(S)-1-Carb­oxy-2-(4-nitro­phen­yl)ethanaminium bromide

Wang, B.

doi:10.1107/S1600536809035211

organic compounds

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Volume 65| Part 10| October 2009| Page o2420

doi:10.1107/S1600536809035211

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(S)-1-Carboxy-2-(4-nitrophenyl)ethanaminium bromide

Bo Wang ^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 19 August 2009; accepted 1 September 2009; online 9 September 2009)

In the crystal structure of the title compound, C₉H₁₁N₂O₄⁺·Br⁻, the ethanaminium cations and Br⁻ anions are linked together by N—H⋯Br and O—H⋯Br hydrogen bonding. In the cation, the nitro group is twisted with respect to the benzene ring, making a dihedral angle of 21.43 (5)°.

Related literature

For amino acid derivatives as ligands for the construction of metal-organic frameworks, see: Fu et al. (2007 ).

Experimental

Crystal data

C₉H₁₁N₂O₄⁺·Br⁻
M_r = 291.11
Monoclinic, P 2₁
a = 5.5378 (11) Å
b = 7.4158 (15) Å
c = 14.246 (3) Å
β = 91.15 (3)°
V = 584.9 (2) Å³
Z = 2
Mo Kα radiation
μ = 3.52 mm⁻¹
T = 298 K
0.40 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.76, T_max = 0.84
5994 measured reflections
2633 independent reflections
2427 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.069
S = 1.04
2633 reflections
146 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.31 e Å⁻³
Absolute structure: Flack (1983 ), 1202 Friedel pairs
Flack parameter: −0.025 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1ⁱ	0.89	2.54	3.355 (3)	153
N1—H1B⋯Br1	0.89	2.46	3.340 (2)	168
N1—H1C⋯Br1ⁱⁱ	0.89	2.59	3.440 (3)	161
O1—H1⋯Br1ⁱⁱⁱ	0.85	2.38	3.174 (3)	155
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z]$ ; (ii) x-1, y, z; (iii) x-1, y-1, z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL/PC (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL/PC; molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809035211/xu2595sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035211/xu2595Isup2.hkl

checkCIF report

Comment top

Amino acid derivatives are a class of excellent ligands for the construction of novel metal-organic frameworks (Fu et al., 2007). We report here the crystal structure of the title compound.

The title compound is built up from a Br^- anion and a protonated amino group cation (Fig. 1). The nitro group is twisted from the benzene ring plane by a dihedral angle of 21.43 (5)°, and the 2-aminopropanoate substituent group is a zig-zag chain.

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

Related literature top

For amino acid derivatives as ligands for the construction of metal-organic frameworks, see: Fu et al. (2007).

Experimental top

A mixture of 2-amino-3-phenylpropanoic acid (4.71g, 30 mmol), concentrated nitric acid (4.0 ml, 14 M) and concentrated sulfuric acid (1.5 ml, 18 M) was stirred at 383 K for 3 h under nitrogen atmosphere. 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 by adding dilute HBr (4 ml, 4 M) to yield colorless needle-like single crystals.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXTL/PC (Sheldrick, 2008); program(s) used to refine structure: SHELXTL/PC (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top

Fig. 1. The structure of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

(S)-1-Carboxy-2-(4-nitrophenyl)ethanaminium bromide top

Crystal data top

C₉H₁₁N₂O₄⁺·Br⁻	F(000) = 292
M_r = 291.11	D_x = 1.653 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2427 reflections
a = 5.5378 (11) Å	θ = 3.1–27.4°
b = 7.4158 (15) Å	µ = 3.52 mm⁻¹
c = 14.246 (3) Å	T = 298 K
β = 91.15 (3)°	Needle, colourless
V = 584.9 (2) Å³	0.40 × 0.05 × 0.05 mm
Z = 2

Data collection top

Rigaku Mercury2 diffractometer	2633 independent reflections
Radiation source: fine-focus sealed tube	2427 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.4°, θ_min = 3.1°
CCD profile fitting scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
T_min = 0.76, T_max = 0.84	l = −18→18
5994 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)] = 0.032	H-atom parameters constrained
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.02P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2633 reflections	Δρ_max = 0.26 e Å⁻³
146 parameters	Δρ_min = −0.31 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1202 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.025 (11)

Crystal data top

C₉H₁₁N₂O₄⁺·Br⁻	V = 584.9 (2) Å³
M_r = 291.11	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 5.5378 (11) Å	µ = 3.52 mm⁻¹
b = 7.4158 (15) Å	T = 298 K
c = 14.246 (3) Å	0.40 × 0.05 × 0.05 mm
β = 91.15 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2633 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2427 reflections with I > 2σ(I)
T_min = 0.76, T_max = 0.84	R_int = 0.039
5994 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.069	Δρ_max = 0.26 e Å⁻³
S = 1.04	Δρ_min = −0.31 e Å⁻³
2633 reflections	Absolute structure: Flack (1983), 1202 Friedel pairs
146 parameters	Absolute structure parameter: −0.025 (11)
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
O2	−0.1236 (3)	0.1957 (5)	0.09374 (15)	0.0526 (5)
C7	0.3705 (6)	0.3156 (4)	0.2428 (2)	0.0396 (7)
H7A	0.3926	0.2030	0.2766	0.048*
H7B	0.5266	0.3746	0.2405	0.048*
C9	0.0598 (5)	0.1544 (4)	0.1348 (2)	0.0365 (8)
C8	0.2848 (6)	0.2725 (4)	0.1416 (2)	0.0346 (7)
H8	0.4158	0.2079	0.1109	0.041*
C6	0.2007 (5)	0.4342 (4)	0.29749 (19)	0.0361 (7)
C2	0.0984 (6)	0.7325 (5)	0.3539 (2)	0.0488 (10)
H2	0.1295	0.8556	0.3573	0.059*
C4	−0.1471 (7)	0.4776 (6)	0.3932 (2)	0.0488 (10)
H4	−0.2795	0.4309	0.4242	0.059*
C3	−0.0974 (6)	0.6591 (5)	0.3970 (2)	0.0474 (10)
C5	0.0006 (6)	0.3660 (4)	0.3434 (2)	0.0418 (8)
H5	−0.0333	0.2433	0.3402	0.050*
C1	0.2497 (6)	0.6173 (5)	0.3048 (2)	0.0427 (8)
H1D	0.3860	0.6640	0.2765	0.051*
O4	−0.3908 (5)	0.7160 (9)	0.5059 (2)	0.1119 (15)
N2	−0.2621 (7)	0.7828 (7)	0.4470 (3)	0.0783 (12)
O3	−0.2547 (8)	0.9417 (7)	0.4254 (4)	0.1225 (16)
N1	0.2332 (4)	0.4392 (4)	0.08589 (18)	0.0375 (6)
H1A	0.2284	0.4121	0.0250	0.056*
H1B	0.3490	0.5200	0.0971	0.056*
H1C	0.0915	0.4846	0.1024	0.056*
O1	0.0979 (5)	−0.0009 (3)	0.1777 (2)	0.0697 (9)
H1	−0.0290	−0.0651	0.1733	0.104*
Br1	0.72355 (5)	0.69798 (6)	0.112290 (18)	0.04362 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0343 (11)	0.0513 (12)	0.0719 (14)	−0.0139 (17)	−0.0077 (10)	0.010 (2)
C7	0.0327 (17)	0.0424 (18)	0.0434 (19)	−0.0014 (14)	−0.0097 (13)	−0.0022 (14)
C9	0.0373 (16)	0.032 (2)	0.0404 (16)	−0.0075 (12)	−0.0008 (13)	−0.0020 (12)
C8	0.0312 (16)	0.0363 (16)	0.0361 (16)	−0.0054 (12)	−0.0016 (12)	−0.0049 (13)
C6	0.0351 (16)	0.0460 (18)	0.0267 (15)	−0.0042 (14)	−0.0064 (12)	0.0013 (13)
C2	0.060 (2)	0.047 (3)	0.0399 (17)	−0.0022 (17)	−0.0021 (16)	−0.0023 (15)
C4	0.0346 (18)	0.076 (3)	0.036 (2)	−0.0130 (19)	0.0044 (14)	−0.0054 (17)
C3	0.0413 (19)	0.065 (3)	0.0356 (17)	0.0010 (17)	−0.0043 (13)	−0.0170 (16)
C5	0.0438 (19)	0.0447 (19)	0.0368 (18)	−0.0144 (14)	−0.0050 (15)	0.0010 (14)
C1	0.045 (2)	0.052 (2)	0.0310 (17)	−0.0108 (15)	0.0004 (14)	−0.0024 (14)
O4	0.074 (2)	0.156 (4)	0.108 (2)	−0.038 (3)	0.0436 (19)	−0.074 (3)
N2	0.064 (3)	0.099 (3)	0.072 (3)	−0.001 (2)	0.002 (2)	−0.046 (2)
O3	0.123 (4)	0.095 (3)	0.150 (4)	0.034 (3)	0.027 (3)	−0.037 (3)
N1	0.0355 (14)	0.0441 (16)	0.0330 (13)	−0.0151 (12)	0.0001 (10)	−0.0006 (12)
O1	0.072 (2)	0.0427 (15)	0.092 (2)	−0.0215 (13)	−0.0365 (17)	0.0197 (14)
Br1	0.04125 (17)	0.04304 (17)	0.04656 (17)	−0.01590 (17)	0.00035 (11)	0.00473 (18)

Geometric parameters (Å, º) top

O2—C9	1.201 (3)	C2—H2	0.9300
C7—C6	1.515 (4)	C4—C5	1.371 (5)
C7—C8	1.543 (4)	C4—C3	1.375 (6)
C7—H7A	0.9700	C4—H4	0.9300
C7—H7B	0.9700	C3—N2	1.486 (5)
C9—O1	1.318 (4)	C5—H5	0.9300
C9—C8	1.525 (4)	C1—H1D	0.9300
C8—N1	1.493 (4)	O4—N2	1.217 (5)
C8—H8	0.9800	N2—O3	1.219 (6)
C6—C1	1.388 (5)	N1—H1A	0.8900
C6—C5	1.393 (4)	N1—H1B	0.8900
C2—C3	1.369 (5)	N1—H1C	0.8900
C2—C1	1.395 (5)	O1—H1	0.8500

C6—C7—C8	114.7 (3)	C5—C4—H4	120.3
C6—C7—H7A	108.6	C3—C4—H4	120.3
C8—C7—H7A	108.6	C2—C3—C4	122.1 (3)
C6—C7—H7B	108.6	C2—C3—N2	117.9 (4)
C8—C7—H7B	108.6	C4—C3—N2	119.9 (4)
H7A—C7—H7B	107.6	C4—C5—C6	120.8 (3)
O2—C9—O1	125.0 (3)	C4—C5—H5	119.6
O2—C9—C8	124.5 (3)	C6—C5—H5	119.6
O1—C9—C8	110.5 (3)	C6—C1—C2	121.2 (3)
N1—C8—C9	107.1 (2)	C6—C1—H1D	119.4
N1—C8—C7	112.2 (2)	C2—C1—H1D	119.4
C9—C8—C7	114.4 (3)	O4—N2—O3	126.2 (5)
N1—C8—H8	107.6	O4—N2—C3	117.0 (5)
C9—C8—H8	107.6	O3—N2—C3	116.8 (4)
C7—C8—H8	107.6	C8—N1—H1A	109.5
C1—C6—C5	118.4 (3)	C8—N1—H1B	109.5
C1—C6—C7	119.0 (3)	H1A—N1—H1B	109.5
C5—C6—C7	122.6 (3)	C8—N1—H1C	109.5
C3—C2—C1	118.0 (3)	H1A—N1—H1C	109.5
C3—C2—H2	121.0	H1B—N1—H1C	109.5
C1—C2—H2	121.0	C9—O1—H1	109.3
C5—C4—C3	119.3 (3)

O2—C9—C8—N1	−1.9 (4)	C5—C4—C3—N2	177.2 (3)
O1—C9—C8—N1	176.0 (3)	C3—C4—C5—C6	0.6 (5)
O2—C9—C8—C7	123.1 (3)	C1—C6—C5—C4	1.2 (5)
O1—C9—C8—C7	−58.9 (4)	C7—C6—C5—C4	179.1 (3)
C6—C7—C8—N1	55.2 (4)	C5—C6—C1—C2	−2.3 (5)
C6—C7—C8—C9	−67.1 (3)	C7—C6—C1—C2	179.6 (3)
C8—C7—C6—C1	−99.1 (3)	C3—C2—C1—C6	1.7 (5)
C8—C7—C6—C5	82.9 (4)	C2—C3—N2—O4	−159.6 (4)
C1—C2—C3—C4	0.2 (5)	C4—C3—N2—O4	21.8 (5)
C1—C2—C3—N2	−178.4 (3)	C2—C3—N2—O3	20.1 (6)
C5—C4—C3—C2	−1.3 (5)	C4—C3—N2—O3	−158.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1ⁱ	0.89	2.54	3.355 (3)	153
N1—H1B···Br1	0.89	2.46	3.340 (2)	168
N1—H1C···Br1ⁱⁱ	0.89	2.59	3.440 (3)	161
O1—H1···Br1ⁱⁱⁱ	0.85	2.38	3.174 (3)	155

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₂O₄⁺·Br⁻
M_r	291.11
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	5.5378 (11), 7.4158 (15), 14.246 (3)
β (°)	91.15 (3)
V (Å³)	584.9 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.52
Crystal size (mm)	0.40 × 0.05 × 0.05

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.76, 0.84
No. of measured, independent and observed [I > 2σ(I)] reflections	5994, 2633, 2427
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.069, 1.04
No. of reflections	2633
No. of parameters	146
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.31
Absolute structure	Flack (1983), 1202 Friedel pairs
Absolute structure parameter	−0.025 (11)

Computer programs: CrystalClear (Rigaku, 2005), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1ⁱ	0.89	2.54	3.355 (3)	152.9
N1—H1B···Br1	0.89	2.46	3.340 (2)	168.2
N1—H1C···Br1ⁱⁱ	0.89	2.59	3.440 (3)	161.1
O1—H1···Br1ⁱⁱⁱ	0.85	2.38	3.174 (3)	155.3

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

Acknowledgements

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

References

Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Fu, D.-W., Song, Y.-M., Wang, G.-X., Ye, Q., Xiong, R.-G., Akutagawa, T., Nakamura, T., Chan, P. W. H. & Huang, S. P. D. (2007). J. Am. Chem. Soc. 129, 5346–5347. Web of Science CSD CrossRef PubMed CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar