Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113009311/wq3030sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113009311/wq3030Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113009311/wq3030IIsup3.hkl |
CCDC references: 950396; 950397
For related literature, see: Allen (2002); Flack (1983); Kückmann et al. (2007); Kern et al. (2008); Lerner (2005); Lerner et al. (2002, 2007, 2012); Lerner, Scholz, Wiberg, Polborn, Bolte & Wagner (2005); Röder et al. (2008); Reisinger et al. (2007).
For the preparation of [InCl2{O(HO)Si(tBu)2}]2, (I), a mixture of InCl3 (0.43 g, 1.95 mmol), (tBu)2Si(OH)2 (1.47 g, 8.35 mmol) and NEt3 (0.95 g, 9.41 mmol) was dissolved in benzene (30 ml). After stirring for 24 h at room temperature, the reaction mixture was filtered to remove any insoluble material. Single crystals of (I) were grown from this solution at ambient temperature (yield 55%).
For the preparation of [Li(thf)4][B(CH2SiMe3)4], (II), a solution (0.78 m) [ml or mol?] of Li[CH2SiMe3] in hexane (25.6 ml) was added dropwise to a cooled (273 K) solution of BCl3 (5.0 mmol) in heptane (5 ml). The precipitate obtained was filtered off (Celite). The solution was first diluted with tetrahydrofuran (20 ml) and then concentrated to 20 ml. After cooling to 248 K, single crystals of (II) were obtained (yield 60%).
The hydroxy H atom in (I) was found in a difference map but was refined as riding, with O—H = 0.84 Å and Uiso(H) = 1.5Ueq(O). C-bound H atoms in (I) and (II) were refined using a riding model, with methyl C—H = 0.98 Å and secondary C—H = 0.99 Å, and with Uiso(H) = 1.5Ueq(C) for methyl or 1.2Ueq(C) for secondary H atoms. The crystal of (I) was a nonmerohedral twin with a fractional contribution of 0.088 (2) for the minor domain. The twin law is (100/010/0.5 0 1).
In (II), three of the four tetrahydrofuran rings show disorder. In one ring [Atom numbers?], two methylene groups are disordered over two positions, with a site-occupancy factor of 0.69 (3) for the major occupied site. In the second ring [Atom numbers?], one methylene group is disordered over two positions, with a site-occupancy factor of 0.63 (3) for the major occupied site. In the third ring [Atom numbers?], all methylene groups are disordered over two positions, with a site-occupancy factor of 0.74 (2) for the major occupied site. The C52'—C53', C63—C64, C73—C74, C84—C85 and C84'—C85' bond lengths were restrained to 1.50 (1) Å. The displacement ellipsoids of the disordered atoms were restrained to isotropic behaviour, with an effective standard deviation of 0.01 Å2. The Flack x parameter (Flack, 1983) for (II) refined to 0.17 (16).
Weakly coordinating anions have gained prominence in a wide variety of applications in both research laboratories and industry. One approach to create such anions is by the tetrasubstitution of trieles to [EX4]- (where E = B, Al, Ga or In). Normally, the use of alkyl substituents (X = R) is inadequate for this approach, because the [ER4]- anions are too reactive and most of them ignite in the presence of traces of water or oxygen. In contrast with alkyl substituents, alkoxy or alkynyl ligands can stabilize this type of anion {e.g. [EX4]- with X = C≡CSiMe3 or C≡CSi(iPr)3 (Lerner et al., 2007, 2012) or X = OC(CF3)3 (Reisinger et al., 2007)}. In addition, the related anions [E(cat)2]- (where cat is C6H4O22-, the catecholate dianion, as ligand for E3+ = B3+, Al3+, Ga3+ or In3+) also find applications, e.g. as electrolytes in cyclic voltammetry (Röder et al., 2008). In this context, weakly coordinating anions which are soluble in organic solvents are of great interest.
In the course of our long-standing studies of silanolate (siloxide) ligands (Kern et al., 2008; Kückmann et al., 2007; Lerner, 2005; Lerner et al., 2002, 2005), we have found a convenient preparation route for the silandiol tBu2Si(OH)2. Therefore, it was obvious to introduce tBu2Si(OH)2 as a chelating ligand to prepare the corresponding indium siloxide complexes. In a second approach, we prepared a novel alkyl-substituted borate, Li[B(CH2SiMe3)4], which possesses bulky silyl substituents on the chain ends. In this paper, we report the crystal structures of the indium siloxide [InCl2{O(HO)Si(tBu)2}]2, (I), and the lithium borate [Li(thf)4][B(CH2SiMe3)4] (thf is tetrahydrofuran), (II).
Siloxide (I) can be prepared from InCl3 and (tBu)2Si(OH)2, as shown in Scheme 1. When InCl3 was treated with an excess of the silandiol (tBu)2Si(OH)2 in the presence of +NEt3 in benzene at ambient temperature, [InCl2{O(HO)Si(tBu)2}]2 was formed, rather than [InCl{O2Si(tBu)2}] or {[In{O2Si(tBu)2}]2}-. X-ray quality crystals of (I) were grown from the reaction solution at ambient temperature.
Another approach to creating weakly coordinating anions is to stabilize alkyl-substituted borates using bulky end groups, e.g. SiMe3. Therefore, we decided to prepare [Li(thf)4][B(CH2SiMe3)4], (II), which was synthesized in good yield from BCl3 and Li[CH2SiMe3], as shown in Scheme 2. X-ray quality crystals of (II) were obtained from a hexane solution at ambient temperature.
Compound (I) features a centrosymmetric two-centre indium complex (Fig. 1). Each In centre is pentacoordinated by two terminal chloride ligands and three O atoms. The two In—Cl bonds are of comparable length, but there are two short In—O bonds to bridging O atoms and a longer In—O bond to the hydroxy O atom (Table 1). The central In2O2 ring is exactly planar due to inversion symmetry. The InSiO2 rings are essentially planar (r.m.s. deviation = 0.024 Å) and close to coplanar with the In2O2 ring, with a dihedral angle of 3.0 (4)° between the two rings. The coordination geometry of the In centres can be described as a distorted trigonal bipyramid. The bond angle between the two axial ligands, the hydroxy O atom and one of the bridging O atoms [142.7 (2)°] is significantly distorted from idealized linear geometry, but the bond angles in the equatorial plane are reasonably close to the ideal value of 120° (Table 1). The Si—O bond to the hydroxy O atom is significantly longer than that to the bridging O atom, but the two Si—C bonds are not significantly different (Table 1). In the crystal structure, molecules of (I) are linked by O—H···Cl hydrogen bonds into chains running along the a axis (Fig. 2 and Table 2). There are no further short contacts between the molecules. This structure is the first example of an In2O2 ring which is annulated with two Si—O units to form a ring system composed of three rings [Cambridge Structural Database (CSD), Version 5.34, November 2012 plus one update; Allen, 2002]. A search of the CSD for an In2O2 ring with the In atoms carrying any two halogen ligands gave no hits. However, a search for just an In2O2 ring yielded 36 hits, with a mean In—O bond length of 2.24 (7) Å, which is slightly longer than the In—O bond lengths [2.122 (5) and 2.160 (5) Å] in the In2O2 ring of (I).
Compound (II) crystallizes with discrete tetrakis(thf)lithium cations and tetrakis[(trimethylsilyl)methyl]borate anions in the asymmetric unit (Fig. 3). The coordination geometry around the Li atom is tetrahedral, with three Li—O bonds of almost equal length and one slightly longer one. All the O—Li—O angles are close to idealized tetrahedral values (Table 3). The B atom is also tetrahedrally coordinated. There are no appreciable differences between the B—C bonds and all C—B—C angles are close to the ideal tetrahedral value (Table 3). It is noteworthy that all four B—C—Si angles are significantly widened to more than 120°, due to steric repulsion between the SiMe3 and BC3 units (Table 3). The crystal packing of (II) shows that the molecules are located in planes parallel to (110) (Fig. 4), within which the cations and anions adopt alternating positions. There are no short contacts, either between molecules within the plane or between adjacent planes. Compound (II) is the first example of a structure with a boron centre bonded to four –CH2Si units (CSD). A search of the CSD for the B(CH2)4 fragment yielded nine hits. Eight of these were for tetraethylborate and one was a tetra-n-butylborate. The mean B—C bond length in all these fragments is 1.65 (1) Å, which is not significantly different from the mean B—C bond [1.67 (1) Å] in (II).
For related literature, see: Allen (2002); Flack (1983); Kückmann et al. (2007); Kern et al. (2008); Lerner (2005); Lerner et al. (2002, 2007, 2012); Lerner, Scholz, Wiberg, Polborn, Bolte & Wagner (2005); Röder et al. (2008); Reisinger et al. (2007).
For both compounds, data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-AREA (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
[In2(C8H19O2Si)2Cl4] | F(000) = 720 |
Mr = 722.08 | Dx = 1.653 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6359 reflections |
a = 8.3467 (10) Å | θ = 3.5–25.6° |
b = 10.453 (1) Å | µ = 2.06 mm−1 |
c = 16.7393 (18) Å | T = 173 K |
β = 96.689 (9)° | Block, colourless |
V = 1450.5 (3) Å3 | 0.16 × 0.14 × 0.13 mm |
Z = 2 |
Stoe IPDS II two-circle diffractometer | 2690 independent reflections |
Radiation source: fine-focus sealed tube | 2137 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.071 |
ω scans | θmax = 25.6°, θmin = 3.5° |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | h = −10→10 |
Tmin = 0.734, Tmax = 0.776 | k = −12→12 |
7213 measured reflections | l = −3→20 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0621P)2 + 9.1817P] where P = (Fo2 + 2Fc2)/3 |
2690 reflections | (Δ/σ)max < 0.001 |
128 parameters | Δρmax = 1.18 e Å−3 |
0 restraints | Δρmin = −1.05 e Å−3 |
[In2(C8H19O2Si)2Cl4] | V = 1450.5 (3) Å3 |
Mr = 722.08 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.3467 (10) Å | µ = 2.06 mm−1 |
b = 10.453 (1) Å | T = 173 K |
c = 16.7393 (18) Å | 0.16 × 0.14 × 0.13 mm |
β = 96.689 (9)° |
Stoe IPDS II two-circle diffractometer | 2690 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | 2137 reflections with I > 2σ(I) |
Tmin = 0.734, Tmax = 0.776 | Rint = 0.071 |
7213 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.06 | Δρmax = 1.18 e Å−3 |
2690 reflections | Δρmin = −1.05 e Å−3 |
128 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
In1 | 0.68156 (6) | 0.55896 (5) | 0.48517 (3) | 0.01843 (19) | |
Si1 | 0.7219 (3) | 0.3474 (2) | 0.60948 (13) | 0.0187 (4) | |
Cl1 | 0.7714 (3) | 0.7569 (2) | 0.53770 (17) | 0.0393 (6) | |
Cl2 | 0.7831 (2) | 0.4956 (2) | 0.36461 (13) | 0.0307 (5) | |
O1 | 0.8612 (6) | 0.4359 (6) | 0.5667 (4) | 0.0244 (12) | |
H1 | 0.9625 | 0.4348 | 0.5734 | 0.037* | |
O2 | 0.5676 (6) | 0.4189 (5) | 0.5548 (3) | 0.0204 (12) | |
C1 | 0.7289 (10) | 0.3914 (8) | 0.7195 (5) | 0.0254 (18) | |
C2 | 0.7414 (10) | 0.1756 (8) | 0.5789 (5) | 0.0226 (17) | |
C11 | 0.7197 (15) | 0.5382 (9) | 0.7256 (6) | 0.041 (2) | |
H11A | 0.6198 | 0.5684 | 0.6948 | 0.062* | |
H11B | 0.8125 | 0.5764 | 0.7037 | 0.062* | |
H11C | 0.7208 | 0.5631 | 0.7820 | 0.062* | |
C12 | 0.8855 (11) | 0.3459 (11) | 0.7679 (6) | 0.036 (2) | |
H12A | 0.9779 | 0.3840 | 0.7455 | 0.054* | |
H12B | 0.8922 | 0.2525 | 0.7650 | 0.054* | |
H12C | 0.8867 | 0.3723 | 0.8241 | 0.054* | |
C13 | 0.5859 (11) | 0.3317 (11) | 0.7559 (6) | 0.036 (2) | |
H13A | 0.4848 | 0.3594 | 0.7251 | 0.054* | |
H13B | 0.5878 | 0.3593 | 0.8120 | 0.054* | |
H13C | 0.5937 | 0.2382 | 0.7539 | 0.054* | |
C21 | 0.6107 (14) | 0.0905 (9) | 0.6096 (7) | 0.041 (2) | |
H21A | 0.5037 | 0.1243 | 0.5900 | 0.062* | |
H21B | 0.6244 | 0.0902 | 0.6685 | 0.062* | |
H21C | 0.6208 | 0.0030 | 0.5897 | 0.062* | |
C22 | 0.7227 (13) | 0.1705 (10) | 0.4862 (5) | 0.036 (2) | |
H22A | 0.6166 | 0.2041 | 0.4650 | 0.053* | |
H22B | 0.7324 | 0.0818 | 0.4685 | 0.053* | |
H22C | 0.8072 | 0.2225 | 0.4661 | 0.053* | |
C23 | 0.9093 (13) | 0.1224 (11) | 0.6097 (8) | 0.048 (3) | |
H23A | 0.9926 | 0.1765 | 0.5903 | 0.073* | |
H23B | 0.9193 | 0.0349 | 0.5896 | 0.073* | |
H23C | 0.9230 | 0.1217 | 0.6686 | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
In1 | 0.0170 (3) | 0.0180 (3) | 0.0200 (3) | −0.0025 (2) | 0.00106 (19) | 0.0021 (3) |
Si1 | 0.0209 (10) | 0.0174 (10) | 0.0171 (11) | 0.0002 (8) | −0.0006 (8) | 0.0005 (9) |
Cl1 | 0.0409 (12) | 0.0197 (11) | 0.0554 (16) | −0.0077 (9) | −0.0020 (11) | −0.0072 (11) |
Cl2 | 0.0239 (10) | 0.0467 (13) | 0.0217 (10) | −0.0016 (9) | 0.0034 (8) | −0.0012 (10) |
O1 | 0.016 (3) | 0.024 (3) | 0.033 (3) | −0.002 (2) | 0.003 (2) | 0.008 (3) |
O2 | 0.018 (2) | 0.019 (3) | 0.023 (3) | −0.004 (2) | −0.002 (2) | 0.004 (2) |
C1 | 0.031 (4) | 0.022 (4) | 0.023 (4) | 0.002 (4) | 0.003 (3) | 0.001 (4) |
C2 | 0.027 (4) | 0.017 (4) | 0.023 (4) | 0.001 (3) | 0.001 (3) | 0.003 (3) |
C11 | 0.069 (7) | 0.025 (5) | 0.031 (5) | 0.002 (5) | 0.010 (5) | −0.004 (4) |
C12 | 0.038 (5) | 0.051 (6) | 0.019 (4) | −0.006 (5) | −0.002 (4) | 0.003 (4) |
C13 | 0.038 (5) | 0.051 (6) | 0.020 (4) | −0.006 (5) | 0.003 (4) | −0.002 (5) |
C21 | 0.059 (7) | 0.019 (5) | 0.047 (6) | −0.008 (4) | 0.015 (5) | −0.004 (4) |
C22 | 0.059 (6) | 0.030 (5) | 0.019 (4) | 0.004 (4) | 0.010 (4) | −0.004 (4) |
C23 | 0.046 (6) | 0.034 (6) | 0.062 (8) | 0.016 (5) | −0.006 (5) | −0.009 (6) |
In1—O2i | 2.122 (5) | C11—H11A | 0.9800 |
In1—O2 | 2.160 (5) | C11—H11B | 0.9800 |
In1—O1 | 2.300 (6) | C11—H11C | 0.9800 |
In1—Cl1 | 2.337 (2) | C12—H12A | 0.9800 |
In1—Cl2 | 2.372 (2) | C12—H12B | 0.9800 |
In1—Si1 | 3.028 (2) | C12—H12C | 0.9800 |
In1—In1i | 3.3619 (11) | C13—H13A | 0.9800 |
Si1—O2 | 1.668 (6) | C13—H13B | 0.9800 |
Si1—O1 | 1.707 (6) | C13—H13C | 0.9800 |
Si1—C2 | 1.879 (9) | C21—H21A | 0.9800 |
Si1—C1 | 1.893 (9) | C21—H21B | 0.9800 |
O1—H1 | 0.8400 | C21—H21C | 0.9800 |
O2—In1i | 2.122 (5) | C22—H22A | 0.9800 |
C1—C12 | 1.530 (13) | C22—H22B | 0.9800 |
C1—C13 | 1.535 (12) | C22—H22C | 0.9800 |
C1—C11 | 1.541 (13) | C23—H23A | 0.9800 |
C2—C21 | 1.541 (13) | C23—H23B | 0.9800 |
C2—C23 | 1.540 (13) | C23—H23C | 0.9800 |
C2—C22 | 1.543 (12) | ||
O2i—In1—O2 | 76.5 (2) | C21—C2—C23 | 109.4 (8) |
O2i—In1—O1 | 142.7 (2) | C21—C2—C22 | 108.8 (8) |
O2—In1—O1 | 66.31 (19) | C23—C2—C22 | 107.8 (8) |
O2i—In1—Cl1 | 106.36 (16) | C21—C2—Si1 | 111.9 (6) |
O2—In1—Cl1 | 122.63 (17) | C23—C2—Si1 | 111.0 (6) |
O1—In1—Cl1 | 96.51 (17) | C22—C2—Si1 | 107.8 (6) |
O2i—In1—Cl2 | 101.33 (16) | C1—C11—H11A | 109.5 |
O2—In1—Cl2 | 119.54 (16) | C1—C11—H11B | 109.5 |
O1—In1—Cl2 | 94.36 (16) | H11A—C11—H11B | 109.5 |
Cl1—In1—Cl2 | 115.89 (9) | C1—C11—H11C | 109.5 |
O2i—In1—Si1 | 108.83 (15) | H11A—C11—H11C | 109.5 |
O2—In1—Si1 | 32.32 (15) | H11B—C11—H11C | 109.5 |
O1—In1—Si1 | 34.01 (14) | C1—C12—H12A | 109.5 |
Cl1—In1—Si1 | 112.51 (8) | C1—C12—H12B | 109.5 |
Cl2—In1—Si1 | 111.00 (7) | H12A—C12—H12B | 109.5 |
O2i—In1—In1i | 38.67 (14) | C1—C12—H12C | 109.5 |
O2—In1—In1i | 37.86 (14) | H12A—C12—H12C | 109.5 |
O1—In1—In1i | 104.12 (14) | H12B—C12—H12C | 109.5 |
Cl1—In1—In1i | 121.61 (7) | C1—C13—H13A | 109.5 |
Cl2—In1—In1i | 116.15 (6) | C1—C13—H13B | 109.5 |
Si1—In1—In1i | 70.17 (4) | H13A—C13—H13B | 109.5 |
O2—Si1—O1 | 92.7 (3) | C1—C13—H13C | 109.5 |
O2—Si1—C2 | 111.4 (3) | H13A—C13—H13C | 109.5 |
O1—Si1—C2 | 108.6 (3) | H13B—C13—H13C | 109.5 |
O2—Si1—C1 | 111.1 (3) | C2—C21—H21A | 109.5 |
O1—Si1—C1 | 109.3 (4) | C2—C21—H21B | 109.5 |
C2—Si1—C1 | 120.2 (4) | H21A—C21—H21B | 109.5 |
O1—Si1—In1 | 48.9 (2) | C2—C21—H21C | 109.5 |
C2—Si1—In1 | 121.1 (3) | H21A—C21—H21C | 109.5 |
C1—Si1—In1 | 118.7 (3) | H21B—C21—H21C | 109.5 |
Si1—O1—In1 | 97.1 (2) | C2—C22—H22A | 109.5 |
Si1—O1—H1 | 131.4 | C2—C22—H22B | 109.5 |
In1—O1—H1 | 131.6 | H22A—C22—H22B | 109.5 |
Si1—O2—In1i | 152.6 (3) | C2—C22—H22C | 109.5 |
Si1—O2—In1 | 103.9 (3) | H22A—C22—H22C | 109.5 |
In1i—O2—In1 | 103.5 (2) | H22B—C22—H22C | 109.5 |
C12—C1—C13 | 108.7 (8) | C2—C23—H23A | 109.5 |
C12—C1—C11 | 108.7 (8) | C2—C23—H23B | 109.5 |
C13—C1—C11 | 109.4 (8) | H23A—C23—H23B | 109.5 |
C12—C1—Si1 | 111.5 (6) | C2—C23—H23C | 109.5 |
C13—C1—Si1 | 110.5 (6) | H23A—C23—H23C | 109.5 |
C11—C1—Si1 | 108.0 (6) | H23B—C23—H23C | 109.5 |
O2i—In1—Si1—O2 | −1.7 (4) | C1—Si1—O2—In1 | 109.9 (4) |
O1—In1—Si1—O2 | −177.4 (4) | O2i—In1—O2—Si1 | 178.3 (4) |
Cl1—In1—Si1—O2 | 115.9 (3) | O1—In1—O2—Si1 | 1.6 (3) |
Cl2—In1—Si1—O2 | −112.4 (3) | Cl1—In1—O2—Si1 | −80.7 (3) |
In1i—In1—Si1—O2 | −1.1 (3) | Cl2—In1—O2—Si1 | 82.8 (3) |
O2i—In1—Si1—O1 | 175.6 (3) | In1i—In1—O2—Si1 | 178.3 (4) |
O2—In1—Si1—O1 | 177.4 (4) | O2i—In1—O2—In1i | 0.0 |
Cl1—In1—Si1—O1 | −66.7 (3) | O1—In1—O2—In1i | −176.7 (3) |
Cl2—In1—Si1—O1 | 65.0 (3) | Cl1—In1—O2—In1i | 101.0 (2) |
In1i—In1—Si1—O1 | 176.3 (3) | Cl2—In1—O2—In1i | −95.5 (2) |
O2i—In1—Si1—C2 | 87.5 (3) | Si1—In1—O2—In1i | −178.3 (4) |
O2—In1—Si1—C2 | 89.2 (4) | O2—Si1—C1—C12 | −170.0 (6) |
O1—In1—Si1—C2 | −88.2 (4) | O1—Si1—C1—C12 | −69.1 (7) |
Cl1—In1—Si1—C2 | −154.9 (3) | C2—Si1—C1—C12 | 57.4 (8) |
Cl2—In1—Si1—C2 | −23.2 (3) | In1—Si1—C1—C12 | −122.1 (6) |
In1i—In1—Si1—C2 | 88.1 (3) | O2—Si1—C1—C13 | 69.0 (7) |
O2i—In1—Si1—C1 | −93.0 (4) | O1—Si1—C1—C13 | 169.9 (6) |
O2—In1—Si1—C1 | −91.3 (4) | C2—Si1—C1—C13 | −63.6 (8) |
O1—In1—Si1—C1 | 91.3 (4) | In1—Si1—C1—C13 | 116.9 (6) |
Cl1—In1—Si1—C1 | 24.6 (3) | O2—Si1—C1—C11 | −50.6 (7) |
Cl2—In1—Si1—C1 | 156.3 (3) | O1—Si1—C1—C11 | 50.3 (7) |
In1i—In1—Si1—C1 | −92.4 (3) | C2—Si1—C1—C11 | 176.8 (6) |
O2—Si1—O1—In1 | 1.8 (3) | In1—Si1—C1—C11 | −2.7 (8) |
C2—Si1—O1—In1 | 115.5 (3) | O2—Si1—C2—C21 | −74.8 (7) |
C1—Si1—O1—In1 | −111.6 (3) | O1—Si1—C2—C21 | −175.5 (6) |
O2i—In1—O1—Si1 | −6.8 (5) | C1—Si1—C2—C21 | 57.7 (8) |
O2—In1—O1—Si1 | −1.5 (2) | In1—Si1—C2—C21 | −122.8 (6) |
Cl1—In1—O1—Si1 | 121.3 (2) | O2—Si1—C2—C23 | 162.6 (7) |
Cl2—In1—O1—Si1 | −122.0 (2) | O1—Si1—C2—C23 | 61.9 (8) |
In1i—In1—O1—Si1 | −3.6 (3) | C1—Si1—C2—C23 | −64.9 (8) |
O1—Si1—O2—In1i | 174.5 (7) | In1—Si1—C2—C23 | 114.6 (7) |
C2—Si1—O2—In1i | 63.3 (8) | O2—Si1—C2—C22 | 44.8 (7) |
C1—Si1—O2—In1i | −73.6 (8) | O1—Si1—C2—C22 | −55.9 (7) |
In1—Si1—O2—In1i | 176.5 (9) | C1—Si1—C2—C22 | 177.2 (6) |
O1—Si1—O2—In1 | −2.0 (3) | In1—Si1—C2—C22 | −3.3 (7) |
C2—Si1—O2—In1 | −113.2 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Cl2ii | 0.84 | 2.37 | 3.139 (6) | 153 |
Symmetry code: (ii) −x+2, −y+1, −z+1. |
[Li(C4H8O)4](C16H44BSi4) | F(000) = 728 |
Mr = 655.04 | Dx = 0.969 Mg m−3 |
Monoclinic, Pn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P -2yac | Cell parameters from 10358 reflections |
a = 10.5661 (7) Å | θ = 3.5–25.2° |
b = 11.7334 (10) Å | µ = 0.16 mm−1 |
c = 18.1342 (12) Å | T = 173 K |
β = 93.153 (5)° | Block, colourless |
V = 2244.8 (3) Å3 | 0.32 × 0.31 × 0.20 mm |
Z = 2 |
Stoe IPDS II two-circle diffractometer | 8399 independent reflections |
Radiation source: fine-focus sealed tube | 4944 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.089 |
ω scans | θmax = 25.7°, θmin = 3.5° |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | h = −12→12 |
Tmin = 0.951, Tmax = 0.969 | k = −14→14 |
30264 measured reflections | l = −22→22 |
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)] = 0.071 | H-atom parameters constrained |
wR(F2) = 0.135 | w = 1/[σ2(Fo2) + (0.0412P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max = 0.001 |
8399 reflections | Δρmax = 0.24 e Å−3 |
445 parameters | Δρmin = −0.24 e Å−3 |
91 restraints | Absolute structure: Flack (1983), with 4774 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.17 (16) |
[Li(C4H8O)4](C16H44BSi4) | V = 2244.8 (3) Å3 |
Mr = 655.04 | Z = 2 |
Monoclinic, Pn | Mo Kα radiation |
a = 10.5661 (7) Å | µ = 0.16 mm−1 |
b = 11.7334 (10) Å | T = 173 K |
c = 18.1342 (12) Å | 0.32 × 0.31 × 0.20 mm |
β = 93.153 (5)° |
Stoe IPDS II two-circle diffractometer | 8399 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | 4944 reflections with I > 2σ(I) |
Tmin = 0.951, Tmax = 0.969 | Rint = 0.089 |
30264 measured reflections |
R[F2 > 2σ(F2)] = 0.071 | H-atom parameters constrained |
wR(F2) = 0.135 | Δρmax = 0.24 e Å−3 |
S = 0.96 | Δρmin = −0.24 e Å−3 |
8399 reflections | Absolute structure: Flack (1983), with 4774 Friedel pairs |
445 parameters | Absolute structure parameter: 0.17 (16) |
91 restraints |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
B1 | 0.6387 (5) | 0.8507 (4) | 0.3473 (3) | 0.0323 (12) | |
Si1 | 0.49480 (14) | 1.05393 (11) | 0.27056 (8) | 0.0398 (4) | |
Si2 | 0.89748 (14) | 0.90862 (11) | 0.27955 (9) | 0.0395 (4) | |
Si3 | 0.50492 (14) | 0.61682 (11) | 0.31190 (9) | 0.0429 (4) | |
Si4 | 0.62049 (15) | 0.84902 (12) | 0.51766 (9) | 0.0474 (4) | |
C1 | 0.6006 (5) | 0.9899 (3) | 0.3450 (3) | 0.0339 (11) | |
H1A | 0.6814 | 1.0327 | 0.3456 | 0.041* | |
H1B | 0.5619 | 1.0071 | 0.3923 | 0.041* | |
C2 | 0.7496 (4) | 0.8221 (4) | 0.2871 (3) | 0.0331 (11) | |
H2A | 0.7058 | 0.8223 | 0.2374 | 0.040* | |
H2B | 0.7774 | 0.7427 | 0.2968 | 0.040* | |
C3 | 0.5100 (4) | 0.7742 (3) | 0.3251 (3) | 0.0320 (11) | |
H3A | 0.4729 | 0.8074 | 0.2786 | 0.038* | |
H3B | 0.4495 | 0.7911 | 0.3635 | 0.038* | |
C4 | 0.6979 (4) | 0.8142 (4) | 0.4312 (2) | 0.0343 (11) | |
H4A | 0.7842 | 0.8470 | 0.4363 | 0.041* | |
H4B | 0.7084 | 0.7304 | 0.4306 | 0.041* | |
C11 | 0.5156 (6) | 1.2147 (4) | 0.2692 (4) | 0.0593 (17) | |
H11A | 0.4601 | 1.2474 | 0.2297 | 0.089* | |
H11B | 0.6041 | 1.2331 | 0.2606 | 0.089* | |
H11C | 0.4935 | 1.2465 | 0.3168 | 0.089* | |
C12 | 0.5194 (6) | 1.0028 (5) | 0.1736 (3) | 0.0604 (16) | |
H12A | 0.4592 | 1.0412 | 0.1389 | 0.091* | |
H12B | 0.5058 | 0.9203 | 0.1709 | 0.091* | |
H12C | 0.6062 | 1.0204 | 0.1607 | 0.091* | |
C13 | 0.3231 (5) | 1.0295 (5) | 0.2871 (4) | 0.0626 (18) | |
H13A | 0.2704 | 1.0634 | 0.2467 | 0.094* | |
H13B | 0.3028 | 1.0648 | 0.3340 | 0.094* | |
H13C | 0.3065 | 0.9474 | 0.2892 | 0.094* | |
C21 | 0.9699 (5) | 0.9697 (4) | 0.3678 (3) | 0.0544 (15) | |
H21A | 1.0458 | 1.0134 | 0.3573 | 0.082* | |
H21B | 0.9931 | 0.9077 | 0.4021 | 0.082* | |
H21C | 0.9085 | 1.0200 | 0.3901 | 0.082* | |
C22 | 0.8715 (6) | 1.0356 (4) | 0.2163 (3) | 0.0587 (16) | |
H22A | 0.9506 | 1.0788 | 0.2144 | 0.088* | |
H22B | 0.8055 | 1.0847 | 0.2352 | 0.088* | |
H22C | 0.8448 | 1.0092 | 0.1666 | 0.088* | |
C23 | 1.0228 (6) | 0.8199 (5) | 0.2384 (4) | 0.0625 (17) | |
H23A | 1.1000 | 0.8655 | 0.2347 | 0.094* | |
H23B | 0.9928 | 0.7944 | 0.1890 | 0.094* | |
H23C | 1.0414 | 0.7534 | 0.2699 | 0.094* | |
C31 | 0.5869 (8) | 0.5299 (5) | 0.3898 (4) | 0.087 (3) | |
H31A | 0.5802 | 0.4485 | 0.3780 | 0.130* | |
H31B | 0.5461 | 0.5450 | 0.4361 | 0.130* | |
H31C | 0.6765 | 0.5516 | 0.3954 | 0.130* | |
C32 | 0.5764 (6) | 0.5715 (5) | 0.2244 (3) | 0.0669 (18) | |
H32A | 0.5723 | 0.4883 | 0.2201 | 0.100* | |
H32B | 0.6651 | 0.5962 | 0.2253 | 0.100* | |
H32C | 0.5293 | 0.6062 | 0.1822 | 0.100* | |
C33 | 0.3360 (6) | 0.5656 (5) | 0.3044 (4) | 0.0670 (18) | |
H33A | 0.3346 | 0.4827 | 0.2974 | 0.100* | |
H33B | 0.2910 | 0.6024 | 0.2621 | 0.100* | |
H33C | 0.2943 | 0.5849 | 0.3497 | 0.100* | |
C41 | 0.4445 (7) | 0.8366 (7) | 0.5125 (4) | 0.091 (2) | |
H41A | 0.4120 | 0.8572 | 0.5603 | 0.137* | |
H41B | 0.4202 | 0.7580 | 0.5002 | 0.137* | |
H41C | 0.4087 | 0.8881 | 0.4742 | 0.137* | |
C42 | 0.6583 (7) | 1.0008 (5) | 0.5488 (4) | 0.074 (2) | |
H42A | 0.6155 | 1.0171 | 0.5943 | 0.112* | |
H42B | 0.6287 | 1.0543 | 0.5101 | 0.112* | |
H42C | 0.7501 | 1.0090 | 0.5582 | 0.112* | |
C43 | 0.6859 (8) | 0.7602 (6) | 0.5977 (3) | 0.090 (3) | |
H43A | 0.6428 | 0.7806 | 0.6424 | 0.135* | |
H43B | 0.7770 | 0.7746 | 0.6057 | 0.135* | |
H43C | 0.6719 | 0.6793 | 0.5867 | 0.135* | |
Li1 | 0.0293 (10) | 0.4131 (8) | 0.4574 (6) | 0.062 (3) | |
O51 | −0.1117 (5) | 0.3835 (4) | 0.5165 (3) | 0.1044 (18) | |
C52 | −0.1713 (16) | 0.2805 (11) | 0.5287 (11) | 0.094 (5) | 0.69 (3) |
H52A | −0.1072 | 0.2201 | 0.5388 | 0.113* | 0.69 (3) |
H52B | −0.2245 | 0.2584 | 0.4843 | 0.113* | 0.69 (3) |
C53 | −0.2477 (19) | 0.2930 (11) | 0.5900 (10) | 0.103 (5) | 0.69 (3) |
H53A | −0.1986 | 0.2749 | 0.6366 | 0.123* | 0.69 (3) |
H53B | −0.3222 | 0.2418 | 0.5852 | 0.123* | 0.69 (3) |
C52' | −0.225 (3) | 0.296 (3) | 0.486 (2) | 0.096 (10) | 0.31 (3) |
H52C | −0.2696 | 0.3233 | 0.4395 | 0.115* | 0.31 (3) |
H52D | −0.1944 | 0.2170 | 0.4789 | 0.115* | 0.31 (3) |
C53' | −0.303 (3) | 0.308 (2) | 0.5508 (18) | 0.068 (9) | 0.31 (3) |
H53C | −0.3932 | 0.2974 | 0.5347 | 0.081* | 0.31 (3) |
H53D | −0.2797 | 0.2460 | 0.5862 | 0.081* | 0.31 (3) |
C54 | −0.2890 (8) | 0.4165 (7) | 0.5889 (5) | 0.099 (2) | |
H54A | −0.3028 | 0.4449 | 0.6392 | 0.119* | 0.69 (3) |
H54B | −0.3672 | 0.4278 | 0.5571 | 0.119* | 0.69 (3) |
H54C | −0.2739 | 0.4047 | 0.6427 | 0.119* | 0.31 (3) |
H54D | −0.3661 | 0.4636 | 0.5802 | 0.119* | 0.31 (3) |
C55 | −0.1744 (7) | 0.4740 (6) | 0.5563 (4) | 0.075 (2) | |
H55A | −0.2019 | 0.5364 | 0.5223 | 0.091* | |
H55B | −0.1166 | 0.5058 | 0.5960 | 0.091* | |
O61 | 0.0945 (4) | 0.5631 (3) | 0.4840 (2) | 0.0651 (12) | |
C62 | 0.0564 (9) | 0.6757 (6) | 0.4602 (4) | 0.095 (3) | |
H62A | −0.0353 | 0.6765 | 0.4455 | 0.114* | |
H62B | 0.1039 | 0.6989 | 0.4172 | 0.114* | |
C63 | 0.0829 (9) | 0.7551 (6) | 0.5219 (4) | 0.106 (3) | |
H63A | 0.1389 | 0.8175 | 0.5068 | 0.127* | |
H63B | 0.0031 | 0.7887 | 0.5382 | 0.127* | |
C64 | 0.1453 (8) | 0.6879 (6) | 0.5816 (4) | 0.089 (2) | |
H64A | 0.0860 | 0.6712 | 0.6206 | 0.106* | |
H64B | 0.2198 | 0.7289 | 0.6039 | 0.106* | |
C65 | 0.1854 (8) | 0.5791 (6) | 0.5441 (4) | 0.082 (2) | |
H65A | 0.2717 | 0.5871 | 0.5260 | 0.099* | |
H65B | 0.1846 | 0.5139 | 0.5787 | 0.099* | |
O71 | −0.0174 (5) | 0.4109 (3) | 0.3537 (3) | 0.0819 (14) | |
C72 | −0.0776 (19) | 0.3173 (9) | 0.3168 (8) | 0.084 (6) | 0.63 (3) |
H72A | −0.1575 | 0.2982 | 0.3400 | 0.101* | 0.63 (3) |
H72B | −0.0216 | 0.2496 | 0.3196 | 0.101* | 0.63 (3) |
C72' | 0.021 (4) | 0.314 (2) | 0.2894 (16) | 0.112 (11) | 0.37 (3) |
H72C | 0.1022 | 0.3299 | 0.2668 | 0.135* | 0.37 (3) |
H72D | 0.0179 | 0.2340 | 0.3069 | 0.135* | 0.37 (3) |
C73 | −0.1048 (11) | 0.3516 (7) | 0.2372 (5) | 0.133 (4) | |
H73A | −0.0714 | 0.2938 | 0.2035 | 0.160* | 0.63 (3) |
H73B | −0.1973 | 0.3593 | 0.2262 | 0.160* | 0.63 (3) |
H73C | −0.1175 | 0.3070 | 0.1910 | 0.160* | 0.37 (3) |
H73D | −0.1840 | 0.3564 | 0.2638 | 0.160* | 0.37 (3) |
C74 | −0.0419 (8) | 0.4603 (7) | 0.2280 (4) | 0.097 (3) | |
H74A | −0.0954 | 0.5120 | 0.1963 | 0.116* | |
H74B | 0.0403 | 0.4496 | 0.2053 | 0.116* | |
C75 | −0.0230 (8) | 0.5067 (6) | 0.3028 (4) | 0.088 (2) | |
H75A | 0.0568 | 0.5509 | 0.3075 | 0.105* | |
H75B | −0.0941 | 0.5578 | 0.3138 | 0.105* | |
O81 | 0.1599 (5) | 0.3009 (4) | 0.4784 (3) | 0.0883 (16) | |
C82 | 0.1561 (15) | 0.2048 (12) | 0.5278 (7) | 0.089 (4) | 0.74 (2) |
H82A | 0.0850 | 0.1533 | 0.5127 | 0.107* | 0.74 (2) |
H82B | 0.1454 | 0.2305 | 0.5790 | 0.107* | 0.74 (2) |
C83 | 0.2784 (16) | 0.1463 (14) | 0.5222 (9) | 0.127 (6) | 0.74 (2) |
H83A | 0.3174 | 0.1298 | 0.5719 | 0.152* | 0.74 (2) |
H83B | 0.2669 | 0.0736 | 0.4949 | 0.152* | 0.74 (2) |
C84 | 0.3582 (17) | 0.2247 (16) | 0.4822 (10) | 0.128 (7) | 0.74 (2) |
H84A | 0.4198 | 0.1827 | 0.4532 | 0.154* | 0.74 (2) |
H84B | 0.4047 | 0.2776 | 0.5165 | 0.154* | 0.74 (2) |
C85 | 0.2631 (13) | 0.2872 (12) | 0.4326 (7) | 0.086 (4) | 0.74 (2) |
H85A | 0.2966 | 0.3618 | 0.4173 | 0.104* | 0.74 (2) |
H85B | 0.2385 | 0.2418 | 0.3881 | 0.104* | 0.74 (2) |
C82' | 0.214 (3) | 0.243 (3) | 0.5476 (16) | 0.058 (9) | 0.26 (2) |
H82C | 0.1973 | 0.2914 | 0.5907 | 0.070* | 0.26 (2) |
H82D | 0.1687 | 0.1698 | 0.5538 | 0.070* | 0.26 (2) |
C83' | 0.337 (3) | 0.222 (3) | 0.5477 (17) | 0.075 (11) | 0.26 (2) |
H83C | 0.3501 | 0.1398 | 0.5574 | 0.091* | 0.26 (2) |
H83D | 0.3789 | 0.2642 | 0.5895 | 0.091* | 0.26 (2) |
C84' | 0.405 (4) | 0.253 (4) | 0.477 (3) | 0.114 (17) | 0.26 (2) |
H84C | 0.4888 | 0.2902 | 0.4863 | 0.136* | 0.26 (2) |
H84D | 0.4104 | 0.1896 | 0.4411 | 0.136* | 0.26 (2) |
C85' | 0.298 (4) | 0.334 (4) | 0.460 (3) | 0.121 (17) | 0.26 (2) |
H85C | 0.2972 | 0.3508 | 0.4063 | 0.145* | 0.26 (2) |
H85D | 0.3196 | 0.4062 | 0.4861 | 0.145* | 0.26 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
B1 | 0.038 (3) | 0.024 (2) | 0.036 (3) | −0.005 (2) | 0.005 (3) | 0.000 (2) |
Si1 | 0.0433 (9) | 0.0293 (7) | 0.0463 (9) | 0.0000 (7) | −0.0023 (7) | 0.0041 (7) |
Si2 | 0.0401 (9) | 0.0367 (8) | 0.0431 (9) | −0.0098 (7) | 0.0139 (7) | −0.0013 (7) |
Si3 | 0.0533 (11) | 0.0270 (7) | 0.0476 (9) | −0.0096 (7) | −0.0042 (7) | −0.0012 (6) |
Si4 | 0.0603 (11) | 0.0477 (9) | 0.0348 (8) | −0.0004 (8) | 0.0091 (7) | −0.0044 (7) |
C1 | 0.034 (3) | 0.031 (2) | 0.036 (3) | −0.004 (2) | 0.003 (2) | 0.001 (2) |
C2 | 0.031 (3) | 0.032 (2) | 0.036 (3) | −0.004 (2) | 0.006 (2) | −0.001 (2) |
C3 | 0.030 (3) | 0.027 (2) | 0.039 (3) | −0.003 (2) | 0.005 (2) | −0.008 (2) |
C4 | 0.034 (3) | 0.033 (2) | 0.036 (3) | −0.007 (2) | 0.002 (2) | 0.002 (2) |
C11 | 0.068 (5) | 0.033 (3) | 0.076 (4) | 0.003 (3) | −0.001 (4) | 0.009 (3) |
C12 | 0.076 (4) | 0.057 (3) | 0.047 (3) | 0.006 (3) | −0.010 (3) | 0.000 (3) |
C13 | 0.040 (4) | 0.057 (4) | 0.089 (5) | −0.003 (3) | −0.015 (3) | 0.001 (3) |
C21 | 0.049 (4) | 0.053 (3) | 0.062 (4) | −0.020 (3) | 0.006 (3) | −0.003 (3) |
C22 | 0.071 (4) | 0.054 (3) | 0.051 (4) | −0.026 (3) | 0.010 (3) | 0.010 (3) |
C23 | 0.048 (4) | 0.061 (4) | 0.081 (5) | −0.012 (3) | 0.025 (3) | −0.004 (3) |
C31 | 0.129 (6) | 0.034 (3) | 0.091 (5) | −0.014 (3) | −0.047 (5) | 0.014 (3) |
C32 | 0.069 (4) | 0.053 (3) | 0.079 (5) | −0.007 (3) | 0.008 (3) | −0.028 (3) |
C33 | 0.067 (4) | 0.056 (4) | 0.078 (5) | −0.021 (3) | 0.004 (3) | 0.003 (3) |
C41 | 0.085 (5) | 0.113 (6) | 0.080 (5) | −0.016 (5) | 0.036 (4) | −0.030 (4) |
C42 | 0.094 (5) | 0.061 (4) | 0.066 (5) | −0.006 (4) | −0.011 (4) | −0.015 (4) |
C43 | 0.148 (8) | 0.078 (5) | 0.046 (4) | 0.010 (5) | 0.019 (5) | 0.007 (3) |
Li1 | 0.065 (7) | 0.049 (5) | 0.074 (7) | 0.006 (5) | 0.008 (5) | −0.001 (5) |
O51 | 0.102 (4) | 0.073 (3) | 0.145 (5) | −0.015 (3) | 0.060 (4) | −0.012 (3) |
C52 | 0.100 (9) | 0.069 (6) | 0.114 (9) | −0.026 (6) | 0.032 (7) | −0.018 (6) |
C53 | 0.124 (9) | 0.080 (7) | 0.105 (8) | −0.023 (6) | 0.016 (7) | −0.008 (6) |
C52' | 0.113 (14) | 0.077 (12) | 0.098 (13) | −0.011 (9) | 0.014 (9) | −0.007 (9) |
C53' | 0.061 (11) | 0.056 (10) | 0.087 (12) | −0.013 (8) | 0.007 (8) | −0.006 (8) |
C54 | 0.113 (7) | 0.090 (6) | 0.096 (6) | 0.006 (5) | 0.022 (5) | 0.014 (5) |
C55 | 0.065 (5) | 0.075 (5) | 0.085 (5) | 0.011 (4) | 0.002 (4) | −0.008 (4) |
O61 | 0.081 (3) | 0.050 (2) | 0.063 (3) | 0.003 (2) | −0.011 (2) | −0.002 (2) |
C62 | 0.141 (8) | 0.059 (4) | 0.083 (6) | 0.024 (4) | −0.022 (5) | −0.006 (4) |
C63 | 0.140 (8) | 0.077 (5) | 0.098 (6) | 0.019 (5) | −0.023 (6) | −0.036 (5) |
C64 | 0.122 (7) | 0.086 (5) | 0.057 (5) | −0.042 (5) | 0.000 (5) | −0.011 (4) |
C65 | 0.101 (6) | 0.070 (5) | 0.075 (5) | −0.021 (4) | −0.009 (4) | 0.012 (4) |
O71 | 0.120 (4) | 0.050 (2) | 0.073 (3) | −0.013 (3) | −0.016 (3) | −0.006 (2) |
C72 | 0.110 (10) | 0.058 (7) | 0.082 (8) | −0.019 (6) | −0.021 (6) | −0.005 (5) |
C72' | 0.119 (15) | 0.097 (12) | 0.120 (14) | −0.009 (9) | −0.005 (9) | −0.008 (9) |
C73 | 0.194 (12) | 0.102 (7) | 0.099 (7) | −0.023 (7) | −0.034 (7) | −0.013 (6) |
C74 | 0.113 (7) | 0.106 (6) | 0.071 (5) | −0.025 (5) | 0.010 (5) | −0.016 (5) |
C75 | 0.107 (7) | 0.072 (4) | 0.086 (6) | −0.012 (4) | 0.006 (5) | 0.003 (4) |
O81 | 0.106 (4) | 0.067 (3) | 0.097 (4) | 0.033 (3) | 0.040 (3) | 0.033 (3) |
C82 | 0.103 (8) | 0.092 (7) | 0.073 (7) | 0.003 (6) | 0.005 (6) | 0.027 (6) |
C83 | 0.130 (9) | 0.122 (9) | 0.127 (9) | 0.045 (7) | −0.009 (7) | 0.036 (7) |
C84 | 0.095 (9) | 0.154 (10) | 0.138 (10) | 0.031 (8) | 0.020 (8) | 0.003 (8) |
C85 | 0.098 (7) | 0.081 (6) | 0.083 (7) | 0.026 (6) | 0.022 (6) | 0.012 (5) |
C82' | 0.056 (12) | 0.075 (12) | 0.045 (11) | −0.007 (8) | 0.018 (8) | 0.015 (8) |
C83' | 0.069 (13) | 0.094 (14) | 0.063 (13) | −0.001 (9) | 0.002 (9) | 0.013 (9) |
C84' | 0.11 (2) | 0.112 (19) | 0.116 (19) | −0.010 (10) | −0.002 (10) | 0.004 (10) |
C85' | 0.118 (19) | 0.123 (19) | 0.122 (19) | −0.002 (10) | 0.008 (10) | 0.000 (10) |
B1—C3 | 1.661 (7) | C53—C54 | 1.513 (16) |
B1—C4 | 1.669 (7) | C53—H53A | 0.9900 |
B1—C2 | 1.678 (7) | C53—H53B | 0.9900 |
B1—C1 | 1.683 (6) | C52'—C53' | 1.483 (10) |
Si1—C1 | 1.863 (5) | C52'—H52C | 0.9900 |
Si1—C13 | 1.877 (6) | C52'—H52D | 0.9900 |
Si1—C12 | 1.889 (5) | C53'—C54 | 1.45 (2) |
Si1—C11 | 1.900 (5) | C53'—H53C | 0.9900 |
Si2—C23 | 1.872 (6) | C53'—H53D | 0.9900 |
Si2—C2 | 1.874 (5) | C54—C55 | 1.533 (10) |
Si2—C21 | 1.878 (6) | C54—H54A | 0.9900 |
Si2—C22 | 1.891 (5) | C54—H54B | 0.9900 |
Si3—C3 | 1.862 (4) | C54—H54C | 0.9900 |
Si3—C32 | 1.871 (6) | C54—H54D | 0.9900 |
Si3—C33 | 1.881 (6) | C55—H55A | 0.9900 |
Si3—C31 | 1.912 (6) | C55—H55B | 0.9900 |
Si4—C4 | 1.854 (5) | O61—C65 | 1.425 (7) |
Si4—C41 | 1.862 (8) | O61—C62 | 1.441 (7) |
Si4—C43 | 1.887 (7) | C62—C63 | 1.471 (9) |
Si4—C42 | 1.904 (6) | C62—H62A | 0.9900 |
C1—H1A | 0.9900 | C62—H62B | 0.9900 |
C1—H1B | 0.9900 | C63—C64 | 1.466 (7) |
C2—H2A | 0.9900 | C63—H63A | 0.9900 |
C2—H2B | 0.9900 | C63—H63B | 0.9900 |
C3—H3A | 0.9900 | C64—C65 | 1.518 (10) |
C3—H3B | 0.9900 | C64—H64A | 0.9900 |
C4—H4A | 0.9900 | C64—H64B | 0.9900 |
C4—H4B | 0.9900 | C65—H65A | 0.9900 |
C11—H11A | 0.9800 | C65—H65B | 0.9900 |
C11—H11B | 0.9800 | O71—C72 | 1.419 (11) |
C11—H11C | 0.9800 | O71—C75 | 1.453 (7) |
C12—H12A | 0.9800 | O71—C72' | 1.70 (3) |
C12—H12B | 0.9800 | C72—C73 | 1.511 (15) |
C12—H12C | 0.9800 | C72—H72A | 0.9900 |
C13—H13A | 0.9800 | C72—H72B | 0.9900 |
C13—H13B | 0.9800 | C72'—C73 | 1.65 (3) |
C13—H13C | 0.9800 | C72'—H72C | 0.9900 |
C21—H21A | 0.9800 | C72'—H72D | 0.9900 |
C21—H21B | 0.9800 | C73—C74 | 1.452 (8) |
C21—H21C | 0.9800 | C73—H73A | 0.9900 |
C22—H22A | 0.9800 | C73—H73B | 0.9900 |
C22—H22B | 0.9800 | C73—H73C | 0.9900 |
C22—H22C | 0.9800 | C73—H73D | 0.9900 |
C23—H23A | 0.9800 | C74—C75 | 1.465 (9) |
C23—H23B | 0.9800 | C74—H74A | 0.9900 |
C23—H23C | 0.9800 | C74—H74B | 0.9900 |
C31—H31A | 0.9800 | C75—H75A | 0.9900 |
C31—H31B | 0.9800 | C75—H75B | 0.9900 |
C31—H31C | 0.9800 | O81—C85 | 1.416 (12) |
C32—H32A | 0.9800 | O81—C82 | 1.441 (11) |
C32—H32B | 0.9800 | O81—C82' | 1.51 (3) |
C32—H32C | 0.9800 | O81—C85' | 1.57 (4) |
C33—H33A | 0.9800 | C82—C83 | 1.472 (17) |
C33—H33B | 0.9800 | C82—H82A | 0.9900 |
C33—H33C | 0.9800 | C82—H82B | 0.9900 |
C41—H41A | 0.9800 | C83—C84 | 1.47 (2) |
C41—H41B | 0.9800 | C83—H83A | 0.9900 |
C41—H41C | 0.9800 | C83—H83B | 0.9900 |
C42—H42A | 0.9800 | C84—C85 | 1.502 (9) |
C42—H42B | 0.9800 | C84—H84A | 0.9900 |
C42—H42C | 0.9800 | C84—H84B | 0.9900 |
C43—H43A | 0.9800 | C85—H85A | 0.9900 |
C43—H43B | 0.9800 | C85—H85B | 0.9900 |
C43—H43C | 0.9800 | C82'—C83' | 1.32 (4) |
Li1—O51 | 1.914 (12) | C82'—H82C | 0.9900 |
Li1—O71 | 1.918 (12) | C82'—H82D | 0.9900 |
Li1—O81 | 1.930 (11) | C83'—C84' | 1.55 (6) |
Li1—O61 | 1.941 (10) | C83'—H83C | 0.9900 |
O51—C52 | 1.386 (12) | C83'—H83D | 0.9900 |
O51—C55 | 1.464 (8) | C84'—C85' | 1.496 (10) |
O51—C52' | 1.65 (3) | C84'—H84C | 0.9900 |
C52—C53 | 1.418 (15) | C84'—H84D | 0.9900 |
C52—H52A | 0.9900 | C85'—H85C | 0.9900 |
C52—H52B | 0.9900 | C85'—H85D | 0.9900 |
C3—B1—C4 | 110.0 (4) | C53—C54—C55 | 101.2 (8) |
C3—B1—C2 | 109.1 (4) | C53'—C54—H54A | 135.8 |
C4—B1—C2 | 107.6 (4) | C53—C54—H54A | 111.5 |
C3—B1—C1 | 109.1 (4) | C55—C54—H54A | 111.5 |
C4—B1—C1 | 110.4 (4) | C53'—C54—H54B | 77.4 |
C2—B1—C1 | 110.7 (4) | C53—C54—H54B | 111.5 |
C1—Si1—C13 | 111.7 (3) | C55—C54—H54B | 111.5 |
C1—Si1—C12 | 116.0 (2) | H54A—C54—H54B | 109.4 |
C13—Si1—C12 | 106.5 (3) | C53'—C54—H54C | 110.7 |
C1—Si1—C11 | 110.1 (2) | C53—C54—H54C | 79.8 |
C13—Si1—C11 | 105.5 (3) | C55—C54—H54C | 110.7 |
C12—Si1—C11 | 106.4 (3) | H54A—C54—H54C | 33.1 |
C23—Si2—C2 | 109.8 (2) | H54B—C54—H54C | 132.7 |
C23—Si2—C21 | 106.8 (3) | C53'—C54—H54D | 110.7 |
C2—Si2—C21 | 116.5 (2) | C53—C54—H54D | 140.4 |
C23—Si2—C22 | 106.2 (3) | C55—C54—H54D | 110.7 |
C2—Si2—C22 | 112.1 (2) | H54A—C54—H54D | 78.3 |
C21—Si2—C22 | 104.8 (3) | H54B—C54—H54D | 34.8 |
C3—Si3—C32 | 112.4 (3) | H54C—C54—H54D | 108.8 |
C3—Si3—C33 | 110.3 (3) | O51—C55—C54 | 105.0 (6) |
C32—Si3—C33 | 105.9 (3) | O51—C55—H55A | 110.7 |
C3—Si3—C31 | 115.2 (2) | C54—C55—H55A | 110.7 |
C32—Si3—C31 | 106.7 (3) | O51—C55—H55B | 110.7 |
C33—Si3—C31 | 105.8 (3) | C54—C55—H55B | 110.7 |
C4—Si4—C41 | 115.2 (3) | H55A—C55—H55B | 108.8 |
C4—Si4—C43 | 111.7 (3) | C65—O61—C62 | 105.9 (5) |
C41—Si4—C43 | 108.5 (4) | C65—O61—Li1 | 121.7 (5) |
C4—Si4—C42 | 111.2 (3) | C62—O61—Li1 | 131.9 (5) |
C41—Si4—C42 | 106.3 (3) | O61—C62—C63 | 108.3 (6) |
C43—Si4—C42 | 103.1 (3) | O61—C62—H62A | 110.0 |
B1—C1—Si1 | 122.8 (3) | C63—C62—H62A | 110.0 |
B1—C1—H1A | 106.6 | O61—C62—H62B | 110.0 |
Si1—C1—H1A | 106.6 | C63—C62—H62B | 110.0 |
B1—C1—H1B | 106.6 | H62A—C62—H62B | 108.4 |
Si1—C1—H1B | 106.6 | C64—C63—C62 | 106.3 (6) |
H1A—C1—H1B | 106.6 | C64—C63—H63A | 110.5 |
B1—C2—Si2 | 123.6 (3) | C62—C63—H63A | 110.5 |
B1—C2—H2A | 106.4 | C64—C63—H63B | 110.5 |
Si2—C2—H2A | 106.4 | C62—C63—H63B | 110.5 |
B1—C2—H2B | 106.4 | H63A—C63—H63B | 108.7 |
Si2—C2—H2B | 106.4 | C63—C64—C65 | 104.3 (6) |
H2A—C2—H2B | 106.5 | C63—C64—H64A | 110.9 |
B1—C3—Si3 | 125.8 (3) | C65—C64—H64A | 110.9 |
B1—C3—H3A | 105.9 | C63—C64—H64B | 110.9 |
Si3—C3—H3A | 105.9 | C65—C64—H64B | 110.9 |
B1—C3—H3B | 105.9 | H64A—C64—H64B | 108.9 |
Si3—C3—H3B | 105.9 | O61—C65—C64 | 105.1 (6) |
H3A—C3—H3B | 106.2 | O61—C65—H65A | 110.7 |
B1—C4—Si4 | 123.7 (3) | C64—C65—H65A | 110.7 |
B1—C4—H4A | 106.4 | O61—C65—H65B | 110.7 |
Si4—C4—H4A | 106.4 | C64—C65—H65B | 110.7 |
B1—C4—H4B | 106.4 | H65A—C65—H65B | 108.8 |
Si4—C4—H4B | 106.4 | C72—O71—C75 | 107.2 (6) |
H4A—C4—H4B | 106.5 | C72—O71—C72' | 43.3 (10) |
Si1—C11—H11A | 109.5 | C75—O71—C72' | 94.9 (11) |
Si1—C11—H11B | 109.5 | C72—O71—Li1 | 123.9 (7) |
H11A—C11—H11B | 109.5 | C75—O71—Li1 | 127.7 (5) |
Si1—C11—H11C | 109.5 | C72'—O71—Li1 | 128.7 (9) |
H11A—C11—H11C | 109.5 | O71—C72—C73 | 107.6 (9) |
H11B—C11—H11C | 109.5 | O71—C72—H72A | 110.2 |
Si1—C12—H12A | 109.5 | C73—C72—H72A | 110.2 |
Si1—C12—H12B | 109.5 | O71—C72—H72B | 110.2 |
H12A—C12—H12B | 109.5 | C73—C72—H72B | 110.2 |
Si1—C12—H12C | 109.5 | H72A—C72—H72B | 108.5 |
H12A—C12—H12C | 109.5 | C73—C72'—O71 | 90.0 (17) |
H12B—C12—H12C | 109.5 | C73—C72'—H72C | 113.6 |
Si1—C13—H13A | 109.5 | O71—C72'—H72C | 113.6 |
Si1—C13—H13B | 109.5 | C73—C72'—H72D | 113.6 |
H13A—C13—H13B | 109.5 | O71—C72'—H72D | 113.6 |
Si1—C13—H13C | 109.5 | H72C—C72'—H72D | 110.9 |
H13A—C13—H13C | 109.5 | C74—C73—C72 | 106.2 (8) |
H13B—C13—H13C | 109.5 | C74—C73—C72' | 86.7 (13) |
Si2—C21—H21A | 109.5 | C72—C73—C72' | 43.5 (11) |
Si2—C21—H21B | 109.5 | C74—C73—H73A | 110.5 |
H21A—C21—H21B | 109.5 | C72—C73—H73A | 110.5 |
Si2—C21—H21C | 109.5 | C72'—C73—H73A | 82.3 |
H21A—C21—H21C | 109.5 | C74—C73—H73B | 110.5 |
H21B—C21—H21C | 109.5 | C72—C73—H73B | 110.5 |
Si2—C22—H22A | 109.5 | C72'—C73—H73B | 153.4 |
Si2—C22—H22B | 109.5 | H73A—C73—H73B | 108.7 |
H22A—C22—H22B | 109.5 | C74—C73—H73C | 114.2 |
Si2—C22—H22C | 109.5 | C72—C73—H73C | 132.5 |
H22A—C22—H22C | 109.5 | C72'—C73—H73C | 114.2 |
H22B—C22—H22C | 109.5 | H73A—C73—H73C | 32.2 |
Si2—C23—H23A | 109.5 | H73B—C73—H73C | 78.0 |
Si2—C23—H23B | 109.5 | C74—C73—H73D | 114.2 |
H23A—C23—H23B | 109.5 | C72—C73—H73D | 70.7 |
Si2—C23—H23C | 109.5 | C72'—C73—H73D | 114.2 |
H23A—C23—H23C | 109.5 | H73A—C73—H73D | 132.8 |
H23B—C23—H23C | 109.5 | H73B—C73—H73D | 40.8 |
Si3—C31—H31A | 109.5 | H73C—C73—H73D | 111.4 |
Si3—C31—H31B | 109.5 | C73—C74—C75 | 105.1 (7) |
H31A—C31—H31B | 109.5 | C73—C74—H74A | 110.7 |
Si3—C31—H31C | 109.5 | C75—C74—H74A | 110.7 |
H31A—C31—H31C | 109.5 | C73—C74—H74B | 110.7 |
H31B—C31—H31C | 109.5 | C75—C74—H74B | 110.7 |
Si3—C32—H32A | 109.5 | H74A—C74—H74B | 108.8 |
Si3—C32—H32B | 109.5 | O71—C75—C74 | 107.5 (6) |
H32A—C32—H32B | 109.5 | O71—C75—H75A | 110.2 |
Si3—C32—H32C | 109.5 | C74—C75—H75A | 110.2 |
H32A—C32—H32C | 109.5 | O71—C75—H75B | 110.2 |
H32B—C32—H32C | 109.5 | C74—C75—H75B | 110.2 |
Si3—C33—H33A | 109.5 | H75A—C75—H75B | 108.5 |
Si3—C33—H33B | 109.5 | C85—O81—C82 | 108.9 (7) |
H33A—C33—H33B | 109.5 | C85—O81—C82' | 99.7 (13) |
Si3—C33—H33C | 109.5 | C82—O81—C82' | 32.3 (11) |
H33A—C33—H33C | 109.5 | C85—O81—C85' | 31.2 (18) |
H33B—C33—H33C | 109.5 | C82—O81—C85' | 112.6 (16) |
Si4—C41—H41A | 109.5 | C82'—O81—C85' | 89 (2) |
Si4—C41—H41B | 109.5 | C85—O81—Li1 | 121.8 (6) |
H41A—C41—H41B | 109.5 | C82—O81—Li1 | 127.8 (7) |
Si4—C41—H41C | 109.5 | C82'—O81—Li1 | 134.8 (12) |
H41A—C41—H41C | 109.5 | C85'—O81—Li1 | 117.0 (15) |
H41B—C41—H41C | 109.5 | O81—C82—C83 | 105.5 (10) |
Si4—C42—H42A | 109.5 | O81—C82—H82A | 110.6 |
Si4—C42—H42B | 109.5 | C83—C82—H82A | 110.6 |
H42A—C42—H42B | 109.5 | O81—C82—H82B | 110.6 |
Si4—C42—H42C | 109.5 | C83—C82—H82B | 110.6 |
H42A—C42—H42C | 109.5 | H82A—C82—H82B | 108.8 |
H42B—C42—H42C | 109.5 | C84—C83—C82 | 105.8 (10) |
Si4—C43—H43A | 109.5 | C84—C83—H83A | 110.6 |
Si4—C43—H43B | 109.5 | C82—C83—H83A | 110.6 |
H43A—C43—H43B | 109.5 | C84—C83—H83B | 110.6 |
Si4—C43—H43C | 109.5 | C82—C83—H83B | 110.6 |
H43A—C43—H43C | 109.5 | H83A—C83—H83B | 108.7 |
H43B—C43—H43C | 109.5 | C83—C84—C85 | 102.6 (12) |
O51—Li1—O71 | 112.3 (6) | C83—C84—H84A | 111.2 |
O51—Li1—O81 | 109.6 (5) | C85—C84—H84A | 111.2 |
O71—Li1—O81 | 109.1 (5) | C83—C84—H84B | 111.2 |
O51—Li1—O61 | 107.6 (5) | C85—C84—H84B | 111.2 |
O71—Li1—O61 | 108.9 (5) | H84A—C84—H84B | 109.2 |
O81—Li1—O61 | 109.2 (5) | O81—C85—C84 | 102.4 (10) |
C52—O51—C55 | 109.4 (7) | O81—C85—H85A | 111.3 |
C55—O51—C52' | 106.2 (10) | C84—C85—H85A | 111.3 |
C52—O51—Li1 | 128.5 (7) | O81—C85—H85B | 111.3 |
C55—O51—Li1 | 122.1 (5) | C84—C85—H85B | 111.3 |
C52'—O51—Li1 | 119.7 (9) | H85A—C85—H85B | 109.2 |
O51—C52—C53 | 108.6 (10) | C83'—C82'—O81 | 114 (2) |
O51—C52—H52A | 110.0 | C83'—C82'—H82C | 108.7 |
C53—C52—H52A | 110.0 | O81—C82'—H82C | 108.7 |
O51—C52—H52B | 110.0 | C83'—C82'—H82D | 108.7 |
C53—C52—H52B | 110.0 | O81—C82'—H82D | 108.7 |
H52A—C52—H52B | 108.4 | H82C—C82'—H82D | 107.6 |
C52—C53—C54 | 105.3 (11) | C82'—C83'—C84' | 117 (3) |
C52—C53—H53A | 110.7 | C82'—C83'—H83C | 108.0 |
C54—C53—H53A | 110.7 | C84'—C83'—H83C | 108.0 |
C52—C53—H53B | 110.7 | C82'—C83'—H83D | 108.0 |
C54—C53—H53B | 110.7 | C84'—C83'—H83D | 108.0 |
H53A—C53—H53B | 108.8 | H83C—C83'—H83D | 107.2 |
C53'—C52'—O51 | 95.4 (18) | C85'—C84'—C83' | 86 (3) |
C53'—C52'—H52C | 112.7 | C85'—C84'—H84C | 114.3 |
O51—C52'—H52C | 112.7 | C83'—C84'—H84C | 114.3 |
C53'—C52'—H52D | 112.7 | C85'—C84'—H84D | 114.3 |
O51—C52'—H52D | 112.7 | C83'—C84'—H84D | 114.3 |
C54—C53'—C52' | 114.6 (19) | H84C—C84'—H84D | 111.4 |
C54—C53'—H53C | 108.6 | C84'—C85'—O81 | 120 (3) |
C52'—C53'—H53C | 108.6 | C84'—C85'—H85C | 107.3 |
C54—C53'—H53D | 108.6 | O81—C85'—H85C | 107.3 |
C52'—C53'—H53D | 108.6 | C84'—C85'—H85D | 107.3 |
H53C—C53'—H53D | 107.6 | O81—C85'—H85D | 107.3 |
C53'—C54—C55 | 105.3 (10) | H85C—C85'—H85D | 106.9 |
C3—B1—C1—Si1 | −42.5 (5) | Li1—O61—C65—C64 | −140.4 (6) |
C4—B1—C1—Si1 | −163.5 (3) | C63—C64—C65—O61 | −29.4 (8) |
C2—B1—C1—Si1 | 77.5 (5) | O51—Li1—O71—C72 | −55.8 (13) |
C13—Si1—C1—B1 | 81.2 (4) | O81—Li1—O71—C72 | 65.9 (12) |
C12—Si1—C1—B1 | −41.1 (5) | O61—Li1—O71—C72 | −175.0 (11) |
C11—Si1—C1—B1 | −161.9 (4) | O51—Li1—O71—C75 | 110.6 (7) |
C3—B1—C2—Si2 | 167.8 (3) | O81—Li1—O71—C75 | −127.7 (7) |
C4—B1—C2—Si2 | −72.9 (4) | O61—Li1—O71—C75 | −8.5 (9) |
C1—B1—C2—Si2 | 47.8 (5) | O51—Li1—O71—C72' | −110.0 (18) |
C23—Si2—C2—B1 | 156.3 (4) | O81—Li1—O71—C72' | 11.7 (19) |
C21—Si2—C2—B1 | 34.8 (5) | O61—Li1—O71—C72' | 130.8 (18) |
C22—Si2—C2—B1 | −85.9 (4) | C75—O71—C72—C73 | 8.0 (16) |
C4—B1—C3—Si3 | −64.3 (5) | C72'—O71—C72—C73 | −70.5 (17) |
C2—B1—C3—Si3 | 53.5 (5) | Li1—O71—C72—C73 | 176.8 (9) |
C1—B1—C3—Si3 | 174.5 (3) | C72—O71—C72'—C73 | 55.4 (14) |
C32—Si3—C3—B1 | −72.4 (5) | C75—O71—C72'—C73 | −54.6 (15) |
C33—Si3—C3—B1 | 169.8 (4) | Li1—O71—C72'—C73 | 156.5 (7) |
C31—Si3—C3—B1 | 50.1 (5) | O71—C72—C73—C74 | 8.1 (17) |
C3—B1—C4—Si4 | −70.6 (4) | O71—C72—C73—C72' | 75.0 (17) |
C2—B1—C4—Si4 | 170.7 (3) | O71—C72'—C73—C74 | 67.4 (13) |
C1—B1—C4—Si4 | 49.8 (5) | O71—C72'—C73—C72 | −50.4 (12) |
C41—Si4—C4—B1 | 39.1 (5) | C72—C73—C74—C75 | −20.7 (13) |
C43—Si4—C4—B1 | 163.5 (4) | C72'—C73—C74—C75 | −60.1 (15) |
C42—Si4—C4—B1 | −82.0 (4) | C72—O71—C75—C74 | −21.3 (12) |
O71—Li1—O51—C52 | 75.1 (14) | C72'—O71—C75—C74 | 21.1 (15) |
O81—Li1—O51—C52 | −46.3 (15) | Li1—O71—C75—C74 | 170.4 (7) |
O61—Li1—O51—C52 | −165.0 (13) | C73—C74—C75—O71 | 26.2 (10) |
O71—Li1—O51—C55 | −104.2 (7) | O51—Li1—O81—C85 | 166.7 (9) |
O81—Li1—O51—C55 | 134.3 (6) | O71—Li1—O81—C85 | 43.3 (11) |
O61—Li1—O51—C55 | 15.6 (8) | O61—Li1—O81—C85 | −75.6 (11) |
O71—Li1—O51—C52' | 33.3 (18) | O51—Li1—O81—C82 | 2.5 (12) |
O81—Li1—O51—C52' | −88.1 (18) | O71—Li1—O81—C82 | −120.9 (10) |
O61—Li1—O51—C52' | 153.2 (17) | O61—Li1—O81—C82 | 120.2 (10) |
C55—O51—C52—C53 | −15.6 (15) | O51—Li1—O81—C82' | −40 (2) |
C52'—O51—C52—C53 | −107 (2) | O71—Li1—O81—C82' | −163 (2) |
Li1—O51—C52—C53 | 165.0 (10) | O61—Li1—O81—C82' | 78 (2) |
O51—C52—C53—C54 | 30.4 (16) | O51—Li1—O81—C85' | −158 (2) |
C52—O51—C52'—C53' | 64.9 (17) | O71—Li1—O81—C85' | 79 (2) |
C55—O51—C52'—C53' | −36 (2) | O61—Li1—O81—C85' | −40 (2) |
Li1—O51—C52'—C53' | −179.4 (14) | C85—O81—C82—C83 | 13.2 (15) |
O51—C52'—C53'—C54 | 28 (3) | C82'—O81—C82—C83 | −65 (2) |
C52'—C53'—C54—C53 | −99 (3) | C85'—O81—C82—C83 | −20 (3) |
C52'—C53'—C54—C55 | −11 (3) | Li1—O81—C82—C83 | 179.0 (9) |
C52—C53—C54—C53' | 69.0 (19) | O81—C82—C83—C84 | 11.9 (17) |
C52—C53—C54—C55 | −31.7 (13) | C82—C83—C84—C85 | −30.8 (17) |
C52—O51—C55—C54 | −5.4 (12) | C82—O81—C85—C84 | −32.1 (15) |
C52'—O51—C55—C54 | 31.7 (16) | C82'—O81—C85—C84 | −0.1 (19) |
Li1—O51—C55—C54 | 174.1 (6) | C85'—O81—C85—C84 | 71 (3) |
C53'—C54—C55—O51 | −14.2 (17) | Li1—O81—C85—C84 | 161.0 (10) |
C53—C54—C55—O51 | 22.3 (11) | C83—C84—C85—O81 | 38.3 (16) |
O51—Li1—O61—C65 | 86.5 (7) | C85—O81—C82'—C83' | 12 (3) |
O71—Li1—O61—C65 | −151.5 (6) | C82—O81—C82'—C83' | 123 (4) |
O81—Li1—O61—C65 | −32.5 (8) | C85'—O81—C82'—C83' | −17 (3) |
O51—Li1—O61—C62 | −83.4 (8) | Li1—O81—C82'—C83' | −145 (2) |
O71—Li1—O61—C62 | 38.7 (9) | O81—C82'—C83'—C84' | −3 (5) |
O81—Li1—O61—C62 | 157.7 (6) | C82'—C83'—C84'—C85' | 22 (5) |
C65—O61—C62—C63 | −22.5 (9) | C83'—C84'—C85'—O81 | −37 (5) |
Li1—O61—C62—C63 | 148.5 (7) | C85—O81—C85'—C84' | −74 (5) |
O61—C62—C63—C64 | 3.5 (11) | C82—O81—C85'—C84' | 15 (5) |
C62—C63—C64—C65 | 15.5 (10) | C82'—O81—C85'—C84' | 37 (5) |
C62—O61—C65—C64 | 31.8 (7) | Li1—O81—C85'—C84' | 178 (4) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [In2(C8H19O2Si)2Cl4] | [Li(C4H8O)4](C16H44BSi4) |
Mr | 722.08 | 655.04 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, Pn |
Temperature (K) | 173 | 173 |
a, b, c (Å) | 8.3467 (10), 10.453 (1), 16.7393 (18) | 10.5661 (7), 11.7334 (10), 18.1342 (12) |
β (°) | 96.689 (9) | 93.153 (5) |
V (Å3) | 1450.5 (3) | 2244.8 (3) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.06 | 0.16 |
Crystal size (mm) | 0.16 × 0.14 × 0.13 | 0.32 × 0.31 × 0.20 |
Data collection | ||
Diffractometer | Stoe IPDS II two-circle | Stoe IPDS II two-circle |
Absorption correction | Multi-scan (MULABS; Spek, 2009; Blessing, 1995) | Multi-scan (MULABS; Spek, 2009; Blessing, 1995) |
Tmin, Tmax | 0.734, 0.776 | 0.951, 0.969 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7213, 2690, 2137 | 30264, 8399, 4944 |
Rint | 0.071 | 0.089 |
(sin θ/λ)max (Å−1) | 0.607 | 0.609 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.140, 1.06 | 0.071, 0.135, 0.96 |
No. of reflections | 2690 | 8399 |
No. of parameters | 128 | 445 |
No. of restraints | 0 | 91 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.18, −1.05 | 0.24, −0.24 |
Absolute structure | ? | Flack (1983), with 4774 Friedel pairs |
Absolute structure parameter | ? | 0.17 (16) |
Computer programs: X-AREA (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 2008), publCIF (Westrip, 2010).
In1—O2i | 2.122 (5) | Si1—O2 | 1.668 (6) |
In1—O2 | 2.160 (5) | Si1—O1 | 1.707 (6) |
In1—O1 | 2.300 (6) | Si1—C2 | 1.879 (9) |
In1—Cl1 | 2.337 (2) | Si1—C1 | 1.893 (9) |
In1—Cl2 | 2.372 (2) | ||
O2i—In1—O1 | 142.7 (2) | O2—In1—Cl2 | 119.54 (16) |
O2—In1—Cl1 | 122.63 (17) | Cl1—In1—Cl2 | 115.89 (9) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Cl2ii | 0.84 | 2.37 | 3.139 (6) | 153.1 |
Symmetry code: (ii) −x+2, −y+1, −z+1. |
B1—C3 | 1.661 (7) | Si3—C3 | 1.862 (4) |
B1—C4 | 1.669 (7) | Si4—C4 | 1.854 (5) |
B1—C2 | 1.678 (7) | Li1—O51 | 1.914 (12) |
B1—C1 | 1.683 (6) | Li1—O71 | 1.918 (12) |
Si1—C1 | 1.863 (5) | Li1—O81 | 1.930 (11) |
Si2—C2 | 1.874 (5) | Li1—O61 | 1.941 (10) |
C3—B1—C4 | 110.0 (4) | B1—C3—Si3 | 125.8 (3) |
C3—B1—C2 | 109.1 (4) | B1—C4—Si4 | 123.7 (3) |
C4—B1—C2 | 107.6 (4) | O51—Li1—O71 | 112.3 (6) |
C3—B1—C1 | 109.1 (4) | O51—Li1—O81 | 109.6 (5) |
C4—B1—C1 | 110.4 (4) | O71—Li1—O81 | 109.1 (5) |
C2—B1—C1 | 110.7 (4) | O51—Li1—O61 | 107.6 (5) |
B1—C1—Si1 | 122.8 (3) | O71—Li1—O61 | 108.9 (5) |
B1—C2—Si2 | 123.6 (3) | O81—Li1—O61 | 109.2 (5) |
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Weakly coordinating anions have gained prominence in a wide variety of applications in both research laboratories and industry. One approach to create such anions is by the tetrasubstitution of trieles to [EX4]- (where E = B, Al, Ga or In). Normally, the use of alkyl substituents (X = R) is inadequate for this approach, because the [ER4]- anions are too reactive and most of them ignite in the presence of traces of water or oxygen. In contrast with alkyl substituents, alkoxy or alkynyl ligands can stabilize this type of anion {e.g. [EX4]- with X = C≡CSiMe3 or C≡CSi(iPr)3 (Lerner et al., 2007, 2012) or X = OC(CF3)3 (Reisinger et al., 2007)}. In addition, the related anions [E(cat)2]- (where cat is C6H4O22-, the catecholate dianion, as ligand for E3+ = B3+, Al3+, Ga3+ or In3+) also find applications, e.g. as electrolytes in cyclic voltammetry (Röder et al., 2008). In this context, weakly coordinating anions which are soluble in organic solvents are of great interest.
In the course of our long-standing studies of silanolate (siloxide) ligands (Kern et al., 2008; Kückmann et al., 2007; Lerner, 2005; Lerner et al., 2002, 2005), we have found a convenient preparation route for the silandiol tBu2Si(OH)2. Therefore, it was obvious to introduce tBu2Si(OH)2 as a chelating ligand to prepare the corresponding indium siloxide complexes. In a second approach, we prepared a novel alkyl-substituted borate, Li[B(CH2SiMe3)4], which possesses bulky silyl substituents on the chain ends. In this paper, we report the crystal structures of the indium siloxide [InCl2{O(HO)Si(tBu)2}]2, (I), and the lithium borate [Li(thf)4][B(CH2SiMe3)4] (thf is tetrahydrofuran), (II).
Siloxide (I) can be prepared from InCl3 and (tBu)2Si(OH)2, as shown in Scheme 1. When InCl3 was treated with an excess of the silandiol (tBu)2Si(OH)2 in the presence of +NEt3 in benzene at ambient temperature, [InCl2{O(HO)Si(tBu)2}]2 was formed, rather than [InCl{O2Si(tBu)2}] or {[In{O2Si(tBu)2}]2}-. X-ray quality crystals of (I) were grown from the reaction solution at ambient temperature.
Another approach to creating weakly coordinating anions is to stabilize alkyl-substituted borates using bulky end groups, e.g. SiMe3. Therefore, we decided to prepare [Li(thf)4][B(CH2SiMe3)4], (II), which was synthesized in good yield from BCl3 and Li[CH2SiMe3], as shown in Scheme 2. X-ray quality crystals of (II) were obtained from a hexane solution at ambient temperature.
Compound (I) features a centrosymmetric two-centre indium complex (Fig. 1). Each In centre is pentacoordinated by two terminal chloride ligands and three O atoms. The two In—Cl bonds are of comparable length, but there are two short In—O bonds to bridging O atoms and a longer In—O bond to the hydroxy O atom (Table 1). The central In2O2 ring is exactly planar due to inversion symmetry. The InSiO2 rings are essentially planar (r.m.s. deviation = 0.024 Å) and close to coplanar with the In2O2 ring, with a dihedral angle of 3.0 (4)° between the two rings. The coordination geometry of the In centres can be described as a distorted trigonal bipyramid. The bond angle between the two axial ligands, the hydroxy O atom and one of the bridging O atoms [142.7 (2)°] is significantly distorted from idealized linear geometry, but the bond angles in the equatorial plane are reasonably close to the ideal value of 120° (Table 1). The Si—O bond to the hydroxy O atom is significantly longer than that to the bridging O atom, but the two Si—C bonds are not significantly different (Table 1). In the crystal structure, molecules of (I) are linked by O—H···Cl hydrogen bonds into chains running along the a axis (Fig. 2 and Table 2). There are no further short contacts between the molecules. This structure is the first example of an In2O2 ring which is annulated with two Si—O units to form a ring system composed of three rings [Cambridge Structural Database (CSD), Version 5.34, November 2012 plus one update; Allen, 2002]. A search of the CSD for an In2O2 ring with the In atoms carrying any two halogen ligands gave no hits. However, a search for just an In2O2 ring yielded 36 hits, with a mean In—O bond length of 2.24 (7) Å, which is slightly longer than the In—O bond lengths [2.122 (5) and 2.160 (5) Å] in the In2O2 ring of (I).
Compound (II) crystallizes with discrete tetrakis(thf)lithium cations and tetrakis[(trimethylsilyl)methyl]borate anions in the asymmetric unit (Fig. 3). The coordination geometry around the Li atom is tetrahedral, with three Li—O bonds of almost equal length and one slightly longer one. All the O—Li—O angles are close to idealized tetrahedral values (Table 3). The B atom is also tetrahedrally coordinated. There are no appreciable differences between the B—C bonds and all C—B—C angles are close to the ideal tetrahedral value (Table 3). It is noteworthy that all four B—C—Si angles are significantly widened to more than 120°, due to steric repulsion between the SiMe3 and BC3 units (Table 3). The crystal packing of (II) shows that the molecules are located in planes parallel to (110) (Fig. 4), within which the cations and anions adopt alternating positions. There are no short contacts, either between molecules within the plane or between adjacent planes. Compound (II) is the first example of a structure with a boron centre bonded to four –CH2Si units (CSD). A search of the CSD for the B(CH2)4 fragment yielded nine hits. Eight of these were for tetraethylborate and one was a tetra-n-butylborate. The mean B—C bond length in all these fragments is 1.65 (1) Å, which is not significantly different from the mean B—C bond [1.67 (1) Å] in (II).