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_1570454
_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         'C184 H210 O39 Ti8'
_chemical_formula_sum            'C184 H210 O39 Ti8'
_chemical_formula_weight         3428.71
_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.cc2bzp56
_audit_creation_date             2022-05-23
_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                 115.25(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   39.32(4)
_cell_length_b                   32.41(4)
_cell_length_c                   37.78(3)
_cell_measurement_reflns_used    9414
_cell_measurement_temperature    150
_cell_measurement_theta_max      42.126
_cell_measurement_theta_min      3.088
_cell_volume                     43545(8)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection
;
CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)
;
_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 2013/2 (Sheldrick, 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.571
_diffrn_measured_fraction_theta_max 0.975
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  Rigaku_AFC12K_724P_007HF_Mo
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34138
_diffrn_reflns_av_R_equivalents  0.1877
_diffrn_reflns_av_unetI/netI     0.2491
_diffrn_reflns_Laue_measured_fraction_full 0.571
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            111052
_diffrn_reflns_point_group_measured_fraction_full 0.571
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         42.318
_diffrn_reflns_theta_min         2.359
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           2.86
_diffrn_source_power             0.1997996
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           69.86
_exptl_absorpt_coefficient_mu    1.836
_exptl_absorpt_correction_T_max  0.7483
_exptl_absorpt_correction_T_min  0.4553
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1693 before and 0.1084 after correction.
The Ratio of minimum to maximum transmission is 0.6084.
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    1.046
_exptl_crystal_description       block
_exptl_crystal_F_000             14416
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.907
_refine_diff_density_min         -0.389
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2115
_refine_ls_number_reflns         22518
_refine_ls_number_restraints     536
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.2195
_refine_ls_R_factor_gt           0.1598
_refine_ls_shift/su_max          0.000
_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^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3794
_refine_ls_wR_factor_ref         0.4374
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10323
_reflns_number_total             22518
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06046b2.cif
_cod_data_source_block           Ti16L4-1-H2Oa
_cod_depositor_comments
'Adding full bibliography for 1570454--1570469.cif.'
_cod_original_cell_volume        43536(74)
_cod_database_code               1570454
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.609
_shelx_estimated_absorpt_t_min   0.460
_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
 O4-C23
 1.27 with sigma of 0.01
 C44-C23
 1.45 with sigma of 0.01
 C44-O15
 1.27 with sigma of 0.01
 O1-C30
 1.27 with sigma of 0.01
 O2-C51
 1.27 with sigma of 0.01
 C30-C51
 1.45 with sigma of 0.01
 C5-C2
 1.45 with sigma of 0.01
 C10-C11
 2.2 with sigma of 0.01
 C60-C61
 1.45 with sigma of 0.01
 C59-C61
 1.45 with sigma of 0.01
 C45-C61
 1.45 with sigma of 0.01
 C40-C6
 1.45 with sigma of 0.01
 C2-C4
 1.45 with sigma of 0.01
 C41-C11
 1.45 with sigma of 0.01
 C41-C10
 1.45 with sigma of 0.01
 C14-C15
 1.45 with sigma of 0.01
 C17-C15
 1.45 with sigma of 0.01
 C22-C35
 1.45 with sigma of 0.01
 C9-C11
 2.5 with sigma of 0.01
 C5-C4
 2.2 with sigma of 0.01
 C45-C59
 2.4 with sigma of 0.01
 C7-C8
 2.4 with sigma of 0.01
 C45-C60
 2.6 with sigma of 0.01
 C13-C74
 2.2 with sigma of 0.01
 C12-C72
 1.45 with sigma of 0.01
 C03A-C037
 1.45 with sigma of 0.01
 C03N-C05P
 1.45 with sigma of 0.01
 C03W-C04I
 1.45 with sigma of 0.01
 C61-C04U
 1.45 with sigma of 0.01
 H13B-H02O
 2.2 with sigma of 0.01
 H36-H45B
 2.2 with sigma of 0.01
 C63-C65
 1.45 with sigma of 0.01
 C04N-C04S
 1.35 with sigma of 0.01
 H03K-H68A
 2 with sigma of 0.01
 H10B-H11B
 2 with sigma of 0.01
 C04H-C04U
 1.35 with sigma of 0.01
 H14B-H16C
 2 with sigma of 0.01
 H05C-H05G
 2 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C2 \\sim C5: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C11 \\sim C41: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C59 \\sim C60 \\sim C45 \\sim C61 \\sim C04U \\sim C30: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C49 \\sim C50 \\sim C46 \\sim C20: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C6 \\sim C7 \\sim C8 \\sim C40: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C62 \\sim C63 \\sim C65 \\sim C64: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C25 \\sim C24 \\sim C66 \\sim C27: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
O2 \\sim C51: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C67 \\sim C68 \\sim C71 \\sim C53: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C72 \\sim C13 \\sim C74 \\sim C12: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C30 \\sim O5: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C2 \\sim C1 \\sim C3 \\sim C4 \\sim C5: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Uanis(O23) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(O8) \\sim Ueq, Uanis(O3) \\sim
Ueq, Uanis(O6) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C47) \\sim Ueq,
Uanis(C33) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C6)
\\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq,
Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C2)
\\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C16) \\sim Ueq,
Uanis(C17) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C13)
\\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C64) \\sim Ueq,
Uanis(C30) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C52)
\\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C44) \\sim Ueq,
Uanis(C59) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C71)
\\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C57) \\sim Ueq,
Uanis(C55) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C42) \\sim Ueq,
Uanis(C28) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C28)
\\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C43) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4.a Riding coordinates:
 C24(H24A,H24B,H24C), C49(H49A,H49B,H49C), C06D(H06A,H06B,H06C), C72(H72A,H72B,
 H72C), C6(H6A,H6B,H6C), C11(H11A,H11B,H11C), C64(H64A,H64B,H64C), C8(H8A,H8B,
 H8C), C71(H71A,H71B,H71C), C60(H60A,H60B,H60C), C9(H9A,H9B,H9C), C4(H4A,H4B,
 H4C), C59(H59A,H59B,H59C), C50(H50A,H50B,H50C), C5(H5A,H5B,H5C)
4.b Secondary CH2 refined with riding coordinates:
 C01E(H01A,H01B), C01X(H01C,H01D), C01Z(H01E,H01F), C02A(H02A,H02B), C02H(H02C,
 H02E), C02R(H02F,H02G), C02Y(H02H,H02L), C03F(H03A,H03B), C03H(H03C,H03F),
 C03S(H03L,H03M), C03W(H03N,H03O), C04A(H04A,H04B), C04R(H04G,H04I), C033(H03S,
 H03V), C038(H03W,H03Y), C039(H03Z,H), C040(H04M,H04Q), C053(H05J,H05K)
4.c Aromatic/amide H refined with riding coordinates:
 C34(H34), C01R(H01R), C01V(H01V), C02D(H02D), C02I(H02I), C02J(H02J),
 C02K(H02K), C02O(H02O), C32(H32), C03D(H03D), C03E(H03E), C03J(H03J),
 C03K(H03K), C03T(H03T), C03U(H03U), C03X(H03X), C04D(H04D), C69(H69),
 C04H(H04H), C04N(H04N), C04O(H04O), C04P(H04P), C18(H18), C36(H36), C19(H19),
 C025(H025), C037(H037), C041(H041), C042(H042), C046(H046)
4.d Idealised Me refined as rotating group:
 C03P(H03G,H03H,H03I), C03Y(H03P,H03Q,H03R), C04L(H04C,H04E,H04F), C04Z(H04J,
 H04K,H04L), C05I(H05A,H05B,H05C), C05K(H05D,H05E,H05F), C05P(H05G,H05H,H05I),
 C20(H20A,H20B,H20C), C13(H13A,H13B,H13C), C31(H31A,H31B,H31C), C3(H3A,H3B,H3C),
  C06F(H06D,H06E,H06F), C16(H16A,H16B,H16C), C14(H14A,H14B,H14C), C33(H33A,H33B,
 H33C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C17(H17A,H17B,H17C), C65(H65A,
 H65B,H65C), C52(H52A,H52B,H52C), C7(H7A,H7B,H7C), C62(H62A,H62B,H62C),
 C68(H68A,H68B,H68C), C53(H53A,H53B,H53C), C55(H55A,H55B,H55C), C22(H22A,H22B,
 H22C), C10(H10A,H10B,H10C), C74(H74A,H74B,H74C), C45(H45A,H45B,H45C), C27(H27A,
 H27B,H27C), C66(H66A,H66B,H66C), C061(H06G,H06H,H06I), C54(H54A,H54B,H54C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              92656
_shelx_fab_checksum              49431
_olex2_submission_special_instructions 'No special instructions were received'