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, 30071 Murcia, Spain. Fax: +34 968 364148; Tel: +34 968 367455; E-mail: jruiz@um.es b Institut für Makromolekulare Chemie, Universität Freiburg, Stefan-Meier-Str. 31, D-79104 Freiburg, Germany. Fax: +49 761 2036306; Tel: +49 761 2036314; E-mail: anke.hoffmann@makro.uni-freiburg.de c Institut für Anorganische und Analytische Chemie, Universität Freiburg, Albertstr. 21, 79104 Freiburg, Germany. Fax: +49 761 2036147; Tel: +49 761 2036127; E-mail: janiak@unifreiburg.de Fig. S1 CPMAS 13 C NMR spectrum of 1 0.25C 6 H 5 CH 3 (Z' = 2) (cf. Fig. 3a in manuscript). 1
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
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
Fig. S6 Packing diagram for 1 0.25C 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 1 0.25C 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
Table S1 Distances (d/å) and angles ( ) for supramolecular CH- contacts in the crystal structures of 1 1.5C 6 H 5 CH 3, 1 0.25C 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 2.64 2.63 3.3 154 3.553(3) (N-CH 2)-C31-H31B ringc25-c30 vi 2.94 2.67 24.9 164 3.899(3) (N-CH 3)-C32-H32A ringc25-c30 vi 2.99 2.68 26.2 152 3.885(3) inter iminato-phenyl C13-H13 ringc17-c22 i 2.88 2.77 15.7 147 3.713(4) iminato-ph toluene solvent C19-H19 toluene C35-C40 iv 2.67 2.67 3.5 154 3.550(4) C22-H22 toluene C42-C47 v 2.92 2.89 8.6 137 3.675(5) ringc11-c16 i H41A-C41(tol-CH 3) 2.83 2.68 18.4 171 3.80(1) 1 0.25C 6H 5CH 3 (Z' = 2) Pd1,Pd2 Pd1',Pd2' (N-CH 2)-C7-H7A benzyl-c1-c6 i 2.68 2.60 13.7 173 3.661(4) (N-CH 2)-C7-H7B benzyl-c25-c30 i 2.69 2.68 6.5 161 3.647(4) Pd3,Pd4 Pd3',Pd4' (N-CH 2)-C64-H64A benzyl-c58-c63 iii 2.46 2.46 3.0 164 3.423(4) (N-CH 2)-C64-H64B benzyl-c34-c39 iii 2.78 2.76 7.7 156 3.712(4) Pd1,Pd2 Pd3,Pd4 (N-CH 3)-C9-H9A iminato-c45-c49 ii 2.68 2.63 12.08 134 3.439(4) iminato-c14-h14 benzyl-c58-c63 2.96 2.93 7.8 148 3.801(4) benzyl-c25-c30 H53-C53-iminato 2.95 2.87 13.07 155 3.826(4) 1 1.5C 6H 6 (N-CH 2)-C7-H7B benzyl-c25-c30 vi 2.67 2.67 1.6 152 3.567(2) (N-CH 2)-C7-H7A benzyl-c1-c6 vi 3.01 164 3.964(2) (N-CH 3)-C8-H8C benzyl-c1-c6 vi 2.99 2.69 25.8 155 3.895(3) inter iminato-phenyl C19-H19 ringc11-c26 vii 2.86 2.78 13.5 151 3.712(3) iminato-ph benzene solvent C13-H13 benzene C41-C56 2.92 2.84 14.0 134 3.639(8) 1 C 6H 14 (N-CH 2)-C7-H7A benzyl-c1-c6 iix 2.96 2.64 27.1 166 3.935(3) (N-CH 2)-C7-H7A benzyl-c25-c30 iix 2.60 2.60 2.3 156 3.536(3) (N-CH 3)-C33-H33C benzyl-c25-c30 ix 2.78 2.65 17.6 156 3.691(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