Direct Synthesis of N,N-Dimethylated and β-Methyl N,N-Dimethylated Amines from Nitriles Using Methanol: Experimental and Computational Studies
Paul, Bhaskar; Shee, Sujan; Panja, Dibyajyoti; Chakrabarti, Kaushik; Kundu, Sabuj; ACS Catalysis 8 (2018) 2890–; doi:10.1021/acscatal.8b00021

data_4514401
_publ_section_title
;
 Direct Synthesis of N,N-Dimethylated and \b-Methyl N,N-Dimethylated
 Amines from Nitriles Using Methanol: Experimental and Computational
 Studies
;
_journal_issue                   4
_journal_name_full               'ACS Catalysis'
_journal_page_first              2890
_journal_paper_doi               10.1021/acscatal.8b00021
_journal_volume                  8
_journal_year                    2018
_chemical_formula_moiety         'C54 H43 Cl N3 P2 Ru, F6 P, C H2 Cl2, C6 H6'
_chemical_formula_sum            'C61 H51 Cl3 F6 N3 P3 Ru'
_chemical_formula_weight         1240.44
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_primary     direct
_audit_creation_date             2017-11-02
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.922(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.0272(6)
_cell_length_b                   23.3260(13)
_cell_length_c                   22.7595(12)
_cell_measurement_reflns_used    9967
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.31
_cell_measurement_theta_min      2.22
_cell_volume                     5294.9(5)
_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  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.9975
_diffrn_measured_fraction_theta_max 0.9975
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1912
_diffrn_reflns_av_unetI/netI     0.1748
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            80245
_diffrn_reflns_theta_full        28.4310
_diffrn_reflns_theta_max         28.43
_diffrn_reflns_theta_min         2.00
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.605
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5848
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0928 before and 0.0671 after correction.
The Ratio of minimum to maximum transmission is 0.7842.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'reddish red'
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.5559
_exptl_crystal_description       block
_exptl_crystal_F_000             2527.1363
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         2.2068
_refine_diff_density_min         -2.0627
_refine_diff_density_rms         0.4179
_refine_ls_d_res_high            0.7464
_refine_ls_d_res_low             10.1834
_refine_ls_goodness_of_fit_ref   1.0774
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    99
_refine_ls_number_parameters     695
_refine_ls_number_reflns         13309
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0774
_refine_ls_R_factor_all          0.1801
_refine_ls_R_factor_gt           0.0816
_refine_ls_shift/su_max          0.0003
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0984P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1682
_refine_ls_wR_factor_ref         0.2110
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              13
_reflns_limit_h_min              -13
_reflns_limit_k_max              31
_reflns_limit_k_min              0
_reflns_limit_l_max              30
_reflns_limit_l_min              0
_reflns_number_gt                7124
_reflns_number_total             13309
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            cs8b00021_si_002.cif
_cod_data_source_block           Complex1b
_cod_depositor_comments          'Adding full bibliography for 4514401.cif.'
_cod_database_code               4514401
_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.a Secondary CH2 refined with riding coordinates:
 C072(H07a,H07b)
2.b Aromatic/amide H refined with riding coordinates:
 C012(H012), C015(H015), C017(H017), C019(H019), C020(H020), C022(H022),
 C023(H023), C024(H024), C027(H027), C028(H028), C029(H029), C031(H031),
 C032(H032), C033(H033), C034(H034), C035(H035), C036(H036), C038(H038),
 C042(H042), C043(H043), C044(H044), C046(H046), C047(H047), C048(H048),
 C049(H049), C050(H050), C054(H054), C055(H055), C056(H056), C057(H057),
 C058(H058), C059(H059), C060(H060), C061(H061), C062(H062), C065(H065),
 C066(H066), C068(H068), C069(H069), C070(H070), C071(H071), C074(H074),
 C075(H075), C078(H078), C(H), C1(H1)
2.c Idealised Me refined as rotating group:
 C053(H05a,H05b,H05c)
;
_olex2_submission_original_sample_id 'Complex 1b'
_olex2_submission_special_instructions 'No special instructions were received'