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In the title compound, C12H18N4OS2+·2HSO4·H2O, the protonated thia­mine cation exhibits the frequently observed F conformation with respect to the methyl­ene bridge atom. The value of the torsion angle φ formed by the side chain is quite different from the frequently observed range, possibly because of the packing specificity/hydrogen bonding of the crystal structure. The thia­zolium and pyrimidine rings inter­act with the anions through inter­molecular/electrostatic contacts. The thia­mine cations form `head-to-head' hydrogen-bonded dimers. The bis­ulfate anions are dimerized themselves and an extensive three-dimensional network of classical hydrogen bonds is observed through the anionic dimers. The anions occupy positions close to the `anionic holes' of the thia­mine cation, leading to a host–guest structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805041620/rz6148sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805041620/rz6148Isup2.hkl
Contains datablock I

CCDC reference: 298524

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.037
  • wR factor = 0.106
  • Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for S1 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for S2 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3 H O4 S PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 4 H2 O
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL/PC (Bruker, 2000); program(s) used to refine structure: SHELXTL/PC; molecular graphics: SHELXTL/PC and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Thiaminium bis(bisulfate) monohydrate top
Crystal data top
C12H18N4OS2+·2HSO4·H2OZ = 2
Mr = 478.52F(000) = 500
Triclinic, P1Dx = 1.612 Mg m3
Dm = 1.601 Mg m3
Dm measured by flotation using a mixture of carbon tetrachloride and bromoform
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.686 (3) ÅCell parameters from 25 reflections
b = 10.801 (7) Åθ = 11.1–14.2°
c = 12.881 (9) ŵ = 0.44 mm1
α = 68.83 (4)°T = 293 K
β = 82.67 (6)°Block, colorless
γ = 83.23 (5)°0.25 × 0.20 × 0.12 mm
V = 986.0 (11) Å3
Data collection top
Nonius MACH3 sealed-tube
diffractometer
2898 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.010
Graphite monochromatorθmax = 25.0°, θmin = 2.0°
ω–2θ scansh = 19
Absorption correction: ψ scan
(North et al., 1968)
k = 1212
Tmin = 0.911, Tmax = 0.954l = 1515
4297 measured reflections3 standard reflections every 60 min
3457 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0485P)2 + 1.0125P]
where P = (Fo2 + 2Fc2)/3
3457 reflections(Δ/σ)max = 0.001
273 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.58 e Å3
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
xyzUiso*/Ueq
N10.1480 (3)0.4585 (2)0.28037 (17)0.0347 (5)
H10.05020.43160.31790.042*
C20.1944 (3)0.4382 (2)0.1837 (2)0.0323 (5)
C210.0738 (4)0.3675 (3)0.1457 (3)0.0478 (7)
H21A0.03330.35490.19440.072*
H21B0.12960.28250.14770.072*
H21C0.04750.41980.07080.072*
N30.3405 (3)0.47765 (19)0.12273 (17)0.0314 (4)
C40.4493 (3)0.5414 (2)0.1588 (2)0.0298 (5)
N410.5944 (3)0.5797 (2)0.09383 (19)0.0413 (5)
H41A0.61600.56410.03240.050*
H41B0.66740.62040.11290.050*
C50.4062 (3)0.5634 (2)0.2624 (2)0.0304 (5)
C60.2519 (3)0.5202 (2)0.3199 (2)0.0336 (5)
H60.21720.53330.38730.040*
C70.5282 (3)0.6218 (2)0.3115 (2)0.0336 (5)
H7A0.49330.59880.39090.040*
H7B0.64640.58160.30330.040*
N80.5312 (3)0.76825 (19)0.25995 (16)0.0291 (4)
C90.6386 (3)0.8379 (2)0.2956 (2)0.0299 (5)
C910.7607 (4)0.7659 (3)0.3829 (2)0.0428 (6)
H91A0.69490.71320.44970.064*
H91B0.82040.82910.39910.064*
H91C0.84540.70880.35640.064*
C100.6183 (3)0.9702 (2)0.2391 (2)0.0332 (5)
S110.46545 (10)1.00560 (7)0.14321 (6)0.0433 (2)
C120.4324 (3)0.8441 (3)0.1807 (2)0.0361 (6)
H120.35360.81180.14930.043*
C130.7135 (4)1.0794 (3)0.2476 (3)0.0409 (6)
H13A0.81541.09490.19310.049*
H13B0.75551.05010.32120.049*
C140.6021 (4)1.2085 (3)0.2288 (3)0.0459 (7)
H14A0.67611.27710.22490.055*
H14B0.55301.23470.15760.055*
O150.4637 (3)1.2002 (2)0.3137 (2)0.0598 (6)
H150.50771.23190.35540.116 (18)*
S10.99096 (9)0.79812 (6)0.07022 (6)0.03742 (18)
O111.0025 (3)0.8811 (2)0.14258 (18)0.0534 (5)
H111.03470.95450.10290.080*
O121.1662 (3)0.7611 (2)0.0341 (2)0.0571 (6)
O130.8921 (3)0.8836 (2)0.02639 (19)0.0570 (6)
O140.8906 (3)0.6874 (2)0.13748 (19)0.0566 (6)
S21.20797 (9)0.71565 (7)0.53626 (6)0.03922 (18)
O211.1873 (3)0.8025 (2)0.41292 (17)0.0581 (6)
H211.18930.88120.40480.087*
O221.1417 (3)0.5941 (2)0.55027 (19)0.0588 (6)
O231.3941 (3)0.6997 (3)0.5507 (2)0.0608 (6)
O241.1068 (3)0.7829 (3)0.6057 (2)0.0631 (6)
O1W1.1846 (5)1.0472 (3)0.3800 (4)0.1186 (16)
H1W1.099 (8)1.092 (6)0.403 (5)0.119 (19)*
H2W1.278 (9)1.092 (7)0.367 (6)0.16 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0298 (11)0.0382 (11)0.0357 (11)0.0086 (9)0.0026 (9)0.0124 (9)
C20.0323 (13)0.0286 (12)0.0355 (13)0.0033 (10)0.0056 (10)0.0097 (10)
C210.0454 (17)0.0553 (18)0.0492 (16)0.0218 (14)0.0049 (13)0.0206 (14)
N30.0336 (11)0.0291 (10)0.0346 (11)0.0052 (8)0.0021 (9)0.0147 (9)
C40.0309 (13)0.0264 (11)0.0340 (13)0.0030 (9)0.0034 (10)0.0124 (10)
N410.0399 (13)0.0536 (14)0.0409 (12)0.0198 (11)0.0070 (10)0.0277 (11)
C50.0337 (13)0.0272 (12)0.0312 (12)0.0029 (10)0.0030 (10)0.0111 (10)
C60.0383 (14)0.0327 (13)0.0303 (12)0.0023 (11)0.0030 (10)0.0119 (10)
C70.0377 (14)0.0317 (13)0.0336 (13)0.0041 (10)0.0073 (11)0.0123 (10)
N80.0288 (10)0.0323 (10)0.0308 (10)0.0020 (8)0.0065 (8)0.0155 (9)
C90.0274 (12)0.0367 (13)0.0324 (12)0.0027 (10)0.0062 (10)0.0191 (11)
C910.0415 (15)0.0459 (15)0.0446 (15)0.0038 (12)0.0192 (12)0.0149 (12)
C100.0299 (13)0.0377 (14)0.0391 (14)0.0008 (10)0.0088 (10)0.0207 (11)
S110.0493 (4)0.0335 (4)0.0515 (4)0.0015 (3)0.0259 (3)0.0148 (3)
C120.0364 (14)0.0367 (14)0.0416 (14)0.0016 (11)0.0147 (11)0.0182 (11)
C130.0361 (14)0.0391 (14)0.0553 (17)0.0061 (11)0.0087 (12)0.0235 (13)
C140.0471 (17)0.0379 (15)0.0595 (18)0.0078 (12)0.0070 (14)0.0230 (13)
O150.0474 (13)0.0658 (14)0.0825 (16)0.0076 (11)0.0003 (12)0.0467 (13)
S10.0324 (3)0.0351 (3)0.0474 (4)0.0032 (3)0.0102 (3)0.0152 (3)
O110.0604 (14)0.0542 (13)0.0544 (12)0.0141 (11)0.0056 (10)0.0267 (10)
O120.0438 (12)0.0548 (13)0.0709 (15)0.0059 (10)0.0016 (10)0.0241 (11)
O130.0576 (13)0.0481 (12)0.0682 (14)0.0023 (10)0.0361 (11)0.0142 (10)
O140.0528 (13)0.0493 (12)0.0668 (14)0.0189 (10)0.0096 (11)0.0136 (11)
S20.0336 (4)0.0495 (4)0.0374 (4)0.0057 (3)0.0003 (3)0.0192 (3)
O210.0716 (15)0.0548 (13)0.0453 (12)0.0108 (12)0.0063 (11)0.0126 (10)
O220.0631 (14)0.0542 (13)0.0573 (13)0.0096 (11)0.0026 (11)0.0185 (11)
O230.0391 (12)0.0830 (16)0.0711 (15)0.0022 (11)0.0073 (10)0.0399 (13)
O240.0524 (13)0.0861 (17)0.0635 (14)0.0024 (12)0.0013 (11)0.0460 (13)
O1W0.0601 (19)0.0520 (16)0.217 (5)0.0062 (15)0.032 (2)0.030 (2)
Geometric parameters (Å, º) top
N1—C21.339 (3)C91—H91C0.9600
N1—C61.348 (3)C10—C131.503 (3)
N1—H10.8600C10—S111.724 (3)
C2—N31.306 (3)S11—C121.675 (3)
C2—C211.494 (4)C12—H120.9300
C21—H21A0.9600C13—C141.504 (4)
C21—H21B0.9600C13—H13A0.9700
C21—H21C0.9600C13—H13B0.9700
N3—C41.362 (3)C14—O151.411 (4)
C4—N411.317 (3)C14—H14A0.9700
C4—C51.429 (4)C14—H14B0.9700
N41—H41A0.8600O15—H150.8500
N41—H41B0.8600S1—O121.428 (2)
C5—C61.353 (4)S1—O141.440 (2)
C5—C71.502 (3)S1—O131.492 (2)
C6—H60.9300S1—O111.524 (2)
C7—N81.480 (3)O11—H110.8200
C7—H7A0.9700S2—O221.407 (3)
C7—H7B0.9700S2—O241.446 (2)
N8—C121.318 (3)S2—O231.448 (2)
N8—C91.396 (3)S2—O211.543 (2)
C9—C101.349 (4)O21—H210.8200
C9—C911.489 (4)O1W—H1W0.85 (6)
C91—H91A0.9600O1W—H2W0.87 (7)
C91—H91B0.9600
C2—N1—C6121.1 (2)H91A—C91—H91B109.5
C2—N1—H1119.4C9—C91—H91C109.5
C6—N1—H1119.4H91A—C91—H91C109.5
N3—C2—N1122.1 (2)H91B—C91—H91C109.5
N3—C2—C21119.7 (2)C9—C10—C13128.7 (2)
N1—C2—C21118.2 (2)C9—C10—S11110.65 (18)
C2—C21—H21A109.5C13—C10—S11120.6 (2)
C2—C21—H21B109.5C12—S11—C1091.53 (13)
H21A—C21—H21B109.5N8—C12—S11111.94 (19)
C2—C21—H21C109.5N8—C12—H12124.0
H21A—C21—H21C109.5S11—C12—H12124.0
H21B—C21—H21C109.5C10—C13—C14113.8 (2)
C2—N3—C4118.9 (2)C10—C13—H13A108.8
N41—C4—N3116.4 (2)C14—C13—H13A108.8
N41—C4—C5122.8 (2)C10—C13—H13B108.8
N3—C4—C5120.8 (2)C14—C13—H13B108.8
C4—N41—H41A120.0H13A—C13—H13B107.7
C4—N41—H41B120.0O15—C14—C13112.9 (3)
H41A—N41—H41B120.0O15—C14—H14A109.0
C6—C5—C4116.5 (2)C13—C14—H14A109.0
C6—C5—C7120.1 (2)O15—C14—H14B109.0
C4—C5—C7123.2 (2)C13—C14—H14B109.0
N1—C6—C5120.5 (2)H14A—C14—H14B107.8
N1—C6—H6119.7C14—O15—H15102.0
C5—C6—H6119.7O12—S1—O14114.32 (15)
N8—C7—C5114.1 (2)O12—S1—O13111.35 (15)
N8—C7—H7A108.7O14—S1—O13109.27 (14)
C5—C7—H7A108.7O12—S1—O11107.80 (14)
N8—C7—H7B108.7O14—S1—O11106.70 (14)
C5—C7—H7B108.7O13—S1—O11107.03 (14)
H7A—C7—H7B107.6S1—O11—H11109.5
C12—N8—C9114.4 (2)O22—S2—O24112.33 (15)
C12—N8—C7124.3 (2)O22—S2—O23111.84 (16)
C9—N8—C7121.3 (2)O24—S2—O23112.31 (14)
C10—C9—N8111.5 (2)O22—S2—O21104.81 (14)
C10—C9—C91127.7 (2)O24—S2—O21107.99 (16)
N8—C9—C91120.8 (2)O23—S2—O21107.06 (16)
C9—C91—H91A109.5S2—O21—H21109.5
C9—C91—H91B109.5H1W—O1W—H2W107 (5)
C6—N1—C2—N30.6 (4)C12—N8—C9—C100.6 (3)
C6—N1—C2—C21179.2 (2)C7—N8—C9—C10178.7 (2)
N1—C2—N3—C40.1 (4)C12—N8—C9—C91178.7 (2)
C21—C2—N3—C4179.7 (2)C7—N8—C9—C913.2 (3)
C2—N3—C4—N41179.6 (2)N8—C9—C10—C13177.1 (2)
C2—N3—C4—C50.9 (3)C91—C9—C10—C130.8 (5)
N41—C4—C5—C6179.2 (2)N8—C9—C10—S110.3 (3)
N3—C4—C5—C61.3 (3)C91—C9—C10—S11178.2 (2)
N41—C4—C5—C75.2 (4)C9—C10—S11—C120.1 (2)
N3—C4—C5—C7174.3 (2)C13—C10—S11—C12177.7 (2)
C2—N1—C6—C50.0 (4)C9—N8—C12—S110.7 (3)
C4—C5—C6—N10.8 (4)C7—N8—C12—S11178.72 (18)
C7—C5—C6—N1174.9 (2)C10—S11—C12—N80.4 (2)
C6—C5—C7—N8105.8 (3)C9—C10—C13—C14146.9 (3)
C4—C5—C7—N878.7 (3)S11—C10—C13—C1436.0 (3)
C5—C7—N8—C122.5 (3)C10—C13—C14—O1566.8 (3)
C5—C7—N8—C9179.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O22i0.862.062.864 (4)155
N41—H41A···N3ii0.862.183.039 (4)178
N41—H41B···O140.862.042.877 (3)164
O15—H15···O23iii0.851.8942.746 (3)179
O11—H11···O13iv0.821.792.604 (4)176
O21—H21···O1W0.821.702.519 (4)176
O1W—H1W···O24iii0.85 (6)1.94 (6)2.754 (4)158 (5)
O1W—H2W···O15v0.87 (7)1.86 (7)2.722 (4)170 (6)
C12—H12···O12vi0.932.433.346 (4)169
C6—H6···O22vi0.932.403.326 (4)173
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+1, z; (iii) x+2, y+2, z+1; (iv) x+2, y+2, z; (v) x+1, y, z; (vi) x1, y, z.
 

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