Ferric nitrene-promoted anti-Markovnikov ring-opening of epoxides and nucleophilic functionalization of benzylic C-H bonds under photo-irradiation.
Hou, Ming; Jia, Mengjie; Qi, Rui; Zhang, Zhide; He, Linli; Bai, Tianwen; Bao, Chen; Qiu, Guanyinsheng; Chemical communications (Cambridge, England) 61 (2025) 1435–1438; doi:10.1039/d4cc04236k

data_7134056
_publ_section_title
;
 Ferric nitrene-promoted anti-Markovnikov ring-opening of epoxides and
 nucleophilic functionalization of benzylic C-H bonds under
 photo-irradiation.
;
_journal_issue                   7
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              1435
_journal_page_last               1438
_journal_paper_doi               10.1039/d4cc04236k
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         '2(C10 H9 Br O3)'
_chemical_formula_sum            'C20 H18 Br2 O6'
_chemical_formula_weight         514.16
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2g1d86
_audit_creation_date             2023-03-22
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2023-05-25 deposited with the CCDC.	2024-12-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.7195(4)
_cell_length_b                   14.0637(5)
_cell_length_c                   13.2599(8)
_cell_measurement_reflns_used    1574
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      71.9270
_cell_measurement_theta_min      5.1650
_cell_volume                     1999.01(16)
_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)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0802
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.970
_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     47.00  74.00   1.00    1.11    --   36.58 -99.00   0.00   27
  2  \w     -3.00  26.00   1.00    1.11    --   36.58 -99.00   0.00   29
  3  \w     60.00 108.00   1.00    1.11    --   36.58 178.00 -30.00   48
  4  \w     59.00  94.00   1.00    1.11    --   36.58 178.00-180.00   35
  5  \w     69.00  95.00   1.00    1.11    --   36.58  77.00 -60.00   26
  6  \w     58.00  94.00   1.00    1.11    --   36.58 178.00 120.00   36
  7  \w     33.00  66.00   1.00    1.11    --   36.58 -99.00-150.00   33
  8  \w     97.00 173.00   1.00    4.43    --  108.00  61.00 -30.00   76
  9  \w    100.00 164.00   1.00    4.43    --  108.00 111.00-150.00   64
 10  \w     60.00 117.00   1.00    4.43    --  108.00 -45.00  60.00   57
 11  \w    101.00 176.00   1.00    4.43    --  108.00 111.00   0.00   75
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1057042000
_diffrn_orient_matrix_UB_12      -0.0240160000
_diffrn_orient_matrix_UB_13      -0.0233744000
_diffrn_orient_matrix_UB_21      0.0005958000
_diffrn_orient_matrix_UB_22      -0.1122083000
_diffrn_orient_matrix_UB_23      0.0726348000
_diffrn_orient_matrix_UB_31      -0.0286993000
_diffrn_orient_matrix_UB_32      0.0864758000
_diffrn_orient_matrix_UB_33      0.0876583000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0344
_diffrn_reflns_av_unetI/netI     0.0351
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            4346
_diffrn_reflns_point_group_measured_fraction_full 0.615
_diffrn_reflns_point_group_measured_fraction_max 0.594
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.153
_diffrn_reflns_theta_min         5.188
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.449
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.34014
_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            colorless
_exptl_crystal_density_diffrn    1.708
_exptl_crystal_description       block
_exptl_crystal_F_000             1024
_refine_diff_density_max         0.636
_refine_diff_density_min         -0.776
_refine_diff_density_rms         0.152
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.06(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.227
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     255
_refine_ls_number_reflns         2352
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.226
_refine_ls_R_factor_all          0.0685
_refine_ls_R_factor_gt           0.0593
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1702
_refine_ls_wR_factor_ref         0.1810
_reflns_Friedel_coverage         0.170
_reflns_Friedel_fraction_full    0.191
_reflns_Friedel_fraction_max     0.182
_reflns_number_gt                1941
_reflns_number_total             2352
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc04236k2.cif
_cod_data_source_block           20230321-2
_cod_depositor_comments          'Adding full bibliography for 7134056.cif.'
_cod_database_code               7134056
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H O N Br'
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C00R(H00N,H00O), C9(H9A,H9B)
2.b Aromatic/amide H refined with riding coordinates:
 C00A(H00A), C00B(H00B), C00D(H00F), C00H(H00H), C00I(H00I), C00L(H00L),
 C00M(H00M), C00P(H00P)
2.c Idealised Me refined as rotating group:
 C00N(H00C,H00D,H00E), C00Q(H00G,H00J,H00K)
;
_shelx_res_checksum              65350
_shelx_hkl_checksum              22217
_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 3.037
_oxdiff_exptl_absorpt_empirical_full_min 0.675