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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2011 Sep 17;67(Pt 10):o2681. doi: 10.1107/S1600536811037019

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

Mehbub I K Momin a, Neil Koorbanally a, Deresh Ramjugernath b, Muhammad D Bala a,*
PMCID: PMC3201492  PMID: 22064802

Abstract

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.

Related literature

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 ▶).graphic file with name e-67-o2681-scheme1.jpg

Experimental

Crystal data

  • C8H6O4

  • M r = 166.13

  • Monoclinic, Inline graphic

  • a = 6.4916 (3) Å

  • b = 12.8242 (7) Å

  • c = 16.7122 (8) Å

  • β = 96.258 (3)°

  • V = 1382.99 (12) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.13 mm−1

  • T = 173 K

  • 0.38 × 0.11 × 0.10 mm

Data collection

  • Bruker APEXII CCD diffractometer

  • 10746 measured reflections

  • 2708 independent reflections

  • 1348 reflections with I > 2σ(I)

  • R int = 0.081

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045

  • wR(F 2) = 0.125

  • S = 0.94

  • 2708 reflections

  • 219 parameters

  • H-atom parameters constrained

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT-Plus (Bruker, 2009 ▶); data reduction: SAINT-Plus; 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 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811037019/qm2028sup1.cif

e-67-o2681-sup1.cif (22.8KB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037019/qm2028Isup2.hkl

e-67-o2681-Isup2.hkl (130.3KB, hkl)

Supplementary material file. DOI: 10.1107/S1600536811037019/qm2028Isup3.cml

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—H1⋯O4 0.84 1.92 2.652 (3) 146
O5—H5⋯O8 0.84 1.91 2.645 (3) 145
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Acknowledgments

We wish to thank Dr Manuel Fernandes (University of the Witwatersrand) for the data collection and the NRF and the University of KwaZulu-Natal for financial support. This work is based upon research supported by the South African Research Chairs Initiative of the Department of Science and Technology.

supplementary crystallographic information

Comment

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.

Experimental

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).

Refinement

All H-atoms were refined using a riding model, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aromatic, C—H = 0.99 Å and Uiso(H) = 1.2Ueq(C) for CH2.

Figures

Fig. 1.

Fig. 1.

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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.

Crystal data

C8H6O4 F(000) = 688
Mr = 166.13 Dx = 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
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Data collection

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

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(Fo2) + (0.0556P)2] where P = (Fo2 + 2Fc2)/3
2708 reflections (Δ/σ)max < 0.001
219 parameters Δρmax = 0.19 e Å−3
0 restraints Δρmin = −0.31 e Å−3
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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.
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
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)
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Atomic displacement parameters (Å2)

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)
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Geometric parameters (Å, °)

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)
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Hydrogen-bond geometry (Å, °)

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.
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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: QM2028).

References

  1. Akselsen, Ø. W., Skattebøl, L. & Hansen, T. V. (2009). Tetrahedron Lett. 50, 6339–6341.
  2. Bailly, F., Queffelec, C., Mbemba, G., Mouscadet, J.-F. & Cotelle, P. (2005). Bioorg. Med. Chem. Lett. 15, 5053–5056. [DOI] [PubMed]
  3. Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.
  4. Bruker (2009). APEX2 and SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  5. Cueva, J. P., Giorgioni, G., Grubbs, R. A., Chemel, B. R., Watts, V. J. & Nichols, D. E. (2006). J. Med. Chem. 49, 6848–6857. [DOI] [PubMed]
  6. Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
  7. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
  8. Juhász, L., Docsa, T., Brunyászki, A., Gergely, P. & Antus, S. (2007). Bioorg. Med. Chem. 15, 4048–4056. [DOI] [PubMed]
  9. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811037019/qm2028sup1.cif

e-67-o2681-sup1.cif (22.8KB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037019/qm2028Isup2.hkl

e-67-o2681-Isup2.hkl (130.3KB, hkl)

Supplementary material file. DOI: 10.1107/S1600536811037019/qm2028Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography

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