Terminal methylene phosphonium ions: precursors for transient monosubstituted phosphinocarbenes.
Löwe, Pawel; Wünsche, Marius A; Purtscher, Felix R. S.; Gamper, Jakob; Hofer, Thomas S.; Wilm, Lukas F. B.; Röthel, Maike B; Dielmann, Fabian; Chemical science 14 (2023) 7928–7935; doi:10.1039/d3sc02899b

data_1569384
_publ_section_title
;
 Terminal methylene phosphonium ions: precursors for transient
 monosubstituted phosphinocarbenes.
;
_journal_issue                   29
_journal_name_full               'Chemical science'
_journal_page_first              7928
_journal_page_last               7935
_journal_paper_doi               10.1039/d3sc02899b
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C46 H94 N12 O P2, 2(C32 H12 B F24)'
_chemical_formula_sum            'C110 H118 B2 F48 N12 O P2'
_chemical_formula_weight         2619.72
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-06-02
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-23 deposited with the CCDC.	2023-06-29 downloaded from the CCDC.
;
_cell_angle_alpha                74.076(3)
_cell_angle_beta                 82.009(3)
_cell_angle_gamma                67.187(4)
_cell_formula_units_Z            2
_cell_length_a                   13.7117(5)
_cell_length_b                   16.9823(9)
_cell_length_c                   29.5424(8)
_cell_measurement_reflns_used    26823
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      26.3030
_cell_measurement_theta_min      2.2520
_cell_volume                     6093.5(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.964
_diffrn_measured_fraction_theta_max 0.968
_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     -7.53 177.27   0.30   40.00    --   20.00  73.73 -25.73  616
  2  \w     -7.53 177.27   0.30   40.00    --   20.00  73.73  94.27  616
  3  \w     -7.53 177.27   0.30   40.00    --   20.00  73.73-145.73  616
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0067126000
_diffrn_orient_matrix_UB_12      0.0060527000
_diffrn_orient_matrix_UB_13      -0.0242559000
_diffrn_orient_matrix_UB_21      -0.0537883000
_diffrn_orient_matrix_UB_22      0.0273374000
_diffrn_orient_matrix_UB_23      0.0025024000
_diffrn_orient_matrix_UB_31      0.0146770000
_diffrn_orient_matrix_UB_32      0.0373678000
_diffrn_orient_matrix_UB_33      -0.0054422000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0549
_diffrn_reflns_av_unetI/netI     0.0542
_diffrn_reflns_Laue_measured_fraction_full 0.964
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            67073
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         2.152
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.161
_exptl_absorpt_correction_T_max  0.95159
_exptl_absorpt_correction_T_min  0.95159
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Spherical absorption correction
using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.428
_exptl_crystal_description       block
_exptl_crystal_F_000             2684
_exptl_crystal_size_max          0.439
_exptl_crystal_size_mid          0.382
_exptl_crystal_size_min          0.356
_exptl_crystal_size_rad          0.400
_refine_diff_density_max         0.719
_refine_diff_density_min         -0.525
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1809
_refine_ls_number_reflns         24114
_refine_ls_number_restraints     716
_refine_ls_restrained_S_all      1.120
_refine_ls_R_factor_all          0.0664
_refine_ls_R_factor_gt           0.0545
_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^)+(0.0729P)^2^+2.6138P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1386
_refine_ls_wR_factor_ref         0.1503
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19954
_reflns_number_total             24114
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02899b2.cif
_cod_data_source_block           pl210324_ap_abs
_cod_depositor_comments
'Adding full bibliography for 1569380--1569388.cif.'
_cod_original_cell_volume        6093.6(5)
_cod_database_code               1569384
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.933
_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
 C107-C110 \\sim C107-C111
 with sigma of 0.02
 F46A-C110 \\sim F48A-C110 \\sim F47A-C110 \\sim F46B-C110 \\sim F48B-C110
\\sim F47B-C110
 with sigma of 0.02
 F37A-C101 \\sim F37B-C70 \\sim F38B-C70 \\sim F38A-C101 \\sim F39B-C70 \\sim
F39A-C101
 with sigma of 0.02
 F16B-C1B \\sim F16A-C1B \\sim F1C-C1B \\sim F18A-C1B \\sim F18B-C1B \\sim
F1A-C1B \\sim F17A-C1B ~
 F17B-C1B \\sim F1B-C1B
 with sigma of 0.02
 F43B-C109 \\sim F43A-C109 \\sim F44C-C109 \\sim F44B-C109 \\sim F44A-C109
\\sim F45C-C109 \\sim F45B-
 C109 \\sim F43C-C109 \\sim F45A-C109
 with sigma of 0.02
 C97-C101 \\sim C97-C70
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F48A \\sim F47B \\sim F47A \\sim F46B \\sim F46A \\sim F48B \\sim C110 \\sim
C111: within 1.9A with sigma of 0.01 and sigma for terminal atoms of 0.01
within 1.9A
F24 \\sim F22 \\sim F23 \\sim C78 \\sim F22A \\sim F23A \\sim F24A: within 1.9A
with sigma of 0.01 and sigma for terminal atoms of 0.01 within 1.9A
F16B \\sim F17A \\sim F18A \\sim F18B \\sim F16A \\sim F17B \\sim C1B \\sim F1A
\\sim F1B \\sim F1C: within 1.9A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 1.9A
F45A \\sim F43A \\sim F44A \\sim F44B \\sim F45B \\sim F43B \\sim C109 \\sim
F44C \\sim F43C \\sim F45C: within 1.9A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 1.9A
C101 \\sim F37A \\sim F38A \\sim F39A \\sim F38B \\sim F39B \\sim F37B \\sim
C70: within 1.9A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
1.9A
4. Others
 Fixed Sof: F24(0.87) F22(0.87) F23(0.87) C101(0.78) C110(0.59) F16B(0.43)
 F17A(0.31) F18A(0.31) F37A(0.78) F38A(0.78) F39A(0.78) F18B(0.43) F16A(0.31)
 F17B(0.43) F46A(0.59) F45A(0.39) F47A(0.59) F43A(0.39) F44A(0.39) F44B(0.37)
 F45B(0.37) F43B(0.37) F48A(0.59) F46B(0.41) F38B(0.22) F39B(0.22) F37B(0.22)
 F48B(0.41) F47B(0.41) F22A(0.13) F23A(0.13) F24A(0.13) C70(0.22) F44C(0.24)
 F43C(0.24) F45C(0.24) F1A(0.26) F1B(0.26) F1C(0.26) C111(0.41)
5.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C11(H11A,H11B), C10(H10A,H10B), C14(H14A,H14B), C4(H4A,H4B),
 C8(H8A,H8B), C5(H5A,H5B), C7(H7A,H7B)
5.b Aromatic/amide H refined with riding coordinates:
 C56(H56), C76(H76), C64(H64), C60(H60), C48(H48), C100(H100), C72(H72),
 C82(H82), C84(H84), C80(H80), C58(H58), C52(H52), C66(H66), C68(H68), C74(H74),
  C50(H50), C96(H96), C88(H88), C92(H92), C108(H108), C104(H104), C106(H106),
 C98(H98), C90(H90)
5.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C1(H1A,H1B,H1C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C),
 C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C22(H22A,H22B,H22C), C40(H40A,H40B,
 H40C), C30(H30A,H30B,H30C), C44(H44A,H44B,H44C), C32(H32A,H32B,H32C), C46(H46A,
 H46B,H46C), C36(H36A,H36B,H36C), C33(H33A,H33B,H33C), C18(H18A,H18B,H18C),
 C45(H45A,H45B,H45C), C37(H37A,H37B,H37C), C20(H20A,H20B,H20C), C34(H34A,H34B,
 H34C), C17(H17A,H17B,H17C), C38(H38A,H38B,H38C), C24(H24A,H24B,H24C), C26(H26A,
 H26B,H26C), C21(H21A,H21B,H21C), C16(H16A,H16B,H16C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              37848
_shelx_hkl_checksum              11071
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.805
_oxdiff_exptl_absorpt_empirical_full_min 0.627