organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Glycine methyl ester hydro­chloride

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[Handelsman-Benory, E., Botoshansky, M. & Kaftory, M. (1995). Acta Cryst. C51, 2362-2364.]). For detailed background to the role of hydrogen bonds in the supra­molecular organization of organic crystals, see: Nangia & Desiraju (1998[Nangia, A. & Desiraju, G. R. (1998). Topics in Current Chemistry, Vol. 198, edited by E. Weber, pp. 57-96. Berlin Heidelberg: Springer Verlag.]). For general background studies on crystal engineering approaches from our research group, see: Shi et al. (2008[Shi, F.-N., Cunha-Silva, L., Sá Ferreira, R. A., Mafra, L., Trindade, T., Carlos, L. D., Paz, F. A. A. & Rocha, J. (2008). J. Am. Chem. Soc. 130, 150-167.]); Paz & Klinowski (2003[Paz, F. A. A. & Klinowski, J. (2003). CrystEngComm, 5, 238-244.]); Paz et al. (2002[Paz, F. A. A., Bond, A. D., Khimyak, Y. Z. & Klinowski, J. (2002). New J. Chem. 26, 381-383.]). For a description of the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]).

[Scheme 1]

Experimental

Crystal data
  • C3H8NO2+·Cl

  • Mr = 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[Sheldrick, G. M. (1997). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.957, Tmax = 0.989

  • 5189 measured reflections

  • 1539 independent reflections

  • 923 reflections with I > 2σ(I)

  • Rint = 0.070

Refinement
  • R[F2 > 2σ(F2)] = 0.069

  • wR(F2) = 0.184

  • S = 1.08

  • 1539 reflections

  • 66 parameters

  • H-atom parameters constrained

  • Δρmax = 1.05 e Å−3

  • Δρmin = −0.55 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2006). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2005[Bruker (2005). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009[Brandenburg, K. (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXTL.

Supporting information


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 dD···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; νasym(C—O—C) = 1259vs.

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 = 0.98 Å and N—H = 0.91 Å. The isotropic thermal displacement parameters for these atoms were fixed at 1.2 (for the —CH2— group) or 1.5 (for the pendant —NH3+ and —CH3 moieties) times Ueq of the atom to which they are attached.

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
[Figure 1] 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.
[Figure 2] 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.
[Figure 3] 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.
[Figure 4] 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+·ClF(000) = 264
Mr = 125.55Dx = 1.437 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 793 reflections
a = 8.352 (2) Åθ = 3.0–24.8°
b = 12.505 (3) ŵ = 0.55 mm1
c = 5.6369 (14) ÅT = 150 K
β = 99.730 (9)°Needle, colourless
V = 580.3 (2) Å30.08 × 0.02 × 0.02 mm
Z = 4
Data collection top
Bruker X8 Kappa CCD APEXII
diffractometer
1539 independent reflections
Radiation source: fine-focus sealed tube923 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.070
ϕ scansθmax = 29.1°, θmin = 4.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)
h = 1111
Tmin = 0.957, Tmax = 0.989k = 1716
5189 measured reflectionsl = 77
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.184H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0649P)2 + 1.246P]
where P = (Fo2 + 2Fc2)/3
1539 reflections(Δ/σ)max < 0.001
66 parametersΔρmax = 1.05 e Å3
0 restraintsΔρmin = 0.55 e Å3
Crystal data top
C3H8NO2+·ClV = 580.3 (2) Å3
Mr = 125.55Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.352 (2) ŵ = 0.55 mm1
b = 12.505 (3) ÅT = 150 K
c = 5.6369 (14) Å0.08 × 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)
Tmin = 0.957, Tmax = 0.989Rint = 0.070
5189 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0690 restraints
wR(F2) = 0.184H-atom parameters constrained
S = 1.08Δρmax = 1.05 e Å3
1539 reflectionsΔρmin = 0.55 e Å3
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
xyzUiso*/Ueq
Cl10.47434 (13)0.11638 (8)0.24634 (19)0.0210 (3)
C10.7947 (5)0.0942 (3)0.8596 (8)0.0200 (10)
H1D0.78340.01550.85020.024*
H1E0.83970.11351.02800.024*
C20.9087 (5)0.1308 (3)0.6967 (8)0.0190 (9)
C31.1805 (6)0.1209 (5)0.6290 (10)0.0348 (12)
H3A1.13480.11610.45730.052*
H3B1.27330.07230.66600.052*
H3C1.21630.19440.66820.052*
N10.6341 (4)0.1443 (3)0.7897 (6)0.0178 (8)
H1A0.64520.21670.79150.027*
H1B0.56830.12460.89540.027*
H1C0.58950.12250.63900.027*
O11.0566 (4)0.0911 (3)0.7714 (6)0.0295 (8)
O20.8701 (4)0.1866 (3)0.5246 (6)0.0251 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0258 (6)0.0195 (5)0.0182 (6)0.0065 (5)0.0049 (4)0.0014 (5)
C10.016 (2)0.014 (2)0.030 (3)0.0018 (17)0.0031 (17)0.0025 (17)
C20.021 (2)0.0111 (19)0.026 (3)0.0028 (16)0.0058 (17)0.0028 (18)
C30.020 (2)0.040 (3)0.047 (3)0.000 (2)0.013 (2)0.003 (3)
N10.0204 (19)0.0166 (18)0.017 (2)0.0018 (14)0.0050 (14)0.0001 (14)
O10.0223 (18)0.0313 (18)0.036 (2)0.0042 (15)0.0086 (14)0.0102 (16)
O20.0268 (18)0.0239 (17)0.0253 (19)0.0024 (14)0.0065 (14)0.0065 (14)
Geometric parameters (Å, º) top
C1—N11.472 (5)C3—H3A0.9800
C1—C21.502 (6)C3—H3B0.9800
C1—H1D0.9900C3—H3C0.9800
C1—H1E0.9900N1—H1A0.9100
C2—O21.194 (5)N1—H1B0.9100
C2—O11.332 (5)N1—H1C0.9100
C3—O11.461 (5)
N1—C1—C2110.5 (4)H3A—C3—H3B109.5
N1—C1—H1D109.6O1—C3—H3C109.5
C2—C1—H1D109.6H3A—C3—H3C109.5
N1—C1—H1E109.6H3B—C3—H3C109.5
C2—C1—H1E109.6C1—N1—H1A109.5
H1D—C1—H1E108.1C1—N1—H1B109.5
O2—C2—O1125.7 (4)H1A—N1—H1B109.5
O2—C2—C1124.2 (4)C1—N1—H1C109.5
O1—C2—C1110.1 (4)H1A—N1—H1C109.5
O1—C3—H3A109.5H1B—N1—H1C109.5
O1—C3—H3B109.5C2—O1—C3115.9 (4)
N1—C1—C2—O25.0 (6)O2—C2—O1—C30.9 (7)
N1—C1—C2—O1175.7 (3)C1—C2—O1—C3179.7 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl1i0.912.523.269 (4)140
N1—H1B···Cl1ii0.912.253.112 (4)158
N1—H1C···Cl10.912.263.147 (4)165
C1—H1D···Cl1iii0.992.693.448 (4)133
C1—H1E···O2i0.992.512.928 (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 formulaC3H8NO2+·Cl
Mr125.55
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)8.352 (2), 12.505 (3), 5.6369 (14)
β (°) 99.730 (9)
V3)580.3 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.55
Crystal size (mm)0.08 × 0.02 × 0.02
Data collection
DiffractometerBruker X8 Kappa CCD APEXII
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1997)
Tmin, Tmax0.957, 0.989
No. of measured, independent and
observed [I > 2σ(I)] reflections
5189, 1539, 923
Rint0.070
(sin θ/λ)max1)0.685
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.069, 0.184, 1.08
No. of reflections1539
No. of parameters66
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1A···Cl1i0.912.523.269 (4)140.3
N1—H1B···Cl1ii0.912.253.112 (4)157.9
N1—H1C···Cl10.912.263.147 (4)164.5
C1—H1D···Cl1iii0.992.693.448 (4)133
C1—H1E···O2i0.992.512.928 (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

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationBrandenburg, K. (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationBruker (2005). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2006). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationHandelsman-Benory, E., Botoshansky, M. & Kaftory, M. (1995). Acta Cryst. C51, 2362–2364.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationNangia, A. & Desiraju, G. R. (1998). Topics in Current Chemistry, Vol. 198, edited by E. Weber, pp. 57–96. Berlin Heidelberg: Springer Verlag.  Google Scholar
First citationPaz, F. A. A., Bond, A. D., Khimyak, Y. Z. & Klinowski, J. (2002). New J. Chem. 26, 381–383.  Google Scholar
First citationPaz, F. A. A. & Klinowski, J. (2003). CrystEngComm, 5, 238–244.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (1997). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
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First citationShi, F.-N., Cunha-Silva, L., Sá Ferreira, R. A., Mafra, L., Trindade, T., Carlos, L. D., Paz, F. A. A. & Rocha, J. (2008). J. Am. Chem. Soc. 130, 150–167.  Web of Science CSD CrossRef PubMed CAS Google Scholar

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