Stepwise assembly of Ni–N2S2 catalytic sites and porphyrin photosensitizers in a metal–organic framework for bioinspired photocatalysis
Gu, Yu-Hao; Xu, Xinyu; Zhu, Chenyu; Luo, Rengan; Yuan, Shuai; CrystEngComm 27 (2025) 5841–5847; doi:10.1039/D5CE00634A

data_7250703
_publ_section_title
;
 Stepwise assembly of Ni--N2S2 catalytic sites and porphyrin
 photosensitizers in a metal--organic framework for bioinspired
 photocatalysis
;
_journal_issue                   35
_journal_name_full               CrystEngComm
_journal_page_first              5841
_journal_page_last               5847
_journal_paper_doi               10.1039/D5CE00634A
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C18 H14 N6 Ni O4 S2, 2(C6 H16 N), 2(C2 H3 N)'
_chemical_formula_sum            'C34 H52 N10 Ni O4 S2'
_chemical_formula_weight         787.68
_chemical_name_systematic        Ni-TSC-COOH
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yac'
_space_group_name_H-M_alt        'P 1 n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-24
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-24 deposited with the CCDC.	2025-07-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.017(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.5393(6)
_cell_length_b                   7.7694(3)
_cell_length_c                   17.4897(8)
_cell_measurement_reflns_used    9792
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      29.997
_cell_measurement_theta_min      2.334
_cell_volume                     1970.81(14)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      193.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0521
_diffrn_reflns_av_unetI/netI     0.0452
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            49886
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.059
_diffrn_reflns_theta_min         1.888
_exptl_absorpt_coefficient_mu    0.648
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.6767
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1128 before and 0.0681 after correction.
The Ratio of minimum to maximum transmission is 0.9071.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.327
_exptl_crystal_description       block
_exptl_crystal_F_000             836
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.897
_refine_diff_density_min         -0.502
_refine_diff_density_rms         0.085
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.501(15)
_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     489
_refine_ls_number_reflns         11306
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0560
_refine_ls_R_factor_gt           0.0492
_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^)+(0.0636P)^2^+1.1449P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1179
_refine_ls_wR_factor_ref         0.1243
_reflns_Friedel_coverage         0.965
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                10049
_reflns_number_total             11306
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00634a2.cif
_cod_data_source_block           Ni_TSC_COOH
_cod_depositor_comments          'Adding full bibliography for 7250703.cif.'
_cod_database_code               7250703
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.892
_shelx_estimated_absorpt_t_min   0.820
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.499(15)
 0.501(15)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Others
 Sof(H8B)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=
 1-FVAR(1)
 Sof(H8A)=Sof(C25A)=Sof(H25C)=Sof(H25D)=Sof(C26A)=Sof(H26D)=Sof(H26E)=
 Sof(H26F)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 N7(H7A), N8(H8B), N8(H8A)
4.b Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C21(H21A,H21B), C23(H23A,H23B), C25(H25A,H25B), C25A(H25C,
 H25D), C27(H27A,H27B), C29(H29A,H29B)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C7(H7), C8(H8), C11(H11), C13(H13), C14(H14),
 C16(H16), C17(H17)
4.d X=CH2 refined with riding coordinates:
 N3(H3A,H3B), N6(H6A,H6B)
4.e Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C26(H26A,H26B,
 H26C), C26A(H26D,H26E,H26F), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C),
 C32(H32A,H32B,H32C), C34(H34A,H34B,H34C)
;
_shelx_res_checksum              13441
_olex2_submission_special_instructions 'No special instructions were received'