(S)-1-Methoxy­carbonyl-3-(4-nitro­phen­yl)propan-2-aminium bromide

Wang, B.

doi:10.1107/S1600536809034904

organic compounds

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Volume 65| Part 10| October 2009| Page o2397

doi:10.1107/S1600536809034904

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(S)-1-Methoxycarbonyl-3-(4-nitrophenyl)propan-2-aminium 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 20 August 2009; accepted 31 August 2009; online 9 September 2009)

In the crystal structure of the title compound, C₁₀H₁₃N₂O₄⁺·Br⁻, intermolecular N—H⋯Br and N—H⋯(O,Br) hydrogen bonds link the cations and anions into a two-dimensional network parallel to the ab plane.

Related literature

For applications of metal-organic coordination compounds, see: Xiong et al. (1999 ); Fu, Zhang et al. (2008 ); Fu & Xiong (2008 ). For metal-organic frameworks with amino acid derivatives, see: Chen et al. (2000 ); Xie et al. (2002 ); Fu et al. (2007 ).

Experimental

Crystal data

C₁₀H₁₃N₂O₄⁺·Br⁻
M_r = 305.13
Monoclinic, P 2₁
a = 4.9323 (10) Å
b = 8.6233 (17) Å
c = 15.226 (3) Å
β = 95.77 (3)°
V = 644.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 3.20 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 = 0.90, T_max = 1.00
6658 measured reflections
2917 independent reflections
2532 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.085
S = 1.04
2917 reflections
154 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.30 e Å⁻³
Absolute structure: Flack (1983 ), 1202 Friedel pairs
Flack parameter: 0.008 (5)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.87	2.61	3.031 (4)	111
N1—H1A⋯Br1ⁱⁱ	0.87	2.61	3.290 (3)	135
N1—H1B⋯Br1ⁱⁱⁱ	0.93	2.51	3.303 (3)	143
N1—H1C⋯Br1^iv	1.00	2.55	3.495 (3)	157
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+2]$ ; (ii) x, y, z+1; (iii) x-1, y, z+1; (iv) $[-x+1, y-{\script{1\over 2}}, -z+1]$ .

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/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809034904/cv2604sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034904/cv2604Isup2.hkl

checkCIF report

Comment top

The construction of metal-organic coordination compounds has attracted much attention owing to potential functions, such as permittivity, fluorescence, magnetism and optical properties (Fu, Zhang et al., 2008; Xiong et al., 1999; Fu & Xiong, 2008). Amino acid derivatives constitute a class of excellent ligands for the construction of novel metal-organic frameworks (Fu et al., 2007; Xie et al., 2002; Chen et al., 2000). 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 and the benzene ring are nearly coplanar being twisted to each other by 2.39 (6)°. The S absolute configuration at C8 is deduced from the synthetic pathway and confirmed by the X-ray analysis.

The crystal packing is stabilized by N—H···Br and N—H···O H-bonds (Table 1) building an infinite two-dimensional network parallel to ab plane (Fig.2).

Related literature top

For applications of metal-organic coordination compounds, see: Xiong et al. (1999); Fu, Zhang et al. (2008); Fu & Xiong (2008). For metal-organic frameworks with amino acid derivatives, see: Chen et al. (2000); Xie et al. (2002); Fu et al. (2007).

Experimental top

Under nitrogen protection, methyl 2-amino-3-(4-nitrophenyl)propanoate (30 mmol), nitric acid (50 mmol) and sulfuric acid (20 mmol) were added in a flask. The mixture was stirred at 110 °C for 3 hours. The resulting solution was poured into ice water (100mL), then filtered and washed with distilled water. The crude product was recrystallized with distilled water by adding 4ml HBr to yield colourless needle-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/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A portion of the crystal packing, viewed along the c axis. Dashed lines denote N—H···Br and N—H···O hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted for clarity.

(S)-1-Methoxycarbonyl-3-(4-nitrophenyl)propan-2-aminium bromide top

Crystal data top

C₁₀H₁₃N₂O₄⁺·Br⁻	F(000) = 308
M_r = 305.13	D_x = 1.573 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2532 reflections
a = 4.9323 (10) Å	θ = 3.6–27.5°
b = 8.6233 (17) Å	µ = 3.20 mm⁻¹
c = 15.226 (3) Å	T = 298 K
β = 95.77 (3)°	Needle, colourless
V = 644.3 (2) Å³	0.40 × 0.05 × 0.05 mm
Z = 2

Data collection top

Rigaku Mercury2 diffractometer	2917 independent reflections
Radiation source: fine-focus sealed tube	2532 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.6°
CCD profile fitting scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
T_min = 0.90, T_max = 1.00	l = −19→19
6658 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)] = 0.042	H-atom parameters constrained
wR(F²) = 0.085	w = 1/[σ²(F_o²)]
S = 1.04	(Δ/σ)_max < 0.001
2917 reflections	Δρ_max = 0.62 e Å⁻³
154 parameters	Δρ_min = −0.30 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1202 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.008 (5)

Crystal data top

C₁₀H₁₃N₂O₄⁺·Br⁻	V = 644.3 (2) Å³
M_r = 305.13	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 4.9323 (10) Å	µ = 3.20 mm⁻¹
b = 8.6233 (17) Å	T = 298 K
c = 15.226 (3) Å	0.40 × 0.05 × 0.05 mm
β = 95.77 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2917 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2532 reflections with I > 2σ(I)
T_min = 0.90, T_max = 1.00	R_int = 0.055
6658 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.085	Δρ_max = 0.62 e Å⁻³
S = 1.04	Δρ_min = −0.30 e Å⁻³
2917 reflections	Absolute structure: Flack (1983), 1202 Friedel pairs
154 parameters	Absolute structure parameter: 0.008 (5)
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
C6	0.4984 (8)	0.4001 (4)	0.7127 (2)	0.0390 (9)
C2	0.8039 (10)	0.2806 (6)	0.6203 (3)	0.0565 (12)
H2	0.9359	0.2063	0.6122	0.068*
C7	0.3794 (8)	0.4113 (5)	0.7995 (2)	0.0438 (10)
H7A	0.3349	0.3081	0.8188	0.053*
H7B	0.2118	0.4708	0.7916	0.053*
C3	0.7186 (9)	0.3798 (6)	0.5544 (3)	0.0527 (12)
C5	0.4128 (9)	0.5000 (5)	0.6421 (3)	0.0554 (11)
H5	0.2796	0.5742	0.6489	0.067*
C4	0.5236 (10)	0.4886 (6)	0.5644 (3)	0.0642 (15)
H4	0.4667	0.5550	0.5180	0.077*
C1	0.6940 (9)	0.2910 (5)	0.6986 (3)	0.0481 (11)
H1	0.7523	0.2226	0.7439	0.058*
O1	0.7970 (5)	0.6832 (4)	0.79876 (16)	0.0488 (7)
C9	0.6074 (6)	0.6629 (6)	0.85319 (19)	0.0360 (7)
O2	0.4710 (6)	0.7600 (3)	0.88109 (18)	0.0495 (7)
C8	0.5764 (8)	0.4886 (4)	0.8712 (2)	0.0325 (8)
H8	0.7551	0.4384	0.8731	0.039*
N2	0.8359 (11)	0.3691 (6)	0.4697 (3)	0.0759 (13)
O3	1.0072 (9)	0.2696 (7)	0.4603 (2)	0.1077 (17)
O4	0.7514 (11)	0.4561 (6)	0.4108 (3)	0.1200 (18)
C10	0.8330 (12)	0.8435 (6)	0.7701 (3)	0.0717 (15)
H10A	0.9736	0.8472	0.7308	0.107*
H10B	0.8837	0.9076	0.8206	0.107*
H10C	0.6653	0.8808	0.7399	0.107*
N1	0.4679 (6)	0.4728 (4)	0.95973 (18)	0.0391 (8)
H1A	0.6015	0.4736	1.0021	0.059*
H1B	0.3245	0.5428	0.9591	0.059*
H1C	0.3835	0.3672	0.9607	0.059*
Br1	0.99538 (6)	0.66497 (4)	0.05395 (2)	0.04632 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C6	0.045 (2)	0.043 (2)	0.029 (2)	−0.0124 (19)	0.0045 (17)	−0.0031 (18)
C2	0.065 (3)	0.061 (3)	0.045 (3)	0.003 (2)	0.009 (2)	−0.018 (2)
C7	0.042 (2)	0.050 (2)	0.041 (2)	−0.014 (2)	0.0121 (18)	−0.006 (2)
C3	0.064 (3)	0.064 (3)	0.032 (2)	−0.019 (2)	0.015 (2)	−0.014 (2)
C5	0.062 (3)	0.056 (3)	0.049 (3)	0.007 (2)	0.006 (2)	0.002 (2)
C4	0.096 (4)	0.064 (3)	0.033 (3)	−0.005 (3)	0.010 (3)	0.008 (2)
C1	0.063 (3)	0.041 (2)	0.040 (2)	0.003 (2)	0.005 (2)	−0.0061 (19)
O1	0.0659 (16)	0.0393 (17)	0.0455 (14)	−0.0094 (17)	0.0266 (12)	−0.0001 (15)
C9	0.0413 (16)	0.0386 (16)	0.0280 (16)	−0.001 (3)	0.0032 (13)	0.001 (2)
O2	0.0603 (18)	0.0379 (16)	0.0533 (18)	0.0130 (15)	0.0201 (14)	0.0078 (14)
C8	0.039 (2)	0.0319 (19)	0.0278 (19)	0.0033 (17)	0.0099 (15)	−0.0005 (16)
N2	0.098 (4)	0.094 (3)	0.039 (3)	−0.028 (3)	0.024 (3)	−0.021 (2)
O3	0.109 (4)	0.151 (5)	0.070 (3)	−0.003 (3)	0.044 (3)	−0.034 (3)
O4	0.177 (5)	0.142 (4)	0.049 (3)	−0.017 (4)	0.048 (3)	0.001 (3)
C10	0.103 (4)	0.058 (3)	0.059 (3)	−0.015 (3)	0.031 (3)	0.010 (2)
N1	0.054 (2)	0.0350 (17)	0.0299 (17)	0.0033 (15)	0.0137 (15)	0.0039 (14)
Br1	0.0471 (2)	0.0436 (2)	0.0490 (2)	0.0020 (3)	0.00881 (15)	−0.0088 (3)

Geometric parameters (Å, º) top

C6—C1	1.380 (6)	O1—C9	1.322 (4)
C6—C5	1.408 (5)	O1—C10	1.466 (6)
C6—C7	1.503 (5)	C9—O2	1.180 (5)
C2—C3	1.353 (6)	C9—C8	1.538 (6)
C2—C1	1.363 (5)	C8—N1	1.506 (4)
C2—H2	0.9300	C8—H8	0.9800
C7—C8	1.538 (5)	N2—O4	1.210 (6)
C7—H7A	0.9700	N2—O3	1.223 (6)
C7—H7B	0.9700	C10—H10A	0.9600
C3—C4	1.363 (6)	C10—H10B	0.9600
C3—N2	1.468 (6)	C10—H10C	0.9600
C5—C4	1.356 (5)	N1—H1A	0.8742
C5—H5	0.9300	N1—H1B	0.9289
C4—H4	0.9300	N1—H1C	1.0023
C1—H1	0.9300

C1—C6—C5	117.4 (4)	O2—C9—O1	126.6 (5)
C1—C6—C7	121.4 (4)	O2—C9—C8	124.0 (3)
C5—C6—C7	121.2 (4)	O1—C9—C8	109.3 (4)
C3—C2—C1	119.1 (4)	N1—C8—C9	107.4 (3)
C3—C2—H2	120.4	N1—C8—C7	109.9 (3)
C1—C2—H2	120.4	C9—C8—C7	111.4 (3)
C6—C7—C8	112.1 (3)	N1—C8—H8	109.4
C6—C7—H7A	109.2	C9—C8—H8	109.4
C8—C7—H7A	109.2	C7—C8—H8	109.4
C6—C7—H7B	109.2	O4—N2—O3	122.6 (5)
C8—C7—H7B	109.2	O4—N2—C3	118.3 (6)
H7A—C7—H7B	107.9	O3—N2—C3	119.0 (5)
C2—C3—C4	121.5 (4)	O1—C10—H10A	109.5
C2—C3—N2	119.4 (5)	O1—C10—H10B	109.5
C4—C3—N2	119.1 (5)	H10A—C10—H10B	109.5
C4—C5—C6	120.3 (4)	O1—C10—H10C	109.5
C4—C5—H5	119.8	H10A—C10—H10C	109.5
C6—C5—H5	119.8	H10B—C10—H10C	109.5
C5—C4—C3	119.9 (4)	C8—N1—H1A	110.5
C5—C4—H4	120.1	C8—N1—H1B	105.7
C3—C4—H4	120.1	H1A—N1—H1B	121.3
C2—C1—C6	121.8 (4)	C8—N1—H1C	106.3
C2—C1—H1	119.1	H1A—N1—H1C	106.2
C6—C1—H1	119.1	H1B—N1—H1C	105.9
C9—O1—C10	115.2 (4)

C1—C6—C7—C8	75.9 (5)	C10—O1—C9—O2	−1.2 (5)
C5—C6—C7—C8	−104.6 (4)	C10—O1—C9—C8	175.3 (3)
C1—C2—C3—C4	−0.6 (7)	O2—C9—C8—N1	−29.0 (4)
C1—C2—C3—N2	−179.9 (4)	O1—C9—C8—N1	154.3 (3)
C1—C6—C5—C4	−0.8 (6)	O2—C9—C8—C7	91.3 (4)
C7—C6—C5—C4	179.7 (4)	O1—C9—C8—C7	−85.4 (3)
C6—C5—C4—C3	0.1 (7)	C6—C7—C8—N1	−170.5 (3)
C2—C3—C4—C5	0.6 (7)	C6—C7—C8—C9	70.7 (4)
N2—C3—C4—C5	179.9 (4)	C2—C3—N2—O4	178.0 (5)
C3—C2—C1—C6	−0.2 (7)	C4—C3—N2—O4	−1.3 (7)
C5—C6—C1—C2	0.9 (6)	C2—C3—N2—O3	0.6 (7)
C7—C6—C1—C2	−179.7 (4)	C4—C3—N2—O3	−178.7 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.87	2.61	3.031 (4)	111
N1—H1A···Br1ⁱⁱ	0.87	2.61	3.290 (3)	135
N1—H1B···Br1ⁱⁱⁱ	0.93	2.51	3.303 (3)	143
N1—H1C···Br1^iv	1.00	2.55	3.495 (3)	157

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₂O₄⁺·Br⁻
M_r	305.13
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	4.9323 (10), 8.6233 (17), 15.226 (3)
β (°)	95.77 (3)
V (Å³)	644.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.20
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	0.90, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	6658, 2917, 2532
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.085, 1.04
No. of reflections	2917
No. of parameters	154
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.30
Absolute structure	Flack (1983), 1202 Friedel pairs
Absolute structure parameter	0.008 (5)

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.87	2.61	3.031 (4)	110.6
N1—H1A···Br1ⁱⁱ	0.87	2.61	3.290 (3)	135.3
N1—H1B···Br1ⁱⁱⁱ	0.93	2.51	3.303 (3)	143.3
N1—H1C···Br1^iv	1.00	2.55	3.495 (3)	157.3

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