Mechanistic insights into the visible-light-driven <i>O</i>-arylation of carboxylic acids catalyzed by xanthine-based nickel complexes.
Rodriguez-Lugo, Rafael E; Sander, Joan; Dietzmann, Simon; Rittner, Thomas; Rückel, Jannes; Landaeta, Vanessa R.; Park, Jiyong; Nuernberger, Patrick; Baik, Mu-Hyun; Wolf, Robert; Chemical science 16 (2025) 2751–2762; doi:10.1039/d4sc04257c

data_1573573
_publ_section_title
;
 Mechanistic insights into the visible-light-driven <i>O</i>-arylation of
 carboxylic acids catalyzed by xanthine-based nickel complexes.
;
_journal_issue                   6
_journal_name_full               'Chemical science'
_journal_page_first              2751
_journal_page_last               2762
_journal_paper_doi               10.1039/d4sc04257c
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         '4(C18 H16 N6 O2), H0.73 O0.37'
_chemical_formula_sum            'C20.57 H18.49 N6.86 O2.39'
_chemical_formula_weight         400.01
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-11-23
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2024-05-10 deposited with the CCDC.	2025-01-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.1520(10)
_cell_angle_gamma                90
_cell_formula_units_Z            14
_cell_length_a                   13.0278(2)
_cell_length_b                   14.7154(2)
_cell_length_c                   34.4476(5)
_cell_measurement_reflns_used    10143
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      72.8270
_cell_measurement_theta_min      4.5200
_cell_volume                     6519.86(16)
_computing_cell_refinement       'CrysAlisPro 1.171.43.36a (Rigaku OD, 2022)'
_computing_data_collection
'CrysAlisPro system (CCD 40.66a (release 14-11-2019))'
_computing_data_reduction        'CrysAlisPro 1.171.43.36a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXD  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1773
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.965
_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    -14.00  13.00   1.00    2.00    --  -42.05  37.00 -60.00   27
  2  \w   -117.00 -18.00   1.00    2.00    --  -42.05 -37.00 120.00   99
  3  \w    -38.00  31.00   1.00    2.00    --  -42.05  37.00 -90.00   69
  4  \w     66.00  92.00   1.00    2.00    --   42.05-125.00-180.00   26
  5  \w     80.00 156.00   1.00    4.00    --  104.39  45.00  90.00   76
  6  \w     31.00 105.00   1.00    4.00    --  104.39-125.00   0.00   74
  7  \w     86.00 113.00   1.00    4.00    --  104.39  30.00-150.00   27
  8  \w     35.00  61.00   1.00    4.00    --  104.39-125.00 -60.00   26
  9  \w    130.00 158.00   1.00    4.00    --  104.39  30.00-180.00   28
 10  \w     77.00 127.00   1.00    4.00    --  104.39  30.00-180.00   50
 11  \w     70.00 103.00   1.00    4.00    --  104.39-125.00 -60.00   33
 12  \w     32.00  69.00   1.00    4.00    --  104.39 -61.00-180.00   37
 13  \w     91.00 157.00   1.00    4.00    --  104.39 125.00   0.00   66
 14  \w    127.00 155.00   1.00    4.00    --  104.39  30.00-150.00   28
 15  \w     59.00 112.00   1.00    4.00    --  104.39-125.00 150.00   53
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1122842000
_diffrn_orient_matrix_UB_12      0.0014571000
_diffrn_orient_matrix_UB_13      0.0222863000
_diffrn_orient_matrix_UB_21      -0.0406598000
_diffrn_orient_matrix_UB_22      0.0265123000
_diffrn_orient_matrix_UB_23      0.0380690000
_diffrn_orient_matrix_UB_31      -0.0090726000
_diffrn_orient_matrix_UB_32      -0.1012751000
_diffrn_orient_matrix_UB_33      0.0102964000
_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  0.0153
_diffrn_reflns_av_unetI/netI     0.0162
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            13874
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.750
_diffrn_reflns_theta_min         4.566
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.810
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.150
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.36a (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 light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.426
_exptl_crystal_description       block
_exptl_crystal_F_000             2927
_exptl_crystal_size_max          0.624
_exptl_crystal_size_mid          0.489
_exptl_crystal_size_min          0.382
_refine_diff_density_max         0.211
_refine_diff_density_min         -0.180
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     481
_refine_ls_number_reflns         6280
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0380
_refine_ls_R_factor_gt           0.0361
_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^)+(0.0414P)^2^+5.3093P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0901
_refine_ls_wR_factor_ref         0.0913
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6016
_reflns_number_total             6280
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04257c2.cif
_cod_data_source_block           test2m
_cod_depositor_comments
'Adding full bibliography for 1573571--1573578.cif.'
_cod_database_code               1573573
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C18 H16 N6 O2'
_chemical_oxdiff_usercomment
'Blocks from slow diffusion of hexane into CHCl3 solution'
_reflns_odcompleteness_completeness 98.05
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     43.31
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Others
 Sof(O1)=Sof(H1A)=Sof(H1B)=FVAR(1)
3.a Free rotating group:
 O1(H1A,H1B)
3.b Aromatic/amide H refined with riding coordinates:
 C00R(H00R), C00U(H00U), C00V(H00V), C010(H010), C011(H011), C013(H013),
 C017(H017), C018(H018), C01A(H01J), C01B(H01R), C01D(H01K), C01E(H01V),
 C01F(H01W), C01G(H01X)
3.c Idealised Me refined as rotating group:
 C012(H01A,H01B,H01C), C014(H01D,H01E,H01F), C015(H01L,H01M,H01N), C016(H01O,
 H01P,H01Q), C019(H01G,H01H,H01I), C01C(H01S,H01T,H01U)
;
_shelx_res_checksum              70886
_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 1.277
_oxdiff_exptl_absorpt_empirical_full_min 0.800