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

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

doi:10.1107/S1600536808011203

organic compounds

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Volume 64| Part 6| June 2008| Page o974

doi:10.1107/S1600536808011203

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(S)-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 17 April 2008; accepted 20 April 2008; online 3 May 2008)

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 ); Arki et al. (2004 ); Hauck et al. (2006 ); Azim et al. (2006 ).

Experimental

Crystal data

C₉H₁₀N₂O₄·H₂O
M_r = 228.21
Orthorhombic, P 2₁ 2₁ 2₁
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 ) 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[F² > 2σ(F²)] = 0.043
wR(F²) = 0.113
S = 1.09
1466 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O1W	0.89	1.88	2.760 (3)	168
N2—H2A⋯O1Wⁱ	0.89	2.43	3.029 (3)	125
N2—H2A⋯O4ⁱⁱ	0.89	2.29	2.913 (3)	127
N2—H2C⋯O3ⁱⁱⁱ	0.89	1.92	2.797 (3)	166
O1W—H1WB⋯O3^iv	0.85	2.23	2.764 (3)	121
O1W—H1WC⋯O4^v	0.85	2.00	2.740 (3)	146
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x-1, y, z; (iv) x-1, y-1, z; (v) x, 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/S1600536808011203/dn2340sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808011203/dn2340Isup2.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 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.

Related literature top

For details of 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 a axis and all hydrogen atoms not involved in hydrogen bonding (dashed lines) were omitted for clarity.

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

Crystal data top

C₉H₁₀N₂O₄·H₂O	F(000) = 480
M_r = 228.21	D_x = 1.476 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1470 reflections
a = 5.3141 (8) Å	θ = 3.0–27.5°
b = 6.2823 (7) Å	µ = 0.12 mm⁻¹
c = 30.752 (4) Å	T = 293 K
V = 1026.7 (2) Å³	Block, colourless
Z = 4	0.25 × 0.20 × 0.20 mm

Data collection top

Rigaku Mercury2 diffractometer	1466 independent reflections
Radiation source: fine-focus sealed tube	1261 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.8°, θ_min = 3.3°
ω scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→8
T_min = 0.970, T_max = 0.974	l = −40→40
10728 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0645P)² + 0.0774P] where P = (F_o² + 2F_c²)/3
1466 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₉H₁₀N₂O₄·H₂O	V = 1026.7 (2) Å³
M_r = 228.21	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.3141 (8) Å	µ = 0.12 mm⁻¹
b = 6.2823 (7) Å	T = 293 K
c = 30.752 (4) Å	0.25 × 0.20 × 0.20 mm

Data collection top

Rigaku Mercury2 diffractometer	1466 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1261 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.974	R_int = 0.046
10728 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.09	Δρ_max = 0.25 e Å⁻³
1466 reflections	Δρ_min = −0.22 e Å⁻³
146 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
O3	0.8183 (3)	0.4808 (3)	0.17549 (6)	0.0391 (4)
N2	0.2254 (4)	0.2416 (3)	0.20604 (6)	0.0346 (5)
H2A	0.2535	0.2749	0.2337	0.052*
H2B	0.1637	0.1101	0.2044	0.052*
H2C	0.1152	0.3328	0.1947	0.052*
O4	0.5036 (4)	0.5887 (3)	0.21776 (6)	0.0452 (5)
O1	1.3141 (4)	−0.0801 (4)	0.00871 (7)	0.0588 (6)
C1	1.0030 (5)	−0.0711 (4)	0.06148 (7)	0.0342 (6)
N1	1.2123 (5)	−0.1761 (4)	0.03883 (7)	0.0410 (5)
C7	0.4109 (5)	0.2328 (4)	0.13231 (8)	0.0369 (6)
H7A	0.2588	0.1496	0.1284	0.044*
H7B	0.3801	0.3735	0.1205	0.044*
C9	0.6059 (5)	0.4594 (4)	0.19280 (7)	0.0301 (5)
C8	0.4651 (4)	0.2532 (4)	0.18137 (7)	0.0283 (5)
H8	0.5704	0.1325	0.1901	0.034*
C3	0.6976 (6)	−0.0771 (4)	0.11762 (8)	0.0391 (6)
H3	0.6180	−0.1481	0.1403	0.047*
C5	0.7376 (5)	0.2308 (4)	0.07239 (8)	0.0376 (6)
H5	0.6850	0.3663	0.0643	0.045*
C4	0.6219 (5)	0.1297 (4)	0.10701 (7)	0.0327 (5)
C2	0.8872 (5)	−0.1774 (4)	0.09522 (8)	0.0405 (6)
H2	0.9366	−0.3146	0.1027	0.049*
C6	0.9322 (5)	0.1322 (4)	0.04943 (8)	0.0397 (6)
H6	1.0122	0.2016	0.0266	0.048*
O2	1.2768 (5)	−0.3521 (4)	0.05090 (7)	0.0589 (6)
O1W	0.0704 (4)	−0.1769 (3)	0.21144 (6)	0.0468 (5)
H1WB	0.0482	−0.2262	0.1860	0.070*
H1WC	0.1824	−0.2497	0.2244	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0300 (9)	0.0402 (10)	0.0470 (10)	−0.0064 (8)	0.0032 (7)	0.0024 (8)
N2	0.0329 (10)	0.0331 (10)	0.0377 (11)	−0.0040 (10)	0.0050 (8)	−0.0008 (9)
O4	0.0382 (10)	0.0407 (10)	0.0568 (11)	−0.0015 (9)	−0.0003 (9)	−0.0179 (9)
O1	0.0581 (13)	0.0682 (14)	0.0501 (12)	0.0028 (12)	0.0185 (10)	−0.0021 (11)
C1	0.0371 (14)	0.0365 (12)	0.0291 (11)	−0.0012 (11)	−0.0015 (10)	−0.0080 (10)
N1	0.0388 (12)	0.0467 (13)	0.0374 (11)	0.0022 (11)	−0.0027 (9)	−0.0075 (10)
C7	0.0366 (13)	0.0428 (13)	0.0311 (12)	0.0021 (12)	−0.0043 (10)	−0.0044 (11)
C9	0.0295 (12)	0.0295 (11)	0.0312 (11)	0.0004 (10)	−0.0057 (9)	0.0031 (10)
C8	0.0274 (11)	0.0284 (11)	0.0293 (11)	−0.0003 (10)	0.0012 (9)	0.0001 (9)
C3	0.0486 (15)	0.0338 (12)	0.0349 (12)	−0.0017 (12)	0.0074 (12)	0.0008 (11)
C5	0.0471 (15)	0.0344 (12)	0.0313 (12)	0.0031 (12)	−0.0031 (11)	0.0021 (10)
C4	0.0348 (13)	0.0351 (12)	0.0283 (11)	−0.0023 (11)	−0.0019 (9)	−0.0050 (10)
C2	0.0537 (16)	0.0315 (12)	0.0364 (12)	0.0009 (12)	0.0017 (12)	0.0013 (11)
C6	0.0473 (15)	0.0415 (14)	0.0304 (11)	0.0002 (12)	0.0038 (12)	0.0001 (11)
O2	0.0594 (14)	0.0560 (12)	0.0612 (13)	0.0206 (12)	0.0009 (12)	−0.0009 (11)
O1W	0.0493 (11)	0.0347 (9)	0.0563 (11)	−0.0032 (9)	−0.0051 (9)	−0.0047 (9)

Geometric parameters (Å, º) top

O3—C9	1.255 (3)	C7—H7B	0.9700
N2—C8	1.484 (3)	C9—C8	1.537 (3)
N2—H2A	0.8900	C8—H8	0.9800
N2—H2B	0.8900	C3—C2	1.374 (4)
N2—H2C	0.8900	C3—C4	1.398 (4)
O4—C9	1.243 (3)	C3—H3	0.9300
O1—N1	1.231 (3)	C5—C4	1.384 (3)
C1—C2	1.379 (4)	C5—C6	1.397 (4)
C1—C6	1.382 (4)	C5—H5	0.9300
C1—N1	1.469 (3)	C2—H2	0.9300
N1—O2	1.216 (3)	C6—H6	0.9300
C7—C4	1.511 (3)	O1W—H1WB	0.8502
C7—C8	1.541 (3)	O1W—H1WC	0.8496
C7—H7A	0.9700

C8—N2—H2A	109.5	N2—C8—C7	109.62 (18)
C8—N2—H2B	109.5	C9—C8—C7	112.6 (2)
H2A—N2—H2B	109.5	N2—C8—H8	108.1
C8—N2—H2C	109.5	C9—C8—H8	108.1
H2A—N2—H2C	109.5	C7—C8—H8	108.1
H2B—N2—H2C	109.5	C2—C3—C4	121.3 (2)
C2—C1—C6	121.9 (2)	C2—C3—H3	119.3
C2—C1—N1	118.5 (2)	C4—C3—H3	119.3
C6—C1—N1	119.6 (2)	C4—C5—C6	120.9 (2)
O2—N1—O1	123.5 (3)	C4—C5—H5	119.5
O2—N1—C1	118.5 (2)	C6—C5—H5	119.5
O1—N1—C1	118.0 (2)	C5—C4—C3	118.6 (2)
C4—C7—C8	113.6 (2)	C5—C4—C7	121.9 (2)
C4—C7—H7A	108.8	C3—C4—C7	119.5 (2)
C8—C7—H7A	108.8	C3—C2—C1	118.8 (2)
C4—C7—H7B	108.8	C3—C2—H2	120.6
C8—C7—H7B	108.8	C1—C2—H2	120.6
H7A—C7—H7B	107.7	C1—C6—C5	118.4 (2)
O4—C9—O3	125.8 (2)	C1—C6—H6	120.8
O4—C9—C8	118.6 (2)	C5—C6—H6	120.8
O3—C9—C8	115.5 (2)	H1WB—O1W—H1WC	109.4
N2—C8—C9	110.03 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1W	0.89	1.88	2.760 (3)	168
N2—H2A···O1Wⁱ	0.89	2.43	3.029 (3)	125
N2—H2A···O4ⁱⁱ	0.89	2.29	2.913 (3)	127
N2—H2C···O3ⁱⁱⁱ	0.89	1.92	2.797 (3)	166
O1W—H1WB···O3^iv	0.85	2.23	2.764 (3)	121
O1W—H1WC···O4^v	0.85	2.00	2.740 (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.

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₂O₄·H₂O
M_r	228.21
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	5.3141 (8), 6.2823 (7), 30.752 (4)
V (Å³)	1026.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.970, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	10728, 1466, 1261
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.657

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.113, 1.09
No. of reflections	1466
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.22

Computer programs: CrystalClear (Rigaku, 2005), 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—H2B···O1W	0.89	1.88	2.760 (3)	168.4
N2—H2A···O1Wⁱ	0.89	2.43	3.029 (3)	125.1
N2—H2A···O4ⁱⁱ	0.89	2.29	2.913 (3)	126.7
N2—H2C···O3ⁱⁱⁱ	0.89	1.92	2.797 (3)	166.1
O1W—H1WB···O3^iv	0.85	2.23	2.764 (3)	120.6
O1W—H1WC···O4^v	0.85	2.00	2.740 (3)	145.6

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.

Acknowledgements

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

References

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