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The title complex, [Li2(D2O)6][Li(C9H27SSiO3)2]2·2D2O, is the first compound with an S-M bond (M = alkali metal) within an unusual type of lithate anion, [Li(SR)2]- {where R is Si[OC(CH3)3]3}. There is a centre of symmetry located in the middle of the Li2O2 ring of the cation. All Li atoms are four-coordinate, with LiO4 (cations) and LiO2S2 (anions) cores. The singly charged [Li(SR)2]- anions are well separated from the doubly charged [Li2(D2O)6]2+ cations; the distance between Li atoms from differently charged ions is greater than 5 Å. Both ion types are held within an extended network of O-D...O and O-D...S hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106041746/sk3045sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106041746/sk3045Isup2.hkl
Contains datablock I

CCDC reference: 628505

Comment top

Thiolates, selenolates and tellurolates of the s-block elements are very often used as precursors of chalcogenolates of other metals. Special attention has therefore been devoted to their structure, which can sometimes be controlled by an appropriate method of synthesis (Englich & Ruhlandt-Senge, 2000). The most common lithium thiolates are monomeric (Chadwick & Ruhlandt-Senge, 1998; Ives et al., 2003) or dimeric (Bjernemose et al., 2004; Komuro et al., 2004). However, trimeric (Ruhlandt-Senge et al., 1996; Niemeyer & Power, 1996), hexameric (Janssen et al., 1996) and polymeric forms (Ruth et al., 2005; Hampe et al., 2005) are also known. In the case of lithium compounds, where the most common coordination number is four, the central atoms are frequently coordinated by solvent molecules, with O– and N-donor solvents preferred.

Silanethiolates of the s-block metals are much less numerous and the structural data of only a few alkali metal derivatives have been described to date. Compounds with Si—S—Li (Baranowska et al., 2002; Komuro et al., 2004; Jesionka et al., 2005) and Si—S—Na bond systems (Wojnowski et al., 1986; Chadwick et al., 1997) have been reported. None of them, however, is similar to the title compound, (I), described in the present paper. This lithate is not only the first compound with an S—Li bond within the [M(SR)2] type of anion {where M is an alkali metal and R is Si[OC(CH3)3]3}, but is also the first ionic thiolate where both ions are metal complexes and both are based on lithium.

Compound (I) can be obtained using the procedure described in the Experimental section. Fig. 1 shows the complete parts of complex (I), along with the atom-numbering scheme. Selected bond lengths and angles are presented in Table 1. Because of the doubly charged complex bimetallic lithium cation, two singly charged complex lithate anions are required to balance the charge. Two solvent heavy water molecules complete the structure.

The central atom in the lithate [Li(SR)2] anion is coordinated by two silanethiolate S atoms and two siloxy O atoms from two undoubtedly chelating (tBuO)3SiS ligands. This leads to the central LiO2S2 core which, due to the O—Li—S chelate bite angle, shows a severely distorted tetrahedral arrangement of atoms, with angles between 80.29 (12) and 148.2 (2)°. The Li—S and Li—O bond lengths within the lithate anion seem to be unexceptional, being comparable with those found in two other known neutral lithium tri-tert-butoxysilanethiolates (Jesionka et al., 2005). Moreover, the Li—O bond lengths in the lithate anion fall within the limits set by the bonds present in the accompanying [Li2(D2O)6]2+ cation. The cation contains two Li atoms, both coordinated only by O atoms from D2O molecules. Two of these D2O ligands are in bridging and four in terminal positions. The geometry of the resulting LiO4 core can also be described as a distorted tetrahedron. Moreover, the bimetallic cation system created by the bridging molecules of heavy water leads to the formation of a planar centrosymetric Li2(µ-O)2 ring.

Outside the bimetallic complex cation, two other solvent heavy water molecules are present within the crystal structure. Their presence has important consequences. Although all heavy water molecules are engaged in the formation of hydrogen bonds, each ligating D2O forms only two such bonds. On the other hand, each solvating D2O molecule forms four hydrogen bonds. It is simultaneously a donor of O—D···O and O—D···S hydrogen bonds to one of the [Li(SR)2] lithate anions and an acceptor of two O···D—O hydrogen bonds from two different [Li2(D2O)6]2+ cations. Both ion types are therefore held within an extended network of O—D···O and O—D···S hydrogen bonds. This is illustrated in Fig. 2 and data for eight different hydrogen bonds are summarized in Table 2. The hydrogen-bond network in some respect `covers' the bimetallic cations, which are placed in the space between two lithate anions as shown in Fig. 3. Because of these interactions between the complex cations and the solvent D2O molecules, the one-dimensional hydrogen-bond network which is formed runs in the a direction, as shown in Fig. 4.

Isolation of the distinct ionic domains in compound (I) is further evidenced by the intermetallic distances. The bimetallic [Li2(D2O)6]2+ cation may serve as an example of a lithium complex, with an Li···Li distance of 2.876 (7) Å. A similar distance can be found in the Li2(µ-S)2 ring in two neutral tri-tert-butoxysilanethiolates of lithium (Jesionka et al., 2005). In the case of (I), the distances between the Li atom of the lithate anion and either of the two Li atoms within the cation are much larger, at 5.279 (5) and 5.261 (5) Å. In fact, the structure of (I) shown in Fig. 5 can be roughly described as side-by-side packed tetragonal columns interacting only by van der Waals forces. These columns, composed of negative lithate anions, have in their interior another columnar structure formed of complex cations, embedded with and covered by the hydrogen-bond network.

Experimental top

The synthesis of (I) was carried out using standard vacuum-line (argon) and Schlenk techniques. All solvents were dried by standard methods and distilled under argon prior to use. An excess of a freshly cut metallic lithium was added to a solution of [(tBuO)3SiS]3SnCl (3.12 mmol, 3.1 g) (Kloskowska et al. 2006) in tetrahydrofuran (30 ml) and the mixture was stirred for 15 min at 313 K and then at room temperature for the next 3 d. The mixture was then filtered and heavy water (0.5 ml, 27.5 mmol) was added to the filtrate. Extraction with toluene and crystallization from n-hexane gave complex (I) (m.p. 431 K) in good yield, with consistent elemental analyses for C, H and S. EI MS (70 eV) m/z: 1186.5 ({[Li2(D2O)2][Li(C12H27O3SSi)2]2}+, <15%).

Refinement top

Methyl H atoms were positioned geometrically and refined as riding on their parent C atoms, with C—H = 0.98 Å [Please check added text] and with Uiso(H) = 1.2Ueq(C). Deuterium atoms from the heavy water molecules were found in a Fourier electron-density map and refined with no restraints. The highest electron-density peak is located 1.03 Å from atom Si1.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED; data reduction: CrysAlis RED (Oxford Diffraction, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. A view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and D atoms are shown as small spheres of arbitrary radii. H atoms have been omitted for clarity. [Symmetry code: (i) −x, −y + 1, −z + 1.]
[Figure 2] Fig. 2. The hydrogen-bond network in (I). All methyl groups have been omitted for clarity. [Symmetry codes (i) −x, −y + 1, −z + 1; (ii) x − 1, y, z; (v) −x + 1, −y + 1, −z + 1.]
[Figure 3] Fig. 3. The arrangement of anions, cations and solvent D2O molecules within the unit cell of (I), viewed along the a axis. Dashed lines represent hydrogen bonds.
[Figure 4] Fig. 4. Interactions between the complex cations and solvent D2O molecules, leading to the hydrogen-bond network running in the a direction. [Symmetry codes (i) −x, −y + 1, −z + 1; (ii) x − 1, y, z; (iii) −x − 1, −y + 1, −z + 1; (iv) x − 2, y, z; (v) −x + 1, −y + 1, −z + 1.]
[Figure 5] Fig. 5. The packing of (I) in the crystal structure, viewed along the a axis.
bis(µ2-aqua-d2)tetrakis(aqua-d2)dilithium(I) bis[bis(tri-tert-butoxysilanethiolato-κ2O,S)lithate(I)] dihydrate-d2 top
Crystal data top
[Li2(D2O)6][Li(C12H27O3SSi)2]2·2D2OZ = 1
Mr = 1305.92F(000) = 704
Triclinic, P1Dx = 1.124 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.5218 (6) ÅCell parameters from 6255 reflections
b = 14.0107 (11) Åθ = 2.5–32°
c = 17.4337 (14) ŵ = 0.24 mm1
α = 99.743 (7)°T = 120 K
β = 99.712 (7)°Prism, colourless
γ = 105.197 (7)°0.52 × 0.41 × 0.4 mm
V = 1929.4 (3) Å3
Data collection top
Kuma KM-4 CCD area-detector
diffractometer
Rint = 0.053
Graphite monochromatorθmax = 25.1°, θmin = 2.7°
ω scansh = 1010
13004 measured reflectionsk = 1616
6815 independent reflectionsl = 2020
6228 reflections with I > 2σ(I)
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0501P)2 + 2.0875P]
where P = (Fo2 + 2Fc2)/3
6815 reflections(Δ/σ)max = 0.018
411 parametersΔρmax = 0.45 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
[Li2(D2O)6][Li(C12H27O3SSi)2]2·2D2Oγ = 105.197 (7)°
Mr = 1305.92V = 1929.4 (3) Å3
Triclinic, P1Z = 1
a = 8.5218 (6) ÅMo Kα radiation
b = 14.0107 (11) ŵ = 0.24 mm1
c = 17.4337 (14) ÅT = 120 K
α = 99.743 (7)°0.52 × 0.41 × 0.4 mm
β = 99.712 (7)°
Data collection top
Kuma KM-4 CCD area-detector
diffractometer
6228 reflections with I > 2σ(I)
13004 measured reflectionsRint = 0.053
6815 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.120H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.45 e Å3
6815 reflectionsΔρmin = 0.28 e Å3
411 parameters
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
Si10.28660 (7)0.70442 (4)0.32553 (3)0.01302 (14)
S10.42205 (6)0.60366 (4)0.33514 (3)0.01748 (13)
O10.38301 (18)0.81479 (10)0.31188 (8)0.0169 (3)
O20.19575 (18)0.72825 (10)0.39965 (8)0.0168 (3)
O30.12977 (17)0.64048 (10)0.24788 (8)0.0147 (3)
C100.5191 (3)0.84935 (16)0.27368 (12)0.0176 (4)
C110.6833 (3)0.86083 (17)0.33089 (14)0.0239 (5)
H11A0.69680.91120.37990.029*
H11B0.77640.88330.30540.029*
H11C0.6820.79540.3440.029*
C120.4973 (3)0.77517 (17)0.19536 (13)0.0246 (5)
H12A0.50770.71050.20630.029*
H12B0.58330.80310.16750.029*
H12C0.38670.76410.16180.029*
C130.5101 (3)0.95177 (17)0.25854 (15)0.0269 (5)
H13A0.40280.94310.2230.032*
H13B0.6010.98020.23350.032*
H13C0.52060.9980.30940.032*
C200.2397 (3)0.81618 (16)0.46656 (12)0.0219 (5)
C210.2014 (4)0.90440 (18)0.43568 (15)0.0329 (6)
H21A0.26960.92250.39740.039*
H21B0.22670.96280.48040.039*
H21C0.0830.88480.40930.039*
C220.1282 (4)0.78417 (19)0.52299 (14)0.0319 (6)
H22A0.01110.76240.49420.038*
H22B0.14710.84160.56780.038*
H22C0.15460.72780.54330.038*
C230.4220 (3)0.8412 (2)0.50706 (14)0.0348 (6)
H23A0.44250.78140.5240.042*
H23B0.44990.89740.55380.042*
H23C0.49150.86090.46960.042*
C300.0249 (3)0.66089 (16)0.21516 (12)0.0182 (4)
C310.0122 (3)0.77079 (17)0.20746 (14)0.0261 (5)
H31A0.05660.8160.26060.031*
H31B0.09080.78250.18220.031*
H31C0.09460.78460.17460.031*
C320.0906 (3)0.58944 (18)0.13287 (13)0.0273 (5)
H32A0.00740.60380.10050.033*
H32B0.19430.59950.10670.033*
H32C0.11230.5190.13850.033*
C330.1478 (3)0.63630 (18)0.26838 (14)0.0243 (5)
H33A0.16330.56650.27480.029*
H33B0.25520.64340.24380.029*
H33C0.1040.68320.32080.029*
Si20.04500 (7)0.29223 (4)0.18733 (3)0.01334 (14)
S20.06724 (6)0.37158 (4)0.25917 (3)0.01723 (13)
O40.17626 (17)0.38435 (10)0.15997 (8)0.0150 (3)
O50.16723 (18)0.23567 (10)0.23287 (8)0.0175 (3)
O60.07361 (18)0.20507 (11)0.11062 (8)0.0177 (3)
C400.3099 (3)0.38382 (16)0.11702 (12)0.0195 (4)
C410.2554 (3)0.29160 (17)0.04762 (13)0.0240 (5)
H41A0.23710.22970.06830.029*
H41B0.34250.29510.0170.029*
H41C0.15160.29060.01290.029*
C420.3384 (3)0.48159 (18)0.08689 (14)0.0305 (6)
H42A0.23510.48090.05190.037*
H42B0.42680.48690.0570.037*
H42C0.37160.53990.13240.037*
C430.4646 (3)0.38493 (19)0.17543 (13)0.0264 (5)
H43A0.49360.44330.22060.032*
H43B0.55760.39010.14850.032*
H43C0.44250.32210.19490.032*
C500.1333 (3)0.13225 (16)0.24416 (13)0.0227 (5)
C510.1488 (4)0.06494 (18)0.16925 (15)0.0352 (6)
H51A0.06510.06570.12350.042*
H51B0.13060.00470.17650.042*
H51C0.26060.09050.15960.042*
C520.2676 (4)0.13578 (19)0.31506 (15)0.0342 (6)
H52A0.37790.16350.30440.041*
H52B0.25510.0670.32350.041*
H52C0.25630.17910.3630.041*
C530.0383 (4)0.0962 (2)0.26096 (18)0.0410 (7)
H53A0.04770.1440.30670.049*
H53B0.05540.02890.27310.049*
H53C0.12310.09220.2140.049*
C600.2296 (3)0.19307 (17)0.05677 (12)0.0209 (4)
C610.2322 (3)0.29244 (18)0.03398 (13)0.0263 (5)
H61A0.22680.34270.08160.032*
H61B0.33540.28180.00540.032*
H61C0.1360.31710.0110.032*
C620.2365 (3)0.11329 (19)0.01643 (14)0.0337 (6)
H62A0.14290.13870.04080.04*
H62B0.34190.09930.05530.04*
H62C0.22930.05070.00020.04*
C630.3727 (3)0.15511 (19)0.09659 (15)0.0310 (5)
H63A0.37090.08970.10890.037*
H63B0.4790.14690.06040.037*
H63C0.36010.20440.1460.037*
O70.06193 (19)0.53075 (13)0.43377 (9)0.0183 (3)
O80.2741 (2)0.39517 (13)0.51759 (11)0.0261 (4)
O90.3020 (2)0.61146 (13)0.61277 (10)0.0270 (4)
O100.6324 (2)0.61798 (13)0.62791 (9)0.0201 (3)
Li10.1617 (4)0.5047 (3)0.2335 (2)0.0200 (7)
Li20.1621 (5)0.4949 (3)0.5349 (2)0.0217 (7)
D7A0.111 (5)0.588 (3)0.4279 (19)0.051 (10)*
D7B0.053 (4)0.495 (3)0.394 (2)0.039 (9)*
D8A0.307 (5)0.386 (3)0.475 (2)0.061 (11)*
D8B0.339 (4)0.382 (2)0.550 (2)0.043 (9)*
D9A0.405 (4)0.617 (2)0.6231 (16)0.029 (7)*
D9B0.278 (4)0.631 (2)0.6526 (19)0.040 (9)*
D10A0.634 (4)0.562 (3)0.6375 (19)0.047 (9)*
D10B0.694 (4)0.658 (3)0.668 (2)0.047 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Si10.0118 (3)0.0119 (3)0.0148 (3)0.0027 (2)0.0032 (2)0.0028 (2)
S10.0144 (3)0.0148 (2)0.0227 (3)0.0052 (2)0.00119 (19)0.00472 (19)
O10.0150 (7)0.0142 (7)0.0226 (7)0.0040 (6)0.0069 (6)0.0050 (6)
O20.0163 (7)0.0149 (7)0.0163 (7)0.0011 (6)0.0053 (5)0.0002 (5)
O30.0127 (7)0.0152 (7)0.0157 (7)0.0052 (6)0.0013 (5)0.0028 (5)
C100.0135 (10)0.0167 (10)0.0229 (10)0.0024 (8)0.0067 (8)0.0060 (8)
C110.0170 (11)0.0214 (11)0.0322 (12)0.0024 (9)0.0057 (9)0.0083 (9)
C120.0251 (12)0.0262 (12)0.0235 (11)0.0059 (10)0.0109 (9)0.0059 (9)
C130.0242 (12)0.0227 (11)0.0377 (13)0.0057 (10)0.0124 (10)0.0142 (10)
C200.0256 (12)0.0186 (10)0.0181 (10)0.0030 (9)0.0071 (9)0.0018 (8)
C210.0460 (16)0.0213 (12)0.0335 (13)0.0112 (11)0.0167 (11)0.0023 (10)
C220.0423 (15)0.0277 (12)0.0249 (12)0.0065 (11)0.0176 (11)0.0000 (9)
C230.0275 (13)0.0424 (15)0.0225 (12)0.0006 (11)0.0000 (10)0.0038 (10)
C300.0136 (10)0.0194 (10)0.0214 (10)0.0066 (8)0.0007 (8)0.0056 (8)
C310.0232 (12)0.0223 (11)0.0341 (12)0.0107 (10)0.0001 (9)0.0100 (9)
C320.0239 (12)0.0295 (12)0.0251 (11)0.0093 (10)0.0040 (9)0.0042 (9)
C330.0157 (11)0.0269 (12)0.0325 (12)0.0097 (9)0.0049 (9)0.0082 (9)
Si20.0128 (3)0.0124 (3)0.0139 (3)0.0028 (2)0.0033 (2)0.0017 (2)
S20.0152 (3)0.0170 (3)0.0186 (3)0.0041 (2)0.00681 (19)0.00013 (19)
O40.0134 (7)0.0151 (7)0.0168 (7)0.0038 (6)0.0056 (5)0.0027 (5)
O50.0174 (7)0.0125 (7)0.0221 (7)0.0045 (6)0.0027 (6)0.0046 (6)
O60.0158 (7)0.0175 (7)0.0169 (7)0.0046 (6)0.0014 (6)0.0006 (6)
C400.0186 (11)0.0206 (11)0.0185 (10)0.0026 (9)0.0095 (8)0.0021 (8)
C410.0244 (12)0.0250 (11)0.0230 (11)0.0069 (10)0.0117 (9)0.0006 (9)
C420.0384 (14)0.0232 (12)0.0300 (12)0.0013 (11)0.0200 (11)0.0063 (10)
C430.0147 (11)0.0362 (13)0.0267 (11)0.0072 (10)0.0076 (9)0.0004 (10)
C500.0261 (12)0.0131 (10)0.0303 (12)0.0064 (9)0.0055 (9)0.0078 (9)
C510.0500 (17)0.0209 (12)0.0369 (14)0.0188 (12)0.0063 (12)0.0025 (10)
C520.0429 (16)0.0223 (12)0.0367 (14)0.0128 (11)0.0031 (11)0.0120 (10)
C530.0352 (15)0.0394 (15)0.0576 (17)0.0084 (12)0.0183 (13)0.0318 (13)
C600.0165 (11)0.0224 (11)0.0198 (10)0.0040 (9)0.0007 (8)0.0013 (8)
C610.0265 (12)0.0265 (12)0.0234 (11)0.0085 (10)0.0007 (9)0.0048 (9)
C620.0365 (15)0.0298 (13)0.0236 (12)0.0062 (11)0.0045 (10)0.0067 (10)
C630.0200 (12)0.0305 (13)0.0367 (13)0.0008 (10)0.0027 (10)0.0062 (10)
O70.0199 (8)0.0181 (8)0.0146 (8)0.0015 (6)0.0061 (6)0.0022 (6)
O80.0249 (9)0.0370 (10)0.0201 (8)0.0161 (8)0.0034 (7)0.0067 (7)
O90.0156 (9)0.0364 (10)0.0244 (9)0.0050 (7)0.0058 (7)0.0023 (7)
O100.0196 (8)0.0177 (8)0.0210 (8)0.0041 (7)0.0013 (6)0.0046 (7)
Li10.0180 (18)0.0181 (17)0.0224 (17)0.0057 (14)0.0048 (14)0.0000 (13)
Li20.0174 (18)0.0259 (19)0.0221 (18)0.0075 (15)0.0046 (14)0.0042 (14)
Geometric parameters (Å, º) top
Si1—O11.6270 (14)O4—Li11.983 (4)
Si1—O21.6456 (14)O5—C501.455 (2)
Si1—O31.6650 (14)O6—C601.444 (3)
Si1—S12.0549 (8)C40—C431.519 (3)
Si1—Li12.807 (3)C40—C411.522 (3)
S1—Li12.493 (4)C40—C421.524 (3)
O1—C101.449 (2)C41—H41A0.98
O2—C201.464 (2)C41—H41B0.98
O3—C301.464 (2)C41—H41C0.98
O3—Li11.972 (4)C42—H42A0.98
C10—C121.520 (3)C42—H42B0.98
C10—C131.521 (3)C42—H42C0.98
C10—C111.528 (3)C43—H43A0.98
C11—H11A0.98C43—H43B0.98
C11—H11B0.98C43—H43C0.98
C11—H11C0.98C50—C531.513 (3)
C12—H12A0.98C50—C521.520 (3)
C12—H12B0.98C50—C511.523 (3)
C12—H12C0.98C51—H51A0.98
C13—H13A0.98C51—H51B0.98
C13—H13B0.98C51—H51C0.98
C13—H13C0.98C52—H52A0.98
C20—C231.515 (3)C52—H52B0.98
C20—C211.517 (3)C52—H52C0.98
C20—C221.521 (3)C53—H53A0.98
C21—H21A0.98C53—H53B0.98
C21—H21B0.98C53—H53C0.98
C21—H21C0.98C60—C611.516 (3)
C22—H22A0.98C60—C631.524 (3)
C22—H22B0.98C60—C621.529 (3)
C22—H22C0.98C61—H61A0.98
C23—H23A0.98C61—H61B0.98
C23—H23B0.98C61—H61C0.98
C23—H23C0.98C62—H62A0.98
C30—C311.523 (3)C62—H62B0.98
C30—C321.524 (3)C62—H62C0.98
C30—C331.525 (3)C63—H63A0.98
C31—H31A0.98C63—H63B0.98
C31—H31B0.98C63—H63C0.98
C31—H31C0.98O7—D7B0.76 (3)
C32—H32A0.98O7—D7A0.83 (4)
C32—H32B0.98O7—Li22.027 (4)
C32—H32C0.98O7—Li2i2.032 (4)
C33—H33A0.98O8—D8B0.80 (4)
C33—H33B0.98O8—D8A0.83 (4)
C33—H33C0.98O8—Li21.899 (4)
Si2—O61.6264 (14)O9—D9B0.78 (3)
Si2—O51.6463 (15)O9—D9A0.85 (3)
Si2—O41.6663 (14)O9—Li21.901 (4)
Si2—S22.0519 (7)O10—D10B0.81 (4)
Si2—Li12.805 (4)O10—D10A0.84 (4)
S2—Li12.481 (4)Li2—O7i2.032 (4)
O4—C401.466 (2)Li2—Li2i2.876 (7)
O1—Si1—O2105.60 (7)C43—C40—C42110.95 (19)
O1—Si1—O3111.09 (7)C41—C40—C42110.81 (18)
O2—Si1—O3104.62 (7)C40—C41—H41A109.5
O1—Si1—S1116.96 (6)C40—C41—H41B109.5
O2—Si1—S1115.70 (6)H41A—C41—H41B109.5
O3—Si1—S1102.23 (6)C40—C41—H41C109.5
O1—Si1—Li1136.24 (9)H41A—C41—H41C109.5
O2—Si1—Li1114.75 (9)H41B—C41—H41C109.5
S1—Si1—Li159.31 (8)C40—C42—H42A109.5
Si1—S1—Li175.55 (8)C40—C42—H42B109.5
C10—O1—Si1133.37 (13)H42A—C42—H42B109.5
C20—O2—Si1131.02 (13)C40—C42—H42C109.5
C30—O3—Si1131.57 (12)H42A—C42—H42C109.5
C30—O3—Li1124.57 (16)H42B—C42—H42C109.5
Si1—O3—Li1100.70 (13)C40—C43—H43A109.5
O1—C10—C12110.49 (16)C40—C43—H43B109.5
O1—C10—C13105.30 (17)H43A—C43—H43B109.5
C12—C10—C13110.46 (18)C40—C43—H43C109.5
O1—C10—C11108.66 (16)H43A—C43—H43C109.5
C12—C10—C11111.03 (18)H43B—C43—H43C109.5
C13—C10—C11110.73 (18)O5—C50—C53110.47 (19)
C10—C11—H11A109.5O5—C50—C52105.82 (17)
C10—C11—H11B109.5C53—C50—C52110.7 (2)
H11A—C11—H11B109.5O5—C50—C51108.23 (18)
C10—C11—H11C109.5C53—C50—C51111.3 (2)
H11A—C11—H11C109.5C52—C50—C51110.1 (2)
H11B—C11—H11C109.5C50—C51—H51A109.5
C10—C12—H12A109.5C50—C51—H51B109.5
C10—C12—H12B109.5H51A—C51—H51B109.5
H12A—C12—H12B109.5C50—C51—H51C109.5
C10—C12—H12C109.5H51A—C51—H51C109.5
H12A—C12—H12C109.5H51B—C51—H51C109.5
H12B—C12—H12C109.5C50—C52—H52A109.5
C10—C13—H13A109.5C50—C52—H52B109.5
C10—C13—H13B109.5H52A—C52—H52B109.5
H13A—C13—H13B109.5C50—C52—H52C109.5
C10—C13—H13C109.5H52A—C52—H52C109.5
H13A—C13—H13C109.5H52B—C52—H52C109.5
H13B—C13—H13C109.5C50—C53—H53A109.5
O2—C20—C23109.35 (19)C50—C53—H53B109.5
O2—C20—C21109.00 (17)H53A—C53—H53B109.5
C23—C20—C21112.1 (2)C50—C53—H53C109.5
O2—C20—C22105.58 (17)H53A—C53—H53C109.5
C23—C20—C22110.8 (2)H53B—C53—H53C109.5
C21—C20—C22109.8 (2)O6—C60—C61110.60 (17)
C20—C21—H21A109.5O6—C60—C63109.02 (17)
C20—C21—H21B109.5C61—C60—C63110.9 (2)
H21A—C21—H21B109.5O6—C60—C62104.80 (18)
C20—C21—H21C109.5C61—C60—C62110.61 (19)
H21A—C21—H21C109.5C63—C60—C62110.70 (19)
H21B—C21—H21C109.5C60—C61—H61A109.5
C20—C22—H22A109.5C60—C61—H61B109.5
C20—C22—H22B109.5H61A—C61—H61B109.5
H22A—C22—H22B109.5C60—C61—H61C109.5
C20—C22—H22C109.5H61A—C61—H61C109.5
H22A—C22—H22C109.5H61B—C61—H61C109.5
H22B—C22—H22C109.5C60—C62—H62A109.5
C20—C23—H23A109.5C60—C62—H62B109.5
C20—C23—H23B109.5H62A—C62—H62B109.5
H23A—C23—H23B109.5C60—C62—H62C109.5
C20—C23—H23C109.5H62A—C62—H62C109.5
H23A—C23—H23C109.5H62B—C62—H62C109.5
H23B—C23—H23C109.5C60—C63—H63A109.5
O3—C30—C31110.07 (17)C60—C63—H63B109.5
O3—C30—C32104.71 (16)H63A—C63—H63B109.5
C31—C30—C32110.21 (18)C60—C63—H63C109.5
O3—C30—C33109.36 (16)H63A—C63—H63C109.5
C31—C30—C33111.67 (18)H63B—C63—H63C109.5
C32—C30—C33110.59 (18)D7B—O7—D7A105 (3)
C30—C31—H31A109.5D7B—O7—Li2118 (2)
C30—C31—H31B109.5D7A—O7—Li2115 (2)
H31A—C31—H31B109.5D7B—O7—Li2i109 (2)
C30—C31—H31C109.5D7A—O7—Li2i120 (2)
H31A—C31—H31C109.5Li2—O7—Li2i90.22 (16)
H31B—C31—H31C109.5D8B—O8—D8A106 (3)
C30—C32—H32A109.5D8B—O8—Li2127 (2)
C30—C32—H32B109.5D8A—O8—Li2118 (3)
H32A—C32—H32B109.5D9B—O9—D9A108 (3)
C30—C32—H32C109.5D9B—O9—Li2123 (2)
H32A—C32—H32C109.5D9A—O9—Li2116.2 (18)
H32B—C32—H32C109.5D10B—O10—D10A103 (3)
C30—C33—H33A109.5O3—Li1—O4148.2 (2)
C30—C33—H33B109.5O3—Li1—S2114.47 (16)
H33A—C33—H33B109.5O4—Li1—S280.41 (13)
C30—C33—H33C109.5O3—Li1—S180.29 (12)
H33A—C33—H33C109.5O4—Li1—S1115.77 (16)
H33B—C33—H33C109.5S2—Li1—S1123.98 (15)
O6—Si2—O5104.46 (8)O3—Li1—Si2152.83 (18)
O6—Si2—O4111.76 (7)O4—Li1—Si235.80 (7)
O5—Si2—O4103.92 (8)S2—Li1—Si245.17 (6)
O6—Si2—S2118.05 (6)S1—Li1—Si2124.76 (14)
O5—Si2—S2115.58 (6)O3—Li1—Si135.65 (7)
O4—Si2—S2102.36 (6)O4—Li1—Si1153.96 (18)
O6—Si2—Li1138.34 (9)S2—Li1—Si1123.89 (13)
O5—Si2—Li1113.72 (9)S1—Li1—Si145.14 (6)
S2—Si2—Li159.04 (7)Si2—Li1—Si1162.69 (15)
Si2—S2—Li175.79 (8)O8—Li2—O9110.8 (2)
C40—O4—Si2132.00 (13)O8—Li2—O7114.11 (19)
C40—O4—Li1124.92 (16)O9—Li2—O7112.3 (2)
Si2—O4—Li1100.08 (12)O8—Li2—O7i124.2 (2)
C50—O5—Si2130.77 (13)O9—Li2—O7i103.98 (18)
C60—O6—Si2134.37 (13)O7—Li2—O7i89.78 (16)
O4—C40—C43108.63 (16)O8—Li2—Li2i133.2 (2)
O4—C40—C41110.46 (17)O9—Li2—Li2i116.0 (2)
C43—C40—C41111.36 (19)O7—Li2—Li2i44.97 (11)
O4—C40—C42104.39 (17)O7i—Li2—Li2i44.82 (11)
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—D7B···S20.76 (3)2.54 (3)3.2765 (17)163 (3)
O7—D7A···O20.83 (4)2.08 (4)2.906 (2)170 (3)
O8—D8B···S1ii0.80 (4)2.54 (4)3.3192 (19)164 (3)
O8—D8A···O10ii0.83 (4)1.95 (4)2.776 (2)171 (4)
O9—D9A···O100.85 (3)1.92 (3)2.759 (2)170 (3)
O9—D9B···S2i0.78 (3)2.55 (3)3.2584 (19)151 (3)
O10—D10A···S1ii0.84 (4)2.39 (4)3.2086 (18)168 (3)
O10—D10B···O5ii0.81 (4)2.03 (4)2.845 (2)175 (3)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Li2(D2O)6][Li(C12H27O3SSi)2]2·2D2O
Mr1305.92
Crystal system, space groupTriclinic, P1
Temperature (K)120
a, b, c (Å)8.5218 (6), 14.0107 (11), 17.4337 (14)
α, β, γ (°)99.743 (7), 99.712 (7), 105.197 (7)
V3)1929.4 (3)
Z1
Radiation typeMo Kα
µ (mm1)0.24
Crystal size (mm)0.52 × 0.41 × 0.4
Data collection
DiffractometerKuma KM-4 CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
13004, 6815, 6228
Rint0.053
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.120, 1.06
No. of reflections6815
No. of parameters411
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.45, 0.28

Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), CrysAlis RED (Oxford Diffraction, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Si1—O11.6270 (14)Si2—S22.0519 (7)
Si1—O21.6456 (14)S2—Li12.481 (4)
Si1—O31.6650 (14)O4—Li11.983 (4)
Si1—S12.0549 (8)O7—Li22.027 (4)
S1—Li12.493 (4)O7—Li2i2.032 (4)
O3—Li11.972 (4)O8—Li21.899 (4)
Si2—O61.6264 (14)O9—Li21.901 (4)
Si2—O51.6463 (15)Li2—Li2i2.876 (7)
Si2—O41.6663 (14)
Si1—S1—Li175.55 (8)S2—Li1—S1123.98 (15)
Si2—S2—Li175.79 (8)O8—Li2—O9110.8 (2)
O3—Li1—O4148.2 (2)O8—Li2—O7114.11 (19)
O3—Li1—S2114.47 (16)O9—Li2—O7112.3 (2)
O4—Li1—S280.41 (13)O8—Li2—O7i124.2 (2)
O3—Li1—S180.29 (12)O9—Li2—O7i103.98 (18)
O4—Li1—S1115.77 (16)O7—Li2—O7i89.78 (16)
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—D7B···S20.76 (3)2.54 (3)3.2765 (17)163 (3)
O7—D7A···O20.83 (4)2.08 (4)2.906 (2)170 (3)
O8—D8B···S1ii0.80 (4)2.54 (4)3.3192 (19)164 (3)
O8—D8A···O10ii0.83 (4)1.95 (4)2.776 (2)171 (4)
O9—D9A···O100.85 (3)1.92 (3)2.759 (2)170 (3)
O9—D9B···S2i0.78 (3)2.55 (3)3.2584 (19)151 (3)
O10—D10A···S1ii0.84 (4)2.39 (4)3.2086 (18)168 (3)
O10—D10B···O5ii0.81 (4)2.03 (4)2.845 (2)175 (3)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z+1.
 

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