Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of sp(3) C-H Bonds.
Trammell, Rachel; See, Yi Yang; Herrmann, Aaron T.; Xie, Nan; Díaz, Daniel E; Siegler, Maxime A.; Baran, Phil S.; Garcia-Bosch, Isaac; The Journal of organic chemistry 82 (2017) 7887–7904; doi:10.1021/acs.joc.7b01069

data_4032745
_publ_section_title
;
 Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of
 sp(3) C-H Bonds.
;
_journal_issue                   15
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              7887
_journal_page_last               7904
_journal_paper_doi               10.1021/acs.joc.7b01069
_journal_volume                  82
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H44 Cu N4, F6 P, 0.5(C4 H10 O)'
_chemical_formula_sum            'C34 H49 Cu F6 N4 O0.5 P'
_chemical_formula_weight         730.28
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 107.5219(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.6953(2)
_cell_length_b                   9.71833(14)
_cell_length_c                   24.2042(4)
_cell_measurement_reflns_used    11709
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      72.09
_cell_measurement_theta_min      1.88
_cell_volume                     3744.93(10)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'SHELXTL v6.10 (Sheldrick, 2008)'
_computing_publication_material  'SHELXTL v6.10 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-2014/7 (Sheldrick, 2015)'
_diffrn_ambient_temperature      110(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_source         'SuperNova (Cu) X-ray Source'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0205
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            23883
_diffrn_reflns_point_group_measured_fraction_full 0.859
_diffrn_reflns_point_group_measured_fraction_max 0.847
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.891
_diffrn_reflns_theta_min         1.914
_exptl_absorpt_coefficient_mu    1.738
_exptl_absorpt_correction_T_max  0.903
_exptl_absorpt_correction_T_min  0.624
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.295
_exptl_crystal_description       lath
_exptl_crystal_F_000             1532
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.416
_refine_diff_density_min         -0.276
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 3706 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.023(9)
_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     1149
_refine_ls_number_reflns         12437
_refine_ls_number_restraints     2854
_refine_ls_restrained_S_all      0.959
_refine_ls_R_factor_all          0.0463
_refine_ls_R_factor_gt           0.0404
_refine_ls_shift/su_max          0.020
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0489P)^2^+1.6892P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1024
_refine_ls_wR_factor_ref         0.1084
_reflns_Friedel_coverage         0.596
_reflns_Friedel_fraction_full    0.700
_reflns_Friedel_fraction_max     0.675
_reflns_number_gt                11068
_reflns_number_total             12437
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01069_si_007.cif
_cod_data_source_block           '[(S1)2CuI](PF6)'
_cod_depositor_comments
;

2025-10-08
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C68 H98 Cu2 F12 N8 O P2'
_cod_original_formula_weight         1460.56
_cod_original_formula_moiety         '2(C32 H44 Cu N4), 2(F6 P), C4 H10 O'
_cod_original_formula_units_Z            2
_cod_database_code               4032745
_shelx_shelxl_version_number     2014/7
_shelx_res_checksum              25246
_shelx_hkl_checksum              68646
_shelx_fab_checksum              83009