H. Mei et al. / Journal of Fluorine Chemistry 145 (2013) 35–40
39
CF3ASO2N(M)CF2BCF2CCF2DCF2ECF2FCF2GSO2NMSO2PhNH2c-p
Table 5
Crystallographic data for 19.
18 (4.2 g, 88%): 19F NMR (CD3CN) dA ꢁ78.9 (3F,s), dG+B ꢁ112.4 (4F,
t), dF+C ꢁ119.5 (4F, m), dD+E ꢁ120.8 (4F, t). 1H NMR (CD3CN)
(2H, d), db 6.60 (2H, d), Jab = 9 Hz, dc 4.56 (2H, s).
da 7.53
Empirical formula
Formula weight
C7 H4 F3 N3 O4 S2
315.25
Temperature
173(2) K
´
˚
Wavelength
0.71073 A
3.6. Synthesis of p-N2+PhSO2NꢁSO2Rf 19–22
Crystal system, space group
Unit cell dimensions
Orthorhombic, Pbca
´
˚
a = 12.539(3) A, alpha = 908
´
˚
b = 9.6700(19) A, beta = 908
A typical procedure consisted of dissolving p-NH2PhSO2N(M)-
SO2CF3 (4.63 g, 15.23 mmol) in hydrochloric acid (36.5%, 10 mL) in
a 50-mL round-bottomed flask with good stirring. To the solution
was then added the mixture of hydrochloric acid (36.5%, 3 mL) and
sodium nitrite (1.06 g, 15.36 mmol for 19 and 20 and 30.72 mmol
for 21 and 22) at 0 8C. After the solution was stirred for 2 h at 22 8C,
the solution was poured into a mixture of cracked ice and water.
The precipitate was filtered out and dried under dynamic vacuum
to give products 19–22.
´
˚
c = 18.927(4) A, gamma = 908
´
3
˚
Volume
2294.9(8) A
Z, Calculated density
Absorption coefficient
F(0 0 0)
8, 1.825 Mg/m3
0.520 mmꢁ1
1264
Crystal size
0.46 mm ꢂ 0.12 mm ꢂ 0.07 mm
2.15–25.108
ꢁ14 ꢄ h ꢄ 14, ꢁ11 ꢄ k ꢄ 11, ꢁ22 ꢄ l ꢄ 20
18,695/2040 [R(int) = 0.1071]
99.8%
Theta range for data collection
Limiting indices
Reflections collected/unique
Completeness to theta = 25.10
Absorption correction
Max. and min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2sigma(I)]
R indices (all data)
p-N2+PhSO2NꢁSO2CF3 19 (4.14 g, 86%): 19F NMR (CD3CN):
A
REQAB (multi-scan)
0.9645 and 0.7961
Full-matrix least-squares on F2
2040/0/176
A
dA ꢁ78.24. 1H NMR (CD3CN) da 8.50 (2H,d), db 8.33 (2H,d),
Jab = 9 Hz. IR (cmꢁ1
)
(KBr pellet) 2287 (m, –N2+),3101(s),
1568(s),1410(s),1332(vs),1191(vs),1136(vs),1159(vs),1056(v-
s),1091(s), 841(m), 743(m);
Crystals of 19 for X-ray were obtained from CH3CN. The
crystallographic data are given in Table 5.
1.104
R1 = 0.0684, wR2 = 0.1643
R1 = 0.1032, wR2 = 0.1876
´
ꢁ3
˚
Largest diff. peak and hole
0.440 and ꢁ0.331 e A
Intensity data were collected using a Rigaku Mercury CCD
detector and an AFC8S diffractometer. Data reduction including
the application of Lp and absorption corrections was done using
the CrystalClear program [20]. The structure was solved by
direct methods and subsequent Fourier difference techniques,
and refined anisotropically, by full-matrix least squares, on F2
using SHELXTL 6.10 [21]. Hydrogen atom positions were
calculated from ideal geometry with coordinates riding on the
parent atom.
give pure product. The compound was protected from light by Al
foil.
0
0
CF3ASO2N(H)DSO2CF2B CF2C CF2CCF2BSO2NꢁSO2PhN2+-p 23 (1.4 g,
76%): 19F NMR (CD3CN): dA ꢁ8.9 (3F, s), dB+B ꢁ112.3 (4F, m), dC+C
0
0
ꢁ119.5 (4F,m). 1H NMR (CD3CN) da 8.55 (2H, d), db 8.32(2H, d)
Jab = 9 Hz, d
D 3.40 (1H, m). IR (cmꢁ1) (KBr pellet, acetone): 2291 (s, –
N2+), 3104(s), 1706(m), 1569(m), 1411.1(m), 1335(vs), 1196(vs),
Crystallographic data have been deposited with the Crystallo-
graphic Data Center CCDC 607981. Copies may be obtained free of
charge on application to the Director CCDC, 12 Union Road,
1148(vs), 1092(s), 1060(s), 840(m), 787(m)
+
CF3ASO2N(H)HSO2CF2BCF2CCF2DCF2ECF2FCF2GSO2NꢁSO2PhN2
-
p 24 (1.7 g, 80%): 19F NMR (CD3CN): dA ꢁ78.9 (3F, s), dG+B ꢁ112.3
(4F, t), dF+C ꢁ119.4 (4F, m), dD+E ꢁ120.9 (4F, m). 1H NMR (CD3CN) da
8.54 (2H, d), db 8.31 (2H, d) Jab = 9 Hz, d )
H 3.51 (1H, m). IR (cmꢁ1
p-N2+PhSO2NꢁSO2 CF2ACF2BCF2CCF3 20 (4.4 g, 80%): 19F NMR
(KBr pellet, acetone): 2289 (s, –N2+),3103 (s), 1709 (m), 1571(m),
1411 (m), 1334 (vs), 1203 (vs), 1148 (vs), 1093 (s), 1068 (s), 841
(m), 784 (m).
D
(CD3CN) dD ꢁ80.31 (3F, t), dC ꢁ112.37 (2F, m), dB ꢁ120.47 (2F, m),
dA ꢁ125.22 (2F, t). 1H NMR (CD3CN):
da 8.55 (2H, d), db 8.33 (2H,d)
Jab = 9 Hz. IR (cmꢁ1, KBr pellet, nujol): 2287 (s, –N2+), 3100(s),
1567(s), 1458(s),1408(s),1333(vs),1313(s), 1300(s), 1232(s),
Acknowledgements
1194(vs), 1145(vs), 1090(s), 1074(s), 847(m), 817(m);
(p-N+2PhSO2NꢁSO2 CF2ACF2
) 21 (5.96 g, 85%, 95% purity by
2
B
Financial support of this work by the U.S. National Science
Foundation, Grant DMI-0303645, and the U.S. Department of
Energy, Contract DE-FG02-05ER15718, is gratefully acknowledged.
19F NMR): 19F NMR (CD3CN): dA ꢁ112.1 (4F, t), dB ꢁ119.4 (4F, t).
1H NMR (CD3CN) da 8.65 (2H, d), db 8.28 (2H, d), Jab = 9 Hz. IR
(cmꢁ1) (KBr pellet, nujol): 2294 (s, –N2+), 3100(s), 1569(s),
1520(s), 1336(vs),1309(s), 1300(s), 1200(vs), 1147(vs), 1093(s),
1078(s), 1053(s), 1611(m), 1569(m), 1520(m), 1409(s), 855(m),
References
7401(m);
(p-N+2PhSO2NꢁSO2CF2ACF2BCF2
)
22 (6.3 g, 88%): 19F NMR
2
C
[1] S.J. Hamrock, M.A. Yandrasits, J. Macromol. Sci. Part C: Polym. Rev. 46 (3) (2006);
V. Mehta, J.S. Cooper, J. Power Sources 114 (1) (2003) 32–53.
[2] J.-F. Wu, X.-Z. Yuan, J.J. Martin, H.-J. Wang, J.-J. Zhang, J. Shen, S.-H. Wu, W. Merida,
J. Power Sources 1 (15) (2008) 104–119.
[3] S.C. Savett, J.R. Atkins, C.R. Sides, J.L. Harris, B.H. Thomas, S.E. Creager, W.T.
Pennington, D.D. DesMarteau, J. Electrochem. Soc. 149 (12) (2002) A1527–A1532.
[4] L.A. Ford, D.D. DesMarteau, D.W. Smith Jr., J. Fluorine Chem. 126 (2005) 653–660.
[5] L.-X. Xue, C.W. Padgett, D.D. DesMarteau, W.T. Pennington, Solid State Sci. 4 (11–
12) (2002) 1535–1545.
(CD3CN): dA ꢁ112.2 (4F, t), dB ꢁ119.6 (4F, m), dC ꢁ121.1 (4F, t). 1H
NMR (CD3CN) da 8.55 (2H, d), db 8.32 (2H, d) Jab = 9 Hz. IR (cmꢁ1
)
(KBr pellet, nujol): 2288 (s, –N2+), 3100(s), 1569(m),
1458(vs),1465(vs), 1408 (m), 1376(s), 1334 (s), 1306 (s), 1210
(vs), 1150 (vs), 1090 (s), 1077 (s), 840 (m), 7212 (m).
[6] D.D. DesMarteau, J. Fluorine Chem. 72 (2) (1995) 203–208;
B.H. Thomas, G. Shafer, J.J. Ma, M.-H. Tu, D.D. DesMarteau, J. Fluorine Chem. 125
(8) (2004) 1231–1240.
[7] S. Litster, G. Mclean, J. Power. Sources 130 (2004) 61–76.
[8] M. Weissmann, S. Baranton, C. Coutanceau, Langmuir 26 (18) (2010) 15002–
15009;
3.6.1. Compounds 23–24 (n = 4,6)
A typical procedure consisted of mixing p-NH2PhSO2N(Na)-
SO2(CF2)4SO2N(Na)SO2CF3 (2.0 g, 2.89 mmol) with absolute alco-
hol (4 mL) in a 100 mL two-necked round bottom flask with good
stirring. To the solution was then added absolute alcohol (30 mL)
saturated with hydrogen chloride gas. Isoamyl nitrite (2 mL) in
ether (10 mL) was then added drop wise over 5 min at ꢁ5 8C. After
stirring for another 20 min, the precipitate was filtered out,
washed with cold ether (20 mL) and dried under high vacuum to
K.H. Vase, A.H. Holm, K. Norrman, S.U. Pederson, K. Daasbjerg, Langmuir 24 (2008)
182–188;
M.M. Chehimi, G. Hallais, T. Matrab, J. Pinson, F.I. Podvorica, J. Phys. Chem. C 112
(2008) 18559–18565.
[9] J. Pinson, F. Podvorica, Chem. Soc. Rev. 34 (2005) 429–439;
M. Toupin, D. Belanger, Langmuir 24 (2008) 1910–1917.