A Novel Cadmium-Containing Porphyrin-Based Metal-Organic Framework Enables Oxidation of Inert C(sp 3 )-H Bonds
Liu, Xudong; Shen, Keshen; Jia, Ruiming; Jing, Xu; Duan, Chunying; Dalton Transactions  (2026) –; doi:10.1039/D6DT00587J

data_7720874
_publ_section_title
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 A novel cadmium-containing porphyrin-based metal-organic framework
 enables oxidation of inert C(sp<sup>3</sup>)-H bonds.
;
_journal_issue                   18
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              7149
_journal_page_last               7155
_journal_paper_doi               10.1039/d6dt00587j
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C48 H24 Cd Cl Mn N4 O8, 1.6[H2O]'
_chemical_formula_sum            'C48 H27.2 Cd Cl Mn N4 O9.6'
_chemical_formula_weight         1016.33
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-01
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2026-01-04 deposited with the CCDC.	2026-04-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.0074(7)
_cell_length_b                   17.0074(7)
_cell_length_c                   17.4421(9)
_cell_measurement_reflns_used    9825
_cell_measurement_temperature    170.00
_cell_measurement_theta_max      60.65
_cell_measurement_theta_min      3.16
_cell_volume                     5045.2(4)
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      170.00
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0803
_diffrn_reflns_av_unetI/netI     0.0433
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            89853
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         60.730
_diffrn_reflns_theta_min         3.157
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.373
_exptl_absorpt_correction_T_max  0.7519
_exptl_absorpt_correction_T_min  0.5955
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'metallic dark red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.338
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             2040
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.091
_refine_diff_density_min         -0.686
_refine_diff_density_rms         0.095
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.45(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     297
_refine_ls_number_reflns         5813
_refine_ls_number_restraints     103
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.0837
_refine_ls_R_factor_gt           0.0764
_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^)+(0.1544P)^2^+3.8278P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2352
_refine_ls_wR_factor_ref         0.2448
_reflns_Friedel_coverage         0.750
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                4946
_reflns_number_total             5813
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00587j2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7720874--7720875.cif.'
_cod_original_cell_volume        5045.2(5)
_cod_original_formula_sum        'C48 H27.20 Cd Cl Mn N4 O9.60'
_cod_database_code               7720874
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.541
_shelx_estimated_absorpt_t_min   0.287
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.55(3)
 0.45(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3. Restrained distances
 C02A-C02V = C02V-C03A
 1.4 with sigma of 0.02
 C02V-C03A = C03A-C02Q
 1.4 with sigma of 0.02
 C2-C02A
 1.5 with sigma of 0.02
 C016-C01Q
 1.3 with sigma of 0.02
 C02A-C2
 1.4 with sigma of 0.02
 C02A-C03A
 2.425 with sigma of 0.04
 C02V-C02Q
 2.425 with sigma of 0.04
4. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C2, O013
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
5. Others
 Fixed Sof: Cl2(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C00V(H00V), C015(H015), C01E(H01E), C01N(H01N), C01R(H01R), C021(H021),
 C022(H022), C02U(H02U), C02V(H02V), C02X(H02X), C031(H031), C03A(H03A)
;
_smtbx_masks_special_details
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A solvent mask was calculated and 62 electrons were 
found in a volume of 1776\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1.6[H2O] per Asymmetric Unit 
which account for 64 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              41155
_shelx_fab_checksum              72244
_olex2_submission_special_instructions 'No special instructions were received'