From cubane-assembled Mn-oxo clusters to monodispersed manganese oxide colloidal nanocrystals.
He, Yan; Liu, Yang; Zheng, Huijuan; Xiang, Zhen; Zhou, Zheng; Geng, Fengting; Geng, Longlong; Dikarev, Evgeny V.; Han, Haixiang; Chemical science 15 (2024) 10381–10391; doi:10.1039/d4sc01451k

data_1571813
_publ_section_title
;
 From cubane-assembled Mn-oxo clusters to monodispersed manganese oxide
 colloidal nanocrystals.
;
_journal_issue                   27
_journal_name_full               'Chemical science'
_journal_page_first              10381
_journal_page_last               10391
_journal_paper_doi               10.1039/d4sc01451k
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C64 H139 Mn18 N O49, C H4 O, 8[CH3OH]'
_chemical_formula_sum            'C73 H175 Mn18 N O58'
_chemical_formula_weight         2984.05
_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   mixed
_audit_creation_date             2024-01-12
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-01-12 deposited with the CCDC.	2024-06-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.465(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.7116(5)
_cell_length_b                   31.6354(5)
_cell_length_c                   23.4460(5)
_cell_measurement_reflns_used    1587
_cell_measurement_temperature    150
_cell_measurement_theta_max      30.820
_cell_measurement_theta_min      1.963
_cell_volume                     11613.1(5)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.825
_diffrn_measurement_device_type  'multiwire proportional'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0770
_diffrn_reflns_av_unetI/netI     0.0650
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.825
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            153634
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.825
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.820
_diffrn_reflns_theta_min         2.142
_exptl_absorpt_coefficient_mu    1.971
_exptl_absorpt_correction_T_max  0.889
_exptl_absorpt_correction_T_min  0.790
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'clear black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.707
_exptl_crystal_description       block
_exptl_crystal_F_000             6136
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.915
_refine_diff_density_min         -1.432
_refine_diff_density_rms         0.169
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1411
_refine_ls_number_reflns         30057
_refine_ls_number_restraints     781
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.1447
_refine_ls_R_factor_gt           0.0958
_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^)+(0.0996P)^2^+134.5343P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2399
_refine_ls_wR_factor_ref         0.2714
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18805
_reflns_number_total             30057
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01451k2.cif
_cod_data_source_block           hh
_cod_depositor_comments
'Adding full bibliography for 1571813--1571814.cif.'
_cod_database_code               1571813
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.891
_shelx_estimated_absorpt_t_min   0.798
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O21-H21
 0.87 with sigma of 0.01
 O47-H47
 0.87 with sigma of 0.01
 Mn0G-H21
 2.800097 with sigma of 0.02
 C70-H47
 1.895604 with sigma of 0.02
 C28-H21
 1.917016 with sigma of 0.02
 Mn0I-H47
 2.800327 with sigma of 0.02
 C22-C15 \\sim C22-C11 \\sim C22-C45 \\sim C15-C11 \\sim C15-C45 \\sim C11-C45
 with sigma of 0.04
 C7-C22 \\sim C7-C15 \\sim C7-C11 \\sim C7-C45
 with sigma of 0.02
 C7-C15 \\sim C7-C19
 with sigma of 0.02
 C7-C11 \\sim C7-C75
 with sigma of 0.02
 C7-C45 \\sim C7-C35
 with sigma of 0.02
 C15-C11 \\sim C15-C45 \\sim C11-C45 \\sim C19-C35 \\sim C19-C75 \\sim C35-C75
 with sigma of 0.04
 C7-C22 \\sim C7-C15 \\sim C7-C11 \\sim C7-C45 \\sim C7-C19 \\sim C7-C35 \\sim
C7-C75
 with sigma of 0.02
 C4-C1 \\sim C10-C8
 with sigma of 0.02
 C4-C6 \\sim C8-C6
 with sigma of 0.02
 Mn0I-N022 \\sim Mn0I-N0
 with sigma of 0.02
 N022-C1 \\sim N0-C17
 with sigma of 0.02
 N022-C10 \\sim N0-C2
 with sigma of 0.02
 C1-C4 \\sim C17-C67
 with sigma of 0.02
 C10-C8 \\sim C2-C65
 with sigma of 0.02
 C4-C6 \\sim C67-C33
 with sigma of 0.02
 C6-C8 \\sim C33-C65
 with sigma of 0.02
 Mn0I-C1 \\sim Mn0I-C17
 with sigma of 0.04
 Mn0I-C10 \\sim Mn0I-C2
 with sigma of 0.04
 N022-C4 \\sim N0-C67
 with sigma of 0.04
 N022-C8 \\sim N0-C65
 with sigma of 0.04
 C1-C10 \\sim C17-C2
 with sigma of 0.04
 C1-C6 \\sim C17-C33
 with sigma of 0.04
 C10-C6 \\sim C2-C33
 with sigma of 0.04
 C4-C8 \\sim C67-C65
 with sigma of 0.04
 Mn0I-N0 \\sim Mn0I-N022
 with sigma of 0.02
 Mn0G-O9 \\sim Mn0G-O51
 with sigma of 0.02
 O9-C3 \\sim O51-C73
 with sigma of 0.02
 Mn0G-C3 \\sim Mn0G-C73
 with sigma of 0.04
 Mn0G-O51 \\sim Mn0G-O9
 with sigma of 0.02
 O51-C73 \\sim O9-C3
 with sigma of 0.02
 C41-C76 \\sim C71-C76
 with sigma of 0.02
 C76-C43 \\sim C76-C37
 with sigma of 0.02
 C76-C23 \\sim C76-C69
 with sigma of 0.02
 C41-C43 \\sim C41-C23 \\sim C43-C23 \\sim C71-C69 \\sim C71-C37 \\sim C69-C37
 with sigma of 0.04
 C76-C68 \\sim C76-C41 \\sim C76-C43 \\sim C76-C23 \\sim C76-C71 \\sim C76-C69
\\sim C76-C37
 with sigma of 0.02
 Mn0I-C21 \\sim Mn0I-C9
 with sigma of 0.04
 Mn0I-O3 \\sim Mn0I-O25
 with sigma of 0.02
 Mn0I-O47 \\sim Mn0I-O49
 with sigma of 0.02
 C70-O47 \\sim C77-O49
 with sigma of 0.02
 Mn0I-C70 \\sim Mn0I-C77
 with sigma of 0.04
 O49-C77 \\sim O47-C70
 with sigma of 0.02
 Mn0I-O3 \\sim Mn0I-O49 \\sim Mn0I-O47
 with sigma of 0.02
 C60-C78 \\sim C60-C39 \\sim C60-C47 \\sim C78-C47 \\sim C39-C47
 with sigma of 0.04
 C52-C60 \\sim C52-C78 \\sim C52-C39 \\sim C52-C47
 with sigma of 0.02
 Mn0I-O25 \\sim Mn0I-O3
 with sigma of 0.02
 O3-C21 \\sim O25-C9
 with sigma of 0.02
3. Restrained planarity
 N022, C1, C6, C4, C10, C8
 with sigma of 0.1
 C33, C67, C2, C17, C65
 with sigma of 0.1
 C1, C6, C4, C10, C8
 with sigma of 0.1
4. Rigid bond restraints
 C68, C76, C41, C43, C23, C69, C71, C37
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
Mn0G \\sim O9 \\sim C3 \\sim O51 \\sim C73: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
N022 \\sim C1 \\sim C4 \\sim C6 \\sim C8 \\sim N0 \\sim C33 \\sim C67 \\sim C2
\\sim C17 \\sim C65: within 2A with sigma of 0.001 and sigma for terminal atoms
of 0.002 within 2A
C68 \\sim C76 \\sim C41 \\sim C43 \\sim C23 \\sim C69 \\sim C71 \\sim C37:
within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
C9 \\sim C21 \\sim O25 \\sim O3 \\sim Mn0I: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C31 \\sim C72 \\sim C74 \\sim C64 \\sim C58: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
O2 \\sim C22 \\sim O43 \\sim Mn0G \\sim Mn09: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
C10 \\sim N022 \\sim Mn0I \\sim C1 \\sim C4 \\sim C6 \\sim C8: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C12 \\sim C57 \\sim C42 \\sim C27 \\sim C66: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
O36 \\sim C58 \\sim O35: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
6. Rigid body (RIGU) restrains
 C22, C11, C45, C7, C15, C35, C75, C19
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Mn0G, O9, C3, C25, O51, C73
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O9, C3, O51, C73
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N022, C1, C4, C6, C8, N0, C33, C67, C2, C17, C65
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C68, C76, C41, C43, C23, C69, C71, C37
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O3, C21, O25, C9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O47, C70, O49, C77
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C5, O27
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O3, H3, C21, H21A, H21B, H21C, H29A, O25, H25, C9, H9A, H9B, H9C, Mn0I
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C72, C31, C64, C74, C58
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
7. Others
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=1-FVAR(1)
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(1)
 Sof(N0)=Sof(C2)=Sof(H2)=Sof(C65)=Sof(H65)=Sof(C33)=Sof(H33)=Sof(C67)=Sof(H67)=
 Sof(C17)=Sof(H17)=1-FVAR(2)
 Sof(N022)=Sof(C1)=Sof(H1)=Sof(C4)=Sof(H4)=Sof(C6)=Sof(H6)=Sof(C8)=Sof(H8)=
 Sof(C10)=Sof(H10)=FVAR(2)
 Sof(O51)=Sof(H51)=Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=1-FVAR(3)
 Sof(O9)=Sof(H9)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=FVAR(3)
 Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=1-FVAR(4)
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(4)
 Sof(O25)=Sof(H25)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=1-FVAR(5)
 Sof(O3)=Sof(H3)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(5)
 Sof(O49)=Sof(H49)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=1-FVAR(6)
 Sof(O47)=Sof(H47)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=FVAR(6)
8.a Me refined with riding coordinates:
 C50(H50A,H50B,H50C), C5(H5A,H5B,H5C), C21(H21A,H21B,H21C), C9(H9A,H9B,H9C)
8.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C6(H6), C8(H8), C10(H10), C2(H2), C65(H65), C33(H33),
 C67(H67), C17(H17)
8.c Fitted hexagon refined as free rotating group:
 N022(C1,C4,C6,C8,C10), N0(C2,C65,C33,C67,C17)
8.d Tetrahedral OH refined with riding coordinates:
 O3(H3), O25(H25)
8.e Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C20(H20A,H20B,H20C), C24(H24A,H24B,H24C), C26(H26A,H26B,
 H26C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C34(H34A,
 H34B,H34C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C42(H42A,H42B,H42C),
 C44(H44A,H44B,H44C), C46(H46A,H46B,H46C), C48(H48A,H48B,H48C), C54(H54A,H54B,
 H54C), C56(H56A,H56B,H56C), C60(H60A,H60B,H60C), C62(H62A,H62B,H62C), C66(H66A,
 H66B,H66C), C70(H70A,H70B,H70C), C72(H72A,H72B,H72C), C74(H74A,H74B,H74C),
 C78(H78A,H78B,H78C), C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C43(H43A,H43B,
 H43C), C11(H11A,H11B,H11C), C45(H45A,H45B,H45C), C23(H23A,H23B,H23C), C3(H3A,
 H3B,H3C), C25(H25A,H25B,H25C), C53(H53A,H53B,H53C), C55(H55A,H55B,H55C),
 C57(H57A,H57B,H57C), C29(H29A,H29B,H29C), C59(H59A,H59B,H59C), C15(H15A,H15B,
 H15C), C61(H61A,H61B,H61C), C31(H31A,H31B,H31C), C63(H63A,H63B,H63C), C69(H69A,
 H69B,H69C), C35(H35A,H35B,H35C), C71(H71A,H71B,H71C), C73(H73A,H73B,H73C),
 C37(H37A,H37B,H37C), C75(H75A,H75B,H75C), C19(H19A,H19B,H19C), C77(H77A,H77B,
 H77C), C79(H79A,H79B,H79C)
8.f Idealised tetrahedral OH refined as rotating group:
 O15(H15), O9(H9), O49(H49), O51(H51), O1(H1A)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 560 electrons were 
found in a volume of 1588\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
8[CH3OH] per Formula Unit 
which account for 576 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              82941
_shelx_hkl_checksum              76654
_shelx_fab_checksum              42641
_olex2_submission_special_instructions 'No special instructions were received'