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_1546255
_publ_section_title
;
 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         'C39 H32 F2 N P Pt, 1.2(C H Cl3), 0.2(C Cl3)'
_chemical_formula_sum            'C40.4 H33.2 Cl4.2 F2 N P Pt'
_chemical_formula_weight         945.63
_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             2016-06-02
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2017-03-27 deposited with the CCDC.
2017-06-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.6391(12)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.61871(18)
_cell_length_b                   17.9381(3)
_cell_length_c                   28.6293(4)
_cell_measurement_reflns_used    23293
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      31.9380
_cell_measurement_theta_min      2.6870
_cell_volume                     7422.34(19)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43d (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2833
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.961
_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    -59.00  50.00   1.00   15.00    --   17.29 -77.00  30.00  109
  2  \w    -56.00  45.00   1.00   15.00    --   17.29 -57.00 -90.00  101
  3  \w    -25.00  58.00   1.00   15.00    --   17.29 -99.00 150.00   83
  4  \w    -25.00  23.00   1.00   15.00    --  -18.22 -99.00-180.00   48
  5  \w   -107.00 -57.00   1.00   15.00    --  -18.22-178.00  90.00   50
  6  \w    -25.00  23.00   1.00   15.00    --  -18.22 -99.00 -90.00   48
  7  \w     -7.00  92.00   1.00   15.00    --   17.29  38.00 -30.00   99
  8  \w    -11.00  90.00   1.00   15.00    --   17.29  57.00  60.00  101
  9  \w     -7.00  92.00   1.00   15.00    --   17.29  38.00-180.00   99
 10  \w     35.00 106.00   1.00   15.00    --   17.29 178.00 -60.00   71
 11  \w    -25.00  23.00   1.00   15.00    --  -18.22 -99.00 120.00   48
 12  \w    -51.00  21.00   1.00   15.00    --  -18.22  77.00  30.00   72
 13  \w    -94.00 -39.00   1.00   15.00    --  -18.22 156.00-161.00   55
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0132614000
_diffrn_orient_matrix_UB_12      -0.0001835000
_diffrn_orient_matrix_UB_13      0.0248707000
_diffrn_orient_matrix_UB_21      -0.0047510000
_diffrn_orient_matrix_UB_22      -0.0393458000
_diffrn_orient_matrix_UB_23      0.0001959000
_diffrn_orient_matrix_UB_31      0.0470104000
_diffrn_orient_matrix_UB_32      -0.0039202000
_diffrn_orient_matrix_UB_33      -0.0030687000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0573
_diffrn_reflns_av_unetI/netI     0.0396
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            113385
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.378
_diffrn_reflns_theta_min         2.439
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.167
_exptl_absorpt_correction_T_max  0.972
_exptl_absorpt_correction_T_min  0.775
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43d (Rigaku Oxford Diffraction, 2015)
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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.692
_exptl_crystal_description       block
_exptl_crystal_F_000             3720
_exptl_crystal_size_max          0.567
_exptl_crystal_size_mid          0.107
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.700
_refine_diff_density_min         -1.275
_refine_diff_density_rms         0.135
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     503
_refine_ls_number_reflns         12768
_refine_ls_number_restraints     22
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0646
_refine_ls_R_factor_gt           0.0393
_refine_ls_shift/su_max          0.003
_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^+25.3287P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0870
_refine_ls_wR_factor_ref         0.0958
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9624
_reflns_number_total             12768
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc01361b2.cif
_cod_data_source_block           ps32
_cod_original_cell_volume        7422.36(19)
_cod_original_formula_sum        'C40.40 H33.20 Cl4.20 F2 N P Pt'
_cod_database_code               1546255
_chemical_oxdiff_formula         'C20 H20 N F2 P Pt'
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.01
_olex2_refinement_description
;
The asymmetric unit contains the complex and a lot of surrounding diffuse electron density. 
This was modeled as very disordered chloroform solvent. In one position, a molecule of 
chloroform was modeled over three very closely related positions. The occupancy was 
originally linked to free variables but the occupancy of the components was fixed at 
80:10:10 based on thermal parameters. Only the major component was refined 
anisotropically. 
The other electron density was also modeled a chloroform disordered over two closely 
related positions behind a PART -1 and PART -2 instruction as it straddled the 
2 fold axis. Both these components were refined isotropically at 40% occupancy.
Many DFIX, SIMU and DELU restraints were used to give these disordered components 
reasonable bond lengths angles and thermal parameters.
The methyl substituent on the pyridine ligand was also disordered over two positions.
The occupancy of the two positions was linked to a free variable which refined to 77:23. 
The minor component was refined isotropically.
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
 C1C-Cl1B = C1C-Cl2B = C1C-Cl3B
 1.7 with sigma of 0.004
 Cl1B-Cl2B = Cl2B-Cl3B = Cl3B-Cl1B
 2.9 with sigma of 0.02
 C1E-Cl1D = C1E-Cl2D = C1E-Cl3D
 1.7 with sigma of 0.004
 Cl1D-Cl2D = Cl2D-Cl3D = Cl3D-Cl1D
 2.9 with sigma of 0.02
 C1F-Cl1E = C1F-Cl2E = C1F-Cl3E
 1.7 with sigma of 0.004
 Cl1E-Cl2E = Cl2E-Cl3E = Cl3E-Cl1E
 2.9 with sigma of 0.02
 H10-H13B
 2.1 with sigma of 0.02
 H10-H13C
 2.1 with sigma of 0.02
3. Rigid bond restraints
 C1F, Cl1E, Cl2E, Cl3E
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
C1E \\sim Cl1D \\sim Cl2D \\sim Cl3D: within 1.7A with sigma of 0.002 and sigma
for terminal atoms of 0.004
C1F \\sim Cl1E \\sim Cl2E \\sim Cl3E: within 1.7A with sigma of 0.003 and sigma
for terminal atoms of 0.006
5. Others
 Sof(H5)=Sof(C13A)=Sof(H13A)=Sof(H13B)=Sof(H13C)=1-FVAR(1)
 Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(H13)=FVAR(1)
 Fixed Sof: C1E(0.2) H1E(0.2) Cl1A(0.8) C1F(0.2) C1D(0.1) H1D(0.1) Cl1B(0.1)
 Cl1D(0.2) C1B(0.8) H1B(0.8) Cl1E(0.2) C1C(0.1) H1C(0.1) Cl1C(0.1) Cl2A(0.8)
 Cl2E(0.2) Cl2B(0.1) Cl2C(0.1) Cl2D(0.2) Cl3D(0.2) Cl3B(0.1) Cl3E(0.2)
 Cl3C(0.1) Cl3A(0.8)
6.a Ternary CH refined with riding coordinates:
 C1E(H1E), C1D(H1D), C1B(H1B), C1C(H1C)
6.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C25(H25A,H25B), C32(H32A,H32B)
6.c Me refined with riding coordinates:
 C13A(H13A,H13B,H13C)
6.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C13(H13), C14(H14),
 C16(H16), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C27(H27), C28(H28),
  C29(H29), C30(H30), C31(H31), C34(H34), C35(H35), C36(H36), C37(H37), C38(H38)
6.e Idealised Me refined as rotating group:
 C5A(H5AA,H5AB,H5AC)
;
_shelx_res_checksum              18379
_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 1.170
_oxdiff_exptl_absorpt_empirical_full_min 0.908