research communications
Crystal structures, Hirshfeld atom refinements and Hirshfeld surface analyses of tris(4,5-dihydrofuran-2-yl)methylsilane and tris(4,5-dihydrofuran-2-yl)phenylsilane
aTechnische Universität Dortmund, Fakultät Chemie und Chemische Biologie, Otto-Hahn-Strasse 6, 44227 Dortmund, Germany
*Correspondence e-mail: carsten.strohmann@tu-dortmund.de
The title compounds, C13H18O3Si (1) and C18H20O3Si (2), represent functionalizable dihydrofuranylsilanes, which permit substitution by a variety of nucleophiles. The crystal structures of 1 and 2 display weak intermolecular C—H⋯O hydrogen-bonding interactions (quantified by Hirshfeld surface analysis), leading to a two-dimensional supramolecular network for 1 and a one-dimensional supramolecular network for 2. The crystal structures of 1 and 2 were refined both on the basis of the independent atom model (IAM) and the Hirshfeld atom (HAR) approach, and the results are comparatively discussed.
1. Chemical context
Tris(4,5-dihydrofuran-2-yl)methylsilane (1) and -phenylsilane (2) are interesting starting materials for the selective synthesis of functionalized organosilanes in molecular chemistry.
In the 1980s, Lukevits and co-workers first introduced the dihydrofuranyl group (DHF) as a substitutable silicon-carbon et al., 1989). The DHF group allows substitution by a number of nucleophiles including hydrides, lithiated lithium alkyls and (Lukevits et al., 1993). Multiple nucleophilic substitutions using chlorosilanes show high reactivity and low selectivity. In general, the Si—O bond shows high reactivity and selectivity compared to the less or even non-reactive Si—C bond. Nonetheless, the DHF group shows a significant increase in reactivity and selectivity in the bond cleavage of Si—C bonds, which can extend the selectivity profile of functionalized organosilanes (Koller et al., 2017). Furthermore, the pre-coordination by a methoxy group plays an important role in the control of reactions with metal-containing nucleophiles and leads to the question of whether this also applies to the DHF group (Barth et al., 2019). In order to understand the coordination possibilities, the alignment of the dihydrofuranyl group and thus the arrangement of the oxygen atoms in the are interesting. In this context, we here report the crystal structures of 1 and 2, both refined on basis of the independent atom model (IAM) and a Hirshfeld atom (HAR) approach.
(Gevorgyan2. Structural commentary
The molecular structure of compound 1 is illustrated in Fig. 1, and selected bond lengths and angles using the results of IAM and HAR refinements are given in Table 1. In the molecule of 1, the Si—C bond lengths of the silicon–DHF groups are in a typical range and slightly longer than the silicon–methyl bond length. However, all Si—C bonds are as expected (Allen et al., 1987). The silicon atom in 1 has a slightly distorted tetrahedral environment, as shown by the deviation of the C—Si—C angles from the ideal value of 109.47°. This flexibility is often observed for Si—C single bonds (Otte et al., 2017; Glidewell & Sheldrick, 1971; Kückmann et al., 2005). The length of each of the C=C double bonds of the DHF groups (C1=C2, C5=C6, C9=C10) also corresponds well with the literature (Allen et al., 1987).
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The molecular structure of compound 2 is depicted in Fig. 2, and selected bond lengths and angles using the results of IAM and HAR refinements are collated in Table 2. The Si—C bond lengths and angles in the molecule of 2 differ only marginally from those of 1. In 2, there is a weak intramolecular C2—H2⋯O3 hydrogen-bonding interaction between the H2 atom of the C1=C2 group of one DHF molecule and the O3 atom of a neighbouring DHF group (Table 4), leading to a graph-set motif S11(6) (Etter et al., 1990).
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The Si—C bond lengths and C—Si—C angles of the IAM and HAR refinements coincide well. Slight deviations in the C=C double bond of the DHF group can be observed and the trend shows that the double bonds from HAR
are slightly longer.3. Hirshfeld atom refinements
The independent atom model (IAM) approach for crystal-structure ab initio quantum-mechanical electron densities. This approach allows for an accurate localization of hydrogen atoms, bonding electrons and an anisotropic of hydrogen atoms (Jayatilaka & Dittrich, 2008; Capelli et al., 2014).
cannot reliably model bonding electrons or any distortion of the electron density. An approach that takes this into consideration is Hirshfeld atom (HAR), which uses aspherical atomic scattering factors calculated from tailor-madeIn previous (unpublished) structure refinements of compounds with dihydrofuranyl rings performed by our group, we observed slight disorders of the oxygen atom and the methine atom of the dihydrofuranyl ring. Therefore, results of HARs for such compounds are interesting in order to draw conclusions about the residual electron densities to exclude and/or model disorder. For 1 and 2, the minimum and maximum values of residual electron density are significantly lower than those of IAM results (1: IAM Δρmin = −0.21 e Å−3, Δρmax = 0.55 e Å−3; HAR Δρmin,max = ±0.21 e Å−3; 2: IAM Δρmin = −0.23 e Å−3, Δρmax = 0.47 e Å−3; HAR Δρmin = −0.17 e Å−3, Δρmax = 0.26 e Å−3). In all cases, the residual densities do not indicate any disorder. For compound 1, the residual electron density on the basis of the HAR is close to O1 and H8A and for 2 is near C15 and H3B. Another aim of the Hirshfeld atom was the accurate localization of hydrogen atoms. From a comparison of the C—H bond lengths of the methine groups using IAM and HAR approaches, it can be clearly observed that the C—H bonds of the HAR model are significantly longer than those of the AIM model (Table 5). Woińska et al. (2016) have already reported that the positions of hydrogen atoms and their corresponding bond lengths show a significantly improved agreement with neutron diffraction by with HAR.
When using HAR, an improved R1 value of 0.023 was observed for compound 1, compared to the using IAM with an R1 value of 0.035 (compound 2: R1 for HAR = 0.024 versus IAM = 0.037).
4. Hirshfeld analyses and supramolecular features
In the crystal of compound 1, the molecules are linked by a number of C—H⋯O hydrogen bonds, forming a network along the [012] direction (Fig. 3, Table 3). Considering the C⋯O distances, the strength of the hydrogen bonds can be classified as weak according to Desiraju & Steiner (1999). Hydrogen bonds C6—H6⋯O1i and C11—H11A⋯O2i lead to the formation of chains described by the graph-set motifs C11(6) and C11(7), respectively. The third hydrogen bond, C8—H8A⋯O3ii, leads to rings with graph-set motif R22(14) (Etter et al., 1990). For the C11—H11A⋯O2i hydrogen bond, a significant interaction can be visualized using Hirshfeld surface analysis (Spackman & Jayatilaka, 2009) generated by CrystalExplorer (Turner et al., 2017), here indicated by the red spots (Fig. 4). The Hirshfeld surface mapped over dnorm is in the range from −0.1450 to 1.0518 a.u. The contributions of different types of intermolecular interactions for 1 are shown in the two-dimensional fingerprint plots (McKinnon et al., 2007) in Fig. 5. On the Hirshfeld surface, the weak van der Waals H⋯H contacts appear in the largest region (73.5% contribution). The fingerprint plot for the O⋯H/H⋯O (18.9%) interactions shows sharp spikes, which highlight the hydrogen bond between two molecules. The C⋯H/H⋯C (7.5%) interactions also appear as two spikes. In summary, H⋯H, C⋯H/H⋯C and especially O⋯H/H⋯O are significant contributors, suggesting the relevance of these contacts in the packing arrangement of the crystal structure.
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The crystal packing of compound 2 is illustrated in Fig. 6 and shows a ribbon-like supramolecular network structure propagating along the b-axis direction. The molecules are linked by a C—H⋯O hydrogen bond between the O2i atom of a DHF group and the C16—H16para group of the phenyl ring (Table 4), leading to the formation of chains with graph-set motif C11(8). Compared to compound 1 where the methyl group shows no hydrogen-bonding interactions, the phenyl group is important for the crystal packing, as emphasized in Fig. 7. Again, the strengths of the hydrogen bonds can be classified as weak (Desiraju & Steiner, 1999). A Hirshfeld surface analysis of 2 was carried out with dnorm in the range from −0.1662 to 1.2663 a.u.. The characteristic red spots in Fig. 8 indicate the C16—H16⋯O2i interactions. The two-dimensional fingerprint plots are displayed in Fig. 9. Compared to compound 1, the C⋯H/H⋯C contacts appear to be more important for 2 than the O⋯H/H⋯O contacts. Nevertheless, H⋯H, C⋯H/H⋯C and O⋯H/H⋯O are likewise significant contributors to the packing arrangement within the crystal structure.
5. Synthesis and crystallization
5-Lithio-2,3-dihydrofuran was prepared as described in the literature (Gevorgyan et al., 1990). The subsequent implementation of the lithiated species with the chlorosilane was also carried out as previously described (Erchak et al., 1981; Gevorgyan et al., 1997).
Tris(4,5-dihydrofuran-2-yl)methylsilane (1) is a colourless crystalline solid at room temperature:
1H NMR (400 MHz, C6H6): δ = 0.65 (s, 3H; SiCH3), 2.25 [dt, 3JHH = 2.57 Hz, 3JHH = 9.66 Hz, 6H; Si(CCHCH2)3], 4.06 [t, 3JHH = 9.66 Hz, 6H; Si(COCH2)3], 5.59 [t, 3JHH = 2.57 Hz, 3H; Si(CCH)3] ppm.
{1H}13C NMR (100 MHz, C6H6): δ = −5.7 (1C; SiCH3), 31.4 [3C; Si(CCHCH2)3], 70.9 [3C; Si(COCH2)3], 115.6 [3C; Si(CCH)3], 157.5 [3C; Si(CO)3] ppm.
{1H}29Si NMR (79 MHz, C6H6): −36.65 [1Si; Si(DHF)3] ppm.
GC/EI–MS tR = 5.40 min [353 K (1 min) – 40 K min−1 – 543 K (5.5 min)]; m/z (%): 250 (100) [M+], 207 (4) [(M − C2H3O)+], 121 (56) [(DHFSiCCH]+], 97 (13) [(SiDHF)+].
Tris(4,5-dihydrofuran-2-yl)phenylsilane (2) is a colourless crystalline solid at room temperature:
1H NMR (400 MHz, C6H6): δ = 2.25 [dt, 3JHH = 2.57 Hz, 3JHH = 9.66 Hz, 6H; Si(CCHCH2)3], 4.07 [t, 3JHH = 9.66 Hz, 6H; Si(COCH2)3], 5.72 [t, 3JHH = 2.57 Hz, 3H; Si(CCH)3], 7.18–7.27 (m, 3H; Ph–Hortho,para), 8.11–8.14 (m, 2H; Ph–Hmeta) ppm.
{1H}13C NMR (100 MHz, C6H6): δ = 31.4 [3C; Si(CCHCH2)3], 71.1 [3C; Si(COCH2)3]; 117.8 [3C; Si(CCH)3]; 128.4 (2C; Ph–Cortho); 130.8 (1C, Ph–Cpara); 134.3 (1C; Ph–Cipso); 136.3 (2C; Ph–Cmeta); 156.4 [3C; Si(CO)3] ppm.
{1H}29Si NMR (79 MHz, C6H6): −41.74 [1Si; Si(DHF)3] ppm.
GC/EI–MS tR = 6.88 min [353 K (1 min) – 40 K min−1 – 543 K(5.5 min)]; m/z (%): 312 (100) [M+], 255 (21) [(M − C3H5O)+], 105 (53) [(SiPh]+], 77 (12) [Ph+], 69 (6) [DHF+].
6. Refinement
Crystal data, data collection and structure . For the IAM approach using SHELXL (Sheldrick, 2015b), the H atoms were positioned geometrically (C—H = 0.95–1.00 Å) and were refined using a riding model, with Uiso(H) = 1.2Ueq(C) for CH2 and CH hydrogen atoms and Uiso(H) = 1.5Ueq(C) for CH3 hydrogen atoms. Hydrogen atoms H6, H8A,B and H11A,B for compound 1 and H2 and H16 for compound 2 were refined independently.
details are summarized in Table 6
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HARs were performed with the HARt implementation in OLEX2 (Dolomanov et al., 2009), using the restricted Khom–Sham method with the basis set x2c-TZVP. The results of previous IAM refinements using - served as an input (Fugel et al., 2018). For the HAR approach, all H atoms were refined anistropically and independently.
Supporting information
https://doi.org/10.1107/S2056989020011470/wm5561sup1.cif
contains datablocks 1, 1HAR, 2, 2HAR. DOI:Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989020011470/wm55611sup2.hkl
Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989020011470/wm55612sup3.hkl
Structure factors: contains datablock 1HAR. DOI: https://doi.org/10.1107/S2056989020011470/wm55611HARsup4.hkl
Structure factors: contains datablock 2HAR. DOI: https://doi.org/10.1107/S2056989020011470/wm55612HARsup5.hkl
Data collection: APEX2 (Bruker, 2018) for (1), (2). Cell
SAINT (Bruker, 2016) for (1), (2). Data reduction: SAINT (Bruker, 2016) for (1), (2). For all structures, program(s) used to solve structure: SHELXT (Sheldrick, 2015a). Program(s) used to refine structure: SHELXL (Sheldrick, 2015b) for (1), (2); TONTO (Jayatilaka & Grimwood, 2003) for 1HAR, 2HAR. Molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2020) for (1), (2). Software used to prepare material for publication: publCIF (Westrip, 2010) for (1), (2).C13H18O3Si | F(000) = 536 |
Mr = 250.36 | Dx = 1.273 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.9801 (4) Å | Cell parameters from 9906 reflections |
b = 12.2381 (5) Å | θ = 2.3–36.3° |
c = 13.3712 (7) Å | µ = 0.17 mm−1 |
β = 90.134 (2)° | T = 100 K |
V = 1305.84 (11) Å3 | Block, colourless |
Z = 4 | 0.39 × 0.14 × 0.07 mm |
Bruker D8 Venture diffractometer | 5737 independent reflections |
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs | 4936 reflections with I > 2σ(I) |
HELIOS mirror optics monochromator | Rint = 0.034 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 35.0°, θmin = 2.3° |
ω and φ scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | k = −19→19 |
Tmin = 0.536, Tmax = 0.567 | l = −21→21 |
51391 measured reflections |
Refinement on F2 | Primary atom site location: iterative |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: mixed |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.048P)2 + 0.3601P] where P = (Fo2 + 2Fc2)/3 |
5737 reflections | (Δ/σ)max = 0.001 |
175 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Si1 | 0.18345 (3) | 0.59411 (2) | 0.25638 (2) | 0.01471 (6) | |
O1 | 0.35857 (8) | 0.66915 (6) | 0.09264 (5) | 0.02745 (14) | |
O2 | 0.27937 (10) | 0.62127 (6) | 0.45636 (5) | 0.02791 (14) | |
O3 | −0.09090 (9) | 0.45569 (7) | 0.22765 (6) | 0.02990 (15) | |
C5 | 0.23012 (9) | 0.54481 (6) | 0.38536 (6) | 0.01714 (13) | |
C9 | 0.06571 (10) | 0.48340 (6) | 0.19167 (6) | 0.01715 (13) | |
C1 | 0.37989 (10) | 0.61563 (7) | 0.18350 (6) | 0.01739 (13) | |
C6 | 0.21595 (12) | 0.44438 (7) | 0.42270 (7) | 0.02353 (16) | |
C2 | 0.53927 (11) | 0.59006 (9) | 0.20150 (6) | 0.02569 (18) | |
H2 | 0.578431 | 0.552875 | 0.259375 | 0.031* | |
C4 | 0.51776 (11) | 0.66560 (9) | 0.04067 (7) | 0.02635 (17) | |
H4A | 0.546606 | 0.738778 | 0.014252 | 0.032* | |
H4B | 0.512329 | 0.613546 | −0.015913 | 0.032* | |
C13 | 0.06191 (11) | 0.72335 (7) | 0.25968 (7) | 0.02361 (16) | |
H13A | −0.045763 | 0.710554 | 0.292773 | 0.035* | |
H13B | 0.042121 | 0.748958 | 0.191220 | 0.035* | |
H13C | 0.125193 | 0.778791 | 0.296792 | 0.035* | |
C10 | 0.11013 (13) | 0.42563 (8) | 0.11202 (8) | 0.02825 (18) | |
H10 | 0.213876 | 0.432901 | 0.077964 | 0.034* | |
C7 | 0.26064 (14) | 0.44446 (9) | 0.53240 (7) | 0.02880 (19) | |
H7A | 0.365266 | 0.403255 | 0.545241 | 0.035* | |
H7B | 0.169216 | 0.413336 | 0.573425 | 0.035* | |
C11 | −0.02632 (16) | 0.34719 (9) | 0.08321 (10) | 0.0370 (2) | |
C3 | 0.64834 (11) | 0.62855 (10) | 0.11701 (7) | 0.0310 (2) | |
H3A | 0.718425 | 0.568501 | 0.090423 | 0.037* | |
H3B | 0.721462 | 0.689775 | 0.138009 | 0.037* | |
C8 | 0.28359 (15) | 0.56597 (9) | 0.55268 (7) | 0.03038 (19) | |
C12 | −0.14684 (16) | 0.36115 (9) | 0.16999 (10) | 0.0395 (3) | |
H12A | −0.262120 | 0.373096 | 0.144753 | 0.047* | |
H12B | −0.146562 | 0.294897 | 0.212480 | 0.047* | |
H6 | 0.1832 (19) | 0.3836 (12) | 0.3884 (11) | 0.035 (4)* | |
H8A | 0.1907 (19) | 0.5968 (12) | 0.5948 (11) | 0.035 (4)* | |
H11A | 0.015 (2) | 0.2753 (16) | 0.0766 (12) | 0.053 (5)* | |
H8B | 0.392 (2) | 0.5853 (13) | 0.5845 (12) | 0.042 (4)* | |
H11B | −0.076 (2) | 0.3644 (14) | 0.0192 (13) | 0.047 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1 | 0.01370 (9) | 0.01620 (10) | 0.01424 (9) | 0.00092 (6) | 0.00108 (7) | −0.00036 (6) |
O1 | 0.0200 (3) | 0.0374 (4) | 0.0249 (3) | 0.0039 (2) | 0.0039 (2) | 0.0152 (3) |
O2 | 0.0421 (4) | 0.0257 (3) | 0.0159 (3) | −0.0068 (3) | −0.0033 (3) | −0.0018 (2) |
O3 | 0.0213 (3) | 0.0398 (4) | 0.0286 (3) | −0.0118 (3) | 0.0024 (2) | −0.0029 (3) |
C5 | 0.0158 (3) | 0.0207 (3) | 0.0149 (3) | 0.0010 (2) | 0.0013 (2) | −0.0010 (2) |
C9 | 0.0165 (3) | 0.0180 (3) | 0.0169 (3) | −0.0002 (2) | −0.0007 (2) | 0.0012 (2) |
C1 | 0.0163 (3) | 0.0204 (3) | 0.0154 (3) | −0.0006 (2) | 0.0012 (2) | 0.0017 (2) |
C6 | 0.0299 (4) | 0.0217 (4) | 0.0190 (3) | 0.0017 (3) | 0.0001 (3) | 0.0010 (3) |
C2 | 0.0161 (3) | 0.0447 (5) | 0.0162 (3) | 0.0010 (3) | 0.0006 (3) | 0.0068 (3) |
C4 | 0.0208 (4) | 0.0371 (5) | 0.0211 (4) | −0.0031 (3) | 0.0030 (3) | 0.0080 (3) |
C13 | 0.0232 (4) | 0.0205 (3) | 0.0271 (4) | 0.0054 (3) | 0.0017 (3) | −0.0009 (3) |
C10 | 0.0278 (4) | 0.0302 (4) | 0.0267 (4) | 0.0011 (3) | −0.0006 (3) | −0.0112 (3) |
C7 | 0.0354 (5) | 0.0320 (4) | 0.0190 (4) | 0.0062 (4) | 0.0005 (3) | 0.0060 (3) |
C11 | 0.0436 (6) | 0.0244 (4) | 0.0428 (6) | 0.0007 (4) | −0.0175 (5) | −0.0110 (4) |
C3 | 0.0160 (3) | 0.0553 (6) | 0.0218 (4) | −0.0025 (4) | 0.0017 (3) | 0.0088 (4) |
C8 | 0.0380 (5) | 0.0382 (5) | 0.0149 (3) | −0.0043 (4) | −0.0022 (3) | 0.0001 (3) |
C12 | 0.0399 (6) | 0.0301 (5) | 0.0486 (7) | −0.0174 (4) | −0.0110 (5) | 0.0057 (4) |
Si1—C5 | 1.8640 (8) | C4—C3 | 1.5259 (13) |
Si1—C9 | 1.8610 (8) | C13—H13A | 0.9800 |
Si1—C1 | 1.8664 (8) | C13—H13B | 0.9800 |
Si1—C13 | 1.8559 (9) | C13—H13C | 0.9800 |
O1—C1 | 1.3904 (10) | C10—H10 | 0.9500 |
O1—C4 | 1.4500 (11) | C10—C11 | 1.5011 (15) |
O2—C5 | 1.3892 (10) | C7—H7A | 0.9900 |
O2—C8 | 1.4552 (12) | C7—H7B | 0.9900 |
O3—C9 | 1.3825 (10) | C7—C8 | 1.5226 (16) |
O3—C12 | 1.4596 (13) | C11—C12 | 1.519 (2) |
C5—C6 | 1.3315 (12) | C11—H11A | 0.944 (19) |
C9—C10 | 1.3273 (12) | C11—H11B | 0.966 (18) |
C1—C2 | 1.3312 (11) | C3—H3A | 0.9900 |
C6—C7 | 1.5088 (13) | C3—H3B | 0.9900 |
C6—H6 | 0.912 (15) | C8—H8A | 1.005 (16) |
C2—H2 | 0.9500 | C8—H8B | 0.995 (17) |
C2—C3 | 1.5034 (13) | C12—H12A | 0.9900 |
C4—H4A | 0.9900 | C12—H12B | 0.9900 |
C4—H4B | 0.9900 | ||
C5—Si1—C1 | 111.25 (4) | H13B—C13—H13C | 109.5 |
C9—Si1—C5 | 107.10 (4) | C9—C10—H10 | 124.7 |
C9—Si1—C1 | 106.48 (4) | C9—C10—C11 | 110.59 (9) |
C13—Si1—C5 | 110.92 (4) | C11—C10—H10 | 124.7 |
C13—Si1—C9 | 111.61 (4) | C6—C7—H7A | 111.4 |
C13—Si1—C1 | 109.38 (4) | C6—C7—H7B | 111.4 |
C1—O1—C4 | 107.40 (6) | C6—C7—C8 | 101.64 (7) |
C5—O2—C8 | 107.31 (7) | H7A—C7—H7B | 109.3 |
C9—O3—C12 | 106.64 (8) | C8—C7—H7A | 111.4 |
O2—C5—Si1 | 118.03 (6) | C8—C7—H7B | 111.4 |
C6—C5—Si1 | 128.96 (6) | C10—C11—C12 | 101.09 (8) |
C6—C5—O2 | 112.93 (7) | C10—C11—H11A | 111.5 (11) |
O3—C9—Si1 | 118.21 (6) | C10—C11—H11B | 112.6 (10) |
C10—C9—Si1 | 128.71 (7) | C12—C11—H11A | 113.5 (10) |
C10—C9—O3 | 113.07 (8) | C12—C11—H11B | 113.2 (10) |
O1—C1—Si1 | 114.93 (6) | H11A—C11—H11B | 105.3 (14) |
C2—C1—Si1 | 132.51 (6) | C2—C3—C4 | 101.55 (7) |
C2—C1—O1 | 112.56 (7) | C2—C3—H3A | 111.5 |
C5—C6—C7 | 110.11 (8) | C2—C3—H3B | 111.5 |
C5—C6—H6 | 126.0 (10) | C4—C3—H3A | 111.5 |
C7—C6—H6 | 123.9 (10) | C4—C3—H3B | 111.5 |
C1—C2—H2 | 124.9 | H3A—C3—H3B | 109.3 |
C1—C2—C3 | 110.19 (8) | O2—C8—C7 | 107.10 (7) |
C3—C2—H2 | 124.9 | O2—C8—H8A | 107.8 (9) |
O1—C4—H4A | 110.4 | O2—C8—H8B | 106.7 (9) |
O1—C4—H4B | 110.4 | C7—C8—H8A | 112.2 (8) |
O1—C4—C3 | 106.62 (7) | C7—C8—H8B | 114.4 (9) |
H4A—C4—H4B | 108.6 | H8A—C8—H8B | 108.4 (13) |
C3—C4—H4A | 110.4 | O3—C12—C11 | 107.41 (8) |
C3—C4—H4B | 110.4 | O3—C12—H12A | 110.2 |
Si1—C13—H13A | 109.5 | O3—C12—H12B | 110.2 |
Si1—C13—H13B | 109.5 | C11—C12—H12A | 110.2 |
Si1—C13—H13C | 109.5 | C11—C12—H12B | 110.2 |
H13A—C13—H13B | 109.5 | H12A—C12—H12B | 108.5 |
H13A—C13—H13C | 109.5 | ||
Si1—C5—C6—C7 | −177.42 (7) | C1—Si1—C5—C6 | −103.58 (9) |
Si1—C9—C10—C11 | −178.07 (7) | C1—Si1—C9—O3 | −176.31 (6) |
Si1—C1—C2—C3 | −179.13 (8) | C1—Si1—C9—C10 | 2.60 (9) |
O1—C1—C2—C3 | 0.50 (12) | C1—O1—C4—C3 | −12.68 (11) |
O1—C4—C3—C2 | 12.29 (11) | C1—C2—C3—C4 | −8.04 (12) |
O2—C5—C6—C7 | −0.69 (11) | C6—C7—C8—O2 | −9.06 (11) |
O3—C9—C10—C11 | 0.88 (12) | C4—O1—C1—Si1 | −172.41 (6) |
C5—Si1—C9—O3 | 64.58 (7) | C4—O1—C1—C2 | 7.89 (11) |
C5—Si1—C9—C10 | −116.51 (9) | C13—Si1—C5—O2 | −42.17 (7) |
C5—Si1—C1—O1 | −169.89 (6) | C13—Si1—C5—C6 | 134.42 (8) |
C5—Si1—C1—C2 | 9.73 (11) | C13—Si1—C9—O3 | −57.01 (7) |
C5—O2—C8—C7 | 9.17 (11) | C13—Si1—C9—C10 | 121.90 (9) |
C5—C6—C7—C8 | 6.12 (11) | C13—Si1—C1—O1 | −47.00 (7) |
C9—Si1—C5—O2 | −164.18 (6) | C13—Si1—C1—C2 | 132.62 (10) |
C9—Si1—C5—C6 | 12.41 (9) | C10—C11—C12—O3 | 10.49 (12) |
C9—Si1—C1—O1 | 73.74 (7) | C8—O2—C5—Si1 | 171.65 (7) |
C9—Si1—C1—C2 | −106.64 (10) | C8—O2—C5—C6 | −5.47 (11) |
C9—O3—C12—C11 | −10.57 (11) | C12—O3—C9—Si1 | −174.71 (7) |
C9—C10—C11—C12 | −7.14 (12) | C12—O3—C9—C10 | 6.21 (11) |
C1—Si1—C5—O2 | 79.83 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O1i | 0.912 (15) | 2.658 (15) | 3.4264 (12) | 142.5 (12) |
C8—H8A···O3ii | 1.005 (16) | 2.587 (15) | 3.3291 (13) | 130.5 (11) |
C11—H11A···O2i | 0.944 (19) | 2.538 (19) | 3.4369 (14) | 159.2 (15) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x, −y+1, −z+1. |
C13H18O3Si | F(000) = 536 |
Mr = 250.37 | Dx = 1.273 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.710730 Å |
Hall symbol: -P 2yn | Cell parameters from 9906 reflections |
a = 7.9801 (4) Å | θ = 2.3–36.3° |
b = 12.2381 (5) Å | µ = 0.17 mm−1 |
c = 13.3712 (7) Å | T = 100 K |
β = 90.134 (2)° | Block, colourless |
V = 1305.84 (11) Å3 | 0.39 × 0.14 × 0.07 mm |
Z = 4 |
Bruker D8 Venture diffractometer | 4984 reflections with F > 0 & F/σ(F) > 3.0 & |F_calc| > 10−3 |
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs | Rint = 0.034 |
ω and φ scans | θmax = 35.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −12→12 |
Tmin = 0.536, Tmax = 0.567 | k = −19→19 |
51391 measured reflections | l = −21→21 |
4984 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.023 | All H-atom parameters refined |
wR(F2) = 0.017 | Weighting scheme based on measured s.u.'s w = 1/σ(F) |
S = 1.94 | (Δ/σ)max = 0.003 |
5737 reflections | Δρmax = 0.21 e Å−3 |
316 parameters | Δρmin = −0.21 e Å−3 |
Refinement. HAR makes use of tailor-made aspherical atomic form factors calculated on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from spherical-atom form factors. The ED is calculated from a gaussian basis set single determinant SCF wavefunction - either SCF or DFT - for a fragment of the crystal embedded in an electrostatic crystal field. If constraints were applied they are defined by zero eigenvalues of the least-squares hessian, see the value of _refine_ls_SVD_threshold. Specify symmetry and Friedel pair averaging. Only reflections which satisfy the threshold expression are listed below, and only they are considered observed, thus the *_gt, *_all and *_total data are always the same. |
x | y | z | Uiso*/Ueq | ||
Si1 | 0.183455 (16) | 0.594139 (9) | 0.256364 (10) | 0.01424 (6) | |
O1 | 0.35916 (4) | 0.66896 (3) | 0.09282 (3) | 0.02767 (19) | |
O2 | 0.27908 (5) | 0.62086 (3) | 0.45636 (3) | 0.02813 (19) | |
O3 | −0.09045 (4) | 0.45535 (3) | 0.22732 (3) | 0.0301 (2) | |
C5 | 0.23019 (6) | 0.54500 (3) | 0.38543 (3) | 0.0170 (2) | |
C9 | 0.06532 (6) | 0.48336 (3) | 0.19172 (3) | 0.0170 (2) | |
C1 | 0.37970 (6) | 0.61577 (3) | 0.18334 (3) | 0.0173 (2) | |
C6 | 0.21614 (7) | 0.44418 (4) | 0.42274 (4) | 0.0235 (3) | |
C2 | 0.53945 (6) | 0.58979 (4) | 0.20154 (4) | 0.0259 (3) | |
H2 | 0.5844 (8) | 0.5495 (6) | 0.2686 (5) | 0.061 (5) | |
C4 | 0.51774 (7) | 0.66579 (5) | 0.04077 (4) | 0.0268 (3) | |
H4a | 0.5037 (9) | 0.6060 (6) | −0.0230 (5) | 0.068 (6) | |
H4b | 0.5396 (8) | 0.7450 (5) | 0.0115 (6) | 0.059 (5) | |
C13 | 0.06171 (7) | 0.72340 (4) | 0.25969 (5) | 0.0237 (3) | |
H13a | −0.0569 (9) | 0.7113 (6) | 0.2949 (6) | 0.059 (5) | |
H13b | 0.1302 (9) | 0.7857 (5) | 0.2996 (6) | 0.057 (5) | |
H13c | 0.0403 (9) | 0.7530 (5) | 0.1851 (5) | 0.053 (5) | |
C10 | 0.11010 (7) | 0.42565 (4) | 0.11191 (4) | 0.0284 (3) | |
H10 | 0.2281 (9) | 0.4377 (6) | 0.0729 (6) | 0.061 (5) | |
C7 | 0.26051 (8) | 0.44426 (5) | 0.53234 (4) | 0.0287 (3) | |
H7a | 0.1622 (10) | 0.4119 (5) | 0.5786 (6) | 0.062 (6) | |
H7b | 0.3746 (10) | 0.3987 (6) | 0.5462 (6) | 0.069 (6) | |
C11 | −0.02599 (8) | 0.34719 (5) | 0.08313 (5) | 0.0365 (3) | |
H11a | −0.0846 (11) | 0.3677 (6) | 0.0135 (6) | 0.076 (6) | |
C3 | 0.64824 (7) | 0.62856 (6) | 0.11700 (5) | 0.0316 (3) | |
H3a | 0.7276 (10) | 0.6974 (7) | 0.1396 (6) | 0.070 (6) | |
H3b | 0.7330 (9) | 0.5667 (7) | 0.0885 (6) | 0.077 (6) | |
C8 | 0.28357 (9) | 0.56612 (5) | 0.55253 (4) | 0.0303 (3) | |
H8a | 0.4015 (11) | 0.5861 (6) | 0.5874 (6) | 0.071 (6) | |
C12 | −0.14713 (9) | 0.36145 (5) | 0.17009 (6) | 0.0397 (4) | |
H12a | −0.1438 (12) | 0.2899 (6) | 0.2200 (7) | 0.104 (8) | |
H12b | −0.2711 (10) | 0.3785 (6) | 0.1467 (7) | 0.077 (6) | |
H6 | 0.1795 (9) | 0.3737 (5) | 0.3807 (5) | 0.053 (5) | |
H8b | 0.1825 (11) | 0.5983 (5) | 0.5968 (5) | 0.069 (6) | |
H11b | 0.0170 (10) | 0.2642 (6) | 0.0788 (7) | 0.086 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1 | 0.01329 (6) | 0.01572 (6) | 0.01373 (6) | 0.00096 (4) | 0.00107 (4) | −0.00037 (5) |
O1 | 0.02067 (18) | 0.03649 (19) | 0.0259 (2) | 0.00403 (15) | 0.00302 (15) | 0.01491 (15) |
O2 | 0.0418 (2) | 0.02546 (17) | 0.01715 (18) | −0.00624 (15) | −0.00304 (16) | −0.00187 (14) |
O3 | 0.02182 (19) | 0.0400 (2) | 0.0283 (2) | −0.01124 (15) | 0.00259 (16) | −0.00231 (16) |
C5 | 0.0172 (2) | 0.0196 (2) | 0.0144 (2) | 0.00110 (16) | 0.00094 (17) | −0.00006 (17) |
C9 | 0.0174 (2) | 0.0178 (2) | 0.0158 (2) | −0.00049 (16) | −0.00031 (17) | −0.00022 (16) |
C1 | 0.0144 (2) | 0.0215 (2) | 0.0159 (2) | −0.00071 (16) | 0.00120 (17) | 0.00195 (16) |
C6 | 0.0310 (3) | 0.0206 (2) | 0.0190 (3) | 0.0011 (2) | 0.0000 (2) | 0.00156 (19) |
C2 | 0.0153 (2) | 0.0457 (3) | 0.0166 (2) | 0.0016 (2) | 0.00047 (19) | 0.0074 (2) |
H2 | 0.028 (4) | 0.121 (6) | 0.032 (5) | 0.013 (4) | −0.003 (4) | 0.033 (5) |
C4 | 0.0214 (3) | 0.0372 (3) | 0.0218 (3) | −0.0036 (2) | 0.0024 (2) | 0.0093 (2) |
H4a | 0.058 (5) | 0.119 (7) | 0.026 (5) | 0.001 (5) | −0.007 (4) | −0.039 (5) |
H4b | 0.051 (5) | 0.049 (4) | 0.077 (6) | −0.015 (4) | 0.010 (4) | 0.019 (4) |
C13 | 0.0232 (3) | 0.0205 (2) | 0.0275 (3) | 0.0061 (2) | 0.0015 (2) | −0.0010 (2) |
H13a | 0.040 (5) | 0.065 (5) | 0.073 (7) | 0.010 (4) | 0.024 (4) | 0.006 (4) |
H13b | 0.064 (5) | 0.033 (4) | 0.074 (6) | 0.006 (4) | −0.019 (5) | −0.026 (4) |
H13c | 0.069 (6) | 0.044 (4) | 0.045 (5) | 0.017 (4) | −0.006 (4) | 0.020 (4) |
C10 | 0.0281 (3) | 0.0307 (3) | 0.0266 (3) | 0.0009 (2) | 0.0001 (2) | −0.0123 (2) |
H10 | 0.046 (5) | 0.079 (5) | 0.058 (6) | −0.017 (4) | 0.027 (4) | −0.036 (4) |
C7 | 0.0354 (3) | 0.0320 (3) | 0.0188 (3) | 0.0064 (2) | 0.0007 (2) | 0.0065 (2) |
H7a | 0.084 (6) | 0.056 (5) | 0.046 (6) | −0.018 (4) | 0.015 (5) | 0.013 (4) |
H7b | 0.067 (6) | 0.077 (6) | 0.062 (6) | 0.035 (5) | −0.014 (5) | 0.017 (4) |
C11 | 0.0432 (4) | 0.0245 (3) | 0.0418 (4) | 0.0001 (2) | −0.0167 (3) | −0.0106 (3) |
H11a | 0.086 (6) | 0.101 (6) | 0.041 (6) | −0.017 (5) | −0.026 (5) | −0.005 (5) |
C3 | 0.0155 (3) | 0.0572 (4) | 0.0220 (3) | −0.0028 (3) | 0.0020 (2) | 0.0090 (3) |
H3a | 0.069 (6) | 0.099 (6) | 0.042 (5) | −0.037 (5) | −0.006 (4) | 0.005 (5) |
H3b | 0.034 (5) | 0.123 (7) | 0.073 (7) | 0.042 (5) | 0.021 (4) | 0.044 (5) |
C8 | 0.0374 (3) | 0.0381 (3) | 0.0153 (3) | −0.0043 (3) | −0.0021 (2) | −0.0008 (2) |
H8a | 0.081 (6) | 0.087 (6) | 0.047 (6) | −0.041 (5) | −0.031 (5) | 0.003 (4) |
C12 | 0.0379 (4) | 0.0320 (3) | 0.0492 (4) | −0.0167 (3) | −0.0099 (3) | 0.0057 (3) |
H12a | 0.149 (9) | 0.035 (5) | 0.128 (9) | −0.037 (5) | 0.009 (7) | 0.040 (5) |
H12b | 0.053 (6) | 0.083 (6) | 0.096 (8) | 0.002 (5) | −0.027 (5) | −0.032 (5) |
H6 | 0.091 (6) | 0.034 (4) | 0.033 (5) | −0.010 (4) | −0.010 (4) | −0.004 (3) |
H8b | 0.110 (7) | 0.063 (5) | 0.033 (5) | 0.011 (5) | 0.039 (5) | −0.005 (4) |
H11b | 0.088 (7) | 0.047 (5) | 0.124 (9) | 0.001 (5) | −0.023 (6) | −0.037 (5) |
Si1—C5 | 1.8643 (5) | C6—H6 | 1.070 (6) |
Si1—C9 | 1.8628 (5) | C2—H2 | 1.084 (6) |
Si1—C1 | 1.8663 (5) | C4—H4a | 1.129 (6) |
Si1—C13 | 1.8570 (5) | C4—H4b | 1.060 (6) |
O1—C1 | 1.3837 (6) | C13—H13a | 1.068 (7) |
O1—C4 | 1.4461 (6) | C13—H13b | 1.078 (6) |
O2—C5 | 1.3827 (5) | C13—H13c | 1.074 (7) |
O2—C8 | 1.4502 (7) | C10—H10 | 1.088 (7) |
O3—C9 | 1.3756 (6) | C7—H7a | 1.075 (7) |
O3—C12 | 1.4522 (7) | C7—H7b | 1.083 (7) |
C5—C6 | 1.3357 (6) | C11—H11a | 1.071 (8) |
C9—C10 | 1.3294 (7) | C11—H11b | 1.073 (7) |
C1—C2 | 1.3356 (6) | C3—H3a | 1.096 (7) |
C6—C7 | 1.5069 (7) | C3—H3b | 1.085 (8) |
C2—C3 | 1.5038 (8) | C8—H8a | 1.078 (7) |
C4—C3 | 1.5251 (8) | C8—H8b | 1.077 (7) |
C10—C11 | 1.4991 (8) | C12—H12a | 1.101 (7) |
C7—C8 | 1.5266 (8) | C12—H12b | 1.058 (8) |
C11—C12 | 1.5239 (10) | ||
Si1—C5—O2 | 118.29 (3) | C10—C11—C12 | 101.03 (5) |
Si1—C9—O3 | 118.53 (3) | C5—C6—H6 | 124.9 (4) |
Si1—C1—O1 | 115.25 (3) | C9—C10—H10 | 123.2 (3) |
Si1—C5—C6 | 128.82 (4) | C1—C2—H2 | 125.0 (4) |
Si1—C9—C10 | 128.50 (4) | C6—C7—H7a | 112.9 (4) |
Si1—C1—C2 | 132.27 (4) | C6—C7—H7b | 111.2 (4) |
Si1—C13—H13a | 110.9 (4) | C2—C3—H3a | 111.7 (4) |
Si1—C13—H13b | 110.4 (4) | C2—C3—H3b | 113.9 (4) |
Si1—C13—H13c | 110.3 (4) | C4—C3—H3a | 110.3 (4) |
O1—C1—C2 | 112.48 (4) | C4—C3—H3b | 113.5 (4) |
O1—C4—C3 | 106.46 (4) | C10—C11—H11a | 112.8 (4) |
O2—C5—C6 | 112.81 (4) | C10—C11—H11b | 112.8 (4) |
O2—C8—C7 | 106.96 (4) | C7—C6—H6 | 125.1 (4) |
O3—C9—C10 | 112.97 (4) | C7—C8—H8a | 113.8 (4) |
O3—C12—C11 | 107.18 (5) | C7—C8—H8b | 111.4 (4) |
O1—C4—H4a | 107.2 (4) | C11—C10—H10 | 126.2 (4) |
O1—C4—H4b | 107.3 (4) | C11—C12—H12a | 110.9 (5) |
O2—C8—H8a | 107.4 (4) | C11—C12—H12b | 113.0 (5) |
O2—C8—H8b | 107.5 (4) | C3—C2—H2 | 125.1 (4) |
O3—C12—H12a | 107.6 (5) | C3—C4—H4a | 112.1 (4) |
O3—C12—H12b | 106.9 (4) | C3—C4—H4b | 114.1 (4) |
C5—Si1—C9 | 107.14 (2) | C8—C7—H7a | 110.2 (4) |
C5—Si1—C1 | 111.33 (2) | C8—C7—H7b | 111.8 (4) |
C5—Si1—C13 | 110.86 (2) | C12—C11—H11a | 111.1 (5) |
C9—Si1—C1 | 106.55 (2) | C12—C11—H11b | 110.7 (5) |
C9—Si1—C13 | 111.52 (2) | H4a—C4—H4b | 109.3 (6) |
C1—Si1—C13 | 109.36 (2) | H13a—C13—H13b | 109.2 (5) |
C5—O2—C8 | 107.72 (4) | H13a—C13—H13c | 108.4 (5) |
C9—O3—C12 | 107.19 (4) | H13b—C13—H13c | 107.5 (5) |
C1—O1—C4 | 107.84 (4) | H7a—C7—H7b | 109.0 (6) |
C5—C6—C7 | 110.06 (5) | H11a—C11—H11b | 108.3 (6) |
C9—C10—C11 | 110.51 (5) | H3a—C3—H3b | 105.9 (6) |
C1—C2—C3 | 109.90 (5) | H8a—C8—H8b | 109.5 (6) |
C6—C7—C8 | 101.57 (4) | H12a—C12—H12b | 110.9 (7) |
C2—C3—C4 | 101.66 (4) |
C18H20O3Si | F(000) = 664 |
Mr = 312.43 | Dx = 1.294 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4936 (6) Å | Cell parameters from 9914 reflections |
b = 8.6802 (7) Å | θ = 2.6–30.5° |
c = 19.747 (2) Å | µ = 0.16 mm−1 |
β = 99.743 (4)° | T = 100 K |
V = 1603.8 (2) Å3 | Block, colourless |
Z = 4 | 1 × 0.58 × 0.36 mm |
Bruker D8 Venture diffractometer | 5830 independent reflections |
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs | 5318 reflections with I > 2σ(I) |
HELIOS mirror optics monochromator | Rint = 0.030 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 32.6°, θmin = 2.2° |
φ and ω scans | h = −14→14 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | k = −13→10 |
Tmin = 0.484, Tmax = 0.566 | l = −29→29 |
25027 measured reflections |
Refinement on F2 | Primary atom site location: iterative |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: mixed |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.053P)2 + 0.5057P] where P = (Fo2 + 2Fc2)/3 |
5830 reflections | (Δ/σ)max = 0.001 |
207 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Si1 | 0.74752 (2) | 0.58226 (3) | 0.61267 (2) | 0.01607 (7) | |
O1 | 0.84911 (9) | 0.80595 (8) | 0.53080 (4) | 0.02920 (16) | |
O2 | 0.88956 (8) | 0.53532 (11) | 0.74733 (4) | 0.03192 (18) | |
H16 | 0.2962 (19) | 0.928 (2) | 0.6921 (9) | 0.047 (5)* | |
O3 | 0.76383 (8) | 0.26869 (8) | 0.57693 (4) | 0.02727 (15) | |
C1 | 0.80711 (9) | 0.65298 (10) | 0.53302 (4) | 0.01795 (15) | |
C2 | 0.81525 (11) | 0.57638 (11) | 0.47539 (5) | 0.02286 (17) | |
C3 | 0.86553 (11) | 0.68235 (12) | 0.42379 (5) | 0.02608 (18) | |
H3A | 0.789037 | 0.701732 | 0.383993 | 0.031* | |
H3B | 0.950565 | 0.640314 | 0.407290 | 0.031* | |
C4 | 0.90202 (13) | 0.82803 (12) | 0.46668 (6) | 0.0301 (2) | |
H4A | 1.006696 | 0.844635 | 0.475727 | 0.036* | |
H4B | 0.856062 | 0.918995 | 0.441956 | 0.036* | |
C5 | 0.90600 (9) | 0.58711 (10) | 0.68271 (4) | 0.01867 (15) | |
C6 | 1.03720 (10) | 0.63899 (12) | 0.68063 (5) | 0.02363 (17) | |
H6 | 1.068129 | 0.679122 | 0.640851 | 0.028* | |
C7 | 1.12966 (10) | 0.62499 (14) | 0.75036 (5) | 0.02814 (19) | |
H7A | 1.165349 | 0.726797 | 0.768255 | 0.034* | |
H7B | 1.211792 | 0.555409 | 0.749084 | 0.034* | |
C8 | 1.02544 (11) | 0.55684 (15) | 0.79288 (5) | 0.0315 (2) | |
H8A | 1.061678 | 0.456899 | 0.812821 | 0.038* | |
H8B | 1.013588 | 0.627441 | 0.830884 | 0.038* | |
C9 | 0.67580 (9) | 0.38311 (10) | 0.59588 (4) | 0.01827 (15) | |
C10 | 0.54408 (10) | 0.33313 (11) | 0.59899 (5) | 0.02234 (16) | |
H10 | 0.469616 | 0.395021 | 0.611087 | 0.027* | |
C11 | 0.53018 (12) | 0.16494 (12) | 0.58064 (6) | 0.0311 (2) | |
H11A | 0.461907 | 0.148488 | 0.537473 | 0.037* | |
H11B | 0.499404 | 0.103890 | 0.617896 | 0.037* | |
C12 | 0.68264 (12) | 0.12463 (11) | 0.57197 (6) | 0.0299 (2) | |
H12A | 0.725657 | 0.052135 | 0.608368 | 0.036* | |
H12B | 0.682858 | 0.075547 | 0.526732 | 0.036* | |
C13 | 0.60089 (9) | 0.70098 (10) | 0.63790 (4) | 0.01831 (15) | |
C14 | 0.46938 (10) | 0.71555 (11) | 0.59371 (5) | 0.02264 (16) | |
H14 | 0.457310 | 0.669609 | 0.549436 | 0.027* | |
C15 | 0.35611 (11) | 0.79615 (12) | 0.61354 (6) | 0.0288 (2) | |
H15 | 0.267229 | 0.802831 | 0.583237 | 0.035* | |
C16 | 0.37284 (12) | 0.86642 (13) | 0.67724 (7) | 0.0321 (2) | |
C17 | 0.50218 (14) | 0.85581 (14) | 0.72086 (6) | 0.0345 (2) | |
H17 | 0.514213 | 0.905500 | 0.764322 | 0.041* | |
C18 | 0.61587 (12) | 0.77307 (12) | 0.70212 (5) | 0.02617 (18) | |
H18 | 0.703783 | 0.765721 | 0.733122 | 0.031* | |
H2 | 0.7893 (18) | 0.466 (2) | 0.4669 (8) | 0.039 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1 | 0.01588 (11) | 0.01536 (11) | 0.01726 (11) | −0.00151 (7) | 0.00365 (8) | −0.00197 (7) |
O1 | 0.0477 (4) | 0.0159 (3) | 0.0283 (3) | −0.0049 (3) | 0.0187 (3) | −0.0032 (2) |
O2 | 0.0213 (3) | 0.0488 (5) | 0.0239 (3) | −0.0110 (3) | −0.0011 (2) | 0.0123 (3) |
O3 | 0.0240 (3) | 0.0166 (3) | 0.0415 (4) | 0.0008 (2) | 0.0065 (3) | −0.0049 (3) |
C1 | 0.0172 (3) | 0.0165 (3) | 0.0208 (3) | −0.0008 (3) | 0.0051 (3) | −0.0013 (3) |
C2 | 0.0258 (4) | 0.0220 (4) | 0.0221 (4) | −0.0058 (3) | 0.0079 (3) | −0.0042 (3) |
C3 | 0.0281 (4) | 0.0297 (5) | 0.0223 (4) | −0.0047 (4) | 0.0097 (3) | −0.0026 (3) |
C4 | 0.0422 (6) | 0.0218 (4) | 0.0309 (5) | −0.0046 (4) | 0.0196 (4) | −0.0009 (4) |
C5 | 0.0185 (3) | 0.0178 (3) | 0.0195 (3) | −0.0018 (3) | 0.0026 (3) | −0.0009 (3) |
C6 | 0.0194 (4) | 0.0282 (4) | 0.0232 (4) | −0.0045 (3) | 0.0035 (3) | 0.0000 (3) |
C7 | 0.0194 (4) | 0.0338 (5) | 0.0294 (4) | −0.0052 (4) | −0.0012 (3) | 0.0032 (4) |
C8 | 0.0250 (4) | 0.0425 (6) | 0.0247 (4) | −0.0097 (4) | −0.0024 (3) | 0.0045 (4) |
C9 | 0.0196 (3) | 0.0161 (3) | 0.0187 (3) | −0.0009 (3) | 0.0021 (3) | −0.0013 (3) |
C10 | 0.0212 (4) | 0.0219 (4) | 0.0239 (4) | −0.0048 (3) | 0.0035 (3) | −0.0002 (3) |
C11 | 0.0311 (5) | 0.0215 (4) | 0.0392 (5) | −0.0094 (4) | 0.0014 (4) | 0.0020 (4) |
C12 | 0.0324 (5) | 0.0154 (4) | 0.0377 (5) | −0.0002 (3) | −0.0060 (4) | −0.0030 (4) |
C13 | 0.0200 (3) | 0.0166 (3) | 0.0197 (3) | −0.0012 (3) | 0.0072 (3) | −0.0011 (3) |
C14 | 0.0208 (4) | 0.0206 (4) | 0.0269 (4) | 0.0013 (3) | 0.0052 (3) | −0.0026 (3) |
C15 | 0.0210 (4) | 0.0213 (4) | 0.0458 (6) | 0.0003 (3) | 0.0109 (4) | 0.0002 (4) |
C16 | 0.0344 (5) | 0.0243 (4) | 0.0439 (6) | 0.0036 (4) | 0.0247 (5) | 0.0019 (4) |
C17 | 0.0489 (6) | 0.0325 (5) | 0.0265 (5) | 0.0084 (5) | 0.0188 (4) | −0.0030 (4) |
C18 | 0.0323 (5) | 0.0264 (4) | 0.0204 (4) | 0.0032 (4) | 0.0061 (3) | −0.0042 (3) |
Si1—C1 | 1.8633 (9) | C7—C8 | 1.5215 (15) |
Si1—C5 | 1.8638 (9) | C8—H8A | 0.9900 |
Si1—C9 | 1.8670 (9) | C8—H8B | 0.9900 |
Si1—C13 | 1.8662 (9) | C9—C10 | 1.3348 (12) |
O1—C1 | 1.3892 (11) | C10—H10 | 0.9500 |
O1—C4 | 1.4518 (12) | C10—C11 | 1.5046 (14) |
O2—C5 | 1.3865 (11) | C11—H11A | 0.9900 |
O2—C8 | 1.4544 (12) | C11—H11B | 0.9900 |
O3—C9 | 1.3894 (11) | C11—C12 | 1.5267 (17) |
O3—C12 | 1.4635 (12) | C12—H12A | 0.9900 |
C1—C2 | 1.3314 (12) | C12—H12B | 0.9900 |
C2—C3 | 1.5090 (13) | C13—C14 | 1.4027 (13) |
C2—H2 | 0.995 (17) | C13—C18 | 1.3995 (12) |
C3—H3A | 0.9900 | C14—H14 | 0.9500 |
C3—H3B | 0.9900 | C14—C15 | 1.3934 (13) |
C3—C4 | 1.5288 (15) | C15—H15 | 0.9500 |
C4—H4A | 0.9900 | C15—C16 | 1.3827 (17) |
C4—H4B | 0.9900 | C16—H16 | 0.987 (18) |
C5—C6 | 1.3317 (12) | C16—C17 | 1.3785 (19) |
C6—H6 | 0.9500 | C17—H17 | 0.9500 |
C6—C7 | 1.5074 (14) | C17—C18 | 1.3975 (15) |
C7—H7A | 0.9900 | C18—H18 | 0.9500 |
C7—H7B | 0.9900 | ||
C1—Si1—C5 | 107.26 (4) | O2—C8—H8B | 110.2 |
C1—Si1—C9 | 107.99 (4) | C7—C8—H8A | 110.2 |
C1—Si1—C13 | 112.97 (4) | C7—C8—H8B | 110.2 |
C5—Si1—C9 | 112.15 (4) | H8A—C8—H8B | 108.5 |
C5—Si1—C13 | 109.53 (4) | O3—C9—Si1 | 119.46 (6) |
C13—Si1—C9 | 107.01 (4) | C10—C9—Si1 | 127.52 (7) |
C1—O1—C4 | 107.29 (7) | C10—C9—O3 | 113.01 (8) |
C5—O2—C8 | 107.54 (7) | C9—C10—H10 | 124.8 |
C9—O3—C12 | 107.15 (8) | C9—C10—C11 | 110.42 (9) |
O1—C1—Si1 | 118.11 (6) | C11—C10—H10 | 124.8 |
C2—C1—Si1 | 128.81 (7) | C10—C11—H11A | 111.4 |
C2—C1—O1 | 113.08 (8) | C10—C11—H11B | 111.4 |
C1—C2—C3 | 110.09 (8) | C10—C11—C12 | 101.72 (8) |
C1—C2—H2 | 125.1 (10) | H11A—C11—H11B | 109.3 |
C3—C2—H2 | 124.8 (9) | C12—C11—H11A | 111.4 |
C2—C3—H3A | 111.5 | C12—C11—H11B | 111.4 |
C2—C3—H3B | 111.5 | O3—C12—C11 | 107.17 (8) |
C2—C3—C4 | 101.42 (8) | O3—C12—H12A | 110.3 |
H3A—C3—H3B | 109.3 | O3—C12—H12B | 110.3 |
C4—C3—H3A | 111.5 | C11—C12—H12A | 110.3 |
C4—C3—H3B | 111.5 | C11—C12—H12B | 110.3 |
O1—C4—C3 | 107.13 (8) | H12A—C12—H12B | 108.5 |
O1—C4—H4A | 110.3 | C14—C13—Si1 | 120.61 (7) |
O1—C4—H4B | 110.3 | C18—C13—Si1 | 121.52 (7) |
C3—C4—H4A | 110.3 | C18—C13—C14 | 117.82 (8) |
C3—C4—H4B | 110.3 | C13—C14—H14 | 119.4 |
H4A—C4—H4B | 108.5 | C15—C14—C13 | 121.22 (9) |
O2—C5—Si1 | 118.24 (6) | C15—C14—H14 | 119.4 |
C6—C5—Si1 | 128.79 (7) | C14—C15—H15 | 119.9 |
C6—C5—O2 | 112.93 (8) | C16—C15—C14 | 120.12 (10) |
C5—C6—H6 | 124.8 | C16—C15—H15 | 119.9 |
C5—C6—C7 | 110.34 (8) | C15—C16—H16 | 122.2 (11) |
C7—C6—H6 | 124.8 | C17—C16—H16 | 118.3 (10) |
C6—C7—H7A | 111.4 | C17—C16—C15 | 119.48 (9) |
C6—C7—H7B | 111.4 | C16—C17—H17 | 119.5 |
C6—C7—C8 | 101.71 (8) | C16—C17—C18 | 121.00 (10) |
H7A—C7—H7B | 109.3 | C18—C17—H17 | 119.5 |
C8—C7—H7A | 111.4 | C13—C18—H18 | 119.8 |
C8—C7—H7B | 111.4 | C17—C18—C13 | 120.34 (10) |
O2—C8—C7 | 107.47 (8) | C17—C18—H18 | 119.8 |
O2—C8—H8A | 110.2 | ||
Si1—C1—C2—C3 | 178.37 (7) | C6—C7—C8—O2 | 0.87 (12) |
Si1—C5—C6—C7 | 178.02 (7) | C8—O2—C5—Si1 | −177.67 (7) |
Si1—C9—C10—C11 | 179.13 (7) | C8—O2—C5—C6 | 0.44 (12) |
Si1—C13—C14—C15 | 176.12 (8) | C9—Si1—C1—O1 | 172.60 (7) |
Si1—C13—C18—C17 | −177.23 (8) | C9—Si1—C1—C2 | −7.02 (10) |
O1—C1—C2—C3 | −1.27 (12) | C9—Si1—C5—O2 | −59.87 (8) |
O2—C5—C6—C7 | 0.15 (12) | C9—Si1—C5—C6 | 122.36 (9) |
O3—C9—C10—C11 | −0.06 (11) | C9—Si1—C13—C14 | −58.05 (8) |
C1—Si1—C5—O2 | −178.26 (7) | C9—Si1—C13—C18 | 119.39 (8) |
C1—Si1—C5—C6 | 3.96 (10) | C9—O3—C12—C11 | 7.11 (11) |
C1—Si1—C9—O3 | 59.03 (8) | C9—C10—C11—C12 | 4.34 (11) |
C1—Si1—C9—C10 | −120.11 (9) | C10—C11—C12—O3 | −6.80 (11) |
C1—Si1—C13—C14 | 60.67 (8) | C12—O3—C9—Si1 | 176.20 (6) |
C1—Si1—C13—C18 | −121.89 (8) | C12—O3—C9—C10 | −4.54 (11) |
C1—O1—C4—C3 | 9.46 (12) | C13—Si1—C1—O1 | 54.45 (8) |
C1—C2—C3—C4 | 6.79 (11) | C13—Si1—C1—C2 | −125.17 (9) |
C2—C3—C4—O1 | −9.64 (11) | C13—Si1—C5—O2 | 58.79 (8) |
C4—O1—C1—Si1 | 175.01 (7) | C13—Si1—C5—C6 | −118.98 (9) |
C4—O1—C1—C2 | −5.31 (12) | C13—Si1—C9—O3 | −179.07 (7) |
C5—Si1—C1—O1 | −66.35 (8) | C13—Si1—C9—C10 | 1.79 (10) |
C5—Si1—C1—C2 | 114.04 (9) | C13—C14—C15—C16 | 1.35 (15) |
C5—Si1—C9—O3 | −58.93 (8) | C14—C13—C18—C17 | 0.28 (15) |
C5—Si1—C9—C10 | 121.92 (9) | C14—C15—C16—C17 | −0.10 (16) |
C5—Si1—C13—C14 | −179.84 (7) | C15—C16—C17—C18 | −1.03 (17) |
C5—Si1—C13—C18 | −2.40 (9) | C16—C17—C18—C13 | 0.94 (17) |
C5—O2—C8—C7 | −0.84 (13) | C18—C13—C14—C15 | −1.42 (14) |
C5—C6—C7—C8 | −0.64 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···O2i | 0.987 (18) | 2.474 (18) | 3.4394 (13) | 165.9 (15) |
C2—H2···O3 | 0.995 (17) | 2.809 (17) | 3.4238 (13) | 120.6 (12) |
Symmetry code: (i) −x+1, y+1/2, −z+3/2. |
C18H20O3Si | F(000) = 664 |
Mr = 312.44 | Dx = 1.294 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.710730 Å |
Hall symbol: -P 2ybc | Cell parameters from 9914 reflections |
a = 9.4936 (6) Å | θ = 2.6–30.5° |
b = 8.6802 (7) Å | µ = 0.16 mm−1 |
c = 19.747 (2) Å | T = 100 K |
β = 99.743 (4)° | Block, colourless |
V = 1603.8 (2) Å3 | 1 × 0.58 × 0.36 mm |
Z = 4 |
Bruker D8 Venture diffractometer | 5359 reflections with F > 0 & F/σ(F) > 3.0 & |F_calc| > 10−3 |
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs | Rint = 0.030 |
φ and ω scans | θmax = 32.6°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −14→14 |
Tmin = 0.484, Tmax = 0.566 | k = −13→10 |
25027 measured reflections | l = −29→29 |
5359 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.024 | All H-atom parameters refined |
wR(F2) = 0.021 | Weighting scheme based on measured s.u.'s w = 1/σ(F) |
S = 2.07 | (Δ/σ)max = 0.002 |
5830 reflections | Δρmax = 0.26 e Å−3 |
379 parameters | Δρmin = −0.17 e Å−3 |
Refinement. HAR makes use of tailor-made aspherical atomic form factors calculated on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from spherical-atom form factors. The ED is calculated from a gaussian basis set single determinant SCF wavefunction - either SCF or DFT - for a fragment of the crystal embedded in an electrostatic crystal field. If constraints were applied they are defined by zero eigenvalues of the least-squares hessian, see the value of _refine_ls_SVD_threshold. Specify symmetry and Friedel pair averaging. Only reflections which satisfy the threshold expression are listed below, and only they are considered observed, thus the *_gt, *_all and *_total data are always the same. |
x | y | z | Uiso*/Ueq | ||
Si1 | 0.747546 (14) | 0.582292 (15) | 0.612664 (7) | 0.01528 (6) | |
O1 | 0.84901 (5) | 0.80558 (4) | 0.53062 (2) | 0.0292 (2) | |
O2 | 0.89013 (4) | 0.53540 (5) | 0.74723 (2) | 0.0314 (2) | |
H16 | 0.2846 (9) | 0.9319 (11) | 0.6920 (5) | 0.074 (7) | |
O3 | 0.76344 (4) | 0.26862 (4) | 0.57700 (2) | 0.0272 (2) | |
C1 | 0.80726 (5) | 0.65332 (6) | 0.53303 (2) | 0.0174 (2) | |
C2 | 0.81512 (6) | 0.57618 (7) | 0.47531 (3) | 0.0227 (2) | |
C3 | 0.86534 (7) | 0.68228 (7) | 0.42380 (3) | 0.0264 (3) | |
H3a | 0.9585 (9) | 0.6409 (10) | 0.4044 (5) | 0.063 (6) | |
H3b | 0.7823 (9) | 0.7044 (12) | 0.3813 (4) | 0.066 (6) | |
C4 | 0.90164 (8) | 0.82785 (7) | 0.46665 (3) | 0.0301 (3) | |
H4a | 0.8576 (12) | 0.9288 (11) | 0.4439 (5) | 0.086 (8) | |
H4b | 1.0174 (10) | 0.8428 (12) | 0.4793 (5) | 0.078 (7) | |
C5 | 0.90593 (5) | 0.58701 (6) | 0.68281 (2) | 0.0183 (2) | |
C6 | 1.03741 (6) | 0.63895 (7) | 0.68061 (3) | 0.0233 (2) | |
H6 | 1.0707 (8) | 0.6836 (11) | 0.6349 (4) | 0.054 (6) | |
C7 | 1.12977 (6) | 0.62511 (8) | 0.75034 (3) | 0.0281 (3) | |
H7a | 1.2215 (9) | 0.5525 (13) | 0.7488 (5) | 0.076 (7) | |
H7b | 1.1704 (10) | 0.7364 (10) | 0.7693 (5) | 0.071 (7) | |
C8 | 1.02519 (7) | 0.55702 (9) | 0.79273 (3) | 0.0318 (3) | |
H8a | 1.0062 (10) | 0.6346 (16) | 0.8331 (6) | 0.101 (9) | |
H8b | 1.0587 (10) | 0.4467 (14) | 0.8157 (7) | 0.101 (9) | |
C9 | 0.67596 (5) | 0.38297 (6) | 0.59582 (2) | 0.0176 (2) | |
C10 | 0.54408 (6) | 0.33323 (6) | 0.59894 (3) | 0.0221 (2) | |
H10 | 0.4616 (8) | 0.4016 (9) | 0.6120 (5) | 0.051 (6) | |
C11 | 0.53018 (7) | 0.16494 (7) | 0.58067 (4) | 0.0312 (3) | |
H11a | 0.4968 (10) | 0.1008 (11) | 0.6216 (5) | 0.069 (7) | |
H11b | 0.4532 (8) | 0.1460 (10) | 0.5330 (5) | 0.058 (6) | |
C12 | 0.68277 (7) | 0.12475 (7) | 0.57208 (3) | 0.0298 (3) | |
H12a | 0.6906 (10) | 0.0754 (10) | 0.5224 (5) | 0.064 (6) | |
H12b | 0.7323 (10) | 0.0499 (10) | 0.6124 (5) | 0.076 (7) | |
C13 | 0.60087 (5) | 0.70104 (6) | 0.63796 (2) | 0.0178 (2) | |
C14 | 0.46947 (6) | 0.71578 (6) | 0.59372 (3) | 0.0222 (2) | |
H14 | 0.4539 (8) | 0.6612 (10) | 0.5433 (4) | 0.050 (5) | |
C15 | 0.35609 (6) | 0.79613 (7) | 0.61351 (3) | 0.0287 (3) | |
H15 | 0.2540 (8) | 0.8044 (11) | 0.5787 (5) | 0.062 (6) | |
C16 | 0.37264 (7) | 0.86670 (7) | 0.67727 (3) | 0.0322 (3) | |
C17 | 0.50259 (7) | 0.85587 (7) | 0.72103 (3) | 0.0340 (3) | |
H17 | 0.5195 (10) | 0.9123 (11) | 0.7706 (5) | 0.072 (7) | |
C18 | 0.61593 (7) | 0.77294 (7) | 0.70210 (3) | 0.0260 (3) | |
H2 | 0.7895 (10) | 0.4556 (9) | 0.4679 (4) | 0.056 (6) | |
H18 | 0.7151 (9) | 0.7604 (10) | 0.7373 (4) | 0.055 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1 | 0.01511 (6) | 0.01445 (6) | 0.01659 (6) | −0.00151 (5) | 0.00356 (5) | −0.00195 (5) |
O1 | 0.0473 (2) | 0.01601 (18) | 0.0284 (2) | −0.00392 (16) | 0.01778 (19) | −0.00359 (16) |
O2 | 0.02147 (18) | 0.0467 (3) | 0.02463 (18) | −0.01067 (18) | 0.00006 (15) | 0.01162 (18) |
H16 | 0.062 (5) | 0.073 (7) | 0.103 (9) | 0.024 (5) | 0.060 (6) | −0.008 (6) |
O3 | 0.02383 (18) | 0.01780 (18) | 0.0400 (2) | 0.00088 (14) | 0.00591 (17) | −0.00434 (16) |
C1 | 0.0182 (2) | 0.0164 (2) | 0.0186 (2) | −0.00123 (17) | 0.00588 (18) | −0.00205 (18) |
C2 | 0.0270 (2) | 0.0215 (3) | 0.0212 (2) | −0.0059 (2) | 0.0085 (2) | −0.0053 (2) |
C3 | 0.0286 (3) | 0.0308 (3) | 0.0217 (3) | −0.0047 (2) | 0.0098 (2) | −0.0025 (2) |
H3a | 0.078 (6) | 0.053 (6) | 0.073 (8) | −0.009 (5) | 0.058 (6) | −0.016 (5) |
H3b | 0.053 (5) | 0.113 (9) | 0.030 (5) | −0.002 (5) | 0.002 (5) | 0.014 (5) |
C4 | 0.0428 (3) | 0.0204 (3) | 0.0317 (3) | −0.0047 (2) | 0.0195 (3) | −0.0010 (2) |
H4a | 0.156 (10) | 0.044 (6) | 0.070 (8) | 0.036 (6) | 0.054 (8) | 0.024 (6) |
H4b | 0.061 (6) | 0.102 (9) | 0.082 (9) | −0.049 (6) | 0.048 (6) | −0.050 (7) |
C5 | 0.0165 (2) | 0.0183 (2) | 0.0196 (2) | −0.00281 (18) | 0.00220 (18) | −0.00111 (18) |
C6 | 0.0181 (2) | 0.0284 (3) | 0.0235 (2) | −0.0054 (2) | 0.0035 (2) | 0.0002 (2) |
H6 | 0.050 (5) | 0.084 (7) | 0.035 (5) | −0.011 (5) | 0.024 (4) | 0.011 (5) |
C7 | 0.0190 (3) | 0.0341 (3) | 0.0293 (3) | −0.0051 (2) | −0.0015 (2) | 0.0035 (2) |
H7a | 0.020 (4) | 0.133 (10) | 0.075 (7) | 0.018 (5) | 0.006 (5) | 0.033 (7) |
H7b | 0.101 (8) | 0.041 (6) | 0.058 (6) | −0.050 (6) | −0.022 (6) | 0.004 (5) |
C8 | 0.0260 (3) | 0.0430 (4) | 0.0244 (3) | −0.0099 (3) | −0.0016 (2) | 0.0054 (3) |
H8a | 0.052 (6) | 0.175 (13) | 0.079 (8) | −0.028 (7) | 0.022 (6) | −0.088 (9) |
H8b | 0.055 (7) | 0.102 (9) | 0.130 (10) | −0.021 (6) | −0.031 (7) | 0.076 (8) |
C9 | 0.0179 (2) | 0.0152 (2) | 0.0194 (2) | −0.00212 (18) | 0.00223 (18) | −0.00130 (17) |
C10 | 0.0198 (2) | 0.0212 (3) | 0.0255 (2) | −0.0049 (2) | 0.0040 (2) | −0.0005 (2) |
H10 | 0.037 (5) | 0.040 (5) | 0.079 (7) | −0.005 (4) | 0.021 (5) | −0.008 (5) |
C11 | 0.0314 (3) | 0.0213 (3) | 0.0393 (3) | −0.0103 (2) | 0.0014 (3) | 0.0026 (2) |
H11a | 0.074 (6) | 0.056 (6) | 0.083 (8) | −0.008 (5) | 0.036 (6) | 0.005 (6) |
H11b | 0.043 (5) | 0.045 (6) | 0.075 (7) | −0.008 (4) | −0.020 (5) | −0.019 (5) |
C12 | 0.0326 (3) | 0.0156 (2) | 0.0369 (3) | 0.0006 (2) | −0.0068 (3) | −0.0028 (2) |
H12a | 0.084 (7) | 0.052 (6) | 0.054 (6) | −0.001 (5) | 0.010 (6) | −0.026 (5) |
H12b | 0.076 (7) | 0.036 (6) | 0.095 (7) | −0.002 (5) | −0.044 (6) | 0.014 (5) |
C13 | 0.0190 (2) | 0.0170 (2) | 0.0186 (2) | −0.00053 (17) | 0.00679 (18) | −0.00205 (18) |
C14 | 0.0191 (2) | 0.0211 (2) | 0.0266 (3) | 0.00204 (19) | 0.0048 (2) | −0.0030 (2) |
H14 | 0.042 (5) | 0.069 (6) | 0.037 (5) | 0.016 (4) | −0.004 (4) | −0.012 (4) |
C15 | 0.0206 (2) | 0.0217 (3) | 0.0461 (4) | 0.0013 (2) | 0.0121 (2) | −0.0016 (2) |
H15 | 0.013 (4) | 0.073 (7) | 0.094 (8) | 0.006 (4) | −0.004 (5) | −0.009 (6) |
C16 | 0.0336 (3) | 0.0255 (3) | 0.0433 (4) | 0.0037 (2) | 0.0236 (3) | 0.0013 (3) |
C17 | 0.0467 (3) | 0.0336 (3) | 0.0258 (3) | 0.0093 (3) | 0.0181 (3) | −0.0035 (3) |
H17 | 0.107 (8) | 0.073 (7) | 0.042 (6) | 0.033 (6) | 0.027 (6) | −0.017 (5) |
C18 | 0.0320 (3) | 0.0272 (3) | 0.0194 (2) | 0.0045 (2) | 0.0062 (2) | −0.0053 (2) |
H2 | 0.092 (7) | 0.036 (5) | 0.045 (6) | −0.037 (5) | 0.027 (5) | −0.019 (4) |
H18 | 0.061 (6) | 0.057 (6) | 0.038 (5) | 0.018 (5) | −0.013 (5) | −0.020 (4) |
Si1—C1 | 1.8643 (5) | C16—C17 | 1.3844 (10) |
Si1—C5 | 1.8646 (5) | C17—C18 | 1.3971 (8) |
Si1—C9 | 1.8680 (5) | C2—H2 | 1.079 (7) |
Si1—C13 | 1.8672 (5) | C3—H3a | 1.082 (8) |
O1—C1 | 1.3830 (6) | C3—H3b | 1.067 (9) |
O1—C4 | 1.4479 (6) | C4—H4a | 1.039 (9) |
O2—C5 | 1.3804 (6) | C4—H4b | 1.093 (9) |
O2—C8 | 1.4481 (7) | C6—H6 | 1.077 (7) |
O3—C9 | 1.3847 (6) | C7—H7a | 1.080 (9) |
O3—C12 | 1.4596 (7) | C7—H7b | 1.083 (8) |
C1—C2 | 1.3350 (7) | C8—H8a | 1.081 (9) |
C2—C3 | 1.5081 (7) | C8—H8b | 1.085 (10) |
C3—C4 | 1.5272 (8) | C10—H10 | 1.049 (8) |
C5—C6 | 1.3348 (7) | C11—H11a | 1.072 (9) |
C6—C7 | 1.5069 (8) | C11—H11b | 1.102 (8) |
C7—C8 | 1.5222 (8) | C12—H12a | 1.085 (8) |
C9—C10 | 1.3356 (7) | C12—H12b | 1.072 (9) |
C10—C11 | 1.5052 (8) | C14—H14 | 1.089 (8) |
C11—C12 | 1.5271 (9) | C15—H15 | 1.092 (8) |
C13—C14 | 1.4025 (7) | C16—H16 | 1.089 (7) |
C13—C18 | 1.3975 (7) | C17—H17 | 1.083 (9) |
C14—C15 | 1.3929 (7) | C18—H18 | 1.076 (8) |
C15—C16 | 1.3851 (9) | ||
Si1—C1—O1 | 118.36 (3) | C1—C2—H2 | 124.0 (4) |
Si1—C5—O2 | 118.53 (3) | C2—C3—H3a | 114.0 (5) |
Si1—C9—O3 | 119.68 (3) | C2—C3—H3b | 111.4 (5) |
Si1—C1—C2 | 128.55 (4) | C3—C2—H2 | 126.2 (4) |
Si1—C5—C6 | 128.62 (4) | C3—C4—H4a | 114.9 (6) |
Si1—C9—C10 | 127.36 (4) | C3—C4—H4b | 110.4 (5) |
Si1—C13—C14 | 120.58 (4) | C4—C3—H3a | 110.4 (5) |
Si1—C13—C18 | 121.50 (4) | C4—C3—H3b | 110.8 (6) |
O1—C1—C2 | 113.09 (4) | C5—C6—H6 | 123.9 (4) |
O1—C4—C3 | 107.11 (4) | C6—C7—H7a | 111.6 (6) |
O2—C5—C6 | 112.81 (5) | C6—C7—H7b | 111.3 (5) |
O2—C8—C7 | 107.48 (5) | C7—C6—H6 | 125.9 (4) |
O3—C9—C10 | 112.96 (5) | C7—C8—H8a | 111.7 (6) |
O3—C12—C11 | 107.10 (5) | C7—C8—H8b | 113.6 (6) |
O1—C4—H4a | 108.4 (5) | C8—C7—H7a | 113.1 (5) |
O1—C4—H4b | 107.4 (5) | C8—C7—H7b | 112.6 (5) |
O2—C8—H8a | 107.3 (5) | C9—C10—H10 | 125.0 (4) |
O2—C8—H8b | 108.1 (6) | C10—C11—H11a | 110.4 (5) |
O3—C12—H12a | 106.4 (5) | C10—C11—H11b | 111.6 (5) |
O3—C12—H12b | 108.1 (5) | C11—C10—H10 | 124.7 (4) |
C1—Si1—C5 | 107.29 (2) | C11—C12—H12a | 113.7 (5) |
C1—Si1—C9 | 108.03 (2) | C11—C12—H12b | 111.2 (6) |
C1—Si1—C13 | 112.96 (2) | C12—C11—H11a | 111.9 (5) |
C5—Si1—C9 | 112.08 (2) | C12—C11—H11b | 112.0 (5) |
C5—Si1—C13 | 109.47 (2) | C13—C14—H14 | 119.9 (4) |
C9—Si1—C13 | 107.08 (2) | C13—C18—H18 | 118.9 (4) |
C1—O1—C4 | 107.51 (4) | C14—C15—H15 | 120.1 (5) |
C5—O2—C8 | 107.87 (4) | C15—C14—H14 | 118.8 (4) |
C9—O3—C12 | 107.43 (4) | C15—C16—H16 | 119.9 (6) |
C1—C2—C3 | 109.84 (5) | C16—C15—H15 | 119.7 (5) |
C2—C3—C4 | 101.48 (4) | C16—C17—H17 | 120.9 (5) |
C5—C6—C7 | 110.24 (5) | C17—C16—H16 | 120.8 (6) |
C6—C7—C8 | 101.58 (5) | C17—C18—H18 | 120.6 (4) |
C9—C10—C11 | 110.34 (5) | C18—C17—H17 | 118.2 (5) |
C10—C11—C12 | 101.65 (5) | H3a—C3—H3b | 108.7 (7) |
C13—C14—C15 | 121.27 (5) | H4a—C4—H4b | 108.3 (8) |
C13—C18—C17 | 120.48 (6) | H7a—C7—H7b | 106.8 (7) |
C14—C13—C18 | 117.88 (5) | H8a—C8—H8b | 108.4 (10) |
C14—C15—C16 | 120.16 (6) | H11a—C11—H11b | 109.2 (7) |
C15—C16—C17 | 119.30 (5) | H12a—C12—H12b | 110.1 (7) |
C16—C17—C18 | 120.89 (5) |
IAM | HAR | IAM | HAR | ||
Si1—C1 | 1.8664 (8) | 1.8663 (5) | C1—Si1—C5 | 111.25 (4) | 111.33 (2) |
Si1—C5 | 1.8640 (8) | 1.8643 (5) | C1—Si1—C9 | 106.48 (4) | 106.55 (2) |
Si1—C9 | 1.8610 (8) | 1.8628 (5) | C1—Si1—C13 | 109.38 (4) | 109.36 (2) |
Si1—C13 | 1.8559 (9) | 1.8570 (5) | C5—Si1—C9 | 107.10 (4) | 107.14 (2) |
C5—Si1—C13 | 110.92 (4) | 110.86 (2) | |||
C1—C2 | 1.3312 (11) | 1.3356 (6) | C9—Si1—C13 | 111.61 (4) | 111.52 (2) |
C5—C6 | 1.3315 (12) | 1.3357 (6) | |||
C9—C10 | 1.3273 (12) | 1.3294 (7) |
IAM | HAR | IAM | HAR | ||
Si1—C1 | 1.8633 (9) | 1.8643 (5) | C1—Si1—C5 | 107.26 (4) | 107.29 (2) |
Si1—C5 | 1.8638 (9) | 1.8646 (5) | C1—Si1—C9 | 107.99 (4) | 108.03 (2) |
Si1—C9 | 1.8670 (9) | 1.8680 (5) | C1—Si1—C13 | 112.97 (4) | 112.96 (2) |
Si1—C13 | 1.8662 (9) | 1.8672 (5) | C5—Si1—C9 | 112.15 (4) | 112.08 (2) |
C5—Si1—C13 | 109.53 (4) | 109.47 (2) | |||
C1—C2 | 1.3314 (12) | 1.3350 (7) | C9—Si1—C13 | 107.01 (4) | 107.08 (2) |
C5—C6 | 1.3317 (12) | 1.3348 (7) | |||
C9—C10 | 1.3348 (12) | 1.3356 (7) |
1 | 2 | |||||
C2—H2 | C6—H6 | C10—H10 | C2—H2 | C6—H6 | C10—H10 | |
IAM | 0.9500 | 0.912 (15)a | 0.9500 | 0.995 (17)a | 0.9500 | 0.9500 |
HAR | 1.084 (6) | 1.070 (6) | 1.088 (7) | 1.079 (7) | 1.077 (7) | 1.049 (8) |
Note: (a) Hydrogen atoms were refined independently. |
Funding information
ERB would like to thank the `Fonds der Chemischen Industrie' for a doctoral fellowship. RS would like to thank the `Studienstiftung des Deutschen Volkes' for a doctoral fellowship.
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