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Xerox University Microfilms 300 North Zeeb Road Ann Arbor, Michigan 48106 75-11,374 KERSHAW, Richard Allen, Jr., 1947- THE CRYSTAL AND MOLECULAR STRUCTURES OF SEVERAL BICYCL0[5.1.0]0CTANES. The Ohio State University, Ph.D., 1974 Chemistry, physical Xerox University Microfilms,Ann Arbor, Michigan 48106 © 1975 RICHARD ALLEN KERSHAW, JR. ALL RIGHTS RESERVED THE CRYSTAL AND MOLECULAR STRUCTURES OF SEVERAL BICYCLO[5. 1. 0]OCTANES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Richard Allen Kershaw, Jr., B.Sc., M.S. # The Ohio State University 197^ Reading Committee: Dr. G. G. Christoph Dr. P.G. Gassman Dr. C.W. Mathews Department of Chemistry ACKWOVILEDGEMENTc I would like to thank friends and family for their generous support throughout this project. Special thanks, however, must go to Dr. P.W.R. Corfield for his counsel and guidance during my graduate career and to Dr. Gary G. Christoph who helped bring this work to its conclusion. Most of all, I must thank my wife, Gladys, however, for her understanding through the many rough places and whose nimble fingers typed the finished copy. VITA Richard Allen Kershaw, J r ., the son of Richard Allen and Betty Barbara, was horn in Cleveland, Ohio on May 2k , 19^7- He received his elementary and secondary education in Euclid, Ohio. In September, 1 9 6 5 , he entered the Ohio State University where he received the B. Sc. degree in Chemistry in June, 19^9* He then went on to graduate study at that university in the fall of 1 9 6 9. 0n March 21, 1970 he married Gladys McIntosh of South Lebanon, Ohio, whom he had met while an under­ graduate at Ohio State University. In December, 1972, he received the M.S. degree in physical Chemistry from the Ohio State University. His thesis was entitled "The Crystal and Molecular Structure of Potassium trans-Bicyclo[5*l*0]octane-U-carboxylate Monohydrate". During the course of his graduate studies he held appointments as a teaching associate except during the period when he was a research assistant under his advisor, Dr. P.W.R. Corfield. During the 1971-1972 school year he was given the additional responsibilities of special assistant in charge of the physical chemistry laboratories. His graduate career was temporarily interrupted so that he might attend several m ilitary schools for the U.S. Army where he holds a commission as Second Lieuten­ ant in the Chemical Corps which is now part of the Ordnance Corps. i i i TABLE OF CONTENTS ACKNOWLEDGEMENTS............................................................................................................................. i i VITA.......................................................................................................................................................i i 'i LIST OF TABLES..................................................................................................................................v i LIST OF FIGURES.................................................................................................................................. x I . INTRODUCTION A. The Twist Bent Bond .....................................................................................1 B. S y n th e tic M ethods ..................................................................................... 5 C. S t r a i n ................................................................................................................... 8 D. Anchimeric Assistance ..............................................................................13 I I . SURVEY OF STRUCTURES.......................................................................................... 19 I I I . cis-BICYCLO[5. 1» OlQCTA-ex o -YL p-BROMOBENZENE SULFONATE A. Photographic Preliminaries, Space Group, and Density..26 B. Alignment .......................................................................................................... 28 C. Intensity Collection ................................................................................ 35 IV. DATA REDUCTION A. Attenuator Corrections ........................................................................... 3^ B. B ackground C o rre c tio n s ........................................................................... 35 C. Lorentz and Polarization Corrections ...........................................39 1. The Lorentz Factor 2. The Polarization Factor D. Evaluation of Check Reflections-Decomposition ......................4 l E. Absorption Corrections ........................................................................... ^9 F. Deletions and Averages ........................................................................... 51 G. The Wilson Plot ............................................................................................52 V. SOLUTION OF THE STRUCTURE A. The Patterson Function ................... 57 B. The T r i a l S tr u c t u r e ...................... 62 C. Initial Refinement .................................................................................... 65 TABLE OF CONTENTS (continued) D. Anisotropic Refinements ............................................................. 69 E. Full Matrix Refinements and Hydrogen Atoms ............................ 72 F. Extinction ....................................................................................................... 73 VI. DISCUSSION OF THE STRUCTURE A. The Crystal Structure ............................................................................. 82 B. The Molecular Structure .........................................................................96 V II. t r a n s -BICYCLOf3 .1 . 01OCTANE-4-CARBOXYLIC ACID A. Photographic Prelim inaries, Space Group and Density.. 1^0 B. Intensity Collection ..............................................................................1^3 C. Data Reduction ................................... Ikk V III. SOLUTION OF THE STRUCTURE A. The Patterson and Superposition Functions ............................ 152 B. In itial Refinements - The Isotropic Model ............................ 156 C. Anisotropic Refinements .......................................................................159 IX. trans-B IC Y C L 0r5.1. OlOCTANE-U-METHAtTOL p-BROMOBENZENE SULFONATE A. Photographic Prelim inaries, Space Group and Density.. 164 B. Data Collection. .................................................................................. 167 C. Data Reduction .......................................................................................... 170 X. SOLUTION OF THE STRUCTURE A. The Patterson Function and the Trial Structure ................ 178 B. Refinement of the Structure .............................................................182 XI. STRUCTURES OF THE tra n s-B IC Y C L 0 [5 .1. 0]0CTANES A. The Crystal and Molecular Structure of trans-Bicyclo- [5.1. 0]octane-4- carboxylic Acid ...................................................194 B. The Crystal and Molecular Structure of trans-Bicyclo- [5.1. Opjoctane-4-methanol p-Bromobenzene Sulfonate.... 206 APPENDIX........................................................... 224 REFERENCES......................................................................................................................................... 225 v LIST OF TABLES T a b le Page 1. Survey of Compounds Studied .................................................................................20 2. cis-Bicyclo[ 5 -1 • 0 3oct-H-endo-yl p-Bromobenzene Sulfonate ............ 2k 3. cis-Bicyclo[5.1.0joct-^-exo-yl p-Bromobenzene Sulfonate ................31 k.