(μ-Tri-tert-butoxysilanethiol­ato)­bis[(tetra­hydro­furan)lithium(I)] and catena-poly[[bis­(μ-tri-tert-butoxy­silanethiol­ato)dilithium(I)]-μ-dimethoxy­ethane]: solvent coordination as the structure-forming factor

The title compounds, μ-(tri-tert-butoxy­silanethiol­ato-κ²S:S)-bis[(tetra­hydro­furan-κO)lithium(I)], [Li₂(C₁₂H₂₇O₃SSi)₂(C₄H₈O)₂], (I), and catena-poly[[bis­(μ-tri-tert-butoxysilanethiol­ato)-1:2κ²S;1κS:2κS,O-dilithium(I)]-μ-dimethoxy­ethane-κ²O:O′], [Li₂(C₁₂H₂₇O₃SSi)₂(C₄H₁₀O₂)]_n, (II), were obtained by the reaction of tri-tert-butoxy­silanethiol with metallic lithium. The crude product, when recrystallized from tetra­hydro­furan (THF) yields (I), and when recrystallized from 1,2-dimethoxy­ethane (DME) gives (II). Compound (I) forms centrosymmetric dimers in the solid state with an Li₂S₂ central core, whereas (II) forms infinitely long chains, in which the centrosymmetric dimeric units are linked together by the bidentate DME ligand (also residing on an inversion centre), thus forming a coordination polymer. The formation of a one-dimensional structure in (II) is a consequence of replacement of a monodentate THF solvent mol­ecule with a bidentate DME mol­ecule.

S1. Comment

Structural studies on thiolates, selenolates and tellurolates of the s-block elements are important because the compounds often serve as starting materials in both inorganic and organic syntheses (Englich & Ruhlandt-Senge, 2000). The most common structural features observed for the lithium derivatives are monomeric or dimeric formulations, but lithium chalcogenolate chemistry has seen higher degrees of aggregation, e.g. trimers, tetramers or hexamers. A metal coordination number of four is observed for the majority of these compounds (Niemeyer & Power, 1996; Ruhlandt-Senge et al., 1996; Ellison & Power, 1994; Janssen et al., 1996). The structure and chemistry of silanethiolates have been the subject of research by us (Wojnowski et al., 1985, 1994) and other groups (Kovacs et al., 2000; Komuro et al., 2002, 2003). We have attempted to introduce a different type of thiolate ligand, which contains S bound to an Si atom instead of a C atom. A tri-tert-butoxysilanethiolate ligand, (^tBuO)₃SiS⁻, has been used in much of our work because of its unique features, namely large steric hindrance at the Si created by the three bulky tert-butoxy groups, its chelating capability as an O– and S-ligand, and its non-polar exterior and polar interior.

Most of the papers mentioned above concern the silanethiolates of transition metals (Becker et al., 1992) and of the p-block metals (Wojnowski, Wojnowska et al., 1986; Peters et al., 1997). However, structural data regarding silanethiolates of alkali metals are scarce (Wojnowski, Peters et al., 1986; Chadwick et al., 1997) and only one report describes a lithium silanethiolate (Baranowska et al., 2002). Here, we present the structures of two new lithium silanethiolates, the title compounds, (I) and (II).

Compound (I), [(^tBuO)₃SiSLi·(THF)]₂, resides on an inversion centre and comprises two silanethiolate ligands (Fig. 1). Each S atom bridges two Li⁺ cations, forming a planar central Li₂S₂ core, with two THF molecules bound to the two Li atoms. The THF molecules are disordered [site occupancy factors 0.693 (16)/0.307 (16)] and are positioned above and below the Li₂S₂ plane. Additionally, atom O3 from each of the two silanethiolate ligands chelates the Li atom, resulting in an S,S,O,O distorted tetrahedral coordination of the Li cores, with `tetrahedral' angles between 79.9 (2) and 120.2 (3)°. The longer Si—O3 bond is a consequence of chelation of the Li by atom O3. The Si—S bond length in (I) is considerably shorter than the distance in covalent silanethiolate compounds and is comparable with the values observed in ionic silanethiolate compounds (Becker et al., 2004).

Compound (II) (Fig. 2), [(^tBuO)₃SiSLi·(DME)]₂, resides on an inversion centre and exhibits an apparently similar dimeric structure to (I). The dimer halves are related to each other by an inversion centre located at the centre of the Li₂S₂ unit, a planar four-membered ring of alternating Li and S atoms. Again, each Li cation is surrounded, in a distorted tetrahedral fashion, by two S and two O atoms. One of the three butoxy groups of the thiolate ligand supplies the first chelating O atom and the second O atom comes from the DME molecule. The Si—O bond is considerably longer for the bond to the chelating O3 atom. The `tetrahedral' angles at Li range from 80.61 (15) to 122.6 (2)°. The smallest angle is observed between the chelating donors O3—Li1—S1, while the largest angle, O3—Li1—O4, can be found between the heteroleptic donor atoms. Molecules of (I) and (II) are examples of lithium thiolates with Li···Li short contacts of 2.889 (14) and 2.788 (9) Å, respectively. Similar distances can be found in LiOH·H₂O (Ojamäe et al., 1994).

The title compounds consist of very similar dimeric units but there is a basic difference between them. Compound (I) has Li⁺ cations coordinated by a THF molecule and having only one donor atom, generating an isolated dimer, whereas compound (II) has Li⁺ cations coordinated by a DME molecule containing two O donor atoms. The first, atom O4, coordinates to atom Li1, while the second, atom O4ⁱⁱ, coordinates to atom Li1ⁱⁱ from the neighbouring dimeric unit (Fig. 2; symmetry code as in Fig. 2). This arrangement combines the dimers together into infinitely long chains, in contrast to (I). The chain of the coordination polymer passes parallel to the b axis.

Dimers of (I) and chains of (II) are free of intermolecular interactions, apart from van der Waals forces. Compound (II) is hence an example of a coordination polymer (Braga et al., 2005) in which monomeric units are linked by coordination bonds. This study shows the fundamental role a solvent can play in the formation of the overall structure of solvated salts. The formation of a higher-order structure, namely the polymeric chains, was made possible by the replacement of a monodentate solvent by a bidentate one.

S2. Experimental

The synthesis was carried out using a standard vacuum, N₂ line and Schlenk techniques. Both compounds (I) and (II) were synthesized by direct reaction of (^tBuO)₃SiSH (Piękoś & Wojnowski, 1962) with an excess of metallic Li. The mixture was stirred and heated for 4 h, yielding a white precipitate. To dissolve this, tetrahydrofuran (THF) was added to part of the precipitate. The solution was separated from the excess metal by filtration, and crystallization by slow evaporation of the solvent afforded colourless crystals of (I) suitable for X-ray diffraction analysis. The second part of the white precipitate was dissolved in 1,2-dimethoxyethane (DME) and filtered in order to separate excess Li. Colourless crystals of (II) were obtained by crystallization from DME. Crystals of (I) and (II) are stable at room temperature and are fairly resistant to oxidation but sensitive to moist air, which makes diffraction experiments possible only at low temperatures, preferably 200 K and below.

S3. Refinement

All H atoms were refined as riding, with C—H distances in the range 0.97–0.99 Å and with U_iso(H) = 1.2U_iso(C). Please check added text. The disorder of the THF molecule was determined by constraining the ellipsoids of atoms C14–C16 to be the same [EADP instruction; SHELXL97 (Sheldrick, 1997)]. Additionally, the C13—C14 and O4—C16 bonds were constrained to be equal in both disordered parts (SADI in SHELXL97). Note that data for (I) were measured at 200 K and for (II) at 120 K.

Computing details

Data collection: KM4 Software (Gałdecki et al., 1996) for (I); CrysAlis CCD (Oxford Diffraction, 2003) for (II). Cell refinement: KM4 Software for (I); CrysAlis RED (Oxford Diffraction, 2003) for (II). Data reduction: DATAPROC (Gałdecki et al., 1996) for (I); CrysAlis RED for (II). For both compounds, 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) for (I); Please provide missing details for (II). For both compounds, software used to prepare material for publication: Please provide missing details.

Figures

Fig. 1. The molecular structure of (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. All H atoms have been omitted. [Symmetry code: (i) 1 − x, −y, −z.]

Fig. 2. The molecular structure of (II), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. All H atoms have been omitted. The asymmetric unit contains a (^tBuO)3SiS^− anion, an Li^+ cation and half the DME molecule. To illustrate the polymeric nature of (II), two DME molecules are shown, together with related cations Li1^ii (left) and Li1^iii (right). [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) 1 − x, 2 − y, 1 − z; (iii) −x, −1 − y, −z.]

(I) µ-Tri-tert-butylsilanethiolato-κ²S:S-bis[(tetrahydrofuran-κO)lithium(I)]

Crystal data

[Li2(C12H27O3SSi)2(C4H8O)2]	F(000) = 784
Mr = 717.06	Dx = 1.109 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 47 reflections
a = 9.789 (2) Å	θ = 2.3–17.5°
b = 20.083 (4) Å	µ = 0.22 mm^−1
c = 11.746 (2) Å	T = 200 K
β = 111.52 (3)°	Block, colourless
V = 2148.2 (8) Å^3	0.5 × 0.4 × 0.2 mm
Z = 2

Data collection

Kuma KM4, point detector diffractometer	Rint = 0.071
Radiation source: fine-focus sealed tube	θmax = 25.6°, θmin = 2.0°
Graphite monochromator	h = −11→11
ω/2θ scans	k = 0→24
4228 measured reflections	l = −13→0
4007 independent reflections	3 standard reflections every 200 reflections
2806 reflections with I > 2σ(I)	intensity decay: 8.4%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.220	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.1129P)^2 + 2.9823P] where P = (Fo^2 + 2Fc^2)/3
4007 reflections	(Δ/σ)max = 0.001
212 parameters	Δρmax = 0.50 e Å^−3
2 restraints	Δρmin = −0.50 e Å^−3

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	0.61759 (10)	0.08201 (5)	−0.00057 (9)	0.0318 (3)
Si1	0.47437 (11)	0.10708 (5)	−0.17217 (9)	0.0266 (3)
Li1	0.5259 (8)	−0.0280 (3)	−0.1035 (6)	0.0362 (15)
O1	0.5467 (3)	0.14233 (15)	−0.2612 (2)	0.0368 (7)
O2	0.3342 (3)	0.15382 (14)	−0.1838 (2)	0.0330 (6)
O3	0.4018 (3)	0.03417 (14)	−0.2319 (2)	0.0316 (6)
C1	0.6888 (6)	0.1465 (3)	−0.2681 (5)	0.0537 (13)
C2	0.7553 (9)	0.0783 (4)	−0.2578 (8)	0.097 (3)
H2B	0.7682	0.0592	−0.1777	0.145*
H2C	0.8509	0.0815	−0.2665	0.145*
H2A	0.6901	0.0496	−0.3225	0.145*
C3	0.7822 (6)	0.1933 (4)	−0.1660 (6)	0.085 (2)
H3A	0.7337	0.2367	−0.1752	0.127*
H3B	0.8792	0.1988	−0.1712	0.127*
H3C	0.7933	0.1742	−0.0863	0.127*
C4	0.6617 (8)	0.1767 (3)	−0.3937 (6)	0.0761 (19)
H4A	0.5971	0.1473	−0.4573	0.114*
H4B	0.7555	0.1817	−0.4050	0.114*
H4C	0.6151	0.2204	−0.3993	0.114*
C5	0.3165 (4)	0.2245 (2)	−0.1810 (4)	0.0387 (10)
C6	0.4350 (6)	0.2534 (3)	−0.0695 (6)	0.0689 (17)
H6A	0.4278	0.2339	0.0046	0.103*
H6C	0.4225	0.3018	−0.0683	0.103*
H6B	0.5316	0.2433	−0.0724	0.103*
C7	0.3214 (6)	0.2558 (3)	−0.2978 (5)	0.0625 (15)
H7A	0.4195	0.2497	−0.3005	0.094*
H7C	0.2995	0.3034	−0.2987	0.094*
H7B	0.2484	0.2342	−0.3691	0.094*
C8	0.1659 (6)	0.2356 (3)	−0.1757 (6)	0.0588 (14)
H8A	0.0911	0.2156	−0.2480	0.088*
H8B	0.1474	0.2835	−0.1742	0.088*
H8C	0.1615	0.2148	−0.1016	0.088*
C9	0.2704 (5)	0.0194 (2)	−0.3369 (4)	0.0408 (10)
C10	0.2598 (7)	0.0631 (3)	−0.4431 (4)	0.0705 (17)
H10A	0.2535	0.1098	−0.4212	0.106*
H10B	0.1718	0.0513	−0.5136	0.106*
H10C	0.3471	0.0568	−0.4641	0.106*
C11	0.1385 (5)	0.0282 (3)	−0.2991 (5)	0.0679 (17)
H11A	0.1468	−0.0024	−0.2319	0.102*
H11B	0.0482	0.0185	−0.3690	0.102*
H11C	0.1354	0.0742	−0.2722	0.102*
C12	0.2843 (7)	−0.0530 (3)	−0.3655 (5)	0.0671 (16)
H12A	0.3715	−0.0591	−0.3867	0.101*
H12B	0.1967	−0.0668	−0.4346	0.101*
H12C	0.2938	−0.0802	−0.2937	0.101*
C13	0.8283 (6)	−0.0734 (3)	−0.0400 (5)	0.0620 (12)
H13B	0.8327	−0.0967	0.0335	0.074*
H13A	0.8590	−0.0277	−0.0190	0.074*
O4	0.6817 (4)	−0.07583 (17)	−0.1315 (3)	0.0497 (8)
C14	0.9223 (9)	−0.1142 (6)	−0.0923 (8)	0.0620 (12)	0.693 (16)
H14B	1.0238	−0.0967	−0.0650	0.074*	0.693 (16)
H14A	0.9253	−0.1616	−0.0682	0.074*	0.693 (16)
C15	0.8457 (11)	−0.1060 (7)	−0.2263 (9)	0.0620 (12)	0.693 (16)
H15B	0.8669	−0.1438	−0.2712	0.074*	0.693 (16)
H15A	0.8760	−0.0641	−0.2548	0.074*	0.693 (16)
C16	0.6871 (10)	−0.1040 (6)	−0.2441 (8)	0.0620 (12)	0.693 (16)
H16A	0.6318	−0.0758	−0.3152	0.074*	0.693 (16)
H16B	0.6446	−0.1494	−0.2578	0.074*	0.693 (16)
C14B	0.928 (2)	−0.0769 (13)	−0.1179 (17)	0.060 (6)*	0.307 (16)
H14C	0.9319	−0.0340	−0.1583	0.072*	0.307 (16)
H14D	1.0294	−0.0919	−0.0690	0.072*	0.307 (16)
C15A	0.839 (3)	−0.1307 (13)	−0.210 (2)	0.066 (7)*	0.307 (16)
H15C	0.8403	−0.1215	−0.2928	0.079*	0.307 (16)
H15D	0.8820	−0.1754	−0.1841	0.079*	0.307 (16)
C16A	0.686 (2)	−0.1278 (9)	−0.2123 (17)	0.050 (5)*	0.307 (16)
H16C	0.6164	−0.1185	−0.2962	0.060*	0.307 (16)
H16D	0.6593	−0.1708	−0.1850	0.060*	0.307 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0263 (5)	0.0353 (6)	0.0309 (5)	−0.0047 (4)	0.0070 (4)	0.0024 (4)
Si1	0.0237 (5)	0.0288 (6)	0.0287 (5)	−0.0009 (4)	0.0112 (4)	0.0012 (4)
Li1	0.040 (4)	0.032 (4)	0.040 (4)	0.000 (3)	0.019 (3)	0.004 (3)
O1	0.0323 (15)	0.0433 (18)	0.0412 (16)	0.0020 (12)	0.0211 (13)	0.0110 (13)
O2	0.0260 (14)	0.0336 (16)	0.0405 (15)	−0.0012 (11)	0.0136 (12)	0.0004 (12)
O3	0.0309 (14)	0.0322 (15)	0.0289 (13)	−0.0016 (11)	0.0077 (11)	−0.0028 (11)
C1	0.051 (3)	0.057 (3)	0.072 (3)	0.014 (2)	0.044 (3)	0.024 (3)
C2	0.114 (6)	0.086 (5)	0.140 (6)	0.053 (4)	0.106 (5)	0.051 (5)
C3	0.043 (3)	0.105 (6)	0.102 (5)	−0.022 (3)	0.021 (3)	0.021 (4)
C4	0.099 (5)	0.073 (4)	0.089 (4)	0.021 (4)	0.074 (4)	0.033 (3)
C5	0.030 (2)	0.036 (2)	0.052 (2)	0.0092 (17)	0.0170 (19)	0.0009 (19)
C6	0.060 (3)	0.048 (3)	0.083 (4)	0.002 (3)	0.007 (3)	−0.022 (3)
C7	0.065 (3)	0.052 (3)	0.080 (4)	0.021 (3)	0.038 (3)	0.023 (3)
C8	0.042 (3)	0.054 (3)	0.088 (4)	0.014 (2)	0.033 (3)	0.004 (3)
C9	0.036 (2)	0.048 (3)	0.031 (2)	−0.0089 (19)	0.0028 (17)	−0.0064 (18)
C10	0.080 (4)	0.076 (4)	0.035 (2)	−0.023 (3)	−0.002 (3)	0.005 (3)
C11	0.033 (3)	0.096 (5)	0.067 (3)	−0.012 (3)	0.008 (2)	−0.022 (3)
C12	0.067 (4)	0.055 (3)	0.062 (3)	−0.009 (3)	0.002 (3)	−0.024 (3)
C13	0.059 (2)	0.068 (3)	0.064 (2)	0.016 (2)	0.0267 (18)	0.002 (2)
O4	0.0480 (19)	0.052 (2)	0.0564 (19)	0.0086 (16)	0.0275 (16)	−0.0028 (16)
C14	0.059 (2)	0.068 (3)	0.064 (2)	0.016 (2)	0.0267 (18)	0.002 (2)
C15	0.059 (2)	0.068 (3)	0.064 (2)	0.016 (2)	0.0267 (18)	0.002 (2)
C16	0.059 (2)	0.068 (3)	0.064 (2)	0.016 (2)	0.0267 (18)	0.002 (2)

Geometric parameters (Å, º)

S1—Si1	2.0515 (16)	C8—H8C	0.9800
S1—Li1^i	2.429 (7)	C9—C10	1.497 (7)
S1—Li1	2.521 (7)	C9—C12	1.510 (7)
Si1—O1	1.625 (3)	C9—C11	1.523 (7)
Si1—O2	1.626 (3)	C10—H10A	0.9800
Si1—O3	1.666 (3)	C10—H10B	0.9800
Si1—Li1	2.823 (7)	C10—H10C	0.9800
Li1—O3	1.992 (7)	C11—H11A	0.9800
Li1—O4	1.929 (8)	C11—H11B	0.9800
Li1—S1^i	2.429 (7)	C11—H11C	0.9800
Li1—Li1^i	2.889 (14)	C12—H12A	0.9800
O1—C1	1.425 (5)	C12—H12B	0.9800
O2—C5	1.431 (5)	C12—H12C	0.9800
O3—C9	1.449 (5)	C13—O4	1.444 (6)
C1—C2	1.502 (8)	C13—C14	1.520 (9)
C1—C3	1.534 (9)	C13—C14B	1.569 (15)
C1—C4	1.525 (7)	C13—H13B	0.9700
C2—H2B	0.9800	C13—H13A	0.9700
C2—H2C	0.9800	O4—C16A	1.422 (13)
C2—H2A	0.9800	O4—C16	1.457 (8)
C3—H3A	0.9800	C14—C15	1.483 (13)
C3—H3B	0.9800	C14—H14B	0.9900
C3—H3C	0.9800	C14—H14A	0.9900
C4—H4A	0.9800	C15—C16	1.489 (13)
C4—H4B	0.9800	C15—H15B	0.9900
C4—H4C	0.9800	C15—H15A	0.9900
C5—C6	1.511 (7)	C16—H16A	0.9900
C5—C8	1.515 (6)	C16—H16B	0.9900
C5—C7	1.526 (7)	C14B—C15A	1.55 (3)
C6—H6A	0.9800	C14B—H14C	0.9900
C6—H6C	0.9800	C14B—H14D	0.9900
C6—H6B	0.9800	C15A—C16A	1.49 (3)
C7—H7A	0.9800	C15A—H15C	0.9900
C7—H7C	0.9800	C15A—H15D	0.9900
C7—H7B	0.9800	C16A—H16C	0.9900
C8—H8A	0.9800	C16A—H16D	0.9900
C8—H8B	0.9800
Si1—S1—Li1^i	106.91 (17)	H8A—C8—H8C	109.5
Si1—S1—Li1	75.48 (16)	H8B—C8—H8C	109.5
Li1^i—S1—Li1	71.4 (3)	O3—C9—C10	111.0 (4)
O1—Si1—O2	104.35 (15)	O3—C9—C12	105.2 (4)
O1—Si1—O3	109.31 (15)	C10—C9—C12	111.4 (4)
O2—Si1—O3	104.83 (15)	O3—C9—C11	108.1 (3)
O1—Si1—S1	115.95 (12)	C10—C9—C11	111.6 (5)
O2—Si1—S1	118.38 (11)	C12—C9—C11	109.4 (5)
O3—Si1—S1	103.32 (11)	C9—C10—H10A	109.5
O1—Si1—Li1	121.90 (18)	C9—C10—H10B	109.5
O2—Si1—Li1	129.46 (18)	H10A—C10—H10B	109.5
S1—Si1—Li1	59.82 (15)	C9—C10—H10C	109.5
O3—Li1—S1	79.9 (2)	H10A—C10—H10C	109.5
O3—Li1—S1^i	110.9 (3)	H10B—C10—H10C	109.5
O4—Li1—S1^i	120.2 (3)	C9—C11—H11A	109.5
O4—Li1—S1	110.7 (3)	C9—C11—H11B	109.5
O3—Li1—O4	118.9 (4)	H11A—C11—H11B	109.5
S1^i—Li1—S1	108.6 (3)	C9—C11—H11C	109.5
O4—Li1—Si1	119.9 (3)	H11A—C11—H11C	109.5
S1^i—Li1—Si1	119.8 (3)	H11B—C11—H11C	109.5
O4—Li1—Li1^i	137.0 (5)	C9—C12—H12A	109.5
O3—Li1—Li1^i	98.4 (4)	C9—C12—H12B	109.5
S1^i—Li1—Li1^i	55.8 (2)	H12A—C12—H12B	109.5
S1—Li1—Li1^i	52.8 (2)	C9—C12—H12C	109.5
Si1—Li1—Li1^i	78.3 (3)	H12A—C12—H12C	109.5
C1—O1—Si1	136.6 (3)	H12B—C12—H12C	109.5
C5—O2—Si1	132.5 (2)	O4—C13—C14	105.4 (5)
C9—O3—Si1	130.3 (3)	O4—C13—C14B	103.2 (8)
C9—O3—Li1	128.3 (3)	O4—C13—H13B	110.7
Si1—O3—Li1	100.7 (2)	C14—C13—H13B	105.3
O1—C1—C2	110.2 (5)	C14B—C13—H13B	131.7
O1—C1—C4	104.6 (4)	O4—C13—H13A	110.6
C2—C1—C4	110.9 (5)	C14—C13—H13A	115.8
O1—C1—C3	107.8 (4)	C14B—C13—H13A	89.3
C2—C1—C3	112.3 (6)	H13B—C13—H13A	108.8
C4—C1—C3	110.8 (5)	C16A—O4—C13	104.8 (8)
C1—C2—H2B	109.5	C13—O4—C16	109.4 (5)
C1—C2—H2C	109.5	C16A—O4—Li1	134.4 (8)
H2B—C2—H2C	109.5	C13—O4—Li1	119.2 (4)
C1—C2—H2A	109.5	C16—O4—Li1	129.9 (5)
H2B—C2—H2A	109.5	C15—C14—C13	102.9 (6)
H2C—C2—H2A	109.5	C15—C14—H14B	111.2
C1—C3—H3A	109.5	C13—C14—H14B	111.2
C1—C3—H3B	109.5	C15—C14—H14A	111.2
H3A—C3—H3B	109.5	C13—C14—H14A	111.2
C1—C3—H3C	109.5	H14B—C14—H14A	109.1
H3A—C3—H3C	109.5	C14—C15—C16	104.3 (8)
H3B—C3—H3C	109.5	C14—C15—H15B	110.9
C1—C4—H4A	109.5	C16—C15—H15B	110.9
C1—C4—H4B	109.5	C14—C15—H15A	110.9
H4A—C4—H4B	109.5	C16—C15—H15A	110.9
C1—C4—H4C	109.5	H15B—C15—H15A	108.9
H4A—C4—H4C	109.5	O4—C16—C15	105.4 (7)
H4B—C4—H4C	109.5	O4—C16—H16A	110.7
O2—C5—C6	109.9 (4)	C15—C16—H16A	110.7
O2—C5—C8	105.9 (4)	O4—C16—H16B	110.7
C6—C5—C8	110.9 (4)	C15—C16—H16B	110.7
O2—C5—C7	110.1 (4)	H16A—C16—H16B	108.8
C6—C5—C7	110.7 (5)	C15A—C14B—C13	97.3 (14)
C8—C5—C7	109.2 (4)	C15A—C14B—H14C	112.3
C5—C6—H6A	109.5	C13—C14B—H14C	112.3
C5—C6—H6C	109.5	C15A—C14B—H14D	112.3
H6A—C6—H6C	109.5	C13—C14B—H14D	112.3
C5—C6—H6B	109.5	H14C—C14B—H14D	109.9
H6A—C6—H6B	109.5	C16A—C15A—C14B	106.7 (17)
H6C—C6—H6B	109.5	C16A—C15A—H15C	110.4
C5—C7—H7A	109.5	C14B—C15A—H15C	110.4
C5—C7—H7C	109.5	C16A—C15A—H15D	110.4
H7A—C7—H7C	109.5	C14B—C15A—H15D	110.4
C5—C7—H7B	109.5	H15C—C15A—H15D	108.6
H7A—C7—H7B	109.5	O4—C16A—C15A	107.2 (14)
H7C—C7—H7B	109.5	O4—C16A—H16C	110.3
C5—C8—H8A	109.5	C15A—C16A—H16C	110.3
C5—C8—H8B	109.5	O4—C16A—H16D	110.3
H8A—C8—H8B	109.5	C15A—C16A—H16D	110.3
C5—C8—H8C	109.5	H16C—C16A—H16D	108.5

Symmetry code: (i) −x+1, −y, −z.

(II) catena-poly[[bis(µ-tri-tert-butylsilanethiolato)-1:2κ²S;1κS:2κS,O- dilithium(I)]-µ-dimethoxyethane-κ²O:O']

Crystal data

[Li2(C12H27O3SSi)2(C4H10O2)]	Z = 2
Mr = 331.49	F(000) = 362
Triclinic, P1	Dx = 1.124 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.721 (2) Å	Cell parameters from 3123 reflections
b = 9.305 (2) Å	θ = 2–20°
c = 14.048 (3) Å	µ = 0.24 mm^−1
α = 82.24 (3)°	T = 120 K
β = 72.91 (3)°	Rod, colourless
γ = 64.01 (3)°	0.4 × 0.2 × 0.2 mm
V = 979.4 (5) Å^3

Data collection

Kuma KM4, Sapphire2 CCD area detector diffractometer	Rint = 0.027
Graphite monochromator	θmax = 25.5°, θmin = 2.8°
ω scans, 612 frames	h = −8→10
5576 measured reflections	k = −11→11
3638 independent reflections	l = −16→16
3362 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0341P)^2 + 2.4894P] where P = (Fo^2 + 2Fc^2)/3
3638 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 0.54 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

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
S1	0.39933 (8)	0.51368 (8)	0.38284 (5)	0.01799 (17)
Si1	0.64125 (9)	0.46593 (8)	0.28166 (5)	0.01596 (18)
Li1	0.5520 (6)	0.6222 (5)	0.4601 (3)	0.0196 (9)
O1	0.6362 (2)	0.5571 (2)	0.17438 (13)	0.0201 (4)
O2	0.7704 (2)	0.2787 (2)	0.25352 (13)	0.0200 (4)
O3	0.7429 (2)	0.5242 (2)	0.34096 (13)	0.0164 (4)
C1	0.5314 (4)	0.7128 (3)	0.1407 (2)	0.0219 (6)
C2	0.4836 (5)	0.8407 (4)	0.2144 (2)	0.0356 (7)
H2A	0.4103	0.8218	0.2781	0.043*
H2B	0.4177	0.9461	0.1882	0.043*
H2C	0.5919	0.8369	0.2244	0.043*
C3	0.3662 (4)	0.7104 (4)	0.1272 (2)	0.0328 (7)
H3A	0.2942	0.693	0.1919	0.039*
H3B	0.4	0.6238	0.0819	0.039*
H3C	0.2978	0.8129	0.099	0.039*
C4	0.6459 (4)	0.7387 (4)	0.0411 (2)	0.0358 (7)
H4A	0.7518	0.7402	0.0511	0.043*
H4B	0.5788	0.8409	0.0122	0.043*
H4C	0.681	0.6517	−0.0041	0.043*
C5	0.7913 (4)	0.1825 (3)	0.1737 (2)	0.0236 (6)
C6	0.6118 (4)	0.2130 (4)	0.1617 (2)	0.0333 (7)
H6A	0.5413	0.1877	0.2244	0.04*
H6B	0.628	0.1452	0.1086	0.04*
H6C	0.5503	0.3256	0.1445	0.04*
C7	0.9057 (5)	0.2199 (4)	0.0781 (2)	0.0360 (8)
H7A	0.844	0.3312	0.0584	0.043*
H7B	0.9289	0.1486	0.0252	0.043*
H7C	1.018	0.2041	0.0891	0.043*
C8	0.8850 (4)	0.0099 (4)	0.2050 (2)	0.0329 (7)
H8A	0.8106	−0.0129	0.2668	0.039*
H8B	0.9978	−0.007	0.2158	0.039*
H8C	0.9071	−0.0616	0.1525	0.039*
C9	0.9272 (3)	0.4987 (3)	0.3201 (2)	0.0192 (5)
C10	0.9222 (4)	0.6257 (3)	0.3804 (2)	0.0238 (6)
H10A	0.8554	0.732	0.3556	0.029*
H10B	1.0431	0.6113	0.3736	0.029*
H10C	0.8647	0.6155	0.4506	0.029*
C11	1.0319 (4)	0.3316 (3)	0.3563 (2)	0.0267 (6)
H11A	1.0335	0.2517	0.3167	0.032*
H11B	0.9761	0.3193	0.4265	0.032*
H11C	1.1533	0.3164	0.3488	0.032*
C12	1.0025 (4)	0.5193 (4)	0.2095 (2)	0.0280 (6)
H12A	1.0041	0.4367	0.1722	0.034*
H12B	1.1232	0.5093	0.1976	0.034*
H12C	0.9286	0.6252	0.1874	0.034*
O4	0.4265 (2)	0.8526 (2)	0.47834 (14)	0.0226 (4)
C13	0.4894 (4)	0.9293 (3)	0.5299 (2)	0.0225 (6)
H13A	0.6045	0.8519	0.5411	0.027*
H13B	0.4046	0.9663	0.5957	0.027*
C14	0.2380 (4)	0.9227 (4)	0.4979 (2)	0.0288 (6)
H14A	0.1855	0.9137	0.5692	0.035*
H14B	0.2033	0.8667	0.4597	0.035*
H14C	0.1961	1.0358	0.4782	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0147 (3)	0.0207 (3)	0.0173 (3)	−0.0083 (3)	−0.0017 (2)	0.0009 (2)
Si1	0.0145 (3)	0.0175 (4)	0.0150 (3)	−0.0071 (3)	−0.0024 (3)	0.0007 (3)
Li1	0.020 (2)	0.023 (2)	0.017 (2)	−0.0085 (18)	−0.0063 (17)	−0.0030 (17)
O1	0.0201 (9)	0.0240 (10)	0.0163 (9)	−0.0104 (8)	−0.0044 (7)	0.0023 (7)
O2	0.0217 (9)	0.0198 (9)	0.0179 (9)	−0.0078 (8)	−0.0042 (7)	−0.0042 (7)
O3	0.0129 (8)	0.0208 (9)	0.0182 (9)	−0.0091 (7)	−0.0044 (7)	−0.0012 (7)
C1	0.0254 (14)	0.0245 (14)	0.0191 (13)	−0.0127 (12)	−0.0096 (11)	0.0061 (11)
C2	0.052 (2)	0.0243 (16)	0.0370 (18)	−0.0193 (15)	−0.0183 (15)	0.0051 (13)
C3	0.0262 (15)	0.0386 (18)	0.0324 (16)	−0.0122 (13)	−0.0123 (13)	0.0084 (13)
C4	0.0360 (17)	0.0457 (19)	0.0283 (16)	−0.0221 (15)	−0.0114 (14)	0.0157 (14)
C5	0.0327 (15)	0.0236 (14)	0.0186 (13)	−0.0168 (12)	−0.0017 (11)	−0.0064 (11)
C6	0.0466 (19)	0.0343 (17)	0.0327 (17)	−0.0263 (15)	−0.0136 (14)	−0.0032 (13)
C7	0.051 (2)	0.0370 (18)	0.0229 (15)	−0.0278 (16)	0.0054 (14)	−0.0091 (13)
C8	0.0418 (18)	0.0240 (15)	0.0261 (16)	−0.0116 (14)	0.0013 (13)	−0.0094 (12)
C9	0.0119 (12)	0.0260 (14)	0.0221 (13)	−0.0101 (11)	−0.0042 (10)	−0.0010 (11)
C10	0.0202 (13)	0.0262 (15)	0.0297 (15)	−0.0121 (11)	−0.0089 (11)	−0.0023 (12)
C11	0.0217 (14)	0.0245 (15)	0.0370 (17)	−0.0081 (12)	−0.0137 (12)	−0.0026 (12)
C12	0.0205 (14)	0.0418 (18)	0.0255 (15)	−0.0193 (13)	0.0001 (11)	−0.0041 (13)
O4	0.0239 (10)	0.0175 (9)	0.0267 (10)	−0.0082 (8)	−0.0065 (8)	−0.0037 (8)
C13	0.0297 (15)	0.0184 (14)	0.0214 (14)	−0.0120 (12)	−0.0064 (11)	−0.0007 (11)
C14	0.0248 (14)	0.0257 (15)	0.0384 (17)	−0.0097 (12)	−0.0104 (13)	−0.0060 (12)

Geometric parameters (Å, º)

S1—Si1	2.0629 (13)	C6—H6A	0.98
S1—Li1^i	2.444 (4)	C6—H6B	0.98
S1—Li1	2.509 (4)	C6—H6C	0.98
Si1—O1	1.6290 (19)	C7—H7A	0.98
Si1—O2	1.633 (2)	C7—H7B	0.98
Si1—O3	1.6587 (18)	C7—H7C	0.98
Si1—Li1	2.802 (4)	C8—H8A	0.98
Li1—O3	1.962 (5)	C8—H8B	0.98
Li1—O4	1.946 (5)	C8—H8C	0.98
Li1—S1^i	2.444 (4)	C9—C10	1.522 (4)
Li1—Li1^i	2.788 (9)	C9—C11	1.524 (4)
O1—C1	1.437 (3)	C9—C12	1.521 (4)
O2—C5	1.449 (3)	C10—H10A	0.98
O3—C9	1.461 (3)	C10—H10B	0.98
C1—C2	1.519 (4)	C10—H10C	0.98
C1—C3	1.517 (4)	C11—H11A	0.98
C1—C4	1.521 (4)	C11—H11B	0.98
C2—H2A	0.98	C11—H11C	0.98
C2—H2B	0.98	C12—H12A	0.98
C2—H2C	0.98	C12—H12B	0.98
C3—H3A	0.98	C12—H12C	0.98
C3—H3B	0.98	O4—C14	1.430 (3)
C3—H3C	0.98	O4—C13	1.433 (3)
C4—H4A	0.98	C13—C13^ii	1.514 (5)
C4—H4B	0.98	C13—H13A	0.99
C4—H4C	0.98	C13—H13B	0.99
C5—C6	1.520 (4)	C14—H14A	0.98
C5—C7	1.520 (4)	C14—H14B	0.98
C5—C8	1.520 (4)	C14—H14C	0.98
Si1—S1—Li1^i	108.86 (11)	C6—C5—C7	111.4 (3)
Si1—S1—Li1	74.89 (11)	C5—C6—H6A	109.5
Li1^i—S1—Li1	68.50 (17)	C5—C6—H6B	109.5
O1—Si1—O2	104.46 (10)	H6A—C6—H6B	109.5
O1—Si1—O3	110.23 (10)	C5—C6—H6C	109.5
O2—Si1—O3	105.80 (10)	H6A—C6—H6C	109.5
O1—Si1—S1	116.06 (8)	H6B—C6—H6C	109.5
O2—Si1—S1	116.91 (8)	C5—C7—H7A	109.5
O3—Si1—S1	102.94 (7)	C5—C7—H7B	109.5
O1—Si1—Li1	123.58 (12)	H7A—C7—H7B	109.5
O2—Si1—Li1	128.33 (12)	C5—C7—H7C	109.5
S1—Si1—Li1	59.82 (10)	H7A—C7—H7C	109.5
O4—Li1—O3	122.6 (2)	H7B—C7—H7C	109.5
O4—Li1—S1^i	110.81 (19)	C5—C8—H8A	109.5
O3—Li1—S1^i	115.2 (2)	C5—C8—H8B	109.5
O4—Li1—S1	112.28 (19)	H8A—C8—H8B	109.5
O3—Li1—S1	80.61 (15)	C5—C8—H8C	109.5
S1^i—Li1—S1	111.50 (17)	H8A—C8—H8C	109.5
O4—Li1—Li1^i	130.7 (3)	H8B—C8—H8C	109.5
O3—Li1—Li1^i	103.1 (2)	O3—C9—C12	110.6 (2)
S1^i—Li1—Li1^i	56.86 (15)	O3—C9—C10	104.8 (2)
S1—Li1—Li1^i	54.64 (14)	C12—C9—C10	110.8 (2)
O4—Li1—Si1	124.6 (2)	O3—C9—C11	108.4 (2)
S1^i—Li1—Si1	124.48 (18)	C12—C9—C11	111.2 (2)
Li1^i—Li1—Si1	82.13 (19)	C10—C9—C11	110.7 (2)
C1—O1—Si1	135.70 (17)	C9—C10—H10A	109.5
C5—O2—Si1	130.84 (17)	C9—C10—H10B	109.5
C9—O3—Si1	131.68 (16)	H10A—C10—H10B	109.5
C9—O3—Li1	126.95 (19)	C9—C10—H10C	109.5
Si1—O3—Li1	101.08 (15)	H10A—C10—H10C	109.5
O1—C1—C3	108.3 (2)	H10B—C10—H10C	109.5
O1—C1—C2	111.0 (2)	C9—C11—H11A	109.5
C3—C1—C2	110.8 (3)	C9—C11—H11B	109.5
O1—C1—C4	105.5 (2)	H11A—C11—H11B	109.5
C3—C1—C4	110.4 (2)	C9—C11—H11C	109.5
C2—C1—C4	110.7 (3)	H11A—C11—H11C	109.5
C1—C2—H2A	109.5	H11B—C11—H11C	109.5
C1—C2—H2B	109.5	C9—C12—H12A	109.5
H2A—C2—H2B	109.5	C9—C12—H12B	109.5
C1—C2—H2C	109.5	H12A—C12—H12B	109.5
H2A—C2—H2C	109.5	C9—C12—H12C	109.5
H2B—C2—H2C	109.5	H12A—C12—H12C	109.5
C1—C3—H3A	109.5	H12B—C12—H12C	109.5
C1—C3—H3B	109.5	C14—O4—C13	113.3 (2)
H3A—C3—H3B	109.5	C14—O4—Li1	117.9 (2)
C1—C3—H3C	109.5	C13—O4—Li1	118.5 (2)
H3A—C3—H3C	109.5	O4—C13—C13^ii	110.4 (3)
H3B—C3—H3C	109.5	O4—C13—H13A	109.6
C1—C4—H4A	109.5	C13^ii—C13—H13A	109.6
C1—C4—H4B	109.5	O4—C13—H13B	109.6
H4A—C4—H4B	109.5	C13^ii—C13—H13B	109.6
C1—C4—H4C	109.5	H13A—C13—H13B	108.1
H4A—C4—H4C	109.5	O4—C14—H14A	109.5
H4B—C4—H4C	109.5	O4—C14—H14B	109.5
O2—C5—C8	105.5 (2)	H14A—C14—H14B	109.5
O2—C5—C6	110.5 (2)	O4—C14—H14C	109.5
C8—C5—C6	110.1 (2)	H14A—C14—H14C	109.5
O2—C5—C7	109.1 (2)	H14B—C14—H14C	109.5
C8—C5—C7	110.1 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+1.