PdII and PtII complexes bearing acetamide and thioacetamide functionalized heteroscorpionates and their application in the hydrosilylation of terminal alkynes
Ortiz-Hernández, M.; Noguez-Maldonado, V. I.; Salazar-Pereda, V.; Gonzalez-Montiel, S.; Mendoza-Espinosa, D.; Suárez, A.; Cristobal, C.; New Journal of Chemistry 50 (2026) 4415–4424; doi:10.1039/D5NJ04709A

data_7064225
_publ_section_title
;
 PdII and PtII complexes bearing acetamide and thioacetamide
 functionalized heteroscorpionates and their application in the
 hydrosilylation of terminal alkynes
;
_journal_issue                   10
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              4415
_journal_page_last               4424
_journal_paper_doi               10.1039/D5NJ04709A
_journal_volume                  50
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety
'C2 H3 N, C36 H42 N10 Pd S2, 2(Cl), 0.564(H2 O)'
_chemical_formula_sum            'C38 H46.13 Cl2 N11 O0.56 Pd S2'
_chemical_formula_weight         907.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-02
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-12-03 deposited with the CCDC.	2026-02-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.705(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.2262(2)
_cell_length_b                   15.3698(4)
_cell_length_c                   15.0703(4)
_cell_measurement_reflns_used    35216
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.4500
_cell_measurement_theta_min      3.5170
_cell_volume                     2134.66(9)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3659
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -34.00  65.00   1.00   25.00    --   -9.96  37.00 -60.00   99
  2  \w    -83.00  21.00   1.00   25.00    --   -9.96 -69.00 139.00  104
  3  \w    -25.00  31.00   1.00   25.00    --   -9.96 -99.00 -30.00   56
  4  \w    -83.00  18.00   1.00   25.00    --   -9.96 -57.00  30.00  101
  5  \w    -84.00  14.00   1.00   25.00    --   -9.96 -37.00-120.00   98
  6  \w    -25.00  52.00   1.00   25.00    --   11.45 -99.00  30.00   77
  7  \w    -84.00  14.00   1.00   25.00    --   -9.96 -37.00-180.00   98
  8  \w    -43.00  66.00   1.00   25.00    --   -9.96  77.00-180.00  109
  9  \w    -25.00  52.00   1.00   25.00    --   11.45 -99.00  90.00   77
 10  \w    -25.00  52.00   1.00   25.00    --   11.45 -99.00 -60.00   77
 11  \w    -25.00  52.00   1.00   25.00    --   11.45 -99.00-180.00   77
 12  \w    -34.00   0.00   1.00   25.00    --   -9.96  37.00-180.00   34
 13  \w    -25.00  52.00   1.00   25.00    --   11.45 -99.00 -30.00   77
 14  \w    -25.00  52.00   1.00   25.00    --   11.45 -99.00 150.00   77
 15  \w    -25.00  52.00   1.00   25.00    --   11.45 -99.00-120.00   77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0069235000
_diffrn_orient_matrix_UB_12      0.0325472000
_diffrn_orient_matrix_UB_13      0.0333048000
_diffrn_orient_matrix_UB_21      0.0633052000
_diffrn_orient_matrix_UB_22      0.0159359000
_diffrn_orient_matrix_UB_23      -0.0194525000
_diffrn_orient_matrix_UB_31      -0.0432273000
_diffrn_orient_matrix_UB_32      0.0285571000
_diffrn_orient_matrix_UB_33      -0.0270782000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0281
_diffrn_reflns_av_unetI/netI     0.0145
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            66109
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.348
_diffrn_reflns_theta_min         2.959
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.701
_exptl_absorpt_correction_T_max  0.752
_exptl_absorpt_correction_T_min  0.697
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.412
_exptl_crystal_description       block
_exptl_crystal_F_000             935
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.29
_refine_diff_density_max         0.190
_refine_diff_density_min         -0.161
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 3539 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.027(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     549
_refine_ls_number_reflns         7795
_refine_ls_number_restraints     96
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0196
_refine_ls_R_factor_gt           0.0181
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0254P)^2^+0.3449P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0451
_refine_ls_wR_factor_ref         0.0462
_reflns_Friedel_coverage         0.923
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                7564
_reflns_number_total             7795
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj04709a2.cif
_cod_data_source_block           sgmo_18_2021_dmo
_cod_depositor_comments
'Adding full bibliography for 7064225--7064228.cif.'
_cod_original_cell_volume        2134.67(9)
_cod_database_code               7064225
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C24 H16 N4 S1 Pd1 Cl2'
_shelx_estimated_absorpt_t_max   0.823
_shelx_estimated_absorpt_t_min   0.753
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C37-N11
 1.15 with sigma of 0.01
 C37-C38
 1.5 with sigma of 0.01
 C38-N11
 2.65 with sigma of 0.01
 N5-H5
 0.86 with sigma of 0.01
 N10-H10
 0.86 with sigma of 0.01
 O1-H1A = O1-H1B
 0.84 with sigma of 0.01
 H1A-H1B
 1.4 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C38 \\sim C37 \\sim N11 \\sim C38A \\sim C37A \\sim N11A: within 2A with sigma
of 0.001 and sigma for terminal atoms of 0.002 within 2A
4. Rigid body (RIGU) restrains
 C38, C37, N11, C38A, C37A, N11A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C38, C37, N11} sigma for 1-2: 0.001, 1-3: 0.001
as in
{C38A, C37A, N11A}
6. Others
 Sof(O1)=Sof(H1A)=Sof(H1B)=FVAR(1)
 Sof(C38A)=Sof(H38D)=Sof(H38E)=Sof(H38F)=Sof(C37A)=Sof(N11A)=1-FVAR(2)
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C37)=Sof(N11)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C1(H1), C19(H19)
7.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C9(H9), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C22(H22),
 C27(H27), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36)
7.c Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C38A(H38D,H38E,H38F), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C),
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              39129
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.135
_oxdiff_exptl_absorpt_empirical_full_min 0.892