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_4122735
_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
'C69 H62 Ca Mn3 N10 O11, C F3 O3 S, 3.62(C6 H6), 0.55(C4 H10 O), O'
_chemical_formula_sum            'C93.91 H91.19 Ca F3 Mn3 N10 O15.55 S'
_chemical_formula_weight         1902.55
_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                101.260(3)
_cell_angle_beta                 102.405(3)
_cell_angle_gamma                102.535(3)
_cell_formula_units_Z            2
_cell_length_a                   13.9463(15)
_cell_length_b                   16.9456(18)
_cell_length_c                   21.456(2)
_cell_measurement_reflns_used    9882
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      23.46
_cell_measurement_theta_min      2.18
_cell_volume                     4676.1(8)
_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 0.695
_diffrn_measured_fraction_theta_max 0.999
_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  0.1394
_diffrn_reflns_av_unetI/netI     0.1073
_diffrn_reflns_Laue_measured_fraction_full 0.695
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            74550
_diffrn_reflns_point_group_measured_fraction_full 0.695
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         22.212
_diffrn_reflns_theta_min         1.553
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.549
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8592
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/2 (Bruker,2014) was used for absorption correction. wR2(int) was 0.0882 before and 0.0719 after correction. The Ratio of minimum to maximum transmission is 0.8592. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.351
_exptl_crystal_description       plate
_exptl_crystal_F_000             1932
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.810
_refine_diff_density_min         -0.714
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1431
_refine_ls_number_reflns         11789
_refine_ls_number_restraints     3076
_refine_ls_restrained_S_all      0.958
_refine_ls_R_factor_all          0.1404
_refine_ls_R_factor_gt           0.0760
_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^)+(0.1048P)^2^+18.6537P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1878
_refine_ls_wR_factor_ref         0.2244
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7050
_reflns_number_total             11789
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja508160x_si_004.cif
_cod_data_source_block           a14035
_cod_depositor_comments
'Adding full bibliography for 4122734--4122736.cif.'
_cod_original_cell_volume        4676.2(8)
_cod_database_code               4122735
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.927
_shelx_estimated_absorpt_t_min   0.884
_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. Restrained planarity
 C11U, C12U, C13U, C14U, C15U, C16U
 with sigma of 0.1
 C11V, C12V, C13V, C14V, C15V, C16V
 with sigma of 0.1
 C21U, C22U, C23U, C24U, C25U, C26U
 with sigma of 0.1
 C21V, C22V, C23V, C24V, C25V, C26V
 with sigma of 0.1
 C31U, C32U, C33U, C34U, C35U, C36U
 with sigma of 0.1
 C41U, C42U, C43U, C44U, C45U, C46U
 with sigma of 0.1
 C41V, C42V, C43V, C44V, C45V, C46V
 with sigma of 0.1
 C31W, C32W, C33W, C34W, C35W, C36W
 with sigma of 0.1
3. Rigid bond restraints
 C11U, C12U, C13U, C14U, C15U, C16U, C11V, C12V, C13V, C14V, C15V, C16V, C21U,
 C22U, C23U, C24U, C25U, C26U, C21V, C22V, C23V, C24V, C25V, C26V, C31U, C32U,
 C33U, C34U, C35U, C36U, C41U, C42U, C43U, C44U, C45U, C46U, C41V, C42V, C43V,
 C44V, C45V, C46V, O1W, C11W, C12W, C13W, C14W, O2W, C21W, C22W, C23W, C24W,
 C31W, C32W, C33W, C34W, C35W, C36W
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
C11U \\sim C12U \\sim C13U \\sim C14U \\sim C15U \\sim C16U \\sim C11V \\sim
C12V \\sim C13V \\sim C14V \\sim C15V \\sim C16V \\sim C21U \\sim C22U \\sim
C23U \\sim C24U \\sim C25U \\sim C26U \\sim C21V \\sim C22V \\sim C23V \\sim
C24V \\sim C25V \\sim C26V \\sim C31U \\sim C32U \\sim C33U \\sim C34U \\sim
C35U \\sim C36U \\sim C41U \\sim C42U \\sim C43U \\sim C44U \\sim C45U \\sim
C46U \\sim C41V \\sim C42V \\sim C43V \\sim C44V \\sim C45V \\sim C46V \\sim
O1W \\sim C11W \\sim C12W \\sim C13W \\sim C14W \\sim O2W \\sim C21W \\sim C22W
\\sim C23W \\sim C24W \\sim C31W \\sim C32W \\sim C33W \\sim C34W \\sim C35W
\\sim C36W: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(O1W) = Uanis(C11W) = Uanis(C12W) = Uanis(C13W) = Uanis(C14W)
5. Same fragment restrains
{C12U, C13U, C14U, C15U, C16U, C11U}
as
{C11U, C12U, C13U, C14U, C15U, C16U}
{C11U, C12U, C13U, C14U, C15U, C16U}
as
{C11V, C12V, C13V, C14V, C15V, C16V}
{C11U, C12U, C13U, C14U, C15U, C16U}
as
{C21U, C22U, C23U, C24U, C25U, C26U}
{C11U, C12U, C13U, C14U, C15U, C16U}
as
{C21V, C22V, C23V, C24V, C25V, C26V}
{C11U, C12U, C13U, C14U, C15U, C16U}
as
{C31U, C32U, C33U, C34U, C35U, C36U}
{C11U, C12U, C13U, C14U, C15U, C16U}
as
{C41U, C42U, C43U, C44U, C45U, C46U}
{C11U, C12U, C13U, C14U, C15U, C16U}
as
{C41V, C42V, C43V, C44V, C45V, C46V}
{O1W, C13W, C14W, C11W, C12W}
{O2W, C21W, C22W, C23W, C24W}
as
{O1W, C11W, C12W, C13W, C14W}
{C11U, C12U, C13U, C14U, C15U, C16U}
as
{C31W, C32W, C33W, C34W, C35W, C36W}
6. Others
 1*[Sof(O1W)+Sof(C11W)+Sof(H11A)+Sof(H11B)+Sof(C12W)+Sof(H12A)+Sof(H12B)+
 Sof(H12C)+Sof(C13W)+Sof(H13A)+Sof(H13B)+Sof(C14W)+Sof(H14A)+Sof(H14B)+
 Sof(H14C)]+1*[Sof(O2W)+Sof(C21W)+Sof(H21A)+Sof(H21B)+Sof(C22W)+Sof(H22A)+
 Sof(H22B)+Sof(H22C)+Sof(C23W)+Sof(H23A)+Sof(H23B)+Sof(C24W)+Sof(H24A)+
 Sof(H24B)+Sof(H24C)]+1*[Sof(C21U)+Sof(H21U)+Sof(C22U)+Sof(H22U)+Sof(C23U)+
 Sof(H23U)+Sof(C24U)+Sof(H24U)+Sof(C25U)+Sof(H25U)+Sof(C26U)+Sof(H26U)+
 Sof(C21V)+Sof(H21V)+Sof(C22V)+Sof(H22V)+Sof(C23V)+Sof(H23V)+Sof(C24V)+
 Sof(H24V)+Sof(C25V)+Sof(H25V)+Sof(C26V)+Sof(H26V)+Sof(C31W)+Sof(H31W)+
 Sof(C32W)+Sof(H32W)+Sof(C33W)+Sof(H33W)+Sof(C34W)+Sof(H34W)+Sof(C35W)+
 Sof(H35W)+Sof(C36W)+Sof(H36W)]=1 with esd of 0
 Sof(O1W)=Sof(C11W)=Sof(H11A)=Sof(H11B)=Sof(C12W)=Sof(H12A)=Sof(H12B)=
 Sof(H12C)=Sof(C13W)=Sof(H13A)=Sof(H13B)=Sof(C14W)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=FVAR(1)
 Sof(O2W)=Sof(C21W)=Sof(H21A)=Sof(H21B)=Sof(C22W)=Sof(H22A)=Sof(H22B)=
 Sof(H22C)=Sof(C23W)=Sof(H23A)=Sof(H23B)=Sof(C24W)=Sof(H24A)=Sof(H24B)=
 Sof(H24C)=FVAR(2)
 Sof(C21U)=Sof(H21U)=Sof(C22U)=Sof(H22U)=Sof(C23U)=Sof(H23U)=Sof(C24U)=
 Sof(H24U)=Sof(C25U)=Sof(H25U)=Sof(C26U)=Sof(H26U)=1-FVAR(3)
 Sof(C21V)=Sof(H21V)=Sof(C22V)=Sof(H22V)=Sof(C23V)=Sof(H23V)=Sof(C24V)=
 Sof(H24V)=Sof(C25V)=Sof(H25V)=Sof(C26V)=Sof(H26V)=Sof(C31W)=Sof(H31W)=
 Sof(C32W)=Sof(H32W)=Sof(C33W)=Sof(H33W)=Sof(C34W)=Sof(H34W)=Sof(C35W)=
 Sof(H35W)=Sof(C36W)=Sof(H36W)=FVAR(3)
 Sof(C11V)=Sof(H11V)=Sof(C12V)=Sof(H12V)=Sof(C13V)=Sof(H13V)=Sof(C14V)=
 Sof(H14V)=Sof(C15V)=Sof(H15V)=Sof(C16V)=Sof(H16V)=1-FVAR(4)
 Sof(C11U)=Sof(H11U)=Sof(C12U)=Sof(H12U)=Sof(C13U)=Sof(H13U)=Sof(C14U)=
 Sof(H14U)=Sof(C15U)=Sof(H15U)=Sof(C16U)=Sof(H16U)=FVAR(4)
 Sof(C41V)=Sof(H41V)=Sof(C42V)=Sof(H42V)=Sof(C43V)=Sof(H43V)=Sof(C44V)=
 Sof(H44V)=Sof(C45V)=Sof(H45V)=Sof(C46V)=Sof(H46V)=0.5*(1-FVAR(6))
 Sof(C41U)=Sof(H41U)=Sof(C42U)=Sof(H42U)=Sof(C43U)=Sof(H43U)=Sof(C44U)=
 Sof(H44U)=Sof(C45U)=Sof(H45U)=Sof(C46U)=Sof(H46U)=0.5*FVAR(6)
 Sof(C31U)=Sof(H31U)=Sof(C32U)=Sof(H32U)=Sof(C33U)=Sof(H33U)=Sof(C34U)=
 Sof(H34U)=Sof(C35U)=Sof(H35U)=Sof(C36U)=Sof(H36U)=FVAR(5)
7.a Secondary CH2 refined with riding coordinates:
 C75(H75A,H75B), C77(H77A,H77B), C78(H78A,H78B), C80(H80A,H80B), C11W(H11A,
 H11B), C13W(H13A,H13B), C21W(H21A,H21B), C23W(H23A,H23B)
7.b Me refined with riding coordinates:
 C12W(H12A,H12B,H12C), C14W(H14A,H14B,H14C), C22W(H22A,H22B,H22C), C24W(H24A,
 H24B,H24C)
7.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C13(H13), C14(H14), C15(H15), C16(H16), C42(H42),
 C43(H43), C44(H44), C45(H45), C47(H47), C48(H48), C49(H49), C50(H50), C23(H23),
  C24(H24), C25(H25), C26(H26), C52(H52), C53(H53), C54(H54), C55(H55),
 C57(H57), C58(H58), C59(H59), C60(H60), C33(H33), C34(H34), C35(H35), C36(H36),
  C62(H62), C63(H63), C64(H64), C65(H65), C67(H67), C68(H68), C69(H69),
 C70(H70), C11U(H11U), C12U(H12U), C13U(H13U), C14U(H14U), C15U(H15U),
 C16U(H16U), C11V(H11V), C12V(H12V), C13V(H13V), C14V(H14V), C15V(H15V),
 C16V(H16V), C21U(H21U), C22U(H22U), C23U(H23U), C24U(H24U), C25U(H25U),
 C26U(H26U), C21V(H21V), C22V(H22V), C23V(H23V), C24V(H24V), C25V(H25V),
 C26V(H26V), C31U(H31U), C32U(H32U), C33U(H33U), C34U(H34U), C35U(H35U),
 C36U(H36U), C41U(H41U), C42U(H42U), C43U(H43U), C44U(H44U), C45U(H45U),
 C46U(H46U), C41V(H41V), C42V(H42V), C43V(H43V), C44V(H44V), C45V(H45V),
 C46V(H46V), C31W(H31W), C32W(H32W), C33W(H33W), C34W(H34W), C35W(H35W),
 C36W(H36W)
7.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)
;
_olex2_submission_special_instructions 'No special instructions were received'