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_1551176
_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 H79 N8 P4, 4(C F3 O3 S), 2(C2 H3 N)'
_chemical_formula_sum            'C52 H85 F12 N10 O12 P4 S4'
_chemical_formula_weight         1522.41
_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
_audit_creation_date             2018-12-10
_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                 105.4253(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.31294(18)
_cell_length_b                   16.76136(17)
_cell_length_c                   23.1443(2)
_cell_measurement_reflns_used    22416
_cell_measurement_temperature    104.6(7)
_cell_measurement_theta_max      76.4770
_cell_measurement_theta_min      3.2810
_cell_volume                     7222.19(12)
_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      104.6(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 0.988
_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    -30.00  -4.00   0.50    2.00    --   42.62 -38.00  90.00   52
  2  \w      1.00  83.00   0.50    2.00    --   42.62 -99.00  30.00  164
  3  \w     23.00  67.00   0.50    2.00    --   42.62-125.00 -30.00   88
  4  \w     60.00  93.00   0.50    8.00    --  111.00 -94.00-150.00   66
  5  \w     98.00 131.00   0.50    8.00    --  111.00 -61.00-120.00   66
  6  \w    101.00 132.00   0.50    8.00    --  111.00  45.00 -60.00   62
  7  \w     97.00 176.00   0.50    8.00    --  111.00  83.00 -26.00  158
  8  \w    130.00 178.00   0.50    8.00    --  111.00 125.00 -60.00   96
  9  \w    110.00 172.00   0.50    8.00    --  111.00 125.00 -90.00  124
 10  \w    134.00 161.00   0.50    8.00    --  111.00  30.00  30.00   54
 11  \w     89.00 172.00   0.50    8.00    --  111.00  45.00 -30.00  166
 12  \w     88.00 163.00   0.50    8.00    --  111.00  77.00 -90.00  150
 13  \w     52.00 107.00   0.50    8.00    --  111.00 -94.00 120.00  110
 14  \w     42.00 121.00   0.50    8.00    --  111.00-125.00   0.00  158
 15  \w     55.00  80.00   0.50    8.00    --  111.00-125.00 -90.00   50
 16  \w     44.00  92.00   0.50    8.00    --  111.00 -94.00 -90.00   96
 17  \w     30.00 106.00   0.50    8.00    --  111.00 -94.00  90.00  152
 18  \w    -63.00 -25.00   0.50    2.00    --  -38.50  57.00-180.00   76
 19  \w   -108.00 -21.00   0.50    2.00    --  -38.50 -38.00 150.00  174
;
_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      0.0807340000
_diffrn_orient_matrix_UB_12      0.0047899000
_diffrn_orient_matrix_UB_13      0.0321547000
_diffrn_orient_matrix_UB_21      -0.0049597000
_diffrn_orient_matrix_UB_22      -0.0800336000
_diffrn_orient_matrix_UB_23      0.0314571000
_diffrn_orient_matrix_UB_31      0.0175164000
_diffrn_orient_matrix_UB_32      -0.0449521000
_diffrn_orient_matrix_UB_33      -0.0523799000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0372
_diffrn_reflns_av_unetI/netI     0.0350
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            45993
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.813
_diffrn_reflns_theta_min         2.373
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.851
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73524
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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    1.400
_exptl_crystal_description       block
_exptl_crystal_F_000             3180
_exptl_crystal_size_max          0.313
_exptl_crystal_size_mid          0.273
_exptl_crystal_size_min          0.124
_refine_diff_density_max         1.277
_refine_diff_density_min         -0.639
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1040
_refine_ls_number_reflns         15049
_refine_ls_number_restraints     313
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0613
_refine_ls_R_factor_gt           0.0559
_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^)+(0.0915P)^2^+5.6436P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1547
_refine_ls_wR_factor_ref         0.1621
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13385
_reflns_number_total             15049
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01701a2.cif
_cod_data_source_block           3OTf4
_cod_original_cell_volume        7222.20(13)
_cod_database_code               1551176
_chemical_oxdiff_formula         C51H85F12N10O12P4S4
_reflns_odcompleteness_completeness 99.99
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C28A-C26
 1.51 with sigma of 0.01
 C28B-C26
 1.51 with sigma of 0.01
 C27A-C26
 1.51 with sigma of 0.01
 C27B-C26
 1.51 with sigma of 0.01
 S3A-O7A \\sim S3A-O8A \\sim S3A-O9A \\sim S3-O7 \\sim S3-O9 \\sim S3-O8
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
F11 \\sim S4 \\sim O12 \\sim O11 \\sim O10 \\sim C48 \\sim F12 \\sim F10 \\sim
O10A \\sim S4A \\sim O11A \\sim O12A \\sim C48A \\sim F10A \\sim F11A \\sim
F12A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C28A \\sim C28B \\sim C26: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
4. Same fragment restrains
{C28B, C26, C27B} sigma for 1-2: 0.02, 1-3: 0.02
as
{C31, C29, C30}
{S4, O12, O11, O10, C48, F12, F10, F11} sigma for 1-2: 0.02, 1-3: 0.02
{S4A, O10A, O11A, O12A, C48A, F10A, F11A, F12A} sigma for 1-2: 0.02, 1-3: 0.02
as
{S1, O3, O1, O2, C45, F2, F1, F3}
5. Others
 Sof(C28B)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C27B)=Sof(H27A)=Sof(H27B)=
 Sof(H27C)=1-FVAR(1)
 Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C27A)=Sof(H27D)=Sof(H27E)=
 Sof(H27F)=FVAR(1)
 Sof(S4A)=Sof(O10A)=Sof(O11A)=Sof(O12A)=Sof(C48A)=Sof(F10A)=Sof(F11A)=
 Sof(F12A)=1-FVAR(2)
 Sof(S4)=Sof(O12)=Sof(O11)=Sof(O10)=Sof(C48)=Sof(F12)=Sof(F10)=Sof(F11)=FVAR(2)
 Sof(O7A)=Sof(O9A)=Sof(O8A)=Sof(S3A)=Sof(C47A)=Sof(F8A)=Sof(F9A)=Sof(F7A)=1-
 FVAR(3)
 Sof(O9)=Sof(O8)=Sof(O7)=Sof(S3)=Sof(C47)=Sof(F7)=Sof(F8)=Sof(F9)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C4(H4), C7(H7), C15(H15), C18(H18), C29(H29), C37(H37), C40(H40)
6.b Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C11(H11A,H11B,H11C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C28B(H28A,H28B,H28C), C27B(H27A,H27B,H27C), C28A(H28D,H28E,H28F),
 C27A(H27D,H27E,H27F), C31(H31A,H31B,H31C), C30(H30A,H30B,H30C), C32(H32A,H32B,
 H32C), C33(H33A,H33B,H33C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C41(H41A,
 H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C),
 C51(H51A,H51B,H51C), C49(H49A,H49B,H49C)
;
_shelx_res_checksum              23667
_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 1.324
_oxdiff_exptl_absorpt_empirical_full_min 0.718