From the bottle: simple iron salts for the efficient synthesis of pyrrolidines <i>via</i> catalytic C-H bond amination.
Stroek, Wowa; Hoareau, Lilian; Albrecht, Martin; Catalysis science & technology 13 (2023) 958–962; doi:10.1039/d2cy02065c

data_1568329
_publ_section_title
;
 From the bottle: simple iron salts for the efficient synthesis of
 pyrrolidines <i>via</i> catalytic C-H bond amination.
;
_journal_issue                   4
_journal_name_full               'Catalysis science &amp; technology'
_journal_page_first              958
_journal_page_last               962
_journal_paper_doi               10.1039/d2cy02065c
_journal_volume                  13
_journal_year                    2023
_chemical_formula_moiety         'Br, C12 H18 N'
_chemical_formula_sum            'C12 H18 Br N'
_chemical_formula_weight         256.18
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2022-01-21
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-09-21 deposited with the CCDC.	2023-01-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.4950(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.16550(10)
_cell_length_b                   10.60420(10)
_cell_length_c                   14.47160(10)
_cell_measurement_reflns_used    19746
_cell_measurement_temperature    249.97(10)
_cell_measurement_theta_max      78.8490
_cell_measurement_theta_min      3.1110
_cell_volume                     1223.40(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.105a (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    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      249.97(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -61.00  -3.00   0.50    0.20    --  -23.00 112.00-105.00  116
  2  \w     41.00 108.00   0.50    0.66    --  111.50-112.00 161.00  134
  3  \w    -37.00  49.00   0.50    0.20    --  -23.00  61.00   0.00  172
  4  \w    -28.00  50.00   0.50    0.20    --  -23.00  15.00 150.00  156
  5  \w    -94.00 -10.00   0.50    0.20    --  -23.00 -57.00 150.00  168
  6  \w    -21.00  62.00   0.50    0.20    --   49.64 -57.00 120.00  166
  7  \w    -23.00  23.00   0.50    0.20    --   49.64 -19.00-120.00   92
  8  \w     25.00  88.00   0.50    0.20    --   49.64-112.00 161.00  126
  9  \w     42.00 121.00   0.50    0.20    --   49.64  38.00 -90.00  158
 10  \w    -23.00  23.00   0.50    0.20    --   49.64 -19.00 -30.00   92
 11  \w     41.00 105.00   0.50    0.66    --  111.50 -94.00   0.00  128
 12  \w     41.00 102.00   0.50    0.66    --  111.50 -77.00 150.00  122
 13  \w     41.00 105.00   0.50    0.66    --  111.50 -94.00 -90.00  128
 14  \w     41.00  68.00   0.50    0.66    --  111.50 -61.00  60.00   54
 15  \w    102.00 177.00   0.50    0.66    --  111.50  45.00   0.00  150
 16  \w     97.00 177.00   0.50    0.66    --  111.50  61.00-120.00  160
 17  \w     41.00 160.00   0.50    0.66    --  111.50   0.00-120.00  238
 18  \w     41.00 102.00   0.50    0.66    --  111.50 -77.00  30.00  122
 19  \w     41.00  68.00   0.50    0.66    --  111.50 -61.00-150.00   54
 20  \w    104.00 177.00   0.50    0.66    --  111.50  15.00 -60.00  146
 21  \w     41.00  68.00   0.50    0.66    --  111.50 -61.00  90.00   54
 22  \w     41.00  68.00   0.50    0.66    --  111.50 -61.00 150.00   54
 23  \w     41.00 105.00   0.50    0.66    --  111.50 -94.00 150.00  128
 24  \w     41.00  68.00   0.50    0.66    --  111.50 -61.00 -30.00   54
 25  \w     41.00 105.00   0.50    0.66    --  111.50 -94.00-120.00  128
 26  \w     41.00 105.00   0.50    0.66    --  111.50 -94.00 -30.00  128
 27  \w     41.00 102.00   0.50    0.66    --  111.50 -77.00  60.00  122
 28  \w    104.00 177.00   0.50    0.66    --  111.50  15.00 120.00  146
 29  \w     41.00 107.00   0.50    0.66    --  111.50-104.00 -17.64  132
 30  \w     41.00  68.00   0.50    0.66    --  111.50 -61.00-180.00   54
 31  \w     41.00 105.00   0.50    0.66    --  111.50 -94.00-180.00  128
 32  \w    104.00 177.00   0.50    0.66    --  111.50  15.00  90.00  146
 33  \w     41.00  68.00   0.50    0.66    --  111.50 -61.00   0.00   54
 34  \w    102.00 177.00   0.50    0.66    --  111.50  45.00 -90.00  150
 35  \w     97.00 177.00   0.50    0.66    --  111.50  61.00 -30.00  160
 36  \w     41.00 105.00   0.50    0.66    --  111.50 -94.00  30.00  128
 37  \w     91.00 177.00   0.50    0.66    --  111.50  77.00-180.00  172
 38  \w     91.00 177.00   0.50    0.66    --  111.50  77.00  30.00  172
 39  \w     41.00 102.00   0.50    0.66    --  111.50 -77.00  90.00  122
 40  \w     29.00 122.00   0.50    0.20    --   49.64  77.00 -60.00  186
 41  \w     29.00 122.00   0.50    0.20    --   49.64  77.00 120.00  186
 42  \w     29.00 122.00   0.50    0.20    --   49.64  77.00-180.00  186
 43  \w     29.00 122.00   0.50    0.20    --   49.64  77.00   0.00  186
 44  \w     29.00 122.00   0.50    0.20    --   49.64  77.00-120.00  186
 45  \w     29.00 122.00   0.50    0.20    --   49.64  77.00  30.00  186
;
_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      -0.0803472000
_diffrn_orient_matrix_UB_12      -0.0632178000
_diffrn_orient_matrix_UB_13      -0.0948486000
_diffrn_orient_matrix_UB_21      -0.0052106000
_diffrn_orient_matrix_UB_22      0.1283713000
_diffrn_orient_matrix_UB_23      -0.0503515000
_diffrn_orient_matrix_UB_31      0.1756817000
_diffrn_orient_matrix_UB_32      -0.0249878000
_diffrn_orient_matrix_UB_33      -0.0189397000
_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  0.0282
_diffrn_reflns_av_unetI/netI     0.0099
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            23375
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.122
_diffrn_reflns_theta_min         5.215
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.271
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72407
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.105a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.391
_exptl_crystal_description       block
_exptl_crystal_F_000             528
_exptl_crystal_size_max          0.229
_exptl_crystal_size_mid          0.204
_exptl_crystal_size_min          0.161
_refine_diff_density_max         1.168
_refine_diff_density_min         -0.635
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     129
_refine_ls_number_reflns         2285
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.0428
_refine_ls_R_factor_gt           0.0425
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0493P)^2^+1.6441P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1090
_refine_ls_wR_factor_ref         0.1092
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2264
_reflns_number_total             2285
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cy02065c2.cif
_cod_data_source_block           1bHBr
_cod_depositor_comments          'Adding full bibliography for 1568329.cif.'
_cod_database_code               1568329
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C12NBrH19
_shelx_estimated_absorpt_t_max   0.546
_shelx_estimated_absorpt_t_min   0.441
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.2
Uanis(C2) \\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of 0.009 and sigma for
terminal atoms of 0.01
Uanis(C8) \\sim Ueq, Uanis(C2) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.005
Uanis(C8) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.003
3.a Ternary CH refined with riding coordinates:
 C7(H7)
3.b Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), C9(H9A,H9B), C8(H8A,H8B)
3.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C1(H1), C4(H4), C3(H3), C2(H2)
3.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              1988
_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 1.630
_oxdiff_exptl_absorpt_empirical_full_min 0.816