Accurate assembly of ferrocene-functionalized {Ti22Fc4} clusters with photocatalytic amine oxidation activity.
Han, Er-Meng; Yu, Wei-Dong; Li, Lei-Jiao; Yi, Xiao-Yi; Yan, Jun; Liu, Chao; Chemical communications (Cambridge, England) 57 (2021) 2792–2795; doi:10.1039/d1cc00019e

data_7127902
_publ_section_title
;
 Accurate assembly of ferrocene-functionalized {Ti22Fc4} clusters with
 photocatalytic amine oxidation activity.
;
_journal_issue                   22
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              2792
_journal_page_last               2795
_journal_paper_doi               10.1039/d1cc00019e
_journal_volume                  57
_journal_year                    2021
_chemical_formula_moiety
'C83 H138.125 Fe2 N5 O41 Ti11, C83 H135 Fe2 N7 O39 Ti11'
_chemical_formula_sum            'C166 H273.12 Fe4 N12 O80 Ti22'
_chemical_formula_weight         4994.27
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-01-03
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2021-01-03 deposited with the CCDC.	2021-02-03 downloaded from the CCDC.
;
_cell_angle_alpha                114.7150(10)
_cell_angle_beta                 95.4110(10)
_cell_angle_gamma                91.8360(10)
_cell_formula_units_Z            2
_cell_length_a                   22.0941(6)
_cell_length_b                   22.6404(7)
_cell_length_c                   25.2924(8)
_cell_measurement_reflns_used    2856
_cell_measurement_temperature    120
_cell_measurement_theta_max      69.98
_cell_measurement_theta_min      4.1090
_cell_volume                     11405.8(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      120
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0622
_diffrn_reflns_av_unetI/netI     0.0870
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            118806
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.259
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.2
_diffrn_source_power             0.06
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.048
_exptl_absorpt_correction_T_max  0.732
_exptl_absorpt_correction_T_min  0.321
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.454
_exptl_crystal_description       needle
_exptl_crystal_F_000             5162
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.773
_refine_diff_density_min         -0.948
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2698
_refine_ls_number_reflns         39999
_refine_ls_number_restraints     283
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.1631
_refine_ls_R_factor_gt           0.0858
_refine_ls_shift/su_max          0.084
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1487P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2366
_refine_ls_wR_factor_ref         0.2683
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21135
_reflns_number_total             39999
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc00019e2.cif
_cod_data_source_block           Ti22Fc4
_cod_depositor_comments
'Adding full bibliography for 7127900--7127902.cif.'
_cod_database_code               7127902
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.174
_shelx_estimated_absorpt_t_min   0.094
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H3A,H3B} of C3, {H105,H10D} of C105, {H35,H35A} of C35
 At 1.5 times of:
  All C(H,H,H) groups, {H82A,H82B} of C82
2. Restrained distances
 C35-C36
 1.45 with sigma of 0.01
 C21-C23
 1.45 with sigma of 0.01
 C155-C109
 1.45 with sigma of 0.01
 C83-C85
 1.45 with sigma of 0.01
 C102-C103
 1.45 with sigma of 0.01
 C153-C47
 1.45 with sigma of 0.01
 C82-H82A
 0.87 with sigma of 0.01
 O30-C109
 1.45 with sigma of 0.01
 C13-C15
 1.6 with sigma of 0.01
3. Rigid bond restraints
 C155, C109
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C153, C47
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C150, C149
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C52, C51
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C153, C154
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C1, C3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C109, C155
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C15, C13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C56, C58
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C21, O01E
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C156, C109
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C155 \\sim C109: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.01 within 2A
C153 \\sim C47: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.01 within 2A
C150 \\sim C149: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.01 within 2A
C52 \\sim C51: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.01 within 2A
C153 \\sim C154: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.01 within 2A
C1 \\sim C3: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.01
within 2A
C109 \\sim C155: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.01 within 2A
C15 \\sim C13: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.01 within 2A
C56 \\sim C58: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.01 within 2A
C21 \\sim O01E: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.01 within 2A
C156 \\sim C109: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.01 within 2A
Uanis(C22) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C12)
\\sim Ueq, Uanis(C107) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C28) \\sim Ueq,
Uanis(C91) \\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(C153) \\sim Ueq, Uanis(C154)
\\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C116) \\sim Ueq, Uanis(C117) \\sim Ueq,
Uanis(C118) \\sim Ueq, Uanis(C113) \\sim Ueq, Uanis(C115) \\sim Ueq, Uanis(C52)
\\sim Ueq, Uanis(C109) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C156) \\sim Ueq,
Uanis(C53) \\sim Ueq, Uanis(C157) \\sim Ueq, Uanis(C158) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C13) \\sim Ueq,
Uanis(C3) \\sim Ueq, Uanis(O30) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C14)
\\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(C56) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
5. Others
 Sof(Ti17)=1-FVAR(1)
 Sof(Ti23)=FVAR(1)
 Sof(O18)=Sof(H47A)=Sof(H47B)=Sof(H47C)=1-FVAR(2)
 Sof(O11)=FVAR(2)
 Sof(O31)=1-FVAR(3)
 Sof(O30)=FVAR(3)
 Sof(H10D)=Sof(C158)=Sof(H15P)=Sof(H15Q)=Sof(H15R)=1-FVAR(4)
 Sof(H105)=Sof(C107)=Sof(H10N)=Sof(H10O)=Sof(H10P)=FVAR(4)
 Sof(H35A)=Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(5)
 Sof(H35)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=FVAR(5)
 Sof(C14A)=Sof(H14S)=Sof(H14T)=Sof(H14U)=1-FVAR(6)
 Sof(C14)=Sof(H14P)=Sof(H14Q)=Sof(H14R)=FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C125(H125), C138(H138), C105(H105), C105(H10D), C93(H93), C97(H97), C83(H83),
 C87(H87), C06V(H06V), C120(H120), C103(H103), C90(H90), C064(H064), C141(H141),
  C35(H35), C35(H35A), C54(H54), C7(H7), C29(H29), C33(H33), C27(H27), C25(H25),
  C60(H60), C4(H4), C51(H51)
6.b Aromatic/amide H refined with riding coordinates:
 C110(H110), C111(H111), C131(H131), C136(H136), C129(H129), C134(H134),
 C127(H127), C152(H152), C112(H112), C113(H113), C132(H132), C135(H135),
 C118(H118), C117(H117), C116(H116), C130(H130), C42(H42), C69(H69), C71(H71),
 C44(H44), C43(H43), C65(H65), C66(H66), C67(H67), C40(H40), C46(H46), C68(H68),
  C48(H48), C64(H64), C45(H45), C41(H41), C049(H049)
6.c X=CH2 refined with riding coordinates:
 C3(H3A,H3B)
6.d Idealised Me refined as rotating group:
 C89(H89A,H89B,H89C), C143(H14A,H14B,H14C), C121(H12A,H12B,H12C), C147(H14D,
 H14E,H14F), C102(H10A,H10B,H10C), C47(H47A,H47B,H47C), C86(H86A,H86B,H86C),
 C96(H96A,H96B,H96C), C106(H10E,H10F,H10G), C85(H85A,H85B,H85C), C137(H13A,H13B,
 H13C), C104(H10H,H10I,H10J), C06J(H06A,H06B,H06C), C92(H92A,H92B,H92C),
 C142(H14G,H14H,H14I), C126(H12D,H12E,H12F), C122(H12G,H12H,H12I), C88(H88A,
 H88B,H88C), C99(H99A,H99B,H99C), C146(H14J,H14K,H14L), C124(H12J,H12K,H12L),
 C139(H13D,H13E,H13F), C150(H15A,H15B,H15C), C154(H15D,H15E,H15F), C070(H07A,
 H07B,H07C), C119(H11A,H11B,H11C), C074(H07D,H07E,H07F), C94(H94A,H94B,H94C),
 C91(H91A,H91B,H91C), C101(H10K,H10L,H10M), C84(H84A,H84B,H84C), C140(H14M,H14N,
 H14O), C95(H95A,H95B,H95C), C11(H11D,H11E,H11F), C62(H62A,H62B,H62C), C75(H75A,
 H75B,H75C), C24(H24A,H24B,H24C), C61(H61A,H61B,H61C), C28(H28A,H28B,H28C),
 C34(H34A,H34B,H34C), C78(H78A,H78B,H78C), C5(H5A,H5B,H5C), C8(H8A,H8B,H8C),
 C2(H2A,H2B,H2C), C12(H12M,H12N,H12O), C79(H79A,H79B,H79C), C55(H55A,H55B,H55C),
  C6(H6A,H6B,H6C), C53(H53A,H53B,H53C), C31(H31A,H31B,H31C), C32(H32A,H32B,
 H32C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C23(H23A,H23B,H23C),
 C07A(H07G,H07H,H07I), C74(H74A,H74B,H74C), C37(H37A,H37B,H37C), C26(H26A,H26B,
 H26C), C22(H22A,H22B,H22C), C58(H58A,H58B,H58C), C36(H36A,H36B,H36C), C30(H30A,
 H30B,H30C), C9(H9A,H9B,H9C), C59(H59A,H59B,H59C), C50(H50A,H50B,H50C),
 C52(H52A,H52B,H52C), C107(H10N,H10O,H10P), C155(H15G,H15H,H15I), C156(H15J,
 H15K,H15L), C157(H15M,H15N,H15O), C158(H15P,H15Q,H15R), C36A(H36D,H36E,H36F),
 C14(H14P,H14Q,H14R), C15(H15S,H15T,H15U), C14A(H14S,H14T,H14U)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              16584
_shelx_fab_checksum              73832
_olex2_submission_special_instructions 'No special instructions were received'