Supplementary Information

Synthesis, spectroscopic characterization, X-ray structure, DFT calculations

and antimicrobial studies of diorganotin(IV) complexes of monotopic oxygen

nitrogen donor Schiff base

e-mail for correspondence: shaukat.shujah@yahoo.com

CONTENTS

Fig. S1 Mass spectrum of dimethyltin(IV) complex (1)

Fig. S2 Mass spectrum of di-n-octyltin(IV) complex (5)

Fig. S3 1H NMR spectrum of dimethyltin(IV) complex (1)

Fig. S4 1H NMR spectrum of dibutyltin(IV) complex (3)

Fig. S5 13C NMR spectrum of dibutyltin(IV) complex (3)

Fig. S6 Numbering scheme for optimized geometry of complex (4)

Fig. S7 Numbering scheme for optimized geometry of complex (5)

Fig. S8 Simulated IR spectra of ligand and tin complexes (1-7)

Fig. S9 Mulliken’s atomic charges for H2L and complexes.

Fig. S10. MEP plots of Schiff base ligand (H2L) and diorganotin(IV) complexes (1-7)

Table S1 Theoretical chemical shift values (in ppm) along with assignments of 1H-NMR signals

Table S2 Theoretical chemical shift values (in ppm) along with assignments of 13C-NMR signals

Cif File (Word format)

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Fig. S1 Mass spectrum of dimethyltin(IV) complex (1)

Fig. S2 Mass spectrum of di-n-octyltin(IV) complex (5)

Fig. S3 1H NMR spectrum of dimethyltin(IV) complex (1)

Fig. S4 1H NMR spectrum of dibutyltin(IV) complex (3)

Fig. S5 13C NMR spectrum of dibutyltin(IV) complex (3)

Fig. S6 Numbering scheme for optimized geometry of complex (4)

Fig. S7 Numbering scheme for optimized geometry of complex (5)

Fig. S8 Simulated IR spectra of ligand and tin complexes (1-7)

Fig. S9 Mulliken’s atomic charges for H2L and complexes.

Fig. S10 MEP plots of Schiff base ligand (H2L) and diorganotin(IV) complexes (1-7)

Table S1 Theoretical chemical shift values (in ppm) along with assignments of 1H-NMR signals

Ligand H2L Complex (1) Complex (2)

chemical Shift (ppm)

H-atoms numbering

chemical Shift (ppm)

H-atoms numbering

chemical Shift (ppm)

H-atoms numbering

Theo. Exp. Theo. Exp. Theo. Exp.11.443 41 8.737 8.78 30 8.812 8.79 30 8.900 42 8.397 8.02 31 8.400 8.03 31 8.407 8.64 27 8.216 8.02 34 8.248 8.03 34 8.206 31 7.654 7.46 33 7.655 7.34 33 7.816 7.89 30,28 7.486 7.35,

7.4627,32

7.506 7.34 27

7.641 7.56 29 7.206 7.20 29 7.430 7.46 327.570 7.30 24 6.915 6.80 28 7.216 7.18 297.502 7.22 26 6.678 6.76 26 6.946 6.81 287.248 6.95 23 1.641 1.37 40,43 6.684 6.73 267.129 6.92 25 1.551 1.37 45,46 1.648 1.36 42,391.598 1.32 35,40 1.241 1.37 39,42 1.551 1.36 44,451.477 1.32 32,34 1.020 1.37 38,41 1.327 1.32 49,541.265 1.32 36,39,33 0.966 1.37 44 1.246 1.36 38,411.058 1.32 38 0.455 0.85 37,48 1.118 1. 40-

1.5136,46,35,47

0.984 1.32 37 0.354 0.85 49,35,36,47

1.021 1.36 40,55,51,37,43

0.928 1.32 50,53Complex (3) Complex (4) Complex (5)

8.793 8.78 30 8.913 8.79 40 8.883 8.77 308.395 8.05 31 8.558 8.23,

7.92-7.96

44,50,45,41

8.341 8.04 31

8.238 8.05 34 8.333 7.92-7.96

54,49 8.262 8.04 34

7.629 7.48 33 7.690 7.36,7.40-7.50

46,51,37,47,52,43

7.619 7.47 32

7.508 7.34 27 7.486 7.55 42,48,53 7.492 7.47 337.345 7.34 32 7.377 7.15,

6.8039,38 7.437 7.34 27

7.218 7.19 29 6.880 6.76 36 7.216 7.18 296.942 6.80 28 1.620 1.42 60,57 6.925 6.81 28

6.706 6.74 26 1.510 1.42 62,63 6.750 6.74 261.666 1.38 39 1.266 1.42 56,59 1.506 1.38 39,42,45,441.600 1.38 42 1.147 1.42 61 1.285 1.53-

1.5850

1.525 1.38,1.64-1.72

45,44 1.064 1.42 58,55 1.088 1.38,1.53-1.58,1.23-1.29,0.88

49,53,52,57,74,84,83,73,56,59,58,90,89,68,67,41,81,70,80,71,38,64,65,37,63,78,40,91,62,43

1.374 1.52-1.59

53,50 0.871 1.65-1.77

46,35,36

1.284 1.38,1.52-1.59, 1.35-1.42

52,49,41,59,57,58,56

0.752 1.65-1.77

47,76,77,86,87

1.195 1.38 381.047 1.38,

1.64-1.72

46,36,47,37,35,43,64,65,40

0.637 0.90 67,62,66,63

Complex (6) Complex (7)

9.076 8.80 29 8.828 8.86 308.420 8.09 33,30 8.417 8.01 317.611 7.34,

7.4931,32,26 8.222 8.01 34

7.452 7.18 28 7.557 7.36 33,277.215 6.86 27 7.336 7.52 326.975 6.72 25 7.273 7.20 291.780 1.36 44,43 7.081 6.84 281.601 1.38 47,36,46,4

2,41,396.731 6.82 26

1.468 1.36 49,50 2.009 1.76-1.84

53,63,59,57

1.305 1.38 38 1.608 1.32 64,56,37,40,54,61

1.168 1.38 35,40,34,54

1.482 1.32 43,42

1.002 1.38 37 1.266 1.32 390.798 1.36 52,53 1.206 1.32 36,52

1.065 1.32 65,66,51,41,35,38

0.807 0.97 62,55,60,5

80.631 0.97 50,67

Table S2 Theoretical chemical shift values (in ppm) along with assignments of 13C-NMR signals

Ligand H2L Complex (1) Complex (2)

chemical Shift (ppm)

C-atoms numbering

chemical Shift (ppm)

C-atoms numbering

chemical Shift (ppm)

C-atoms numbering

Theo. Exp. Theo. Exp. Theo. Exp.

168.589 163.2 12 173.598 166.3 9 175.186 167.1 9166.793 158.0 5 171.637 169.3 2 172.288 169.7 2164.674 155.4 16 165.985 161.1 12 166.942 161.2 12153.056 148.6 11 162.709 154.6 16 162.271 154.5 16137.469 131.8 7 141.082 135.1 7 141.230 135.0 7136.737 130.0 9 140.142 134.1 11 140.321 134.1 11135.716 130.5 13 134.359 130.4 1 134.820 130.5 1133.801 17 133.019 18 132.877 18133.628 18 132.242 127.4 14 132.234 127.4 14130.189 128.0 14 132.111 125.2 15 132.115 125.2 15129.300 125.8 15 128.750 17 128.335 17123.599 119.8 8 125.308 121.7 8 125.297 121.6 8123.044 119.1 10 121.167 117.2 10 121.195 116.9 10121.033 116.9 6 120.426 116.8 6 120.289 116.8 6 42.445 35.2 19 41.848 34.9 21 41.877 34.9 21 32.857 31.4 21 32.220 31.2 23,22 32.714 31.2 23 32.091 22 28.295 24 31.899 22 28.749 20 -5.539 1.4 20,25 28.429 24

12.805 14.3 20,25 8.371 9.3 48,52

Complex (3) Complex (4) Complex (5)

174.966 166.9 9 173.282 167.2 9 174.213 166.9 9172.203 169.6 2 172.532 169.2 2 171.582 169.6 2166.965 160.9 12 166.457 161.2 12 166.047 160.8 12162.177 154.4 16 162.427 154.8 16 161.237 154.4 16

141.231 134.9 7 142.867 139.2 20,21 139.849 134.9 7140.473 134.1 11 142.371 136.3 27,22 139.304 134.1 11134.808 130.6 1 141.746 31,26 134.028 130.6 1132.999 18 141.285 135.3 7 132.066 18132.065 127.4 14 140.665 134.3 11 130.7291 127.8 14131.940 125.2 15 135.177 24,29 130.520 125.1 15128.141 17 134.529 130.5 1 127.578 17125.203 121.6 8 133.404 18 124.626 121.6 8121.206 117.1 10 133.348 130.4 23,28 119.736 117.0 10120.257 116.8 6 132.921 128.9 25,30 119.594 116.8 6 42.011 34.9 21 131.905 127.7 14 39.989 34.9 21 32.927 31.3 22 130.741 125.3 15 39.672 55,54 32.093 26.9 55,54 128.386 17 36.892 69 31.853 23 125.765 122.1 8 36.800 33.4 79 30.020 26.5 48,51 122.297 117.5 10 35.262 31.2 88,66 28.435 24 121.352 116.9 6 34.741 29.2 60 20.707 22.2 25 42.308 35.0 32 34.632 29.1 61 20.622 20 32.486 31.2 34,33 32.276 31.2 23 14.533 13.6 60,61 27.808 35 32.094 22

27.936 24 27.586 24.7 51 27.482 22.7 82,72 27.369 22.5 48 18.923 20 18.787 25 14.925 14.1 75,85

Complex (6) Complex (7)

174.146 168.0 9 174.453 165.9 9171.539 169.4 2 172.186 166.6 2166.791 160.7 12 166.972 158.1 12163.531 154.3 16 161.955 154.7 16141.338 134.7 7 140.657 135.0 7139.929 133.9 11 140.447 134.6 11133.898 18 134.938 130.6 1133.266 130.8 1 132.983 18132.583 127.4 15 131.750 127.5 14131.568 125.2 14 131.570 125.7 15128.896 17 128.098 17126.393 121.7 8 125.580 122.1 8122.659 117.0 6 122.293 118.0 10121.749 116.5 10 120.337 117.1 6 40.876 34.9 20 42.357 20 32.870 31.3 21 42.216 35.2 21 32.270 22 42.088 25 32.138 40.4 48 32.610 31.4 22

30.763 29.7 45 32.118 23 28.459 23 29.168 44 25.023 24 29.041 28.8 47,48 14.526 51 28.795 27.4 45

28.410 25.6 46 28.283 49 28.075 24

Cif File (Word format)

AUDIT DETAILS

_audit_creation_date '2008-08-18 09:44:56'_audit_creation_method ; PLATON <TABLE ACC> option (version :: 80708) SHELXL97-2 & Manual Editing ;_audit_update_record

CHEMICAL DATA

_chemical_name_systematic ;;_chemical_name_common ?_chemical_melting_point ?_chemical_formula_moiety 'C18 H20 N2 O2'# Ex: 'C12 H16 N2 O6, H2 O' and '(Cd 2+)3, (C6 N6 Cr 3-)2, 2(H2 O)' _chemical_formula_structural ?_chemical_formula_sum 'C18 H20 N2 O2'_chemical_formula_iupac ?_chemical_formula_weight 296.37_chemical_compound_source

loop__atom_type_symbol

_atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

CRYSTAL DATA

_symmetry_cell_setting orthorhombic_symmetry_space_group_name_Hall '-P 2ac 2ab'_symmetry_space_group_name_H-M 'P b c a'_symmetry_Int_Tables_number 61

loop__symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 x,y,z 2 1/2-x,-y,1/2+z 3 1/2+x,1/2-y,-z 4 -x,1/2+y,1/2-z 5 -x,-y,-z 6 1/2+x,y,1/2-z 7 1/2-x,1/2+y,z 8 x,1/2-y,1/2+z

_cell_length_a 13.982(4)_cell_length_b 9.269(3)_cell_length_c 24.557(7)_cell_angle_alpha 90_cell_angle_beta 90_cell_angle_gamma 90_cell_volume 3182.6(16)_cell_formula_units_Z 8

_cell_measurement_temperature 100(1)_cell_measurement_reflns_used 3074_cell_measurement_theta_min 3.12_cell_measurement_theta_max 26.72_cell_special_details; The final unit cell was obtained from the xyz centroids of 3074 reflections after integration using the SAINTPLUS software package (Bruker, 2007).

Reduced cell calculations did not indicate any higher metric lattice symmetry and examination of the final atomic coordinates of the structure did not yield extra symmetry elements (Spek, 1988; Le Page 1987, 1988);

_exptl_crystal_description 'needle'_exptl_crystal_colour 'colourless'_exptl_crystal_size_max 0.61 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.14 _exptl_crystal_size_rad ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.237 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1264 _exptl_absorpt_coefficient_mu 0.081 _exptl_absorpt_correction_type 'multi-scan' _exptl_absorpt_process_details '(SADABS, (Bruker, 2007))'_exptl_absorpt_correction_T_min 0.9416_exptl_absorpt_correction_T_max 0.9887

EXPERIMENTAL DATA

_exptl_special_details ;;_diffrn_ambient_temperature 100(1)_diffrn_radiation_wavelength 0.71073_diffrn_radiation_type 'MoK\a'_diffrn_radiation_source 'fine focus sealed Siemens Mo tube '_diffrn_radiation_monochromator 'parallel mounted graphite'

_diffrn_radiation_detector ; CCD area-detector;_diffrn_measurement_device_type ; Bruker Smart Apex; CCD area detector ;_diffrn_measurement_method '\f and \w scans'_diffrn_special_details ; Crystal into the cold nitrogen stream of the low-temparature unit (KRYOFLEX, (Bruker, 2007)).;_diffrn_detector_area_resol_mean 66.06

_diffrn_standards_number 0_diffrn_standards_interval_count ._diffrn_standards_interval_time ._diffrn_standards_decay_% 0

loop__diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l ? ? ?

# number of measured reflections (redundant set)_diffrn_reflns_number 14719 _diffrn_reflns_av_R_equivalents 0.0823 _diffrn_reflns_av_sigmaI/netI 0.0819 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -30 _diffrn_reflns_limit_l_max 30 _diffrn_reflns_theta_min 2.76 _diffrn_reflns_theta_max 26.37 _diffrn_measured_fraction_theta_max 0.994

_diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.997

_diffrn_reflns_reduction_process ; Intensity data were corrected for Lorentz and polarization effects, decay and absorption and reduced to F~o~^2^ using SAINT-Plus & SADABS (Bruker, 2007).;

# number of unique reflections_reflns_number_total 3234 _reflns_number_gt 1946 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'SMART (Bruker, 2007)'_computing_cell_refinement 'SAINT-Plus (Bruker, 2007)'_computing_data_reduction 'SAINT-Plus (Bruker, 2007)'_computing_structure_solution ; SIR2004 (Burla et al., 2005);_computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)'_computing_molecular_graphics ; PLATON (Spek, 2003) PLUTO (Meetsma, 2008) ;_computing_publication_material 'PLATON (Spek, 2003)'

REFINEMENT DATA

_refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R-

factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0565P)^2^+0.0P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary direct _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment refall_refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details ?_chemical_absolute_configuration '.' _refine_ls_abs_structure_Flack ? _refine_ls_number_reflns 3234 _refine_ls_number_parameters 279 _refine_ls_number_restraints 0 _refine_ls_number_constraints ? _refine_ls_R_factor_all 0.1048 _refine_ls_R_factor_gt 0.0486 _refine_ls_wR_factor_ref 0.1264 _refine_ls_wR_factor_gt 0.1053 _refine_ls_goodness_of_fit_ref 1.007 _refine_ls_restrained_S_all 1.007 _refine_ls_shift/su_max 0.063 _refine_ls_shift/su_mean 0.003 _refine_diff_density_max 0.231 _refine_diff_density_min -0.193 _refine_diff_density_rms 0.050 ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS

loop__atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x

_atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags O1 O Uani 0.42746(11) 0.18330(16) 0.02399(6) 1.000 0.0253(5) . . O2 O Uani 0.18238(10) 0.26387(14) 0.10316(5) 1.000 0.0224(5) . . N1 N Uani 0.34370(12) 0.39929(17) 0.07475(6) 1.000 0.0185(6) . . N2 N Uani 0.26417(12) 0.47420(19) 0.09238(6) 1.000 0.0183(6) . . C1 C Uani 0.51020(15) 0.2560(2) 0.03426(8) 1.000 0.0200(7) . . C2 C Uani 0.59548(16) 0.1890(3) 0.02001(8) 1.000 0.0252(8) . . C3 C Uani 0.68133(17) 0.2593(3) 0.02874(8) 1.000 0.0273(8) . . C4 C Uani 0.68359(16) 0.3973(2) 0.05126(9) 1.000 0.0268(8) . . C5 C Uani 0.59904(15) 0.4639(2) 0.06529(8) 1.000 0.0240(7) . . C6 C Uani 0.51080(14) 0.3954(2) 0.05762(8) 1.000 0.0186(7) . . C7 C Uani 0.42378(15) 0.4679(2) 0.07451(8) 1.000 0.0198(7) . . C8 C Uani 0.18597(14) 0.3974(2) 0.10718(8) 1.000 0.0172(7) . . C9 C Uani 0.10450(14) 0.4803(2) 0.13022(8) 1.000 0.0164(6) . . C10 C Uani 0.11374(16) 0.6144(2) 0.15456(8) 1.000 0.0196(7) . . C11 C Uani 0.03704(15) 0.6802(2) 0.17995(8) 1.000 0.0204(7) . . C12 C Uani -0.05266(14) 0.6146(2) 0.18179(8) 1.000 0.0196(7) . . C13 C Uani -0.06200(16) 0.4818(2) 0.15530(9) 1.000 0.0261(8) . . C14 C Uani 0.01464(15) 0.4152(2) 0.13023(9) 1.000 0.0235(7) . . C15 C Uani -0.13451(15) 0.6781(2) 0.21472(8) 1.000 0.0261(7) . . C16 C Uani -0.1178(2) 0.8372(3) 0.22929(11) 1.000 0.0369(9) . . C17 C Uani -0.22913(17) 0.6676(3) 0.18321(10) 1.000 0.0320(9) . . C18 C Uani -0.1417(2) 0.5886(4) 0.26746(10) 1.000 0.0410(10) . . H2 H Uiso 0.5926(14) 0.089(2) 0.0044(8) 1.000 0.028(6) . . H3 H Uiso 0.7391(17) 0.211(2) 0.0175(9) 1.000 0.038(7) . . H4 H Uiso 0.7424(15) 0.448(2) 0.0557(8) 1.000 0.027(6) . . H5 H Uiso 0.6001(12) 0.567(2) 0.0828(7) 1.000 0.010(5) . . H7 H Uiso 0.4281(15) 0.569(2) 0.0871(8) 1.000 0.034(6) . . H10 H Uiso 0.1728(15) 0.661(2) 0.1547(8) 1.000 0.022(6) . . H11 H Uiso 0.0485(14) 0.775(2) 0.1972(8) 1.000 0.022(5) . . H13 H Uiso -0.1238(16) 0.433(2) 0.1540(9) 1.000 0.035(6) . . H14 H Uiso 0.0069(15) 0.323(2) 0.1128(9) 1.000 0.037(6) . . H16 H Uiso -0.1071(15) 0.903(2) 0.1960(9) 1.000 0.033(6) . . H16' H Uiso -0.1752(16) 0.878(2) 0.2480(9) 1.000 0.038(6) . . H16" H Uiso -0.0600(18) 0.851(3) 0.2529(10) 1.000 0.054(8) . . H17 H Uiso -0.2455(15) 0.564(2) 0.1739(8) 1.000 0.036(6) . .

H17' H Uiso -0.2830(17) 0.710(2) 0.2048(9) 1.000 0.041(7) . . H17" H Uiso -0.2262(17) 0.733(3) 0.1476(10) 1.000 0.051(7) . . H18 H Uiso -0.0806(19) 0.597(2) 0.2879(9) 1.000 0.044(7) . . H18' H Uiso -0.1960(17) 0.629(2) 0.2897(9) 1.000 0.046(7) . . H18" H Uiso -0.1536(19) 0.485(3) 0.2594(11) 1.000 0.063(9) . . H21 H Uiso 0.379(2) 0.241(3) 0.0383(12) 1.000 0.069(10) . . H31 H Uiso 0.2679(15) 0.575(2) 0.0948(8) 1.000 0.036(6) . .

loop__atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 O1 0.0218(9) 0.0219(9) 0.0322(9) -0.0053(7) 0.0027(7) 0.0007(7) O2 0.0224(8) 0.0127(8) 0.0321(8) -0.0028(6) 0.0004(6) 0.0008(7) N1 0.0157(10) 0.0174(10) 0.0225(9) 0.0009(7) 0.0030(7) 0.0042(8) N2 0.0162(10) 0.0107(9) 0.0280(10) -0.0022(7) 0.0042(7) 0.0010(8) C1 0.0192(12) 0.0216(12) 0.0192(11) 0.0033(9) 0.0020(8) 0.0008(10) C2 0.0274(14) 0.0228(13) 0.0253(12) 0.0010(10) 0.0068(10) 0.0042(11) C3 0.0242(14) 0.0313(14) 0.0263(12) 0.0051(10) 0.0081(10) 0.0090(11) C4 0.0194(13) 0.0297(14) 0.0313(13) 0.0053(10) 0.0000(10) 0.0000(11) C5 0.0218(13) 0.0206(13) 0.0297(12) 0.0006(10) 0.0020(9) -0.0001(10) C6 0.0190(12) 0.0173(12) 0.0196(10) 0.0033(8) 0.0025(8) 0.0026(9) C7 0.0201(12) 0.0171(12) 0.0223(11) 0.0007(9) 0.0010(8) 0.0004(10) C8 0.0196(12) 0.0138(12) 0.0182(10) -0.0009(8) -0.0023(8) -0.0009(9) C9 0.0174(12) 0.0129(11) 0.0190(10) 0.0012(8) -0.0014(8) 0.0019(9) C10 0.0168(12) 0.0185(12) 0.0234(11) 0.0001(9) -0.0015(9) -0.0017(10) C11 0.0217(12) 0.0164(12) 0.0232(11) -0.0035(9) 0.0011(9) 0.0013(10) C12 0.0184(12) 0.0208(12) 0.0196(11) 0.0019(9) -0.0001(9) 0.0033(9) C13 0.0175(13) 0.0254(13) 0.0354(13) -0.0025(10) 0.0024(10) -0.0036(10) C14 0.0228(13) 0.0151(12) 0.0326(12) -0.0063(9) 0.0008(9) -0.0027(10) C15 0.0198(12) 0.0298(13) 0.0287(12) -0.0011(10) 0.0043(9) 0.0061(10) C16 0.0280(15) 0.0385(16) 0.0443(16) -0.0164(13) 0.0052(12) 0.0110(13) C17 0.0207(14) 0.0376(16) 0.0378(15) 0.0001(12) 0.0040(11) 0.0077(12) C18 0.0315(17) 0.062(2) 0.0296(14) 0.0039(13) 0.0098(12) 0.0165(15)

MOLECULAR GEOMETRY

_geom_special_details ; Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles;

loop__geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag O1 C1 1.362(3) . . yes O2 C8 1.243(2) . . yes O1 H21 0.93(3) . . no N1 C7 1.288(3) . . yes N1 N2 1.381(2) . . yes N2 C8 1.354(3) . . yes N2 H31 0.938(19) . . no C1 C2 1.389(3) . . no C1 C6 1.414(3) . . no C2 C3 1.383(3) . . no C3 C4 1.394(3) . . no C4 C5 1.377(3) . . no C5 C6 1.400(3) . . no C6 C7 1.451(3) . . no C8 C9 1.486(3) . . no C9 C10 1.385(3) . . no C9 C14 1.394(3) . . no C10 C11 1.382(3) . . no C11 C12 1.395(3) . . no C12 C15 1.520(3) . . no C12 C13 1.398(3) . . no C13 C14 1.381(3) . . no C15 C18 1.541(4) . . no C15 C16 1.535(3) . . no C15 C17 1.536(3) . . no

C2 H2 1.004(19) . . no C3 H3 0.96(2) . . no C4 H4 0.95(2) . . no C5 H5 1.048(18) . . no C7 H7 0.989(19) . . no C10 H10 0.93(2) . . no C11 H11 0.989(19) . . no C13 H13 0.98(2) . . no C14 H14 0.962(19) . . no C16 H16 1.03(2) . . no C16 H16' 1.00(2) . . no C16 H16" 1.00(3) . . no C17 H17 1.013(19) . . no C17 H17' 1.00(2) . . no C17 H17" 1.07(3) . . no C18 H18 0.99(3) . . no C18 H18' 1.01(2) . . no C18 H18" 0.99(3) . . no

loop__geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C1 O1 H21 105.3(17) . . . no N2 N1 C7 116.96(16) . . . yes N1 N2 C8 118.04(16) . . . yes C8 N2 H31 123.5(13) . . . no N1 N2 H31 118.4(13) . . . no O1 C1 C6 122.16(18) . . . yes C2 C1 C6 120.4(2) . . . no O1 C1 C2 117.46(18) . . . yes C1 C2 C3 119.7(2) . . . no C2 C3 C4 120.9(2) . . . no C3 C4 C5 119.4(2) . . . no C4 C5 C6 121.29(18) . . . no C1 C6 C5 118.31(18) . . . no

C1 C6 C7 122.31(18) . . . no C5 C6 C7 119.38(17) . . . no N1 C7 C6 120.12(17) . . . yes O2 C8 N2 122.33(18) . . . yes O2 C8 C9 120.95(17) . . . yes N2 C8 C9 116.70(16) . . . yes C8 C9 C10 123.83(18) . . . no C10 C9 C14 118.19(18) . . . no C8 C9 C14 117.85(17) . . . no C9 C10 C11 121.21(19) . . . no C10 C11 C12 121.33(18) . . . no C11 C12 C13 116.92(18) . . . no C11 C12 C15 121.71(17) . . . no C13 C12 C15 121.20(18) . . . no C12 C13 C14 121.89(19) . . . no C9 C14 C13 120.39(18) . . . no C12 C15 C18 106.72(18) . . . no C16 C15 C18 109.3(2) . . . no C17 C15 C18 109.46(19) . . . no C16 C15 C17 108.02(19) . . . no C12 C15 C16 112.42(18) . . . no C12 C15 C17 110.86(17) . . . no C1 C2 H2 118.3(11) . . . no C3 C2 H2 122.0(11) . . . no C2 C3 H3 117.7(12) . . . no C4 C3 H3 121.4(12) . . . no C3 C4 H4 121.2(12) . . . no C5 C4 H4 119.4(12) . . . no C4 C5 H5 119.9(9) . . . no C6 C5 H5 118.8(9) . . . no N1 C7 H7 121.3(12) . . . no C6 C7 H7 118.5(12) . . . no C9 C10 H10 120.0(12) . . . no C11 C10 H10 118.8(12) . . . no C10 C11 H11 117.4(11) . . . no C12 C11 H11 121.3(11) . . . no C12 C13 H13 120.4(12) . . . no C14 C13 H13 117.7(12) . . . no C9 C14 H14 119.1(13) . . . no C13 C14 H14 120.5(13) . . . no C15 C16 H16 113.9(11) . . . no

C15 C16 H16' 110.4(11) . . . no C15 C16 H16" 112.3(16) . . . no H16 C16 H16' 104.9(16) . . . no H16 C16 H16" 105.4(19) . . . no H16' C16 H16" 109.5(19) . . . no C15 C17 H17 111.6(12) . . . no C15 C17 H17' 110.9(13) . . . no C15 C17 H17" 110.2(13) . . . no H17 C17 H17' 108.8(17) . . . no H17 C17 H17" 111.3(18) . . . no H17' C17 H17" 103.9(18) . . . no C15 C18 H18 109.0(13) . . . no C15 C18 H18' 107.7(12) . . . no C15 C18 H18" 111.3(16) . . . no H18 C18 H18' 110.2(18) . . . no H18 C18 H18" 108.7(19) . . . no H18' C18 H18" 109.9(19) . . . no

loop__geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C7 N1 N2 C8 -162.35(17) . . . . no N2 N1 C7 C6 178.69(16) . . . . no N1 N2 C8 O2 -3.2(3) . . . . no N1 N2 C8 C9 175.14(16) . . . . no O1 C1 C2 C3 178.91(18) . . . . no C6 C1 C2 C3 0.0(3) . . . . no O1 C1 C6 C5 -178.16(18) . . . . no O1 C1 C6 C7 2.9(3) . . . . no C2 C1 C6 C5 0.7(3) . . . . no C2 C1 C6 C7 -178.27(19) . . . . no C1 C2 C3 C4 -0.6(3) . . . . no C2 C3 C4 C5 0.4(3) . . . . no

C3 C4 C5 C6 0.3(3) . . . . no C4 C5 C6 C1 -0.9(3) . . . . no C4 C5 C6 C7 178.15(19) . . . . no C1 C6 C7 N1 8.6(3) . . . . no C5 C6 C7 N1 -170.44(18) . . . . no O2 C8 C9 C10 154.96(19) . . . . no O2 C8 C9 C14 -21.0(3) . . . . no N2 C8 C9 C10 -23.4(3) . . . . no N2 C8 C9 C14 160.68(18) . . . . no C8 C9 C10 C11 -173.66(19) . . . . no C14 C9 C10 C11 2.3(3) . . . . no C8 C9 C14 C13 174.40(19) . . . . no C10 C9 C14 C13 -1.8(3) . . . . no C9 C10 C11 C12 -0.4(3) . . . . no C10 C11 C12 C13 -2.0(3) . . . . no C10 C11 C12 C15 173.29(18) . . . . no C11 C12 C13 C14 2.5(3) . . . . no C15 C12 C13 C14 -172.82(19) . . . . no C11 C12 C15 C16 17.9(3) . . . . no C11 C12 C15 C17 138.9(2) . . . . no C11 C12 C15 C18 -102.0(2) . . . . no C13 C12 C15 C16 -167.0(2) . . . . no C13 C12 C15 C17 -46.0(3) . . . . no C13 C12 C15 C18 73.1(2) . . . . no C12 C13 C14 C9 -0.6(3) . . . . no

loop__geom_contact_atom_site_label_1 _geom_contact_atom_site_label_2 _geom_contact_distance _geom_contact_site_symmetry_1 _geom_contact_site_symmetry_2 _geom_contact_publ_flag O1 N1 2.633(2) . . no O1 C9 3.247(3) . 7_545 no O1 C10 3.320(3) . 7_545 no O2 N1 2.674(2) . . no O2 C3 3.246(3) . 3_455 no O2 C10 3.412(3) . 7_545 no O2 C2 3.289(3) . 3_455 no O2 C7 3.198(3) . 7_545 no

O2 N2 2.800(2) . 7_545 no O1 H2 2.633(19) . 5_655 no O2 H14 2.53(2) . . no O2 H18' 2.92(2) . 4_545 no O2 H7 2.41(2) . 7_545 no O2 H10 2.57(2) . 7_545 no O2 H31 1.895(19) . 7_545 no N1 O1 2.633(2) . . no N1 O2 2.674(2) . . no N1 C10 3.342(3) . 7_545 no N2 O2 2.800(2) . 7_555 no N1 H21 1.79(3) . . no N1 H3 2.88(2) . 3_455 no N2 H10 2.64(2) . . no C2 O2 3.289(3) . 3_555 no C2 C8 3.464(3) . 3_555 no C3 O2 3.246(3) . 3_555 no C5 C7 3.505(3) . 5_665 no C6 C6 3.444(3) . 5_665 no C7 O2 3.198(3) . 7_555 no C7 C5 3.505(3) . 5_665 no C8 C2 3.464(3) . 3_455 no C9 O1 3.247(3) . 7_555 no C10 N1 3.342(3) . 7_555 no C10 O1 3.320(3) . 7_555 no C10 O2 3.412(3) . 7_555 no C3 H17" 3.00(2) . 7_545 no C4 H17" 2.88(3) . 7_545 no C7 H21 2.37(3) . . no C8 H31 3.072(19) . 7_545 no C8 H2 3.04(2) . 3_455 no C10 H31 2.63(2) . . no C10 H18' 3.00(2) . 6_555 no C10 H21 3.09(3) . 7_555 no C11 H16 2.91(2) . . no C11 H16" 2.75(3) . . no C13 H17 2.72(2) . . no C13 H18" 2.86(3) . . no C13 H16" 3.08(3) . 4_545 no C14 H16" 3.00(2) . 4_545 no C16 H11 2.52(2) . . no

C17 H13 2.72(2) . . no H2 C8 3.04(2) . 3_555 no H2 O1 2.633(19) . 5_655 no H3 N1 2.88(2) . 3_555 no H3 H21 2.43(4) . 3_555 no H5 H7 2.41(3) . . no H7 H5 2.41(3) . . no H7 H31 2.25(3) . . no H7 O2 2.41(2) . 7_555 no H10 N2 2.64(2) . . no H10 H31 2.14(3) . . no H10 H18' 2.31(3) . 6_555 no H10 O2 2.57(2) . 7_555 no H11 C16 2.52(2) . . no H11 H16 2.48(3) . . no H11 H16" 2.16(3) . . no H13 C17 2.72(2) . . no H13 H17 2.15(3) . . no H14 O2 2.53(2) . . no H16 C11 2.91(2) . . no H16 H11 2.48(3) . . no H16 H17" 2.58(3) . . no H16' H17' 2.41(3) . . no H16' H18' 2.54(3) . . no H16" C11 2.75(3) . . no H16" H11 2.16(3) . . no H16" H18 2.52(3) . . no H16" C13 3.08(3) . 4_555 no H16" C14 3.00(2) . 4_555 no H17 C13 2.72(2) . . no H17 H13 2.15(3) . . no H17 H18" 2.57(3) . . no H17' H16' 2.41(3) . . no H17' H18' 2.53(3) . . no H17" H16 2.58(3) . . no H17" C3 3.00(2) . 7_555 no H17" C4 2.88(3) . 7_555 no H18 H16" 2.52(3) . . no H18' H16' 2.54(3) . . no H18' H17' 2.53(3) . . no H18' O2 2.92(2) . 4_555 no

H18' C10 3.00(2) . 6_455 no H18' H10 2.31(3) . 6_455 no H18" C13 2.86(3) . . no H18" H17 2.57(3) . . no H21 N1 1.79(3) . . no H21 C7 2.37(3) . . no H21 H3 2.43(4) . 3_455 no H21 C10 3.09(3) . 7_545 no H31 C10 2.63(2) . . no H31 H7 2.25(3) . . no H31 H10 2.14(3) . . no H31 O2 1.895(19) . 7_555 no H31 C8 3.072(19) . 7_555 no

loop__geom_hbond_atom_site_label_D_geom_hbond_atom_site_label_H_geom_hbond_atom_site_label_A_geom_hbond_distance_DH_geom_hbond_distance_HA_geom_hbond_distance_DA_geom_hbond_angle_DHA_geom_hbond_site_symmetry_A_geom_hbond_publ_flag##D H A D - H H...A D...A D - H...A symm(A)#O1 H21 N1 0.93(3) 1.79(3) 2.633(2) 149(3) . yes N2 H31 O2 0.938(19) 1.895(19) 2.800(2) 161.4(19) 7_555 yes C7 H7 O2 0.989(19) 2.41(2) 3.198(3) 136.3(16) 7_555 yes C10 H10 O2 0.93(2) 2.57(2) 3.412(3) 150.2(16) 7_555 yes

#===END of Crystallographic Information File

Table S3 Mode number (#M), calculated harmonic (Harm.) and scaled (Scal.) IR frequencies (in cm-1) for each compounds.

Ligand H2L Complex (1) Complex (2) Complex (3) Complex (4) Complex (5) Complex (6) Complex (7)#M Har. Scal. #M Har. Scal. #M Har. Scal. #M Har. Scal. #M Har. Scal. #M Har. Scal. #M Har. Scal. #M Har. Scal.

1 20 19.7 1 8.43 8.33 1 8.09 7.99 1 8.84 8.73 1 15.1 14.9 1 7.18 7.09 1 12.7 12.6 1 13.3 13.12 24.3 24 2 22.7 22.4 2 24.9 24.6 2 14.9 14.7 2 16.2 16 2 8.08 7.98 2 16.9 16.6 2 21.9 21.73 33.9 33.5 3 27.6 27.3 3 29.2 28.8 3 18.5 18.3 3 19.6 19.4 3 12.5 12.3 3 22.6 22.3 3 26.1 25.84 48.9 48.4 4 50.8 50.2 4 39.9 39.5 4 19.6 19.4 4 28 27.7 4 14.5 14.3 4 27.2 26.9 4 32 31.65 69.5 68.6 5 51.7 51.1 5 42.3 41.8 5 30.4 30.1 5 38.4 37.9 5 25.3 25 5 44.7 44.2 5 35.1 34.76 73.6 72.7 6 62.4 61.7 6 50.2 49.5 6 35.7 35.3 6 40.5 40 6 30.5 30.2 6 50.8 50.2 6 45.2 44.67 104 103 7 74.6 73.7 7 52.6 51.9 7 48.9 48.3 7 42.3 41.8 7 36.1 35.6 7 57 56.3 7 46.1 45.58 131 129 8 82.8 81.8 8 60.8 60.1 8 50.5 49.9 8 43.1 42.6 8 38.2 37.8 8 60.3 59.6 8 58.4 57.79 168 166 9 84.7 83.7 9 66.1 65.3 9 58.5 57.8 9 57.9 57.2 9 41.8 41.3 9 62.2 61.4 9 59.9 59.2

10 193 191 10 117 115 10 75 74.1 10 66.4 65.6 10 64.9 64.1 10 45.5 44.9 10 75.8 74.9 10 67.1 66.311 211 209 11 126 124 11 117 115 11 70.9 70.1 11 65.9 65.1 11 47.8 47.2 11 112 111 11 87.6 86.612 231 228 12 140 138 12 125 123 12 80.3 79.3 12 108 106 12 53.4 52.8 12 118 117 12 114 11313 238 235 13 152 150 13 141 139 13 99.3 98.1 13 136 134 13 56.7 56 13 132 131 13 136 13514 256 253 14 154 152 14 146 144 14 118 117 14 143 142 14 61 60.3 14 136 134 14 147 14515 269 265 15 161 159 15 150 148 15 121 119 15 145 143 15 62.3 61.5 15 152 150 15 150 14816 287 284 16 169 167 16 156 154 16 131 130 16 149 148 16 75.1 74.2 16 159 157 16 150 14917 296 293 17 205 203 17 201 198 17 136 135 17 182 180 17 90.1 89 17 161 159 17 199 19718 323 319 18 215 213 18 209 207 18 150 148 18 186 184 18 93.8 92.7 18 174 172 18 201 19919 333 329 19 228 226 19 224 221 19 163 161 19 197 195 19 98.2 97 19 205 202 19 207 20520 346 342 20 229 226 20 226 223 20 167 165 20 203 200 20 102 101 20 213 210 20 215 21221 354 350 21 252 249 21 239 237 21 168 166 21 221 218 21 108 107 21 225 222 21 220 21722 396 391 22 255 252 22 247 244 22 174 172 22 225 222 22 113 112 22 241 238 22 226 22323 412 407 23 275 272 23 251 248 23 206 203 23 234 232 23 133 131 23 243 240 23 232 22924 417 412 24 317 313 24 252 249 24 206 204 24 245 242 24 142 140 24 246 243 24 246 24325 447 442 25 319 315 25 254 251 25 226 224 25 249 246 25 146 144 25 259 256 25 247 24426 455 449 26 334 330 26 275 271 26 228 225 26 249 246 26 147 146 26 268 265 26 248 24527 474 468 27 351 347 27 275 272 27 229 226 27 259 255 27 152 150 27 271 268 27 249 246

28 476 471 28 355 350 28 316 312 28 244 241 28 267 264 28 159 157 28 315 311 28 258 25429 477 471 29 369 364 29 319 315 29 247 244 29 280 277 29 160 158 29 318 314 29 262 25930 509 503 30 375 371 30 336 332 30 247 244 30 317 314 30 161 159 30 335 331 30 273 26931 558 551 31 418 413 31 352 348 31 254 251 31 326 322 31 171 169 31 342 337 31 277 27332 561 555 32 429 424 32 353 349 32 274 271 32 338 334 32 176 174 32 356 352 32 287 28433 576 569 33 456 450 33 367 363 33 274 271 33 353 348 33 180 178 33 358 354 33 292 28834 588 581 34 470 465 34 377 373 34 316 312 34 355 351 34 194 191 34 373 369 34 295 29235 651 643 35 475 470 35 417 412 35 320 317 35 372 367 35 211 209 35 380 375 35 298 29536 668 660 36 485 479 36 428 423 36 335 331 36 386 382 36 216 213 36 383 379 36 316 31237 716 707 37 507 501 37 455 449 37 351 347 37 407 402 37 230 228 37 418 413 37 323 31938 737 728 38 540 533 38 469 463 38 353 349 38 409 404 38 234 231 38 430 425 38 337 33339 740 731 39 552 546 39 476 471 39 367 363 39 417 412 39 244 241 39 458 452 39 351 34740 752 743 40 555 548 40 484 478 40 374 369 40 432 427 40 247 244 40 472 467 40 353 34941 769 760 41 562 555 41 496 490 41 381 377 41 454 449 41 253 250 41 477 471 41 366 36142 780 771 42 573 566 42 508 502 42 389 385 42 455 450 42 256 253 42 494 488 42 377 37243 789 780 43 601 593 43 551 544 43 417 412 43 465 460 43 275 271 43 554 547 43 382 37744 842 832 44 616 609 44 553 547 44 428 423 44 469 463 44 278 274 44 556 549 44 384 38045 846 836 45 653 645 45 561 555 45 455 450 45 487 482 45 290 286 45 563 556 45 386 38146 865 855 46 674 666 46 570 563 46 469 463 46 488 482 46 318 315 46 582 575 46 389 38447 869 859 47 720 711 47 599 592 47 476 470 47 553 546 47 326 322 47 603 596 47 417 41248 888 877 48 737 729 48 615 607 48 485 479 48 554 548 48 330 326 48 606 599 48 429 42449 927 916 49 747 738 49 653 645 49 551 544 49 563 556 49 334 330 49 621 613 49 453 44850 938 926 50 749 740 50 674 666 50 553 546 50 576 569 50 342 338 50 652 644 50 466 46151 939 928 51 764 755 51 683 675 51 560 554 51 600 593 51 356 352 51 676 668 51 483 47852 941 930 52 771 762 52 696 688 52 570 563 52 617 610 52 359 354 52 693 685 52 484 47853 962 950 53 784 775 53 719 711 53 596 589 53 632 625 53 371 367 53 725 716 53 503 49754 963 952 54 787 777 54 747 738 54 599 592 54 633 625 54 387 382 54 748 739 54 518 51255 969 957 55 799 790 55 752 743 55 603 596 55 652 644 55 417 412 55 756 747 55 550 54356 980 969 56 819 809 56 764 755 56 615 607 56 670 662 56 430 425 56 756 747 56 554 54757 999 987 57 844 833 57 783 773 57 653 645 57 674 666 57 432 427 57 769 760 57 562 55658 1032 1020 58 857 847 58 813 803 58 673 665 58 675 667 58 434 428 58 788 778 58 567 560

59 1041 1029 59 869 859 59 844 833 59 682 674 59 718 710 59 456 451 59 815 805 59 597 59060 1047 1035 60 871 860 60 857 847 60 692 683 60 720 711 60 471 465 60 843 833 60 613 60661 1053 1041 61 911 900 61 868 858 61 718 710 61 721 713 61 478 472 61 855 845 61 652 64562 1080 1067 62 929 918 62 870 859 62 747 738 62 747 738 62 479 473 62 871 860 62 674 66663 1128 1115 63 939 928 63 910 899 63 754 745 63 751 742 63 486 480 63 874 864 63 718 70964 1137 1123 64 949 938 64 929 918 64 754 745 64 753 744 64 490 484 64 887 876 64 747 73865 1146 1133 65 955 944 65 939 928 65 756 747 65 759 749 65 553 546 65 891 880 65 757 74866 1172 1158 66 961 949 66 949 938 66 764 755 66 769 759 66 556 550 66 910 899 66 767 75867 1180 1166 67 988 976 67 954 942 67 782 772 67 784 775 67 565 558 67 926 915 67 781 77268 1217 1202 68 989 977 68 960 949 68 813 803 68 813 803 68 572 566 68 938 927 68 802 79269 1221 1206 69 990 978 69 973 961 69 843 833 69 842 832 69 600 593 69 954 942 69 805 79570 1225 1210 70 999 987 70 975 963 70 857 846 70 854 844 70 603 596 70 954 943 70 812 80271 1228 1213 71 1032 1020 71 977 965 71 868 858 71 869 859 71 608 600 71 961 949 71 843 83372 1258 1243 72 1041 1028 72 984 972 72 869 859 72 871 860 72 617 609 72 990 978 72 855 84573 1262 1247 73 1045 1032 73 987 976 73 879 869 73 873 863 73 653 646 73 990 978 73 869 85874 1284 1269 74 1048 1035 74 988 976 74 884 874 74 874 863 74 674 666 74 992 980 74 870 85975 1307 1292 75 1054 1041 75 990 978 75 889 879 75 910 899 75 683 675 75 997 985 75 910 89976 1330 1314 76 1126 1112 76 999 987 76 893 882 76 927 915 76 692 684 76 1005 993 76 927 91677 1340 1324 77 1139 1125 77 1018 1006 77 910 900 77 936 925 77 720 712 77 1033 1020 77 938 92778 1350 1334 78 1149 1135 78 1032 1020 78 928 917 78 946 934 78 734 725 78 1041 1028 78 946 93579 1382 1366 79 1172 1158 79 1034 1021 79 939 928 79 947 936 79 734 725 79 1046 1033 79 947 93580 1399 1383 80 1178 1163 80 1041 1028 80 949 938 80 952 940 80 741 732 80 1048 1035 80 948 93781 1400 1383 81 1215 1201 81 1044 1032 81 955 943 81 954 942 81 742 733 81 1049 1036 81 950 93882 1418 1401 82 1221 1206 82 1048 1035 82 959 948 82 959 947 82 748 739 82 1050 1038 82 951 93983 1432 1415 83 1222 1208 83 1054 1041 83 985 973 83 986 974 83 760 751 83 1060 1047 83 955 94384 1434 1417 84 1234 1219 84 1126 1112 84 988 976 84 989 977 84 772 763 84 1098 1085 84 959 94785 1484 1466 85 1252 1237 85 1139 1125 85 989 977 85 992 980 85 774 765 85 1126 1112 85 967 95586 1488 1470 86 1256 1241 86 1149 1135 86 999 987 86 998 986 86 776 766 86 1140 1127 86 967 95687 1489 1472 87 1270 1255 87 1172 1158 87 1003 991 87 1003 991 87 785 776 87 1149 1136 87 987 97588 1492 1474 88 1284 1268 88 1177 1163 88 1006 994 88 1004 992 88 813 803 88 1173 1159 88 989 97789 1505 1487 89 1329 1313 89 1215 1200 89 1032 1020 89 1010 998 89 839 829 89 1179 1164 89 993 982

90 1510 1492 90 1334 1318 90 1221 1206 90 1040 1028 90 1010 998 90 842 832 90 1200 1186 90 998 98691 1516 1498 91 1342 1326 91 1223 1208 91 1041 1028 91 1014 1002 91 843 833 91 1216 1201 91 1030 101792 1522 1503 92 1375 1359 92 1233 1219 92 1043 1031 92 1015 1003 92 858 847 92 1220 1206 92 1032 102093 1537 1518 93 1387 1370 93 1242 1227 93 1047 1035 93 1032 1019 93 873 862 93 1223 1209 93 1034 102294 1551 1533 94 1398 1381 94 1243 1228 94 1048 1035 94 1039 1027 94 875 864 94 1229 1214 94 1035 102395 1599 1580 95 1400 1384 95 1267 1252 95 1053 1040 95 1041 1029 95 898 887 95 1237 1222 95 1037 102596 1605 1586 96 1414 1397 96 1268 1253 96 1054 1041 96 1042 1030 96 898 887 96 1271 1256 96 1040 102797 1647 1627 97 1431 1414 97 1273 1257 97 1055 1042 97 1046 1034 97 912 901 97 1284 1268 97 1045 103298 1656 1636 98 1433 1416 98 1284 1268 98 1093 1080 98 1048 1035 98 921 910 98 1306 1290 98 1047 103499 1668 1648 99 1458 1440 99 1329 1313 99 1100 1087 99 1057 1044 99 924 913 99 1326 1310 99 1054 104110

0 1750 1729 100 1460 1442 100 1334 1318 100 1126 1112 100 1089 1076 100 927 916 100 1327 1311 100 1125 111210

1 3022 2901 101 1462 1445 101 1343 1327 101 1138 1125 101 1091 1078 101 939 928 101 1331 1315 101 1139 112510

2 3022 2901 102 1467 1450 102 1375 1359 102 1149 1135 102 1093 1080 102 949 938 102 1337 1321 102 1149 113510

3 3028 2907 103 1476 1458 103 1387 1370 103 1173 1159 103 1094 1081 103 957 945 103 1340 1324 103 1173 115910

4 3029 2908 104 1482 1465 104 1398 1381 104 1177 1163 104 1125 1112 104 963 951 104 1373 1356 104 1177 116310

5 3084 2961 105 1488 1470 105 1400 1383 105 1198 1184 105 1139 1126 105 977 966 105 1381 1364 105 1195 118110

6 3085 2962 106 1491 1473 106 1414 1397 106 1199 1185 106 1149 1135 106 982 971 106 1386 1370 106 1196 118110

7 3090 2966 107 1497 1479 107 1417 1400 107 1215 1200 107 1173 1159 107 987 975 107 1398 1382 107 1214 120010

8 3093 2969 108 1504 1486 108 1418 1401 108 1221 1206 108 1178 1164 108 990 978 108 1399 1383 108 1215 120010

9 3097 2973 109 1510 1492 109 1431 1414 109 1223 1208 109 1183 1169 109 993 981 109 1412 1395 109 1220 120511

0 3100 2976 110 1521 1503 110 1433 1416 110 1229 1214 110 1183 1169 110 1000 988 110 1414 1397 110 1221 120611 3155 3029 111 1532 1514 111 1458 1440 111 1231 1216 111 1211 1196 111 1004 992 111 1432 1415 111 1222 1207

111

2 3161 3035 112 1543 1524 112 1460 1442 112 1234 1219 112 1211 1197 112 1007 995 112 1433 1416 112 1223 120811

3 3170 3043 113 1570 1551 113 1475 1457 113 1270 1254 113 1215 1201 113 1007 995 113 1452 1435 113 1224 120911

4 3175 3048 114 1608 1589 114 1482 1464 114 1283 1268 114 1221 1206 114 1008 996 114 1473 1455 114 1234 121911

5 3190 3062 115 1632 1612 115 1488 1470 115 1306 1291 115 1223 1208 115 1034 1022 115 1483 1465 115 1270 125411

6 3197 3069 116 1645 1625 116 1491 1473 116 1307 1292 116 1234 1219 116 1037 1024 116 1487 1469 116 1283 126811

7 3197 3070 117 1650 1630 117 1496 1478 117 1327 1311 117 1271 1256 117 1039 1027 117 1488 1470 117 1329 131311

8 3203 3075 118 3021 2900 118 1503 1485 118 1327 1311 118 1284 1268 118 1044 1031 118 1491 1473 118 1333 131711

9 3429 3291 119 3021 2900 119 1503 1485 119 1329 1313 119 1307 1291 119 1046 1034 119 1497 1479 119 1341 132412

0 3529 3388 120 3029 2907 120 1504 1486 120 1334 1318 120 1308 1292 120 1047 1034 120 1498 1480 120 1373 1357121 3046 2924 121 1510 1492 121 1340 1324 121 1329 1313 121 1048 1036 121 1499 1481 121 1385 1368122 3047 2925 122 1510 1492 122 1344 1327 122 1332 1316 122 1049 1037 122 1504 1486 122 1397 1381123 3083 2960 123 1511 1493 123 1347 1331 123 1339 1323 123 1055 1043 123 1509 1491 123 1398 1381124 3083 2960 124 1521 1503 124 1375 1358 124 1356 1340 124 1061 1048 124 1510 1492 124 1400 1383125 3090 2967 125 1533 1515 125 1387 1370 125 1357 1341 125 1061 1049 125 1521 1503 125 1401 1384126 3091 2967 126 1543 1524 126 1387 1370 126 1372 1356 126 1067 1054 126 1525 1507 126 1402 1385127 3096 2972 127 1570 1551 127 1387 1371 127 1384 1368 127 1067 1054 127 1543 1525 127 1403 1386128 3098 2975 128 1608 1589 128 1398 1381 128 1396 1380 128 1068 1055 128 1573 1554 128 1413 1396129 3127 3002 129 1631 1612 129 1399 1383 129 1397 1381 129 1072 1059 129 1607 1588 129 1428 1411130 3128 3003 130 1644 1624 130 1414 1397 130 1414 1397 130 1128 1114 130 1632 1613 130 1431 1414131 3128 3003 131 1650 1630 131 1414 1397 131 1430 1413 131 1130 1117 131 1645 1625 131 1432 1415132 3141 3015 132 3019 2898 132 1414 1397 132 1432 1415 132 1132 1118 132 1649 1629 132 1432 1415133 3141 3016 133 3019 2898 133 1431 1414 133 1460 1442 133 1140 1126 133 3006 2885 133 1473 1455134 3159 3032 134 3020 2900 134 1432 1415 134 1460 1443 134 1150 1136 134 3014 2893 134 1480 1462

135 3166 3040 135 3021 2900 135 1456 1438 135 1474 1457 135 1175 1160 135 3020 2899 135 1482 1464136 3173 3046 136 3028 2907 136 1457 1440 136 1482 1464 136 1177 1163 136 3021 2900 136 1483 1465137 3191 3063 137 3039 2918 137 1475 1457 137 1487 1469 137 1187 1173 137 3022 2901 137 1486 1469138 3192 3064 138 3041 2920 138 1482 1464 138 1491 1473 138 1189 1175 138 3028 2907 138 1487 1469139 3196 3069 139 3073 2950 139 1487 1470 139 1497 1479 139 1211 1197 139 3029 2908 139 1488 1470140 3203 3075 140 3073 2951 140 1488 1470 140 1504 1486 140 1212 1197 140 3048 2926 140 1489 1471141 3207 3079 141 3078 2955 141 1488 1470 141 1508 1490 141 1217 1202 141 3051 2929 141 1492 1474

142 3078 2955 142 1491 1473 142 1510 1492 142 1222 1207 142 3081 2958 142 1492 1474143 3083 2960 143 1496 1478 143 1511 1493 143 1224 1210 143 3083 2960 143 1497 1479144 3083 2960 144 1497 1479 144 1522 1503 144 1234 1219 144 3084 2961 144 1502 1484145 3090 2966 145 1497 1479 145 1532 1514 145 1249 1234 145 3086 2962 145 1504 1486146 3091 2967 146 1500 1482 146 1543 1524 146 1251 1236 146 3091 2967 146 1506 1488147 3095 2972 147 1500 1482 147 1573 1554 147 1254 1239 147 3092 2968 147 1508 1490148 3098 2974 148 1504 1486 148 1606 1587 148 1254 1239 148 3097 2973 148 1508 1490149 3099 2975 149 1509 1491 149 1608 1589 149 1270 1255 149 3101 2977 149 1509 1491150 3099 2975 150 1510 1492 150 1611 1592 150 1284 1269 150 3102 2978 150 1514 1495151 3126 3001 151 1510 1492 151 1621 1602 151 1290 1275 151 3133 3007 151 1518 1500152 3158 3032 152 1521 1503 152 1622 1602 152 1292 1277 152 3163 3036 152 1522 1503153 3166 3039 153 1533 1514 153 1635 1615 153 1305 1289 153 3170 3043 153 1535 1517154 3173 3046 154 1543 1524 154 1644 1625 154 1305 1290 154 3173 3046 154 1542 1524155 3190 3062 155 1570 1551 155 1649 1630 155 1323 1307 155 3193 3066 155 1571 1552156 3191 3063 156 1608 1589 156 3020 2900 156 1325 1309 156 3194 3066 156 1608 1589157 3196 3068 157 1631 1612 157 3021 2900 157 1328 1312 157 3199 3071 157 1632 1612158 3203 3074 158 1644 1624 158 3029 2908 158 1330 1314 158 3203 3075 158 1644 1624159 3207 3079 159 1650 1630 159 3083 2959 159 1330 1314 159 3209 3080 159 1649 1629

160 3002 2882 160 3083 2960 160 1336 1320 160 2989 2870161 3002 2882 161 3090 2967 161 1337 1321 161 2989 2870162 3010 2890 162 3092 2968 162 1340 1324 162 2990 2870163 3010 2890 163 3096 2972 163 1342 1326 163 2990 2871164 3019 2898 164 3099 2975 164 1346 1330 164 2995 2875165 3019 2898 165 3128 3003 165 1349 1333 165 2997 2877

166 3020 2899 166 3157 3031 166 1352 1335 166 3020 2899167 3021 2900 167 3157 3031 167 1352 1336 167 3021 2900168 3023 2902 168 3160 3034 168 1377 1360 168 3028 2907169 3023 2902 169 3166 3039 169 1384 1367 169 3051 2929170 3028 2907 170 3166 3039 170 1384 1367 170 3052 2930171 3032 2911 171 3167 3040 171 1389 1373 171 3054 2932172 3034 2912 172 3172 3045 172 1399 1383 172 3055 2932173 3046 2924 173 3177 3050 173 1400 1383 173 3057 2935174 3046 2924 174 3177 3050 174 1400 1383 174 3059 2937175 3079 2956 175 3184 3056 175 1401 1384 175 3083 2959176 3079 2956 176 3184 3057 176 1402 1386 176 3083 2960177 3083 2959 177 3188 3060 177 1403 1386 177 3085 2961178 3083 2960 178 3188 3061 178 1416 1399 178 3085 2962179 3083 2960 179 3189 3062 179 1417 1400 179 3090 2966180 3084 2960 180 3191 3063 180 1417 1400 180 3091 2967181 3084 2960 181 3197 3069 181 1433 1415 181 3095 2971182 3084 2961 182 3204 3076 182 1435 1417 182 3098 2974183 3089 2966 183 3206 3078 183 1457 1439 183 3099 2975184 3091 2967 184 1460 1442 184 3100 2976185 3095 2971 185 1478 1460 185 3102 2978186 3098 2974 186 1485 1467 186 3102 2978187 3126 3001 187 1486 1468 187 3125 3000188 3158 3031 188 1486 1468 188 3158 3032189 3165 3039 189 1488 1470 189 3165 3039190 3172 3045 190 1488 1470 190 3172 3045191 3189 3062 191 1489 1472 191 3189 3061192 3191 3063 192 1490 1472 192 3191 3063193 3196 3068 193 1490 1473 193 3196 3068194 3202 3074 194 1494 1476 194 3203 3075195 3207 3078 195 1495 1477 195 3206 3078

196 1495 1477

197 1499 1481198 1501 1483199 1502 1484200 1503 1485201 1503 1485202 1506 1488203 1511 1492204 1511 1493205 1511 1493206 1517 1498207 1517 1499208 1524 1506209 1539 1521210 1545 1526211 1573 1554212 1611 1592213 1635 1616214 1649 1629215 1653 1633216 2992 2873217 2993 2873218 2994 2874219 2994 2874220 2997 2877221 2997 2877222 3003 2883223 3003 2883224 3009 2889225 3009 2889226 3010 2889227 3010 2889

228 3013 2892229 3013 2893230 3015 2894231 3015 2894232 3019 2899233 3019 2899234 3022 2901235 3023 2902236 3023 2902237 3023 2902238 3030 2909239 3035 2913240 3035 2914241 3035 2914242 3037 2915243 3047 2925244 3047 2925245 3056 2934246 3057 2934247 3080 2957248 3080 2957249 3084 2961250 3085 2961251 3085 2961252 3085 2962253 3086 2963254 3088 2965255 3093 2969256 3093 2969257 3100 2976258 3103 2979

259 3128 3003260 3158 3031261 3165 3038262 3172 3045263 3190 3062264 3193 3066265 3196 3068266 3205 3077267 3209 3080