Ferrocene-Functionalized Polyoxo-Titanium Cluster for CO2 Photoreduction
Liu, Jing-Jing; Li, Ning; Sun, Jia-Wei; Liu, Jiang; Dong, Long-Zhang; Yao, Su-Juan; Zhang, Lei; Xin, Zhi-Feng; Shi, Jing-Wen; Wang, Jing-Xuan; Li, Shun-Li; Lan, Ya-Qian; ACS Catalysis  (2021) 4510–4519; doi:10.1021/acscatal.0c04495

data_4518587
_publ_section_title
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 Ferrocene-Functionalized Polyoxo-Titanium Cluster for CO2 Photoreduction
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_journal_name_full               'ACS Catalysis'
_journal_page_first              4510
_journal_page_last               4519
_journal_paper_doi               10.1021/acscatal.0c04495
_journal_year                    2021
_chemical_formula_moiety         'C90 H122 Fe4 N2 O36 Ti8, 4(C3 H8 O)'
_chemical_formula_sum            'C102 H154 Fe4 N2 O40 Ti8'
_chemical_formula_weight         2654.86
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-07-26
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.16 svn.r6f6c53a7 for OlexSys, GUI svn.r6139)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.699(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.3397(16)
_cell_length_b                   15.543(2)
_cell_length_c                   34.356(5)
_cell_measurement_reflns_used    8338
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      25.26
_cell_measurement_theta_min      2.21
_cell_volume                     6588.9(15)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 2016)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.966
_diffrn_measured_fraction_theta_max 0.963
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0556
_diffrn_reflns_av_unetI/netI     0.0683
_diffrn_reflns_Laue_measured_fraction_full 0.966
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            33825
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.485
_diffrn_reflns_theta_min         1.438
_diffrn_source                   'sealed tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.955
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6339
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0870 before and 0.0542 after correction.
The Ratio of minimum to maximum transmission is 0.8506.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.338
_exptl_crystal_description       rhombohedral
_exptl_crystal_F_000             2760
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.459
_refine_diff_density_min         -0.360
_refine_diff_density_rms         0.083
_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     716
_refine_ls_number_reflns         11774
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.009
_refine_ls_R_factor_all          0.0888
_refine_ls_R_factor_gt           0.0543
_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^)+(0.0923P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1454
_refine_ls_wR_factor_ref         0.1635
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7774
_reflns_number_total             11774
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c04495_si_002.cif
_cod_data_source_block           mo_ti8-Fcdc
_cod_original_cell_volume        6589.0(15)
_cod_database_code               4518587
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.954
_shelx_estimated_absorpt_t_min   0.928
_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, All O(H) groups
2. Restrained distances
 O20-C51
 1.4 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O20) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C48)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
4.a Riding coordinates:
 C48(H48A,H48B,H48C), C50(H50A,H50B,H50C)
4.b Ternary CH refined with riding coordinates:
 C17(H17), C21(H21), C22(H22), C24(H24), C27(H27), C33(H33), C42(H42), C51(H51)
4.c Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C20(H20A,H20B), C26(H26A,H26B), C29(H29A,H29B), C32(H32A,H32B)
4.d Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C8(H8), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16),
 C18(H18), C23(H23), C25(H25), C28(H28), C30(H30), C31(H31), C34(H34), C35(H35)
4.e X=CH2 refined with riding coordinates:
 C43(H43A,H43B)
4.f Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,
 H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C44(H44A,H44B,H44C), C45(H45A,
 H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C)
4.g Idealised tetrahedral OH refined as rotating group:
 O19(H19), O20(H20)
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_shelx_res_checksum              70644
_shelx_hkl_checksum              46056
_shelx_fab_checksum              5632
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'