1. Graham. J. Tizzard, Michael. B. Hursthouse; School of Chemistry, University of Southampton, UK. Structure-Property Relationships in Crystal Structures of Molecules With Non-centrosymmetric Polymorphs References [1] XPac; T. Gelbrich; 2002; University of Southampton, UK. [5] A. K. Cheetham, M. C. Grossel, J. M. Newsam; J. Am. Chem. Soc.; 103; 5363; 1981. [2] Mercury v1.2.1; CCDC, Cambridge, UK. [6] M. Calligaris, F. Giordano, L. Randaccio; Ric. Sci., Parte 1; 36; 1333; 1966. [3] Spartan’04; Wavefunction, Inc.; Irvine, CA, USA. [7] D. Seebach, I. M. Lyapkalo, R. Dahinden; Helv Chim Acta; 82; 1829; 1999. [4] F. H. Allen, O. Kennard; Chem. Des. Autom. News; 8; 31; 1993. Acknowledgements We gratefully acknowledge the support of the EPSRC e-Science programme (GR/R67729, Comb-e-Chem). Figure 1. shows the packing arrangements of BAWSAT01 viewed along the c-axis (left) and BAWSAT viewed between the a and c axes (right). The XPac algorithm revealed that a 1d chain along these respective axes was common to both crystal structures and these have been picked out in green in both diagrams. The figures in dark green show the same chain motif interspaced between the original. The data in the tables below show that the short contacts between molecules in the chain are very weak or non-existent in both polymorphs so this is unlikely to be a ‘structure-forming’ interaction. Figure 2. shows the short contact ‘coordination spheres’ (blue) wrt one molecule (red) derived from the data in the tables below. Each molecule in BAWSAT01 (left) and BAWSAT (right) has short contacts with 8 neighbouring molecules although none of these is particularly strong. The electrostatic charge data does not correlate with the short contact data at all in BAWSAT and in only 4/10 short contacts in BAWSAT01. This suggests that electrostatic interactions play very little roll in the formation of these crystals and that other interactions such as simple space-filling dictate these structures. As shown in the table to the right, two polymorphs of 4’-Bromo-trans-1,4-dihydro-4- tritylbiphenyl have been identified from the Cambridge Structural Database (CSD) [4], of which BAWSAT is non-centrosymmetric. 4’-Bromo-trans-1,4- dihydro-4-tritylbiphenyl Figure 3. shows the packing arrangements of BPNECH (top) and BPNECH01 (bottom) viewed along the b-axis. The XPac algorithm revealed that a 2d sheet along these respective axes was common to both crystal structures and these have been picked out in green in both diagrams. Whereas in BPNECH both highlighted sheets are identical, in BPNECH01 sheet highlighted in red is the same sheet structure after a 2 1 screw operation. The fact that the majority of the short contacts for any one molecule are between neighbours in the same sheet suggests that this is a ‘structure-forming’ interaction. Figure 5. shows the short contact ‘coordination spheres’ (blue) wrt one molecule (red) derived from the data in the tables below. Each molecule in BPNECH (top) and BPNECH01 (right) has short contacts with 8 neighbouring molecules. From the tables below it can be seen that the short contacts are significantly stronger than in BAWSAT and BAWSAT01 and that for both polymorphs they correlate with the electrostatic charge data. This suggests that electrostatic interactions may be significant in the formation of both of these crystal systems. As shown in the table to the right, two polymorphs of 2-(α-p-Bromophenyl-β- nitroethyl)-cyclohexanone have been identified from the CSD, of which BPNECH01is non-centrosymmetric. 2-(α-p-Bromophenyl-β- nitroethyl)-cyclohexanone Background There are a number of different attractive forces which determine the packing in molecular crystals and they can be approximately classified as follows: dispersion or London forces, multipolar forces, hydrogen bonding and charge transfer forces. It is the complex interplay of these forces along with repulsion energy which can lead to many local minima in the lattice energy of a crystal which can thus result in polymorphism. In the study of polymorphism, hydrogen bonds are the highest energy interactions in molecular crystals and thus appear to be the most important attractive force. There is clear evidence that multifunctional molecules (e.g. pharmaceuticals) with multiple H- bonding sites promote polymorphism and that the polymorphism exhibited by these molecules can be ascribed to the different H-bonding topologies. However, polymorphism also occurs in systems without strong hydrogen bonds (N – H ∙∙∙ X, O – H ∙∙∙ X, S – H ∙∙∙ X; X = N, O, S, F, Cl, Br, I). In these cases, although H-bonding may still be present in the form of weaker interactions such as C – H ∙∙∙ X and C – H ∙∙∙ П, the overarching importance of hydrogen bonding in defining polymorphism is greatly reduced. This project is concerned with making a detailed study of the latter type of the above systems. In these systems electrostatic interactions are expected to exert a greater influence on the crystal structure adopted. A particular point of interest is the occurrence of polymorphs, in what are essentially achiral molecules, that have both centrosymmetric and non-centrosymmetric crystal structures. Interest in the second of these is very important for the development of useful materials with nonlinear optical properties. In this poster we present results from a variety of analyses for two small families of compounds with non-centrosymmetric polymorphs in which the hydrogen bonding appears to be weak or non-existent according to normal criteria. From the above work several points are worth noting. The overall analysis involves several techniques and it would be hard to draw any conclusions using them in isolation. The XPac analysis takes a ’top-down’ approach where information is derived from the crystal structures of the polymorphs analysed whereas the modelling of electrostatic charges is a ‘bottom-up’ approach deriving information from the molecule. One of the goals of the Comb-e-Chem project has been to combine data from different analyses to derive novel data and to develop techniques to process this into meaningful knowledge. The major ‘bottlenecks’ throughout this project have been workflow related through the transfer of data from one application to another and also from ‘driving’ the applications to obtain the data. Methods of automation are being investigated including the use of perl to write data-transfer scripts and spreadsheets to automate calculations. This is with the ultimate aim of providing a complete analysis of the electrostatic interactions of a molecule in the context of its crystal packing as a single ‘callable’ process. Comment CSD codeBAWSATBAWSAT01 Crystal Systemorthorhombicmonoclinic Space Group (No.)Pnam (62) Pc (7) a / Å13.0129.011 b / Å17.26416.187 c / Å10.4318.463 α / º90 β / º90108.98 γ / º90 Cell Volume / Å 3 2343.2111167.309 Z42 Z’0.51.0 Reference[5] CSD codeBPNECHBPNECH01 Crystal Systemmonoclinicorthorhombic Space Group (No.)P2 1 /c (14) P2 1 2 1 2 1 (19) a / Å5.6305.539 b / Å8.5608.495 c / Å30.57030.777 α / º90 β / º90.3090 γ / º90 Cell Volume / Å 3 1473.2341448.175 Z44 Z’1.0 Reference[6][7] Analyses The analyses of the crystal structures below were carried out using various techniques. The first results shown were derived from XPac [1], an algorithm used to look for similarity between different crystal structures. This similarity can be either dimer pairs (0d similarity), chains (1d), sheets (2d) or networks (3d – isostructurality). Many polymorphic families of a compound show no similarity when analysed with this algorithm, however for those that do a ‘structure-forming’ motif may be able to be elucidated from the results. The second set of results are derived from a combination of short contact (i.e. distances between molecules in a crystal structure < sum of the VdW radii of the atoms involved) analysis using Mercury v1.2.1 [2] and molecular modelling of electrostatic charges using Spartan’04 for windows [3]. A correlation between short contact distances and a matching of potentials would suggest these are important in a crystal structure. Short Contacts - BAWSAT01 Ato m1 Electrostati c charge 1 Ato m2 Electrostati c charge 2 Sym m. Op 1Symm. Op 2 Lengt h Length- VdW H80.130679H240.136779x,y,z1+x,1-y,-1/2+z2.314-0.086 H240.136779H80.130679x,y,z-1+x,1-y,1/2+z2.314-0.086 H30.097207Br1-0.117756x,y,z-1+x,y,z2.97-0.08 Br1-0.117756H30.097207x,y,z1+x,y,z2.97-0.08 H130.104592H190.120092x,y,z-1+x,-y,-1/2+z2.342-0.058 H190.120092H130.104592x,y,z1+x,-y,1/2+z2.342-0.058 H40.155091C28-0.191035x,y,zx,1-y,-1/2+z2.844-0.056 C28-0.191035H40.155091x,y,zx,1-y,1/2+z2.844-0.056 H220.136788H40.155091x,y,zx,1-y,1/2+z2.359-0.041 H40.155091H220.136788x,y,zx,1-y,-1/2+z2.359-0.041 Short Contacts - BAWSAT Ato m1 Electrosta tic charge 1 Ato m2 Electrosta tic charge 2 Sym m. Op 1Symm. Op 2 Lengt h Lengt h- VdW H130.104592H40.155091x,y,z1.5-x,-1/2+y,1/2+z2.28-0.12 H40.155091H180.104591x,y,z1.5-x,1/2+y,1/2+z2.28-0.12 H40.155091H130.104592x,y,z1.5-x,1/2+y,-1/2+z2.28-0.12 H180.104591H40.155091x,y,z1.5-x,-1/2+y,-1/2+z2.28-0.12 H30.097207H50.097216x,y,z1-x,-y,1/2+z2.298-0.102 H50.097216H30.097207x,y,z1-x,-y,-1/2+z2.298-0.102 H130.104592H180.104591x,y,zx,y,1+z2.37-0.03 H180.104591H130.104592x,y,zx,y,-1+z2.37-0.03 H50.097216C30.078511x,y,z1-x,-y,-1/2+z2.898-0.002 C50.078478H30.097207x,y,z1-x,-y,-1/2+z2.898-0.002 C30.078511H50.097216x,y,z1-x,-y,1/2+z2.898-0.002 H30.097207C50.078478x,y,z1-x,-y,1/2+z2.898-0.002 Short Contacts - BPNECH01 Ato m1 Electrosta tic charge 1 Ato m2 Electrosta tic charge 2 Sym m. Op 1Symm. Op 2 Lengt h Lengt h- VdW O2-0.434661H130.166816x,y,z-1+x,y,z2.498-0.222 H130.166816O2-0.434661x,y,z1+x,y,z2.498-0.222 H120.203696O2-0.434661x,y,z1+x,y,z2.508-0.212 O2-0.434661H120.203696x,y,z-1+x,y,z2.508-0.212 O2-0.434661H10.130828x,y,z-x,1/2+y,1.5-z2.596-0.124 H10.130828O2-0.434661x,y,z-x,-1/2+y,1.5-z2.596-0.124 O1-0.447545H70.106818x,y,zx,1+y,z2.636-0.084 H70.106818O1-0.447545x,y,zx,-1+y,z2.636-0.084 H50.093177Br1-0.05641x,y,z1/2+x,1.5-y,1-z2.987-0.063 Br1-0.05641H50.093177x,y,z-1/2+x,1.5-y,1-z2.987-0.063 O3-0.451598H20.12995x,y,z-1+x,y,z2.661-0.059 H20.12995O3-0.451598x,y,z1+x,y,z2.661-0.059 Short Contacts - BPNECH Ato m1 Electrosta tic charge 1 Ato m2 Electrosta tic charge 2 Sym m. Op 1Symm. Op 2 Lengt h Lengt h- VdW H10.130828O2-0.434661x,y,z-1-x,-1/2+y,1/2-z2.394-0.326 O2-0.434661H10.130828x,y,z-1-x,1/2+y,1/2-z2.394-0.326 O2-0.434661H10.1308283x,y,z-1+x,y,z2.45-0.27 H10.1308283O2-0.434661x,y,z1+x,y,z2.45-0.27 H10.1308282O2-0.434661x,y,z1+x,y,z2.496-0.224 O2-0.434661H10.1308282x,y,z-1+x,y,z2.496-0.224 H20.12995O3-0.451598x,y,z1+x,y,z2.575-0.145 O3-0.451598H20.12995x,y,z-1+x,y,z2.575-0.145 H70.106818O1-0.447545x,y,zx,-1+y,z2.624-0.096 O1-0.447545H70.106818x,y,zx,1+y,z2.624-0.096 O1-0.447545Br1-0.05641x,y,z-1-x,-y,-z3.313-0.057 Br1-0.05641O1-0.447545x,y,z-1-x,-y,-z3.313-0.057 H90.06238O2-0.434661x,y,z1+x,y,z2.672-0.048 O2-0.434661H90.06238x,y,z-1+x,y,z2.672-0.048 O3-0.451598H30.062736x,y,z-x,1/2+y,1/2-z2.691-0.029 H30.062736O3-0.451598x,y,z-x,-1/2+y,1/2-z2.691-0.029