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_1569386
_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 H73 N6 P'
_chemical_formula_sum            'C55 H73 N6 P'
_chemical_formula_weight         849.16
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-03-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2023-02-23 deposited with the CCDC.	2023-06-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.9440(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.9765(2)
_cell_length_b                   20.2016(4)
_cell_length_c                   20.2590(4)
_cell_measurement_reflns_used    9868
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.31
_cell_measurement_theta_min      2.27
_cell_volume                     5131.20(17)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_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  0.0642
_diffrn_reflns_av_unetI/netI     0.0460
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            73164
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.346
_diffrn_reflns_theta_min         1.449
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.094
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.6985
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1119 before and 0.0558 after correction. The Ratio of minimum to maximum transmission is 0.6985. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.099
_exptl_crystal_description       block
_exptl_crystal_F_000             1840
_exptl_crystal_size_max          0.272
_exptl_crystal_size_mid          0.143
_exptl_crystal_size_min          0.112
_refine_diff_density_max         0.488
_refine_diff_density_min         -0.323
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     626
_refine_ls_number_reflns         12743
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0869
_refine_ls_R_factor_gt           0.0606
_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^)+(0.0736P)^2^+2.3079P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1412
_refine_ls_wR_factor_ref         0.1534
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9461
_reflns_number_total             12743
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02899b2.cif
_cod_data_source_block           p21n_a
_cod_depositor_comments
'Adding full bibliography for 1569380--1569388.cif.'
_cod_database_code               1569386
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.975
_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. Uiso/Uaniso restraints and constraints
Uanis(C38A) \\sim Ueq, Uanis(C42A) \\sim Ueq, Uanis(C43A) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
3. Others
 Sof(H41A)=Sof(C42A)=Sof(H42D)=Sof(H42E)=Sof(H42F)=Sof(C43A)=Sof(H43D)=
 Sof(H43E)=Sof(H43F)=1-FVAR(1)
 Sof(H41)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C43)=Sof(H43A)=Sof(H43B)=
 Sof(H43C)=FVAR(1)
 Sof(C38A)=Sof(H38A)=Sof(C39B)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40B)=
 Sof(H40A)=Sof(H40B)=Sof(H40C)=1-FVAR(2)
 Sof(C38B)=Sof(H38B)=Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C40A)=
 Sof(H40D)=Sof(H40E)=Sof(H40F)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C5(H5), C11(H11), C14(H14), C23(H23), C26(H26), C38B(H38B), C38A(H38A),
 C41(H41), C41(H41A), C50(H50), C53(H53)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), 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)
4.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), C28(H28A,
 H28B,H28C), C39A(H39D,H39E,H39F), C39B(H39A,H39B,H39C), C40A(H40D,H40E,H40F),
 C40B(H40A,H40B,H40C), C42(H42A,H42B,H42C), C42A(H42D,H42E,H42F), C43(H43A,H43B,
 H43C), C43A(H43D,H43E,H43F), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C),
 C54(H54A,H54B,H54C), C55(H55A,H55B,H55C)
;
_shelx_res_checksum              60230
_shelx_hkl_checksum              86538
_olex2_date_sample_data_collection 2018-02-18
_olex2_date_sample_submission    2018-02-18
_olex2_submission_original_sample_id maw180218
_olex2_submission_special_instructions 'No special instructions were received'