Stacked, twisted, and porous: structural diversity in photoactive porphyrin-based metal-organic frameworks.
Kenny, Mitchell S.; Gładysiak, Andrzej; Lessard, Jacob M.; Pyle, Dylan; Stylianou, Kyriakos C.; Chemical communications (Cambridge, England) 61 (2025) 18906–18909; doi:10.1039/d5cc03635f

data_7135002
_publ_section_title
;
 Stacked, twisted, and porous: structural diversity in photoactive
 porphyrin-based metal-organic frameworks.
;
_journal_issue                   95
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              18906
_journal_page_last               18909
_journal_paper_doi               10.1039/d5cc03635f
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety
'C56 H36 N10 O9 Pd Zn2, 0.375[], 0.125[], 0.5[]'
_chemical_formula_sum            'C56 H36 N10 O9 Pd Zn2'
_chemical_formula_weight         1230.09
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2025-07-25
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7311)
;
_audit_update_record
;
2025-07-26 deposited with the CCDC.	2025-09-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.346(9)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   33.103(3)
_cell_length_b                   10.1085(8)
_cell_length_c                   43.600(4)
_cell_measurement_reflns_used    14566
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      75.4490
_cell_measurement_theta_min      3.6250
_cell_volume                     14435(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.128a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.128a 64-bit (release 20-06-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.128a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.928
_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     36.00  71.00   0.50    1.19    --  103.49 -61.00 150.00   70
  2  \w     32.00  67.00   0.50    1.19    --  103.49 -61.00  30.00   70
  3  \w     38.00  64.00   0.50    1.19    --  103.49 -61.00   0.00   52
  4  \w     37.00  71.00   0.50    1.19    --  103.49 -61.00  60.00   68
  5  \w     38.00  70.00   0.50    1.19    --  103.49 -61.00 120.00   64
  6  \w    -13.00  14.00   0.50    0.54    --   46.49 -19.00 -22.00   54
  7  \w     34.00  70.00   0.50    1.19    --  103.49 -61.00-120.00   72
  8  \w     42.00  69.00   0.50    1.19    --  103.49 -61.00-180.00   54
  9  \w     36.00  68.00   0.50    1.19    --  103.49-125.00-120.00   64
 10  \w     82.00 109.00   0.50    1.19    --  103.49-125.00-120.00   54
 11  \w     34.00  78.00   0.50    1.19    --  103.49 -94.00 -90.00   88
 12  \w     91.00 136.00   0.50    1.19    --  103.49  15.00-120.00   90
 13  \w    148.00 173.00   0.50    1.19    --  103.49  15.00-120.00   50
 14  \w     92.00 177.00   0.50    1.19    --  103.49  19.00 145.00  170
 15  \w     34.00 117.00   0.50    0.54    --   46.49  19.00 145.00  166
 16  \w    -27.00  15.00   0.50    0.54    --  -46.49  19.00 145.00   84
 17  \w    -25.00  29.00   0.50    0.54    --  -46.49  19.00 -90.00  108
 18  \w    -20.00  29.00   0.50    0.54    --  -46.49  19.00-180.00   98
 19  \w   -124.00 -79.00   0.50    1.19    --  -91.75 -19.00 -22.00   90
 20  \w   -151.00-111.00   0.50    1.19    --  -91.75 -77.00 -60.00   80
 21  \w   -157.00-123.00   0.50    1.19    --  -91.75 -77.00-150.00   68
 22  \w   -106.00 -40.00   0.50    0.54    --  -46.49 -19.00 -22.00  132
 23  \w    -58.00 -33.00   0.50    1.19    --  -91.75 125.00-180.00   50
 24  \w   -105.00 -65.00   0.50    1.19    --  -91.75  77.00 -60.00   80
 25  \w    -58.00 -19.00   0.50    1.19    --  -91.75  77.00 -60.00   78
 26  \w    -51.00 -25.00   0.50    1.19    --  -91.75  45.00 120.00   52
 27  \w    -51.00 -24.00   0.50    1.19    --  -91.75  45.00 150.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0274504000
_diffrn_orient_matrix_UB_12      -0.0168588000
_diffrn_orient_matrix_UB_13      -0.0314181000
_diffrn_orient_matrix_UB_21      -0.0362621000
_diffrn_orient_matrix_UB_22      -0.0327586000
_diffrn_orient_matrix_UB_23      0.0169562000
_diffrn_orient_matrix_UB_31      -0.0118570000
_diffrn_orient_matrix_UB_32      0.1481353000
_diffrn_orient_matrix_UB_33      -0.0000282000
_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  0.1132
_diffrn_reflns_av_unetI/netI     0.0580
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.928
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -41
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       51
_diffrn_reflns_limit_l_min       -54
_diffrn_reflns_number            42132
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.928
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.221
_diffrn_reflns_theta_min         3.142
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.176
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71227
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.128a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dull orangish red'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.132
_exptl_crystal_description       block
_exptl_crystal_F_000             4960
_exptl_crystal_size_max          0.274
_exptl_crystal_size_mid          0.197
_exptl_crystal_size_min          0.074
_refine_diff_density_max         5.265
_refine_diff_density_min         -2.314
_refine_diff_density_rms         0.177
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     705
_refine_ls_number_reflns         14207
_refine_ls_number_restraints     177
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.1635
_refine_ls_R_factor_gt           0.1483
_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^)+(0.1444P)^2^+448.7052P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3564
_refine_ls_wR_factor_ref         0.3680
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11724
_reflns_number_total             14207
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc03635f2.cif
_cod_data_source_block           BVR-26
_cod_depositor_comments
'Adding full bibliography for 7135001--7135004.cif.'
_cod_database_code               7135002
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C57H48Zn2Pd1O9N9
_shelx_estimated_absorpt_t_max   0.799
_shelx_estimated_absorpt_t_min   0.477
_olex2_refinement_description
;
1. Fixed Uiso
 At 1 times of:
  All N(H,H) groups
 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
 C19-C17 = C17-C16 = C16-C15 = C15-C14 = C14-C20 = C20-C19
 1.39 with sigma of 0.01
 C38-C39 = C39-C40 = C40-C41 = C41-C43 = C43-C44 = C44-C38
 1.39 with sigma of 0.01
 C5-C6 = C6-C7 = C7-C2 = C2-C3 = C3-C4 = C4-C5
 1.39 with sigma of 0.01
 N3D-C4D
 1.5 with sigma of 0.02
 C19-C16 \\sim C17-C15 \\sim C16-C14 \\sim C15-C20 \\sim C14-C19 \\sim C20-C17
 with sigma of 0.02
 C38-C40 \\sim C39-C41 \\sim C40-C43 \\sim C41-C44 \\sim C43-C38 \\sim C44-C39
 with sigma of 0.02
 C5-C7 \\sim C6-C2 \\sim C7-C3 \\sim C2-C4 \\sim C3-C5 \\sim C4-C6
 with sigma of 0.02
 C4D-C2D \\sim C2D-C5D
 with sigma of 0.02
 C5D-N3D \\sim N3D-C4D
 with sigma of 0.02
 C2D-N3D \\sim N3D-C5D
 with sigma of 0.02
3. Restrained planarity
 C19, C17, C16, C15, C14, C20
 with sigma of 0.1
 C38, C39, C40, C41, C43, C44
 with sigma of 0.1
 C5, C6, C7, C2, C3, C4
 with sigma of 0.1
 C5D, C4D, N3D, C2D
 with sigma of 0.1
 N3D, C4D, C5D, C2D
 with sigma of 0.1
4. Rigid bond restraints
 O1D, C2D, C4D, N3D, C5D
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C26 \\sim C32 \\sim C31 \\sim C29: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C16 \\sim C17 \\sim C15: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C18 \\sim O4 \\sim O3: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C30 \\sim O6 \\sim O5: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(O4) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C32) \\sim Ueq, Uanis(C31) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(O1) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(O2) \\sim Ueq: with sigma of
0.1 and sigma for terminal atoms of 0.2
6.a Aromatic/amide H refined with riding coordinates:
 C46(H46), C39(H39), C43(H43), C47(H47), C44(H44), C19(H19), C40(H40),
 C35(H35), C23(H23), C6(H6), C7(H7), C20(H20), C10(H10), C4(H4), C22(H22),
 C34(H34), C11(H11), C27(H27), C28(H28), C16(H16), C15(H15), C3(H3), C31(H31),
 C32(H32), C8A(H8A), N3A(H3A), C2A(H2A), C4D(H4D)
6.b X=CH2 refined with riding coordinates:
 N10A(H10A,H10B)
6.c Idealised Me refined as rotating group:
 C2D(H2DA,H2DB,H2DC), C5D(H5DA,H5DB,H5DC)
;
_shelx_res_checksum              8810
_shelx_hkl_checksum              22118
_shelx_fab_checksum              11607
_platon_squeeze_void_probe_radius 1.20
_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 1.432
_oxdiff_exptl_absorpt_empirical_full_min 0.628