Hemicubane topological analogs of the oxygen-evolving complex of photosystem II mediating water-assisted propylene carbonate oxidation
Koellner, Connor A.; Gau, Michael; Polyak, Aleksander; Bayana, Manish; Zdilla, Michael John; Chemical Communications  (2022) –; doi:10.1039/D1CC05825H

data_7129564
_publ_section_title
;
 Hemicubane topological analogs of the oxygen-evolving complex of
 photosystem II mediating water-assisted propylene carbonate oxidation
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC05825H
_journal_year                    2022
_chemical_formula_moiety         'C72 H96 Ca2 Mn4 N12 O10 Si4, 5.27(C4 H8 O)'
_chemical_formula_sum            'C93.08 H138.16 Ca2 Mn4 N12 O15.27 Si4'
_chemical_formula_weight         2081.87
_chemical_properties_physical    Air-sensitive
_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
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-09-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-09-18 deposited with the CCDC.	2022-01-12 downloaded from the CCDC.
;
_cell_angle_alpha                79.579(5)
_cell_angle_beta                 73.067(5)
_cell_angle_gamma                83.215(5)
_cell_formula_units_Z            1
_cell_length_a                   13.071(4)
_cell_length_b                   14.016(5)
_cell_length_c                   15.223(5)
_cell_measurement_reflns_used    9221
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.661
_cell_measurement_theta_min      2.799
_cell_volume                     2617.6(15)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'COSMO (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    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      99.97
_diffrn_detector_area_resol_mean 8.333
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_device_type  'Bruker KAPPA APEX II DUO'
_diffrn_measurement_method       '\f, \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0549
_diffrn_reflns_av_unetI/netI     0.0732
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            44632
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.906
_diffrn_reflns_theta_min         1.415
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.680
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6805
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0591 before and 0.0492 after correction.
The Ratio of minimum to maximum transmission is 0.9127.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.321
_exptl_crystal_description       block
_exptl_crystal_F_000             1099
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.161
_refine_diff_density_min         -0.558
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     760
_refine_ls_number_reflns         12166
_refine_ls_number_restraints     698
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.1067
_refine_ls_R_factor_gt           0.0555
_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^)+(0.0754P)^2^+2.3493P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1341
_refine_ls_wR_factor_ref         0.1589
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7689
_reflns_number_total             12166
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc05825h2.cif
_cod_data_source_block           4
_cod_original_cell_volume        2617.7(15)
_cod_database_code               7129564
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.935
_shelx_estimated_absorpt_t_min   0.870
_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
 N1-C5A = N1-C5
 1.34 with sigma of 0.02
 C2A-C1 = C2-C1 = C3A-C2A = C3-C2 = C4A-C3A = C4-C3 = C5A-C4A = C5-C4
 1.39 with sigma of 0.02
 C6A-C5A = C6-C5
 1.5 with sigma of 0.02
 C8T-C5T = C8T-C7T = C7T-C6T = C6S-C5S = C7S-C6S = C8S-C7S = C4T-C3S = C4S-C3S
 = C3S-C2S = C2S-C1S = C9S-C10S = C11S-C10S = C12S-C11S = C9T-C10T = C11T-C10T =
  C12T-C11T
 1.54 with sigma of 0.02
 O2T-C6T = O2T-C5T = O2S-C8S = O2S-C5S = O3T-C9T = O3T-C12T = O3S-C12S = O3S-
 C9S = O1S-C4T = O1S-C4S = O1S-C1S
 1.54 with sigma of 0.02
 O2T-C5T = O2T-C6T = O2S-C5S = O2S-C8S = O1S-C4T = O1S-C4S = O1S-C1S = O3T-C9T
 = O3T-C12T = O3S-C12S = O3S-C9S
 1.45 with sigma of 0.02
 N1-C4A
 2.34 with sigma of 0.04
 N1-C4
 2.34 with sigma of 0.04
 N1-C2A
 2.34 with sigma of 0.04
 N1-C2
 2.34 with sigma of 0.04
 C5A-C1
 2.32 with sigma of 0.04
 C5-C1
 2.32 with sigma of 0.04
 C5A-C3A
 2.41 with sigma of 0.04
 C4A-C2A
 2.41 with sigma of 0.04
 C3A-C1
 2.41 with sigma of 0.04
 C5-C3
 2.41 with sigma of 0.04
 C4-C2
 2.41 with sigma of 0.04
 C3-C1
 2.41 with sigma of 0.04
 C4A-C6A
 2.5 with sigma of 0.04
 C4-C6
 2.5 with sigma of 0.04
 N1-C6A
 2.46 with sigma of 0.04
 N1-C6
 2.46 with sigma of 0.04
 O2S-C7S
 2.44 with sigma of 0.04
 O2S-C6S
 2.44 with sigma of 0.04
 O1S-C3S
 2.44 with sigma of 0.04
 O1S-C2S
 2.44 with sigma of 0.04
 O3T-C11T
 2.44 with sigma of 0.04
 O3T-C10T
 2.44 with sigma of 0.04
 O3S-C11S
 2.44 with sigma of 0.04
 O3S-C10S
 2.44 with sigma of 0.04
 C8S-C5S
 2.29 with sigma of 0.04
 C5T-C6T
 2.29 with sigma of 0.04
 C12T-C9T
 2.29 with sigma of 0.04
 C12S-C9S
 2.29 with sigma of 0.04
 C1S-C4T
 2.29 with sigma of 0.04
 C1S-C4S
 2.29 with sigma of 0.04
 C6T-C8T
 2.52 with sigma of 0.04
 C7T-C5T
 2.52 with sigma of 0.04
 C5S-C7S
 2.52 with sigma of 0.04
 C6S-C8S
 2.52 with sigma of 0.04
 C9T-C11T
 2.52 with sigma of 0.04
 C10T-C12T
 2.52 with sigma of 0.04
 C12S-C10S
 2.52 with sigma of 0.04
 C11S-C9S
 2.52 with sigma of 0.04
 C4T-C2S
 2.52 with sigma of 0.04
 C4S-C2S
 2.52 with sigma of 0.04
 C3S-C1S
 2.52 with sigma of 0.04
3. Restrained planarity
 N1, C1, C2A, C3A, C4A, C5A, C6A
 with sigma of 0.1
 N1, C1, C2, C3, C4, C5, C6
 with sigma of 0.1
4. Rigid bond restraints
 N1, C1, C2, C2A, C3, C3A, C4, C4A, C5, C5A, C6, C6A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O1S, C1S, C2S, C3S, C4S, C4T, O2S, C5S, C6S, C7S, C8S, O2T, C5T, C6T, C7T,
 C8T, O3S, C9S, C10S, C11S, C12S, O3T, C9T, C10T, C11T, C12T
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
N1 \\sim C1 \\sim C2 \\sim C2A \\sim C3 \\sim C3A \\sim C4 \\sim C4A \\sim C5
\\sim C5A \\sim C6 \\sim C6A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
O1S \\sim C1S \\sim C2S \\sim C3S \\sim C4S \\sim C4T \\sim O2S \\sim C5S \\sim
C6S \\sim C7S \\sim C8S \\sim O2T \\sim C5T \\sim C6T \\sim C7T \\sim C8T \\sim
O3S \\sim C9S \\sim C10S \\sim C11S \\sim C12S \\sim O3T \\sim C9T \\sim C10T
\\sim C11T \\sim C12T: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
6. Others
 Sof(H3SC)=Sof(H3SD)=Sof(C4T)=Sof(H4TA)=Sof(H4TB)=1-FVAR(1)
 Sof(H3SA)=Sof(H3SB)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=FVAR(1)
 Sof(O2S)=Sof(C5S)=Sof(H5SA)=Sof(H5SB)=Sof(C6S)=Sof(H6SA)=Sof(H6SB)=Sof(C7S)=
 Sof(H7SA)=Sof(H7SB)=Sof(C8S)=Sof(H8SA)=Sof(H8SB)=FVAR(2)
 Sof(O2T)=Sof(C5T)=Sof(H5TA)=Sof(H5TB)=Sof(C6T)=Sof(H6TA)=Sof(H6TB)=Sof(C7T)=
 Sof(H7TA)=Sof(H7TB)=Sof(C8T)=Sof(H8TA)=Sof(H8TB)=FVAR(3)
 Sof(O3S)=Sof(C9S)=Sof(H9SA)=Sof(H9SB)=Sof(C10S)=Sof(H10A)=Sof(H10B)=Sof(C11S)=
 Sof(H11A)=Sof(H11B)=Sof(C12S)=Sof(H12C)=Sof(H12D)=FVAR(4)
 Sof(O3T)=Sof(C9T)=Sof(H9TA)=Sof(H9TB)=Sof(C10T)=Sof(H10C)=Sof(H10D)=Sof(C11T)=
 Sof(H11C)=Sof(H11D)=Sof(C12T)=Sof(H12E)=Sof(H12F)=FVAR(5)
 Sof(H1B)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=1-FVAR(6)
 Sof(H1A)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(C6)=
 Sof(H6B)=Sof(H6A)=FVAR(6)
7.a Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB), C2S(H2SA,H2SB), C3S(H3SA,H3SB), C3S(H3SC,H3SD), C4S(H4SA,
 H4SB), C4T(H4TA,H4TB), C5S(H5SA,H5SB), C6S(H6SA,H6SB), C7S(H7SA,H7SB),
 C8S(H8SA,H8SB), C5T(H5TA,H5TB), C6T(H6TA,H6TB), C7T(H7TA,H7TB), C8T(H8TA,H8TB),
  C9S(H9SA,H9SB), C10S(H10A,H10B), C11S(H11A,H11B), C12S(H12C,H12D), C9T(H9TA,
 H9TB), C10T(H10C,H10D), C11T(H11C,H11D), C12T(H12E,H12F), C6(H6B,H6A),
 C6A(H6AA,H6AB), C12(H12A,H12B), C18(H18A,H18B), C24(H24A,H24B), C30(H30A,H30B)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1A), C1(H1B), C2(H2), C2A(H2A), C3(H3), C3A(H3A), C4(H4), C4A(H4A),
 C7(H7), C8(H8), C9(H9), C10(H10), C13(H13), C14(H14), C15(H15), C16(H16),
 C19(H19), C20(H20), C21(H21), C22(H22), C25(H25), C26(H26), C27(H27), C28(H28)
7.c Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,
 H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C)
;
_shelx_res_checksum              26618
_olex2_submission_special_instructions 'No special instructions were received'