Tetranuclear [Mn<sup>III</sup>Mn<sub>3</sub><sup>IV</sup>O<sub>4</sub>] Complexes as Spectroscopic Models of the S<sub>2</sub> State of the Oxygen Evolving Complex in Photosystem II.
Lee, Heui Beom; Shiau, Angela A.; Oyala, Paul H.; Marchiori, David A.; Gul, Sheraz; Chatterjee, Ruchira; Yano, Junko; Britt, R. David; Agapie, Theodor; Journal of the American Chemical Society 140 (2018) 17175–17187; doi:10.1021/jacs.8b09961

data_4133418
_publ_section_title
;
 Tetranuclear [Mn<sup>III</sup>Mn<sub>3</sub><sup>IV</sup>O<sub>4</sub>]
 Complexes as Spectroscopic Models of the S<sub>2</sub> State of the
 Oxygen Evolving Complex in Photosystem II.
;
_journal_issue                   49
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              17175
_journal_page_last               17187
_journal_paper_doi               10.1021/jacs.8b09961
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C93 H69 Mn4 N6 O13 P3, C F3 O3 S, C H2 Cl2'
_chemical_formula_sum            'C95 H71 Cl2 F3 Mn4 N6 O16 P3 S'
_chemical_formula_weight         2025.20
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.255(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.3608(9)
_cell_length_b                   27.4932(17)
_cell_length_c                   23.6617(14)
_cell_measurement_reflns_used    9298
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      35.032
_cell_measurement_theta_min      2.389
_cell_volume                     9162.5(10)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 10.24
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0541
_diffrn_reflns_av_unetI/netI     0.0346
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       45
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            470337
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         36.332
_diffrn_reflns_theta_min         2.136
_diffrn_source                   'I\mS HB micro-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.748
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9232
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0939 before and 0.0570 after correction. The Ratio of minimum to maximum transmission is 0.9232. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.468
_exptl_crystal_description       plate
_exptl_crystal_F_000             4132
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_exptl_transmission_factor_max   1.0000
_exptl_transmission_factor_min   0.9232
_refine_diff_density_max         2.156
_refine_diff_density_min         -2.324
_refine_diff_density_rms         0.150
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1211
_refine_ls_number_reflns         43739
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0861
_refine_ls_R_factor_gt           0.0590
_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^)+(0.0780P)^2^+14.9819P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1539
_refine_ls_wR_factor_ref         0.1739
_reflns_Friedel_coverage         0.000
_reflns_number_gt                32809
_reflns_number_total             43739
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09961_si_002.cif
_cod_data_source_block           2-ox
_cod_database_code               4133418
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.929
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 S1-O14 \\sim S1-O17 \\sim S1-O15 \\sim S2-O14 \\sim S2-O16 \\sim S2-O15
 with sigma of 0.02
 F3-C95 \\sim F1-C95 \\sim F4-C96 \\sim F2-C95 \\sim F6-C96 \\sim F5-C96
 with sigma of 0.02
3. Others
 Sof(S2)=Sof(O16)=Sof(F6)=Sof(F5)=Sof(C96)=Sof(F4)=1-FVAR(1)
 Sof(S1)=Sof(F1)=Sof(F3)=Sof(F2)=Sof(O17)=Sof(C95)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C94(H94A,H94B)
4.b Aromatic/amide H refined with riding coordinates:
 C62(H62), C61(H61), C59(H59), C60(H60), C86(H86), C83(H83), C66(H66),
 C74(H74), C48(H48), C37(H37), C89(H89), C84(H84), C93(H93), C55(H55), C73(H73),
  C85(H85), C24(H24), C32(H32), C69(H69), C30(H30), C18(H18), C36(H36),
 C91(H91), C80(H80), C77(H77), C23(H23), C49(H49), C33(H33), C68(H68), C26(H26),
  C14(H14), C51(H51), C67(H67), C57(H57), C79(H79), C34(H34), C50(H50),
 C17(H17), C56(H56), C35(H35), C29(H29), C78(H78), C38(H38), C58(H58), C16(H16),
  C40(H40), C71(H71), C28(H28), C72(H72), C12(H12), C39(H39), C15(H15),
 C27(H27), C22(H22), C20(H20), C8(H8), C44(H44), C47(H47), C5(H5), C21(H21),
 C45(H45), C4(H4), C46(H46), C6(H6), C9(H9), C11(H11), C2(H2), C3(H3), C10(H10)
;
_shelx_res_checksum              62447
_shelx_hkl_checksum              17729
_shelx_fab_checksum              98359
_olex2_submission_special_instructions 'No special instructions were received'