organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

(Received 27 July 2012; accepted 22 August 2012; online 31 August 2012)

The title compound, C24H26O2Si2, has C2 crystallographic symmetry. 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 crystal structure, only van de Waals interactions occur.

Related literature

For the structure of benzil, see Brown & Sadanaga (1965[Brown, C. J. & Sadanaga, R. (1965). Acta Cryst. 18, 158-164.]); Gabe et al. (1981[Gabe, E. J., Le Page, Y., Lee, F. L. & Barclay, L. R. C. (1981). Acta Cryst. B37, 197-200.]); More et al. (1987[More, M., Odou, G. & Lefebvre, J. (1987). Acta Cryst. B43, 398-405.]). For the synthesis see: Garcia et al. (1995[Garcia, J. G., Ramos, B., Pratt, L. M. & Rodríguez, A. (1995). Tetrahedron Lett. 36, 7391-7394.]). For the determination of absolute configuration from Bijvoet pairs, see: Hooft et al. (2008[Hooft, R. W. W., Straver, L. H. & Spek, A. L. (2008). J. Appl. Cryst. 41, 96-103.]).

[Scheme 1]

Experimental

Crystal data
  • C24H26O2Si2

  • Mr = 402.63

  • Trigonal, P 32 21

  • a = 9.2241 (1) Å

  • c = 23.7787 (5) Å

  • V = 1752.13 (5) Å3

  • Z = 3

  • Mo Kα radiation

  • μ = 0.17 mm−1

  • T = 120 K

  • 0.25 × 0.25 × 0.25 mm

Data collection
  • Nonius KappaCCD diffractometer

  • Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) Tmin = 0.959, Tmax = 0.959

  • 23012 measured reflections

  • 3410 independent reflections

  • 2325 reflections with I > 2σ(I)

  • Rint = 0.047

Refinement
  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.103

  • S = 1.00

  • 3410 reflections

  • 131 parameters

  • H-atom parameters constrained

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.21 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 1419 Bijvoet pairs

  • Flack parameter: 0.0 (1)

Data collection: COLLECT (Nonius, 2000[Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR2002 (Burla et al., 2003[Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


Comment top

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.

Related literature top

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 absolute configuration from Bijvoet pairs, see: Hooft et al. (2008).

Experimental top

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).

Refinement top

The space group assignment and absolute structure 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.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: 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).

Figures top
Figure 1. View of (I) (50% probability displacement ellipsoids)
1,2-Bis{2-[2-(trimethylsilyl)ethynyl]phenyl}ethane-1,2-dione top
Crystal data top
C24H26O2Si2Dx = 1.145 Mg m3
Mr = 402.63Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3221Cell parameters from 3424 reflections
Hall symbol: P 32 2"θ = 2.5–30.0°
a = 9.2241 (1) ŵ = 0.17 mm1
c = 23.7787 (5) ÅT = 120 K
V = 1752.13 (5) Å3Rhombohedron, yellow
Z = 30.25 × 0.25 × 0.25 mm
F(000) = 642
Data collection top
Nonius KappaCCD
diffractometer
3410 independent reflections
Radiation source: sealed tube2325 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromatorRint = 0.047
Detector resolution: 9 pixels mm-1θmax = 30.0°, θmin = 2.6°
ω and ϕ scansh = 1212
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
k = 1010
Tmin = 0.959, Tmax = 0.959l = 3133
23012 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-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 reflectionsΔρmax = 0.25 e Å3
131 parametersΔρmin = 0.21 e Å3
0 restraintsAbsolute structure: Flack (1983), 1419 Bijvoet pairs
0 constraintsAbsolute structure parameter: 0.0 (1)
Primary atom site location: structure-invariant direct methods
Crystal data top
C24H26O2Si2Z = 3
Mr = 402.63Mo Kα radiation
Trigonal, P3221µ = 0.17 mm1
a = 9.2241 (1) ÅT = 120 K
c = 23.7787 (5) Å0.25 × 0.25 × 0.25 mm
V = 1752.13 (5) Å3
Data collection top
Nonius KappaCCD
diffractometer
3410 independent reflections
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
2325 reflections with I > 2σ(I)
Tmin = 0.959, Tmax = 0.959Rint = 0.047
23012 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.103Δρmax = 0.25 e Å3
S = 1.00Δρmin = 0.21 e Å3
3410 reflectionsAbsolute structure: Flack (1983), 1419 Bijvoet pairs
131 parametersAbsolute structure parameter: 0.0 (1)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.4411 (3)0.1681 (3)0.00979 (9)0.0487 (6)
H1A0.54790.09850.00950.073*
H1B0.35390.2330.0180.073*
H1C0.45220.24470.03570.073*
C20.1985 (3)0.1571 (4)0.09491 (10)0.0714 (8)
H2A0.22220.22470.12110.107*
H2B0.10220.23090.07140.107*
H2C0.17310.08150.11620.107*
C30.3475 (4)0.1018 (3)0.00053 (11)0.0802 (10)
H3A0.32090.17630.02190.12*
H3B0.25390.03140.02450.12*
H3C0.44870.16880.02190.12*
C40.5616 (2)0.1008 (2)0.09647 (7)0.0310 (4)
C50.6750 (2)0.1814 (2)0.12846 (7)0.0282 (4)
C60.8026 (2)0.2815 (2)0.16901 (6)0.0283 (4)
C70.8414 (2)0.4474 (2)0.17783 (8)0.0346 (5)
H70.78810.49310.15580.042*
C80.9559 (2)0.5446 (2)0.21811 (8)0.0385 (5)
H80.9820.65720.22330.046*
C91.0332 (2)0.4800 (2)0.25096 (7)0.0381 (5)
H91.11160.54790.27890.046*
C100.9970 (2)0.3169 (2)0.24337 (7)0.0352 (4)
H101.04970.27250.26640.042*
C110.8830 (2)0.2166 (2)0.20188 (7)0.0274 (4)
C120.8518 (2)0.0429 (2)0.19563 (7)0.0309 (4)
O10.88376 (18)0.02847 (17)0.23231 (6)0.0457 (4)
Si10.38331 (7)0.03278 (7)0.04974 (2)0.03309 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0621 (15)0.0523 (14)0.0410 (11)0.0355 (13)0.0166 (11)0.0167 (10)
C20.0331 (13)0.092 (2)0.0657 (15)0.0134 (14)0.0059 (12)0.0155 (14)
C30.108 (2)0.0446 (14)0.0940 (18)0.0423 (15)0.0758 (18)0.0214 (13)
C40.0351 (10)0.0292 (10)0.0311 (9)0.0178 (9)0.0057 (8)0.0005 (8)
C50.0316 (10)0.0258 (9)0.0288 (9)0.0156 (8)0.0008 (8)0.0041 (8)
C60.0246 (9)0.0290 (10)0.0243 (8)0.0083 (8)0.0013 (7)0.0042 (8)
C70.0346 (11)0.0295 (11)0.0344 (10)0.0120 (9)0.0044 (8)0.0022 (8)
C80.0361 (12)0.0273 (11)0.0401 (11)0.0068 (10)0.0020 (9)0.0008 (8)
C90.0256 (10)0.0386 (11)0.0312 (9)0.0019 (9)0.0042 (8)0.0033 (8)
C100.0233 (9)0.0403 (11)0.0339 (9)0.0098 (9)0.0013 (8)0.0075 (8)
C110.0194 (8)0.0302 (9)0.0260 (8)0.0075 (8)0.0033 (7)0.0069 (7)
C120.0196 (9)0.0329 (10)0.0361 (10)0.0101 (8)0.0025 (8)0.0105 (8)
O10.0440 (9)0.0402 (9)0.0499 (8)0.0188 (8)0.0108 (7)0.0125 (7)
Si10.0354 (3)0.0283 (3)0.0372 (3)0.0172 (3)0.0128 (2)0.0072 (2)
Geometric parameters (Å, º) top
C1—Si11.847 (2)C5—C61.443 (2)
C1—H1A0.98C6—C71.403 (3)
C1—H1B0.98C6—C111.401 (3)
C1—H1C0.98C7—C81.375 (3)
C2—Si11.849 (2)C7—H70.95
C2—H2A0.98C8—C91.378 (3)
C2—H2B0.98C8—H80.95
C2—H2C0.98C9—C101.380 (3)
C3—Si11.852 (2)C9—H90.95
C3—H3A0.98C10—C111.401 (2)
C3—H3B0.98C10—H100.95
C3—H3C0.98C11—C121.487 (3)
C4—C51.203 (2)C12—O11.214 (2)
C4—Si11.8522 (19)C12—C12i1.538 (4)
Si1—C1—H1A109.5C8—C7—H7119.7
Si1—C1—H1B109.5C6—C7—H7119.7
H1A—C1—H1B109.5C9—C8—C7120.52 (19)
Si1—C1—H1C109.5C9—C8—H8119.7
H1A—C1—H1C109.5C7—C8—H8119.7
H1B—C1—H1C109.5C8—C9—C10120.12 (17)
Si1—C2—H2A109.5C8—C9—H9119.9
Si1—C2—H2B109.5C10—C9—H9119.9
H2A—C2—H2B109.5C9—C10—C11120.31 (17)
Si1—C2—H2C109.5C9—C10—H10119.8
H2A—C2—H2C109.5C11—C10—H10119.8
H2B—C2—H2C109.5C6—C11—C10119.58 (17)
Si1—C3—H3A109.5C6—C11—C12123.09 (16)
Si1—C3—H3B109.5C10—C11—C12117.32 (17)
H3A—C3—H3B109.5O1—C12—C11122.93 (17)
Si1—C3—H3C109.5O1—C12—C12i115.72 (18)
H3A—C3—H3C109.5C11—C12—C12i120.33 (17)
H3B—C3—H3C109.5C3—Si1—C1109.67 (11)
C5—C4—Si1177.01 (16)C3—Si1—C2111.37 (14)
C4—C5—C6175.7 (2)C1—Si1—C2111.58 (13)
C7—C6—C11118.82 (16)C3—Si1—C4109.27 (10)
C7—C6—C5118.66 (17)C1—Si1—C4107.33 (9)
C11—C6—C5122.44 (17)C2—Si1—C4107.49 (9)
C8—C7—C6120.63 (18)
C11—C6—C7—C80.2 (3)C9—C10—C11—C61.6 (3)
C5—C6—C7—C8176.61 (16)C9—C10—C11—C12179.24 (16)
C6—C7—C8—C90.7 (3)C6—C11—C12—O1159.64 (18)
C7—C8—C9—C100.5 (3)C10—C11—C12—O119.5 (3)
C8—C9—C10—C110.7 (3)C6—C11—C12—C12i32.4 (2)
C7—C6—C11—C101.3 (2)C10—C11—C12—C12i148.44 (13)
C5—C6—C11—C10175.35 (16)C11—C12—C12i—C11i132.9 (2)
C7—C6—C11—C12179.56 (16)C11—C12—C12i—O1i58.36 (11)
C5—C6—C11—C123.8 (3)O1—C12—C12i—O1i110.4 (3)
Symmetry code: (i) xy, y, z+1/3.

Experimental details

Crystal data
Chemical formulaC24H26O2Si2
Mr402.63
Crystal system, space groupTrigonal, P3221
Temperature (K)120
a, c (Å)9.2241 (1), 23.7787 (5)
V3)1752.13 (5)
Z3
Radiation typeMo Kα
µ (mm1)0.17
Crystal size (mm)0.25 × 0.25 × 0.25
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.959, 0.959
No. of measured, independent and
observed [I > 2σ(I)] reflections
23012, 3410, 2325
Rint0.047
(sin θ/λ)max1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.103, 1.00
No. of reflections3410
No. of parameters131
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.21
Absolute structureFlack (1983), 1419 Bijvoet pairs
Absolute structure parameter0.0 (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

First citationBrown, C. J. & Sadanaga, R. (1965). Acta Cryst. 18, 158–164.  CSD CrossRef CAS IUCr Journals Web of Science
First citationBurla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103.  CrossRef IUCr Journals
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals
First citationGabe, E. J., Le Page, Y., Lee, F. L. & Barclay, L. R. C. (1981). Acta Cryst. B37, 197–200.  CSD CrossRef CAS Web of Science IUCr Journals
First citationGarcia, J. G., Ramos, B., Pratt, L. M. & Rodríguez, A. (1995). Tetrahedron Lett. 36, 7391–7394.  CrossRef CAS
First citationHooft, R. W. W., Straver, L. H. & Spek, A. L. (2008). J. Appl. Cryst. 41, 96–103.  Web of Science CrossRef CAS IUCr Journals
First citationMore, M., Odou, G. & Lefebvre, J. (1987). Acta Cryst. B43, 398–405.  CSD CrossRef CAS Web of Science IUCr Journals
First citationNonius (2000). COLLECT. Nonius BV, Delft, The Netherlands.
First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds