1-Phenyl-5-{[2-(trimethyl-sil-yl)eth-yl]sulfon-yl}-1H-tetra-zole.

The title compound, C(12)H(18)N(4)O(2)SSi, was synthesized to be employed in a Julia-Kocieński olefination. In the mol-ecule, the dihedral angle between the phenyl ring and the tetra-zole ring is 41.50 (5)°. The significantly longer Si-C(methyl-ene) bond [1.8786 (13) Å] and the shortened adjacent C-C bond [1.5172 (18) Å], as well as the significant deviation of the corresponding Si-C-C angle [114.16 (9)°] from the ideal tetra-hedral angle, can be attributed to the β-effect of silicon. In the crystal, mol-ecules are held together by van der Waals inter-actions.

Related literature

For Julia–Kocieński olefination, see: Blakemore et al. (1998 ▶). For the use of unsaturated α-keto esters in intra­molecular carbonyl-ene reactions in natural product synthen class="Chemical">sis, see: Helmboldt & Hiersemann (2009 ▶); Helmboldt et al. (2006 ▶); Schnabel & Hiersemann (2009 ▶); Schnabel et al. (2011 ▶) The title compound was synthesized using a reduction of ethyl 2-(trimethyl­sil­yl)acetate (Gerlach, 1977 ▶) followed by a Mitsunobu reaction (Mitsunobu & Yamada, 1967 ▶; Mitsunobu et al., 1967 ▶) and a subsequent Mo-(VI)-catalyzed oxidation of the thio­ether (Schultz et al., 1963 ▶).

Experimental

Crystal data

C12H18N4O2SSi

M = 310.45

Monoclinic,

a = 11.3126 (4) Å

b = 13.2707 (4) Å

c = 10.8277 (4) Å

β = 106.902 (4)°

V = 1555.31 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.29 mm−1

T = 173 K

0.50 × 0.50 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur S CCD diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T min = 0.868, T max = 0.944

22841 measured reflections

3384 independent reflections

2961 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.079

S = 1.10

3384 reflections

184 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.37 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis n class="Disease">CCD; data reduction: CrysAlis CCD; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL-Plus (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811030492/hg5066sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811030492/hg5066Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811030492/hg5066Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H18N4O2SSi	F(000) = 656
Mr = 310.45	Dx = 1.326 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 16653 reflections
a = 11.3126 (4) Å	θ = 2.4–29.2°
b = 13.2707 (4) Å	µ = 0.29 mm−1
c = 10.8277 (4) Å	T = 173 K
β = 106.902 (4)°	Block, colourless
V = 1555.31 (9) Å3	0.50 × 0.50 × 0.20 mm
Z = 4

Oxford Diffraction Xcalibur S CCD diffractometer	3384 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2961 reflections with I > 2σ(I)
graphite	Rint = 0.024
Detector resolution: 16.0560 pixels mm-1	θmax = 27.0°, θmin = 2.4°
ω scans	h = −14→14
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −16→16
Tmin = 0.868, Tmax = 0.944	l = −13→13
22841 measured reflections

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0465P)2 + 0.3668P] where P = (Fo2 + 2Fc2)/3
3384 reflections	(Δ/σ)max = 0.001
184 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.37 (release 24-10-2008) Empirical absorption correction using sperical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

	x	y	z	Uiso*/Ueq
Si	0.47993 (3)	0.79710 (3)	1.25192 (3)	0.01949 (10)
C1	0.47042 (15)	0.87175 (12)	1.39384 (14)	0.0341 (3)
H1A	0.3933	0.8557	1.4135	0.051*
H1B	0.4722	0.9438	1.3744	0.051*
H1C	0.5408	0.8552	1.4684	0.051*
C2	0.61720 (14)	0.83876 (13)	1.20403 (15)	0.0346 (3)
H2A	0.6923	0.8247	1.2743	0.052*
H2B	0.6114	0.9113	1.1862	0.052*
H2C	0.6203	0.8022	1.1263	0.052*
C3	0.48654 (13)	0.66005 (11)	1.28620 (15)	0.0310 (3)
H3A	0.4895	0.6228	1.2090	0.046*
H3B	0.4130	0.6399	1.3105	0.046*
H3C	0.5607	0.6450	1.3573	0.046*
C4	0.33521 (12)	0.81809 (10)	1.11572 (13)	0.0255 (3)
H4A	0.3418	0.7802	1.0393	0.031*
H4B	0.2643	0.7903	1.1407	0.031*
C5	0.30914 (11)	0.92782 (10)	1.07831 (12)	0.0206 (3)
H5A	0.3797	0.9573	1.0541	0.025*
H5B	0.2977	0.9664	1.1523	0.025*
S	0.17351 (3)	0.93484 (2)	0.94605 (3)	0.01563 (9)
O1	0.19901 (9)	0.90232 (7)	0.83074 (9)	0.0253 (2)
O2	0.07296 (8)	0.89053 (7)	0.98167 (9)	0.0222 (2)
C6	0.14770 (11)	1.06672 (9)	0.93227 (12)	0.0162 (2)
N1	0.20780 (10)	1.12950 (8)	1.02188 (10)	0.0209 (2)
N2	0.16789 (11)	1.22251 (8)	0.97617 (11)	0.0253 (3)
N3	0.08670 (11)	1.21661 (8)	0.86430 (11)	0.0233 (2)
N4	0.07262 (9)	1.11767 (8)	0.83393 (10)	0.0172 (2)
C10	−0.01458 (11)	1.08607 (10)	0.71540 (12)	0.0187 (3)
C11	−0.02014 (13)	1.14131 (11)	0.60586 (13)	0.0254 (3)
H11	0.0318	1.1982	0.6096	0.030*
C12	−0.10312 (14)	1.11189 (12)	0.49061 (13)	0.0320 (3)
H12	−0.1085	1.1485	0.4138	0.038*
C13	−0.17799 (14)	1.02960 (12)	0.48703 (14)	0.0331 (3)
H13	−0.2349	1.0098	0.4075	0.040*
C14	−0.17131 (13)	0.97537 (11)	0.59818 (14)	0.0295 (3)
H14	−0.2235	0.9187	0.5945	0.035*
C15	−0.08875 (12)	1.00359 (10)	0.71465 (13)	0.0223 (3)
H15	−0.0834	0.9672	0.7916	0.027*

	U11	U22	U33	U12	U13	U23
Si	0.01680 (18)	0.01994 (18)	0.02019 (18)	0.00148 (13)	0.00294 (13)	0.00318 (13)
C1	0.0433 (9)	0.0335 (8)	0.0261 (7)	0.0030 (7)	0.0110 (6)	0.0011 (6)
C2	0.0267 (7)	0.0423 (9)	0.0372 (8)	−0.0053 (7)	0.0130 (6)	−0.0001 (7)
C3	0.0248 (7)	0.0253 (7)	0.0384 (8)	0.0043 (6)	0.0022 (6)	0.0080 (6)
C4	0.0224 (6)	0.0195 (6)	0.0288 (7)	0.0011 (5)	−0.0019 (5)	0.0030 (5)
C5	0.0172 (6)	0.0206 (6)	0.0198 (6)	0.0009 (5)	−0.0012 (5)	0.0015 (5)
S	0.01427 (15)	0.01592 (15)	0.01611 (15)	0.00142 (11)	0.00350 (11)	0.00039 (10)
O1	0.0287 (5)	0.0278 (5)	0.0199 (5)	0.0066 (4)	0.0081 (4)	−0.0022 (4)
O2	0.0181 (4)	0.0204 (5)	0.0283 (5)	−0.0012 (4)	0.0069 (4)	0.0039 (4)
C6	0.0142 (5)	0.0170 (6)	0.0184 (6)	0.0009 (4)	0.0064 (4)	0.0012 (4)
N1	0.0185 (5)	0.0195 (5)	0.0242 (5)	−0.0010 (4)	0.0055 (4)	−0.0021 (4)
N2	0.0255 (6)	0.0192 (6)	0.0300 (6)	−0.0004 (4)	0.0064 (5)	−0.0022 (5)
N3	0.0266 (6)	0.0157 (5)	0.0278 (6)	−0.0007 (4)	0.0081 (5)	−0.0010 (4)
N4	0.0188 (5)	0.0152 (5)	0.0182 (5)	0.0011 (4)	0.0064 (4)	0.0017 (4)
C10	0.0176 (6)	0.0202 (6)	0.0174 (6)	0.0052 (5)	0.0039 (5)	−0.0006 (5)
C11	0.0289 (7)	0.0250 (7)	0.0233 (6)	0.0073 (6)	0.0092 (5)	0.0056 (5)
C12	0.0391 (8)	0.0355 (8)	0.0196 (7)	0.0160 (7)	0.0058 (6)	0.0050 (6)
C13	0.0326 (8)	0.0369 (8)	0.0223 (7)	0.0143 (7)	−0.0040 (6)	−0.0076 (6)
C14	0.0250 (7)	0.0250 (7)	0.0331 (8)	0.0032 (6)	−0.0004 (6)	−0.0061 (6)
C15	0.0218 (6)	0.0212 (6)	0.0224 (6)	0.0034 (5)	0.0039 (5)	0.0008 (5)

Si—C3	1.8534 (15)	S—O2	1.4295 (9)
Si—C1	1.8575 (15)	S—C6	1.7734 (13)
Si—C2	1.8586 (15)	C6—N1	1.3093 (16)
Si—C4	1.8786 (13)	C6—N4	1.3366 (15)
C1—H1A	0.9800	N1—N2	1.3573 (16)
C1—H1B	0.9800	N2—N3	1.2924 (16)
C1—H1C	0.9800	N3—N4	1.3517 (15)
C2—H2A	0.9800	N4—C10	1.4353 (15)
C2—H2B	0.9800	C10—C15	1.3778 (19)
C2—H2C	0.9800	C10—C11	1.3802 (18)
C3—H3A	0.9800	C11—C12	1.382 (2)
C3—H3B	0.9800	C11—H11	0.9500
C3—H3C	0.9800	C12—C13	1.376 (2)
C4—C5	1.5172 (18)	C12—H12	0.9500
C4—H4A	0.9900	C13—C14	1.385 (2)
C4—H4B	0.9900	C13—H13	0.9500
C5—S	1.7710 (12)	C14—C15	1.3850 (18)
C5—H5A	0.9900	C14—H14	0.9500
C5—H5B	0.9900	C15—H15	0.9500
S—O1	1.4275 (9)
C3—Si—C1	111.49 (7)	H5A—C5—H5B	108.3
C3—Si—C2	111.06 (7)	O1—S—O2	119.38 (6)
C1—Si—C2	109.04 (8)	O1—S—C5	110.09 (6)
C3—Si—C4	106.14 (6)	O2—S—C5	109.30 (6)
C1—Si—C4	108.88 (7)	O1—S—C6	107.15 (6)
C2—Si—C4	110.18 (7)	O2—S—C6	107.71 (6)
Si—C1—H1A	109.5	C5—S—C6	101.69 (6)
Si—C1—H1B	109.5	N1—C6—N4	109.95 (11)
H1A—C1—H1B	109.5	N1—C6—S	121.89 (9)
Si—C1—H1C	109.5	N4—C6—S	128.11 (9)
H1A—C1—H1C	109.5	C6—N1—N2	105.22 (10)
H1B—C1—H1C	109.5	N3—N2—N1	110.92 (10)
Si—C2—H2A	109.5	N2—N3—N4	106.75 (10)
Si—C2—H2B	109.5	C6—N4—N3	107.16 (10)
H2A—C2—H2B	109.5	C6—N4—C10	132.60 (11)
Si—C2—H2C	109.5	N3—N4—C10	120.20 (10)
H2A—C2—H2C	109.5	C15—C10—C11	122.78 (12)
H2B—C2—H2C	109.5	C15—C10—N4	119.77 (11)
Si—C3—H3A	109.5	C11—C10—N4	117.45 (12)
Si—C3—H3B	109.5	C10—C11—C12	118.37 (14)
H3A—C3—H3B	109.5	C10—C11—H11	120.8
Si—C3—H3C	109.5	C12—C11—H11	120.8
H3A—C3—H3C	109.5	C13—C12—C11	120.05 (13)
H3B—C3—H3C	109.5	C13—C12—H12	120.0
C5—C4—Si	114.16 (9)	C11—C12—H12	120.0
C5—C4—H4A	108.7	C12—C13—C14	120.69 (13)
Si—C4—H4A	108.7	C12—C13—H13	119.7
C5—C4—H4B	108.7	C14—C13—H13	119.7
Si—C4—H4B	108.7	C15—C14—C13	120.17 (14)
H4A—C4—H4B	107.6	C15—C14—H14	119.9
C4—C5—S	108.77 (9)	C13—C14—H14	119.9
C4—C5—H5A	109.9	C10—C15—C14	117.94 (13)
S—C5—H5A	109.9	C10—C15—H15	121.0
C4—C5—H5B	109.9	C14—C15—H15	121.0
S—C5—H5B	109.9
C3—Si—C4—C5	176.60 (11)	S—C6—N4—N3	−177.75 (9)
C1—Si—C4—C5	56.46 (12)	N1—C6—N4—C10	−177.91 (11)
C2—Si—C4—C5	−63.07 (13)	S—C6—N4—C10	4.50 (19)
Si—C4—C5—S	178.07 (7)	N2—N3—N4—C6	0.40 (14)
C4—C5—S—O1	−74.32 (11)	N2—N3—N4—C10	178.48 (10)
C4—C5—S—O2	58.65 (11)	C6—N4—C10—C15	40.14 (19)
C4—C5—S—C6	172.32 (9)	N3—N4—C10—C15	−137.36 (12)
O1—S—C6—N1	−127.27 (10)	C6—N4—C10—C11	−140.07 (13)
O2—S—C6—N1	103.12 (11)	N3—N4—C10—C11	42.42 (16)
C5—S—C6—N1	−11.74 (12)	C15—C10—C11—C12	−0.5 (2)
O1—S—C6—N4	50.06 (12)	N4—C10—C11—C12	179.73 (12)
O2—S—C6—N4	−79.55 (12)	C10—C11—C12—C13	0.3 (2)
C5—S—C6—N4	165.59 (11)	C11—C12—C13—C14	0.0 (2)
N4—C6—N1—N2	−0.12 (13)	C12—C13—C14—C15	0.0 (2)
S—C6—N1—N2	177.64 (9)	C11—C10—C15—C14	0.5 (2)
C6—N1—N2—N3	0.38 (14)	N4—C10—C15—C14	−179.75 (11)
N1—N2—N3—N4	−0.49 (14)	C13—C14—C15—C10	−0.2 (2)
N1—C6—N4—N3	−0.17 (14)