Crystallographic and experimental data_
| Crystal description | white block |
| Crystal size | 0.5 mm3 × 0.3 mm3 × 0.2 mm3 |
| Empirical formula | H2Li2O5S |
| Formula weight | 127.96 g |
| Radiation, wavelength | MoKα, 0.71073 Å |
| Unit cell dimensions | a = 5.4512(8) Å, b = 4.8726(6) Å, c = 8.1724(10) Å, α = 90°, β = 107.291° (3), = 90° |
| Crystal system | monoclinic |
| Space group | P 21 |
| Unit cell volume | 207.26(5) Å−3 |
| No. of molecules per unit cell, Z | 2 |
| Temperature | 296(2) K |
| Absorption coefficient | 0.676 mm−1 |
| F(0 0 0) | 128 |
| Scan mode | ω scan |
| θ range for entire data collection | 2.61° < θ < 28.32° |
| Range of indices | h = −6 to 5, k = −6 to 6.1 = −10 to 10 |
| Reflections collected/unique | 1348/453 |
| Reflections observed | (I > 2σ (I)) 451 |
| Rint | 0.0206 |
| Rsigma | 0.0193 |
| Structure determination | Direct methods |
| Refinement | Full-matrix least-squares on F2 |
| No. of parameters refined | 82 |
| Final R | 0.0174 |
| wR(F2) | 0.0472 |
| Weight | |
| Goodness-of-fit | 1.287 |
| Final residual electron density | −0.308 eÅ−3 < Δρ < 0.161 eÅ−3 |
Force constant (k) values for different vibrations of LSMH crystals_
| Frequency [cm−1] | Vibrational assignment | Force constant k [N/m] |
|---|---|---|
| 3471 | O–H stretching | 643 |
| 1614 | S–O stretching | 1575 |
| 1095 | S–O stretching | 725 |
Bond lengths [Å], bond angles [°] and torsion angles for LSMH atoms (e_s_d_’s are given in parentheses)_
| Bond distances | |||
| S1–O1 | 1.4774(16) | S1–O2 | 1.4734(16) |
| S1–O3 | 1.4598(16) | S1–O4 | 1.475(2) |
| O1–Li1 | 1.950(4) | O2–Li2 | 1.957(5) |
| Li1–05ix | 1.905(4) | O5–H2 | 0.89(6) |
| O5–H1 | 0.64(5) | ||
| Bond angles | |||
| O4–S1–O2 | 108.88(10) | O2–S1–O1 | 108.88(10) |
| O3–S1–O2 | 110.14(10) | O3–S1–O4 | 110.56(10) |
| O4–S1–O1 | 108.89(10) | O3–S1–O1 | 109.46(10) |
| S1–O2–Li2 | 120.33(14) | S1–O1–Li1 | 119.02(14) |
| O5ix–Li1–O1 | 107.1(2) | Li1–O5–H1 | 133(5) |
| Li1–O5–H2 | 106(3) | H2–O5–H1 | 115(6) |
| Torsion angles | |||
| O3–S1–O2–Li2 | –41.44(18) | ||
| O4–S1–O2–Li2 | –162.82(15) | ||
| O4–S1–O1–Li1ii | 48.0(2) | ||
| O3–S1–O1–Li1ii | –73.0(2) | ||
| S1–O1–Li1–O5ix | 95.49(19) | ||
Intermolecular hydrogen bonding of the O–H…O type_
| D–H… A | D–H | H…A | D… A | D–H… A |
|---|---|---|---|---|
| [Å] | [Å] | [Å] | [°] | |
| O5–H1…O3i | 0 65 | 2.30 | 2.90 | 155 |
| O5–H2… O5ii | 0.89 | 2.11 | 2.96 | 161 |
Calculated data for LSMH single crystal_
| Parameters | Values |
|---|---|
| Plasma energy [eV] | 18.86 |
| Penn gap [eV] | 8.0 |
| Fermi energy [eV] | 14.80 |
| Polarizability [cm−3] using Penn analysis | 1.6 × 10−23 |
| Polarizability [cm−3] using Clausius-Mossoti equation | 1.68 × 10−23 |