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Acta Cryst. (2009). E65, o2420    [ doi:10.1107/S1600536809035211 ]

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

B. Wang

Abstract top

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)°.

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.

Refinement top

H atoms were positioned geometrically and treated as riding with C—H = 0.93 (aromatic), 0.97 (methylene), 0.98 Å (methine) and N—H = 0.89 Å, O—H = 0.85 Å with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.5Ueq(O,N).

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
[Figure 1] 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
Mr = 291.11Dx = 1.653 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 2427 reflections
a = 5.5378 (11) Åθ = 3.1–27.4°
b = 7.4158 (15) ŵ = 3.52 mm−1
c = 14.246 (3) ÅT = 298 K
β = 91.15 (3)°Needle, colourless
V = 584.9 (2) Å30.40 × 0.05 × 0.05 mm
Z = 2
Data collection top
Rigaku Mercury2
diffractometer		2633 independent reflections
Radiation source: fine-focus sealed tube2427 reflections with I > 2σ(I)
graphiteRint = 0.039
Detector resolution: 13.6612 pixels mm-1θmax = 27.4°, θmin = 3.1°
CCD profile fitting scansh = −7→7
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −9→9
Tmin = 0.76, Tmax = 0.84l = −18→18
5994 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.069 w = 1/[σ2(Fo2) + (0.02P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2633 reflectionsΔρmax = 0.26 e Å−3
146 parametersΔρmin = −0.31 e Å−3
1 restraintAbsolute structure: Flack (1983), 1202 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.025 (11)
Crystal data top
C9H11N2O4+·Br−V = 584.9 (2) Å3
Mr = 291.11Z = 2
Monoclinic, P21Mo Kα radiation
a = 5.5378 (11) ŵ = 3.52 mm−1
b = 7.4158 (15) ÅT = 298 K
c = 14.246 (3) Å0.40 × 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)
Tmin = 0.76, Tmax = 0.84Rint = 0.039
5994 measured reflectionsθmax = 27.4°
Refinement top
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.069Δρmax = 0.26 e Å−3
S = 1.04Δρmin = −0.31 e Å−3
2633 reflectionsAbsolute structure: Flack (1983), 1202 Friedel pairs
146 parametersFlack 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
xyzUiso*/Ueq
O2−0.1236 (3)0.1957 (5)0.09374 (15)0.0526 (5)
C70.3705 (6)0.3156 (4)0.2428 (2)0.0396 (7)
H7A0.39260.20300.27660.048*
H7B0.52660.37460.24050.048*
C90.0598 (5)0.1544 (4)0.1348 (2)0.0365 (8)
C80.2848 (6)0.2725 (4)0.1416 (2)0.0346 (7)
H80.41580.20790.11090.041*
C60.2007 (5)0.4342 (4)0.29749 (19)0.0361 (7)
C20.0984 (6)0.7325 (5)0.3539 (2)0.0488 (10)
H20.12950.85560.35730.059*
C4−0.1471 (7)0.4776 (6)0.3932 (2)0.0488 (10)
H4−0.27950.43090.42420.059*
C3−0.0974 (6)0.6591 (5)0.3970 (2)0.0474 (10)
C50.0006 (6)0.3660 (4)0.3434 (2)0.0418 (8)
H5−0.03330.24330.34020.050*
C10.2497 (6)0.6173 (5)0.3048 (2)0.0427 (8)
H1D0.38600.66400.27650.051*
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)
N10.2332 (4)0.4392 (4)0.08589 (18)0.0375 (6)
H1A0.22840.41210.02500.056*
H1B0.34900.52000.09710.056*
H1C0.09150.48460.10240.056*
O10.0979 (5)−0.0009 (3)0.1777 (2)0.0697 (9)
H1−0.0290−0.06510.17330.104*
Br10.72355 (5)0.69798 (6)0.112290 (18)0.04362 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O20.0343 (11)0.0513 (12)0.0719 (14)−0.0139 (17)−0.0077 (10)0.010 (2)
C70.0327 (17)0.0424 (18)0.0434 (19)−0.0014 (14)−0.0097 (13)−0.0022 (14)
C90.0373 (16)0.032 (2)0.0404 (16)−0.0075 (12)−0.0008 (13)−0.0020 (12)
C80.0312 (16)0.0363 (16)0.0361 (16)−0.0054 (12)−0.0016 (12)−0.0049 (13)
C60.0351 (16)0.0460 (18)0.0267 (15)−0.0042 (14)−0.0064 (12)0.0013 (13)
C20.060 (2)0.047 (3)0.0399 (17)−0.0022 (17)−0.0021 (16)−0.0023 (15)
C40.0346 (18)0.076 (3)0.036 (2)−0.0130 (19)0.0044 (14)−0.0054 (17)
C30.0413 (19)0.065 (3)0.0356 (17)0.0010 (17)−0.0043 (13)−0.0170 (16)
C50.0438 (19)0.0447 (19)0.0368 (18)−0.0144 (14)−0.0050 (15)0.0010 (14)
C10.045 (2)0.052 (2)0.0310 (17)−0.0108 (15)0.0004 (14)−0.0024 (14)
O40.074 (2)0.156 (4)0.108 (2)−0.038 (3)0.0436 (19)−0.074 (3)
N20.064 (3)0.099 (3)0.072 (3)−0.001 (2)0.002 (2)−0.046 (2)
O30.123 (4)0.095 (3)0.150 (4)0.034 (3)0.027 (3)−0.037 (3)
N10.0355 (14)0.0441 (16)0.0330 (13)−0.0151 (12)0.0001 (10)−0.0006 (12)
O10.072 (2)0.0427 (15)0.092 (2)−0.0215 (13)−0.0365 (17)0.0197 (14)
Br10.04125 (17)0.04304 (17)0.04656 (17)−0.01590 (17)0.00035 (11)0.00473 (18)
Geometric parameters (Å, °) top
O2—C91.201 (3)C2—H20.9300
C7—C61.515 (4)C4—C51.371 (5)
C7—C81.543 (4)C4—C31.375 (6)
C7—H7A0.9700C4—H40.9300
C7—H7B0.9700C3—N21.486 (5)
C9—O11.318 (4)C5—H50.9300
C9—C81.525 (4)C1—H1D0.9300
C8—N11.493 (4)O4—N21.217 (5)
C8—H80.9800N2—O31.219 (6)
C6—C11.388 (5)N1—H1A0.8900
C6—C51.393 (4)N1—H1B0.8900
C2—C31.369 (5)N1—H1C0.8900
C2—C11.395 (5)O1—H10.8500
C6—C7—C8114.7 (3)C5—C4—H4120.3
C6—C7—H7A108.6C3—C4—H4120.3
C8—C7—H7A108.6C2—C3—C4122.1 (3)
C6—C7—H7B108.6C2—C3—N2117.9 (4)
C8—C7—H7B108.6C4—C3—N2119.9 (4)
H7A—C7—H7B107.6C4—C5—C6120.8 (3)
O2—C9—O1125.0 (3)C4—C5—H5119.6
O2—C9—C8124.5 (3)C6—C5—H5119.6
O1—C9—C8110.5 (3)C6—C1—C2121.2 (3)
N1—C8—C9107.1 (2)C6—C1—H1D119.4
N1—C8—C7112.2 (2)C2—C1—H1D119.4
C9—C8—C7114.4 (3)O4—N2—O3126.2 (5)
N1—C8—H8107.6O4—N2—C3117.0 (5)
C9—C8—H8107.6O3—N2—C3116.8 (4)
C7—C8—H8107.6C8—N1—H1A109.5
C1—C6—C5118.4 (3)C8—N1—H1B109.5
C1—C6—C7119.0 (3)H1A—N1—H1B109.5
C5—C6—C7122.6 (3)C8—N1—H1C109.5
C3—C2—C1118.0 (3)H1A—N1—H1C109.5
C3—C2—H2121.0H1B—N1—H1C109.5
C1—C2—H2121.0C9—O1—H1109.3
C5—C4—C3119.3 (3)
O2—C9—C8—N1−1.9 (4)C5—C4—C3—N2177.2 (3)
O1—C9—C8—N1176.0 (3)C3—C4—C5—C60.6 (5)
O2—C9—C8—C7123.1 (3)C1—C6—C5—C41.2 (5)
O1—C9—C8—C7−58.9 (4)C7—C6—C5—C4179.1 (3)
C6—C7—C8—N155.2 (4)C5—C6—C1—C2−2.3 (5)
C6—C7—C8—C9−67.1 (3)C7—C6—C1—C2179.6 (3)
C8—C7—C6—C1−99.1 (3)C3—C2—C1—C61.7 (5)
C8—C7—C6—C582.9 (4)C2—C3—N2—O4−159.6 (4)
C1—C2—C3—C40.2 (5)C4—C3—N2—O421.8 (5)
C1—C2—C3—N2−178.4 (3)C2—C3—N2—O320.1 (6)
C5—C4—C3—C2−1.3 (5)C4—C3—N2—O3−158.4 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Br1i0.892.543.355 (3)153
N1—H1B···Br10.892.463.340 (2)168
N1—H1C···Br1ii0.892.593.440 (3)161
O1—H1···Br1iii0.852.383.174 (3)155
Symmetry codes: (i) −x+1, y−1/2, −z; (ii) x−1, y, z; (iii) x−1, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Br1i0.892.543.355 (3)153
N1—H1B···Br10.892.463.340 (2)168
N1—H1C···Br1ii0.892.593.440 (3)161
O1—H1···Br1iii0.852.383.174 (3)155
Symmetry codes: (i) −x+1, y−1/2, −z; (ii) x−1, y, z; (iii) x−1, y−1, z.
Acknowledgements top

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

references
References top

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

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.

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.