π-Extended ligands with dual-binding behavior: hindered rotation unlocks unexpected reactivity in cyclometalated Pt complexes.
Ota, Seiya; Soto, Miguel A.; Patrick, Brian O.; Kamal, Saeid; Lelj, Francesco; MacLachlan, Mark J.; Chemical science 15 (2024) 14644–14650; doi:10.1039/d4sc04799k

data_1572572
_publ_section_title
;
 &#x3c0;-Extended ligands with dual-binding behavior: hindered rotation
 unlocks unexpected reactivity in cyclometalated Pt complexes.
;
_journal_issue                   36
_journal_name_full               'Chemical science'
_journal_page_first              14644
_journal_page_last               14650
_journal_paper_doi               10.1039/d4sc04799k
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety
'C38 H24 Cl2 N2 Pt, 0.331(C H2 Cl2), 0.25[], 0.125[], 0.125[]'
_chemical_formula_sum            'C38.33 H24.66 Cl2.66 N2 Pt'
_chemical_formula_weight         802.73
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-04-02
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-05-21 deposited with the CCDC.	2024-08-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.571(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.839(3)
_cell_length_b                   19.399(3)
_cell_length_c                   16.667(2)
_cell_measurement_reflns_used    9941
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.24
_cell_measurement_theta_min      2.16
_cell_volume                     6962.8(17)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device       'Bruker D8 Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'TRIUMPH curved-crystal'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0580
_diffrn_reflns_av_unetI/netI     0.0431
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            105825
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.340
_diffrn_reflns_theta_min         1.239
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.35
_diffrn_source_voltage           45.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.263
_exptl_absorpt_correction_T_max  0.843
_exptl_absorpt_correction_T_min  0.589
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0650 before and 0.0485 after correction.
The Ratio of minimum to maximum transmission is 0.6980.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.532
_exptl_crystal_description       needle
_exptl_crystal_F_000             3135
_exptl_crystal_recrystallization_method
'The material was recrystallised from DCM by slow evaporation'
_exptl_crystal_size_max          0.55
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         7.635
_refine_diff_density_min         -6.032
_refine_diff_density_rms         0.243
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     853
_refine_ls_number_reflns         17243
_refine_ls_number_restraints     882
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.1245
_refine_ls_R_factor_gt           0.0831
_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^)+298.2174P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1657
_refine_ls_wR_factor_ref         0.1945
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12393
_reflns_number_total             17243
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04799k2.cif
_cod_data_source_block           mm574_sq_sq_sq
_cod_depositor_comments
'Adding full bibliography for 1572565--1572572.cif.'
_cod_database_code               1572572
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.848
_shelx_estimated_absorpt_t_min   0.203
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9390(8)
 0.0610(8)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Restrained distances
 Cl6-C77 \\sim Cl5-C77
 with sigma of 0.02
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C47A)=Sof(C52A)=Sof(C51A)=Sof(H51A)=Sof(C50A)=Sof(H50A)=Sof(C49A)=
 Sof(H49A)=Sof(C48A)=Sof(H48A)=Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(H55A)=1-FVAR(1)
 Sof(C47)=Sof(C52)=Sof(C51)=Sof(H51)=Sof(C50)=Sof(H50)=Sof(C49)=Sof(H49)=
 Sof(C48)=Sof(H48)=Sof(C53)=Sof(H53)=Sof(C54)=Sof(H55)=FVAR(1)
 Sof(Cl5)=Sof(Cl6)=Sof(C77)=Sof(H77A)=Sof(H77B)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C77(H77A,H77B)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C8(H8), C10(H10), C11(H11), C12(H12),
 C13(H13), C15(H15), C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23),
  C26(H26), C27(H27), C28(H28), C30(H30), C32(H32), C33(H33), C34(H34),
 C35(H35), C39(H39), C40(H40), C41(H41), C42(H42), C46(H46), C51(H51), C50(H50),
  C49(H49), C48(H48), C51A(H51A), C50A(H50A), C49A(H49A), C48A(H48A), C53(H53),
 C53A(H53A), C55(H55A), C55(H55), C56(H56), C58(H58), C59(H59), C60(H60),
 C61(H61), C64(H64), C65(H65), C66(H66), C68(H68), C70(H70), C71(H71), C72(H72),
  C73(H73)
6.c Fitted hexagon refined as free rotating group:
 C47(C52,C51,C50,C49,C48), C47A(C52A,C51A,C50A,C49A,C48A)
;
_shelx_res_checksum              51834
_shelx_hkl_checksum              139
_shelx_fab_checksum              85591
_platon_squeeze_void_probe_radius 1.20
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop in oil'
_olex2_submission_original_sample_id ANTIPtIV56
_olex2_submission_special_instructions 'No special instructions were received'