Formation of an imidazoliumyl-substituted [(LC)4P4]4+ tetracation and transition metal mediated fragmentation and insertion reaction (LC = NHC)
Weigand, Jan J.; Schwedtmann, Kai; Haberstroh, Jan; Roediger, Sven; Hennersdorf, Felix; Frontera, Antonio; Bauza, Antonio; Chemical Science  (2019) –; doi:10.1039/C9SC01701A

data_1551174
_publ_section_title
;
 Formation of an imidazoliumyl-substituted [(LC)4P4]4+ tetracation and
 transition metal mediated fragmentation and insertion reaction (LC = NHC)
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC01701A
_journal_year                    2019
_chemical_formula_moiety         'C58 H70 N4 P4 Pt, 2(C F3 O3 S), 3(C6 H5 F)'
_chemical_formula_sum            'C78 H85 F9 N4 O6 P4 Pt S2'
_chemical_formula_weight         1728.58
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-02-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2019-04-06 deposited with the CCDC.    2019-05-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.6799(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.98968(8)
_cell_length_b                   19.89396(13)
_cell_length_c                   25.71449(16)
_cell_measurement_reflns_used    33605
_cell_measurement_temperature    100.0(5)
_cell_measurement_theta_max      76.4240
_cell_measurement_theta_min      2.7940
_cell_volume                     7664.87(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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_environment      N~2~
_diffrn_ambient_temperature      100.0(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2850
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_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    -94.00  -2.00   0.50    4.25    --  -38.50 125.00 -60.00  184
  2  \w    -61.00  34.00   0.50    4.25    --  -38.50  38.00-180.00  190
  3  \w   -109.00 -12.00   0.50    4.25    --  -38.50 -57.00-180.00  194
  4  \w      1.00  82.00   0.50    4.25    --   42.50 -99.00  60.00  162
  5  \w     30.00 109.00   0.50   17.00    --  111.00 -94.00 -30.00  158
  6  \w     40.00 135.00   0.50   17.00    --  111.00 -45.00  30.00  190
  7  \w     90.00 176.00   0.50   17.00    --  111.00  30.00 -90.00  172
  8  \w     94.00 149.00   0.50   17.00    --  111.00 125.00 120.00  110
  9  \w     42.00  98.00   0.50   17.00    --  111.00 -94.00 -90.00  112
 10  \w     87.00 178.00   0.50   17.00    --  111.00  45.00 -60.00  182
 11  \w     90.00 129.00   0.50   17.00    --  111.00  45.00-150.00   78
 12  \w     53.00 105.00   0.50   17.00    --  111.00 -94.00-150.00  104
 13  \w     92.00 174.00   0.50   17.00    --  111.00  45.00  60.00  164
 14  \w     44.00 107.00   0.50   17.00    --  111.00-125.00-180.00  126
 15  \w     47.00 115.00   0.50   17.00    --  111.00-125.00  30.00  136
 16  \w     40.00 121.00   0.50   17.00    --  111.00-125.00-150.00  162
;
_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      0.0201893000
_diffrn_orient_matrix_UB_12      0.0175073000
_diffrn_orient_matrix_UB_13      -0.0568120000
_diffrn_orient_matrix_UB_21      -0.0436995000
_diffrn_orient_matrix_UB_22      0.0694106000
_diffrn_orient_matrix_UB_23      0.0067805000
_diffrn_orient_matrix_UB_31      0.0908638000
_diffrn_orient_matrix_UB_32      0.0294891000
_diffrn_orient_matrix_UB_33      0.0178850000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0295
_diffrn_reflns_av_unetI/netI     0.0269
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            57628
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.778
_diffrn_reflns_theta_min         2.809
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.371
_exptl_absorpt_correction_T_max  0.906
_exptl_absorpt_correction_T_min  0.604
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
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    1.498
_exptl_crystal_description       needle
_exptl_crystal_F_000             3520
_exptl_crystal_size_max          0.263
_exptl_crystal_size_mid          0.043
_exptl_crystal_size_min          0.034
_refine_diff_density_max         1.246
_refine_diff_density_min         -1.237
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1149
_refine_ls_number_reflns         15980
_refine_ls_number_restraints     649
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0358
_refine_ls_R_factor_gt           0.0323
_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^)+(0.0544P)^2^+5.5025P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0846
_refine_ls_wR_factor_ref         0.0875
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14507
_reflns_number_total             15980
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01701a2.cif
_cod_data_source_block           14OTf2
_cod_original_cell_volume        7664.88(8)
_cod_database_code               1551174
_chemical_oxdiff_formula         'C312 H340 F36 N16 O24 P16 Pd4 S8 '
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F8A-C67A \\sim F8B-C70A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
S2A \\sim S2B \\sim F4A \\sim F4B \\sim F5A \\sim F5B \\sim F6A \\sim F6B \\sim
O4A \\sim O5A \\sim O6A \\sim O6B \\sim C60A \\sim C60B: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02
F9A \\sim C73A \\sim C74A \\sim C75A \\sim C76A \\sim C77A \\sim C78A \\sim F9B
\\sim C73B \\sim C74B \\sim C75B \\sim C76B \\sim C77B \\sim C78B: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
O1A \\sim O2A \\sim O3A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O1A \\sim O1B \\sim O2A \\sim O2B \\sim O3A \\sim O3B: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
F7A \\sim C61A \\sim C62A \\sim C63A \\sim C64A \\sim C65A \\sim C66A \\sim F7B
\\sim C61B \\sim C62B \\sim C63B \\sim C64B \\sim C65B \\sim C66B: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(S2B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=Sof(O6B)=Sof(C60B)=1-FVAR(1)
 Sof(S2A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(O6A)=Sof(C60A)=FVAR(1)
 Sof(F9B)=Sof(C78B)=Sof(H78B)=Sof(C73B)=Sof(C74B)=Sof(H74B)=Sof(C75B)=
 Sof(H75B)=Sof(C76B)=Sof(H76B)=Sof(C77B)=Sof(H77B)=1-FVAR(2)
 Sof(F9A)=Sof(C73A)=Sof(C74A)=Sof(H74A)=Sof(C75A)=Sof(H75A)=Sof(C76A)=
 Sof(H76A)=Sof(C77A)=Sof(H77A)=Sof(C78A)=Sof(H78A)=FVAR(2)
 Sof(F8B)=Sof(H67A)=1-FVAR(3)
 Sof(F8A)=Sof(H70A)=FVAR(3)
 Sof(F7B)=Sof(C66B)=Sof(H66B)=Sof(C61B)=Sof(C62B)=Sof(H62B)=Sof(C63B)=
 Sof(H63B)=Sof(C64B)=Sof(H64B)=Sof(C65B)=Sof(H65B)=1-FVAR(4)
 Sof(F7A)=Sof(C61A)=Sof(C62A)=Sof(H62A)=Sof(C63A)=Sof(H63A)=Sof(C64A)=
 Sof(H64A)=Sof(C65A)=Sof(H65A)=Sof(C66A)=Sof(H66A)=FVAR(4)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(O1B)=Sof(O2B)=Sof(O3B)=1-FVAR(5)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(O1A)=Sof(O2A)=Sof(O3A)=FVAR(5)
5.a Ternary CH refined with riding coordinates:
 C4A(H4A), C9A(H9A), C15A(H15A), C20A(H20A)
5.b Aromatic/amide H refined with riding coordinates:
 C24A(H24A), C25A(H25A), C26A(H26A), C27A(H27A), C28A(H28A), C30A(H30A),
 C31A(H31A), C32A(H32A), C33A(H33A), C34A(H34A), C36A(H36A), C37A(H37A),
 C38A(H38A), C39A(H39A), C40A(H40A), C42A(H42A), C43A(H43A), C44A(H44A),
 C45A(H45A), C46A(H46A), C48A(H48A), C49A(H49A), C50A(H50A), C51A(H51A),
 C52A(H52A), C54A(H54A), C55A(H55A), C56A(H56A), C57A(H57A), C58A(H58A),
 C62A(H62A), C63A(H63A), C64A(H64A), C65A(H65A), C66A(H66A), C66B(H66B),
 C62B(H62B), C63B(H63B), C64B(H64B), C65B(H65B), C67A(H67A), C68A(H68A),
 C69A(H69A), C70A(H70A), C71A(H71A), C72A(H72A), C74A(H74A), C75A(H75A),
 C76A(H76A), C77A(H77A), C78A(H78A), C78B(H78B), C74B(H74B), C75B(H75B),
 C76B(H76B), C77B(H77B)
5.c Fitted hexagon refined as free rotating group:
 C61A(C62A,C63A,C64A,C65A,C66A), C66B(C61B,C62B,C63B,C64B,C65B), C73A(C74A,
 C75A,C76A,C77A,C78A), C78B(C73B,C74B,C75B,C76B,C77B)
5.d Idealised Me refined as rotating group:
 C5A(H5AA,H5AB,H5AC), C6A(H6AA,H6AB,H6AC), C7A(H7AA,H7AB,H7AC), C8A(H8AA,H8AB,
 H8AC), C10A(H10A,H10B,H10C), C11A(H11A,H11B,H11C), C16A(H16A,H16B,H16C),
 C17A(H17A,H17B,H17C), C18A(H18A,H18B,H18C), C19A(H19A,H19B,H19C), C21A(H21A,
 H21B,H21C), C22A(H22A,H22B,H22C)
;
_shelx_res_checksum              46432
_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 1.558
_oxdiff_exptl_absorpt_empirical_full_min 0.700