Exploring catalytic activity modulations: photoredox catalysis with substituted copper(i)-dipyridylamine derivatives
Villegas-Menares, Alondra; Hansmann, Yannik Sebastian; Bayas, Max; Verdugo, Camilo; Erazo, Ignacio; Zuñiga, Cesar; Gonzalez, Iván; Galdámez, Antonio; Villa, Lucrezia; Natali, Mirco; Cabrera, Alan R.; Dalton Transactions 54 (2025) 7306–7314; doi:10.1039/D4DT03337J

data_7718513
_publ_section_title
;
 Exploring catalytic activity modulations: photoredox catalysis with
 substituted copper(i)-dipyridylamine derivatives
;
_journal_issue                   18
_journal_name_full               'Dalton Transactions'
_journal_page_first              7306
_journal_page_last               7314
_journal_paper_doi               10.1039/D4DT03337J
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety
'C54.479 H40.733 Cu F2.62 N2.62 O0.873 P2, 0.8(C1 H2 Cl2), B F4, 0.127(C12 H10 F3 N3 O)'
_chemical_formula_sum            'C56.8 H43.6 B Cl1.6 Cu F7 N3 O P2'
_chemical_formula_weight         1110.15
_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   mixed
_audit_creation_date             2025-02-28
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-28 deposited with the CCDC.	2025-03-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1556(3)
_cell_length_b                   19.4730(6)
_cell_length_c                   21.5417(6)
_cell_measurement_reflns_used    22576
_cell_measurement_temperature    99.94(13)
_cell_measurement_theta_max      27.8050
_cell_measurement_theta_min      2.6650
_cell_volume                     5099.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 41.123a 64-bit (release 20-01-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.94(13)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.945
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0532
_diffrn_reflns_av_unetI/netI     0.0521
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            67425
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.915
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.468
_diffrn_reflns_theta_min         2.295
_exptl_absorpt_coefficient_mu    0.645
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.702
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.105a (Rigaku Oxford Diffraction, 2024)
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            colourless
_exptl_crystal_density_diffrn    1.446
_exptl_crystal_description       block
_exptl_crystal_F_000             2270
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.332
_refine_diff_density_min         -0.308
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 3990 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.014(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     852
_refine_ls_number_reflns         12956
_refine_ls_number_restraints     799
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0623
_refine_ls_R_factor_gt           0.0404
_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^)+(0.0254P)^2^+2.2072P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0715
_refine_ls_wR_factor_ref         0.0789
_reflns_Friedel_coverage         0.769
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.879
_reflns_number_gt                10595
_reflns_number_total             12956
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03337j2.cif
_cod_data_source_block           acc-365_v2
_cod_depositor_comments
'Adding full bibliography for 7718511--7718513.cif.'
_cod_original_formula_sum        'C56.80 H43.60 B Cl1.60 Cu F7 N3 O P2'
_cod_database_code               7718513
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N2-H2A = N2A-H2AB
 0.86 with sigma of 0.01
 O6-C3A
 1.35 with sigma of 0.01
 O6-C59
 1.44 with sigma of 0.01
 C1-C2 \\sim C1A-C2A
 with sigma of 0.02
 N2-H2A \\sim N2-H2AB
 with sigma of 0.02
 C1-H2A \\sim C1A-H2AB
 with sigma of 0.01
 C7-H2A \\sim C7A-H2AB
 with sigma of 0.01
 N3A-C11A \\sim N3-C11 \\sim N3A-C7A \\sim N3-C7 \\sim N1A-C1A \\sim N1-C1
\\sim N1-C5 \\sim N1A-C5A
 with sigma of 0.01
 Cu1-N1 \\sim Cu1-N1A \\sim Cu1-N3 \\sim Cu1-N3A
 with sigma of 0.01
 C11A-C10A \\sim C11-C10 \\sim C9A-C10A \\sim C9-C10 \\sim C9-C8 \\sim C9A-C8A
\\sim C8-C7 \\sim C8A-C7A ~
 C2-C1 \\sim C2A-C1A \\sim C3A-C2A \\sim C3-C2 \\sim C4A-C3A \\sim C4-C3 \\sim
C5A-C4A \\sim C5-C4
 with sigma of 0.01
 O1-C9 \\sim O6-C3A
 with sigma of 0.01
 C9A-C58 \\sim C6-C3
 with sigma of 0.01
 O6-C59 \\sim O1-C12
 with sigma of 0.01
 N2A-C7A \\sim N2-C7 \\sim N2-C1 \\sim N2A-C1A
 with sigma of 0.01
 F8-C58 \\sim F9-C58 \\sim F10-C58 \\sim F3-C6 \\sim F2-C6 \\sim F1-C6
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim N3 \\sim O1 \\sim F8
\\sim F9 \\sim F10 \\sim C58 \\sim C7A \\sim C8A \\sim C9A \\sim C10A \\sim N3A
\\sim C11A \\sim N2A \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim N1
\\sim N2 \\sim C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim N1A \\sim C6
\\sim F1 \\sim F2 \\sim F3 \\sim O6 \\sim C59: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Uanis(Cl2) = Uanis(Cl2A)
Uanis(Cl1A) = Uanis(Cl1)
Uanis(C59) = Uanis(F3)
Uanis(C57) = Uanis(C57A)
4. Others
 1*[Sof(C57)+Sof(H57A)+Sof(H57B)+Sof(Cl1)+Sof(Cl2)]+1*[Sof(Cl2A)+Sof(C57A)+
 Sof(H57C)+Sof(H57D)+Sof(Cl1A)]=0.8 with esd of 0
 Sof(F8)=Sof(F9)=Sof(F10)=Sof(C58)=Sof(C7A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=
 Sof(C10A)=Sof(H10A)=Sof(N3A)=Sof(C11A)=Sof(H11A)=Sof(C1A)=Sof(C2A)=Sof(H2AA)=
 Sof(C3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(N1A)=Sof(N2A)=Sof(H2AB)=
 Sof(O6)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=1-FVAR(1)
 Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=Sof(C6)=
 Sof(C7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=Sof(C12)=
 Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(N1)=Sof(N2)=Sof(H2A)=Sof(N3)=Sof(O1)=Sof(F1)=
 Sof(F2)=Sof(F3)=FVAR(1)
 Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(Cl1)=Sof(Cl2)=FVAR(2)
 Sof(Cl2A)=Sof(C57A)=Sof(H57C)=Sof(H57D)=Sof(Cl1A)=FVAR(3)
5.a Secondary CH2 refined with riding coordinates:
 C57(H57A,H57B), C57A(H57C,H57D)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C8(H8), C10(H10), C11(H11), C14(H14), C15(H15),
 C16(H16), C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24),
  C29(H29), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C37(H37),
 C38(H38), C41(H41), C42(H42), C43(H43), C44(H44), C46(H46), C47(H47), C48(H48),
  C49(H49), C50(H50), C52(H52), C53(H53), C54(H54), C55(H55), C56(H56),
 C8A(H8A), C10A(H10A), C11A(H11A), C2A(H2AA), C4A(H4A), C5A(H5A)
5.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C59(H59A,H59B,H59C)
;
_shelx_res_checksum              55488
_shelx_hkl_checksum              54296
_olex2_submission_special_instructions 'No special instructions were received'