Iodo­(triphen­yl)silane

Schödel, F.; Lerner, H.-W.; Trageser, T.; Bolte, M.

doi:10.1107/S2414314619009593

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 7| July 2019| x190959

https://doi.org/10.1107/S2414314619009593

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Iodo(triphenyl)silane

Frauke Schödel,^a Hans-Wolfram Lerner,^a Timo Trageser ^a and Michael Bolte ^a ^*

^aInstitut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main, Germany
^*Correspondence e-mail: bolte@chemie.uni-frankfurt.de

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 3 July 2019; accepted 4 July 2019; online 9 July 2019)

The molecular structure of the title compound, C₁₈H₁₅ISi, which crystallizes in the space group C2/c, does not exhibit any unusual features. Two weak C—H⋯π interactions may help to consolidate the packing. The present structure is not isostructural with the known Ph₃SiX (X = F, Cl or Br) compounds.

Keywords: crystal structure; silicon; iodine; C—H⋯π interactions.

CCDC reference: 1938347

Structure description

The chemistry and properties of Si—B compounds are of great importance as they are already widely adopted in organic syntheses. Despite the long existence and common usage of these compounds, their reactivity has not yet been thoroughly investigated. In a preliminary study, we investigated the chemical behaviour of supersilylated trieles (Wiberg et al., 1998 ), which had been synthesized from appropriate triel halides and the donor-unsupported silanide Na[Si^tBu₃] (Lerner, 2005 ). It has been shown that the halides (^tBu₃Si)BX₂ and (^tBu₃Si)₂BX (X = F, Cl and Br) are more labile than the corresponding hydrogen derivatives (Wiberg et al., 2001 ). In this paper, we report the structure of one of the products from the reaction of BI₃ with donor-unsupported K[SiPh₃] (Alig et al., 2019 ).

The molecular structure of the title compound (Fig. 1) does not exhibit any unusual features. The Si—I bond has a length of 2.478 (2) Å, which compares well with the value of 2.48 (3) Å retrieved from the Cambridge Structural Database (Version 5.40 of November 2018 plus one update; Groom et al., 2016 ) for a comparable fragment. The crystal packing features two C—H⋯π interactions, with H⋯Cg distances less than 3 Å, viz. C25—H25⋯Cg(C11–C16)ⁱ = 2.77 Å and C15—H15⋯Cg(C1–C6)ⁱⁱ = 2.98 Å [symmetry codes: (i) −x + 1, −y, −z + 1; (ii) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ].

Figure 1
A perspective view of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms are drawn with an arbitrary radius.

The crystal structures of fluoro(triphenyl)silane (Brendler et al., 2012 ), chloro(triphenyl)silane (Lobkovskii et al., 1981 ) and bromo(triphenyl)silane (Steinert et al., 2008 ; Brendler et al., 2012) have already been determined. Whereas Ph₃SiCl and Ph₃SiBr display isomorphous structures (space group P2₁/c with Z = 8), Ph₃SiF (space group P2₁/c with Z = 4) and the title compound (space group C2/c with Z = 8) crystallize in a different way.

Synthesis and crystallization

Neat BI₃ (39 mg, 0.10 mmol) was added to K[SiPh₃] (28 mg, 13.87 mmol) suspended in benzene (1 ml) at room temperature. Insoluble material was removed by filtration. The liquor was stored at room temperature for a period of approximately one month, yielding colourless blocks of the title compound (Fig. 2).

Figure 2
Reaction scheme for the synthesis of the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms were refined using a riding model, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C).

Table 1
Experimental details

Crystal data
Chemical formula	C₁₈H₁₅ISi
M_r	386.29
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	16.0488 (8), 11.2984 (6), 19.648 (1)
β (°)	112.379 (4)
V (Å³)	3294.4 (3)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	2.01
Crystal size (mm)	0.23 × 0.14 × 0.13

Data collection
Diffractometer	Stoe IPDS II two-circle
Absorption correction	Multi-scan (X-AREA; Stoe & Cie, 2001 )
T_min, T_max	0.411, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12164, 2901, 2338
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.153, 1.34
No. of reflections	2901
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.02, −0.80
Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS and XP in SHELXTL-Plus (Sheldrick, 2008 ), SHELXL2018 (Sheldrick, 2015 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1938347

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314619009593/hb4304sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619009593/hb4304Isup2.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015) and publCIF (Westrip, 2010).

Iodo(triphenyl)silane top

Crystal data top

C₁₈H₁₅ISi	F(000) = 1520
M_r = 386.29	D_x = 1.558 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.0488 (8) Å	Cell parameters from 12164 reflections
b = 11.2984 (6) Å	θ = 3.4–26.2°
c = 19.648 (1) Å	µ = 2.01 mm⁻¹
β = 112.379 (4)°	T = 173 K
V = 3294.4 (3) Å³	Block, colourless
Z = 8	0.23 × 0.14 × 0.13 mm

Data collection top

Stoe IPDS II two-circle diffractometer	2338 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray source	R_int = 0.052
ω scans	θ_max = 25.0°, θ_min = 3.5°
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001)	h = −19→19
T_min = 0.411, T_max = 1.000	k = −13→13
12164 measured reflections	l = −23→23
2901 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.073	H-atom parameters constrained
wR(F²) = 0.153	w = 1/[σ²(F_o²) + (0.0192P)² + 60.7486P] where P = (F_o² + 2F_c²)/3
S = 1.34	(Δ/σ)_max < 0.001
2901 reflections	Δρ_max = 1.02 e Å⁻³
181 parameters	Δρ_min = −0.80 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
I1	0.48451 (4)	0.29151 (7)	0.36275 (4)	0.0545 (3)
Si1	0.37819 (15)	0.2688 (2)	0.42609 (12)	0.0318 (5)
C1	0.3086 (5)	0.4064 (7)	0.4073 (4)	0.0286 (18)
C2	0.3497 (6)	0.5180 (8)	0.4247 (5)	0.040 (2)
H2	0.413607	0.523733	0.445319	0.048*
C3	0.2981 (7)	0.6198 (8)	0.4121 (5)	0.046 (2)
H3	0.326338	0.694979	0.424663	0.055*
C4	0.2059 (7)	0.6116 (8)	0.3814 (6)	0.051 (3)
H4	0.170471	0.681529	0.372985	0.062*
C5	0.1639 (6)	0.5031 (9)	0.3626 (5)	0.044 (2)
H5	0.100048	0.498101	0.340368	0.053*
C6	0.2161 (6)	0.4014 (8)	0.3766 (5)	0.0342 (19)
H6	0.187274	0.326477	0.364695	0.041*
C11	0.3062 (5)	0.1356 (7)	0.3867 (5)	0.0319 (19)
C12	0.2905 (6)	0.0529 (8)	0.4309 (5)	0.038 (2)
H12	0.319523	0.061021	0.482753	0.046*
C13	0.2340 (6)	−0.0425 (8)	0.4028 (5)	0.038 (2)
H13	0.223722	−0.098452	0.434838	0.045*
C14	0.1922 (6)	−0.0554 (8)	0.3269 (5)	0.044 (2)
H14	0.153113	−0.120504	0.306742	0.052*
C15	0.2075 (6)	0.0254 (8)	0.2818 (5)	0.044 (2)
H15	0.179228	0.016171	0.229906	0.053*
C16	0.2637 (6)	0.1206 (8)	0.3105 (5)	0.040 (2)
H16	0.273743	0.176448	0.278260	0.048*
C21	0.4477 (5)	0.2505 (7)	0.5266 (5)	0.0320 (19)
C22	0.4370 (6)	0.3288 (8)	0.5773 (5)	0.039 (2)
H22	0.395100	0.392077	0.560743	0.047*
C23	0.4872 (7)	0.3149 (9)	0.6516 (5)	0.046 (2)
H23	0.480875	0.369976	0.685812	0.055*
C24	0.5469 (6)	0.2206 (9)	0.6765 (5)	0.045 (2)
H24	0.579917	0.209497	0.727698	0.054*
C25	0.5576 (6)	0.1433 (9)	0.6260 (5)	0.047 (2)
H25	0.599434	0.079949	0.642366	0.056*
C26	0.5082 (6)	0.1578 (8)	0.5524 (5)	0.044 (2)
H26	0.515407	0.103099	0.518381	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0438 (4)	0.0704 (5)	0.0570 (4)	0.0112 (4)	0.0277 (3)	0.0091 (4)
Si1	0.0317 (12)	0.0303 (12)	0.0301 (12)	0.0037 (10)	0.0080 (10)	−0.0003 (10)
C1	0.032 (4)	0.029 (4)	0.025 (4)	0.002 (3)	0.010 (3)	0.004 (3)
C2	0.036 (5)	0.044 (5)	0.043 (5)	0.000 (4)	0.018 (4)	0.000 (4)
C3	0.056 (6)	0.027 (5)	0.058 (6)	0.003 (4)	0.025 (5)	−0.001 (4)
C4	0.063 (7)	0.030 (5)	0.069 (7)	0.018 (5)	0.034 (6)	0.013 (5)
C5	0.024 (4)	0.050 (6)	0.056 (6)	0.012 (4)	0.013 (4)	0.003 (5)
C6	0.037 (5)	0.028 (4)	0.035 (5)	−0.004 (4)	0.012 (4)	0.001 (4)
C11	0.029 (4)	0.030 (4)	0.036 (5)	0.012 (4)	0.011 (4)	0.002 (4)
C12	0.041 (5)	0.040 (5)	0.028 (5)	0.005 (4)	0.007 (4)	−0.008 (4)
C13	0.045 (5)	0.038 (5)	0.036 (5)	−0.006 (4)	0.021 (4)	−0.003 (4)
C14	0.040 (5)	0.033 (5)	0.055 (6)	−0.007 (4)	0.015 (5)	−0.012 (5)
C15	0.047 (5)	0.046 (6)	0.030 (5)	−0.002 (4)	0.003 (4)	−0.010 (4)
C16	0.048 (5)	0.042 (5)	0.026 (4)	0.011 (4)	0.010 (4)	0.008 (4)
C21	0.032 (4)	0.023 (4)	0.039 (5)	−0.006 (3)	0.011 (4)	−0.002 (3)
C22	0.036 (5)	0.045 (5)	0.034 (5)	0.011 (4)	0.010 (4)	0.006 (4)
C23	0.056 (6)	0.045 (6)	0.032 (5)	−0.004 (5)	0.011 (4)	0.000 (4)
C24	0.038 (5)	0.055 (6)	0.034 (5)	−0.001 (5)	0.005 (4)	0.013 (5)
C25	0.031 (5)	0.045 (6)	0.053 (6)	0.008 (4)	0.003 (4)	0.006 (5)
C26	0.036 (5)	0.037 (5)	0.048 (6)	0.011 (4)	0.006 (4)	−0.003 (4)

Geometric parameters (Å, º) top

I1—Si1	2.478 (2)	C13—C14	1.389 (13)
Si1—C1	1.867 (8)	C13—H13	0.9500
Si1—C21	1.873 (9)	C14—C15	1.360 (13)
Si1—C11	1.876 (9)	C14—H14	0.9500
C1—C6	1.374 (11)	C15—C16	1.379 (13)
C1—C2	1.405 (12)	C15—H15	0.9500
C2—C3	1.384 (12)	C16—H16	0.9500
C2—H2	0.9500	C21—C26	1.386 (12)
C3—C4	1.373 (14)	C21—C22	1.391 (12)
C3—H3	0.9500	C22—C23	1.382 (12)
C4—C5	1.380 (14)	C22—H22	0.9500
C4—H4	0.9500	C23—C24	1.391 (13)
C5—C6	1.387 (12)	C23—H23	0.9500
C5—H5	0.9500	C24—C25	1.381 (14)
C6—H6	0.9500	C24—H24	0.9500
C11—C12	1.363 (12)	C25—C26	1.368 (13)
C11—C16	1.399 (12)	C25—H25	0.9500
C12—C13	1.382 (12)	C26—H26	0.9500
C12—H12	0.9500

C1—Si1—C21	111.8 (4)	C12—C13—C14	119.1 (8)
C1—Si1—C11	111.0 (4)	C12—C13—H13	120.5
C21—Si1—C11	111.9 (4)	C14—C13—H13	120.5
C1—Si1—I1	106.8 (3)	C15—C14—C13	119.8 (8)
C21—Si1—I1	107.0 (3)	C15—C14—H14	120.1
C11—Si1—I1	108.0 (3)	C13—C14—H14	120.1
C6—C1—C2	118.2 (8)	C14—C15—C16	120.6 (8)
C6—C1—Si1	121.2 (6)	C14—C15—H15	119.7
C2—C1—Si1	120.6 (6)	C16—C15—H15	119.7
C3—C2—C1	120.6 (8)	C15—C16—C11	120.6 (8)
C3—C2—H2	119.7	C15—C16—H16	119.7
C1—C2—H2	119.7	C11—C16—H16	119.7
C4—C3—C2	119.7 (9)	C26—C21—C22	118.6 (8)
C4—C3—H3	120.2	C26—C21—Si1	121.5 (7)
C2—C3—H3	120.2	C22—C21—Si1	119.9 (6)
C3—C4—C5	120.8 (9)	C23—C22—C21	120.2 (8)
C3—C4—H4	119.6	C23—C22—H22	119.9
C5—C4—H4	119.6	C21—C22—H22	119.9
C4—C5—C6	119.1 (8)	C22—C23—C24	120.4 (9)
C4—C5—H5	120.4	C22—C23—H23	119.8
C6—C5—H5	120.4	C24—C23—H23	119.8
C1—C6—C5	121.6 (8)	C25—C24—C23	119.2 (8)
C1—C6—H6	119.2	C25—C24—H24	120.4
C5—C6—H6	119.2	C23—C24—H24	120.4
C12—C11—C16	117.8 (8)	C26—C25—C24	120.2 (9)
C12—C11—Si1	121.4 (6)	C26—C25—H25	119.9
C16—C11—Si1	120.8 (7)	C24—C25—H25	119.9
C11—C12—C13	122.2 (8)	C25—C26—C21	121.4 (9)
C11—C12—H12	118.9	C25—C26—H26	119.3
C13—C12—H12	118.9	C21—C26—H26	119.3

C21—Si1—C1—C6	−118.2 (7)	Si1—C11—C12—C13	176.6 (7)
C11—Si1—C1—C6	7.5 (8)	C11—C12—C13—C14	0.7 (14)
I1—Si1—C1—C6	125.0 (7)	C12—C13—C14—C15	0.0 (14)
C21—Si1—C1—C2	61.3 (8)	C13—C14—C15—C16	−0.4 (14)
C11—Si1—C1—C2	−173.0 (7)	C14—C15—C16—C11	0.1 (14)
I1—Si1—C1—C2	−55.5 (7)	C12—C11—C16—C15	0.5 (13)
C6—C1—C2—C3	0.9 (13)	Si1—C11—C16—C15	−177.0 (7)
Si1—C1—C2—C3	−178.7 (7)	C1—Si1—C21—C26	−176.4 (7)
C1—C2—C3—C4	−0.9 (14)	C11—Si1—C21—C26	58.4 (8)
C2—C3—C4—C5	−0.3 (16)	I1—Si1—C21—C26	−59.8 (7)
C3—C4—C5—C6	1.4 (15)	C1—Si1—C21—C22	5.8 (8)
C2—C1—C6—C5	0.3 (13)	C11—Si1—C21—C22	−119.4 (7)
Si1—C1—C6—C5	179.8 (7)	I1—Si1—C21—C22	122.4 (7)
C4—C5—C6—C1	−1.4 (14)	C26—C21—C22—C23	1.2 (13)
C1—Si1—C11—C12	−109.8 (7)	Si1—C21—C22—C23	179.1 (7)
C21—Si1—C11—C12	15.9 (8)	C21—C22—C23—C24	−1.8 (14)
I1—Si1—C11—C12	133.5 (6)	C22—C23—C24—C25	2.1 (14)
C1—Si1—C11—C16	67.7 (8)	C23—C24—C25—C26	−1.7 (15)
C21—Si1—C11—C16	−166.6 (7)	C24—C25—C26—C21	1.2 (15)
I1—Si1—C11—C16	−49.1 (7)	C22—C21—C26—C25	−0.9 (14)
C16—C11—C12—C13	−0.9 (13)	Si1—C21—C26—C25	−178.7 (7)

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