Artificial synthetic Mn(IV)Ca-oxido complexes mimic the oxygen-evolving complex in photosystem II.
Chen, Changhui; Zhang, Chunxi; Dong, Hongxing; Zhao, Jingquan; Dalton transactions (Cambridge, England : 2003) 44 (2015) 4431–4435; doi:10.1039/c4dt03459g

data_7033848
_publ_section_title
;
 Artificial synthetic Mn(IV)Ca-oxido complexes mimic the oxygen-evolving
 complex in photosystem II.
;
_journal_issue                   10
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              4431
_journal_page_last               4435
_journal_paper_doi               10.1039/c4dt03459g
_journal_volume                  44
_journal_year                    2015
_chemical_formula_moiety         'C50 H98 Ca2 Mn6 O33,5(C5 H10 O2),C6 H14'
_chemical_formula_sum            'C81 H162 Ca2 Mn6 O43'
_chemical_formula_weight         2233.90
_chemical_name_systematic
;
 ?
;
_chemical_properties_physical
'Moisture-sensitive, Hygroscopic, Efflorescent'
_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   mixed
_audit_creation_date             2014-06-23
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_audit_update_record
;
2015-01-27 deposited with the CCDC.
2015-01-29 downloaded from the CCDC.
;
_cell_angle_alpha                93.680(2)
_cell_angle_beta                 97.730(3)
_cell_angle_gamma                112.599(3)
_cell_formula_units_Z            2
_cell_length_a                   14.878(3)
_cell_length_b                   15.831(3)
_cell_length_c                   26.221(5)
_cell_measurement_reflns_used    18286
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.4852
_cell_measurement_theta_min      1.4046
_cell_volume                     5604.4(19)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2013)'
_computing_structure_solution
;
'SHELXS (Sheldrick, 2013)'
;
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.968
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device
;
Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'MM007-HF CCD(Saturn 724+)'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      -0.0124
_diffrn_orient_matrix_UB_12      0.0053
_diffrn_orient_matrix_UB_13      0.0727
_diffrn_orient_matrix_UB_21      0.0439
_diffrn_orient_matrix_UB_22      0.0423
_diffrn_orient_matrix_UB_23      0.0323
_diffrn_orient_matrix_UB_31      -0.0229
_diffrn_orient_matrix_UB_32      0.0313
_diffrn_orient_matrix_UB_33      0.0006
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0748
_diffrn_reflns_av_unetI/netI     0.1045
_diffrn_reflns_Laue_measured_fraction_full 0.968
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            42124
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.522
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0000
_diffrn_source_power             1.2000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    0.825
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.5986
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.324
_exptl_crystal_description       block
_exptl_crystal_F_000             2364
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.434
_refine_diff_density_min         -1.156
_refine_diff_density_rms         0.134
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1210
_refine_ls_number_reflns         19641
_refine_ls_number_restraints     231
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.1148
_refine_ls_R_factor_gt           0.0907
_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^)+(0.1228P)^2^+12.8794P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2389
_refine_ls_wR_factor_ref         0.2570
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14392
_reflns_number_total             19641
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4dt03459g2.cif
_cod_data_source_block           ComplexA
_cod_depositor_comments
'Adding full bibliography for 7033847--7033849.cif.'
_cod_original_cell_volume        5604(2)
_cod_database_code               7033848
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.887
_shelx_estimated_absorpt_t_min   0.853
_diffrn_number_total             25507
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All O(H) groups, {H5A,H5B,H5C} of C5, {H4A,H4B,H4C} of C4, {H3A,H3B,H3C} of
  C3, {H29A,H29B,H29C} of C29, {H28A,H28B,H28C} of C28, {H25A,H25B,H25C} of C25,
   {H24C,H24D,H24E} of C24, {H23C,H23D,H23E} of C23, {H20A,H20B,H20C} of C20,
  {H19A,H19B,H19C} of C19, {H15A,H15B,H15C} of C15, {H14A,H14B,H14C} of C14,
  {H13A,H13B,H13C} of C13, {H10A,H10B,H10C} of C10, {H9A,H9B,H9C} of C9, {H8A,
  H8B,H8C} of C8, {H43A,H43B,H43C} of C43, {H40A,H40B,H40C} of C40, {H39A,H39B,
  H39C} of C39, {H38A,H38B,H38C} of C38, {H35A,H35B,H35C} of C35, {H34A,H34B,
  H34C} of C34, {H33A,H33B,H33C} of C33, {H30A,H30B,H30C} of C30, {H44A,H44B,
  H44C} of C44, {H60A,H60B,H60C} of C60, {H59A,H59B,H59C} of C59, {H58A,H58B,
  H58C} of C58, {H55A,H55B,H55C} of C55, {H54A,H54B,H54C} of C54, {H53A,H53B,
  H53C} of C53, {H50A,H50B,H50C} of C50, {H49A,H49B,H49C} of C49, {H48A,H48B,
  H48C} of C48, {H45A,H45B,H45C} of C45, {H75A,H75B,H75C} of C75, {H60D,H60E,
  H60F} of C60A, {H59D,H59E,H59F} of C59A, {H58D,H58E,H58F} of C58A, {H69A,H69B,
  H69C} of C69, {H68A,H68B,H68C} of C68, {H65A,H65B,H65C} of C65, {H70A,H70B,
  H70C} of C70, {H73A,H73B,H73C} of C73, {H74A,H74B,H74C} of C74, {H64A,H64B,
  H64C} of C64, {H63A,H63B,H63C} of C63, All O(H,H) groups
 At 1.2 times of:
  {H18A,H18B,H18C} of C18
2. Restrained distances
 C60-C57 = C60A-C57 = C58A-C57 = C58-C57 = C59A-C57 = C59-C57
 1.54 with sigma of 0.01
 C19-C17 = C18-C17 = C20-C17
 1.54 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C17) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C18)
\\sim Ueq, Uanis(C60A) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C58A) \\sim Ueq,
Uanis(C58) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C59A) \\sim Ueq, Uanis(C38)
\\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C55) \\sim Ueq,
Uanis(C53) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C74)
\\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C72) \\sim Ueq,
Uanis(C15) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C12)
\\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C64) \\sim Ueq,
Uanis(C63) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C67)
\\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C7) \\sim Ueq,
Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Sof(C58A)=Sof(H58D)=Sof(H58E)=Sof(H58F)=Sof(C59A)=Sof(H59D)=Sof(H59E)=
 Sof(H59F)=Sof(C60A)=Sof(H60D)=Sof(H60E)=Sof(H60F)=1-FVAR(1)
 Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=
 Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=FVAR(1)
5.a Riding coordinates:
 O22(H22A,H22B), O24(H24A,H24B), C19(H19A,H19B,H19C), C58(H58A,H58B,H58C),
 C18(H18A,H18B,H18C)
5.b Rotating group:
 O21(H21A,H21B), O23(H23A,H23B)
5.c Me refined with riding coordinates:
 C14(H14A,H14B,H14C), C48(H48A,H48B,H48C), C58A(H58D,H58E,H58F)
5.d Tetrahedral OH refined with riding coordinates:
 O35(H35), O38(H38)
5.e Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C8(H8A,H8B,H8C), C9(H9A,
 H9B,H9C), C10(H10A,H10B,H10C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C),
 C20(H20A,H20B,H20C), C23(H23C,H23D,H23E), C24(H24C,H24D,H24E), C25(H25A,H25B,
 H25C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C33(H33A,
 H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C38(H38A,H38B,H38C),
 C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C43(H43A,H43B,H43C), C44(H44A,H44B,
 H44C), C45(H45A,H45B,H45C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C53(H53A,
 H53B,H53C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C59(H59A,H59B,H59C),
 C60(H60A,H60B,H60C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C65(H65A,H65B,
 H65C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C73(H73A,
 H73B,H73C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C59A(H59D,H59E,H59F),
 C60A(H60D,H60E,H60F)
5.f Idealised tetrahedral OH refined as rotating group:
 O37(H37), O41(H41), O43(H43)
;
_shelx_res_checksum              83697