Structure solid-state CPMAS 13 C NMR correlation in palladacycle solvates (pseudo-polymorphs) with a transformation from Z' = 1 to Z' = 2

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1 Electronic Supplementary Information (ESI) Structure solid-state CPMAS 13 C NMR correlation in palladacycle solvates (pseudo-polymorphs) with a transformation from Z' = 1 to Z' = 2 José Ruiz,* a Venancio Rodríguez, a Natalia Cutillas, a Anke Hoffmann,* b Anne-Christine Chamayou, c Karolina Kazmierczak, c and Christoph Janiak* c a Departamento de Química Inorgánica, Facultad de Química, Universidad de Murcia, Murcia, Spain. Fax: ; Tel: ; jruiz@um.es b Institut für Makromolekulare Chemie, Universität Freiburg, Stefan-Meier-Str. 31, D Freiburg, Germany. Fax: ; Tel: ; anke.hoffmann@makro.uni-freiburg.de c Institut für Anorganische und Analytische Chemie, Universität Freiburg, Albertstr. 21, Freiburg, Germany. Fax: ; Tel: ; janiak@unifreiburg.de Fig. S1 CPMAS 13 C NMR spectrum of C 6 H 5 CH 3 (Z' = 2) (cf. Fig. 3a in manuscript). 1

2 Fig. S2 CPMAS 13 C NMR spectrum of 1 1.5C 6 D 6 (cf. Fig. 3c in manuscript). Fig. S3 13 C NMR spectrum of crystals of 1 1.5C 6 H 5 CH 3 in mother liquor from a quick scan (cf. Fig. 11a in manuscript). 2

3 Fig. S4 13 C NMR spectrum of crystals of 1 1.5C 6 H 5 CH 3 in mother liquor after 30 min (cf. Fig. 11b in manuscript). Fig. S5 13 C NMR spectrum of crystals of 1 1.5C 6 H 5 CH 3 in mother liquor after 10 h (cf. Fig. 11c in manuscript). 3

4 Fig. S6 Packing diagram for C 6 H 5 CH 3 (Z' = 2) (50% ellipsoids, Pd with fixed radius) similar to Fig. 4 in manuscript. The semi-transparency of the disordered toluene solvent atoms (shown in green) should indicate their partial occupancy. In total each disordered toluene positions is half-occupied. Thus, for each four Pd 2 molecules in the unit cell there is only one toluene molecule: The two toluene positions in the center of the bc-faces each belong to two unit cells: 2 toluene position x ½ (shared by two unit cells) x ½ occupancy = 1/2. The eight toluene positions in the corners each belong to eight unit cells: 8 toluene positions x 1/8 (shared by eight unit cells) x ½ occupancy = 1/2 In reality there cannot be half a toluene molecule at a position, thus, statistically every second toluene position is empty as shown in Fig. S7. The occupied positions then contain a full toluene molecule. Fig. S7 Packing diagram for C 6 H 5 CH 3 (Z' = 2) (50% ellipsoids, Pd with fixed radius) with statistically every second toluene position left empty to illustrate the actual structure. 4

5 Table S1 Distances (d/å) and angles ( ) for supramolecular CH- contacts in the crystal structures of 1 1.5C 6 H 5 CH 3, C 6 H 5 CH 3 (Z' = 2), 1 1.5C 6 H 6 and 1 C 6 H a 14 compound, CH- interactions d[h Cg] b d[h ] c d [CH Cg] e d[c Cg] f 1 1.5C 6H 5CH 3 (N-CH 2)-C31-H31A ringc1-c6 vi (3) (N-CH 2)-C31-H31B ringc25-c30 vi (3) (N-CH 3)-C32-H32A ringc25-c30 vi (3) inter iminato-phenyl C13-H13 ringc17-c22 i (4) iminato-ph toluene solvent C19-H19 toluene C35-C40 iv (4) C22-H22 toluene C42-C47 v (5) ringc11-c16 i H41A-C41(tol-CH 3) (1) C 6H 5CH 3 (Z' = 2) Pd1,Pd2 Pd1',Pd2' (N-CH 2)-C7-H7A benzyl-c1-c6 i (4) (N-CH 2)-C7-H7B benzyl-c25-c30 i (4) Pd3,Pd4 Pd3',Pd4' (N-CH 2)-C64-H64A benzyl-c58-c63 iii (4) (N-CH 2)-C64-H64B benzyl-c34-c39 iii (4) Pd1,Pd2 Pd3,Pd4 (N-CH 3)-C9-H9A iminato-c45-c49 ii (4) iminato-c14-h14 benzyl-c58-c (4) benzyl-c25-c30 H53-C53-iminato (4) 1 1.5C 6H 6 (N-CH 2)-C7-H7B benzyl-c25-c30 vi (2) (N-CH 2)-C7-H7A benzyl-c1-c6 vi (2) (N-CH 3)-C8-H8C benzyl-c1-c6 vi (3) inter iminato-phenyl C19-H19 ringc11-c26 vii (3) iminato-ph benzene solvent C13-H13 benzene C41-C (8) 1 C 6H 14 (N-CH 2)-C7-H7A benzyl-c1-c6 iix (3) (N-CH 2)-C7-H7A benzyl-c25-c30 iix (3) (N-CH 3)-C33-H33C benzyl-c25-c30 ix (3) a For a graphical depiction of distances and angles in the assessment of the -contacts, see Scheme S1. b H-centroid distance. c Perpendicular distance of H on ring plane. d Angle between the C-H vector and the normal to the -plane. e C-H-centroid angle. f C-centroid distance. Symmetry transformations: i = 1 X, 1 Y, 2 Z; ii = X, Y, 1+Z; iii = 2 X, Y, 1 Z; iv = X, 1+Y, Z; v = 1+X, Y, Z; vi = 1 X, 1 Y, 1 Z; vii = 1 X, 1 Y, Z; iix = X, 1 Y, 2 Z; ix = X, 1/2 Y, 1/2+Z. d[c Cg] C H [CH Cg] d[h Cg] d[h ] Cg Scheme S1 Graphical presentation of the parameters used in Table S1 for the description of CH- interactions. 5