Glycine methyl ester hydro­chloride

Vilela, S.M.F.; Almeida Paz, F.A.; Tomé, J.P.C.; Zea Bermudez, V. de; Cavaleiro, J.A.S.; Rocha, J.

doi:10.1107/S1600536809028414

organic compounds

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Volume 65| Part 8| August 2009| Page o1970

doi:10.1107/S1600536809028414

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Glycine methyl ester hydrochloride

Sérgio M. F. Vilela,^a Filipe A. Almeida Paz,^a ^* João P. C. Tomé,^b Verónica de Zea Bermudez,^c José A. S. Cavaleiro ^b and João Rocha ^a

^aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal, ^bDepartment of Chemistry, University of Aveiro, QOPNA, 3810-193 Aveiro, Portugal, and ^cDepartment of Chemistry, CQ-VR, University of Trás-os-Montes e Alto Douro, 5001-801 Vila Real, Portugal
^*Correspondence e-mail: filipe.paz@ua.pt

(Received 14 July 2009; accepted 17 July 2009; online 25 July 2009)

The title compound [systematic name: (methoxycarbonylmethyl)ammonium chloride], crystallizes as a salt, C₃H₈NO₂⁺·Cl⁻, with the charged species interacting mutually via strong and highly directional N⁺—H⋯Cl⁻ hydrogen bonds which lead to the formation of a supramolecular tape running parallel to the c axis. Tapes close pack in the solid state mediated by multipoint recognition synthons based on weak C—H⋯O interactions and van der Waals contacts between adjacent methyl groups.

Related literature

For related structures, see: Handelsman-Benory et al. (1995 ). For detailed background to the role of hydrogen bonds in the supramolecular organization of organic crystals, see: Nangia & Desiraju (1998 ). For general background studies on crystal engineering approaches from our research group, see: Shi et al. (2008 ); Paz & Klinowski (2003 ); Paz et al. (2002 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₃H₈NO₂⁺·Cl⁻
M_r = 125.55
Monoclinic, P 2₁ /c
a = 8.352 (2) Å
b = 12.505 (3) Å
c = 5.6369 (14) Å
β = 99.730 (9)°
V = 580.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.55 mm⁻¹
T = 150 K
0.08 × 0.02 × 0.02 mm

Data collection

Bruker X8 Kappa CCD APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.957, T_max = 0.989
5189 measured reflections
1539 independent reflections
923 reflections with I > 2σ(I)
R_int = 0.070

Refinement

R[F² > 2σ(F²)] = 0.069
wR(F²) = 0.184
S = 1.08
1539 reflections
66 parameters
H-atom parameters constrained
Δρ_max = 1.05 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.91	2.52	3.269 (4)	140
N1—H1B⋯Cl1ⁱⁱ	0.91	2.25	3.112 (4)	158
N1—H1C⋯Cl1	0.91	2.26	3.147 (4)	165
C1—H1D⋯Cl1ⁱⁱⁱ	0.99	2.69	3.448 (4)	133
C1—H1E⋯O2ⁱ	0.99	2.51	2.928 (4)	105
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x, y, z+1; (iii) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT-Plus (Bruker, 2005 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028414/hg2539sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809028414/hg2539Isup2.hkl

checkCIF report

Comment top

Following our interest in crystal engineering (Shi et al., 2008; Paz & Klinowski, 2003; Paz et al., 2002), we recently started to prepare novel organic ligands based on amino acid moieties, which can be ultimately employed as building units in the construction of multi-dimensional coordination polymers. Even though the latest release of the Cambridge Structural Database (CSD, Version of November 2008 with three updates; Allen, 2002) contains the remarkable number of 70 determinations of zwiterionic glycine, the structure of the title compound has never been reported to date. It is important to emphasize that crystallization of this compound is not trivial, typically leading to microcrystalline powders with needle-like crystal habit. Larger single crystals could only be obtained when a 1: 1 chloroform: methanol mixture was used (Fig. 1).

The asymmetric unit of the title compound, (I), is composed of a cationic glycinium methyl ester moiety and a chloride anion as depicted in Fig. 2. In the crystal structure, the three crystallographically independent N—H moieties are engaged in strong and highly directional [<(DHA) greater than 140°] N⁺—H···Cl^- hydrogen bonds with three symmetry-related Cl^- anions (Fig. 3). These interactions promote the formation of a tape of C₃H₈NO₂^+.Cl^- moieties running parallel to the c axis. It is noteworthy to emphasize that the N⁺—H···Cl^- interactions can be divided into two families according to the registered d_D···A distances: while the two outer interactions of the tape have interatomic distances ranging from 3.112 (4) to 3.112 (4) Å, the inner hydrogen bond is weaker with the corresponding value being 3.269 (4) Å. Indeed, FT—IR studies on the title compound support this assumption clearly revealing the presence of two stretching bands centered at ca 2628 and 2682 cm^-1 and attributed to two ν(N⁺—H) families, respectively.

Hydrogen-bonded supramolecular C₃H₈NO₂^+.Cl^- chains close pack in the solid state mediated by a combination multipoint recognition synthons involving weak C—H···O hydrogen bonds (not shown; Nangia & Desiraju, 1998) and the need to effectively fill the available space (i.e., van der Waals interactions; Fig. 4). This packing behavior is strikingly distinct from that reported by Handelsman-Benory et al. (1995): while in (I) all H atoms bound to nitrogen are engaged in N⁺—H···Cl^- interactions, in glycyl-glycyl-glycine methyl ester hydrochloride the N—H and C=O moieties from the middle of the chain establish further hydrogen bonding connections with neighboring molecules; the final connectivity of the compounds results in a three-dimensional network of strong and highly directional hydrogen bonds.

Related literature top

For related structures, see: Handelsman-Benory et al. (1995). For detailed background to the role of hydrogen bonds in the supramolecular organization of organic crystals, see: Nangia & Desiraju (1998). For general background studies on crystal engineering approaches from our research group, see: Shi et al. (2008); Paz & Klinowski (2003); Paz et al. (2002). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Glycine methyl ester hydrochloride (99% purity) was purchased from Sigma-Aldrich and used without further purification. Crystalline material suitable for single-crystal studies (Fig. 1) was isolated from the slow evaporation (at ambient temperature) of a 1: 1 chloroform: methanol solution.

Fourier-Transform Infrared (FT—IR) spectra were obtained as KBr (Aldrich 99%+, FT—IR grade) pellets using a Mattson 7000 instrument. Selected FT—IR bands (in cm^-1): overtone ν(C=O) = 3400br,m; ν(N⁺—H) = 2682m and 2628m; ν(C=O) = 1749vs; ν_asym(C—O—C) = 1259vs.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Optical photographs of the (micro-)crystalline material composing the title compound. The inset shows the single-crystal used for data collection, emphasizing morphology (thin needle) and small crystal size. Optical photographs were taken on a Stemi 2000 stereomicroscope equipped with Carl Zeiss lenses and a digital high-resolution AxioCam MRc5 digital camera connected to a personal computer.
	Fig. 2. Asymmetric unit of the title compound. Non-hydrogen atoms are represented as thermal displacement ellipsoids drawn at the 50% probability level and hydrogen atoms as small spheres with arbitrary radii. The atomic labeling is provided for all atoms. Bond lengths and angles are provided in the following Tables.
	Fig. 3. Schematic representation of the N⁺—H···Cl^- hydrogen bonding interactions which lead to the formation of a one-dimensional supramolecular tape running parallel to the c axis. For details on the hydrogen bonding geometry see Table 1. Symmetry transformations used to generate equivalent atoms: (i) x, -y + 1/2, z+1/2; (ii) x, y, z+1.
	Fig. 4. Perspective view along the [001] direction of the crystal packing of the title compound. N⁺—H···Cl^- hydrogen bonds are represented as light-blue dashed lines.

(methoxycarbonylmethyl)ammonium chloride top

Crystal data top

C₃H₈NO₂⁺·Cl⁻	F(000) = 264
M_r = 125.55	D_x = 1.437 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 793 reflections
a = 8.352 (2) Å	θ = 3.0–24.8°
b = 12.505 (3) Å	µ = 0.55 mm⁻¹
c = 5.6369 (14) Å	T = 150 K
β = 99.730 (9)°	Needle, colourless
V = 580.3 (2) Å³	0.08 × 0.02 × 0.02 mm
Z = 4

Data collection top

Bruker X8 Kappa CCD APEXII diffractometer	1539 independent reflections
Radiation source: fine-focus sealed tube	923 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.070
ϕ scans	θ_max = 29.1°, θ_min = 4.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −11→11
T_min = 0.957, T_max = 0.989	k = −17→16
5189 measured reflections	l = −7→7

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.184	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0649P)² + 1.246P] where P = (F_o² + 2F_c²)/3
1539 reflections	(Δ/σ)_max < 0.001
66 parameters	Δρ_max = 1.05 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

C₃H₈NO₂⁺·Cl⁻	V = 580.3 (2) Å³
M_r = 125.55	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.352 (2) Å	µ = 0.55 mm⁻¹
b = 12.505 (3) Å	T = 150 K
c = 5.6369 (14) Å	0.08 × 0.02 × 0.02 mm
β = 99.730 (9)°

Data collection top

Bruker X8 Kappa CCD APEXII diffractometer	1539 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	923 reflections with I > 2σ(I)
T_min = 0.957, T_max = 0.989	R_int = 0.070
5189 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.069	0 restraints
wR(F²) = 0.184	H-atom parameters constrained
S = 1.08	Δρ_max = 1.05 e Å⁻³
1539 reflections	Δρ_min = −0.55 e Å⁻³
66 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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

	x	y	z	U_iso*/U_eq
Cl1	0.47434 (13)	0.11638 (8)	0.24634 (19)	0.0210 (3)
C1	0.7947 (5)	0.0942 (3)	0.8596 (8)	0.0200 (10)
H1D	0.7834	0.0155	0.8502	0.024*
H1E	0.8397	0.1135	1.0280	0.024*
C2	0.9087 (5)	0.1308 (3)	0.6967 (8)	0.0190 (9)
C3	1.1805 (6)	0.1209 (5)	0.6290 (10)	0.0348 (12)
H3A	1.1348	0.1161	0.4573	0.052*
H3B	1.2733	0.0723	0.6660	0.052*
H3C	1.2163	0.1944	0.6682	0.052*
N1	0.6341 (4)	0.1443 (3)	0.7897 (6)	0.0178 (8)
H1A	0.6452	0.2167	0.7915	0.027*
H1B	0.5683	0.1246	0.8954	0.027*
H1C	0.5895	0.1225	0.6390	0.027*
O1	1.0566 (4)	0.0911 (3)	0.7714 (6)	0.0295 (8)
O2	0.8701 (4)	0.1866 (3)	0.5246 (6)	0.0251 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0258 (6)	0.0195 (5)	0.0182 (6)	−0.0065 (5)	0.0049 (4)	−0.0014 (5)
C1	0.016 (2)	0.014 (2)	0.030 (3)	−0.0018 (17)	0.0031 (17)	0.0025 (17)
C2	0.021 (2)	0.0111 (19)	0.026 (3)	−0.0028 (16)	0.0058 (17)	−0.0028 (18)
C3	0.020 (2)	0.040 (3)	0.047 (3)	0.000 (2)	0.013 (2)	0.003 (3)
N1	0.0204 (19)	0.0166 (18)	0.017 (2)	0.0018 (14)	0.0050 (14)	−0.0001 (14)
O1	0.0223 (18)	0.0313 (18)	0.036 (2)	0.0042 (15)	0.0086 (14)	0.0102 (16)
O2	0.0268 (18)	0.0239 (17)	0.0253 (19)	0.0024 (14)	0.0065 (14)	0.0065 (14)

Geometric parameters (Å, º) top

C1—N1	1.472 (5)	C3—H3A	0.9800
C1—C2	1.502 (6)	C3—H3B	0.9800
C1—H1D	0.9900	C3—H3C	0.9800
C1—H1E	0.9900	N1—H1A	0.9100
C2—O2	1.194 (5)	N1—H1B	0.9100
C2—O1	1.332 (5)	N1—H1C	0.9100
C3—O1	1.461 (5)

N1—C1—C2	110.5 (4)	H3A—C3—H3B	109.5
N1—C1—H1D	109.6	O1—C3—H3C	109.5
C2—C1—H1D	109.6	H3A—C3—H3C	109.5
N1—C1—H1E	109.6	H3B—C3—H3C	109.5
C2—C1—H1E	109.6	C1—N1—H1A	109.5
H1D—C1—H1E	108.1	C1—N1—H1B	109.5
O2—C2—O1	125.7 (4)	H1A—N1—H1B	109.5
O2—C2—C1	124.2 (4)	C1—N1—H1C	109.5
O1—C2—C1	110.1 (4)	H1A—N1—H1C	109.5
O1—C3—H3A	109.5	H1B—N1—H1C	109.5
O1—C3—H3B	109.5	C2—O1—C3	115.9 (4)

N1—C1—C2—O2	−5.0 (6)	O2—C2—O1—C3	0.9 (7)
N1—C1—C2—O1	175.7 (3)	C1—C2—O1—C3	−179.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.91	2.52	3.269 (4)	140
N1—H1B···Cl1ⁱⁱ	0.91	2.25	3.112 (4)	158
N1—H1C···Cl1	0.91	2.26	3.147 (4)	165
C1—H1D···Cl1ⁱⁱⁱ	0.99	2.69	3.448 (4)	133
C1—H1E···O2ⁱ	0.99	2.51	2.928 (4)	105

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, y, z+1; (iii) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₃H₈NO₂⁺·Cl⁻
M_r	125.55
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	8.352 (2), 12.505 (3), 5.6369 (14)
β (°)	99.730 (9)
V (Å³)	580.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.55
Crystal size (mm)	0.08 × 0.02 × 0.02

Data collection
Diffractometer	Bruker X8 Kappa CCD APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.957, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	5189, 1539, 923
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.184, 1.08
No. of reflections	1539
No. of parameters	66
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.05, −0.55

Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.91	2.52	3.269 (4)	140.3
N1—H1B···Cl1ⁱⁱ	0.91	2.25	3.112 (4)	157.9
N1—H1C···Cl1	0.91	2.26	3.147 (4)	164.5
C1—H1D···Cl1ⁱⁱⁱ	0.99	2.69	3.448 (4)	133
C1—H1E···O2ⁱ	0.99	2.51	2.928 (4)	105

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, y, z+1; (iii) −x+1, −y, −z+1.

Acknowledgements

We are grateful to Fundação para a Ciência e a Tecnologia (FCT, Portugal) for their general financial support and also for specific funding toward the purchase of the single-crystal diffractometer. SV wishes to acknowledge the Associated Laboratory CICECO for a research grant.

References

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