4-aminophenylacetic acid

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This is the published version of a paper published in Acta Crystallographica Section E:

Structure Reports Online.

Citation for the original published paper (version of record):

Gracin, S., Svärd, M., Fischer, A. (2005) 4-aminophenylacetic acid

Acta Crystallographica Section E: Structure Reports Online, 61(6): O1536-O1537 https://doi.org/10.1107/s1600536805012754

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organic papers

Acta Cryst. (2005). E61, o1919–o1920 doi:10.1107/S1600536805016405 Gracin and Fischer
C8H8O3 o1919

Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

4-Hydroxyphenylacetic acid

Sandra Gracin^aand Andreas Fischer^b*

aDepartment of Chemical Engineering and Technology, Royal Institute of Technology, 100 44 Stockholm, Sweden, and^bInorganic Chemistry, Royal Institute of Technology, 100 44 Stockholm, Sweden

Correspondence e-mail: andif@inorg.kth.se

Key indicators Single-crystal X-ray study T = 299 K

Mean
(C–C) = 0.004 A˚ R factor = 0.044 wR factor = 0.111 Data-to-parameter ratio = 8.6

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

The crystal structure of commercially available 4-hydroxy- phenylacetic acid, C8H8O3, is non-centrosymmetric, with four hydrogen bonds between each molecule and adjacent mol- ecules. The hydrogen bonds link the molecules in the crystal structure into an infinite three-dimensional framework.

Comment

We are currently studying surface phenomena and inter- actions between solid compounds and species in solution in contact with the solid phases. One of the compounds studied is 4-hydroxyphenylacetic acid, (I), the structure of which has not been determined so far. Since knowledge of structure, in particular hydrogen-bonding patterns, is crucial for an understanding of the above-mentioned phenomena, we decided to determine the crystal structure. The quality of the crystals in the sample of the commercially available compound was sufficient for collection of reasonable X-ray diffraction data. Therefore, we did not make any attempts to recrystallize the sample. The results of the structure determination are presented here.

The geometry of the 4-hydroxyphenylacetic acid molecule (Fig. 1) is unexceptional. Although the molecule is not chiral, the compound crystallizes in the non-centrosymmetric space group P212121.

Unlike 4-aminophenylacetic acid, the structure of which has been determined recently (Gracin et al., 2005) and which crystallizes as a zwitterion, 4-hydroxyphenylacetic acid is present as a neutral uncharged molecule, because of the much lower basicity of the OH group compared with that of the NH2

group.

Both phenolic and carboxylic OH groups act as hydrogen- bond donors. Phenol atom O3 also serves as a hydrogen-bond acceptor; the second hydrogen bond uses carbonyl atom O2 as an acceptor (Table 1). The three-dimensional network thus formed is shown in Fig. 2.

Received 4 May 2005 Accepted 23 May 2005 Online 28 May 2005

Experimental

A crystal of the purchased material (Sigma–Aldrich, catalogue No.

H5,000-4) was used for the structure determination.

Crystal data C₈H₈O₃ Mr= 152.15

Orthorhombic, P2₁2₁2₁ a = 5.3100 (3) A˚ b = 9.0392 (4) A˚ c = 15.3871 (8) A˚ V = 738.55 (7) A˚³ Z = 4

Dx= 1.368 Mg m^3

Mo K radiation Cell parameters from 74

reflections

 = 4.5–21.2^

 = 0.10 mm^1 T = 299 K Block, colourless 0.49  0.18  0.16 mm

Data collection

Nonius KappaCCD diffractometer

’ and ! scans

Absorption correction: none 6743 measured reflections 871 independent reflections 706 reflections with I > 2
(I)

Rint= 0.049

max= 26.0^ h = 5 ! 6 k = 10 ! 11 l = 18 ! 18

Refinement Refinement on F² R[F²> 2
(F²)] = 0.044 wR(F²) = 0.111 S = 1.08 871 reflections 101 parameters

H-atom parameters constrained

w = 1/[
²(Fo2

) + (0.0415P)² + 0.28P]

where P = (Fo2

+ 2Fc2

)/3 (
/
)_max< 0.001

max= 0.22 e A˚^3

_min= 0.15 e A˚^3

Extinction correction: SHELXL97 Extinction coefficient: 0.036 (8)

Table 1

Hydrogen-bond geometry (A˚ ,^).

D—H  A D—H H  A D  A D—H  A

O3—H3A  O2ⁱ 0.98 1.71 2.676 (4) 166

O1—H1A  O3ⁱⁱ 0.95 1.74 2.689 (3) 175

Symmetry codes: (i) x þ 2; y ¹₂; z þ¹₂; (ii) x þ³₂; y þ 1; z þ¹₂.

All H atoms were located in a difference Fourier map (C—H = 0.90–1.03 A˚ ) and then included in the refinement using a riding model, with Uiso(H) = 1.2Ueq(carrier atoms). In the absence of significant anomalous dispersion effects, Friedel pairs were averaged.

Data collection: COLLECT (Nonius, 1999); cell refinement:

DIRAX/LSQ (Duisenberg, 1992); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure:

SHELXS97 (Sheldrick, 1997); program(s) used to refine structure:

SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publi- cation: MAXUS (Mackay et al., 1999).

The Swedish Research Council (VR) is acknowledged for providing funding for the single-crystal diffractometer.

References

Brandenburg, K. (2001). DIAMOND. Release 2.1e. Crystal Impact GbR, Bonn, Germany.

Duisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92–96.

Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003).

J. Appl. Cryst. 36, 220–229.

Gracin, S., Sva¨rd, M. & Fischer, A. (2005). Acta Cryst. E61, o1536–o1537.

Mackay, S., Gilmore, C. J., Edwards, C., Stewart, N. & Shankland, K. (1999).

MAXUS. Nonius BV, Delft, The Netherlands, MacScience, Japan, and The University of Glasgow, Scotland.

Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

organic papers

o1920 Gracin and Fischer
C8H8O3 Acta Cryst. (2005). E61, o1919–o1920 Figure 1

The molecule of p-hydroxyphenylacetic acid. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2

Packing diagram of p-hydroxyphenylacetic acid, showing the network formed by hydrogen-bonded acid molecules. The packing is viewed approximately along the a axis of the crystal. Hydrogen bonds are shown as dashed lines.

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Acta Cryst. (2005). E61, o1919–o1920

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Acta Cryst. (2005). E61, o1919–o1920 [https://doi.org/10.1107/S1600536805016405]

4-Hydroxyphenylacetic acid Sandra Gracin and Andreas Fischer

4-Hydroxyphenylacetic acid

Crystal data C8H8O3

Mr = 152.15

Orthorhombic, P212121

Hall symbol: P 2ac 2ab a = 5.3100 (3) Šb = 9.0392 (4) Šc = 15.3871 (8) ŠV = 738.55 (7) ų Z = 4

F(000) = 320 Dx = 1.368 Mg m⁻³

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 74 reflections θ = 4.5–21.2°

µ = 0.10 mm⁻¹ T = 299 K Block, colourless 0.49 × 0.18 × 0.16 mm Data collection

Nonius KappaCCD diffractometer

Radiation source: fine-focus sealed tube φ and ω scans

6743 measured reflections 871 independent reflections

706 reflections with I > 2σ(I) Rint = 0.049

θmax = 26.0°, θmin = 4.5°

h = −5→6 k = −10→11 l = −18→18 Refinement

Refinement on F² Least-squares matrix: full R[F² > 2σ(F²)] = 0.044 wR(F²) = 0.111 S = 1.08 871 reflections 101 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

H-atom parameters constrained w = 1/[σ²(Fo2) + (0.0415P)² + 0.28P]

where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001

Δρmax = 0.22 e Å⁻³ Δρmin = −0.15 e Å⁻³

Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4 Extinction coefficient: 0.036 (8) 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.

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Acta Cryst. (2005). E61, o1919–o1920

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

C3 0.6679 (8) 0.3560 (4) 0.1561 (2) 0.0602 (9)

H3 0.6120 0.4049 0.1018 0.072*

C2 0.8732 (6) 0.2648 (3) 0.15162 (17) 0.0485 (8)

C6 0.8141 (7) 0.1979 (4) 0.29934 (19) 0.0557 (9)

H6 0.8838 0.1379 0.3430 0.067*

C5 0.6080 (6) 0.2880 (3) 0.30619 (18) 0.0518 (8)

C8 0.5346 (7) 0.4459 (3) 0.43709 (18) 0.0522 (8)

C1 0.9466 (6) 0.1847 (4) 0.22287 (18) 0.0547 (8)

H1 1.0998 0.1157 0.2165 0.066*

C4 0.5353 (7) 0.3669 (4) 0.2333 (2) 0.0629 (9)

H4 0.3745 0.4230 0.2343 0.075*

C7 0.4698 (8) 0.3061 (4) 0.3902 (2) 0.0671 (11)

H7A 0.2979 0.3199 0.3823 0.080*

H7B 0.4221 0.2281 0.4226 0.080*

O3 1.0014 (5) 0.2594 (2) 0.07362 (12) 0.0631 (7)

H3A 1.0902 0.1649 0.0648 0.076*

O1 0.3664 (5) 0.4870 (3) 0.49453 (13) 0.0680 (8)

H1A 0.4185 0.5783 0.5193 0.082*

O2 0.7267 (6) 0.5102 (4) 0.42620 (19) 0.0973 (11)

Atomic displacement parameters (Ų)

U¹¹ U²² U³³ U¹² U¹³ U²³

C3 0.075 (2) 0.0557 (19) 0.0498 (17) 0.013 (2) −0.0044 (17) 0.0068 (15) C2 0.0586 (19) 0.0437 (15) 0.0430 (14) 0.0049 (16) 0.0011 (13) 0.0011 (12) C6 0.065 (2) 0.0575 (19) 0.0449 (16) −0.0048 (18) −0.0087 (15) 0.0073 (15) C5 0.0602 (19) 0.0466 (16) 0.0484 (16) −0.0158 (16) 0.0018 (15) −0.0074 (14) C8 0.061 (2) 0.0515 (17) 0.0436 (15) −0.0108 (17) 0.0077 (15) −0.0008 (13) C1 0.0583 (18) 0.0566 (18) 0.0490 (16) 0.0066 (17) −0.0032 (15) 0.0059 (14) C4 0.063 (2) 0.0559 (19) 0.069 (2) 0.0103 (19) 0.0047 (19) −0.0020 (16) C7 0.079 (2) 0.061 (2) 0.0616 (19) −0.027 (2) 0.0211 (19) −0.0136 (16) O3 0.0820 (17) 0.0580 (13) 0.0492 (11) 0.0191 (13) 0.0154 (11) 0.0096 (10) O1 0.0757 (17) 0.0677 (15) 0.0605 (13) −0.0091 (15) 0.0182 (12) −0.0136 (12) O2 0.096 (2) 0.0910 (19) 0.105 (2) −0.0453 (18) 0.0437 (18) −0.0510 (18)

Geometric parameters (Å, º)

C3—C2 1.368 (5) C8—O2 1.186 (4)

C3—C4 1.383 (5) C8—O1 1.310 (4)

C3—H3 0.9915 C8—C7 1.496 (4)

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Acta Cryst. (2005). E61, o1919–o1920

C2—C1 1.371 (4) C1—H1 1.0299

C2—O3 1.381 (3) C4—H4 0.9931

C6—C5 1.368 (5) C7—H7A 0.9291

C6—C1 1.376 (4) C7—H7B 0.8995

C6—H6 0.9402 O3—H3A 0.9850

C5—C4 1.385 (5) O1—H1A 0.9504

C5—C7 1.496 (4)

C2—C3—C4 119.5 (3) C2—C1—C6 119.5 (3)

C2—C3—H3 117.7 C2—C1—H1 117.9

C4—C3—H3 122.6 C6—C1—H1 122.6

C3—C2—C1 120.3 (3) C3—C4—C5 121.1 (3)

C3—C2—O3 117.3 (3) C3—C4—H4 119.2

C1—C2—O3 122.4 (3) C5—C4—H4 119.3

C5—C6—C1 121.8 (3) C8—C7—C5 113.3 (3)

C5—C6—H6 127.1 C8—C7—H7A 100.2

C1—C6—H6 111.1 C5—C7—H7A 112.5

C6—C5—C4 117.9 (3) C8—C7—H7B 117.4

C6—C5—C7 121.6 (3) C5—C7—H7B 122.0

C4—C5—C7 120.5 (3) H7A—C7—H7B 84.4

O2—C8—O1 122.9 (3) C2—O3—H3A 112.7

O2—C8—C7 122.9 (3) C8—O1—H1A 108.6

O1—C8—C7 114.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O3—H3A···O2ⁱ 0.98 1.71 2.676 (4) 166

O1—H1A···O3ⁱⁱ 0.95 1.74 2.689 (3) 175

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