Synthesis of wave-shaped Cu(ii) porphyrin arrays and their electrocatalytic hydrogen evolution activity.
Jiang, Tao; Zhou, Yuanbo; Ye, Tao; Liu, Shihao; Li, Ke; Zhao, Xiaohui; Sun, Zhongti; Aratani, Naoki; Yamada, Hiroko; Qiu, Fengxian; Pan, Jianming; Teranishi, Toshiharu; Xue, Songlin; Chemical science 16 (2025) 22498–22503; doi:10.1039/d5sc07383a

data_1576062
_publ_section_title
;
 Synthesis of wave-shaped Cu(ii) porphyrin arrays and their
 electrocatalytic hydrogen evolution activity.
;
_journal_issue                   47
_journal_name_full               'Chemical science'
_journal_page_first              22498
_journal_page_last               22503
_journal_paper_doi               10.1039/d5sc07383a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C94 H82 N8'
_chemical_formula_sum            'C94 H82 N8'
_chemical_formula_weight         1323.67
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-10
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-09-21 deposited with the CCDC.	2025-10-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            9
_cell_length_a                   41.5602(10)
_cell_length_b                   41.5602(10)
_cell_length_c                   12.1635(3)
_cell_measurement_reflns_used    9166
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.5830
_cell_measurement_theta_min      3.6680
_cell_volume                     18194.7(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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     52.00  97.00   0.50    0.30    --  107.55 -77.00   0.00   90
  2  \w     35.00  61.00   0.50    0.30    --  107.55 -77.00 -30.00   52
  3  \w     39.00  66.00   0.50    0.30    --  107.55 -61.00 -30.00   54
  4  \w     38.00  64.00   0.50    0.30    --  107.55 -61.00   0.00   52
  5  \w     35.00  68.00   0.50    0.30    --  107.55 -61.00 150.00   66
  6  \w    -35.00  -9.00   0.50    0.05    --   42.63 -19.00-180.00   52
  7  \w   -160.00-134.00   0.50    0.30    --  -97.00 -68.00 -94.00   52
  8  \w   -128.00 -75.00   0.50    0.30    --  -97.00 -68.00 -94.00  106
  9  \w    -64.00 -38.00   0.50    0.30    --  -97.00  61.00-150.00   52
 10  \w    -83.00 -22.00   0.50    0.05    --  -42.63 104.00 -80.00  122
 11  \w    -50.00 -25.00   0.50    0.30    --  -97.00  45.00 -60.00   50
 12  \w    -50.00 -25.00   0.50    0.30    --  -97.00  45.00   0.00   50
 13  \w    -54.00 -28.00   0.50    0.30    --  -97.00  45.00 150.00   52
 14  \w   -168.00-107.00   0.50    0.30    --  -97.00-104.00 178.00  122
 15  \w    -94.00 -52.00   0.50    0.05    --  -42.75 125.00 -30.00   84
 16  \w     -3.00  23.00   0.50    0.05    --   42.75 -19.00 -60.00   52
 17  \w    -27.00  40.00   0.50    0.05    --   42.75 -38.00-180.00  134
 18  \w    -12.00  23.00   0.50    0.05    --   42.75 -19.00-120.00   70
 19  \w    -37.00  20.00   0.50    0.05    --   42.75 -19.00 120.00  114
 20  \w     28.00 100.00   0.50    0.05    --   42.75  57.00   0.00  144
 21  \w    -37.00  21.00   0.50    0.05    --   42.75 -19.00-150.00  116
 22  \w    -37.00  23.00   0.50    0.05    --   42.75 -19.00  60.00  120
 23  \w    -49.00 -24.00   0.50    0.30    --  -97.00  45.00  30.00   50
 24  \w   -116.00 -73.00   0.50    0.30    --  -97.00 -70.00 145.07   86
 25  \w   -109.00 -33.00   0.50    0.30    --  -97.00 125.00  60.00  152
 26  \w   -173.00-133.00   0.50    0.30    --  -97.00 -45.00  30.00   80
 27  \w    -69.00 -43.00   0.50    0.30    --  -97.00 140.00 123.02   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0279094000
_diffrn_orient_matrix_UB_12      0.0014988000
_diffrn_orient_matrix_UB_13      -0.0803336000
_diffrn_orient_matrix_UB_21      0.0294948000
_diffrn_orient_matrix_UB_22      0.0138112000
_diffrn_orient_matrix_UB_23      -0.0917465000
_diffrn_orient_matrix_UB_31      -0.0136029000
_diffrn_orient_matrix_UB_32      -0.0404512000
_diffrn_orient_matrix_UB_33      -0.0343449000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0639
_diffrn_reflns_av_unetI/netI     0.0453
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       48
_diffrn_reflns_limit_h_min       -49
_diffrn_reflns_limit_k_max       47
_diffrn_reflns_limit_k_min       -47
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            36834
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        66.548
_diffrn_reflns_theta_max         66.548
_diffrn_reflns_theta_min         3.684
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.489
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61649
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.127a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_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    1.087
_exptl_crystal_description       block
_exptl_crystal_F_000             6318
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.379
_refine_diff_density_min         -0.410
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     522
_refine_ls_number_reflns         7070
_refine_ls_number_restraints     53
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.1124
_refine_ls_R_factor_gt           0.0871
_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^)+(0.1168P)^2^+53.1043P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2229
_refine_ls_wR_factor_ref         0.2397
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5216
_reflns_number_total             7070
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07383a2.cif
_cod_data_source_block           1
_cod_depositor_comments          'Adding full bibliography for 1576062.cif.'
_cod_original_cell_volume        18194.7(10)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               1576062
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         chn
_cell_oxdiff_angle_alpha         89.999(2)
_cell_oxdiff_angle_beta          90.0324(19)
_cell_oxdiff_angle_gamma         120.001(3)
_cell_oxdiff_length_a            41.5393(9)
_cell_oxdiff_length_b            41.5939(12)
_cell_oxdiff_length_c            12.1599(3)
_cell_oxdiff_measurement_reflns_used 9165
_cell_oxdiff_volume              18194.6(8)
_shelx_estimated_absorpt_t_max   0.953
_shelx_estimated_absorpt_t_min   0.917
_diffrn_oxdiff_digest_hkl
;
43b1a02cd7867e71687821a068381874ac6128
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C44-C47 \\sim C44-C47A
 with sigma of 0.02
 C44-C45 \\sim C44-C45A
 with sigma of 0.02
 C44-C46 \\sim C44-C46A
 with sigma of 0.02
3. Rigid bond restraints
 C43, C39A
 with sigma for 1-2 distances of 0.0008 and sigma for 1-3 distances of 0.0004
 C44, C46A
 with sigma for 1-2 distances of 0.008 and sigma for 1-3 distances of 0.004
4. Uiso/Uaniso restraints and constraints
Uanis(C45) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C41A) \\sim Ueq, Uanis(C42A) \\sim Ueq, Uanis(C45A) \\sim Ueq,
Uanis(C47A) \\sim Ueq, Uanis(C46A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C47) \\sim Ueq, Uanis(C46A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C38A) \\sim Ueq, Uanis(C45A) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
5. Others
 Sof(C42A)=Sof(H42A)=Sof(C38A)=Sof(H38A)=Sof(C39A)=Sof(H39A)=Sof(C41A)=
 Sof(H41A)=1-FVAR(1)
 Sof(C42)=Sof(H42)=Sof(C41)=Sof(H41)=Sof(C38)=Sof(H38)=Sof(C39)=Sof(H39)=FVAR(1)
 Sof(C47A)=Sof(H47D)=Sof(H47E)=Sof(H47F)=Sof(C46A)=Sof(H46D)=Sof(H46E)=
 Sof(H46F)=Sof(C45A)=Sof(H45D)=Sof(H45E)=Sof(H45F)=1-FVAR(2)
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=
 Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 N2(H2), N4(H4), C13(H13), C14(H14), C27(H27), C4(H4A), C23(H23), C7(H7),
 C31(H31), C6(H6), C24(H24), C3(H3), C30(H30), C34(H34), C35(H35), C17(H17),
 C20(H20), C19(H19), C42(H42), C18(H18), C41(H41), C38(H38), C39(H39),
 C42A(H42A), C38A(H38A), C39A(H39A), C41A(H41A)
6.b Fitted hexagon refined as free rotating group:
 C42A(C37,C38A,C39A,C43,C41A)
6.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C47(H47A,H47B,
 H47C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47A(H47D,H47E,H47F),
 C46A(H46D,H46E,H46F), C45A(H45D,H45E,H45F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              3971
_shelx_fab_checksum              50304
_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 1.604
_oxdiff_exptl_absorpt_empirical_full_min 0.372