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_1570455
_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         '0.25(C384 H472 Cl4 O64 Ti16)'
_chemical_formula_sum            'C96 H118 Cl O16 Ti4'
_chemical_formula_weight         1754.95
_space_group_crystal_system      tetragonal
_space_group_IT_number           97
_space_group_name_Hall           'I 4 2'
_space_group_name_H-M_alt        'I 4 2 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2bznyy
_audit_creation_date             2022-04-21
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-05-23 deposited with the CCDC.	2023-11-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   38.021(13)
_cell_length_b                   38.021(13)
_cell_length_c                   19.702(4)
_cell_measurement_reflns_used    9493
_cell_measurement_temperature    297
_cell_measurement_theta_max      46.712
_cell_measurement_theta_min      2.856
_cell_volume                     28481(15)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_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    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      297
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34138
_diffrn_reflns_av_R_equivalents  0.1087
_diffrn_reflns_av_unetI/netI     0.0612
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            72899
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        48.388
_diffrn_reflns_theta_max         48.388
_diffrn_reflns_theta_min         2.860
_diffrn_source_current           2.86
_diffrn_source_power             0.1997996
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           69.86
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.580
_exptl_absorpt_correction_T_max  0.7495
_exptl_absorpt_correction_T_min  0.5596
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1522 before and 0.0789 after correction.
The Ratio of minimum to maximum transmission is 0.7466.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    0.819
_exptl_crystal_description       block
_exptl_crystal_F_000             7416
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.503
_refine_diff_density_min         -0.384
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.408(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.994
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     644
_refine_ls_number_reflns         10333
_refine_ls_number_restraints     317
_refine_ls_restrained_S_all      1.005
_refine_ls_R_factor_all          0.0860
_refine_ls_R_factor_gt           0.0591
_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^)+(0.1227P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1627
_refine_ls_wR_factor_ref         0.1802
_reflns_Friedel_coverage         0.829
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                7396
_reflns_number_total             10333
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06046b2.cif
_cod_data_source_block           Ti16L4-3
_cod_depositor_comments
'Adding full bibliography for 1570454--1570469.cif.'
_cod_original_cell_volume        28481(20)
_cod_database_code               1570455
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.592(14)
 0.408(14)
2. 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
3. Restrained distances
 C11-C21
 2.5 with sigma of 0.02
 C39A-C24A
 2.5 with sigma of 0.02
 C27-C19A
 1.5 with sigma of 0.02
 C43A-C11A
 2.5 with sigma of 0.02
 C5-C21A
 1.5 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C24) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C43)
\\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C9) \\sim Ueq,
Uanis(C35) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C11A) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C43A) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C21A) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C46) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C46A)
\\sim Ueq, Uanis(C47A) \\sim Ueq, Uanis(C48A) \\sim Ueq, Uanis(C49) \\sim Ueq,
Uanis(C50) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C21) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C39A) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(C24)
\\sim Ueq, Uanis(C19A) \\sim Ueq, Uanis(C19) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C7, C46, C46A, C47, C47A, C48, C48A, C49, C50
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C5, C11, C11A, C21, C21A, C28, C43, C43A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C19, C19A, C24, C24A, C27, C39, C39A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C19, C19A, C24, C24A, C27, C36, C39, C39A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C11A)=Sof(H11d)=Sof(H11e)=Sof(H11f)=Sof(C21A)=Sof(H21d)=Sof(H21e)=
 Sof(H21f)=Sof(C43A)=Sof(H43d)=Sof(H43e)=Sof(H43f)=1-FVAR(1)
 Sof(C11)=Sof(H11a)=Sof(H11b)=Sof(H11c)=Sof(C21)=Sof(H21a)=Sof(H21b)=Sof(H21c)=
 Sof(C43)=Sof(H43a)=Sof(H43b)=Sof(H43c)=FVAR(1)
 Sof(C19A)=Sof(H19d)=Sof(H19e)=Sof(H19f)=Sof(C24A)=Sof(H24d)=Sof(H24e)=
 Sof(H24f)=Sof(C39A)=Sof(H39d)=Sof(H39e)=Sof(H39f)=1-FVAR(2)
 Sof(C19)=Sof(H19a)=Sof(H19b)=Sof(H19c)=Sof(C24)=Sof(H24a)=Sof(H24b)=Sof(H24c)=
 Sof(C39)=Sof(H39a)=Sof(H39b)=Sof(H39c)=FVAR(2)
 Fixed Sof: C46(0.5) C46A(0.5) C47(0.5) H47a(0.5) H47b(0.5) H47c(0.5)
 C47A(0.5) H47d(0.5) H47e(0.5) H47f(0.5) C48(0.5) H48a(0.5) H48b(0.5) H48c(0.5)
 C48A(0.5) H48d(0.5) H48e(0.5) H48f(0.5) C49(0.5) H49a(0.5) H49b(0.5) H49c(0.5)
 C50(0.5) H50a(0.5) H50b(0.5) H50c(0.5)
7.a Riding coordinates:
 C21(H21a,H21b,H21c)
7.b Ternary CH refined with riding coordinates:
 C9(H9)
7.c Secondary CH2 refined with riding coordinates:
 C3(H3a,H3b), C8(H8a,H8b), C13(H13a,H13b), C44(H44a,H44b)
7.d Aromatic/amide H refined with riding coordinates:
 C15(H15), C20(H20), C23(H23), C25(H25), C31(H31), C32(H32), C34(H34), C38(H38)
7.e Idealised Me refined as rotating group:
 C2(H2a,H2b,H2c), C11(H11a,H11b,H11c), C11A(H11d,H11e,H11f), C19(H19a,H19b,
 H19c), C19A(H19d,H19e,H19f), C21A(H21d,H21e,H21f), C24(H24a,H24b,H24c),
 C24A(H24d,H24e,H24f), C33(H33a,H33b,H33c), C35(H35a,H35b,H35c), C37(H37a,H37b,
 H37c), C39(H39a,H39b,H39c), C39A(H39d,H39e,H39f), C41(H41a,H41b,H41c),
 C43(H43a,H43b,H43c), C43A(H43d,H43e,H43f), C47(H47a,H47b,H47c), C47A(H47d,H47e,
 H47f), C48(H48a,H48b,H48c), C48A(H48d,H48e,H48f), C49(H49a,H49b,H49c),
 C50(H50a,H50b,H50c)
;
_shelx_res_checksum              47552
_shelx_fab_checksum              89194
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'