An umpolung of Lewis acidity/basicity at nitrogen by deprotonation of a cyclic (amino)(aryl)nitrenium cation.
Zhou, Jiliang; Liu, Liu Leo; Cao, Levy L.; Stephan, Douglas W.; Chemical communications (Cambridge, England) 54 (2018) 4390–4393; doi:10.1039/c8cc01331d

data_7121349
_publ_section_title
;
 An umpolung of Lewis acidity/basicity at nitrogen by deprotonation of a
 cyclic (amino)(aryl)nitrenium cation.
;
_journal_issue                   35
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              4390
_journal_page_last               4393
_journal_paper_doi               10.1039/c8cc01331d
_journal_volume                  54
_journal_year                    2018
_chemical_formula_moiety         '0.5(C35 H32 N2 P), C6 H4 Cl2, 0.5(B F4)'
_chemical_formula_sum            'C23.5 H20 B0.5 Cl2 F2 N P0.5'
_chemical_formula_weight         446.19
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-01-20
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-02-13 deposited with the CCDC.
2018-03-05 downloaded from the CCDC.
;
_cell_angle_alpha                89.741(4)
_cell_angle_beta                 87.191(4)
_cell_angle_gamma                87.511(4)
_cell_formula_units_Z            4
_cell_length_a                   10.6050(13)
_cell_length_b                   10.7240(12)
_cell_length_c                   18.967(2)
_cell_measurement_reflns_used    9492
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      26.79
_cell_measurement_theta_min      2.82
_cell_volume                     2152.4(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      149.99
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.992
_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  0.0379
_diffrn_reflns_av_unetI/netI     0.0472
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            31682
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.199
_diffrn_reflns_theta_min         1.075
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.366
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.7065
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0683 before and 0.0464 after correction.
The Ratio of minimum to maximum transmission is 0.9477.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.377
_exptl_crystal_description       block
_exptl_crystal_F_000             920
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.628
_refine_diff_density_min         -0.626
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     535
_refine_ls_number_reflns         9505
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0808
_refine_ls_R_factor_gt           0.0492
_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^)+(0.0527P)^2^+2.0878P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1143
_refine_ls_wR_factor_ref         0.1326
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6785
_reflns_number_total             9505
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc01331d2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 7121346--7121351.cif.'
_cod_original_cell_volume        2152.5(4)
_cod_original_formula_sum        'C23.50 H20 B0.50 Cl2 F2 N P0.50'
_cod_database_code               7121349
_shelx_shelxl_version_number     2014/7
_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
2.a Ternary CH refined with riding coordinates:
 C20(H20)
2.b Aromatic/amide H refined with riding coordinates:
 C18(H18), C9(H9), C26(H26), C7(H7), C25(H25), C22(H22), C4(H4), C15(H15),
 C12(H12), C10(H10), C11(H11), C17(H17), C5(H5), C6(H6), C16(H16), C32(H32),
 C24(H24), C23(H23), C31(H31), C38(H38), C28(H28), C36(H36), C41(H41), C37(H37),
  C30(H30), C29(H29), C43(H43), C46(H46), C45(H45), C44(H44)
2.c Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              18924
_olex2_submission_special_instructions 'No special instructions were received'