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_1573576
_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         '0.5(C19 H17 N5 O3), 0.5(C4 H8 O)'
_chemical_formula_sum            'C11.5 H12.5 N2.5 O2'
_chemical_formula_weight         217.74
_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
_audit_creation_date             2023-05-17
_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                 94.448(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.8012(2)
_cell_length_b                   8.1826(2)
_cell_length_c                   27.1202(6)
_cell_measurement_reflns_used    16106
_cell_measurement_temperature    123.01(10)
_cell_measurement_theta_max      66.4400
_cell_measurement_theta_min      5.3830
_cell_volume                     2168.47(8)
_computing_cell_refinement       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.89a (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_temperature      123.15
_diffrn_detector_area_resol_mean 4.2047
_diffrn_detector_type            TitanS2
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_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    -39.00 -14.00   1.00    5.00    --  -42.98  93.00  44.00   25
  2  \w     42.00  77.00   1.00    5.00    --   42.98 -93.00 -67.00   35
  3  \w      3.00  40.00   1.00    5.00    --   42.98 -93.00 -67.00   37
  4  \w     18.00  43.00   1.00   20.00    --   86.50 -93.00 -67.00   25
  5  \w     96.00 121.00   1.00   20.00    --   86.50  93.00  44.00   25
  6  \w    -81.00 -56.00   1.00   20.00    --  -90.00  93.00  44.00   25
  7  \w    -75.00 -48.00   1.00    5.00    --  -42.98 125.00 -90.00   27
  8  \w     21.00 114.00   1.00    5.00    --   42.98  37.00-150.00   93
  9  \w     17.00 112.00   1.00    5.00    --   42.98  57.00  90.00   95
 10  \w   -106.00 -80.00   1.00   20.00    --  -90.00  61.00-120.00   26
 11  \w   -162.00-137.00   1.00   20.00    --  -90.00-125.00 -30.00   25
 12  \w   -100.00 -46.00   1.00   20.00    --  -90.00 108.00  87.30   54
 13  \w   -109.00 -28.00   1.00   20.00    --  -90.00 125.00-180.00   81
 14  \w   -113.00 -87.00   1.00   20.00    --  -90.00  61.00  30.00   26
 15  \w    -59.00 -26.00   1.00   20.00    --  -90.00  61.00  30.00   33
 16  \w   -109.00 -67.00   1.00   20.00    --  -90.00 125.00 120.00   42
 17  \w    -66.00 -21.00   1.00   20.00    --  -90.00  61.00   0.00   45
 18  \w   -123.00 -97.00   1.00   20.00    --  -90.00-125.00 -30.00   26
 19  \w   -103.00 -77.00   1.00   20.00    --  -90.00 125.00-120.00   26
 20  \w   -103.00 -59.00   1.00   20.00    --  -90.00 125.00  90.00   44
 21  \w    -81.00 -51.00   1.00   20.00    --  -90.00  30.00 -30.00   30
 22  \w   -128.00 -70.00   1.00   20.00    --  -90.00  15.00-150.00   58
 23  \w    -92.00 -28.00   1.00   20.00    --  -90.00 125.00 150.00   64
 24  \w    -96.00 -28.00   1.00   20.00    --  -90.00  61.00  60.00   68
 25  \w    -60.00 -34.00   1.00   20.00    --  -90.00  30.00 -90.00   26
 26  \w    -62.00 -37.00   1.00   20.00    --  -90.00 125.00  30.00   25
 27  \w    -96.00 -67.00   1.00   20.00    --  -90.00 -45.00 120.00   29
 28  \w   -117.00 -86.00   1.00   20.00    --  -90.00  61.00   0.00   31
 29  \w    -95.00 -69.00   1.00   20.00    --  -90.00  77.00  30.00   26
 30  \w   -162.00-103.00   1.00   20.00    --  -90.00 -77.00-120.00   59
 31  \w    -57.00 -28.00   1.00   20.00    --  -90.00 125.00 -90.00   29
 32  \w   -154.00-111.00   1.00   20.00    --  -90.00 -94.00  30.00   43
 33  \w   -156.00-131.00   1.00   20.00    --  -90.00 -61.00-180.00   25
 34  \w   -105.00 -63.00   1.00   20.00    --  -90.00 -61.00-180.00   42
 35  \w   -164.00-107.00   1.00   20.00    --  -90.00 -77.00   0.00   57
 36  \w   -173.00-115.00   1.00   20.00    --  -90.00 -95.00 172.41   58
 37  \w   -167.00-104.00   1.00   20.00    --  -90.00 -93.00 -34.73   63
 38  \w   -149.00-104.00   1.00   20.00    --  -90.00 -94.00 -90.00   45
 39  \w    -65.00 -39.00   1.00   20.00    --  -90.00  15.00-150.00   26
 40  \w    -99.00 -74.00   1.00   20.00    --  -90.00 125.00-150.00   25
 41  \w   -108.00 -66.00   1.00   20.00    --  -90.00 -61.00  90.00   42
 42  \w    -72.00 -45.00   1.00   20.00    --  -90.00  77.00  60.00   27
 43  \w    -66.00 -40.00   1.00   20.00    --  -90.00  77.00 150.00   26
 44  \w   -162.00-137.00   1.00   20.00    --  -90.00 -77.00-180.00   25
 45  \w   -120.00 -91.00   1.00   20.00    --  -90.00 134.00-105.64   29
 46  \w   -109.00 -76.00   1.00   20.00    --  -90.00 112.00  57.70   33
 47  \w   -121.00 -95.00   1.00   20.00    --  -90.00 -45.00-120.00   26
 48  \w   -154.00 -91.00   1.00   20.00    --  -90.00 -45.00 -90.00   63
 49  \w   -152.00-124.00   1.00   20.00    --  -90.00 -77.00 -30.00   28
 50  \w    -47.00 -22.00   1.00   20.00    --  -90.00  61.00-180.00   25
 51  \w   -116.00 -76.00   1.00   20.00    --  -90.00  30.00-120.00   40
 52  \w    -53.00 -27.00   1.00   20.00    --  -90.00  30.00-120.00   26
 53  \w   -130.00-103.00   1.00   20.00    --  -90.00 -77.00  30.00   27
 54  \w    -81.00 -56.00   1.00   20.00    --  -90.00  77.00  90.00   25
 55  \w   -120.00 -95.00   1.00   20.00    --  -90.00  84.00-122.05   25
 56  \w    -68.00 -43.00   1.00   20.00    --  -90.00  84.00-122.05   25
 57  \w   -163.00-136.00   1.00   20.00    --  -90.00 -93.00 -67.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dualflex, TitanS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0761
_diffrn_reflns_av_unetI/netI     0.0310
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            30627
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        66.791
_diffrn_reflns_theta_max         66.791
_diffrn_reflns_theta_min         4.525
_exptl_absorpt_coefficient_mu    0.768
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63207
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.89a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.334
_exptl_crystal_description       plate
_exptl_crystal_F_000             920
_exptl_crystal_size_max          0.527
_exptl_crystal_size_mid          0.141
_exptl_crystal_size_min          0.063
_refine_diff_density_max         0.320
_refine_diff_density_min         -0.257
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     292
_refine_ls_number_reflns         3834
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0584
_refine_ls_R_factor_gt           0.0540
_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^)+(0.1052P)^2^+0.6565P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1476
_refine_ls_wR_factor_ref         0.1545
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3420
_reflns_number_total             3834
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04257c2.cif
_cod_data_source_block           sd86_sd1
_cod_depositor_comments
'Adding full bibliography for 1573571--1573578.cif.'
_cod_original_formula_sum        'C11.50 H12.50 N2.50 O2'
_cod_database_code               1573576
_shelx_shelxl_version_number     2018/3
_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:
 C00T(H00O,H00R), C00U(H00T,H00U), C00V(H00V,H00W), C00W(H00X,H00Y)
2.b Aromatic/amide H refined with riding coordinates:
 C00H(H00H), C00I(H00I), C00J(H00J), C00M(H00M), C00N(H00N), C00P(H00P),
 C00Q(H00Q), C00S(H00S)
2.c Idealised Me refined as rotating group:
 C00L(H00A,H00B,H00C), C00O(H00D,H00E,H00F), C00R(H00G,H00K,H00L)
;
_shelx_res_checksum              93589
_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
;