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The crystal structure of sodium thiosulfate pentahydrate, Na2S2O3.5H2O, has been refined to an R value of 0.022 for 1621 observed reflections. All the water-H atoms were located.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (S-O) = 0.001 Å
- R factor = 0.022
- wR factor = 0.060
- Data-to-parameter ratio = 10.8
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
The X-ray diffraction data of the crystal was collected by mistake as it was
supposed to be a crystal of a calcium complex of aspartic acid. When all
attempts to solve the structure failed, the structure was refined blindfold
with all significant peaks obtained in the E-map computed with the phase set
with the highest combined figure of merit, varying the occupany factors of all
the atoms except one. The structure refined rapidly and was then identified as
that of sodium thiosulfate pentahydrate. This is an excellent demonstration of
the power of direct methods in revealing structures when nothing is known
about the crystal composition.
All hydrogen atoms belonging to the five water molecules were located from a
difference map and refined by least squares.
Data collection: CAD-4 Software (Enraf-Nonius,1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: MULTAN80 (Main at el., 1980); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: NORTON EDITOR.
" Sodium thiosulfate pentahydrate"
top
Crystal data top
Na2S2O3·5H2O | F(000) = 512 |
Mr = 248.2 | Dx = 1.758 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 5.947 (1) Å | θ = 9.2–15.4° |
b = 21.574 (2) Å | µ = 0.67 mm−1 |
c = 7.526 (1) Å | T = 293 K |
β = 103.82 (1)° | Hexagonal prism, colourless |
V = 937.6 (2) Å3 | 0.65 × 0.35 × 0.30 mm |
Z = 4 | |
Data collection top
Enraf-Nonius CAD-4 four-circle diffractometer | Rint = 0.018 |
Radiation source: fine focus sealed tube | θmax = 25.0°, θmin = 2.9° |
Graphite monochromator | h = 0→7 |
Profile data from ω scans | k = 0→25 |
1637 measured reflections | l = −8→8 |
1615 independent reflections | 3 standard reflections every 50 reflections |
1571 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.022 | All H-atom parameters refined |
wR(F2) = 0.060 | w = 1/[σ2(Fo2) + (0.0424P)2 + 0.2426P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
1615 reflections | Δρmax = 0.48 e Å−3 |
150 parameters | Δρmin = −0.34 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0413 (25) |
Crystal data top
Na2S2O3·5H2O | V = 937.6 (2) Å3 |
Mr = 248.2 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.947 (1) Å | µ = 0.67 mm−1 |
b = 21.574 (2) Å | T = 293 K |
c = 7.526 (1) Å | 0.65 × 0.35 × 0.30 mm |
β = 103.82 (1)° | |
Data collection top
Enraf-Nonius CAD-4 four-circle diffractometer | Rint = 0.018 |
1637 measured reflections | 3 standard reflections every 50 reflections |
1615 independent reflections | intensity decay: none |
1571 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.060 | All H-atom parameters refined |
S = 1.07 | Δρmax = 0.48 e Å−3 |
1615 reflections | Δρmin = −0.34 e Å−3 |
150 parameters | |
Special details top
Geometry. All e.s.d.'s 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, and angles; correlations between e.s.d.'s in cell parameters are
only used when they are defined by crystal symmetry. |
Refinement. Refinement on F2 for ALL reflections. Weighted R-factors
wR and all goodnesses of fit S are based on F2,
conventional R-factors R are based on F, with F
set to zero for negative F2. The observed criterion of F2 >
σ(F2) is used only for calculating _R_factor_obs 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.10195 (6) | 0.068133 (15) | 0.10657 (5) | 0.02504 (14) | |
S2 | 0.14816 (5) | 0.141498 (14) | 0.27735 (4) | 0.01896 (14) | |
Na1 | 0.72332 (9) | 0.15883 (3) | 0.57405 (7) | 0.0273 (2) | |
Na2 | 0.25417 (9) | 0.09162 (3) | 0.71538 (8) | 0.0316 (2) | |
O1 | 0.3378 (2) | 0.12783 (5) | 0.43492 (14) | 0.0341 (3) | |
O2 | −0.0670 (2) | 0.15331 (5) | 0.33426 (15) | 0.0317 (3) | |
O3 | 0.2029 (2) | 0.19531 (4) | 0.17411 (14) | 0.0293 (3) | |
O4 | 0.6228 (2) | 0.26513 (5) | 0.5974 (2) | 0.0353 (3) | |
H1 | 0.711 (4) | 0.2831 (10) | 0.668 (3) | 0.037 (5)* | |
H2 | 0.505 (5) | 0.2723 (10) | 0.618 (3) | 0.058 (7)* | |
O5 | 1.0904 (2) | 0.18611 (5) | 0.7782 (2) | 0.0282 (2) | |
H3 | 1.105 (3) | 0.1873 (9) | 0.888 (3) | 0.039 (5)* | |
H4 | 1.130 (4) | 0.2195 (10) | 0.750 (3) | 0.044 (6)* | |
O6 | 0.6149 (2) | 0.13221 (6) | 0.8563 (2) | 0.0318 (3) | |
H5 | 0.729 (4) | 0.1137 (11) | 0.914 (3) | 0.055 (6)* | |
H6 | 0.620 (4) | 0.1617 (10) | 0.927 (3) | 0.045 (6)* | |
O7 | 0.8634 (2) | 0.05229 (5) | 0.6093 (2) | 0.0323 (3) | |
H7 | 0.855 (4) | 0.0254 (10) | 0.672 (3) | 0.044 (6)* | |
H8 | 0.802 (4) | 0.0409 (11) | 0.503 (4) | 0.054 (6)* | |
O8 | 0.6465 (2) | 0.01482 (5) | 0.2468 (2) | 0.0352 (3) | |
H9 | 0.532 (5) | 0.0301 (10) | 0.211 (3) | 0.050 (6)* | |
H10 | 0.731 (5) | 0.0331 (12) | 0.191 (4) | 0.070 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0240 (2) | 0.0230 (2) | 0.0276 (2) | −0.00089 (12) | 0.00505 (14) | −0.00195 (13) |
S2 | 0.0127 (2) | 0.0233 (2) | 0.0213 (2) | −0.00003 (10) | 0.00475 (13) | 0.00066 (11) |
Na1 | 0.0188 (3) | 0.0330 (3) | 0.0304 (3) | 0.0010 (2) | 0.0064 (2) | 0.0009 (2) |
Na2 | 0.0211 (3) | 0.0296 (3) | 0.0432 (4) | −0.0008 (2) | 0.0059 (2) | −0.0018 (2) |
O1 | 0.0221 (5) | 0.0457 (6) | 0.0291 (5) | −0.0001 (4) | −0.0043 (4) | −0.0014 (5) |
O2 | 0.0221 (5) | 0.0425 (6) | 0.0355 (6) | 0.0052 (4) | 0.0169 (4) | 0.0022 (5) |
O3 | 0.0330 (6) | 0.0233 (5) | 0.0356 (6) | −0.0034 (4) | 0.0163 (4) | 0.0000 (4) |
O4 | 0.0205 (6) | 0.0377 (6) | 0.0467 (7) | 0.0004 (5) | 0.0061 (5) | −0.0041 (5) |
O5 | 0.0285 (5) | 0.0271 (6) | 0.0289 (6) | −0.0041 (4) | 0.0068 (4) | 0.0021 (4) |
O6 | 0.0201 (6) | 0.0414 (6) | 0.0326 (6) | 0.0016 (4) | 0.0035 (4) | −0.0028 (5) |
O7 | 0.0322 (6) | 0.0288 (6) | 0.0343 (6) | −0.0014 (4) | 0.0045 (5) | 0.0026 (5) |
O8 | 0.0224 (6) | 0.0351 (6) | 0.0489 (7) | 0.0035 (5) | 0.0100 (5) | 0.0053 (5) |
Geometric parameters (Å, º) top
S1—S2 | 2.0159 (5) | Na1—O6 | 2.4311 (13) |
S1—Na2i | 3.3192 (8) | Na1—O7 | 2.4377 (13) |
S2—O1 | 1.4581 (11) | Na1—Na2ii | 3.4052 (9) |
S2—O2 | 1.4653 (10) | Na1—Na2 | 3.5264 (9) |
S2—O3 | 1.4759 (10) | Na2—O6 | 2.3251 (12) |
S2—Na2 | 3.3808 (8) | Na2—O5iii | 2.3552 (12) |
Na1—O1 | 2.3777 (12) | Na2—O8iv | 2.3713 (13) |
Na1—O4 | 2.3871 (13) | Na2—O1 | 2.4112 (13) |
Na1—O5 | 2.4230 (12) | Na2—O7iii | 2.4230 (13) |
Na1—O2ii | 2.4293 (11) | Na2—S1v | 3.3192 (8) |
| | | |
S2—S1—Na2i | 114.91 (2) | O8iv—Na2—O1 | 108.74 (5) |
O1—S2—O2 | 110.93 (7) | O6—Na2—O7iii | 171.84 (5) |
O1—S2—O3 | 111.25 (6) | O5iii—Na2—O7iii | 87.67 (4) |
O2—S2—O3 | 109.56 (6) | O8iv—Na2—O7iii | 83.81 (4) |
O1—S2—S1 | 108.71 (5) | O1—Na2—O7iii | 101.96 (5) |
O2—S2—S1 | 109.10 (5) | O6—Na2—S1v | 94.04 (3) |
O3—S2—S1 | 107.19 (4) | O5iii—Na2—S1v | 74.96 (3) |
O1—S2—Na2 | 38.26 (5) | O8iv—Na2—S1v | 81.86 (4) |
O2—S2—Na2 | 75.10 (5) | O1—Na2—S1v | 169.38 (4) |
O3—S2—Na2 | 138.63 (4) | O7iii—Na2—S1v | 78.19 (4) |
S1—S2—Na2 | 109.70 (2) | O6—Na2—S2 | 105.16 (4) |
O1—Na1—O4 | 94.05 (5) | O5iii—Na2—S2 | 86.02 (3) |
O1—Na1—O5 | 167.31 (5) | O8iv—Na2—S2 | 114.11 (4) |
O4—Na1—O5 | 85.61 (4) | O1—Na2—S2 | 21.99 (3) |
O1—Na1—O2ii | 105.73 (4) | O7iii—Na2—S2 | 81.35 (4) |
O4—Na1—O2ii | 106.49 (4) | S1v—Na2—S2 | 152.46 (2) |
O5—Na1—O2ii | 86.47 (4) | O6—Na2—Na1iii | 131.88 (4) |
O1—Na1—O6 | 83.64 (4) | O5iii—Na2—Na1iii | 45.36 (3) |
O4—Na1—O6 | 92.25 (5) | O8iv—Na2—Na1iii | 129.46 (4) |
O5—Na1—O6 | 83.70 (4) | O1—Na2—Na1iii | 87.61 (3) |
O2ii—Na1—O6 | 158.09 (5) | O7iii—Na2—Na1iii | 45.70 (3) |
O1—Na1—O7 | 92.94 (4) | S1v—Na2—Na1iii | 85.02 (2) |
O4—Na1—O7 | 169.41 (5) | S2—Na2—Na1iii | 67.47 (2) |
O5—Na1—O7 | 85.82 (4) | O6—Na2—Na1 | 43.32 (3) |
O2ii—Na1—O7 | 79.16 (4) | O5iii—Na2—Na1 | 95.72 (3) |
O6—Na1—O7 | 80.63 (5) | O8iv—Na2—Na1 | 104.01 (4) |
O1—Na1—Na2ii | 137.93 (4) | O1—Na2—Na1 | 42.21 (3) |
O4—Na1—Na2ii | 128.01 (4) | O7iii—Na2—Na1 | 144.12 (4) |
O5—Na1—Na2ii | 43.75 (3) | S1v—Na2—Na1 | 137.17 (2) |
O2ii—Na1—Na2ii | 66.99 (3) | S2—Na2—Na1 | 63.37 (2) |
O6—Na1—Na2ii | 92.65 (3) | Na1iii—Na2—Na1 | 118.17 (2) |
O7—Na1—Na2ii | 45.35 (3) | S2—O1—Na1 | 141.11 (7) |
O1—Na1—Na2 | 42.95 (3) | S2—O1—Na2 | 119.76 (6) |
O4—Na1—Na2 | 98.21 (4) | Na1—O1—Na2 | 94.84 (4) |
O5—Na1—Na2 | 124.51 (4) | S2—O2—Na1iii | 149.84 (7) |
O2ii—Na1—Na2 | 141.95 (3) | Na2ii—O5—Na1 | 90.89 (4) |
O6—Na1—Na2 | 41.00 (3) | Na2—O6—Na1 | 95.68 (5) |
O7—Na1—Na2 | 81.60 (3) | Na2ii—O7—Na1 | 88.95 (4) |
Na2ii—Na1—Na2 | 118.17 (2) | H1—O4—H2 | 105 (4) |
O6—Na2—O5iii | 87.89 (4) | H3—O5—H4 | 106 (3) |
O6—Na2—O8iv | 97.69 (5) | H5—O6—H6 | 97 (3) |
O5iii—Na2—O8iv | 156.50 (5) | H7—O7—H8 | 106 (3) |
O6—Na2—O1 | 85.21 (4) | H9—O8—H10 | 102 (4) |
O5iii—Na2—O1 | 94.42 (4) | | |
Symmetry codes: (i) x, y, z−1; (ii) x+1, y, z; (iii) x−1, y, z; (iv) −x+1, −y, −z+1; (v) x, y, z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H1···O2vi | 0.76 (2) | 2.10 (2) | 2.847 (2) | 169 (2) |
O4—H2···O3vii | 0.77 (2) | 2.06 (2) | 2.826 (2) | 171 (2) |
O5—H3···O3viii | 0.81 (2) | 2.10 (2) | 2.900 (2) | 169 (2) |
O5—H4···O3vi | 0.80 (2) | 2.00 (2) | 2.803 (2) | 175 (2) |
O6—H5···S1viii | 0.82 (2) | 2.54 (2) | 3.353 (3) | 173 (2) |
O6—H6···O4vii | 0.83 (2) | 2.03 (2) | 2.857 (2) | 178 (2) |
O7—H7···S1iv | 0.76 (2) | 2.59 (2) | 3.340 (2) | 170 (2) |
O7—H8···O8 | 0.83 (2) | 2.01 (2) | 2.843 (2) | 178 (2) |
O8—H9···S1 | 0.75 (2) | 2.62 (2) | 3.360 (2) | 170 (2) |
O8—H10···S1ii | 0.82 (2) | 2.55 (2) | 3.337 (2) | 159 (2) |
Symmetry codes: (ii) x+1, y, z; (iv) −x+1, −y, −z+1; (vi) x+1, −y+1/2, z+1/2; (vii) x, −y+1/2, z+1/2; (viii) x+1, y, z+1. |
Experimental details
Crystal data |
Chemical formula | Na2S2O3·5H2O |
Mr | 248.2 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 5.947 (1), 21.574 (2), 7.526 (1) |
β (°) | 103.82 (1) |
V (Å3) | 937.6 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.67 |
Crystal size (mm) | 0.65 × 0.35 × 0.30 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 four-circle diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1637, 1615, 1571 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.594 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.060, 1.07 |
No. of reflections | 1615 |
No. of parameters | 150 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.48, −0.34 |
Selected geometric parameters (Å, º) topS1—S2 | 2.0159 (5) | S2—O2 | 1.4653 (10) |
S1—Na2i | 3.3192 (8) | S2—O3 | 1.4759 (10) |
S2—O1 | 1.4581 (11) | | |
| | | |
O1—S2—O2 | 110.93 (7) | H1—O4—H2 | 105 (4) |
O1—S2—O3 | 111.25 (6) | H3—O5—H4 | 106 (3) |
O2—S2—O3 | 109.56 (6) | H5—O6—H6 | 97 (3) |
O1—S2—S1 | 108.71 (5) | H7—O7—H8 | 106 (3) |
O2—S2—S1 | 109.10 (5) | H9—O8—H10 | 102 (4) |
O3—S2—S1 | 107.19 (4) | | |
Symmetry code: (i) x, y, z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H1···O2ii | 0.76 (2) | 2.10 (2) | 2.847 (2) | 169 (2) |
O4—H2···O3iii | 0.77 (2) | 2.06 (2) | 2.826 (2) | 171 (2) |
O5—H3···O3iv | 0.81 (2) | 2.10 (2) | 2.900 (2) | 169 (2) |
O5—H4···O3ii | 0.80 (2) | 2.00 (2) | 2.803 (2) | 175 (2) |
O6—H5···S1iv | 0.82 (2) | 2.54 (2) | 3.353 (3) | 173 (2) |
O6—H6···O4iii | 0.83 (2) | 2.03 (2) | 2.857 (2) | 178 (2) |
O7—H7···S1v | 0.76 (2) | 2.59 (2) | 3.3396 (23) | 170 (2) |
O7—H8···O8 | 0.83 (2) | 2.01 (2) | 2.843 (2) | 178 (2) |
O8—H9···S1 | 0.75 (2) | 2.62 (2) | 3.360 (2) | 170 (2) |
O8—H10···S1vi | 0.82 (2) | 2.55 (2) | 3.337 (2) | 159 (2) |
Symmetry codes: (ii) x+1, −y+1/2, z+1/2; (iii) x, −y+1/2, z+1/2; (iv) x+1, y, z+1; (v) −x+1, −y, −z+1; (vi) x+1, y, z. |
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The crystal structure of the title compound (I) was determined by Taylor & Beevers (1952) using two-dimensional X-ray diffraction data. El Saffar (1968) reported the positional parameters of H atoms deduced from NMR studies. Padmanabhan et al. (1971) refined the structure with two-dimensional neutron diffraction data which confirmed the H-bonding scheme proposed by Taylor & Beevers (1952) with the exception of atom H9. In all these works, the role of the hydrogen atom H9 remained inconclusive.
Up to now, the highest precision refinement of the structure of sodium thiosulfate pentahydrate was that reported by Uraz & Armagan (1977) who refined the structure with densitometer-measured photographic data to an R value of 0.089 for 1359 observed reflections. The s.u.'s of the bond lengths for non-hydrogen atoms ranged from 0.003 for S1—S2 to 0.007 Å for Na1—O4 and Na1—O7 and those of bond angles from 0.2 to 0.3°. The present work reports the results of a much higher precision refinement of the structure with an R value of 0.0223 for 1615 reflections. The s.u.'s for bond lengths range from 0.0005 Å for S1—S2 to 0.0013 Å for Na1—O4 and Na1—O7. while those of bond angles are 0.02–0.06°. The hydrogen bonding scheme suggested by Uraz & Armagan (1977) is confirmed. However, the O—H distances are much shorter, varying from 0.75 (2) to 0.83 (2) Å, compared with those obtained by Uraz & Armagan (1977). H—O—H angles are close to the tetrahedral value, varing from 96 (2) to 106 (2)°. An ORTEP plot (Farrugia, 1997) of the asymmetric unit is shown in Fig. 1.