# Supplementary Material (ESI) for Dalton Transactions
# This journal is (c) The Royal Society of Chemistry 2009

data_global

_journal_coden_Cambridge         222

loop_
_publ_author_name
'John Spencer'
'Samantha Callear'
'Angela Casini'
'Paul Joseph Dyson'
'Michael B. Hursthouse'
'Michel Pfeffer'
'Rajendra P. Rathnam'
'Santosh K. Velhanda'
'Olivier Zava'

_publ_contact_author_name        'John Spencer'
_publ_contact_author_email       J.SPENCER@GRE.AC.UK

_publ_section_title              
;
Excellent correlation between cathepsin B
inhibition and cytotoxicity for a series of palladacycles

;

# Attachment 'Pdcycle_cif.txt'

data_5b
_database_code_depnum_ccdc_archive 'CCDC 736873'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C14 H21 Cl N3 P Pd S'
_chemical_formula_weight         436.22

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 '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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pd Pd -0.9988 1.0072 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   P21/c

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   6.2066(3)
_cell_length_b                   17.1960(8)
_cell_length_c                   15.1712(6)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.442(2)
_cell_angle_gamma                90.00
_cell_volume                     1619.15(13)
_cell_formula_units_Z            4
_cell_measurement_temperature    120(2)
_cell_measurement_reflns_used    16828
_cell_measurement_theta_min      2.91
_cell_measurement_theta_max      27.48

_exptl_crystal_description       plate
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.01
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.789
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             880
_exptl_absorpt_coefficient_mu    1.535
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8742
_exptl_absorpt_correction_T_max  0.9848
_exptl_absorpt_process_details   'SADABS 2007/2 (Sheldrick, G.M., 2007)'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      120(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'Bruker-Nonius FR591 rotating anode'
_diffrn_radiation_monochromator  '10cm confocal mirrors'
_diffrn_measurement_device_type  
'Bruker-Nonius APEX II CCD camera on \k-goniostat'
_diffrn_measurement_method       '\f & \w scans'
_diffrn_detector_area_resol_mean '4096x4096pixels / 62x62mm'
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            15933
_diffrn_reflns_av_R_equivalents  0.1108
_diffrn_reflns_av_sigmaI/netI    0.0836
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.94
_diffrn_reflns_theta_max         25.00
_reflns_number_total             2837
_reflns_number_gt                2098
_reflns_threshold_expression     >2\s(I)

_computing_data_collection       'COLLECT (Hooft, R.W.W., 1998)'
_computing_cell_refinement       
'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, R.W.W., 1998)'
#Although determined using DirAx, the cell is refined in the HKL
#package during data reduction
_computing_data_reduction        
'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, R.W.W., 1998)'
_computing_structure_solution    'SHELXS97 (G. M. Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_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^ > 2\s(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^)+(0.0000P)^2^+28.3993P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2837
_refine_ls_number_parameters     191
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1154
_refine_ls_R_factor_gt           0.0780
_refine_ls_wR_factor_ref         0.1527
_refine_ls_wR_factor_gt          0.1363
_refine_ls_goodness_of_fit_ref   1.168
_refine_ls_restrained_S_all      1.168
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.2540(15) 0.6738(5) 0.1832(6) 0.016(2) Uani 1 1 d . . .
C2 C 0.2038(17) 0.6916(6) 0.2687(6) 0.024(2) Uani 1 1 d . . .
H2 H 0.0661 0.7123 0.2822 0.028 Uiso 1 1 calc R . .
C3 C 0.3542(18) 0.6794(6) 0.3355(7) 0.029(3) Uani 1 1 d . . .
H3 H 0.3219 0.6946 0.3942 0.035 Uiso 1 1 calc R . .
C4 C 0.547(2) 0.6458(7) 0.3177(8) 0.038(3) Uani 1 1 d . . .
H4 H 0.6484 0.6388 0.3643 0.046 Uiso 1 1 calc R . .
C5 C 0.6006(18) 0.6217(6) 0.2343(9) 0.034(3) Uani 1 1 d . . .
H5 H 0.7331 0.5959 0.2232 0.041 Uiso 1 1 calc R . .
C6 C 0.4506(17) 0.6365(6) 0.1655(7) 0.024(2) Uani 1 1 d . . .
C7 C 0.4993(17) 0.6122(6) 0.0735(7) 0.028(3) Uani 1 1 d . . .
H7A H 0.6055 0.5692 0.0734 0.034 Uiso 1 1 calc R . .
H7B H 0.5586 0.6563 0.0395 0.034 Uiso 1 1 calc R . .
C8 C 0.299(2) 0.5902(7) -0.0898(6) 0.033(3) Uani 1 1 d . . .
H8A H 0.4238 0.5581 -0.1051 0.049 Uiso 1 1 calc R . .
H8B H 0.3298 0.6448 -0.1032 0.049 Uiso 1 1 calc R . .
H8C H 0.1733 0.5731 -0.1243 0.049 Uiso 1 1 calc R . .
C9 C 0.0727(18) 0.8670(6) 0.2115(7) 0.025(2) Uani 1 1 d . . .
H9A H 0.0672 0.8374 0.2674 0.030 Uiso 1 1 calc R . .
H9B H 0.2261 0.8754 0.1968 0.030 Uiso 1 1 calc R . .
C11 C -0.2617(19) 0.9338(7) 0.2466(8) 0.035(3) Uani 1 1 d . . .
H11A H -0.2702 0.9002 0.2994 0.043 Uiso 1 1 calc R . .
H11B H -0.3210 0.9853 0.2627 0.043 Uiso 1 1 calc R . .
C13 C -0.3356(16) 0.8194(7) 0.1611(9) 0.035(3) Uani 1 1 d . . .
H13B H -0.4343 0.7976 0.1159 0.042 Uiso 1 1 calc R . .
H13A H -0.3535 0.7886 0.2158 0.042 Uiso 1 1 calc R . .
C14 C -0.062(2) 0.8852(6) 0.0368(7) 0.029(3) Uani 1 1 d . . .
H14A H 0.0869 0.8947 0.0163 0.035 Uiso 1 1 calc R . .
H14B H -0.1479 0.8665 -0.0142 0.035 Uiso 1 1 calc R . .
C16 C -0.0261(17) 0.9898(6) 0.1423(7) 0.027(3) Uani 1 1 d . . .
H16A H -0.0763 1.0431 0.1554 0.032 Uiso 1 1 calc R . .
H16B H 0.1258 0.9934 0.1234 0.032 Uiso 1 1 calc R . .
C17 C -0.3750(19) 0.9480(7) 0.0988(8) 0.038(3) Uani 1 1 d . . .
H17A H -0.4589 0.9231 0.0508 0.046 Uiso 1 1 calc R . .
H17B H -0.4394 0.9997 0.1099 0.046 Uiso 1 1 calc R . .
N10 N -0.0344(14) 0.9437(5) 0.2239(6) 0.025(2) Uani 1 1 d . . .
N12 N -0.3963(15) 0.9008(5) 0.1787(7) 0.035(2) Uani 1 1 d . . .
N15 N -0.1546(15) 0.9589(5) 0.0693(6) 0.025(2) Uani 1 1 d . . .
P1 P -0.0570(4) 0.80951(16) 0.12304(16) 0.0179(6) Uani 1 1 d . . .
S1 S 0.2434(4) 0.58012(16) 0.02589(17) 0.0241(6) Uani 1 1 d . . .
Cl1 Cl -0.1329(4) 0.71129(15) -0.05990(16) 0.0236(6) Uani 1 1 d . . .
Pd1 Pd 0.06606(12) 0.69335(5) 0.07482(5) 0.0175(2) Uani 1 1 d . . .

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
C1 0.016(5) 0.015(6) 0.017(5) 0.001(4) -0.004(4) 0.001(4)
C2 0.032(6) 0.024(6) 0.015(5) 0.007(5) -0.004(4) -0.008(5)
C3 0.041(7) 0.023(7) 0.024(6) 0.004(5) -0.004(5) -0.011(5)
C4 0.052(8) 0.025(7) 0.037(7) 0.006(6) -0.026(6) -0.002(6)
C5 0.023(6) 0.015(6) 0.065(9) 0.008(6) -0.014(6) 0.003(5)
C6 0.026(6) 0.019(6) 0.026(6) -0.004(5) 0.000(5) -0.006(5)
C7 0.028(6) 0.016(6) 0.041(7) 0.005(5) -0.001(6) 0.002(4)
C8 0.046(7) 0.042(7) 0.009(5) -0.004(5) 0.004(5) 0.010(6)
C9 0.036(6) 0.017(6) 0.021(6) -0.011(5) -0.009(5) 0.006(5)
C11 0.048(8) 0.020(6) 0.038(7) 0.001(5) 0.030(6) 0.012(5)
C13 0.017(5) 0.029(7) 0.058(8) -0.002(6) -0.002(5) -0.003(5)
C14 0.050(7) 0.018(6) 0.020(6) 0.001(5) -0.011(5) 0.001(5)
C16 0.022(6) 0.019(6) 0.039(7) -0.004(5) 0.006(5) -0.012(5)
C17 0.036(7) 0.031(7) 0.047(8) -0.002(6) -0.016(6) 0.007(5)
N10 0.036(5) 0.017(5) 0.021(5) -0.001(4) -0.008(4) 0.005(4)
N12 0.030(5) 0.021(5) 0.055(7) -0.003(5) 0.008(5) 0.000(4)
N15 0.039(6) 0.009(4) 0.025(5) 0.003(4) -0.008(4) 0.000(4)
P1 0.0191(13) 0.0171(14) 0.0173(13) 0.0018(12) -0.0001(10) 0.0002(11)
S1 0.0291(15) 0.0208(15) 0.0224(14) -0.0026(12) 0.0006(12) 0.0035(12)
Cl1 0.0286(14) 0.0249(15) 0.0171(13) 0.0030(11) -0.0043(11) 0.0001(11)
Pd1 0.0193(4) 0.0174(4) 0.0157(4) 0.0005(4) -0.0002(3) 0.0010(4)

_geom_special_details            
;
All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell s.u.'s are taken
into account individually in the estimation of s.u.'s in distances, angles
and torsion angles; correlations between s.u.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 C2 1.370(13) . ?
C1 C6 1.407(14) . ?
C1 Pd1 2.037(9) . ?
C2 C3 1.389(15) . ?
C2 H2 0.9500 . ?
C3 C4 1.359(16) . ?
C3 H3 0.9500 . ?
C4 C5 1.375(17) . ?
C4 H4 0.9500 . ?
C5 C6 1.416(15) . ?
C5 H5 0.9500 . ?
C6 C7 1.491(15) . ?
C7 S1 1.825(11) . ?
C7 H7A 0.9900 . ?
C7 H7B 0.9900 . ?
C8 S1 1.800(10) . ?
C8 H8A 0.9800 . ?
C8 H8B 0.9800 . ?
C8 H8C 0.9800 . ?
C9 N10 1.489(13) . ?
C9 P1 1.847(10) . ?
C9 H9A 0.9900 . ?
C9 H9B 0.9900 . ?
C11 N12 1.438(16) . ?
C11 N10 1.465(14) . ?
C11 H11A 0.9900 . ?
C11 H11B 0.9900 . ?
C13 N12 1.475(14) . ?
C13 P1 1.835(11) . ?
C13 H13B 0.9900 . ?
C13 H13A 0.9900 . ?
C14 N15 1.478(13) . ?
C14 P1 1.846(11) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C16 N15 1.461(13) . ?
C16 N10 1.470(13) . ?
C16 H16A 0.9900 . ?
C16 H16B 0.9900 . ?
C17 N15 1.455(15) . ?
C17 N12 1.465(15) . ?
C17 H17A 0.9900 . ?
C17 H17B 0.9900 . ?
P1 Pd1 2.262(3) . ?
S1 Pd1 2.359(3) . ?
Cl1 Pd1 2.400(3) . ?

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_3
_geom_angle_publ_flag
C2 C1 C6 119.1(9) . . ?
C2 C1 Pd1 126.5(7) . . ?
C6 C1 Pd1 114.4(7) . . ?
C1 C2 C3 120.1(10) . . ?
C1 C2 H2 120.0 . . ?
C3 C2 H2 120.0 . . ?
C4 C3 C2 120.5(11) . . ?
C4 C3 H3 119.8 . . ?
C2 C3 H3 119.8 . . ?
C3 C4 C5 122.1(11) . . ?
C3 C4 H4 119.0 . . ?
C5 C4 H4 119.0 . . ?
C4 C5 C6 117.5(11) . . ?
C4 C5 H5 121.3 . . ?
C6 C5 H5 121.3 . . ?
C1 C6 C5 120.6(10) . . ?
C1 C6 C7 119.3(9) . . ?
C5 C6 C7 120.1(10) . . ?
C6 C7 S1 105.9(7) . . ?
C6 C7 H7A 110.6 . . ?
S1 C7 H7A 110.6 . . ?
C6 C7 H7B 110.6 . . ?
S1 C7 H7B 110.6 . . ?
H7A C7 H7B 108.7 . . ?
S1 C8 H8A 109.5 . . ?
S1 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
S1 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?
N10 C9 P1 111.9(7) . . ?
N10 C9 H9A 109.2 . . ?
P1 C9 H9A 109.2 . . ?
N10 C9 H9B 109.2 . . ?
P1 C9 H9B 109.2 . . ?
H9A C9 H9B 107.9 . . ?
N12 C11 N10 115.7(9) . . ?
N12 C11 H11A 108.4 . . ?
N10 C11 H11A 108.4 . . ?
N12 C11 H11B 108.4 . . ?
N10 C11 H11B 108.4 . . ?
H11A C11 H11B 107.4 . . ?
N12 C13 P1 112.8(7) . . ?
N12 C13 H13B 109.0 . . ?
P1 C13 H13B 109.0 . . ?
N12 C13 H13A 109.0 . . ?
P1 C13 H13A 109.0 . . ?
H13B C13 H13A 107.8 . . ?
N15 C14 P1 111.8(7) . . ?
N15 C14 H14A 109.3 . . ?
P1 C14 H14A 109.3 . . ?
N15 C14 H14B 109.3 . . ?
P1 C14 H14B 109.3 . . ?
H14A C14 H14B 107.9 . . ?
N15 C16 N10 114.9(8) . . ?
N15 C16 H16A 108.6 . . ?
N10 C16 H16A 108.6 . . ?
N15 C16 H16B 108.6 . . ?
N10 C16 H16B 108.6 . . ?
H16A C16 H16B 107.5 . . ?
N15 C17 N12 114.6(9) . . ?
N15 C17 H17A 108.6 . . ?
N12 C17 H17A 108.6 . . ?
N15 C17 H17B 108.6 . . ?
N12 C17 H17B 108.6 . . ?
H17A C17 H17B 107.6 . . ?
C11 N10 C16 107.4(8) . . ?
C11 N10 C9 111.0(9) . . ?
C16 N10 C9 110.6(8) . . ?
C11 N12 C17 108.5(9) . . ?
C11 N12 C13 110.9(9) . . ?
C17 N12 C13 110.6(10) . . ?
C17 N15 C16 108.8(9) . . ?
C17 N15 C14 111.3(9) . . ?
C16 N15 C14 110.7(9) . . ?
C13 P1 C14 98.5(6) . . ?
C13 P1 C9 97.4(5) . . ?
C14 P1 C9 98.2(5) . . ?
C13 P1 Pd1 120.3(4) . . ?
C14 P1 Pd1 113.4(4) . . ?
C9 P1 Pd1 124.1(3) . . ?
C8 S1 C7 100.6(5) . . ?
C8 S1 Pd1 108.7(4) . . ?
C7 S1 Pd1 91.9(4) . . ?
C1 Pd1 P1 94.4(3) . . ?
C1 Pd1 S1 81.5(3) . . ?
P1 Pd1 S1 171.90(10) . . ?
C1 Pd1 Cl1 175.3(3) . . ?
P1 Pd1 Cl1 89.37(9) . . ?
S1 Pd1 Cl1 94.38(9) . . ?

_diffrn_measured_fraction_theta_max 0.996
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.996
_refine_diff_density_max         0.851
_refine_diff_density_min         -0.779
_refine_diff_density_rms         0.206