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_1570469
_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
'C368 H420 O76 Ti16, 2(C2 H3 N), 30[H2O], 1.5[H2O], 6[H2O], 1.5[H2O]'
_chemical_formula_sum            'C372 H426 N2 O76 Ti16'
_chemical_formula_weight         6907.52
_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
_audit_block_doi                 10.5517/ccdc.csd.cc2bzp45
_audit_creation_date             2023-03-24
_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                 115.418(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   38.8238(16)
_cell_length_b                   32.5568(14)
_cell_length_c                   37.8922(16)
_cell_measurement_reflns_used    9494
_cell_measurement_temperature    150
_cell_measurement_theta_max      51.34
_cell_measurement_theta_min      3.09
_cell_volume                     43259(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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 2018/2 (Sheldrick, 2018)'
_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 APEX2 microsource'
_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     1.34139
_diffrn_reflns_av_R_equivalents  0.0758
_diffrn_reflns_av_unetI/netI     0.0461
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       45
_diffrn_reflns_limit_h_min       -45
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            258562
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        51.539
_diffrn_reflns_theta_max         51.539
_diffrn_reflns_theta_min         2.351
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           2.86
_diffrn_source_power             0.1997996
_diffrn_source_target            Mo
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           69.86
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.943
_exptl_absorpt_correction_T_max  0.7501
_exptl_absorpt_correction_T_min  0.5611
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1462 before and 0.1015 after correction.
The Ratio of minimum to maximum transmission is 0.7480.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear reddish pink'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.061
_exptl_crystal_description       block
_exptl_crystal_F_000             14528
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.829
_refine_diff_density_min         -0.660
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2225
_refine_ls_number_reflns         35703
_refine_ls_number_restraints     375
_refine_ls_restrained_S_all      1.144
_refine_ls_R_factor_all          0.0926
_refine_ls_R_factor_gt           0.0810
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1836P)^2^+21.9787P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2623
_refine_ls_wR_factor_ref         0.2729
_reflns_Friedel_coverage         0.000
_reflns_number_gt                27109
_reflns_number_total             35703
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06046b2.cif
_cod_data_source_block           Ti16L4-1-HGa
_cod_depositor_comments
'Adding full bibliography for 1570454--1570469.cif.'
_cod_database_code               1570469
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.593
_shelx_estimated_absorpt_t_min   0.443
_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
2. Restrained distances
 C38-C36
 2.2 with sigma of 0.01
 C5-C15A
 2.2 with sigma of 0.01
 C34-C6
 1.45 with sigma of 0.01
 C34-C29
 2.4 with sigma of 0.01
 C29-C6
 1.45 with sigma of 0.01
 C22A-C23A
 2.2 with sigma of 0.01
 C19-C20
 1.45 with sigma of 0.01
 C37-C39
 1.45 with sigma of 0.01
 C43-C45
 1.45 with sigma of 0.01
 H21A-H03V
 2 with sigma of 0.01
 H36A-H38A
 2 with sigma of 0.01
 C05D-C24 \\sim C05D-C24A
 with sigma of 0.02
 C05D-C22 \\sim C05D-C22A
 with sigma of 0.02
 C05D-C23 \\sim C05D-C23A
 with sigma of 0.02
 Ti07-O1 \\sim Ti07-O1A
 with sigma of 0.02
 Ti08-O6 \\sim Ti08-O6A
 with sigma of 0.04
 O1-C02V \\sim O1A-C02V
 with sigma of 0.02
 C02D-O6 \\sim C02D-O6A
 with sigma of 0.04
 C35-C15 \\sim C35-C15A
 with sigma of 0.02
 C35-C14 \\sim C35-C5
 with sigma of 0.02
 C35-C13 \\sim C35-C27
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C28 \\sim C8 \\sim C9 \\sim C7: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.01 within 2A
C27 \\sim C35 \\sim C5 \\sim C15: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.01 within 2A
C37 \\sim C38 \\sim C36 \\sim C39: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.01 within 2A
C29 \\sim C6 \\sim C33 \\sim C34: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.01 within 2A
C19 \\sim C44 \\sim C20 \\sim C21: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.01 within 2A
C1 \\sim C2 \\sim C3 \\sim C4: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.01 within 2A
Uanis(C7) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C21) \\sim Ueq,
Uanis(C19) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq,
Uanis(C15) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18)
\\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C22) \\sim Ueq,
Uanis(C23) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C6)
\\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(O3) \\sim Ueq,
Uanis(O1) \\sim Ueq, Uanis(C23A) \\sim Ueq, Uanis(C22A) \\sim Ueq, Uanis(O1)
\\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C15A) \\sim Ueq,
Uanis(C20) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C38)
\\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(C43) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C15A, C5, C27
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C15, C14, C13
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=
 Sof(H24F)=Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(1)
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(1)
 Sof(O6A)=1-FVAR(2)
 Sof(O6)=FVAR(2)
 Sof(O1A)=1-FVAR(3)
 Sof(O1)=FVAR(3)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=1-FVAR(4)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=FVAR(4)
6.a Riding coordinates:
 C33(H33A,H33B,H33C), C40(H40A,H40B,H40C), C34(H34A,H34B,H34C), C27(H27A,H27B,
 H27C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C)
6.b Secondary CH2 refined with riding coordinates:
 C018(H01A,H01B), C01V(H01C,H01D), C021(H02A,H02B), C023(H02C,H02D), C027(H02E,
 H02F), C02C(H02G,H02H), C02I(H02K,H02L), C02J(H02M,H02N), C02L(H02O,H02P),
 C02T(H02S,H02T), C02W(H02U,H02V), C02Z(H02W,H02Y), C031(H03A,H03B), C03M(H03C,
 H03E), C03S(H03G,H03H), C043(H04A,H04B)
6.c Aromatic/amide H refined with riding coordinates:
 C01H(H01H), C01J(H01J), C020(H020), C029(H029), C02E(H02I), C02H(H02J),
 C02M(H02Q), C02N(H02R), C02X(H02X), C032(H032), C034(H034), C038(H038),
 C039(H039), C03D(H03D), C03F(H03F), C03J(H03J), C03L(H03L), C03Q(H03Q),
 C03T(H03T), C03U(H03U), C03V(H03V), C03W(H03W), C03X(H03X), C03Y(H03Y),
 C03Z(H03Z), C041(H041), C044(H044), C045(H045), C048(H048), C04A(H04C),
 C04B(H04D), C04H(H04K), C057(H057), C05B(H05B)
6.d Idealised Me refined as rotating group:
 C04E(H04E,H04F,H04G), C04F(H04H,H04I,H04J), C04I(H04L,H04M,H04N), C04M(H04O,
 H04P,H04Q), C04R(H04R,H04S,H04T), C04V(H04U,H04V,H04W), C04Y(H04X,H04Y,H),
 C04Z(H04Z,HA,HB), C32(H32A,H32B,H32C), C10(H10A,H10B,H10C), C11(H11A,H11B,
 H11C), C42(H42A,H42B,H42C), C41(H41A,H41B,H41C), C29(H29A,H29B,H29C), C17(H17A,
 H17B,H17C), C18(H18A,H18B,H18C), C30(H30A,H30B,H30C), C05U(H05A,H05C,H05D),
 C15(H15A,H15B,H15C), C05X(H05E,H05F,H05G), C4(H4A,H4B,H4C), C062(H06A,H06B,
 H06C), C065(H06D,H06E,H06F), C24(H24A,H24B,H24C), C068(H06G,H06H,H06I), C3(H3A,
 H3B,H3C), C14(H14A,H14B,H14C), C21(H21A,H21B,H21C), C06E(H06J,H06K,H06L),
 C28(H28A,H28B,H28C), C31(H31A,H31B,H31C), C7(H7A,H7B,H7C), C25(H25A,H25B,H25C),
  C13(H13A,H13B,H13C), C16(H16A,H16B,H16C), C22(H22A,H22B,H22C), C19(H19A,H19B,
 H19C), C12(H12A,H12B,H12C), C8(H8A,H8B,H8C), C44(H44A,H44B,H44C), C23(H23A,
 H23B,H23C), C22A(H22D,H22E,H22F), C24A(H24D,H24E,H24F), C23A(H23D,H23E,H23F),
 C5(H5A,H5B,H5C), C15A(H15D,H15E,H15F), C39(H39A,H39B,H39C), C45(H45A,H45B,
 H45C), C1(H1A,H1B,H1C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              32828
_shelx_fab_checksum              18749
_olex2_submission_special_instructions 'No special instructions were received'