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

Wen, X.-C.

doi:10.1107/S1600536808028390

organic compounds

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Volume 64| Part 10| October 2008| Page o1905

doi:10.1107/S1600536808028390

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

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 1 September 2008; accepted 4 September 2008; online 13 September 2008)

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).

Related literature

For details of α-amino acid derivatives, see: Lucchese et al. (2007 ); Arki et al. (2004 ); Hauck et al. (2006 ); Dai & Fu (2008 ); Wen (2008 ); Azim et al. (2006 ).

Experimental

Crystal data

C₁₀H₁₃N₂O₄⁺·NO₃⁻
M_r = 287.23
Monoclinic, P 2₁
a = 5.3722 (11) Å
b = 8.4244 (17) Å
c = 15.380 (3) Å
β = 93.67 (3)°
V = 694.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 298 (2) K
0.25 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.94, T_max = 0.96
7232 measured reflections
1682 independent reflections
1164 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.160
S = 1.04
1682 reflections
181 parameters
7 restraints
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O5ⁱ	0.89	1.90	2.771 (4)	166
N2—H2B⋯N3ⁱ	0.89	2.60	3.402 (4)	151
N2—H2B⋯O6ⁱ	0.89	2.61	3.218 (5)	126
N2—H2C⋯O6ⁱⁱ	0.89	2.35	2.950 (5)	124
N2—H2C⋯O3ⁱⁱⁱ	0.89	2.41	2.929 (5)	117
N2—H2C⋯O7ⁱⁱⁱ	0.89	2.47	3.176 (5)	137
N2—H2A⋯O7	0.89	2.12	2.993 (5)	166
N2—H2A⋯O5	0.89	2.26	2.917 (4)	130
N2—H2A⋯N3	0.89	2.56	3.402 (4)	158
Symmetry codes: (i) x+1, y, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+2, y+{\script{1\over 2}}, -z+1]$ .

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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808028390/ci2667sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808028390/ci2667Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	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
M_r = 287.23	D_x = 1.373 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1657 reflections
a = 5.3722 (11) Å	θ = 3.6–27.5°
b = 8.4244 (17) Å	µ = 0.12 mm⁻¹
c = 15.380 (3) Å	T = 298 K
β = 93.67 (3)°	Block, colourless
V = 694.6 (2) Å³	0.25 × 0.20 × 0.20 mm
Z = 2

Data collection top

Rigaku Mercury2 diffractometer	1682 independent reflections
Radiation source: fine-focus sealed tube	1164 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.6°
ω scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.94, T_max = 0.96	l = −19→19
7232 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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0812P)² + 0.1127P] where P = (F_o² + 2F_c²)/3
1682 reflections	(Δ/σ)_max = 0.001
181 parameters	Δρ_max = 0.24 e Å⁻³
7 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₀H₁₃N₂O₄⁺·NO₃⁻	V = 694.6 (2) Å³
M_r = 287.23	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 5.3722 (11) Å	µ = 0.12 mm⁻¹
b = 8.4244 (17) Å	T = 298 K
c = 15.380 (3) Å	0.25 × 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)
T_min = 0.94, T_max = 0.96	R_int = 0.048
7232 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	7 restraints
wR(F²) = 0.160	H-atom parameters constrained
S = 1.04	Δρ_max = 0.24 e Å⁻³
1682 reflections	Δρ_min = −0.35 e Å⁻³
181 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 > 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
O6	0.2827 (6)	0.2359 (4)	0.41323 (19)	0.0739 (9)
N2	0.9977 (5)	0.4443 (4)	0.55140 (18)	0.0502 (8)
H2A	0.8876	0.4035	0.5118	0.075*
H2B	1.1460	0.3995	0.5461	0.075*
H2C	1.0094	0.5485	0.5431	0.075*
O4	0.7381 (10)	0.2064 (5)	0.7129 (2)	0.1100 (13)
N3	0.4793 (6)	0.2783 (4)	0.4504 (2)	0.0551 (8)
C8	0.9152 (6)	0.4134 (5)	0.6393 (2)	0.0450 (8)
H8	0.7528	0.4645	0.6444	0.054*
O7	0.6843 (6)	0.2597 (5)	0.4190 (2)	0.0895 (11)
O3	0.9747 (8)	0.1395 (4)	0.6053 (2)	0.0883 (12)
C4	0.9935 (7)	0.4905 (5)	0.7975 (2)	0.0549 (10)
C7	1.1003 (7)	0.4825 (6)	0.7094 (2)	0.0600 (10)
H7A	1.2495	0.4175	0.7135	0.072*
H7B	1.1478	0.5885	0.6921	0.072*
O5	0.4776 (5)	0.3493 (7)	0.5199 (2)	0.0973 (15)
C9	0.8833 (9)	0.2365 (6)	0.6494 (2)	0.0620 (11)
C2	0.9717 (13)	0.4069 (9)	0.9457 (3)	0.0971 (19)
H2	1.0311	0.3444	0.9924	0.117*
C5	0.7944 (10)	0.5923 (6)	0.8092 (3)	0.0721 (13)
H5	0.7337	0.6558	0.7631	0.086*
C3	1.0808 (10)	0.3984 (8)	0.8659 (3)	0.0818 (14)
H3	1.2137	0.3297	0.8593	0.098*
C1	0.7795 (11)	0.5067 (8)	0.9543 (3)	0.0828 (16)
N1	0.6608 (16)	0.5128 (10)	1.0390 (3)	0.120 (2)
C6	0.6851 (10)	0.6006 (7)	0.8881 (3)	0.0839 (15)
H6	0.5514	0.6682	0.8957	0.101*
O2	0.4950 (14)	0.6095 (13)	1.0471 (4)	0.172 (3)
C10	0.6934 (16)	0.0396 (7)	0.7309 (4)	0.1130 (13)
H10A	0.5863	0.0308	0.7784	0.170*
H10B	0.8492	−0.0121	0.7463	0.170*
H10C	0.6150	−0.0099	0.6801	0.170*
O1	0.7474 (15)	0.4254 (10)	1.0972 (3)	0.179 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O6	0.081 (2)	0.067 (2)	0.0724 (19)	−0.0210 (17)	−0.0044 (16)	−0.0037 (17)
N2	0.0498 (16)	0.0528 (19)	0.0501 (16)	−0.0008 (14)	0.0186 (13)	0.0031 (14)
O4	0.196 (4)	0.0643 (19)	0.0772 (17)	−0.047 (2)	0.069 (2)	−0.0111 (15)
N3	0.0503 (18)	0.057 (2)	0.059 (2)	0.0003 (15)	0.0103 (15)	−0.0039 (17)
C8	0.0437 (17)	0.051 (2)	0.0413 (17)	−0.0039 (16)	0.0150 (14)	−0.0033 (16)
O7	0.074 (2)	0.102 (3)	0.095 (2)	0.019 (2)	0.0339 (18)	−0.010 (2)
O3	0.143 (3)	0.0526 (18)	0.075 (2)	0.0141 (19)	0.044 (2)	0.0034 (17)
C4	0.064 (2)	0.054 (2)	0.0467 (19)	−0.0102 (19)	0.0012 (16)	−0.0040 (18)
C7	0.055 (2)	0.069 (3)	0.056 (2)	−0.006 (2)	0.0083 (17)	0.005 (2)
O5	0.0501 (16)	0.153 (4)	0.089 (2)	0.005 (2)	0.0032 (16)	−0.057 (3)
C9	0.092 (3)	0.053 (2)	0.0432 (18)	−0.004 (2)	0.0229 (19)	−0.0008 (19)
C2	0.138 (5)	0.105 (5)	0.047 (2)	−0.012 (5)	−0.002 (3)	0.009 (3)
C5	0.095 (3)	0.066 (3)	0.054 (2)	0.003 (3)	0.006 (2)	−0.003 (2)
C3	0.095 (3)	0.090 (4)	0.060 (3)	0.007 (3)	−0.001 (2)	0.012 (3)
C1	0.103 (4)	0.094 (4)	0.053 (3)	−0.030 (3)	0.022 (3)	−0.020 (3)
N1	0.166 (6)	0.144 (6)	0.052 (3)	−0.059 (5)	0.028 (3)	−0.027 (4)
C6	0.099 (4)	0.089 (4)	0.066 (3)	0.001 (3)	0.018 (3)	−0.027 (3)
O2	0.183 (6)	0.240 (9)	0.102 (4)	−0.022 (6)	0.070 (4)	−0.058 (5)
C10	0.199 (4)	0.067 (2)	0.0810 (18)	−0.046 (2)	0.067 (2)	−0.0103 (17)
O1	0.265 (8)	0.211 (8)	0.065 (3)	−0.043 (6)	0.046 (4)	0.005 (4)

Geometric parameters (Å, º) top

O6—N3	1.222 (4)	C7—H7A	0.97
N2—C8	1.473 (4)	C7—H7B	0.97
N2—H2A	0.89	C2—C1	1.344 (8)
N2—H2B	0.89	C2—C3	1.396 (7)
N2—H2C	0.89	C2—H2	0.93
O4—C9	1.312 (5)	C5—C6	1.384 (6)
O4—C10	1.455 (7)	C5—H5	0.93
N3—O5	1.225 (5)	C3—H3	0.93
N3—O7	1.241 (4)	C1—C6	1.361 (8)
C8—C9	1.509 (6)	C1—N1	1.488 (7)
C8—C7	1.534 (6)	N1—O2	1.219 (11)
C8—H8	0.98	N1—O1	1.227 (10)
O3—C9	1.189 (5)	C6—H6	0.93
C4—C3	1.366 (6)	C10—H10A	0.96
C4—C5	1.392 (7)	C10—H10B	0.96
C4—C7	1.506 (5)	C10—H10C	0.96

C8—N2—H2A	109.5	O3—C9—C8	124.5 (4)
C8—N2—H2B	109.5	O4—C9—C8	110.1 (4)
H2A—N2—H2B	109.5	C1—C2—C3	119.1 (5)
C8—N2—H2C	109.5	C1—C2—H2	120.4
H2A—N2—H2C	109.5	C3—C2—H2	120.4
H2B—N2—H2C	109.5	C6—C5—C4	121.2 (5)
C9—O4—C10	116.2 (4)	C6—C5—H5	119.4
O6—N3—O5	119.8 (3)	C4—C5—H5	119.4
O6—N3—O7	122.9 (4)	C4—C3—C2	120.4 (5)
O5—N3—O7	117.2 (4)	C4—C3—H3	119.8
N2—C8—C9	108.2 (3)	C2—C3—H3	119.8
N2—C8—C7	111.0 (3)	C2—C1—C6	122.8 (5)
C9—C8—C7	112.0 (4)	C2—C1—N1	118.8 (7)
N2—C8—H8	108.5	C6—C1—N1	118.4 (7)
C9—C8—H8	108.5	O2—N1—O1	124.9 (7)
C7—C8—H8	108.5	O2—N1—C1	118.0 (8)
C3—C4—C5	118.6 (4)	O1—N1—C1	117.0 (9)
C3—C4—C7	122.4 (4)	C1—C6—C5	117.9 (5)
C5—C4—C7	118.9 (4)	C1—C6—H6	121.0
C4—C7—C8	112.4 (3)	C5—C6—H6	121.0
C4—C7—H7A	109.1	O4—C10—H10A	109.5
C8—C7—H7A	109.1	O4—C10—H10B	109.5
C4—C7—H7B	109.1	H10A—C10—H10B	109.5
C8—C7—H7B	109.1	O4—C10—H10C	109.5
H7A—C7—H7B	107.8	H10A—C10—H10C	109.5
O3—C9—O4	125.4 (4)	H10B—C10—H10C	109.5

C3—C4—C7—C8	112.3 (5)	C5—C4—C3—C2	0.0 (8)
C5—C4—C7—C8	−66.0 (5)	C7—C4—C3—C2	−178.3 (5)
N2—C8—C7—C4	165.5 (3)	C1—C2—C3—C4	0.1 (9)
C9—C8—C7—C4	−73.4 (5)	C3—C2—C1—C6	0.1 (9)
C10—O4—C9—O3	1.7 (9)	C3—C2—C1—N1	178.8 (5)
C10—O4—C9—C8	−179.2 (6)	C2—C1—N1—O2	176.4 (7)
N2—C8—C9—O3	19.3 (6)	C6—C1—N1—O2	−4.9 (9)
C7—C8—C9—O3	−103.4 (5)	C2—C1—N1—O1	0.3 (8)
N2—C8—C9—O4	−159.9 (4)	C6—C1—N1—O1	179.1 (6)
C7—C8—C9—O4	77.5 (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—C6	178.2 (4)	C4—C5—C6—C1	0.4 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O5ⁱ	0.89	1.90	2.771 (4)	166
N2—H2B···N3ⁱ	0.89	2.60	3.402 (4)	151
N2—H2B···O6ⁱ	0.89	2.61	3.218 (5)	126
N2—H2C···O6ⁱⁱ	0.89	2.35	2.950 (5)	124
N2—H2C···O3ⁱⁱⁱ	0.89	2.41	2.929 (5)	117
N2—H2C···O7ⁱⁱⁱ	0.89	2.47	3.176 (5)	137
N2—H2A···O7	0.89	2.12	2.993 (5)	166
N2—H2A···O5	0.89	2.26	2.917 (4)	130
N2—H2A···N3	0.89	2.56	3.402 (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.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₂O₄⁺·NO₃⁻
M_r	287.23
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	5.3722 (11), 8.4244 (17), 15.380 (3)
β (°)	93.67 (3)
V (Å³)	694.6 (2)
Z	2
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	0.94, 0.96
No. of measured, independent and observed [I > 2σ(I)] reflections	7232, 1682, 1164
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.160, 1.04
No. of reflections	1682
No. of parameters	181
No. of restraints	7
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −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—H2B···O5ⁱ	0.89	1.90	2.771 (4)	166
N2—H2B···N3ⁱ	0.89	2.60	3.402 (4)	151
N2—H2B···O6ⁱ	0.89	2.61	3.218 (5)	126
N2—H2C···O6ⁱⁱ	0.89	2.35	2.950 (5)	124
N2—H2C···O3ⁱⁱⁱ	0.89	2.41	2.929 (5)	117
N2—H2C···O7ⁱⁱⁱ	0.89	2.47	3.176 (5)	137
N2—H2A···O7	0.89	2.12	2.993 (5)	166
N2—H2A···O5	0.89	2.26	2.917 (4)	130
N2—H2A···N3	0.89	2.56	3.402 (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

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

References

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