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_4132781
_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
'C67 H48 F3 Fe3 Mn N12 O7 S, 0.23(C Cl2), 1.19(C4 H4 O), 1.37(C4 H6 O), 0.64(C4 O), C1.04 O0.27, C24 H20 B'
_chemical_formula_sum
'C105.06 H80.97 B Cl0.46 F3 Fe3 Mn N12 O10.47 S'
_chemical_formula_weight         2017.51
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_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                71.236(4)
_cell_angle_beta                 75.366(2)
_cell_angle_gamma                70.262(4)
_cell_formula_units_Z            2
_cell_length_a                   14.2908(12)
_cell_length_b                   15.9691(13)
_cell_length_c                   24.3709(17)
_cell_measurement_reflns_used    9016
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      32.60
_cell_measurement_theta_min      2.24
_cell_volume                     4891.6(7)
_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      99.99
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0616
_diffrn_reflns_av_unetI/netI     0.0352
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            269409
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.222
_diffrn_reflns_theta_min         2.538
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.668
_exptl_absorpt_correction_T_max  0.746
_exptl_absorpt_correction_T_min  0.6907
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.370
_exptl_crystal_description       plate
_exptl_crystal_F_000             2076
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.05
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_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1432
_refine_ls_number_reflns         29027
_refine_ls_number_restraints     166
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0892
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_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0962P)^2^+7.0590P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1716
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_reflns_Friedel_coverage         0.000
_reflns_number_gt                21566
_reflns_number_total             29027
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b06426_si_001.cif
_cod_data_source_block           p17539
_cod_database_code               4132781
_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
2. Restrained distances
 C114-C113
 1.4 with sigma of 0.02
 C122-C123
 1.4 with sigma of 0.02
 C121-C120
 1.3 with sigma of 0.02
 C107-O102
 1.2 with sigma of 0.02
 C107-C106
 1.5 with sigma of 0.02
 C111-C109
 1.4 with sigma of 0.02
 O102-C106
 2.3 with sigma of 0.05
 O101-C109
 2.3 with sigma of 0.04
 O202-O204
 3 with sigma of 0.08
3. Uiso/Uaniso restraints and constraints
O103 \\sim C112 \\sim C113 \\sim C114 \\sim C115: within 1.7A with sigma of
0.02 and sigma for terminal atoms of 0.04
O105 \\sim C120 \\sim C121 \\sim C122 \\sim C123: within 1.7A with sigma of
0.02 and sigma for terminal atoms of 0.04
Cl10 \\sim Cl1 \\sim C124: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02
O101 \\sim C108 \\sim C109 \\sim C110 \\sim C111: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
S201 \\sim F201 \\sim F205 \\sim O202 \\sim O204 \\sim C201: within 1.9A with
sigma of 0.02 and sigma for terminal atoms of 0.04
S200 \\sim F202 \\sim F203 \\sim F204 \\sim O201 \\sim C200: within 2.1A with
sigma of 0.01 and sigma for terminal atoms of 0.03
Uanis(F200) = Uanis(F203)
4. Same fragment restrains
{S200, F204, F200, F202, O201, C200} sigma for 1-2: 0.01, 1-3: 0.02
as
{S201, F201, F203, F205, O204, C201}
5. Others
 1*[Sof(O105)+Sof(C120)+Sof(C122)+Sof(C123)]+1*[Sof(Cl10)+Sof(Cl1)+Sof(C124)+
 Sof(C121)]+1*[Sof(O104)+Sof(C116)+Sof(C117)+Sof(C118)+Sof(C119)]=1 with esd of
 0.01
 Sof(O105)=Sof(C120)=Sof(C122)=Sof(C123)=FVAR(1)
 Sof(Cl10)=Sof(Cl1)=Sof(C124)=Sof(C121)=FVAR(2)
 Sof(O104)=Sof(C116)=Sof(C117)=Sof(C118)=Sof(C119)=FVAR(3)
 Sof(O101)=Sof(C108)=Sof(H10K)=Sof(H10L)=Sof(C109)=Sof(H10M)=Sof(H10N)=
 Sof(C110)=Sof(C111)=1-FVAR(4)
 Sof(O102)=Sof(C104)=Sof(H10A)=Sof(H10B)=Sof(C105)=Sof(H10C)=Sof(H10D)=
 Sof(C106)=Sof(H10E)=Sof(H10F)=Sof(C107)=FVAR(4)
 Sof(O103)=Sof(C112)=Sof(H11A)=Sof(H11B)=Sof(C113)=Sof(H11C)=Sof(H11D)=
 Sof(C114)=Sof(C115)=Sof(H11E)=Sof(H11F)=FVAR(5)
 Sof(S200)=Sof(F200)=Sof(F202)=Sof(F204)=Sof(O201)=Sof(O203)=Sof(C200)=1-FVAR(6)
 Sof(S201)=Sof(F201)=Sof(F203)=Sof(F205)=Sof(O204)=Sof(C201)=Sof(O202)=FVAR(6)
6.a Secondary CH2 refined with riding coordinates:
 C100(H10G,H10H), C103(H10I,H10J), C108(H10K,H10L), C109(H10M,H10N), C104(H10A,
 H10B), C105(H10C,H10D), C106(H10E,H10F), C112(H11A,H11B), C113(H11C,H11D),
 C115(H11E,H11F)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C13(H13), C14(H14), C15(H15), C16(H16), C23(H23),
 C24(H24), C25(H25), C26(H26), C33(H33), C34(H34), C35(H35), C36(H36), C40(H40),
  C41(H41), C42(H42), C43(H43), C46(H46), C47(H47), C48(H48), C49(H49),
 C50(H50), C51(H51), C52(H52), C53(H53), C56(H56), C57(H57), C58(H58), C59(H59),
  C60(H60), C61(H61), C62(H62), C63(H63), C66(H66), C67(H67), C68(H68),
 C69(H69), C71(H71), C72(H72), C73(H73), C81(H81), C82(H82), C83(H83), C91(H91),
  C92(H92), C93(H93), C204(H204), C205(H205), C206(H206), C207(H207),
 C208(H208), C210(H210), C211(H211), C212(H212), C213(H213), C214(H214),
 C216(H216), C217(H217), C218(H218), C219(H219), C220(H220), C222(H222),
 C223(H223), C224(H224), C225(H225), C226(H226)
;
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_olex2_submission_special_instructions 'No special instructions were received'