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_1569388
_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
'2(C56 H75 F3 N6 O3 P S), 2(C F3 O3 S), 0.5(C4 H10 O), 0.25(C7 H8)'
_chemical_formula_sum            'C117.75 H157 F12 N12 O12.5 P2 S4'
_chemical_formula_weight         2358.72
_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'
_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                90
_cell_angle_beta                 92.090(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.5828(4)
_cell_length_b                   48.1844(12)
_cell_length_c                   19.0661(5)
_cell_measurement_reflns_used    9158
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.02
_cell_measurement_theta_min      2.21
_cell_volume                     12470.1(6)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.985
_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  0.0677
_diffrn_reflns_av_unetI/netI     0.0643
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       60
_diffrn_reflns_limit_k_min       -60
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            120521
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        26.450
_diffrn_reflns_theta_max         26.450
_diffrn_reflns_theta_min         1.149
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    0.182
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6458
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 SADABS 2016/2: Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D.,
 J. Appl. Cryst. 48 (2015) 3-10
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.256
_exptl_crystal_description       Plate
_exptl_crystal_F_000             4998
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.975
_refine_diff_density_min         -0.600
_refine_diff_density_rms         0.097
_refine_ls_extinction_coef       0.00023(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.130
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1707
_refine_ls_number_reflns         25293
_refine_ls_number_restraints     552
_refine_ls_restrained_S_all      1.126
_refine_ls_R_factor_all          0.1184
_refine_ls_R_factor_gt           0.0981
_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^)+97.6187P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2195
_refine_ls_wR_factor_ref         0.2281
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20019
_reflns_number_total             25293
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02899b2.cif
_cod_data_source_block           mw1
_cod_depositor_comments
'Adding full bibliography for 1569380--1569388.cif.'
_cod_original_formula_sum        'C117.75 H157 F12 N12 O12.50 P2 S4'
_cod_database_code               1569388
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.931
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, H7 of C7, H18 of C18, H20 of C20, H22 of C22, H3 of C3,
  H2 of C2, H13 of C13, H6 of C6, H10 of C10, H19 of C19, H8 of C8, H45 of C45,
  H46 of C46, H35 of C35, H47 of C47, H33 of C33, H30 of C30, H49 of C49, H29
  of C29, H34 of C34, H37 of C37, H52 of C52, H40 of C40, H64 of C64, H75 of
  C75, H76 of C76, H59 of C59, H58 of C58, H74 of C74, H66 of C66, H81 of C81,
  H63 of C63, H69 of C69, H62 of C62, H78 of C78, H101 of C101, H102 of C102,
  H105 of C105, H91 of C91, H89 of C89, H93 of C93, H96 of C96, H86 of C86,
  H103 of C103, H108 of C108, H85 of C85, H90 of C90, H1E of C1E, H1C of C1C,
  H1D of C1D, H1F of C1F, H1G of C1G, H25 of C25
 At 1.5 times of:
  All H(H) groups, H15A of C15, All C(H,H,H) groups
2. Restrained distances
 F12A-C116 = F14A-C116 = F13A-C116
 1.35 with sigma of 0.02
 C1G-C1B = C1G-C1F = C1F-C1E = C1E-C1D = C1D-C1C = C1C-C1B
 1.39 with sigma of 0.02
 C1B-C1F \\sim C1B-C1D \\sim C1G-C1E \\sim C1C-C1G \\sim C1D-C1F \\sim C1C-C1E
 with sigma of 0.04
 S2-O4 \\sim S2A-O4 \\sim S2A-O6A \\sim S2-O6 \\sim S2-O5 \\sim S2A-O5A
 with sigma of 0.02
 O4-O6A \\sim O6A-O5A \\sim O5A-O4
 with sigma of 0.02
 F14A-F13A \\sim F13A-F12A \\sim F12A-F14A
 with sigma of 0.02
 C1A-C1G \\sim C1A-C1C
 with sigma of 0.04
 S1A-C56A \\sim S1-C56
 with sigma of 0.02
 F1A-C56A \\sim F2A-C56A \\sim F3A-C56A \\sim F1-C56 \\sim F3-C56 \\sim F2-C56
 with sigma of 0.02
 C204-C203 \\sim C201-C200
 with sigma of 0.02
 S4A-C116 \\sim S4-C114
 with sigma of 0.02
 F5A-C115 \\sim F4A-C115 \\sim F6A-C115 \\sim F5-C112 \\sim F4-C112 \\sim
F6-C112
 with sigma of 0.02
 S2A-C115 \\sim S2-C112
 with sigma of 0.02
3. Restrained planarity
 C1E, C1D, C1C, C1B, C1G, C1A, C1F
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
O6A \\sim O6 \\sim S2A \\sim S2 \\sim O5A \\sim O5 \\sim C115 \\sim F5A \\sim
F4A \\sim F4 \\sim F6 \\sim C112 \\sim F5 \\sim F6A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.01 within 2A
F13A \\sim F14A \\sim C116 \\sim F12A \\sim S4A \\sim O13A \\sim O12A \\sim
O14A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.01 within
2A
C1E \\sim C1F \\sim C1G \\sim C1B \\sim C1C \\sim C1D \\sim C1A: within 1.9A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 1.9A
C200 \\sim C201 \\sim O202 \\sim C203 \\sim C204: within 1.9A with sigma of
0.02 and sigma for terminal atoms of 0.03 within 1.9A
S1A \\sim S1 \\sim O2 \\sim F1A \\sim C56A \\sim F2A \\sim F3A \\sim F1 \\sim
F3 \\sim F2 \\sim C56 \\sim O3A: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C1F) \\sim Ueq, Uanis(C1G) \\sim Ueq, Uanis(C1A) \\sim Ueq: with sigma of
0.02 and sigma for terminal atoms of 0.02
5. Others
 Sof(O3A)=Sof(S1A)=Sof(C56A)=Sof(F2A)=Sof(F1A)=Sof(F3A)=1-FVAR(1)
 Sof(S1)=Sof(O2)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(C56)=FVAR(1)
 Sof(O6A)=Sof(S2A)=Sof(O5A)=Sof(F4A)=Sof(C115)=Sof(F6A)=Sof(F5A)=1-FVAR(2)
 Sof(S2)=Sof(O5)=Sof(O6)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(C112)=FVAR(2)
 Sof(F14A)=Sof(F13A)=Sof(C116)=Sof(F12A)=Sof(S4A)=Sof(O13A)=Sof(O12A)=
 Sof(O14A)=1-FVAR(3)
 Sof(S4)=Sof(O12)=Sof(O13)=Sof(O14)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(C114)=FVAR(3)
 Fixed Sof: C200(0.5) H20A(0.5) H20B(0.5) H20C(0.5) C201(0.5) H20D(0.5)
 H20E(0.5) O202(0.5) C203(0.5) H20F(0.5) H20G(0.5) C204(0.5) H20H(0.5)
 H20I(0.5) H20J(0.5) C1A(0.25) H1AA(0.25) H1AB(0.25) H1AC(0.25) C1B(0.25)
 C1C(0.25) H1C(0.25) C1D(0.25) H1D(0.25) C1E(0.25) H1E(0.25) C1F(0.25)
 H1F(0.25) C1G(0.25) H1G(0.25)
 Fixed Uiso: H15B(0.05)
6.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C22(H22), C25(H25), C37(H37), C40(H40), C49(H49),
 C52(H52), C66(H66), C69(H69), C78(H78), C81(H81), C93(H93), C96(H96),
 C105(H105), C108(H108)
6.b Secondary CH2 refined with riding coordinates:
 C201(H20D,H20E), C203(H20F,H20G)
6.c Me refined with riding coordinates:
 C11(H11G,H11H,H11I), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C41(H41A,H41B,H41C),
 C42(H42A,H42B,H42C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C53(H53A,H53B,
 H53C), 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), C111(H11D,H11E,H11F), C200(H20A,H20B,H20C), C204(H20H,H20I,H20J)
6.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C8(H8), C18(H18), C19(H19), C20(H20),
 C29(H29), C30(H30), C33(H33), C34(H34), C35(H35), C45(H45), C46(H46), C47(H47),
  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), C1C(H1C), C1D(H1D), C1E(H1E), C1F(H1F), C1G(H1G)
6.e Idealised Me refined as rotating group:
 C1A(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              71981
_shelx_hkl_checksum              11940
_olex2_submission_special_instructions 'No special instructions were received'