Tuning the Reactivity of Cofacial Porphyrin Prisms for Oxygen Reduction Using Modular Building Blocks
Crawley, Matthew R.; Zhang, Daoyang; Oldacre, Amanda N.; Beavers, Christine M.; Friedman, Alan E.; Cook, Timothy R.; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c11895

data_4135442
_publ_section_title
;
 Tuning the Reactivity of Cofacial Porphyrin Prisms for Oxygen Reduction
 Using Modular Building Blocks
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c11895
_journal_year                    2020
_chemical_formula_moiety
'C224 H192 F24 N24 O10 Ru8 Zn2, 4(C F3 O3 S), 4[CF3O3S], 2[CH4O]'
_chemical_formula_sum            'C228 H192 F36 N24 O22 Ru8 S4 Zn2'
_chemical_formula_weight         5371.58
_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
_audit_creation_date             2020-10-21
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_cell_angle_alpha                90
_cell_angle_beta                 127.7260(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   41.929(2)
_cell_length_b                   28.7680(14)
_cell_length_c                   25.7008(14)
_cell_measurement_reflns_used    9859
_cell_measurement_temperature    100
_cell_measurement_theta_max      20.8
_cell_measurement_theta_min      2.27
_cell_volume                     24520(2)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker D8 Venture PHOTON 2'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1453
_diffrn_reflns_av_unetI/netI     0.0478
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            147684
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        20.916
_diffrn_reflns_theta_max         20.916
_diffrn_reflns_theta_min         1.228
_exptl_absorpt_coefficient_mu    0.795
_exptl_absorpt_correction_T_max  0.7446
_exptl_absorpt_correction_T_min  0.6543
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS-2016/2
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.455
_exptl_crystal_description       block
_exptl_crystal_F_000             10816
_exptl_crystal_recrystallization_method
'Crystals were grown from a 1:1 DCM:MeOH solution which diethyl ether was diffused onto.'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.573
_refine_diff_density_min         -0.701
_refine_diff_density_rms         0.157
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.555
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1312
_refine_ls_number_reflns         12917
_refine_ls_number_restraints     1738
_refine_ls_restrained_S_all      1.668
_refine_ls_R_factor_all          0.2043
_refine_ls_R_factor_gt           0.1500
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4041
_refine_ls_wR_factor_ref         0.4517
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6568
_reflns_number_total             12917
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c11895_si_003.cif
_cod_data_source_block           sad_a
_cod_database_code               4135442
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.925
_shelx_estimated_absorpt_t_min   0.925
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F12-F01B
 2.125 with sigma of 0.02
 F00Y-F12
 2.125 with sigma of 0.02
 F01B-F00Y
 2.125 with sigma of 0.001
 C028-F12
 1.4 with sigma of 0.02
 F00Y-C028
 1.328 with sigma of 0.02
 F12-C028
 1.328 with sigma of 0.02
 F01B-C028
 1.328 with sigma of 0.02
 C2AA-C22
 2.4 with sigma of 0.02
 N00Q-C2AA
 1.39 with sigma of 0.02
 N00Q-C22
 1.39 with sigma of 0.02
 C028-C02W
 1.5 with sigma of 0.02
 C01W-C23
 1.5 with sigma of 0.02
 F00Y-C028 \\sim F01B-C028 \\sim F12-C028
 with sigma of 0.02
 F12-C028 \\sim F00Y-F01B
 with sigma of 0.02
 C42-C20 \\sim C42-C30 \\sim C03F-C027 \\sim C03C-C027
 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(O11) \\sim Ueq, Uanis(S4) \\sim Ueq, Uanis(O9) \\sim Ueq, Uanis(O10)
\\sim Ueq, Uanis(C1I) \\sim Ueq, Uanis(F17) \\sim Ueq, Uanis(F18) \\sim Ueq,
Uanis(F19) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(O11) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
5. Rigid body (RIGU) restrains
 S4, O9, O10, O11, C1I, F17, F18, F19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C028, F00Y, F01B, F12, C02W
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: S2(0.5) O4(0.5) O5(0.5) O6(0.5) C6(0.5) F1(0.5) F2(0.5) F9(0.5)
 S4(0.5) O9(0.5) O10(0.5) O11(0.5) C1I(0.5) F17(0.5) F18(0.5) F19(0.5)
7.a Free rotating group:
 S2(O4,O5,O6,C6,F1,F2,F9), C2(C3,C1,C5,C7,C8,C9,F3,F10,F11), C15(C17,C18,C19,
 C1A,C1B,C1C,F4,F5,F6), C10(C14,C1D,C1E,C1F,C1G,C1H,F7,F8,F13), S3(O3,O7,O8,C4,
 F14,F15,F16), S4(O9,O10,O11,C1I,F17,F18,F19), C1J(C1K,C1L,C1M,C1N,C1O,C1P,C1Q,
 C1R,C1T), C1U(C1W,C1X,C1Y,C1Z,C21,C24,C25,C26,C27)
7.b Ternary CH refined with riding coordinates:
 C027(H027), C42(H42), C1P(H1P), C24(H24)
7.c Me refined with riding coordinates:
 C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C20(H20A,H20B,H20C), C1Q(H1QA,H1QB,
 H1QC), C1R(H1RA,H1RB,H1RC), C1T(H1TA,H1TB,H1TC), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C27(H27A,H27B,H27C)
7.d Aromatic/amide H refined with riding coordinates:
 C0G(H0G), C01R(H01R), C01C(H01C), C01I(H01I), C01Q(H01Q), C0L(H0L), C0S(H0S),
 C0AA(H0AA), C12(H12), C0O(H0O), C00Z(H00Z), C010(H010), C011(H011), C013(H013),
  C01G(H01G), C01L(H01L), C02S(H02S), C02E(H02E), C02U(H02U), C02V(H02V),
 C01Z(H01Z), C023(H023), C02A(H02A), C02G(H02G), C02H(H02H), C02L(H02L),
 C02M(H02M), C02N(H02N), C13(H13), C16(H16), C22(H22), C0BA(H0BA), C1S(H1S),
 C033(H033), C02C(H02C), C2AA(H2AA), C3(H3), C1(H1), C8(H8), C9(H9), C17(H17),
 C18(H18), C1B(H1B), C1C(H1C), C14(H14), C1D(H1D), C1G(H1G), C1H(H1H), C1K(H1K),
  C1L(H1L), C1N(H1N), C1O(H1O), C1W(H1W), C1X(H1X), C1Z(H1Z), C21(H21)
7.e Fitted hexagon refined as free rotating group:
 N00H(C01R,C01C,C01D,C01I,C01Q), C0L(C0J,C0S,C0AA,N00B,C12), C01Y(C02S,C02E,
 C02W,C02U,C02V), C0BA(C1S,C025,C033,C02C,C1V)
7.f Idealised Me refined as rotating group:
 C03C(H03A,H03B,H03C), C03E(H03D,H03E,H03F), C03F(H03G,H03H,H03I)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              56903
_shelx_hkl_checksum              35556
_shelx_fab_checksum              64914
_olex2_submission_special_instructions 'No special instructions were received'