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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o446.
Published online 2008 January 16. doi:  10.1107/S1600536807068560
PMCID: PMC2960383

l-Glutamic acid hydro­chloride at 153 K

Abstract

The title compound [systematic name: (S)-1,3-dicarboxy­propanaminium chloride], C5H10NO4 +·Cl, has been investigated previously by Dawson [Acta Cryst. (1953). 6, 81–83], with R = 0.106 and without the location of H atoms, and then by Sequeira, Rajagopal & Chidambaram [Acta Cryst. (1972). B28, 2514–2519] using neutron diffraction with R = 0.043. The present determination at 153 K has R = 0.017 and all the H atoms are located. There are obvious differences in some C—C bond lengths between the present and previous studies. In the present structure, l-glutamic acid is protonated and is linked to the Cl anion by an O—H(...)Cl hydrogen bond. The crystal structure is established by a three-dimensional network of O—H(...)O, N—H(...)O and N—H(...)Cl hydrogen bonds.

Related literature

For related literature, see: Delfino et al. (1978 [triangle]); Kirfel & Wallrafen (1985 [triangle]). For previous structure determinations, see: Dawson (1953 [triangle]) [Cambridge Structural Database (CSD; Version 5.26; Allen, 2002 [triangle]) refcode LGLUTA01]; Sequeira et al. (1972 [triangle]) (refcode LGLUTA).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o446-scheme1.jpg

Experimental

Crystal data

  • C5H10NO4 +·Cl
  • M r = 183.59
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o446-efi1.jpg
  • a = 5.1016 (1) Å
  • b = 11.6386 (4) Å
  • c = 13.2500 (3) Å
  • V = 786.73 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.45 mm−1
  • T = 153 (2) K
  • 0.49 × 0.48 × 0.35 mm

Data collection

  • Siemens P4 diffractometer
  • Absorption correction: ψ scan (SHELXTL; Bruker, 1998 [triangle]) T min = 0.808, T max = 0.858
  • 7742 measured reflections
  • 1798 independent reflections
  • 1775 reflections with I > 2σ(I)
  • R int = 0.016

Refinement

  • R[F 2 > 2σ(F 2)] = 0.019
  • wR(F 2) = 0.055
  • S = 1.15
  • 1798 reflections
  • 101 parameters
  • H-atom parameters constrained
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.25 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 725 Friedel pairs
  • Flack parameter: 0.02 (4)

Data collection: PROCESS-AUTO (Rigaku, 1998 [triangle]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Bruker, 1998 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068560/si2055sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068560/si2055Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The crystal structure of the title compound has been investigated by Dawson (1953) using the multiple-film technique for h0l and 0kl intensity data collection, then by Sequeira et al. (1972) using neutron diffraction. Besides, the L-glutamic acid (LGA) halogen acid salts of LGA hydroiodide (Kirfel & Wallrafen, 1985), LGA HBr and LGA HCl HBr (Delfino et al., 1978) have been reported before. Recently we have made a structure determination of the title compound at 153 K and make comparisons with Dawson's and Sequeira's studies, hereby.

The unit-cell parameters and space group of the title compound (see crystal data) and the respective values in Dawson's structure [a = 5.16 (1), b = 11.80 (2), c = 13.30 (2) Å] and Sequeira's structure [a = 5.151 (6), b = 11.789 (19), c = 13.347 (20) Å] demonstrate the high quality of modern X-ray diffractometer and software. The final R value of the present case [0.0171] is much smaller than that of Dawson's [0.106] and Sequeira's [0.043]. The hydrogen atoms were not determined in Dawson's study, due to the incompleteness of the estimated intensity data.

The C4—C5 [1.5066 (15) Å] bond length intermediates Dawson's [1.54 Å] and Sequeira's [1.475 (7) Å] (Table 1). The C2—C3 distance [1.5312 (15) Å] differs from that of Dawson's [1.55 Å], the C1—C2 [1.5156 (16) Å] deviates from that of Sequeira's [1.535 (7) Å]. The C—O, C—N and the other C—C bond lengths of these three cases have little distinctions respectively. Between the present and Dawson's study, the major distinctions of bond angles lie in C1—C2—N1 and C3—C2—N1 [108.02 (9) and 111.94 (9)° for present, 111 and 110° for Dawson's case, respectively]. The torsion angles of the main skeleton are finely coherent with those in Sequeira's study, respectively (Table 1). But, some torsion angles related to H atoms that are involed in hydrogen bonds are deviated greatly from those in Sequeira's study, respectively [H1C—N1—C2—C1 (-60.0, -48.0°), H1B—N1—C2—C1 (60.0, 73.2°) and H1A—N1—C2—C1 (-180.0, -165.1°); H1—O1—C1—C2 (179.8, 168.9°), the former and latter values for the present (Table 1) and Sequeira's study, repectively].

In the title compound, L-glutamic acid is protonated and is linked with the Cl- anion by a O—H···Cl hydrogen bond (Fig. 1, Table 2). The crystal structure is established by a three-dimensional network of O—H···O, N—H···O and N—H···Cl classic hydrogen bonds (Fig. 2, Table 2).

Experimental

L-Glutamic acid and hydrochloric acid in equal molar ratio were mixed together with enough water, and heated to a temperatur where clear solution was obtained. The solution were layed in a ventilative place. Colorless single crystals of the title compound were obtained from the solution by slow volatilization of water at room temperature for 7 days.

Refinement

All hydrogen atoms were placed in calculated positions and allowed to ride on their parent atoms at distances of 0.99 (methylene), 1.00 (methine), 0.91Å (N—H), 0.84Å (O—H), with Uiso(H) values 1.2–1.5 times Ueq of the parent atoms.

Figures

Fig. 1.
A view of the title compound showing with 40% probability displacement ellipsoids. Hydrogen bonds are indicated by thin lines.
Fig. 2.
The packing diagram of the title compound viewed down along the a axis. Hydrogen bonds are indicated by thin lines.

Crystal data

C5H10NO4+·ClF000 = 384
Mr = 183.59Dx = 1.550 Mg m3
Orthorhombic, P212121Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 7746 reflections
a = 5.1016 (1) Åθ = 3.1–27.5º
b = 11.6386 (4) ŵ = 0.45 mm1
c = 13.2500 (3) ÅT = 153 (2) K
V = 786.73 (4) Å3Block, colorless
Z = 40.49 × 0.48 × 0.35 mm

Data collection

Siemens P4 diffractometer1798 independent reflections
Radiation source: fine-focus sealed tube1775 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.016
T = 153(2) Kθmax = 27.5º
ω scansθmin = 3.1º
Absorption correction: ψ scan(SHELXTL; Bruker, 1998)h = −6→6
Tmin = 0.809, Tmax = 0.858k = −15→15
7742 measured reflectionsl = −15→16

Refinement

Refinement on F2H-atom parameters constrained
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0313P)2 + 0.1681P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.019(Δ/σ)max = 0.001
wR(F2) = 0.055Δρmax = 0.29 e Å3
S = 1.15Δρmin = −0.25 e Å3
1798 reflectionsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
101 parametersExtinction coefficient: 0.058 (4)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 725 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.02 (4)
Hydrogen site location: inferred from neighbouring sites

Special details

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)

xyzUiso*/Ueq
Cl11.05471 (5)0.93130 (2)0.26203 (2)0.01395 (9)
O10.4387 (2)0.53632 (7)0.07337 (7)0.0205 (2)
H10.33410.51020.03010.031*
O20.20701 (18)0.69846 (7)0.05162 (7)0.0161 (2)
O30.4214 (2)0.55251 (8)0.45585 (6)0.0204 (2)
O40.70041 (18)0.67059 (8)0.53439 (6)0.0167 (2)
H40.64540.63610.58590.025*
N10.5606 (2)0.82410 (8)0.15658 (7)0.0120 (2)
H1A0.67010.85690.20250.018*
H1B0.39390.84900.16760.018*
H1C0.61170.84420.09320.018*
C10.3864 (2)0.64491 (10)0.08985 (9)0.0116 (2)
C20.5705 (2)0.69659 (9)0.16728 (8)0.0102 (2)
H20.75320.66890.15470.012*
C30.4798 (2)0.65720 (10)0.27187 (8)0.0115 (2)
H3A0.30740.69260.28630.014*
H3B0.45500.57280.27050.014*
C40.6668 (2)0.68690 (10)0.35714 (8)0.0124 (2)
H4A0.84580.66100.33950.015*
H4B0.67120.77130.36660.015*
C50.5815 (3)0.63012 (9)0.45392 (8)0.0119 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.01329 (14)0.01559 (13)0.01296 (14)−0.00183 (11)−0.00097 (10)0.00137 (10)
O10.0232 (4)0.0145 (4)0.0238 (4)0.0019 (4)−0.0111 (4)−0.0082 (3)
O20.0166 (4)0.0164 (4)0.0153 (4)0.0004 (3)−0.0052 (3)0.0000 (3)
O30.0284 (5)0.0194 (5)0.0134 (4)−0.0119 (4)0.0021 (4)0.0018 (3)
O40.0214 (5)0.0196 (4)0.0089 (4)−0.0053 (4)−0.0014 (4)0.0029 (3)
N10.0134 (4)0.0119 (4)0.0105 (4)−0.0028 (4)−0.0012 (4)0.0014 (3)
C10.0119 (6)0.0148 (5)0.0081 (5)−0.0022 (4)0.0004 (4)0.0006 (4)
C20.0107 (5)0.0100 (5)0.0101 (5)−0.0009 (5)−0.0006 (5)−0.0006 (4)
C30.0121 (5)0.0128 (5)0.0096 (5)−0.0025 (4)0.0006 (4)0.0016 (4)
C40.0138 (5)0.0146 (5)0.0089 (5)−0.0039 (5)0.0011 (4)0.0014 (4)
C50.0139 (6)0.0114 (5)0.0105 (5)0.0002 (4)0.0007 (5)0.0005 (4)

Geometric parameters (Å, °)

O1—C11.3101 (15)C1—C21.5156 (16)
O1—H10.8400C2—C31.5312 (15)
O2—C11.2176 (15)C2—H21.0000
O3—C51.2183 (15)C3—C41.5184 (16)
O4—C51.3139 (14)C3—H3A0.9900
O4—H40.8400C3—H3B0.9900
N1—C21.4916 (14)C4—C51.5066 (15)
N1—H1A0.9100C4—H4A0.9900
N1—H1B0.9100C4—H4B0.9900
N1—H1C0.9100
C1—O1—H1109.5C3—C2—H2109.7
C5—O4—H4109.5C4—C3—C2114.55 (9)
C2—N1—H1A109.5C4—C3—H3A108.6
C2—N1—H1B109.5C2—C3—H3A108.6
H1A—N1—H1B109.5C4—C3—H3B108.6
C2—N1—H1C109.5C2—C3—H3B108.6
H1A—N1—H1C109.5H3A—C3—H3B107.6
H1B—N1—H1C109.5C5—C4—C3110.63 (10)
O2—C1—O1125.29 (11)C5—C4—H4A109.5
O2—C1—C2122.99 (10)C3—C4—H4A109.5
O1—C1—C2111.67 (10)C5—C4—H4B109.5
N1—C2—C1108.02 (9)C3—C4—H4B109.5
N1—C2—C3111.94 (9)H4A—C4—H4B108.1
C1—C2—C3107.85 (9)O3—C5—O4123.93 (10)
N1—C2—H2109.7O3—C5—C4122.46 (10)
C1—C2—H2109.7O4—C5—C4113.59 (10)
O2—C1—C2—N1−21.37 (15)C3—C4—C5—O314.84 (16)
O1—C1—C2—N1161.21 (10)C3—C4—C5—O4−166.61 (10)
O2—C1—C2—C399.80 (13)H1C—N1—C2—C1−60.0
O1—C1—C2—C3−77.62 (12)H1B—N1—C2—C160.0
N1—C2—C3—C4−69.92 (13)H1A—N1—C2—C1−180.0
C1—C2—C3—C4171.39 (9)H1—O1—C1—C2179.8
C2—C3—C4—C5−171.71 (9)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl10.912.293.1406 (10)157
N1—H1B···Cl1i0.912.343.1890 (10)155
N1—H1C···O2ii0.912.042.8700 (13)151
O1—H1···O3iii0.841.792.6208 (13)170
O4—H4···Cl1iv0.842.213.0389 (9)168

Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+3/2, −z; (iii) −x+1/2, −y+1, z−1/2; (iv) x−1/2, −y+3/2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2055).

References

  • Allen, F. H. (2002). Acta Cryst. B58, 380–388. [PubMed]
  • Bruker (1998). SHELXTL Bruker AXS Inc., Madison, Wisconsin, USA.
  • Dawson, B. (1953). Acta Cryst.6, 81–87.
  • Delfino, M., Loiacono, G. M. & Nicolosi, J. A. (1978). J. Solid State Chem.23, 289–296.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Kirfel, A. & Wallrafen, F. (1985). Z. Kristallogr.171, 121–126.
  • Rigaku (1998). PROCESS-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2004). CrystalStructure. Version 3.6.0. Rigaku/MSC, The Woodlands, Texas, USA.
  • Sequeira, A., Rajagopal, H. & Chidambaram, R. (1972). Acta Cryst. B28, 2514–2519.
  • Sheldrick, G. M. (2008). Acta Cryst A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography