Glycine ethyl ester hydro­chloride

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.

Key indicators

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.027
• wR factor = 0.064
• Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          4

Alert level G
PLAT432_ALERT_2_G Short Inter X...Y Contact  O2     ..  C2      ..       2.86 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  O2     ..  C1      ..       2.91 Ang.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          3

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

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 U_eq of the atom to which they are attached.

Computing details

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

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 50% probability level.
	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

Crystal data

C4H10NO2^+·Cl^−	F(000) = 296
Mr = 139.58	Dx = 1.421 Mg m^−3
Monoclinic, P21/c	Melting point: 145(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.965 (3) Å	Cell parameters from 1964 reflections
b = 12.543 (4) Å	θ = 3.3–27.5°
c = 5.972 (2) Å	µ = 0.50 mm^−1
β = 103.630 (5)°	T = 123 K
V = 652.6 (4) Å^3	Block, colorless
Z = 4	0.33 × 0.33 × 0.23 mm

Data collection

Rigaku SPIDER diffractometer	1294 reflections with I > 2σ(I)
Radiation source: Rotating Anode	Rint = 0.024
Graphite monochromator	θmax = 27.5°, θmin = 3.3°
ω scans	h = −10→11
4996 measured reflections	k = −16→11
1489 independent reflections	l = −7→7

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.064	w = 1/[σ^2(Fo^2) + (0.031P)^2 + 0.160P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
1489 reflections	Δρmax = 0.40 e Å^−3
87 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	−0.00205 (3)	0.38254 (2)	0.24012 (5)	0.01640 (11)
O1	0.52878 (10)	0.38513 (7)	0.85715 (16)	0.0168 (2)
O2	0.34886 (10)	0.29775 (7)	0.59414 (15)	0.0171 (2)
N1	0.11868 (13)	0.36318 (9)	0.7845 (2)	0.0144 (2)
C2	0.38589 (14)	0.35635 (9)	0.7575 (2)	0.0132 (3)
C1	0.27318 (14)	0.40847 (10)	0.8745 (2)	0.0136 (3)
H1A	0.3056	0.3965	1.0429	0.016*
H1B	0.2709	0.4863	0.8461	0.016*
C3	0.64973 (15)	0.34018 (11)	0.7579 (2)	0.0184 (3)
H3A	0.6205	0.2672	0.7010	0.022*
H3B	0.7464	0.3354	0.8786	0.022*
C4	0.67496 (16)	0.40810 (11)	0.5624 (2)	0.0222 (3)
H4A	0.5809	0.4096	0.4392	0.027*
H4B	0.7589	0.3782	0.5029	0.027*
H4C	0.7015	0.4808	0.6179	0.027*
H0A	0.0807 (19)	0.3806 (11)	0.635 (3)	0.022 (4)*
H0B	0.054 (2)	0.3873 (13)	0.869 (3)	0.035 (5)*
H0C	0.1184 (19)	0.2925 (15)	0.797 (3)	0.033 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.01827 (17)	0.01928 (19)	0.01196 (16)	0.00511 (12)	0.00419 (11)	0.00078 (11)
O1	0.0131 (4)	0.0206 (5)	0.0171 (5)	−0.0019 (4)	0.0045 (4)	−0.0039 (4)
O2	0.0163 (4)	0.0191 (5)	0.0157 (5)	−0.0003 (4)	0.0033 (4)	−0.0049 (4)
N1	0.0149 (5)	0.0166 (6)	0.0128 (5)	−0.0010 (4)	0.0055 (4)	−0.0022 (4)
C2	0.0150 (6)	0.0120 (6)	0.0131 (6)	−0.0006 (5)	0.0043 (5)	0.0027 (4)
C1	0.0136 (6)	0.0132 (6)	0.0141 (6)	−0.0010 (5)	0.0038 (5)	−0.0020 (5)
C3	0.0130 (6)	0.0224 (7)	0.0202 (7)	0.0013 (5)	0.0046 (5)	−0.0017 (5)
C4	0.0216 (7)	0.0228 (7)	0.0252 (7)	−0.0032 (5)	0.0115 (6)	−0.0029 (6)

Geometric parameters (Å, º)

O1—C2	1.3290 (15)	C1—H1A	0.9900
O1—C3	1.4654 (16)	C1—H1B	0.9900
O2—C2	1.2040 (15)	C3—C4	1.505 (2)
N1—C1	1.4762 (16)	C3—H3A	0.9900
N1—H0A	0.902 (17)	C3—H3B	0.9900
N1—H0B	0.906 (19)	C4—H4A	0.9800
N1—H0C	0.890 (18)	C4—H4B	0.9800
C2—C1	1.5065 (18)	C4—H4C	0.9800
C2—O1—C3	116.20 (10)	C2—C1—H1B	109.7
C1—N1—H0A	111.7 (10)	H1A—C1—H1B	108.2
C1—N1—H0B	109.8 (12)	O1—C3—C4	110.89 (11)
H0A—N1—H0B	109.0 (16)	O1—C3—H3A	109.5
C1—N1—H0C	111.9 (11)	C4—C3—H3A	109.5
H0A—N1—H0C	108.6 (14)	O1—C3—H3B	109.5
H0B—N1—H0C	105.6 (15)	C4—C3—H3B	109.5
O2—C2—O1	125.54 (12)	H3A—C3—H3B	108.0
O2—C2—C1	123.62 (12)	C3—C4—H4A	109.5
O1—C2—C1	110.83 (11)	C3—C4—H4B	109.5
N1—C1—C2	109.79 (10)	H4A—C4—H4B	109.5
N1—C1—H1A	109.7	C3—C4—H4C	109.5
C2—C1—H1A	109.7	H4A—C4—H4C	109.5
N1—C1—H1B	109.7	H4B—C4—H4C	109.5
C3—O1—C2—O2	−0.45 (18)	O1—C2—C1—N1	−171.55 (10)
C3—O1—C2—C1	−179.62 (10)	C2—O1—C3—C4	86.87 (14)
O2—C2—C1—N1	9.27 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H0A···Cl1	0.904 (17)	2.300 (17)	3.1845 (16)	166.1 (12)
N1—H0B···Cl1^i	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···Cl1^ii	0.99	2.79	3.7529 (18)	164

Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z+1.