Site-selective electrochemical C(sp3)–H late-stage functionalization of pyrazolones
Zhang, Jing-Yi; Li, Ming-Han; Cui, Yu-Shun; Yang, Ying; Lai, Miao; Gao, Zi-Xun; Zheng, Lin-Yu; Lu, Si-Ao; Liu, Bin-Tao; Lu, Fang-Ling; Feng, Yu-Lin; Green Chemistry 27 (2025) 14783–14791; doi:10.1039/D5GC02947C

data_7251194
_publ_section_title
;
 Site-selective electrochemical C(sp3)--H late-stage functionalization of
 pyrazolones
;
_journal_issue                   46
_journal_name_full               'Green Chemistry'
_journal_page_first              14783
_journal_page_last               14791
_journal_paper_doi               10.1039/D5GC02947C
_journal_volume                  27
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C13 H14 N2 O3'
_chemical_formula_sum            'C13 H14 N2 O3'
_chemical_formula_weight         246.26
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-10-15
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-03-03 deposited with the CCDC.	2025-10-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.13570(10)
_cell_length_b                   10.63280(10)
_cell_length_c                   14.3118(2)
_cell_measurement_reflns_used    5333
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      71.2320
_cell_measurement_theta_min      4.1300
_cell_volume                     1238.05(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.985
_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     80.00 131.00   0.50    0.50    --   42.30  77.00-120.00  102
  2  \w    -31.00  15.00   0.50    0.50    --   42.30 -82.00-180.00   92
  3  \w     82.00 117.00   0.50    0.50    --   42.30  77.00 150.00   70
  4  \w     92.00 117.00   0.50    0.50    --   42.30  77.00  30.00   50
  5  \w     63.00 127.00   0.50    0.50    --   42.30  57.00 120.00  128
  6  \w     18.00  44.00   0.50    0.50    --   42.30  57.00 120.00   52
  7  \w     53.00  78.00   0.50    0.50    --   42.30 -82.00-180.00   50
  8  \w    108.00 133.00   0.50    0.50    --  101.60  82.00-120.00   50
  9  \w     32.00 133.00   0.50    0.50    --  101.60 -50.00   0.00  202
 10  \w     89.00 191.00   0.50    0.50    --  101.60  82.00 120.00  204
 11  \w     86.00 133.00   0.50    0.50    --  101.60 -64.00   0.00   94
 12  \w    113.00 171.00   0.50    0.50    --  101.60  50.00 150.00  116
 13  \w     12.00  84.00   0.50    0.50    --  101.60 -77.00 -30.00  144
 14  \w     14.00  79.00   0.50    0.50    --  101.60 -64.00   0.00  130
 15  \w    100.00 191.00   0.50    0.50    --  101.60  38.00-150.00  182
 16  \w     54.00  97.00   0.50    0.50    --  101.60  38.00-150.00   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0249630000
_diffrn_orient_matrix_UB_12      0.0887725000
_diffrn_orient_matrix_UB_13      0.0838603000
_diffrn_orient_matrix_UB_21      0.0950253000
_diffrn_orient_matrix_UB_22      -0.0921847000
_diffrn_orient_matrix_UB_23      0.0630478000
_diffrn_orient_matrix_UB_31      0.1618199000
_diffrn_orient_matrix_UB_32      0.0679974000
_diffrn_orient_matrix_UB_33      -0.0240825000
_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  0.0209
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            5898
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.627
_diffrn_reflns_theta_min         5.182
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.787
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66755
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.33c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale colourless'
_exptl_crystal_density_diffrn    1.321
_exptl_crystal_description       block
_exptl_crystal_F_000             520
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.168
_refine_diff_density_min         -0.137
_refine_diff_density_rms         0.029
_refine_ls_abs_structure_details
;
 Flack x determined using 950 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(6)
_refine_ls_extinction_coef       0.0172(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     166
_refine_ls_number_reflns         2347
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0248
_refine_ls_R_factor_gt           0.0244
_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^)+(0.0277P)^2^+0.2075P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0624
_refine_ls_wR_factor_ref         0.0625
_reflns_Friedel_coverage         0.696
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.958
_reflns_number_gt                2320
_reflns_number_total             2347
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5gc02947c2.cif
_cod_data_source_block           z-1
_cod_depositor_comments          'Adding full bibliography for 7251194.cif.'
_cod_database_code               7251194
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.925
_shelx_estimated_absorpt_t_min   0.891
_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:
 C11(H11A,H11B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8)
2.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              57379
_shelx_hkl_checksum              72565
_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 2.264
_oxdiff_exptl_absorpt_empirical_full_min 0.317