Ammonium (E)-3-(4-hy­droxy-3-meth­oxy­phen­yl)prop-2-enoate monohydrate

In structure of the title compound ammonium ferulate monohydrate, NH₄⁺·C₁₀H₉O₄⁻·H₂O, O—H...O and N—H...O hydrogen bonds link the ammonium cations, ferulate anions and water mol­ecules into a three-dimensional array. The ferulate anion is approximately planar, with a maximum deviation of 0.307 (2) Å.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.043
• wR factor = 0.111
• Data-to-parameter ratio = 12.6

checkCIF/PLATON results

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Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.599          6
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          7
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

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

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S1. 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). Attention was paid to the structural modifications 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 ammonium cation, one singly deprotonated 3-(4-hydroxy-3-methoxyphenyl)-2-propenoate anion, and one water molecule. The molecules are self-assembled by various O—H···O and N—H···O hydrogen bonds (Table 1 and Fig. 2), resulting in the formation of a three-dimensional supramolecular network.

Related literature

For the biological activity of ferulic acid, see: Hirabayashi et al. (1995); Liyama et al. (1994); Nomura et al. (2003); Ogiwara et al. (2002); Ou et al. (2003).

S2. Experimental

A mixture of ferulic acid (0.388 g, 2 mmol) and ammonia (0.15 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.

S3. Refinement

The H atoms of water molecule and ammonium cation were found from difference Fourier maps and refined isotropically with a restraint of O—H = 0.87 (2) Å and H_1W···H_2W = 1.39 (2) Å for water molecule, N—H = 0.87 (2) Å for ammonium cation, and U_iso(H) = 1.5 U_eq(O, N). All other H atoms were positioned geometrically and refined as riding, with C—H = 0.93–0.96 Å, O—H = 0.82 Å, and with U_iso(H) = 1.2 or 1.5 U_eq(C, O).

Computing details

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

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

Ammonium (E)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoate monohydrate

Crystal data

NH4^+·C10H9O4^−·H2O	F(000) = 488
Mr = 229.23	Dx = 1.305 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1012 reflections
a = 8.6613 (19) Å	θ = 2.5–21.0°
b = 8.3282 (18) Å	µ = 0.11 mm^−1
c = 16.457 (4) Å	T = 296 K
β = 100.525 (3)°	Block, colourless
V = 1167.1 (5) Å^3	0.30 × 0.27 × 0.26 mm
Z = 4

Data collection

Bruker APEXII diffractometer	1348 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.040
Graphite monochromator	θmax = 25.2°, θmin = 2.5°
φ and ω scan	h = −9→10
5831 measured reflections	k = −9→9
2090 independent reflections	l = −19→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.111	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 0.106P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
2090 reflections	Δρmax = 0.18 e Å^−3
166 parameters	Δρmin = −0.18 e Å^−3
7 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (2)

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.9208 (2)	−0.0647 (2)	0.33845 (13)	0.0374 (5)
C2	0.9382 (2)	0.0503 (2)	0.27793 (12)	0.0361 (5)
C3	0.8765 (2)	0.2015 (2)	0.28226 (13)	0.0413 (5)
H3	0.8884	0.2782	0.2428	0.050*
C4	0.7969 (2)	0.2398 (3)	0.34519 (14)	0.0432 (6)
H4	0.7547	0.3421	0.3470	0.052*
C5	0.7786 (2)	0.1292 (2)	0.40548 (13)	0.0387 (5)
C6	0.8419 (2)	−0.0247 (2)	0.40114 (13)	0.0402 (5)
H6	0.8306	−0.1007	0.4410	0.048*
C7	0.9605 (3)	−0.3375 (3)	0.38312 (16)	0.0617 (7)
H7A	1.0047	−0.3081	0.4389	0.093*
H7B	1.0094	−0.4342	0.3687	0.093*
H7C	0.8496	−0.3550	0.3785	0.093*
C8	0.6979 (2)	0.1798 (3)	0.47158 (13)	0.0438 (6)
H8	0.6529	0.2815	0.4650	0.053*
C9	0.6790 (2)	0.1034 (3)	0.53912 (13)	0.0438 (6)
H9	0.7113	−0.0031	0.5454	0.053*
C10	0.6093 (3)	0.1780 (3)	0.60560 (14)	0.0413 (5)
O1	0.98669 (18)	−0.21136 (16)	0.32848 (9)	0.0492 (4)
O2	1.01519 (18)	0.00231 (17)	0.21705 (9)	0.0479 (4)
H2	1.0125	0.0744	0.1829	0.072*
O3	0.5464 (2)	0.31626 (18)	0.59297 (9)	0.0557 (5)
O4	0.61918 (18)	0.10581 (17)	0.67298 (9)	0.0503 (4)
N1	0.6808 (3)	0.7821 (2)	0.69610 (14)	0.0506 (5)
H10	0.674 (3)	0.894 (2)	0.6905 (15)	0.076*
H11	0.595 (2)	0.740 (3)	0.7154 (16)	0.076*
H12	0.685 (3)	0.733 (3)	0.6460 (12)	0.076*
H13	0.764 (2)	0.748 (3)	0.7335 (14)	0.076*
O1W	0.3143 (2)	0.3867 (2)	0.45407 (11)	0.0698 (6)
H1W	0.381 (3)	0.358 (3)	0.4970 (14)	0.105*
H2W	0.340 (3)	0.481 (2)	0.4400 (18)	0.105*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0408 (12)	0.0330 (12)	0.0394 (13)	−0.0007 (9)	0.0098 (10)	−0.0022 (9)
C2	0.0411 (12)	0.0403 (12)	0.0302 (12)	−0.0040 (10)	0.0150 (10)	−0.0019 (9)
C3	0.0522 (14)	0.0365 (12)	0.0379 (13)	0.0032 (10)	0.0157 (11)	0.0069 (10)
C4	0.0514 (14)	0.0374 (12)	0.0436 (14)	0.0050 (10)	0.0160 (11)	0.0022 (10)
C5	0.0458 (13)	0.0380 (12)	0.0351 (12)	0.0004 (10)	0.0146 (10)	−0.0029 (10)
C6	0.0506 (13)	0.0395 (12)	0.0325 (12)	−0.0025 (10)	0.0128 (10)	0.0036 (10)
C7	0.0783 (19)	0.0395 (14)	0.0704 (19)	0.0025 (12)	0.0220 (15)	0.0129 (12)
C8	0.0524 (14)	0.0392 (12)	0.0431 (14)	0.0014 (10)	0.0171 (11)	−0.0034 (10)
C9	0.0572 (14)	0.0362 (12)	0.0414 (14)	0.0010 (11)	0.0182 (11)	−0.0016 (10)
C10	0.0491 (14)	0.0399 (13)	0.0374 (13)	−0.0037 (11)	0.0143 (11)	−0.0042 (11)
O1	0.0673 (10)	0.0356 (9)	0.0503 (10)	0.0052 (7)	0.0253 (8)	0.0039 (7)
O2	0.0635 (10)	0.0432 (9)	0.0443 (10)	0.0073 (8)	0.0290 (8)	0.0043 (7)
O3	0.0868 (13)	0.0443 (10)	0.0416 (10)	0.0147 (8)	0.0259 (9)	0.0026 (7)
O4	0.0731 (11)	0.0449 (9)	0.0375 (9)	0.0043 (8)	0.0223 (8)	0.0025 (7)
N1	0.0660 (15)	0.0430 (12)	0.0436 (13)	−0.0077 (11)	0.0120 (11)	0.0037 (10)
O1W	0.0854 (14)	0.0635 (12)	0.0582 (13)	0.0016 (11)	0.0068 (10)	−0.0008 (10)

Geometric parameters (Å, º)

C1—O1	1.371 (2)	C7—H7C	0.9600
C1—C6	1.378 (3)	C8—C9	1.317 (3)
C1—C2	1.409 (3)	C8—H8	0.9300
C2—O2	1.361 (2)	C9—C10	1.480 (3)
C2—C3	1.375 (3)	C9—H9	0.9300
C3—C4	1.383 (3)	C10—O4	1.250 (2)
C3—H3	0.9300	C10—O3	1.274 (2)
C4—C5	1.384 (3)	O2—H2	0.8200
C4—H4	0.9300	N1—H10	0.942 (17)
C5—C6	1.401 (3)	N1—H11	0.927 (17)
C5—C8	1.458 (3)	N1—H12	0.926 (17)
C6—H6	0.9300	N1—H13	0.903 (17)
C7—O1	1.428 (2)	O1W—H1W	0.863 (16)
C7—H7A	0.9600	O1W—H2W	0.863 (16)
C7—H7B	0.9600
O1—C1—C6	125.42 (19)	O1—C7—H7C	109.5
O1—C1—C2	114.84 (18)	H7A—C7—H7C	109.5
C6—C1—C2	119.74 (19)	H7B—C7—H7C	109.5
O2—C2—C3	123.65 (18)	C9—C8—C5	129.8 (2)
O2—C2—C1	116.80 (18)	C9—C8—H8	115.1
C3—C2—C1	119.54 (18)	C5—C8—H8	115.1
C2—C3—C4	120.12 (19)	C8—C9—C10	123.5 (2)
C2—C3—H3	119.9	C8—C9—H9	118.3
C4—C3—H3	119.9	C10—C9—H9	118.3
C3—C4—C5	121.45 (19)	O4—C10—O3	122.48 (19)
C3—C4—H4	119.3	O4—C10—C9	118.9 (2)
C5—C4—H4	119.3	O3—C10—C9	118.6 (2)
C4—C5—C6	118.34 (19)	C1—O1—C7	117.54 (17)
C4—C5—C8	118.43 (19)	C2—O2—H2	109.5
C6—C5—C8	123.21 (19)	H10—N1—H11	111 (2)
C1—C6—C5	120.79 (19)	H10—N1—H12	111 (2)
C1—C6—H6	119.6	H11—N1—H12	108 (2)
C5—C6—H6	119.6	H10—N1—H13	114 (2)
O1—C7—H7A	109.5	H11—N1—H13	104 (2)
O1—C7—H7B	109.5	H12—N1—H13	108 (2)
H7A—C7—H7B	109.5	H1W—O1W—H2W	108 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···O3^i	0.86 (2)	2.07 (2)	2.918 (2)	167 (3)
O1W—H1W···O3	0.86 (2)	1.96 (2)	2.817 (2)	173 (3)
N1—H13···O4^ii	0.90 (2)	2.06 (2)	2.904 (3)	156 (2)
N1—H12···O1W^i	0.93 (2)	1.93 (2)	2.850 (3)	175 (2)
N1—H11···O1^iii	0.93 (2)	2.25 (2)	3.043 (3)	144 (2)
N1—H11···O2^iii	0.93 (2)	2.14 (2)	2.823 (2)	130 (2)
N1—H10···O4^iv	0.94 (2)	1.83 (2)	2.761 (3)	169 (2)
O2—H2···O3^v	0.82	1.81	2.594 (2)	160

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