2-Carb­oxy-1-(3-nitro­phen­yl)ethanaminium perchlorate

Liang, W.-X.; Li, Y.; Wang, G.; Qu, Z.-R.

doi:10.1107/S1600536809051319

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o117

doi:10.1107/S1600536809051319

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2-Carboxy-1-(3-nitrophenyl)ethanaminium perchlorate

Wen-Xian Liang,^a Yan Li,^a Gang Wang ^a and Zhi-Rong Qu ^a ^*

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

(Received 25 November 2009; accepted 28 November 2009; online 12 December 2009)

In the cation of the title compound, C₉H₁₁N₂O₄⁺·ClO₄⁻, the conformation is stabilized by an intramolecular N—H⋯O hydrogen bond. In the crystal packing, centrosymmetrically related cations interact through intermolecular O—H⋯O hydrogen bonds involving the carboxy groups, forming dimers. The dimers and the perchlorate anions are further linked into layers parallel to the ab plane by C—H⋯O and N—H⋯O hydrogen-bonding interactions.

Related literature

For the synthesis of β-amino acids, see: Cohen et al. (2002 ); Qu et al. (2004 ); Zhao (2007 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ); Etter et al. (1990 ).

Experimental

Crystal data

C₉H₁₁N₂O₄⁺·ClO₄⁻
M_r = 310.65
Triclinic, $[P \overline 1]$
a = 7.5932 (8) Å
b = 7.8843 (1) Å
c = 11.8615 (6) Å
α = 94.745 (3)°
β = 99.780 (7)°
γ = 116.323 (4)°
V = 617.11 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 293 K
0.45 × 0.30 × 0.15 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.884, T_max = 0.950
6395 measured reflections
2799 independent reflections
1732 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.237
S = 0.99
2799 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O4	0.89	2.36	2.953 (4)	124
N2—H2A⋯O8	0.89	2.15	2.884 (5)	139
N2—H2B⋯O5ⁱ	0.89	2.31	3.113 (5)	150
N2—H2B⋯O6ⁱ	0.89	2.34	3.120 (5)	147
N2—H2C⋯O2ⁱⁱ	0.89	2.15	2.960 (5)	152
O3—H3⋯O4ⁱⁱⁱ	0.82	1.89	2.690 (4)	167
C2—H2⋯O8^iv	0.93	2.58	3.420 (5)	150
C6—H6⋯O2ⁱⁱ	0.93	2.54	3.445 (5)	163
C8—H8A⋯O6^iv	0.97	2.50	3.403 (5)	154
C8—H8B⋯O7^v	0.97	2.57	3.134 (6)	117
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x-1, y-1, z; (iii) -x, -y+1, -z+1; (iv) -x+1, -y+1, -z+1; (v) -x, -y, -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: PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809051319/rz2399sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051319/rz2399Isup2.hkl

checkCIF report

Comment top

β-Amino acids are important molecules due to their pharmacological properties. Recently, there have been an increased interest in the enantiomeric preparation of β-amino acids as precursors for the synthesis of novel biologically active compounds (Cohen et al., 2002). In addition, β-amino acids are attractive ligands for use in the generation of polar coordination polymers, especially when one considers that the ferroelectric compounds (Qu et al., 2004).

The asymmetric unit of the title compound (Fig. 1) contains one 1-(3-nitrophenyl)-2-carboxyethanaminium and one perchlorate anion. The conformation of the cation is stabilized by an intramolecular N—H···O hydrogen bond (Table 1). In the crystal packing, centrosymmetrically related cations at (x, y, z) and (-x, 1-y, 1-z) are linked into a dimer by intermolecular O—H···O hydrogen bonds involving the carboxy groups forming an eigth-membered ring of graph set motif R² ₂(8) (Etter et al., 1990; Bernstein et al., 1995). The dimers and the perchlorate anions are further connected into layers parallel to the ab plane (Fig. 2) by C—H···O and N—H···O hydrogen bonding interactions.

Related literature top

For the synthesis of β-amino acids, see: Cohen et al. (2002); Qu et al. (2004); Zhao et al. (2007). For hydrogen-bond motifs, see: Bernstein et al. (1995); Etter et al. (1990).

Experimental top

Under nitrogen protection, 3-nitrobenzaldehyde (4.53 g, 30 mmol), malonic acid (5.0 g, 48 mmol) and ammonium acetate (6.0 g, 78 mmol) were added in a flask and refluxed for 12 h yielding a white precipitate. After being cooled to room temperature, the solution was filtered, and the 3-amino-3-(3-nitrophenyl)propanoic acid obtained was dissolved in ethanol and perchloric acid. After slow evaporation of the solution over a period of 3 d, colourless prismatic crystals of the title compound suitable for X-ray diffraction analysis were isolated.

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: PRPKAPPA (Ferguson, 1999).

Figures top

Fig. 1. The asymmetric unit in the title compound, with the displacement ellipsoids were drawn at the 30% probability level. Intramolecular hydrogen bonds are shown as dashed lines.

2-Carboxy-1-(3-nitrophenyl)ethanaminium perchlorate top

Crystal data top

C₉H₁₁N₂O₄⁺·ClO₄⁻	Z = 2
M_r = 310.65	F(000) = 320
Triclinic, P1	D_x = 1.672 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5932 (8) Å	Cell parameters from 1641 reflections
b = 7.8843 (1) Å	θ = 3.1–27.5°
c = 11.8615 (6) Å	µ = 0.35 mm⁻¹
α = 94.745 (3)°	T = 293 K
β = 99.780 (7)°	Prism, colourless
γ = 116.323 (4)°	0.45 × 0.30 × 0.15 mm
V = 617.11 (7) Å³

Data collection top

Rigaku SCXmini diffractometer	2799 independent reflections
Radiation source: fine-focus sealed tube	1732 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.9°
CCD Profile fitting scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.884, T_max = 0.950	l = −15→15
6395 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)] = 0.058	H-atom parameters constrained
wR(F²) = 0.237	w = 1/[σ²(F_o²) + (0.1426P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max < 0.001
2799 reflections	Δρ_max = 0.58 e Å⁻³
183 parameters	Δρ_min = −0.53 e Å⁻³
0 restraints	Extinction correction: SHELXL
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0014 (1)

Crystal data top

C₉H₁₁N₂O₄⁺·ClO₄⁻	γ = 116.323 (4)°
M_r = 310.65	V = 617.11 (7) Å³
Triclinic, P1	Z = 2
a = 7.5932 (8) Å	Mo Kα radiation
b = 7.8843 (1) Å	µ = 0.35 mm⁻¹
c = 11.8615 (6) Å	T = 293 K
α = 94.745 (3)°	0.45 × 0.30 × 0.15 mm
β = 99.780 (7)°

Data collection top

Rigaku SCXmini diffractometer	2799 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1732 reflections with I > 2σ(I)
T_min = 0.884, T_max = 0.950	R_int = 0.049
6395 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.237	H-atom parameters constrained
S = 0.99	Δρ_max = 0.58 e Å⁻³
2799 reflections	Δρ_min = −0.53 e Å⁻³
183 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
Cl1	0.34320 (15)	0.01534 (15)	0.65117 (8)	0.0463 (4)
O5	0.3304 (6)	−0.1381 (5)	0.5737 (3)	0.0772 (11)
O6	0.5400 (5)	0.1058 (5)	0.7279 (3)	0.0763 (11)
O7	0.1979 (6)	−0.0555 (6)	0.7205 (3)	0.0867 (13)
O8	0.3233 (9)	0.1574 (7)	0.5920 (3)	0.0996 (16)
O4	0.1696 (4)	0.4174 (4)	0.4775 (2)	0.0423 (7)
O3	0.0141 (5)	0.5359 (5)	0.3563 (2)	0.0523 (8)
H3	−0.0234	0.5592	0.4138	0.079*
C3	0.7013 (5)	0.4845 (5)	0.1024 (3)	0.0343 (8)
C2	0.6238 (5)	0.4860 (5)	0.1994 (3)	0.0346 (8)
H2	0.6888	0.5908	0.2602	0.042*
C1	0.4454 (5)	0.3264 (5)	0.2039 (3)	0.0315 (7)
N1	0.8866 (5)	0.6592 (5)	0.0985 (3)	0.0467 (9)
N2	0.2618 (5)	0.1458 (5)	0.3442 (3)	0.0444 (8)
H2A	0.2265	0.1591	0.4110	0.067*
H2B	0.3490	0.0984	0.3536	0.067*
H2C	0.1525	0.0659	0.2896	0.067*
C9	0.1278 (5)	0.4556 (5)	0.3827 (3)	0.0345 (8)
C7	0.3587 (5)	0.3383 (5)	0.3081 (3)	0.0338 (8)
H7	0.4696	0.4278	0.3728	0.041*
C6	0.3520 (5)	0.1742 (5)	0.1112 (3)	0.0366 (8)
H6	0.2322	0.0683	0.1136	0.044*
O1	0.9505 (5)	0.6627 (5)	0.0093 (3)	0.0696 (10)
C5	0.4334 (6)	0.1763 (6)	0.0143 (3)	0.0386 (8)
H5	0.3682	0.0730	−0.0475	0.046*
O2	0.9618 (5)	0.7907 (5)	0.1799 (3)	0.0722 (10)
C4	0.6139 (6)	0.3347 (6)	0.0106 (3)	0.0394 (9)
H4	0.6728	0.3382	−0.0524	0.047*
C8	0.2089 (6)	0.4171 (6)	0.2816 (3)	0.0370 (8)
H8A	0.2741	0.5361	0.2528	0.044*
H8B	0.0960	0.3263	0.2198	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0496 (6)	0.0469 (6)	0.0457 (6)	0.0250 (5)	0.0138 (4)	0.0040 (4)
O5	0.077 (3)	0.055 (2)	0.092 (3)	0.0231 (19)	0.034 (2)	−0.0077 (19)
O6	0.054 (2)	0.071 (2)	0.082 (2)	0.0171 (19)	−0.0018 (18)	0.013 (2)
O7	0.062 (2)	0.103 (3)	0.084 (3)	0.023 (2)	0.040 (2)	0.002 (2)
O8	0.185 (5)	0.119 (3)	0.047 (2)	0.119 (4)	0.017 (2)	0.022 (2)
O4	0.0490 (15)	0.0624 (18)	0.0341 (14)	0.0396 (15)	0.0155 (12)	0.0111 (12)
O3	0.0618 (18)	0.086 (2)	0.0394 (14)	0.0580 (18)	0.0179 (14)	0.0155 (15)
C3	0.0284 (17)	0.041 (2)	0.0417 (19)	0.0200 (16)	0.0139 (15)	0.0149 (16)
C2	0.0292 (18)	0.0376 (19)	0.0381 (19)	0.0168 (16)	0.0071 (15)	0.0057 (15)
C1	0.0296 (17)	0.0360 (18)	0.0319 (17)	0.0174 (15)	0.0082 (14)	0.0056 (14)
N1	0.0353 (18)	0.049 (2)	0.065 (2)	0.0217 (17)	0.0210 (17)	0.0245 (19)
N2	0.056 (2)	0.052 (2)	0.0401 (17)	0.0335 (18)	0.0215 (16)	0.0162 (15)
C9	0.0336 (18)	0.0391 (19)	0.0350 (18)	0.0198 (16)	0.0111 (15)	0.0045 (15)
C7	0.0297 (17)	0.0371 (19)	0.0349 (18)	0.0149 (15)	0.0101 (14)	0.0070 (15)
C6	0.0341 (18)	0.0330 (18)	0.0413 (19)	0.0137 (16)	0.0119 (15)	0.0046 (15)
O1	0.062 (2)	0.080 (2)	0.088 (2)	0.0352 (19)	0.053 (2)	0.041 (2)
C5	0.042 (2)	0.040 (2)	0.0376 (19)	0.0215 (18)	0.0115 (16)	0.0028 (16)
O2	0.055 (2)	0.054 (2)	0.074 (2)	−0.0025 (17)	0.0133 (18)	0.0074 (19)
C4	0.043 (2)	0.056 (2)	0.0359 (18)	0.032 (2)	0.0193 (16)	0.0173 (17)
C8	0.043 (2)	0.045 (2)	0.0356 (18)	0.0273 (18)	0.0198 (16)	0.0116 (16)

Geometric parameters (Å, º) top

Cl1—O5	1.414 (3)	N1—O1	1.234 (4)
Cl1—O8	1.419 (4)	N2—C7	1.501 (5)
Cl1—O7	1.429 (4)	N2—H2A	0.8900
Cl1—O6	1.433 (4)	N2—H2B	0.8900
O4—C9	1.214 (4)	N2—H2C	0.8900
O3—C9	1.292 (4)	C9—C8	1.506 (4)
O3—H3	0.8200	C7—C8	1.521 (5)
C3—C4	1.366 (5)	C7—H7	0.9800
C3—C2	1.380 (5)	C6—C5	1.392 (5)
C3—N1	1.481 (5)	C6—H6	0.9300
C2—C1	1.395 (5)	C5—C4	1.397 (5)
C2—H2	0.9300	C5—H5	0.9300
C1—C6	1.384 (5)	C4—H4	0.9300
C1—C7	1.511 (5)	C8—H8A	0.9700
N1—O2	1.207 (5)	C8—H8B	0.9700

O5—Cl1—O8	111.9 (2)	O4—C9—O3	125.3 (3)
O5—Cl1—O7	110.5 (2)	O4—C9—C8	122.8 (3)
O8—Cl1—O7	111.6 (3)	O3—C9—C8	111.9 (3)
O5—Cl1—O6	107.7 (2)	N2—C7—C1	111.0 (3)
O8—Cl1—O6	107.2 (3)	N2—C7—C8	111.1 (3)
O7—Cl1—O6	107.7 (2)	C1—C7—C8	110.1 (3)
C9—O3—H3	109.5	N2—C7—H7	108.2
C4—C3—C2	123.7 (3)	C1—C7—H7	108.2
C4—C3—N1	119.4 (3)	C8—C7—H7	108.2
C2—C3—N1	116.9 (3)	C1—C6—C5	121.4 (3)
C3—C2—C1	118.3 (3)	C1—C6—H6	119.3
C3—C2—H2	120.9	C5—C6—H6	119.3
C1—C2—H2	120.9	C6—C5—C4	119.4 (3)
C6—C1—C2	119.1 (3)	C6—C5—H5	120.3
C6—C1—C7	124.0 (3)	C4—C5—H5	120.3
C2—C1—C7	116.7 (3)	C3—C4—C5	117.9 (3)
O2—N1—O1	124.1 (4)	C3—C4—H4	121.0
O2—N1—C3	118.7 (3)	C5—C4—H4	121.0
O1—N1—C3	117.1 (4)	C9—C8—C7	115.3 (3)
C7—N2—H2A	109.5	C9—C8—H8A	108.4
C7—N2—H2B	109.5	C7—C8—H8A	108.4
H2A—N2—H2B	109.5	C9—C8—H8B	108.4
C7—N2—H2C	109.5	C7—C8—H8B	108.4
H2A—N2—H2C	109.5	H8A—C8—H8B	107.5
H2B—N2—H2C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4	0.89	2.36	2.953 (4)	124
N2—H2A···O8	0.89	2.15	2.884 (5)	139
N2—H2B···O5ⁱ	0.89	2.31	3.113 (5)	150
N2—H2B···O6ⁱ	0.89	2.34	3.120 (5)	147
N2—H2C···O2ⁱⁱ	0.89	2.15	2.960 (5)	152
O3—H3···O4ⁱⁱⁱ	0.82	1.89	2.690 (4)	167
C2—H2···O8^iv	0.93	2.58	3.420 (5)	150
C6—H6···O2ⁱⁱ	0.93	2.54	3.445 (5)	163
C8—H8A···O6^iv	0.97	2.50	3.403 (5)	154
C8—H8B···O7^v	0.97	2.57	3.134 (6)	117

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₂O₄⁺·ClO₄⁻
M_r	310.65
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.5932 (8), 7.8843 (1), 11.8615 (6)
α, β, γ (°)	94.745 (3), 99.780 (7), 116.323 (4)
V (Å³)	617.11 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.45 × 0.30 × 0.15

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.884, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	6395, 2799, 1732
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.237, 0.99
No. of reflections	2799
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.53

Computer programs: CrystalClear (Rigaku 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4	0.89	2.36	2.953 (4)	123.7
N2—H2A···O8	0.89	2.15	2.884 (5)	139.1
N2—H2B···O5ⁱ	0.89	2.31	3.113 (5)	150.1
N2—H2B···O6ⁱ	0.89	2.34	3.120 (5)	147.0
N2—H2C···O2ⁱⁱ	0.89	2.15	2.960 (5)	151.8
O3—H3···O4ⁱⁱⁱ	0.82	1.89	2.690 (4)	166.7
C2—H2···O8^iv	0.93	2.58	3.420 (5)	150.2
C6—H6···O2ⁱⁱ	0.93	2.54	3.445 (5)	163.3
C8—H8A···O6^iv	0.97	2.50	3.403 (5)	154.2
C8—H8B···O7^v	0.97	2.57	3.134 (6)	117.2

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

Acknowledgements

This work was supported by the Technical Fund Financing Projects (No. 9207042464 and 9207041482) from Southeast University to ZRQ.

References

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