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_7129565
_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 Ca Mn5 N12 O10 Si4, 2(C4 H8 O)'
_chemical_formula_sum            'C80 H112 Ca Mn5 N12 O12 Si4'
_chemical_formula_weight         1860.95
_chemical_properties_physical    Air-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 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                90
_cell_angle_beta                 91.079(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.598(4)
_cell_length_b                   16.828(4)
_cell_length_c                   43.150(11)
_cell_measurement_reflns_used    3940
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      19.546
_cell_measurement_theta_min      2.29
_cell_volume                     11324(5)
_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      100.03
_diffrn_detector_area_resol_mean 8.333
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_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  0.1078
_diffrn_reflns_av_unetI/netI     0.0938
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            50837
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        20.936
_diffrn_reflns_theta_max         20.936
_diffrn_reflns_theta_min         1.535
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.680
_exptl_absorpt_correction_T_max  0.7445
_exptl_absorpt_correction_T_min  0.5360
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0815 before and 0.0642 after correction.
The Ratio of minimum to maximum transmission is 0.7199.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.092
_exptl_crystal_description       block
_exptl_crystal_F_000             3892
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.981
_refine_diff_density_min         -0.569
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1195
_refine_ls_number_reflns         11966
_refine_ls_number_restraints     730
_refine_ls_restrained_S_all      0.984
_refine_ls_R_factor_all          0.1111
_refine_ls_R_factor_gt           0.0679
_refine_ls_shift/su_max          0.013
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1030P)^2^+19.0916P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1652
_refine_ls_wR_factor_ref         0.1896
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7754
_reflns_number_total             11966
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc05825h2.cif
_cod_data_source_block           3
_cod_database_code               7129565
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.935
_shelx_estimated_absorpt_t_min   0.727
_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 distances
 O1S-C1S = O1T-C1T = O1T-C4T = O1S-C4S
 1.45 with sigma of 0.02
 C2S-C1S = C2T-C1T = C3S-C2S = C3T-C2T = C4T-C3T = C4S-C3S
 1.54 with sigma of 0.02
 O2T-C8T = O2S-C8S = O2T-C5T = O2S-C5S
 1.45 with sigma of 0.02
 C8S-C7S = C8T-C7T = C7T-C6T = C7S-C6S = C6T-C5T = C6S-C5S
 1.54 with sigma of 0.02
 N7-C37 = N7A-C37A = N7A-C41A = N7-C41
 1.34 with sigma of 0.02
 C41A-C40A = C41-C40 = C40A-C39A = C40-C39 = C39A-C38A = C39-C38 = C38A-C37A =
 C38-C37
 1.39 with sigma of 0.02
 C42A-C41A = C42-C41
 1.5 with sigma of 0.02
 O7-C42A = O7-C42
 1.45 with sigma of 0.02
 Mn2-N7 = Mn2-N7A
 2.27 with sigma of 0.02
 C1T-C4T
 2.29 with sigma of 0.04
 C4S-C1S
 2.29 with sigma of 0.04
 O1S-C2S
 2.44 with sigma of 0.04
 O1S-C3S
 2.44 with sigma of 0.04
 O1T-C2T
 2.44 with sigma of 0.04
 O1T-C3T
 2.44 with sigma of 0.04
 C1T-C3T
 2.52 with sigma of 0.04
 C2T-C4T
 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
 O2S-C7S
 2.44 with sigma of 0.04
 O2S-C6S
 2.44 with sigma of 0.04
 O2T-C6T
 2.44 with sigma of 0.04
 O2T-C7T
 2.44 with sigma of 0.04
 C8T-C5T
 2.29 with sigma of 0.04
 C8S-C5S
 2.29 with sigma of 0.04
 C8T-C6T
 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
 C41A-C37A
 2.32 with sigma of 0.04
 C41-C37
 2.32 with sigma of 0.04
 N7A-C40A
 2.36 with sigma of 0.04
 N7A-C38A
 2.36 with sigma of 0.04
 N7-C40
 2.36 with sigma of 0.04
 N7-C38
 2.36 with sigma of 0.04
 C41A-C39A
 2.41 with sigma of 0.04
 C40A-C38A
 2.41 with sigma of 0.04
 C39A-C37A
 2.41 with sigma of 0.04
 C37-C39
 2.41 with sigma of 0.04
 C38-C40
 2.41 with sigma of 0.04
 C39-C41
 2.41 with sigma of 0.04
 C42A-C40A
 2.5 with sigma of 0.04
 C42-C40
 2.5 with sigma of 0.04
 N7A-C42A
 2.46 with sigma of 0.04
 C42-N7
 2.46 with sigma of 0.04
3. Rigid bond restraints
 O1S, O1T, C1S, C1T, C2S, C2T, C3S, C3T, C4S, C4T
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O2S, O2T, C5S, C5T, C6S, C6T, C7S, C7T, C8S, C8T
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N7, C37, C38, C39, C40, C41, C42, C37A, C38A, N7A, C42A, C40A, C39A, C41A, O7
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O1S \\sim O1T \\sim C1S \\sim C1T \\sim C2S \\sim C2T \\sim C3S \\sim C3T \\sim
C4S \\sim C4T: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
O2S \\sim O2T \\sim C5S \\sim C5T \\sim C6S \\sim C6T \\sim C7S \\sim C7T \\sim
C8S \\sim C8T: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
N7 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C37A \\sim
C38A \\sim N7A \\sim C42A \\sim C40A \\sim C39A \\sim C41A \\sim O7: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N7) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C39)
\\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq,
Uanis(C37A) \\sim Ueq, Uanis(C38A) \\sim Ueq, Uanis(N7A) \\sim Ueq, Uanis(C42A)
\\sim Ueq, Uanis(C40A) \\sim Ueq, Uanis(C39A) \\sim Ueq, Uanis(C41A) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(O1T)=Sof(C1T)=Sof(H1TA)=Sof(H1TB)=Sof(C2T)=Sof(H2TA)=Sof(H2TB)=Sof(C3T)=
 Sof(H3TA)=Sof(H3TB)=Sof(C4T)=Sof(H4TA)=Sof(H4TB)=1-FVAR(1)
 Sof(O1S)=Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(C3S)=
 Sof(H3SA)=Sof(H3SB)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=FVAR(1)
 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)=1-FVAR(2)
 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(C37A)=Sof(H37A)=Sof(C38A)=Sof(H38A)=Sof(N7A)=Sof(C42A)=Sof(H42C)=
 Sof(H42D)=Sof(C40A)=Sof(H40A)=Sof(C39A)=Sof(H39A)=Sof(C41A)=1-FVAR(3)
 Sof(N7)=Sof(C37)=Sof(H37)=Sof(C38)=Sof(H38)=Sof(C39)=Sof(H39)=Sof(C40)=
 Sof(H40)=Sof(C41)=Sof(C42)=Sof(H42A)=Sof(H42B)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB), C1T(H1TA,H1TB), C2S(H2SA,H2SB), C2T(H2TA,H2TB), C3S(H3SA,
 H3SB), C3T(H3TA,H3TB), C4S(H4SA,H4SB), C4T(H4TA,H4TB), C5S(H5SA,H5SB),
 C5T(H5TA,H5TB), C6(H6A,H6B), C6S(H6SA,H6SB), C6T(H6TA,H6TB), C7S(H7SA,H7SB),
 C7T(H7TA,H7TB), C8S(H8SA,H8SB), C8T(H8TA,H8TB), C12(H12A,H12B), C18(H18A,H18B),
  C24(H24A,H24B), C30(H30A,H30B), C36(H36A,H36B), C42(H42A,H42B), C48(H48A,
 H48B), C54(H54A,H54B), C60(H60A,H60B), C42A(H42C,H42D)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), 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), C31(H31), C32(H32), C33(H33), C34(H34),
 C37(H37), C38(H38), C39(H39), C40(H40), C43(H43), C44(H44), C45(H45), C46(H46),
  C49(H49), C50(H50), C51(H51), C52(H52), C55(H55), C56(H56), C57(H57),
 C58(H58), C37A(H37A), C38A(H38A), C40A(H40A), C39A(H39A)
6.c Idealised Me refined as rotating group:
 C61(H61A,H61B,H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,
 H64C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C68(H68A,
 H68B,H68C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C71(H71A,H71B,H71C),
 C72(H72A,H72B,H72C)
;
_shelx_res_checksum              61448
_shelx_fab_checksum              69411
_olex2_submission_special_instructions 'No special instructions were received'