π-Extended Cis- and Trans-Bis(Tetracyanobutadiene) Cu-Porphyrins with Unusual Multiredox Behavior
Jangra, Reena; Bulbul, Amir Sohel; Sankar, Muniappan; Chemical Communications  (2025) –; doi:10.1039/D5CC04942C

data_7135064
_publ_section_title
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 \p-Extended Cis- and Trans-Bis(Tetracyanobutadiene) Cu-Porphyrins with
 Unusual Multiredox Behavior
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_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D5CC04942C
_journal_year                    2025
_chemical_formula_moiety         'C88 H44 Cu N12, 0.5[H2O], 0.5[CH4O]'
_chemical_formula_sum            'C88.5 H47 Cu N12 O'
_chemical_formula_weight         1357.92
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-09-20
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
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_audit_update_record
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2025-09-27 deposited with the CCDC.	2025-10-14 downloaded from the CCDC.
;
_cell_angle_alpha                79.204(9)
_cell_angle_beta                 73.104(8)
_cell_angle_gamma                77.349(9)
_cell_formula_units_Z            2
_cell_length_a                   13.047(3)
_cell_length_b                   13.520(3)
_cell_length_c                   21.777(5)
_cell_measurement_reflns_used    2334
_cell_measurement_temperature    103.00
_cell_measurement_theta_max      11.4256
_cell_measurement_theta_min      2.3457
_cell_volume                     3554.7(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  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      103.00
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_device_type  'Bruker D8 QUEST Photon III C7'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.3919
_diffrn_reflns_av_unetI/netI     0.2977
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_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            148428
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.334
_diffrn_reflns_theta_min         1.657
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.365
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.5793
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1119 before and 0.0959 after correction.
The Ratio of minimum to maximum transmission is 0.7774.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'metallic dark violet'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.269
_exptl_crystal_description       block
_exptl_crystal_F_000             1398
_exptl_crystal_size_max          0.176
_exptl_crystal_size_mid          0.067
_exptl_crystal_size_min          0.052
_refine_diff_density_max         0.704
_refine_diff_density_min         -0.584
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.959
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     910
_refine_ls_number_reflns         12654
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      0.958
_refine_ls_R_factor_all          0.2848
_refine_ls_R_factor_gt           0.1017
_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^)+(0.1486P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2297
_refine_ls_wR_factor_ref         0.3194
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4187
_reflns_number_total             12654
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04942c2.cif
_cod_data_source_block           ms_rj_cutcbd2_f1_1564_0m
_cod_original_cell_volume        3554.6(14)
_cod_original_formula_sum        'C88.50 H47 Cu N12 O'
_cod_database_code               7135064
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.938
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C51) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C53) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C7) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C85) \\sim Ueq: with sigma of 0.0001 and sigma for terminal atoms of
0.0002
Uanis(C86) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
3.a Aromatic/amide H refined with riding coordinates:
 C56(H56), C18(H18), C68(H68), C26(H26), C67(H67), C70(H70), C17(H17),
 C78(H78), C22(H22), C24(H24), C57(H57), C82(H82), C71(H71), C69(H69), C23(H23),
  C33(H33), C60(H60), C79(H79), C8(H8), C84(H84), C25(H25), C59(H59), C46(H46),
 C85(H85), C58(H58), C37(H37), C88(H88), C80(H80), C36(H36), C87(H87), C44(H44),
  C53(H53), C81(H81), C47(H47), C34(H34), C48(H48), C50(H50), C45(H45),
 C86(H86), C35(H35), C52(H52), C51(H51), C7(H7), C54(H54)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 25 electrons were 
found in a volume of 481\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
0.5[H2O], 0.5[CH4O] per Unit Cell 
which account for 28 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              77617
_shelx_hkl_checksum              77798
_shelx_fab_checksum              19449
_olex2_submission_special_instructions 'No special instructions were received'