3-(Trimethyl­sil­yl)prop-2-ynyl p-toluene­sulfonate

Schmitt, D.C.; Morales, G.A.; Fronczek, F.R.; Watkins, S.F.

doi:10.1107/S1600536811043595

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3110

doi:10.1107/S1600536811043595

Open

access

3-(Trimethylsilyl)prop-2-ynyl p-toluenesulfonate

Devin C. Schmitt,^a Guillermo A. Morales,^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 3 October 2011; accepted 20 October 2011; online 29 October 2011)

In the title compound, C₁₃H₁₈O₃SSi, the SO₃ group displays a partial rotational (ca 50°) disorder about the C—S bond, with relative proportions 0.7744 (13):0.2256 (13). This disorder also forces the propynyl CH₂ group to be disordered.

Related literature

For information on the title compound, see: Westmijze & Vermeer (1979 ); Tanabe et al. (1995 ); Morales (1995 ).

Experimental

Crystal data

C₁₃H₁₈O₃SSi
M_r = 282.42
Monoclinic, P 2₁ /c
a = 10.6857 (4) Å
b = 12.9413 (5) Å
c = 11.8793 (4) Å
β = 113.471 (2)°
V = 1506.83 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 90 K
0.33 × 0.18 × 0.17 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.910, T_max = 0.952
9135 measured reflections
4721 independent reflections
3257 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.108
S = 1.03
4721 reflections
177 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.76 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); 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/S1600536811043595/fj2461sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811043595/fj2461Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811043595/fj2461Isup3.cml

checkCIF report

Comment top

The title compound was prepared as an intermediate in the synthesis of 3-methyl substituted benz[f]indole derivatives (Morales, 1995). It has been described as a colorless liquid at room temperature (Tanabe et al., 1995; Westmijze & Vermeer, 1979). Our initial synthesis, by treating 3-trimethylsilylpropargyl alcohol with freshly powdered KOH and freshly recrystallized p-toluenesulfonyl chloride in ether at -50°C, also yielded the desired sulfonate as a liquid. However, after several recrystallizations from hexanes, suitable single crystals were obtained as colorless needles with melting point 43–44°C.

3-Trimethylsilyl-2-propynyl p-toluenesulfonate contains a p-toluenesulfonate group with the S(O)₂OCH₂ group partially (22.56 (13)%) disordered by rotation of ca 50° about the C–S bond. The disorder was modelled with constrained partial occupancy of two O₃ and two H₂ sites. The disordered O–C bond distances were restrained to be approximately equal (to within σ = 0.002 Å) to compensate for disorder of the C atom itself. The two partial S–O bonds average 1.574 (2) Å, and the four partial S═O bonds average 1.435 (1) Å.

Related literature top

For information on the title compound, see: Westmijze & Vermeer (1979); Tanabe et al. (1995); Morales (1995).

Experimental top

The title compound was prepared according to the procedure of Westmijze & Vermeer (1979): Commercially available 3-trimethylsilylpropargyl alcohol (5.13 g, 40.0 mmol) and freshly purified tosyl chloride (9.53 g, 50.0 mmol) were mixed in anhydrous diethyl ether under an Ar atmosphere. The mixture was cooled to -50 °C, and freshly powdered KOH (15.0 g, 268 mmol) was added at once under vigorous stirring. The temperature of the resulting thick mixture was slowly raised to 0 °C, and the mixture was stirred at this temperature for 30 min. This mixture was poured onto water (200 ml), extracted with ethyl ether (3 τimes 50 ml), washed with water (100 ml), and concentrated under reduced pressure to give a light brown oil. Repeated crystallization from hexanes afforded colorless needles (7.93 g, 70.3% yield).

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); 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

Fig. 1. View of (I) showing 50% probability displacement ellipsoids. The two disordered components of the sulfonate group are shown, while only the major component of the attached disordered methylene group is drawn.

3-(Trimethylsilyl)prop-2-ynyl p-toluenesulfonate top

Crystal data top

C₁₃H₁₈O₃SSi	F(000) = 600
M_r = 282.42	D_x = 1.245 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4768 reflections
a = 10.6857 (4) Å	θ = 2.6–31.0°
b = 12.9413 (5) Å	µ = 0.29 mm⁻¹
c = 11.8793 (4) Å	T = 90 K
β = 113.471 (2)°	Needle, colorless
V = 1506.83 (10) Å³	0.33 × 0.18 × 0.17 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	4721 independent reflections
Radiation source: fine-focus sealed tube	3257 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 9 pixels mm^-1	θ_max = 30.9°, θ_min = 2.6°
ω and ϕ scans	h = −15→15
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −18→18
T_min = 0.910, T_max = 0.952	l = −17→16
9135 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0404P)² + 0.7293P] where P = (F_o² + 2F_c²)/3
4721 reflections	(Δ/σ)_max = 0.001
177 parameters	Δρ_max = 0.76 e Å⁻³
1 restraint	Δρ_min = −0.54 e Å⁻³
3 constraints

Crystal data top

C₁₃H₁₈O₃SSi	V = 1506.83 (10) Å³
M_r = 282.42	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.6857 (4) Å	µ = 0.29 mm⁻¹
b = 12.9413 (5) Å	T = 90 K
c = 11.8793 (4) Å	0.33 × 0.18 × 0.17 mm
β = 113.471 (2)°

Data collection top

Nonius KappaCCD diffractometer	4721 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	3257 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.952	R_int = 0.041
9135 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	1 restraint
wR(F²) = 0.108	H-atom parameters constrained
S = 1.03	Δρ_max = 0.76 e Å⁻³
4721 reflections	Δρ_min = −0.54 e Å⁻³
177 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	1.00481 (4)	0.33704 (3)	0.46346 (4)	0.01708 (10)
Si1	0.49810 (5)	0.23584 (4)	0.04270 (4)	0.02127 (12)
O1	0.87983 (15)	0.41268 (11)	0.42804 (13)	0.0207 (3)	0.7744 (13)
O2	1.08780 (16)	0.36473 (12)	0.39833 (15)	0.0237 (3)	0.7744 (13)
O3	1.06468 (17)	0.33877 (12)	0.59590 (14)	0.0250 (3)	0.7744 (13)
O1A	0.9453 (3)	0.4058 (4)	0.3433 (4)	0.0207 (3)	0.2256 (13)
O2A	1.1404 (6)	0.3363 (4)	0.4827 (5)	0.0237 (3)	0.2256 (13)
O3A	0.9569 (6)	0.3761 (4)	0.5540 (5)	0.0250 (3)	0.2256 (13)
C1	0.93291 (17)	0.21448 (12)	0.41521 (15)	0.0178 (3)
C2	0.86434 (19)	0.16667 (14)	0.47865 (16)	0.0240 (4)
H2	0.8564	0.1997	0.5469	0.029*
C3	0.8077 (2)	0.06981 (14)	0.44071 (17)	0.0282 (4)
H3	0.7606	0.0364	0.4836	0.034*
C4	0.81874 (18)	0.02064 (13)	0.34052 (16)	0.0257 (4)
C5	0.88776 (18)	0.07073 (13)	0.27880 (16)	0.0246 (4)
H5	0.8955	0.038	0.2102	0.03*
C6	0.94568 (17)	0.16762 (13)	0.31531 (15)	0.0212 (3)
H6	0.993	0.2011	0.2728	0.025*
C7	0.7575 (2)	−0.08509 (15)	0.3004 (2)	0.0377 (5)
H7A	0.7553	−0.1005	0.2188	0.057*
H7C	0.6645	−0.0864	0.2972	0.057*
H7B	0.8131	−0.137	0.3591	0.057*
C8	0.81275 (19)	0.45147 (14)	0.30416 (16)	0.0272 (4)
H8A	0.8829	0.4663	0.2715	0.033*	0.7744 (13)
H8B	0.7671	0.5175	0.3066	0.033*	0.7744 (13)
H8A'	0.8112	0.518	0.2626	0.033*	0.2256 (13)
H8B'	0.7906	0.4652	0.3762	0.033*	0.2256 (13)
C9	0.71152 (19)	0.38092 (14)	0.21960 (16)	0.0237 (4)
C10	0.62740 (19)	0.32454 (14)	0.14905 (16)	0.0247 (4)
C11	0.58308 (19)	0.15508 (16)	−0.03569 (18)	0.0314 (4)
H11A	0.6075	0.1983	−0.0916	0.047*
H11B	0.5207	0.1003	−0.0824	0.047*
H11C	0.6658	0.1241	0.0257	0.047*
C12	0.4334 (2)	0.15281 (15)	0.13563 (19)	0.0333 (4)
H12A	0.51	0.1164	0.1983	0.05*
H12B	0.3686	0.1023	0.0821	0.05*
H12C	0.3876	0.1959	0.1755	0.05*
C13	0.36123 (19)	0.31849 (14)	−0.06735 (17)	0.0270 (4)
H13A	0.3137	0.355	−0.0237	0.041*
H13B	0.2962	0.2751	−0.1317	0.041*
H13C	0.4018	0.3688	−0.1045	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01972 (19)	0.01537 (18)	0.01643 (19)	−0.00309 (16)	0.00751 (15)	−0.00186 (15)
Si1	0.0256 (2)	0.0199 (2)	0.0190 (2)	−0.0004 (2)	0.00962 (19)	−0.00338 (19)
O1	0.0220 (7)	0.0174 (7)	0.0228 (8)	−0.0009 (6)	0.0091 (6)	−0.0038 (6)
O2	0.0242 (8)	0.0217 (8)	0.0295 (8)	−0.0020 (6)	0.0152 (7)	0.0019 (6)
O3	0.0322 (8)	0.0222 (8)	0.0168 (7)	−0.0078 (7)	0.0058 (6)	−0.0022 (6)
O1A	0.0220 (7)	0.0174 (7)	0.0228 (8)	−0.0009 (6)	0.0091 (6)	−0.0038 (6)
O2A	0.0242 (8)	0.0217 (8)	0.0295 (8)	−0.0020 (6)	0.0152 (7)	0.0019 (6)
O3A	0.0322 (8)	0.0222 (8)	0.0168 (7)	−0.0078 (7)	0.0058 (6)	−0.0022 (6)
C1	0.0199 (8)	0.0136 (7)	0.0176 (8)	−0.0008 (6)	0.0050 (6)	−0.0020 (6)
C2	0.0311 (9)	0.0206 (8)	0.0227 (8)	−0.0059 (7)	0.0134 (7)	−0.0051 (7)
C3	0.0346 (10)	0.0207 (9)	0.0307 (10)	−0.0075 (8)	0.0144 (8)	−0.0006 (7)
C4	0.0253 (9)	0.0159 (8)	0.0268 (9)	0.0007 (7)	0.0006 (7)	−0.0028 (7)
C5	0.0294 (9)	0.0199 (8)	0.0200 (8)	0.0056 (7)	0.0049 (7)	−0.0058 (7)
C6	0.0246 (8)	0.0203 (8)	0.0184 (8)	0.0035 (7)	0.0083 (7)	−0.0008 (7)
C7	0.0426 (12)	0.0185 (9)	0.0417 (12)	−0.0053 (8)	0.0059 (10)	−0.0078 (8)
C8	0.0314 (9)	0.0178 (8)	0.0256 (9)	0.0002 (7)	0.0043 (8)	0.0018 (7)
C9	0.0291 (9)	0.0212 (8)	0.0224 (9)	0.0032 (7)	0.0120 (7)	0.0018 (7)
C10	0.0317 (10)	0.0241 (9)	0.0199 (8)	0.0008 (7)	0.0120 (7)	−0.0004 (7)
C11	0.0257 (9)	0.0394 (11)	0.0267 (9)	0.0020 (8)	0.0079 (8)	−0.0119 (8)
C12	0.0434 (12)	0.0255 (10)	0.0342 (11)	−0.0013 (9)	0.0191 (9)	0.0022 (8)
C13	0.0299 (9)	0.0251 (9)	0.0250 (9)	0.0012 (7)	0.0100 (8)	−0.0014 (7)

Geometric parameters (Å, º) top

S1—O2A	1.374 (5)	C5—C6	1.389 (2)
S1—O2	1.4352 (15)	C5—H5	0.95
S1—O3	1.4434 (15)	C6—H6	0.95
S1—O3A	1.454 (6)	C7—H7A	0.98
S1—O1	1.5720 (15)	C7—H7C	0.98
S1—O1A	1.584 (5)	C7—H7B	0.98
S1—C1	1.7561 (16)	C8—C9	1.465 (2)
Si1—C10	1.8526 (19)	C8—H8A	0.99
Si1—C11	1.8594 (19)	C8—H8B	0.99
Si1—C12	1.8600 (19)	C8—H8A'	0.99
Si1—C13	1.8625 (19)	C8—H8B'	0.99
O1—C8	1.446 (2)	C9—C10	1.201 (3)
O1A—C8	1.430 (3)	C11—H11A	0.98
C1—C6	1.387 (2)	C11—H11B	0.98
C1—C2	1.388 (2)	C11—H11C	0.98
C2—C3	1.387 (2)	C12—H12A	0.98
C2—H2	0.95	C12—H12B	0.98
C3—C4	1.396 (3)	C12—H12C	0.98
C3—H3	0.95	C13—H13A	0.98
C4—C5	1.390 (3)	C13—H13B	0.98
C4—C7	1.510 (2)	C13—H13C	0.98

O2—S1—O3	118.88 (10)	C4—C7—H7A	109.5
O2A—S1—O3A	122.5 (3)	C4—C7—H7C	109.5
O2—S1—O1	109.98 (9)	H7A—C7—H7C	109.5
O3—S1—O1	104.04 (9)	C4—C7—H7B	109.5
O2A—S1—O1A	99.9 (3)	H7A—C7—H7B	109.5
O3A—S1—O1A	109.7 (3)	H7C—C7—H7B	109.5
O2A—S1—C1	110.1 (2)	O1A—C8—C9	109.3 (2)
O2—S1—C1	109.48 (9)	O1—C8—C9	114.37 (15)
O3—S1—C1	108.43 (8)	O1—C8—H8A	108.7
O3A—S1—C1	108.6 (2)	C9—C8—H8A	108.7
O1—S1—C1	105.10 (8)	O1—C8—H8B	108.7
O1A—S1—C1	104.31 (19)	C9—C8—H8B	108.7
C10—Si1—C11	108.03 (9)	H8A—C8—H8B	107.6
C10—Si1—C12	107.80 (9)	O1A—C8—H8A'	109.8
C11—Si1—C12	110.10 (10)	C9—C8—H8A'	109.8
C10—Si1—C13	106.66 (8)	O1A—C8—H8B'	109.8
C11—Si1—C13	112.01 (9)	C9—C8—H8B'	109.8
C12—Si1—C13	112.01 (9)	H8A'—C8—H8B'	108.3
C8—O1—S1	120.83 (12)	C10—C9—C8	178.9 (2)
C8—O1A—S1	121.0 (3)	C9—C10—Si1	178.90 (17)
C6—C1—C2	121.51 (15)	Si1—C11—H11A	109.5
C6—C1—S1	119.66 (13)	Si1—C11—H11B	109.5
C2—C1—S1	118.83 (12)	H11A—C11—H11B	109.5
C3—C2—C1	118.87 (16)	Si1—C11—H11C	109.5
C3—C2—H2	120.6	H11A—C11—H11C	109.5
C1—C2—H2	120.6	H11B—C11—H11C	109.5
C2—C3—C4	121.00 (17)	Si1—C12—H12A	109.5
C2—C3—H3	119.5	Si1—C12—H12B	109.5
C4—C3—H3	119.5	H12A—C12—H12B	109.5
C5—C4—C3	118.69 (16)	Si1—C12—H12C	109.5
C5—C4—C7	120.67 (17)	H12A—C12—H12C	109.5
C3—C4—C7	120.64 (18)	H12B—C12—H12C	109.5
C6—C5—C4	121.35 (16)	Si1—C13—H13A	109.5
C6—C5—H5	119.3	Si1—C13—H13B	109.5
C4—C5—H5	119.3	H13A—C13—H13B	109.5
C1—C6—C5	118.58 (16)	Si1—C13—H13C	109.5
C1—C6—H6	120.7	H13A—C13—H13C	109.5
C5—C6—H6	120.7	H13B—C13—H13C	109.5

O2—S1—O1—C8	36.57 (16)	O3—S1—C1—C2	40.01 (17)
O3—S1—O1—C8	164.93 (14)	O3A—S1—C1—C2	−10.1 (3)
C1—S1—O1—C8	−81.18 (15)	O1—S1—C1—C2	−70.77 (15)
O2A—S1—O1A—C8	−163.6 (4)	O1A—S1—C1—C2	−127.00 (18)
O3A—S1—O1A—C8	−33.6 (5)	C6—C1—C2—C3	0.0 (3)
C1—S1—O1A—C8	82.5 (4)	S1—C1—C2—C3	−179.91 (14)
O2A—S1—C1—C6	−53.4 (3)	C1—C2—C3—C4	−0.1 (3)
O2—S1—C1—C6	−8.82 (17)	C2—C3—C4—C5	−0.1 (3)
O3—S1—C1—C6	−139.95 (14)	C2—C3—C4—C7	179.61 (18)
O3A—S1—C1—C6	170.0 (3)	C3—C4—C5—C6	0.3 (3)
O1—S1—C1—C6	109.28 (14)	C7—C4—C5—C6	−179.42 (17)
O1A—S1—C1—C6	53.05 (19)	C2—C1—C6—C5	0.1 (3)
O2A—S1—C1—C2	126.6 (3)	S1—C1—C6—C5	−179.91 (13)
O2—S1—C1—C2	171.14 (14)	C4—C5—C6—C1	−0.3 (3)

Experimental details

Crystal data
Chemical formula	C₁₃H₁₈O₃SSi
M_r	282.42
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	90
a, b, c (Å)	10.6857 (4), 12.9413 (5), 11.8793 (4)
β (°)	113.471 (2)
V (Å³)	1506.83 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.33 × 0.18 × 0.17

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.910, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	9135, 4721, 3257
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.722

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.108, 1.03
No. of reflections	4721
No. of parameters	177
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.76, −0.54

Computer programs: COLLECT (Nonius, 2000), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Footnotes

‡Current address: Morales Consulting, LLC, 11474 Perkins Street, Carmel, IN 46032 USA.

Acknowledgements

The purchase of the diffractometer was made possible by grant No. LEQSF (1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.

References

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Morales, A. (1995). PhD dissertation, Louisiana State University, Baton Rouge, USA. Google Scholar
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
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. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tanabe, Y., Yamamoto, H., Yoshida, Y., Miyawaki, T. & Utsumi, N. (1995). Bull. Chem. Soc. Jpn, 68, 297. CrossRef Web of Science Google Scholar
Westmijze, H. & Vermeer, P. (1979). Synthesis, 5, 390–392. CrossRef Google Scholar