ABSTRACT
The electron density distribution of the molecular pyroelectric material phosphangulene has been studied by multipolar modeling of X-ray diffraction data. The "in-crystal" molecular dipole moment has been evaluated to 4.7 D corresponding to a 42% dipole moment enhancement compared with the dipole moment measured in a chloroform solution. It is substantiated that the estimated standard deviation of the dipole moment is about 0.8 D. The standard uncertainty (s.u.) of the derived dipole moment has been derived by splitting the dataset into three independent data-sets. A novel method for obtaining pyroelectric coefficients has been introduced by combining the derived dipole moment with temperature-dependent measurements of the unit cell volume. The derived pyroelectric coefficient of 3.8(7) x 10-6 Cm 2K-1 is in very good agreement with the measured pyroelectric coefficient of p = 3 +/- 1 x 10-6 Cm-2 K-1. This method for obtaining the pyroelectric coefficient uses information from the X-ray diffraction experiment alone and can be applied to much smaller crystals than traditional methods.
ABSTRACT
The geometry of the 4,8,12-trioxa-4,8,12,12c-tetrahydrodibenzo[cd,mn]pyrene system in the cationic state was established by X-ray structural resolution of the salts formed between the cation and various anions. The geometry was found to be planar for the 4,8,12-trioxa-4,8,12,12c-tetrahydrodibenzo[cd,mn]pyrenylium and 2,6,10-tri(tert-butyl)-4,8,12-trioxa-4,8,12,12c-tetrahydrodibenzo[cd,mn]pyrenylium cations with the monovalent anions I(-), BF(4)(-), PF(6)(-), AsF(6)(-), HNO(3).NO(3)(-) and CF(3)SO(3)(-), and the divalent anions S(2)O(6)(2-) and Mo(6)Cl(14)(2-). The salts were found to crystallize in distinct space groups following a characteristic pattern. Mixed cation-anion stacking resulted in space groups with high symmetry: Pbca in three cases and R3;c in one; a temperature study of the latter was made at ten different temperatures. The formation of dimers of anions and cations resulted in lower-symmetry space groups, mainly monoclinic (P2(1)/n, P2(1)/c and C2/c), but also P1;.
