Iron-Catalyzed Oxidative Functionalization of C(sp3)−H Bonds under Bromide-synergized Mild Conditions
Wei, Yongge; Yu, Han; Zhao, Qixing; Wei, Zheyu; Wu, Zhikang; Li, Qi; Han, Sheng; Chemical Communications  (2019) –; doi:10.1039/C9CC03939B

data_7123633
_publ_section_title
;
 Iron-Catalyzed Oxidative Functionalization of C(sp3)&#x2212;H Bonds under
 Bromide-synergized Mild Conditions
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC03939B
_journal_year                    2019
_chemical_formula_moiety         'Co H7 Mo6 O24, Cl, 3(C16 H36 N)'
_chemical_formula_sum            'C48 H115 Cl Co Mo6 N3 O24'
_chemical_formula_weight         1788.44
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2018-12-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-12-03 deposited with the CCDC.    2019-06-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.6138(13)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   26.1667(4)
_cell_length_b                   16.5284(2)
_cell_length_c                   32.6499(4)
_cell_measurement_reflns_used    24843
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.3260
_cell_measurement_theta_min      3.5920
_cell_volume                     13922.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4273
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.876
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -23.00  84.25   0.75    3.65    --    9.97  77.00 -60.00  143
  2  \w    -57.00  32.25   0.75    3.65    --    9.97 -38.00   0.00  119
  3  \w    -19.00  50.00   0.75    3.65    --    9.97 -99.00 150.00   92
  4  \w    -59.00 -17.75   0.75    3.65    --    9.97 -57.00 -90.00   55
  5  \w    -16.00  16.25   0.75    3.65    --  -11.85 -99.00 150.00   43
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0266000000
_diffrn_orient_matrix_UB_12      -0.0093817000
_diffrn_orient_matrix_UB_13      -0.0063078000
_diffrn_orient_matrix_UB_21      -0.0059533000
_diffrn_orient_matrix_UB_22      0.0418899000
_diffrn_orient_matrix_UB_23      -0.0013968000
_diffrn_orient_matrix_UB_31      0.0035520000
_diffrn_orient_matrix_UB_32      0.0000298000
_diffrn_orient_matrix_UB_33      -0.0210629000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0411
_diffrn_reflns_av_unetI/netI     0.0452
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.876
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            64474
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.876
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.500
_diffrn_reflns_theta_min         3.365
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.388
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85977
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light green'
_exptl_crystal_density_diffrn    1.706
_exptl_crystal_description       irregular
_exptl_crystal_F_000             7296
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.684
_refine_diff_density_min         -0.760
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     788
_refine_ls_number_reflns         17009
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0486
_refine_ls_R_factor_gt           0.0325
_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^)+(0.0192P)^2^+20.9868P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0619
_refine_ls_wR_factor_ref         0.0679
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13594
_reflns_number_total             17009
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc03939b2.cif
_cod_data_source_block           como6cl
_cod_database_code               7123633
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Co Mo Cl C N O'
_reflns_odcompleteness_completeness 99.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O1-H1 = O2-H2 = O3-H3 = O5-H5 = O4-H4 = O6-H6 = O11-H11
 0.85 with sigma of 0.001
3.a Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C23(H23A,H23B), C30(H30A,H30B), C21(H21A,H21B), C22(H22A,
 H22B), C29(H29A,H29B), C46(H46A,H46B), C26(H26A,H26B), C5(H5A,H5B), C25(H25A,
 H25B), C41(H41A,H41B), C19(H19A,H19B), C1(H1A,H1B), C45(H45A,H45B), C18(H18A,
 H18B), C31(H31A,H31B), C17(H17A,H17B), C7(H7A,H7B), C38(H38A,H38B), C2(H2A,
 H2B), C34(H34A,H34B), C9(H9A,H9B), C37(H37A,H37B), C13(H13A,H13B), C35(H35A,
 H35B), C42(H42A,H42B), C39(H39A,H39B), C33(H33A,H33B), C47(H47A,H47B),
 C43(H43A,H43B), C15(H15A,H15B), C10(H10A,H10B), C3(H3A,H3B), C14(H14A,H14B),
 C6(H6A,H6B), C11(H11A,H11B)
3.b Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C28(H28A,H28B,H28C), C4(H4A,H4B,H4C), C40(H40A,H40B,
 H40C), C8(H8A,H8B,H8C), C20(H20A,H20B,H20C), C44(H44A,H44B,H44C), C48(H48A,
 H48B,H48C), C36(H36A,H36B,H36C), C16(H16A,H16B,H16C), C32(H32A,H32B,H32C),
 C12(H12A,H12B,H12C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.481
_oxdiff_exptl_absorpt_empirical_full_min 0.778