1-Carb­oxy-3-phenyl­propan-2-aminium chloride

Hosten, E.; Gerber, T.; Betz, R.

doi:10.1107/S1600536811041638

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2947

doi:10.1107/S1600536811041638

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1-Carboxy-3-phenylpropan-2-aminium chloride

Eric Hosten,^a Thomas Gerber ^a and Richard Betz ^a ^*

^aNelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth 6031, South Africa
^*Correspondence e-mail: richard.betz@webmail.co.za

(Received 19 September 2011; accepted 10 October 2011; online 12 October 2011)

The title compound, C₉H₁₂NO₂⁺·Cl⁻, is the hydrochloride of an N-substituted glycine derivative. The non-H atoms of the alkyl part of the molecule lie nearly in a plane (r.m.s. deviation of all fitted non-H atoms = 0.0142 Å). In the crystal structure, O—H⋯Cl, N—H⋯Cl and C—H⋯O hydrogen bonds involving both O atoms as well as C—H⋯Cl contacts connect the components of the title compound into a three-dimensional network.

Related literature

For the crystal structure of a palladium coordination compound featuring the ethyl ester of N-benzylglycine as a ligand, see: Freiesleben et al. (1995 ). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ); Bernstein et al. (1995 ).

Experimental

Crystal data

C₉H₁₂NO₂⁺·Cl⁻
M_r = 201.65
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.0290 (7) Å
b = 5.4900 (8) Å
c = 36.254 (5) Å
V = 1000.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 200 K
0.53 × 0.40 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.585, T_max = 1.000
7535 measured reflections
2376 independent reflections
2273 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.080
wR(F²) = 0.177
S = 1.34
2376 reflections
125 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.57 e Å⁻³
Absolute structure: Flack (1983 ), 903 Friedel pairs
Flack parameter: 0.1 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Cl1ⁱ	0.84	2.26	3.048 (3)	157
N1—H71⋯Cl1ⁱⁱ	0.86 (6)	2.31 (6)	3.166 (5)	178 (6)
N1—H72⋯Cl1	1.07 (6)	2.15 (6)	3.148 (5)	154 (5)
C2—H2A⋯O1ⁱⁱⁱ	0.99	2.48	3.364 (7)	148
C2—H2B⋯O1^iv	0.99	2.50	3.383 (7)	148
C16—H16⋯Cl1ⁱⁱ	0.95	2.78	3.654 (6)	154
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) x+1, y, z.

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811041638/aa2029sup1.cif

Supporting information file. DOI: 10.1107/S1600536811041638/aa2029Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536811041638/aa2029Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536811041638/aa2029Isup4.cml

checkCIF report

Comment top

Amino acids play a major role in the metabolism of living creatures and are characterized by their omnipresence as well as their easy availability in both nature as well as industry. From a chemical viewpoint, their molecular set-up denotes them as potential chelate ligands whose denticity and charge can be influenced by simple variation of the pH value. Coordination compounds featuring amino acids in their ligand sphere might have interesting pharmaceutical properties, especially when keeping in mind that derivatization of the respective amino acids can be used for fine-tuning thermodynamic as well as kinetic characteristics of the compounds and the tailoring of secretion rates on grounds of hydrophilicity. In our continuous efforts in elucidating the rules guiding the formation of N,O-supported chelate ligands, we investigated the crystal structure of the title compound to enable comparative studies of metrical parameters in envisioned metal complexes. Information about the molecular and crystal structure of a palladium coordination compound featuring the ethyl ester of N-benzylglycine is apparent in the literature (Freiesleben et al., 1995).

Intracyclic C–C–C angles cover a range of 118.0 (5)–121.5 (6) ° with the smallest angle found on the substituted carbon atom and the biggest angle in ortho position to this atom. The non-hydrogen atoms of the alkyl part of the molecule are nearly in plane (r.m.s of all fitted non-hydrogen atoms = 0.0142 Å). The least-squares planes defined by these atoms on the one hand and the carbon atoms of the aromatic system on the other hand enclose an angle of 60.21 (21) ° (Fig. 1).

In the crystal structure, classical hydrogen bonds as well as C–H···O contacts and C–H···Cl contacts whose range falls by up to more than 0.2 Å below the sum of van-der-Waals radii of the respective atoms are observed. The classical hydrogen bonds are apparent between the nitrogen- and oxygen-bonded hydrogen atoms as donors and – exclusively – the chloride anion as acceptor While the C–H···O contacts are apparent between both hydrogen atoms of the amino acid's methylene group and the oxygen atom of the hydroxyl group, the C–H···Cl contacts stem from one of the aromatic system's hydrogen atoms in ortho position to the substituent. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for the classical hydrogen bonds is DDD on the unitary level while the C–H-supported contacts necessitate a DC¹₁(4)C¹₁(4) descriptor on the same level. The C–H···O contacts are present as antidromic chains. In total, the entities of the title compound are connected to a three-dimensional network. π-Stacking is not a prominent feature with the shortest intercentroid distance between two aromatic systems found at 5.029 (4) Å, the length of the a axis (Fig. 2).

The packing of the title compound in the crystal is shown in Figure 3.

Related literature top

For the crystal structure of a palladium coordination compound featuring the ethyl ester of N-benzylglycine as a ligand, see: Freiesleben et al. (1995). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990); Bernstein et al. (1995).

Experimental top

The compound was obtained commercially (Fluka). Crystals suitable for the X-ray diffraction study were obtained upon slow evaporation of an aqueous solution of the compound at ambient temperature.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level).
	Fig. 2. Selected intermolecular contacts, viewed along [0 - 1 0]. Blue dashed lines indicate classical hydrogen bonds, green dashed lines C–H···O contacts. Symmetry operators: ⁱ -x + 1, y - 1/2, -z + 1/2; ⁱⁱ -x + 2, y - 1/2, -z + 1/2.
	Fig. 3. Molecular packing of the title compound, viewed along [0 1 0] (anisotropic displacement ellipsoids drawn at 50% probability level).

1-Carboxy-3-phenylpropan-2-aminium chloride top

Crystal data top

C₉H₁₂NO₂⁺·Cl⁻	F(000) = 424
M_r = 201.65	D_x = 1.338 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7358 reflections
a = 5.0290 (7) Å	θ = 2.3–28.5°
b = 5.4900 (8) Å	µ = 0.35 mm⁻¹
c = 36.254 (5) Å	T = 200 K
V = 1000.9 (2) Å³	Platelet, colourless
Z = 4	0.53 × 0.40 × 0.07 mm

Data collection top

Bruker APEXII CCD diffractometer	2376 independent reflections
Radiation source: fine-focus sealed tube	2273 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ϕ and ω scans	θ_max = 28.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −6→6
T_min = 0.585, T_max = 1.000	k = −7→6
7535 measured reflections	l = −47→47

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)] = 0.080	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.177	w = 1/[σ²(F_o²) + (0.P)² + 3.0055P] where P = (F_o² + 2F_c²)/3
S = 1.34	(Δ/σ)_max < 0.001
2376 reflections	Δρ_max = 0.33 e Å⁻³
125 parameters	Δρ_min = −0.57 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 903 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.1 (3)

Crystal data top

C₉H₁₂NO₂⁺·Cl⁻	V = 1000.9 (2) Å³
M_r = 201.65	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.0290 (7) Å	µ = 0.35 mm⁻¹
b = 5.4900 (8) Å	T = 200 K
c = 36.254 (5) Å	0.53 × 0.40 × 0.07 mm

Data collection top

Bruker APEXII CCD diffractometer	2376 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2273 reflections with I > 2σ(I)
T_min = 0.585, T_max = 1.000	R_int = 0.048
7535 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.080	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.177	Δρ_max = 0.33 e Å⁻³
S = 1.34	Δρ_min = −0.57 e Å⁻³
2376 reflections	Absolute structure: Flack (1983), 903 Friedel pairs
125 parameters	Absolute structure parameter: 0.1 (3)
0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.8269 (6)	0.7682 (8)	0.26326 (8)	0.0246 (7)
H1	0.7157	0.7732	0.2805	0.037*
O2	0.4647 (6)	0.7619 (9)	0.22798 (8)	0.0277 (7)
N1	0.7400 (7)	0.7563 (9)	0.16416 (10)	0.0223 (7)
H71	0.661 (12)	0.894 (12)	0.1630 (17)	0.033*
H72	0.585 (12)	0.623 (10)	0.1641 (16)	0.033*
C1	0.7017 (8)	0.7659 (11)	0.23163 (12)	0.0225 (8)
C2	0.8894 (8)	0.7703 (11)	0.19964 (11)	0.0252 (9)
H2A	0.9953	0.9222	0.2003	0.030*
H2B	1.0136	0.6308	0.2014	0.030*
C3	0.9244 (10)	0.7587 (12)	0.13153 (11)	0.0314 (9)
H3A	1.0672	0.6371	0.1353	0.038*
H3B	1.0085	0.9212	0.1294	0.038*
C11	0.7770 (10)	0.7013 (9)	0.09631 (13)	0.0292 (11)
C12	0.8329 (16)	0.4968 (12)	0.07646 (18)	0.0483 (17)
H12	0.9657	0.3870	0.0849	0.058*
C13	0.6936 (18)	0.4473 (14)	0.04329 (18)	0.056 (2)
H13	0.7350	0.3046	0.0296	0.068*
C14	0.5016 (16)	0.6007 (14)	0.03072 (17)	0.0542 (19)
H14	0.4067	0.5654	0.0087	0.065*
C15	0.4480 (15)	0.8087 (12)	0.05065 (15)	0.0494 (17)
H15	0.3177	0.9202	0.0420	0.059*
C16	0.5817 (13)	0.8566 (11)	0.08306 (15)	0.0396 (13)
H16	0.5390	0.9994	0.0966	0.048*
Cl1	0.4309 (2)	0.2582 (2)	0.16068 (3)	0.0287 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0225 (13)	0.0257 (17)	0.0256 (14)	0.0029 (17)	−0.0031 (11)	0.0055 (18)
O2	0.0164 (13)	0.0295 (16)	0.0370 (16)	−0.0029 (19)	−0.0019 (12)	−0.001 (2)
N1	0.0199 (16)	0.0205 (16)	0.0266 (16)	−0.0063 (19)	−0.0008 (13)	0.000 (2)
C1	0.0207 (18)	0.012 (2)	0.035 (2)	−0.002 (2)	−0.0030 (16)	0.005 (2)
C2	0.0186 (19)	0.027 (2)	0.030 (2)	0.011 (2)	−0.0074 (16)	−0.001 (2)
C3	0.026 (2)	0.035 (2)	0.034 (2)	0.002 (4)	0.0066 (19)	0.002 (3)
C11	0.030 (2)	0.031 (3)	0.027 (2)	−0.008 (2)	0.0090 (19)	0.0008 (19)
C12	0.069 (5)	0.034 (3)	0.042 (3)	0.007 (3)	0.008 (3)	−0.002 (3)
C13	0.082 (6)	0.049 (4)	0.039 (3)	−0.007 (4)	0.012 (4)	−0.013 (3)
C14	0.063 (5)	0.069 (5)	0.031 (3)	−0.019 (4)	−0.002 (3)	−0.010 (3)
C15	0.052 (4)	0.064 (5)	0.032 (3)	−0.002 (4)	−0.007 (3)	−0.003 (3)
C16	0.040 (3)	0.048 (3)	0.031 (3)	−0.001 (3)	0.002 (3)	−0.005 (2)
Cl1	0.0357 (5)	0.0192 (4)	0.0312 (5)	−0.0014 (7)	0.0024 (5)	−0.0005 (6)

Geometric parameters (Å, º) top

O1—C1	1.308 (5)	C3—H3B	0.9900
O1—H1	0.8400	C11—C12	1.363 (8)
O2—C1	1.199 (5)	C11—C16	1.386 (8)
N1—C2	1.492 (5)	C12—C13	1.418 (10)
N1—C3	1.503 (5)	C12—H12	0.9500
N1—H71	0.86 (6)	C13—C14	1.360 (11)
N1—H72	1.07 (6)	C13—H13	0.9500
C1—C2	1.496 (6)	C14—C15	1.378 (9)
C2—H2A	0.9900	C14—H14	0.9500
C2—H2B	0.9900	C15—C16	1.379 (8)
C3—C11	1.510 (6)	C15—H15	0.9500
C3—H3A	0.9900	C16—H16	0.9500

C1—O1—H1	109.5	C11—C3—H3B	109.4
C2—N1—C3	111.5 (3)	H3A—C3—H3B	108.0
C2—N1—H71	103 (4)	C12—C11—C16	118.0 (5)
C3—N1—H71	104 (4)	C12—C11—C3	121.1 (5)
C2—N1—H72	114 (3)	C16—C11—C3	120.8 (5)
C3—N1—H72	117 (3)	C11—C12—C13	120.2 (7)
H71—N1—H72	105 (5)	C11—C12—H12	119.9
O2—C1—O1	125.1 (4)	C13—C12—H12	119.9
O2—C1—C2	122.8 (4)	C14—C13—C12	121.1 (7)
O1—C1—C2	112.1 (4)	C14—C13—H13	119.5
N1—C2—C1	110.5 (3)	C12—C13—H13	119.5
N1—C2—H2A	109.6	C13—C14—C15	118.5 (6)
C1—C2—H2A	109.6	C13—C14—H14	120.8
N1—C2—H2B	109.6	C15—C14—H14	120.8
C1—C2—H2B	109.6	C14—C15—C16	120.6 (7)
H2A—C2—H2B	108.1	C14—C15—H15	119.7
N1—C3—C11	111.1 (4)	C16—C15—H15	119.7
N1—C3—H3A	109.4	C15—C16—C11	121.5 (6)
C11—C3—H3A	109.4	C15—C16—H16	119.2
N1—C3—H3B	109.4	C11—C16—H16	119.2

C3—N1—C2—C1	−179.6 (5)	C3—C11—C12—C13	−179.5 (6)
O2—C1—C2—N1	−2.8 (9)	C11—C12—C13—C14	−0.4 (11)
O1—C1—C2—N1	177.5 (5)	C12—C13—C14—C15	1.1 (11)
C2—N1—C3—C11	170.2 (5)	C13—C14—C15—C16	−1.6 (10)
N1—C3—C11—C12	−115.9 (6)	C14—C15—C16—C11	1.3 (10)
N1—C3—C11—C16	64.6 (7)	C12—C11—C16—C15	−0.5 (9)
C16—C11—C12—C13	0.0 (9)	C3—C11—C16—C15	179.0 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1ⁱ	0.84	2.26	3.048 (3)	157
N1—H71···Cl1ⁱⁱ	0.86 (6)	2.31 (6)	3.166 (5)	178 (6)
N1—H72···Cl1	1.07 (6)	2.15 (6)	3.148 (5)	154 (5)
C2—H2A···O1ⁱⁱⁱ	0.99	2.48	3.364 (7)	148
C2—H2B···O1^iv	0.99	2.50	3.383 (7)	148
C2—H2B···O2^v	0.99	2.57	3.070 (5)	111
C16—H16···Cl1ⁱⁱ	0.95	2.78	3.654 (6)	154

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

Experimental details

Crystal data
Chemical formula	C₉H₁₂NO₂⁺·Cl⁻
M_r	201.65
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	200
a, b, c (Å)	5.0290 (7), 5.4900 (8), 36.254 (5)
V (Å³)	1000.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.53 × 0.40 × 0.07

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.585, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7535, 2376, 2273
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.080, 0.177, 1.34
No. of reflections	2376
No. of parameters	125
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.57
Absolute structure	Flack (1983), 903 Friedel pairs
Absolute structure parameter	0.1 (3)

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SIR97 (Altomare et al., 1999), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1ⁱ	0.84	2.26	3.048 (3)	157.0
N1—H71···Cl1ⁱⁱ	0.86 (6)	2.31 (6)	3.166 (5)	178 (6)
N1—H72···Cl1	1.07 (6)	2.15 (6)	3.148 (5)	154 (5)
C2—H2A···O1ⁱⁱⁱ	0.99	2.48	3.364 (7)	148.4
C2—H2B···O1^iv	0.99	2.50	3.383 (7)	148.4
C2—H2B···O2^v	0.99	2.57	3.070 (5)	111.4
C16—H16···Cl1ⁱⁱ	0.95	2.78	3.654 (6)	154.1

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

Acknowledgements

The authors thank Dr Marc van der Vyver for helpful discussions.

References

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