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_4133420
_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         'C66 H55 Mn4 N8 O11, C F3 O3 S, C H2 Cl2'
_chemical_formula_sum            'C68 H57 Cl2 F3 Mn4 N8 O14 S'
_chemical_formula_weight         1589.93
_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
_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                81.151(6)
_cell_angle_beta                 84.367(6)
_cell_angle_gamma                66.925(7)
_cell_formula_units_Z            2
_cell_length_a                   12.925(2)
_cell_length_b                   15.479(2)
_cell_length_c                   18.467(3)
_cell_measurement_reflns_used    9538
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      74.57
_cell_measurement_theta_min      3.12
_cell_volume                     3355.7(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  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.04
_diffrn_detector_area_resol_mean 10.24
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device_type  'Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0684
_diffrn_reflns_av_unetI/netI     0.0600
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            51382
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         75.401
_diffrn_reflns_theta_min         3.128
_diffrn_source                   'I\mS HB micro-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    7.697
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7718
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0915 before and 0.0737 after correction.
The Ratio of minimum to maximum transmission is 0.7718.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.574
_exptl_crystal_description       chunk
_exptl_crystal_F_000             1620
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_exptl_transmission_factor_max   1.0000
_exptl_transmission_factor_min   0.7718
_refine_diff_density_max         3.125
_refine_diff_density_min         -1.557
_refine_diff_density_rms         0.135
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     914
_refine_ls_number_reflns         13628
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.1078
_refine_ls_R_factor_gt           0.0786
_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^)+(0.1342P)^2^+11.6888P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2145
_refine_ls_wR_factor_ref         0.2416
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9932
_reflns_number_total             13628
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09961_si_002.cif
_cod_data_source_block           3-ox
_cod_original_cell_volume        3355.5(9)
_cod_database_code               4133420
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.861
_shelx_estimated_absorpt_t_min   0.861
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H67C)=Sof(H67D)=Sof(Cl3)=1-FVAR(1)
 Sof(H67A)=Sof(H67B)=Sof(Cl2)=FVAR(1)
3.a Secondary CH2 refined with riding coordinates:
 C67(H67A,H67B), C67(H67C,H67D), C7(H7A,H7B), C5(H5A,H5B), C6(H6A,H6B)
3.b Aromatic/amide H refined with riding coordinates:
 N6(H6), C47(H47), C35(H35), C66(H66), C62(H62), C46(H46), C56(H56), C34(H34),
 C33(H33), C44(H44), C22(H22), C10(H10), C32(H32), C50(H50), C23(H23), C64(H64),
  C17(H17), C39(H39), C21(H21), C58(H58), C20(H20), C53(H53), C52(H52),
 C40(H40), C51(H51), C59(H59), C41(H41), C45(H45), C31(H31), C42(H42), C11(H11),
  C18(H18), C30(H30), C57(H57), C19(H19), C12(H12), C13(H13), C24(H24),
 C29(H29), C28(H28)
3.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C2(H2A,H2B,H2C), C9(H9A,H9B,H9C)
;
_shelx_res_checksum              48750
_shelx_hkl_checksum              61657
_shelx_fab_checksum              78276
_olex2_submission_special_instructions 'No special instructions were received'