Direct preparation of unprotected aminimides (R<sub>3</sub>N<sup>+</sup>-NH<sup>-</sup>) from natural aliphatic tertiary alkaloids (R<sub>3</sub>N) by [Mn(TDCPP)Cl]-catalysed N-amination reaction.
Zhang, Shilong; Liu, Yungen; Xing, Fangrong; Che, Chi-Ming; Chemical communications (Cambridge, England) 56 (2020) 9102–9105; doi:10.1039/d0cc02934c

data_7126863
_publ_section_title
;
 Direct preparation of unprotected aminimides
 (R<sub>3</sub>N<sup>+</sup>-NH<sup>-</sup>) from natural aliphatic
 tertiary alkaloids (R<sub>3</sub>N) by [Mn(TDCPP)Cl]-catalysed
 N-amination reaction.
;
_journal_issue                   64
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              9102
_journal_page_last               9105
_journal_paper_doi               10.1039/d0cc02934c
_journal_volume                  56
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H25 N2 O4, Cl, 2(H2 O)'
_chemical_formula_sum            'C19 H29 Cl N2 O6'
_chemical_formula_weight         416.89
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2444k0
_audit_creation_date             2019-09-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-12-05 deposited with the CCDC.	2020-07-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.2666(5)
_cell_length_b                   14.4440(9)
_cell_length_c                   19.5127(13)
_cell_measurement_reflns_used    9942
_cell_measurement_temperature    100
_cell_measurement_theta_max      68.56
_cell_measurement_theta_min      3.81
_cell_volume                     2048.0(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'Bruker PHOTON 100 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker CMOS area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0383
_diffrn_reflns_av_unetI/netI     0.0198
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            32519
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.553
_diffrn_reflns_theta_min         3.807
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.980
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6195
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1111 before and 0.0550 after correction. The Ratio of minimum to maximum transmission is 0.8226. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.352
_exptl_crystal_description       block
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.31
_refine_diff_density_max         0.223
_refine_diff_density_min         -0.144
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 1567 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.001(3)
_refine_ls_extinction_coef       0.0069(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     257
_refine_ls_number_reflns         3771
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0215
_refine_ls_R_factor_gt           0.0214
_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^)+(0.0287P)^2^+0.5696P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0566
_refine_ls_wR_factor_ref         0.0567
_reflns_Friedel_coverage         0.735
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                3753
_reflns_number_total             3771
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc02934c2.cif
_cod_data_source_block           zsl-sinomenine-n-amine
_cod_depositor_comments
'Adding full bibliography for 7126862--7126864.cif.'
_cod_database_code               7126863
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2.a Riding coordinates:
 O3(H3), N2(H2A,H2B), O5(H5A,H5B), O6(H6A,H6B)
2.b Ternary CH refined with riding coordinates:
 C6(H6), C5(H5)
2.c Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C18(H18A,H18B), C10(H10A,H10B), C8(H8A,H8B)
2.d Aromatic/amide H refined with riding coordinates:
 C16(H16), C4(H4), C15(H15)
2.e Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C14(H14A,H14B,H14C), C3(H3A,H3B,H3C)
;
_olex2_submission_special_instructions 'No special instructions were received'