An Anionic Porphyrinylphosphonate‐Based Hydrogen-Bonded Organic Framework: Optimization of the Proton Conductivity through the Exchange of Counterions
Zhigileva, Ekaterina A.; Enakieva, Yulia Y.; Sinelshchikova, Anna A.; Chernyshev, Vladimir V.; Senchikhin, Ivan N.; Kovalenko, Konstantin A.; Stenina, Irina A.; Yaroslavtsev, Andrey B.; Gorbunova, Yulia G.; Tsivadze, Aslan Yu; Dalton Transactions  (2023) –; doi:10.1039/D3DT01118F

data_7713058
_publ_section_title
;
 An Anionic Porphyrinylphosphonate&#x2010;Based Hydrogen-Bonded Organic
 Framework: Optimization of the Proton Conductivity through the Exchange
 of Counterions
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT01118F
_journal_year                    2023
_chemical_formula_moiety         'C44 H29 N4 O12 P4 Pd, 3(C2 H8 N), C3 H7 N O'
_chemical_formula_sum            'C53 H60 N8 O13 P4 Pd'
_chemical_formula_weight         1247.37
_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             2020-09-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-02-10 deposited with the CCDC.	2023-05-17 downloaded from the CCDC.
;
_cell_angle_alpha                70.315(2)
_cell_angle_beta                 82.445(2)
_cell_angle_gamma                78.492(2)
_cell_formula_units_Z            2
_cell_length_a                   13.0985(7)
_cell_length_b                   13.8588(7)
_cell_length_c                   17.8550(9)
_cell_measurement_reflns_used    8014
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.73
_cell_measurement_theta_min      3.17
_cell_volume                     2983.2(3)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0422
_diffrn_reflns_av_unetI/netI     0.0609
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            34308
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.500
_diffrn_reflns_theta_min         4.078
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.484
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9610
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.0528 before and 0.0462 after correction. The Ratio of minimum to maximum transmission is 0.9610. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.389
_exptl_crystal_description       block
_exptl_crystal_F_000             1288
_exptl_crystal_recrystallization_method 'DMF, solvothermal'
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.612
_refine_diff_density_min         -0.928
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     808
_refine_ls_number_reflns         13510
_refine_ls_number_restraints     44
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0766
_refine_ls_R_factor_gt           0.0533
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0680P)^2^+7.1256P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1360
_refine_ls_wR_factor_ref         0.1501
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10237
_reflns_number_total             13510
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01118f2.cif
_cod_data_source_block           mof88
_cod_database_code               7713058
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C1S-C2S \\sim C5S-C6S
 with sigma of 0.02
 N1S-C1S \\sim N1S-C2S \\sim N3S-C5S \\sim N3S-C6S
 with sigma of 0.02
 N2S-C3S \\sim N2S-C4S
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C10S) \\sim Ueq, Uanis(O2S) \\sim Ueq, Uanis(C12S) \\sim Ueq, Uanis(N5S)
\\sim Ueq, Uanis(C6S) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.03
Uanis(C8S) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Others
 Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=Sof(C18A)=Sof(H18A)=Sof(C19A)=
 Sof(H19A)=1-FVAR(1)
 Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=Sof(C16)=Sof(H16)=Sof(C15)=Sof(H15)=FVAR(1)
 Fixed Sof: O2S(0.5) N5S(0.5) C11S(0.5) H11B(0.5) H11C(0.5) H11D(0.5)
 C12S(0.5) H12S(0.5) C10S(0.5) H10A(0.5) H10B(0.5) H10C(0.5) O1S(0.5) N4S(0.5)
 C9S(0.5) H9S(0.5) C7S(0.5) H7SA(0.5) H7SB(0.5) H7SC(0.5) C8S(0.5) H8SA(0.5)
 H8SB(0.5) H8SC(0.5)
5.a Secondary CH2 refined with riding coordinates:
 N2S(H2SA,H2SB), N1S(H1SA,H1SB), N3S(H3SD,H3SE)
5.b Me refined with riding coordinates:
 C8S(H8SA,H8SB,H8SC)
5.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C32(H32), C27(H27), C33(H33), C11(H11A), C30(H30), C29(H29), C8(H8),
  C4(H4), C5(H5), C26(H26), C41(H41), C7(H7), C40(H40), C37(H37), C38(H38),
 C43(H43), C22(H22), C44(H44), C21(H21), C18(H18), C19(H19), C16(H16), C15(H15),
  C15A(H15A), C16A(H16A), C18A(H18A), C19A(H19A), C12S(H12S), C9S(H9S)
5.d Idealised Me refined as rotating group:
 C4S(H4SA,H4SB,H4SC), C3S(H3SA,H3SB,H3SC), C2S(H2SC,H2SD,H2SE), C1S(H1SC,H1SD,
 H1SE), C5S(H5SA,H5SB,H5SC), C6S(H6SA,H6SB,H6SC), C11S(H11B,H11C,H11D),
 C10S(H10A,H10B,H10C), C7S(H7SA,H7SB,H7SC)
5.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O11(H11), O6(H6), O9(H9), O12(H12)
;
_shelx_res_checksum              89318
_shelx_hkl_checksum              19365
_olex2_submission_special_instructions 'No special instructions were received'