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_7121350
_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         'C32 H22 Cl3 Ga N2, C3 H3, 0.5(C5 H12)'
_chemical_formula_sum            'C37.5 H31 Cl3 Ga N2'
_chemical_formula_weight         685.71
_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             2018-01-21
_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                85.260(4)
_cell_angle_beta                 78.703(4)
_cell_angle_gamma                68.857(5)
_cell_formula_units_Z            2
_cell_length_a                   10.1320(16)
_cell_length_b                   11.6757(18)
_cell_length_c                   15.355(2)
_cell_measurement_reflns_used    9458
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      26.03
_cell_measurement_theta_min      3.61
_cell_volume                     1661.2(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      150.0
_diffrn_measured_fraction_theta_full 0.994
_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  0.0490
_diffrn_reflns_av_unetI/netI     0.0461
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            35986
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.103
_diffrn_reflns_theta_min         3.963
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.098
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6952
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0707 before and 0.0525 after correction.
The Ratio of minimum to maximum transmission is 0.9324.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.371
_exptl_crystal_description       block
_exptl_crystal_F_000             704
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.617
_refine_diff_density_min         -0.426
_refine_diff_density_rms         0.073
_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     415
_refine_ls_number_reflns         7277
_refine_ls_number_restraints     40
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0580
_refine_ls_R_factor_gt           0.0367
_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^)+(0.0492P)^2^+0.5557P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0874
_refine_ls_wR_factor_ref         0.0966
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5641
_reflns_number_total             7277
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc01331d2.cif
_cod_data_source_block           5
_cod_depositor_comments
'Adding full bibliography for 7121346--7121351.cif.'
_cod_original_formula_sum        'C37.50 H31 Cl3 Ga N2'
_cod_database_code               7121350
_shelx_shelxl_version_number     2014/7
_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. Restrained distances
 C36-C37 \\sim C37-C38
 with sigma of 0.002
 C37-C38 \\sim C38-C39
 with sigma of 0.002
 C39-C40 \\sim C39-C38
 with sigma of 0.002
 C36-C38 \\sim C37-C39
 with sigma of 0.002
 C36-C38 \\sim C38-C40
 with sigma of 0.002
3. Rigid bond restraints
 C36, C37, C38, C39, C40
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01
5. Others
 Fixed Sof: C36(0.5) H36A(0.5) H36B(0.5) H36C(0.5) C37(0.5) H37A(0.5)
 H37B(0.5) C38(0.5) H38A(0.5) H38B(0.5) C39(0.5) H39A(0.5) H39B(0.5) C40(0.5)
 H40A(0.5) H40B(0.5) H40C(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B)
6.b Me refined with riding coordinates:
 C36(H36A,H36B,H36C), C40(H40A,H40B,H40C)
6.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C18(H18), C7(H7), C26(H26), C9(H9), C12(H12), C23(H23), C11(H11),
 C10(H10), C15(H15), C31(H31), C4(H4), C30(H30), C32(H32), C28(H28), C5(H5),
 C17(H17), C6(H6), C16(H16), C25(H25), C24(H24), C29(H29), C35(H35), C34(H34),
 C33(H33)
;
_shelx_res_checksum              77580
_olex2_submission_special_instructions 'No special instructions were received'