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_1569387
_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         'C55 H74 N6 P, 1(C F3 O3 S)'
_chemical_formula_sum            'C56 H74 F3 N6 O3 P S'
_chemical_formula_weight         999.24
_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   mixed
_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                106.5338(7)
_cell_angle_beta                 90.8992(7)
_cell_angle_gamma                91.4357(7)
_cell_formula_units_Z            4
_cell_length_a                   12.1219(2)
_cell_length_b                   21.3779(3)
_cell_length_c                   22.6000(3)
_cell_measurement_reflns_used    9855
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.39
_cell_measurement_theta_min      2.36
_cell_volume                     5611.07(14)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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_temperature      100.02
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0357
_diffrn_reflns_av_unetI/netI     0.0395
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            74124
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.417
_diffrn_reflns_theta_min         0.994
_exptl_absorpt_coefficient_mu    0.143
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8166
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1013 before and 0.0315 after correction.
The Ratio of minimum to maximum transmission is 0.8166.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.183
_exptl_crystal_description       plate
_exptl_crystal_F_000             2136
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.793
_refine_diff_density_min         -0.438
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1485
_refine_ls_number_reflns         23011
_refine_ls_number_restraints     555
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0741
_refine_ls_R_factor_gt           0.0529
_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^)+(0.0587P)^2^+5.3178P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1282
_refine_ls_wR_factor_ref         0.1390
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17523
_reflns_number_total             23011
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02899b2.cif
_cod_data_source_block           p-1
_cod_depositor_comments
'Adding full bibliography for 1569380--1569388.cif.'
_cod_database_code               1569387
_shelx_shelxl_version_number     2018/3
_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
 S2B-O4B = S2B-O6B = S2B-O5B
 1.44 with sigma of 0.02
 C112-F4 \\sim C112-F5 \\sim C112-F6
 with sigma of 0.02
 S2-O6 \\sim S2-O5 \\sim S2-O4
 with sigma of 0.02
 C114-F5B \\sim C114-F4B \\sim C114-F6B
 with sigma of 0.02
 S2B-O6B \\sim S2B-O5B \\sim S2B-O4B
 with sigma of 0.02
 F6B-C114 \\sim F5B-C114 \\sim F4B-C114
 with sigma of 0.02
 F5B-F4B \\sim F4B-F6B \\sim F6B-F5B
 with sigma of 0.02
 C113-F5C \\sim C113-F6C \\sim C113-F4C
 with sigma of 0.02
 S2C-O6C \\sim S2C-O5C \\sim S2C-O4C
 with sigma of 0.02
 S2B-C114 \\sim S2C-C113 \\sim S2-C112
 with sigma of 0.02
 F4C-C113 \\sim F5C-C113 \\sim F6C-C113
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C114 \\sim F5B \\sim F4B \\sim F6B \\sim S2B \\sim O6B \\sim O5B \\sim O4B:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C113 \\sim C112 \\sim F4 \\sim F5 \\sim F6 \\sim S2 \\sim O6 \\sim O5 \\sim O4
\\sim S2C \\sim C114 \\sim S2B \\sim O4B \\sim F4C \\sim F6C \\sim O4C \\sim
F4B \\sim O6C \\sim O5B \\sim O5C \\sim F5C \\sim F5B \\sim F6B \\sim O6B:
within 1.9A with sigma of 0.01 and sigma for terminal atoms of 0.01 within 1.9A
4. Others
 Sof(H26A)=Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28A)=Sof(H28D)=
 Sof(H28E)=Sof(H28F)=1-FVAR(1)
 Sof(H26)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28)=Sof(H28A)=Sof(H28B)=
 Sof(H28C)=FVAR(1)
 Sof(H81A)=Sof(C82A)=Sof(H82D)=Sof(H82E)=Sof(H82F)=1-FVAR(2)
 Sof(H81)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=FVAR(2)
 Fixed Sof: C112(0.71) F4(0.71) F5(0.71) F6(0.71) S2(0.71) O6(0.71) O5(0.71)
 O4(0.71) C114(0.14) F5B(0.14) F4B(0.14) F6B(0.14) S2B(0.14) O6B(0.14)
 O5B(0.14) O4B(0.14) C113(0.15) F5C(0.15) F6C(0.15) F4C(0.15) S2C(0.15)
 O6C(0.15) O5C(0.15) O4C(0.15)
5.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C23(H23), C26(H26), C26(H26A), C38(H38), C41(H41),
 C50(H50), C53(H53), C66(H66), C69(H69), C78(H78), C81(H81), C81(H81A),
 C93(H93), C96(H96), C105(H105), C108(H108)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C19(H19), C20(H20), C21(H21),
 C30(H30), C31(H31), C34(H34), C35(H35), C36(H36), C46(H46), C47(H47), C48(H48),
  C58(H58), C59(H59), C62(H62), C63(H63), C64(H64), C74(H74), C75(H75),
 C76(H76), C85(H85), C86(H86), C89(H89), C90(H90), C91(H91), C101(H101),
 C102(H102), C103(H103)
5.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C),
 C27A(H27D,H27E,H27F), C28(H28A,H28B,H28C), C28A(H28D,H28E,H28F), C39(H39A,H39B,
 H39C), C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C51(H51A,
 H51B,H51C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C),
 C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C70(H70A,H70B,H70C), C71(H71A,H71B,
 H71C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C), C82(H82A,H82B,H82C), C83(H83A,
 H83B,H83C), C94(H94A,H94B,H94C), C95(H95A,H95B,H95C), C97(H97A,H97B,H97C),
 C98(H98A,H98B,H98C), C106(H10A,H10B,H10C), C107(H10D,H10E,H10F), C109(H10G,
 H10H,H10I), C110(H11A,H11B,H11C), C82A(H82D,H82E,H82F)
;
_shelx_res_checksum              6012
_shelx_hkl_checksum              83442
_olex2_submission_special_instructions 'No special instructions were received'