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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o3008.
Published online 2010 October 31. doi:  10.1107/S1600536810043412
PMCID: PMC3009012

Anilinium 3-(4-hy­droxy-3-meth­oxy­phenyl)prop-2-enoate

Abstract

The structure of the title salt, C6H8N+·C10H9O4 , is stabilized by N—H(...)O and O—H(...)O hydrogen bonding between 3-(4-hy­droxy-3-meth­oxy­phen­yl)prop-2-enoate anions and anilinium cations, which links the components into a two-dimensional array.

Related literature

For ferulic acid [3-(4-hy­droxy-3-meth­oxy­phen­yl)-2-propenoic acid] and its pharmacological activity, see: Hirabayashi et al. (1995 [triangle]); Liyama et al. (1994 [triangle]); Nomura et al. (2003 [triangle]); Ogiwara et al. (2002 [triangle]); Ou et al. (2003 [triangle]). For crystal structures on hydrogen-bond motifs in organic ammonium salts, see: Ni et al. (2007 [triangle]); Smith et al. (2004 [triangle]).

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Object name is e-66-o3008-scheme1.jpg

Experimental

Crystal data

  • C6H8N+·C10H9O4
  • M r = 287.31
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3008-efi1.jpg
  • a = 6.2047 (7) Å
  • b = 8.2668 (9) Å
  • c = 28.790 (3) Å
  • V = 1476.7 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 296 K
  • 0.30 × 0.28 × 0.25 mm

Data collection

  • Bruker APEXII area-detector diffractometer
  • 7666 measured reflections
  • 1586 independent reflections
  • 1325 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.079
  • S = 1.04
  • 1586 reflections
  • 193 parameters
  • H-atom parameters constrained
  • Δρmax = 0.11 e Å−3
  • Δρmin = −0.11 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810043412/om2374sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810043412/om2374Isup2.hkl

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

Acknowledgments

The authors acknowledge South China Normal University for supporting this work.

supplementary crystallographic information

Comment

3-(4-Hydroxy-3-methoxyphenyl)-2-propenoic acid, also known as ferulic acid, is one of the main endogenous phenolic acids in plant kingdom (Liyama et al., 1994). More attention was paid to the structural modification of ferulic acid owing to its extensive bioactivities including anti-platelet aggregation, anti-oxidation, anti-inflammation, anti-tumor, anti-mutagenicity, antibiosis and immunity enchancement (Hirabayashi et al., 1995; Ogiwara et al., 2002). A series of ferulic acid derivatives were designed and synthesized, such as their salts, esters, ethers and amides, and some of them show the better bioactivities than those of ferulic acid (Nomura et al., 2003; Ou et al., 2003). The molecular and crystal structure of the title compound is presented in this article.

In the asymmetric unit of the title compound, illustrated in Fig. 1, there are an anilinium cation and one singly deprotonated 3-(4-hydroxy-3-methoxyphenyl)prop-2-enoate anion. The bond distances and angles in the title compound are normal (Ni et al., 2007; Smith et al., 2004). In the crystal the cations and anions are self-assembled by various O—H···O and N—H···O hydrogen bonds (Table 1 and Fig. 2) to form a superamolecular network. The network can be viewed as the linkages of two-dimensional 3-(4-hydroxy-3-methoxyphenyl)prop-2-enoate and anilinium layers.

Experimental

A mixture of ferulic acid (0.388 g, 2 mmol) and aniline (0.19 ml, 2 mmol) was stirred with methanol (20 ml) for 0.5 h at room temperature. After several days colourless block-like crystals, suitable for X-ray diffraction analysis, were obtained by slow evaporation of the solution.

Refinement

All H atoms were placed at calculated positions and were treated as riding, with C—H = 0.93–0.96 Å, O—H = 0.82 Å, and N—H = 0.89 Å, respectively, and with Uiso(H) = 1.2 or 1.5Ueq(C,O,N).

Figures

Fig. 1.
The molecular structure showing the atomic-numbering scheme and displacement ellipsoids drawn at the 50% probability level.
Fig. 2.
The molecular packing showing the hydrogen-bonding interactions as broken lines.

Crystal data

C6H8N+·C10H9O4F(000) = 608
Mr = 287.31Dx = 1.292 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2062 reflections
a = 6.2047 (7) Åθ = 2.6–23.1°
b = 8.2668 (9) ŵ = 0.09 mm1
c = 28.790 (3) ÅT = 296 K
V = 1476.7 (3) Å3Block, colourless
Z = 40.30 × 0.28 × 0.25 mm

Data collection

Bruker APEXII area-detector diffractometer1325 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.031
graphiteθmax = 25.2°, θmin = 2.6°
[var phi] and ω scansh = −7→7
7666 measured reflectionsk = −9→6
1586 independent reflectionsl = −32→34

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0375P)2 + 0.170P] where P = (Fo2 + 2Fc2)/3
1586 reflections(Δ/σ)max = 0.001
193 parametersΔρmax = 0.11 e Å3
0 restraintsΔρmin = −0.11 e Å3

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 (Å2)

xyzUiso*/Ueq
C10.3231 (5)0.4376 (3)0.92787 (9)0.0626 (7)
H10.20830.50190.91830.075*
C20.3238 (7)0.2733 (4)0.91830 (10)0.0799 (10)
H20.20920.22720.90220.096*
C30.4919 (7)0.1789 (4)0.93232 (10)0.0794 (10)
H30.49190.06870.92580.095*
C40.6609 (7)0.2469 (4)0.95602 (11)0.0792 (9)
H40.77520.18230.96570.095*
C50.6628 (5)0.4108 (3)0.96573 (9)0.0609 (7)
H50.77780.45700.98170.073*
C60.4920 (4)0.5044 (3)0.95139 (7)0.0422 (5)
C70.8501 (4)1.0202 (3)0.79047 (7)0.0434 (6)
C80.6513 (4)1.0959 (3)0.79226 (7)0.0494 (6)
H80.57771.10160.82040.059*
C90.5597 (4)1.1639 (3)0.75247 (8)0.0509 (6)
H90.42881.21850.75430.061*
C100.6649 (4)1.1496 (3)0.71042 (7)0.0447 (6)
C110.8608 (4)1.0664 (3)0.70800 (7)0.0417 (6)
C120.9540 (4)1.0060 (3)0.74787 (8)0.0443 (6)
H121.08760.95530.74630.053*
C130.9606 (4)0.9557 (3)0.83187 (7)0.0451 (6)
H131.10980.94730.82990.054*
C140.8738 (4)0.9089 (3)0.87121 (7)0.0437 (6)
H140.72500.91670.87440.052*
C150.9992 (4)0.8447 (3)0.91045 (7)0.0375 (5)
C161.1413 (5)0.9702 (4)0.65865 (9)0.0711 (9)
H16A1.12520.86150.66980.107*
H16B1.25241.02380.67600.107*
H16C1.17980.96810.62640.107*
N10.4930 (3)0.6767 (2)0.96199 (5)0.0411 (5)
H1A0.47500.69080.99240.062*
H1B0.38630.72520.94670.062*
H1C0.61840.71950.95330.062*
O11.2000 (3)0.8328 (2)0.90760 (5)0.0467 (4)
O20.8938 (3)0.8013 (2)0.94615 (5)0.0536 (5)
O30.5753 (3)1.2193 (3)0.67198 (5)0.0578 (5)
H3A0.66471.22220.65100.087*
O40.9441 (3)1.0547 (2)0.66423 (5)0.0535 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0678 (18)0.0590 (18)0.0609 (16)−0.0043 (16)−0.0183 (15)−0.0011 (14)
C20.105 (3)0.0604 (19)0.0737 (19)−0.014 (2)−0.012 (2)−0.0107 (17)
C30.116 (3)0.0483 (17)0.074 (2)0.002 (2)0.025 (2)−0.0048 (16)
C40.084 (2)0.063 (2)0.091 (2)0.0227 (19)0.013 (2)0.0134 (17)
C50.0573 (18)0.0609 (18)0.0644 (16)0.0078 (16)−0.0051 (14)0.0067 (15)
C60.0482 (14)0.0475 (14)0.0309 (11)0.0000 (12)0.0042 (11)0.0030 (10)
C70.0476 (14)0.0472 (14)0.0353 (11)0.0003 (12)−0.0062 (11)0.0048 (10)
C80.0545 (16)0.0578 (15)0.0358 (12)0.0016 (14)0.0036 (12)0.0035 (12)
C90.0449 (14)0.0592 (16)0.0486 (13)0.0042 (13)−0.0044 (12)0.0063 (12)
C100.0461 (14)0.0510 (14)0.0370 (12)−0.0037 (13)−0.0093 (11)0.0065 (11)
C110.0457 (14)0.0442 (13)0.0352 (11)−0.0001 (12)−0.0049 (10)0.0044 (11)
C120.0443 (14)0.0475 (14)0.0411 (12)0.0034 (12)−0.0045 (10)0.0058 (11)
C130.0459 (14)0.0503 (14)0.0391 (11)0.0010 (12)−0.0033 (11)0.0009 (11)
C140.0428 (14)0.0536 (14)0.0348 (11)0.0025 (12)−0.0047 (10)−0.0010 (11)
C150.0464 (14)0.0374 (12)0.0286 (11)−0.0038 (12)−0.0052 (10)−0.0022 (9)
C160.0608 (19)0.101 (2)0.0509 (15)0.0196 (19)0.0077 (14)0.0040 (16)
N10.0404 (10)0.0512 (12)0.0317 (9)0.0005 (10)−0.0024 (8)0.0043 (8)
O10.0436 (10)0.0584 (11)0.0381 (8)0.0026 (9)−0.0049 (7)0.0040 (8)
O20.0523 (10)0.0775 (12)0.0310 (8)−0.0123 (10)−0.0013 (7)0.0068 (8)
O30.0490 (10)0.0807 (12)0.0439 (9)0.0115 (10)−0.0081 (8)0.0188 (10)
O40.0577 (11)0.0665 (11)0.0364 (8)0.0128 (10)−0.0014 (8)0.0083 (8)

Geometric parameters (Å, °)

C1—C61.365 (4)C10—O31.366 (3)
C1—C21.386 (4)C10—C111.399 (3)
C1—H10.9300C11—O41.365 (3)
C2—C31.363 (5)C11—C121.379 (3)
C2—H20.9300C12—H120.9300
C3—C41.372 (5)C13—C141.313 (3)
C3—H30.9300C13—H130.9300
C4—C51.384 (4)C14—C151.470 (3)
C4—H40.9300C14—H140.9300
C5—C61.375 (4)C15—O11.253 (3)
C5—H50.9300C15—O21.270 (3)
C6—N11.457 (3)C16—O41.418 (3)
C7—C81.384 (4)C16—H16A0.9600
C7—C121.390 (3)C16—H16B0.9600
C7—C131.475 (3)C16—H16C0.9600
C8—C91.397 (3)N1—H1A0.8900
C8—H80.9300N1—H1B0.8900
C9—C101.381 (3)N1—H1C0.8900
C9—H90.9300O3—H3A0.8200
C6—C1—C2119.5 (3)O4—C11—C12125.8 (2)
C6—C1—H1120.3O4—C11—C10114.18 (19)
C2—C1—H1120.3C12—C11—C10120.1 (2)
C3—C2—C1120.3 (3)C11—C12—C7120.6 (2)
C3—C2—H2119.8C11—C12—H12119.7
C1—C2—H2119.8C7—C12—H12119.7
C2—C3—C4119.8 (3)C14—C13—C7127.8 (2)
C2—C3—H3120.1C14—C13—H13116.1
C4—C3—H3120.1C7—C13—H13116.1
C3—C4—C5120.6 (3)C13—C14—C15123.5 (2)
C3—C4—H4119.7C13—C14—H14118.2
C5—C4—H4119.7C15—C14—H14118.2
C6—C5—C4118.9 (3)O1—C15—O2122.9 (2)
C6—C5—H5120.6O1—C15—C14120.3 (2)
C4—C5—H5120.6O2—C15—C14116.8 (2)
C1—C6—C5120.9 (2)O4—C16—H16A109.5
C1—C6—N1120.2 (2)O4—C16—H16B109.5
C5—C6—N1118.9 (2)H16A—C16—H16B109.5
C8—C7—C12119.0 (2)O4—C16—H16C109.5
C8—C7—C13123.2 (2)H16A—C16—H16C109.5
C12—C7—C13117.8 (2)H16B—C16—H16C109.5
C7—C8—C9120.9 (2)C6—N1—H1A109.5
C7—C8—H8119.5C6—N1—H1B109.5
C9—C8—H8119.5H1A—N1—H1B109.5
C10—C9—C8119.5 (2)C6—N1—H1C109.5
C10—C9—H9120.3H1A—N1—H1C109.5
C8—C9—H9120.3H1B—N1—H1C109.5
O3—C10—C9118.8 (2)C10—O3—H3A109.5
O3—C10—C11121.4 (2)C11—O4—C16117.76 (18)
C9—C10—C11119.8 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.891.842.721 (2)170
N1—H1B···O1ii0.891.842.724 (2)170
N1—H1C···O20.891.852.730 (3)170
O3—H3A···O1iii0.822.092.841 (2)151
O3—H3A···O40.822.252.671 (2)112

Symmetry codes: (i) x−1/2, −y+3/2, −z+2; (ii) x−1, y, z; (iii) −x+2, y+1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: OM2374).

References

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  • Ni, S.-F., Feng, W.-J., Guo, H. & Jin, Z.-M. (2007). Acta Cryst. E63, o3866.
  • Nomura, E., Kashiwada, A., Hosoda, A., Nakamura, K., Morishita, H., Tsuno, T. & Taniguchi, H. (2003). Bioorg. Med. Chem.11, 3807–3813. [PubMed]
  • Ogiwara, T., Satoh, K., Kadoma, Y., Murakami, Y., Unten, S., Atsumi, T., Sakagami, H. & Fujisawa, S. (2002). Anticancer Res.22, 2711–2717. [PubMed]
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  • Smith, G., Wermuth, U. D. & Healy, P. C. (2004). Acta Cryst. E60, o1800–o1803.

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