# Electronic Supplementary Material (ESI) for Polymer Chemistry.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_1_sq
_database_code_depnum_ccdc_archive 'CCDC 1868503'
_audit_update_record             
;
2018-09-29 deposited with the CCDC.
2018-12-06 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C31 H38 Cl2 O5 P S'
_chemical_formula_weight         624.54

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'
O O 0.0106 0.0060 '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'

_space_group_crystal_system      hexagonal
_space_group_IT_number           170
_space_group_name_H-M_alt        'P 65'
_space_group_name_Hall           'P 65'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z+2/3'
'-x+y, -x, z+1/3'
'-x, -y, z+1/2'
'y, -x+y, z+1/6'
'x-y, x, z+5/6'

_cell_length_a                   22.6855(8)
_cell_length_b                   22.6855(8)
_cell_length_c                   10.7563(7)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     4793.9(5)
_cell_formula_units_Z            6
_cell_measurement_temperature    185(2)
_cell_measurement_reflns_used    4824
_cell_measurement_theta_min      2.6096
_cell_measurement_theta_max      19.7500

_exptl_crystal_description       block
_exptl_crystal_colour            white
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.298
_exptl_crystal_F_000             1974
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.320
_exptl_crystal_size_mid          0.110
_exptl_crystal_size_min          0.080
_exptl_absorpt_coefficient_mu    0.356
_shelx_estimated_absorpt_T_min   0.895
_shelx_estimated_absorpt_T_max   0.972
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      185(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            24765
_diffrn_reflns_av_unetI/netI     0.0472
_diffrn_reflns_av_R_equivalents  0.0598
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         1.795
_diffrn_reflns_theta_max         24.987
_diffrn_reflns_theta_full        24.987
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.890
_diffrn_reflns_point_group_measured_fraction_full 0.890
_reflns_number_total             5002
_reflns_number_gt                4358
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.682
_reflns_Friedel_fraction_max     0.766
_reflns_Friedel_fraction_full    0.766

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          SQUEEZE
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1187P)²+2.4333P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 1463 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.05(5)
_chemical_absolute_configuration ad
_refine_ls_number_reflns         5002
_refine_ls_number_parameters     365
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0623
_refine_ls_R_factor_gt           0.0514
_refine_ls_wR_factor_ref         0.1592
_refine_ls_wR_factor_gt          0.1419
_refine_ls_goodness_of_fit_ref   0.934
_refine_ls_restrained_S_all      0.934
_refine_ls_shift/su_max          0.059
_refine_ls_shift/su_mean         0.003

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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
S1 S 0.37081(7) 0.33395(7) 0.27029(16) 0.0340(4) Uani 1 1 d . . . . .
P1 P 0.29131(6) 0.42204(7) 0.32748(14) 0.0249(3) Uani 1 1 d . . . . .
C1 C 0.3143(2) 0.3389(2) 0.1610(6) 0.0270(11) Uani 1 1 d . . . . .
C2 C 0.2818(3) 0.3772(3) 0.1827(5) 0.0262(11) Uani 1 1 d . . . . .
C3 C 0.2390(3) 0.3801(3) 0.0936(6) 0.0314(12) Uani 1 1 d . . . . .
H3A H 0.2183 0.4060 0.1083 0.038 Uiso 1 1 calc R U . . .
C4 C 0.2269(3) 0.3449(3) -0.0161(7) 0.0412(14) Uani 1 1 d . . . . .
H4A H 0.1977 0.3465 -0.0748 0.049 Uiso 1 1 calc R U . . .
C5 C 0.2583(3) 0.3071(3) -0.0395(6) 0.0425(15) Uani 1 1 d . . . . .
H5A H 0.2502 0.2833 -0.1138 0.051 Uiso 1 1 calc R U . . .
C6 C 0.3018(3) 0.3049(3) 0.0485(6) 0.0350(13) Uani 1 1 d . . . . .
H6A H 0.3232 0.2800 0.0315 0.042 Uiso 1 1 calc R U . . .
C7 C 0.2303(2) 0.3660(3) 0.4439(6) 0.0291(12) Uani 1 1 d . . . . .
H7A H 0.2484 0.3378 0.4761 0.035 Uiso 1 1 calc R U . . .
C8 C 0.2248(3) 0.4049(3) 0.5561(6) 0.0302(12) Uani 1 1 d . . . . .
H8A H 0.2040 0.4310 0.5259 0.036 Uiso 1 1 calc R U . . .
C9 C 0.1753(3) 0.3534(3) 0.6505(6) 0.0423(15) Uani 1 1 d . . . . .
H9A H 0.1949 0.3272 0.6839 0.051 Uiso 1 1 calc R U . . .
H9B H 0.1692 0.3778 0.7189 0.051 Uiso 1 1 calc R U . . .
C10 C 0.1069(3) 0.3054(3) 0.5943(7) 0.0470(17) Uani 1 1 d . . . . .
H10A H 0.0782 0.2729 0.6570 0.056 Uiso 1 1 calc R U . . .
H10B H 0.0853 0.3311 0.5686 0.056 Uiso 1 1 calc R U . . .
C11 C 0.1118(3) 0.2671(3) 0.4837(7) 0.0386(14) Uani 1 1 d . . . . .
H11A H 0.1305 0.2388 0.5126 0.046 Uiso 1 1 calc R U . . .
C12 C 0.1601(3) 0.3162(3) 0.3870(6) 0.0365(14) Uani 1 1 d . . . . .
H12A H 0.1405 0.3419 0.3517 0.044 Uiso 1 1 calc R U . . .
H12B H 0.1659 0.2907 0.3205 0.044 Uiso 1 1 calc R U . . .
C13 C 0.2942(3) 0.4562(3) 0.6117(6) 0.0342(13) Uani 1 1 d . . . . .
H13A H 0.3204 0.4889 0.5461 0.041 Uiso 1 1 calc R U . . .
C14 C 0.2880(4) 0.4964(4) 0.7195(7) 0.0516(18) Uani 1 1 d . . . . .
H14A H 0.3325 0.5277 0.7510 0.077 Uiso 1 1 calc R U . . .
H14B H 0.2666 0.5212 0.6909 0.077 Uiso 1 1 calc R U . . .
H14C H 0.2610 0.4656 0.7843 0.077 Uiso 1 1 calc R U . . .
C15 C 0.3365(3) 0.4237(4) 0.6564(8) 0.0508(17) Uani 1 1 d . . . . .
H15A H 0.3410 0.3981 0.5896 0.076 Uiso 1 1 calc R U . . .
H15B H 0.3808 0.4589 0.6819 0.076 Uiso 1 1 calc R U . . .
H15C H 0.3139 0.3940 0.7253 0.076 Uiso 1 1 calc R U . . .
C16 C 0.0415(3) 0.2199(4) 0.4273(8) 0.0558(19) Uani 1 1 d . . . . .
H16A H 0.0461 0.1963 0.3574 0.084 Uiso 1 1 calc R U . . .
H16B H 0.0127 0.1875 0.4887 0.084 Uiso 1 1 calc R U . . .
H16C H 0.0215 0.2464 0.4006 0.084 Uiso 1 1 calc R U . . .
C17 C 0.2827(3) 0.4955(3) 0.3020(5) 0.0258(11) Uani 1 1 d . . . . .
C18 C 0.2168(3) 0.4868(3) 0.2876(5) 0.0303(12) Uani 1 1 d . . . . .
H18A H 0.1792 0.4431 0.2864 0.036 Uiso 1 1 calc R U . . .
C19 C 0.2076(3) 0.5419(3) 0.2753(6) 0.0364(14) Uani 1 1 d . . . . .
H19A H 0.1641 0.5356 0.2650 0.044 Uiso 1 1 calc R U . . .
C20 C 0.2630(3) 0.6061(3) 0.2785(7) 0.0411(15) Uani 1 1 d . . . . .
H20A H 0.2567 0.6435 0.2724 0.049 Uiso 1 1 calc R U . . .
C21 C 0.3282(3) 0.6163(3) 0.2906(7) 0.0391(15) Uani 1 1 d . . . . .
H21A H 0.3651 0.6604 0.2914 0.047 Uiso 1 1 calc R U . . .
C22 C 0.3393(3) 0.5614(3) 0.3016(6) 0.0289(12) Uani 1 1 d . . . . .
C23 C 0.4109(3) 0.5752(3) 0.3135(6) 0.0289(12) Uani 1 1 d . . . . .
C24 C 0.4408(3) 0.5587(3) 0.2162(6) 0.0322(12) Uani 1 1 d . . . . .
C25 C 0.5098(3) 0.5775(3) 0.2245(7) 0.0415(15) Uani 1 1 d . . . . .
H25A H 0.5306 0.5675 0.1599 0.050 Uiso 1 1 calc R U . . .
C26 C 0.5463(3) 0.6107(3) 0.3284(7) 0.0425(15) Uani 1 1 d . . . . .
H26A H 0.5920 0.6233 0.3325 0.051 Uiso 1 1 calc R U . . .
C27 C 0.5175(3) 0.6259(3) 0.4270(7) 0.0377(14) Uani 1 1 d . . . . .
H27A H 0.5428 0.6471 0.4979 0.045 Uiso 1 1 calc R U . . .
C28 C 0.4497(3) 0.6089(3) 0.4178(6) 0.0325(13) Uani 1 1 d . . . . .
C29 C 0.4246(4) 0.4954(3) 0.0292(7) 0.0454(16) Uani 1 1 d . . . . .
H29A H 0.3907 0.4727 -0.0340 0.068 Uiso 1 1 calc R U . . .
H29B H 0.4655 0.5309 -0.0079 0.068 Uiso 1 1 calc R U . . .
H29C H 0.4341 0.4633 0.0693 0.068 Uiso 1 1 calc R U . . .
C30 C 0.4527(3) 0.6515(4) 0.6235(6) 0.0458(16) Uani 1 1 d . . . . .
H30A H 0.4242 0.6587 0.6801 0.069 Uiso 1 1 calc R U . . .
H30B H 0.4655 0.6210 0.6603 0.069 Uiso 1 1 calc R U . . .
H30C H 0.4929 0.6942 0.6060 0.069 Uiso 1 1 calc R U . . .
C100 C 0.0694(6) 0.2087(6) 0.0357(12) 0.106(4) Uani 1 1 d . . . . .
H10C H 0.1063 0.2085 0.0808 0.127 Uiso 1 1 calc R U . . .
H10D H 0.0746 0.2536 0.0447 0.127 Uiso 1 1 calc R U . . .
O1 O 0.3800(2) 0.2795(2) 0.2250(6) 0.0562(13) Uani 1 1 d . . . . .
O2 O 0.3353(2) 0.3202(3) 0.3870(5) 0.0532(13) Uani 1 1 d . . . . .
O3 O 0.4309(2) 0.3993(2) 0.2656(5) 0.0494(12) Uani 1 1 d . . . . .
O5 O 0.41642(18) 0.6227(2) 0.5105(4) 0.0375(10) Uani 1 1 d . . . . .
O4 O 0.3997(2) 0.5245(2) 0.1197(4) 0.0373(10) Uani 1 1 d . . . . .
Cl1 Cl -0.00332(17) 0.1522(2) 0.0984(4) 0.1324(14) Uani 1 1 d . . . . .
Cl2 Cl 0.07635(18) 0.19324(18) -0.1266(3) 0.1127(11) Uani 1 1 d . . . . .
H1 H 0.350(3) 0.443(2) 0.370(5) 0.022(13) Uiso 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds 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
S1 O3 1.428(4) . ?
S1 O2 1.438(5) . ?
S1 O1 1.437(5) . ?
S1 C1 1.784(6) . ?
P1 C17 1.795(5) . ?
P1 C2 1.812(6) . ?
P1 C7 1.828(6) . ?
C1 C6 1.386(8) . ?
C1 C2 1.412(7) . ?
C2 C3 1.390(8) . ?
C3 C4 1.374(9) . ?
C4 C5 1.383(8) . ?
C5 C6 1.386(9) . ?
C7 C12 1.546(8) . ?
C7 C8 1.536(8) . ?
C8 C9 1.531(8) . ?
C8 C13 1.536(8) . ?
C9 C10 1.508(9) . ?
C10 C11 1.509(10) . ?
C11 C16 1.534(9) . ?
C11 C12 1.518(8) . ?
C13 C14 1.525(9) . ?
C13 C15 1.549(8) . ?
C17 C22 1.402(8) . ?
C17 C18 1.414(7) . ?
C18 C19 1.373(7) . ?
C19 C20 1.368(9) . ?
C20 C21 1.384(8) . ?
C21 C22 1.394(7) . ?
C22 C23 1.499(7) . ?
C23 C28 1.393(8) . ?
C23 C24 1.396(8) . ?
C24 O4 1.351(7) . ?
C24 C25 1.404(8) . ?
C25 C26 1.371(10) . ?
C26 C27 1.377(10) . ?
C27 C28 1.389(8) . ?
C28 O5 1.378(7) . ?
C29 O4 1.439(7) . ?
C30 O5 1.430(8) . ?
C100 Cl1 1.645(13) . ?
C100 Cl2 1.803(14) . ?

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
O3 S1 O2 113.3(3) . . ?
O3 S1 O1 114.0(3) . . ?
O2 S1 O1 114.6(3) . . ?
O3 S1 C1 104.7(2) . . ?
O2 S1 C1 104.3(3) . . ?
O1 S1 C1 104.4(3) . . ?
C17 P1 C2 110.6(3) . . ?
C17 P1 C7 110.8(2) . . ?
C2 P1 C7 111.2(3) . . ?
C6 C1 C2 117.6(5) . . ?
C6 C1 S1 119.6(4) . . ?
C2 C1 S1 122.8(4) . . ?
C3 C2 C1 120.5(5) . . ?
C3 C2 P1 117.1(4) . . ?
C1 C2 P1 122.4(4) . . ?
C4 C3 C2 120.3(5) . . ?
C5 C4 C3 120.2(6) . . ?
C4 C5 C6 119.6(6) . . ?
C1 C6 C5 121.8(5) . . ?
C12 C7 C8 112.3(4) . . ?
C12 C7 P1 112.5(4) . . ?
C8 C7 P1 112.9(4) . . ?
C9 C8 C13 113.7(5) . . ?
C9 C8 C7 108.8(5) . . ?
C13 C8 C7 113.2(4) . . ?
C10 C9 C8 112.5(6) . . ?
C11 C10 C9 112.7(5) . . ?
C10 C11 C16 111.2(5) . . ?
C10 C11 C12 110.6(5) . . ?
C16 C11 C12 111.0(6) . . ?
C11 C12 C7 111.5(5) . . ?
C14 C13 C8 112.5(5) . . ?
C14 C13 C15 108.2(6) . . ?
C8 C13 C15 113.8(5) . . ?
C22 C17 C18 119.4(5) . . ?
C22 C17 P1 121.6(4) . . ?
C18 C17 P1 119.0(4) . . ?
C19 C18 C17 120.9(5) . . ?
C20 C19 C18 119.5(5) . . ?
C19 C20 C21 121.0(5) . . ?
C20 C21 C22 121.0(5) . . ?
C21 C22 C17 118.3(5) . . ?
C21 C22 C23 118.9(5) . . ?
C17 C22 C23 122.9(4) . . ?
C28 C23 C24 119.5(5) . . ?
C28 C23 C22 120.3(5) . . ?
C24 C23 C22 120.0(5) . . ?
O4 C24 C23 116.3(5) . . ?
O4 C24 C25 124.6(6) . . ?
C23 C24 C25 119.1(6) . . ?
C26 C25 C24 119.6(6) . . ?
C25 C26 C27 122.3(5) . . ?
C26 C27 C28 118.2(6) . . ?
O5 C28 C23 116.1(5) . . ?
O5 C28 C27 122.7(6) . . ?
C23 C28 C27 121.2(6) . . ?
Cl1 C100 Cl2 113.4(7) . . ?
C28 O5 C30 117.6(4) . . ?
C24 O4 C29 117.8(5) . . ?

_refine_diff_density_max         0.312
_refine_diff_density_min         -0.436
_refine_diff_density_rms         0.063



####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_1
_database_code_depnum_ccdc_archive 'CCDC 1868504'
_audit_update_record             
;
2018-09-29 deposited with the CCDC.
2018-12-06 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C34 H38 F2 N O3 P Pd S'
_chemical_formula_weight         716.08

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'
Pd Pd -0.9988 1.0072 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

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

_cell_length_a                   9.1697(6)
_cell_length_b                   9.5203(6)
_cell_length_c                   36.333(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3171.9(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    185(2)
_cell_measurement_reflns_used    2276
_cell_measurement_theta_min      2.2114
_cell_measurement_theta_max      19.6671

_exptl_crystal_description       plate
_exptl_crystal_colour            transparent
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.500
_exptl_crystal_F_000             1472
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.310
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.050
_exptl_absorpt_coefficient_mu    0.749
_shelx_estimated_absorpt_T_min   0.801
_shelx_estimated_absorpt_T_max   0.964
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      185(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            16352
_diffrn_reflns_av_unetI/netI     0.0869
_diffrn_reflns_av_R_equivalents  0.0751
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         2.211
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_full        25.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             5595
_reflns_number_gt                4534
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.745
_reflns_Friedel_fraction_max     1.000
_reflns_Friedel_fraction_full    1.000

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0369P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    'riding mode'
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 1553 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(3)
_chemical_absolute_configuration ad
_refine_ls_number_reflns         5595
_refine_ls_number_parameters     388
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0662
_refine_ls_R_factor_gt           0.0468
_refine_ls_wR_factor_ref         0.0898
_refine_ls_wR_factor_gt          0.0837
_refine_ls_goodness_of_fit_ref   0.964
_refine_ls_restrained_S_all      0.964
_refine_ls_shift/su_max          0.000
_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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
N1 N 0.6289(6) 0.4086(6) 0.15825(17) 0.0250(15) Uani 1 1 d . . . . .
S1 S 0.2454(2) 0.3030(2) 0.19912(5) 0.0266(5) Uani 1 1 d . . . . .
Pd1 Pd 0.46711(6) 0.27404(6) 0.13678(2) 0.02369(16) Uani 1 1 d . . . . .
P1 P 0.2851(2) 0.1456(2) 0.11363(5) 0.0223(5) Uani 1 1 d . . . . .
F1 F 0.1795(5) -0.2883(5) 0.15310(12) 0.0488(13) Uani 1 1 d . . . . .
F2 F 0.5831(5) 0.0045(5) 0.17219(14) 0.0438(14) Uani 1 1 d . . . . .
C1 C 0.1282(8) 0.1666(8) 0.1820(2) 0.0247(18) Uani 1 1 d . . . . .
C2 C 0.1437(8) 0.1019(7) 0.14771(19) 0.0217(18) Uani 1 1 d . . . . .
C3 C 0.0459(8) -0.0057(7) 0.1391(2) 0.0282(17) Uani 1 1 d . . . . .
H3A H 0.0567 -0.0535 0.1170 0.034 Uiso 1 1 calc R U . . .
C4 C -0.0656(9) -0.0432(8) 0.1624(2) 0.038(2) Uani 1 1 d . . . . .
H4A H -0.1304 -0.1136 0.1555 0.046 Uiso 1 1 calc R U . . .
C5 C -0.0821(9) 0.0227(9) 0.1957(3) 0.042(2) Uani 1 1 d . . . . .
H5A H -0.1568 -0.0027 0.2117 0.050 Uiso 1 1 calc R U . . .
C6 C 0.0151(8) 0.1276(8) 0.2049(2) 0.033(2) Uani 1 1 d . . . . .
H6A H 0.0041 0.1736 0.2273 0.039 Uiso 1 1 calc R U . . .
C7 C 0.1837(7) 0.2356(8) 0.07545(18) 0.0242(17) Uani 1 1 d . . . . .
H7A H 0.2479 0.2334 0.0539 0.029 Uiso 1 1 calc R U . . .
C8 C 0.0330(9) 0.1798(7) 0.0625(2) 0.0262(17) Uani 1 1 d . . . . .
H8A H -0.0299 0.1793 0.0842 0.031 Uiso 1 1 calc R U . . .
C9 C -0.0367(9) 0.2818(7) 0.0352(2) 0.0353(18) Uani 1 1 d . . . . .
H9A H -0.1345 0.2493 0.0296 0.042 Uiso 1 1 calc R U . . .
H9B H 0.0189 0.2800 0.0125 0.042 Uiso 1 1 calc R U . . .
C10 C -0.0454(10) 0.4330(7) 0.0488(2) 0.033(2) Uani 1 1 d . . . . .
H10A H -0.0882 0.4916 0.0298 0.039 Uiso 1 1 calc R U . . .
H10B H -0.1078 0.4375 0.0704 0.039 Uiso 1 1 calc R U . . .
C11 C 0.1031(9) 0.4875(8) 0.0584(2) 0.030(2) Uani 1 1 d . . . . .
H11A H 0.1634 0.4825 0.0362 0.036 Uiso 1 1 calc R U . . .
C12 C 0.1726(9) 0.3919(7) 0.0874(2) 0.031(2) Uani 1 1 d . . . . .
H12A H 0.1156 0.3974 0.1098 0.037 Uiso 1 1 calc R U . . .
H12B H 0.2697 0.4264 0.0929 0.037 Uiso 1 1 calc R U . . .
C13 C 0.0295(10) 0.0295(7) 0.0469(2) 0.0297(19) Uani 1 1 d . . . . .
H13A H 0.0937 -0.0277 0.0623 0.036 Uiso 1 1 calc R U . . .
C14 C -0.1217(10) -0.0342(8) 0.0493(3) 0.043(2) Uani 1 1 d . . . . .
H14A H -0.1568 -0.0270 0.0741 0.065 Uiso 1 1 calc R U . . .
H14B H -0.1865 0.0153 0.0331 0.065 Uiso 1 1 calc R U . . .
H14C H -0.1176 -0.1313 0.0423 0.065 Uiso 1 1 calc R U . . .
C15 C 0.0869(10) 0.0187(9) 0.0073(2) 0.047(3) Uani 1 1 d . . . . .
H15A H 0.1826 0.0592 0.0060 0.071 Uiso 1 1 calc R U . . .
H15B H 0.0915 -0.0783 0.0001 0.071 Uiso 1 1 calc R U . . .
H15C H 0.0226 0.0683 -0.0090 0.071 Uiso 1 1 calc R U . . .
C16 C 0.1001(11) 0.6381(8) 0.0708(2) 0.053(3) Uani 1 1 d . . . . .
H16A H 0.1973 0.6682 0.0766 0.079 Uiso 1 1 calc R U . . .
H16B H 0.0614 0.6958 0.0514 0.079 Uiso 1 1 calc R U . . .
H16C H 0.0395 0.6465 0.0922 0.079 Uiso 1 1 calc R U . . .
C17 C 0.3611(8) -0.0195(8) 0.0967(2) 0.0227(18) Uani 1 1 d . . . . .
C18 C 0.4010(9) -0.0324(8) 0.0600(2) 0.033(2) Uani 1 1 d . . . . .
H18A H 0.3761 0.0399 0.0440 0.039 Uiso 1 1 calc R U . . .
C19 C 0.4747(11) -0.1451(9) 0.0460(2) 0.047(2) Uani 1 1 d . . . . .
H19A H 0.4966 -0.1493 0.0211 0.057 Uiso 1 1 calc R U . . .
C20 C 0.5160(10) -0.2519(9) 0.0691(2) 0.055(3) Uani 1 1 d . . . . .
H20A H 0.5681 -0.3284 0.0601 0.066 Uiso 1 1 calc R U . . .
C21 C 0.4796(10) -0.2446(8) 0.1058(2) 0.048(2) Uani 1 1 d . . . . .
H21A H 0.5065 -0.3176 0.1214 0.057 Uiso 1 1 calc R U . . .
C22 C 0.4038(9) -0.1309(8) 0.1201(2) 0.030(2) Uani 1 1 d . . . . .
C23 C 0.3773(9) -0.1352(8) 0.1609(2) 0.0269(19) Uani 1 1 d . . . . .
C24 C 0.2727(8) -0.2201(8) 0.1766(2) 0.0336(19) Uani 1 1 d . . . . .
C25 C 0.2560(9) -0.2424(9) 0.2135(2) 0.039(2) Uani 1 1 d . . . . .
H25A H 0.1834 -0.3014 0.2225 0.047 Uiso 1 1 calc R U . . .
C26 C 0.3512(10) -0.1738(9) 0.2368(2) 0.044(2) Uani 1 1 d . . . . .
H26A H 0.3425 -0.1868 0.2621 0.053 Uiso 1 1 calc R U . . .
C27 C 0.4583(10) -0.0869(8) 0.2235(2) 0.037(2) Uani 1 1 d . . . . .
H27A H 0.5209 -0.0396 0.2394 0.044 Uiso 1 1 calc R U . . .
C28 C 0.4703(10) -0.0719(8) 0.1861(2) 0.0336(19) Uani 1 1 d . . . . .
C29 C 0.5579(8) 0.2899(9) 0.08615(19) 0.039(2) Uani 1 1 d . . . . .
H29A H 0.5027 0.2346 0.0690 0.058 Uiso 1 1 calc R U . . .
H29B H 0.5574 0.3864 0.0785 0.058 Uiso 1 1 calc R U . . .
H29C H 0.6565 0.2561 0.0870 0.058 Uiso 1 1 calc R U . . .
C30 C 0.7732(8) 0.3929(9) 0.1541(2) 0.035(2) Uani 1 1 d . . . . .
H30A H 0.8070 0.3195 0.1395 0.041 Uiso 1 1 calc R U . . .
C31 C 0.8729(9) 0.4802(9) 0.1703(3) 0.041(2) Uani 1 1 d . . . . .
H31A H 0.9722 0.4654 0.1669 0.049 Uiso 1 1 calc R U . . .
C32 C 0.8242(10) 0.5905(9) 0.1919(2) 0.042(2) Uani 1 1 d . . . . .
H32A H 0.8898 0.6526 0.2026 0.051 Uiso 1 1 calc R U . . .
C33 C 0.6771(9) 0.6060(8) 0.1969(2) 0.035(2) Uani 1 1 d . . . . .
H33A H 0.6411 0.6778 0.2117 0.042 Uiso 1 1 calc R U . . .
C34 C 0.5825(9) 0.5135(8) 0.1797(2) 0.028(2) Uani 1 1 d . . . . .
H34A H 0.4828 0.5248 0.1832 0.034 Uiso 1 1 calc R U . . .
O1 O 0.3946(5) 0.2503(5) 0.19269(12) 0.0258(12) Uani 1 1 d . . . . .
O3 O 0.2135(6) 0.3149(6) 0.23763(14) 0.0399(15) Uani 1 1 d . . . . .
O2 O 0.2159(6) 0.4267(5) 0.17771(15) 0.0346(14) Uani 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds 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
N1 C30 1.340(9) . ?
N1 C34 1.335(9) . ?
N1 Pd1 2.110(6) . ?
S1 O3 1.434(5) . ?
S1 O2 1.436(6) . ?
S1 O1 1.476(4) . ?
S1 C1 1.796(8) . ?
Pd1 C29 2.025(7) . ?
Pd1 O1 2.150(4) . ?
Pd1 P1 2.233(2) . ?
P1 C17 1.826(8) . ?
P1 C2 1.840(7) . ?
P1 C7 1.877(7) . ?
F1 C24 1.373(8) . ?
F2 C28 1.362(9) . ?
C1 C6 1.380(10) . ?
C1 C2 1.398(9) . ?
C2 C3 1.397(9) . ?
C3 C4 1.374(10) . ?
C4 C5 1.374(12) . ?
C5 C6 1.379(11) . ?
C7 C8 1.553(10) . ?
C7 C12 1.553(10) . ?
C8 C9 1.527(9) . ?
C8 C13 1.539(9) . ?
C9 C10 1.524(9) . ?
C10 C11 1.499(11) . ?
C11 C16 1.503(11) . ?
C11 C12 1.531(10) . ?
C13 C15 1.534(11) . ?
C13 C14 1.516(12) . ?
C17 C18 1.389(10) . ?
C17 C22 1.415(10) . ?
C18 C19 1.365(10) . ?
C19 C20 1.373(11) . ?
C20 C21 1.375(10) . ?
C21 C22 1.388(10) . ?
C22 C23 1.502(10) . ?
C23 C24 1.378(11) . ?
C23 C28 1.389(11) . ?
C24 C25 1.364(10) . ?
C25 C26 1.382(11) . ?
C26 C27 1.372(12) . ?
C27 C28 1.372(10) . ?
C30 C31 1.369(11) . ?
C31 C32 1.383(12) . ?
C32 C33 1.369(12) . ?
C33 C34 1.385(11) . ?

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
C30 N1 C34 117.6(7) . . ?
C30 N1 Pd1 125.8(5) . . ?
C34 N1 Pd1 116.5(5) . . ?
O3 S1 O2 115.2(3) . . ?
O3 S1 O1 111.7(3) . . ?
O2 S1 O1 111.5(3) . . ?
O3 S1 C1 105.8(3) . . ?
O2 S1 C1 107.0(3) . . ?
O1 S1 C1 104.7(3) . . ?
C29 Pd1 N1 90.1(3) . . ?
C29 Pd1 O1 173.6(3) . . ?
N1 Pd1 O1 86.1(2) . . ?
C29 Pd1 P1 90.3(2) . . ?
N1 Pd1 P1 175.70(18) . . ?
O1 Pd1 P1 93.84(13) . . ?
C17 P1 C2 107.5(3) . . ?
C17 P1 C7 109.5(3) . . ?
C2 P1 C7 104.6(3) . . ?
C17 P1 Pd1 108.2(2) . . ?
C2 P1 Pd1 113.4(2) . . ?
C7 P1 Pd1 113.5(2) . . ?
C6 C1 C2 119.7(7) . . ?
C6 C1 S1 115.8(6) . . ?
C2 C1 S1 124.5(6) . . ?
C1 C2 C3 117.2(7) . . ?
C1 C2 P1 124.9(6) . . ?
C3 C2 P1 117.9(6) . . ?
C4 C3 C2 122.1(8) . . ?
C5 C4 C3 120.4(8) . . ?
C4 C5 C6 118.2(8) . . ?
C5 C6 C1 122.4(8) . . ?
C8 C7 C12 110.7(6) . . ?
C8 C7 P1 120.6(5) . . ?
C12 C7 P1 105.3(5) . . ?
C9 C8 C7 110.6(6) . . ?
C9 C8 C13 110.1(6) . . ?
C7 C8 C13 116.7(7) . . ?
C8 C9 C10 114.4(6) . . ?
C11 C10 C9 110.8(7) . . ?
C10 C11 C16 112.5(7) . . ?
C10 C11 C12 109.4(6) . . ?
C16 C11 C12 111.7(7) . . ?
C11 C12 C7 113.9(6) . . ?
C15 C13 C14 110.0(7) . . ?
C15 C13 C8 113.6(6) . . ?
C14 C13 C8 111.7(7) . . ?
C18 C17 C22 116.0(7) . . ?
C18 C17 P1 120.0(6) . . ?
C22 C17 P1 123.3(6) . . ?
C19 C18 C17 123.9(8) . . ?
C18 C19 C20 119.4(8) . . ?
C21 C20 C19 119.2(7) . . ?
C20 C21 C22 121.7(7) . . ?
C21 C22 C17 119.9(8) . . ?
C21 C22 C23 115.5(7) . . ?
C17 C22 C23 124.7(7) . . ?
C24 C23 C28 114.1(7) . . ?
C24 C23 C22 122.6(7) . . ?
C28 C23 C22 122.6(8) . . ?
C23 C24 F1 116.9(7) . . ?
C23 C24 C25 125.2(8) . . ?
F1 C24 C25 117.9(7) . . ?
C24 C25 C26 117.2(8) . . ?
C27 C26 C25 121.5(8) . . ?
C26 C27 C28 118.0(8) . . ?
F2 C28 C23 117.0(7) . . ?
F2 C28 C27 119.0(8) . . ?
C23 C28 C27 124.0(9) . . ?
N1 C30 C31 122.9(8) . . ?
C30 C31 C32 119.3(8) . . ?
C31 C32 C33 118.3(8) . . ?
C34 C33 C32 119.2(8) . . ?
N1 C34 C33 122.6(8) . . ?
S1 O1 Pd1 113.6(2) . . ?

_refine_diff_density_max         0.674
_refine_diff_density_min         -0.412
_refine_diff_density_rms         0.085

