Microenvironment Regulation of Active Sites for Efficient Photocatalytic Reduction of Nitrobenzene
Liu, Jiang; Xu, Sha-Sha; Liang, Jia-Zheng; Yao, Su-Juan; Li, Ning; Shi, Jing-Wen; Lan, Yaqian; Chemical Communications  (2025) –; doi:10.1039/D5CC04423E

data_7135176
_publ_section_title
;
 Microenvironment Regulation of Active Sites for Efficient Photocatalytic
 Reduction of Nitrobenzene
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D5CC04423E
_journal_year                    2025
_chemical_formula_moiety
'C72.7 H41.94 Mn4 N6 O22.67, C3 H6 N O, 7.23(H2 O)'
_chemical_formula_sum            'C75.7 H62.42 Mn4 N7 O30.91'
_chemical_formula_weight         1784.49
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-11-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-11-17 deposited with the CCDC.	2025-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.574(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.6796(9)
_cell_length_b                   13.6040(5)
_cell_length_c                   21.4970(8)
_cell_measurement_reflns_used    9904
_cell_measurement_temperature    210
_cell_measurement_theta_max      72.36
_cell_measurement_theta_min      5.58
_cell_volume                     7214.7(5)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      210.0
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'D8 Venture'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0453
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            63634
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.487
_diffrn_reflns_theta_min         3.710
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.423
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5328
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1539 before and 0.0599 after correction. The Ratio of minimum to maximum transmission is 0.7070. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.643
_exptl_crystal_description       block
_exptl_crystal_F_000             3652
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.374
_refine_diff_density_min         -0.754
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     658
_refine_ls_number_reflns         7130
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0435
_refine_ls_R_factor_gt           0.0402
_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^)+(0.0682P)^2^+5.5095P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1129
_refine_ls_wR_factor_ref         0.1159
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6486
_reflns_number_total             7130
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04423e2.cif
_cod_data_source_block           cu_hhjj_0m
_cod_original_formula_sum        'C75.70 H62.42 Mn4 N7 O30.91'
_cod_database_code               7135176
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.882
_shelx_estimated_absorpt_t_min   0.783
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2. Uiso/Uaniso restraints and constraints
O17 \\sim O2 \\sim O7 \\sim O15: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
O24 \\sim O3 \\sim C41 \\sim O22: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O11) \\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(O23) \\sim Ueq, Uanis(O21)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Sof(O24)=Sof(O3)=Sof(C41)=Sof(H41)=1-FVAR(1)
 Sof(O22)=Sof(H22)=FVAR(1)
 Sof(O20)=Sof(H20A)=Sof(H20B)=FVAR(2)
 Sof(O17)=Sof(H17A)=Sof(H17B)=FVAR(3)
 Sof(O7)=Sof(H7A)=Sof(H7B)=1-FVAR(4)
 Sof(O15)=Sof(H15A)=Sof(H15B)=FVAR(4)
 Sof(O2)=Sof(H2A)=Sof(H2B)=FVAR(5)
 Sof(Mn2)=1-FVAR(6)
 Sof(Mn3)=FVAR(6)
 Sof(O9)=Sof(N5)=1-FVAR(7)
 Sof(O16)=Sof(N2)=FVAR(7)
 Sof(O19)=Sof(N3A)=1-FVAR(8)
 Sof(O18)=Sof(N3)=FVAR(8)
 Sof(O23)=Sof(H23A)=Sof(H23B)=1-FVAR(9)
 Sof(O21)=Sof(H21A)=Sof(H21B)=FVAR(9)
 Sof(O11)=Sof(H11A)=Sof(H11B)=1-FVAR(10)
 Sof(O5)=Sof(H5A)=Sof(H5B)=FVAR(10)
 Fixed Sof: O13(0.5)
4.a Riding coordinates:
 O7(H7A,H7B), O15(H15A,H15B), O2(H2A,H2B), O17(H17A,H17B), O5(H5A,H5B),
 O21(H21A,H21B), O23(H23A,H23B)
4.b Free rotating group:
 O20(H20A,H20B), O11(H11A,H11B)
4.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C15(H15), C16(H16), C18(H18), C21(H21), C23(H23), C24(H24),
 C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C32(H32), C33(H33),
  C34(H34), C35(H35), C36(H36), C41(H41)
4.d Tetrahedral OH refined with riding coordinates:
 O22(H22)
4.e Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C)
;
_shelx_res_checksum              64971
_olex2_submission_special_instructions 'No special instructions were received'