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_1570461
_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         'C388 H472 Cl2 O68 Ti16, 4(C2 H3 N)'
_chemical_formula_sum            'C396 H484 Cl2 N4 O68 Ti16'
_chemical_formula_weight         7225.14
_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_block_doi                 10.5517/ccdc.csd.cc2bznxx
_audit_creation_date             2022-04-22
_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                 121.288(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   53.303(2)
_cell_length_b                   19.9467(8)
_cell_length_c                   50.645(2)
_cell_measurement_reflns_used    9829
_cell_measurement_temperature    150
_cell_measurement_theta_max      52.980
_cell_measurement_theta_min      3.735
_cell_volume                     46016(3)
_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 2013/2 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 5.6
_diffrn_detector_type            'Bruker SMART CCD 6000 area detector'
_diffrn_measured_fraction_theta_full 0.976
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0537
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       63
_diffrn_reflns_limit_h_min       -63
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       56
_diffrn_reflns_limit_l_min       -60
_diffrn_reflns_number            319443
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         53.185
_diffrn_reflns_theta_min         2.104
_diffrn_source                   '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    1.810
_exptl_absorpt_correction_T_max  0.581
_exptl_absorpt_correction_T_min  0.440
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.043
_exptl_crystal_description       needle
_exptl_crystal_F_000             15272
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.886
_refine_diff_density_min         -1.485
_refine_diff_density_rms         0.159
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.008
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2369
_refine_ls_number_reflns         40618
_refine_ls_number_restraints     195
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.1051
_refine_ls_R_factor_gt           0.0929
_refine_ls_shift/su_max          0.050
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.2000P)^2^+100.0000P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2724
_refine_ls_wR_factor_ref         0.2872
_reflns_Friedel_coverage         0.000
_reflns_number_gt                33414
_reflns_number_total             40618
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06046b2.cif
_cod_data_source_block           Ti16L4-2
_cod_depositor_comments
'Adding full bibliography for 1570454--1570469.cif.'
_cod_database_code               1570461
_shelxl_version_number           2013-2
_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
 C14-C24
 1.45 with sigma of 0.01
 C054-C05L
 1.45 with sigma of 0.01
 C16-C18
 2.5 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
Uanis(C15) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim
Ueq, Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C14)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C25) \\sim Ueq,
Uanis(C26) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29)
\\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq,
Uanis(C33) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C11) \\sim Ueq,
Uanis(C3) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18)
\\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq,
Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=1-FVAR(1)
 Sof(C06K)=Sof(H06Y)=Sof(HX)=Sof(HY)=FVAR(1)
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=1-FVAR(2)
 Sof(C06J)=Sof(H06V)=Sof(H06W)=Sof(H06X)=FVAR(2)
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=1-FVAR(3)
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(3)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=1-FVAR(4)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=FVAR(4)
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=1-FVAR(5)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=FVAR(5)
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=1-FVAR(6)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(6)
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=1-FVAR(7)
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=FVAR(7)
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=1-FVAR(8)
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=FVAR(8)
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=1-FVAR(9)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=FVAR(9)
 Sof(Ti2A)=1-FVAR(10)
 Sof(Ti2)=FVAR(10)
 Sof(Ti3A)=1-FVAR(11)
 Sof(Ti3)=FVAR(11)
5.a Ternary CH refined with riding coordinates:
 C05E(H05Z), C05Y(H10)
5.b Secondary CH2 refined with riding coordinates:
 C01M(H01A,H01B), C01Q(H01C,H01D), C01V(H01E,H01F), C01X(H01G,H01H), C029(H02A,
 H02B), C02O(H02D,H02E), C02R(H02G,H02H), C02S(H02I,H02L), C02Y(H02M,H02N),
 C03D(H03A,H03B), C03E(H03C,H03D), C03P(H03E,H03F), C03W(H03G,H03H), C04F(H04G,
 H04H), C04I(H04J,H04K)
5.c Aromatic/amide H refined with riding coordinates:
 C01R(H01R), C021(H021), C028(H028), C02B(H02C), C02J(H02J), C02K(H02K),
 C02P(H02P), C02T(H02T), C02W(H02W), C02X(H02X), C030(H030), C033(H033),
 C036(H036), C23(H23), C039(H039), C03I(H03I), C03J(H03J), C03K(H03K),
 C03N(H03N), C03R(H03R), C03S(H03S), C03U(H03U), C03Y(H03Y), C04G(H04I),
 C04J(H04L), C04K(H04M), C04L(H04N), C04M(H04O), C04Q(H04S), C04R(H04T),
 C04V(H04V), C35(H35)
5.d Idealised Me refined as rotating group:
 C03Q(H03L,H03M,H03O), C04D(H04A,H04B,H04C), C04E(H04D,H04E,H04F), C04P(H04P,
 H04Q,H04R), C04Y(H04U,H04W,H04X), C051(H05A,H05B,H05C), C053(H05D,H05E,H05F),
 C054(H05G,H05H,H05I), C055(H05J,H05K,H05L), C056(H05M,H05N,H05O), C058(H05P,
 H05Q,H05R), C059(H05S,H05T,H05U), C05A(H05V,H05W,H05X), C22(H22A,H22B,H22C),
 C20(H20A,H20B,H20C), C05D(H05Y,H,HA), C05F(H05,HB,HC), C05G(H1,HD,HE), C05H(H2,
 HF,HG), C05I(H3,HH,HI), C13(H13A,H13B,H13C), C3(H3A,H3B,H3C), C05M(H4,HJ,HK),
 C05N(H5,HL,HM), C05Q(H6,HN,HO), C05S(H7,HP,HQ), C05T(H11,HR,HS), C8(H8A,H8B,
 H8C), C05V(H8,HT,HU), C21(H21A,H21B,H21C), C05X(H9,HV,HW), C26(H26A,H26B,H26C),
  C061(H06A,H06B,H06C), C062(H06D,H06E,H06F), C063(H06G,H06H,H06I), C064(H06J,
 H06K,H06L), C25(H25A,H25B,H25C), C066(H06M,H06N,H06O), C2(H2A,H2B,H2C),
 C17(H17A,H17B,H17C), C9(H9A,H9B,H9C), C06B(H06P,H06Q,H06R), C4(H4A,H4B,H4C),
 C5(H5A,H5B,H5C), C18(H18A,H18B,H18C), C06F(H06S,H06T,H06U), C10(H10A,H10B,
 H10C), C15(H15A,H15B,H15C), C11(H11A,H11B,H11C), C06J(H06V,H06W,H06X),
 C06K(H06Y,HX,HY), C06L(H06Z,HZ,H12), C7(H7A,H7B,H7C), C06O(H06,H13,H14),
 C27(H27A,H27B,H27C), C12(H12A,H12B,H12C), C6(H6A,H6B,H6C), C14(H14A,H14B,H14C),
  C16(H16A,H16B,H16C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,
 H34B,H34C), C37(H37A,H37B,H37C), C36(H36A,H36B,H36C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              24914
_shelx_fab_checksum              72479
_olex2_submission_special_instructions 'No special instructions were received'