(Z,Z)-1,4-Diiodo-1,4-bis­(trimethyl­silyl)buta-1,3-diene

Bats, J.W.; Urschel, B.; Müller, T.

doi:10.1107/S160053680803482X

organic compounds

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Volume 64| Part 11| November 2008| Page o2235

doi:10.1107/S160053680803482X

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(Z,Z)-1,4-Diiodo-1,4-bis(trimethylsilyl)buta-1,3-diene

Jan W. Bats,^a ^* Birgit Urschel ^b and Thomas Müller ^c

^aInstitut für Organische Chemie, Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany, ^bInstitut für Anorganische Chemie, Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany, and ^cInstitut für Reine und Angewandte Chemie, Universität Oldenburg, Carl-von-Ossietzky-Strasse 9-11, D-26129 Oldenburg, Germany
^*Correspondence e-mail: bats@chemie.uni-frankfurt.de

(Received 23 October 2008; accepted 24 October 2008; online 31 October 2008)

The asymmetric unit of the title compound, C₁₀H₂₀I₂Si₂, contains two half-molecules. Both complete molecules are generated by crystallographic inversion centers located at the mid-points of the central C—C single bonds; the butadiene groups are planar, with a trans conformation about the central C—C bond. The molecules show short intramolecular H⋯I contacts of 2.89 and 2.92 Å. The crystal packing shows no short intermolecular contacts.

Related literature

For the synthesis of the title compound, see: Yamaguchi et al. (1998 ). For related structures, see: Saito et al. (2007 ); Yamamoto et al. (2002 ). For van der Waals radii, see: Bondi (1964 ).

Experimental

Crystal data

C₁₀H₂₀I₂Si₂
M_r = 450.24
Triclinic, $[P \overline 1]$
a = 6.3553 (17) Å
b = 11.502 (2) Å
c = 11.698 (2) Å
α = 103.027 (13)°
β = 90.555 (17)°
γ = 90.99 (2)°
V = 832.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 3.89 mm⁻¹
T = 155 (2) K
0.46 × 0.36 × 0.28 mm

Data collection

Siemens SMART 1K CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ) T_min = 0.275, T_max = 0.336
15331 measured reflections
5837 independent reflections
5272 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.059
S = 1.03
5837 reflections
134 parameters
H-atom parameters constrained
Δρ_max = 1.12 e Å⁻³
Δρ_min = −0.94 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯I1ⁱ	0.95	2.92	3.394 (2)	112
C6—H6⋯I2ⁱⁱ	0.95	2.89	3.378 (2)	113
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+1, -y+2, -z+1.

Data collection: SMART (Siemens, 1995 ); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680803482X/su2074sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680803482X/su2074Isup2.hkl

checkCIF report

Comment top

The title compound crystallized with two independent centrosymmetric molecules in the unit cell (Fig.1). Each molecule has a crystallographic inversion center at the midpoint of the central C—C single bond. The geometrical parameters of both molecules are similar. The butadiene groups are planar with a trans-conformation about the central C—C bond. The trimethylsilyl groups adopt orientations with a methyl group syn-periplanar with the nearest C=C double bond: torsion angles C3—Si1—C2—C1 = -12.1 (2)° and C9—Si2—C7—C6 = -21.2 (2)°. The molecules show intramolecular H···I contacts of 2.89 Å and 2.92 Å (Table 1), which are shorter than the van der Waals contact distance of 3.18 Å (Bondi, 1964).

The crystal packing of the title compound (Fig. 2) shows no short intermolecular contacts. The shortest intermolecular I···I distances of 3.876 (1) Å [I1···I2ⁱ; symmetry operation i) = 1+x, y, z] and 3.973 (1) Å [I1···I2] are comparable to the van der Waals contact distance of 3.96 Å.

Related literature top

For the synthesis of the title compound, see: Yamaguchi et al. (1998). For related structures, see: Saito et al. (2007); Yamamoto et al. (2002). For van der Waals radii, see: Bondi (1964).

Experimental top

The title compound was prepared as described by Yamaguchi et al. (1998), and recrystallized from n-hexane at 153 K.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the two independent molecules of the title compound, with displacement ellipsoids drawn at the 50% probability level (Unlabeled atoms are related to labeled atoms by inversion centers at the midpoints of the molecules).
	Fig. 2. The crystal packing of the title compound, viewed down the a axis (the displacement ellipsoids are drawn at the 50% probability level).

(Z,Z)-1,4-Diiodo-1,4-bis(trimethylsilyl)buta-1,3-diene top

Crystal data top

C₁₀H₂₀I₂Si₂	Z = 2
M_r = 450.24	F(000) = 428
Triclinic, P1	D_x = 1.795 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.3553 (17) Å	Cell parameters from 124 reflections
b = 11.502 (2) Å	θ = 3–23°
c = 11.698 (2) Å	µ = 3.89 mm⁻¹
α = 103.027 (13)°	T = 155 K
β = 90.555 (17)°	Block, colorless
γ = 90.99 (2)°	0.46 × 0.36 × 0.28 mm
V = 832.9 (3) Å³

Data collection top

Siemens SMART 1K CCD diffractometer	5837 independent reflections
Radiation source: normal-focus sealed tube	5272 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 32.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −9→9
T_min = 0.275, T_max = 0.336	k = −17→17
15331 measured reflections	l = −17→17

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)] = 0.021	H-atom parameters constrained
wR(F²) = 0.059	w = 1/[σ²(F_o²) + (0.02P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.002
5837 reflections	Δρ_max = 1.12 e Å⁻³
134 parameters	Δρ_min = −0.94 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0130 (5)

Crystal data top

C₁₀H₂₀I₂Si₂	γ = 90.99 (2)°
M_r = 450.24	V = 832.9 (3) Å³
Triclinic, P1	Z = 2
a = 6.3553 (17) Å	Mo Kα radiation
b = 11.502 (2) Å	µ = 3.89 mm⁻¹
c = 11.698 (2) Å	T = 155 K
α = 103.027 (13)°	0.46 × 0.36 × 0.28 mm
β = 90.555 (17)°

Data collection top

Siemens SMART 1K CCD diffractometer	5837 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	5272 reflections with I > 2σ(I)
T_min = 0.275, T_max = 0.336	R_int = 0.021
15331 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	0 restraints
wR(F²) = 0.059	H-atom parameters constrained
S = 1.03	Δρ_max = 1.12 e Å⁻³
5837 reflections	Δρ_min = −0.94 e Å⁻³
134 parameters

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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
I1	0.631493 (18)	0.679368 (10)	0.508829 (10)	0.02900 (4)
I2	0.124665 (17)	0.825214 (9)	0.402449 (9)	0.02623 (4)
Si1	0.76330 (7)	0.63323 (4)	0.77198 (4)	0.02223 (9)
Si2	0.47343 (7)	0.86551 (4)	0.19545 (4)	0.02225 (9)
C1	0.9715 (3)	0.51656 (14)	0.56130 (13)	0.0211 (3)
H1	1.0502	0.4804	0.6129	0.025*
C2	0.8224 (2)	0.59143 (13)	0.61143 (13)	0.0198 (3)
C3	0.9030 (3)	0.53065 (18)	0.84764 (16)	0.0321 (4)
H3A	0.8575	0.5446	0.9293	0.048*
H3B	1.0552	0.5455	0.8458	0.048*
H3C	0.8702	0.4478	0.8077	0.048*
C4	0.8577 (4)	0.79022 (18)	0.8278 (2)	0.0405 (5)
H4A	0.8270	0.8157	0.9116	0.061*
H4B	0.7858	0.8422	0.7848	0.061*
H4C	1.0098	0.7953	0.8165	0.061*
C5	0.4740 (3)	0.62065 (18)	0.79288 (17)	0.0322 (4)
H5A	0.4456	0.6250	0.8759	0.048*
H5B	0.4206	0.5442	0.7457	0.048*
H5C	0.4037	0.6862	0.7680	0.048*
C6	0.5181 (3)	0.98312 (14)	0.43727 (13)	0.0221 (3)
H6	0.6391	1.0180	0.4103	0.027*
C7	0.4013 (3)	0.90828 (14)	0.35421 (13)	0.0210 (3)
C8	0.6036 (3)	0.71790 (16)	0.16638 (17)	0.0332 (4)
H8A	0.7252	0.7220	0.2194	0.050*
H8B	0.6506	0.6974	0.0849	0.050*
H8C	0.5034	0.6567	0.1796	0.050*
C9	0.6592 (3)	0.98330 (18)	0.16797 (18)	0.0361 (4)
H9A	0.7846	0.9870	0.2182	0.054*
H9B	0.5901	1.0607	0.1859	0.054*
H9C	0.7005	0.9641	0.0854	0.054*
C10	0.2345 (3)	0.85504 (18)	0.09994 (16)	0.0342 (4)
H10A	0.2759	0.8370	0.0174	0.051*
H10B	0.1613	0.9312	0.1182	0.051*
H10C	0.1404	0.7914	0.1139	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.02999 (7)	0.03118 (7)	0.02837 (7)	0.01194 (4)	0.00029 (5)	0.01117 (5)
I2	0.02378 (7)	0.02802 (7)	0.02598 (6)	−0.00570 (4)	−0.00083 (4)	0.00471 (4)
Si1	0.0211 (2)	0.0241 (2)	0.01973 (19)	0.00282 (16)	0.00184 (15)	0.00115 (16)
Si2	0.0263 (2)	0.0217 (2)	0.01793 (19)	0.00165 (16)	0.00037 (16)	0.00277 (15)
C1	0.0221 (7)	0.0224 (7)	0.0191 (6)	0.0036 (5)	0.0002 (5)	0.0049 (5)
C2	0.0193 (7)	0.0203 (7)	0.0200 (6)	0.0019 (5)	−0.0005 (5)	0.0046 (5)
C3	0.0302 (9)	0.0438 (10)	0.0248 (8)	0.0096 (7)	0.0031 (7)	0.0123 (7)
C4	0.0426 (12)	0.0312 (9)	0.0408 (11)	−0.0023 (8)	−0.0044 (9)	−0.0063 (8)
C5	0.0224 (9)	0.0423 (10)	0.0307 (9)	0.0045 (7)	0.0053 (7)	0.0050 (7)
C6	0.0213 (7)	0.0223 (7)	0.0217 (7)	−0.0019 (5)	0.0011 (5)	0.0030 (5)
C7	0.0219 (7)	0.0203 (7)	0.0207 (7)	0.0013 (5)	0.0008 (5)	0.0045 (5)
C8	0.0414 (11)	0.0279 (9)	0.0284 (8)	0.0081 (7)	−0.0002 (7)	0.0021 (7)
C9	0.0410 (11)	0.0339 (9)	0.0349 (9)	−0.0020 (8)	0.0109 (8)	0.0108 (8)
C10	0.0387 (11)	0.0388 (10)	0.0245 (8)	0.0034 (8)	−0.0048 (7)	0.0060 (7)

Geometric parameters (Å, º) top

I1—C2	2.1207 (16)	C4—H4B	0.9800
I2—C7	2.1276 (17)	C4—H4C	0.9800
Si1—C3	1.8591 (19)	C5—H5A	0.9800
Si1—C4	1.863 (2)	C5—H5B	0.9800
Si1—C5	1.8647 (19)	C5—H5C	0.9800
Si1—C2	1.8742 (16)	C6—C7	1.350 (2)
Si2—C10	1.863 (2)	C6—C6ⁱⁱ	1.453 (3)
Si2—C8	1.8644 (19)	C6—H6	0.9500
Si2—C9	1.866 (2)	C8—H8A	0.9800
Si2—C7	1.8744 (16)	C8—H8B	0.9800
C1—C2	1.339 (2)	C8—H8C	0.9800
C1—C1ⁱ	1.450 (3)	C9—H9A	0.9800
C1—H1	0.9500	C9—H9B	0.9800
C3—H3A	0.9800	C9—H9C	0.9800
C3—H3B	0.9800	C10—H10A	0.9800
C3—H3C	0.9800	C10—H10B	0.9800
C4—H4A	0.9800	C10—H10C	0.9800

C3—Si1—C4	110.85 (10)	Si1—C5—H5A	109.5
C3—Si1—C5	109.79 (9)	Si1—C5—H5B	109.5
C4—Si1—C5	110.45 (10)	H5A—C5—H5B	109.5
C3—Si1—C2	109.04 (8)	Si1—C5—H5C	109.5
C4—Si1—C2	107.21 (9)	H5A—C5—H5C	109.5
C5—Si1—C2	109.45 (8)	H5B—C5—H5C	109.5
C10—Si2—C8	109.30 (9)	C7—C6—C6ⁱⁱ	128.06 (19)
C10—Si2—C9	110.53 (10)	C7—C6—H6	116.0
C8—Si2—C9	110.39 (10)	C6ⁱⁱ—C6—H6	116.0
C10—Si2—C7	110.61 (9)	C6—C7—Si2	123.88 (12)
C8—Si2—C7	108.94 (8)	C6—C7—I2	119.83 (12)
C9—Si2—C7	107.04 (8)	Si2—C7—I2	116.23 (8)
C2—C1—C1ⁱ	128.56 (19)	Si2—C8—H8A	109.5
C2—C1—H1	115.7	Si2—C8—H8B	109.5
C1ⁱ—C1—H1	115.7	H8A—C8—H8B	109.5
C1—C2—Si1	126.01 (12)	Si2—C8—H8C	109.5
C1—C2—I1	120.61 (12)	H8A—C8—H8C	109.5
Si1—C2—I1	113.35 (8)	H8B—C8—H8C	109.5
Si1—C3—H3A	109.5	Si2—C9—H9A	109.5
Si1—C3—H3B	109.5	Si2—C9—H9B	109.5
H3A—C3—H3B	109.5	H9A—C9—H9B	109.5
Si1—C3—H3C	109.5	Si2—C9—H9C	109.5
H3A—C3—H3C	109.5	H9A—C9—H9C	109.5
H3B—C3—H3C	109.5	H9B—C9—H9C	109.5
Si1—C4—H4A	109.5	Si2—C10—H10A	109.5
Si1—C4—H4B	109.5	Si2—C10—H10B	109.5
H4A—C4—H4B	109.5	H10A—C10—H10B	109.5
Si1—C4—H4C	109.5	Si2—C10—H10C	109.5
H4A—C4—H4C	109.5	H10A—C10—H10C	109.5
H4B—C4—H4C	109.5	H10B—C10—H10C	109.5

C1ⁱ—C1—C2—Si1	−178.07 (17)	C6ⁱⁱ—C6—C7—Si2	−176.55 (18)
C1ⁱ—C1—C2—I1	0.2 (3)	C6ⁱⁱ—C6—C7—I2	0.6 (3)
C3—Si1—C2—C1	−12.13 (17)	C10—Si2—C7—C6	−141.69 (15)
C4—Si1—C2—C1	107.93 (16)	C8—Si2—C7—C6	98.15 (16)
C5—Si1—C2—C1	−132.25 (15)	C9—Si2—C7—C6	−21.21 (17)
C3—Si1—C2—I1	169.49 (8)	C10—Si2—C7—I2	41.11 (11)
C4—Si1—C2—I1	−70.44 (11)	C8—Si2—C7—I2	−79.04 (11)
C5—Si1—C2—I1	49.37 (11)	C9—Si2—C7—I2	161.59 (9)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···I1ⁱ	0.95	2.92	3.394 (2)	112
C6—H6···I2ⁱⁱ	0.95	2.89	3.378 (2)	113

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₂₀I₂Si₂
M_r	450.24
Crystal system, space group	Triclinic, P1
Temperature (K)	155
a, b, c (Å)	6.3553 (17), 11.502 (2), 11.698 (2)
α, β, γ (°)	103.027 (13), 90.555 (17), 90.99 (2)
V (Å³)	832.9 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.89
Crystal size (mm)	0.46 × 0.36 × 0.28

Data collection
Diffractometer	Siemens SMART 1K CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2000)
T_min, T_max	0.275, 0.336
No. of measured, independent and observed [I > 2σ(I)] reflections	15331, 5837, 5272
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.756

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.059, 1.03
No. of reflections	5837
No. of parameters	134
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.12, −0.94

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···I1ⁱ	0.95	2.92	3.394 (2)	112
C6—H6···I2ⁱⁱ	0.95	2.89	3.378 (2)	113

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z+1.

References

Bondi, A. (1964). J. Phys. Chem. 68, 441–451. CrossRef CAS Web of Science Google Scholar
Saito, M., Nakamura, M., Tajima, T. & Yoshioka, M. (2007). Angew. Chem. Int. Ed. 46, 1504–1507. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2000). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1995). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Yamaguchi, S., Jin, R.-Z., Tamao, K. & Sato, F. (1998). J. Org. Chem. 63, 10060–10062. Web of Science CrossRef CAS Google Scholar
Yamamoto, Y., Ohno, T. & Itoh, K. (2002). Chem. Eur. J. 8, 4734–4741. CrossRef PubMed CAS Google Scholar

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