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ISSN: 2056-9890

Glycine ethyl ester hydro­chloride

aJiangsu Institute of Nuclear Medicine, Wuxi 214063, People's Republic of China
*Correspondence e-mail: yongjunhe001@hotmail.com

(Received 12 May 2010; accepted 20 July 2010; online 24 July 2010)

In the crystal structure of the title compound, C4H10NO2+·Cl (systematic name: 3-eth­oxy-3-oxopropan-1-aminium chlor­ide), there are strong inter­molecular N—H⋯Cl, C—H⋯Cl and C—H⋯O hydrogen-bonding inter­actions between the free chloride anion and the organic cation, resulting in a two-dimensional supra­molecular network in the ab plane.

Related literature

The title compound is an inter­mediate in the synthesis of dichloro­vinyl­cyclo­propane carb­oxy­lic acid, see: Xue (1995[Xue, Z. X. (1995). Pesticides, 34, 29-33.]). For related structures, see: Taubald et al. (1984[Taubald, U., Nagel, U. & Beck, W. (1984). Chem. Ber. 117, 1003-1012.]); Gainsford et al. (1986[Gainsford, G. J., Jackson, W. G. & Sargeson, A. M. (1986). Aust. J. Chem. 39, 1331-1336.]); Eduok et al. (1994[Eduok, E. E., Kashyap, R. P., Nagl, A., Bourne, S. A. & Watson, W. H. (1994). J. Chem. Crystallogr. 24, 627-638.]).

[Scheme 1]

Experimental

Crystal data
  • C4H10NO2+·Cl

  • Mr = 139.58

  • Monoclinic, P 21 /c

  • a = 8.965 (3) Å

  • b = 12.543 (4) Å

  • c = 5.972 (2) Å

  • β = 103.630 (5)°

  • V = 652.6 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.50 mm−1

  • T = 123 K

  • 0.33 × 0.33 × 0.23 mm

Data collection
  • Rigaku SPIDER diffractometer

  • 4996 measured reflections

  • 1489 independent reflections

  • 1294 reflections with I > 2σ(I)

  • Rint = 0.024

Refinement
  • R[F2 > 2σ(F2)] = 0.027

  • wR(F2) = 0.064

  • S = 1.00

  • 1489 reflections

  • 87 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.40 e Å−3

  • Δρmin = −0.21 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H0A⋯Cl1 0.904 (17) 2.300 (17) 3.1845 (16) 166.1 (12)
N1—H0B⋯Cl1i 0.906 (18) 2.386 (18) 3.1658 (16) 144.3 (15)
N1—H0C⋯Cl1 0.890 (19) 2.435 (19) 3.2566 (16) 153.7 (15)
C1—H1A⋯O2 0.99 2.47 2.9072 (18) 106
C3—H3B⋯Cl1ii 0.99 2.79 3.7529 (18) 164
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z+1.

Data collection: RAPID-AUTO (Rigaku, 2004[Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

The title compound, glycine ethyl ester hydrochloride is used in the preparation of dichlorovinylcyclopropane carboxylic acid, an important pesticide intermediate (Xue,1995).It is also used in the preparation of function material, the crystal structures of dichloro-bis(glycine ethyl ester)-palladium(II) (Taubald, et al., 1984),p,p-(µ2-peroxo) -bis(tris(2-aminoethyl)-amine-N,N',N'',N''')-bis(ethylglycinate-N)-cobalt(II) tetraperchlorate (Gainsford et al., 1986),cis-β2-((s,s)-chloro-(glycine ethyl ester-N)-(triethylenetetramine)-cobalt(III) dichloride trihydrate (Eduok et al., 1994) have been reported. The molecular structure of(I) is shown in Fig.1. The three crystallographically independent N—H moieties are engaged in highly directional N+—H···Cl- hydrogen bonds with three symmetry-related Cl- anions. These interactions promote the formation of a tape of C4H10NO2 +.Cl- moieties running parallel to the c axis.

Related literature top

The title compound is an intermediate in the synthesis of dichlorovinylcyclopropane carboxylic acid, see: Xue (1995). For related structures, see: Taubald et al. (1984); Gainsford et al. (1986); Eduok et al. (1994).

Experimental top

Glycine ethyl ester hydrochloride (0.1 mmol, Sigma Aldrich at 99% purity) was dissolved methanol (20 ml) and gently heated under reflux for 1 h. After cooling the solution to ambient temperature, crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of the solvent after few days.

Refinement top

Hydrogen atoms bound to nitrogen and carbon were located at their idealized positions and were included in the final structural model in riding-motion approximation with C—H = 0.98Å and N—H = 0.90 Å. The isotropic thermal displacement parameters for these atoms were fixed at 1.2 (for the -CH2- and -CH3 group) or 1.5 (for the pendant -NH3+ moieties) times Ueq of the atom to which they are attached.

Structure description top

The title compound, glycine ethyl ester hydrochloride is used in the preparation of dichlorovinylcyclopropane carboxylic acid, an important pesticide intermediate (Xue,1995).It is also used in the preparation of function material, the crystal structures of dichloro-bis(glycine ethyl ester)-palladium(II) (Taubald, et al., 1984),p,p-(µ2-peroxo) -bis(tris(2-aminoethyl)-amine-N,N',N'',N''')-bis(ethylglycinate-N)-cobalt(II) tetraperchlorate (Gainsford et al., 1986),cis-β2-((s,s)-chloro-(glycine ethyl ester-N)-(triethylenetetramine)-cobalt(III) dichloride trihydrate (Eduok et al., 1994) have been reported. The molecular structure of(I) is shown in Fig.1. The three crystallographically independent N—H moieties are engaged in highly directional N+—H···Cl- hydrogen bonds with three symmetry-related Cl- anions. These interactions promote the formation of a tape of C4H10NO2 +.Cl- moieties running parallel to the c axis.

The title compound is an intermediate in the synthesis of dichlorovinylcyclopropane carboxylic acid, see: Xue (1995). For related structures, see: Taubald et al. (1984); Gainsford et al. (1986); Eduok et al. (1994).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 50% probability level.
[Figure 2] Fig. 2. A view of the packing arrangement of the title compound. Hydogran bonds are shown by dashed lines.
3-ethoxy-3-oxopropan-1-aminium chloride top
Crystal data top
C4H10NO2+·ClF(000) = 296
Mr = 139.58Dx = 1.421 Mg m3
Monoclinic, P21/cMelting point: 145(1) K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 8.965 (3) ÅCell parameters from 1964 reflections
b = 12.543 (4) Åθ = 3.3–27.5°
c = 5.972 (2) ŵ = 0.50 mm1
β = 103.630 (5)°T = 123 K
V = 652.6 (4) Å3Block, colorless
Z = 40.33 × 0.33 × 0.23 mm
Data collection top
Rigaku SPIDER
diffractometer
1294 reflections with I > 2σ(I)
Radiation source: Rotating AnodeRint = 0.024
Graphite monochromatorθmax = 27.5°, θmin = 3.3°
ω scansh = 1011
4996 measured reflectionsk = 1611
1489 independent reflectionsl = 77
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.064 w = 1/[σ2(Fo2) + (0.031P)2 + 0.160P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
1489 reflectionsΔρmax = 0.40 e Å3
87 parametersΔρmin = 0.21 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.011 (3)
Crystal data top
C4H10NO2+·ClV = 652.6 (4) Å3
Mr = 139.58Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.965 (3) ŵ = 0.50 mm1
b = 12.543 (4) ÅT = 123 K
c = 5.972 (2) Å0.33 × 0.33 × 0.23 mm
β = 103.630 (5)°
Data collection top
Rigaku SPIDER
diffractometer
1294 reflections with I > 2σ(I)
4996 measured reflectionsRint = 0.024
1489 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.064H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.40 e Å3
1489 reflectionsΔρmin = 0.21 e Å3
87 parameters
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 > σ(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
xyzUiso*/Ueq
Cl10.00205 (3)0.38254 (2)0.24012 (5)0.01640 (11)
O10.52878 (10)0.38513 (7)0.85715 (16)0.0168 (2)
O20.34886 (10)0.29775 (7)0.59414 (15)0.0171 (2)
N10.11868 (13)0.36318 (9)0.7845 (2)0.0144 (2)
C20.38589 (14)0.35635 (9)0.7575 (2)0.0132 (3)
C10.27318 (14)0.40847 (10)0.8745 (2)0.0136 (3)
H1A0.30560.39651.04290.016*
H1B0.27090.48630.84610.016*
C30.64973 (15)0.34018 (11)0.7579 (2)0.0184 (3)
H3A0.62050.26720.70100.022*
H3B0.74640.33540.87860.022*
C40.67496 (16)0.40810 (11)0.5624 (2)0.0222 (3)
H4A0.58090.40960.43920.027*
H4B0.75890.37820.50290.027*
H4C0.70150.48080.61790.027*
H0A0.0807 (19)0.3806 (11)0.635 (3)0.022 (4)*
H0B0.054 (2)0.3873 (13)0.869 (3)0.035 (5)*
H0C0.1184 (19)0.2925 (15)0.797 (3)0.033 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.01827 (17)0.01928 (19)0.01196 (16)0.00511 (12)0.00419 (11)0.00078 (11)
O10.0131 (4)0.0206 (5)0.0171 (5)0.0019 (4)0.0045 (4)0.0039 (4)
O20.0163 (4)0.0191 (5)0.0157 (5)0.0003 (4)0.0033 (4)0.0049 (4)
N10.0149 (5)0.0166 (6)0.0128 (5)0.0010 (4)0.0055 (4)0.0022 (4)
C20.0150 (6)0.0120 (6)0.0131 (6)0.0006 (5)0.0043 (5)0.0027 (4)
C10.0136 (6)0.0132 (6)0.0141 (6)0.0010 (5)0.0038 (5)0.0020 (5)
C30.0130 (6)0.0224 (7)0.0202 (7)0.0013 (5)0.0046 (5)0.0017 (5)
C40.0216 (7)0.0228 (7)0.0252 (7)0.0032 (5)0.0115 (6)0.0029 (6)
Geometric parameters (Å, º) top
O1—C21.3290 (15)C1—H1A0.9900
O1—C31.4654 (16)C1—H1B0.9900
O2—C21.2040 (15)C3—C41.505 (2)
N1—C11.4762 (16)C3—H3A0.9900
N1—H0A0.902 (17)C3—H3B0.9900
N1—H0B0.906 (19)C4—H4A0.9800
N1—H0C0.890 (18)C4—H4B0.9800
C2—C11.5065 (18)C4—H4C0.9800
C2—O1—C3116.20 (10)C2—C1—H1B109.7
C1—N1—H0A111.7 (10)H1A—C1—H1B108.2
C1—N1—H0B109.8 (12)O1—C3—C4110.89 (11)
H0A—N1—H0B109.0 (16)O1—C3—H3A109.5
C1—N1—H0C111.9 (11)C4—C3—H3A109.5
H0A—N1—H0C108.6 (14)O1—C3—H3B109.5
H0B—N1—H0C105.6 (15)C4—C3—H3B109.5
O2—C2—O1125.54 (12)H3A—C3—H3B108.0
O2—C2—C1123.62 (12)C3—C4—H4A109.5
O1—C2—C1110.83 (11)C3—C4—H4B109.5
N1—C1—C2109.79 (10)H4A—C4—H4B109.5
N1—C1—H1A109.7C3—C4—H4C109.5
C2—C1—H1A109.7H4A—C4—H4C109.5
N1—C1—H1B109.7H4B—C4—H4C109.5
C3—O1—C2—O20.45 (18)O1—C2—C1—N1171.55 (10)
C3—O1—C2—C1179.62 (10)C2—O1—C3—C486.87 (14)
O2—C2—C1—N19.27 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H0A···Cl10.904 (17)2.300 (17)3.1845 (16)166.1 (12)
N1—H0B···Cl1i0.906 (18)2.386 (18)3.1658 (16)144.3 (15)
N1—H0C···Cl10.890 (19)2.435 (19)3.2566 (16)153.7 (15)
C1—H1A···O20.992.472.9072 (18)106
C3—H3B···Cl1ii0.992.793.7529 (18)164
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z+1.

Experimental details

Crystal data
Chemical formulaC4H10NO2+·Cl
Mr139.58
Crystal system, space groupMonoclinic, P21/c
Temperature (K)123
a, b, c (Å)8.965 (3), 12.543 (4), 5.972 (2)
β (°) 103.630 (5)
V3)652.6 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.50
Crystal size (mm)0.33 × 0.33 × 0.23
Data collection
DiffractometerRigaku SPIDER
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4996, 1489, 1294
Rint0.024
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.064, 1.00
No. of reflections1489
No. of parameters87
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.40, 0.21

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H0A···Cl10.904 (17)2.300 (17)3.1845 (16)166.1 (12)
N1—H0B···Cl1i0.906 (18)2.386 (18)3.1658 (16)144.3 (15)
N1—H0C···Cl10.890 (19)2.435 (19)3.2566 (16)153.7 (15)
C1—H1A···O20.99002.47002.9072 (18)106.00
C3—H3B···Cl1ii0.99002.79003.7529 (18)164.00
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z+1.
 

Acknowledgements

This work was supported by the Science Foundation of the Health Department of Jiangsu Province (No. H200934).

References

First citationEduok, E. E., Kashyap, R. P., Nagl, A., Bourne, S. A. & Watson, W. H. (1994). J. Chem. Crystallogr. 24, 627–638.  CSD CrossRef CAS Web of Science Google Scholar
First citationGainsford, G. J., Jackson, W. G. & Sargeson, A. M. (1986). Aust. J. Chem. 39, 1331–1336.  CrossRef CAS Google Scholar
First citationRigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationTaubald, U., Nagel, U. & Beck, W. (1984). Chem. Ber. 117, 1003–1012.  CrossRef CAS Web of Science Google Scholar
First citationXue, Z. X. (1995). Pesticides, 34, 29–33.  Google Scholar

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