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_1570460
_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
'C364 H436 Na4 O80 Ti16, 25[H2O], 0[H2O], 7[H2O], 1[H2O]'
_chemical_formula_sum            'C364 H502 Na4 O113 Ti16'
_chemical_formula_weight         7543.99
_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     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2bzp23
_audit_creation_date             2023-03-30
_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                 113.349(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   37.982(7)
_cell_length_b                   33.195(6)
_cell_length_c                   36.904(7)
_cell_measurement_reflns_used    9728
_cell_measurement_temperature    150
_cell_measurement_theta_max      47.47
_cell_measurement_theta_min      2.39
_cell_volume                     42719(14)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_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  0.0869
_diffrn_reflns_av_unetI/netI     0.0676
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            187652
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        48.238
_diffrn_reflns_theta_max         48.238
_diffrn_reflns_theta_min         2.392
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           2.23
_diffrn_source_power             0.1557878
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           69.86
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.056
_exptl_absorpt_correction_T_max  0.7495
_exptl_absorpt_correction_T_min  0.5643
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1310 before and 0.0752 after correction.
The Ratio of minimum to maximum transmission is 0.7529.
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    1.173
_exptl_crystal_description       needle
_exptl_crystal_F_000             15944
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.784
_refine_diff_density_min         -0.622
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2223
_refine_ls_number_reflns         30448
_refine_ls_number_restraints     606
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.1313
_refine_ls_R_factor_gt           0.0929
_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^)+(0.1858P)^2^+45.2443P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2702
_refine_ls_wR_factor_ref         0.3040
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18322
_reflns_number_total             30448
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06046b2.cif
_cod_data_source_block           Ti16L4-1-HFa-b
_cod_depositor_comments
'Adding full bibliography for 1570454--1570469.cif.'
_cod_original_cell_volume        42718(14)
_cod_database_code               1570460
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.577
_shelx_estimated_absorpt_t_min   0.426
_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
 C70-C144
 1.45 with sigma of 0.01
 C112-C111
 2.2 with sigma of 0.01
 C125-C130
 1.45 with sigma of 0.01
 C69-C70
 2.2 with sigma of 0.01
 C119-C47
 2.2 with sigma of 0.01
 C122-C104
 1.45 with sigma of 0.01
 C122-C139
 1.45 with sigma of 0.01
 C122-C47
 1.45 with sigma of 0.01
 C7-C9
 1.45 with sigma of 0.01
 C7-C8
 1.45 with sigma of 0.01
 C7-C10
 1.45 with sigma of 0.01
3. Rigid bond restraints
 C144, C70
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C122 \\sim C47: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C116 \\sim C102: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C97 \\sim C68 \\sim C79 \\sim C6: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Na2 \\sim O3 \\sim O34: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C27 \\sim C119 \\sim C47 \\sim C139 \\sim C127 \\sim C104 \\sim C122: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C132 \\sim C128 \\sim C110 \\sim C111 \\sim C112 \\sim C101: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C114 \\sim C115 \\sim C117 \\sim C103: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C33 \\sim C38 \\sim C37 \\sim C131: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C12 \\sim C13 \\sim C14: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C140 \\sim C141 \\sim C142 \\sim O4: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C135 \\sim C108 \\sim C109: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C144 \\sim C70: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C7 \\sim C9: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C130 \\sim C123 \\sim C138 \\sim C125: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C3 \\sim C4 \\sim C2 \\sim C1: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C105) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C112)
\\sim Ueq, Uanis(C117) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C121) \\sim Ueq,
Uanis(C134) \\sim Ueq, Uanis(C130) \\sim Ueq, Uanis(C123) \\sim Ueq, Uanis(C10)
\\sim Ueq, Uanis(C125) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C33) \\sim Ueq,
Uanis(C38) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C118) \\sim Ueq, Uanis(C1)
\\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C110) \\sim Ueq,
Uanis(C128) \\sim Ueq, Uanis(C122) \\sim Ueq, Uanis(C102) \\sim Ueq,
Uanis(C115) \\sim Ueq, Uanis(C132) \\sim Ueq, Uanis(C145) \\sim Ueq, Uanis(C61)
\\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C111) \\sim Ueq, Uanis(C70) \\sim Ueq,
Uanis(C111) \\sim Ueq, Uanis(C136) \\sim Ueq, Uanis(C138) \\sim Ueq, Uanis(C40)
\\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C131) \\sim Ueq,
Uanis(C64) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C113) \\sim Ueq, Uanis(C137)
\\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C119) \\sim Ueq, Uanis(C97) \\sim Ueq,
Uanis(C51) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C127) \\sim Ueq, Uanis(C104)
\\sim Ueq, Uanis(C139) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C69) \\sim Ueq,
Uanis(C3) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C42) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(C128)=Sof(H12p)=Sof(H12q)=Sof(H12r)=Sof(C111)=Sof(H11u)=Sof(H11v)=
 Sof(H11w)=1-FVAR(1)
 Sof(C132)=Sof(H13j)=Sof(H13k)=Sof(H13l)=Sof(C110)=Sof(H11r)=Sof(H11s)=
 Sof(H11t)=FVAR(1)
 Sof(C70)=Sof(H70a)=Sof(H70b)=Sof(H70c)=Sof(C137)=Sof(H13s)=Sof(H13t)=
 Sof(H13u)=1-FVAR(2)
 Sof(C78)=Sof(H78a)=Sof(H78b)=Sof(H78c)=Sof(C145)=Sof(H14a)=Sof(H14b)=
 Sof(H14c)=FVAR(2)
 Sof(C104)=Sof(H10s)=Sof(H10t)=Sof(H10u)=Sof(C139)=Sof(H13v)=Sof(H13w)=
 Sof(H13x)=Sof(C27)=Sof(H27a)=Sof(H27b)=Sof(H27c)=1-FVAR(3)
 Sof(C127)=Sof(H12s)=Sof(H12t)=Sof(H12u)=Sof(C47)=Sof(H47a)=Sof(H47b)=
 Sof(H47c)=Sof(C119)=Sof(H11x)=Sof(H11y)=Sof(H)=FVAR(3)
 Fixed Sof: C118(0.5) H11i(0.5) H11j(0.5) H11k(0.5) C136(0.5) H13p(0.5)
 H13q(0.5) H13r(0.5)
6.a Riding coordinates:
 C9(H9a,H9b,H9c), C123(H12m,H12n,H12o), C70(H70a,H70b,H70c)
6.b Rotating group:
 O1(H1d,H1e), O12(H12v,H12w), O2(H2d,H2e), O36(H36a,H36b)
6.c Secondary CH2 refined with riding coordinates:
 C01U(H01a,H01b), C01W(H01c,H01d), C32(H32a,H32b), C24(H24a,H24b), C02C(H02a,
 H02b), C02L(H02c,H02d), C02Q(H02e,H02f), C02W(H02g,H02h), C02Y(H02i,H02j),
 C90(H90a,H90b), C11(H11a,H11b), C03I(H03a,H03b), C03N(H03d,H03f), C67(H67a,
 H67b), C044(H04a,H04b), C04L(H04c,H04d)
6.d Aromatic/amide H refined with riding coordinates:
 C20(H20), C34(H34), C02N(H02N), C13(H13), C28(H28), C30(H30), C91(H91),
 C033(H033), C36(H36), C18(H18), C038(H038), C03C(H03C), C03E(H03E), C15(H15),
 C03J(H03J), C54(H54), C95(H95), C03P(H03P), C82(H82), C85(H85), C03W(H03W),
 C041(H041), C89(H89), C109(H109), C72(H72), C80(H80), C76(H76), C04N(H04N),
 C42(H42), C04T(H04T), C52(H52), C63(H63), C39(H39), C65(H65)
6.e Idealised Me refined as rotating group:
 C46(H46a,H46b,H46c), C44(H44a,H44b,H44c), C129(H12a,H12b,H12c), C134(H13a,
 H13b,H13c), C43(H43a,H43b,H43c), C126(H12d,H12e,H12f), C120(H12g,H12h,H12i),
 C68(H68a,H68b,H68c), C133(H13d,H13e,H13f), C107(H10a,H10b,H10c), C105(H10d,
 H10e,H10f), C106(H10g,H10h,H10i), C71(H71a,H71b,H71c), C69(H69a,H69b,H69c),
 C6(H6a,H6b,H6c), C10(H10j,H10k,H10l), C58(H58a,H58b,H58c), C51(H51a,H51b,H51c),
  C103(H10m,H10n,H10o), C38(H38a,H38b,H38c), C78(H78a,H78b,H78c), C33(H33a,H33b,
 H33c), C48(H48a,H48b,H48c), C61(H61a,H61b,H61c), C49(H49a,H49b,H49c), C4(H4a,
 H4b,H4c), C112(H11c,H11d,H11e), C8(H8a,H8b,H8c), C125(H12j,H12k,H12l),
 C131(H13g,H13h,H13i), C97(H97a,H97b,H97c), C102(H10p,H10q,H10r), C113(H11f,
 H11g,H11h), C118(H11i,H11j,H11k), C59(H59a,H59b,H59c), C145(H14a,H14b,H14c),
 C1(H1a,H1b,H1c), C2(H2a,H2b,H2c), C117(H11l,H11m,H11n), C115(H11o,H11p,H11q),
 C132(H13j,H13k,H13l), C110(H11r,H11s,H11t), C128(H12p,H12q,H12r), C111(H11u,
 H11v,H11w), C138(H13m,H13n,H13o), C136(H13p,H13q,H13r), C137(H13s,H13t,H13u),
 C127(H12s,H12t,H12u), C47(H47a,H47b,H47c), C119(H11x,H11y,H), C104(H10s,H10t,
 H10u), C139(H13v,H13w,H13x), C27(H27a,H27b,H27c)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              95705
_shelx_fab_checksum              61425
_olex2_submission_special_instructions 'No special instructions were received'