Reversible C-C bond formation at a triply cyclometallated platinum(IV) centre
Shaw, Paul Anthony; Clarkson, Guy James; Rourke, Jonathan P.; Chem. Sci.  (2017) –; doi:10.1039/C7SC01361B

data_1546254
_publ_section_title
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 Reversible C-C bond formation at a triply cyclometallated platinum(IV)
 centre
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC01361B
_journal_year                    2017
_chemical_formula_moiety         '3(C H Cl3), C39 H31 Cl F2 N O P Pt'
_chemical_formula_sum            'C42 H34 Cl10 F2 N O P Pt'
_chemical_formula_weight         1187.26
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-10-17
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2017-03-27 deposited with the CCDC.
2017-06-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.1991(19)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.6952(4)
_cell_length_b                   14.2502(3)
_cell_length_c                   27.6824(5)
_cell_measurement_reflns_used    19047
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.6650
_cell_measurement_theta_min      2.9150
_cell_volume                     9100.3(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3046
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.890
_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     -4.00  26.00   1.00   16.00    --  -14.15 -99.00  60.00   30
  2  \w     39.00  66.00   1.00   16.00    --   15.24 178.00-180.00   27
  3  \w      2.00  88.00   1.00   16.00    --   15.24  37.00 -30.00   86
  4  \w    -58.00  43.00   1.00   16.00    --   15.24 -57.00-180.00  101
  5  \w     -3.00  86.00   1.00   16.00    --   15.28  37.00  60.00   89
  6  \w     -5.00   3.00   1.00   16.00    --   15.28 -99.00 -60.00    8
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0193493000
_diffrn_orient_matrix_UB_12      0.0079766000
_diffrn_orient_matrix_UB_13      -0.0157023000
_diffrn_orient_matrix_UB_21      -0.0231581000
_diffrn_orient_matrix_UB_22      -0.0057252000
_diffrn_orient_matrix_UB_23      -0.0211209000
_diffrn_orient_matrix_UB_31      -0.0058808000
_diffrn_orient_matrix_UB_32      0.0487978000
_diffrn_orient_matrix_UB_33      0.0000975000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0299
_diffrn_reflns_av_unetI/netI     0.0351
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.890
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            41772
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.890
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.958
_diffrn_reflns_theta_min         2.518
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.749
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58031
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.733
_exptl_crystal_description       block
_exptl_crystal_F_000             4656
_exptl_crystal_size_max          0.423
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.094
_refine_diff_density_max         2.092
_refine_diff_density_min         -1.603
_refine_diff_density_rms         0.155
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     557
_refine_ls_number_reflns         12881
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0513
_refine_ls_R_factor_gt           0.0404
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0433P)^2^+85.9545P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0951
_refine_ls_wR_factor_ref         0.1033
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10962
_reflns_number_total             12881
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc01361b2.cif
_cod_data_source_block           ps40
_cod_database_code               1546254
_chemical_oxdiff_formula         'C42 H34 N O2 F2 P2 Cl2 Pt'
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.02
_olex2_refinement_description
;

One of the benzene rings of a benzyl of the phosphine was modeled as disordered over two positions. 
The occupancy was linked to a free variable which refined to 77:23. The minor component was refined 
isotropically. Both rings were refined with an AFIX 66 restraint. Two of the chloroforms were 
modeled as disordered about the carbon. The occupancy of the disordered components were fixed 
at 75:25. The minor components were refined isotropically. Several SIMU and DFIX restraints were 
used in the refinement of the disordered solvent.

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
 C40-Cl5A
 1.75 with sigma of 0.02
 C40-Cl6A
 1.75 with sigma of 0.02
 C40-Cl7A
 1.75 with sigma of 0.02
 C41-Cl0A
 1.75 with sigma of 0.02
 C41-Cl8A
 1.75 with sigma of 0.02
 C41-Cl9A
 1.75 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl5 \\sim Cl5A \\sim Cl7 \\sim Cl6A \\sim Cl6 \\sim Cl7A \\sim C40: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02
C33A \\sim C38A \\sim C37A \\sim C36A \\sim C35A \\sim C34A: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08
4. Others
 Sof(C38A)=Sof(H38A)=Sof(C37A)=Sof(H37A)=Sof(C36A)=Sof(H36A)=Sof(C35A)=
 Sof(H35A)=Sof(C34A)=Sof(H34A)=1-FVAR(1)
 Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35)=Sof(C36)=Sof(H36)=Sof(C37)=Sof(H37)=
 Sof(C38)=Sof(H38)=FVAR(1)
 Fixed Sof: H40(0.75) H40A(0.25) Cl5(0.75) Cl6(0.75) Cl7(0.75) Cl5A(0.25)
 Cl6A(0.25) Cl7A(0.25) Cl0A(0.25) Cl8(0.75) Cl8A(0.25) Cl9(0.75) Cl9A(0.25)
 Cl10(0.75) H41(0.75) H41A(0.25)
5.a Ternary CH refined with riding coordinates:
 C40(H40), C40(H40A), C39(H39), C41(H41), C41(H41A)
5.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C25(H25A,H25B), C32(H32A,H32B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C19(H19), C4(H4), C5(H5), C34(H34), C35(H35), C36(H36), C37(H37),
 C38(H38), C38A(H38A), C37A(H37A), C36A(H36A), C35A(H35A), C34A(H34A), C8(H8),
 C20(H20), C21(H21), C9(H9), C22(H22), C10(H10), C27(H27), C28(H28), C29(H29),
 C30(H30), C31(H31), C14(H14), C16(H16)
5.d Fitted hexagon refined as free rotating group:
 C33A(C34,C35,C36,C37,C38)
5.e Idealised Me refined as rotating group:
 C13A(H13A,H13B,H13C)
;
_shelx_res_checksum              50551
_shelx_shelxl_version_number     2014/7
_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 1.654
_oxdiff_exptl_absorpt_empirical_full_min 0.730