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_1570466
_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 H456 O72 Ti16'
_chemical_formula_sum            'C380 H456 O72 Ti16'
_chemical_formula_weight         6941.82
_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.cc2bznzz
_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                 113.305(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   37.9325(16)
_cell_length_b                   32.9482(15)
_cell_length_c                   37.0574(16)
_cell_measurement_reflns_used    9502
_cell_measurement_temperature    90.0
_cell_measurement_theta_max      48.10
_cell_measurement_theta_min      2.39
_cell_volume                     42536(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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      90.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.795
_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  0.0823
_diffrn_reflns_av_unetI/netI     0.0533
_diffrn_reflns_Laue_measured_fraction_full 0.795
_diffrn_reflns_Laue_measured_fraction_max 0.995
_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       41
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            290561
_diffrn_reflns_point_group_measured_fraction_full 0.795
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         48.329
_diffrn_reflns_theta_min         2.200
_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    1.971
_exptl_absorpt_correction_T_max  0.5569
_exptl_absorpt_correction_T_min  0.314
_exptl_absorpt_correction_type   multi-scan
_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    1.084
_exptl_crystal_description       block
_exptl_crystal_F_000             14656
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.384
_refine_diff_density_min         -0.887
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2322
_refine_ls_number_reflns         30587
_refine_ls_number_restraints     286
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0993
_refine_ls_R_factor_gt           0.0839
_refine_ls_shift/su_max          0.033
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.1582P)^2^+96.5700P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2501
_refine_ls_wR_factor_ref         0.2668
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23541
_reflns_number_total             30587
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06046b2.cif
_cod_data_source_block           Ti16L4-1-1
_cod_depositor_comments
'Adding full bibliography for 1570454--1570469.cif.'
_cod_database_code               1570466
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.589
_shelx_estimated_absorpt_t_min   0.439
_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
 C23-C48
 1.5 with sigma of 0.01
 C06L-C25 \\sim C29-C2A
 with sigma of 0.04
 C04P-C25 \\sim C04P-C2A
 with sigma of 0.02
 C04P-C32 \\sim C04P-C31
 with sigma of 0.04
 C06L-C32 \\sim C29-C31
 with sigma of 0.04
 C25-C32 \\sim C2A-C31
 with sigma of 0.04
 C04P-C06L \\sim C04P-C29
 with sigma of 0.04
 C23-C49 \\sim C23-C50
 with sigma of 0.02
 C33-C23 \\sim C52-C23
 with sigma of 0.02
 C23-C51 \\sim C23-C48
 with sigma of 0.02
 C063-C066 \\sim C26-C20
 with sigma of 0.04
 C044-C05C \\sim C044-C19
 with sigma of 0.02
 C05C-C063 \\sim C19-C26
 with sigma of 0.04
 C044-C066 \\sim C044-C20
 with sigma of 0.02
 C044-C063 \\sim C044-C26
 with sigma of 0.04
 C05C-C066 \\sim C19-C20
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C23 \\sim C33: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C4 \\sim C6 \\sim C7 \\sim C8: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C30) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C31)
\\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C23) \\sim Ueq,
Uanis(C49) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C50)
\\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C47) \\sim Ueq,
Uanis(C21) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C33)
\\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C46) \\sim Ueq,
Uanis(C42) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C26)
\\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C53) \\sim Ueq,
Uanis(C16) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C8)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=1-FVAR(1)
 Sof(C06L)=Sof(H06G)=Sof(H06H)=Sof(H06I)=Sof(C25)=Sof(H25A)=Sof(H25B)=
 Sof(H25C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(1)
 Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=
 Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=1-FVAR(2)
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=FVAR(2)
 Sof(C47)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C24)=Sof(H24A)=Sof(H24B)=
 Sof(H24C)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C42)=Sof(H42)=Sof(C45)=
 Sof(C46)=Sof(H46)=1-FVAR(3)
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C34)=Sof(C30)=Sof(H30A)=Sof(H30B)=
 Sof(H30C)=Sof(C35)=Sof(H35)=Sof(C27)=Sof(C13)=Sof(H13)=Sof(C40)=Sof(H40A)=
 Sof(H40B)=Sof(H40C)=FVAR(3)
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=1-FVAR(4)
 Sof(C05C)=Sof(H05D)=Sof(H05E)=Sof(H05F)=Sof(C063)=Sof(H06P)=Sof(H06Q)=
 Sof(H06R)=Sof(C066)=Sof(H06S)=Sof(H06T)=Sof(H06U)=FVAR(4)
5.a Riding coordinates:
 C19(H19A,H19B,H19C)
5.b Ternary CH refined with riding coordinates:
 C04O(H04O), C05H(H05P)
5.c Secondary CH2 refined with riding coordinates:
 C01N(H01A,H01B), C02H(H02A,H02B), C02O(H02D,H02E), C02S(H02F,H02G), C02T(H02H,
 H02I), C02Y(H02J,H02M), C03C(H03A,H03B), C03D(H03C,H03D), C03J(H03F,H03G),
 C03M(H03I,H03J), C03Q(H03K,H03M), C03V(H03N,H03O), C5(H5A,H5B), C026(H02N,
 H02O), C029(H02Q,H02S), C1(H1A,H1B)
5.d Aromatic/amide H refined with riding coordinates:
 C01U(H01U), C02C(H02C), C02K(H02K), C02L(H02L), C02P(H02P), C02R(H02R),
 C02X(H02X), C02Z(H02Z), C03E(H03E), C03H(H03H), C03L(H03L), C03R(H03R),
 C03S(H03S), C03U(H03U), C03X(H03X), C04C(H04D), C04R(H04R), C35(H35), C13(H13),
  C8(H8), C022(H022), C027(H027), C030(H030), C031(H031), C032(H032),
 C034(H034), C6(H6), C038(H038), C42(H42), C46(H46), C046(H046), C049(H049),
 C055(H055), C056(H056)
5.e Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C2A(H2AA,H2AB,H2AC), C20(H20A,H20B,H20C), C04A(H04A,H04B,
 H04C), C04M(H04E,H04F,H04G), C04N(H04H,H04I,H04J), C04Q(H04K,H04L,H04M),
 C04S(H04N,H04P,H04Q), C04U(H04S,H04T,H04U), C04V(H04V,H04W,H04X), C04W(H04Y,H,
 HA), C04X(H04Z,HB,HC), C04Y(H04,HD,HE), C04Z(H1,HF,HG), C21(H21A,H21B,H21C),
 C05B(H05A,H05B,H05C), C05C(H05D,H05E,H05F), C05D(H05G,H05H,H05I), C17(H17A,
 H17B,H17C), C05F(H05J,H05K,H05L), C05G(H05M,H05N,H05O), C05I(H05Q,H05R,H05S),
 C05N(H05T,H05U,H05V), C05O(H05W,H05X,H05Y), C05R(H05Z,HH,HI), C05V(H05,HJ,HK),
 C05W(H2,HL,HM), C05X(H3,HN,HO), C05Y(H4,HP,HQ), C05Z(H5,HR,HS), C24(H24A,H24B,
 H24C), C06A(H06A,H06B,H06C), C16(H16A,H16B,H16C), C06H(H06D,H06E,H06F),
 C06L(H06G,H06H,H06I), C51(H51A,H51B,H51C), C43(H43A,H43B,H43C), C22(H22A,H22B,
 H22C), C30(H30A,H30B,H30C), C48(H48A,H48B,H48C), C50(H50A,H50B,H50C), C52(H52A,
 H52B,H52C), C25(H25A,H25B,H25C), C49(H49A,H49B,H49C), C12(H12A,H12B,H12C),
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C), C32(H32A,H32B,
 H32C), C9(H9A,H9B,H9C), C40(H40A,H40B,H40C), C11(H11A,H11B,H11C), C043(H7,HT,
 HU), C33(H33A,H33B,H33C), C44(H44A,H44B,H44C), C052(H9,HV,HW), C053(H10,HX,HY),
  C058(H11,HZ,H12), C060(H06J,H06K,H06L), C062(H06M,H06N,H06O), C063(H06P,H06Q,
 H06R), C14(H14A,H14B,H14C), C066(H06S,H06T,H06U), C53(H53A,H53B,H53C),
 C068(H06V,H06W,H06X)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              87509
_shelx_fab_checksum              11971
_olex2_submission_special_instructions 'No special instructions were received'