A well-defined phosphine-free metal-ligand cooperative route for <i>N</i>-alkylation of aromatic amines <i>via</i> activation of renewable alcohols catalyzed by NNN pincer cobalt(II) complexes.
Saini, Rahul; Kukreti, Prashant; Chauhan, Rahul; Panwar, Abhishek; Ghosh, Kaushik; Dalton transactions (Cambridge, England : 2003) 54 (2025) 5838–5848; doi:10.1039/d4dt03095h

data_7718179
_publ_section_title
;
 A well-defined phosphine-free metal-ligand cooperative route for
 <i>N</i>-alkylation of aromatic amines <i>via</i> activation of renewable
 alcohols catalyzed by NNN pincer cobalt(II) complexes.
;
_journal_issue                   14
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              5838
_journal_page_last               5848
_journal_paper_doi               10.1039/d4dt03095h
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         '(C18 H16 Cl2 Co N4)'
_chemical_formula_sum            'C18 H16 Cl2 Co N4'
_chemical_formula_weight         418.18
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2020-11-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-09-30 deposited with the CCDC.	2025-02-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.866(4)
_cell_length_b                   8.914(2)
_cell_length_c                   15.975(4)
_cell_measurement_reflns_used    111
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.136
_cell_measurement_theta_min      1.14
_cell_volume                     1832.1(8)
_computing_cell_refinement       'Bruker Kappa Apex'
_computing_data_collection       'Bruker Kappa Apex'
_computing_data_reduction        'Bruker SAINT'
_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    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Bruker Kappa Apex'
_diffrn_measurement_method       'phi omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0418
_diffrn_reflns_av_unetI/netI     0.0502
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            22037
_diffrn_reflns_point_group_measured_fraction_full 0.951
_diffrn_reflns_point_group_measured_fraction_max 0.913
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.136
_diffrn_reflns_theta_min         2.285
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   '(SADABS; Bruker, 2000)'
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    1.516
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       flat
_exptl_crystal_F_000             852.0
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.2
_exptl_transmission_factor_max   0
_exptl_transmission_factor_min   0
_refine_diff_density_max         0.859
_refine_diff_density_min         -0.575
_refine_diff_density_rms         0.206
_refine_ls_abs_structure_details
;
 Flack x determined using 1167 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.020(8)
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         4089
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0654
_refine_ls_R_factor_gt           0.0418
_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^)+(0.0715P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1021
_refine_ls_wR_factor_ref         0.1180
_reflns_Friedel_coverage         0.785
_reflns_Friedel_fraction_full    0.905
_reflns_Friedel_fraction_max     0.834
_reflns_number_gt                3097
_reflns_number_total             4476
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03095h2.cif
_cod_data_source_block           shelx
_cod_depositor_comments
'Adding full bibliography for 7718179--7718180.cif.'
_cod_original_formula_sum        '(C18 H16 Cl2 Co N4)'
_cod_database_code               7718179
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_min   0.697
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C16(H16), C5(H5), C8(H8), C4(H4), C17(H17), C2(H2), C12(H12),
 C15(H15), C9(H9), C6(H6), C7(H7), C14(H14), C13(H13)
;
_shelx_res_checksum              84471
_shelx_hkl_checksum              40393
_olex2_submission_special_instructions 'No special instructions were received'