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_4133419
_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 H54 Mn4 N8 O11, C H2 Cl2, 1.57(C4 O), 0.25(C Cl2)'
_chemical_formula_sum            'C73.55 H56 Cl2.51 Mn4 N8 O12.57'
_chemical_formula_weight         1561.80
_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             2018-07-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                89.004(5)
_cell_angle_beta                 85.374(5)
_cell_angle_gamma                82.474(5)
_cell_formula_units_Z            2
_cell_length_a                   13.2586(18)
_cell_length_b                   15.443(3)
_cell_length_c                   18.255(3)
_cell_measurement_reflns_used    9499
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      34.825
_cell_measurement_theta_min      2.389
_cell_volume                     3693.4(11)
_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      100.0
_diffrn_detector_area_resol_mean 10.24
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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  0.0305
_diffrn_reflns_av_unetI/netI     0.0250
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            130778
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.563
_diffrn_reflns_theta_min         2.496
_diffrn_source                   'I\mS HB micro-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.825
_exptl_absorpt_correction_T_max  0.7471
_exptl_absorpt_correction_T_min  0.7071
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0631 before and 0.0520 after correction. The Ratio of minimum to maximum transmission is 0.9465. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.404
_exptl_crystal_description       block
_exptl_crystal_F_000             1593
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   0.7471
_exptl_transmission_factor_min   0.7071
_refine_diff_density_max         2.248
_refine_diff_density_min         -1.472
_refine_diff_density_rms         0.129
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     935
_refine_ls_number_reflns         22581
_refine_ls_number_restraints     37
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0781
_refine_ls_R_factor_gt           0.0626
_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^)+(0.1137P)^2^+7.4758P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1885
_refine_ls_wR_factor_ref         0.2028
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18281
_reflns_number_total             22581
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09961_si_002.cif
_cod_data_source_block           3
_cod_original_cell_volume        3693.5(10)
_cod_database_code               4133419
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.922
_shelx_estimated_absorpt_t_min   0.922
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl2-C68 \\sim Cl1-C68 \\sim Cl4-C69 \\sim Cl3-C69
 with sigma of 0.01
 O13-C72 \\sim O13-C71 \\sim O14-C75 \\sim O14-C76 \\sim O15-C79 \\sim O15-C80
 with sigma of 0.01
 C73-C72 \\sim C71-C70 \\sim C74-C75 \\sim C77-C76 \\sim C79-C78 \\sim C80-C81
 with sigma of 0.01
 Cl1-Cl2 \\sim Cl3-Cl4
 with sigma of 0.01
3. Others
 Sof(O5)=Sof(N3)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H3BC)=Sof(H3BD)=Sof(C7)=
 Sof(H7A)=Sof(H7B)=1-FVAR(1)
 Sof(O7)=Sof(N1)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H3AA)=Sof(H3AB)=Sof(C4)=
 Sof(H4A)=Sof(H4B)=FVAR(1)
 Sof(C73)=Sof(C70)=Sof(O13)=Sof(C71)=Sof(C72)=FVAR(2)
 Sof(C74)=Sof(O14)=Sof(C75)=Sof(C76)=Sof(C77)=FVAR(3)
 Sof(C81)=Sof(C78)=Sof(O15)=Sof(C79)=Sof(C80)=FVAR(4)
 Sof(Cl3)=Sof(C69)=Sof(Cl4)=FVAR(5)
4.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C5(H5A,H5B), C3(H3BC,H3BD), C3(H3AA,H3AB), C7(H7A,H7B), C4(H4A,
 H4B), C68(H68A,H68B)
4.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C26(H26), C30(H30), C31(H31), C62(H62), C34(H34), C48(H48),
 C37(H37), C52(H52), C23(H23), C46(H46), C19(H19), C40(H40), C47(H47), C14(H14),
  C54(H54), C32(H32), C33(H33), C42(H42), C60(H60), C51(H51), C59(H59),
 C35(H35), C57(H57), C58(H58), C43(H43), C24(H24), C64(H64), C45(H45), C66(H66),
  C25(H25), C13(H13), C20(H20), C41(H41), C36(H36), C53(H53), C21(H21),
 C12(H12), C22(H22)
4.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              74517
_shelx_hkl_checksum              393
_olex2_submission_special_instructions 'No special instructions were received'