Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051604/sk3175sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051604/sk3175IVsup2.hkl |
CCDC reference: 667436
Key indicators
- Single-crystal X-ray study
- T = 100 K
- R factor = 0.037
- wR factor = 0.098
- Data-to-parameter ratio = 18.4
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
For related literature, see: Armaroli et al. (2006); Hitchcock et al. (1957); Kuwano et al. (2003); Noyori (2002); Oita & Gilman (1957); Sheldrick (2005, 2007); Zhang et al. (2006); Kranenburg et al. (1995).
The title compound was prepared by a modification of the published method (Oita & Gilman, 1957). A solution of diphenyl ether (8 ml, 50.3 mmol) in THF (50 ml) was added dropwise to a mixture of n-BuLi (92.3 ml, 110 mmol, 1.6 M in hexanes) and TMEDA (16.7 ml, 110 mmol) and the mixture was stirred for 12 h. A solution of silicon tetrachloride (2.9 ml, 50.3 mmol) in THF (30 ml) was added and stirring was continued for a further period of 16 h. To the stirred solution 20 ml of water was added and the organic layer was separated. After extracting the aqueous layer twice with diethyl ether, the combined organic layers were treated with activated charcoal and dried with anhydrous MgSO4. The solvent was removed in vacuo to obtain a yellow solid which was purified by chromatography and recrystallized from a 1:2 mixture of dichloromethane and petroleum ether. Yield: 3.5 g (39%). Mp: >523 K. Anal. Calcd for C24H16SiO2: C,79.09; H, 4.43%. Found: C, 78.73; H, 3.95%. MS, EI (m/z): 364.5 (M+). 1H NMR (CDCl3): δ 6.95–7.50 (m, phenyl).
From 1170 reflections harvested from diverse regions of reciprocal space and having I/σ(I) > 15 it was determined (CELL_NOW (Sheldrick, 2005)) that the compound crystallized in the monoclinic system and that the crystal was twinned by a 177.4° rotation about the b axis. Integration of the raw data was performed with the 2-component version of SAINT+ as controlled by the 2-component instruction file generated by CELL_NOW. Correction for absorption and crystal decay as well as deconvolution of the overlapped reflections was performed with TWINABS (Sheldrick, 2007) which also generated a reflection file containing only the single reflections from the major component which was used for the solution and preliminary refinement of the structure. Final refinement was carried out with a reflection file containing all single reflections from the major twin component plus that portion of all composite reflections attibutable to that component. The twin fraction is 0.31
The syntheses of diphenylether derivatives such as 2,2'-dilithiodiphenylether (I), 10,10'-diphenylphenoxasilane (II), 10-diphenylphenoxyphosphine (III) and 10,10'-spirobi(dibenzo[b,e][1,4]oxa)silane (IV) were first reported by Hitchcock et al. (1957) and Oita & Gilman (1957). Subsequently, some of these derivatives were used extensively to make interesting phosphorus(III) based ligands for coordination chemistry (Noyori, 2002), luminescence (Armaroli et al., 2006) and sensor materials (Zhang et al., 2006), organic light emitting devices and catalytic applications (Kranenburg et al., 1995) (Kuwano et al., 2003). Despite the wide interest in this class of compounds, structural data are not available for the spirocyclic derivative IV.
A perspective view of IV is presented in Figure 1. The geometry about silicon is slightly distorted tetrahedral as can be seen from the data in Table 1 and the dihedral angle of 86.14 (3)° between the Si1 O1 C1 C6 C7 C12 and Si1 O2 C13 C18 C19 C24 planes. Each 1-Si,2-O—C6H4 moiety is within 0.04 Å of planarity but in the half of the molecule containing C1—C12, Si1 and O1, the two 1-Si,2-O—C6H4 moieties are folded about the Si1—O1 line by 5.66 (4)° while in the other half of the molecule the fold angle is 9.30 (5)°. Assisting in assembling the crystal structure are π-π and C—H–π-ring interactions. The first occurs between the C1—C6 ring and the C7—C12 ring in the molecule at 2 - x, 1 - y, -z where the dihedral angle between the planes is 6.54°, the distance between the centers of gravity (Cg) of the rings is 3.6907 (7) Å and the average perpendicular distance between the rings is 3.34 Å. The second occrs between C15—H15 and the ring consisting of C1—C6 at x, 1.5 - y, -1/2 + z where the distance from H15 to the center of gravity of the ring is 2.68 Å and the C—H–Cg angle is 148°.
For related literature, see: Armaroli et al. (2006); Hitchcock et al. (1957); Kuwano et al. (2003); Noyori (2002); Oita & Gilman (1957); Sheldrick (2005, 2007); Zhang et al. (2006); Kranenburg et al. (1995).
Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: APEX2 (Bruker, 2007); software used to prepare material for publication: APEX2 (Bruker, 2007).
Fig. 1. Perspective view of IV. Displacement ellipsoids are drawn at the 50% level and H-atoms are represented by spheres of arbitrary radius. | |
Fig. 2. The structures of (I), (II) and (III). |
C24H16O2Si | F(000) = 760 |
Mr = 364.46 | Dx = 1.398 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4009 reflections |
a = 10.7975 (7) Å | θ = 2.6–29.1° |
b = 11.4290 (7) Å | µ = 0.15 mm−1 |
c = 14.0515 (9) Å | T = 100 K |
β = 92.756 (1)° | Block, colourless |
V = 1732.0 (2) Å3 | 0.28 × 0.12 × 0.12 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 4517 independent reflections |
Radiation source: fine-focus sealed tube | 3962 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
φ and ω scans | θmax = 28.9°, θmin = 2.3° |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2007) | h = −14→14 |
Tmin = 0.881, Tmax = 0.982 | k = −15→15 |
31348 measured reflections | l = −19→19 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.047P)2 + 0.6911P] where P = (Fo2 + 2Fc2)/3 |
4517 reflections | (Δ/σ)max = 0.001 |
245 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C24H16O2Si | V = 1732.0 (2) Å3 |
Mr = 364.46 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.7975 (7) Å | µ = 0.15 mm−1 |
b = 11.4290 (7) Å | T = 100 K |
c = 14.0515 (9) Å | 0.28 × 0.12 × 0.12 mm |
β = 92.756 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 4517 independent reflections |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2007) | 3962 reflections with I > 2σ(I) |
Tmin = 0.881, Tmax = 0.982 | Rint = 0.038 |
31348 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.42 e Å−3 |
4517 reflections | Δρmin = −0.26 e Å−3 |
245 parameters |
Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5 °. in omega, colllected at phi = 0.00, 90.00 and 180.00 °. and 2 sets of 800 frames, each of width 0.45 ° in phi, collected at omega = -30.00 and 210.00 °. The scan time was 20 sec/frame. |
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. H-atoms were placed in calculated positions (C—H = 0.95 Å) and included as riding contributions with isotropic displacement parameters 1.2 times those of the attached carbon atoms. |
x | y | z | Uiso*/Ueq | ||
Si1 | 0.79679 (3) | 0.68709 (3) | 0.09949 (2) | 0.01172 (9) | |
O1 | 0.93646 (8) | 0.44025 (8) | 0.10359 (6) | 0.01635 (19) | |
O2 | 0.61910 (9) | 0.91110 (8) | 0.09843 (7) | 0.0195 (2) | |
C1 | 0.94750 (11) | 0.64573 (11) | 0.15843 (8) | 0.0131 (2) | |
C2 | 1.02066 (11) | 0.72674 (11) | 0.21191 (9) | 0.0151 (2) | |
H2 | 0.9918 | 0.8048 | 0.2175 | 0.018* | |
C3 | 1.13318 (12) | 0.69630 (11) | 0.25648 (9) | 0.0170 (2) | |
H3 | 1.1798 | 0.7524 | 0.2929 | 0.020* | |
C4 | 1.17750 (11) | 0.58234 (12) | 0.24735 (9) | 0.0166 (2) | |
H4 | 1.2549 | 0.5609 | 0.2774 | 0.020* | |
C5 | 1.10929 (11) | 0.50053 (11) | 0.19476 (9) | 0.0147 (2) | |
H5 | 1.1400 | 0.4232 | 0.1880 | 0.018* | |
C6 | 0.99463 (11) | 0.53219 (10) | 0.15140 (8) | 0.0128 (2) | |
C7 | 0.82770 (11) | 0.44887 (11) | 0.04799 (8) | 0.0130 (2) | |
C8 | 0.79146 (11) | 0.34298 (11) | 0.00550 (9) | 0.0150 (2) | |
H8 | 0.8387 | 0.2741 | 0.0179 | 0.018* | |
C9 | 0.68621 (12) | 0.33901 (11) | −0.05482 (9) | 0.0163 (2) | |
H9 | 0.6610 | 0.2670 | −0.0835 | 0.020* | |
C10 | 0.61712 (12) | 0.43994 (12) | −0.07369 (9) | 0.0170 (2) | |
H10 | 0.5463 | 0.4377 | −0.1164 | 0.020* | |
C11 | 0.65286 (11) | 0.54342 (11) | −0.02949 (9) | 0.0157 (2) | |
H11 | 0.6047 | 0.6118 | −0.0420 | 0.019* | |
C12 | 0.75802 (11) | 0.55123 (11) | 0.03337 (8) | 0.0134 (2) | |
C13 | 0.80137 (11) | 0.82187 (10) | 0.02678 (8) | 0.0131 (2) | |
C14 | 0.89247 (11) | 0.84005 (11) | −0.04049 (9) | 0.0155 (2) | |
H14 | 0.9499 | 0.7792 | −0.0516 | 0.019* | |
C15 | 0.90084 (12) | 0.94368 (12) | −0.09083 (9) | 0.0175 (2) | |
H15 | 0.9639 | 0.9539 | −0.1350 | 0.021* | |
C16 | 0.81571 (12) | 1.03291 (11) | −0.07603 (9) | 0.0183 (3) | |
H16 | 0.8212 | 1.1045 | −0.1099 | 0.022* | |
C17 | 0.72353 (12) | 1.01763 (11) | −0.01233 (9) | 0.0183 (3) | |
H17 | 0.6647 | 1.0779 | −0.0032 | 0.022* | |
C18 | 0.71743 (11) | 0.91282 (11) | 0.03863 (9) | 0.0145 (2) | |
C19 | 0.60334 (11) | 0.82827 (11) | 0.16857 (9) | 0.0144 (2) | |
C20 | 0.50531 (12) | 0.85513 (11) | 0.22636 (9) | 0.0174 (3) | |
H20 | 0.4576 | 0.9240 | 0.2149 | 0.021* | |
C21 | 0.47822 (12) | 0.78099 (12) | 0.30027 (9) | 0.0182 (3) | |
H21 | 0.4115 | 0.7988 | 0.3395 | 0.022* | |
C22 | 0.54843 (12) | 0.68018 (12) | 0.31746 (9) | 0.0183 (3) | |
H22 | 0.5306 | 0.6294 | 0.3686 | 0.022* | |
C23 | 0.64470 (11) | 0.65506 (11) | 0.25895 (9) | 0.0160 (2) | |
H23 | 0.6923 | 0.5863 | 0.2711 | 0.019* | |
C24 | 0.67474 (11) | 0.72721 (11) | 0.18228 (8) | 0.0132 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1 | 0.01153 (16) | 0.00995 (16) | 0.01365 (17) | 0.00109 (11) | 0.00041 (12) | −0.00008 (11) |
O1 | 0.0161 (4) | 0.0115 (4) | 0.0209 (4) | 0.0018 (3) | −0.0052 (3) | −0.0014 (3) |
O2 | 0.0205 (5) | 0.0154 (4) | 0.0235 (5) | 0.0070 (4) | 0.0088 (4) | 0.0056 (4) |
C1 | 0.0127 (5) | 0.0137 (5) | 0.0130 (5) | 0.0008 (4) | 0.0021 (4) | 0.0013 (4) |
C2 | 0.0160 (5) | 0.0148 (6) | 0.0148 (5) | −0.0004 (4) | 0.0019 (4) | −0.0014 (4) |
C3 | 0.0161 (6) | 0.0199 (6) | 0.0150 (6) | −0.0034 (5) | 0.0000 (4) | −0.0012 (5) |
C4 | 0.0125 (5) | 0.0228 (6) | 0.0144 (5) | 0.0003 (5) | −0.0001 (4) | 0.0034 (5) |
C5 | 0.0145 (5) | 0.0146 (6) | 0.0151 (5) | 0.0018 (4) | 0.0023 (4) | 0.0037 (4) |
C6 | 0.0140 (5) | 0.0120 (5) | 0.0125 (5) | −0.0014 (4) | 0.0017 (4) | 0.0008 (4) |
C7 | 0.0132 (5) | 0.0137 (5) | 0.0123 (5) | 0.0001 (4) | 0.0010 (4) | 0.0005 (4) |
C8 | 0.0165 (6) | 0.0124 (5) | 0.0162 (6) | 0.0009 (4) | 0.0012 (4) | 0.0001 (4) |
C9 | 0.0179 (6) | 0.0160 (6) | 0.0151 (6) | −0.0037 (5) | 0.0017 (4) | −0.0021 (4) |
C10 | 0.0151 (5) | 0.0201 (6) | 0.0156 (6) | −0.0011 (5) | −0.0009 (4) | −0.0014 (5) |
C11 | 0.0147 (5) | 0.0156 (6) | 0.0168 (6) | 0.0018 (4) | −0.0003 (4) | 0.0003 (4) |
C12 | 0.0134 (5) | 0.0134 (5) | 0.0134 (5) | 0.0001 (4) | 0.0012 (4) | −0.0004 (4) |
C13 | 0.0132 (5) | 0.0122 (5) | 0.0138 (5) | 0.0000 (4) | −0.0010 (4) | −0.0006 (4) |
C14 | 0.0147 (5) | 0.0157 (6) | 0.0160 (6) | 0.0008 (4) | 0.0006 (4) | −0.0001 (5) |
C15 | 0.0186 (6) | 0.0199 (6) | 0.0142 (5) | −0.0025 (5) | 0.0022 (5) | 0.0006 (5) |
C16 | 0.0248 (6) | 0.0138 (6) | 0.0163 (6) | −0.0021 (5) | 0.0003 (5) | 0.0013 (5) |
C17 | 0.0233 (6) | 0.0122 (6) | 0.0196 (6) | 0.0040 (5) | 0.0017 (5) | 0.0005 (5) |
C18 | 0.0159 (5) | 0.0132 (5) | 0.0147 (5) | 0.0000 (4) | 0.0015 (4) | −0.0005 (4) |
C19 | 0.0147 (5) | 0.0130 (6) | 0.0156 (6) | −0.0010 (4) | 0.0010 (4) | −0.0002 (4) |
C20 | 0.0167 (6) | 0.0154 (6) | 0.0202 (6) | 0.0030 (5) | 0.0025 (5) | −0.0024 (5) |
C21 | 0.0156 (6) | 0.0223 (6) | 0.0170 (6) | −0.0022 (5) | 0.0035 (4) | −0.0048 (5) |
C22 | 0.0188 (6) | 0.0208 (6) | 0.0152 (6) | −0.0029 (5) | 0.0017 (5) | 0.0015 (5) |
C23 | 0.0151 (5) | 0.0154 (6) | 0.0173 (6) | −0.0005 (4) | −0.0015 (4) | 0.0010 (5) |
C24 | 0.0129 (5) | 0.0126 (5) | 0.0141 (5) | −0.0005 (4) | −0.0007 (4) | −0.0018 (4) |
Si1—C12 | 1.847 (1) | C10—C11 | 1.382 (2) |
Si1—C13 | 1.850 (1) | C10—H10 | 0.9500 |
Si1—C1 | 1.852 (1) | C11—C12 | 1.408 (2) |
Si1—C24 | 1.857 (1) | C11—H11 | 0.9500 |
O1—C6 | 1.382 (1) | C13—C18 | 1.394 (2) |
O1—C7 | 1.382 (1) | C13—C14 | 1.412 (2) |
O2—C19 | 1.383 (2) | C14—C15 | 1.385 (2) |
O2—C18 | 1.385 (2) | C14—H14 | 0.9500 |
C1—C6 | 1.399 (2) | C15—C16 | 1.395 (2) |
C1—C2 | 1.410 (2) | C15—H15 | 0.9500 |
C2—C3 | 1.384 (2) | C16—C17 | 1.381 (2) |
C2—H2 | 0.9500 | C16—H16 | 0.9500 |
C3—C4 | 1.396 (2) | C17—C18 | 1.399 (2) |
C3—H3 | 0.9500 | C17—H17 | 0.9500 |
C4—C5 | 1.382 (2) | C19—C24 | 1.397 (2) |
C4—H4 | 0.9500 | C19—C20 | 1.399 (2) |
C5—C6 | 1.401 (2) | C20—C21 | 1.383 (2) |
C5—H5 | 0.9500 | C20—H20 | 0.9500 |
C7—C8 | 1.397 (2) | C21—C22 | 1.394 (2) |
C7—C12 | 1.401 (2) | C21—H21 | 0.9500 |
C8—C9 | 1.386 (2) | C22—C23 | 1.386 (2) |
C8—H8 | 0.9500 | C22—H22 | 0.9500 |
C9—C10 | 1.392 (2) | C23—C24 | 1.407 (2) |
C9—H9 | 0.9500 | C23—H23 | 0.9500 |
C12—Si1—C13 | 115.69 (6) | C12—C11—H11 | 118.8 |
C12—Si1—C1 | 100.57 (6) | C7—C12—C11 | 116.8 (1) |
C13—Si1—C1 | 114.41 (5) | C7—C12—Si1 | 121.41 (9) |
C12—Si1—C24 | 111.85 (5) | C11—C12—Si1 | 121.70 (9) |
C13—Si1—C24 | 100.31 (6) | C18—C13—C14 | 116.6 (1) |
C1—Si1—C24 | 114.70 (5) | C18—C13—Si1 | 121.32 (9) |
C6—O1—C7 | 125.07 (9) | C14—C13—Si1 | 122.01 (9) |
C19—O2—C18 | 124.5 (1) | C15—C14—C13 | 122.2 (1) |
C6—C1—C2 | 116.8 (1) | C15—C14—H14 | 118.9 |
C6—C1—Si1 | 121.34 (9) | C13—C14—H14 | 118.9 |
C2—C1—Si1 | 121.90 (9) | C14—C15—C16 | 119.3 (1) |
C3—C2—C1 | 122.2 (1) | C14—C15—H15 | 120.3 |
C3—C2—H2 | 118.9 | C16—C15—H15 | 120.3 |
C1—C2—H2 | 118.9 | C17—C16—C15 | 120.3 (1) |
C2—C3—C4 | 119.4 (1) | C17—C16—H16 | 119.8 |
C2—C3—H3 | 120.3 | C15—C16—H16 | 119.8 |
C4—C3—H3 | 120.3 | C16—C17—C18 | 119.6 (1) |
C5—C4—C3 | 120.3 (1) | C16—C17—H17 | 120.2 |
C5—C4—H4 | 119.9 | C18—C17—H17 | 120.2 |
C3—C4—H4 | 119.9 | O2—C18—C13 | 125.7 (1) |
C4—C5—C6 | 119.66 (11) | O2—C18—C17 | 112.3 (1) |
C4—C5—H5 | 120.2 | C13—C18—C17 | 122.0 (1) |
C6—C5—H5 | 120.2 | O2—C19—C24 | 125.3 (1) |
O1—C6—C1 | 125.5 (1) | O2—C19—C20 | 112.7 (1) |
O1—C6—C5 | 112.7 (1) | C24—C19—C20 | 122.0 (1) |
C1—C6—C5 | 121.7 (1) | C21—C20—C19 | 119.7 (1) |
O1—C7—C8 | 113.1 (1) | C21—C20—H20 | 120.2 |
O1—C7—C12 | 125.3 (1) | C19—C20—H20 | 120.2 |
C8—C7—C12 | 121.6 (1) | C20—C21—C22 | 120.3 (1) |
C9—C8—C7 | 119.6 (1) | C20—C21—H21 | 119.9 |
C9—C8—H8 | 120.2 | C22—C21—H21 | 119.9 |
C7—C8—H8 | 120.2 | C23—C22—C21 | 119.1 (1) |
C8—C9—C10 | 120.4 (1) | C23—C22—H22 | 120.5 |
C8—C9—H9 | 119.8 | C21—C22—H22 | 120.5 |
C10—C9—H9 | 119.8 | C22—C23—C24 | 122.7 (1) |
C11—C10—C9 | 119.2 (1) | C22—C23—H23 | 118.7 |
C11—C10—H10 | 120.4 | C24—C23—H23 | 118.7 |
C9—C10—H10 | 120.4 | C19—C24—C23 | 116.4 (1) |
C10—C11—C12 | 122.4 (1) | C19—C24—Si1 | 121.43 (9) |
C10—C11—H11 | 118.8 | C23—C24—Si1 | 122.12 (9) |
Experimental details
Crystal data | |
Chemical formula | C24H16O2Si |
Mr | 364.46 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 10.7975 (7), 11.4290 (7), 14.0515 (9) |
β (°) | 92.756 (1) |
V (Å3) | 1732.0 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.15 |
Crystal size (mm) | 0.28 × 0.12 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (TWINABS; Sheldrick, 2007) |
Tmin, Tmax | 0.881, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 31348, 4517, 3962 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.679 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.098, 1.04 |
No. of reflections | 4517 |
No. of parameters | 245 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.26 |
Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).
Si1—C12 | 1.847 (1) | Si1—C1 | 1.852 (1) |
Si1—C13 | 1.850 (1) | Si1—C24 | 1.857 (1) |
C12—Si1—C13 | 115.69 (6) | C12—Si1—C24 | 111.85 (5) |
C12—Si1—C1 | 100.57 (6) | C13—Si1—C24 | 100.31 (6) |
C13—Si1—C1 | 114.41 (5) | C1—Si1—C24 | 114.70 (5) |
Planea | Plane | Dihedral angle |
1 | 2 | 86.14 (3) |
3 | 4 | 5.66 (4) |
5 | 6 | 9.30 (5) |
7 | 8 | 6.54 (6) |
Note: (a) atoms defining planes: (1) Si1/O1/C1/C6/C7/C12; (2) Si1/O2/C13/C18/C19/C24; (3) Si1/O1/C1–C6; (4) Si1/O1/C7–C12; (5) Si1/O2/C13–C18; (6) Si1/O2/C19–C24; (7) C1–C6; (8) C7–C12 at (2-x, 1-y, -z). |
Contact | Distance |
Cg(7)···Cg(8)a,b | 3.96 |
d(8···9)c | 3.34 |
C15—H15···Cg(9) | 2.68 |
Notes: (a) atoms defining planes: (7) C1–C6; (8) C7–C12 at (2-x, 1-y, -z); (9) C1–C6 at (x, 1.5+y, -0.5+z); (b) Cg = center of gravity of specified ring; (c) perpendicular distance between specified rings. |
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The syntheses of diphenylether derivatives such as 2,2'-dilithiodiphenylether (I), 10,10'-diphenylphenoxasilane (II), 10-diphenylphenoxyphosphine (III) and 10,10'-spirobi(dibenzo[b,e][1,4]oxa)silane (IV) were first reported by Hitchcock et al. (1957) and Oita & Gilman (1957). Subsequently, some of these derivatives were used extensively to make interesting phosphorus(III) based ligands for coordination chemistry (Noyori, 2002), luminescence (Armaroli et al., 2006) and sensor materials (Zhang et al., 2006), organic light emitting devices and catalytic applications (Kranenburg et al., 1995) (Kuwano et al., 2003). Despite the wide interest in this class of compounds, structural data are not available for the spirocyclic derivative IV.
A perspective view of IV is presented in Figure 1. The geometry about silicon is slightly distorted tetrahedral as can be seen from the data in Table 1 and the dihedral angle of 86.14 (3)° between the Si1 O1 C1 C6 C7 C12 and Si1 O2 C13 C18 C19 C24 planes. Each 1-Si,2-O—C6H4 moiety is within 0.04 Å of planarity but in the half of the molecule containing C1—C12, Si1 and O1, the two 1-Si,2-O—C6H4 moieties are folded about the Si1—O1 line by 5.66 (4)° while in the other half of the molecule the fold angle is 9.30 (5)°. Assisting in assembling the crystal structure are π-π and C—H–π-ring interactions. The first occurs between the C1—C6 ring and the C7—C12 ring in the molecule at 2 - x, 1 - y, -z where the dihedral angle between the planes is 6.54°, the distance between the centers of gravity (Cg) of the rings is 3.6907 (7) Å and the average perpendicular distance between the rings is 3.34 Å. The second occrs between C15—H15 and the ring consisting of C1—C6 at x, 1.5 - y, -1/2 + z where the distance from H15 to the center of gravity of the ring is 2.68 Å and the C—H–Cg angle is 148°.