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_1570459
_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
'C380 H452 N2 O72 Ti16, C2 H3 N, 19[H2O], 14[H2O]'
_chemical_formula_sum            'C382 H479 N3 O80 Ti16'
_chemical_formula_weight         7159.05
_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             2023-03-28
_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                 113.350(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   37.993(4)
_cell_length_b                   33.265(4)
_cell_length_c                   37.218(4)
_cell_measurement_reflns_used    9968
_cell_measurement_temperature    173
_cell_measurement_theta_max      54.47
_cell_measurement_theta_min      3.50
_cell_volume                     43185(8)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      173
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_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  0.1126
_diffrn_reflns_av_unetI/netI     0.0975
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       46
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            225584
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         55.000
_diffrn_reflns_theta_min         2.376
_diffrn_source                   'microfocus sealed X-ray tube'
_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    1.960
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.6138
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1634 before and 0.0862 after correction.
The Ratio of minimum to maximum transmission is 0.8175.
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    1.101
_exptl_crystal_description       block
_exptl_crystal_F_000             15136
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.585
_refine_diff_density_min         -0.875
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2396
_refine_ls_number_reflns         40988
_refine_ls_number_restraints     559
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.1283
_refine_ls_R_factor_gt           0.0920
_refine_ls_shift/su_max          0.058
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1698P)^2^+41.1061P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2646
_refine_ls_wR_factor_ref         0.2941
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25647
_reflns_number_total             40988
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06046b2.cif
_cod_data_source_block           Ti16L4-1-HFa-a
_cod_depositor_comments
'Adding full bibliography for 1570454--1570469.cif.'
_cod_original_cell_volume        43184(9)
_cod_database_code               1570459
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.591
_shelx_estimated_absorpt_t_min   0.441
_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
 C9-C10
 2.2 with sigma of 0.01
 H00A-H4D
 2 with sigma of 0.01
 C1-C2
 1.55 with sigma of 0.01
 C2-N3
 1.25 with sigma of 0.01
 C12-C13
 1.45 with sigma of 0.01
 C13-C14
 1.45 with sigma of 0.01
 C21-C47
 2.2 with sigma of 0.01
 C6-C33
 2.2 with sigma of 0.01
 C5-C33
 1.45 with sigma of 0.01
 H21B-H63B
 2 with sigma of 0.01
 C03R-C55 \\sim C03R-C25
 with sigma of 0.02
 C03R-C56 \\sim C03R-C42
 with sigma of 0.02
 C03R-C57 \\sim C03R-C15
 with sigma of 0.02
3. Rigid bond restraints
 C28
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C43 \\sim C45 \\sim C49 \\sim C50: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C1 \\sim C2 \\sim N3: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
O63 \\sim C12 \\sim C13 \\sim C14: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C13 \\sim C19 \\sim O2: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C28 \\sim C37A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C23 \\sim C46 \\sim C48 \\sim C51: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C53 \\sim C8 \\sim C9 \\sim C10: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C44 \\sim C63 \\sim C21 \\sim C64 \\sim C47: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C27 \\sim C41: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C5 \\sim C6 \\sim C33 \\sim C30: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C38 \\sim C40 \\sim C59 \\sim C3: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
Uanis(C14) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C55)
\\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C46) \\sim Ueq,
Uanis(C23) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C64)
\\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C45) \\sim Ueq,
Uanis(C49) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C9)
\\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C17) \\sim Ueq,
Uanis(C18) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C34)
\\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C32) \\sim Ueq,
Uanis(C65) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C28)
\\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(C13) \\sim Ueq,
Uanis(C26) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C50)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C42) \\sim Ueq,
Uanis(C56) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C36A)
\\sim Ueq, Uanis(C37A) \\sim Ueq, Uanis(C38A) \\sim Ueq, Uanis(C8) \\sim Ueq,
Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C3A)
\\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C31) \\sim Ueq,
Uanis(C38B) \\sim Ueq, Uanis(C37B) \\sim Ueq, Uanis(C36B) \\sim Ueq,
Uanis(C33A) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(N38) \\sim Ueq, Uanis(C4) \\sim Ueq,
Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(N3) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=1-FVAR(1)
 Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=FVAR(1)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=
 Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=1-FVAR(2)
 Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=
 Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=FVAR(2)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=1-FVAR(3)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(3)
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=1-FVAR(4)
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=
 Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=FVAR(4)
 Sof(O1A)=1-FVAR(5)
 Sof(O2)=FVAR(5)
 Sof(C36B)=Sof(H36D)=Sof(H36E)=Sof(H36F)=Sof(C37B)=Sof(H37D)=Sof(H37E)=
 Sof(H37F)=Sof(C38B)=Sof(H38D)=Sof(H38E)=Sof(H38F)=1-FVAR(6)
 Sof(C36A)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C37A)=Sof(H37A)=Sof(H37B)=
 Sof(H37C)=Sof(C38A)=Sof(H38A)=Sof(H38B)=Sof(H38C)=FVAR(6)
 Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=1-FVAR(7)
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=FVAR(7)
 Fixed Sof: C1(0.5) H1C(0.5) H1D(0.5) H1E(0.5) C2(0.5) N3(0.5)
6.a Riding coordinates:
 C43(H43A,H43B,H43C), C36A(H36A,H36B,H36C), C37A(H37A,H37B,H37C), C38A(H38A,
 H38B,H38C), C47(H47A,H47B,H47C), C37B(H37D,H37E,H37F), C6(H6A,H6B,H6C),
 C33A(H33D,H33E,H33F), C36(H36G,H36H,H36I)
6.b Free rotating group:
 O4(H4D,H4E), O6(H6D,H6E), O3(H3A,H3B), O5(H5A,H5B)
6.c Rotating group:
 O00V(H00A,H00B), O1(H1A,H1B)
6.d Ternary CH refined with riding coordinates:
 C04R(H04R), C13(H13)
6.e Secondary CH2 refined with riding coordinates:
 C02K(H02A,H02B), C02R(H02C,H02D), C02S(H02E,H02G), C02U(H02H,H02I), C03D(H03A,
 H03B), C03E(H03C,H03D), C03I(H03E,H03G), C03M(H03I,H03J), C7(H7A,H7B),
 C034(H03K,H03L), C041(H04,HC), C047(H1,HD), C74(H74A,H74B), C75(H75A,H75B),
 C78(H78A,H78B), C81(H81A,H81B)
6.f Aromatic/amide H refined with riding coordinates:
 C02F(H02F), C02M(H02M), C02N(H02N), C02O(H02O), C02P(H02P), C02Q(H02Q),
 C03F(H03F), C03H(H03H), C03N(H03N), C03P(H03P), C03S(H03S), C03W(H03W),
 C03Y(H03Y), C04C(H04C), C04D(H04D), C04P(H04P), C04U(H04U), C17(H17), C18(H18),
  C24(H24), C26(H26), C026(H026), C031(H031), C033(H033), C035(H035),
 C036(H036), C038(H038), C043(H043), C044(H044), C049(H049), C70(H70), C73(H73),
  C79(H79)
6.g Idealised Me refined as rotating group:
 C04L(H04A,H04B,H04E), C04O(H04F,H04G,H04H), C04Q(H04I,H04J,H04K), C04S(H04L,
 H04M,H04N), C04T(H04O,H04Q,H04S), C04X(H04T,H04V,H04W), C04Y(H04X,H04Y,H),
 C04Z(H04Z,HA,HB), C05A(H05A,H05B,H05C), C05D(H05D,H05E,H05F), C05E(H05G,H05H,
 H05I), C05G(H05J,H05K,H05L), C05J(H05M,H05N,H05O), C4(H4A,H4B,H4C), C11(H11A,
 H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C22(H22A,H22B,H22C),
 C23(H23A,H23B,H23C), C29(H29A,H29B,H29C), C21(H21A,H21B,H21C), C63(H63A,H63B,
 H63C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C48(H48A,H48B,H48C), C49(H49A,
 H49B,H49C), C050(H05P,H05Q,H05R), C051(H05S,H05T,H05U), C055(H05V,H05W,H05X),
 C057(H05Y,HE,HF), C059(H05Z,HG,HH), C58(H58A,H58B,H58C), C32(H32A,H32B,H32C),
 C39(H39A,H39B,H39C), C65(H65A,H65B,H65C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C),
 C10(H10A,H10B,H10C), C64(H64A,H64B,H64C), C55(H55A,H55B,H55C), C56(H56A,H56B,
 H56C), C57(H57A,H57B,H57C), C61(H61A,H61B,H61C), C1A(H1AA,H1AB,H1AC), C31(H31A,
 H31B,H31C), C3A(H3AA,H3AB,H3AC), C35(H35A,H35B,H35C), C6A(H6AA,H6AB,H6AC),
 C15(H15A,H15B,H15C), C25(H25A,H25B,H25C), C42(H42A,H42B,H42C), C36B(H36D,H36E,
 H36F), C38B(H38D,H38E,H38F), C30(H30A,H30B,H30C), C33(H33A,H33B,H33C),
 C59(H59A,H59B,H59C), C38(H38G,H38H,H38I), C40(H40A,H40B,H40C), C1(H1C,H1D,H1E)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              40928
_shelx_fab_checksum              18804
_olex2_submission_special_instructions 'No special instructions were received'