dl-Tyrosinium chloride dihydrate.

In the title compound, C(9)H(12)NO(3) (+)·Cl(-)·2H(2)O, 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 mol-ecules 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 = 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

Δρmax = 0.43 e Å−3

Δρmin = −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 ▶)’.

Click here for additional data file.

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

Click here for additional data file.

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

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

C9H12NO3+·Cl−·2H2O	Z = 2
Mr = 253.68	F(000) = 268
Triclinic, P1	Dx = 1.43 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.3330 (2) Å	Cell parameters from 12044 reflections
b = 10.9634 (5) Å	θ = 3.4–30.0°
c = 11.2500 (4) Å	µ = 0.33 mm−1
α = 113.642 (4)°	T = 100 K
β = 94.359 (3)°	Needle, colourless
γ = 98.465 (3)°	0.3 × 0.03 × 0.02 mm
V = 589.34 (5) Å3

Oxford Diffraction Xcalibur Sapphire CCD diffractometer	2780 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 30.0°, θmin = 3.4°
ω scans	h = −7→7
12044 measured reflections	k = −15→15
3445 independent reflections	l = −15→15

Refinement on F2	11 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.032	w = 1/[σ2(Fo2) + (0.0483P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.084	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.43 e Å−3
3445 reflections	Δρmin = −0.30 e Å−3
172 parameters

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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.

	x	y	z	Uiso*/Ueq
Cl1	0.26233 (5)	0.45517 (3)	0.68584 (3)	0.01279 (8)
O2	0.63481 (17)	0.90937 (9)	0.68369 (9)	0.0169 (2)
O1	0.43456 (17)	0.69839 (9)	1.18096 (9)	0.0162 (2)
O1W	0.07015 (18)	0.82478 (9)	0.34641 (9)	0.0165 (2)
H12W	−0.008 (3)	0.7497 (11)	0.3437 (15)	0.025*
H11W	0.177 (2)	0.8037 (15)	0.2947 (14)	0.025*
O3	0.40595 (16)	0.69671 (9)	0.58151 (9)	0.01381 (19)
O2W	0.7642 (2)	0.02475 (10)	0.39042 (10)	0.0255 (2)
H22W	0.832 (3)	−0.0447 (13)	0.3609 (15)	0.038*
H21W	0.807 (3)	0.0653 (16)	0.4715 (9)	0.038*
N1	0.7923 (2)	0.58230 (10)	0.62048 (11)	0.0113 (2)
C5	0.8819 (2)	0.66936 (12)	0.94214 (12)	0.0130 (2)
H5	1.0026	0.6179	0.9052	0.016*
C6	0.7489 (2)	0.64160 (12)	1.03283 (12)	0.0135 (2)
H6	0.7796	0.572	1.0558	0.016*
C1	0.6041 (2)	0.77693 (12)	0.63928 (12)	0.0107 (2)
C7	0.5693 (2)	0.71907 (12)	1.08898 (12)	0.0116 (2)
C3	0.9865 (2)	0.80241 (12)	0.80762 (12)	0.0121 (2)
H3A	1.1505	0.7748	0.8117	0.015*
H3B	1.0206	0.8997	0.8337	0.015*
C9	0.6553 (2)	0.84770 (12)	0.96215 (12)	0.0122 (2)
H9	0.6224	0.9165	0.9384	0.015*
C2	0.8520 (2)	0.73226 (12)	0.66507 (12)	0.0108 (2)
H2A	0.9708	0.7523	0.6101	0.013*
C8	0.5211 (2)	0.82194 (12)	1.05327 (12)	0.0128 (2)
H8	0.3999	0.8731	1.0901	0.015*
C4	0.8385 (2)	0.77273 (12)	0.90528 (11)	0.0109 (2)
H3N	0.925 (2)	0.5502 (14)	0.6426 (14)	0.013*
H2N	0.758 (3)	0.5428 (14)	0.5303 (12)	0.013*
H1N	0.657 (2)	0.5615 (14)	0.6569 (13)	0.013*
H1	0.500 (3)	0.6478 (14)	1.2082 (15)	0.016*
H2	0.494 (2)	0.9367 (14)	0.6636 (14)	0.016*

	U11	U22	U33	U12	U13	U23
Cl1	0.01191 (14)	0.01584 (14)	0.01394 (15)	0.00480 (11)	0.00313 (10)	0.00869 (11)
O2	0.0146 (4)	0.0119 (4)	0.0229 (5)	0.0042 (4)	−0.0028 (4)	0.0065 (4)
O1	0.0190 (5)	0.0204 (5)	0.0170 (5)	0.0102 (4)	0.0075 (4)	0.0128 (4)
O1W	0.0177 (5)	0.0145 (4)	0.0176 (5)	0.0041 (4)	0.0055 (4)	0.0061 (4)
O3	0.0111 (4)	0.0137 (4)	0.0161 (5)	0.0032 (3)	0.0010 (3)	0.0055 (4)
O2W	0.0305 (6)	0.0247 (5)	0.0180 (5)	0.0184 (5)	−0.0029 (4)	0.0022 (4)
N1	0.0103 (5)	0.0130 (5)	0.0108 (5)	0.0045 (4)	0.0012 (4)	0.0045 (4)
C5	0.0127 (5)	0.0140 (6)	0.0121 (6)	0.0066 (5)	0.0013 (4)	0.0041 (5)
C6	0.0161 (6)	0.0136 (6)	0.0128 (6)	0.0066 (5)	0.0014 (5)	0.0064 (5)
C1	0.0127 (5)	0.0131 (5)	0.0084 (6)	0.0045 (5)	0.0031 (4)	0.0056 (4)
C7	0.0113 (5)	0.0134 (5)	0.0091 (6)	0.0018 (4)	0.0006 (4)	0.0043 (4)
C3	0.0105 (5)	0.0136 (6)	0.0115 (6)	0.0020 (5)	−0.0004 (4)	0.0050 (5)
C9	0.0140 (6)	0.0106 (5)	0.0126 (6)	0.0037 (5)	0.0001 (5)	0.0053 (5)
C2	0.0103 (5)	0.0120 (5)	0.0113 (6)	0.0026 (4)	0.0016 (4)	0.0058 (5)
C8	0.0133 (6)	0.0122 (5)	0.0131 (6)	0.0059 (5)	0.0024 (5)	0.0041 (5)
C4	0.0095 (5)	0.0115 (5)	0.0087 (6)	0.0002 (4)	−0.0021 (4)	0.0025 (4)

O1—C7	1.3754 (16)	C3—C4	1.5096 (17)
O2—C1	1.3117 (17)	C4—C9	1.3961 (16)
O3—C1	1.2150 (15)	C4—C5	1.3962 (19)
O1—H1	0.837 (17)	C5—C6	1.3900 (18)
O2—H2	0.894 (12)	C6—C7	1.3925 (17)
O1W—H11W	0.835 (12)	C7—C8	1.390 (2)
O1W—H12W	0.854 (14)	C8—C9	1.3882 (18)
O2W—H21W	0.834 (9)	C2—H2A	0.9800
O2W—H22W	0.847 (16)	C3—H3A	0.9700
N1—C2	1.4887 (18)	C3—H3B	0.9700
N1—H2N	0.920 (12)	C5—H5	0.9300
N1—H1N	0.901 (13)	C6—H6	0.9300
N1—H3N	0.896 (13)	C8—H8	0.9300
C1—C2	1.5225 (16)	C9—H9	0.9300
C2—C3	1.5334 (17)
C7—O1—H1	109.9 (11)	O1—C7—C8	117.48 (10)
C1—O2—H2	112.8 (10)	C6—C7—C8	120.27 (11)
H11W—O1W—H12W	105.2 (16)	O1—C7—C6	122.25 (12)
H21W—O2W—H22W	109.8 (16)	C7—C8—C9	119.46 (11)
H1N—N1—H2N	111.9 (13)	C4—C9—C8	121.56 (13)
C2—N1—H2N	108.2 (10)	N1—C2—H2A	108.00
C2—N1—H3N	112.5 (10)	C3—C2—H2A	108.00
H1N—N1—H3N	109.5 (13)	C1—C2—H2A	108.00
C2—N1—H1N	108.3 (10)	C2—C3—H3B	109.00
H2N—N1—H3N	106.6 (14)	C4—C3—H3A	109.00
O2—C1—O3	125.48 (11)	H3A—C3—H3B	108.00
O2—C1—C2	111.91 (10)	C4—C3—H3B	109.00
O3—C1—C2	122.60 (12)	C2—C3—H3A	109.00
N1—C2—C3	110.77 (11)	C4—C5—H5	119.00
C1—C2—C3	115.02 (10)	C6—C5—H5	119.00
N1—C2—C1	107.62 (10)	C7—C6—H6	120.00
C2—C3—C4	114.94 (10)	C5—C6—H6	120.00
C3—C4—C9	121.35 (12)	C7—C8—H8	120.00
C3—C4—C5	120.83 (10)	C9—C8—H8	120.00
C5—C4—C9	117.82 (11)	C8—C9—H9	119.00
C4—C5—C6	121.52 (11)	C4—C9—H9	119.00
C5—C6—C7	119.36 (13)
O2—C1—C2—N1	175.77 (10)	C9—C4—C5—C6	−0.28 (18)
O2—C1—C2—C3	51.79 (15)	C3—C4—C9—C8	−179.15 (11)
O3—C1—C2—N1	−5.77 (16)	C5—C4—C9—C8	0.53 (18)
O3—C1—C2—C3	−129.75 (13)	C4—C5—C6—C7	−0.41 (18)
N1—C2—C3—C4	−57.63 (13)	C5—C6—C7—O1	−178.84 (11)
C1—C2—C3—C4	64.66 (16)	C5—C6—C7—C8	0.88 (18)
C2—C3—C4—C5	94.83 (14)	O1—C7—C8—C9	179.09 (11)
C2—C3—C4—C9	−85.50 (15)	C6—C7—C8—C9	−0.64 (18)
C3—C4—C5—C6	179.40 (11)	C7—C8—C9—C4	−0.07 (19)

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···O2Wi	0.89 (1)	1.64 (1)	2.5319 (15)	174 (2)
O1W—H11W···O1iv	0.84 (1)	2.10 (1)	2.9044 (13)	162 (2)
O1W—H12W···Cl1v	0.85 (1)	2.33 (1)	3.1784 (11)	172 (2)
O2W—H21W···O1Wi	0.83 (1)	1.91 (1)	2.7429 (14)	173 (2)
O2W—H22W···O1Wvi	0.85 (2)	2.02 (2)	2.8318 (15)	161 (2)

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⋯O1iv	0.84 (1)	2.10 (1)	2.9044 (13)	162 (2)
O1W—H12W⋯Cl1v	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)

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