Experimental and theoretical insights into the trans influence of organo-sulfur and -selenium ligands in 5,6-membered palladium(ii) cationic pincer complexes based on iminophosphoranes
Rodríguez-Álvarez, Aurora; González-Espinoza, Cristina E.; Martínez-De-León, Carla Gabriela; Carrillo-Tripp, Mauricio; Hô, Minhhuy; Grévy, Jean-Michel; New Journal of Chemistry 46 (2022) 9344–9356; doi:10.1039/D2NJ00924B

data_7061440
_publ_section_title
;
 Experimental and theoretical insights into the trans influence of
 organo-sulfur and -selenium ligands in 5,6-membered palladium(ii)
 cationic pincer complexes based on iminophosphoranes
;
_journal_issue                   19
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              9344
_journal_page_last               9356
_journal_paper_doi               10.1039/D2NJ00924B
_journal_volume                  46
_journal_year                    2022
_chemical_formula_moiety         'C26 H24 Cl N P Pd S2, C H2 Cl2, B F4'
_chemical_formula_sum            'C27 H26 B Cl3 F4 N P Pd S2'
_chemical_formula_weight         759.14
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-03-31
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-04-01 deposited with the CCDC.	2022-04-12 downloaded from the CCDC.
;
_cell_angle_alpha                65.103(5)
_cell_angle_beta                 73.145(4)
_cell_angle_gamma                74.459(4)
_cell_formula_units_Z            2
_cell_length_a                   10.3604(4)
_cell_length_b                   12.8764(5)
_cell_length_c                   12.9364(7)
_cell_measurement_reflns_used    5639
_cell_measurement_temperature    100.0(4)
_cell_measurement_theta_max      28.6350
_cell_measurement_theta_min      3.3040
_cell_volume                     1476.85(13)
_computing_cell_refinement
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01)'
_computing_data_collection
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01)'
_computing_data_reduction
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0769
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.849
_diffrn_measurement_details
'#__ type_ start__ end____ width___ exp.time_ 1 omega 5.00 64.00 1.0000 10.5800 omega____ theta____ kappa____ phi______ frames - 15.2374 57.0000 60.0000 59 #__ type_ start__ end____ width___ exp.time_ 2 omega -7.00 83.00 1.0000 10.5800 omega____ theta____ kappa____ phi______ frames - 15.2374 77.0000 120.0000 90 #__ type_ start__ end____ width___ exp.time_ 3 omega 8.00 83.00 1.0000 10.5800 omega____ theta____ kappa____ phi______ frames - 15.2374 77.0000 -150.0000 75 #__ type_ start__ end____ width___ exp.time_ 4 omega -1.00 29.00 1.0000 10.5800 omega____ theta____ kappa____ phi______ frames - -16.1749 57.0000 -180.0000 30 #__ type_ start__ end____ width___ exp.time_ 5 omega -80.00 -29.00 1.0000 10.5800 omega____ theta____ kappa____ phi______ frames - -16.1749 -38.0000 30.0000 51 #__ type_ start__ end____ width___ exp.time_ 6 omega -20.00 54.00 1.0000 10.5800 omega____ theta____ kappa____ phi______ frames - 15.2374 -99.0000 -30.0000 74'
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0037788000
_diffrn_orient_matrix_UB_12      -0.0611656000
_diffrn_orient_matrix_UB_13      0.0233497000
_diffrn_orient_matrix_UB_21      0.0662015000
_diffrn_orient_matrix_UB_22      -0.0059220000
_diffrn_orient_matrix_UB_23      -0.0351229000
_diffrn_orient_matrix_UB_31      0.0294815000
_diffrn_orient_matrix_UB_32      -0.0043411000
_diffrn_orient_matrix_UB_33      0.0450740000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0434
_diffrn_reflns_av_unetI/netI     0.0791
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.849
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            12349
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.849
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.234
_diffrn_reflns_theta_min         2.934
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.141
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63279
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.707
_exptl_crystal_description       irregular
_exptl_crystal_F_000             760
_exptl_crystal_size_max          0.1800
_exptl_crystal_size_mid          0.1400
_exptl_crystal_size_min          0.1100
_refine_diff_density_max         0.679
_refine_diff_density_min         -0.849
_refine_diff_density_rms         0.110
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.999
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     437
_refine_ls_number_reflns         6823
_refine_ls_number_restraints     98
_refine_ls_restrained_S_all      0.996
_refine_ls_R_factor_all          0.0521
_refine_ls_R_factor_gt           0.0389
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0117P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0687
_refine_ls_wR_factor_ref         0.0748
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5615
_reflns_number_total             6823
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj00924b2.cif
_cod_data_source_block           pdbfsme
_cod_depositor_comments
'Adding full bibliography for 7061439--7061443.cif.'
_cod_original_cell_volume        1476.84(13)
_cod_database_code               7061440
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N B F P S Pd Cl '
_shelx_estimated_absorpt_t_max   0.885
_shelx_estimated_absorpt_t_min   0.821
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C27A-Cl2A = C27A-Cl3A = C27B-Cl2B = C27B-Cl3B
 1.75 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Cl2A \\sim Cl3A \\sim C27A \\sim Cl2B \\sim Cl3B \\sim C27B: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 F1A, F2A, F3A, F4A, B1A, F1B, F2B, F3B, F4B, B1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{F1B, F2B, F3B, F4B, B1B} sigma for 1-2: 0.01, 1-3: 0.04
as
{F1A, F2A, F3A, F4A, B1A}
6. Others
 Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=Sof(B1B)=1-FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(B1A)=FVAR(1)
 Sof(Cl2B)=Sof(Cl3B)=Sof(C27B)=Sof(H27C)=Sof(H27D)=1-FVAR(2)
 Sof(Cl2A)=Sof(Cl3A)=Sof(C27A)=Sof(H27A)=Sof(H27B)=FVAR(2)
7.a Secondary CH2 refined with riding coordinates:
 C27A(H27A,H27B), C27B(H27C,H27D)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C15(H15), C16(H16), C17(H17), C18(H18), C22(H22), C23(H23), C24(H24),
  C25(H25), C26(H26)
7.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              21720
_olex2_submission_special_instructions 'No special instructions were received'