3
2
Journal of Chemical Research 43(1-2)
material had occurred. The crude products were both shown
to contain 4-methylbenzenesulfonic acid 16 by H NMR. δH
respectively (−16⩽h⩽15, −15⩽k⩽15, −15⩽l⩽15;
1
2
2θmax =55.0°;R =0.035). FinalR(F)=0.029, wR(F )=0.076
Int
(
400MHz; D O) 2.20 (3H, s), 7.11 (2H, d, J=8.0) and 7.45
2
for 245 parameters and 3610 reflections with I>2σ(I) (cor-
responding R-values based on all 3801 reflections=0.031
max and 0.077, respectively), Flack absolute structure parame-
ter=0.02 (4), CCDC deposition number 1870466.
(
1
2H, d, J=8.0); δ (150MHz; D O) 20.4, 125.2, 129.3,
C
2
39.3 and 142.3. From the irradiation of compound 11, ν
−1
(diamond anvil) 1678cm ; from the irradiation of com-
−1
pound 13, νmax (diamond anvil) 1682cm . Standard of
-methylbenzenesulfonic acid 16 δ (400MHz; D O) 2.10
14: C H NO S, M = 331.37, colourless needle,
1
7
17
4
r
4
2
H
2
0.30 × 0.03 × 0.01 mm , triclinic, space group
(No.
P1
(
3H, s), 7.00 (2H, d, J=8.0) and 7.41 (2H, d, J=8.0); δC
2), Z = 2, a = 5.2869 (4) Å, b = 9.1995 (12) Å, c = 16.829
(2) Å, α = 97.497 (11)°, β = 95.822 (8)°, γ = 94.282 (9)°,
(
150MHz; D O) 20.4, 125.2, 129.3, 139.3 and 142.3; stand-
2
ard of 4-methylbenzenesulfinic acid 17 δ (400MHz; D O)
3
H
2
V = 804.11 (16) Å at 100 K. Number of measured and
2.29 (3H, s), 7.27 (2H, d, J=8.0) and 7.46 (2H, d, J=8.0);
unique reflections = 10,351 and 2857, respectively
δ (150MHz; D O) 20.6, 123.5, 129.6, 141.1 and 150.5.
C
2
(−5 ⩽ h ⩽ 6, −10 ⩽ k ⩽ 10, −19 ⩽ l ⩽ 20; 2θ = 135.0°;
max
2
R = 0.129). Final R(F) = 0.119, wR(F ) = 0.307 for 209
int
parameters and 1982 reflections with I > 2σ(I) (corre-
sponding R-values based on all 2857 reflections = 0.158
Crystal structure determinations
Single crystals of 11–14 were recrystallised from DCM/ and 0.338, respectively), CCDC deposition number
light petroleum ether solution. Intensity data for 11–14 1870467.
were collected at T=100K using a Rigaku AFC11
charge-coupled device (CCD) diffractometer (Mo Kα radi- Acknowledgements
ation, λ=0.71073Å for 11 and 13 and Cu Kα radiation,
We are grateful to the National Mass Spectrometry Foundation,
University of Swansea and to the National Crystallographic
Service Centre, University of Southampton.
λ=1.54184Å for 12 and 14). Each structure was easily
solved by direct methods and the structural models were
completed and optimised by least-squares refinement
2
5
against |F|2 using SHELXL-2014. The crystal quality for
4 was notably poorer than for the other structures. For all
Declaration of conflicting interests
1
The author(s) declared no potential conflicts of interest with
respect to the research, authorship and/or publication of this
article.
structures, the H atoms were geometrically placed (C–
H=0.95–0.98Å) and refined as riding atoms. The methyl
groups were allowed to rotate, but not to tip, to best fit the
electron density. The constraint U (H)=1.2U (C) or
iso
eq
Funding
1
.5U (methyl C) was applied in all cases.
eq
The author(s) received no financial support for the research,
authorship and/or publication of this article.
1
1: C H N O S , M =520.56, pale orange column,
26 20 2 6 2 r
3
0
.23×0.06×0.05mm , triclinic, space group
(No. 2),
P1
Z=2, a=7.9131 (2) Å, b=11.5800 (3) Å, c=14.4677 (3) Å,
α=103.676 (2)°, β=95.088 (2)°, γ=109.671 (2)°,
V=1192.28 (5) Å at 100K. Number of measured and
Supplemental material
3
CCDC deposition numbers 1870464–1870467 contain the supple-
mental crystallographic data for this paper. These data can be
unique reflections=20,472 and 5452, respectively
(
−10⩽h⩽10, −15⩽k⩽15, −18⩽l⩽18; 2θmax =50.5°;
Int
2
R =0.017). Final R(F)=0.035, wR(F )=0.093 for 327
parameters and 4971 reflections with I>2σ(I) (correspond-
ing R-values based on all 5452 reflections=0.039 and 0.095,
respectively), Cambridge Crystallographic Data Centre
References
1
2
(CCDC) deposition number 1870464.
1
2: C H N O S , M =424.48, pale yellow block,
18
20
2
6
2
r
3
. Robinson APG and Lawson RA. Materials and processes for
next generation lithography (Frontiers of Nanoscience, vol.
3
0
.23×0.21×0.18mm , triclinic, space group P1 (No. 2),
Z=4, a=7.06267 (6) Å, b=11.08547 (10) Å, c=25.1261 (2)
Å, α=96.2327 (6)°, β=90.5797 (8)°, γ=95.8034 (7)°,
V=1945.10 (3) Å at 100K. Number of measured and unique
1
1) (ed. RE Palmer). Amsterdam: Elsevier, 2016.
4. Asakura T, Yamoto H, Ohwa M, et al. US6512020 B1, 28
March 2001, Ciba Speciality Chemicals Corporation.
3
reflections=34,798 and 7043, respectively (−8⩽h⩽8,
5. Crivello JV and Lam JHW. Macromolecules 1977; 10:
1
307.
−
13⩽k⩽13, −30⩽l⩽30; 2θ =136.5°; R =0.015).
max
Int
2
6. Crivello JV and Lam JHW. J Poly Sci 1979; 17: 977.
Final R(F)=0.029, wR(F )=0.082 for 509 parameters and
850 reflections with I>2σ(I) (corresponding R-values
7
8
. Crivello JV and Reichmanis E. Chem Mat 2014; 26: 533.
. Dietliker K, Rutsch W, Berner G, et al. US4736055, 11 April
6
based on all 7043 reflections=0.030 and 0.082, respec-
tively), CCDC deposition number 1870465.
1
986, Ciba-Geigy Corporation.
9
. Cho YJ, Ouyang CY, Krysak M, et al. P SPIE Adv Resist Mat
Proc Tech 2011; 7972.
1
3: C H NO S, M =379.42, colourless block,
21 17 4 r
3
0
.27×0.12×0.04mm , monoclinic, space group Ia (No. 9),
Z=4, a=13.0319 (6) Å, b=12.1421 (5) Å, c=11.8439 (5) Å,
1
0. Schroer H, Goliasch K and Beck U. US4233233, 11
November 1980, Bayer Aktiengesellschaft.
β=102.396 (5)°, V=1830.42 (14) Å at 100K. Number of 11. Dietliker K, Kunz M, Yamato H, et al. US0013974 A1, 22
measured and unique reflections=10,604 and 3801,
January 2004, Ciba Speciality Chemicals Corporation.
3