Double axial stabilization of a carbenium ion <i>via</i> convergent PO → C<sup>+</sup> tetrel bonding.
Litle, Elishua D.; Gabbaï, François P; Chemical communications (Cambridge, England) 60 (2024) 690–693; doi:10.1039/d3cc04729f

data_7132457
_publ_section_title
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 Double axial stabilization of a carbenium ion <i>via</i> convergent
 P&#xe001;O &#x2192; C<sup>+</sup> tetrel bonding.
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_journal_issue                   6
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              690
_journal_page_last               693
_journal_paper_doi               10.1039/d3cc04729f
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C45 H39 N O3 P2, 0.5(H2 O)'
_chemical_formula_sum            'C45 H40 N O3.5 P2'
_chemical_formula_weight         712.72
_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
_audit_creation_date             2023-08-17
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2023-09-20 deposited with the CCDC.	2023-12-08 downloaded from the CCDC.
;
_cell_angle_alpha                71.834(3)
_cell_angle_beta                 71.445(3)
_cell_angle_gamma                67.410(3)
_cell_formula_units_Z            2
_cell_length_a                   12.0136(17)
_cell_length_b                   12.8997(18)
_cell_length_c                   13.4490(19)
_cell_measurement_reflns_used    5429
_cell_measurement_temperature    109.99
_cell_measurement_theta_max      31.470
_cell_measurement_theta_min      2.129
_cell_volume                     1781.0(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_diffrn_ambient_temperature      109.99
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1538
_diffrn_reflns_av_unetI/netI     0.1395
_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       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            40080
_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         27.485
_diffrn_reflns_theta_min         2.122
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.168
_exptl_absorpt_correction_T_max  0.7470
_exptl_absorpt_correction_T_min  0.6204
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1238 before and 0.0809 after correction.
The Ratio of minimum to maximum transmission is 0.8305.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.329
_exptl_crystal_description       plate
_exptl_crystal_F_000             750
_exptl_crystal_size_max          0.169
_exptl_crystal_size_mid          0.149
_exptl_crystal_size_min          0.053
_refine_diff_density_max         0.378
_refine_diff_density_min         -0.335
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.180
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     526
_refine_ls_number_reflns         8168
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.177
_refine_ls_R_factor_all          0.2190
_refine_ls_R_factor_gt           0.1369
_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^)+(0.0246P)^2^+6.0420P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2074
_refine_ls_wR_factor_ref         0.2382
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4692
_reflns_number_total             8168
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04729f2.cif
_cod_data_source_block           eli23a_0m_a
_cod_depositor_comments
'Adding full bibliography for 7132454--7132458.cif.'
_cod_original_formula_sum        'C45 H40 N O3.50 P2'
_cod_database_code               7132457
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.972
_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, All O(H) groups, All O(H,H) groups
2. Uiso/Uaniso restraints and constraints
C32' \\sim C33' \\sim C34' \\sim C35' \\sim C36' \\sim C37': within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.4 within 2A
3. Others
 Sof(C18)=Sof(H18)=1-FVAR(1)
 Sof(C18')=Sof(H18')=FVAR(1)
 Sof(H16A)=Sof(C17)=Sof(H17)=1-FVAR(2)
 Sof(H16)=Sof(C17')=Sof(H17')=FVAR(2)
 Sof(C32')=Sof(C33')=Sof(H33')=Sof(C34')=Sof(H34')=Sof(C35')=Sof(H35')=
 Sof(C36')=Sof(H36')=Sof(C37')=Sof(H37')=1-FVAR(3)
 Sof(C32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35)=Sof(C36)=
 Sof(H36)=Sof(C37)=Sof(H37)=FVAR(3)
 Fixed Sof: O4(0.5) H4A(0.5) H4B(0.5)
4.a Free rotating group:
 O4(H4A,H4B)
4.b Aromatic/amide H refined with riding coordinates:
 C39(H39), C25(H25), C23(H23), C40(H40), C43(H43), C24(H24), C3(H3A), C22(H22),
  C8(H8), C31(H31), C42(H42), C4(H4), C6(H6), C9(H9), C5(H5), C27(H27),
 C29(H29), C28(H28), C30(H30), C10(H10), C12(H12), C11(H11), C16(H16),
 C16(H16A), C14(H14), C15(H15), C17'(H17'), C18'(H18'), C18(H18), C17(H17),
 C33(H33), C34(H34), C35(H35), C36(H36), C37(H37), C33'(H33'), C34'(H34'),
 C35'(H35'), C36'(H36'), C37'(H37')
4.c Fitted hexagon refined as free rotating group:
 C32(C33,C34,C35,C36,C37), C32'(C33',C34',C35',C36',C37')
4.d Idealised Me refined as rotating group:
 C44(H44A,H44B,H44C), C45(H45A,H45B,H45C)
4.e Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_shelx_res_checksum              51353
_shelx_hkl_checksum              47647
_olex2_submission_special_instructions 'No special instructions were received'