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_7135001
_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         'C106 H58 N18 O17 Pd2 Zn5, [+solvent]'
_chemical_formula_sum            'C106 H58 N18 O17 Pd2 Zn5'
_chemical_formula_weight         2395.49
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_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                 95.533(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.9191(2)
_cell_length_b                   32.4889(7)
_cell_length_c                   38.6916(9)
_cell_measurement_reflns_used    31919
_cell_measurement_temperature    173
_cell_measurement_theta_max      74.9750
_cell_measurement_theta_min      2.7750
_cell_volume                     12410.7(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      173
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.963
_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 -90.00   0.50    1.98    --  -46.42-141.00 -86.00   50
  2  \w    -96.00 -41.00   0.50    1.98    --  -46.42 141.00 -28.00  110
  3  \w    -51.00 -20.00   0.50    1.98    --  -46.42 128.00 160.00   62
  4  \w     53.00  78.00   0.50    1.98    --   46.42-128.00  85.00   50
  5  \w     50.00  76.00   0.50    1.98    --   46.42-141.00 -86.00   52
  6  \w    -84.00 -59.00   0.50    9.32    --  -91.75 141.00 -28.00   50
  7  \w    -88.00 -63.00   0.50    9.32    --  -91.75-141.00 -86.00   50
  8  \w   -107.00 -73.00   0.50    9.32    --  -91.75-128.00  85.00   68
  9  \w    104.00 129.00   0.50    9.32    --  103.56 141.00 -28.00   50
 10  \w     44.00 123.00   0.50    9.32    --  103.56-141.00 -86.00  158
 11  \w    104.00 134.00   0.50    9.32    --  103.56 128.00 160.00   60
 12  \w     55.00 114.00   0.50    9.32    --  103.56-128.00  85.00  118
 13  \w    -16.00  28.00   0.50    1.98    --  -46.42  19.00 -90.00   88
 14  \w    -26.00  28.00   0.50    1.98    --  -46.42  19.00-120.00  108
 15  \w    -27.00  28.00   0.50    1.98    --  -46.42  19.00-180.00  110
 16  \w    -24.00  17.00   0.50    1.98    --   46.42 -19.00-150.00   82
 17  \w   -103.00 -52.00   0.50    9.32    --  -91.75  77.00-180.00  102
 18  \w    -85.00 -30.00   0.50    9.32    --  -91.75 125.00 -90.00  110
 19  \w    -50.00 -20.00   0.50    9.32    --  -91.75  45.00   0.00   60
 20  \w    -47.00 -20.00   0.50    9.32    --  -91.75  45.00 -30.00   54
 21  \w   -161.00-107.00   0.50    9.32    --  -91.75 -61.00-150.00  108
 22  \w    -48.00 -21.00   0.50    9.32    --  -91.75  45.00-180.00   54
 23  \w     35.00  60.00   0.50    9.32    --  103.56-125.00 150.00   50
 24  \w     46.00  71.00   0.50    9.32    --  103.56 -61.00 -30.00   50
 25  \w     31.00  58.00   0.50    9.32    --  103.56 -61.00 -90.00   54
 26  \w    115.00 172.00   0.50    9.32    --  103.56  77.00-150.00  114
 27  \w     31.00  69.00   0.50    9.32    --  103.56 -61.00-120.00   76
 28  \w     91.00 171.00   0.50    9.32    --  103.56  30.00 -90.00  160
 29  \w     53.00 105.00   0.50    9.32    --  103.56 -94.00-120.00  104
 30  \w     76.00 102.00   0.50    9.32    --  103.56-125.00 150.00   52
 31  \w     34.00  59.00   0.50    9.32    --  103.56 -61.00 -60.00   50
;
_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      0.0276121000
_diffrn_orient_matrix_UB_12      0.0259962000
_diffrn_orient_matrix_UB_13      0.0332403000
_diffrn_orient_matrix_UB_21      0.0292599000
_diffrn_orient_matrix_UB_22      -0.0395452000
_diffrn_orient_matrix_UB_23      0.0213696000
_diffrn_orient_matrix_UB_31      0.1507778000
_diffrn_orient_matrix_UB_32      0.0029800000
_diffrn_orient_matrix_UB_33      -0.0062074000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0193
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            32190
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.360
_diffrn_reflns_theta_min         2.720
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.858
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84565
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.282
_exptl_crystal_description       needle
_exptl_crystal_F_000             6432
_exptl_crystal_size_max          0.304
_exptl_crystal_size_mid          0.083
_exptl_crystal_size_min          0.056
_refine_diff_density_max         2.285
_refine_diff_density_min         -3.185
_refine_diff_density_rms         0.244
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   2.231
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1333
_refine_ls_number_reflns         32190
_refine_ls_number_restraints     607
_refine_ls_restrained_S_all      2.228
_refine_ls_R_factor_all          0.1478
_refine_ls_R_factor_gt           0.1402
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4301
_refine_ls_wR_factor_ref         0.4441
_reflns_Friedel_coverage         0.000
_reflns_number_gt                29447
_reflns_number_total             32190
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.8340\% 
around [-0.00 -0.00 1.00] (reciprocal) or [0.35 -0.00 0.94] (direct)
;
_cod_data_source_file            d5cc03635f2.cif
_cod_data_source_block           red1_BVR-27
_cod_depositor_comments
'Adding full bibliography for 7135001--7135004.cif.'
_cod_database_code               7135001
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C50H50N9O9Zn2Pd1
_cell_oxdiff_angle_alpha         90.0016(14)
_cell_oxdiff_angle_beta          95.581(2)
_cell_oxdiff_angle_gamma         90.0777(18)
_cell_oxdiff_length_a            9.9195(3)
_cell_oxdiff_length_b            32.4881(5)
_cell_oxdiff_length_c            38.6944(7)
_cell_oxdiff_measurement_reflns_used 31429
_cell_oxdiff_volume              12410.7(5)
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups, All N(H,H) groups
2. Restrained distances
 C30-C29
 1.5 with sigma of 0.02
 C31-C29 = C29-C28 = C28-C27 = C27-C26 = C26-C32 = C32-C31
 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
 C3-C2 = C2-C7 = C7-C6 = C6-C5 = C5-C4 = C4-C3
 1.39 with sigma of 0.01
 C16-C17 = C17-C19 = C19-C20 = C20-C14 = C14-C15 = C15-C16
 1.39 with sigma of 0.01
 C41B-C40B = C40B-C39B = C39B-C38B = C38B-C44B = C44B-C43B = C43B-C41B
 1.39 with sigma of 0.01
 C26B-C27B = C27B-C28B = C28B-C29B = C29B-C31B = C31B-C32B = C32B-C26B
 1.39 with sigma of 0.01
 C15B-C14B = C14B-C20B = C20B-C19B = C19B-C17B = C17B-C16B = C16B-C15B
 1.39 with sigma of 0.01
 C6B-C5B = C5B-C4B = C4B-C3B = C3B-C2B = C2B-C7B = C7B-C6B
 1.39 with sigma of 0.01
 C31-C28 \\sim C29-C27 \\sim C28-C26 \\sim C27-C32 \\sim C26-C31 \\sim C32-C29
 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
 C3-C7 \\sim C2-C6 \\sim C7-C5 \\sim C6-C4 \\sim C5-C3 \\sim C4-C2
 with sigma of 0.02
 C16-C19 \\sim C17-C20 \\sim C19-C14 \\sim C20-C15 \\sim C14-C16 \\sim C15-C17
 with sigma of 0.02
 C41B-C39B \\sim C40B-C38B \\sim C39B-C44B \\sim C38B-C43B \\sim C44B-C41B
\\sim C43B-C40B
 with sigma of 0.02
 C26B-C28B \\sim C27B-C29B \\sim C28B-C31B \\sim C29B-C32B \\sim C31B-C26B
\\sim C32B-C27B
 with sigma of 0.02
 C15B-C20B \\sim C14B-C19B \\sim C20B-C17B \\sim C19B-C16B \\sim C17B-C15B
\\sim C16B-C14B
 with sigma of 0.02
 C6B-C4B \\sim C5B-C3B \\sim C4B-C2B \\sim C3B-C7B \\sim C2B-C6B \\sim C7B-C5B
 with sigma of 0.02
3. Restrained planarity
 C31, C29, C28, C27, C26, C32
 with sigma of 0.1
 C38, C39, C40, C41, C43, C44
 with sigma of 0.1
 C3, C2, C7, C6, C5, C4
 with sigma of 0.1
 C16, C17, C19, C20, C14, C15
 with sigma of 0.1
 C41B, C40B, C39B, C38B, C44B, C43B
 with sigma of 0.1
 C26B, C27B, C28B, C29B, C31B, C32B
 with sigma of 0.1
 C15B, C14B, C20B, C19B, C17B, C16B
 with sigma of 0.1
 C6B, C5B, C4B, C3B, C2B, C7B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
N2 \\sim C24: within 2A with sigma of 0.9 and sigma for terminal atoms of 1.8
within 2A
N2 \\sim C21 \\sim C22 \\sim C23 \\sim C24: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
N1 \\sim C9 \\sim C10 \\sim C11 \\sim C12: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
N3 \\sim N4 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C45 \\sim
C46 \\sim C47 \\sim C48: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C38 \\sim C43 \\sim C44: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C26B \\sim C27B \\sim C28B \\sim C29B: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C4B \\sim C5B \\sim C6B \\sim C8B: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C2 \\sim C6 \\sim C7: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
C2 \\sim C3 \\sim C4: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.024 within 2A
N7A \\sim N9A \\sim C8A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C14 \\sim C19 \\sim C20: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C33B \\sim C34B \\sim C35B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
N2B \\sim C21B \\sim C24B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
N4 \\sim C37 \\sim C45 \\sim C46: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C24B \\sim C25B \\sim C26B \\sim C33B: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C37B \\sim C38B \\sim C36B \\sim C45B: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Uanis(C21) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C13)
\\sim Ueq, Uanis(C12) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms
of 0.2
Uanis(C21) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(N2)
\\sim Ueq: with sigma of 0.5 and sigma for terminal atoms of 1
Uanis(C33) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C45)
\\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C21B) \\sim Ueq, Uanis(C19B) \\sim Ueq,
Uanis(C5B) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C27B) \\sim Ueq, Uanis(C37B)
\\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C6B) \\sim Ueq: with sigma of 0.5 and
sigma for terminal atoms of 1
Uanis(N2) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C33)
\\sim Ueq, Uanis(C21B) \\sim Ueq, Uanis(N2B) \\sim Ueq, Uanis(C19B) \\sim Ueq,
Uanis(C37B) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C5B) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C7) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C9B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N2) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C16B) \\sim Ueq, Uanis(C37B) \\sim Ueq, Uanis(C45) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
Uanis(C37B) \\sim Ueq, Uanis(C16B) \\sim Ueq, Uanis(C45) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
5.a Aromatic/amide H refined with riding coordinates:
 N1A(H1A), N1C(H1C), C2C(H2C), C2A(H2A), C3(H3), C3B(H3B), C4(H4), C4B(H4B),
 C6B(H6B), C6(H6), C7B(H7B), C7(H7), C8A(H8A), C8C(H8C), C10B(H10C), C10(H10),
 C11B(H11B), C11(H11), C15B(H15B), C15(H15), C16B(H16B), C16(H16), C19(H19),
 C19B(H19B), C20(H20), C20B(H20B), C22B(H22B), C22(H22), C23B(H23B), C23(H23),
 C27B(H27B), C27(H27), C28(H28), C28B(H28B), C31(H31), C31B(H31B), C32B(H32B),
 C32(H32), C34(H34), C34B(H34B), C35(H35), C35B(H35B), C39B(H39B), C39(H39),
 C40(H40), C40B(H40B), C43B(H43B), C43(H43), C44(H44), C44B(H44B), C46(H46),
 C46B(H46B), C47B(H47B), C47(H47)
5.b X=CH2 refined with riding coordinates:
 N10A(H10A,H10B), N89(H89A,H89B)
;
_shelx_res_checksum              66833
_shelx_hkl_checksum              30177
_shelx_fab_checksum              28402
_platon_squeeze_special_details
;
A solvent mask was calculated and 1636 electrons were 
found in a volume of 4257\%A^3^ in 4 voids per unit cell. 
This is consistent with the presence of 
10.25 DMF (C3H7NO) per Formula Unit 
which account for 1640 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 1.639
_oxdiff_exptl_absorpt_empirical_full_min 0.668
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2