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_1551178
_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 Pd, 2(C F3 O3 S), 3(C6 H5 F)'
_chemical_formula_sum            'C78 H85 F9 N4 O6 P4 Pd S2'
_chemical_formula_weight         1639.90
_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             2018-02-21
_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                 91.3090(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.02480(18)
_cell_length_b                   19.8179(3)
_cell_length_c                   25.7120(4)
_cell_measurement_reflns_used    14440
_cell_measurement_temperature    100.1(7)
_cell_measurement_theta_max      76.0720
_cell_measurement_theta_min      2.7980
_cell_volume                     7654.01(19)
_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      100.1(7)
_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 0.985
_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      4.00  31.00   0.50   12.50    --  -38.50  57.00   0.00   54
  2  \w    -58.00 -17.00   0.50   12.50    --  -38.50  57.00   0.00   82
  3  \w   -110.00 -16.00   0.50   12.50    --  -38.50 -38.00  60.00  188
  4  \w    -61.00  34.00   0.50   12.50    --  -38.50  38.00-120.00  190
  5  \w    137.00 165.00   0.50   50.00    --  111.00 125.00-150.00   56
  6  \w     61.00  88.00   0.50   50.00    --  111.00 -30.00 150.00   54
  7  \w    105.00 178.00   0.50   50.00    --  111.00  77.00  30.00  146
  8  \w     50.00 116.00   0.50   50.00    --  111.00-125.00   0.00  132
  9  \w     95.00 162.00   0.50   50.00    --  111.00  30.00-150.00  134
 10  \w    119.00 178.00   0.50   50.00    --  111.00  45.00 -90.00  118
 11  \w    133.00 177.00   0.50   50.00    --  111.00 125.00-120.00   88
 12  \w    129.00 156.00   0.50   50.00    --  111.00  61.00 120.00   54
 13  \w     94.00 153.00   0.50   50.00    --  111.00 125.00-180.00  118
 14  \w     32.00  59.00   0.50   50.00    --  111.00 -94.00   0.00   54
 15  \w     63.00  96.00   0.50   50.00    --  111.00 -94.00   0.00   66
 16  \w     58.00 133.00   0.50   50.00    --  111.00 -45.00  60.00  150
 17  \w     93.00 175.00   0.50   50.00    --  111.00  30.00 -30.00  164
 18  \w     97.00 134.00   0.50   50.00    --  111.00 -30.00  30.00   74
 19  \w     37.00  89.00   0.50   50.00    --  111.00 -30.00  30.00  104
;
_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      0.0381187000
_diffrn_orient_matrix_UB_12      -0.0225999000
_diffrn_orient_matrix_UB_13      -0.0523274000
_diffrn_orient_matrix_UB_21      0.0677076000
_diffrn_orient_matrix_UB_22      0.0583297000
_diffrn_orient_matrix_UB_23      0.0027151000
_diffrn_orient_matrix_UB_31      0.0669258000
_diffrn_orient_matrix_UB_32      -0.0461186000
_diffrn_orient_matrix_UB_33      0.0291335000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0458
_diffrn_reflns_av_unetI/netI     0.0521
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            44109
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.619
_diffrn_reflns_theta_min         2.815
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.905
_exptl_absorpt_correction_T_max  0.905
_exptl_absorpt_correction_T_min  0.694
_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    1.423
_exptl_crystal_description       needle
_exptl_crystal_F_000             3392
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.043
_exptl_crystal_size_min          0.031
_refine_diff_density_max         1.242
_refine_diff_density_min         -1.067
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1081
_refine_ls_number_reflns         15851
_refine_ls_number_restraints     463
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0644
_refine_ls_R_factor_gt           0.0501
_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^)+(0.0635P)^2^+6.3233P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1234
_refine_ls_wR_factor_ref         0.1328
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12830
_reflns_number_total             15851
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01701a2.cif
_cod_data_source_block           13OTf2
_cod_original_cell_volume        7654.00(19)
_cod_database_code               1551178
_chemical_oxdiff_formula         'C312 H340 F36 N16 O24 P16 Pd4 S8 '
_reflns_odcompleteness_completeness 99.59
_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
 F9A-C76B \\sim F9B-C73B
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
F9A \\sim F9B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C76B \\sim C77B \\sim C78B \\sim C73B \\sim C74B \\sim C75B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
F8A \\sim F8B \\sim C71B \\sim C70B \\sim C69B \\sim C68B \\sim C67B \\sim C72B
\\sim C67A \\sim C68A \\sim C69A \\sim C70A \\sim C71A \\sim C72A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
C66A \\sim C61A \\sim C62A \\sim C63A \\sim C64A \\sim C65A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C62B \\sim C63B \\sim C64B \\sim C65B \\sim C66B \\sim C61B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
F7A \\sim F7B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C63B \\sim F7B \\sim C61B \\sim C62B \\sim C66B \\sim C65B \\sim C64B \\sim
C65A \\sim F7A \\sim C61A \\sim C66A \\sim C62A \\sim C63A \\sim C64A: 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(F3)=Sof(F4A)=Sof(F5)=Sof(O6A)=Sof(C60A)=FVAR(1)
 Sof(F8B)=Sof(C71B)=Sof(H71B)=Sof(C70B)=Sof(H70B)=Sof(C69B)=Sof(H69B)=
 Sof(C68B)=Sof(H68B)=Sof(C67B)=Sof(C72B)=Sof(H72B)=Sof(F9B)=Sof(H76B)=1-FVAR(2)
 Sof(F8A)=Sof(F9A)=Sof(H73B)=Sof(C67A)=Sof(C68A)=Sof(H68A)=Sof(C69A)=Sof(H69A)=
 Sof(C70A)=Sof(H70A)=Sof(C71A)=Sof(H71A)=Sof(C72A)=Sof(H72A)=FVAR(2)
 Sof(F7B)=Sof(C62B)=Sof(H62B)=Sof(C63B)=Sof(H63B)=Sof(C64B)=Sof(H64B)=
 Sof(C65B)=Sof(H65B)=Sof(C66B)=Sof(H66B)=Sof(C61B)=1-FVAR(3)
 Sof(F7A)=Sof(C66A)=Sof(H66A)=Sof(C61A)=Sof(C62A)=Sof(H62A)=Sof(C63A)=
 Sof(H63A)=Sof(C64A)=Sof(H64A)=Sof(C65A)=Sof(H65A)=FVAR(3)
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),
 C62B(H62B), C63B(H63B), C64B(H64B), C65B(H65B), C66B(H66B), C71B(H71B),
 C70B(H70B), C69B(H69B), C68B(H68B), C72B(H72B), C76B(H76B), C77B(H77B),
 C78B(H78B), C73B(H73B), C74B(H74B), C75B(H75B), C66A(H66A), C62A(H62A),
 C63A(H63A), C64A(H64A), C65A(H65A), C68A(H68A), C69A(H69A), C70A(H70A),
 C71A(H71A), C72A(H72A)
5.c Fitted hexagon refined as free rotating group:
 C62B(C63B,C64B,C65B,C66B,C61B), C71B(C70B,C69B,C68B,C67B,C72B), C76B(C77B,
 C78B,C73B,C74B,C75B), C66A(C61A,C62A,C63A,C64A,C65A), C67A(C68A,C69A,C70A,C71A,
 C72A)
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              43982
_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 2.059
_oxdiff_exptl_absorpt_empirical_full_min 0.689