Denitrogenative dismantling of heteroaromatics by nucleophilic substitution reactions with diazomethyl compounds.
Biswas, Soumen; Empel, Claire; Sanchez-Palestino, Luis Mario; Arman, Hadi; Koenigs, Rene M.; Doyle, Michael P.; Chemical science 15 (2024) 11065–11071; doi:10.1039/d4sc01578a

data_1571926
_publ_section_title
;
 Denitrogenative dismantling of heteroaromatics by nucleophilic
 substitution reactions with diazomethyl compounds.
;
_journal_issue                   28
_journal_name_full               'Chemical science'
_journal_page_first              11065
_journal_page_last               11071
_journal_paper_doi               10.1039/d4sc01578a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C14 H11 F3 O3'
_chemical_formula_sum            'C14 H11 F3 O3'
_chemical_formula_weight         284.23
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-06-02
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2023-07-29 deposited with the CCDC.	2024-06-17 downloaded from the CCDC.
;
_cell_angle_alpha                97.571(3)
_cell_angle_beta                 107.127(4)
_cell_angle_gamma                95.412(4)
_cell_formula_units_Z            2
_cell_length_a                   7.1427(3)
_cell_length_b                   9.1744(4)
_cell_length_c                   9.7896(4)
_cell_measurement_reflns_used    6959
_cell_measurement_temperature    100.01(11)
_cell_measurement_theta_max      75.7210
_cell_measurement_theta_min      4.7990
_cell_volume                     601.69(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (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      100.01(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.924
_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     36.00 111.00   0.50    0.60    --  106.29-125.00 150.00  150
  2  \w     36.00 111.00   0.50    0.60    --  106.29-125.00 120.00  150
  3  \w     33.00 105.00   0.50    0.60    --  106.29 -94.00   0.00  144
  4  \w     33.00 105.00   0.50    0.60    --  106.29 -94.00 120.00  144
  5  \w     36.00 111.00   0.50    0.60    --  106.29-125.00 -30.00  150
  6  \w     33.00 105.00   0.50    0.60    --  106.29 -94.00 -60.00  144
  7  \w     33.00 105.00   0.50    0.60    --  106.29 -94.00-180.00  144
  8  \w     33.00 101.00   0.50    0.60    --  106.29 -77.00-180.00  136
  9  \w     33.00  71.00   0.50    0.60    --  106.29 -61.00-120.00   76
 10  \w    -26.00  62.00   0.50    0.15    --   45.90 -57.00-120.00  176
 11  \w     33.00  71.00   0.50    0.60    --  106.29 -61.00 120.00   76
 12  \w    -29.00  33.00   0.50    0.15    --   45.90 -24.00 105.00  124
 13  \w     92.00 178.00   0.50    0.60    --  106.29  24.00 -90.00  172
 14  \w     31.00 120.00   0.50    0.15    --   45.90  37.00 -60.00  178
 15  \w     31.00 120.00   0.50    0.15    --   45.90  37.00   0.00  178
 16  \w     32.00 122.00   0.50    0.15    --   45.90  24.00 -90.00  180
 17  \w     31.00 120.00   0.50    0.15    --   45.90  37.00-120.00  178
 18  \w     31.00 120.00   0.50    0.15    --   45.90  37.00-150.00  178
 19  \w     31.00 120.00   0.50    0.15    --   45.90  37.00-180.00  178
 20  \w    -43.00  28.00   0.50    0.15    --  -45.90  37.00 -60.00  142
 21  \w    -33.00  30.00   0.50    0.15    --  -45.90  24.00 -90.00  126
 22  \w    -30.00  30.00   0.50    0.15    --  -45.90  19.00  60.00  120
 23  \w    -51.00 -19.00   0.50    0.60    --  -91.75  45.00 150.00   64
 24  \w   -101.00 -19.00   0.50    0.60    --  -91.75  77.00  60.00  164
 25  \w    -71.00 -19.00   0.50    0.60    --  -91.75  61.00 -30.00  104
 26  \w    -51.00 -19.00   0.50    0.60    --  -91.75  45.00 -30.00   64
 27  \w    -51.00 -19.00   0.50    0.60    --  -91.75  45.00 -90.00   64
 28  \w    -51.00 -19.00   0.50    0.60    --  -91.75  45.00-180.00   64
 29  \w    -51.00 -19.00   0.50    0.60    --  -91.75  45.00-120.00   64
 30  \w    -51.00 -19.00   0.50    0.60    --  -91.75  45.00  90.00   64
 31  \w    -85.00 -22.00   0.50    0.60    --  -91.75 125.00 150.00  126
 32  \w   -122.00 -31.00   0.50    0.15    --  -45.90 -24.00 105.00  182
 33  \w   -120.00 -31.00   0.50    0.15    --  -45.90 -37.00  30.00  178
 34  \w   -120.00 -31.00   0.50    0.15    --  -45.90 -37.00 -30.00  178
 35  \w   -120.00 -31.00   0.50    0.15    --  -45.90 -37.00 -90.00  178
 36  \w   -164.00 -77.00   0.50    0.60    --  -91.75 -45.00   0.00  174
 37  \w   -164.00 -77.00   0.50    0.60    --  -91.75 -45.00  60.00  174
 38  \w   -167.00 -77.00   0.50    0.60    --  -91.75 -24.00 105.00  180
 39  \w   -164.00-100.00   0.50    0.60    --  -91.75 -94.00 -90.00  128
 40  \w   -164.00-100.00   0.50    0.60    --  -91.75 -94.00-120.00  128
 41  \w   -164.00-100.00   0.50    0.60    --  -91.75 -94.00-150.00  128
;
_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      -0.2263709000
_diffrn_orient_matrix_UB_12      -0.0437319000
_diffrn_orient_matrix_UB_13      -0.0524841000
_diffrn_orient_matrix_UB_21      -0.0267797000
_diffrn_orient_matrix_UB_22      0.1638379000
_diffrn_orient_matrix_UB_23      -0.0067646000
_diffrn_orient_matrix_UB_31      0.0013897000
_diffrn_orient_matrix_UB_32      -0.0227552000
_diffrn_orient_matrix_UB_33      -0.1584312000
_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  0.0275
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.924
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            9968
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.924
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.802
_diffrn_reflns_theta_min         4.795
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.220
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.649
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.79a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.569
_exptl_crystal_description       plate
_exptl_crystal_F_000             292
_exptl_crystal_size_max          0.119
_exptl_crystal_size_mid          0.103
_exptl_crystal_size_min          0.091
_refine_diff_density_max         0.278
_refine_diff_density_min         -0.236
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     185
_refine_ls_number_reflns         2315
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0414
_refine_ls_R_factor_gt           0.0365
_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^)+(0.0625P)^2^+0.1901P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0994
_refine_ls_wR_factor_ref         0.1034
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2023
_reflns_number_total             2315
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01578a2.cif
_cod_data_source_block           hpd718_auto
_cod_depositor_comments
'Adding full bibliography for 1571926--1571927.cif.'
_cod_database_code               1571926
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O'
_chemical_oxdiff_usercomment     SB2-167A
_shelx_estimated_absorpt_t_max   0.897
_shelx_estimated_absorpt_t_min   0.868
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, H7 of C7, H5 of C5, H6 of C6, H4 of C4, H1A of C1
 At 1.5 times of:
  All C(H,H,H) groups, H1 of C12
2.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C1(H1A), C7(H7), C6(H6), C5(H5)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C)
;
_shelx_res_checksum              23277
_shelx_hkl_checksum              20211
_olex2_exptl_crystal_mounting_method 'nylo loop'
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.439
_oxdiff_exptl_absorpt_empirical_full_min 0.737