Self-sensitized Cu(ii)-complex catalyzed solar driven CO<sub>2</sub> reduction.
Das, Soumadip; Roy, Aritra; Chakrabarti, Navonil; Mukhopadhyay, Narottam; Sarkar, Aniruddha; Sen Gupta, Sayam; Chemical science 16 (2025) 3114–3123; doi:10.1039/d4sc06354f

data_1573621
_publ_section_title
;
 Self-sensitized Cu(ii)-complex catalyzed solar driven CO<sub>2</sub>
 reduction.
;
_journal_issue                   7
_journal_name_full               'Chemical science'
_journal_page_first              3114
_journal_page_last               3123
_journal_paper_doi               10.1039/d4sc06354f
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C40 H42 Cl Cu N5 O3, 2[C2H3N]'
_chemical_formula_sum            'C44 H48 Cl Cu N7 O3'
_chemical_formula_weight         821.88
_chemical_name_systematic        CuNDPA-Cl_N2O2
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-07-11
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-07-13 deposited with the CCDC.	2025-01-08 downloaded from the CCDC.
;
_cell_angle_alpha                96.743(3)
_cell_angle_beta                 90.805(3)
_cell_angle_gamma                99.865(3)
_cell_formula_units_Z            2
_cell_length_a                   9.6787(3)
_cell_length_b                   10.7885(4)
_cell_length_c                   20.4415(8)
_cell_measurement_reflns_used    12176
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      67.5630
_cell_measurement_theta_min      2.1720
_cell_volume                     2087.09(13)
_computing_cell_refinement       'CrysAlisPro 1.171.43.119a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.119a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.119a (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)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_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  \w     21.00  79.00   0.50    4.85    --   40.58-108.00 -28.00  116
  2  \w   -150.00 -82.00   0.50   19.42    --  -82.50-108.00 -28.00  136
  3  \w    -83.00 -15.00   0.50   19.42    --  -82.50 108.00  69.00  136
  4  \w    103.00 164.00   0.50   19.42    --   96.35 108.00  69.00  122
  5  \w     29.00 108.00   0.50   19.42    --   96.35-108.00 -28.00  158
  6  \w     29.00 108.00   0.50   19.42    --   96.35-108.00 -28.00  158
  7  \w    -79.00   1.00   0.50    4.85    --  -40.58 108.00  69.00  160
  8  \w   -108.00 -27.00   0.50    4.85    --  -40.58 -32.00   0.00  162
  9  \w    -67.00  28.00   0.50    4.85    --  -40.58  77.00-180.00  190
 10  \w    -24.00  35.00   0.50    4.85    --  -40.58  11.00-150.00  118
 11  \w   -107.00 -20.00   0.50    4.85    --  -40.58 -54.00  30.00  174
 12  \w   -107.00 -20.00   0.50    4.85    --  -40.58 -54.00  30.00  174
 13  \w    -37.00  27.00   0.50    4.85    --  -40.58  32.00 -30.00  128
 14  \w    -67.00  28.00   0.50    4.85    --  -40.58  77.00-180.00  190
 15  \w   -109.00 -63.00   0.50    4.85    --  -40.58-139.00 -30.00   92
 16  \w    -37.00  27.00   0.50    4.85    --  -40.58  32.00   0.00  128
 17  \w    -61.00  26.00   0.50    4.85    --  -40.58  54.00 -90.00  174
 18  \w    -61.00  26.00   0.50    4.85    --  -40.58  54.00 -90.00  174
 19  \w   -108.00 -27.00   0.50    4.85    --  -40.58 -32.00   0.00  162
 20  \w    -35.00  24.00   0.50    4.85    --   40.58 -11.00-150.00  118
 21  \w    -26.00  61.00   0.50    4.85    --   40.58 -54.00   0.00  174
 22  \w    -21.00  72.00   0.50    4.85    --   40.58 -90.00 150.00  186
 23  \w    -21.00  72.00   0.50    4.85    --   40.58 -90.00 150.00  186
 24  \w     14.00 109.00   0.50    4.85    --   40.58  77.00 -30.00  190
 25  \w    -26.00  61.00   0.50    4.85    --   40.58 -54.00   0.00  174
 26  \w     14.00 109.00   0.50    4.85    --   40.58  77.00 -30.00  190
 27  \w    -47.00 -15.00   0.50   19.42    --  -82.50  42.00 -60.00   64
 28  \w    -47.00 -15.00   0.50   19.42    --  -82.50  42.00-120.00   64
 29  \w   -150.00 -69.00   0.50   19.42    --  -82.50 -33.00 150.00  162
 30  \w    -47.00 -15.00   0.50   19.42    --  -82.50  42.00  60.00   64
 31  \w    -47.00 -15.00   0.50   19.42    --  -82.50  42.00-180.00   64
 32  \w    -47.00 -15.00   0.50   19.42    --  -82.50  42.00 120.00   64
 33  \w    -84.00 -18.00   0.50   19.42    --  -82.50 117.00-120.00  132
 34  \w    -47.00 -15.00   0.50   19.42    --  -82.50  42.00 -90.00   64
 35  \w    -57.00 -16.00   0.50   19.42    --  -82.50  50.00  30.00   82
 36  \w     83.00 164.00   0.50   19.42    --   96.35  33.00 120.00  162
 37  \w     28.00  68.00   0.50   19.42    --   96.35 -59.00-150.00   80
 38  \w     99.00 160.00   0.50   19.42    --   96.35 117.00   0.00  122
 39  \w     29.00  83.00   0.50   19.42    --   96.35 -68.00   0.00  108
 40  \w     44.00 127.00   0.50   19.42    --   96.35-145.00-150.00  166
 41  \w     28.00 105.00   0.50   19.42    --   96.35 -77.00 -30.00  154
 42  \w     30.00  57.00   0.50   19.42    --   96.35 -50.00   0.00   54
 43  \w     81.00 167.00   0.50   19.42    --   96.35  25.00-150.00  172
 44  \w     23.00 106.00   0.50   19.42    --   96.35 -96.00 -30.00  166
 45  \w     44.00 127.00   0.50   19.42    --   96.35-145.00 -30.00  166
 46  \w     33.00 110.00   0.50   19.42    --   96.35-117.00  90.00  154
 47  \w     75.00 165.00   0.50   19.42    --   96.35  59.00  30.00  180
 48  \w     75.00 165.00   0.50   19.42    --   96.35  59.00  30.00  180
 49  \w     33.00 110.00   0.50   19.42    --   96.35-117.00  90.00  154
 50  \w     30.00  57.00   0.50   19.42    --   96.35 -50.00 -30.00   54
 51  \w     33.00 110.00   0.50   19.42    --   96.35-117.00-120.00  154
 52  \w     33.00 110.00   0.50   19.42    --   96.35-117.00-120.00  154
 53  \w     37.00 174.00   0.50   19.42    --   96.35   8.00  60.00  274
 54  \w    105.00 170.00   0.50   19.42    --   96.35  96.00 120.00  130
 55  \w     23.00 106.00   0.50   19.42    --   96.35 -96.00-120.00  166
 56  \w     23.00 106.00   0.50   19.42    --   96.35 -96.00 -30.00  166
 57  \w     23.00 106.00   0.50   19.42    --   96.35 -96.00-120.00  166
 58  \w     30.00  57.00   0.50   19.42    --   96.35 -50.00-150.00   54
 59  \w     37.00 174.00   0.50   19.42    --   96.35   8.00  60.00  274
 60  \w     44.00 127.00   0.50   19.42    --   96.35-145.00-150.00  166
 61  \w     29.00  83.00   0.50   19.42    --   96.35 -68.00 -90.00  108
 62  \w    105.00 170.00   0.50   19.42    --   96.35  96.00-120.00  130
 63  \w     23.00 106.00   0.50   19.42    --   96.35 -96.00 120.00  166
 64  \w     30.00  57.00   0.50   19.42    --   96.35 -50.00 150.00   54
 65  \w     23.00 106.00   0.50   19.42    --   96.35 -96.00  90.00  166
 66  \w     28.00  68.00   0.50   19.42    --   96.35 -59.00 -60.00   80
 67  \w     83.00 164.00   0.50   19.42    --   96.35  33.00  90.00  162
 68  \w    105.00 170.00   0.50   19.42    --   96.35  96.00 -90.00  130
 69  \w     30.00  57.00   0.50   19.42    --   96.35 -50.00 120.00   54
 70  \w     30.00  57.00   0.50   19.42    --   96.35 -50.00  90.00   54
 71  \w     28.00 105.00   0.50   19.42    --   96.35 -77.00 150.00  154
 72  \w   -109.00 -14.00   0.50    4.85    --  -40.58 -77.00 150.00  190
 73  \w   -108.00 -27.00   0.50    4.85    --  -40.58 -32.00-120.00  162
 74  \w   -109.00 -17.00   0.50    4.85    --  -40.58 -66.00 -30.00  184
 75  \w   -109.00 -14.00   0.50    4.85    --  -40.58 -77.00  90.00  190
 76  \w   -109.00 -14.00   0.50    4.85    --  -40.58 -77.00-150.00  190
 77  \w   -109.00 -14.00   0.50    4.85    --  -40.58 -77.00  30.00  190
 78  \w   -109.00 -14.00   0.50    4.85    --  -40.58 -77.00 -90.00  190
 79  \w   -107.00 -20.00   0.50    4.85    --  -40.58 -54.00-150.00  174
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0643
_diffrn_reflns_av_unetI/netI     0.0397
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            40872
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        66.597
_diffrn_reflns_theta_max         66.597
_diffrn_reflns_theta_min         2.178
_exptl_absorpt_coefficient_mu    1.708
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87827
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.119a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'Dark red'
_exptl_crystal_density_diffrn    1.308
_exptl_crystal_description       Block
_exptl_crystal_F_000             862
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.977
_refine_diff_density_min         -0.529
_refine_diff_density_rms         0.156
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.400
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     431
_refine_ls_number_reflns         7376
_refine_ls_number_restraints     116
_refine_ls_restrained_S_all      1.409
_refine_ls_R_factor_all          0.1406
_refine_ls_R_factor_gt           0.1256
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3404
_refine_ls_wR_factor_ref         0.3535
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5647
_reflns_number_total             7376
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06354f2.cif
_cod_data_source_block           complex2
_cod_depositor_comments
'Adding full bibliography for 1573620--1573621.cif.'
_cod_database_code               1573621
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All H(H) groups, All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C40-C38
 1.54 with sigma of 0.02
 C12-C11 = C12-C13
 1.55 with sigma of 0.02
 C14-C12 = C12-C15
 1.54 with sigma of 0.02
 C11-O2
 1.26 with sigma of 0.02
 N5-H5
 0.9 with sigma of 0.02
 C14-C11 = C14-C13
 2.52 with sigma of 0.04
 C14-C15
 2.56 with sigma of 0.04
 C12-C15 \\sim C12-C11 \\sim C12-C13 \\sim C12-C14
 with sigma of 0.02
 C15-C11 \\sim C15-C13 \\sim C11-C13
 with sigma of 0.04
 C14-C15 \\sim C14-C11 \\sim C14-C13
 with sigma of 0.04
3. Rigid bond restraints
 C40, C38
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C28, C27
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C38, C39
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C11, N2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C14 \\sim C12 \\sim C15 \\sim C11 \\sim C13: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Uanis(C15) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq: with sigma of
0.004 and sigma for terminal atoms of 0.008
Uanis(N2) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(O2) \\sim Ueq: with sigma of
0.04 and sigma for terminal atoms of 0.08
Uanis(N2) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C39) = Uanis(C40) = Uanis(C29) = Uanis(C28)
Uanis(C38) = Uanis(C27)
5. Rigid body (RIGU) restrains
 C14, C12, C15, C11, C13
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Ternary CH refined with riding coordinates:
 C27(H27), C38(H38)
6.b Me refined with riding coordinates:
 C28(H28A,H28B,H28C), C13(H13A,H13B,H13C)
6.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C19(H19), C4(H4A), C3(H3), C37(H37), C36(H36), C34(H34), C33(H33),
 C31(H31), C24(H24), C8(H8), C25(H25), C17(H17), C16(H16), C30(H30), C9(H9)
6.d Fitted hexagon refined as free rotating group:
 C32(C37,C36,C35,C34,C33)
6.e Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C14(H14A,H14B,
 H14C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              81532
_shelx_fab_checksum              11183
_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
;