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_4132783
_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 H50 Fe3 Mn N12 O5, 2(C F3 O3 S), H2 O, C4 H10 O'
_chemical_formula_sum            'C72 H62 F6 Fe3 Mn N12 O13 S2'
_chemical_formula_weight         1703.94
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-01-24
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.393(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.2685(6)
_cell_length_b                   29.896(2)
_cell_length_c                   19.6152(17)
_cell_measurement_reflns_used    9630
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      74.37
_cell_measurement_theta_min      2.70
_cell_volume                     7188.2(9)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.02
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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  0.1912
_diffrn_reflns_av_unetI/netI     0.0717
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            201519
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         74.755
_diffrn_reflns_theta_min         2.696
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    7.461
_exptl_absorpt_correction_T_max  0.7538
_exptl_absorpt_correction_T_min  0.4701
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1516 before and 0.1131 after correction. The Ratio of minimum to maximum transmission is 0.6307. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.575
_exptl_crystal_description       block
_exptl_crystal_F_000             3484
_refine_diff_density_max         1.320
_refine_diff_density_min         -1.006
_refine_diff_density_rms         0.137
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.140
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     988
_refine_ls_number_reflns         14693
_refine_ls_number_restraints     104
_refine_ls_restrained_S_all      1.150
_refine_ls_R_factor_all          0.1424
_refine_ls_R_factor_gt           0.1109
_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^)+107.3221P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2060
_refine_ls_wR_factor_ref         0.2230
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11345
_reflns_number_total             14693
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b06426_si_001.cif
_cod_data_source_block           p17560_f
_cod_database_code               4132783
_shelx_shelxl_version_number     2016/6
_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,H) groups
2. Uiso/Uaniso restraints and constraints
C103 \\sim O100 \\sim C102 \\sim C101 \\sim HE \\sim HF \\sim C100 \\sim HG
\\sim HH \\sim HI \\sim HJ \\sim HK \\sim HB \\sim HC \\sim HD: within 1.9A
with sigma of 0.02 and sigma for terminal atoms of 0.04
3.a Free rotating group:
 O101(H,HA)
3.b Rotating group:
 O2(H2A,H2B)
3.c Secondary CH2 refined with riding coordinates:
 C102(HE,HF), C101(HG,HH)
3.d Aromatic/amide H refined with riding coordinates:
 C47(H47), C6(H6), C2(H2), C40(H40), C83(H83), C59(H59), C16(H16), C63(H63),
 C61(H61), C69(H69), C57(H57), C49(H49), C73(H73), C35(H35), C48(H48), C43(H43),
  C25(H25), C52(H52), C24(H24), C82(H82), C26(H26), C58(H58), C71(H71),
 C23(H23), C66(H66), C56(H56), C91(H91), C93(H93), C60(H60), C33(H33), C15(H15),
  C62(H62), C51(H51), C92(H92), C34(H34), C41(H41), C81(H81), C67(H67),
 C36(H36), C72(H72), C46(H46), C4(H4), C14(H14), C13(H13), C68(H68), C53(H53),
 C50(H50), C42(H42)
3.e Idealised Me refined as rotating group:
 C100(HB,HC,HD), C103(HI,HJ,HK)
;
_shelx_res_checksum              84586
_shelx_hkl_checksum              91857
_olex2_submission_special_instructions 'No special instructions were received'