organic compounds
4-[(2-Carboxyethyl)amino]benzoic acid monohydrate
aKey Laboratory of Tropical Biological Resources of the Ministry of Education, Hainan University, Haikou 570228, People's Republic of China
*Correspondence e-mail: wbyuan@fjirsm.ac.cn
In the title compound, C10H11NO4·H2O, the carboxyl group is twisted at a dihedral angle of 6.1 (3)° with respect to the benzene ring. In the crystal, the organic molecules are linked by pairs of O—H⋯O hydrogen bonds involving both carboxyl groups, forming zigzag chains propagating along the b-axis direction. The water molecules form [100] chains linked by O—H⋯O hydrogen bonds. The organic molecule and water chains are cross-linked by N—H⋯Owater and Owater—H⋯O hydrogen bonds, generating (001) sheets.
Experimental
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear; data reduction: CrystalClear; 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: SHELXTL.
Supporting information
10.1107/S1600536812009518/hb6663sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812009518/hb6663Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812009518/hb6663Isup3.cml
The title compound (I) was prepared using a slightly modified published procedure (Yong et al. 2004). A solution of KOH (11.2 g, 0.2 mol) in water (60 ml) was added dropwise to a solution of 3-chloropropanonic acid (10.9 g, 0.1 mol) in water (50 ml). To the resulting alkline solution, p-aminobenzonic(13.7 g, 0.1 mol) was slowly added, and the mixture was refluxed for 36 h. The solution was filtered and cooled to room temperature, then acidified with HCl solution until the desired white precipitated, which were collected by filtration. Pure compound (I) was obstained by crystallizing from methanol. Colourless blocks of (I) were obstained by slow evaporation of methanol solution.
H atoms were positioned geometrically (C–H = 0.95–0.99 Å) and allowed to ride on their parent atoms with Uiso(H) = 1.2 Ueq(C).
The N-substitute β-alanine derivatives, as chelating or bridging muti-caboxylate ligands, have been applied to synthesis various novel metal-organic coordination polymers(Yong et al. 2004). It was firstly reported the reaction of propiolactone with aniline derivatives to synthesis the title compound I (Kurd & Hayao 1952). The molecular structure of the title compound I is shown in Fig. 1.
In the compound I, the carboxyl group attached to the benzene ring is twisted from its plane at 6.05 (29)°. For this compound, there are four main hydrongen bonds, and their distances are 2.622(O3—H1···O1i), 2.662(O2—H2···O4iv), 2.889(O5—H5B···O5iii) and 3.009(N7—H7···O5)Å, respectively. Throngh the intermolecular hydrogen bonds(O3—H1···O1i, O2—H2···O4iv) in carboxyl groups, generating R22(8) loops, two title compound I moleculars connect together and form a Z-type one-dimensional polymer. The crystal waters form the water chains in the structure via hydrogen bonds(O5—H5B···O5iii). Morever, there are hydrogen bonds N7—H7···O5 between the crystal waters and compounds. As a result, all these hydrogen bonds connect the title compond I molculars into a layer (Fig. 2).
Symmetry codes: (i) -x + 3/2, y - 1/2, z; (ii) -x + 1, -y + 1, -z + 1; (iii) x + 1/2, -y + 1/2, -z + 1; (iv) -x + 3/2, y + 1/2, z.
For synthetic background, see: Kurd & Hayao (1952); Yong et al. (2004).
Data collection: CrystalClear (Rigaku, 2005); cell
CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: SHELXTL (Sheldrick, 2008).C10H11NO4·H2O | F(000) = 960 |
Mr = 227.21 | Dx = 1.435 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 4011 reflections |
a = 4.9387 (19) Å | θ = 2.3–27.4° |
b = 19.700 (7) Å | µ = 0.12 mm−1 |
c = 21.616 (8) Å | T = 298 K |
V = 2103.1 (14) Å3 | Prism, colourless |
Z = 8 | 0.50 × 0.20 × 0.10 mm |
Rigaku AFC-7S Mercury diffractometer | 2401 independent reflections |
Radiation source: Rotating Anode | 2059 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.037 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
CCD_Profile_fitting scans | h = −6→6 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −25→17 |
Tmin = 0.944, Tmax = 0.989 | l = −27→28 |
15116 measured reflections |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.167 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0855P)2 + 0.7233P] where P = (Fo2 + 2Fc2)/3 |
2401 reflections | (Δ/σ)max < 0.001 |
146 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C10H11NO4·H2O | V = 2103.1 (14) Å3 |
Mr = 227.21 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 4.9387 (19) Å | µ = 0.12 mm−1 |
b = 19.700 (7) Å | T = 298 K |
c = 21.616 (8) Å | 0.50 × 0.20 × 0.10 mm |
Rigaku AFC-7S Mercury diffractometer | 2401 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 2059 reflections with I > 2σ(I) |
Tmin = 0.944, Tmax = 0.989 | Rint = 0.037 |
15116 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.167 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.21 e Å−3 |
2401 reflections | Δρmin = −0.29 e Å−3 |
146 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O4 | 0.0461 (3) | 0.17797 (7) | 0.60257 (7) | 0.0513 (4) | |
O3 | 0.2084 (3) | 0.20433 (7) | 0.69553 (7) | 0.0560 (4) | |
O1 | 0.9408 (3) | 0.60527 (7) | 0.68389 (8) | 0.0552 (4) | |
C2 | 0.7123 (4) | 0.51980 (9) | 0.62835 (9) | 0.0386 (4) | |
O2 | 1.0540 (3) | 0.58943 (8) | 0.58500 (7) | 0.0570 (4) | |
C8 | −0.0056 (4) | 0.33809 (9) | 0.67078 (9) | 0.0397 (4) | |
H8A | −0.1384 | 0.3739 | 0.6760 | 0.048* | |
H8B | 0.0950 | 0.3338 | 0.7091 | 0.048* | |
C7 | 0.5435 (4) | 0.50574 (9) | 0.67792 (9) | 0.0381 (4) | |
H6 | 0.5525 | 0.5327 | 0.7132 | 0.046* | |
N7 | 0.1779 (3) | 0.35565 (8) | 0.62101 (7) | 0.0420 (4) | |
C6 | 0.3618 (4) | 0.45234 (9) | 0.67594 (9) | 0.0382 (4) | |
H5 | 0.2502 | 0.4438 | 0.7097 | 0.046* | |
C5 | 0.3452 (4) | 0.41113 (9) | 0.62324 (9) | 0.0369 (4) | |
C10 | 0.0490 (4) | 0.21407 (9) | 0.65073 (9) | 0.0395 (4) | |
C9 | −0.1486 (4) | 0.27183 (10) | 0.65677 (10) | 0.0427 (5) | |
H9A | −0.2760 | 0.2618 | 0.6897 | 0.051* | |
H9B | −0.2500 | 0.2764 | 0.6186 | 0.051* | |
C4 | 0.5114 (4) | 0.42647 (10) | 0.57240 (9) | 0.0447 (5) | |
H4 | 0.4999 | 0.4004 | 0.5366 | 0.054* | |
C3 | 0.6909 (4) | 0.47976 (10) | 0.57507 (9) | 0.0450 (5) | |
H3 | 0.7995 | 0.4893 | 0.5410 | 0.054* | |
C1 | 0.9125 (4) | 0.57462 (9) | 0.63300 (9) | 0.0403 (4) | |
O5 | 0.1077 (4) | 0.28799 (9) | 0.49724 (8) | 0.0680 (5) | |
H1 | 0.3415 | 0.1673 | 0.6803 | 0.082* | |
H5A | 0.1216 | 0.3062 | 0.4601 | 0.082* | |
H5B | 0.2810 | 0.2725 | 0.4992 | 0.082* | |
H2 | 1.1723 | 0.6267 | 0.5907 | 0.082* | |
H7 | 0.1518 | 0.3363 | 0.5801 | 0.059 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O4 | 0.0567 (9) | 0.0465 (8) | 0.0507 (9) | 0.0084 (6) | −0.0045 (7) | −0.0030 (6) |
O3 | 0.0587 (9) | 0.0514 (8) | 0.0578 (10) | 0.0159 (7) | −0.0138 (7) | −0.0084 (7) |
O1 | 0.0605 (10) | 0.0455 (8) | 0.0597 (10) | −0.0115 (7) | −0.0070 (7) | −0.0042 (7) |
C2 | 0.0365 (9) | 0.0352 (9) | 0.0441 (10) | −0.0001 (7) | −0.0031 (7) | 0.0057 (7) |
O2 | 0.0542 (9) | 0.0586 (9) | 0.0583 (10) | −0.0170 (7) | −0.0009 (7) | 0.0130 (7) |
C8 | 0.0384 (9) | 0.0364 (9) | 0.0444 (10) | 0.0031 (7) | 0.0034 (8) | −0.0010 (7) |
C7 | 0.0408 (9) | 0.0322 (9) | 0.0412 (10) | 0.0028 (7) | −0.0032 (8) | −0.0012 (7) |
N7 | 0.0443 (9) | 0.0409 (8) | 0.0407 (9) | −0.0052 (7) | 0.0030 (7) | −0.0046 (6) |
C6 | 0.0381 (9) | 0.0366 (9) | 0.0401 (10) | 0.0021 (7) | 0.0020 (7) | 0.0007 (7) |
C5 | 0.0354 (9) | 0.0340 (8) | 0.0414 (10) | 0.0026 (7) | −0.0020 (7) | 0.0020 (7) |
C10 | 0.0386 (9) | 0.0339 (9) | 0.0460 (11) | −0.0030 (7) | 0.0019 (8) | 0.0044 (7) |
C9 | 0.0344 (9) | 0.0407 (10) | 0.0530 (11) | −0.0004 (7) | 0.0003 (8) | −0.0001 (8) |
C4 | 0.0487 (11) | 0.0481 (11) | 0.0372 (10) | −0.0052 (9) | 0.0023 (8) | −0.0043 (8) |
C3 | 0.0447 (10) | 0.0510 (11) | 0.0392 (10) | −0.0048 (8) | 0.0029 (8) | 0.0049 (8) |
C1 | 0.0394 (9) | 0.0375 (9) | 0.0441 (10) | 0.0004 (7) | −0.0030 (8) | 0.0065 (8) |
O5 | 0.0777 (12) | 0.0765 (12) | 0.0498 (10) | −0.0008 (10) | 0.0038 (8) | 0.0037 (8) |
O4—C10 | 1.261 (2) | C7—H6 | 0.9300 |
O3—C10 | 1.263 (2) | N7—C5 | 1.371 (2) |
O3—H1 | 1.0351 | N7—H7 | 0.9720 |
O1—C1 | 1.262 (2) | C6—C5 | 1.401 (3) |
C2—C7 | 1.386 (3) | C6—H5 | 0.9300 |
C2—C3 | 1.400 (3) | C5—C4 | 1.404 (3) |
C2—C1 | 1.468 (3) | C10—C9 | 1.505 (3) |
O2—C1 | 1.284 (2) | C9—H9A | 0.9700 |
O2—H2 | 0.9458 | C9—H9B | 0.9700 |
C8—N7 | 1.448 (3) | C4—C3 | 1.375 (3) |
C8—C9 | 1.515 (3) | C4—H4 | 0.9300 |
C8—H8A | 0.9700 | C3—H3 | 0.9300 |
C8—H8B | 0.9700 | O5—H5A | 0.8817 |
C7—C6 | 1.383 (3) | O5—H5B | 0.9095 |
C10—O3—H1 | 105.0 | N7—C5—C4 | 119.75 (17) |
C7—C2—C3 | 118.57 (17) | C6—C5—C4 | 118.51 (17) |
C7—C2—C1 | 119.96 (17) | O4—C10—O3 | 123.67 (18) |
C3—C2—C1 | 121.45 (17) | O4—C10—C9 | 119.40 (17) |
C1—O2—H2 | 114.0 | O3—C10—C9 | 116.92 (17) |
N7—C8—C9 | 110.43 (16) | C10—C9—C8 | 111.50 (15) |
N7—C8—H8A | 109.6 | C10—C9—H9A | 109.3 |
C9—C8—H8A | 109.6 | C8—C9—H9A | 109.3 |
N7—C8—H8B | 109.6 | C10—C9—H9B | 109.3 |
C9—C8—H8B | 109.6 | C8—C9—H9B | 109.3 |
H8A—C8—H8B | 108.1 | H9A—C9—H9B | 108.0 |
C6—C7—C2 | 121.22 (17) | C3—C4—C5 | 120.54 (18) |
C6—C7—H6 | 119.4 | C3—C4—H4 | 119.7 |
C2—C7—H6 | 119.4 | C5—C4—H4 | 119.7 |
C5—N7—C8 | 122.78 (15) | C4—C3—C2 | 120.87 (18) |
C5—N7—H7 | 115.1 | C4—C3—H3 | 119.6 |
C8—N7—H7 | 119.9 | C2—C3—H3 | 119.6 |
C7—C6—C5 | 120.24 (17) | O1—C1—O2 | 122.35 (18) |
C7—C6—H5 | 119.9 | O1—C1—C2 | 119.08 (17) |
C5—C6—H5 | 119.9 | O2—C1—C2 | 118.57 (17) |
N7—C5—C6 | 121.71 (17) | H5A—O5—H5B | 96.1 |
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7···O5 | 0.97 | 2.04 | 3.009 (2) | 175 |
O2—H2···O4i | 0.95 | 1.74 | 2.662 (2) | 165 |
O3—H1···O1ii | 1.04 | 1.63 | 2.622 (2) | 159 |
O5—H5A···O2iii | 0.88 | 2.44 | 3.103 (2) | 133 |
O5—H5A···O4iv | 0.88 | 2.52 | 3.129 (2) | 127 |
O5—H5B···O5iv | 0.91 | 2.01 | 2.890 (2) | 163 |
Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) −x+3/2, y−1/2, z; (iii) −x+1, −y+1, −z+1; (iv) x+1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C10H11NO4·H2O |
Mr | 227.21 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 298 |
a, b, c (Å) | 4.9387 (19), 19.700 (7), 21.616 (8) |
V (Å3) | 2103.1 (14) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.50 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Rigaku AFC-7S Mercury |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.944, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15116, 2401, 2059 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.167, 1.09 |
No. of reflections | 2401 |
No. of parameters | 146 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.29 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7···O5 | 0.97 | 2.04 | 3.009 (2) | 175 |
O2—H2···O4i | 0.95 | 1.74 | 2.662 (2) | 165 |
O3—H1···O1ii | 1.04 | 1.63 | 2.622 (2) | 159 |
O5—H5A···O2iii | 0.88 | 2.44 | 3.103 (2) | 133 |
O5—H5A···O4iv | 0.88 | 2.52 | 3.129 (2) | 127 |
O5—H5B···O5iv | 0.91 | 2.01 | 2.890 (2) | 163 |
Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) −x+3/2, y−1/2, z; (iii) −x+1, −y+1, −z+1; (iv) x+1/2, −y+1/2, −z+1. |
Acknowledgements
The authors would like to acknowledge the NSFC grants (grant Nos. 20761003, 21061005), the Hainan Natural Science Foundation (grant No. 210011), the Education Department of Hainan Province (grant No. Hjkj2008–23) and Hainan University (grant No. qnjj1169) for financial support.
References
Kurd, C. D. & Hayao, S. (1952). J. Am. Chem. Soc. 74, 5889–5893. Google Scholar
Rigaku (2005). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yong, G. P., Wang, Z. Y. & Cui, Y. (2004). Eur. J. Inorg. Chem. 21, 4317–4323. Web of Science CSD CrossRef Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The N-substitute β-alanine derivatives, as chelating or bridging muti-caboxylate ligands, have been applied to synthesis various novel metal-organic coordination polymers(Yong et al. 2004). It was firstly reported the reaction of propiolactone with aniline derivatives to synthesis the title compound I (Kurd & Hayao 1952). The molecular structure of the title compound I is shown in Fig. 1.
In the compound I, the carboxyl group attached to the benzene ring is twisted from its plane at 6.05 (29)°. For this compound, there are four main hydrongen bonds, and their distances are 2.622(O3—H1···O1i), 2.662(O2—H2···O4iv), 2.889(O5—H5B···O5iii) and 3.009(N7—H7···O5)Å, respectively. Throngh the intermolecular hydrogen bonds(O3—H1···O1i, O2—H2···O4iv) in carboxyl groups, generating R22(8) loops, two title compound I moleculars connect together and form a Z-type one-dimensional polymer. The crystal waters form the water chains in the structure via hydrogen bonds(O5—H5B···O5iii). Morever, there are hydrogen bonds N7—H7···O5 between the crystal waters and compounds. As a result, all these hydrogen bonds connect the title compond I molculars into a layer (Fig. 2).
Symmetry codes: (i) -x + 3/2, y - 1/2, z; (ii) -x + 1, -y + 1, -z + 1; (iii) x + 1/2, -y + 1/2, -z + 1; (iv) -x + 3/2, y + 1/2, z.