l-Glutamic acid hydro­chloride at 153 K

Zhang, Y.J.; Shu, Z.; Xu, W.; Chen, G.; Li, Z.-G.

doi:10.1107/S1600536807068560

organic compounds

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doi:10.1107/S1600536807068560

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L-Glutamic acid hydrochloride at 153 K

Yi Jian Zhang,^a Zhan Shu,^b Wei Xu,^b Gang Chen ^b and Zu-Guang Li ^c ^*

^aCollege of Materials Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 310036, People's Republic of China, ^bCollege of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China, and ^cCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: zgdlzg@sina.com

(Received 16 November 2007; accepted 27 December 2007; online 16 January 2008)

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

Experimental

Crystal data

C₅H₁₀NO₄⁺·Cl⁻
M_r = 183.59
Orthorhombic, P 2₁ 2₁ 2₁
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 ) 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[F² > 2σ(F²)] = 0.019
wR(F²) = 0.055
S = 1.15
1798 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ), 725 Friedel pairs
Flack parameter: 0.02 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1	0.91	2.29	3.1406 (10)	157
N1—H1B⋯Cl1ⁱ	0.91	2.34	3.1890 (10)	155
N1—H1C⋯O2ⁱⁱ	0.91	2.04	2.8700 (13)	151
O1—H1⋯O3ⁱⁱⁱ	0.84	1.79	2.6208 (13)	170
O4—H4⋯Cl1^iv	0.84	2.21	3.0389 (9)	168
Symmetry codes: (i) x-1, y, z; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (iii) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures top

	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.

(S)-1,3-dicarboxypropanaminium chloride top

Crystal data top

C₅H₁₀NO₄⁺·Cl⁻	F(000) = 384
M_r = 183.59	D_x = 1.550 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7746 reflections
a = 5.1016 (1) Å	θ = 3.1–27.5°
b = 11.6386 (4) Å	µ = 0.45 mm⁻¹
c = 13.2500 (3) Å	T = 153 K
V = 786.73 (4) Å³	Block, colorless
Z = 4	0.49 × 0.48 × 0.35 mm

Data collection top

Siemens P4 diffractometer	1798 independent reflections
Radiation source: fine-focus sealed tube	1775 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: ψ scan (SHELXTL; Bruker, 1998)	h = −6→6
T_min = 0.809, T_max = 0.858	k = −15→15
7742 measured reflections	l = −15→16

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.019	w = 1/[σ²(F_o²) + (0.0313P)² + 0.1681P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.055	(Δ/σ)_max = 0.001
S = 1.15	Δρ_max = 0.29 e Å⁻³
1798 reflections	Δρ_min = −0.25 e Å⁻³
101 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.058 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 725 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.02 (4)

Crystal data top

C₅H₁₀NO₄⁺·Cl⁻	V = 786.73 (4) Å³
M_r = 183.59	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.1016 (1) Å	µ = 0.45 mm⁻¹
b = 11.6386 (4) Å	T = 153 K
c = 13.2500 (3) Å	0.49 × 0.48 × 0.35 mm

Data collection top

Siemens P4 diffractometer	1798 independent reflections
Absorption correction: ψ scan (SHELXTL; Bruker, 1998)	1775 reflections with I > 2σ(I)
T_min = 0.809, T_max = 0.858	R_int = 0.016
7742 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	H-atom parameters constrained
wR(F²) = 0.055	Δρ_max = 0.29 e Å⁻³
S = 1.15	Δρ_min = −0.25 e Å⁻³
1798 reflections	Absolute structure: Flack (1983), 725 Friedel pairs
101 parameters	Absolute structure parameter: 0.02 (4)
0 restraints

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	1.05471 (5)	0.93130 (2)	0.26203 (2)	0.01395 (9)
O1	0.4387 (2)	0.53632 (7)	0.07337 (7)	0.0205 (2)
H1	0.3341	0.5102	0.0301	0.031*
O2	0.20701 (18)	0.69846 (7)	0.05162 (7)	0.0161 (2)
O3	0.4214 (2)	0.55251 (8)	0.45585 (6)	0.0204 (2)
O4	0.70041 (18)	0.67059 (8)	0.53439 (6)	0.0167 (2)
H4	0.6454	0.6361	0.5859	0.025*
N1	0.5606 (2)	0.82410 (8)	0.15658 (7)	0.0120 (2)
H1A	0.6701	0.8569	0.2025	0.018*
H1B	0.3939	0.8490	0.1676	0.018*
H1C	0.6117	0.8442	0.0932	0.018*
C1	0.3864 (2)	0.64491 (10)	0.08985 (9)	0.0116 (2)
C2	0.5705 (2)	0.69659 (9)	0.16728 (8)	0.0102 (2)
H2	0.7532	0.6689	0.1547	0.012*
C3	0.4798 (2)	0.65720 (10)	0.27187 (8)	0.0115 (2)
H3A	0.3074	0.6926	0.2863	0.014*
H3B	0.4550	0.5728	0.2705	0.014*
C4	0.6668 (2)	0.68690 (10)	0.35714 (8)	0.0124 (2)
H4A	0.8458	0.6610	0.3395	0.015*
H4B	0.6712	0.7713	0.3666	0.015*
C5	0.5815 (3)	0.63012 (9)	0.45392 (8)	0.0119 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01329 (14)	0.01559 (13)	0.01296 (14)	−0.00183 (11)	−0.00097 (10)	0.00137 (10)
O1	0.0232 (4)	0.0145 (4)	0.0238 (4)	0.0019 (4)	−0.0111 (4)	−0.0082 (3)
O2	0.0166 (4)	0.0164 (4)	0.0153 (4)	0.0004 (3)	−0.0052 (3)	0.0000 (3)
O3	0.0284 (5)	0.0194 (5)	0.0134 (4)	−0.0119 (4)	0.0021 (4)	0.0018 (3)
O4	0.0214 (5)	0.0196 (4)	0.0089 (4)	−0.0053 (4)	−0.0014 (4)	0.0029 (3)
N1	0.0134 (4)	0.0119 (4)	0.0105 (4)	−0.0028 (4)	−0.0012 (4)	0.0014 (3)
C1	0.0119 (6)	0.0148 (5)	0.0081 (5)	−0.0022 (4)	0.0004 (4)	0.0006 (4)
C2	0.0107 (5)	0.0100 (5)	0.0101 (5)	−0.0009 (5)	−0.0006 (5)	−0.0006 (4)
C3	0.0121 (5)	0.0128 (5)	0.0096 (5)	−0.0025 (4)	0.0006 (4)	0.0016 (4)
C4	0.0138 (5)	0.0146 (5)	0.0089 (5)	−0.0039 (5)	0.0011 (4)	0.0014 (4)
C5	0.0139 (6)	0.0114 (5)	0.0105 (5)	0.0002 (4)	0.0007 (5)	0.0005 (4)

Geometric parameters (Å, º) top

O1—C1	1.3101 (15)	C1—C2	1.5156 (16)
O1—H1	0.8400	C2—C3	1.5312 (15)
O2—C1	1.2176 (15)	C2—H2	1.0000
O3—C5	1.2183 (15)	C3—C4	1.5184 (16)
O4—C5	1.3139 (14)	C3—H3A	0.9900
O4—H4	0.8400	C3—H3B	0.9900
N1—C2	1.4916 (14)	C4—C5	1.5066 (15)
N1—H1A	0.9100	C4—H4A	0.9900
N1—H1B	0.9100	C4—H4B	0.9900
N1—H1C	0.9100

C1—O1—H1	109.5	C3—C2—H2	109.7
C5—O4—H4	109.5	C4—C3—C2	114.55 (9)
C2—N1—H1A	109.5	C4—C3—H3A	108.6
C2—N1—H1B	109.5	C2—C3—H3A	108.6
H1A—N1—H1B	109.5	C4—C3—H3B	108.6
C2—N1—H1C	109.5	C2—C3—H3B	108.6
H1A—N1—H1C	109.5	H3A—C3—H3B	107.6
H1B—N1—H1C	109.5	C5—C4—C3	110.63 (10)
O2—C1—O1	125.29 (11)	C5—C4—H4A	109.5
O2—C1—C2	122.99 (10)	C3—C4—H4A	109.5
O1—C1—C2	111.67 (10)	C5—C4—H4B	109.5
N1—C2—C1	108.02 (9)	C3—C4—H4B	109.5
N1—C2—C3	111.94 (9)	H4A—C4—H4B	108.1
C1—C2—C3	107.85 (9)	O3—C5—O4	123.93 (10)
N1—C2—H2	109.7	O3—C5—C4	122.46 (10)
C1—C2—H2	109.7	O4—C5—C4	113.59 (10)

O2—C1—C2—N1	−21.37 (15)	C3—C4—C5—O3	14.84 (16)
O1—C1—C2—N1	161.21 (10)	C3—C4—C5—O4	−166.61 (10)
O2—C1—C2—C3	99.80 (13)	H1C—N1—C2—C1	−60.0
O1—C1—C2—C3	−77.62 (12)	H1B—N1—C2—C1	60.0
N1—C2—C3—C4	−69.92 (13)	H1A—N1—C2—C1	−180.0
C1—C2—C3—C4	171.39 (9)	H1—O1—C1—C2	179.8
C2—C3—C4—C5	−171.71 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.91	2.29	3.1406 (10)	157
N1—H1B···Cl1ⁱ	0.91	2.34	3.1890 (10)	155
N1—H1C···O2ⁱⁱ	0.91	2.04	2.8700 (13)	151
O1—H1···O3ⁱⁱⁱ	0.84	1.79	2.6208 (13)	170
O4—H4···Cl1^iv	0.84	2.21	3.0389 (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.

Experimental details

Crystal data
Chemical formula	C₅H₁₀NO₄⁺·Cl⁻
M_r	183.59
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	153
a, b, c (Å)	5.1016 (1), 11.6386 (4), 13.2500 (3)
V (Å³)	786.73 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.49 × 0.48 × 0.35

Data collection
Diffractometer	Siemens P4 diffractometer
Absorption correction	ψ scan (SHELXTL; Bruker, 1998)
T_min, T_max	0.809, 0.858
No. of measured, independent and observed [I > 2σ(I)] reflections	7742, 1798, 1775
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.055, 1.15
No. of reflections	1798
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.25
Absolute structure	Flack (1983), 725 Friedel pairs
Absolute structure parameter	0.02 (4)

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).

Selected geometric parameters (Å, º) top

O1—C1	1.3101 (15)	C1—C2	1.5156 (16)
O2—C1	1.2176 (15)	C2—C3	1.5312 (15)
O3—C5	1.2183 (15)	C3—C4	1.5184 (16)
O4—C5	1.3139 (14)	C4—C5	1.5066 (15)
N1—C2	1.4916 (14)

O2—C1—O1	125.29 (11)	C4—C3—C2	114.55 (9)
O2—C1—C2	122.99 (10)	C5—C4—C3	110.63 (10)
O1—C1—C2	111.67 (10)	O3—C5—O4	123.93 (10)
N1—C2—C1	108.02 (9)	O3—C5—C4	122.46 (10)
N1—C2—C3	111.94 (9)	O4—C5—C4	113.59 (10)
C1—C2—C3	107.85 (9)

O2—C1—C2—N1	−21.37 (15)	H1B—N1—C2—C1	60.0
O1—C1—C2—N1	161.21 (10)	H1A—N1—C2—C1	−180.0
H1C—N1—C2—C1	−60.0	H1—O1—C1—C2	179.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.91	2.29	3.1406 (10)	156.5
N1—H1B···Cl1ⁱ	0.91	2.34	3.1890 (10)	155.0
N1—H1C···O2ⁱⁱ	0.91	2.04	2.8700 (13)	150.9
O1—H1···O3ⁱⁱⁱ	0.84	1.79	2.6208 (13)	170.3
O4—H4···Cl1^iv	0.84	2.21	3.0389 (9)	168.4

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.

References

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doi:10.1107/S1600536807068560

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