.40248 (8)	0.7637 (2)	0.50957 (8)	0.0466 (3)
O3	0.40887 (8)	0.9045 (2)	0.68892 (8)	0.0413 (3)
C1	0.16608 (9)	0.3348 (2)	0.49175 (9)	0.0237 (3)
C2	0.24400 (10)	0.4373 (3)	0.45489 (10)	0.0278 (3)
H2	0.2437	0.3780	0.3829	0.033*
C3	0.32085 (10)	0.6276 (3)	0.52810 (10)	0.0288 (3)
C4	0.32402 (9)	0.7128 (3)	0.63447 (10)	0.0289 (3)
C5	0.24944 (10)	0.6147 (3)	0.67288 (10)	0.0313 (3)
H5	0.2517	0.6729	0.7459	0.038*
C6	0.16949 (10)	0.4234 (3)	0.59852 (10)	0.0278 (3)
H6	0.1161	0.3524	0.6219	0.033*
C7	0.07960 (10)	0.1216 (2)	0.41779 (10)	0.0273 (3)
H7A	0.1056	−0.0740	0.4462	0.033*
H7B	0.0123	0.1557	0.4285	0.033*
C8	0.46503 (11)	0.9200 (3)	0.61560 (12)	0.0400 (3)
H8A	0.5390	0.8357	0.6564	0.048*
H8B	0.4729	1.1221	0.5970	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0408 (5)	0.0245 (5)	0.0225 (4)	0.0006 (4)	0.0095 (4)	−0.0013 (3)
O2	0.0419 (6)	0.0602 (7)	0.0433 (6)	−0.0214 (5)	0.0235 (5)	−0.0135 (5)
O3	0.0384 (5)	0.0441 (6)	0.0354 (5)	−0.0124 (4)	0.0104 (4)	−0.0105 (4)
C1	0.0271 (6)	0.0186 (5)	0.0231 (5)	0.0045 (4)	0.0085 (4)	0.0038 (4)
C2	0.0334 (6)	0.0276 (6)	0.0234 (6)	0.0013 (5)	0.0130 (5)	−0.0010 (5)
C3	0.0274 (6)	0.0298 (6)	0.0295 (6)	0.0004 (5)	0.0125 (5)	0.0023 (5)
C4	0.0292 (6)	0.0255 (6)	0.0250 (6)	0.0000 (5)	0.0049 (5)	−0.0016 (5)
C5	0.0402 (7)	0.0308 (7)	0.0221 (6)	0.0018 (5)	0.0128 (5)	−0.0019 (5)
C6	0.0328 (6)	0.0266 (6)	0.0259 (6)	0.0017 (5)	0.0145 (5)	0.0026 (4)
C7	0.0342 (6)	0.0214 (6)	0.0238 (6)	0.0001 (5)	0.0099 (5)	0.0029 (4)
C8	0.0344 (7)	0.0417 (8)	0.0383 (7)	−0.0099 (6)	0.0103 (6)	−0.0020 (6)

Geometric parameters (Å, º)

O1—C7	1.4319 (14)	C2—H2	0.9500
O1—H1	0.91 (2)	C3—C4	1.3854 (17)
O2—C3	1.3799 (15)	C4—C5	1.3740 (17)
O2—C8	1.4393 (16)	C5—C6	1.4072 (17)
O3—C4	1.3845 (15)	C5—H5	0.9500
O3—C8	1.4314 (18)	C6—H6	0.9500
C1—C6	1.3935 (16)	C7—H7A	0.9900
C1—C2	1.4078 (16)	C7—H7B	0.9900
C1—C7	1.5158 (16)	C8—H8A	0.9900
C2—C3	1.3794 (17)	C8—H8B	0.9900
C7—O1—H1	105.7 (12)	C6—C5—H5	121.7
C3—O2—C8	105.65 (10)	C1—C6—C5	122.11 (11)
C4—O3—C8	105.61 (9)	C1—C6—H6	118.9
C6—C1—C2	120.13 (11)	C5—C6—H6	118.9
C6—C1—C7	119.20 (10)	O1—C7—C1	113.72 (9)
C2—C1—C7	120.65 (10)	O1—C7—H7A	108.8
C3—C2—C1	117.00 (10)	C1—C7—H7A	108.8
C3—C2—H2	121.5	O1—C7—H7B	108.8
C1—C2—H2	121.5	C1—C7—H7B	108.8
C2—C3—O2	127.73 (11)	H7A—C7—H7B	107.7
C2—C3—C4	122.44 (11)	O3—C8—O2	108.28 (10)
O2—C3—C4	109.82 (11)	O3—C8—H8A	110.0
C5—C4—O3	128.27 (11)	O2—C8—H8A	110.0
C5—C4—C3	121.74 (11)	O3—C8—H8B	110.0
O3—C4—C3	109.98 (11)	O2—C8—H8B	110.0
C4—C5—C6	116.58 (11)	H8A—C8—H8B	108.4
C4—C5—H5	121.7
C6—C1—C2—C3	−0.71 (17)	O2—C3—C4—O3	−0.76 (14)
C7—C1—C2—C3	−179.07 (10)	O3—C4—C5—C6	178.68 (11)
C1—C2—C3—O2	−177.66 (11)	C3—C4—C5—C6	−0.12 (18)
C1—C2—C3—C4	1.18 (18)	C2—C1—C6—C5	−0.15 (18)
C8—O2—C3—C2	−175.52 (13)	C7—C1—C6—C5	178.22 (10)
C8—O2—C3—C4	5.52 (14)	C4—C5—C6—C1	0.57 (18)
C8—O3—C4—C5	176.71 (13)	C6—C1—C7—O1	155.02 (10)
C8—O3—C4—C3	−4.37 (14)	C2—C1—C7—O1	−26.61 (15)
C2—C3—C4—C5	−0.78 (19)	C4—O3—C8—O2	7.72 (14)
O2—C3—C4—C5	178.24 (11)	C3—O2—C8—O3	−8.18 (14)
C2—C3—C4—O3	−179.79 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1^i	0.91 (2)	1.82 (2)	2.7256 (9)	173.2 (18)

Symmetry code: (i) −x, y+1/2, −z+1/2.