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_1573574
_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         '0.364(C34 H28 Br2 N12 Ni O4), 0.727(C2 H3 N)'
_chemical_formula_sum            'C13.82 H12.36 Br0.73 N5.09 Ni0.36 O1.45'
_chemical_formula_weight         352.48
_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     dual
_audit_creation_date             2023-05-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2024-05-10 deposited with the CCDC.	2025-01-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.7150(10)
_cell_angle_gamma                90
_cell_formula_units_Z            11
_cell_length_a                   17.17420(10)
_cell_length_b                   13.64150(10)
_cell_length_c                   17.85070(10)
_cell_measurement_reflns_used    30224
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.6820
_cell_measurement_theta_min      2.6280
_cell_volume                     4062.85(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.83a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.83a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.83a (Rigaku OD, 2020)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.990
_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     93.00 118.00   0.50    0.40    --   83.00  80.00 -66.18   50
  2  \w     93.00 118.00   0.50    0.40    --   83.00  54.00 -63.56   50
  3  \w     85.00 110.00   0.50    0.40    --   83.00  77.00-114.76   50
  4  \w     50.00  82.00   0.50    0.40    --   42.00  58.00-151.37   64
  5  \w     60.00  94.00   0.50    0.40    --   54.00  70.00 -95.77   68
  6  \w     60.00 117.00   0.50    0.40    --   83.00  21.00-131.82  114
  7  \w     67.00 108.00   0.50    0.40    --   83.00  24.00   4.40   82
  8  \w     56.00  86.00   0.50    0.40    --   83.00  15.00 118.54   60
  9  \w     70.00  96.00   0.50    0.40    --   83.00  23.00 144.99   52
 10  \w     75.00 131.00   0.50    0.40    --   83.00  20.00 138.89  112
 11  \w     98.00 123.00   0.50    0.40    --   83.00  15.00 118.54   50
 12  \w     47.00  93.00   0.50    0.40    --   83.00   8.00  86.15   92
 13  \w     98.00 124.00   0.50    0.40    --   83.00   5.00 -97.36   52
 14  \w     50.00  75.00   0.50    0.40    --   83.00   5.00 -97.36   50
 15  \w    -97.00 -72.00   0.50    0.40    --  -74.72 140.00 -94.00   50
 16  \w   -108.00 -29.00   0.50    0.40    --  -74.72 130.00  91.00  158
 17  \w    -80.00 -55.00   0.50    0.40    --  -61.57 130.00  91.00   50
 18  \w     44.00  79.00   0.50    0.40    --   83.00-154.00 130.12   70
 19  \w     97.00 128.00   0.50    0.40    --   83.00-154.00 130.12   62
 20  \w     94.00 119.00   0.50    0.40    --   83.00-135.00 119.95   50
 21  \w     63.00  88.00   0.50    0.40    --   83.00-135.00 119.95   50
 22  \w     33.00  58.00   0.50    0.40    --   60.14-130.00  19.00   50
 23  \w     30.00 107.00   0.50    0.40    --   73.73-130.00  19.00  154
 24  \w     83.00 110.00   0.50    0.40    --   79.72-130.00  19.00   54
 25  \w     81.00 110.00   0.50    0.40    --   79.72-125.00  60.00   58
 26  \w     85.00 110.00   0.50    0.40    --   83.00-121.00 154.77   50
 27  \w     74.00 124.00   0.50    0.40    --   83.00-143.00 -62.63  100
 28  \w     73.00  98.00   0.50    0.40    --   79.72-140.00-153.00   50
 29  \w     38.00  64.00   0.50    0.40    --   83.00-123.00 -67.09   52
 30  \w     56.00  82.00   0.50    0.40    --   82.00-126.00 -40.13   52
 31  \w     38.00  88.00   0.50    0.40    --   83.00-120.00  74.22  100
 32  \w     72.00  99.00   0.50    0.40    --   83.00-112.00 113.47   54
 33  \w     44.00  69.00   0.50    0.40    --   83.00-112.00 113.47   50
 34  \w     45.00  77.00   0.50    0.40    --   83.00-110.00 123.00   64
 35  \w     59.00  90.00   0.50    0.40    --   83.00 -93.00 127.60   62
 36  \w     37.00  83.00   0.50    0.40    --   73.73 -95.00  60.00   92
 37  \w     47.00  77.00   0.50    0.40    --   83.00 -84.00 125.78   60
 38  \w     51.00  77.00   0.50    0.40    --   83.00 -83.00  12.57   52
 39  \w     45.00  99.00   0.50    0.40    --   83.00-104.00  -1.37  108
 40  \w     44.00  69.00   0.50    0.40    --   83.00 -93.00-153.23   50
 41  \w     52.00  80.00   0.50    0.40    --   83.00 -79.00 -74.84   56
 42  \w     40.00  65.00   0.50    0.40    --   83.00 -61.00-108.95   50
 43  \w     41.00  69.00   0.50    0.40    --   83.00 -58.00 -36.16   56
 44  \w     44.00  77.00   0.50    0.40    --   83.00 -70.00 149.39   66
 45  \w     39.00  71.00   0.50    0.40    --   83.00 -60.00 175.89   64
 46  \w     87.00 116.00   0.50    0.40    --   83.00  83.00 155.16   58
 47  \w     76.00 101.00   0.50    0.40    --   79.72 130.00  91.00   50
 48  \w     74.00 111.00   0.50    0.40    --   79.72 140.00 -94.00   74
 49  \w   -118.00 -81.00   0.50    0.40    --  -70.00 -41.00 -15.02   74
 50  \w   -119.00 -94.00   0.50    0.40    --  -79.25 -64.00-125.19   50
 51  \w   -114.00 -78.00   0.50    0.40    --  -70.00 -54.00-158.33   72
 52  \w   -117.00 -91.00   0.50    0.40    --  -79.25 -70.00  16.29   52
 53  \w   -116.00 -89.00   0.50    0.40    --  -79.25 -50.00 100.95   54
 54  \w   -109.00 -83.00   0.50    0.40    --  -74.72-130.00  19.00   52
 55  \w   -115.00 -90.00   0.50    0.40    --  -74.72-140.00-153.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0036482000
_diffrn_orient_matrix_UB_12      -0.0635403000
_diffrn_orient_matrix_UB_13      0.0720858000
_diffrn_orient_matrix_UB_21      0.0016151000
_diffrn_orient_matrix_UB_22      -0.0932680000
_diffrn_orient_matrix_UB_23      -0.0482572000
_diffrn_orient_matrix_UB_31      0.0922639000
_diffrn_orient_matrix_UB_32      0.0041711000
_diffrn_orient_matrix_UB_33      0.0190034000
_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  0.0287
_diffrn_reflns_av_unetI/netI     0.0137
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            61094
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.120
_diffrn_reflns_theta_min         2.648
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.489
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78091
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.83a (Rigaku Oxford Diffraction, 2020)
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    1.585
_exptl_crystal_description       plate
_exptl_crystal_F_000             1960
_exptl_crystal_size_max          0.191
_exptl_crystal_size_mid          0.161
_exptl_crystal_size_min          0.088
_refine_diff_density_max         0.530
_refine_diff_density_min         -0.597
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.104
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     538
_refine_ls_number_reflns         8420
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.0426
_refine_ls_R_factor_gt           0.0390
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0470P)^2^+5.8111P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1112
_refine_ls_wR_factor_ref         0.1133
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7532
_reflns_number_total             8420
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04257c2.cif
_cod_data_source_block           test1
_cod_depositor_comments
'Adding full bibliography for 1573571--1573578.cif.'
_cod_database_code               1573574
_shelx_shelxl_version_number     SHELXL-2018/3
_chemical_oxdiff_formula         'C38 H34 N14 O4 Ni Br2'
_chemical_oxdiff_usercomment     'Green crystals from MeCN/Et2O'
_exptl_absorpt_special_details   none
_reflns_odcompleteness_completeness 97.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     76.86
_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
2.a Aromatic/amide H refined with riding coordinates:
 C00V(H00V), C00W(H00W), C00Y(H00Y), C010(H010), C012(H012), C013(H013),
 C015(H015), C016(H016), C017(H017), C019(H019), C01B(H01J), C01C(H01K),
 C01D(H01L), C01E(H01M), C01G(H01Q), C01H(H01R)
2.b Idealised Me refined as rotating group:
 C011(H01A,H01B,H01C), C014(H01D,H01E,H01F), C01A(H01G,H01H,H01I), C01F(H01N,
 H01O,H01P), C01J(H01V,H01W,H01X), C01M(H01S,H01T,H01U)
;
_shelx_res_checksum              32033
_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 1.921
_oxdiff_exptl_absorpt_empirical_full_min 0.574