Oxophosphonium-Alkyne Cycloaddition Reactions: Reversible Formation of 1,2-Oxaphosphetes and Six-membered Phosphorus Heterocycles.
Löwe, Pawel; Feldt, Milica; Wünsche, Marius A; Wilm, Lukas F. B.; Dielmann, Fabian; Journal of the American Chemical Society 142 (2020) 9818–9826; doi:10.1021/jacs.0c03494

data_4134987
_publ_section_title
;
 Oxophosphonium-Alkyne Cycloaddition Reactions: Reversible Formation of
 1,2-Oxaphosphetes and Six-membered Phosphorus Heterocycles.
;
_journal_issue                   21
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9818
_journal_page_last               9826
_journal_paper_doi               10.1021/jacs.0c03494
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         'C64 H81 N7 O P, C32 H12 B F24'
_chemical_formula_sum            'C96 H93 B F24 N7 O P'
_chemical_formula_weight         1858.55
_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             2018-09-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.973(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.4315(9)
_cell_length_b                   33.871(2)
_cell_length_c                   19.0779(11)
_cell_measurement_reflns_used    9372
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.271
_cell_measurement_theta_min      2.245
_cell_volume                     9211.3(10)
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.999
_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  0.0247
_diffrn_reflns_av_unetI/netI     0.0160
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       45
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            143649
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.287
_diffrn_reflns_theta_min         1.550
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.130
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8921
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0681 before and 0.0312 after correction. The Ratio of minimum to maximum transmission is 0.8921. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.340
_exptl_crystal_description       block
_exptl_crystal_F_000             3848
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.27
_refine_diff_density_max         1.161
_refine_diff_density_min         -0.987
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1356
_refine_ls_number_reflns         22814
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0842
_refine_ls_R_factor_gt           0.0751
_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^)+(0.1125P)^2^+13.9160P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2072
_refine_ls_wR_factor_ref         0.2163
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19604
_reflns_number_total             22814
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c03494_si_003.cif
_cod_data_source_block           compound3
_cod_depositor_comments
'Adding full bibliography for 4134986--4134987.cif.'
_cod_original_cell_volume        9211.2(10)
_cod_database_code               4134987
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.966
_shelx_estimated_absorpt_t_min   0.958
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C35A) \\sim Ueq, Uanis(C31A) \\sim Ueq, Uanis(C27A) \\sim Ueq, Uanis(C8A)
\\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(C37A) \\sim Ueq:
with sigma of 0.006 and sigma for terminal atoms of 0.01
3. Others
 Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(C10)=
 Sof(H10)=1-FVAR(1)
 Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9A)=
 Sof(C10A)=Sof(H10A)=FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(2)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(2)
 Sof(C27)=Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=Sof(C31)=
 Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(H34D)=Sof(H34E)=
 Sof(H34F)=Sof(C35)=Sof(H35)=Sof(C36)=Sof(H36D)=Sof(H36E)=Sof(H36F)=Sof(C37)=
 Sof(H37A)=Sof(H37B)=Sof(H37C)=1-FVAR(3)
 Sof(C27A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=
 Sof(C31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=
 Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C35A)=Sof(H35A)=Sof(C36A)=Sof(H36A)=
 Sof(H36B)=Sof(H36C)=Sof(C37A)=Sof(H37D)=Sof(H37E)=Sof(H37F)=FVAR(3)
4.a Ternary CH refined with riding coordinates:
 C20(H20), C23(H23), C32(H32), C32A(H32A), C35A(H35A), C35(H35), C47(H47),
 C50(H50), C59(H59), C62(H62)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C6A(H6A), C6(H6), C7(H7), C7A(H7A), C8(H8), C8A(H8A), C9A(H9A),
 C9(H9), C10A(H10A), C10(H10), C12(H12), C13(H13), C16(H16), C17(H17), C18(H18),
  C28A(H28A), C28(H28), C29A(H29A), C29(H29), C30(H30), C30A(H30A), C39(H39),
 C40(H40), C43(H43), C44(H44), C45(H45), C55(H55), C56(H56), C57(H57), C66(H66),
  C68(H68), C70(H70), C74(H74), C76(H76), C78(H78), C82(H82), C84(H84),
 C86(H86), C90(H90), C92(H92), C94(H94)
4.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C24(H24A,H24B,
 H24C), C25(H25A,H25B,H25C), C33(H33A,H33B,H33C), C33A(H33D,H33E,H33F),
 C34(H34A,H34B,H34C), C34(H34D,H34E,H34F), C36A(H36A,H36B,H36C), C36(H36D,H36E,
 H36F), C37(H37A,H37B,H37C), C37A(H37D,H37E,H37F), C48(H48A,H48B,H48C),
 C49(H49A,H49B,H49C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C60(H60A,H60B,
 H60C), C61(H61A,H61B,H61C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C)
;
_shelx_res_checksum              65039
_shelx_hkl_checksum              91492
_olex2_submission_special_instructions 'No special instructions were received'