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_1551175
_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
'C33 H60 N6 P7, 3(C F3 O3 S), 0.88(C2 H3 N), 1.69(C H2 Cl2)'
_chemical_formula_sum            'C39.44 H66.01 Cl3.37 F9 N6.88 O9 P7 S3'
_chemical_formula_weight         1384.11
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-11-07
_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                101.3965(7)
_cell_angle_beta                 103.3332(8)
_cell_angle_gamma                104.3661(8)
_cell_formula_units_Z            4
_cell_length_a                   13.83853(13)
_cell_length_b                   17.90754(17)
_cell_length_c                   27.2960(2)
_cell_measurement_reflns_used    73168
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.2520
_cell_measurement_theta_min      2.6420
_cell_volume                     6138.79(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (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 0.990
_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     18.00  45.00   0.50    3.00    --   50.00  82.00 -80.12   54
  2  \w     35.00 103.00   0.50    3.00    --   66.00  76.00 -42.11  136
  3  \w    135.00 173.00   0.50   12.00    --  111.00  77.00-120.00   76
  4  \w    148.00 178.00   0.50   12.00    --  111.00  77.00-180.00   60
  5  \w    124.00 176.00   0.50   12.00    --  111.00  77.00-150.00  104
  6  \w    125.00 152.00   0.50   12.00    --  111.00  77.00 -60.00   54
  7  \w    126.00 174.00   0.50   12.00    --  111.00  77.00 -30.00   96
  8  \w    138.00 174.00   0.50   12.00    --  111.00  77.00  30.00   72
  9  \w    141.00 178.00   0.50   12.00    --  111.00  77.00  60.00   74
 10  \w    129.00 178.00   0.50   12.00    --  111.00  77.00 150.00   98
 11  \w    126.00 176.00   0.50   12.00    --  111.00  77.00 120.00  100
 12  \w    126.00 176.00   0.50   12.00    --  111.00  77.00  90.00  100
 13  \w    125.00 178.00   0.50   12.00    --  111.00  77.00   0.00  106
 14  \w    126.00 178.00   0.50   12.00    --  111.00  77.00 -90.00  104
 15  \w    121.00 148.00   0.50    3.00    --   74.00  77.00-161.78   54
 16  \w    115.00 157.00   0.50   12.00    --  111.00  61.00-120.00   84
 17  \w     98.00 125.00   0.50    3.00    --   62.00  77.00-145.49   54
 18  \w     80.00 112.00   0.50   12.00    --  111.00  77.00-120.00   64
 19  \w     84.00 164.00   0.50   12.00    --  111.00  61.00 -90.00  160
 20  \w    102.00 137.00   0.50    3.00    --   74.00  77.00  62.72   70
 21  \w    107.00 132.00   0.50    3.00    --   66.00  76.00 121.27   50
 22  \w    103.00 148.00   0.50    3.00    --   74.00  77.00 157.36   90
 23  \w     83.00 164.00   0.50   12.00    --  111.00  61.00  60.00  162
 24  \w     80.00 107.00   0.50   12.00    --  111.00  77.00 150.00   54
 25  \w     83.00 152.00   0.50   12.00    --  111.00  61.00 150.00  138
 26  \w     83.00 157.00   0.50   12.00    --  111.00  61.00  30.00  148
 27  \w     84.00 145.00   0.50   12.00    --  111.00  61.00  90.00  122
 28  \w     80.00 106.00   0.50   12.00    --  111.00  77.00  60.00   52
 29  \w     80.00 106.00   0.50   12.00    --  111.00  77.00  30.00   52
 30  \w     80.00 120.00   0.50   12.00    --  111.00  77.00   0.00   80
 31  \w     80.00 106.00   0.50   12.00    --  111.00  77.00 -60.00   52
 32  \w     80.00 106.00   0.50   12.00    --  111.00  77.00 -30.00   52
 33  \w     83.00 139.00   0.50   12.00    --  111.00  61.00   0.00  112
 34  \w     80.00 106.00   0.50   12.00    --  111.00  77.00 120.00   52
 35  \w     83.00 151.00   0.50   12.00    --  111.00  61.00 120.00  136
 36  \w     83.00 145.00   0.50   12.00    --  111.00  61.00 -30.00  124
 37  \w     80.00 106.00   0.50   12.00    --  111.00  77.00-150.00   52
 38  \w     83.00 166.00   0.50   12.00    --  111.00  61.00-180.00  166
 39  \w     80.00 135.00   0.50   12.00    --  111.00  77.00-180.00  110
 40  \w     83.00 150.00   0.50   12.00    --  111.00  61.00-150.00  134
 41  \w     80.00 106.00   0.50   12.00    --  111.00  77.00 -90.00   52
 42  \w     83.00 114.00   0.50   12.00    --  111.00  61.00-120.00   62
 43  \w     83.00 163.00   0.50   12.00    --  111.00  61.00 -60.00  160
 44  \w     80.00 106.00   0.50   12.00    --  111.00  77.00  90.00   52
 45  \w     39.00  65.00   0.50    3.00    --   70.00  76.00 -22.49   52
 46  \w     39.00  65.00   0.50    3.00    --   70.00  77.00   6.37   52
 47  \w     43.00  69.00   0.50    3.00    --   74.00  77.00  32.68   52
 48  \w     43.00  82.00   0.50    3.00    --   74.00  77.00  62.72   78
 49  \w     35.00  67.00   0.50    3.00    --   66.00  76.00 121.27   64
 50  \w     43.00  69.00   0.50    3.00    --   74.00  77.00 157.36   52
 51  \w     17.00  45.00   0.50    3.00    --   50.00  82.00  91.26   56
 52  \w     17.00  42.00   0.50    3.00    --   50.00  82.00  33.30   50
 53  \w     22.00  47.00   0.50    3.00    --   54.00  78.00 -22.36   50
 54  \w     17.00  44.00   0.50    3.00    --   50.00  82.00 -44.94   54
 55  \w     22.00  48.00   0.50    3.00    --   54.00  78.00-102.51   52
 56  \w     31.00  57.00   0.50    3.00    --   62.00  77.00-145.49   52
 57  \w     43.00  70.00   0.50    3.00    --   74.00  77.00-161.78   54
 58  \w     43.00  69.00   0.50    3.00    --   74.00  76.00-129.66   52
 59  \w     55.00 104.00   0.50   12.00    --   86.00  74.00 -86.96   98
 60  \w     43.00  69.00   0.50    3.00    --   74.00  76.00 -94.03   52
 61  \w     27.00  53.00   0.50    3.00    --   58.00  77.00-179.26   52
 62  \w     13.00  38.00   0.50    3.00    --   46.00  83.00-179.42   50
 63  \w     -3.00  22.00   0.50    3.00    --   34.00  92.00-116.34   50
 64  \w     41.00 139.00   0.50   12.00    --  111.00 -61.00 -30.00  196
 65  \w     91.00 121.00   0.50   12.00    --  111.00-125.00  90.00   60
 66  \w     73.00 127.00   0.50   12.00    --  111.00-136.00  -8.00  108
 67  \w     61.00 120.00   0.50   12.00    --  111.00-125.00 150.00  118
 68  \w     44.00  71.00   0.50   12.00    --  111.00-125.00  90.00   54
 69  \w     39.00 108.00   0.50   12.00    --  111.00 -94.00 -30.00  138
 70  \w     49.00 109.00   0.50   12.00    --  111.00 -94.00 -90.00  120
 71  \w     69.00 107.00   0.50   12.00    --  111.00-125.00-180.00   76
 72  \w     40.00 106.00   0.50   12.00    --  111.00 -94.00-150.00  132
 73  \w     39.00 121.00   0.50   12.00    --  111.00-125.00-150.00  164
 74  \w     30.00 104.00   0.50    3.00    --   42.50-136.00  -8.00  148
 75  \w      1.00  72.00   0.50    3.00    --   42.50 -99.00 120.00  142
 76  \w    -64.00  31.00   0.50    3.00    --  -38.50  57.00-150.00  190
 77  \w    -89.00  -2.00   0.50    3.00    --  -38.50 -19.00-180.00  174
 78  \w   -109.00 -12.00   0.50    3.00    --  -38.50 -57.00  60.00  194
 79  \w   -110.00 -16.00   0.50    3.00    --  -38.50 -38.00 120.00  188
;
_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      0.0765857000
_diffrn_orient_matrix_UB_12      0.0422010000
_diffrn_orient_matrix_UB_13      0.0550796000
_diffrn_orient_matrix_UB_21      -0.0859125000
_diffrn_orient_matrix_UB_22      -0.0326421000
_diffrn_orient_matrix_UB_23      0.0244063000
_diffrn_orient_matrix_UB_31      0.0348370000
_diffrn_orient_matrix_UB_32      -0.0752447000
_diffrn_orient_matrix_UB_33      0.0003390000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0279
_diffrn_reflns_av_unetI/netI     0.0147
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            145167
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.878
_diffrn_reflns_theta_min         2.646
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.894
_exptl_absorpt_correction_T_max  0.640
_exptl_absorpt_correction_T_min  0.253
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.498
_exptl_crystal_description       block
_exptl_crystal_F_000             2857
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.104
_refine_diff_density_max         0.838
_refine_diff_density_min         -0.743
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1645
_refine_ls_number_reflns         25653
_refine_ls_number_restraints     434
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0466
_refine_ls_R_factor_gt           0.0449
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0608P)^2^+6.7177P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1247
_refine_ls_wR_factor_ref         0.1262
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24333
_reflns_number_total             25653
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01701a2.cif
_cod_data_source_block           9OTf3
_cod_original_cell_volume        6138.77(10)
_cod_database_code               1551175
_chemical_oxdiff_formula         C39.5H66Cl3.3F9N6.9O9P7S3
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Restrained distances
 Cl4B-C41B \\sim C41B-Cl3B
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
S4A \\sim F10A \\sim F11A \\sim F12A \\sim O10A \\sim O11A \\sim O12A \\sim
C37A \\sim S4B \\sim F10B \\sim F11B \\sim F12B \\sim O10B \\sim O11B \\sim
O12B \\sim C37B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
Cl5A \\sim Cl6A \\sim C42A \\sim Cl5B \\sim Cl6B \\sim C42B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
S5B \\sim F13B \\sim F14B \\sim F15B \\sim O13B \\sim O14B \\sim O15B \\sim
C38B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Cl3A \\sim Cl4A \\sim C41A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
N7 \\sim C43 \\sim C44 \\sim Cl7 \\sim Cl8 \\sim C49: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
Cl3A \\sim Cl4A \\sim C41A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
S4C \\sim F10C \\sim F11C \\sim F12C \\sim O10C \\sim O11C \\sim O12C \\sim
C37C: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Same fragment restrains
{S4B, F12B, F11B, F10B, O10B, O12B, O11B, C37B} sigma for 1-2: 0.02, 1-3: 0.02
{S4C, F12C, F10C, F11C, O10C, O12C, O11C, C37C} sigma for 1-2: 0.02, 1-3: 0.02
as
{S4A, F10A, F11A, F12A, O10A, O11A, O12A, C37A}
{N8, C45, C46} sigma for 1-2: 0.02, 1-3: 0.02
{N7, C43, C44} sigma for 1-2: 0.02, 1-3: 0.02
as
{N9, C47, C48}
{Cl10, Cl9, C50} sigma for 1-2: 0.02, 1-3: 0.02
{Cl3B, Cl4B, C41B} sigma for 1-2: 0.02, 1-3: 0.02
{Cl2, Cl1, C40} sigma for 1-2: 0.02, 1-3: 0.02
{Cl7, Cl8, C49} sigma for 1-2: 0.02, 1-3: 0.02
{Cl3A, Cl4A, C41A} sigma for 1-2: 0.02, 1-3: 0.02
as
{Cl11, Cl12, C51}
5. Others
 1*[Sof(S4A)+Sof(F10A)+Sof(F11A)+Sof(F12A)+Sof(O10A)+Sof(O11A)+Sof(O12A)+
 Sof(C37A)]+1*[Sof(S4B)+Sof(F12B)+Sof(F11B)+Sof(F10B)+Sof(O10B)+Sof(O12B)+
 Sof(O11B)+Sof(C37B)]+1*[Sof(S4C)+Sof(F12C)+Sof(F10C)+Sof(F11C)+Sof(O10C)+
 Sof(O12C)+Sof(O11C)+Sof(C37C)]=1 with esd of 0
 Sof(Cl5B)=Sof(Cl6B)=Sof(C42B)=Sof(H42A)=Sof(H42B)=1-FVAR(1)
 Sof(Cl5A)=Sof(Cl6A)=Sof(C42A)=Sof(H42C)=Sof(H42D)=FVAR(1)
 Sof(S4A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(O10A)=Sof(O11A)=Sof(O12A)=
 Sof(C37A)=FVAR(2)
 Sof(Cl3A)=Sof(Cl4A)=Sof(C41A)=Sof(H41A)=Sof(H41B)=FVAR(3)
 Sof(Cl7)=Sof(Cl8)=Sof(C49)=Sof(H49A)=Sof(H49B)=1-FVAR(4)
 Sof(N7)=Sof(C43)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=FVAR(4)
 Sof(Cl11)=Sof(Cl12)=Sof(C51)=Sof(H51A)=Sof(H51B)=FVAR(5)
 Sof(N9)=Sof(C47)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=FVAR(6)
 Sof(S5B)=Sof(F13B)=Sof(F14B)=Sof(F15B)=Sof(O13B)=Sof(O14B)=Sof(O15B)=
 Sof(C38B)=1-FVAR(7)
 Sof(S5A)=Sof(F13A)=Sof(F14A)=Sof(F15A)=Sof(O13A)=Sof(O14A)=Sof(O15A)=
 Sof(C38A)=FVAR(7)
 Sof(Cl3B)=Sof(Cl4B)=Sof(C41B)=Sof(H41C)=Sof(H41D)=FVAR(8)
 Sof(N8)=Sof(C45)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=FVAR(9)
 Sof(S4B)=Sof(F12B)=Sof(F11B)=Sof(F10B)=Sof(O10B)=Sof(O12B)=Sof(O11B)=
 Sof(C37B)=FVAR(10)
 Sof(S4C)=Sof(F12C)=Sof(F10C)=Sof(F11C)=Sof(O10C)=Sof(O12C)=Sof(O11C)=
 Sof(C37C)=FVAR(11)
 Sof(Cl10)=Sof(Cl9)=Sof(C50)=Sof(H50A)=Sof(H50B)=FVAR(12)
6.a Ternary CH refined with riding coordinates:
 C4A(H4A), C7A(H7A), C15A(H15A), C18A(H18A), C26A(H26A), C29A(H29A), C4B(H4B),
 C7B(H7B), C15B(H15B), C18B(H18B), C26B(H26B), C29B(H29B)
6.b Secondary CH2 refined with riding coordinates:
 C50(H50A,H50B), C41B(H41C,H41D), C49(H49A,H49B), C51(H51A,H51B), C42A(H42C,
 H42D), C40(H40A,H40B), C41A(H41A,H41B), C42B(H42A,H42B)
6.c Idealised Me refined as rotating group:
 C5A(H5AA,H5AB,H5AC), C6A(H6AA,H6AB,H6AC), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,
 H9AC), C10A(H10A,H10B,H10C), C11A(H11A,H11B,H11C), C16A(H16A,H16B,H16C),
 C17A(H17A,H17B,H17C), C19A(H19A,H19B,H19C), C20A(H20A,H20B,H20C), C21A(H21A,
 H21B,H21C), C22A(H22A,H22B,H22C), C27A(H27A,H27B,H27C), C28A(H28A,H28B,H28C),
 C30A(H30A,H30B,H30C), C31A(H31A,H31B,H31C), C32A(H32A,H32B,H32C), C33A(H33A,
 H33B,H33C), C5B(H5BA,H5BB,H5BC), C6B(H6BA,H6BB,H6BC), C8B(H8BA,H8BB,H8BC),
 C9B(H9BA,H9BB,H9BC), C10B(H10D,H10E,H10F), C11B(H11D,H11E,H11F), C16B(H16D,
 H16E,H16F), C17B(H17D,H17E,H17F), C19B(H19D,H19E,H19F), C20B(H20D,H20E,H20F),
 C21B(H21D,H21E,H21F), C22B(H22D,H22E,H22F), C27B(H27D,H27E,H27F), C28B(H28D,
 H28E,H28F), C30B(H30D,H30E,H30F), C31B(H31D,H31E,H31F), C32B(H32D,H32E,H32F),
 C33B(H33D,H33E,H33F), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C), C48(H48A,H48B,
 H48C)
;
_shelx_res_checksum              52389
_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 1.495
_oxdiff_exptl_absorpt_empirical_full_min 0.570