l-Alanine hydrochloride monohydrate

Yamada, K.; Sato, A.; Shimizu, T.; Yamazaki, T.; Yokoyama, S.

doi:10.1107/S1600536808008751

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o806

doi:10.1107/S1600536808008751

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L-Alanine hydrochloride monohydrate

Kazuhiko Yamada,^a ^* Akira Sato,^a Tadashi Shimizu,^a Toshio Yamazaki ^b and Shigeyuki Yokoyama ^b

^aNational Institute for Materials Science, 3-13, Sakura, Tsukuba 305-0003, Japan, and ^bProtein Research Group, Genomic Sciences Center, Yokohama Institute, RIKEN, 1-7-22 Suehiro, Tsurumi, Yokohama 230-0045, Japan
^*Correspondence e-mail: yamada.kazuhiko@nims.go.jp

(Received 6 March 2008; accepted 1 April 2008; online 4 April 2008)

Colorless crystals of L-alanine hydrochloride monohydrate, C₃H₈NO₂⁺·Cl⁻·H₂O, were obtained from a powder sample that had been left standing in a refrigerator for a few years. The structure displays several intermolecular hydrogen bonds: the hydroxyl O atom is involved in a single hydrogen bond to the chloride anion, while the ammonium group forms one hydrogen bond to the chloride anion and two hydrogen bonds to water molecules. An intermolecular bond between the carbonyl O atom and the ammonium group [2.8459 (15) Å] is also found.

Related literature

For the crystal structures of L-alanine and DL-alanine, see: Simpson & Marsh, (1966 ); Dunitz & Ryan, (1966 ); Lehmann et al. (1972 ); Destro et al. (1988 ); Donohue, (1950 ); Subha Nandhini et al. (2001 ). For the crystal structures of D-alanine hydrochloride and DL-alanine hydrochloride, see: di Blasio et al. (1977 ); Trotter, (1962 ). For the preparation of the title compound with respect to ¹⁷O-labelling, see: Steinschneider et al. (1981 ).

Experimental

Crystal data

C₃H₈NO₂⁺·Cl⁻·H₂O
M_r = 143.57
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.1925 (13) Å
b = 9.929 (2) Å
c = 11.759 (3) Å
V = 723.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 150 (2) K
0.45 × 0.40 × 0.35 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker 2001 ) T_min = 0.819, T_max = 0.855
5762 measured reflections
1467 independent reflections
1452 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.053
S = 1.11
1467 reflections
84 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 533 Friedel pairs
Flack parameter: 0.02 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—HA⋯O3	0.89	1.96	2.8479 (14)	174
N—HB⋯Clⁱ	0.89	2.31	3.1957 (11)	171
N—HC⋯O3ⁱⁱ	0.89	1.95	2.8380 (15)	180
O2—H2⋯Cl	0.82	2.23	3.0446 (11)	175
O3—H4⋯Clⁱⁱⁱ	0.82 (2)	2.35 (2)	3.1432 (12)	161.0 (17)
O3—H5⋯Cl^iv	0.78 (2)	2.38 (2)	3.1283 (11)	163.3 (16)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ ; (iii) x+1, y, z; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{5\over 2}}]$ .

Data collection: SMART for WNT/2000 (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808008751/hg2382sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808008751/hg2382Isup2.hkl

checkCIF report

Comment top

L-Alanine is one of the 20 proteinogenic amino acids and has been currently recognized as one of the most abundant amino acids in natural proteins. In general, amino acids very often have polymorphs. The crystal structures of L-alanine (Simpson & Marsh, 1966; Dunitz & Ryan, 1966; Lehmann et al., 1972; Destro et al., 1988), DL-alanine (Donohue, 1950; Subha Nandhini et al., 2001; Trotter, 1962), and D-alanine hydrochloride (di Blasio et al., 1977) have been reported. In the present study, a single-crystal structure determination of L-alanine hydrochloride monohydrate, (I), is reported.

The distances and angles of the present L-alanine molecule are consistent in the typical values reported in the literature of L-alanine molecules (See Table 1 and Figure 1). The atoms N, C2, C3, O1, and O2 are found to be nearly coplanar. The torsion angles of O2—C2—C3—N and O1—C2—C3—N are 174.27 (9) and -6.07 (18), respectively. The angles of O1—C2—O2 and O1—C2—C3, for example, are 125.35 (11) and 123.71 (11)°, respectively. These observations are in reasonable agreement with those of D-alanine hydrochloride reported previously (di Blasio et al., 1977). The torsion angle of O2—C2—C3—C1 was observed to be -64.37 (14)°, which is slightly different from that of L-alanine, the corresponding angle was -76.0° (Lehmann et al., 1972).

The single-crystal diffraction analysis exhibits that the titled compound contains several intermolecular hydrogen bonds. O2 is involved to a single hydrogen bond to a chloride ion with the hydrogen bond distance of 3.0446 (11) Å, while O1 is not involved to hydrogen bonds. Instead, a short contact is observed between O1 and N with the intermolecular bond length of 2.8450 (15) Å. A water molecule donates four hydrogen bonds to two chlorides and two ammonium groups, while a chloride ion accepts four hydrogen bonds from two water molecules, and ammonium and hydroxyl groups (See Table 2 and Figure 2).

It is interesting to compare the present structure with that of D-alanine hydrochloride (di Blasio et al., 1977). In the anhydrous D-alanine hydrochloride crystal, O1 (carbonyl oxygen) exhibits a single hydrogen bond to an ammonium group, and O2 (hydroxyl oxygen) also forms a single hydrogen bond to a chloride ion. The chloride anion, on the other hand, forms three hydrogen bonds, two of which with ammonium groups and one of which with a hydroxyl group. These intermolecular environments are different from the present observations.

Related literature top

For he crystal structures of L-alanine and DL-alanine, see: Simpson & Marsh, (1966); Dunitz & Ryan, (1966); Lehmann et al. (1972); Destro et al. (1988); Donohue, (1950); Subha Nandhini et al. (2001). For the crystal structures of D-alanine hydrochloride and DL-alanine hydrochloride, see: di Blasio et al. (1977); Trotter, (1962). For the preparation of the title compound with respect to ¹⁷O-labelling, see: Steinschneider et al. (1981).

Experimental top

In the title compound, oxygen-17 isotope enrichments were carried out to the carboxyl group with the aim to perform solid-state ¹⁷O NMR experiments. L-alanine hydrochloride was obtained by acid-catalyzed exchange (Steinschneider et al., 1981) with L-alanine and H₂¹⁷O (20% ¹⁷O atom, purchased from Taiyo Nippon Sanso Corp., Tokyo, Japan). Colorless crystals of the title compound were obtained from the powder sample after it was left standing in a refrigerator for a few years.

Computing details top

Data collection: SMART for WNT/2000 (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecular structure of (I), showing the atom labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I) viewed from a axis. Broken lines indicate the hydrogen bonds.

L-Alanine hydrochloride monohydrate top

Crystal data top

C₃H₈NO₂⁺·Cl⁻·H₂O	F(000) = 304
M_r = 143.57	D_x = 1.319 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 902 reflections
a = 6.1925 (13) Å	θ = 7.4–53.9°
b = 9.929 (2) Å	µ = 0.46 mm⁻¹
c = 11.759 (3) Å	T = 150 K
V = 723.0 (3) Å³	Plate, colourless
Z = 4	0.45 × 0.40 × 0.35 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1467 independent reflections
Radiation source: fine-focus sealed tube	1452 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 27.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker 2001)	h = −7→7
T_min = 0.819, T_max = 0.855	k = −11→12
5762 measured reflections	l = −14→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.019	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.053	w = 1/[σ²(F_o²) + (0.0308P)² + 0.0901P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
1467 reflections	Δρ_max = 0.19 e Å⁻³
84 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 533 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (6)

Crystal data top

C₃H₈NO₂⁺·Cl⁻·H₂O	V = 723.0 (3) Å³
M_r = 143.57	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.1925 (13) Å	µ = 0.46 mm⁻¹
b = 9.929 (2) Å	T = 150 K
c = 11.759 (3) Å	0.45 × 0.40 × 0.35 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1467 independent reflections
Absorption correction: multi-scan (SADABS; Bruker 2001)	1452 reflections with I > 2σ(I)
T_min = 0.819, T_max = 0.855	R_int = 0.022
5762 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.053	Δρ_max = 0.19 e Å⁻³
S = 1.11	Δρ_min = −0.20 e Å⁻³
1467 reflections	Absolute structure: Flack (1983), 533 Friedel pairs
84 parameters	Absolute structure parameter: 0.02 (6)
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
Cl	0.19971 (4)	0.55991 (3)	1.25180 (2)	0.02475 (10)
C1	0.8057 (2)	0.60202 (13)	0.88317 (11)	0.0295 (3)
H1A	0.9301	0.6167	0.8360	0.044*
H1B	0.7483	0.6872	0.9073	0.044*
H1C	0.6979	0.5540	0.8407	0.044*
C2	0.6780 (2)	0.49201 (12)	1.06398 (10)	0.0249 (2)
N	0.96092 (17)	0.38728 (10)	0.95162 (8)	0.0230 (2)
HA	1.0116	0.3443	1.0124	0.034*
HB	1.0676	0.4003	0.9021	0.034*
HC	0.8577	0.3381	0.9193	0.034*
O3	1.13229 (15)	0.26883 (10)	1.15289 (8)	0.0261 (2)
O1	0.60730 (17)	0.38141 (9)	1.08180 (8)	0.0342 (2)
O2	0.60094 (18)	0.60494 (10)	1.10708 (9)	0.0374 (2)
H2	0.4967	0.5880	1.1476	0.056*
C3	0.87031 (18)	0.51981 (12)	0.98686 (10)	0.0228 (2)
H3	0.9801	0.5694	1.0299	0.027*
H4	1.159 (3)	0.335 (2)	1.1930 (16)	0.047 (5)*
H5	1.050 (3)	0.2271 (18)	1.1882 (14)	0.036 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.02114 (14)	0.02522 (15)	0.02790 (15)	0.00128 (9)	0.00012 (12)	−0.00516 (12)
C1	0.0308 (6)	0.0239 (6)	0.0337 (6)	0.0021 (5)	0.0026 (5)	0.0073 (5)
C2	0.0260 (5)	0.0230 (5)	0.0256 (5)	0.0013 (5)	0.0015 (5)	−0.0018 (5)
N	0.0232 (5)	0.0200 (5)	0.0257 (5)	0.0019 (4)	0.0028 (4)	0.0023 (4)
O3	0.0281 (5)	0.0235 (4)	0.0268 (5)	−0.0044 (4)	0.0023 (4)	−0.0008 (4)
O1	0.0398 (5)	0.0238 (4)	0.0389 (5)	−0.0059 (4)	0.0160 (4)	−0.0029 (4)
O2	0.0384 (5)	0.0244 (4)	0.0494 (6)	0.0011 (4)	0.0183 (5)	−0.0046 (4)
C3	0.0227 (5)	0.0183 (5)	0.0274 (6)	−0.0003 (4)	0.0011 (5)	−0.0002 (4)

Geometric parameters (Å, º) top

C1—C3	1.5209 (17)	N—HA	0.8900
C1—H1A	0.9600	N—HB	0.8900
C1—H1B	0.9600	N—HC	0.8900
C1—H1C	0.9600	O3—H4	0.82 (2)
C2—O1	1.2006 (16)	O3—H5	0.78 (2)
C2—O2	1.3196 (15)	O2—H2	0.8200
C2—C3	1.5223 (16)	C3—H3	0.9800
N—C3	1.4893 (15)

C3—C1—H1A	109.5	C3—N—HC	109.5
C3—C1—H1B	109.5	HA—N—HC	109.5
H1A—C1—H1B	109.5	HB—N—HC	109.5
C3—C1—H1C	109.5	H4—O3—H5	104.4 (17)
H1A—C1—H1C	109.5	C2—O2—H2	109.5
H1B—C1—H1C	109.5	N—C3—C1	110.50 (10)
O1—C2—O2	125.34 (11)	N—C3—C2	107.48 (9)
O1—C2—C3	123.71 (11)	C1—C3—C2	111.65 (11)
O2—C2—C3	110.95 (10)	N—C3—H3	109.1
C3—N—HA	109.5	C1—C3—H3	109.1
C3—N—HB	109.5	C2—C3—H3	109.1
HA—N—HB	109.5

O1—C2—C3—N	−6.06 (18)	O1—C2—C3—C1	115.28 (14)
O2—C2—C3—N	174.26 (9)	O2—C2—C3—C1	−64.39 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—HA···O3	0.89	1.96	2.8479 (14)	174
N—HB···Clⁱ	0.89	2.31	3.1957 (11)	171
N—HC···O3ⁱⁱ	0.89	1.95	2.8380 (15)	180
O2—H2···Cl	0.82	2.23	3.0446 (11)	175
O3—H4···Clⁱⁱⁱ	0.82 (2)	2.35 (2)	3.1432 (12)	161.0 (17)
O3—H5···Cl^iv	0.78 (2)	2.38 (2)	3.1283 (11)	163.3 (16)

Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) x−1/2, −y+1/2, −z+2; (iii) x+1, y, z; (iv) −x+1, y−1/2, −z+5/2.

Experimental details

Crystal data
Chemical formula	C₃H₈NO₂⁺·Cl⁻·H₂O
M_r	143.57
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	150
a, b, c (Å)	6.1925 (13), 9.929 (2), 11.759 (3)
V (Å³)	723.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.45 × 0.40 × 0.35

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker 2001)
T_min, T_max	0.819, 0.855
No. of measured, independent and observed [I > 2σ(I)] reflections	5762, 1467, 1452
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.053, 1.11
No. of reflections	1467
No. of parameters	84
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.20
Absolute structure	Flack (1983), 533 Friedel pairs
Absolute structure parameter	0.02 (6)

Computer programs: SMART for WNT/2000 (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Selected geometric parameters (Å, º) top

C2—O1	1.2006 (16)	C2—C3	1.5223 (16)
C2—O2	1.3196 (15)	N—C3	1.4893 (15)

O1—C2—O2	125.34 (11)	O2—C2—C3	110.95 (10)
O1—C2—C3	123.71 (11)

O1—C2—C3—N	−6.06 (18)	O1—C2—C3—C1	115.28 (14)
O2—C2—C3—N	174.26 (9)	O2—C2—C3—C1	−64.39 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—HA···O3	0.89	1.96	2.8479 (14)	173.8
N—HB···Clⁱ	0.89	2.31	3.1957 (11)	170.6
N—HC···O3ⁱⁱ	0.89	1.95	2.8380 (15)	179.5
O2—H2···Cl	0.82	2.23	3.0446 (11)	174.6
O3—H4···Clⁱⁱⁱ	0.82 (2)	2.35 (2)	3.1432 (12)	161.0 (17)
O3—H5···Cl^iv	0.78 (2)	2.38 (2)	3.1283 (11)	163.3 (16)

Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) x−1/2, −y+1/2, −z+2; (iii) x+1, y, z; (iv) −x+1, y−1/2, −z+5/2.

Acknowledgements

KY appreciates support from the Nanotechnology Support Project of the Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan. SY and TY appreciate support from the RIKEN Structural Genomics/Proteomics Initiative (RSGI), the National Project on Protein Structural and Functional Analyses, and MEXT.

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