dl-Tyrosinium chloride dihydrate

Fatiha Guenifa; Lamia Bendjeddou; Aouatef Cherouana; Slimane Dahaoui; Claude Lecomte

doi:10.1107/S1600536812043899

. 2012 Oct 27;68(Pt 11):o3227–o3228. doi: 10.1107/S1600536812043899

dl-Tyrosinium chloride dihydrate

Fatiha Guenifa ^a, Lamia Bendjeddou ^a,^*, Aouatef Cherouana ^a, Slimane Dahaoui ^b, Claude Lecomte ^b

PMCID: PMC3515310 PMID: 23284530

Abstract

In the title compound, C₉H₁₂NO₃ ⁺·Cl⁻·2H₂O, the cation has a protonated amino group resulting from proton transfer from chloridric acid. The structure displays double layers parallel to the [010] direction held together by N—H⋯O, N—H⋯Cl, O—H⋯O and O—H⋯Cl hydrogen bonds. These layers are stacked along the c axis at b = 1/2; within each layer, the tyrosinium cations are arranged in an alternating head-to-tail sequence, forming inversion dimers [R ₂ ²(10) motif]. The water molecules allow for the construction of a three-dimensional hydrogen-bonded network formed by centrosymmetric R ₆ ⁶(28) and R ₈ ⁸(34) motifs.

Related literature

For other examples of organic salts of amino acids, see: Zeghouan et al. (2012 ▶); Guenifa et al. (2009 ▶). For the structure of bis(l-tyrosinium) sulfate monohydrate, see: Sridhar et al. (2002 ▶). For other examples of amino acids with non-polar side chains, see: Torii & Iitaka (1973 ▶); Harding & Long (1968 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₉H₁₂NO₃ ⁺·Cl⁻·2H₂O
M _r = 253.68
Triclinic,
a = 5.3330 (2) Å
b = 10.9634 (5) Å
c = 11.2500 (4) Å
α = 113.642 (4)°
β = 94.359 (3)°
γ = 98.465 (3)°
V = 589.34 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 100 K
0.3 × 0.03 × 0.02 mm

Data collection

Oxford Diffraction Xcalibur Sapphire CCD diffractometer
12044 measured reflections
3445 independent reflections
2780 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.084
S = 1.02
3445 reflections
172 parameters
11 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2008 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶), PARST97 (Nardelli, 1995 ▶), Mercury (Macrae et al., 2006 ▶) and POVRay (Persistence of Vision Team, 2004 ▶)’.

Supplementary Material

Click here for additional data file.^{(21.8KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812043899/nk2187sup1.cif

e-68-o3227-sup1.cif^{(21.8KB, cif)}

Click here for additional data file.^{(165.5KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812043899/nk2187Isup2.hkl

e-68-o3227-Isup2.hkl^{(165.5KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯Cl1	0.90 (1)	2.36 (1)	3.2326 (12)	162 (1)
N1—H2N⋯Cl1ⁱ	0.92 (1)	2.44 (1)	3.2872 (12)	154 (1)
N1—H2N⋯O3ⁱ	0.92 (1)	2.40 (2)	2.9574 (15)	119 (1)
N1—H3N⋯Cl1ⁱⁱ	0.90 (1)	2.32 (1)	3.2151 (12)	176 (1)
O1—H1⋯Cl1ⁱⁱⁱ	0.84 (2)	2.36 (2)	3.1858 (11)	169 (1)
O2—H2⋯O2W ⁱ	0.89 (1)	1.64 (1)	2.5319 (15)	174 (2)
O1W—H11W⋯O1^iv	0.84 (1)	2.10 (1)	2.9044 (13)	162 (2)
O1W—H12W⋯Cl1^v	0.85 (1)	2.33 (1)	3.1784 (11)	172 (2)
O2W—H21W⋯O1W ⁱ	0.83 (1)	1.91 (1)	2.7429 (14)	173 (2)
O2W—H22W⋯O1W ^vi	0.85 (2)	2.02 (2)	2.8318 (15)	161 (2)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Acknowledgments

Technical support (X-ray measurements at SCDRX) from Université Henry Poincaré, Nancy 1, is gratefully acknowledged.

supplementary crystallographic information

Comment

We report the crystal structure of DL-tyrosinium chloride dihydrate (I), as part of our research with organic salts of amino acids (Zeghouan et al., 2012; Guenifa et al., 2009).

The asymmetric unit of (I) contains a tyrosinium cation, chloride anion and two water molecules (Fig.1). As expected, tyrosine form protonated units in (I) with the transfer of an H atom from chloridric acid. A similar situation is observed in bis(L-tyrosinium) sulfate monohydrate, (Sridhar et al., 2002).

In the crystal structure of (I), the ions are connected into a three-dimensional hydrogen-bonded network via N—H···O, N—H···Cl, O—H···O and O—H···Cl hydrogen bonds (Table 1). The tyrosinium cations are held together by N—H···O hydrogen bonds, forming a centrosymmetric dimer (R²₂(10) motif; Bernstein et al., 1995) centred at (1/2, 1/2, 1/2). This centrosymmetric dimer is further connected along [100] direction to either side of the chloride anions by N—H···Cl hydrogen bonds [R²₄(8) and R³₅(13) motifs] (Fig. 2). The aggregation of the rings motifs results in an overall two-dimensional hydrogen-bonded network.

The water molecules, which plays a dual role as both donor and acceptor in hydrogen bonding interactions, generating the centrosymmetric hydrogen-bonded (R²₄(8) motif) via O2w—H21w···O1w⁽ⁱ⁾ and O2w—H22w···O1w^(vi) (Fig. 3), and are involved in two centred hydrogen bonding with the cations to produce a centrosymmetric R⁶₆(28) and R⁸₈(34) motifs, thus completing the three-dimensional hydrogen-bonded network. The structures of many amino acids with non-polar side chains have the arrangement of a double layers of carboxyl and amino groups held together by hydrogen bonds (Torii & Iitaka, 1973; Harding & Long, 1968).

The molecule packing of (I), consists of double layers stacked along the c axis, at b = 1/2, where in each layer the tyrosinium cations are arranged with alternating head-to-tail sequence.

Experimental

The compound was obtained as colourless crystals with melting points of 370°, after few days, by slow evaporation from an aqueous solution of tyrosine and chloridric acid in stoechiometric ratio of 1:1.