organic compounds
1,2-Bis{2-[2-(trimethylsilyl)ethynyl]phenyl}ethane-1,2-dione
aDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804, USA
*Correspondence e-mail: ffroncz@lsu.edu
The title compound, C24H26O2Si2, has C2 The dihedral angle between the aromatic rings is 84.5 (2)°. The acetylene group is slightly non-linear, with angles at the acetylene C atoms of 175.7 (2) and 177.0 (2)°. In the only van de Waals interactions occur.
Related literature
For the structure of benzil, see Brown & Sadanaga (1965); Gabe et al. (1981); More et al. (1987). For the synthesis see: Garcia et al. (1995). For the determination of from Bijvoet pairs, see: Hooft et al. (2008).
Experimental
Crystal data
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Data collection: COLLECT (Nonius, 2000); cell DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
10.1107/S160053681203663X/bx2422sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681203663X/bx2422Isup2.hkl
Supporting information file. DOI: 10.1107/S160053681203663X/bx2422Isup3.cml
The title compound was supplied by J. Gabriel Garcia, having been synthesized from 1,2-bis-(2-bromophenyl)-ethane-1,2-dione and trimethylsilyl acetylene (Garcia et al., 1995).
The
assignment and are based on analysis of 1419 Bijvoet pairs, Flack (1983) parameter x = 0.0 (1), Hooft et al. (2008) parameter y = -0.04 (7), and Hooft P2(true) = 1.000.All H atoms were placed in calculated positions with C—H distances of 0.95 (aromatic) and 0.98 Å (methyl) and Uiso = 1.2 or 1.5 Ueq of the attached sp2 or sp3 C atom, and thereafter treated as riding. A torsional parameter was refined for each methyl group.
Data collection: COLLECT (Nonius, 2000); cell
DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).C24H26O2Si2 | Dx = 1.145 Mg m−3 |
Mr = 402.63 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, P3221 | Cell parameters from 3424 reflections |
Hall symbol: P 32 2" | θ = 2.5–30.0° |
a = 9.2241 (1) Å | µ = 0.17 mm−1 |
c = 23.7787 (5) Å | T = 120 K |
V = 1752.13 (5) Å3 | Rhombohedron, yellow |
Z = 3 | 0.25 × 0.25 × 0.25 mm |
F(000) = 642 |
Nonius KappaCCD diffractometer | 3410 independent reflections |
Radiation source: sealed tube | 2325 reflections with I > 2σ(I) |
Horizonally mounted graphite crystal monochromator | Rint = 0.047 |
Detector resolution: 9 pixels mm-1 | θmax = 30.0°, θmin = 2.6° |
ω and ϕ scans | h = −12→12 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −10→10 |
Tmin = 0.959, Tmax = 0.959 | l = −31→33 |
23012 measured reflections |
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)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0519P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
3410 reflections | Δρmax = 0.25 e Å−3 |
131 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1419 Bijvoet pairs |
0 constraints | Absolute structure parameter: 0.0 (1) |
Primary atom site location: structure-invariant direct methods |
C24H26O2Si2 | Z = 3 |
Mr = 402.63 | Mo Kα radiation |
Trigonal, P3221 | µ = 0.17 mm−1 |
a = 9.2241 (1) Å | T = 120 K |
c = 23.7787 (5) Å | 0.25 × 0.25 × 0.25 mm |
V = 1752.13 (5) Å3 |
Nonius KappaCCD diffractometer | 3410 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 2325 reflections with I > 2σ(I) |
Tmin = 0.959, Tmax = 0.959 | Rint = 0.047 |
23012 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.103 | Δρmax = 0.25 e Å−3 |
S = 1.00 | Δρmin = −0.21 e Å−3 |
3410 reflections | Absolute structure: Flack (1983), 1419 Bijvoet pairs |
131 parameters | Absolute structure parameter: 0.0 (1) |
0 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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.4411 (3) | −0.1681 (3) | 0.00979 (9) | 0.0487 (6) | |
H1A | 0.5479 | −0.0985 | −0.0095 | 0.073* | |
H1B | 0.3539 | −0.233 | −0.018 | 0.073* | |
H1C | 0.4522 | −0.2447 | 0.0357 | 0.073* | |
C2 | 0.1985 (3) | −0.1571 (4) | 0.09491 (10) | 0.0714 (8) | |
H2A | 0.2222 | −0.2247 | 0.1211 | 0.107* | |
H2B | 0.1022 | −0.2309 | 0.0714 | 0.107* | |
H2C | 0.1731 | −0.0815 | 0.1162 | 0.107* | |
C3 | 0.3475 (4) | 0.1018 (3) | 0.00053 (11) | 0.0802 (10) | |
H3A | 0.3209 | 0.1763 | 0.0219 | 0.12* | |
H3B | 0.2539 | 0.0314 | −0.0245 | 0.12* | |
H3C | 0.4487 | 0.1688 | −0.0219 | 0.12* | |
C4 | 0.5616 (2) | 0.1008 (2) | 0.09647 (7) | 0.0310 (4) | |
C5 | 0.6750 (2) | 0.1814 (2) | 0.12846 (7) | 0.0282 (4) | |
C6 | 0.8026 (2) | 0.2815 (2) | 0.16901 (6) | 0.0283 (4) | |
C7 | 0.8414 (2) | 0.4474 (2) | 0.17783 (8) | 0.0346 (5) | |
H7 | 0.7881 | 0.4931 | 0.1558 | 0.042* | |
C8 | 0.9559 (2) | 0.5446 (2) | 0.21811 (8) | 0.0385 (5) | |
H8 | 0.982 | 0.6572 | 0.2233 | 0.046* | |
C9 | 1.0332 (2) | 0.4800 (2) | 0.25096 (7) | 0.0381 (5) | |
H9 | 1.1116 | 0.5479 | 0.2789 | 0.046* | |
C10 | 0.9970 (2) | 0.3169 (2) | 0.24337 (7) | 0.0352 (4) | |
H10 | 1.0497 | 0.2725 | 0.2664 | 0.042* | |
C11 | 0.8830 (2) | 0.2166 (2) | 0.20188 (7) | 0.0274 (4) | |
C12 | 0.8518 (2) | 0.0429 (2) | 0.19563 (7) | 0.0309 (4) | |
O1 | 0.88376 (18) | −0.02847 (17) | 0.23231 (6) | 0.0457 (4) | |
Si1 | 0.38331 (7) | −0.03278 (7) | 0.04974 (2) | 0.03309 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0621 (15) | 0.0523 (14) | 0.0410 (11) | 0.0355 (13) | −0.0166 (11) | −0.0167 (10) |
C2 | 0.0331 (13) | 0.092 (2) | 0.0657 (15) | 0.0134 (14) | −0.0059 (12) | −0.0155 (14) |
C3 | 0.108 (2) | 0.0446 (14) | 0.0940 (18) | 0.0423 (15) | −0.0758 (18) | −0.0214 (13) |
C4 | 0.0351 (10) | 0.0292 (10) | 0.0311 (9) | 0.0178 (9) | −0.0057 (8) | −0.0005 (8) |
C5 | 0.0316 (10) | 0.0258 (9) | 0.0288 (9) | 0.0156 (8) | −0.0008 (8) | 0.0041 (8) |
C6 | 0.0246 (9) | 0.0290 (10) | 0.0243 (8) | 0.0083 (8) | 0.0013 (7) | 0.0042 (8) |
C7 | 0.0346 (11) | 0.0295 (11) | 0.0344 (10) | 0.0120 (9) | −0.0044 (8) | 0.0022 (8) |
C8 | 0.0361 (12) | 0.0273 (11) | 0.0401 (11) | 0.0068 (10) | 0.0020 (9) | −0.0008 (8) |
C9 | 0.0256 (10) | 0.0386 (11) | 0.0312 (9) | 0.0019 (9) | −0.0042 (8) | −0.0033 (8) |
C10 | 0.0233 (9) | 0.0403 (11) | 0.0339 (9) | 0.0098 (9) | −0.0013 (8) | 0.0075 (8) |
C11 | 0.0194 (8) | 0.0302 (9) | 0.0260 (8) | 0.0075 (8) | 0.0033 (7) | 0.0069 (7) |
C12 | 0.0196 (9) | 0.0329 (10) | 0.0361 (10) | 0.0101 (8) | 0.0025 (8) | 0.0105 (8) |
O1 | 0.0440 (9) | 0.0402 (9) | 0.0499 (8) | 0.0188 (8) | −0.0108 (7) | 0.0125 (7) |
Si1 | 0.0354 (3) | 0.0283 (3) | 0.0372 (3) | 0.0172 (3) | −0.0128 (2) | −0.0072 (2) |
C1—Si1 | 1.847 (2) | C5—C6 | 1.443 (2) |
C1—H1A | 0.98 | C6—C7 | 1.403 (3) |
C1—H1B | 0.98 | C6—C11 | 1.401 (3) |
C1—H1C | 0.98 | C7—C8 | 1.375 (3) |
C2—Si1 | 1.849 (2) | C7—H7 | 0.95 |
C2—H2A | 0.98 | C8—C9 | 1.378 (3) |
C2—H2B | 0.98 | C8—H8 | 0.95 |
C2—H2C | 0.98 | C9—C10 | 1.380 (3) |
C3—Si1 | 1.852 (2) | C9—H9 | 0.95 |
C3—H3A | 0.98 | C10—C11 | 1.401 (2) |
C3—H3B | 0.98 | C10—H10 | 0.95 |
C3—H3C | 0.98 | C11—C12 | 1.487 (3) |
C4—C5 | 1.203 (2) | C12—O1 | 1.214 (2) |
C4—Si1 | 1.8522 (19) | C12—C12i | 1.538 (4) |
Si1—C1—H1A | 109.5 | C8—C7—H7 | 119.7 |
Si1—C1—H1B | 109.5 | C6—C7—H7 | 119.7 |
H1A—C1—H1B | 109.5 | C9—C8—C7 | 120.52 (19) |
Si1—C1—H1C | 109.5 | C9—C8—H8 | 119.7 |
H1A—C1—H1C | 109.5 | C7—C8—H8 | 119.7 |
H1B—C1—H1C | 109.5 | C8—C9—C10 | 120.12 (17) |
Si1—C2—H2A | 109.5 | C8—C9—H9 | 119.9 |
Si1—C2—H2B | 109.5 | C10—C9—H9 | 119.9 |
H2A—C2—H2B | 109.5 | C9—C10—C11 | 120.31 (17) |
Si1—C2—H2C | 109.5 | C9—C10—H10 | 119.8 |
H2A—C2—H2C | 109.5 | C11—C10—H10 | 119.8 |
H2B—C2—H2C | 109.5 | C6—C11—C10 | 119.58 (17) |
Si1—C3—H3A | 109.5 | C6—C11—C12 | 123.09 (16) |
Si1—C3—H3B | 109.5 | C10—C11—C12 | 117.32 (17) |
H3A—C3—H3B | 109.5 | O1—C12—C11 | 122.93 (17) |
Si1—C3—H3C | 109.5 | O1—C12—C12i | 115.72 (18) |
H3A—C3—H3C | 109.5 | C11—C12—C12i | 120.33 (17) |
H3B—C3—H3C | 109.5 | C3—Si1—C1 | 109.67 (11) |
C5—C4—Si1 | 177.01 (16) | C3—Si1—C2 | 111.37 (14) |
C4—C5—C6 | 175.7 (2) | C1—Si1—C2 | 111.58 (13) |
C7—C6—C11 | 118.82 (16) | C3—Si1—C4 | 109.27 (10) |
C7—C6—C5 | 118.66 (17) | C1—Si1—C4 | 107.33 (9) |
C11—C6—C5 | 122.44 (17) | C2—Si1—C4 | 107.49 (9) |
C8—C7—C6 | 120.63 (18) | ||
C11—C6—C7—C8 | −0.2 (3) | C9—C10—C11—C6 | −1.6 (3) |
C5—C6—C7—C8 | 176.61 (16) | C9—C10—C11—C12 | 179.24 (16) |
C6—C7—C8—C9 | −0.7 (3) | C6—C11—C12—O1 | −159.64 (18) |
C7—C8—C9—C10 | 0.5 (3) | C10—C11—C12—O1 | 19.5 (3) |
C8—C9—C10—C11 | 0.7 (3) | C6—C11—C12—C12i | 32.4 (2) |
C7—C6—C11—C10 | 1.3 (2) | C10—C11—C12—C12i | −148.44 (13) |
C5—C6—C11—C10 | −175.35 (16) | C11—C12—C12i—C11i | −132.9 (2) |
C7—C6—C11—C12 | −179.56 (16) | C11—C12—C12i—O1i | 58.36 (11) |
C5—C6—C11—C12 | 3.8 (3) | O1—C12—C12i—O1i | −110.4 (3) |
Symmetry code: (i) x−y, −y, −z+1/3. |
Experimental details
Crystal data | |
Chemical formula | C24H26O2Si2 |
Mr | 402.63 |
Crystal system, space group | Trigonal, P3221 |
Temperature (K) | 120 |
a, c (Å) | 9.2241 (1), 23.7787 (5) |
V (Å3) | 1752.13 (5) |
Z | 3 |
Radiation type | Mo Kα |
µ (mm−1) | 0.17 |
Crystal size (mm) | 0.25 × 0.25 × 0.25 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.959, 0.959 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23012, 3410, 2325 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.103, 1.00 |
No. of reflections | 3410 |
No. of parameters | 131 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.21 |
Absolute structure | Flack (1983), 1419 Bijvoet pairs |
Absolute structure parameter | 0.0 (1) |
Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Acknowledgements
The purchase of the diffractometer was made possible by grant No. LEQSF(1999–2000)-ESH-TR-13, administered by the Louisiana Board of Regents. We thank Dr J. Gabriel Garcia for providing the sample.
References
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The title compound (I), (C12H13OSi)2, lies on a crystallographic twofold axis. The phenyl ring is planar - all six C atoms have δ/σ < 0.2. However, carbonyl carbon C12 is 0.217 (5) Å above the C11—O1—C12' plane, and the C10—C11—C12—O1 torsion angle is 19.5 (3)°. The ethanedione C12(sp2)—C12(sp2)' distance of 1.538 (4) Å is somewhat longer than expected, but is consistent with values reported for benzil, which average 1.536 (10) Å. The acetylenic moiety is non-linear with deviations from a weighted least-squares line of δ(Si1) = 0.0034 (15), δ(C4) = 0.054 (4), δ(C5) = 0.049 (4), and δ(C6) = 0.047 (4) Å. The crystal structure is stablized by van der Waals interactions.