Atomically accurate site-specific ligand tailoring of highly acid- and alkali-resistant Ti(iv)-based metallamacrocycle for enhanced CO<sub>2</sub> photoreduction.
Tian, Yi-Qi; Dai, Lin-Fang; Mu, Wen-Lei; Yu, Wei-Dong; Yan, Jun; Liu, Chao; Chemical science 14 (2023) 14280–14289; doi:10.1039/d3sc06046b

data_1570458
_publ_section_title
;
 Atomically accurate site-specific ligand tailoring of highly acid- and
 alkali-resistant Ti(iv)-based metallamacrocycle for enhanced
 CO<sub>2</sub> photoreduction.
;
_journal_issue                   48
_journal_name_full               'Chemical science'
_journal_page_first              14280
_journal_page_last               14289
_journal_paper_doi               10.1039/d3sc06046b
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety
'C360 H416 O66.8 Ti16, 8(H2 O), 48[H2O], 3[H2O], 5[H2O]'
_chemical_formula_sum            'C360 H432 O74.81 Ti16'
_chemical_formula_weight         6722.31
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-03-26
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-08-09 deposited with the CCDC.	2023-11-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.837(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   38.634(3)
_cell_length_b                   32.619(3)
_cell_length_c                   37.291(3)
_cell_measurement_reflns_used    9949
_cell_measurement_temperature    180.0
_cell_measurement_theta_max      47.77
_cell_measurement_theta_min      2.19
_cell_volume                     42648(6)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      180.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.956
_diffrn_measured_fraction_theta_max 0.956
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0952
_diffrn_reflns_av_unetI/netI     0.1187
_diffrn_reflns_Laue_measured_fraction_full 0.956
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            86608
_diffrn_reflns_point_group_measured_fraction_full 0.956
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        47.479
_diffrn_reflns_theta_max         47.479
_diffrn_reflns_theta_min         2.379
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           2.86
_diffrn_source_power             0.19977099999999998
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           69.85
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.865
_exptl_absorpt_correction_T_max  0.7495
_exptl_absorpt_correction_T_min  0.4646
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1557 before and 0.0771 after correction.
The Ratio of minimum to maximum transmission is 0.6199.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.047
_exptl_crystal_description       block
_exptl_crystal_F_000             14170
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.981
_refine_diff_density_min         -0.471
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.992
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2094
_refine_ls_number_reflns         28360
_refine_ls_number_restraints     369
_refine_ls_restrained_S_all      1.009
_refine_ls_R_factor_all          0.1727
_refine_ls_R_factor_gt           0.1242
_refine_ls_shift/su_max          0.066
_refine_ls_shift/su_mean         0.003
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^+200.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3362
_refine_ls_wR_factor_ref         0.3708
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15975
_reflns_number_total             28360
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06046b2.cif
_cod_data_source_block           Ti16L4-1-H3PO4
_cod_depositor_comments
'Adding full bibliography for 1570454--1570469.cif.'
_cod_original_cell_volume        42646(6)
_cod_database_code               1570458
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.605
_shelx_estimated_absorpt_t_min   0.456
_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,H) groups
2. Restrained distances
 C5-C66
 2.3 with sigma of 0.01
 C66-C74
 1.45 with sigma of 0.01
 H8B-H11G
 2 with sigma of 0.01
 H18A-H13
 2 with sigma of 0.01
 C24-C23
 1.55 with sigma of 0.01
 H12C-H114
 2 with sigma of 0.01
 H24C-H27
 2 with sigma of 0.01
 H111-H13L
 2 with sigma of 0.01
 C130-C128
 1.45 with sigma of 0.01
 C127-C128
 1.45 with sigma of 0.01
 H80-H85C
 2 with sigma of 0.01
 H13L-H111
 2 with sigma of 0.01
 C128-C129
 1.45 with sigma of 0.02
 H12L-H12M
 2 with sigma of 0.01
 C128-C57
 1.55 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
O2: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C5 \\sim C66 \\sim C74 \\sim C134: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C25 \\sim C24 \\sim C136 \\sim C23: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C18 \\sim C19 \\sim C16 \\sim C17: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C94 \\sim C117 \\sim C93 \\sim C85: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C45 \\sim C46 \\sim C44 \\sim C140: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C20 \\sim C138 \\sim C21 \\sim C22: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C130) \\sim Ueq, Uanis(C129) \\sim Ueq, Uanis(C127) \\sim Ueq, Uanis(C1)
\\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(C17) \\sim Ueq, Uanis(C109) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C111)
\\sim Ueq, Uanis(C139) \\sim Ueq, Uanis(C129) \\sim Ueq, Uanis(C124) \\sim Ueq,
Uanis(C50) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C128)
\\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C120) \\sim Ueq, Uanis(C122) \\sim Ueq,
Uanis(C119) \\sim Ueq, Uanis(C121) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C132)
\\sim Ueq, Uanis(C110) \\sim Ueq, Uanis(C138) \\sim Ueq, Uanis(C64) \\sim Ueq,
Uanis(C125) \\sim Ueq, Uanis(C123) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C47)
\\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C2) \\sim Ueq,
Uanis(C137) \\sim Ueq, Uanis(O8) \\sim Ueq, Uanis(O9) \\sim Ueq, Uanis(O10)
\\sim Ueq, Uanis(O11) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
4.a Riding coordinates:
 C120(H12D,H12E,H12F), C130(H13L,H13M,H13N), C132(H13R,H13S,H13T), C122(H12P,
 H12Q,H12R), C46(H46A,H46B,H46C), C48(H48A,H48B,H48C), C129(H12V,H12W,H12X)
4.b Free rotating group:
 O8(H8A,H8B), O9(H9C,H9D), O11(H11F,H11G), O10(H10F,H10G)
4.c Secondary CH2 refined with riding coordinates:
 C017(H01A,H01B), C67(H67A,H67B), C84(H84A,H84B), C131(H13A,H13B), C32(H32A,
 H32B), C101(H10A,H10B), C02M(H02A,H02B), C02N(H02C,H02D), C9(H9A,H9B),
 C02Z(H02E,H02F), C031(H03A,H03B), C038(H03C,H03D), C03C(H03E,H03F), C041(H04A,
 H04B), C112(H11A,H11B), C04V(H04I,H04J)
4.d Aromatic/amide H refined with riding coordinates:
 C11(H11), C01H(H01H), C13(H13), C62(H62), C88(H88), C96(H96), C58(H58),
 C39(H39), C86(H86), C98(H98), C80(H80), C35(H35), C73(H73), C41(H41),
 C034(H034), C71(H71), C78(H78), C107(H107), C105(H105), C31(H31), C03I(H03I),
 C03K(H03K), C8(H8), C27(H27), C044(H044), C114(H114), C116(H116), C126(H126),
 C139(H139), C56(H56), C52(H52), C111(H111)
4.e Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C77(H77A,H77B,H77C), C047(H04C,H04D,H04E), C59(H59A,H59B,
 H59C), C19(H19A,H19B,H19C), C135(H13C,H13D,H13E), C04J(H04F,H04G,H04H),
 C65(H65A,H65B,H65C), C64(H64A,H64B,H64C), C18(H18A,H18B,H18C), C92(H92A,H92B,
 H92C), C109(H10C,H10D,H10E), C85(H85A,H85B,H85C), C17(H17A,H17B,H17C),
 C94(H94A,H94B,H94C), C76(H76A,H76B,H76C), C4(H4A,H4B,H4C), C134(H13F,H13G,
 H13H), C058(H05A,H05B,H05C), C44(H44A,H44B,H44C), C110(H11C,H11D,H11E),
 C21(H21A,H21B,H21C), C121(H12A,H12B,H12C), C20(H20A,H20B,H20C), C93(H93A,H93B,
 H93C), C49(H49A,H49B,H49C), C1(H1A,H1B,H1C), C137(H13I,H13J,H13K), C24(H24A,
 H24B,H24C), C124(H12G,H12H,H12I), C2(H2A,H2B,H2C), C123(H12J,H12K,H12L),
 C125(H12M,H12N,H12O), C136(H13O,H13P,H13Q), C45(H45A,H45B,H45C), C25(H25A,H25B,
 H25C), C5(H5A,H5B,H5C), C138(H13U,H13V,H13W), C127(H12S,H12T,H12U), C66(H66A,
 H66B,H66C), C47(H47A,H47B,H47C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              20234
_shelx_fab_checksum              49219
_olex2_submission_special_instructions 'No special instructions were received'