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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2895.
Published online 2009 October 28. doi:  10.1107/S1600536809042792
PMCID: PMC2971080

2-Carb­oxy-1-phenyl­ethanaminium nitrate

Abstract

In the title salt, C9H12NO2 +·NO3 , the cation and anion are linked by a bifurcated N—H(...)(O,O) hydrogen bond. The crystal packing is stabilized by inter­molecular N—H(...)O, O—H(...)O and C—H(...)O hydrogen bonds, which connect neighbouring cations and anions, resulting in a two-dimensional network.

Related literature

For details of the preparation of β-amino acids, see: Cohen et al. (2002 [triangle]); Qu et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2895-scheme1.jpg

Experimental

Crystal data

  • C9H12NO2 +·NO3
  • M r = 228.21
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2895-efi1.jpg
  • a = 6.2017 (12) Å
  • b = 10.313 (2) Å
  • c = 18.077 (4) Å
  • β = 105.36 (3)°
  • V = 1114.9 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 293 K
  • 0.50 × 0.30 × 0.15 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.960, T max = 0.982
  • 11050 measured reflections
  • 2549 independent reflections
  • 1652 reflections with I > 2σ(I)
  • R int = 0.061

Refinement

  • R[F 2 > 2σ(F 2)] = 0.080
  • wR(F 2) = 0.231
  • S = 1.11
  • 2549 reflections
  • 149 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.59 e Å−3
  • Δρmin = −0.23 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: PRPKAPPA (Ferguson, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536809042792/sj2656sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809042792/sj2656Isup2.hkl

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

Acknowledgments

This work was supported by the Technical Fund Financing Projects (No. 9207042464 and 9207041482) from Southeast University to ZRQ.

supplementary crystallographic information

Comment

β-Amino acids are important molecules due to their pharmacological properties. Recently, there has been an increased interest in the enantiomeric preparation of β-amino acids as precursors for the synthesis of novel biologically active compounds (Cohen et al., 2002; Qu et al. 2004).

The title compound C9H12NO2+.NO3- exists as two independent ions linked by bifurcated N—H···O hydrogen bonds (Fig. 1). The crystal structure is stabilized by intermolecular N—H···O, O—H···O and C—H ···O hydrogen bonds (Table 1) which connect neighbouring cations and anions, resulting in a two-dimensional network (Fig. 2).

Experimental

Benzaldehyde (1.59 g, 15 mmol), malonic acid (2.5 g, 24 mmol) and ammonium acetate (3.0 g, 39 mmol) were added in a flask under nitrogen and refluxed for 24 h yielding a white precipitate. After cooling to room temperature, the solution was filtered to yield 3-3mino-3-phenylpropionic acid. This was dissolved in ethanol and nitric acid. After slowly evaporating over a period of 5 d, colorless prism-like crystals of the title compound, suitable for X-ray diffraction experiments were isolated.

Refinement

Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C, N atoms to which they are bonded, with C—H = 0.93 to 1.00 Å, Uiso(H) = 1.2 Ueq(C), N—H = 0.88 Å, Uiso(H)= 1.5 Ueq(N).

Figures

Fig. 1.
The asymmetric unit of the title compound, with displacement ellipsoids drawn at the 30% probability level. Intramolecular hydrogen bonds are drawn as a dashed lines.
Fig. 2.
Packing diagram of the title compound, showing the structure along the b axis. Hydrogen bonds are drawn as dashed lines.

Crystal data

C9H12NO2+·NO3F(000) = 480
Mr = 228.21Dx = 1.360 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1797 reflections
a = 6.2017 (12) Åθ = 3.1–27.5°
b = 10.313 (2) ŵ = 0.11 mm1
c = 18.077 (4) ÅT = 293 K
β = 105.36 (3)°Prism, colorless
V = 1114.9 (4) Å30.50 × 0.30 × 0.15 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer2549 independent reflections
Radiation source: fine-focus sealed tube1652 reflections with I > 2σ(I)
graphiteRint = 0.061
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
CCD_Profile_fitting scansh = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −13→13
Tmin = 0.960, Tmax = 0.982l = −23→23
11050 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.080Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.231H-atom parameters constrained
S = 1.11w = 1/[σ2(Fo2) + (0.0829P)2 + 1.0943P] where P = (Fo2 + 2Fc2)/3
2549 reflections(Δ/σ)max < 0.001
149 parametersΔρmax = 0.59 e Å3
1 restraintΔρmin = −0.23 e Å3

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 (Å2)

xyzUiso*/Ueq
O11.1549 (5)0.1241 (2)0.30410 (14)0.0613 (8)
O20.8967 (5)0.2333 (3)0.34151 (16)0.0631 (8)
H20.92520.18130.37710.095*
N10.7398 (5)0.3900 (2)0.11238 (14)0.0382 (6)
H1A0.60200.38680.08230.066 (12)*
H1B0.76880.46970.13050.050 (10)*
H1C0.83520.36900.08560.050 (11)*
C31.0254 (6)0.2102 (3)0.29593 (19)0.0466 (8)
C40.6953 (6)0.1620 (3)0.14746 (19)0.0442 (8)
C10.7597 (6)0.2980 (3)0.17750 (18)0.0434 (8)
H10.65400.32550.20630.052*
C20.9930 (6)0.3062 (3)0.23070 (19)0.0505 (9)
H2A1.10150.28900.20190.061*
H2B1.01900.39330.25140.061*
C70.5759 (11)−0.0891 (4)0.0971 (3)0.0857 (17)
H70.5361−0.17330.08050.103*
C80.4647 (9)−0.0261 (5)0.1410 (4)0.0903 (18)
H80.3468−0.06750.15410.108*
C50.8088 (8)0.0973 (4)0.1026 (2)0.0620 (11)
H50.92740.13740.08920.074*
C90.5224 (7)0.1002 (4)0.1675 (3)0.0649 (11)
H90.44480.14170.19820.078*
C60.7458 (10)−0.0285 (5)0.0774 (3)0.0817 (16)
H60.8219−0.07110.04660.098*
O30.3218 (4)0.3769 (3)−0.01018 (15)0.0562 (7)
O40.2293 (5)0.3826 (3)0.09586 (15)0.0706 (9)
O5−0.0245 (4)0.3499 (3)−0.00958 (16)0.0597 (7)
N20.1772 (5)0.3697 (3)0.02545 (17)0.0457 (7)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.094 (2)0.0400 (14)0.0476 (15)0.0168 (14)0.0138 (14)0.0082 (11)
O20.0649 (18)0.0546 (16)0.0658 (18)0.0237 (13)0.0100 (14)0.0187 (13)
N10.0436 (15)0.0318 (14)0.0352 (14)−0.0020 (11)0.0035 (12)0.0044 (11)
C30.060 (2)0.0397 (18)0.0345 (17)0.0015 (16)0.0034 (15)−0.0028 (14)
C40.053 (2)0.0337 (16)0.0381 (17)−0.0049 (14)−0.0023 (15)0.0075 (14)
C10.0523 (19)0.0366 (17)0.0377 (17)−0.0064 (14)0.0055 (14)0.0062 (13)
C20.059 (2)0.0430 (19)0.043 (2)−0.0033 (16)0.0017 (17)0.0061 (15)
C70.110 (4)0.037 (2)0.079 (3)−0.010 (3)−0.028 (3)0.002 (2)
C80.081 (3)0.058 (3)0.110 (4)−0.032 (3)−0.012 (3)0.022 (3)
C50.078 (3)0.046 (2)0.056 (2)0.0012 (19)0.009 (2)0.0072 (18)
C90.058 (2)0.051 (2)0.082 (3)−0.0113 (18)0.012 (2)0.011 (2)
C60.125 (5)0.052 (3)0.054 (3)0.017 (3)−0.001 (3)−0.002 (2)
O30.0519 (15)0.0685 (17)0.0521 (15)−0.0016 (12)0.0203 (12)0.0067 (13)
O40.0683 (18)0.105 (2)0.0385 (15)0.0053 (16)0.0137 (13)0.0178 (15)
O50.0421 (14)0.0672 (17)0.0668 (18)−0.0069 (12)0.0093 (12)−0.0081 (14)
N20.0524 (17)0.0380 (15)0.0472 (17)0.0036 (12)0.0142 (14)0.0113 (13)

Geometric parameters (Å, °)

O1—C31.180 (4)C2—H2B0.9700
O2—C31.312 (4)C7—C81.349 (8)
O2—H20.8200C7—C61.352 (8)
N1—C11.492 (4)C7—H70.9300
N1—H1A0.8837C8—C91.401 (7)
N1—H1B0.8848C8—H80.9300
N1—H1C0.8849C5—C61.396 (6)
C3—C21.512 (5)C5—H50.9300
C4—C91.375 (5)C9—H90.9300
C4—C51.378 (5)C6—H60.9300
C4—C11.519 (5)O3—N21.237 (4)
C1—C21.513 (5)O4—N21.235 (4)
C1—H10.9800O5—N21.260 (4)
C2—H2A0.9700
C3—O2—H2109.5C3—C2—H2B109.3
C1—N1—H1A109.0C1—C2—H2B109.3
C1—N1—H1B109.4H2A—C2—H2B108.0
H1A—N1—H1B109.4C8—C7—C6119.2 (4)
C1—N1—H1C110.4C8—C7—H7120.4
H1A—N1—H1C109.4C6—C7—H7120.4
H1B—N1—H1C109.3C7—C8—C9121.7 (5)
O1—C3—O2124.4 (3)C7—C8—H8119.2
O1—C3—C2122.4 (3)C9—C8—H8119.2
O2—C3—C2113.2 (3)C4—C5—C6120.0 (5)
C9—C4—C5119.1 (4)C4—C5—H5120.0
C9—C4—C1118.9 (4)C6—C5—H5120.0
C5—C4—C1122.0 (3)C4—C9—C8119.2 (5)
N1—C1—C2109.3 (3)C4—C9—H9120.4
N1—C1—C4110.3 (3)C8—C9—H9120.4
C2—C1—C4113.3 (3)C7—C6—C5121.0 (5)
N1—C1—H1107.9C7—C6—H6119.5
C2—C1—H1107.9C5—C6—H6119.5
C4—C1—H1107.9O4—N2—O3120.2 (3)
C3—C2—C1111.5 (3)O4—N2—O5119.3 (3)
C3—C2—H2A109.3O3—N2—O5120.5 (3)
C1—C2—H2A109.3

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C8—H8···O2i0.932.563.414 (5)152
C2—H2A···O4ii0.972.463.256 (5)140
O2—H2···O5iii0.822.012.743 (4)148
N1—H1C···O5ii0.882.132.979 (4)160
N1—H1C···O4ii0.882.413.129 (4)139
N1—H1B···O1iv0.881.972.830 (4)166
N1—H1A···O40.882.393.101 (4)138
N1—H1A···O30.882.072.933 (4)165

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2656).

References

  • Cohen, J. H., Abdel-Magid, A. F., Almond, H. R. Jr & Maryanoff, C. A. (2002). Tetrahedron Lett.43, 1977–1981.
  • Ferguson, G. (1999). PRPKAPPA University of Guelph, Canada.
  • Qu, Z.-R., Zhao, H., Wang, Y.-P., Wang, X.-S., Ye, Q., Li, Y.-H., Xiong, R.-G., Abrahams, B. F., Liu, Z.-G. & Xue, Z.-L. (2004). Chem. Eur. J.10, 54–60. [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