(S)-1-Methoxy­carbonyl-2-(4-nitro­phen­yl)ethanaminium chloride

Wen, X.-C.

doi:10.1107/S1600536808020874

organic compounds

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Volume 64| Part 8| August 2008| Page o1460

doi:10.1107/S1600536808020874

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(S)-1-Methoxycarbonyl-2-(4-nitrophenyl)ethanaminium chloride

Xiao-Chun Wen ^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 2 July 2008; accepted 6 July 2008; online 12 July 2008)

The title compound, C₁₀H₁₃N₂O₄⁺·Cl⁻, comprises a Cl⁻ anion and a protonated aminium cation. The crystal packing is stabilized by cation–anion N—H⋯Cl hydrogen bonds and N—H⋯O hydrogen bonds, building an infinite two-dimensional network parallel to the (001) plane. The S absolute configuration at the chiral center was deduced from the synthetic pathway and confirmed by the X-ray analysis.

Related literature

For details of α-amino acid derivatives as precursors for the synthesis of novel biologically active compounds, see: Lucchese et al. (2007 ); Arki et al. (2004 ); Hauck et al. (2006 ); Dai et al. (2008 ); Azim et al. (2006 ).

Experimental

Crystal data

C₁₀H₁₃N₂O₄⁺·Cl⁻
M_r = 260.67
Monoclinic, P 2₁
a = 4.825 (3) Å
b = 8.426 (3) Å
c = 15.111 (9) Å
β = 95.64 (4)°
V = 611.4 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 298 (2) K
0.25 × 0.18 × 0.17 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.931, T_max = 0.942
6215 measured reflections
2751 independent reflections
2077 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.112
S = 1.03
2751 reflections
154 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 1259 Friedel pairs
Flack parameter: −0.03 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H11B⋯O4ⁱ	0.89	2.31	2.929 (4)	127
N2—H11B⋯Cl1ⁱ	0.89	2.71	3.380 (3)	133
N2—H11C⋯Cl1ⁱⁱ	0.89	2.42	3.175 (3)	143
N2—H11A⋯Cl1	0.89	2.34	3.151 (3)	151
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (ii) x-1, y, 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) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808020874/dn2364sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808020874/dn2364Isup2.hkl

checkCIF report

Comment top

α-Amino acid derivatives are important molecules due to their pharmacological properties. Recently, there has been an increased interest in the enantiomeric preparation of α-amino acid derivatives 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); Dai et al., (2008)). Here we report the crystal structure of the title compound.

The title compound is built up from a Cl^- anion and a protonated amino group cation (Fig. 1). The nitro group and the benzene ring are nearly planar, they are only twisted to each other by a torsion angles of C2-C1-N1-O1 (2.1 (7)° ) and C6-C1-N1-O2 (4.4 (7)° ), and the methyl 2-aminopropanoate substituent group is a zig-zag chain.

The crystal packing is stabilized by cation-anion N—H···Cl H-bonds and N—H···O H-bonds building an infinite two-dimensional network developping parallel to the (0 0 1) plane.(Table 1, Fig. 2).

The S absolute configuration at C8 is deduced from the synthetic pathway and confirmed by the X-ray analyses.

Related literature top

For details of α-amino acid derivatives as precursors for the synthesis of novel biologically active compounds, see: Lucchese et al. (2007); Arki et al. (2004); Hauck et al. (2006); Dai et al. (2008); 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 nitration amino acid was esterified with H₂SO₄ and CH₃OH at 110 °C for 12 h, the crude product was obtained by evaporated the solution, and then recrystallized with distilled water by adding 1 ml HCl 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) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXTL (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. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. The crystal packing of the title compound viewed along the b axis and all hydrogen atoms not involved in hydrogen bonding (dashed lines) were omitted for clarity.

(S)-1-Methoxycarbonyl-2-(4-nitrophenyl)ethanaminium chloride top

Crystal data top

C₁₀H₁₃N₂O₄⁺·Cl⁻	F(000) = 272
M_r = 260.67	D_x = 1.416 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1445 reflections
a = 4.825 (3) Å	θ = 2.4–27.5°
b = 8.426 (3) Å	µ = 0.32 mm⁻¹
c = 15.111 (9) Å	T = 298 K
β = 95.64 (4)°	Block, colourless
V = 611.4 (6) Å³	0.25 × 0.18 × 0.17 mm
Z = 2

Data collection top

Rigaku Mercury2 diffractometer	2751 independent reflections
Radiation source: fine-focus sealed tube	2077 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.4°, θ_min = 2.7°
ω scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.931, T_max = 0.942	l = −19→19
6215 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0476P)² + 0.0855P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2751 reflections	Δρ_max = 0.30 e Å⁻³
154 parameters	Δρ_min = −0.17 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1259 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (9)

Crystal data top

C₁₀H₁₃N₂O₄⁺·Cl⁻	V = 611.4 (6) Å³
M_r = 260.67	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 4.825 (3) Å	µ = 0.32 mm⁻¹
b = 8.426 (3) Å	T = 298 K
c = 15.111 (9) Å	0.25 × 0.18 × 0.17 mm
β = 95.64 (4)°

Data collection top

Rigaku Mercury2 diffractometer	2751 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2077 reflections with I > 2σ(I)
T_min = 0.931, T_max = 0.942	R_int = 0.038
6215 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.112	Δρ_max = 0.30 e Å⁻³
S = 1.03	Δρ_min = −0.17 e Å⁻³
2751 reflections	Absolute structure: Flack (1983), 1259 Friedel pairs
154 parameters	Absolute structure parameter: −0.03 (9)
1 restraint

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 > 2sigma(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
Cl1	0.98552 (15)	0.75535 (11)	0.54873 (5)	0.0499 (2)
O3	0.8079 (4)	0.7690 (3)	0.30131 (12)	0.0483 (5)
C9	0.6109 (5)	0.7495 (4)	0.35535 (16)	0.0362 (6)
O4	0.4684 (5)	0.8525 (3)	0.38126 (14)	0.0498 (6)
C8	0.5762 (6)	0.5766 (3)	0.37686 (18)	0.0353 (6)
H8A	0.7584	0.5243	0.3803	0.042*
N2	0.4629 (6)	0.5646 (3)	0.46458 (15)	0.0448 (6)
H11A	0.5788	0.6120	0.5058	0.067*
H11B	0.4447	0.4629	0.4787	0.067*
H11C	0.2973	0.6119	0.4617	0.067*
C4	0.4967 (6)	0.4821 (4)	0.21766 (19)	0.0400 (7)
C7	0.3780 (7)	0.4943 (4)	0.3058 (2)	0.0439 (7)
H7A	0.3369	0.3885	0.3262	0.053*
H7B	0.2044	0.5530	0.2980	0.053*
C1	0.7171 (8)	0.4557 (4)	0.0577 (2)	0.0493 (8)
C2	0.8081 (8)	0.3560 (5)	0.1245 (2)	0.0576 (9)
H2C	0.9440	0.2805	0.1165	0.069*
C3	0.6962 (7)	0.3682 (4)	0.2046 (2)	0.0512 (8)
H3A	0.7551	0.2991	0.2506	0.061*
C5	0.4107 (7)	0.5812 (4)	0.1485 (2)	0.0530 (9)
H5A	0.2761	0.6576	0.1561	0.064*
C6	0.5198 (8)	0.5697 (5)	0.0674 (2)	0.0612 (10)
H6A	0.4609	0.6375	0.0207	0.073*
N1	0.8330 (9)	0.4439 (5)	−0.0288 (2)	0.0722 (10)
O1	1.0166 (8)	0.3463 (5)	−0.0366 (2)	0.1027 (12)
O2	0.7365 (9)	0.5296 (5)	−0.0890 (2)	0.1057 (12)
C10	0.8487 (10)	0.9318 (4)	0.2717 (3)	0.0691 (11)
H10A	0.9951	0.9340	0.2331	0.104*
H10B	0.8984	0.9983	0.3224	0.104*
H10C	0.6794	0.9702	0.2402	0.104*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0520 (4)	0.0476 (4)	0.0505 (4)	0.0037 (4)	0.0075 (3)	−0.0092 (4)
O3	0.0588 (12)	0.0420 (12)	0.0475 (11)	−0.0084 (12)	0.0217 (10)	0.0009 (12)
C9	0.0410 (14)	0.0359 (14)	0.0315 (12)	−0.0017 (16)	0.0027 (11)	−0.0029 (15)
O4	0.0582 (14)	0.0403 (12)	0.0521 (13)	0.0093 (11)	0.0123 (11)	0.0021 (11)
C8	0.0429 (16)	0.0342 (15)	0.0303 (14)	0.0008 (13)	0.0109 (12)	0.0018 (12)
N2	0.0599 (17)	0.0372 (14)	0.0390 (14)	−0.0001 (13)	0.0135 (12)	0.0005 (12)
C4	0.0466 (17)	0.0353 (15)	0.0389 (16)	−0.0111 (13)	0.0074 (14)	−0.0071 (13)
C7	0.0428 (17)	0.0444 (18)	0.0460 (17)	−0.0076 (14)	0.0114 (14)	−0.0031 (15)
C1	0.058 (2)	0.056 (2)	0.0364 (17)	−0.0125 (17)	0.0129 (15)	−0.0138 (15)
C2	0.060 (2)	0.062 (2)	0.052 (2)	0.0040 (19)	0.0099 (17)	−0.0160 (19)
C3	0.067 (2)	0.0434 (18)	0.0431 (18)	−0.0007 (17)	0.0073 (16)	−0.0024 (15)
C5	0.060 (2)	0.053 (2)	0.0465 (19)	0.0070 (17)	0.0083 (16)	0.0000 (17)
C6	0.078 (3)	0.064 (2)	0.0403 (19)	−0.006 (2)	0.0023 (18)	0.0038 (18)
N1	0.085 (3)	0.089 (3)	0.0451 (19)	−0.023 (2)	0.0180 (17)	−0.021 (2)
O1	0.094 (2)	0.141 (3)	0.078 (2)	0.008 (2)	0.0345 (19)	−0.035 (2)
O2	0.155 (3)	0.121 (3)	0.0465 (16)	−0.005 (3)	0.0353 (19)	0.0011 (19)
C10	0.090 (3)	0.052 (2)	0.068 (2)	−0.011 (2)	0.022 (2)	0.013 (2)

Geometric parameters (Å, º) top

O3—C9	1.323 (3)	C1—C2	1.353 (5)
O3—C10	1.462 (4)	C1—C6	1.371 (5)
C9—O4	1.196 (4)	C1—N1	1.475 (4)
C9—C8	1.506 (4)	C2—C3	1.377 (4)
C8—N2	1.486 (3)	C2—H2C	0.9300
C8—C7	1.532 (4)	C3—H3A	0.9300
C8—H8A	0.9800	C5—C6	1.384 (5)
N2—H11A	0.8900	C5—H5A	0.9300
N2—H11B	0.8900	C6—H6A	0.9300
N2—H11C	0.8900	N1—O2	1.217 (5)
C4—C5	1.370 (4)	N1—O1	1.223 (5)
C4—C3	1.387 (5)	C10—H10A	0.9600
C4—C7	1.505 (4)	C10—H10B	0.9600
C7—H7A	0.9700	C10—H10C	0.9600
C7—H7B	0.9700

C9—O3—C10	115.6 (3)	C2—C1—C6	122.2 (3)
O4—C9—O3	125.7 (3)	C2—C1—N1	119.8 (4)
O4—C9—C8	123.5 (3)	C6—C1—N1	118.0 (4)
O3—C9—C8	110.8 (3)	C1—C2—C3	118.9 (3)
N2—C8—C9	108.4 (2)	C1—C2—H2C	120.6
N2—C8—C7	109.6 (2)	C3—C2—H2C	120.6
C9—C8—C7	111.2 (2)	C2—C3—C4	121.0 (3)
N2—C8—H8A	109.2	C2—C3—H3A	119.5
C9—C8—H8A	109.2	C4—C3—H3A	119.5
C7—C8—H8A	109.2	C4—C5—C6	121.4 (3)
C8—N2—H11A	109.5	C4—C5—H5A	119.3
C8—N2—H11B	109.5	C6—C5—H5A	119.3
H11A—N2—H11B	109.5	C1—C6—C5	118.2 (3)
C8—N2—H11C	109.5	C1—C6—H6A	120.9
H11A—N2—H11C	109.5	C5—C6—H6A	120.9
H11B—N2—H11C	109.5	O2—N1—O1	123.7 (4)
C5—C4—C3	118.4 (3)	O2—N1—C1	118.1 (4)
C5—C4—C7	121.4 (3)	O1—N1—C1	118.2 (4)
C3—C4—C7	120.2 (3)	O3—C10—H10A	109.5
C4—C7—C8	112.7 (3)	O3—C10—H10B	109.5
C4—C7—H7A	109.1	H10A—C10—H10B	109.5
C8—C7—H7A	109.1	O3—C10—H10C	109.5
C4—C7—H7B	109.1	H10A—C10—H10C	109.5
C8—C7—H7B	109.1	H10B—C10—H10C	109.5
H7A—C7—H7B	107.8

C10—O3—C9—O4	−0.3 (4)	C1—C2—C3—C4	−1.1 (5)
C10—O3—C9—C8	176.6 (3)	C5—C4—C3—C2	0.9 (5)
O4—C9—C8—N2	−29.2 (4)	C7—C4—C3—C2	−179.7 (3)
O3—C9—C8—N2	153.9 (2)	C3—C4—C5—C6	−0.4 (5)
O4—C9—C8—C7	91.4 (3)	C7—C4—C5—C6	−179.9 (3)
O3—C9—C8—C7	−85.5 (3)	C2—C1—C6—C5	−0.4 (6)
C5—C4—C7—C8	−103.2 (4)	N1—C1—C6—C5	−180.0 (3)
C3—C4—C7—C8	77.3 (4)	C4—C5—C6—C1	0.2 (5)
N2—C8—C7—C4	−172.3 (2)	C2—C1—N1—O2	176.2 (4)
C9—C8—C7—C4	67.8 (3)	C6—C1—N1—O2	−4.2 (5)
C6—C1—C2—C3	0.8 (6)	C2—C1—N1—O1	−2.3 (5)
N1—C1—C2—C3	−179.6 (3)	C6—C1—N1—O1	177.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H11B···O4ⁱ	0.89	2.31	2.929 (4)	127
N2—H11B···Cl1ⁱ	0.89	2.71	3.380 (3)	133
N2—H11C···Cl1ⁱⁱ	0.89	2.42	3.175 (3)	143
N2—H11A···Cl1	0.89	2.34	3.151 (3)	151

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₂O₄⁺·Cl⁻
M_r	260.67
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	4.825 (3), 8.426 (3), 15.111 (9)
β (°)	95.64 (4)
V (Å³)	611.4 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.25 × 0.18 × 0.17

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.931, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	6215, 2751, 2077
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.112, 1.03
No. of reflections	2751
No. of parameters	154
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.17
Absolute structure	Flack (1983), 1259 Friedel pairs
Absolute structure parameter	−0.03 (9)

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Bruno et al., 2002), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H11B···O4ⁱ	0.89	2.31	2.929 (4)	126.5
N2—H11B···Cl1ⁱ	0.89	2.71	3.380 (3)	132.5
N2—H11C···Cl1ⁱⁱ	0.89	2.42	3.175 (3)	143.2
N2—H11A···Cl1	0.89	2.34	3.151 (3)	151.3

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

Acknowledgements

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

References

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