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

Vincent Gaumet; Valérie Weber; Valery P Zaitsev; Michel Madesclaire

doi:10.1107/S1600536808012750

. 2008 May 7;64(Pt 6):o1003–o1004. doi: 10.1107/S1600536808012750

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

Vincent Gaumet ^a,^*, Valérie Weber ^b, Valery P Zaitsev ^c, Michel Madesclaire ^b

PMCID: PMC2961501 PMID: 21202530

Abstract

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.

Related literature

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

Crystal data

C₉H₁₁N₂O₅ ⁺·Cl⁻·H₂O
M _r = 280.66
Monoclinic,
a = 8.1286 (17) Å
b = 5.056 (3) Å
c = 15.848 (3) Å
β = 104.626 (17)°
V = 630.2 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 293 (2) K
0.49 × 0.25 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.872, T _max = 0.931
6026 measured reflections
5517 independent reflections
5058 reflections with I > 2σ(I)
R _int = 0.021
3 standard reflections every 63 reflections intensity decay: 3%

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.115
S = 1.09
5517 reflections
216 parameters
1 restraint
All H-atom parameters refined
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.63 e Å⁻³
Absolute structure: Flack (1983 ▶), 2752 Friedel pairs
Flack parameter: 0.00 (4)

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; 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 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808012750/cs2076sup1.cif

e-64-o1003-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808012750/cs2076Isup2.hkl

e-64-o1003-Isup2.hkl^{(264.7KB, hkl)}

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
N10—H101⋯O13ⁱ	0.810 (17)	2.420 (16)	2.9259 (13)	121.5 (14)
N10—H101⋯Clⁱⁱ	0.810 (17)	2.489 (16)	3.2298 (11)	152.7 (15)
N10—H102⋯O14	0.83 (2)	2.265 (19)	2.6759 (14)	110.8 (16)
N10—H102⋯Clⁱⁱⁱ	0.83 (2)	2.62 (2)	3.3409 (14)	145.5 (16)
N10—H103⋯Cl^iv	0.97 (3)	2.28 (3)	3.2435 (14)	176 (3)
O12—H12⋯O17^v	0.78 (5)	1.84 (5)	2.6168 (19)	171 (4)
O14—H14⋯Cl	0.82 (3)	2.25 (3)	3.0539 (13)	166 (3)
O17—H171⋯O16^vi	0.78 (3)	2.33 (3)	3.069 (2)	159 (4)
O17—H172⋯Cl^vii	0.76 (3)	2.45 (3)	3.2170 (13)	178 (3)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

supplementary crystallographic information

Comment

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.

Experimental

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).