Crystal structure of 1-[(1S,2R)-2-hydroxy-1-methyl-2-phenyl­eth­yl]pyrrolidinium 2-amino-5-chloro­benzoate

Yunli Li; Zhanjun Li; Yanjie Hu; Wen Li

doi:10.1107/S2056989015013389

. 2015 Jul 17;71(Pt 8):o584–o585. doi: 10.1107/S2056989015013389

Crystal structure of 1-[(1S,2R)-2-hydroxy-1-methyl-2-phenylethyl]pyrrolidinium 2-amino-5-chlorobenzoate

Yunli Li ^a, Zhanjun Li ^a, Yanjie Hu ^a, Wen Li ^b,^*

PMCID: PMC4571409 PMID: 26396809

Abstract

In the cation of the title molecular salt, C₁₃H₂₀NO⁺·C₇H₅ClNO₂ ⁻, the five-membered ring adopts a twisted conformation about one of the C—N bonds. The exocyclic N—C bond has an equatorial orientation. The dihedral angle between the five-membered ring (all atoms) and the benzene ring is 76.56 (19)°. In the anion, the dihedral angle between the carboxylate group and the benzene ring is 18.57 (14)°, and an intramolecular N—H⋯O hydrogen bond closes an S(6) ring. In the crystal, the components are linked by O—H⋯O and N—H⋯O hydrogen bonds, generating [100] chains.

Keywords: crystal structure; 2-amino-5-chlorobenzoate anion; 1-[(1S,2R)-2-Hydroxy-1-methyl-2-phenylethyl]pyrrolidinium cation; hydrogen bonding

Related literature

For the crystal structures of related compounds, see: Pennemann et al. (2000 ▸); Sugiyama et al. (2002 ▸); Ishida et al. (2001 ▸). For bond-length data of chlorobenzoate derivatives, see: Arora & Pant (1969 ▸). For applications of the title compound and further synthetic details, see: Kanizsai et al. (2006 ▸); Rzaczynska et al. (2000 ▸).

Experimental

Crystal data

C₁₃H₂₀NO⁺·C₇H₅ClNO₂ ⁻
M _r = 376.87
Orthorhombic,
a = 10.6756 (3) Å
b = 11.5541 (3) Å
c = 15.9228 (4) Å
V = 1964.03 (9) Å³
Z = 4
Cu Kα radiation
μ = 1.90 mm⁻¹
T = 291 K
0.20 × 0.18 × 0.16 mm

Data collection

Agilent Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▸) T _min = 0.921, T _max = 1.000
4968 measured reflections
3173 independent reflections
2805 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.121
S = 1.03
3173 reflections
239 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ▸), 1001 Friedel pairs
Absolute structure parameter: −0.01 (3)

Data collection: CrysAlis PRO (Agilent, 2012 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▸); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015013389/hb7464sup1.cif

e-71-0o584-sup1.cif^{(29.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015013389/hb7464Isup2.hkl

e-71-0o584-Isup2.hkl^{(155.7KB, hkl)}

Click here for additional data file.^{(7.4KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015013389/hb7464Isup3.cml

Click here for additional data file.^{(2.9MB, tif)}

. DOI: 10.1107/S2056989015013389/hb7464fig1.tif

The components of the title salt, showing 50% displacement ellipsoids. Hydrogen bonds are illustrated as dashed lines.

Click here for additional data file.^{(1.3MB, tif)}

b . DOI: 10.1107/S2056989015013389/hb7464fig2.tif

An illustration of the unit cell packing of the title salt viewed down along the b axis. H atoms are omitted for clarity, save those involved in hydrogen bonding.

CCDC reference: 1044077

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O1H1O3ⁱ	0.82	1.84	2.652(3)	172
N1H1AO2ⁱ	0.91	1.79	2.673(3)	162
N2H2AO1ⁱⁱ	0.87	2.36	3.137(3)	148
N2H2BO2	0.87	2.07	2.686(3)	126

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors are grateful to the University Analysis and Testing Center, Zhengzhou Henan, People’s Republic of China, for the single-crystal X-ray diffraction data. We thank the Science and Technology Bureau of Henan and the Education Bureau of Henan for funds through the Cooperation Research Project No. 132107000016 and the Major Research Project No. 14 A530007, respectively.

supplementary crystallographic information

S1. Comment

Norephedrine and its derivatives have used widely because of these using for asymmetric synthesis as catalysts or starting materials (Kanizsai et al., 2006); Rzaczynska et al. (2000); The crystal structure of (1R,2R)-aminoalcohol·HCl (Pennemann et al., 2000), aminopyridine (Sugiyama et al., 2002), Morpholinium 5-chloro-2-nitrobenzoate (Ishida et al., 2001) have been reported. To our knowledge, this is the first structural report of a pyrrolidinium system. We here report the crystal structure of the title compound.

In the title compound (Fig.1), the bond lengths and angles are normal (Arora & Pant, 1969). The asymmetric unit contains one cation–anion pair. The molecular packing features an N—H···O hydrogen bond between the amino group and the oxygen of the carbonyl group. In the crystal, the cation and anion are linked by an N—H···O, O—H···O interaction (Table 1 and Fig.2).

S2. Experimental

An crystal structure salt in the 1:1.5 ration of the original partners of the 2-amino-5-chloro-benzoic acid (5.0 g, 0.0224 mol) and added a chiral additive (1R,2S)-1-phenyl-2-(1-pyrrolidinyl)propan-1-ol (6.4 g, 0.0312 mol). Under the condition of sodium hydride (1.4 g, 0.0583 mol) alkali, choosing anhydrous THF (30 ml) inert solvent under nitrogen atmosphere was stirred for 2h and the process was inspected by TLC. At the end of the reaction processing, the pale yellow prismatic crystals were obtained from the solution by slow volatilization from the solvent of the ethyl acetate after at room temperature overnight. (yield 89%, M.pt: 402-404K). ¹H NMR(400Hz, CDCl₃): δ(ppm): 3.0~3.5 (m,5H,Ar), 2.0~2.2 (e, 8H, CH₂), 1.1~1.3 (t,3H,CH₃), 5.5 (s,1H,OH), 6.5(s,1H,CHOH),7.0 (s,1H,CHCH₃),7.3 (s,1H,NH), 7.4~7.5(t,3H,Ar), 8.0 (q,2H,NH₂). ¹³C NMR(100MHz, CDCl₃): δ(ppm) 9.3, 23.1, 52.5, 68.2, 70.9, 77.5, 117.6, 120.5, 125.7, 127.3, 128.3, 131.8, 140.5, 148.4, 174.9.

S3. Refinement

The H atoms attached to N atoms were located in a difference Fourier-map analyses and were allowed to ride in the refinements. The C-bound H atoms were positioned geometrically and allowed to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C) for methyl group and Uiso(H)= 1.5Ueq(O) for hydroxyl H atom and equal to 1.2Ueq(C,N) for other H atoms.