6-Hy­droxy-2H-1,3-benzodioxole-5-carbaldehyde

Momin, M.I.K.; Koorbanally, N.; Ramjugernath, D.; Bala, M.D.

doi:10.1107/S1600536811037019

6-Hydroxy-2H-1,3-benzodioxole-5-carbaldehyde

M. I. K. Momin, N. Koorbanally, D. Ramjugernath and M. D. Bala

The title compound, C₈H₆O₄, crystallizes with two independent molecules in the asymmetric unit. The benzodioxole ring system is almost planar in each molecule, with maximum deviations of 0.008 (1) and 0.007 (1) Å. The molecular structure is characterized by strong electrostatic intramolecular O

O contacts [2.649 (3) Å] and intramolecular O—H

O hydrogen-bonding interactions. Intermolecular O

O interactions [3.001 (2) Å] are observed in the crystal structure.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811037019/qm2028sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811037019/qm2028Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536811037019/qm2028Isup3.cml Supplementary material

CCDC reference: 850584

checkCIF report

Key indicators

Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.004 Å
R factor = 0.045
wR factor = 0.125
Data-to-parameter ratio = 12.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O4     --  C7      ..        6.0 su
PLAT430_ALERT_2_C Short Inter D...A Contact  O2     ..  O6      ..       2.90 Ang.

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT432_ALERT_2_G Short Inter X...Y Contact  O2     ..  C16     ..       3.00 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  O6     ..  C8      ..       2.98 Ang.

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

The title compound 6- hydroxybenzo[d][1,3]dioxole-5-carbaldehyde was obtained as an intermediate product in our research effort aimed at the total synthesis of biologically active compounds. These compounds have been used for HIV-1 integrase inhibitory activities as reported by Bailly et al. (2005), Dopamine D1 receptor full agonist (Cueva, et al. 2006) and glycogen phosphorylase inhibitory activity reported by Juhász et al. (2007). The compound has been previously reported by Juhász et al. (2007) and Akselsen et al. (2009) with 45% yield when it was respectively utilized as a starting material and as an intermediate in the synthesis of the biologically active compounds. However, inspite of the varied biological applications of (I) the crystal structure of the title compound has not been reported to date. The compound has two independent molecules in the asymmetric unit that are related by a crystallographic centre of inversion and a glide plane perpendicular to the (0, 1, 0) axis. The benzodioxole ring systems in the title compound are almost planar and show strong pi-pi interactions in the unit cell. The molecule is stabilized by intra-molecular hydrogen bonding contacts which are however balanced by a network of O···O electrostatic contacts that are both intra- [O1···O4 & O5···O8 = 2.649 (3) Å] and inter-molecular [O4···O8 = 3.001 (2) Å] in nature.

Related literature top

For the preparation, see: Juhász et al. (2007); Akselsen et al. (2009). For hydrogen-bond motifs, see: Bernstein et al. (1995). The title compound is a starting material and an intermediate in the synthesis of biologically active compounds. These compounds have shown HIV-1 integrase inhibitory activity (Bailly et al., 2005), dopamine D1 receptor full agonist (Cueva, et al. 2006) and glycogen phosphorylase inhibitory activity (Juhász et al., 2007).

Experimental top

The compound 2-yydroxy-4,5-methylenedioxybenzaldehyde was synthesized by following the literature method of Akselsen et al. (2009). Brown crystals suitable for X-ray diffraction were grown from hexane:ethyl acetate (95:5). m.p. 125–127 °C. ¹H NMR: δ (p.p.m.): 6.01 (2H,s, O–CH₂–O); 6.46 (1H, s, H-5); 6.86 (1H, s, H-8); 9.62 (1H, s, CHO); 11.79 (1H, s, OH). ¹³C NMR: δ = 98.37, 102.15, 109.35, 113.65, 141.33, 155.17, 161.54, 193.69. HRMS m/z 166.0264 (calcd for C₈H₆O₄: 166.0266).

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. Molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.

6-Hydroxy-2H-1,3-benzodioxole-5-carbaldehyde top

Crystal data top

C₈H₆O₄	F(000) = 688
M_r = 166.13	D_x = 1.596 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1671 reflections
a = 6.4916 (3) Å	θ = 2.5–26.6°
b = 12.8242 (7) Å	µ = 0.13 mm⁻¹
c = 16.7122 (8) Å	T = 173 K
β = 96.258 (3)°	Needle, colourless
V = 1382.99 (12) Å³	0.38 × 0.11 × 0.10 mm
Z = 8

Data collection top

Bruker APEXII CCD diffractometer	1348 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.081
Graphite monochromator	θ_max = 26.0°, θ_min = 2.0°
φ and ω scans	h = −7→8
10746 measured reflections	k = −15→15
2708 independent reflections	l = −18→20

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.0556P)²] where P = (F_o² + 2F_c²)/3
2708 reflections	(Δ/σ)_max < 0.001
219 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₈H₆O₄	V = 1382.99 (12) Å³
M_r = 166.13	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.4916 (3) Å	µ = 0.13 mm⁻¹
b = 12.8242 (7) Å	T = 173 K
c = 16.7122 (8) Å	0.38 × 0.11 × 0.10 mm
β = 96.258 (3)°

Data collection top

Bruker APEXII CCD diffractometer	1348 reflections with I > 2σ(I)
10746 measured reflections	R_int = 0.081
2708 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 0.94	Δρ_max = 0.19 e Å⁻³
2708 reflections	Δρ_min = −0.31 e Å⁻³
219 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
C1	0.0179 (4)	0.62547 (19)	0.46651 (15)	0.0211 (6)
C2	0.2306 (4)	0.6144 (2)	0.49173 (15)	0.0221 (6)
C3	0.3046 (4)	0.6148 (2)	0.57346 (15)	0.0272 (7)
H3	0.4474	0.6059	0.5915	0.033*
C4	0.1604 (4)	0.6288 (2)	0.62576 (14)	0.0233 (6)
C5	−0.0500 (4)	0.6406 (2)	0.60194 (15)	0.0230 (6)
C6	−0.1269 (4)	0.63872 (19)	0.52350 (15)	0.0225 (6)
H6	−0.2710	0.6459	0.5073	0.027*
C7	−0.0596 (4)	0.6209 (2)	0.38261 (16)	0.0265 (7)
H7	−0.2052	0.6268	0.3691	0.032*
C8	−0.0031 (5)	0.6428 (2)	0.73701 (16)	0.0328 (7)
H8A	−0.0324	0.5811	0.7695	0.039*
H8B	−0.0048	0.7056	0.7714	0.039*
C9	0.4907 (4)	0.6181 (2)	0.12152 (15)	0.0240 (6)
C10	0.2786 (4)	0.6096 (2)	0.09607 (15)	0.0247 (6)
C11	0.2024 (4)	0.6141 (2)	0.01456 (14)	0.0248 (7)
H11	0.0591	0.6072	−0.0034	0.030*
C12	0.3487 (4)	0.6294 (2)	−0.03776 (15)	0.0238 (6)
C13	0.5577 (4)	0.6389 (2)	−0.01390 (15)	0.0236 (6)
C14	0.6353 (4)	0.6332 (2)	0.06454 (15)	0.0244 (6)
H14	0.7797	0.6389	0.0807	0.029*
C15	0.5696 (4)	0.6118 (2)	0.20578 (16)	0.0283 (7)
H15	0.7151	0.6174	0.2196	0.034*
C16	0.5093 (4)	0.6575 (2)	−0.14766 (16)	0.0316 (7)
H16A	0.5389	0.6056	−0.1887	0.038*
H16B	0.5077	0.7277	−0.1724	0.038*
O1	0.3710 (3)	0.60201 (16)	0.43841 (10)	0.0301 (5)
H1	0.3094	0.5985	0.3916	0.045*
O2	0.1955 (3)	0.63205 (16)	0.70789 (10)	0.0353 (5)
O3	−0.1564 (3)	0.65199 (16)	0.66900 (10)	0.0343 (5)
O4	0.0485 (3)	0.60984 (15)	0.32659 (10)	0.0314 (5)
O5	0.1369 (3)	0.59693 (17)	0.14948 (11)	0.0336 (5)
H5	0.1983	0.5920	0.1962	0.050*
O6	0.3117 (3)	0.63578 (15)	−0.11966 (11)	0.0331 (5)
O7	0.6644 (3)	0.65268 (16)	−0.08064 (10)	0.0330 (5)
O8	0.4600 (3)	0.59961 (16)	0.26055 (11)	0.0357 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0199 (15)	0.0198 (14)	0.0233 (15)	0.0015 (12)	0.0015 (12)	0.0026 (11)
C2	0.0210 (15)	0.0221 (15)	0.0235 (15)	−0.0035 (12)	0.0041 (12)	0.0004 (11)
C3	0.0176 (15)	0.0323 (17)	0.0310 (17)	−0.0011 (13)	0.0000 (13)	0.0009 (12)
C4	0.0250 (16)	0.0266 (15)	0.0182 (15)	−0.0003 (13)	0.0010 (12)	−0.0011 (11)
C5	0.0215 (15)	0.0252 (15)	0.0238 (16)	0.0018 (13)	0.0088 (12)	−0.0026 (12)
C6	0.0158 (14)	0.0247 (15)	0.0262 (15)	0.0011 (13)	−0.0016 (12)	0.0006 (12)
C7	0.0236 (16)	0.0246 (16)	0.0302 (17)	0.0002 (13)	−0.0020 (13)	0.0032 (12)
C8	0.0281 (17)	0.0458 (19)	0.0248 (16)	0.0026 (15)	0.0042 (13)	−0.0019 (14)
C9	0.0256 (15)	0.0238 (15)	0.0225 (15)	0.0029 (14)	0.0014 (12)	−0.0019 (12)
C10	0.0223 (16)	0.0248 (15)	0.0276 (16)	0.0002 (13)	0.0055 (12)	0.0007 (12)
C11	0.0154 (14)	0.0319 (17)	0.0263 (16)	0.0005 (13)	−0.0009 (12)	0.0011 (12)
C12	0.0261 (16)	0.0254 (15)	0.0191 (14)	0.0010 (13)	−0.0006 (12)	0.0000 (12)
C13	0.0223 (15)	0.0252 (15)	0.0238 (16)	−0.0007 (13)	0.0049 (12)	0.0015 (12)
C14	0.0156 (14)	0.0278 (16)	0.0297 (16)	−0.0017 (13)	0.0020 (12)	−0.0001 (12)
C15	0.0228 (15)	0.0339 (17)	0.0282 (16)	0.0023 (14)	0.0024 (13)	−0.0019 (13)
C16	0.0290 (17)	0.0385 (17)	0.0281 (17)	−0.0045 (15)	0.0073 (14)	0.0025 (13)
O1	0.0191 (11)	0.0496 (13)	0.0217 (11)	0.0002 (10)	0.0035 (8)	0.0014 (10)
O2	0.0234 (12)	0.0598 (14)	0.0224 (11)	0.0034 (10)	0.0015 (9)	−0.0048 (10)
O3	0.0238 (11)	0.0573 (15)	0.0225 (11)	0.0067 (10)	0.0053 (9)	−0.0045 (10)
O4	0.0321 (12)	0.0414 (12)	0.0217 (11)	0.0012 (10)	0.0068 (9)	0.0020 (9)
O5	0.0208 (11)	0.0557 (14)	0.0252 (11)	−0.0006 (10)	0.0061 (9)	0.0015 (10)
O6	0.0271 (12)	0.0484 (13)	0.0232 (11)	−0.0025 (10)	−0.0003 (9)	0.0039 (9)
O7	0.0257 (12)	0.0508 (14)	0.0231 (11)	−0.0075 (10)	0.0051 (9)	0.0011 (9)
O8	0.0335 (13)	0.0493 (14)	0.0250 (11)	0.0020 (11)	0.0062 (9)	−0.0010 (10)

Geometric parameters (Å, º) top

C1—C2	1.407 (4)	C9—C14	1.422 (3)
C1—C6	1.419 (3)	C9—C15	1.447 (4)
C1—C7	1.438 (4)	C10—O5	1.360 (3)
C2—O1	1.351 (3)	C10—C11	1.399 (3)
C2—C3	1.398 (3)	C11—C12	1.373 (4)
C3—C4	1.360 (3)	C11—H11	0.9500
C3—H3	0.9500	C12—O6	1.366 (3)
C4—O2	1.367 (3)	C12—C13	1.378 (4)
C4—C5	1.389 (4)	C13—C14	1.354 (4)
C5—C6	1.351 (3)	C13—O7	1.387 (3)
C5—O3	1.387 (3)	C14—H14	0.9500
C6—H6	0.9500	C15—O8	1.229 (3)
C7—O4	1.238 (3)	C15—H15	0.9500
C7—H7	0.9500	C16—O7	1.423 (3)
C8—O3	1.432 (3)	C16—O6	1.440 (3)
C8—O2	1.433 (3)	C16—H16A	0.9900
C8—H8A	0.9900	C16—H16B	0.9900
C8—H8B	0.9900	O1—H1	0.8400
C9—C10	1.400 (4)	O5—H5	0.8400

C2—C1—C6	120.8 (2)	O5—C10—C11	116.8 (2)
C2—C1—C7	121.0 (2)	O5—C10—C9	121.5 (2)
C6—C1—C7	118.2 (3)	C11—C10—C9	121.6 (2)
O1—C2—C3	117.4 (2)	C12—C11—C10	115.5 (3)
O1—C2—C1	121.7 (2)	C12—C11—H11	122.3
C3—C2—C1	120.9 (2)	C10—C11—H11	122.3
C4—C3—C2	116.2 (3)	O6—C12—C11	126.0 (3)
C4—C3—H3	121.9	O6—C12—C13	110.2 (2)
C2—C3—H3	121.9	C11—C12—C13	123.8 (2)
C3—C4—O2	126.7 (3)	C14—C13—C12	121.7 (2)
C3—C4—C5	123.7 (2)	C14—C13—O7	128.3 (3)
O2—C4—C5	109.6 (2)	C12—C13—O7	109.9 (2)
C6—C5—O3	128.5 (3)	C13—C14—C9	116.9 (3)
C6—C5—C4	121.6 (2)	C13—C14—H14	121.5
O3—C5—C4	109.9 (2)	C9—C14—H14	121.5
C5—C6—C1	116.8 (3)	O8—C15—C9	124.0 (3)
C5—C6—H6	121.6	O8—C15—H15	118.0
C1—C6—H6	121.6	C9—C15—H15	118.0
O4—C7—C1	125.1 (3)	O7—C16—O6	108.3 (2)
O4—C7—H7	117.5	O7—C16—H16A	110.0
C1—C7—H7	117.5	O6—C16—H16A	110.0
O3—C8—O2	108.1 (2)	O7—C16—H16B	110.0
O3—C8—H8A	110.1	O6—C16—H16B	110.0
O2—C8—H8A	110.1	H16A—C16—H16B	108.4
O3—C8—H8B	110.1	C2—O1—H1	109.5
O2—C8—H8B	110.1	C4—O2—C8	106.6 (2)
H8A—C8—H8B	108.4	C5—O3—C8	105.6 (2)
C10—C9—C14	120.4 (2)	C10—O5—H5	109.5
C10—C9—C15	121.6 (2)	C12—O6—C16	105.8 (2)
C14—C9—C15	118.0 (3)	C13—O7—C16	105.4 (2)

C6—C1—C2—O1	−179.8 (2)	C10—C11—C12—O6	179.6 (2)
C7—C1—C2—O1	1.9 (4)	C10—C11—C12—C13	0.6 (4)
C6—C1—C2—C3	0.8 (4)	O6—C12—C13—C14	−178.7 (2)
C7—C1—C2—C3	−177.5 (2)	C11—C12—C13—C14	0.4 (4)
O1—C2—C3—C4	179.1 (2)	O6—C12—C13—O7	0.4 (3)
C1—C2—C3—C4	−1.4 (4)	C11—C12—C13—O7	179.5 (2)
C2—C3—C4—O2	180.0 (2)	C12—C13—C14—C9	−0.8 (4)
C2—C3—C4—C5	1.1 (4)	O7—C13—C14—C9	−179.6 (2)
C3—C4—C5—C6	0.0 (4)	C10—C9—C14—C13	0.1 (4)
O2—C4—C5—C6	−179.0 (2)	C15—C9—C14—C13	−179.9 (2)
C3—C4—C5—O3	179.2 (3)	C10—C9—C15—O8	−0.5 (4)
O2—C4—C5—O3	0.2 (3)	C14—C9—C15—O8	179.5 (3)
O3—C5—C6—C1	−179.8 (2)	C3—C4—O2—C8	−177.1 (3)
C4—C5—C6—C1	−0.7 (4)	C5—C4—O2—C8	2.0 (3)
C2—C1—C6—C5	0.3 (4)	O3—C8—O2—C4	−3.3 (3)
C7—C1—C6—C5	178.7 (2)	C6—C5—O3—C8	176.9 (3)
C2—C1—C7—O4	−1.8 (4)	C4—C5—O3—C8	−2.2 (3)
C6—C1—C7—O4	179.8 (3)	O2—C8—O3—C5	3.4 (3)
C14—C9—C10—O5	−178.8 (3)	C11—C12—O6—C16	177.0 (3)
C15—C9—C10—O5	1.2 (4)	C13—C12—O6—C16	−3.9 (3)
C14—C9—C10—C11	0.9 (4)	O7—C16—O6—C12	6.0 (3)
C15—C9—C10—C11	−179.1 (3)	C14—C13—O7—C16	−177.7 (3)
O5—C10—C11—C12	178.5 (2)	C12—C13—O7—C16	3.4 (3)
C9—C10—C11—C12	−1.2 (4)	O6—C16—O7—C13	−5.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4	0.84	1.92	2.652 (3)	146
O5—H5···O8	0.84	1.91	2.645 (3)	145

Experimental details

Crystal data
Chemical formula	C₈H₆O₄
M_r	166.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	6.4916 (3), 12.8242 (7), 16.7122 (8)
β (°)	96.258 (3)
V (Å³)	1382.99 (12)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.38 × 0.11 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10746, 2708, 1348
R_int	0.081
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.125, 0.94
No. of reflections	2708
No. of parameters	219
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.31

Computer programs: APEX2 (Bruker, 2009), SAINT-Plus (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).