A green route to platinum N-heterocyclic carbene complexes: mechanism and expanded scope
Maliszewski, Benon P.; Ritacco, Ida; Beliš, Marek; Hashim, Ishfaq Ibni; Tzouras, Nikolaos V.; Caporaso, Lucia; Cavallo, Luigi; Van Hecke, Kristof; Nahra, Fady; Cazin, Catherine S. J.; Nolan, Steven P.; Dalton Transactions  (2022) –; doi:10.1039/D2DT00504B

data_7709901
_publ_section_title
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 A green route to platinum N-heterocyclic carbene complexes: mechanism and
 expanded scope
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00504B
_journal_year                    2022
_chemical_formula_moiety
'C29 H54 Cl2 N2 Pt S, 0.167[C5H12], 0.333[C5H12]'
_chemical_formula_sum            'C31.5 H60 Cl2 N2 Pt S'
_chemical_formula_weight         764.86
_chemical_name_systematic        BM176
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-01-20 deposited with the CCDC.	2022-03-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   31.8125(4)
_cell_length_b                   31.8125(4)
_cell_length_c                   17.7813(3)
_cell_measurement_reflns_used    15340
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      29.5130
_cell_measurement_theta_min      2.8940
_cell_volume                     15584.4(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4839
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.859
_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    -70.00  51.00   1.00   52.00    --   10.01 -19.00 150.00  121
  2  \w    -31.00  -6.00   1.00   52.00    --   10.01  19.00 -30.00   25
  3  \w    -42.00  21.00   1.00   52.00    --  -11.19 -77.00  90.00   63
  4  \w    -44.00  21.00   1.00   52.00    --  -11.19  77.00 -30.00   65
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0029921000
_diffrn_orient_matrix_UB_12      -0.0208407000
_diffrn_orient_matrix_UB_13      -0.0193191000
_diffrn_orient_matrix_UB_21      -0.0013543000
_diffrn_orient_matrix_UB_22      0.0102842000
_diffrn_orient_matrix_UB_23      -0.0346588000
_diffrn_orient_matrix_UB_31      0.0255306000
_diffrn_orient_matrix_UB_32      0.0110794000
_diffrn_orient_matrix_UB_33      -0.0041311000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0341
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.859
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            33512
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.859
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.628
_diffrn_reflns_theta_min         2.561
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.288
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.892
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.467
_exptl_crystal_description       block
_exptl_crystal_F_000             7038
_exptl_crystal_preparation       Synthesis
_exptl_crystal_recrystallization_method 'Pentane diffusion in DCM'
_exptl_crystal_size_max          0.165
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.096
_refine_diff_density_max         8.993
_refine_diff_density_min         -3.248
_refine_diff_density_rms         0.162
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     318
_refine_ls_number_reflns         8413
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0533
_refine_ls_R_factor_gt           0.0467
_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^)+(0.0174P)^2^+461.4310P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0932
_refine_ls_wR_factor_ref         0.0964
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7542
_reflns_number_total             8413
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00504b2.cif
_cod_data_source_block           bm176-2
_cod_original_cell_volume        15584.4(5)
_cod_original_sg_symbol_H-M      'R -3'
_cod_original_formula_sum        'C31.50 H60 Cl2 N2 Pt S'
_cod_database_code               7709901
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C29 H55 Cl2 N2 Pt S'
_reflns_odcompleteness_completeness 99.92
_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.a Ternary CH refined with riding coordinates:
 C4(H4), C16(H16)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,
 H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B),
 C15(H15A,H15B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B),
  C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,
 H25B), C26(H26A,H26B), C27(H27A,H27B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3)
2.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 372 electrons were 
found in a volume of 2106\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
3[C5H12] and 6[C5H12] per Unit Cell 
which account for 378 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              84372
_shelx_hkl_checksum              87672
_shelx_fab_checksum              452
_olex2_date_sample_data_collection 2021-02-02
_olex2_exptl_crystal_mounting_method 'Little loop'
_olex2_submission_original_sample_id BM176
_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 1.332
_oxdiff_exptl_absorpt_empirical_full_min 0.885