1,2-Bis{2-[2-(trimethyl­sil­yl)ethyn­yl]phen­yl}ethane-1,2-dione

Sparrow, C.R.; Fronczek, F.R.; Watkins, S.F.

doi:10.1107/S160053681203663X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2809

doi:10.1107/S160053681203663X

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1,2-Bis{2-[2-(trimethylsilyl)ethynyl]phenyl}ethane-1,2-dione

Christopher R. Sparrow,^a Frank R. Fronczek ^a ^* and Steven F. Watkins ^a

^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 ); 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

Crystal data

C₂₄H₂₆O₂Si₂
M_r = 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 ) T_min = 0.959, T_max = 0.959
23012 measured reflections
3410 independent reflections
2325 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.103
S = 1.00
3410 reflections
131 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ), 1419 Bijvoet pairs
Flack parameter: 0.0 (1)

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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681203663X/bx2422sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681203663X/bx2422Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681203663X/bx2422Isup3.cml

checkCIF report

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).

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

C₂₄H₂₆O₂Si₂	D_x = 1.145 Mg m⁻³
M_r = 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

Data collection top

Nonius KappaCCD diffractometer	3410 independent reflections
Radiation source: sealed tube	2325 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	R_int = 0.047
Detector resolution: 9 pixels mm^-1	θ_max = 30.0°, θ_min = 2.6°
ω and ϕ scans	h = −12→12
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −10→10
T_min = 0.959, T_max = 0.959	l = −31→33
23012 measured reflections

Refinement top

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(F_o²) + (0.0519P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
3410 reflections	Δρ_max = 0.25 e Å⁻³
131 parameters	Δρ_min = −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

Crystal data top

C₂₄H₂₆O₂Si₂	Z = 3
M_r = 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

Data collection top

Nonius KappaCCD diffractometer	3410 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	2325 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.959	R_int = 0.047
23012 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.103	Δρ_max = 0.25 e Å⁻³
S = 1.00	Δρ_min = −0.21 e Å⁻³
3410 reflections	Absolute structure: Flack (1983), 1419 Bijvoet pairs
131 parameters	Absolute 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

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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
M_r	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)
T_min, T_max	0.959, 0.959
No. of measured, independent and observed [I > 2σ(I)] reflections	23012, 3410, 2325
R_int	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
Δρ_max, Δρ_min (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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