(Chloro­methyl)­tri­methyl­silane at 160 K

Fraser, S.; Parsons, S.

doi:10.1107/S1600536804005276

organic compounds

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ISSN: 2056-9890

Volume 60| Part 4| April 2004| Pages o564-o565

https://doi.org/10.1107/S1600536804005276

(Chloromethyl)trimethylsilane at 160 K

Stewart Fraser ^a and Simon Parsons ^a ^*

^aSchool of Chemistry, The University of Edinburgh, King's Buildings, West Mains Road, Edinburgh EH9 3JJ, Scotland
^*Correspondence e-mail: s.parsons@ed.ac.uk

(Received 16 February 2004; accepted 8 March 2004; online 24 March 2004)

(Chloromethyl)trimethylsilane, Me₃SiCH₂Cl or C₄H₁₁ClSi, is a liquid at room temperature, and it was crystallized using in situ methods. The C—Si—C bond angles involving the chloromethyl group are somewhat smaller than those involving only methyl groups [105.5 (2)–109.47 (19)° versus 110.01 (19)–111.2 (2)°], which is ascribable to both the electronegative and the steric effects of the Cl atom.

Comment

(Chloromethyl)trimethylsilane, (I), is a liquid under ambient conditions, and a crystal was obtained by in situ crystallization of a sample held in a hand-drawn Pyrex capillary (Boese & Nussbaumer, 1994 ).

Molecules of (I) adopt the expected tetrahedral configuration at Si (Fig. 1). Si—C bond distances fall into the range 1.848 (4)–1.880 (4) Å, although to within experimental error the bond distances and angles have C_s symmetry, with a mirror plane passing through atoms Si1, C1, Cl1 and C4; the C4—Si1—C1—Cl1 torsion angle [175.3 (2)°] shows a somewhat more significant deviation from the symmetry. The bond angles at atom Si1 involving the more electronegative CH₂Cl group are smaller [105.5 (2)–109.47 (19)°] than those involving only methyl groups [110.01 (19)–111.2 (2)°]. The smaller magnitude of C1—Si1—C4 [105.5 (2)°] relative to C1—Si1—C2 [109.4 (2)°] and C1—Si1—C3 [109.47 (19)°] presumably reflects the steric influence of the Cl atom.

The only intermolecular interactions falling within the sum of the van der Waals radii (Bondi, 1964 ) of the participating atoms are weak Cl1⋯H33ⁱ [symmetry code (i): −x, −y, z − $[{1 \over 2}]$ ] interactions (2.93 Å; the sum of the van der Waals radii of Cl and H is 2.95 Å). These result in chains that spiral about the 2₁ axis parallel to the c direction (Fig. 2).

Figure 1
A view of the molecular structure of (I

). Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented as spheres of arbitrary radii.

Figure 2
The molecular packing of (I

), viewed along the b axis. Weak intermolecular Cl1⋯H33 interactions are shown as dotted lines.

Experimental

A sample of (I) was obtained from Aldrich and used as received. Compound (I) is a liquid under ambient conditions and it was crystallized in situ in a capillary (o.d. 0.34 mm) mounted on the diffractometer. A crystal was grown by first establishing a seed in a small volume of the liquid at 182.8 K, and then cooling at a rate of 10 K h⁻¹. The sample was then cooled to 160 K for data collection.

Crystal data

C₄H₁₁ClSi
M_r = 122.67
Orthorhombic, Pna2₁
a = 13.8776 (13) Å
b = 6.3855 (9) Å
c = 8.4000 (10) Å
V = 744.37 (15) Å³
Z = 4
D_x = 1.095 Mg m⁻³
Mo Kα radiation
Cell parameters from 72 reflections
θ = 15–16°
μ = 0.56 mm⁻¹
T = 160 K
Cylinder, colourless
0.50 × 0.39 × 0.39 mm
0.50 mm length, 0.39 mm radius

Data collection

Stoe STADI-4 diffractometer equipped with an Oxford Cryosystems low-temperature device (Cosier & Glazer, 1986 )
ω–θ scans
Absorption correction: ψ scan [azimuthal absorption correction (North et al., 1968 ) applied using XPREP (Sheldrick, 1997 )]T_min = 0.741, T_max = 0.804
3768 measured reflections
1306 independent reflections
1186 reflections with I > 2σ(I)
R_int = 0.030
θ_max = 25.0°
h = −1 → 16
k = −7 → 7
l = −9 → 9
3 standard reflections frequency: 60 min intensity decay: none

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.115
S = 1.02
1305 reflections
56 parameters
H-atom parameters constrained
w = 1/[σ²(F)² + (0.0706P)² + 0.41P] where P = 0.3333max(0,F_o²) + 0.6667F_c²
(Δ/σ)_max = 0.001
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.32 e Å⁻³
Absolute structure: Flack (1983 ), 602 Friedel pairs
Flack parameter = −0.17 (17)

Table 1
Selected geometric parameters (Å, °)

Cl1—C1	1.798 (5)
Si1—C1	1.880 (4)
Si1—C2	1.848 (4)
Si1—C3	1.862 (4)
Si1—C4	1.867 (4)

C1—Si1—C2	109.4 (2)
C1—Si1—C3	109.47 (19)
C1—Si1—C4	105.5 (2)
C2—Si1—C3	110.01 (19)
C2—Si1—C4	111.2 (2)
C3—Si1—C4	111.18 (19)
Cl1—C1—Si1	111.9 (2)

The positions of the H atoms were recalculated geometrically after each refinement cycle, using a C—H distance of 1.00 Å, and they were assigned U_iso(H) = 1.2U_eq(C). The 10,1,0 reflection was omitted as an outlier.

Data collection: DIF4 (Stoe & Cie, 1990 ); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1990); program(s) used to solve structure: DIRDIF (Beurskens et al., 1996 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: CAMERON (Watkin et al., 1996 ) and XP (Sheldrick, 1997); software used to prepare material for publication: CRYSTALS, enCIFer (CCDC, 2003 ) and PLATON (Spek, 2003 ) used within WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536804005276/ya6200sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804005276/ya6200Isup2.hkl

Computing details top

Data collection: DIF4 (Stoe & Cie, 1990); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1990); program(s) used to solve structure: DIRDIF (Beurskens et al., 1996); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996) and XP (Sheldrick, 1997); software used to prepare material for publication: CRYSTALS, enCIFer (CCDC, 2003) and PLATON (Spek, 2003) used within WinGX (Farrugia, 1999).

(Chloromethyl)trimethylsilane top

Crystal data top

C₄H₁₁ClSi	D_x = 1.095 Mg m⁻³
M_r = 122.67	Melting point: 182.8 K
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 72 reflections
a = 13.8776 (13) Å	θ = 15–16°
b = 6.3855 (9) Å	µ = 0.56 mm⁻¹
c = 8.400 (1) Å	T = 160 K
V = 744.37 (15) Å³	Cylinder, colourless
Z = 4	0.50 × 0.39 × 0.39 × 0.39 (radius) mm
F(000) = 264

Data collection top

Stoe STADI-4 diffractometer equipped with an Oxford Cryosystems low-temperature device (Cosier & Glazer, 1986)	R_int = 0.030
Graphite monochromator	θ_max = 25.0°, θ_min = 2.5°
ω–θ scans	h = −1→16
Absorption correction: ψ scan Azimuthal absorption correction (North et al., 1968) applied using XPREP (Sheldrick, 1997)	k = −7→7
T_min = 0.741, T_max = 0.804	l = −9→9
3768 measured reflections	3 standard reflections every 0 reflections
1306 independent reflections	intensity decay: 0.0%
1186 reflections with I > 2σ(I)

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)] = 0.040	H-atom parameters constrained
wR(F²) = 0.115	w = 1/[σ²(F) + (0.0706P)² + 0.41P] where P = 0.333max(F_o²,0) + (1-0.333)F_c² (SHELXL97; Sheldrick, 1997)
S = 1.02	(Δ/σ)_max = 0.001
1305 reflections	Δρ_max = 0.43 e Å⁻³
56 parameters	Δρ_min = −0.32 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 602 Friedel pairs
Primary atom site location: Patterson	Absolute structure parameter: −0.17 (17)

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

	x	y	z	U_iso*/U_eq
Cl1	0.09384 (8)	0.28224 (18)	−0.33332 (15)	0.0602
Si1	0.14648 (6)	0.17201 (14)	0.00888 (17)	0.0327
C1	0.0582 (3)	0.3037 (6)	−0.1281 (5)	0.0430
C2	0.2681 (3)	0.2813 (6)	−0.0252 (5)	0.0492
C3	0.1468 (3)	−0.1149 (6)	−0.0303 (5)	0.0464
C4	0.1032 (3)	0.2305 (7)	0.2146 (5)	0.0522
H11	0.0538	0.4553	−0.0993	0.0516*
H12	−0.0064	0.2366	−0.1147	0.0516*
H21	0.3151	0.2113	0.0476	0.0591*
H22	0.2673	0.4351	−0.0034	0.0591*
H23	0.2874	0.2561	−0.1382	0.0591*
H31	0.1937	−0.1849	0.0426	0.0557*
H32	0.1659	−0.1411	−0.1433	0.0557*
H33	0.0808	−0.1727	−0.0112	0.0557*
H41	0.1477	0.1644	0.2936	0.0629*
H42	0.1024	0.3857	0.2311	0.0629*
H43	0.0368	0.1733	0.2286	0.0629*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0550 (6)	0.0864 (8)	0.0393 (6)	0.0021 (6)	−0.0026 (6)	0.0070 (7)
Si1	0.0317 (4)	0.0313 (4)	0.0350 (5)	0.0017 (4)	0.0013 (5)	−0.0014 (5)
C1	0.041 (2)	0.044 (2)	0.044 (2)	0.0084 (17)	−0.0020 (17)	0.0021 (19)
C2	0.039 (2)	0.050 (2)	0.059 (3)	−0.0074 (17)	0.001 (2)	−0.001 (2)
C3	0.048 (2)	0.0382 (18)	0.053 (3)	0.0006 (17)	0.0011 (19)	−0.0025 (17)
C4	0.060 (3)	0.058 (3)	0.039 (2)	0.006 (2)	0.0051 (19)	−0.0053 (18)

Geometric parameters (Å, º) top

Cl1—C1	1.798 (5)	C2—H22	0.999
Si1—C1	1.880 (4)	C2—H21	1.000
Si1—C2	1.848 (4)	C3—H33	1.000
Si1—C3	1.862 (4)	C3—H32	1.000
Si1—C4	1.867 (4)	C3—H31	1.000
C1—H12	1.000	C4—H43	0.998
C1—H11	1.000	C4—H42	1.000
C2—H23	1.000	C4—H41	0.999

C1—Si1—C2	109.4 (2)	H23—C2—Si1	109.391
C1—Si1—C3	109.47 (19)	H22—C2—Si1	109.438
C1—Si1—C4	105.5 (2)	H21—C2—Si1	109.407
C2—Si1—C3	110.01 (19)	H33—C3—H32	109.483
C2—Si1—C4	111.2 (2)	H33—C3—H31	109.471
C3—Si1—C4	111.18 (19)	H32—C3—H31	109.508
H12—C1—H11	109.474	H33—C3—Si1	109.441
H12—C1—Cl1	108.829	H32—C3—Si1	109.458
H11—C1—Cl1	108.829	H31—C3—Si1	109.467
H12—C1—Si1	108.878	H43—C4—H42	109.610
H11—C1—Si1	108.891	H43—C4—H41	109.690
Cl1—C1—Si1	111.9 (2)	H42—C4—H41	109.489
H23—C2—H22	109.553	H43—C4—Si1	109.412
H23—C2—H21	109.488	H42—C4—Si1	109.281
H22—C2—H21	109.551	H41—C4—Si1	109.344

Acknowledgements

The authors thank the EPSRC and the University of Edinburgh for funding.

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