organic papers
Acta Cryst.(2006). E62, o2395–o2396 doi:10.1107/S1600536806017624 Gaoet al. C
16H16S2
o2395
Acta Crystallographica Section EStructure Reports
Online
ISSN 1600-5368
1-Phenylethyl phenyldithioacetate
Jing Gao, Yingwu Luo and Bogeng Li*
Zhejiang University, The Union State Key Laboratory of Chemical, Engineering, Polymer Reaction Engineering Division, Hangzhou, 310027, People’s Republic of China
Correspondence e-mail: stella_gj@zju.edu.cn
Key indicators
Single-crystal X-ray study
T= 298 K
Mean(C–C) = 0.004 A˚
Rfactor = 0.044
wRfactor = 0.143
Data-to-parameter ratio = 20.8
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
Received 13 January 2006 Accepted 12 May 2006
#2006 International Union of Crystallography All rights reserved
The overall shape of the title compound, C16H16S2, is like a
capital ‘M’, with both planar benzene rings projecting to one side of the central thioacetate portion.
Comment
The title compound, (I), is commonly used as a chain-transfer agent in living-radical polymerizations. The S atom adjacent to the carbon with a double bond can be attacked by radicals and, in a reverse process, yields styrene radicals as shown in the scheme, in which I may indicate either an initiator-born radical or a long-chain propagating radical. The mediation of this compound in free-radical polymerizations leads to a well controlled molecular weight, a narrow molecular-weight distribution and an improvement in the extent of conversion.
Overall, the shape of molecule (I) is like a capital ‘M’, with both planar benzene rings projecting to one side of the central thioacetate portion (Fig. 1). The dihedral angle between the two benzene planes is 126.5 (1). There are no unusually short intermolecular contact distances.
Experimental
Compound (I) was synthesized by the authors, using a literature procedure (Quinn, et al., 2001). Briefly, a simple Grignard reagent
Figure 1
was first synthesized from benzyl chloride and magnesium. The Grignard reagent and carbon disulfide then were used to produce a dithiocarboxylic acid salt, which was then acidified and subsequently underwent an addition reaction with styrene. The product (I) was crystallized by evaporation of a cold (268 K) methanol solution.
Crystal data
C16H16S2
Mr= 272.41 Monoclinic,P21=c
a= 11.311 (2) A˚
b= 6.019 (2) A˚
c= 22.003 (4) A˚ = 98.188 (10)
V= 1482.7 (6) A˚3
Z= 4
Dx= 1.220 Mg m 3 MoKradiation = 0.34 mm 1
T= 298 (1) K Chunk, yellow 0.230.200.13 mm
Data collection
Rigaku RAXIS-RAPID diffractometer !scans
Absorption correction: multi-scan
ABSCOR(Higashi, 1995)
Tmin= 0.916,Tmax= 0.957
13414 measured reflections 3398 independent reflections 2251 reflections withI> 2(I)
Rint= 0.062
max= 27.5
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.044
wR(F2) = 0.143
S= 0.99 3398 reflections 163 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0814P)2]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.21 e A˚ 3
min= 0.29 e A˚ 3
All H atoms were positioned geometrically and refined with riding constraints (C—H = 0.93–0.98 A˚ ). TheUiso(H) values were set equal
to 1.2Ueq(carrier atom).
Data collection:RAPID-AUTO (Rigaku, 1998); cell refinement:
RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure:SIR92 (Altomareet al., 1993); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:ORTEP-3 for Windows(Farrugia, 1997); software used to prepare material for publication:WinGX(Farrugia, 1999).
The authors acknowledge Professor Jianming Gu from the Zhejiang University for help in determining the crystal structure.
References
Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993).J. Appl. Cryst.26, 343–350.
Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837–838.
Higashi, T. (1995).ABSCOR. Rigaku Corporation, Tokyo, Japan.
Quinn, J. F., Rizzardo, E. & Davis, T. P. (2001).Chem. Commun.11, 1044– 1045.
Rigaku (1998).PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Rigaku/MSC (2002).CrystalStructure. Version 3.00. Rigaku/MSC, The
Wood-lands, TX, 77381-5209, USA, and Rigaku Corporation, Akishima, Tokyo, Japan.
supporting information
sup-1 Acta Cryst. (2006). E62, o2395–o2396
supporting information
Acta Cryst. (2006). E62, o2395–o2396 [https://doi.org/10.1107/S1600536806017624]
1-Phenylethyl phenyldithioacetate
Jing Gao, Yingwu Luo and Bogeng Li
phenyl(phenylethylthio)methane-1-thione
Crystal data
C16H16S2
Mr = 272.41 Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 11.311 (1) Å
b = 6.019 (2) Å
c = 22.003 (4) Å
β = 98.188 (10)°
V = 1482.7 (6) Å3
Z = 4
F(000) = 576.00
Dx = 1.220 Mg m−3
Mo Kα radiation, λ = 0.71069 Å Cell parameters from 9800 reflections
θ = 3.4–27.4°
µ = 0.34 mm−1
T = 298 K Chunk, yellow 0.23 × 0.20 × 0.13 mm
Data collection
Rigaku RAXIS-RAPID diffractometer
Radiation source: rotation target Graphite monochromator
Detector resolution: 10.00 pixels mm-1
ω scans
Absorption correction: multi-scan ABSCOR (Higashi, 1995)
Tmin = 0.916, Tmax = 0.957
13414 measured reflections 3398 independent reflections 2251 reflections with I > 2σ(I)
Rint = 0.062
θmax = 27.5°, θmin = 3.5°
h = −12→14
k = −7→7
l = −28→28
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.044
wR(F2) = 0.143
S = 0.99 3398 reflections 163 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.0814P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.21 e Å−3
Δρmin = −0.29 e Å−3
Special details
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)
x y z Uiso*/Ueq
S1 0.88803 (4) 0.51521 (8) 0.09702 (2) 0.05430 (19)
S2 0.81311 (6) 0.07562 (10) 0.04093 (3) 0.0778 (2)
C1 1.02256 (17) 0.3529 (3) 0.12229 (9) 0.0515 (5)
H1 0.9987 0.2081 0.1369 0.062*
C2 1.09156 (16) 0.4766 (3) 0.17583 (9) 0.0469 (4)
C10 0.58652 (18) 0.4278 (3) 0.07781 (10) 0.0592 (6)
C8 0.78974 (18) 0.3373 (3) 0.05458 (9) 0.0557 (5)
C7 1.10863 (17) 0.3803 (4) 0.23364 (9) 0.0564 (5)
H7 1.0744 0.2432 0.2398 0.068*
C9 0.6723 (2) 0.4521 (4) 0.03257 (11) 0.0687 (6)
H9A 0.6869 0.6087 0.0262 0.082*
H9B 0.6375 0.3889 −0.0065 0.082*
C6 1.1764 (2) 0.4874 (4) 0.28213 (11) 0.0734 (7)
H6 1.1875 0.4218 0.3208 0.088*
C3 1.1416 (2) 0.6821 (3) 0.16792 (11) 0.0650 (6)
H3 1.1297 0.7500 0.1296 0.078*
C4 1.2096 (2) 0.7876 (4) 0.21716 (14) 0.0806 (7)
H4 1.2431 0.9259 0.2116 0.097*
C16 1.0948 (2) 0.3155 (5) 0.07044 (11) 0.0814 (8)
H16A 1.0475 0.2351 0.0380 0.122*
H16B 1.1651 0.2313 0.0853 0.122*
H16C 1.1176 0.4562 0.0552 0.122*
C15 0.5205 (2) 0.2334 (4) 0.08041 (13) 0.0785 (7)
H15 0.5294 0.1191 0.0530 0.094*
C5 1.2274 (2) 0.6890 (5) 0.27371 (13) 0.0821 (8)
H5 1.2740 0.7590 0.3064 0.099*
C11 0.5710 (2) 0.5927 (4) 0.11902 (14) 0.0803 (8)
H11 0.6129 0.7253 0.1182 0.096*
C14 0.4429 (3) 0.2058 (5) 0.12213 (19) 0.0999 (10)
H14 0.3996 0.0747 0.1227 0.120*
C12 0.4938 (3) 0.5643 (6) 0.16167 (17) 0.1033 (11)
H12 0.4853 0.6768 0.1897 0.124*
C13 0.4293 (3) 0.3714 (7) 0.16308 (18) 0.1059 (10)
H13 0.3768 0.3536 0.1916 0.127*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
S1 0.0566 (3) 0.0500 (3) 0.0544 (3) 0.0091 (2) 0.0012 (2) −0.0009 (2)
supporting information
sup-3 Acta Cryst. (2006). E62, o2395–o2396
C1 0.0555 (10) 0.0537 (10) 0.0450 (10) 0.0116 (8) 0.0064 (8) −0.0007 (8)
C2 0.0448 (9) 0.0518 (9) 0.0448 (10) 0.0065 (7) 0.0095 (8) −0.0003 (7)
C10 0.0471 (10) 0.0574 (11) 0.0669 (13) 0.0082 (9) −0.0134 (10) 0.0049 (9)
C8 0.0649 (12) 0.0588 (11) 0.0418 (10) 0.0033 (9) 0.0024 (9) 0.0039 (8)
C7 0.0542 (11) 0.0668 (12) 0.0492 (11) 0.0056 (9) 0.0101 (9) 0.0043 (9)
C9 0.0682 (14) 0.0725 (14) 0.0596 (13) 0.0074 (11) −0.0117 (11) 0.0126 (10)
C6 0.0644 (13) 0.1035 (18) 0.0506 (12) 0.0077 (13) 0.0022 (10) −0.0041 (12)
C3 0.0720 (13) 0.0589 (12) 0.0658 (14) −0.0016 (10) 0.0160 (11) 0.0045 (10)
C4 0.0692 (14) 0.0678 (14) 0.107 (2) −0.0143 (12) 0.0210 (15) −0.0215 (14)
C16 0.0690 (14) 0.117 (2) 0.0591 (14) 0.0152 (14) 0.0133 (12) −0.0234 (14)
C15 0.0653 (13) 0.0704 (14) 0.096 (2) 0.0022 (12) −0.0016 (14) 0.0012 (13)
C5 0.0593 (13) 0.107 (2) 0.0771 (18) −0.0025 (13) 0.0007 (12) −0.0367 (15)
C11 0.0611 (13) 0.0727 (15) 0.102 (2) 0.0138 (12) −0.0059 (14) −0.0101 (14)
C14 0.0676 (16) 0.089 (2) 0.143 (3) 0.0016 (15) 0.0171 (19) 0.020 (2)
C12 0.0785 (18) 0.126 (3) 0.105 (2) 0.0331 (19) 0.0134 (18) −0.023 (2)
C13 0.0702 (17) 0.129 (3) 0.122 (3) 0.0236 (19) 0.0261 (18) 0.025 (2)
Geometric parameters (Å, º)
S1—C8 1.720 (2) C3—C4 1.390 (3)
S1—C1 1.8270 (18) C3—H3 0.9300
S2—C8 1.632 (2) C4—C5 1.367 (4)
C1—C16 1.512 (3) C4—H4 0.9300
C1—C2 1.513 (3) C16—H16A 0.9600
C1—H1 0.9800 C16—H16B 0.9600
C2—C3 1.382 (3) C16—H16C 0.9600
C2—C7 1.386 (3) C15—C14 1.367 (4)
C10—C11 1.373 (3) C15—H15 0.9300
C10—C15 1.394 (3) C5—H5 0.9300
C10—C9 1.493 (3) C11—C12 1.380 (5)
C8—C9 1.514 (3) C11—H11 0.9300
C7—C6 1.381 (3) C14—C13 1.367 (5)
C7—H7 0.9300 C14—H14 0.9300
C9—H9A 0.9700 C12—C13 1.374 (5)
C9—H9B 0.9700 C12—H12 0.9300
C6—C5 1.367 (4) C13—H13 0.9300
C6—H6 0.9300
C8—S1—C1 106.15 (9) C2—C3—H3 119.9
C16—C1—C2 112.75 (18) C4—C3—H3 119.9
C16—C1—S1 111.50 (15) C5—C4—C3 120.3 (2)
C2—C1—S1 106.78 (12) C5—C4—H4 119.9
C16—C1—H1 108.6 C3—C4—H4 119.9
C2—C1—H1 108.6 C1—C16—H16A 109.5
S1—C1—H1 108.6 C1—C16—H16B 109.5
C3—C2—C7 118.95 (19) H16A—C16—H16B 109.5
C3—C2—C1 121.16 (18) C1—C16—H16C 109.5
C11—C10—C15 117.4 (3) H16B—C16—H16C 109.5
C11—C10—C9 121.7 (2) C14—C15—C10 121.9 (3)
C15—C10—C9 120.8 (2) C14—C15—H15 119.1
C9—C8—S2 122.65 (15) C10—C15—H15 119.1
C9—C8—S1 111.03 (15) C6—C5—C4 119.9 (2)
S2—C8—S1 126.28 (12) C6—C5—H5 120.1
C6—C7—C2 120.2 (2) C4—C5—H5 120.1
C6—C7—H7 119.9 C10—C11—C12 120.8 (3)
C2—C7—H7 119.9 C10—C11—H11 119.6
C10—C9—C8 111.45 (17) C12—C11—H11 119.6
C10—C9—H9A 109.3 C13—C14—C15 119.8 (3)
C8—C9—H9A 109.3 C13—C14—H14 120.1
C10—C9—H9B 109.3 C15—C14—H14 120.1
C8—C9—H9B 109.3 C13—C12—C11 120.6 (3)
H9A—C9—H9B 108.0 C13—C12—H12 119.7
C5—C6—C7 120.5 (2) C11—C12—H12 119.7
C5—C6—H6 119.7 C14—C13—C12 119.4 (3)
C7—C6—H6 119.7 C14—C13—H13 120.3
