Chemical fixation of atmospheric CO<sub>2</sub> in tricopper(II)-carbonato complexes with tetradentate N-donor ligands: reactive intermediates, probable mechanisms, and catalytic and magneto-structural studies.
Jana, Narayan Ch; Sun, Yu-Chen; Herchel, Radovan; Nandy, Rakhi; Brandão, Paula; Bagh, Bidraha; Wang, Xin-Yi; Panja, Anangamohan; Dalton transactions (Cambridge, England : 2003) 53 (2024) 11514–11530; doi:10.1039/d4dt00503a

data_7716361
_publ_section_title
;
 Chemical fixation of atmospheric CO<sub>2</sub> in
 tricopper(II)-carbonato complexes with tetradentate N-donor ligands:
 reactive intermediates, probable mechanisms, and catalytic and
 magneto-structural studies.
;
_journal_issue                   27
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              11514
_journal_page_last               11530
_journal_paper_doi               10.1039/d4dt00503a
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C43 H75 Cu3 N15 O3, 4(Cl O4)'
_chemical_formula_sum            'C43 H75 Cl4 Cu3 N15 O19'
_chemical_formula_weight         1438.60
_space_group_crystal_system      cubic
_space_group_IT_number           198
_space_group_name_Hall           'P 2ac 2ab 3'
_space_group_name_H-M_alt        'P 21 3'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-07-02
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-01-22 deposited with the CCDC.	2024-06-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.3268(3)
_cell_length_b                   18.3268(3)
_cell_length_c                   18.3268(3)
_cell_measurement_reflns_used    10035
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      31.9970
_cell_measurement_theta_min      3.4840
_cell_volume                     6155.45(17)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.852
_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      7.00  59.00   0.50   14.46    --    7.32-126.00  34.00  104
  2  \w    -42.00  15.00   0.50   14.46    --   -7.95 -77.00  60.00  114
  3  \w    -59.00 -34.00   0.50   14.46    --    7.32 -37.00 120.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0106585000
_diffrn_orient_matrix_UB_12      -0.0321606000
_diffrn_orient_matrix_UB_13      -0.0187702000
_diffrn_orient_matrix_UB_21      0.0371041000
_diffrn_orient_matrix_UB_22      0.0077910000
_diffrn_orient_matrix_UB_23      0.0076416000
_diffrn_orient_matrix_UB_31      -0.0026290000
_diffrn_orient_matrix_UB_32      -0.0201012000
_diffrn_orient_matrix_UB_33      0.0329658000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0634
_diffrn_reflns_av_unetI/netI     0.0573
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.852
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            26464
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.824
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.835
_diffrn_reflns_theta_min         3.335
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.280
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76649
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark green'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.552
_exptl_crystal_description       block
_exptl_crystal_F_000             2980
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.360
_refine_diff_density_min         -0.256
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Flack x determined using 1733 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.029(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     268
_refine_ls_number_reflns         5816
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0633
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0479P)^2^+0.7243P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0876
_refine_ls_wR_factor_ref         0.0961
_reflns_Friedel_coverage         0.790
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.791
_reflns_number_gt                4519
_reflns_number_total             5816
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00503a2.cif
_cod_data_source_block           nj-18
_cod_depositor_comments
'Adding full bibliography for 7716361--7716364.cif.'
_cod_original_cell_volume        6155.5(3)
_cod_database_code               7716361
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C184 H300 Cl16 Cu12 N48 O88 '
_shelx_estimated_absorpt_t_max   0.883
_shelx_estimated_absorpt_t_min   0.784
_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. Others
 Fixed Sof: O10(0.21667) O11(0.11667) O9(0.6) O8(0.4)
3.a Ternary CH refined with riding coordinates:
 N4(H4)
3.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C9(H9A,H9B), C8(H8A,H8B), C11(H11A,H11B), C12(H12A,H12B),
 C13(H13A,H13B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4A), C3(H3)
3.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              78981
_shelx_hkl_checksum              7467
_shelx_fab_checksum              88181
_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 1.269
_oxdiff_exptl_absorpt_empirical_full_min 0.779