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_4125510
_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         'C30 H34 Mn N5 O3, Cl O4, 3(H2 O), O'
_chemical_formula_sum            'C30 H40 Cl Mn N5 O11'
_chemical_formula_weight         737.06
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-04-18
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.652(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.1273(2)
_cell_length_b                   21.7763(6)
_cell_length_c                   17.9055(6)
_cell_measurement_reflns_used    12361
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      29.3150
_cell_measurement_theta_min      3.5870
_cell_volume                     3557.40(17)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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 0.998
_diffrn_measured_fraction_theta_max 0.862
_diffrn_measurement_details
;
  1 omega  -44.00   65.00   1.0000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.3916   77.0000   30.0000 109

  2 omega  -20.00   88.00   1.0000   11.0000
omega____ theta____ kappa____ phi______ frames
    -       12.1728   77.0000  -60.0000 108

  3 omega  -20.00   88.00   1.0000   11.0000
omega____ theta____ kappa____ phi______ frames
    -       12.1728   77.0000  150.0000 108
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0079134000
_diffrn_orient_matrix_UB_12      -0.0143153000
_diffrn_orient_matrix_UB_13      0.0354804000
_diffrn_orient_matrix_UB_21      0.0080780000
_diffrn_orient_matrix_UB_22      0.0292142000
_diffrn_orient_matrix_UB_23      0.0171382000
_diffrn_orient_matrix_UB_31      -0.0769079000
_diffrn_orient_matrix_UB_32      0.0015827000
_diffrn_orient_matrix_UB_33      0.0042892000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0326
_diffrn_reflns_av_unetI/netI     0.0324
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.862
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            30586
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.862
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.747
_diffrn_reflns_theta_min         3.028
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.509
_exptl_absorpt_correction_T_max  0.365
_exptl_absorpt_correction_T_min  0.203
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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            'dull dark gray'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    gray
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_description
;
;
_exptl_crystal_F_000             1540
_exptl_crystal_size_max          0.5828
_exptl_crystal_size_mid          0.4528
_exptl_crystal_size_min          0.329
_refine_diff_density_max         1.309
_refine_diff_density_min         -0.607
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     454
_refine_ls_number_reflns         8744
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0595
_refine_ls_R_factor_gt           0.0500
_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^)+(0.0605P)^2^+4.0601P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1309
_refine_ls_wR_factor_ref         0.1377
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7489
_reflns_number_total             8744
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b08394_si_002.cif
_cod_data_source_block           iviv151026a
_cod_depositor_comments          'Adding full bibliography for 4125510.cif.'
_cod_original_cell_volume        3557.42(17)
_cod_database_code               4125510
_chemical_oxdiff_formula         'C H Mn Cl O N'
_reflns_odcompleteness_completeness 96.49
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.82
_olex2_refinement_description
;
1. 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 O(H) groups, All O(H,H) groups
2. Others
 Fixed Sof: O11(0.5) O12(0.5)
3.a Free rotating group:
 O10(H10A,H10B), O8(H8A,H8B), O9(H9A,H9B)
3.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C23(H23A,H23B), C13(H13A,H13B), C15(H15A,H15B), C7(H7A,H7B),
 C6(H6A,H6B)
3.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C1(H1A), C28(H28), C26(H26), C27(H27), C25(H25), C2(H2), C12(H12),
 C19(H19), C4(H4), C9(H9), C3(H3), C11(H11), C18(H18), C10(H10)
3.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C30(H30A,H30B,H30C)
3.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              14579
_shelx_hkl_checksum              14183
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2015-10-26
_olex2_submission_special_instructions 'No special instructions were received'