2,4,6-Tris(isopropylamino)-1,3,5-trinitrobenzene [Elektronische Ressource] : probing the impact of crystal packing forces in the dimorphs and the cocrystals ; experimental and theoretical study / vorgelegt von Soheir El-Derby

Ak Irngartinger

Informations

• Publié par: ruprecht-karls-universitat_heidelberg
• Publié le: 01 janvier 2004
• Nombre de lectures: 13
• Langue: English
• Poids de l'ouvrage: 6 Mo

Extrait

INAUGULAR - DISSERTATION


Zur

Erlangung der Doktorwürde

der

Naturwissenschaftlich-Mathematischen Gesamtfakultät

der

Ruprecht – Karls - Universität
Heidelberg




















Vorgelegt von

Diplom-Physikerin Soheir El-Derby

aus Ägypten - Kairo

Tag der mündlichen Prüfung: 12-12-2003




1




2,4,6-Tris(isopropylamino)-1,3,5-trinitrobenzene:
Probing the Impact of Crystal Packing Forces in the Dimorphs and the
Cocrystals – Experimental and Theoretical Study





























Gutachter: Prof. Dr. Hermann Irngartinger
Prof. Dr. Rolf Gleiter







2





This work was represented :


1. as poster in:
• ICCC 35, Jul. 21-26, 2002. Heidelberg, Germany.
• Workshop on ‘Intermolecular interactions’, Feb. 09-11, 2003. Aachen, Germany.
• INDABA IV, Workshop on Patterns in Nature, Aug. 17-22, 2003. Skukuza, South
Africa.
• ECM 21 ( European Crystallographic Meeting), Aug. 24-29, 2003. Durban, South
Africa.

2. as lecture in:
• Workshop on ‘Intermolecular interactions’, Feb. 09-11, 2003. Aachen, Germany.
• ECM 21 ( European Crystallographic Meeting), Aug. 24-29, 2003. Durban, South
Africa.
3

Acknowledgments


I am most grateful to Priv.- Doz. Dr. J. Jens Wolff for the interesting idea of this work
and for his kind supervision during the first 18 months of this work, unfortunately he died
after this period suddenly. I wish also to express my deep gratitude and thanks to Prof. Dr.
Hermann Irngartinger for his kind supervision and assistance. Sincere thanks to all the mem-
bers of the group: Dr. Thomas Oeser, Mrs. Uta Wiesinger, Dr. Anton Weber and Dr. Oliver
Kinderman for their support, with special thanks to Dr. Thomas Oeser for his continuous help,
and Mrs. Uta Wiesinger for the performance of the most X-ray single crystal and powder dif-
fraction measurements.

I wish to thank Prof. Dr. Ronald Miletich, Institute of Mineralogy, for given us the
chance to perform the high temperature powder diffraction measurements in his institute, with
special thanks for his co-worker Mrs. Ilse Glass for her support during the performance of
these measurements.

I would like to thank the granting institution DFG (Deutsch Forschunggemeinschft)
for financial support of this work.

Finally, I like to express my deepest thanks to my husband for his support and encour-
agement.
4Summary………………………………………………………………………………………I
Zusammenfassung.....................................................................................................................I
Introduction .............................................................................................................................. 4
1 Theoretical background........................................................................................................8
1-1Thermal analysis................................................................................................................ 8
1-1-1 Differential scanning calorimetry (DSC) .............................................................................. 8
1-1-2 Thermogravimetry (TG)......................................................................................................... 9
1-1-3 Simultaneous and complementary techniques........................................................................ 9
1-2 Computational methods.................................................................................................. 10
1-2-1 Force field method......... 10
1-2-2 Calculating atomic charges: charges derived from the molecular........................................ 11
electrostatic potential.............. 11
1-2-3 Density functional theory ..................................................................................................... 12
2 Results and discussions of the experimental part............................................................. 14
2-1 Dimorphs and cosolvates of 1 ........................................................................................ 14
2-2 Ring and molecular conformation .................................................................................. 16
2-3 Discussion of the packing............................................................................................... 20
2-3 The influence of packing patterns on molecular parameters of 1................................... 30
2-4 Differential scanning calorimetry and thermogravimetry .............................................. 33
2-5 Powder diffraction .......................................................................................................... 40
3 Energy calculations ............................................................................................................. 42
3-1 Method............................................................................................................................ 42
3-2 Results and discussion.................................................................................................... 43
3-2-1 The DFT calculations on the molecular level....................................................................... 43
3-2-2 Force Field calculations in three dimension (on the crystal level) ....................................... 47
3-2-3 Calculation of intermolecular interactions ........................................................................... 51
4 Deprotonated structures ..................................................................................................... 63
4-1 Discussion of the packing.............................................................................................. 63
4-2 Ring conformation.......................................................................................................... 66
5-1 Synthesis......................................................................................................................... 69
5-1-1 Synthesis of 2,4,6-tris(2(S)-butylamino)-1,3,5-trinitrobenzenes 5....................................... 69



15-2 X-ray structure analyses of 5 .......................................................................................... 69
6 Crystallographic data .........................................................................................................71
dimorph 1a............................................................................................................................ 72
dimorph 1b 74
benzene as inclusion compound (1-1)................................................................................... 75
ethylbenzene as inclusion compound (1-2)........................................................................... 76
cumene as inclusion compound (1-3) 77
fluorobenzene as inclusion compound (1-4)......................................................................... 78
chlorobenzene as inclusion compound (1-5) ........................................................................ 79
m-difluorobenzene as inclusion compound (1-6) ................................................................. 80
o-difluorobenzene as inclusion compound (1-7) .................................................................. 81
p-difluorobenzene as inclusion compound (1-8) 82
1,2,4-trifluorobenzene as inclusion compound (1-9)............................................................ 83
hexafluorobenzene as inclusion compound (1-10) ............................................................... 84
phenol 1 as inclusion compound (1-11)................................................................................ 86
phenol 2 as inclusion compound (1-12) 88
anisole as inclusion compound (1-13) .................................................................................. 89
benzonitrile as inclusion compound (1-14)........................................................................... 91
trifluorotoluene as inclusion compound (1-15)..................................................................... 92
DMF as inclusion compound (1-16)..................................................................................... 93
hydroquinone as inclusion compound (1-17) ....................................................................... 94
p-xylene 1 as inclusion compound (1-18)............................................................................. 95
p-nitrophenol as inclusion compound (1-19)........................................................................ 96
p-fluorotoluene as inclusion compound (1-20)..................................................................... 97
o-pound (1-21) 98
p-chlorofluorobenzene as inclusion compound (1-22) ......................................................... 99
m-fluoronitrobenze