Toward Models for the Full Oxygen-Evolving Complex of Photosystem II by Ligand Coordination To Lower the Symmetry of the Mn3CaO4 Cubane: Demonstration That Electronic Effects Facilitate Binding of a Fifth Metal.
Kanady, Jacob S.; Lin, Po-Heng; Carsch, Kurtis M.; Nielsen, Robert J.; Takase, Michael K.; Goddard, 3rd, William A; Agapie, Theodor; Journal of the American Chemical Society 136 (2014) 14373–; doi:10.1021/ja508160x

data_4122736
_publ_section_title
;
 Toward Models for the Full Oxygen-Evolving Complex of Photosystem II by
 Ligand Coordination To Lower the Symmetry of the Mn3CaO4 Cubane:
 Demonstration That Electronic Effects Facilitate Binding of a Fifth
 Metal.
;
_journal_issue                   41
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14373
_journal_paper_doi               10.1021/ja508160x
_journal_volume                  136
_journal_year                    2014
_chemical_formula_moiety
'C72 H69 Gd Mn3 N11 O12, C F3 O3 S, O, C4 H10 O'
_chemical_formula_sum            'C77 H81 F3 Gd Mn3 N11 O17 S'
_chemical_formula_weight         1843.65
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-08-05
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                88.985(3)
_cell_angle_beta                 89.785(3)
_cell_angle_gamma                69.483(3)
_cell_formula_units_Z            2
_cell_length_a                   14.8835(10)
_cell_length_b                   16.1532(11)
_cell_length_c                   16.7758(11)
_cell_measurement_reflns_used    9971
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.69
_cell_measurement_theta_min      2.31
_cell_volume                     3776.7(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.970
_diffrn_measured_fraction_theta_max 0.881
_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  0.0925
_diffrn_reflns_av_unetI/netI     0.1002
_diffrn_reflns_Laue_measured_fraction_full 0.970
_diffrn_reflns_Laue_measured_fraction_max 0.881
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            75528
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.881
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         26.442
_diffrn_reflns_theta_min         1.461
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.470
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8201
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/2 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.0937 before and 0.0707 after correction.
The Ratio of minimum to maximum transmission is 0.8201.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.621
_exptl_crystal_description       flake
_exptl_crystal_F_000             1876
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.06
_refine_diff_density_max         2.600
_refine_diff_density_min         -1.946
_refine_diff_density_rms         0.162
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1120
_refine_ls_number_reflns         13700
_refine_ls_number_restraints     390
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.1131
_refine_ls_R_factor_gt           0.0650
_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^)+(0.1023P)^2^+6.3832P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1574
_refine_ls_wR_factor_ref         0.1808
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9272
_reflns_number_total             13700
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja508160x_si_002.cif
_cod_data_source_block           a13207
_cod_depositor_comments
'Adding full bibliography for 4122734--4122736.cif.'
_cod_database_code               4122736
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.917
_shelx_estimated_absorpt_t_min   0.701
_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
2. Rigid bond restraints
 O11T, O12T, O13T, S1T, C1T, F11T, F12T, F13T, O21T, O22T, O23T, S2T, C2T,
 F21T, F22T, F23T
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O11S, C11S, C12S, C13S, C14S, O21S, C21S, C22S, C23S, C24S
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
O11T \\sim O12T \\sim O13T \\sim S1T \\sim C1T \\sim F11T \\sim F12T \\sim F13T
\\sim O21T \\sim O22T \\sim O23T \\sim S2T \\sim C2T \\sim F21T \\sim F22T
\\sim F23T: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
O11S \\sim C11S \\sim C12S \\sim C13S \\sim C14S \\sim O21S \\sim C21S \\sim
C22S \\sim C23S \\sim C24S: within 1.7A with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(O11S) = Uanis(C11S) = Uanis(C12S) = Uanis(C13S) = Uanis(C14S)
4. Same fragment restrains
{O21T, O22T, O23T, S2T, C2T, F21T, F22T, F23T}
{O12T, O13T, O11T, S1T, C1T, F12T, F13T, F11T}
as
{O11T, O12T, O13T, S1T, C1T, F11T, F12T, F13T}
{O21S, C21S, C22S, C23S, C24S}
{O11S, C13S, C14S, C11S, C12S}
as
{O11S, C11S, C12S, C13S, C14S}
5. Others
 Sof(O21T)=Sof(O22T)=Sof(O23T)=Sof(S2T)=Sof(C2T)=Sof(F21T)=Sof(F22T)=Sof(F23T)=
 1-FVAR(1)
 Sof(O11T)=Sof(O12T)=Sof(O13T)=Sof(S1T)=Sof(C1T)=Sof(F11T)=Sof(F12T)=Sof(F13T)=
 FVAR(1)
 Sof(O21S)=Sof(C21S)=Sof(H21A)=Sof(H21B)=Sof(C22S)=Sof(H22A)=Sof(H22B)=
 Sof(H22C)=Sof(C23S)=Sof(H23A)=Sof(H23B)=Sof(C24S)=Sof(H24A)=Sof(H24B)=
 Sof(H24C)=1-FVAR(2)
 Sof(O11S)=Sof(C11S)=Sof(H11A)=Sof(H11B)=Sof(C12S)=Sof(H12A)=Sof(H12B)=
 Sof(H12C)=Sof(C13S)=Sof(H13A)=Sof(H13B)=Sof(C14S)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C75(H75A,H75B), C77(H77A,H77B), C78(H78A,H78B), C80(H80A,H80B), C11S(H11A,
 H11B), C13S(H13A,H13B), C21S(H21A,H21B), C23S(H23A,H23B)
6.b Me refined with riding coordinates:
 C12S(H12A,H12B,H12C), C14S(H14A,H14B,H14C), C22S(H22A,H22B,H22C), C24S(H24A,
 H24B,H24C)
6.c 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), C42(H42),
  C43(H43), C44(H44), C45(H45), C47(H47), C48(H48), C49(H49), C50(H50),
 C52(H52), C53(H53), C54(H54), C55(H55), C57(H57), C58(H58), C59(H59), C60(H60),
  C62(H62), C63(H63), C64(H64), C65(H65), C67(H67), C68(H68), C69(H69),
 C70(H70), C83(H83)
6.d Idealised Me refined as rotating group:
 C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C76(H76A,H76B,H76C), C79(H79A,H79B,
 H79C), C82(H82A,H82B,H82C), C84(H84A,H84B,H84C), C85(H85A,H85B,H85C)
;
_olex2_submission_special_instructions 'No special instructions were received'