Tripodal S-Ligand Complexes of Copper(I) as Catalysts for Alkene Aziridination, Sulfide Sulfimidation, and C-H Amination.
Lam, Tsz Lung; Tso, Ken Chi-Hang; Cao, Bei; Yang, Chen; Chen, Daqing; Chang, Xiao-Yong; Huang, Jie-Sheng; Che, Chi-Ming; Inorganic chemistry 56 (2017) 4253–4257; doi:10.1021/acs.inorgchem.7b00226

data_4345793
_publ_section_title
;
 Tripodal S-Ligand Complexes of Copper(I) as Catalysts for Alkene
 Aziridination, Sulfide Sulfimidation, and C-H Amination.
;
_journal_issue                   8
_journal_name_full               'Inorganic chemistry'
_journal_page_first              4253
_journal_page_last               4257
_journal_paper_doi               10.1021/acs.inorgchem.7b00226
_journal_volume                  56
_journal_year                    2017
_chemical_formula_moiety         'C45 H37 B Cu N6 P S3'
_chemical_formula_sum            'C45 H37 B Cu N6 P S3'
_chemical_formula_weight         863.30
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3'
_symmetry_space_group_name_Hall  '-R 3'
_symmetry_space_group_name_H-M   'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-03-28
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   24.3221(10)
_cell_length_b                   24.3221(10)
_cell_length_c                   36.4934(16)
_cell_measurement_reflns_used    9893
_cell_measurement_temperature    100
_cell_measurement_theta_max      66.21
_cell_measurement_theta_min      2.42
_cell_volume                     18695.9(14)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0659
_diffrn_reflns_av_unetI/netI     0.0320
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            91756
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        66.858
_diffrn_reflns_theta_max         66.858
_diffrn_reflns_theta_min         2.422
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.831
_exptl_absorpt_correction_T_max  0.7529
_exptl_absorpt_correction_T_min  0.6014
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
'SADABS-2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.1220 before and 0.0896 after correction. The Ratio of minimum to maximum transmission is 0.7988. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.380
_exptl_crystal_description       block
_exptl_crystal_F_000             8028
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.18
_refine_diff_density_max         1.408
_refine_diff_density_min         -1.042
_refine_diff_density_rms         0.125
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.118
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     611
_refine_ls_number_reflns         7296
_refine_ls_number_restraints     1847
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.1138
_refine_ls_R_factor_gt           0.0991
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1600P)^2^+169.8080P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2925
_refine_ls_wR_factor_ref         0.3136
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5821
_reflns_number_total             7296
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic7b00226_si_002.cif
_cod_data_source_block           complex_Cu1
_cod_original_cell_volume        18695.9(17)
_cod_database_code               4345793
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups
2. Restrained distances
 C23A-C22A = C27A-C22A = C27A-C26A = C25A-C26A = C25A-C24A = C23A-C24A
 1.39 with sigma of 0.02
 N3-C10 = N3A-C10A = N4A-C10A = N4-C10
 1.38 with sigma of 0.02
 N3-C11 = N3A-C11A = N4-C12 = N4A-C12A
 1.35 with sigma of 0.02
 C11-C12 = C11A-C12A
 1.35 with sigma of 0.02
 C3A-C2A = C3-C2
 1.29 with sigma of 0.02
 N6A-C19A = N5A-C19A = N1A-C1A = N2A-C1A
 1.35 with sigma of 0.02
 N5A-C20A = N5-C20 = N6A-C21A = N6-C21 = N1A-C2A = N1-C2 = N2-C3 = N2A-C3A
 1.37 with sigma of 0.02
 C14-C13 = C14-C15 = C16-C15 = C18-C13
 1.39 with sigma of 0.02
 C22A-C26A
 2.4 with sigma of 0.04
 C22A-C24A
 2.4 with sigma of 0.04
 C27A-C23A
 2.42 with sigma of 0.04
 C26A-C24A = C25A-C27A
 2.37 with sigma of 0.04
 C23A-C25A
 2.37 with sigma of 0.04
 C10-C11 = C10A-C11A
 2.22 with sigma of 0.04
 C10-C12 = C10A-C12A
 2.22 with sigma of 0.04
 C14A-C18A
 2.42 with sigma of 0.04
 C16A-C14A
 2.37 with sigma of 0.04
 C15A-C17A = C16A-C18A
 2.37 with sigma of 0.04
 C13-C15
 2.4 with sigma of 0.04
 C16-C14
 2.37 with sigma of 0.04
 C14-C18
 2.42 with sigma of 0.04
 C16-C18
 2.37 with sigma of 0.04
 C21A-C20A \\sim C20-C21
 with sigma of 0.02
 C21A-N5A \\sim C20A-N6A \\sim C21-N5 \\sim C20-N6
 with sigma of 0.02
 N5A-B1A \\sim B1-N5 \\sim B1-N3 \\sim N3A-B1A \\sim N1A-B1A \\sim B1-N1
 with sigma of 0.02
3. Restrained planarity
 C22A, C23A, C24A, C25A, C26A, C27A
 with sigma of 0.1
 N3A, N4A, C10A, C11A, C12A
 with sigma of 0.1
 N3, N4, C10, C11, C12
 with sigma of 0.1
 C13, C14, C15, C16, C18
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(C16) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C11) \\sim Ueq,
Uanis(C19) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C22)
\\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(C10) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(N2) \\sim
Ueq, Uanis(N1) \\sim Ueq, Uanis(N5) \\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(N6)
\\sim Ueq, Uanis(N1A) \\sim Ueq, Uanis(N2A) \\sim Ueq, Uanis(N3A) \\sim Ueq,
Uanis(N4A) \\sim Ueq, Uanis(N5A) \\sim Ueq, Uanis(N6A) \\sim Ueq, Uanis(N3)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C9A) \\sim Ueq, Uanis(C6A) \\sim Ueq,
Uanis(C27) \\sim Ueq, Uanis(C4A) \\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(C8A)
\\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C14A) \\sim Ueq,
Uanis(C11A) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C12A) \\sim Ueq, Uanis(C3A)
\\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C26) \\sim Ueq,
Uanis(N2A) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(N1A) \\sim Ueq, Uanis(B1A)
\\sim Ueq, Uanis(N1A) \\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(N2) \\sim Ueq,
Uanis(C4) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(N1) \\sim
Ueq, Uanis(B1) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(N6A)
\\sim Ueq, Uanis(C22A) \\sim Ueq, Uanis(N6A) \\sim Ueq, Uanis(C21A) \\sim Ueq,
Uanis(N5A) \\sim Ueq, Uanis(B1A) \\sim Ueq, Uanis(N5A) \\sim Ueq, Uanis(C20A)
\\sim Ueq, Uanis(N6) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(N6) \\sim Ueq,
Uanis(C21) \\sim Ueq, Uanis(N5) \\sim Ueq, Uanis(B1) \\sim Ueq, Uanis(N5) \\sim
Ueq, Uanis(C20) \\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(N3)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(N4A) \\sim Ueq, Uanis(C10A) \\sim Ueq,
Uanis(N3A) \\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(N2A) \\sim Ueq, Uanis(C1A)
\\sim Ueq, Uanis(N1A) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(N2) \\sim Ueq,
Uanis(C1) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(N6A) \\sim
Ueq, Uanis(C19A) \\sim Ueq, Uanis(N5A) \\sim Ueq, Uanis(C19A) \\sim Ueq,
Uanis(N6) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(N5) \\sim Ueq, Uanis(C19)
\\sim Ueq, Uanis(S3) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(S3) \\sim Ueq,
Uanis(C10A) \\sim Ueq, Uanis(S1) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(S1)
\\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(S2) \\sim Ueq, Uanis(C19A) \\sim Ueq,
Uanis(S2) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(Cu1) \\sim Ueq, Uanis(S3)
\\sim Ueq, Uanis(Cu1) \\sim Ueq, Uanis(S1) \\sim Ueq, Uanis(Cu1) \\sim Ueq,
Uanis(S2) \\sim Ueq, Uanis(Cu1) \\sim Ueq, Uanis(P1) \\sim Ueq, Uanis(C21)
\\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C22) \\sim Ueq,
Uanis(C23) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(C13A)
\\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(N3) \\sim Ueq,
Uanis(B1) \\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(N4A)
\\sim Ueq, Uanis(C12A) \\sim Ueq, Uanis(N4A) \\sim Ueq, Uanis(C13) \\sim Ueq,
Uanis(N3A) \\sim Ueq, Uanis(B1A) \\sim Ueq, Uanis(N3A) \\sim Ueq, Uanis(C11A)
\\sim Ueq, Uanis(N2A) \\sim Ueq, Uanis(C4A) \\sim Ueq, Uanis(C21A) \\sim Ueq,
Uanis(C20A) \\sim Ueq, Uanis(C23A) \\sim Ueq, Uanis(C22A) \\sim Ueq,
Uanis(C27A) \\sim Ueq, Uanis(C22A) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C2)
\\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(C4) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(C5A)
\\sim Ueq, Uanis(C4A) \\sim Ueq, Uanis(C9A) \\sim Ueq, Uanis(C4A) \\sim Ueq,
Uanis(C12A) \\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C13)
\\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C12) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(C18A)
\\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C23) \\sim Ueq,
Uanis(C27) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(C23A)
\\sim Ueq, Uanis(C27A) \\sim Ueq, Uanis(C26A) \\sim Ueq, Uanis(C9) \\sim Ueq,
Uanis(C8) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C6A) \\sim
Ueq, Uanis(C5A) \\sim Ueq, Uanis(C9A) \\sim Ueq, Uanis(C8A) \\sim Ueq,
Uanis(C15) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C15A)
\\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(C18A) \\sim Ueq, Uanis(C17A) \\sim Ueq,
Uanis(C25) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C25)
\\sim Ueq, Uanis(C25A) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(C26A) \\sim Ueq,
Uanis(C25A) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C7)
\\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C6A) \\sim Ueq,
Uanis(C8A) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C16A) \\sim Ueq, Uanis(C15A) \\sim Ueq,
Uanis(C17A) \\sim Ueq, Uanis(C16A) \\sim Ueq, Uanis(C19A) \\sim Ueq,
Uanis(C18A) \\sim Ueq, Uanis(C17A) \\sim Ueq, Uanis(C16A) \\sim Ueq,
Uanis(C15A) \\sim Ueq, Uanis(B1A) \\sim Ueq, Uanis(C21A) \\sim Ueq, Uanis(C20A)
\\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(C23A) \\sim Ueq, Uanis(C22A) \\sim Ueq,
Uanis(C26A) \\sim Ueq, Uanis(C25A) \\sim Ueq, Uanis(B1) \\sim Ueq, Uanis(C27A)
\\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C9) \\sim Ueq,
Uanis(C8) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C22) = Uanis(C22A)
Uanis(C24) = Uanis(C24A)
Uanis(C25) = Uanis(C25A)
Uanis(C26) = Uanis(C26A)
Uanis(C19) = Uanis(C19A)
Uanis(N5) = Uanis(N5A)
Uanis(C20) = Uanis(C20A)
Uanis(C21) = Uanis(C21A)
Uanis(N6) = Uanis(N6A)
Uanis(N3) = Uanis(N3A)
Uanis(C11) = Uanis(C11A)
Uanis(N1) = Uanis(N1A)
Uanis(C2) = Uanis(C2A)
Uanis(C3) = Uanis(C3A)
Uanis(C1) = Uanis(C1A)
Uanis(N2) = Uanis(N2A)
Uanis(C7) = Uanis(C7A)
Uanis(C8) = Uanis(C8A)
Uanis(C9) = Uanis(C9A)
Uanis(C6) = Uanis(C6A)
Uanis(C5) = Uanis(C5A)
Uanis(C4) = Uanis(C4A)
Uanis(C23) = Uanis(C27A)
Uanis(C27) = Uanis(C23A)
Uanis(N4) = Uanis(N4A)
Uanis(C12) = Uanis(C12A)
Uanis(C10) = Uanis(C10A)
Uanis(B1) = Uanis(B1A)
Uanis(C13) = Uanis(C13A)
Uanis(C18A) = Uanis(C14)
Uanis(C17A) = Uanis(C15)
Uanis(C16A) = Uanis(C16)
Uanis(C18) = Uanis(C14A)
5. Others
 Sof(N1A)=Sof(N2A)=Sof(N3A)=Sof(N4A)=Sof(N5A)=Sof(N6A)=Sof(C13)=Sof(C14)=
 Sof(H14)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=Sof(C18)=Sof(H18)=Sof(C1A)=
 Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=
 Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=
 Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=Sof(C19A)=Sof(C20A)=Sof(H20A)=
 Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=
 Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27A)=Sof(B1A)=Sof(H1A)=
 Sof(C17)=Sof(H17)=1-FVAR(1)
 Sof(N1)=Sof(N2)=Sof(N3)=Sof(N4)=Sof(N5)=Sof(N6)=Sof(C1)=Sof(C2)=Sof(H2)=
 Sof(C3)=Sof(H3)=Sof(C4)=Sof(C9)=Sof(H9)=Sof(C8)=Sof(H8)=Sof(C7)=Sof(H7)=
 Sof(C6)=Sof(H6)=Sof(C5)=Sof(H5)=Sof(C10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=
 Sof(C19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(C23)=Sof(H23)=
 Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27)=
 Sof(C13A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=
 Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=Sof(B1)=Sof(H1)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 B1(H1), B1A(H1A)
6.b Aromatic/amide H refined with riding coordinates:
 C29(H29), C30(H30), C31(H31), C32(H32), C33(H33), C35(H35), C36(H36),
 C37(H37), C38(H38), C39(H39), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45),
  C2(H2), C3(H3), C9(H9), C8(H8), C7(H7), C6(H6), C5(H5), C11(H11), C12(H12),
 C14(H14), C15(H15), C16(H16), C18(H18), C20(H20), C21(H21), C23(H23), C24(H24),
  C25(H25), C26(H26), C27(H27), C2A(H2A), C3A(H3A), C5A(H5A), C6A(H6A),
 C7A(H7A), C8A(H8A), C9A(H9A), C11A(H11A), C12A(H12A), C14A(H14A), C15A(H15A),
 C16A(H16A), C17A(H17A), C18A(H18A), C20A(H20A), C21A(H21A), C23A(H23A),
 C24A(H24A), C25A(H25A), C26A(H26A), C27A(H27A), C17(H17)
6.c Fitted hexagon refined as free rotating group:
 C4(C9,C8,C7,C6,C5)
;
_olex2_submission_special_instructions 'No special instructions were received'