Discovery of a simple iron catalyst reveals the intimate steps of C-H amination to form C-N bonds.
Stroek, Wowa; Albrecht, Martin; Chemical science 14 (2023) 2849–2859; doi:10.1039/d2sc04170g

data_1568208
_publ_section_title
;
 Discovery of a simple iron catalyst reveals the intimate steps of C-H
 amination to form C-N bonds.
;
_journal_issue                   11
_journal_name_full               'Chemical science'
_journal_page_first              2849
_journal_page_last               2859
_journal_paper_doi               10.1039/d2sc04170g
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C24 H53 Fe N3 Si4'
_chemical_formula_sum            'C24 H53 Fe N3 Si4'
_chemical_formula_weight         551.9
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-13T10:21:16-00:00
_audit_update_record
;
2022-05-10 deposited with the CCDC.	2022-12-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.3084(8)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.67067(17)
_cell_length_b                   18.94109(18)
_cell_length_c                   18.90816(17)
_cell_measurement_reflns_used    47958
_cell_measurement_temperature    173.01(10)
_cell_measurement_theta_max      78.754
_cell_measurement_theta_min      3.197
_cell_volume                     6667.84(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1
_diffrn_measured_fraction_theta_max 0.999
_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    -35.00  52.00   0.50    2.50    --  -23.00  29.00  37.00  174
  2  \w    -97.00 -10.00   0.50    2.50    --  -23.00 -29.00-123.00  174
  3  \w    -26.00  31.00   0.50    2.50    --   47.70 -29.00-123.00  114
  4  \w     35.00 123.00   0.50    2.50    --   47.70  29.00  37.00  176
  5  \w    101.00 177.00   0.50   10.00    --  113.25  29.00  37.00  152
  6  \w    -36.00  49.00   0.50    2.50    --  -23.00  45.00 -90.00  170
  7  \w    -36.00  49.00   0.50    2.50    --  -23.00  45.00  90.00  170
  8  \w    -70.00 -12.00   0.50    2.50    --  -23.00 125.00-180.00  116
  9  \w    -70.00 -12.00   0.50    2.50    --  -23.00 125.00  60.00  116
 10  \w     25.00 120.00   0.50    2.50    --   47.70  77.00 150.00  190
 11  \w     33.00 120.00   0.50    2.50    --   47.70  57.00 120.00  174
 12  \w     36.00 121.00   0.50    2.50    --   47.70  38.00-150.00  170
 13  \w     25.00 120.00   0.50    2.50    --   47.70  77.00-180.00  190
 14  \w     25.00 120.00   0.50    2.50    --   47.70  77.00 120.00  190
 15  \w     91.00 177.00   0.50   10.00    --  113.25  76.00 158.58  172
 16  \w     97.00 177.00   0.50   10.00    --  113.25  61.00 120.00  160
 17  \w     42.00  67.00   0.50   10.00    --  113.25 -61.00  60.00   50
 18  \w    101.00 128.00   0.50   10.00    --  113.25  45.00 120.00   54
 19  \w     91.00 117.00   0.50   10.00    --  113.25  77.00  60.00   52
 20  \w     42.00  68.00   0.50   10.00    --  113.25 -61.00 -60.00   52
 21  \w    136.00 177.00   0.50   10.00    --  113.25  77.00-180.00   82
 22  \w     91.00 117.00   0.50   10.00    --  113.25  77.00-180.00   52
 23  \w    101.00 135.00   0.50   10.00    --  113.25  45.00 112.18   68
 24  \w     92.00 119.00   0.50   10.00    --  113.25  73.00 157.41   54
 25  \w     97.00 123.00   0.50   10.00    --  113.25  61.00 150.00   52
 26  \w     51.00  95.00   0.50   10.00    --  113.25 -94.00 120.00   88
 27  \w     44.00  87.00   0.50   10.00    --  113.25 -77.00 -30.00   86
 28  \w    102.00 128.00   0.50   10.00    --  113.25  30.00  90.00   52
 29  \w    102.00 127.00   0.50   10.00    --  113.25  45.00 150.00   50
 30  \w     93.00 121.00   0.50   10.00    --  113.25  71.00  75.57   56
 31  \w     42.00  67.00   0.50   10.00    --  113.25 -61.00-150.00   50
 32  \w     97.00 123.00   0.50   10.00    --  113.25  61.00-180.00   52
 33  \w    130.00 176.00   0.50   10.00    --  113.25  77.00  90.00   92
 34  \w     42.00  99.00   0.50   10.00    --  113.25 -77.00  60.00  114
 35  \w    101.00 173.00   0.50   10.00    --  113.25  86.00 -47.52  144
 36  \w    100.00 172.00   0.50   10.00    --  113.25  51.00-162.62  144
 37  \w     91.00 117.00   0.50   10.00    --  113.25  77.00  90.00   52
 38  \w     42.00  67.00   0.50   10.00    --  113.25 -61.00  90.00   50
 39  \w     94.00 120.00   0.50   10.00    --  113.25  68.00 157.73   52
 40  \w     98.00 158.00   0.50   10.00    --  113.25  61.00  90.00  120
 41  \w    118.00 175.00   0.50   10.00    --  113.25  52.00-115.77  114
 42  \w     91.00 118.00   0.50   10.00    --  113.25  76.00 116.79   54
 43  \w     55.00  96.00   0.50   10.00    --  113.25 -94.00 -60.00   82
 44  \w     42.00  67.00   0.50   10.00    --  113.25 -61.00 -90.00   50
 45  \w     50.00  97.00   0.50   10.00    --  113.25 -94.00 150.00   94
 46  \w    101.00 139.00   0.50   10.00    --  113.25  30.00-180.00   76
 47  \w     98.00 123.00   0.50   10.00    --  113.25  61.00  60.00   50
 48  \w    123.00 149.00   0.50   10.00    --  113.25  77.00 120.00   52
 49  \w     42.00  86.00   0.50   10.00    --  113.25 -72.00 152.78   88
 50  \w    101.00 128.00   0.50   10.00    --  113.25  52.00 162.62   54
 51  \w    101.00 135.00   0.50   10.00    --  113.25  47.00 143.11   68
 52  \w     91.00 118.00   0.50   10.00    --  113.25  77.00 120.00   54
 53  \w     66.00 100.00   0.50   10.00    --  113.25 -77.00-180.00   68
 54  \w    127.00 177.00   0.50   10.00    --  113.25  71.00  75.57  100
 55  \w    101.00 170.00   0.50   10.00    --  113.25  45.00-150.00  138
 56  \w    101.00 134.00   0.50   10.00    --  113.25  45.00  90.00   66
 57  \w    102.00 127.00   0.50   10.00    --  113.25  30.00 150.00   50
 58  \w    142.00 169.00   0.50   10.00    --  113.25  42.00  59.80   54
 59  \w    131.00 177.00   0.50   10.00    --  113.25  45.00 150.00   92
 60  \w     42.00  67.00   0.50   10.00    --  113.25 -61.00 120.00   50
 61  \w     42.00  67.00   0.50   10.00    --  113.25 -61.00 150.00   50
 62  \w     43.00  72.00   0.50   10.00    --  113.25-102.00  66.59   58
 63  \w    110.00 137.00   0.50   10.00    --  113.25  45.00  60.00   54
 64  \w    103.00 128.00   0.50   10.00    --  113.25  30.00-150.00   50
 65  \w    102.00 127.00   0.50   10.00    --  113.25  46.00 140.11   50
 66  \w    104.00 176.00   0.50   10.00    --  113.25  45.00 173.85  144
 67  \w     91.00 118.00   0.50   10.00    --  113.25  77.00 150.00   54
 68  \w     43.00 104.00   0.50   10.00    --  113.25-114.00 -55.85  122
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0520583
_diffrn_orient_matrix_UB_12      0.0222479
_diffrn_orient_matrix_UB_13      -0.0553709
_diffrn_orient_matrix_UB_21      0.0642145
_diffrn_orient_matrix_UB_22      -0.0216599
_diffrn_orient_matrix_UB_23      0.0513757
_diffrn_orient_matrix_UB_31      -0.0031055
_diffrn_orient_matrix_UB_32      -0.0751707
_diffrn_orient_matrix_UB_33      -0.0312351
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0583
_diffrn_reflns_av_unetI/netI     0.0601
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            132519
_diffrn_reflns_point_group_measured_fraction_full 1
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.739
_diffrn_reflns_theta_min         3.208
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.11
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.33475
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
        Empirical absorption correction using spherical harmonics,
        implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.1
_exptl_crystal_description       block
_exptl_crystal_F_000             2400
_exptl_crystal_size_max          0.258
_exptl_crystal_size_mid          0.226
_exptl_crystal_size_min          0.083
_refine_diff_density_max         0.972
_refine_diff_density_min         -0.576
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     742
_refine_ls_number_reflns         14043
_refine_ls_number_restraints     90
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0572
_refine_ls_R_factor_gt           0.0509
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0968P)^2^+1.7896P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1462
_refine_ls_wR_factor_ref         0.1523
_reflns_Friedel_coverage         0
_reflns_number_gt                12093
_reflns_number_total             14043
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04170g2.cif
_cod_data_source_block           21MA168_WS381
_cod_depositor_comments          'Adding full bibliography for 1568208.cif.'
_cod_database_code               1568208
_shelx_estimated_absorpt_t_min   0.352
_shelx_estimated_absorpt_t_max   0.676
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.026
_oxdiff_exptl_absorpt_empirical_full_min 0.603
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
        1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
        2. Rigid bond restraints
 Si2, C4, C5, C6
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C14, C19A, C18A, C17A, C16A, C15A
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C14, C19, C18, C17, C16, C15
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
        3. Uiso/Uaniso restraints and constraints
Uanis(C45A) \\sim Ueq, Uanis(C47A) \\sim Ueq, Uanis(C48A) \\sim Ueq: with sigma
        of 0.01 and sigma for terminal atoms of 0.02
Uanis(C16) \\sim Ueq, Uanis(C16A) \\sim Ueq, Uanis(C17A) \\sim Ueq, Uanis(C18A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C35A) \\sim Ueq, Uanis(C34A) \\sim Ueq, Uanis(C36A) \\sim Ueq: with sigma
        of 0.01 and sigma for terminal atoms of 0.02
        4. Others
 Sof(H20C)=Sof(H20D)=Sof(C21A)=Sof(H21C)=Sof(H21D)=Sof(C23A)=Sof(H23D)=
 Sof(H23E)=Sof(H23F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(1)
 Sof(H20A)=Sof(H20B)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C24)=Sof(H24A)=Sof(H24B)=
 Sof(H24C)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(1)
 Sof(H44C)=Sof(H44D)=Sof(C48A)=Sof(H48D)=Sof(H48E)=Sof(H48F)=Sof(C47A)=
 Sof(H47D)=Sof(H47E)=Sof(H47F)=Sof(C45A)=Sof(H45C)=Sof(H45D)=1-FVAR(2)
 Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C48)=Sof(H48A)=Sof(H48B)=
 Sof(H48C)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=FVAR(2)
 Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C18A)=
 Sof(H18A)=Sof(C19A)=Sof(H19A)=1-FVAR(3)
 Sof(C15)=Sof(H15)=Sof(C19)=Sof(H19)=Sof(C16)=Sof(H16)=Sof(C18)=Sof(H18)=
 Sof(C17)=Sof(H17)=FVAR(3)
 Sof(C34A)=Sof(H34D)=Sof(H34E)=Sof(H34F)=Sof(C35A)=Sof(H35D)=Sof(H35E)=
 Sof(H35F)=Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(4)
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(4)
        5.a Ternary CH refined with riding coordinates:
 N3(H3), N6(H6), C13(H13), C37(H37)
        5.b Secondary CH2 refined with riding coordinates:
 C44(H44A,H44B), C44(H44C,H44D), C20(H20A,H20B), C20(H20C,H20D), C45(H45A,
 H45B), C21(H21A,H21B), C21A(H21C,H21D), C45A(H45C,H45D)
        5.c Aromatic/amide H refined with riding coordinates:
 C39(H39), C43(H43), C15(H15), C19(H19), C42(H42), C40(H40), C16(H16),
 C41(H41), C18(H18), C17(H17), C15A(H15A), C16A(H16A), C17A(H17A), C18A(H18A),
 C19A(H19A)
        5.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C26(H26A,H26B,H26C), C10(H10A,H10B,H10C), C29(H29A,H29B,
 H29C), C11(H11A,H11B,H11C), C28(H28A,H28B,H28C), C7(H7A,H7B,H7C), C25(H25A,
 H25B,H25C), C32(H32A,H32B,H32C), C2(H2A,H2B,H2C), C1(H1A,H1B,H1C), C5(H5A,H5B,
 H5C), C33(H33A,H33B,H33C), C8(H8A,H8B,H8C), C12(H12A,H12B,H12C), C31(H31A,H31B,
 H31C), C9(H9A,H9B,H9C), C30(H30A,H30B,H30C), C36(H36A,H36B,H36C), C6(H6A,H6B,
 H6C), C27(H27A,H27B,H27C), C4(H4A,H4B,H4C), C35(H35A,H35B,H35C), C48(H48A,H48B,
 H48C), C47(H47A,H47B,H47C), C24(H24A,H24B,H24C), C34(H34A,H34B,H34C), C23(H23A,
 H23B,H23C), C23A(H23D,H23E,H23F), C24A(H24D,H24E,H24F), C48A(H48D,H48E,H48F),
 C47A(H47D,H47E,H47F), C34A(H34D,H34E,H34F), C35A(H35D,H35E,H35F), C36A(H36D,
 H36E,H36F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              81841
_shelx_hkl_checksum              80325
_shelx_fab_checksum              91274