Quantification of Solid Structure Similarity

1. Quantification of Solid Structure Similarity Thomas Gelbrich University of Southampton

3. Compound A B C D E Polymorphic forms Crystal Structure i ii Construct 3D 2D 1D 0D

4. Formation of crystals • Crystal engineering • Prediction • … “Family” ? Robust building blocks

5. A B Construct

6. A B Method Construct

7. A B ? Construct

8. Construct, Cluster and Shell

9. Construct, Cluster and Shell

10. Construct, Cluster and Shell Shell of a molecule in a crystal structure One molecule + nearest neighbours • Representative cluster of a supramolecular construct • All independent molecules + their nearest neighbours: • Representative • Similar constructs have similar clusters • Component of a shell

11. Construct, Cluster and Shell Similar constructs >> Similar clusters >> Shells will contain certain similar components • Generate all shells • Identify similar components in shells • These are the representative clusters of a common construct

12. Corresponding Points

13. Corresponding Points

14. Corresponding Points

15. Corresponding Points A CPS 1. 2. 3. 4. 5. B C1 C2 O5 S1 N2 C11 C23 O3 S1 N1 Pairs of points which would conceivably adopt similar relative positions in different instances of a supramolecular construct.

16. Example 1

17. Example 1 (i) (ii) II Hecht et al., Z. Anorg. Allg. Chem.,624 (1998), 315.

18. Example 1 – CP CP

19. Example 1 – Parameters

21. Example 1 – Shell (i) (ii)

22. Example 1 (i) (ii)

23. A B CIF, CP CIF, CP General information Corresponding vectors Degree of similarity Construct

24. Families of N Structures

25. N (N-1) / 2 individual tests NT 4 6 20 190 50 1225 200 19900 Construct Construct Construct Construct Construct Construct Families of N Structures N Structures

26. Example 2

27. Five structures based on C1 stacks

28. X~IX~CF3CH3~CF3(X = CF3, I, Br, Cl, F, H) Br~Br(ii) Br~Br (i)I~BrCF3~Cl Br~Br (iii)I~ClI~Br (ii)I~I (iii) CN~Br (i)CN~CN 3D 2D C2 C3 C1 1D I-Dimer 0D

29. Example 3 – Alkali and ammonium H-tartrates Chiral / racemic pairs : hydrogen tartrates racemic chiral

30. H2O QAPTEG ZELRUD LIGXEE BYPTAR10 [ ] H2O ½ ENHTAR H2O NETXAL HIDGOQ Example 3 –144 structures of H-tartrates racemic / chiral: K+, Rb+, Cs+, NH4+, Tl+, mixed crystals

31. Example 3 – Chains

32. Example 3 – Chains A 55 Structures B 34 Structures

33. Example 4 – Small degree of packing similar similarity

34. Example 4 – Small degree of packing similar similarity

35. Examples Racemic / chiral alkali and ammonium H-tartrates Gelbrich et al., Z. Anorg. Allg. Chem.,630 (2004), 1451. AgI/ FeII coordination polymers Krautscheid et al., Z. Anorg. Allg. Chem.,630 (2004), 1427. Polymorphism in TNT Vrcelj et al., Cryst Growth Des.,3 (2003), 1027.

36. Conclusion • Polymorphs • Multi-component structures • Coordination polymers • Small degree of packing similarity • Large families (N > 100)

37. What next? • Reverse search • (find matching structures to a known construct ) • GUI / Output . • . • . • Database of supramolecular constructs