Modulation of Intersystem Crossing Rate by Minor Ligand Modifications in Cyclometalated Platinum(II) Complexes.
Shafikov, Marsel Z.; Kozhevnikov, Dmitry N.; Bodensteiner, Michael; Brandl, Fabian; Czerwieniec, Rafał; Inorganic chemistry 55 (2016) 7457–7466; doi:10.1021/acs.inorgchem.6b00704

data_4347852
_publ_section_title
;
 Modulation of Intersystem Crossing Rate by Minor Ligand Modifications in
 Cyclometalated Platinum(II) Complexes.
;
_journal_issue                   15
_journal_name_full               'Inorganic chemistry'
_journal_page_first              7457
_journal_page_last               7466
_journal_paper_doi               10.1021/acs.inorgchem.6b00704
_journal_volume                  55
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C29 H26 F N O2 Pt S2'
_chemical_formula_sum            'C29 H26 F N O2 Pt S2'
_chemical_formula_weight         698.72
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-11-05
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2015.10.28 svn.r3245 for OlexSys, GUI svn.r5128)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.6742(5)
_cell_length_b                   17.3852(4)
_cell_length_c                   7.07539(16)
_cell_measurement_reflns_used    8912
_cell_measurement_temperature    123.00(14)
_cell_measurement_theta_max      66.6920
_cell_measurement_theta_min      4.9620
_cell_volume                     2543.07(10)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_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      123.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1773
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_details
;
  1 omega  -30.00   69.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       41.7634  -57.0000 -180.0000 99

  2 omega   23.00  130.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -15.0000  -60.0000 107

  3 omega   22.00   73.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -45.0000  -60.0000 51

  4 omega   22.00  106.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -93.0000  -55.6315 84

  5 omega   14.00  114.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       41.7634   57.0000  150.0000 100

  6 omega    9.00  118.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       41.7634   77.0000  -60.0000 109

  7 omega   67.00  166.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   45.0000   60.0000 99

  8 omega   60.00  169.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000  -30.0000 109

  9 omega   63.00  165.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   61.0000  120.0000 102

 10 omega   19.00   96.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000 -125.0000 -180.0000 77

 11 omega   14.00  114.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       41.7634   57.0000 -120.0000 100

 12 omega    9.00  118.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       41.7634   77.0000   30.0000 109

 13 omega   67.00  166.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   45.0000  -90.0000 99

 14 omega   60.00  163.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000 -180.0000 103

 15 omega   10.00   84.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -95.0000 -120.0000 74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0063851000
_diffrn_orient_matrix_UB_12      -0.0883116000
_diffrn_orient_matrix_UB_13      0.0007429000
_diffrn_orient_matrix_UB_21      -0.0010802000
_diffrn_orient_matrix_UB_22      -0.0004297000
_diffrn_orient_matrix_UB_23      -0.2176910000
_diffrn_orient_matrix_UB_31      0.0742230000
_diffrn_orient_matrix_UB_32      0.0075588000
_diffrn_orient_matrix_UB_33      -0.0031016000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0779
_diffrn_reflns_av_unetI/netI     0.0430
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            21311
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        66.886
_diffrn_reflns_theta_max         66.886
_diffrn_reflns_theta_min         3.321
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.150
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.31160
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.825
_exptl_crystal_description       plate
_exptl_crystal_F_000             1368
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         4.326
_refine_diff_density_min         -2.100
_refine_diff_density_rms         0.207
_refine_ls_abs_structure_details
;
 Refined as an inversion twin with 0.48(4) per cent contribution.
;
_refine_ls_abs_structure_Flack   0.0(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     327
_refine_ls_number_reflns         4379
_refine_ls_number_restraints     50
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0671
_refine_ls_R_factor_gt           0.0576
_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^)+(0.1002P)^2^+19.3020P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1571
_refine_ls_wR_factor_ref         0.1694
_reflns_Friedel_coverage         0.834
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                3735
_reflns_number_total             4379
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b00704_si_002.cif
_cod_data_source_block           n011
_cod_original_cell_volume        2543.06(10)
_cod_database_code               4347852
_chemical_oxdiff_formula         'Pt S2 O2 N F C30 H30'
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.52(5) 0.48(5)
2. 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
3. Restrained planarity
 C26, C27, C28, S2
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C27) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(O2)
\\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C21) \\sim Ueq,
Uanis(C28) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.005
5.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C17(H17A,H17B), C18(H18A,H18B), C28(H28A,H28B)
5.b Me refined with riding coordinates:
 C5(H5A,H5B,H5C), C29(H29A,H29B,H29C)
5.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C22(H22), C3(H3), C12(H12), C15(H15), C13(H13), C16(H16), C25(H25),
 C26(H26)
5.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              89586
_shelx_hkl_checksum              56618
_shelx_shelxl_version_number     2014/7
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'
_olex2_computing_structure_solution_long 'ShelXS (Sheldrick, 2008)'
_olex2_diffrn_ambient_temperature_device 'Oxford Instruments, CryoJet'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder with inert oil'
_olex2_submission_special_instructions 'No special instructions were received'