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

Dai, W.; Fu, D.-W.

doi:10.1107/S1600536808017960

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1446

doi:10.1107/S1600536808017960

Open

access

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

Wei Dai ^a and Da-Wei Fu ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 31 May 2008; accepted 12 June 2008; online 9 July 2008)

The title compound, C₉H₁₀N₂O₄·H₂O, exists as a zwitterion with a deprotonated carboxyl group and a protonated amine group. The crystal packing is stabilized by intermolecular N—H⋯O and O—H⋯O hydrogen bonds, building sheets parallel to the (001) plane.

Related literature

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

Experimental

Crystal data

C₉H₁₀N₂O₄·H₂O
M_r = 228.21
Monoclinic, P 2₁
a = 6.2349 (12) Å
b = 5.2990 (11) Å
c = 15.727 (3) Å
β = 101.40 (3)°
V = 509.35 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 (2) K
0.30 × 0.25 × 0.15 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.964, T_max = 0.982
5388 measured reflections
1297 independent reflections
1184 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.140
S = 1.14
1297 reflections
153 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3ⁱ	0.89	2.16	2.745 (4)	123
N2—H2B⋯O4ⁱⁱ	0.89	2.30	2.904 (4)	125
O5—H30⋯O4ⁱⁱⁱ	0.92 (6)	1.81 (6)	2.721 (5)	177 (5)
O5—H31⋯O3^iv	0.79 (8)	2.11 (8)	2.809 (4)	148 (6)
Symmetry codes: (i) x, y-1, z; (ii) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (iii) x+1, y, z; (iv) x+1, y-1, z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808017960/rz2221sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808017960/rz2221Isup2.hkl

checkCIF report

Comment top

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 intermolecular N—H···O and O—H···O hydrogen bonds building sheets parallel to the (001) plane (Table 1, Fig. 2).

Related literature top

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

Experimental top

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.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: 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: SHELXL97 (Sheldrick, 2008).

Figures top

	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 b axis. All hydrogen atoms not involved in hydrogen bonding (dashed lines) are omitted for clarity.

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

Crystal data top

C₉H₁₀N₂O₄·H₂O	F(000) = 240
M_r = 228.21	D_x = 1.488 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1458 reflections
a = 6.2349 (12) Å	θ = 3.3–27.5°
b = 5.2990 (11) Å	µ = 0.12 mm⁻¹
c = 15.727 (3) Å	T = 293 K
β = 101.40 (3)°	Block, colourless
V = 509.35 (18) Å³	0.30 × 0.25 × 0.15 mm
Z = 2

Data collection top

Rigaku Mercury2 (2x2 bin mode) diffractometer	1297 independent reflections
Radiation source: fine-focus sealed tube	1184 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −6→6
T_min = 0.964, T_max = 0.982	l = −20→19
5388 measured reflections

Refinement top

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ²(F_o²) + (0.0664P)² + 0.2902P] where P = (F_o² + 2F_c²)/3
1297 reflections	(Δ/σ)_max < 0.001
153 parameters	Δρ_max = 0.36 e Å⁻³
1 restraint	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₉H₁₀N₂O₄·H₂O	V = 509.35 (18) Å³
M_r = 228.21	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.2349 (12) Å	µ = 0.12 mm⁻¹
b = 5.2990 (11) Å	T = 293 K
c = 15.727 (3) Å	0.30 × 0.25 × 0.15 mm
β = 101.40 (3)°

Data collection top

Rigaku Mercury2 (2x2 bin mode) diffractometer	1297 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1184 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.982	R_int = 0.034
5388 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	1 restraint
wR(F²) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	Δρ_max = 0.36 e Å⁻³
1297 reflections	Δρ_min = −0.35 e Å⁻³
153 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
O1	0.3398 (5)	0.1706 (7)	0.0174 (2)	0.0512 (9)
N2	0.2068 (5)	−0.9188 (6)	0.41031 (19)	0.0286 (7)
H2A	0.2056	−1.0468	0.3736	0.043*
H2B	0.0991	−0.9385	0.4394	0.043*
H2D	0.3345	−0.9154	0.4475	0.043*
O3	−0.0544 (4)	−0.3216 (6)	0.34808 (17)	0.0342 (6)
C1	0.3833 (6)	−0.1391 (8)	0.1227 (2)	0.0283 (8)
C7	0.1506 (6)	−0.7322 (7)	0.2635 (2)	0.0301 (8)
H7A	0.2309	−0.8847	0.2560	0.036*
H7B	−0.0026	−0.7631	0.2392	0.036*
O4	−0.1341 (4)	−0.6381 (6)	0.42852 (18)	0.0367 (7)
O2	0.6547 (5)	0.1366 (7)	0.1010 (2)	0.0537 (9)
C5	0.4472 (6)	−0.4434 (9)	0.2352 (2)	0.0346 (9)
H5A	0.5413	−0.5221	0.2807	0.042*
C9	−0.0204 (5)	−0.5355 (7)	0.3814 (2)	0.0243 (7)
C2	0.1690 (6)	−0.2143 (9)	0.0984 (2)	0.0335 (9)
H2C	0.0766	−0.1372	0.0520	0.040*
C3	0.0930 (6)	−0.4068 (9)	0.1441 (2)	0.0330 (8)
H3A	−0.0516	−0.4600	0.1282	0.040*
N1	0.4628 (5)	0.0705 (7)	0.0771 (2)	0.0351 (8)
C8	0.1756 (5)	−0.6791 (7)	0.3613 (2)	0.0231 (7)
H8A	0.3065	−0.5751	0.3798	0.028*
C6	0.5246 (6)	−0.2510 (9)	0.1903 (2)	0.0334 (9)
H6A	0.6694	−0.1982	0.2055	0.040*
C4	0.2310 (6)	−0.5208 (8)	0.2133 (2)	0.0281 (7)
O5	0.6393 (5)	−1.0768 (7)	0.4286 (2)	0.0412 (7)
H30	0.715 (8)	−0.930 (12)	0.427 (3)	0.047 (14)*
H31	0.681 (11)	−1.158 (18)	0.393 (4)	0.08 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0582 (19)	0.050 (2)	0.0455 (16)	0.0021 (17)	0.0115 (14)	0.0193 (17)
N2	0.0280 (14)	0.0290 (16)	0.0305 (14)	0.0084 (13)	0.0095 (11)	0.0063 (14)
O3	0.0334 (13)	0.0275 (14)	0.0409 (14)	0.0068 (12)	0.0057 (11)	0.0025 (13)
C1	0.0351 (17)	0.0278 (19)	0.0241 (15)	−0.0002 (15)	0.0111 (13)	−0.0019 (15)
C7	0.0401 (19)	0.0273 (19)	0.0246 (16)	−0.0030 (16)	0.0109 (14)	−0.0022 (15)
O4	0.0374 (14)	0.0334 (15)	0.0452 (14)	0.0024 (13)	0.0223 (12)	−0.0027 (13)
O2	0.0545 (19)	0.051 (2)	0.0563 (18)	−0.0224 (17)	0.0128 (15)	0.0021 (17)
C5	0.0274 (17)	0.044 (2)	0.0313 (17)	0.0054 (18)	0.0037 (14)	0.0094 (18)
C9	0.0244 (15)	0.0246 (17)	0.0231 (14)	0.0003 (14)	0.0031 (12)	−0.0061 (14)
C2	0.0333 (18)	0.041 (2)	0.0249 (16)	0.0008 (17)	0.0024 (14)	0.0034 (17)
C3	0.0320 (17)	0.040 (2)	0.0263 (16)	−0.0036 (18)	0.0037 (14)	−0.0015 (17)
N1	0.0443 (18)	0.0350 (18)	0.0289 (15)	−0.0024 (17)	0.0143 (14)	−0.0004 (14)
C8	0.0263 (15)	0.0180 (16)	0.0255 (15)	0.0014 (13)	0.0064 (12)	0.0012 (13)
C6	0.0229 (16)	0.045 (2)	0.0330 (17)	−0.0026 (16)	0.0071 (13)	0.0041 (18)
C4	0.0327 (17)	0.0298 (18)	0.0238 (15)	0.0028 (16)	0.0103 (13)	−0.0024 (16)
O5	0.0308 (14)	0.0402 (19)	0.0557 (18)	0.0035 (14)	0.0160 (13)	−0.0028 (15)

Geometric parameters (Å, º) top

O1—N1	1.211 (4)	O2—N1	1.232 (4)
N2—C8	1.478 (5)	C5—C4	1.385 (5)
N2—H2A	0.8900	C5—C6	1.381 (6)
N2—H2B	0.8900	C5—H5A	0.9300
N2—H2D	0.8900	C9—C8	1.524 (5)
O3—C9	1.249 (5)	C2—C3	1.384 (6)
C1—C6	1.374 (5)	C2—H2C	0.9300
C1—C2	1.374 (5)	C3—C4	1.387 (5)
C1—N1	1.461 (5)	C3—H3A	0.9300
C7—C4	1.512 (5)	C8—H8A	0.9800
C7—C8	1.541 (4)	C6—H6A	0.9300
C7—H7A	0.9700	O5—H30	0.92 (6)
C7—H7B	0.9700	O5—H31	0.79 (8)
O4—C9	1.247 (4)

C8—N2—H2A	109.5	C1—C2—H2C	120.5
C8—N2—H2B	109.5	C3—C2—H2C	120.5
H2A—N2—H2B	109.5	C2—C3—C4	120.4 (3)
C8—N2—H2D	109.5	C2—C3—H3A	119.8
H2A—N2—H2D	109.5	C4—C3—H3A	119.8
H2B—N2—H2D	109.5	O1—N1—O2	122.7 (4)
C6—C1—C2	122.0 (4)	O1—N1—C1	119.3 (3)
C6—C1—N1	118.7 (3)	O2—N1—C1	118.0 (3)
C2—C1—N1	119.3 (3)	N2—C8—C9	110.4 (3)
C4—C7—C8	114.0 (3)	N2—C8—C7	109.9 (3)
C4—C7—H7A	108.7	C9—C8—C7	111.7 (3)
C8—C7—H7A	108.7	N2—C8—H8A	108.2
C4—C7—H7B	108.7	C9—C8—H8A	108.2
C8—C7—H7B	108.7	C7—C8—H8A	108.2
H7A—C7—H7B	107.6	C1—C6—C5	118.6 (3)
C4—C5—C6	120.9 (3)	C1—C6—H6A	120.7
C4—C5—H5A	119.6	C5—C6—H6A	120.7
C6—C5—H5A	119.6	C5—C4—C3	119.2 (4)
O4—C9—O3	125.1 (3)	C5—C4—C7	119.8 (3)
O4—C9—C8	118.6 (3)	C3—C4—C7	121.0 (3)
O3—C9—C8	116.3 (3)	H30—O5—H31	101 (6)
C1—C2—C3	118.9 (3)

C6—C1—C2—C3	0.7 (6)	C4—C7—C8—N2	−150.5 (3)
N1—C1—C2—C3	−177.6 (3)	C4—C7—C8—C9	86.6 (4)
C1—C2—C3—C4	0.2 (6)	C2—C1—C6—C5	−0.5 (6)
C6—C1—N1—O1	180.0 (4)	N1—C1—C6—C5	177.8 (4)
C2—C1—N1—O1	−1.7 (5)	C4—C5—C6—C1	−0.7 (6)
C6—C1—N1—O2	0.6 (5)	C6—C5—C4—C3	1.6 (6)
C2—C1—N1—O2	178.9 (4)	C6—C5—C4—C7	179.9 (4)
O4—C9—C8—N2	−4.9 (4)	C2—C3—C4—C5	−1.3 (6)
O3—C9—C8—N2	175.4 (3)	C2—C3—C4—C7	−179.6 (3)
O4—C9—C8—C7	117.7 (4)	C8—C7—C4—C5	59.3 (5)
O3—C9—C8—C7	−61.9 (4)	C8—C7—C4—C3	−122.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3ⁱ	0.89	2.16	2.745 (4)	123
N2—H2B···O4ⁱⁱ	0.89	2.30	2.904 (4)	125
O5—H30···O4ⁱⁱⁱ	0.92 (6)	1.81 (6)	2.721 (5)	177 (5)
O5—H31···O3^iv	0.79 (8)	2.11 (8)	2.809 (4)	148 (6)

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

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₂O₄·H₂O
M_r	228.21
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	6.2349 (12), 5.2990 (11), 15.727 (3)
β (°)	101.40 (3)
V (Å³)	509.35 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.30 × 0.25 × 0.15

Data collection
Diffractometer	Rigaku Mercury2 (2x2 bin mode) diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.964, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	5388, 1297, 1184
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.140, 1.14
No. of reflections	1297
No. of parameters	153
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.35

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3ⁱ	0.89	2.16	2.745 (4)	123.0
N2—H2B···O4ⁱⁱ	0.89	2.30	2.904 (4)	124.8
O5—H30···O4ⁱⁱⁱ	0.92 (6)	1.81 (6)	2.721 (5)	177 (5)
O5—H31···O3^iv	0.79 (8)	2.11 (8)	2.809 (4)	148 (6)

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

Acknowledgements

This work was supported by a Start-up Grant from Southeast University to Professor Ren-Gen Xiong, and by the Excellent Doctor Degree Foundation from Southeast University to D-WF.

References

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