Bis(L-tyrosinium) sulfate monohydrate

In the title compound, 2C₉H₁₂NO₃⁺·SO₄²⁻·H₂O, the sulfate anion is linked to the tyrosinium residue 1 by a strong O—H...O hydrogen bond, while tyrosinium residue 2 forms a relatively strong O—H...O hydrogen bond with the terminal hydroxyl O atom, O^η, resulting in a hydrogen-bonded helical structure around the b axis. A zigzag (Z1) head-to-tail sequence is observed in residue 2. Ribbons of tyrosinium residues parallel to the a axis are interconnected by sulfate anions and disordered water mol­ecules in a three-dimensional network. The disordered water mol­ecule links the sulfate anion and tyrosinium residue as a chain running along the b axis.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in solvent or counterion
• R factor = 0.030
• wR factor = 0.084
• Data-to-parameter ratio = 8.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_302  Alert C Anion/Solvent Disorder .......................      14.00 Perc.

PLAT_746  Alert C H...A   Calc     2.08(7), Rep     2.08000 ....    Missing s.u.
                     H1W  -O2      1.555   2.646

PLAT_746  Alert C H...A   Calc     2.08(7), Rep     2.08000 ....    Missing s.u.
                     H1W  -O2      1.555   2.646

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           24.98
         From the CIF: _reflns_number_total               2455
         Count of symmetry unique reflns         2083
         Completeness (_total/calc)            117.86%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       372
         Fraction of Friedel pairs measured     0.179
         Are heavy atom types Z>Si present          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 3 Alert Level C = Please check

---

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97.

Bis(L-tyrosinium)sulfate monhydrate

Crystal data

2C9H12NO3^+·O4S^2^−·H2O	F(000) = 504
Mr = 478.47	Dx = 1.480 Mg m^−3 Dm = 1.478 Mg m^−3 Dm measured by flotation using a mixture of carbon tetrachloride and xylene
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 13.473 (2) Å	Cell parameters from 25 reflections
b = 6.134 (1) Å	θ = 11.3–14.2°
c = 13.785 (3) Å	µ = 0.22 mm^−1
β = 109.51 (2)°	T = 293 K
V = 1073.8 (3) Å^3	Needle, colorless
Z = 2	0.5 × 0.4 × 0.3 mm

Data collection

Enraf-Nonis CAD-4 diffractometer	2322 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.015
Graphite monochromator	θmax = 25.0°, θmin = 1.6°
ω–2θ scans	h = −2→16
Absorption correction: ψ scan (North et al., 1968)	k = −1→7
Tmin = 0.862, Tmax = 0.939	l = −16→15
3011 measured reflections	3 standard reflections every 60 min
2455 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.030	w = 1/[σ^2(Fo^2) + (0.0589P)^2 + 0.1816P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.084	(Δ/σ)max = 0.007
S = 1.07	Δρmax = 0.35 e Å^−3
2459 reflections	Δρmin = −0.24 e Å^−3
304 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.011 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.04 (8)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.25941 (4)	0.81125 (11)	0.89163 (4)	0.02933 (16)
O1	0.36827 (14)	0.8817 (4)	0.93233 (19)	0.0640 (6)
O2	0.21975 (19)	0.8441 (4)	0.78079 (14)	0.0628 (6)
O3	0.25070 (14)	0.5815 (4)	0.91718 (14)	0.0468 (5)
O4	0.19654 (17)	0.9470 (4)	0.93750 (16)	0.0536 (6)
O1A	−0.03433 (13)	0.8380 (4)	0.00376 (12)	0.0477 (5)
O1B	0.13875 (13)	0.8430 (4)	0.09357 (12)	0.0508 (6)
H1B	0.1451	0.8601	0.0370	0.076*
C11	0.03881 (18)	0.8262 (5)	0.08282 (16)	0.0354 (5)
C12	0.02644 (16)	0.7944 (5)	0.18729 (15)	0.0322 (5)
H12	0.0589	0.9184	0.2312	0.039*
N11	−0.08765 (14)	0.7891 (4)	0.17486 (13)	0.0342 (5)
H11A	−0.0951	0.7707	0.2361	0.051*
H11B	−0.1185	0.6793	0.1336	0.051*
H11C	−0.1175	0.9143	0.1475	0.051*
C13	0.0803 (2)	0.5842 (5)	0.23941 (18)	0.0372 (6)
H13A	0.0396	0.4605	0.2034	0.045*
H13B	0.1494	0.5753	0.2322	0.045*
C14	0.09296 (18)	0.5661 (5)	0.35209 (17)	0.0333 (5)
C15	0.0662 (2)	0.3757 (5)	0.39208 (19)	0.0395 (6)
H15	0.0332	0.2637	0.3475	0.047*
C16	0.0875 (2)	0.3486 (5)	0.49709 (18)	0.0405 (6)
H16	0.0697	0.2192	0.5224	0.049*
C17	0.13504 (19)	0.5141 (5)	0.56336 (18)	0.0372 (6)
C18	0.1615 (2)	0.7074 (6)	0.52584 (19)	0.0425 (6)
H18	0.1925	0.8207	0.5705	0.051*
C19	0.14098 (19)	0.7292 (5)	0.42106 (18)	0.0393 (6)
H19	0.1601	0.8578	0.3962	0.047*
O1C	0.15267 (16)	0.4830 (4)	0.66619 (12)	0.0516 (5)
H1C	0.1801	0.5924	0.6982	0.077*
O2A	0.4923 (2)	0.4812 (5)	0.84442 (17)	0.0744 (8)
O2B	0.44252 (15)	0.7111 (5)	0.71149 (14)	0.0569 (6)
H2B	0.4049	0.6086	0.6832	0.085*
C21	0.4946 (2)	0.6597 (5)	0.8041 (2)	0.0469 (7)
C22	0.56712 (18)	0.8353 (5)	0.86455 (17)	0.0381 (6)
H22	0.5340	0.9775	0.8430	0.046*
N22	0.58447 (15)	0.8046 (5)	0.97646 (14)	0.0381 (4)
H22A	0.6269	0.9090	1.0123	0.057*
H22B	0.6139	0.6750	0.9965	0.057*
H22C	0.5230	0.8115	0.9873	0.057*
C23	0.67344 (18)	0.8307 (7)	0.84647 (19)	0.0496 (7)
H23A	0.7164	0.9511	0.8832	0.060*
H23B	0.7098	0.6963	0.8743	0.060*
C24	0.66165 (18)	0.8467 (6)	0.7338 (2)	0.0430 (7)
C25	0.6832 (2)	0.6712 (6)	0.6820 (2)	0.0477 (7)
H25	0.7091	0.5433	0.7176	0.057*
C26	0.6666 (2)	0.6823 (6)	0.5766 (2)	0.0486 (7)
H26	0.6807	0.5621	0.5422	0.058*
C27	0.6294 (2)	0.8711 (5)	0.5241 (2)	0.0422 (7)
C28	0.6082 (2)	1.0494 (5)	0.5748 (2)	0.0464 (7)
H28	0.5832	1.1776	0.5389	0.056*
C29	0.6241 (2)	1.0372 (6)	0.6786 (2)	0.0481 (7)
H29	0.6097	1.1579	0.7125	0.058*
O2C	0.61082 (17)	0.8829 (4)	0.42014 (15)	0.0611 (6)
H2C	0.6252	0.7656	0.3996	0.092*
O1W	0.6820 (5)	0.6122 (12)	0.3231 (6)	0.093 (3)	0.609 (12)
O2W	0.6395 (7)	0.6870 (13)	0.2538 (7)	0.066 (3)	0.391 (12)
H1W	0.696 (5)	0.586 (12)	0.264 (5)	0.12 (2)*
H2W1	0.6411	0.4836	0.3110	0.050*	0.609 (12)
H2W2	0.5963	0.7836	0.2239	0.050*	0.391 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0295 (3)	0.0295 (3)	0.0292 (3)	−0.0012 (3)	0.01014 (19)	0.0024 (3)
O1	0.0347 (10)	0.0522 (15)	0.0999 (16)	−0.0101 (10)	0.0155 (10)	−0.0106 (13)
O2	0.1007 (16)	0.0515 (15)	0.0327 (9)	−0.0019 (14)	0.0177 (9)	0.0043 (11)
O3	0.0447 (10)	0.0343 (11)	0.0530 (11)	−0.0022 (9)	0.0050 (8)	0.0109 (10)
O4	0.0632 (12)	0.0532 (13)	0.0592 (11)	0.0231 (11)	0.0400 (9)	0.0201 (11)
O1A	0.0501 (9)	0.0595 (14)	0.0308 (7)	0.0027 (12)	0.0097 (7)	0.0061 (10)
O1B	0.0447 (9)	0.0755 (17)	0.0358 (8)	−0.0086 (12)	0.0184 (7)	0.0092 (11)
C11	0.0434 (12)	0.0323 (13)	0.0307 (10)	−0.0039 (14)	0.0126 (9)	−0.0003 (13)
C12	0.0322 (10)	0.0354 (14)	0.0283 (10)	−0.0025 (12)	0.0090 (8)	−0.0022 (12)
N11	0.0363 (9)	0.0360 (12)	0.0302 (8)	0.0035 (10)	0.0111 (7)	−0.0013 (10)
C13	0.0404 (12)	0.0408 (15)	0.0301 (11)	0.0102 (12)	0.0112 (9)	0.0026 (11)
C14	0.0304 (11)	0.0368 (14)	0.0317 (11)	0.0036 (11)	0.0089 (9)	0.0025 (11)
C15	0.0441 (13)	0.0346 (15)	0.0377 (12)	−0.0027 (12)	0.0108 (10)	−0.0018 (11)
C16	0.0486 (13)	0.0340 (15)	0.0389 (12)	−0.0024 (13)	0.0149 (10)	0.0047 (12)
C17	0.0376 (12)	0.0422 (16)	0.0332 (12)	−0.0004 (12)	0.0135 (10)	0.0034 (12)
C18	0.0478 (14)	0.0410 (15)	0.0343 (12)	−0.0062 (14)	0.0078 (10)	−0.0007 (13)
C19	0.0428 (12)	0.0408 (15)	0.0337 (11)	−0.0076 (13)	0.0119 (10)	0.0047 (12)
O1C	0.0728 (13)	0.0524 (13)	0.0292 (8)	−0.0096 (12)	0.0165 (8)	0.0036 (10)
O2A	0.1066 (19)	0.0471 (15)	0.0535 (12)	−0.0208 (15)	0.0054 (12)	−0.0017 (12)
O2B	0.0569 (11)	0.0591 (14)	0.0446 (10)	−0.0113 (12)	0.0034 (9)	−0.0060 (11)
C21	0.0520 (15)	0.0460 (19)	0.0434 (15)	−0.0071 (14)	0.0170 (12)	−0.0055 (14)
C22	0.0362 (11)	0.0362 (15)	0.0391 (11)	−0.0004 (13)	0.0090 (9)	−0.0022 (13)
N22	0.0362 (9)	0.0348 (11)	0.0421 (10)	−0.0027 (12)	0.0115 (8)	−0.0048 (12)
C23	0.0363 (12)	0.067 (2)	0.0444 (12)	−0.0003 (17)	0.0119 (10)	0.0012 (17)
C24	0.0316 (11)	0.0487 (19)	0.0485 (13)	−0.0001 (13)	0.0132 (10)	0.0024 (14)
C25	0.0453 (14)	0.0439 (18)	0.0532 (16)	0.0086 (14)	0.0157 (12)	0.0083 (14)
C26	0.0475 (14)	0.0466 (18)	0.0538 (16)	0.0098 (15)	0.0195 (12)	0.0011 (16)
C27	0.0379 (12)	0.0433 (18)	0.0458 (13)	0.0002 (13)	0.0145 (10)	0.0036 (13)
C28	0.0482 (14)	0.0378 (16)	0.0543 (16)	0.0033 (14)	0.0187 (12)	0.0052 (14)
C29	0.0481 (15)	0.0412 (17)	0.0587 (17)	0.0000 (14)	0.0228 (13)	−0.0021 (15)
O2C	0.0771 (14)	0.0628 (17)	0.0466 (10)	0.0096 (13)	0.0249 (10)	0.0032 (11)
O1W	0.097 (4)	0.086 (4)	0.088 (5)	0.016 (3)	0.020 (3)	−0.039 (4)
O2W	0.081 (5)	0.054 (4)	0.058 (5)	0.022 (4)	0.017 (4)	−0.008 (4)

Geometric parameters (Å, º)

S1—O1	1.4501 (19)	O2B—C21	1.274 (3)
S1—O2	1.4545 (18)	O2B—H2B	0.8200
S1—O3	1.467 (2)	C21—C22	1.505 (4)
S1—O4	1.472 (2)	C22—N22	1.493 (3)
O1A—C11	1.203 (3)	C22—C23	1.534 (3)
O1B—C11	1.309 (3)	C22—H22	0.9800
O1B—H1B	0.8200	N22—H22A	0.8900
C11—C12	1.517 (3)	N22—H22B	0.8900
C12—N11	1.489 (3)	N22—H22C	0.8900
C12—C13	1.535 (4)	C23—C24	1.511 (3)
C12—H12	0.9800	C23—H23A	0.9700
N11—H11A	0.8900	C23—H23B	0.9700
N11—H11B	0.8900	C24—C25	1.375 (4)
N11—H11C	0.8900	C24—C29	1.394 (4)
C13—C14	1.509 (3)	C25—C26	1.396 (4)
C13—H13A	0.9700	C25—H25	0.9300
C13—H13B	0.9700	C26—C27	1.369 (4)
C14—C19	1.383 (4)	C26—H26	0.9300
C14—C15	1.390 (4)	C27—O2C	1.371 (3)
C15—C16	1.389 (3)	C27—C28	1.378 (4)
C15—H15	0.9300	C28—C29	1.377 (4)
C16—C17	1.373 (4)	C28—H28	0.9300
C16—H16	0.9300	C29—H29	0.9300
C17—O1C	1.370 (3)	O2C—H2C	0.8200
C17—C18	1.387 (4)	O1W—O2W	1.042 (8)
C18—C19	1.384 (4)	O1W—H1W	0.91 (6)
C18—H18	0.9300	O1W—H2W1	0.945 (7)
C19—H19	0.9300	O2W—H1W	0.96 (7)
O1C—H1C	0.8200	O2W—H2W1	1.472 (9)
O2A—C21	1.233 (4)	O2W—H2W2	0.837 (9)
O1—S1—O2	109.53 (14)	O2A—C21—C22	119.7 (3)
O1—S1—O3	110.20 (13)	O2B—C21—C22	114.6 (3)
O2—S1—O3	110.77 (14)	N22—C22—C21	109.3 (2)
O1—S1—O4	108.53 (15)	N22—C22—C23	109.46 (18)
O2—S1—O4	108.09 (13)	C21—C22—C23	111.4 (3)
O3—S1—O4	109.66 (13)	N22—C22—H22	108.9
C11—O1B—H1B	109.5	C21—C22—H22	108.9
O1A—C11—O1B	126.8 (2)	C23—C22—H22	108.9
O1A—C11—C12	123.5 (2)	C22—N22—H22A	109.5
O1B—C11—C12	109.74 (18)	C22—N22—H22B	109.5
N11—C12—C11	109.27 (17)	H22A—N22—H22B	109.5
N11—C12—C13	110.1 (2)	C22—N22—H22C	109.5
C11—C12—C13	111.6 (2)	H22A—N22—H22C	109.5
N11—C12—H12	108.6	H22B—N22—H22C	109.5
C11—C12—H12	108.6	C24—C23—C22	112.49 (19)
C13—C12—H12	108.6	C24—C23—H23A	109.1
C12—N11—H11A	109.5	C22—C23—H23A	109.1
C12—N11—H11B	109.5	C24—C23—H23B	109.1
H11A—N11—H11B	109.5	C22—C23—H23B	109.1
C12—N11—H11C	109.5	H23A—C23—H23B	107.8
H11A—N11—H11C	109.5	C25—C24—C29	118.3 (2)
H11B—N11—H11C	109.5	C25—C24—C23	121.0 (3)
C14—C13—C12	114.6 (2)	C29—C24—C23	120.7 (3)
C14—C13—H13A	108.6	C24—C25—C26	121.0 (3)
C12—C13—H13A	108.6	C24—C25—H25	119.5
C14—C13—H13B	108.6	C26—C25—H25	119.5
C12—C13—H13B	108.6	C27—C26—C25	119.7 (3)
H13A—C13—H13B	107.6	C27—C26—H26	120.2
C19—C14—C15	117.3 (2)	C25—C26—H26	120.2
C19—C14—C13	121.4 (2)	C26—C27—O2C	120.3 (3)
C15—C14—C13	121.0 (2)	C26—C27—C28	120.3 (3)
C16—C15—C14	121.6 (2)	O2C—C27—C28	119.4 (3)
C16—C15—H15	119.2	C29—C28—C27	119.8 (3)
C14—C15—H15	119.2	C29—C28—H28	120.1
C17—C16—C15	119.6 (3)	C27—C28—H28	120.1
C17—C16—H16	120.2	C28—C29—C24	121.0 (3)
C15—C16—H16	120.2	C28—C29—H29	119.5
O1C—C17—C16	117.8 (2)	C24—C29—H29	119.5
O1C—C17—C18	121.8 (2)	C27—O2C—H2C	109.5
C16—C17—C18	120.3 (2)	O2W—O1W—H1W	58 (4)
C19—C18—C17	119.1 (3)	O2W—O1W—H2W1	95.5 (7)
C19—C18—H18	120.5	H1W—O1W—H2W1	89 (4)
C17—C18—H18	120.5	O1W—O2W—H1W	54 (4)
C14—C19—C18	122.1 (3)	O1W—O2W—H2W1	39.7 (5)
C14—C19—H19	118.9	H1W—O2W—H2W1	60 (4)
C18—C19—H19	118.9	O1W—O2W—H2W2	147.4 (9)
C17—O1C—H1C	109.5	H1W—O2W—H2W2	157 (4)
C21—O2B—H2B	109.5	H2W1—O2W—H2W2	138.3 (8)
O2A—C21—O2B	125.7 (3)
O1A—C11—C12—N11	−2.0 (4)	O2A—C21—C22—N22	−28.2 (4)
O1B—C11—C12—N11	176.6 (3)	O2B—C21—C22—N22	154.2 (2)
O1A—C11—C12—C13	120.0 (3)	O2A—C21—C22—C23	92.9 (3)
O1B—C11—C12—C13	−61.4 (3)	O2B—C21—C22—C23	−84.7 (3)
N11—C12—C13—C14	−71.6 (3)	N22—C22—C23—C24	176.4 (3)
C11—C12—C13—C14	166.9 (2)	C21—C22—C23—C24	55.4 (4)
C12—C13—C14—C15	133.1 (3)	C22—C23—C24—C25	−110.1 (3)
C12—C13—C14—C19	−53.4 (3)	C22—C23—C24—C29	67.1 (4)
C19—C14—C15—C16	−0.6 (4)	C29—C24—C25—C26	−0.9 (4)
C13—C14—C15—C16	173.2 (2)	C23—C24—C25—C26	176.3 (2)
C14—C15—C16—C17	0.8 (4)	C24—C25—C26—C27	0.7 (4)
C15—C16—C17—O1C	178.6 (2)	C25—C26—C27—O2C	−178.7 (2)
C15—C16—C17—C18	0.1 (4)	C25—C26—C27—C28	−0.1 (4)
O1C—C17—C18—C19	−179.6 (2)	C26—C27—C28—C29	−0.2 (4)
C16—C17—C18—C19	−1.2 (4)	O2C—C27—C28—C29	178.4 (2)
C15—C14—C19—C18	−0.5 (4)	C27—C28—C29—C24	0.1 (4)
C13—C14—C19—C18	−174.3 (2)	C25—C24—C29—C28	0.5 (4)
C17—C18—C19—C14	1.4 (4)	C23—C24—C29—C28	−176.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1B—H1B···O4^i	0.82	1.81	2.600 (2)	161
N11—H11A···O1C^ii	0.89	2.19	2.875 (3)	133
N11—H11B···O4^iii	0.89	1.85	2.727 (3)	170
N11—H11C···O3^ii	0.89	2.00	2.791 (3)	147
O1C—H1C···O2	0.82	1.89	2.695 (3)	169
O2B—H2B···O2C^iv	0.82	1.95	2.644 (3)	142
N22—H22A···O3^v	0.89	1.93	2.792 (3)	163
N22—H22B···O1^vi	0.89	2.02	2.860 (4)	156
N22—H22C···O1	0.89	2.01	2.810 (3)	148
N22—H22C···O2A^v	0.89	2.61	3.170 (3)	121
O2C—H2C···O1W	0.82	1.77	2.514 (6)	151
O2C—H2C···O2W	0.82	2.14	2.728 (7)	129
O1W—H2W1···O2B^iv	0.945	1.981	2.926 (7)	178.7
O2W—H2W2···O2A^vii	0.837	1.740	2.577 (10)	176.9
O1W—H1W···O2^iv	0.91	2.08	2.788 (6)	134
O2W—H1W···O2^iv	0.96	2.08	2.975 (8)	154

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