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Acta Cryst. (2008). E64, o1905    [ doi:10.1107/S1600536808028390 ]

1-Methoxycarbonyl-2-(4-nitrophenyl)ethanaminium nitrate

X.-C. Wen

Abstract top

In the title compound, C10H13O4N2+·NO3-, the nitro group and the benzene ring are essentially coplanar. The dihedral angle between the benzene ring and the methylcarboxylate plane is 49.6 (3)°. The crystal structure is stabilized by cation-anion N-H...O and N-H...N hydrogen bonds, building sheets parallel to (001).

Comment top

Amino acid derivatives are important compounds due to their biological activities, and there has been an increased interest in the enantiomeric preparation of α-amino acid derivatives as precursors for the synthesis of novel biologically active molecules (Lucchese et al., 2007; Arki et al., 2004; Hauck et al., 2006; Azim et al., 2006; Dai et al., 2008; Wen, 2008). Here we report the crystal structure of the title compound.

The asymmetric unit of the title compound contains a organic cation and a NO3- anion (Fig. 1). The nitro group and the benzene ring are essentially coplanar, and the methyl 2-aminopropanoate substituent group is in an extended conformation. The dihedral angle between the C1–C6 and C8–C10/O3/O4 planes is 49.6 (3)°. The S absolute configuration at C8 was deduced from the synthetic pathway.

The crystal packing is stabilized by cation–anion N—H···O and N—H···N hydrogen bonds (Table 1) building sheets parallel to the (001) (Fig. 2).

Related literature top

For details of α-amino acid derivatives, see: Lucchese et al. (2007); Arki et al. (2004); Hauck et al. (2006); Dai et al. (2008); Wen (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 383 K 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 383 K for 12 h. The crude product obtained by evaporation of the solution was recrystallized with distilled water (15 ml)-HNO3 (1 ml) to yield colourless block-like crystals, suitable for X-ray analysis.

Refinement top

All H atoms attached to C atoms and N atom were placed geometrically and treated as riding with C—H = 0.96 Å (methyl), 0.97 Å (methylene), 0.98 Å (methine), 0.93 Å (aromatic) and N—H = 0.89 Å with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(N and methyl C). In the absence of significant anomalous scattering, Friedel pairs were merged.

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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The crystal packing of the title compound, viewed along the b axis. H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity.
1-Methoxycarbonyl-2-(4-nitrophenyl)ethanaminium nitrate top
Crystal data top
C10H13N2O4+·NO3−F(000) = 300
Mr = 287.23Dx = 1.373 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 1657 reflections
a = 5.3722 (11) Åθ = 3.6–27.5°
b = 8.4244 (17) ŵ = 0.12 mm−1
c = 15.380 (3) ÅT = 298 K
β = 93.67 (3)°Block, colourless
V = 694.6 (2) Å30.25 × 0.20 × 0.20 mm
Z = 2
Data collection top
Rigaku Mercury2
diffractometer		1682 independent reflections
Radiation source: fine-focus sealed tube1164 reflections with I > 2σ(I)
graphiteRint = 0.048
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.6°
ω scansh = −6→6
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −10→10
Tmin = 0.94, Tmax = 0.96l = −19→19
7232 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.160H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0812P)2 + 0.1127P]
where P = (Fo2 + 2Fc2)/3
1682 reflections(Δ/σ)max = 0.001
181 parametersΔρmax = 0.24 e Å−3
7 restraintsΔρmin = −0.35 e Å−3
Crystal data top
C10H13N2O4+·NO3−V = 694.6 (2) Å3
Mr = 287.23Z = 2
Monoclinic, P21Mo Kα radiation
a = 5.3722 (11) ŵ = 0.12 mm−1
b = 8.4244 (17) ÅT = 298 K
c = 15.380 (3) Å0.25 × 0.20 × 0.20 mm
β = 93.67 (3)°
Data collection top
Rigaku Mercury2
diffractometer		1682 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		1164 reflections with I > 2σ(I)
Tmin = 0.94, Tmax = 0.96Rint = 0.048
7232 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.160Δρmax = 0.24 e Å−3
S = 1.04Δρmin = −0.35 e Å−3
1682 reflectionsAbsolute structure: ?
181 parametersFlack parameter: ?
7 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
O60.2827 (6)0.2359 (4)0.41323 (19)0.0739 (9)
N20.9977 (5)0.4443 (4)0.55140 (18)0.0502 (8)
H2A0.88760.40350.51180.075*
H2B1.14600.39950.54610.075*
H2C1.00940.54850.54310.075*
O40.7381 (10)0.2064 (5)0.7129 (2)0.1100 (13)
N30.4793 (6)0.2783 (4)0.4504 (2)0.0551 (8)
C80.9152 (6)0.4134 (5)0.6393 (2)0.0450 (8)
H80.75280.46450.64440.054*
O70.6843 (6)0.2597 (5)0.4190 (2)0.0895 (11)
O30.9747 (8)0.1395 (4)0.6053 (2)0.0883 (12)
C40.9935 (7)0.4905 (5)0.7975 (2)0.0549 (10)
C71.1003 (7)0.4825 (6)0.7094 (2)0.0600 (10)
H7A1.24950.41750.71350.072*
H7B1.14780.58850.69210.072*
O50.4776 (5)0.3493 (7)0.5199 (2)0.0973 (15)
C90.8833 (9)0.2365 (6)0.6494 (2)0.0620 (11)
C20.9717 (13)0.4069 (9)0.9457 (3)0.0971 (19)
H21.03110.34440.99240.117*
C50.7944 (10)0.5923 (6)0.8092 (3)0.0721 (13)
H50.73370.65580.76310.086*
C31.0808 (10)0.3984 (8)0.8659 (3)0.0818 (14)
H31.21370.32970.85930.098*
C10.7795 (11)0.5067 (8)0.9543 (3)0.0828 (16)
N10.6608 (16)0.5128 (10)1.0390 (3)0.120 (2)
C60.6851 (10)0.6006 (7)0.8881 (3)0.0839 (15)
H60.55140.66820.89570.101*
O20.4950 (14)0.6095 (13)1.0471 (4)0.172 (3)
C100.6934 (16)0.0396 (7)0.7309 (4)0.1130 (13)
H10A0.58630.03080.77840.170*
H10B0.8492−0.01210.74630.170*
H10C0.6150−0.00990.68010.170*
O10.7474 (15)0.4254 (10)1.0972 (3)0.179 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O60.081 (2)0.067 (2)0.0724 (19)−0.0210 (17)−0.0044 (16)−0.0037 (17)
N20.0498 (16)0.0528 (19)0.0501 (16)−0.0008 (14)0.0186 (13)0.0031 (14)
O40.196 (4)0.0643 (19)0.0772 (17)−0.047 (2)0.069 (2)−0.0111 (15)
N30.0503 (18)0.057 (2)0.059 (2)0.0003 (15)0.0103 (15)−0.0039 (17)
C80.0437 (17)0.051 (2)0.0413 (17)−0.0039 (16)0.0150 (14)−0.0033 (16)
O70.074 (2)0.102 (3)0.095 (2)0.019 (2)0.0339 (18)−0.010 (2)
O30.143 (3)0.0526 (18)0.075 (2)0.0141 (19)0.044 (2)0.0034 (17)
C40.064 (2)0.054 (2)0.0467 (19)−0.0102 (19)0.0012 (16)−0.0040 (18)
C70.055 (2)0.069 (3)0.056 (2)−0.006 (2)0.0083 (17)0.005 (2)
O50.0501 (16)0.153 (4)0.089 (2)0.005 (2)0.0032 (16)−0.057 (3)
C90.092 (3)0.053 (2)0.0432 (18)−0.004 (2)0.0229 (19)−0.0008 (19)
C20.138 (5)0.105 (5)0.047 (2)−0.012 (5)−0.002 (3)0.009 (3)
C50.095 (3)0.066 (3)0.054 (2)0.003 (3)0.006 (2)−0.003 (2)
C30.095 (3)0.090 (4)0.060 (3)0.007 (3)−0.001 (2)0.012 (3)
C10.103 (4)0.094 (4)0.053 (3)−0.030 (3)0.022 (3)−0.020 (3)
N10.166 (6)0.144 (6)0.052 (3)−0.059 (5)0.028 (3)−0.027 (4)
C60.099 (4)0.089 (4)0.066 (3)0.001 (3)0.018 (3)−0.027 (3)
O20.183 (6)0.240 (9)0.102 (4)−0.022 (6)0.070 (4)−0.058 (5)
C100.199 (4)0.067 (2)0.0810 (18)−0.046 (2)0.067 (2)−0.0103 (17)
O10.265 (8)0.211 (8)0.065 (3)−0.043 (6)0.046 (4)0.005 (4)
Geometric parameters (Å, °) top
O6—N31.222 (4)C7—H7A0.97
N2—C81.473 (4)C7—H7B0.97
N2—H2A0.89C2—C11.344 (8)
N2—H2B0.89C2—C31.396 (7)
N2—H2C0.89C2—H20.93
O4—C91.312 (5)C5—C61.384 (6)
O4—C101.455 (7)C5—H50.93
N3—O51.225 (5)C3—H30.93
N3—O71.241 (4)C1—C61.361 (8)
C8—C91.509 (6)C1—N11.488 (7)
C8—C71.534 (6)N1—O21.219 (11)
C8—H80.98N1—O11.227 (10)
O3—C91.189 (5)C6—H60.93
C4—C31.366 (6)C10—H10A0.96
C4—C51.392 (7)C10—H10B0.96
C4—C71.506 (5)C10—H10C0.96
C8—N2—H2A109.5O3—C9—C8124.5 (4)
C8—N2—H2B109.5O4—C9—C8110.1 (4)
H2A—N2—H2B109.5C1—C2—C3119.1 (5)
C8—N2—H2C109.5C1—C2—H2120.4
H2A—N2—H2C109.5C3—C2—H2120.4
H2B—N2—H2C109.5C6—C5—C4121.2 (5)
C9—O4—C10116.2 (4)C6—C5—H5119.4
O6—N3—O5119.8 (3)C4—C5—H5119.4
O6—N3—O7122.9 (4)C4—C3—C2120.4 (5)
O5—N3—O7117.2 (4)C4—C3—H3119.8
N2—C8—C9108.2 (3)C2—C3—H3119.8
N2—C8—C7111.0 (3)C2—C1—C6122.8 (5)
C9—C8—C7112.0 (4)C2—C1—N1118.8 (7)
N2—C8—H8108.5C6—C1—N1118.4 (7)
C9—C8—H8108.5O2—N1—O1124.9 (7)
C7—C8—H8108.5O2—N1—C1118.0 (8)
C3—C4—C5118.6 (4)O1—N1—C1117.0 (9)
C3—C4—C7122.4 (4)C1—C6—C5117.9 (5)
C5—C4—C7118.9 (4)C1—C6—H6121.0
C4—C7—C8112.4 (3)C5—C6—H6121.0
C4—C7—H7A109.1O4—C10—H10A109.5
C8—C7—H7A109.1O4—C10—H10B109.5
C4—C7—H7B109.1H10A—C10—H10B109.5
C8—C7—H7B109.1O4—C10—H10C109.5
H7A—C7—H7B107.8H10A—C10—H10C109.5
O3—C9—O4125.4 (4)H10B—C10—H10C109.5
C3—C4—C7—C8112.3 (5)C5—C4—C3—C20.0 (8)
C5—C4—C7—C8−66.0 (5)C7—C4—C3—C2−178.3 (5)
N2—C8—C7—C4165.5 (3)C1—C2—C3—C40.1 (9)
C9—C8—C7—C4−73.4 (5)C3—C2—C1—C60.1 (9)
C10—O4—C9—O31.7 (9)C3—C2—C1—N1178.8 (5)
C10—O4—C9—C8−179.2 (6)C2—C1—N1—O2176.4 (7)
N2—C8—C9—O319.3 (6)C6—C1—N1—O2−4.9 (9)
C7—C8—C9—O3−103.4 (5)C2—C1—N1—O10.3 (8)
N2—C8—C9—O4−159.9 (4)C6—C1—N1—O1179.1 (6)
C7—C8—C9—O477.5 (5)C2—C1—C6—C5−0.3 (8)
C3—C4—C5—C6−0.2 (7)N1—C1—C6—C5−179.0 (5)
C7—C4—C5—C6178.2 (4)C4—C5—C6—C10.4 (8)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O5i0.891.902.771 (4)166
N2—H2B···N3i0.892.603.402 (4)151
N2—H2B···O6i0.892.613.218 (5)126
N2—H2C···O6ii0.892.352.950 (5)124
N2—H2C···O3iii0.892.412.929 (5)117
N2—H2C···O7iii0.892.473.176 (5)137
N2—H2A···O70.892.122.993 (5)166
N2—H2A···O50.892.262.917 (4)130
N2—H2A···N30.892.563.402 (4)158
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y+1/2, −z+1; (iii) −x+2, y+1/2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O5i0.891.902.771 (4)166
N2—H2B···N3i0.892.603.402 (4)151
N2—H2B···O6i0.892.613.218 (5)126
N2—H2C···O6ii0.892.352.950 (5)124
N2—H2C···O3iii0.892.412.929 (5)117
N2—H2C···O7iii0.892.473.176 (5)137
N2—H2A···O70.892.122.993 (5)166
N2—H2A···O50.892.262.917 (4)130
N2—H2A···N30.892.563.402 (4)158
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y+1/2, −z+1; (iii) −x+2, y+1/2, −z+1.
Acknowledgements top

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

references
References top

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