mechanochemical synthesis of pyrazine:dicarboxylic acid ... · phthalic acid. the patterns were...
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Mechanochemical Synthesis of Pyrazine:Dicarboxylic Acid
Cocrystals and the study of their Dissociation by
Quantitative Phase Analysis
Mihails Arhangelskis, Gareth O. Lloyd* and William Jones*
Supplementary Information
Electronic Supplementary Material (ESI) for CrystEngCommThis journal is © The Royal Society of Chemistry 2012
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Table S1. Theoretical and experimental weight loss determined by TGA of the
pyrazine cocrystals.
Cocrystal Weight loss
(experimental) / %
Weight loss
(theoretical) / %
pyrazine:terephthalic 30.0 32.5
pyrazine:phthalic 31.4 32.5
pyrazine:succinic 40.0 40.4
pyrazine:fumaric 39.6 40.8
Figure S1. Close contact between atoms H10 and O1 (x, 3/2-y, ½+z) in the pyr:pht
crystal structure.
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Figure S2. Molecular arrangements of the pyr:fum crystal faces. Faces (001) and
(100) display hydrophilic character while faces (011) and (102) are mostly
hydrophobic.
Figure S3. Molecular arrangements of the pyr:succ crystal faces. Faces (101) (10 )
and (002) are hydrophilic.
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Figure S4. Molecular arrangements of the pyr:ter crystal faces. (001) face is
hydrophilic while (011) and (10 ) faces are mostly hydrophobic.
Figure S5. TGA of pyrazine:terephthalic acid cocrystal
Step -68.9038 % -8.9162 mg
Step -30.0234 % -3.8850 mg
!ma1040TGA ma1040TGA, 12.9400 mg
% 50
°C 50 100 150 200 250 300 350 400 450
ma1040TGA 28.02.2011 16:48:16
SW 8.01 e R TA S Lab: METTLER
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Figure S6. TGA of pyrazine:phthalic acid cocrystal
Figure S7. TGA of pyrazine:fumaric acid cocrystal
Step -66.5472 % -9.2501 mg
Step -31.3654 % -4.3598 mg
!MA1096TGA MA1096TGA, 13.9000 mg
% 50
°C 50 100 150 200 250 300 350 400 450
ma1096TGA 23.02.2011 14:16:45
SW 8.01 e R TA S Lab: METTLER
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Figure S8. TGA of pyrazine:succinic acid cocrystal
Figure S9. DSC of pyrazine:terephthalic acid cocrystal
Step
Integral
-59.7749 %
-1444.95 mJ
normalized
-8.0756 mg
-489.81 Jg^-1
Step
Onset
-40.0284 %
361.02 °C
Peak
-5.4078 mg
384.82 °C
!ma1078
Integral
ma1078, 13.5100 mg
-656.79 mJ
%
normalized
50
-222.64 Jg^-1
°C
Onset
50
107.79 °C
100
Peak
150
132.14 °C
200
!&ma1040DSC_open_pan
250
ma1040DSC_open_pan, 2.9500 mg
300
Wg^-1
350
5
400
°C
450
50
ma1078TGA
100
24.02.2011 18:03:08
150
SW 8.01
200
e
250
R
300
TA
350
S
^exo
Lab: METTLER
ma1040DSC_open_pan 02.03.2011 13:55:39
SW 8.01 e R TA S Lab: METTLER
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Figure S10. DSC of pyrazine:phthalic acid cocrystal
Figure S11. DSC of pyrazine:fumaric acid cocrystal
Integral
Integral
-464.36 mJ
-1794.18 mJ
normalized
normalized
-116.09 Jg^-1
-533.98 Jg^-1
Onset
Onset
233.19 °C
266.27 °C
Peak
Peak
257.30 °C
287.59 °C
Integral
Integral
-1208.98 mJ
-1023.58 mJ
normalized
normalized
-302.24 Jg^-1
-304.64 Jg^-1
Onset
Onset
204.72 °C
112.39 °C
Peak
Peak
207.45 °C
138.29 °C
Integral
!ma1074DSC_open
-290.84 mJ
ma1074DSC_open, 3.3600 mg
normalized
Wg^-1
-72.71 Jg^-1
5
Onset
°C
102.63 °C
50
Peak
100
105.22 °C
150
!&ma1096DSC_open
200
ma1096DSC_open, 4.0000 mg
250
Wg^-1
300
5
^exo
°C
ma1074DSC_open_pan
50
10.03.2011 12:53:44
100
SW 8.01
150
e
200
R
250
TA
300
S
^exo
Lab: METTLER
SW 8.01 e R TA S Lab: METTLER
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Figure S12. DSC of pyrazine:succinic acid cocrystal
Figure S13. IR spectrum of pyrazine:terephthalic acid cocrystal
Integral -857.15 mJ normalized -325.91 Jg^-1 Onset 205.84 °C Peak 238.63 °C
Integral -436.04 mJ normalized -165.79 Jg^-1 Onset 187.64 °C Peak 188.13 °C
Integral -591.82 mJ normalized -225.03 Jg^-1 Onset 105.31 °C Peak 125.57 °C
!&ma1084DSC_open_pan ma1084DSC_open_pan, 2.6300 mg
Wg^-1 10
°C 50 100 150 200 250 300 350
^exo ma1084DSC_open_pan 02.03.2011 14:45:11
SW 8.01 e R TA S Lab: METTLER
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Figure S14. IR spectrum of pyrazine: phthalic acid cocrystal
Figure S15. IR spectrum of pyrazine:fumaric acid cocrystal
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Figure S16. IR spectrum of pyrazine:succinic acid cocrystal
Figure S17. PXRD pattern of pyrazine:terephthalic acid cocrystal
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Figure S18. Rietveld refinement of the pyrazine:terephthalic acid cocrystal. The blue
outline shows the experimentally observed diffracted pattern, the red curve shows the
Rietveld fit and the grey outline marks the difference between the calculated fit and
the experimental pattern. Quantitative phase analysis suggests the presence of 3% of
terephthalic acid form II (refcode TEPTH12) impurity.
Figure S19. PXRD pattern of pyrazine: phthalic acid cocrystal
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Figure S20. Rietveld refinement of the pyrazine:phthalic acid cocrystal.
Figure S21. PXRD pattern of pyrazine:fumaric acid cocrystal
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Figure S22. PXRD pattern of pyrazine:succinic acid cocrystal
Figure S23. Example of Rietveld refinement of a PXRD pattern recorded on a sample
of pyrazine:phthalic acid cocrystal recorded during the kinetics measurement.
Refinement of the scale factors of mixture components allows to calculate their
corresponding mass fractions (shown in the top right corner).
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Figure S24. X-ray powder patterns showing the conversion of pyr:pht cocrystal into
phthalic acid. The patterns were recorded at 25°C temperature and room humidity.
The most prominent peaks corresponding to the cocrystal are at 2θ 14.5°, 19.6°, 25.3°
and 29.9°. The major peaks corresponding to phthalic acid are at 2θ 15.1°, 18.2°,
26.6° and 30.2°.
Figure S25. Arrhenius plot describing the dependence of pyr:pht cocrystal
dissociation rate on temperature
-3.00
-2.00
-1.00
0.00
1.00
2.00
3.00
2.96E-03 3.01E-03 3.06E-03 3.11E-03 3.16E-03 3.21E-03 3.26E-03 3.31E-03 3.36E-03
log
(k)
1/T / K-1
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