Platinum(ii) alkyl complexes of chelating dibridgehead diphosphines P((CH2)n)3P (n = 14, 18, 22); facile cis/trans isomerizations interconverting gyroscope and parachute like adducts
Zhu, Yun; Ehnbom, Andreas; Fiedler, Tobias; Shu, Yi; Bhuvanesh, Nattamai; Hall, Michael B.; Gladysz, John A.; Dalton Transactions  (2021) –; doi:10.1039/D1DT02321G

data_7708167
_publ_section_title
;
 Platinum(ii) alkyl complexes of chelating dibridgehead diphosphines
 P((CH2)n)3P (n = 14, 18, 22); facile cis/trans isomerizations
 interconverting gyroscope and parachute like adducts
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT02321G
_journal_year                    2021
_chemical_formula_moiety         'C44 H90 P2 Pt'
_chemical_formula_sum            'C44 H90 P2 Pt'
_chemical_formula_weight         876.18
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2020-09-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2021-08-20 deposited with the CCDC.	2021-08-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.7670(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.3514(4)
_cell_length_b                   15.4895(6)
_cell_length_c                   28.4607(12)
_cell_measurement_reflns_used    9302
_cell_measurement_temperature    110.0
_cell_measurement_theta_max      25.623
_cell_measurement_theta_min      2.374
_cell_volume                     4540.2(3)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_collection       'Bruker APEX3 (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_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_temperature      110.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker QUEST PHOTON-II'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0451
_diffrn_reflns_av_unetI/netI     0.0187
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            102005
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.949
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.188
_exptl_absorpt_correction_T_max  0.4291
_exptl_absorpt_correction_T_min  0.1274
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1216 before and 0.0598 after correction.
The Ratio of minimum to maximum transmission is 0.2969.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.282
_exptl_crystal_description       block
_exptl_crystal_F_000             1848
_exptl_crystal_size_max          0.441
_exptl_crystal_size_mid          0.207
_exptl_crystal_size_min          0.182
_refine_diff_density_max         2.107
_refine_diff_density_min         -2.309
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     566
_refine_ls_number_reflns         7997
_refine_ls_number_restraints     801
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0378
_refine_ls_R_factor_gt           0.0331
_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^)+(0.0116P)^2^+21.1179P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0695
_refine_ls_wR_factor_ref         0.0732
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7301
_reflns_number_total             7997
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02321g3.cif
_cod_data_source_block           ptme2
_cod_database_code               7708167
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.595
_shelx_estimated_absorpt_t_min   0.334
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 P1-C29 \\sim P1-C29A \\sim P2-C42 \\sim P2-C42A
 with sigma of 0.02
 C23A-C22 \\sim C23-C22 \\sim C24-C23 \\sim C24A-C23A \\sim C25-C24A \\sim
C25-C24
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim
C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C29A \\sim C30A
\\sim C31A \\sim C32A \\sim C33A \\sim C34A \\sim C35A \\sim C36A \\sim C37A
\\sim C38A \\sim C39A \\sim C40A \\sim C41A \\sim C42A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C22 \\sim C23 \\sim C24 \\sim C25 \\sim C23A \\sim C24A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C37) = Uanis(C37A)
4. Rigid body (RIGU) restrains
 C29, C30, C31, C32, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, C29A,
 C30A, C31A, C32A, C33A, C34A, C35A, C36A, C37A, C38A, C39A, C40A, C41A, C42A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C22, C23, C24, C25, C23A, C24A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Same fragment restrains
{C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14} sigma for 1-2:
0.005, 1-3: 0.04
as in
{C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28}
{C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14} sigma for 1-2:
0.005, 1-3: 0.04
as in
{C29, C30, C31, C32, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42}
{C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14} sigma for 1-2:
0.005, 1-3: 0.04
as in
{C29A, C30A, C31A, C32A, C33A, C34A, C35A, C36A, C37A, C38A, C39A, C40A, C41A,
C42A}
6. Others
 Sof(C29A)=Sof(H29C)=Sof(H29D)=Sof(C30A)=Sof(H30C)=Sof(H30D)=Sof(C31A)=
 Sof(H31C)=Sof(H31D)=Sof(C32A)=Sof(H32C)=Sof(H32D)=Sof(C33A)=Sof(H33C)=
 Sof(H33D)=Sof(C34A)=Sof(H34C)=Sof(H34D)=Sof(C35A)=Sof(H35C)=Sof(H35D)=
 Sof(C36A)=Sof(H36C)=Sof(H36D)=Sof(C37A)=Sof(H37C)=Sof(H37D)=Sof(C38A)=
 Sof(H38C)=Sof(H38D)=Sof(C39A)=Sof(H39C)=Sof(H39D)=Sof(C40A)=Sof(H40C)=
 Sof(H40D)=Sof(C41A)=Sof(H41C)=Sof(H41D)=Sof(C42A)=Sof(H42C)=Sof(H42D)=1-FVAR(1)
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(C31)=Sof(H31A)=
 Sof(H31B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(C34)=
 Sof(H34A)=Sof(H34B)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=
 Sof(H39B)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C42)=
 Sof(H42A)=Sof(H42B)=FVAR(1)
 Sof(H22C)=Sof(H22D)=Sof(H25C)=Sof(H25D)=Sof(C23A)=Sof(H23C)=Sof(H23D)=
 Sof(C24A)=Sof(H24C)=Sof(H24D)=1-FVAR(2)
 Sof(H22A)=Sof(H22B)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(C24)=Sof(H24A)=Sof(H24B)=
 Sof(H25A)=Sof(H25B)=FVAR(2)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B),
 C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B),
  C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,
 H21B), C22(H22A,H22B), C22(H22C,H22D), C23(H23A,H23B), C24(H24A,H24B),
 C25(H25A,H25B), C25(H25C,H25D), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B),
  C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,
 H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B),
 C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B),
  C29A(H29C,H29D), C30A(H30C,H30D), C31A(H31C,H31D), C32A(H32C,H32D), C33A(H33C,
 H33D), C34A(H34C,H34D), C35A(H35C,H35D), C36A(H36C,H36D), C37A(H37C,H37D),
 C38A(H38C,H38D), C39A(H39C,H39D), C40A(H40C,H40D), C41A(H41C,H41D), C42A(H42C,
 H42D), C23A(H23C,H23D), C24A(H24C,H24D)
7.b Idealised Me refined as rotating group:
 C43(H43A,H43B,H43C), C44(H44A,H44B,H44C)
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_shelx_res_checksum              46921
_olex2_submission_special_instructions 'No special instructions were received'