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Acta Cryst. (2008). E64, o1003-o1004    [ doi:10.1107/S1600536808012750 ]

(2R,3S)-2-Ammonio-3-hydroxy-3-(4-nitrophenyl)propanoic acid chloride monohydrate

V. Gaumet, V. Weber, V. P. Zaitsev and M. Madesclaire

Abstract top

The title compound, C9H11N2O5+·Cl-·H2O, was synthesized from (1S,2S)-2-amino-1-(4-nitrophenyl)propane-1,3-diol in four steps. As demonstrated by this work, no racemization occurs during this synthetic procedure. The crystal structure displays many intermolecular hydrogen bonds between the acidic cation, chloride anions and the water molecules, forming a three-dimensional network. An intramolecular bond between the ammonium group and a hydroxyl O atom is also present.

Comment top

Preparation of new α-amino acids are of constant interest. (1S,2S) and (1R,2R)-2-amino-1- (4-nitrophenyl)-1,3-propanediols, byproducts in the manufacture of the antibiotic Chloramphenicol (Zaitsev et al., 1998), can be used as starting materials in the preparation of corresponding α-amino acid isomers. The title compound (V) was synthesized from (1S,2S)-2-amino-1- (4-nitrophenyl)-1,3-propanediol (I) in four steps according to Figure 1. The intermediate formation of the 2-oxazolidinone derivative (III) allowed to protect both the adjacent amino and hydroxyl groups (Di Giovanni et al., 1996; Crich et al., 2007). The absolute configuration, determined using anomalous dispersion by chlorine, confirms the R and S configurations respectively for C2 and C3 atoms, confirming that no racemization occurs during this synthetic route (note that the Cahn-Ingold-Prelog designation at the α-carbon of the hydroxyl group is reversed by comparison with that of the starting material due to the change in priority of the substituents). As expected, the phenyl ring is planar, r.m.s. deviation from the best plane is ca. 0.007Å. The nitro group is coplanar with the adjacent phenyl ring (O15—N11—C7—C8 = 0.2 (3)° and O16—N11—C7—C8 = 179.9 (2)°). However, the σ bond C7—N11 (1.4704 (17) Å) shows that there is no appreciable π delocalization in the bond between the sp2 hybridized N11 and the phenyl ring.

Related literature top

For related compounds see: Crich et al. (2007); Di Giovanni et al. (1996); Easton et al. (1996); Madesclaire et al. (2006, 2007); Steinreiber et al. (2007); Zaitsev et al. (1998).

Experimental top

Figure 1 summarizes the synthetic route used (Madesclaire et al., 2006 and 2007). Crystals suitable for an X-ray diffraction study were obtained by slow evaporation of a water solution containing compound (V).

Refinement top

The structure was solved by direct methods and refined with anisotropic temperature factors for non-H atoms. All H atoms were found from difference Fourier maps. The H atoms were all refined isotropically with no constraints.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. Synthesis of the title compound (V).
[Figure 2] Fig. 2. The molecular structure of the title compound (V), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 3] Fig. 3. Crystal packing of the title compound. Intra and intermolecular hydrogen bonds are shown as dashed lines. H atoms not involved in the interactions have been omitted.
(2R,3S)-2-Ammonio-3-hydroxy-3-(4-nitrophenyl)propanoic acid chloride monohydrate top
Crystal data top
C9H11N2O5+·Cl–·H2OF000 = 292
Mr = 280.66Dx = 1.479 Mg m−3
Monoclinic, P21Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 25 reflections
a = 8.1286 (17) Åθ = 8–18º
b = 5.056 (3) ŵ = 0.33 mm−1
c = 15.848 (3) ÅT = 293 (2) K
β = 104.626 (17)ºElongated prism, colourless
V = 630.2 (4) Å30.49 × 0.25 × 0.20 mm
Z = 2
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.022
Radiation source: fine-focus sealed tubeθmax = 35.0º
Monochromator: graphiteθmin = 1.3º
T = 293(2) Kh = −13→13
ω/2θ scansk = −8→8
Absorption correction: ψ scan
(North et al., 1968)		l = −25→25
Tmin = 0.872, Tmax = 0.9313 standard reflections
6026 measured reflections every 63 reflections
5517 independent reflections intensity decay: 3%
5058 reflections with I > 2σ(I)
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.043  w = 1/[σ2(Fo2) + (0.0825P)2 + 0.0202P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.115(Δ/σ)max = 0.001
S = 1.09Δρmax = 0.60 e Å−3
5517 reflectionsΔρmin = −0.63 e Å−3
216 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.089 (10)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 2752 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.00 (4)
Crystal data top
C9H11N2O5+·Cl–·H2OV = 630.2 (4) Å3
Mr = 280.66Z = 2
Monoclinic, P21Mo Kα
a = 8.1286 (17) ŵ = 0.33 mm−1
b = 5.056 (3) ÅT = 293 (2) K
c = 15.848 (3) Å0.49 × 0.25 × 0.20 mm
β = 104.626 (17)º
Data collection top
Enraf–Nonius CAD-4
diffractometer		5058 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.022
Tmin = 0.872, Tmax = 0.9313 standard reflections
6026 measured reflections every 63 reflections
5517 independent reflections intensity decay: 3%
Refinement top
R[F2 > 2σ(F2)] = 0.043All H-atom parameters refined
wR(F2) = 0.115Δρmax = 0.60 e Å−3
S = 1.09Δρmin = −0.63 e Å−3
5517 reflectionsAbsolute structure: Flack (1983), 2752 Friedel pairs
216 parametersFlack parameter: 0.00 (4)
1 restraint
Special details top

Experimental. North A.C.T., Phillips D.C. & Mathews F.S. (1968) Acta. Cryst. A24, 351. Number of psi-scan sets used was 4. Theta correction was applied. Weighted transmission curves were used. No Fourier smoothing was applied.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl0.71520 (3)0.93514 (6)0.922526 (17)0.03591 (8)
C1−0.00336 (13)1.2561 (2)0.83505 (7)0.02674 (16)
C20.09722 (12)1.00092 (18)0.85613 (6)0.02405 (15)
C30.27337 (13)1.0067 (2)0.83713 (6)0.02743 (16)
C40.26848 (14)1.0458 (2)0.74189 (7)0.02986 (18)
C50.3717 (2)1.2362 (3)0.71889 (9)0.0427 (3)
C60.3767 (3)1.2672 (4)0.63235 (10)0.0499 (4)
C70.2774 (2)1.1044 (3)0.57084 (8)0.0415 (3)
C80.1743 (2)0.9107 (4)0.59137 (9)0.0506 (4)
C90.1720 (2)0.8796 (3)0.67820 (9)0.0459 (3)
N100.12271 (11)0.9477 (2)0.95052 (5)0.02702 (14)
N110.2786 (2)1.1354 (4)0.47874 (9)0.0569 (4)
O12−0.08726 (19)1.2705 (3)0.75327 (6)0.0491 (3)
O13−0.00519 (12)1.42165 (18)0.88974 (5)0.03491 (16)
O140.34476 (13)0.7557 (2)0.86696 (7)0.03708 (19)
O150.1882 (3)0.9890 (7)0.42545 (9)0.0966 (9)
O160.3691 (3)1.3062 (5)0.45945 (10)0.0847 (6)
H20.034 (3)0.872 (5)0.8304 (13)0.037 (5)*
H30.343 (3)1.127 (5)0.8692 (13)0.032 (5)*
H50.445 (3)1.340 (6)0.7648 (17)0.052 (6)*
H60.453 (4)1.424 (10)0.620 (2)0.091 (10)*
H80.112 (5)0.807 (10)0.548 (2)0.087 (10)*
H90.090 (4)0.766 (8)0.6899 (19)0.073 (9)*
H1010.032 (2)0.927 (4)0.9615 (10)0.025 (3)*
H1020.186 (2)0.816 (4)0.9639 (12)0.030 (4)*
H1030.174 (4)1.087 (7)0.9905 (16)0.058 (7)*
H12−0.147 (5)1.395 (10)0.743 (2)0.087 (10)*
H140.448 (3)0.778 (6)0.8856 (15)0.049 (6)*
O170.29100 (18)0.1787 (3)0.26402 (8)0.0491 (3)
H1710.307 (4)0.250 (8)0.309 (2)0.073 (9)*
H1720.290 (3)0.237 (6)0.2194 (17)0.053 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.03069 (11)0.03544 (12)0.03887 (13)0.00116 (10)0.00372 (8)−0.00215 (10)
C10.0319 (4)0.0221 (3)0.0267 (4)0.0005 (3)0.0084 (3)0.0022 (3)
C20.0281 (3)0.0200 (3)0.0249 (3)−0.0009 (3)0.0083 (3)0.0000 (2)
C30.0288 (4)0.0274 (4)0.0276 (4)−0.0040 (3)0.0099 (3)−0.0011 (3)
C40.0339 (4)0.0297 (4)0.0287 (4)−0.0028 (3)0.0130 (3)−0.0025 (3)
C50.0576 (7)0.0393 (6)0.0359 (5)−0.0182 (6)0.0206 (5)−0.0051 (4)
C60.0705 (10)0.0481 (7)0.0377 (6)−0.0171 (7)0.0260 (6)−0.0004 (5)
C70.0531 (7)0.0457 (7)0.0295 (5)0.0025 (5)0.0176 (5)0.0005 (4)
C80.0595 (8)0.0634 (10)0.0304 (5)−0.0190 (8)0.0141 (5)−0.0110 (6)
C90.0582 (8)0.0504 (8)0.0323 (5)−0.0227 (6)0.0172 (5)−0.0090 (5)
N100.0337 (3)0.0226 (3)0.0266 (3)0.0022 (3)0.0110 (2)0.0036 (3)
N110.0739 (10)0.0692 (11)0.0324 (5)−0.0018 (8)0.0221 (6)0.0009 (6)
O120.0684 (7)0.0451 (5)0.0274 (4)0.0240 (5)0.0005 (4)0.0003 (4)
O130.0471 (4)0.0216 (3)0.0339 (3)0.0039 (3)0.0062 (3)−0.0026 (3)
O140.0310 (4)0.0371 (4)0.0441 (5)0.0061 (3)0.0112 (3)0.0058 (4)
O150.1309 (16)0.127 (2)0.0336 (5)−0.0504 (17)0.0250 (8)−0.0151 (8)
O160.1330 (17)0.0846 (12)0.0465 (7)−0.0305 (13)0.0414 (9)0.0055 (8)
O170.0652 (7)0.0431 (5)0.0357 (5)−0.0145 (5)0.0070 (4)0.0004 (4)
Geometric parameters (Å, °) top
C1—O131.2078 (14)C7—C81.380 (2)
C1—O121.3053 (14)C7—N111.4704 (17)
C1—C21.5188 (15)C8—C91.3898 (18)
C2—N101.4821 (12)C8—H80.91 (4)
C2—C31.5360 (14)C9—H90.94 (4)
C2—H20.87 (2)N10—H1010.810 (17)
C3—O141.4253 (16)N10—H1020.83 (2)
C3—C41.5128 (14)N10—H1030.97 (3)
C3—H30.90 (2)N11—O151.219 (3)
C4—C51.3851 (17)N11—O161.222 (3)
C4—C91.3931 (18)O12—H120.78 (5)
C5—C61.3913 (19)O14—H140.82 (3)
C5—H50.97 (3)O17—H1710.78 (3)
C6—C71.372 (2)O17—H1720.76 (3)
C6—H61.05 (4)
O13—C1—O12125.15 (11)C5—C6—H6115.3 (17)
O13—C1—C2122.31 (10)C6—C7—C8122.79 (12)
O12—C1—C2112.53 (9)C6—C7—N11119.42 (14)
N10—C2—C1107.85 (8)C8—C7—N11117.79 (14)
N10—C2—C3107.55 (8)C7—C8—C9118.33 (14)
C1—C2—C3114.68 (8)C7—C8—H8119 (3)
N10—C2—H2104.6 (14)C9—C8—H8123 (3)
C1—C2—H2108.4 (15)C8—C9—C4120.22 (13)
C3—C2—H2113.1 (14)C8—C9—H9117.0 (19)
O14—C3—C4110.69 (9)C4—C9—H9121.9 (19)
O14—C3—C2103.87 (8)C2—N10—H101109.8 (11)
C4—C3—C2114.02 (9)C2—N10—H102108.8 (13)
O14—C3—H3105.5 (14)H101—N10—H102112 (2)
C4—C3—H3109.3 (13)C2—N10—H103117.1 (17)
C2—C3—H3113.1 (13)H101—N10—H103102 (2)
C5—C4—C9119.76 (11)H102—N10—H103106 (2)
C5—C4—C3119.24 (10)O15—N11—O16123.43 (16)
C9—C4—C3120.81 (10)O15—N11—C7117.97 (18)
C4—C5—C6120.54 (13)O16—N11—C7118.60 (17)
C4—C5—H5118.4 (17)C1—O12—H12113 (2)
C6—C5—H5120.9 (17)C3—O14—H14107 (2)
C7—C6—C5118.32 (13)H171—O17—H172129 (4)
C7—C6—H6126.2 (17)
O15—N11—C7—C6−179.5 (2)O14—C3—C4—C962.57 (15)
O16—N11—C7—C60.2 (3)O14—C3—C4—C5−112.37 (13)
O15—N11—C7—C80.2 (3)C2—C3—C4—C9−54.08 (14)
O16—N11—C7—C8179.9 (2)C5—C4—C9—C8−2.4 (2)
O12—C1—C2—C384.78 (12)C3—C4—C9—C8−177.27 (13)
O12—C1—C2—N10−155.44 (11)C9—C4—C5—C61.6 (2)
O13—C1—C2—N1023.39 (14)C3—C4—C5—C6176.57 (15)
O13—C1—C2—C3−96.39 (12)C4—C5—C6—C7−0.2 (3)
C1—C2—C3—O14176.50 (9)C5—C6—C7—N11179.19 (18)
C1—C2—C3—C4−62.95 (11)C5—C6—C7—C8−0.5 (3)
N10—C2—C3—C4177.11 (8)C6—C7—C8—C9−0.2 (3)
N10—C2—C3—O1456.56 (10)N11—C7—C8—C9−179.96 (17)
C2—C3—C4—C5130.98 (12)C7—C8—C9—C41.7 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N10—H101···O13i0.810 (17)2.420 (16)2.9259 (13)121.5 (14)
N10—H101···Clii0.810 (17)2.489 (16)3.2298 (11)152.7 (15)
N10—H102···O140.83 (2)2.265 (19)2.6759 (14)110.8 (16)
N10—H102···Cliii0.83 (2)2.62 (2)3.3409 (14)145.5 (16)
N10—H103···Cliv0.97 (3)2.28 (3)3.2435 (14)176 (3)
O12—H12···O17v0.78 (5)1.84 (5)2.6168 (19)171 (4)
O14—H14···Cl0.82 (3)2.25 (3)3.0539 (13)166 (3)
O17—H171···O16vi0.78 (3)2.33 (3)3.069 (2)159 (4)
O17—H172···Clvii0.76 (3)2.45 (3)3.2170 (13)178 (3)
Symmetry codes: (i) −x, y−1/2, −z+2; (ii) x−1, y, z; (iii) −x+1, y−1/2, −z+2; (iv) −x+1, y+1/2, −z+2; (v) −x, y+3/2, −z+1; (vi) x, y−1, z; (vii) −x+1, y−1/2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N10—H101···O13i0.810 (17)2.420 (16)2.9259 (13)121.5 (14)
N10—H101···Clii0.810 (17)2.489 (16)3.2298 (11)152.7 (15)
N10—H102···O140.83 (2)2.265 (19)2.6759 (14)110.8 (16)
N10—H102···Cliii0.83 (2)2.62 (2)3.3409 (14)145.5 (16)
N10—H103···Cliv0.97 (3)2.28 (3)3.2435 (14)176 (3)
O12—H12···O17v0.78 (5)1.84 (5)2.6168 (19)171 (4)
O14—H14···Cl0.82 (3)2.25 (3)3.0539 (13)166 (3)
O17—H171···O16vi0.78 (3)2.33 (3)3.069 (2)159 (4)
O17—H172···Clvii0.76 (3)2.45 (3)3.2170 (13)178 (3)
Symmetry codes: (i) −x, y−1/2, −z+2; (ii) x−1, y, z; (iii) −x+1, y−1/2, −z+2; (iv) −x+1, y+1/2, −z+2; (v) −x, y+3/2, −z+1; (vi) x, y−1, z; (vii) −x+1, y−1/2, −z+1.
references
References top

Crich, D. & Li, W. (2007). J. Org. Chem. 72, 2387–2391.

Di Giovanni, M. C., Misiti, D., Villani, C. & Zappia, G. (1996). Tetrahedron Asymmetry, 7, 2277–2286.

Easton, C. J., Hutton, C. A., Merrett, M. C. & Tiekink, E. R. T. (1996). Tetrahedron, 52, 7025–7036.

Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

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

Harms, K. (1996). XCAD4. University of Marburg, Germany.

Madesclaire, M., Coudert, P., Zaitsev, V. P. & Zaitseva, J. V. (2006). Chem. Heterocycl. Compd. 42, 506–511.

Madesclaire, M., Zaitsev, V. P., Zaitseva, J. V. & Sharipova, S. Kh. (2007). Chem. Heterocycl. Compd. 43, 1325–1332.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

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

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Steinreiber, J., Fesko, K., Reisinger, C., Schürmann, M., van Assema, F., Wolberg, M., Mink, D. & Griengl, H. (2007). Tetrahedron, 63, 918–926.

Zaitsev, V. P., Sharipova, S. Kh. & Zhuravleva, I. I. (1998). Pharm. Chem. J. 32, 157–160.