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_7135004
_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         'C58 H33 N14 O8.5 Pd Zn3, [+ solvents]'
_chemical_formula_sum            'C58 H33 N14 O8.5 Pd Zn3'
_chemical_formula_weight         1364.49
_space_group_crystal_system      orthorhombic
_space_group_IT_number           68
_space_group_name_Hall           '-C 2a 2ac'
_space_group_name_H-M_alt        'C c c a :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   33.8282(6)
_cell_length_b                   10.4006(2)
_cell_length_c                   43.8964(8)
_cell_measurement_reflns_used    13689
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      74.4380
_cell_measurement_theta_min      4.5480
_cell_volume                     15444.2(5)
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.938
_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   -115.00 -26.00   1.00    4.33    --  -46.74 -75.00 -80.00   89
  2  \w    -65.00 -21.00   1.00    4.33    --  -46.74  75.00  46.00   44
  3  \w     47.00  72.00   1.00    4.33    --   46.74  75.00  46.00   25
  4  \w    -23.00  23.00   1.00    4.33    --   46.74 -75.00 -80.00   46
  5  \w   -144.00-117.00   1.00   32.13    --  -91.75 -75.00 -80.00   27
  6  \w    -71.00 -45.00   1.00   32.13    --  -91.75  75.00  46.00   26
  7  \w    122.00 176.00   1.00   32.13    --  103.49  75.00  46.00   54
  8  \w     46.00  74.00   1.00   32.13    --  103.49 -75.00 -80.00   28
  9  \w    -27.00  23.00   1.00    4.33    --  -46.74  19.00  60.00   50
 10  \w    -20.00  20.00   1.00    4.33    --   46.74 -19.00 -60.00   40
 11  \w   -157.00 -95.00   1.00   32.13    --  -91.75-125.00-120.00   62
 12  \w    -51.00 -26.00   1.00   32.13    --  -91.75  45.00 150.00   25
 13  \w   -153.00-122.00   1.00   32.13    --  -91.75 -61.00   0.00   31
 14  \w    -47.00 -20.00   1.00   32.13    --  -91.75  45.00-150.00   27
 15  \w    -47.00 -21.00   1.00   32.13    --  -91.75  45.00-180.00   26
 16  \w    -50.00 -24.00   1.00   32.13    --  -91.75  45.00-120.00   26
 17  \w     31.00  56.00   1.00   32.13    --  103.49 -61.00-180.00   25
 18  \w     41.00  67.00   1.00   32.13    --  103.49 -61.00 -30.00   26
 19  \w    134.00 175.00   1.00   32.13    --  103.49  15.00 -30.00   41
 20  \w     91.00 118.00   1.00   32.13    --  103.49  15.00 -30.00   27
 21  \w     43.00  70.00   1.00   32.13    --  103.49 -61.00  60.00   27
;
_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      -0.0092944000
_diffrn_orient_matrix_UB_12      -0.0849931000
_diffrn_orient_matrix_UB_13      0.0278507000
_diffrn_orient_matrix_UB_21      -0.0442050000
_diffrn_orient_matrix_UB_22      0.0015426000
_diffrn_orient_matrix_UB_23      -0.0084746000
_diffrn_orient_matrix_UB_31      0.0058836000
_diffrn_orient_matrix_UB_32      -0.1213060000
_diffrn_orient_matrix_UB_33      -0.0195852000
_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  0.0420
_diffrn_reflns_av_unetI/netI     0.0254
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.938
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -41
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -53
_diffrn_reflns_number            33195
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.742
_diffrn_reflns_theta_min         3.299
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.331
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.092
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.128a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.174
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             5464
_exptl_crystal_size_max          0.421
_exptl_crystal_size_mid          0.294
_exptl_crystal_size_min          0.046
_refine_diff_density_max         2.238
_refine_diff_density_min         -1.455
_refine_diff_density_rms         0.138
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.681
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     385
_refine_ls_number_reflns         7550
_refine_ls_number_restraints     266
_refine_ls_restrained_S_all      1.768
_refine_ls_R_factor_all          0.1102
_refine_ls_R_factor_gt           0.1008
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3503
_refine_ls_wR_factor_ref         0.3716
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6206
_reflns_number_total             7550
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc03635f2.cif
_cod_data_source_block           BVR-28
_cod_depositor_comments
'Adding full bibliography for 7135001--7135004.cif.'
_cod_original_sg_symbol_Hall     '-C 2b 2bc'
_cod_original_sg_symbol_H-M      'C c c a'
_cod_original_formula_sum        'C58 H33 N14 O8.50 Pd Zn3'
_cod_database_code               7135004
_shelx_shelxl_version_number     2019/3
_diffrn_oxdiff_digest_hkl
;
439ff45868c379f3f06ed8d9dd184b2169b39b
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
2. Restrained distances
 C19-C20 = C20-C14 = C14-C15 = C15-C16 = C16-C17 = C17-C19
 1.39 with sigma of 0.01
 C6-C5 = C5-C4 = C4-C3 = C3-C2 = C2-C7 = C7-C6
 1.39 with sigma of 0.01
 C19-C14 \\sim C20-C15 \\sim C14-C16 \\sim C15-C17 \\sim C16-C19 \\sim C17-C20
 with sigma of 0.02
 C6-C4 \\sim C5-C3 \\sim C4-C2 \\sim C3-C7 \\sim C2-C6 \\sim C7-C5
 with sigma of 0.02
3. Restrained planarity
 C14, C15, C16, C17, C19, C20
 with sigma of 0.1
 C2, C3, C4, C5, C6, C7
 with sigma of 0.1
 C21, C22, C13, N2
 with sigma of 0
 C13, C22, C21, N2
 with sigma of 0.02
 C13, C21, N2, C22
 with sigma of 0.001
 C22, N2, N1, N3, Pd1
 with sigma of 0.1
 N1, N3, C23, Pd1, N2, C22
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C20 \\sim C19 \\sim C17 \\sim C16 \\sim C15 \\sim C14: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C16 \\sim C17 \\sim C19 \\sim C20 \\sim C14 \\sim C15: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C6 \\sim C5 \\sim C4 \\sim C3 \\sim C2 \\sim C7: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
O3 \\sim C18 \\sim O4: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(N1) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C21)
\\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C11) \\sim Ueq,
Uanis(C10) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C24)
\\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(C14) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C14) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C21)
\\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C11) \\sim Ueq,
Uanis(C10) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(N3) \\sim
Ueq, Uanis(C8) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C5)
\\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C18) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C20)
\\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C11) \\sim Ueq:
with sigma of 0.02 and sigma for terminal atoms of 0.04
5. Others
 Fixed Sof: H1A(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 N1A(H1A), C2A(H2A), C3(H3), C4(H4), C6(H6), C7(H7), C8A(H8A), C10(H10),
 C11(H11), C15(H15), C16(H16), C19(H19), C20(H20), C22(H22), C23(H23)
6.b X=CH2 refined with riding coordinates:
 N10A(H10A,H10B)
;
_shelx_res_checksum              96409
_shelx_hkl_checksum              741
_shelx_fab_checksum              87997
_platon_squeeze_special_details
;
A solvent mask was calculated and 1808 electrons were 
found in a volume of 6188\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
5.5 DMF molecules (C3H7NO) per Formula Unit 
which account for 1760 electrons 
per unit cell.
;
_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 1.887
_oxdiff_exptl_absorpt_empirical_full_min 0.554