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

Abstract

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,

• a = 5.5378 (11) Å

• b = 7.4158 (15) Å

• c = 14.246 (3) Å

• β = 91.15 (3)°

• V = 584.9 (2) ų

• 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[F ² > 2σ(F ²)] = 0.032

• wR(F ²) = 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)

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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).

Experimental

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

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 U_iso(H) = 1.2U_eq(C) and U_iso(H) = 1.5U_eq(O,N).

Figures

Fig. 1.

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

Crystal data

C9H11N2O4+·Br−	F(000) = 292
Mr = 291.11	Dx = 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

Rigaku Mercury2 diffractometer	2633 independent reflections
Radiation source: fine-focus sealed tube	2427 reflections with I > 2σ(I)
graphite	Rint = 0.039
Detector resolution: 13.6612 pixels mm-1	θmax = 27.4°, θmin = 3.1°
CCD profile fitting scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
Tmin = 0.76, Tmax = 0.84	l = −18→18
5994 measured reflections

Refinement

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(Fo2) + (0.02P)2] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2633 reflections	Δρmax = 0.26 e Å−3
146 parameters	Δρmin = −0.31 e Å−3
1 restraint	Absolute structure: Flack (1983), 1202 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.025 (11)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.