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_7126862
_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 rm
_chemical_formula_moiety         'C16 H19 N2 O4, H2 O, Cl'
_chemical_formula_sum            'C16 H20 Cl N2 O5'
_chemical_formula_weight         356.79
_space_group_crystal_system      trigonal
_space_group_IT_number           145
_space_group_name_Hall           'P 32'
_space_group_name_H-M_alt        'P 32'
_atom_sites_solution_hydrogens   mixed
_audit_block_doi                 10.5517/ccdc.csd.cc2444jz
_audit_creation_date             2019-08-14
_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                120
_cell_formula_units_Z            3
_cell_length_a                   11.3090(4)
_cell_length_b                   11.3090(4)
_cell_length_c                   11.3065(4)
_cell_measurement_reflns_used    9923
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      79.51
_cell_measurement_theta_min      4.51
_cell_volume                     1252.30(8)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.01
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0317
_diffrn_reflns_av_unetI/netI     0.0257
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            13796
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         79.517
_diffrn_reflns_theta_min         4.514
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.290
_exptl_absorpt_correction_T_max  0.7543
_exptl_absorpt_correction_T_min  0.6518
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0719 before and 0.0453 after correction.
The Ratio of minimum to maximum transmission is 0.8641.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.415
_exptl_crystal_description       block
_exptl_crystal_F_000             561
_exptl_crystal_size_max          0.1468
_exptl_crystal_size_mid          0.1253
_exptl_crystal_size_min          0.1106
_refine_diff_density_max         0.202
_refine_diff_density_min         -0.282
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Flack x determined using 1624 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.019(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     253
_refine_ls_number_reflns         3457
_refine_ls_number_restraints     115
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0350
_refine_ls_R_factor_gt           0.0347
_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^)+(0.0569P)^2^+0.4216P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0894
_refine_ls_wR_factor_ref         0.0898
_reflns_Friedel_coverage         0.940
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.920
_reflns_number_gt                3426
_reflns_number_total             3457
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc02934c2.cif
_cod_data_source_block           lycorine-N-amine-trans
_cod_depositor_comments
'Adding full bibliography for 7126862--7126864.cif.'
_cod_original_cell_volume        1252.30(10)
_cod_database_code               7126862
_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, All C(H,H,H,H) groups, All Cl(H) groups
 At 1.5 times of:
  All O(H) groups
2. Uiso/Uaniso restraints and constraints
C00D \\sim O2 \\sim C00O \\sim O3 \\sim C00J: within 3.8A with sigma of 0.01
and sigma for terminal atoms of 0.01
C00D \\sim O4 \\sim C00O \\sim O1 \\sim C00J: within 4A with sigma of 0.01 and
sigma for terminal atoms of 0.01
Uanis(O4) \\sim Ueq, Uanis(O1) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
3. Rigid body (RIGU) restrains
 O4, O1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Others
 Sof(O1)=Sof(H00Q)=Sof(H00R)=Sof(O4)=1-FVAR(1)
 Sof(H00O)=Sof(H00P)=Sof(O2)=Sof(O3)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C00F(H00F), C00G(H00G), C00K(H00K), C00L(H00L)
5.b Secondary CH2 refined with riding coordinates:
 C00I(H00D,H00E), C00M(H00I,H00J), C00N(H00M,H00N), C00O(H00Q,H00R), C00O(H00O,
 H00P)
5.c Aromatic/amide H refined with riding coordinates:
 C009(H009), C00B(H00C), C00H(H00H)
5.d Idealised tetrahedral OH refined as rotating group:
 O002(H002), O003(H003)
;
_olex2_submission_special_instructions 'No special instructions were received'