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_1569385
_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 H75 N6 P'
_chemical_formula_sum            'C55 H75 N6 P'
_chemical_formula_weight         851.18
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   27.9781(6)
_cell_length_b                   12.6688(3)
_cell_length_c                   28.6912(6)
_cell_measurement_reflns_used    9971
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.605
_cell_measurement_theta_min      2.282
_cell_volume                     10169.6(4)
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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  0.0487
_diffrn_reflns_av_unetI/netI     0.0386
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            92278
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.695
_diffrn_reflns_theta_min         1.456
_exptl_absorpt_coefficient_mu    0.095
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8418
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1497 before and 0.0557 after correction.
The Ratio of minimum to maximum transmission is 0.8418.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.112
_exptl_crystal_description       needle
_exptl_crystal_F_000             3696
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.807
_refine_diff_density_min         -0.367
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.38(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1252
_refine_ls_number_reflns         19296
_refine_ls_number_restraints     38
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0748
_refine_ls_R_factor_gt           0.0641
_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^)+(0.0840P)^2^+8.5056P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1602
_refine_ls_wR_factor_ref         0.1679
_reflns_Friedel_coverage         0.955
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                17442
_reflns_number_total             19296
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02899b2.cif
_cod_data_source_block           pca21
_cod_depositor_comments
'Adding full bibliography for 1569380--1569388.cif.'
_cod_database_code               1569385
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.62(13)
 0.38(13)
2. 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
3. Restrained distances
 C107-C103 \\sim C17A-C103
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
N7 \\sim N7A \\sim C56: within 1.9A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 1.9A
C107 \\sim C17A \\sim C103: within 1.9A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 1.9A
5. Others
 Sof(P2A)=Sof(N7A)=Sof(N10A)=Sof(C11A)=Sof(H11A)=Sof(H11B)=Sof(H11C)=1-FVAR(1)
 Sof(P2)=Sof(N7)=Sof(N10)=Sof(C110)=Sof(H11D)=Sof(H11E)=Sof(H11F)=FVAR(1)
 Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19A)=
 Sof(H19A)=Sof(H19B)=Sof(H19C)=1-FVAR(2)
 Sof(C107)=Sof(H107)=Sof(C108)=Sof(H10G)=Sof(H10H)=Sof(H10I)=Sof(C109)=
 Sof(H10J)=Sof(H10K)=Sof(H10L)=FVAR(2)
 Sof(H77A)=Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=Sof(C79)=Sof(H79A)=Sof(H79B)=
 Sof(H79C)=1-FVAR(3)
 Sof(H77)=Sof(C78A)=Sof(H78D)=Sof(H78E)=Sof(H78F)=Sof(C79A)=Sof(H79D)=
 Sof(H79E)=Sof(H79F)=FVAR(3)
 Sof(H37A)=Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=1-FVAR(4)
 Sof(H37)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C17A(H17A), C65(H65), C68(H68), C77(H77), C77(H77A), C80(H80), C92(H92),
 C95(H95), C104(H104), C107(H107), C10(H10), C13(H13), C22(H22), C25(H25),
 C37(H37), C37(H37A), C40(H40), C49(H49), C52(H52)
6.b Aromatic/amide H refined with riding coordinates:
 C57(H57), C58(H58), C61(H61), C62(H62), C63(H63), C73(H73), C74(H74),
 C75(H75), C84(H84), C85(H85), C88(H88), C89(H89), C90(H90), C100(H100),
 C101(H101), C102(H102), 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)
6.c Idealised Me refined as rotating group:
 C11A(H11A,H11B,H11C), C18A(H18A,H18B,H18C), C19A(H19A,H19B,H19C), C66(H66A,
 H66B,H66C), C67(H67A,H67B,H67C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C),
 C78(H78A,H78B,H78C), C78A(H78D,H78E,H78F), C79(H79A,H79B,H79C), C79A(H79D,H79E,
 H79F), C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C93(H93A,H93B,H93C), C94(H94A,
 H94B,H94C), C96(H96A,H96B,H96C), C97(H97A,H97B,H97C), C105(H10A,H10B,H10C),
 C106(H10D,H10E,H10F), C108(H10G,H10H,H10I), C109(H10J,H10K,H10L), C110(H11D,
 H11E,H11F), 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),
 C39A(H39D,H39E,H39F), 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)
;
_shelx_res_checksum              90051
_shelx_hkl_checksum              8467
_olex2_submission_special_instructions 'No special instructions were received'