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

Zhu, L.-C.

doi:10.1107/S1600536810043412

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o3008

https://doi.org/10.1107/S1600536810043412

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

Li-Cai Zhu ^a ^*

^aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510631, People's Republic of China
^*Correspondence e-mail: licaizhu1977@yahoo.com.cn

(Received 24 October 2010; accepted 25 October 2010; online 31 October 2010)

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 ); Liyama et al. (1994 ); Nomura et al. (2003 ); Ogiwara et al. (2002 ); Ou et al. (2003 ). For crystal structures on hydrogen-bond motifs in organic ammonium salts, see: Ni et al. (2007 ); Smith et al. (2004 ).

Experimental

Crystal data

C₆H₈N⁺·C₁₀H₉O₄⁻
M_r = 287.31
Orthorhombic, P 2₁ 2₁ 2₁
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[F² > 2σ(F²)] = 0.032
wR(F²) = 0.079
S = 1.04
1586 reflections
193 parameters
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.89	1.84	2.721 (2)	170
N1—H1B⋯O1ⁱⁱ	0.89	1.84	2.724 (2)	170
N1—H1C⋯O2	0.89	1.85	2.730 (3)	170
O3—H3A⋯O1ⁱⁱⁱ	0.82	2.09	2.841 (2)	151
O3—H3A⋯O4	0.82	2.25	2.671 (2)	112
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+2]$ ; (ii) x-1, y, z; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810043412/om2374Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For ferulic acid [3-(4-hydroxy-3-methoxyphenyl)-2-propenoic acid] and its pharmacological activity, see: Hirabayashi et al. (1995); Liyama et al. (1994); Nomura et al. (2003); Ogiwara et al. (2002); Ou et al. (2003). For related literature [Please state how they are related], see: Ni et al. (2007); Smith et al. (2004).

Experimental top

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.

Structure description top

For ferulic acid [3-(4-hydroxy-3-methoxyphenyl)-2-propenoic acid] and its pharmacological activity, see: Hirabayashi et al. (1995); Liyama et al. (1994); Nomura et al. (2003); Ogiwara et al. (2002); Ou et al. (2003). For related literature [Please state how they are related], see: Ni et al. (2007); Smith et al. (2004).

Computing details top

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

Figures top

	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.

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

Crystal data top

C₆H₈N⁺·C₁₀H₉O₄⁻	F(000) = 608
M_r = 287.31	D_x = 1.292 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2062 reflections
a = 6.2047 (7) Å	θ = 2.6–23.1°
b = 8.2668 (9) Å	µ = 0.09 mm⁻¹
c = 28.790 (3) Å	T = 296 K
V = 1476.7 (3) Å³	Block, colourless
Z = 4	0.30 × 0.28 × 0.25 mm

Data collection top

Bruker APEXII area-detector diffractometer	1325 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 25.2°, θ_min = 2.6°
φ and ω scans	h = −7→7
7666 measured reflections	k = −9→6
1586 independent reflections	l = −32→34

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0375P)² + 0.170P] where P = (F_o² + 2F_c²)/3
1586 reflections	(Δ/σ)_max = 0.001
193 parameters	Δρ_max = 0.11 e Å⁻³
0 restraints	Δρ_min = −0.11 e Å⁻³

Crystal data top

C₆H₈N⁺·C₁₀H₉O₄⁻	V = 1476.7 (3) Å³
M_r = 287.31	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.2047 (7) Å	µ = 0.09 mm⁻¹
b = 8.2668 (9) Å	T = 296 K
c = 28.790 (3) Å	0.30 × 0.28 × 0.25 mm

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 1.04	Δρ_max = 0.11 e Å⁻³
1586 reflections	Δρ_min = −0.11 e Å⁻³
193 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	0.3231 (5)	0.4376 (3)	0.92787 (9)	0.0626 (7)
H1	0.2083	0.5019	0.9183	0.075*
C2	0.3238 (7)	0.2733 (4)	0.91830 (10)	0.0799 (10)
H2	0.2092	0.2272	0.9022	0.096*
C3	0.4919 (7)	0.1789 (4)	0.93232 (10)	0.0794 (10)
H3	0.4919	0.0687	0.9258	0.095*
C4	0.6609 (7)	0.2469 (4)	0.95602 (11)	0.0792 (9)
H4	0.7752	0.1823	0.9657	0.095*
C5	0.6628 (5)	0.4108 (3)	0.96573 (9)	0.0609 (7)
H5	0.7778	0.4570	0.9817	0.073*
C6	0.4920 (4)	0.5044 (3)	0.95139 (7)	0.0422 (5)
C7	0.8501 (4)	1.0202 (3)	0.79047 (7)	0.0434 (6)
C8	0.6513 (4)	1.0959 (3)	0.79226 (7)	0.0494 (6)
H8	0.5777	1.1016	0.8204	0.059*
C9	0.5597 (4)	1.1639 (3)	0.75247 (8)	0.0509 (6)
H9	0.4288	1.2185	0.7543	0.061*
C10	0.6649 (4)	1.1496 (3)	0.71042 (7)	0.0447 (6)
C11	0.8608 (4)	1.0664 (3)	0.70800 (7)	0.0417 (6)
C12	0.9540 (4)	1.0060 (3)	0.74787 (8)	0.0443 (6)
H12	1.0876	0.9553	0.7463	0.053*
C13	0.9606 (4)	0.9557 (3)	0.83187 (7)	0.0451 (6)
H13	1.1098	0.9473	0.8299	0.054*
C14	0.8738 (4)	0.9089 (3)	0.87121 (7)	0.0437 (6)
H14	0.7250	0.9167	0.8744	0.052*
C15	0.9992 (4)	0.8447 (3)	0.91045 (7)	0.0375 (5)
C16	1.1413 (5)	0.9702 (4)	0.65865 (9)	0.0711 (9)
H16A	1.1252	0.8615	0.6698	0.107*
H16B	1.2524	1.0238	0.6760	0.107*
H16C	1.1798	0.9681	0.6264	0.107*
N1	0.4930 (3)	0.6767 (2)	0.96199 (5)	0.0411 (5)
H1A	0.4750	0.6908	0.9924	0.062*
H1B	0.3863	0.7252	0.9467	0.062*
H1C	0.6184	0.7195	0.9533	0.062*
O1	1.2000 (3)	0.8328 (2)	0.90760 (5)	0.0467 (4)
O2	0.8938 (3)	0.8013 (2)	0.94615 (5)	0.0536 (5)
O3	0.5753 (3)	1.2193 (3)	0.67198 (5)	0.0578 (5)
H3A	0.6647	1.2222	0.6510	0.087*
O4	0.9441 (3)	1.0547 (2)	0.66423 (5)	0.0535 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0678 (18)	0.0590 (18)	0.0609 (16)	−0.0043 (16)	−0.0183 (15)	−0.0011 (14)
C2	0.105 (3)	0.0604 (19)	0.0737 (19)	−0.014 (2)	−0.012 (2)	−0.0107 (17)
C3	0.116 (3)	0.0483 (17)	0.074 (2)	0.002 (2)	0.025 (2)	−0.0048 (16)
C4	0.084 (2)	0.063 (2)	0.091 (2)	0.0227 (19)	0.013 (2)	0.0134 (17)
C5	0.0573 (18)	0.0609 (18)	0.0644 (16)	0.0078 (16)	−0.0051 (14)	0.0067 (15)
C6	0.0482 (14)	0.0475 (14)	0.0309 (11)	0.0000 (12)	0.0042 (11)	0.0030 (10)
C7	0.0476 (14)	0.0472 (14)	0.0353 (11)	0.0003 (12)	−0.0062 (11)	0.0048 (10)
C8	0.0545 (16)	0.0578 (15)	0.0358 (12)	0.0016 (14)	0.0036 (12)	0.0035 (12)
C9	0.0449 (14)	0.0592 (16)	0.0486 (13)	0.0042 (13)	−0.0044 (12)	0.0063 (12)
C10	0.0461 (14)	0.0510 (14)	0.0370 (12)	−0.0037 (13)	−0.0093 (11)	0.0065 (11)
C11	0.0457 (14)	0.0442 (13)	0.0352 (11)	−0.0001 (12)	−0.0049 (10)	0.0044 (11)
C12	0.0443 (14)	0.0475 (14)	0.0411 (12)	0.0034 (12)	−0.0045 (10)	0.0058 (11)
C13	0.0459 (14)	0.0503 (14)	0.0391 (11)	0.0010 (12)	−0.0033 (11)	0.0009 (11)
C14	0.0428 (14)	0.0536 (14)	0.0348 (11)	0.0025 (12)	−0.0047 (10)	−0.0010 (11)
C15	0.0464 (14)	0.0374 (12)	0.0286 (11)	−0.0038 (12)	−0.0052 (10)	−0.0022 (9)
C16	0.0608 (19)	0.101 (2)	0.0509 (15)	0.0196 (19)	0.0077 (14)	0.0040 (16)
N1	0.0404 (10)	0.0512 (12)	0.0317 (9)	0.0005 (10)	−0.0024 (8)	0.0043 (8)
O1	0.0436 (10)	0.0584 (11)	0.0381 (8)	0.0026 (9)	−0.0049 (7)	0.0040 (8)
O2	0.0523 (10)	0.0775 (12)	0.0310 (8)	−0.0123 (10)	−0.0013 (7)	0.0068 (8)
O3	0.0490 (10)	0.0807 (12)	0.0439 (9)	0.0115 (10)	−0.0081 (8)	0.0188 (10)
O4	0.0577 (11)	0.0665 (11)	0.0364 (8)	0.0128 (10)	−0.0014 (8)	0.0083 (8)

Geometric parameters (Å, º) top

C1—C6	1.365 (4)	C10—O3	1.366 (3)
C1—C2	1.386 (4)	C10—C11	1.399 (3)
C1—H1	0.9300	C11—O4	1.365 (3)
C2—C3	1.363 (5)	C11—C12	1.379 (3)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.372 (5)	C13—C14	1.313 (3)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.384 (4)	C14—C15	1.470 (3)
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.375 (4)	C15—O1	1.253 (3)
C5—H5	0.9300	C15—O2	1.270 (3)
C6—N1	1.457 (3)	C16—O4	1.418 (3)
C7—C8	1.384 (4)	C16—H16A	0.9600
C7—C12	1.390 (3)	C16—H16B	0.9600
C7—C13	1.475 (3)	C16—H16C	0.9600
C8—C9	1.397 (3)	N1—H1A	0.8900
C8—H8	0.9300	N1—H1B	0.8900
C9—C10	1.381 (3)	N1—H1C	0.8900
C9—H9	0.9300	O3—H3A	0.8200

C6—C1—C2	119.5 (3)	O4—C11—C12	125.8 (2)
C6—C1—H1	120.3	O4—C11—C10	114.18 (19)
C2—C1—H1	120.3	C12—C11—C10	120.1 (2)
C3—C2—C1	120.3 (3)	C11—C12—C7	120.6 (2)
C3—C2—H2	119.8	C11—C12—H12	119.7
C1—C2—H2	119.8	C7—C12—H12	119.7
C2—C3—C4	119.8 (3)	C14—C13—C7	127.8 (2)
C2—C3—H3	120.1	C14—C13—H13	116.1
C4—C3—H3	120.1	C7—C13—H13	116.1
C3—C4—C5	120.6 (3)	C13—C14—C15	123.5 (2)
C3—C4—H4	119.7	C13—C14—H14	118.2
C5—C4—H4	119.7	C15—C14—H14	118.2
C6—C5—C4	118.9 (3)	O1—C15—O2	122.9 (2)
C6—C5—H5	120.6	O1—C15—C14	120.3 (2)
C4—C5—H5	120.6	O2—C15—C14	116.8 (2)
C1—C6—C5	120.9 (2)	O4—C16—H16A	109.5
C1—C6—N1	120.2 (2)	O4—C16—H16B	109.5
C5—C6—N1	118.9 (2)	H16A—C16—H16B	109.5
C8—C7—C12	119.0 (2)	O4—C16—H16C	109.5
C8—C7—C13	123.2 (2)	H16A—C16—H16C	109.5
C12—C7—C13	117.8 (2)	H16B—C16—H16C	109.5
C7—C8—C9	120.9 (2)	C6—N1—H1A	109.5
C7—C8—H8	119.5	C6—N1—H1B	109.5
C9—C8—H8	119.5	H1A—N1—H1B	109.5
C10—C9—C8	119.5 (2)	C6—N1—H1C	109.5
C10—C9—H9	120.3	H1A—N1—H1C	109.5
C8—C9—H9	120.3	H1B—N1—H1C	109.5
O3—C10—C9	118.8 (2)	C10—O3—H3A	109.5
O3—C10—C11	121.4 (2)	C11—O4—C16	117.76 (18)
C9—C10—C11	119.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.89	1.84	2.721 (2)	170
N1—H1B···O1ⁱⁱ	0.89	1.84	2.724 (2)	170
N1—H1C···O2	0.89	1.85	2.730 (3)	170
O3—H3A···O1ⁱⁱⁱ	0.82	2.09	2.841 (2)	151
O3—H3A···O4	0.82	2.25	2.671 (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.

Experimental details

Crystal data
Chemical formula	C₆H₈N⁺·C₁₀H₉O₄⁻
M_r	287.31
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	6.2047 (7), 8.2668 (9), 28.790 (3)
V (Å³)	1476.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.28 × 0.25

Data collection
Diffractometer	Bruker APEXII area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7666, 1586, 1325
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.079, 1.04
No. of reflections	1586
No. of parameters	193
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.11

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.89	1.84	2.721 (2)	169.8
N1—H1B···O1ⁱⁱ	0.89	1.84	2.724 (2)	170.3
N1—H1C···O2	0.89	1.85	2.730 (3)	169.8
O3—H3A···O1ⁱⁱⁱ	0.82	2.09	2.841 (2)	151.3
O3—H3A···O4	0.82	2.25	2.671 (2)	112.2

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.

Acknowledgements

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

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