This journal is © The Royal Society of Chemistry 2000
Supplementary data
Photochemical reactions of N-acylbenzoxazole-2-thiones
Takehiko Nishio,* Ikuo Iida and Kunio Sugiyama#
Department of Chemistry, University of Tsukuba, Tsukuba-shi, Ibaraki, 305-8571 Japan
#
Department of Industrial Chemistry, College of Industrial Technology, Nihon University, Narashino-shi,
Chiba, 275-8575 Japan
Table of Contents
I. Description of Experimental Procedures
A.
Data Collection
B.
Data Reduction
C.
Structure Solution and Refinement
II. Tables
A.
Experimental Details - Crystal Data
B.
Experimental Details - Intensity Measurements
C.
Experimental Details - Structure Solution and Refinement
D.
Positional and Thermal Parameters
E.
General Temperature Factor Expressions, B's
F.
General Temperature Factor Expressions, U's
G.
Root-mean-square (rms) Amplitudes of Thermal Vibration
H.
Bond Distances
I.
Bond Angles
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J.
Intensity Data
Experimental
Data Collection
A Colorless ROD crystal of C15H19 N O3 S2 having approximate dimensions of 0.60 x 0.40 x 0.30
mm was mounted on a glass fiber in a random orientation. Preliminary examination and data collection
were performed with Mo Kradiation (0.70930 Å) on an Enraf-Nonius CAD4 computer controlled
kappa axis diffractometer equipped with a graphite crystal, incident beam monochromator. 
Cell constants and an orientation matrix for data collection were obtained from least-squares
refinement, using the setting angles of 25 reflections in the range 12゜<θ< 13゜, measured by the
computer controlled diagonal slit method of centering.
The monoclinic cell parameters and calculated
volume are: a = 6.375(2), b =11.908(2), c = 10.866(3) Å, β=98.39(1), V = 816.0 Å3 . For Z =2 and F.W.
= 325.44 the calculated density is 1.32 g/cm3. From the systematic absences of :
0 k 0 : k = 2n
and from subsequent least-squares refinement, the space group was determined to be P 2 1(# 4).
The data were collected at a temperature of 23 ± 1 ℃ using the  scan technique. The scan
｡
rate varied from 1 to 5 /min ( in omega). The variable scan rate allows rapid data collection for intense
reflections where a fast scan rate is used and assures good counting statistics for weak reflections where a
slow scan rate is used.
Data were collected to a maximum 2θ of 46.0｡. The scan range (in deg.) was
determined as a function of to correct for the separation of the K doublet (ref 1); the scan width was
calculated as follows:
 scan width = 0.5 + 0.350 tanθ
Moving-crystal moving-counter background counts were made by scanning an additional 25%
above and below this range. Thus the ratio of peak counting time to background counting time was 2:1.
The counter aperture was also adjusted as a function of . The horizontal aperture width ranged from 1.8
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to 2.3 mm; the vertical aperture was set at 4.0 mm. The diameter of the incident beam collimator was 0.8
mm and the crystal to detector distance was 21 cm. For intense reflections an attenuator was automatically
inserted in front of the detector; the attenuator factor was 13.8.
Data Reduction
A total of 1594 reflections were collected of which 1512 were unique and
not systematically
absent. As a check on crystal and electronic stability 3 representative reflections were measured every 120
min. The slope of the least-squares line through a plot of intensity of 2.2%. A linear decay correction
was applied. The correction factors on I ranged from 1.000 to 1.011 with an average value of 1.005
Lorentz and polarization corrections were applied to the data.
The linear absorption coefficient is
2.1 cm-1 for Mo K radiation. No absorption correction was made. An extinction correction was not
necessary. Intensities of equivalent reflection were averaged. 2 reflection were rejected from the average.
The agreement factors for the averaging of the 157 observed and aceepted reflections was 1.3% based on
intensity and 0.7% based on Fo.
Structure Solution and Refinement
The structure was solved by direct methods(ref7). The remaining atoms were
located in
succeeding difference Fourire syntheses . Hydrogen atoms were located and added to the structure factor
calculations but their positions were not refined. The structure was refined in full-matrix least-squares
where the function minimized was w(|Fo|-|Fc|)2 and the weight w is defined as 1.0 for all observed
reflections.
Scattering factors were taken from Cromer and Waber (ref 2). Anomalous dispersion effects were
included in Fc (ref 3.); the values for f' and f" were those of Cromer (ref 4.). Only the 1465 reflections
having intensities greater than 3.0 times their standard deviation were used in the refinements.
The final
cycle of refinement included 189 variable parameters and converged (largest parameter shift was 0.14
times is esd) with unweighted and weighted agreement factors of :
R1 = |Fo-Fc|/|Fo| = 0.031
R2 = SQRT(w(Fo-Fc)2/wFo2) = 0.039
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The standard deviation of an observation of unit weight was 0.56. The highest peak in the final difference
Fourier had a height of 0.15 e/Å3 ; the minimum negative peak had a height of -0.24 e/Å3 (ref 5.). Plots of
w(|Fo|-|Fc|)2 versus |Fo|, reflection order in data collection, sin /, and various classes of indices
showed no unusual trends.
All calculations were performed on a VAX computer using SDP/VAX (ref 6.).
References
(1) "CAD4 Operations Manual", Enraf-Nonius, Delft, 1977.
(2) D. T. Cromer and J. T. Waber, "International Tables for X-Ray Crystallography", vol. IV, The Kynoch
Press, Birmingham, England, 1974, Table 2.2B.
(3) J. A. Ibers and W. C. Hamilton, Acta Crystallogr., 17, 781 (1964).
(4) D. T. Cromer, "International Tables for X-Ray Crystallography," Vol. IV, The Knoch
Press, Birmingham, England, 1974, Table 2.3.1.
(5) D. W. J. Cruickshank, Acta Crystallogr., 2, 154 (1949).
(6) B. A. Frenz, "The Enraf-Nonius CAD 4 SDP-A Real-time System for Concurent X-Ray Data
Colletion and Crystal Structure Determination," in Computing in Crystallography, H. Schenk, R. OlthofHazekamp, H. van
Konoingsveld, and G. C. Bassi, Eds, Delft University Press. Delft, Holland, 1978, pp64-71.
(7)G.M.Sheldrick, `SHELXS-86.Program for crystal structure determination.
Univ . of Goetingen, Federal Republic of Germany` (1986)
Tables of Experimental Details
A. Crystal Data
C15H19 N O3 S2
F.W. 325.44 F(000) = 344
crystal dimensions: 0.60 x 0.40 x 0.30 mm
Mo K radiation ( = 0.70930 Å)
temperature = 23 ±1 ｡C
monoclinic space group P 2 1
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a = 6.375(2) Å b = 11.908 (2) Å c = 10.866 (2) Å
β=98.39(1)
V = 816.0Å3
Z = 2 ρ= 1.32 g/cm3
= 2.1 cm-1
B. Intensity Measurements
Instruments:
Enraf-Nonius CAD4 diffractometer
Monochromator:
Graphite crystal, incident beam
Attenuator:
Zr foil, factor 13.8
Detector aperture:
1.8 to 2.3 mm horizontal 4.0 mm vertical
Crystal-detector dist.:
21 cm
Scan type:
ω-2θ
Scan rate:
1-5 /min (in omega)
Scan width, deg:
0.6+ 0.350 tan θ
46.0゜
No. of refl. measured:
1594 total, 1512 unique
Corrections:
Lorentz-polarizati
Linear decay (from 1.000 to 1.010 on I)
C. Structure Solution and Refinement
Solution:
Direct methods(SHELXS-86)
Hydrogen atoms:
Include as fixed contribution to the structure factor
Refinement:
Full-matrix least-squares
Minimization function:
w(|Fo|-|Fc|)
Least-squares weights:
4Fo2/2(Fo2)
Anomalous dispersion:
All non-hydrogen atoms
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Reflections included:
1465 with Fo2>3.0(Fo2)=I>3.0(I)
Parameters refined:
189
Unweighted agreement factor:
0.031
Weighted agreement factor:
0.039
Factor including unobs. data:
0.032
Esd of Obs. of unit weight:
0.56
Convergence, largest shift:
0.014
High peak in final diff. map:
0.15 (4) e/ Å3
Low peak in final diff. map:
-0.24 ( 0) e /Å3
Computer hardware:
SGI
Computer software:
Open MolEN (Enraf-Nonius )