Thermodynamics of Proton and Electron Transfer in Tetranuclear Clusters with Mn-OH<sub>2</sub>/OH Motifs Relevant to H<sub>2</sub>O Activation by the Oxygen Evolving Complex in Photosystem II.
Reed, Christopher J.; Agapie, Theodor; Journal of the American Chemical Society 140 (2018) 10900–10908; doi:10.1021/jacs.8b06426

data_4132784
_publ_section_title
;
 Thermodynamics of Proton and Electron Transfer in Tetranuclear Clusters
 with Mn-OH<sub>2</sub>/OH Motifs Relevant to H<sub>2</sub>O Activation by
 the Oxygen Evolving Complex in Photosystem II.
;
_journal_issue                   34
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10900
_journal_page_last               10908
_journal_paper_doi               10.1021/jacs.8b06426
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C66 H49 Fe3 Mn N12 O5, O3 S, C F3'
_chemical_formula_sum            'C67 H49 F3 Fe3 Mn N12 O8 S'
_chemical_formula_weight         1461.73
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-01-25
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.474(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.7283(7)
_cell_length_b                   19.3808(10)
_cell_length_c                   45.518(2)
_cell_measurement_reflns_used    9982
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      65.27
_cell_measurement_theta_min      3.77
_cell_volume                     12980.8(11)
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.04
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0812
_diffrn_reflns_av_unetI/netI     0.0563
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       53
_diffrn_reflns_limit_l_min       -53
_diffrn_reflns_number            67797
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        66.249
_diffrn_reflns_theta_max         66.249
_diffrn_reflns_theta_min         3.772
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    7.742
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.5774
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.496
_exptl_crystal_description       block
_exptl_crystal_F_000             5960
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_refine_diff_density_rms         0.157
_refine_ls_extinction_method     none
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_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
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_refine_ls_number_reflns         11178
_refine_ls_number_restraints     475
_refine_ls_restrained_S_all      1.145
_refine_ls_R_factor_all          0.1492
_refine_ls_R_factor_gt           0.1305
_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^)+654.2949P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
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_refine_ls_wR_factor_ref         0.2862
_reflns_Friedel_coverage         0.000
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_cod_data_source_file            ja8b06426_si_001.cif
_cod_data_source_block           p17523
_cod_original_cell_volume        12980.9(11)
_cod_database_code               4132784
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_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2. Shared sites
{S200, C200}
{O202, F200}
{O201, F201}
{O200, F202}
{S201, C201}
3. Restrained distances
 O204-O205
 2.3 with sigma of 0.05
4. Uiso/Uaniso restraints and constraints
C66 \\sim C65 \\sim C11: within 2.1A with sigma of 0.02 and sigma for terminal
atoms of 0.03
C37 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C3 \\sim C31:
within 1.8A with sigma of 0.01 and sigma for terminal atoms of 0.03
N22 \\sim C55 \\sim C59 \\sim C57 \\sim C58: within 2.5A with sigma of 0.01 and
sigma for terminal atoms of 0.02
N24 \\sim N23 \\sim C81 \\sim C82 \\sim C83: within 2.4A with sigma of 0.01 and
sigma for terminal atoms of 0.02
N34 \\sim N33 \\sim C92 \\sim C91 \\sim C93: within 2.4A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C46 \\sim N32 \\sim C45 \\sim C47 \\sim C48: within 2.4A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C65 \\sim N12 \\sim C69 \\sim C68 \\sim C67 \\sim C66: within 2.4A with sigma
of 0.01 and sigma for terminal atoms of 0.02
C31 \\sim C44 \\sim C45 \\sim C32 \\sim O31: within 1.9A with sigma of 0.02 and
sigma for terminal atoms of 0.04
O203 \\sim S201 \\sim O204 \\sim O205 \\sim F203 \\sim F204 \\sim F205 \\sim
C201: within 2.3A with sigma of 0.02 and sigma for terminal atoms of 0.04
C73 \\sim C72 \\sim C71 \\sim C93 \\sim C92 \\sim C91 \\sim C83 \\sim C82 \\sim
C81: within 1.9A with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(S200) = Uanis(C200)
Uanis(O202) = Uanis(F200)
Uanis(O201) = Uanis(F201)
Uanis(O200) = Uanis(F202)
Uanis(C71) = Uanis(C72)
Uanis(S201) = Uanis(C201)
5. Others
 Fixed Sof: S200(0.5) O202(0.5) O201(0.5) O200(0.5) S201(0.5) O204(0.5)
 O203(0.5) F203(0.5) F204(0.5) F205(0.5) O205(0.5) F200(0.5) F201(0.5)
 F202(0.5) C200(0.5) C201(0.5)
6.a Rotating group:
 O2(H2)
6.b Aromatic/amide H refined with riding coordinates:
 C83(H83), C23(H23), C46(H46), C4(H4), C50(H50), C33(H33), C60(H60), C57(H57),
 C59(H59), C82(H82), C58(H58), C49(H49), C52(H52), C24(H24), C56(H56), C61(H61),
  C69(H69), C40(H40), C25(H25), C41(H41), C91(H91), C43(H43), C36(H36),
 C51(H51), C68(H68), C16(H16), C62(H62), C14(H14), C71(H71), C72(H72), C15(H15),
  C73(H73), C13(H13), C67(H67), C26(H26), C47(H47), C6(H6), C81(H81), C48(H48),
 C92(H92), C2(H2A), C53(H53), C63(H63), C42(H42), C35(H35), C34(H34), C93(H93),
 C66(H66)
;
_shelx_res_checksum              68733
_shelx_hkl_checksum              43809
_shelx_fab_checksum              65366
_olex2_submission_special_instructions 'No special instructions were received'