Switching between Inner- and Outer-Sphere PCET Mechanisms of Small-Molecule Activation: Superoxide Dismutation and Oxygen/Superoxide Reduction Reactivity Deriving from the Same Manganese Complex.
Kenkel, Isabell; Franke, Alicja; Dürr, Maximilian; Zahl, Achim; Dücker-Benfer, Carlos; Langer, Jens; Filipović, Milos R; Yu, Meng; Puchta, Ralph; Fiedler, Stephanie R.; Shores, Matthew P.; Goldsmith, Christian R.; Ivanović-Burmazović, Ivana; Journal of the American Chemical Society 139 (2017) 1472–1484; doi:10.1021/jacs.6b08394

data_4125726
_publ_section_title
;
 Switching between Inner- and Outer-Sphere PCET Mechanisms of
 Small-Molecule Activation: Superoxide Dismutation and Oxygen/Superoxide
 Reduction Reactivity Deriving from the Same Manganese Complex.
;
_journal_issue                   4
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1472
_journal_page_last               1484
_journal_paper_doi               10.1021/jacs.6b08394
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C28 H30 Mn N5 O, 1.5(H2 O), Cl O4'
_chemical_formula_sum            'C28 H33 Cl Mn N5 O6.5'
_chemical_formula_weight         633.98
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-26
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                98.641(3)
_cell_angle_beta                 104.363(3)
_cell_angle_gamma                90.039(2)
_cell_formula_units_Z            4
_cell_length_a                   9.5946(3)
_cell_length_b                   16.4468(5)
_cell_length_c                   18.9308(6)
_cell_measurement_reflns_used    26707
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      29.5170
_cell_measurement_theta_min      3.0880
_cell_volume                     2858.82(16)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.992
_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    -12.00  87.00   1.00   13.00    --   12.33  38.00 -90.00   99
  2  \w    -61.00  40.00   1.00   13.00    --   12.33 -57.00-150.00  101
  3  \w    -16.00  85.00   1.00   13.00    --   12.33  57.00   0.00  101
  4  \w    -20.00  29.00   1.00   13.00    --  -11.55 -99.00   0.00   49
  5  \w     34.00  99.00   1.00   13.00    --   12.33-178.00-150.00   65
  6  \w    -20.00  53.00   1.00   13.00    --   12.33 -99.00 -30.00   73
  7  \w    -12.00  87.00   1.00   13.00    --   12.33  38.00-180.00   99
  8  \w    -20.00   7.00   1.00   13.00    --   12.33 -99.00 120.00   27
  9  \w     34.00  99.00   1.00   13.00    --   12.33-178.00  90.00   65
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0226325000
_diffrn_orient_matrix_UB_12      0.0408991000
_diffrn_orient_matrix_UB_13      0.0064710000
_diffrn_orient_matrix_UB_21      -0.0350231000
_diffrn_orient_matrix_UB_22      -0.0027148000
_diffrn_orient_matrix_UB_23      -0.0380097000
_diffrn_orient_matrix_UB_31      -0.0639853000
_diffrn_orient_matrix_UB_32      -0.0150427000
_diffrn_orient_matrix_UB_33      0.0067879000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0991
_diffrn_reflns_av_unetI/netI     0.0235
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            11712
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.442
_diffrn_reflns_theta_min         2.193
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.609
_exptl_absorpt_correction_T_max  -0.010
_exptl_absorpt_correction_T_min  10000000.000
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.473
_exptl_crystal_description       block
_exptl_crystal_F_000             1320
_exptl_crystal_size_max          0.474
_exptl_crystal_size_mid          0.359
_exptl_crystal_size_min          0.293
_refine_diff_density_max         0.777
_refine_diff_density_min         -1.004
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     769
_refine_ls_number_reflns         11712
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0476
_refine_ls_R_factor_gt           0.0440
_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^)+(0.0980P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1194
_refine_ls_wR_factor_ref         0.1211
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10685
_reflns_number_total             11712
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9908\% 
 around [0.90 -0.00 -0.44] (reciprocal) or [1.00 -0.00 -0.00] (direct)
;
_cod_data_source_file            ja6b08394_si_001.cif
_cod_data_source_block           iviv150625_twin
_cod_original_formula_sum        'C28 H33 Cl Mn N5 O6.50'
_cod_database_code               4125726
_chemical_oxdiff_formula         'C H N O Mn Cl'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5386(10) 0.4614(10)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
3.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B),
 C23(H23A,H23B), C36(H36A,H36B), C37(H37A,H37B), C43(H43A,H43B), C44(H44A,H44B),
  C45(H45A,H45B), C51(H51A,H51B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C11(H11), C12(H12), C13(H13), C14(H14), C19(H19),
 C20(H20), C21(H21), C22(H22), C25(H25), C26(H26), C27(H27), C28(H28), C30(H30),
  C31(H31), C33(H33), C39(H39), C40(H40), C41(H41), C42(H42), C47(H47),
 C48(H48), C49(H49), C50(H50), C53(H53), C54(H54), C55(H55), C56(H56)
3.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C35(H35A,H35B,H35C)
;
_shelx_shelxl_version_number     2014/7
_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 1.665
_oxdiff_exptl_absorpt_empirical_full_min 0.645
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2