PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o49.
Published online 2007 December 6. doi:  10.1107/S1600536807062009
PMCID: PMC2915007

3,4-Dihydroxy­phenyl 3,4,5-trimethoxy­benzoate

Abstract

In the title compound, C16H16O7, the dihedral angle between the two benzene rings is 82.02 (7)°. The crystal structure is stabilized by inter­molecular O—H(...)O hydrogen bonds, which link the mol­ecules into a two-dimensional network.

Related literature

For details of the general background of whitening agents, see: Nerya et al. (2003 [triangle]); Dawley et al. (1993 [triangle]); Maeda et al. (1991 [triangle]); Lee, et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-00o49-scheme1.jpg

Experimental

Crystal data

  • C16H16O7
  • M r = 320.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00o49-efi5.jpg
  • a = 11.552 (2) Å
  • b = 12.817 (3) Å
  • c = 10.572 (2) Å
  • β = 105.57 (3)°
  • V = 1507.9 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 295 (2) K
  • 0.2 × 0.2 × 0.16 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: none
  • 4251 measured reflections
  • 3444 independent reflections
  • 2176 reflections with I > 2σ(I)
  • R int = 0.030
  • 3 standard reflections every 400 reflections intensity decay: 2%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.126
  • S = 1.01
  • 3444 reflections
  • 219 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg, 1998 [triangle]); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807062009/lx2033sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062009/lx2033Isup2.hkl

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

Acknowledgments

X-ray data were collected at the Center for Research Facilities in Chungnam National University. This work was partially supported by the New Universities for Regional Innovation fund (05-Na-A-01) from the Ministry of Education and Human Resources Department, Republic of Korea.

supplementary crystallographic information

Comment

A number of whitening agents (Nerya et al., 2003; Dawley et al., 1993; Maeda et al., 1991) are containing hydroxyl (Lee et al., 2007), aromatic, alkene, carbonyl and ether inside their structure and acting as a specific functional group to make the skin white by inhibiting the produce of melanin. In the course of our work on the development of new whitening agents, to complement the inadequacy of current whitening agents and maximize the inhibitory effects of melanin creation, we have synthesized the title compound. Herein we report the molecular and crystal structure of 3,4-dihydroxyphenyl 3,4,5-trimethoxybenzoate (Fig. 1).

The 3,4,5-trimethoxybenzoic acid moiety (except C15 methyl group) and a 3,4-dihydroxyphenyl ring are essentially planar, with a mean devation of 0.018 Å and 0.008 Å, respectively, from the least-squares plane defined by the ten and eght, respectively, constituent aoms. C15H3 methyl group direct toward upside in the plane(Fig. 2), and the angle of C4—O2—C15 is 116.9 (2)°. The dihedral angle between two phenyl rings is 82.02(0.07)°. The intermolecular O—H···O hydrogen bonds link the molecules into a two-dimensional network (Table 1 & Fig.2).

Experimental

The synthesis of the title compound started from sesamol (1 mmol) in THF and 3,4,5-trimethoxybenzoyl chloride (1.2 mmol) with NaH(1.5 mmol) as a catalyst by nucleophilic acyl substitution, then the deprotection of methylenedioxy group was accomplished by treatment of Pb(OAc)4 (1.5 mmol) in refluxing benzene, which generated the intermediate alkoxylated ester. Hydrolysis of alkoxylated ester in aqueous acetic acid gave a mixture as yellowish oil. The mixture was chromatographed on silica gel (30/1 = dichloromethane/ethyl acetate) to give the title compound as light yellow solid (61.8%, m.p. 408 K). Single crystals were obtained by slow evaporation from a solution of the title compound in ethyl acetate at room temperature.

Refinement

Atoms H6O and H7O of the OH group were found in a difference Fourier map and refined freely with an isotropic displacement parameter. The other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å for aromatic H atoms and 0.96 Å for methyl H atoms, and with Uiso(H) = 1.2Ueq(C) for aromatic and 1.5Ueq(C) for methyl H atoms.

Figures

Fig. 1.
The molecular structure of the title compound, showing displacement ellipsoides drawn at the 30% probability level.
Fig. 2.
The O—H···O hydrogen bond interaction (dotted lines) in the title compound. [Symmetry codes: (i) x, y + 1, z; (ii) -x + 1, y + 1/2, -z + 1/2; (iii) -x + 1, y - 1/2, -z + 1/2.]

Crystal data

C16H16O7F000 = 672
Mr = 320.29Dx = 1.411 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 11.552 (2) Åθ = 11.4–14.2º
b = 12.817 (3) ŵ = 0.11 mm1
c = 10.572 (2) ÅT = 295 (2) K
β = 105.57 (3)ºBlock, colorless
V = 1507.9 (6) Å30.2 × 0.2 × 0.16 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometerθmin = 2.4º
Non–profiled ω/2θ scansh = 0→14
Absorption correction: nonek = −16→2
4251 measured reflectionsl = −13→13
3444 independent reflections3 standard reflections
2176 reflections with I > 2σ(I) every 400 reflections
Rint = 0.030 intensity decay: 2%
θmax = 27.5º

Refinement

Refinement on F2H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0489P)2 + 0.3432P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.050(Δ/σ)max < 0.001
wR(F2) = 0.126Δρmax = 0.23 e Å3
S = 1.02Δρmin = −0.20 e Å3
3444 reflectionsExtinction correction: none
219 parameters

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O1−0.00088 (14)−0.18103 (12)0.14141 (16)0.0519 (4)
O20.09341 (15)−0.33144 (11)0.01850 (15)0.0509 (4)
O30.27941 (14)−0.29798 (11)−0.07081 (15)0.0463 (4)
O40.41661 (13)0.07744 (11)0.09149 (15)0.0434 (4)
O50.24027 (13)0.13828 (11)0.11272 (16)0.0482 (4)
O60.24533 (18)0.48003 (14)−0.05695 (17)0.0619 (5)
H6O0.261 (3)0.541 (3)−0.030 (3)0.107 (12)*
O70.39231 (17)0.54885 (12)0.17566 (19)0.0554 (5)
H7O0.448 (3)0.556 (2)0.244 (3)0.083 (11)*
C10.25245 (18)−0.04039 (15)0.07245 (19)0.0339 (5)
C20.15217 (18)−0.05794 (16)0.1181 (2)0.0374 (5)
H20.1214−0.00470.15940.045*
C30.09822 (18)−0.15538 (17)0.1017 (2)0.0384 (5)
C40.14486 (19)−0.23470 (15)0.0401 (2)0.0369 (5)
C50.24393 (19)−0.21565 (15)−0.00864 (19)0.0348 (5)
C60.29865 (18)−0.11831 (15)0.0089 (2)0.0350 (5)
H60.3657−0.1054−0.02160.042*
C70.31335 (19)0.06225 (15)0.09277 (19)0.0353 (5)
C80.28605 (19)0.24148 (15)0.1316 (2)0.0388 (5)
C90.2473 (2)0.31040 (16)0.0299 (2)0.0421 (5)
H90.19660.2881−0.04950.05*
C100.28413 (19)0.41347 (16)0.0461 (2)0.0402 (5)
C110.35900 (18)0.44546 (15)0.1663 (2)0.0383 (5)
C120.3939 (2)0.37553 (18)0.2672 (2)0.0441 (5)
H120.44240.39780.34780.053*
C130.3579 (2)0.27155 (17)0.2510 (2)0.0444 (5)
H130.3820.2240.31940.053*
C14−0.0468 (2)−0.1053 (2)0.2138 (2)0.0520 (6)
H14A0.0153−0.08510.29010.078*
H14B−0.1131−0.13460.24050.078*
H14C−0.0737−0.04520.15960.078*
C150.0859 (2)−0.38926 (18)0.1315 (3)0.0591 (7)
H15A0.1518−0.37060.20480.089*
H15B0.0893−0.46260.11410.089*
H15C0.0115−0.37350.15140.089*
C160.3815 (2)−0.28499 (19)−0.1210 (3)0.0572 (7)
H16A0.3659−0.2304−0.18550.086*
H16B0.3971−0.349−0.16060.086*
H16C0.4502−0.2668−0.05050.086*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0493 (9)0.0470 (9)0.0685 (11)−0.0157 (8)0.0314 (8)−0.0152 (8)
O20.0682 (11)0.0364 (8)0.0530 (9)−0.0229 (8)0.0249 (8)−0.0078 (7)
O30.0567 (10)0.0310 (8)0.0592 (9)−0.0067 (7)0.0293 (8)−0.0079 (7)
O40.0393 (9)0.0319 (8)0.0603 (10)−0.0038 (7)0.0155 (7)−0.0008 (7)
O50.0411 (8)0.0249 (7)0.0802 (12)−0.0018 (7)0.0189 (8)−0.0017 (7)
O60.0868 (14)0.0336 (9)0.0539 (11)−0.0055 (9)−0.0011 (9)0.0021 (8)
O70.0614 (11)0.0327 (9)0.0638 (11)−0.0104 (8)0.0026 (9)−0.0078 (8)
C10.0359 (11)0.0267 (10)0.0374 (11)−0.0018 (9)0.0069 (9)0.0021 (9)
C20.0389 (11)0.0303 (10)0.0433 (12)−0.0017 (9)0.0112 (9)−0.0036 (9)
C30.0375 (11)0.0394 (12)0.0395 (12)−0.0068 (9)0.0123 (10)−0.0023 (10)
C40.0434 (12)0.0304 (11)0.0357 (11)−0.0090 (9)0.0086 (9)−0.0013 (9)
C50.0426 (12)0.0277 (10)0.0345 (11)−0.0003 (9)0.0110 (9)0.0001 (9)
C60.0350 (11)0.0305 (10)0.0408 (12)−0.0022 (9)0.0124 (9)0.0043 (9)
C70.0381 (12)0.0283 (10)0.0379 (11)−0.0007 (9)0.0075 (9)0.0026 (9)
C80.0370 (11)0.0251 (10)0.0575 (14)−0.0007 (9)0.0182 (10)−0.0037 (10)
C90.0418 (12)0.0322 (11)0.0489 (13)−0.0027 (10)0.0066 (10)−0.0087 (10)
C100.0445 (12)0.0290 (11)0.0457 (13)0.0012 (9)0.0096 (10)−0.0008 (10)
C110.0381 (11)0.0278 (10)0.0494 (13)−0.0009 (9)0.0124 (10)−0.0085 (10)
C120.0439 (12)0.0441 (13)0.0420 (12)−0.0013 (10)0.0074 (10)−0.0054 (10)
C130.0477 (13)0.0381 (12)0.0487 (13)0.0031 (10)0.0150 (11)0.0049 (10)
C140.0499 (13)0.0566 (15)0.0554 (15)−0.0032 (12)0.0241 (12)−0.0083 (12)
C150.0704 (17)0.0391 (13)0.0760 (18)−0.0060 (12)0.0340 (15)0.0078 (13)
C160.0606 (16)0.0463 (14)0.0754 (17)−0.0061 (12)0.0369 (14)−0.0136 (13)

Geometric parameters (Å, °)

O1—C31.361 (2)C5—C61.388 (3)
O1—C141.424 (3)C6—H60.93
O2—C41.367 (2)C8—C131.366 (3)
O2—C151.428 (3)C8—C91.371 (3)
O3—C51.363 (2)C9—C101.384 (3)
O3—C161.427 (3)C9—H90.93
O4—C71.212 (2)C10—C111.393 (3)
O5—C71.343 (2)C11—C121.369 (3)
O5—C81.419 (2)C12—C131.393 (3)
O6—C101.362 (3)C12—H120.93
O6—H6O0.83 (3)C13—H130.93
O7—C111.376 (2)C14—H14A0.96
O7—H7O0.84 (3)C14—H14B0.96
C1—C21.388 (3)C14—H14C0.96
C1—C61.388 (3)C15—H15A0.96
C1—C71.480 (3)C15—H15B0.96
C2—C31.386 (3)C15—H15C0.96
C2—H20.93C16—H16A0.96
C3—C41.391 (3)C16—H16B0.96
C4—C51.397 (3)C16—H16C0.96
C3—O1—C14117.83 (17)C10—C9—H9120.2
C4—O2—C15116.87 (18)O6—C10—C9118.3 (2)
C5—O3—C16118.32 (16)O6—C10—C11122.40 (19)
C7—O5—C8118.20 (16)C9—C10—C11119.3 (2)
C10—O6—H6O109 (2)C12—C11—O7123.8 (2)
C11—O7—H7O108 (2)C12—C11—C10119.94 (19)
C2—C1—C6121.14 (18)O7—C11—C10116.3 (2)
C2—C1—C7120.15 (18)C11—C12—C13121.0 (2)
C6—C1—C7118.70 (18)C11—C12—H12119.5
C3—C2—C1119.46 (19)C13—C12—H12119.5
C3—C2—H2120.3C8—C13—C12118.1 (2)
C1—C2—H2120.3C8—C13—H13120.9
O1—C3—C2124.49 (19)C12—C13—H13120.9
O1—C3—C4115.54 (18)O1—C14—H14A109.5
C2—C3—C4119.97 (19)O1—C14—H14B109.5
O2—C4—C3122.36 (19)H14A—C14—H14B109.5
O2—C4—C5117.33 (19)O1—C14—H14C109.5
C3—C4—C5120.22 (18)H14A—C14—H14C109.5
O3—C5—C6125.10 (18)H14B—C14—H14C109.5
O3—C5—C4115.13 (17)O2—C15—H15A109.5
C6—C5—C4119.77 (18)O2—C15—H15B109.5
C1—C6—C5119.39 (19)H15A—C15—H15B109.5
C1—C6—H6120.3O2—C15—H15C109.5
C5—C6—H6120.3H15A—C15—H15C109.5
O4—C7—O5123.18 (18)H15B—C15—H15C109.5
O4—C7—C1124.89 (19)O3—C16—H16A109.5
O5—C7—C1111.93 (17)O3—C16—H16B109.5
C13—C8—C9122.2 (2)H16A—C16—H16B109.5
C13—C8—O5120.3 (2)O3—C16—H16C109.5
C9—C8—O5117.3 (2)H16A—C16—H16C109.5
C8—C9—C10119.5 (2)H16B—C16—H16C109.5
C8—C9—H9120.2
C6—C1—C2—C30.9 (3)C8—O5—C7—O40.8 (3)
C7—C1—C2—C3−178.15 (18)C8—O5—C7—C1−179.03 (18)
C14—O1—C3—C2−5.1 (3)C2—C1—C7—O4158.2 (2)
C14—O1—C3—C4175.30 (19)C6—C1—C7—O4−21.0 (3)
C1—C2—C3—O1−179.38 (19)C2—C1—C7—O5−22.1 (3)
C1—C2—C3—C40.2 (3)C6—C1—C7—O5158.83 (18)
C15—O2—C4—C3−60.4 (3)C7—O5—C8—C13−79.4 (3)
C15—O2—C4—C5123.0 (2)C7—O5—C8—C9105.9 (2)
O1—C3—C4—O21.2 (3)C13—C8—C9—C101.8 (3)
C2—C3—C4—O2−178.35 (19)O5—C8—C9—C10176.44 (19)
O1—C3—C4—C5177.74 (18)C8—C9—C10—O6179.3 (2)
C2—C3—C4—C5−1.9 (3)C8—C9—C10—C11−0.7 (3)
C16—O3—C5—C60.8 (3)O6—C10—C11—C12179.1 (2)
C16—O3—C5—C4−178.79 (19)C9—C10—C11—C12−0.9 (3)
O2—C4—C5—O3−1.2 (3)O6—C10—C11—O7−0.1 (3)
C3—C4—C5—O3−177.91 (18)C9—C10—C11—O7179.9 (2)
O2—C4—C5—C6179.11 (19)O7—C11—C12—C13−179.4 (2)
C3—C4—C5—C62.4 (3)C10—C11—C12—C131.5 (3)
C2—C1—C6—C5−0.3 (3)C9—C8—C13—C12−1.3 (3)
C7—C1—C6—C5178.76 (18)O5—C8—C13—C12−175.74 (19)
O3—C5—C6—C1179.05 (18)C11—C12—C13—C8−0.4 (3)
C4—C5—C6—C1−1.3 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O6—H6O···O3i0.83 (3)2.13 (4)2.882 (2)150 (3)
O7—H7O···O4ii0.84 (3)2.02 (3)2.855 (3)179 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LX2033).

References

  • Brandenburg, K. (1998). DIAMOND Version 2.1. Crystal Impact GbR. Bonn, Germany.
  • Dawley, R. M. & Flurkey, W. H. (1993). J. Food Sci.58, 609–610.
  • Enraf–Nonius (1994). CAD-4 EXPRESS Enraf–Nonius, Delft, The Netherlands.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). Appl. Cryst.32, 837–838.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Lee, C. W., Son, E. M., Kim, H. S. & Xu, P. (2007). Bio. Med. Chem. Lett.17, 5462–5464. [PubMed]
  • Maeda, K. & Fukuda, M. (1991). J. Soc. Cosmet. Chem.42, 361–368.
  • Nerya, O., Vaya, J., Musa, R., Izrael, S., Arie, R. B. & Tamir, S. (2003). J. Agric. Food Chem.51, 1201–1207. [PubMed]
  • Sheldrick, G. M. (1997). SHELXL97 and SHELXS97 University of Göttingen, Germany.

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