Cationic 5-phosphonio-substituted N-heterocyclic carbenes.
Schwedtmann, Kai; Schoemaker, Robin; Hennersdorf, Felix; Bauzá, Antonio; Frontera, Antonio; Weiss, Robert; Weigand, Jan J.; Dalton transactions (Cambridge, England : 2003) 45 (2016) 11384–11396; doi:10.1039/c6dt01871h

data_7039679
_publ_section_title
;
 Cationic 5-phosphonio-substituted N-heterocyclic carbenes.
;
_journal_issue                   28
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              11384
_journal_page_last               11396
_journal_paper_doi               10.1039/c6dt01871h
_journal_volume                  45
_journal_year                    2016
_chemical_formula_moiety
'C80 H94 Ag Cl2 N4 P2, 3(C F3 O3 S), C2 H3 N, 1.5(C4 H10 O)'
_chemical_formula_sum            'C91 H112 Ag Cl2 F9 N5 O10.5 P2 S3'
_chemical_formula_weight         1951.74
_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_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-06-02 deposited with the CCDC.
2016-06-03 downloaded from the CCDC.
;
_cell_angle_alpha                98.7772(11)
_cell_angle_beta                 101.6430(8)
_cell_angle_gamma                97.9382(12)
_cell_formula_units_Z            2
_cell_length_a                   17.14476(19)
_cell_length_b                   17.1735(3)
_cell_length_c                   18.09533(13)
_cell_measurement_reflns_used    30313
_cell_measurement_temperature    100.1(3)
_cell_measurement_theta_max      76.4080
_cell_measurement_theta_min      3.2240
_cell_volume                     5078.05(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      100.1(3)
_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 0.987
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  1  \w      8.00  50.00   0.50    1.50    --   42.75 -99.00 -60.00   84
  2  \w     37.00  66.00   0.50    6.00    --  111.00 -77.00 -60.00   58
  3  \w     46.00 135.00   0.50    6.00    --  111.00 -45.00 -60.00  178
  4  \w    115.00 141.00   0.50    6.00    --  111.00 -77.00 -60.00   52
  5  \w    109.00 138.00   0.50    6.00    --  111.00 -61.00-150.00   58
  6  \w     80.00 121.00   0.50    6.00    --  111.00-125.00-150.00   82
  7  \w     77.00 104.00   0.50    6.00    --  111.00-125.00-180.00   54
  8  \w     61.00 109.00   0.50    6.00    --  111.00 -94.00-150.00   96
  9  \w     59.00  86.00   0.50    6.00    --  111.00 -61.00-150.00   54
 10  \w     42.00 121.00   0.50    6.00    --  111.00-125.00 -90.00  158
 11  \w     78.00 121.00   0.50    6.00    --  111.00-125.00   0.00   86
 12  \w     75.00 121.00   0.50    6.00    --  111.00-125.00  30.00   92
 13  \w     87.00 119.00   0.50    6.00    --  111.00-125.00 120.00   64
 14  \w     94.00 121.00   0.50    6.00    --  111.00 -77.00 150.00   54
 15  \w     61.00  88.00   0.50    6.00    --  111.00 -77.00 150.00   54
 16  \w     56.00 130.00   0.50    6.00    --  111.00 -45.00  90.00  148
 17  \w     88.00 131.00   0.50    6.00    --  111.00  30.00   0.00   86
 18  \w    117.00 178.00   0.50    6.00    --  111.00  45.00 -60.00  122
 19  \w    152.00 178.00   0.50    6.00    --  111.00  15.00-120.00   52
 20  \w    137.00 170.00   0.50    6.00    --  111.00  45.00 -90.00   66
 21  \w    101.00 177.00   0.50    6.00    --  111.00  45.00  30.00  152
 22  \w    138.00 178.00   0.50    6.00    --  111.00  45.00 150.00   80
 23  \w     94.00 178.00   0.50    6.00    --  111.00  30.00  90.00  168
 24  \w     87.00 119.00   0.50    6.00    --  111.00  45.00 150.00   64
 25  \w     53.00  84.00   0.50    6.00    --  111.00 -30.00  30.00   62
 26  \w     43.00 109.00   0.50    6.00    --  111.00 -94.00  90.00  132
 27  \w     71.00 109.00   0.50    6.00    --  111.00 -94.00   0.00   76
 28  \w     41.00 107.00   0.50    6.00    --  111.00-125.00 -30.00  132
 29  \w     31.00  79.00   0.50    6.00    --  111.00 -94.00 120.00   96
 30  \w     89.00 128.00   0.50    6.00    --  111.00  45.00 -90.00   78
 31  \w     73.00 127.00   0.50    6.00    --  111.00  15.00-120.00  108
 32  \w    -27.00  -2.00   0.50    1.50    --  -38.50 125.00-150.00   50
 33  \w    -89.00 -53.00   0.50    1.50    --  -38.50 125.00 -30.00   72
 34  \w   -104.00 -48.00   0.50    1.50    --  -38.50 -77.00-180.00  112
 35  \w   -111.00 -16.00   0.50    1.50    --  -38.50 -38.00 -30.00  190
 36  \w   -108.00 -25.00   0.50    1.50    --  -38.50 -38.00  60.00  166
 37  \w    -94.00  -2.00   0.50    1.50    --  -38.50 125.00-180.00  184
;
_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      0.0014258000
_diffrn_orient_matrix_UB_12      -0.0903479000
_diffrn_orient_matrix_UB_13      -0.0179261000
_diffrn_orient_matrix_UB_21      0.0482561000
_diffrn_orient_matrix_UB_22      0.0137140000
_diffrn_orient_matrix_UB_23      -0.0614394000
_diffrn_orient_matrix_UB_31      0.0796905000
_diffrn_orient_matrix_UB_32      0.0121186000
_diffrn_orient_matrix_UB_33      0.0610786000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0543
_diffrn_reflns_av_unetI/netI     0.0577
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            57825
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.693
_diffrn_reflns_theta_min         2.537
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.550
_exptl_absorpt_correction_T_max  0.841
_exptl_absorpt_correction_T_min  0.426
_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    1.276
_exptl_crystal_description       needle
_exptl_crystal_F_000             2034
_exptl_crystal_size_max          0.482
_exptl_crystal_size_mid          0.108
_exptl_crystal_size_min          0.056
_refine_diff_density_max         1.910
_refine_diff_density_min         -1.482
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1378
_refine_ls_number_reflns         21098
_refine_ls_number_restraints     518
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0818
_refine_ls_R_factor_gt           0.0771
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1255P)^2^+10.0066P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2157
_refine_ls_wR_factor_ref         0.2214
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19184
_reflns_number_total             21098
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6dt01871h2.cif
_cod_data_source_block           22OTf
_cod_depositor_comments
'Adding full bibliography for 7039669--7039682.cif.'
_cod_original_cell_volume        5078.06(12)
_cod_original_formula_sum        'C91 H112 Ag Cl2 F9 N5 O10.50 P2 S3'
_cod_database_code               7039679
_chemical_oxdiff_formula         C88H104AgCl2F9N4.5O10P2S3
_chemical_oxdiff_usercomment     MeCN/Et2O
_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
 C99-C98 \\sim C97-C96 \\sim C94-C95 \\sim C92-C93 \\sim C91-C90 \\sim C88-C89
\\sim C87_$1-C86_$1 ~
 C84_$1-C85_$1
 with sigma of 0.01
 O13-C98 \\sim O13-C97 \\sim O12-C94 \\sim O12-C93 \\sim O11-C90 \\sim O11-C89
\\sim O10_$1-C86_$1 ~
 O10_$1-C85_$1
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
S2B \\sim O6A \\sim O4A \\sim S2A \\sim O5B \\sim O4B \\sim O6B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C101 \\sim C100 \\sim N5 \\sim C102 \\sim C103 \\sim N6: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02
C87 \\sim O10 \\sim C85 \\sim C86 \\sim C84: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C92 \\sim O12 \\sim C94 \\sim C93 \\sim C95 \\sim C91 \\sim O11 \\sim C90 \\sim
C89 \\sim C88 \\sim C98 \\sim C97 \\sim O13 \\sim C96 \\sim C99: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C74A \\sim C79A \\sim C75A \\sim C78A \\sim C77A \\sim C76A \\sim C74B \\sim
C75B \\sim C76B \\sim C77B \\sim C78B \\sim C79B: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
4. Others
 Sof(C74B)=Sof(C75B)=Sof(H75B)=Sof(C76B)=Sof(H76B)=Sof(C77B)=Sof(H77B)=
 Sof(C78B)=Sof(H78B)=Sof(C79B)=Sof(H79B)=1-FVAR(1)
 Sof(C74A)=Sof(C79A)=Sof(H79A)=Sof(C75A)=Sof(H75A)=Sof(C78A)=Sof(H78A)=
 Sof(C77A)=Sof(H77A)=Sof(C76A)=Sof(H76A)=FVAR(1)
 Sof(S2B)=Sof(O5B)=Sof(O4B)=Sof(O6B)=1-FVAR(2)
 Sof(O6A)=Sof(O5A)=Sof(O4A)=Sof(S2A)=FVAR(2)
 Sof(S3B)=1-FVAR(3)
 Sof(S3A)=FVAR(3)
 Sof(C102)=Sof(C103)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(N6)=1-FVAR(4)
 Sof(C101)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C100)=Sof(N5)=FVAR(4)
 Fixed Sof: O10(0.5) C87(0.5) H87A(0.5) H87B(0.5) H87C(0.5) C85(0.5) H85A(0.5)
 H85B(0.5) C86(0.5) H86A(0.5) H86B(0.5) C84(0.5) H84A(0.5) H84B(0.5) H84C(0.5)
 O11(0.33333) C88(0.33333) H88A(0.33333) H88B(0.33333) H88C(0.33333)
 C97(0.33333) H97A(0.33333) H97B(0.33333) C91(0.33333) H91A(0.33333)
 H91B(0.33333) H91C(0.33333) C90(0.33333) H90A(0.33333) H90B(0.33333)
 C89(0.33333) H89A(0.33333) H89B(0.33333) O13(0.33333) C96(0.33333)
 H96A(0.33333) H96B(0.33333) H96C(0.33333) C98(0.33333) H98A(0.33333)
 H98B(0.33333) C99(0.33333) H99A(0.33333) H99B(0.33333) H99C(0.33333)
 O12(0.33333) C92(0.33333) H92A(0.33333) H92B(0.33333) H92C(0.33333)
 C94(0.33333) H94A(0.33333) H94B(0.33333) C93(0.33333) H93A(0.33333)
 H93B(0.33333) C95(0.33333) H95A(0.33333) H95B(0.33333) H95C(0.33333)
5.a Ternary CH refined with riding coordinates:
 C13(H13), C10(H10), C53(H53), C62(H62), C25(H25), C22(H22), C65(H65), C50(H50)
5.b Secondary CH2 refined with riding coordinates:
 C85(H85A,H85B), C86(H86A,H86B), C97(H97A,H97B), C90(H90A,H90B), C89(H89A,
 H89B), C98(H98A,H98B), C94(H94A,H94B), C93(H93A,H93B)
5.c Aromatic/amide H refined with riding coordinates:
 C35(H35), C6(H6), C39(H39), C73(H73), C70(H70), C7(H7), C8(H8), C37(H37),
 C33(H33), C29(H29), C38(H38), C60(H60), C69(H69), C20(H20), C36(H36), C71(H71),
  C31(H31), C32(H32), C72(H72), C48(H48), C30(H30), C58(H58), C59(H59),
 C46(H46), C47(H47), C19(H19), C18(H18), C79A(H79A), C75A(H75A), C78A(H78A),
 C77A(H77A), C76A(H76A), C75B(H75B), C76B(H76B), C77B(H77B), C78B(H78B),
 C79B(H79B)
5.d Idealised Me refined as rotating group:
 C54(H54A,H54B,H54C), C40(H40A,H40B,H40C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C12(H12A,H12B,H12C), C11(H11A,H11B,H11C), C80(H80A,H80B,H80C), C27(H27A,
 H27B,H27C), C23(H23A,H23B,H23C), C55(H55A,H55B,H55C), C24(H24A,H24B,H24C),
 C67(H67A,H67B,H67C), C66(H66A,H66B,H66C), C26(H26A,H26B,H26C), C52(H52A,H52B,
 H52C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C51(H51A,H51B,H51C),
 C101(H10A,H10B,H10C), C87(H87A,H87B,H87C), C84(H84A,H84B,H84C), C88(H88A,H88B,
 H88C), C91(H91A,H91B,H91C), C96(H96A,H96B,H96C), C99(H99A,H99B,H99C),
 C103(H10D,H10E,H10F), C92(H92A,H92B,H92C), C95(H95A,H95B,H95C)
;
_shelx_res_checksum              12560
_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 1.572
_oxdiff_exptl_absorpt_empirical_full_min 0.506