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_1551179
_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
'C44 H80 Au Cl2 N8 P4, 2.5(C H2 Cl2), 3(C F3 O3 S)'
_chemical_formula_sum            'C49.5 H85 Au Cl7 F9 N8 O9 P4 S3'
_chemical_formula_weight         1772.43
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-04-06 deposited with the CCDC.    2019-05-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.738(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   30.6491(6)
_cell_length_b                   11.9065(2)
_cell_length_c                   20.2311(5)
_cell_measurement_reflns_used    34349
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.4850
_cell_measurement_theta_min      2.8750
_cell_volume                     7379.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5700
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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     16.00  70.00   0.50    1.00    --   42.50  57.00 -90.00  108
  2  \w     94.00 124.00   0.50    5.00    --  111.00 -45.00-150.00   60
  3  \w    103.00 129.00   0.50    5.00    --  111.00 -45.00-180.00   52
  4  \w     81.00 107.00   0.50    5.00    --  111.00 -94.00-150.00   52
  5  \w     85.00 111.00   0.50    5.00    --  111.00-125.00-150.00   52
  6  \w     76.00 121.00   0.50    5.00    --  111.00-125.00-120.00   90
  7  \w     95.00 121.00   0.50    5.00    --  111.00-125.00 -30.00   52
  8  \w    104.00 130.00   0.50    5.00    --  111.00 -77.00 -30.00   52
  9  \w     97.00 153.00   0.50    5.00    --  111.00 -15.00   0.00  112
 10  \w    153.00 178.00   0.50    5.00    --  111.00  15.00  30.00   50
 11  \w    118.00 178.00   0.50    5.00    --  111.00  45.00  90.00  120
 12  \w    138.00 164.00   0.50    5.00    --  111.00 125.00 150.00   52
 13  \w     89.00 115.00   0.50    5.00    --  111.00  45.00  90.00   52
 14  \w     83.00 119.00   0.50    5.00    --  111.00  68.00 129.00   72
 15  \w     72.00 127.00   0.50    5.00    --  111.00  15.00  30.00  110
 16  \w     73.00 100.00   0.50    5.00    --  111.00 -77.00 -90.00   54
 17  \w     69.00 109.00   0.50    5.00    --  111.00 -94.00   0.00   80
 18  \w     81.00 106.00   0.50    5.00    --  111.00 -94.00 120.00   50
 19  \w     90.00 121.00   0.50    5.00    --  111.00-125.00 150.00   62
 20  \w     59.00  86.00   0.50    5.00    --  111.00-125.00 150.00   54
 21  \w     47.00 138.00   0.50    5.00    --  111.00 -61.00  60.00  182
 22  \w     48.00  73.00   0.50    5.00    --  111.00-125.00 -30.00   50
 23  \w     41.00  71.00   0.50    5.00    --  111.00 -77.00 -90.00   60
 24  \w     37.00 141.00   0.50    5.00    --  111.00 -77.00-150.00  208
 25  \w     92.00 122.00   0.50    5.00    --  111.00  45.00-180.00   60
 26  \w    142.00 177.00   0.50    5.00    --  111.00  45.00-180.00   70
 27  \w     48.00 112.00   0.50    5.00    --  111.00-125.00  30.00  128
 28  \w     40.00  66.00   0.50    1.00    --   42.50 -57.00 120.00   52
 29  \w     40.00 121.00   0.50    5.00    --  111.00-125.00  60.00  162
 30  \w     38.00  63.00   0.50    5.00    --  111.00 -94.00 120.00   50
 31  \w     34.00 102.00   0.50    5.00    --  111.00 -94.00  60.00  136
 32  \w     35.00  75.00   0.50    5.00    --  111.00 -15.00   0.00   80
 33  \w     31.00 154.00   0.50    5.00    --  111.00 -15.00 120.00  246
 34  \w     43.00  73.00   0.50    5.00    --  111.00 -45.00-150.00   60
 35  \w     46.00  87.00   0.50    5.00    --  111.00 -45.00-180.00   82
 36  \w     38.00  63.00   0.50    5.00    --  111.00 -94.00-150.00   50
 37  \w    -93.00 -39.00   0.50    1.00    --  -38.50 -38.00 -90.00  108
 38  \w   -101.00 -16.00   0.50    1.00    --  -38.50 -38.00 -30.00  170
 39  \w    -80.00  -4.00   0.50    1.00    --  -38.50 125.00  90.00  152
 40  \w    -94.00 -53.00   0.50    1.00    --  -38.50 125.00 -30.00   82
 41  \w   -104.00 -54.00   0.50    1.00    --  -38.50 -38.00  60.00  100
;
_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      -0.0174504000
_diffrn_orient_matrix_UB_12      0.1179123000
_diffrn_orient_matrix_UB_13      -0.0176968000
_diffrn_orient_matrix_UB_21      -0.0350603000
_diffrn_orient_matrix_UB_22      -0.0119989000
_diffrn_orient_matrix_UB_23      0.0525184000
_diffrn_orient_matrix_UB_31      0.0315750000
_diffrn_orient_matrix_UB_32      0.0516958000
_diffrn_orient_matrix_UB_33      0.0522768000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1157
_diffrn_reflns_av_unetI/netI     0.0674
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            79611
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.531
_diffrn_reflns_theta_min         2.885
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.354
_exptl_absorpt_correction_T_max  0.907
_exptl_absorpt_correction_T_min  0.140
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (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            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.595
_exptl_crystal_description       plate
_exptl_crystal_F_000             3588
_exptl_crystal_size_max          0.372
_exptl_crystal_size_mid          0.192
_exptl_crystal_size_min          0.061
_refine_diff_density_max         1.756
_refine_diff_density_min         -4.385
_refine_diff_density_rms         0.181
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     998
_refine_ls_number_reflns         15093
_refine_ls_number_restraints     684
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0646
_refine_ls_R_factor_gt           0.0613
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1199P)^2^+8.7161P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1647
_refine_ls_wR_factor_ref         0.1698
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13873
_reflns_number_total             15093
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01701a2.cif
_cod_data_source_block           15OTf3
_cod_original_formula_sum        'C49.50 H85 Au Cl7 F9 N8 O9 P4 S3'
_cod_database_code               1551179
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C49.5H82AuCl7F9N8O9P4S3
_shelx_estimated_absorpt_t_max   0.630
_shelx_estimated_absorpt_t_min   0.147
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. 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
2. Uiso/Uaniso restraints and constraints
S3 \\sim F7 \\sim F8 \\sim F9 \\sim O7 \\sim O8 \\sim O9 \\sim C47: within 3A
with sigma of 0.01 and sigma for terminal atoms of 0.02
Cl7 \\sim Cl8 \\sim C51: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C48B \\sim S4B \\sim O10B \\sim O11B \\sim O12B \\sim F10B \\sim F11B \\sim
F12B \\sim F10A \\sim S4A \\sim O10A \\sim O11A \\sim O12A \\sim C48A \\sim
F11A \\sim F12A: within 2.5A with sigma of 0.01 and sigma for terminal atoms of
0.02
3. Same fragment restrains
{Cl8, Cl7, C51} sigma for 1-2: 0.02, 1-3: 0.02
as
{Cl3, Cl4, C49}
{S4A, F11A, F12A, F10A, O10A, O11A, O12A, C48A} sigma for 1-2: 0.02, 1-3: 0.02
{S4B, F12B, F10B, F11B, O10B, O12B, O11B, C48B} sigma for 1-2: 0.02, 1-3: 0.02
{S4A, F12A, F10A, F11A, O10A, O12A, O11A, C48A} sigma for 1-2: 0.02, 1-3: 0.02
as
{S2, F4, F5, F6, O4, O5, O6, C46}
4. Others
 Sof(S4B)=Sof(F10B)=Sof(F11B)=Sof(F12B)=Sof(O10B)=Sof(O11B)=Sof(O12B)=
 Sof(C48B)=0.5*(1-FVAR(2))
 Sof(S4A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(O10A)=Sof(O11A)=Sof(O12A)=
 Sof(C48A)=0.5*FVAR(2)
 Fixed Sof: Cl7(0.5) Cl8(0.5) C51(0.5) H51A(0.5) H51B(0.5) S3(0.5) F7(0.5)
 F8(0.5) F9(0.5) O7(0.5) O8(0.5) O9(0.5) C47(0.5)
5.a Ternary CH refined with riding coordinates:
 C6(H6), C9(H9), C17(H17), C20(H20), C28(H28), C31(H31), C39(H39), C42(H42)
5.b Secondary CH2 refined with riding coordinates:
 C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B)
5.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C10(H10A,
 H10B,H10C), C11(H11A,H11B,H11C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C),
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C37(H37A,H37B,H37C),
 C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C43(H43A,H43B,
 H43C), C44(H44A,H44B,H44C)
;
_shelx_res_checksum              32985
_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 3.653
_oxdiff_exptl_absorpt_empirical_full_min 0.387