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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o974.
Published online 2008 May 3. doi:  10.1107/S1600536808011203
PMCID: PMC2961421

(S)-2-Ammonio-3-(4-nitro­phen­yl)propanoate monohydrate

Abstract

The title compound, C9H10N2O4·H2O, exists as a zwitterion with a deprotonated carboxyl group and a protonated amino group. The crystal packing is stabilized by N—H(...)O and O—H(...)O hydrogen bonds, building sheets parallel to the (001) plane. The absolute configuration was deduced from the synthetic pathway.

Related literature

For details of α-amino acids as precursors for the synthesis of novel biologically active compounds, see: Lucchese et al. (2007 [triangle]); Arki et al. (2004 [triangle]); Hauck et al. (2006 [triangle]); Azim et al. (2006 [triangle]).

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Object name is e-64-0o974-scheme1.jpg

Experimental

Crystal data

  • C9H10N2O4·H2O
  • M r = 228.21
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o974-efi1.jpg
  • a = 5.3141 (8) Å
  • b = 6.2823 (7) Å
  • c = 30.752 (4) Å
  • V = 1026.7 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 293 (2) K
  • 0.25 × 0.20 × 0.20 mm

Data collection

  • Rigaku Mercury2 diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.970, T max = 0.974
  • 10728 measured reflections
  • 1466 independent reflections
  • 1261 reflections with I > 2σ(I)
  • R int = 0.046

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.113
  • S = 1.09
  • 1466 reflections
  • 146 parameters
  • H-atom parameters constrained
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; 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/S1600536808011203/dn2340sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808011203/dn2340Isup2.hkl

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

Acknowledgments

This work was supported by a Start-up Grant from Southeast University to Professor Ren-Gen Xiong.

supplementary crystallographic information

Comment

α-Amino acids are important molecules due to their pharmacological properties. Recently, there has been an increased interest in the enantiomeric preparation of α-amino acids as precursors for the synthesis of novel biologically active compounds (Lucchese et al., (2007); Arki et al., (2004); Hauck et al., (2006); Azim et al., (2006)).Here we report the synthesis and crystal structure of the title compound.

The title compound exists as a zwitter ion with a deprotonated carboxyl group and a protonated amino group (Fig. 1). It crystallizes with one water molecule in the asymmetric unit. The crystal packing is stabilized by N—H···O and O—H···O hydrogen bonds building sheets parallel to the (0 0 1) plane (Table 1, Figs. 2).

The S absolute configuration at C8 is deduced from the synthetic pathway.

Experimental

Under nitrogen protection, 2-amino-3-phenylpropanoic acid (30 mmol), nitric acid (50 mmol) and sulfuric acid (20 mmol) were added in a flask. The mixture was stirred at 110 °C for 3 h. The resulting solution was poured into ice water (100 mL), then filtered and washed with distilled water. The crude product was recrystallized with distilled water to yield colorless block-like crystals, suitable for X-ray analysis.

Refinement

All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.98 Å (methine), 0.97 Å (methylene), 0.93 Å (aromatic) and N—H = 0.89 Å with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(N). H atoms of water molecule were located in difference Fourier maps and included in the subsequent refinement using restraints (O-H= 0.85 (1)Å and H···H= 1.39 (2)Å) with Uiso(H) = 1.5Ueq(O). In the last stage of refinement they were treated as riding on their parent O atom.

In the absence of significant anomalous scattering, the absolute configuration could not be reliably determined by the X-ray analyses and then the Friedel pairs were merged and any references to the Flack parameter were removed.

Figures

Fig. 1.
A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
Fig. 2.
The crystal packing of the title compound viewed along the a axis and all hydrogen atoms not involved in hydrogen bonding (dashed lines) were omitted for clarity.

Crystal data

C9H10N2O4·H2OF000 = 480
Mr = 228.21Dx = 1.476 Mg m3
Orthorhombic, P212121Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1470 reflections
a = 5.3141 (8) Åθ = 3.0–27.5º
b = 6.2823 (7) ŵ = 0.12 mm1
c = 30.752 (4) ÅT = 293 (2) K
V = 1026.7 (2) Å3Block, colourless
Z = 40.25 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer1466 independent reflections
Radiation source: fine-focus sealed tube1261 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.046
Detector resolution: 13.6612 pixels mm-1θmax = 27.8º
T = 293(2) Kθmin = 3.3º
ω scansh = −6→6
Absorption correction: multi-scan(CrystalClear; Rigaku, 2005)k = −8→8
Tmin = 0.970, Tmax = 0.974l = −40→40
10728 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.113  w = 1/[σ2(Fo2) + (0.0645P)2 + 0.0774P] where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
1466 reflectionsΔρmax = 0.25 e Å3
146 parametersΔρmin = −0.22 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O30.8183 (3)0.4808 (3)0.17549 (6)0.0391 (4)
N20.2254 (4)0.2416 (3)0.20604 (6)0.0346 (5)
H2A0.25350.27490.23370.052*
H2B0.16370.11010.20440.052*
H2C0.11520.33280.19470.052*
O40.5036 (4)0.5887 (3)0.21776 (6)0.0452 (5)
O11.3141 (4)−0.0801 (4)0.00871 (7)0.0588 (6)
C11.0030 (5)−0.0711 (4)0.06148 (7)0.0342 (6)
N11.2123 (5)−0.1761 (4)0.03883 (7)0.0410 (5)
C70.4109 (5)0.2328 (4)0.13231 (8)0.0369 (6)
H7A0.25880.14960.12840.044*
H7B0.38010.37350.12050.044*
C90.6059 (5)0.4594 (4)0.19280 (7)0.0301 (5)
C80.4651 (4)0.2532 (4)0.18137 (7)0.0283 (5)
H80.57040.13250.19010.034*
C30.6976 (6)−0.0771 (4)0.11762 (8)0.0391 (6)
H30.6180−0.14810.14030.047*
C50.7376 (5)0.2308 (4)0.07239 (8)0.0376 (6)
H50.68500.36630.06430.045*
C40.6219 (5)0.1297 (4)0.10701 (7)0.0327 (5)
C20.8872 (5)−0.1774 (4)0.09522 (8)0.0405 (6)
H20.9366−0.31460.10270.049*
C60.9322 (5)0.1322 (4)0.04943 (8)0.0397 (6)
H61.01220.20160.02660.048*
O21.2768 (5)−0.3521 (4)0.05090 (7)0.0589 (6)
O1W0.0704 (4)−0.1769 (3)0.21144 (6)0.0468 (5)
H1WB0.0482−0.22620.18600.070*
H1WC0.1824−0.24970.22440.070*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O30.0300 (9)0.0402 (10)0.0470 (10)−0.0064 (8)0.0032 (7)0.0024 (8)
N20.0329 (10)0.0331 (10)0.0377 (11)−0.0040 (10)0.0050 (8)−0.0008 (9)
O40.0382 (10)0.0407 (10)0.0568 (11)−0.0015 (9)−0.0003 (9)−0.0179 (9)
O10.0581 (13)0.0682 (14)0.0501 (12)0.0028 (12)0.0185 (10)−0.0021 (11)
C10.0371 (14)0.0365 (12)0.0291 (11)−0.0012 (11)−0.0015 (10)−0.0080 (10)
N10.0388 (12)0.0467 (13)0.0374 (11)0.0022 (11)−0.0027 (9)−0.0075 (10)
C70.0366 (13)0.0428 (13)0.0311 (12)0.0021 (12)−0.0043 (10)−0.0044 (11)
C90.0295 (12)0.0295 (11)0.0312 (11)0.0004 (10)−0.0057 (9)0.0031 (10)
C80.0274 (11)0.0284 (11)0.0293 (11)−0.0003 (10)0.0012 (9)0.0001 (9)
C30.0486 (15)0.0338 (12)0.0349 (12)−0.0017 (12)0.0074 (12)0.0008 (11)
C50.0471 (15)0.0344 (12)0.0313 (12)0.0031 (12)−0.0031 (11)0.0021 (10)
C40.0348 (13)0.0351 (12)0.0283 (11)−0.0023 (11)−0.0019 (9)−0.0050 (10)
C20.0537 (16)0.0315 (12)0.0364 (12)0.0009 (12)0.0017 (12)0.0013 (11)
C60.0473 (15)0.0415 (14)0.0304 (11)0.0002 (12)0.0038 (12)0.0001 (11)
O20.0594 (14)0.0560 (12)0.0612 (13)0.0206 (12)0.0009 (12)−0.0009 (11)
O1W0.0493 (11)0.0347 (9)0.0563 (11)−0.0032 (9)−0.0051 (9)−0.0047 (9)

Geometric parameters (Å, °)

O3—C91.255 (3)C7—H7B0.9700
N2—C81.484 (3)C9—C81.537 (3)
N2—H2A0.8900C8—H80.9800
N2—H2B0.8900C3—C21.374 (4)
N2—H2C0.8900C3—C41.398 (4)
O4—C91.243 (3)C3—H30.9300
O1—N11.231 (3)C5—C41.384 (3)
C1—C21.379 (4)C5—C61.397 (4)
C1—C61.382 (4)C5—H50.9300
C1—N11.469 (3)C2—H20.9300
N1—O21.216 (3)C6—H60.9300
C7—C41.511 (3)O1W—H1WB0.8502
C7—C81.541 (3)O1W—H1WC0.8496
C7—H7A0.9700
C8—N2—H2A109.5N2—C8—C7109.62 (18)
C8—N2—H2B109.5C9—C8—C7112.6 (2)
H2A—N2—H2B109.5N2—C8—H8108.1
C8—N2—H2C109.5C9—C8—H8108.1
H2A—N2—H2C109.5C7—C8—H8108.1
H2B—N2—H2C109.5C2—C3—C4121.3 (2)
C2—C1—C6121.9 (2)C2—C3—H3119.3
C2—C1—N1118.5 (2)C4—C3—H3119.3
C6—C1—N1119.6 (2)C4—C5—C6120.9 (2)
O2—N1—O1123.5 (3)C4—C5—H5119.5
O2—N1—C1118.5 (2)C6—C5—H5119.5
O1—N1—C1118.0 (2)C5—C4—C3118.6 (2)
C4—C7—C8113.6 (2)C5—C4—C7121.9 (2)
C4—C7—H7A108.8C3—C4—C7119.5 (2)
C8—C7—H7A108.8C3—C2—C1118.8 (2)
C4—C7—H7B108.8C3—C2—H2120.6
C8—C7—H7B108.8C1—C2—H2120.6
H7A—C7—H7B107.7C1—C6—C5118.4 (2)
O4—C9—O3125.8 (2)C1—C6—H6120.8
O4—C9—C8118.6 (2)C5—C6—H6120.8
O3—C9—C8115.5 (2)H1WB—O1W—H1WC109.4
N2—C8—C9110.03 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2B···O1W0.891.882.760 (3)168
N2—H2A···O1Wi0.892.433.029 (3)125
N2—H2A···O4ii0.892.292.913 (3)127
N2—H2C···O3iii0.891.922.797 (3)166
O1W—H1WB···O3iv0.852.232.764 (3)121
O1W—H1WC···O4v0.852.002.740 (3)146

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2340).

References

  • Arki, A., Tourwe, D., Solymar, M., Fueloep, F., Armstrong, D. W. & Peter, A. (2004). Chromatographia, 60, S43–S54.
  • Azim, A., Shah, V. & Doncel, G.-F. (2006). Bioconjugate Chem.17, 1523–1529. [PubMed]
  • Hauck, T., Sunkel, K. & Beck, W. (2006). Z. Anorg. Allg. Chem 632, 2305-2309.
  • Lucchese, G., Stufano, A. & Trost, B. (2007). Amino Acids, 33, 703–707. [PubMed]
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography