Ligand-Mediated Modulation in Copper(II) Complexes for Four-Electron Oxygen Reduction in Neutral Medium
Chaudhary, Savi; Murugavel, Ramaswamy; Dalton Transactions  (2026) –; doi:10.1039/D5DT01736J

data_7720004
_publ_section_title
;
 Ligand-Mediated Modulation in Copper(II) Complexes for Four-Electron
 Oxygen Reduction in Neutral Medium
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D5DT01736J
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H54 Cu N2 O9 P2'
_chemical_formula_sum            'C22 H54 Cu N2 O9 P2'
_chemical_formula_weight         616.15
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2025-04-04
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2025-06-23 deposited with the CCDC.	2025-12-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.8691(6)
_cell_length_b                   24.7007(15)
_cell_length_c                   31.117(3)
_cell_measurement_reflns_used    11975
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      20.7410
_cell_measurement_theta_min      1.7090
_cell_volume                     6816.9(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \f    105.99 250.99   1.00    8.00   6.61  -9.84 -31.50    --   145
  2  \w   -100.81  15.19   1.00    8.00    --   -9.84 -59.25  20.08  116
  3  \f    -60.21  84.79   1.00    8.00  15.81  -9.84 -59.25    --   145
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0327367000
_diffrn_orient_matrix_UB_12      0.0251375000
_diffrn_orient_matrix_UB_13      0.0060001000
_diffrn_orient_matrix_UB_21      -0.0670557000
_diffrn_orient_matrix_UB_22      0.0135624000
_diffrn_orient_matrix_UB_23      -0.0063038000
_diffrn_orient_matrix_UB_31      -0.0290327000
_diffrn_orient_matrix_UB_32      -0.0029541000
_diffrn_orient_matrix_UB_33      0.0210832000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1111
_diffrn_reflns_av_unetI/netI     0.0669
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            79430
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         1.774
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.777
_exptl_absorpt_correction_T_max  1.00
_exptl_absorpt_correction_T_min  0.86504
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic bluish blue'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.201
_exptl_crystal_description       plate
_exptl_crystal_F_000             2648
_exptl_crystal_size_max          0.348
_exptl_crystal_size_mid          0.169
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.540
_refine_diff_density_min         -0.499
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;
 Flack x determined using 2896 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.007(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     697
_refine_ls_number_reflns         12015
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0877
_refine_ls_R_factor_gt           0.0628
_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^)+(0.0752P)^2^+4.6526P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1452
_refine_ls_wR_factor_ref         0.1691
_reflns_Friedel_coverage         0.797
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                8985
_reflns_number_total             12015
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01736j2.cif
_cod_data_source_block           rm_sa_126b
_cod_original_cell_volume        6816.9(8)
_cod_database_code               7720004
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.774
_reflns_odcompleteness_completeness 99.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O1-H1B
 1.217 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C15) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.001
Uanis(C11) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.001
Uanis(C40) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.001
4.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C17(H17A,H17B), C40(H40A,H40B), C39(H39A,H39B)
4.b Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C16(H16A,H16B,H16C), C15(H15A,H15B,H15C), C14(H14A,H14B,H14C), C12(H12A,
 H12B,H12C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C8(H8A,H8B,H8C), C7(H7A,
 H7B,H7C), C6(H6A,H6B,H6C), C4(H4A,H4B,H4C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C),
 C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C42(H42A,H42B,H42C), C41(H41A,H41B,
 H41C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C36(H36A,H36B,H36C), C32(H32A,
 H32B,H32C), C34(H34A,H34B,H34C), C33(H33A,H33B,H33C), C30(H30A,H30B,H30C),
 C29(H29A,H29B,H29C), C28(H28A,H28B,H28C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              52046
_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 1.238
_oxdiff_exptl_absorpt_empirical_full_min 0.811