Mesoionic N-heterocyclic Olefin Catalysed Reductive Functionalization of CO2 for Consecutive N-Methylation of Amines
Mandal, Swadhin K.; Maji, Subir; Das, Arpan; Chemical Science  (2021) –; doi:10.1039/D1SC02819G

data_1564324
_publ_section_title
;
 Mesoionic N-heterocyclic Olefin Catalysed Reductive Functionalization of
 CO2 for Consecutive N-Methylation of Amines
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC02819G
_journal_year                    2021
_chemical_formula_moiety         'C48 H61 B N2'
_chemical_formula_sum            'C48 H61 B N2'
_chemical_formula_weight         676.79
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-02-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-02-27 deposited with the CCDC.	2021-08-03 downloaded from the CCDC.
;
_cell_angle_alpha                90.009(3)
_cell_angle_beta                 93.393(2)
_cell_angle_gamma                90.024(3)
_cell_formula_units_Z            4
_cell_length_a                   13.9680(11)
_cell_length_b                   15.6349(13)
_cell_length_c                   22.5739(17)
_cell_measurement_reflns_used    9978
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.35
_cell_measurement_theta_min      2.39
_cell_volume                     4921.2(7)
_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      100.61
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.990
_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  0.1058
_diffrn_reflns_av_unetI/netI     0.1239
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            50073
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.444
_diffrn_reflns_theta_min         2.191
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.052
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.3437
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1577 before and 0.1063 after correction. The Ratio of minimum to maximum transmission is 0.4612. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    0.913
_exptl_crystal_description       block
_exptl_crystal_F_000             1472
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.349
_refine_diff_density_min         -0.348
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     935
_refine_ls_number_reflns         18007
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.1184
_refine_ls_R_factor_gt           0.0761
_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^)+(0.1210P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2034
_refine_ls_wR_factor_ref         0.2410
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10714
_reflns_number_total             18007
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc02819g2.cif
_cod_data_source_block           mo_tkp180121_0ma_a
_cod_depositor_comments
;

2022-04-19
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C96 H122 B2 N4'
_cod_original_formula_weight         1353.59
_cod_original_formula_moiety         '2(C48 H61 B N2)'
_cod_original_formula_units_Z            2
_cod_database_code               1564324
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.990
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C12(H12), C19(H19), C30(H30), C38(H38), C41(H41), C44(H44), B1(H1), C54(H54),
 C62(H62), C72(H72), C80(H80), C89(H89), C93(H93), B2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C42(H42A,H42B), C43(H43A,H43B), C45(H45A,H45B), C46(H46A,H46B),
 C47(H47A,H47B), C48(H48A,H48B), C49(H49A,H49B), C90(H90A,H90B), C91(H91B,H91A),
  C92(H92A,H92B), C94(H94A,H94B), C95(H95A,H95B), C96(H96A,H96B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C15(H15), C16(H16), C17(H17),
 C24(H24), C25(H25), C26(H26), C27(H27), C28(H28), C33(H33), C34(H34), C35(H35),
  C57(H57), C58(H58), C59(H59), C65(H65), C67(H67), C68(H68), C69(H69),
 C70(H70), C75(H75), C76(H76), C77(H77), C84(H84), C85(H85), C86(H86), C87(H87),
  C88(H88)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C), C39(H39A,H39B,H39C), C40(H40A,
 H40B,H40C), C53(H53A,H53B,H53C), C55(H55A,H55B,H55C), C63(H63A,H63B,H63C),
 C64(H64A,H64B,H64C), C71(H71A,H71B,H71C), C73(H73A,H73B,H73C), C81(H81A,H81B,
 H81C), C82(H82A,H82B,H82C)
;
_shelx_res_checksum              26158
_shelx_hkl_checksum              34216
_shelx_fab_checksum              63023
_olex2_submission_special_instructions 'No special instructions were received'