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_1573577
_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         'C37 H47 N5 Ni O4, 0.5(C4 H10 O)'
_chemical_formula_sum            'C39 H52 N5 Ni O4.5'
_chemical_formula_weight         721.56
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-05-30
_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                 91.0070(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   33.3183(3)
_cell_length_b                   9.93460(10)
_cell_length_c                   21.7721(2)
_cell_measurement_reflns_used    11745
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.2730
_cell_measurement_theta_min      2.6330
_cell_volume                     7205.54(12)
_computing_cell_refinement       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_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      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.951
_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     26.00  76.00   0.50    1.50    --   62.55-125.00 -90.00  100
  2  \w     24.00  85.00   0.50    1.50    --   62.55-125.00  90.00  122
  3  \w   -109.00 -48.00   0.50    1.50    --  -68.39 -15.00-150.00  122
  4  \w   -104.00 -49.00   0.50    1.50    --  -68.39 -15.00 150.00  110
  5  \w   -104.00 -44.00   0.50    1.50    --  -68.39 -15.00 -90.00  120
  6  \w    -74.00 -30.00   0.50    1.50    --  -68.39 125.00-120.00   88
  7  \w     36.00  67.00   0.50    4.50    --   75.18-125.00   0.00   62
  8  \w     39.00  96.00   0.50    4.50    --   75.18-125.00 -60.00  114
  9  \w     50.00 114.00   0.50    4.50    --   75.18  15.00-180.00  128
 10  \w     36.00  83.00   0.50    4.50    --   75.18-125.00 120.00   94
 11  \w     53.00 111.00   0.50    4.50    --   75.18  15.00-120.00  116
 12  \w     39.00  99.00   0.50    4.50    --   75.18-125.00-150.00  120
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0196
_diffrn_reflns_av_unetI/netI     0.0202
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            19803
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.028
_diffrn_reflns_theta_min         2.653
_exptl_absorpt_coefficient_mu    1.169
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94918
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.80a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light violet'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.330
_exptl_crystal_description       block
_exptl_crystal_F_000             3080
_exptl_crystal_size_max          0.068
_exptl_crystal_size_mid          0.055
_exptl_crystal_size_min          0.048
_refine_diff_density_max         0.591
_refine_diff_density_min         -0.685
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.262
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     579
_refine_ls_number_reflns         6864
_refine_ls_number_restraints     77
_refine_ls_restrained_S_all      1.263
_refine_ls_R_factor_all          0.0690
_refine_ls_R_factor_gt           0.0652
_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^)+(0.0413P)^2^+35.0741P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1635
_refine_ls_wR_factor_ref         0.1653
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6360
_reflns_number_total             6864
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04257c2.cif
_cod_data_source_block           rr-ur-x135_mc
_cod_depositor_comments
'Adding full bibliography for 1573571--1573578.cif.'
_cod_original_formula_sum        'C39 H52 N5 Ni O4.50'
_cod_database_code               1573577
_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, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O2-C12 \\sim O2A-C12A
 with sigma of 0.02
 O3-C10 \\sim O3-C10A
 with sigma of 0.02
 N4-C12 \\sim N4-C12A
 with sigma of 0.02
 N5-C12 \\sim N5A-C12A
 with sigma of 0.02
 N5-C10 \\sim N5A-C10A
 with sigma of 0.02
 N5-C9 \\sim N5A-C9A
 with sigma of 0.02
 C11-C10 \\sim C11-C10A
 with sigma of 0.02
 O2-N4 \\sim O2A-N4
 with sigma of 0.04
 O2-N5 \\sim O2A-N5A
 with sigma of 0.04
 O3-N5 \\sim O3-N5A
 with sigma of 0.04
 N4-N5 \\sim N4-N5A
 with sigma of 0.04
 N5-C11 \\sim N5A-C11
 with sigma of 0.04
 C12-C10 \\sim C12A-C10A
 with sigma of 0.04
 C12-C9 \\sim C12A-C9A
 with sigma of 0.04
 C10-C9 \\sim C10A-C9A
 with sigma of 0.04
 O3-C10 \\sim O3A-C10
 with sigma of 0.02
 O3-C10A \\sim O3A-C10A
 with sigma of 0.02
 C39-C38 \\sim C40-C1A
 with sigma of 0.02
 N2-C7 \\sim N2-C7A
 with sigma of 0.02
 N3-C11 \\sim N3-C11A
 with sigma of 0.02
 N4-C7 \\sim N4A-C7A
 with sigma of 0.02
 N4-C8 \\sim N4A-C8
 with sigma of 0.02
 N4-C12 \\sim N4A-C12
 with sigma of 0.02
 N4-C12A \\sim N4A-C12A
 with sigma of 0.02
 C7-C11 \\sim C7A-C11A
 with sigma of 0.02
 C11-C10 \\sim C11A-C10
 with sigma of 0.02
 C11-C10A \\sim C11A-C10A
 with sigma of 0.02
 N2-N4 \\sim N2-N4A
 with sigma of 0.04
 N2-C11 \\sim N2-C11A
 with sigma of 0.04
 N3-C7 \\sim N3-C7A
 with sigma of 0.04
 N4-C11 \\sim N4A-C11A
 with sigma of 0.04
 C7-C8 \\sim C7A-C8
 with sigma of 0.04
 C7-C12 \\sim C7A-C12
 with sigma of 0.04
 C7-C10 \\sim C7A-C10
 with sigma of 0.04
 C7-C12A \\sim C7A-C12A
 with sigma of 0.04
 C7-C10A \\sim C7A-C10A
 with sigma of 0.04
 N4-C8 \\sim N4-C8A
 with sigma of 0.02
 C8-N4A \\sim C8A-N4A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C38 \\sim C40 \\sim C1A \\sim C39: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
C7A \\sim C11A \\sim C11 \\sim C7: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C11A \\sim C11 \\sim C7 \\sim C7A: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
C8A \\sim C8: within 2A with sigma of 0.0001 and sigma for terminal atoms of
0.0002 within 2A
Uanis(O5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C12A)=Sof(N5A)=Sof(C10A)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(O2A)=
 1-FVAR(1)
 Sof(O2)=Sof(N5)=Sof(C12)=Sof(C10)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=FVAR(1)
 Sof(O3A)=1-FVAR(2)
 Sof(O3)=FVAR(2)
 Sof(C11A)=Sof(C7A)=Sof(N4A)=1-FVAR(3)
 Sof(N4)=Sof(C7)=Sof(C11)=FVAR(3)
 Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=1-FVAR(4)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=FVAR(4)
 Fixed Sof: C38(0.5) H38A(0.5) H38B(0.5) H38C(0.5) O5(0.5) C39(0.5) H39A(0.5)
 H39B(0.5) C40(0.5) H40A(0.5) H40B(0.5) C1A(0.5) H1AA(0.5) H1AB(0.5) H1AC(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C39(H39A,H39B), C40(H40A,H40B)
5.b Aromatic/amide H refined with riding coordinates:
 O4(H4), C24(H24), C1(H1), C22(H22), C4(H4A), C2(H2), C3(H3), C14(H14),
 C17(H17), C18(H18), C15(H15)
5.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C30(H30A,H30B,H30C), C29(H29A,H29B,H29C), C28(H28A,H28B,
 H28C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C8(H8A,H8B,H8C), C36(H36A,
 H36B,H36C), C19(H19A,H19B,H19C), C35(H35A,H35B,H35C), C37(H37A,H37B,H37C),
 C9(H9A,H9B,H9C), C9A(H9AA,H9AB,H9AC), C38(H38A,H38B,H38C), C1A(H1AA,H1AB,H1AC),
  C8A(H8AA,H8AB,H8AC)
;
_shelx_res_checksum              82089
_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
;