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_7709900
_publ_section_title
;
 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         'C74 H61 Cl2 N3 Pt, C1 H2 Cl2'
_chemical_formula_sum            'C75 H63 Cl4 N3 Pt'
_chemical_formula_weight         1343.17
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6219)
;
_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                90
_cell_formula_units_Z            8
_cell_length_a                   18.0177(3)
_cell_length_b                   19.4122(2)
_cell_length_c                   37.8914(7)
_cell_measurement_reflns_used    20298
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      29.2070
_cell_measurement_theta_min      2.9940
_cell_volume                     13253.0(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 0.997
_diffrn_measured_fraction_theta_max 0.901
_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    -63.00  37.20   0.30   65.00    --   10.17 -57.00  90.00  334
  2  \w    -18.00  82.20   0.30   65.00    --   10.17  57.00-180.00  334
  3  \w    -15.00  10.20   0.30   65.00    --   10.17 -99.00   0.00   84
;
_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      0.0111661000
_diffrn_orient_matrix_UB_12      0.0098546000
_diffrn_orient_matrix_UB_13      0.0172242000
_diffrn_orient_matrix_UB_21      0.0101439000
_diffrn_orient_matrix_UB_22      -0.0345617000
_diffrn_orient_matrix_UB_23      0.0037176000
_diffrn_orient_matrix_UB_31      0.0363647000
_diffrn_orient_matrix_UB_32      0.0065920000
_diffrn_orient_matrix_UB_33      -0.0063144000
_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  0.0551
_diffrn_reflns_av_unetI/netI     0.0594
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.901
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            82491
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.901
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.653
_diffrn_reflns_theta_min         2.492
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.322
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.477
_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    1.346
_exptl_crystal_description       plate
_exptl_crystal_F_000             5440
_exptl_crystal_preparation       Synthesis
_exptl_crystal_recrystallization_method 'Pentane diffusion in DCM'
_exptl_crystal_size_max          0.264
_exptl_crystal_size_mid          0.188
_exptl_crystal_size_min          0.122
_refine_diff_density_max         1.448
_refine_diff_density_min         -1.202
_refine_diff_density_rms         0.132
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     779
_refine_ls_number_reflns         16869
_refine_ls_number_restraints     16
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0886
_refine_ls_R_factor_gt           0.0539
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0518P)^2^+42.4059P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1243
_refine_ls_wR_factor_ref         0.1382
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11878
_reflns_number_total             16869
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00504b2.cif
_cod_data_source_block           bm151-2
_cod_database_code               7709900
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C74 H61 Cl2 N3 Pt'
_reflns_odcompleteness_completeness 99.83
_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
 C57-C64A = C57-C64B
 1.51 with sigma of 0.01
 C64A-C65A = C66A-C67A = C68A-C69A
 1.39 with sigma of 0.01
 C64B-C65B = C66B-C67B = C68B-C69B
 1.39 with sigma of 0.01
 C64A-C69A
 1.39 with sigma of 0.01
 C64B-C69B
 1.39 with sigma of 0.01
 C75A-Cl3A = C75A-Cl4A
 1.746 with sigma of 0.005
 C75B-Cl3B = C75B-Cl4B
 1.746 with sigma of 0.005
 Cl3A-Cl4A
 2.9 with sigma of 0.01
 Cl3B-Cl4B
 2.9 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C64A) = Uanis(C64B)
Uanis(C65A) = Uanis(C65B)
Uanis(C66A) = Uanis(C66B)
Uanis(C67A) = Uanis(C67B)
Uanis(C68A) = Uanis(C68B)
Uanis(C69A) = Uanis(C69B)
Uanis(C75A) = Uanis(C75B)
Uanis(Cl3A) = Uanis(Cl3B)
Uanis(Cl4A) = Uanis(Cl4B)
4. Others
 Sof(H57A)=Sof(C67B)=Sof(H67B)=Sof(C68B)=Sof(H68B)=Sof(C65B)=Sof(H65B)=
 Sof(C69B)=Sof(H69B)=Sof(C64B)=Sof(C66B)=Sof(H66B)=1-FVAR(1)
 Sof(H57)=Sof(C64A)=Sof(C69A)=Sof(H69A)=Sof(C65A)=Sof(H65A)=Sof(C67A)=
 Sof(H67A)=Sof(C66A)=Sof(H66A)=Sof(C68A)=Sof(H68A)=FVAR(1)
 Sof(Cl3B)=Sof(Cl4B)=Sof(C75B)=Sof(H75C)=Sof(H75D)=1-FVAR(2)
 Sof(Cl4A)=Sof(Cl3A)=Sof(C75A)=Sof(H75A)=Sof(H75B)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C43(H43), C10(H10), C24(H24), C57(H57), C57(H57A)
5.b Secondary CH2 refined with riding coordinates:
 C75A(H75A,H75B), C75B(H75C,H75D)
5.c Aromatic/amide H refined with riding coordinates:
 C46(H46), C45(H45), C39(H39), C3(H3), C22(H22), C8(H8), C41(H41), C2(H2),
 C47(H47), C70(H70), C12(H12), C6(H6), C18(H18), C16(H16), C21(H21), C48(H48),
 C49(H49), C74(H74), C26(H26), C20(H20), C71(H71), C51(H51), C13(H13), C55(H55),
  C63(H63), C19(H19), C32(H32), C30(H30), C15(H15), C14(H14), C73(H73),
 C61(H61), C27(H27), C59(H59), C28(H28), C72(H72), C36(H36), C54(H54), C33(H33),
  C29(H29), C62(H62), C53(H53), C52(H52), C60(H60), C35(H35), C34(H34),
 C69A(H69A), C65A(H65A), C67A(H67A), C66A(H66A), C68A(H68A), C67B(H67B),
 C68B(H68B), C65B(H65B), C69B(H69B), C66B(H66B)
5.d Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              49197
_shelx_hkl_checksum              1186
_olex2_date_sample_data_collection 2020-12-14
_olex2_exptl_crystal_mounting_method 'Little loop'
_olex2_submission_original_sample_id BM151
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.581
_oxdiff_exptl_absorpt_empirical_full_min 0.764