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_1570457
_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         'C376 H448 N8 Na4 O84 Ti16, 78[H2O]'
_chemical_formula_sum            'C376 H454 N8 Na4 O84 Ti16'
_chemical_formula_weight         7287.81
_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             2023-03-30
_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                 115.189(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   39.187(3)
_cell_length_b                   33.088(2)
_cell_length_c                   37.420(3)
_cell_measurement_reflns_used    9863
_cell_measurement_temperature    150
_cell_measurement_theta_max      50.75
_cell_measurement_theta_min      3.13
_cell_volume                     43906(6)
_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 2018/3 (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 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.1539
_diffrn_reflns_av_unetI/netI     0.1396
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       46
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            192150
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        52.340
_diffrn_reflns_theta_max         52.340
_diffrn_reflns_theta_min         3.049
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           2.85
_diffrn_source_power             0.199101
_diffrn_source_target            Mo
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           69.86
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.964
_exptl_absorpt_correction_T_max  0.6937
_exptl_absorpt_correction_T_min  0.4972
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1665 before and 0.1191 after correction.
The Ratio of minimum to maximum transmission is 0.7167.
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    1.103
_exptl_crystal_description       block
_exptl_crystal_F_000             15336
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.621
_refine_diff_density_min         -0.872
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.205
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2445
_refine_ls_number_reflns         37451
_refine_ls_number_restraints     388
_refine_ls_restrained_S_all      1.220
_refine_ls_R_factor_all          0.1470
_refine_ls_R_factor_gt           0.1148
_refine_ls_shift/su_max          0.001
_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          0.3252
_refine_ls_wR_factor_ref         0.3510
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24858
_reflns_number_total             37451
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06046b2.cif
_cod_data_source_block           Ti16L4-1-HAma
_cod_depositor_comments
'Adding full bibliography for 1570454--1570469.cif.'
_cod_original_cell_volume        43905(6)
_cod_database_code               1570457
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.590
_shelx_estimated_absorpt_t_min   0.440
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups,
  All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C129-C115
 1.45 with sigma of 0.01
 H13F-H86
 2 with sigma of 0.01
 C49-C47
 1.45 with sigma of 0.01
 C124-C136
 1.55 with sigma of 0.01
 C116-C129
 1.45 with sigma of 0.01
 C49-C50
 1.55 with sigma of 0.01
 C132-C133
 2.2 with sigma of 0.01
 C52-C49
 1.45 with sigma of 0.01
 C50-C48
 2.2 with sigma of 0.01
 C132-C131
 2.5 with sigma of 0.01
 C145-C123
 1.45 with sigma of 0.01
 C145-O17
 1.45 with sigma of 0.01
 C141-N5
 1.45 with sigma of 0.01
 N2-C33
 1.45 with sigma of 0.01
 C1-C2
 1.45 with sigma of 0.01
 N4-C123
 1.45 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C123 \\sim N4: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C109 \\sim C133: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C123 \\sim C145: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
O17 \\sim C145: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C141 \\sim N5: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C134 \\sim C122 \\sim C135 \\sim C4: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
N4 \\sim C123 \\sim C145: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.002 within 2A
C33 \\sim N2 \\sim N3: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C145 \\sim C123 \\sim N4: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(C79) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C130) \\sim Ueq, Uanis(C116)
\\sim Ueq, Uanis(C115) \\sim Ueq, Uanis(C126) \\sim Ueq, Uanis(C51) \\sim Ueq,
Uanis(C111) \\sim Ueq, Uanis(C110) \\sim Ueq, Uanis(C136) \\sim Ueq,
Uanis(C133) \\sim Ueq, Uanis(C134) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C110)
\\sim Ueq, Uanis(C138) \\sim Ueq, Uanis(C136) \\sim Ueq, Uanis(N4) \\sim Ueq,
Uanis(N5) \\sim Ueq, Uanis(C140) \\sim Ueq, Uanis(C141) \\sim Ueq, Uanis(C63)
\\sim Ueq, Uanis(C114) \\sim Ueq, Uanis(C112) \\sim Ueq, Uanis(C86) \\sim Ueq,
Uanis(C136) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C145) \\sim Ueq, Uanis(O17)
\\sim Ueq, Uanis(C131) \\sim Ueq, Uanis(C127) \\sim Ueq, Uanis(C77) \\sim Ueq,
Uanis(C120) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C125) \\sim Ueq, Uanis(C24A)
\\sim Ueq, Uanis(C113) \\sim Ueq, Uanis(C118) \\sim Ueq, Uanis(C2) \\sim Ueq,
Uanis(C132) \\sim Ueq, Uanis(C109) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C124)
\\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C19A) \\sim Ueq,
Uanis(C119) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C121) \\sim Ueq, Uanis(C52)
\\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C142) \\sim Ueq, Uanis(N1) \\sim Ueq,
Uanis(C122) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(N3) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C78)=Sof(H78A)=Sof(H78B)=
 Sof(H78C)=1-FVAR(1)
 Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=
 FVAR(1)
 Sof(C110)=Sof(H11M)=Sof(H11N)=Sof(H11O)=Sof(C120)=Sof(H12Q)=Sof(H12R)=
 Sof(H12S)=1-FVAR(2)
 Sof(C118)=Sof(H11J)=Sof(H11K)=Sof(H11L)=Sof(C138)=Sof(H13R)=Sof(H13S)=
 Sof(H13T)=FVAR(2)
 Sof(C115)=Sof(H11G)=Sof(H11H)=Sof(H11I)=Sof(C125)=Sof(H12K)=Sof(H12L)=
 Sof(H12M)=Sof(C128)=Sof(H12N)=Sof(H12O)=Sof(H12P)=1-FVAR(3)
 Sof(C116)=Sof(H11S)=Sof(H11T)=Sof(H11U)=Sof(C126)=Sof(H12W)=Sof(H12X)=
 Sof(H12Y)=Sof(C127)=Sof(H12Z)=Sof(H)=Sof(HA)=FVAR(3)
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=Sof(C144)=Sof(H14F)=Sof(H14G)=
 Sof(H14H)=1-FVAR(4)
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=
 FVAR(4)
 Sof(C109)=Sof(C132)=Sof(H13L)=Sof(H13M)=Sof(H13N)=Sof(C133)=Sof(H13O)=
 Sof(H13P)=Sof(H13Q)=1-FVAR(5)
 Sof(C113)=Sof(H11P)=Sof(H11Q)=Sof(H11R)=Sof(C124)=Sof(H12T)=Sof(H12U)=
 Sof(H12V)=Sof(C136)=FVAR(5)
 Sof(C19A)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C80)=Sof(H80A)=Sof(H80B)=
 Sof(H80C)=1-FVAR(6)
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C130)=Sof(H13I)=Sof(H13J)=
 Sof(H13K)=FVAR(6)
 Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=
 1-FVAR(7)
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=
 FVAR(7)
 Sof(Ti8A)=1-FVAR(8)
 Sof(Ti8)=FVAR(8)
 Sof(O1A)=1-FVAR(9)
 Sof(O1)=FVAR(9)
 Sof(H33C)=Sof(H33D)=Sof(N3)=Sof(H3A)=Sof(H3B)=1-FVAR(10)
 Sof(H33A)=Sof(H33B)=Sof(N2)=Sof(H2D)=Sof(H2E)=FVAR(10)
5.a Riding coordinates:
 C134(H13A,H13B,H13C), C2(H2A,H2B,H2C), C128(H12N,H12O,H12P), C132(H13L,H13M,
 H13N), C133(H13O,H13P,H13Q)
5.b Rotating group:
 O05F(H05A,H05B), O05S(H05C,H05D), N4(H4), N5(H5A,H5B), N1(H1A,H1B), N2(H2D,
 H2E), N3(H3A,H3B)
5.c Secondary CH2 refined with riding coordinates:
 C01Z(H01A,H01B), C02N(H02A,H02B), C03F(H03A,H03B), C03N(H03D,H03E), C04K(H04D,
 H04E), C33(H33A,H33B), C33(H33C,H33D), C12(H12A,H12B), C36(H36A,H36B),
 C036(H03F,H03H), C58(H58A,H58B), C059(H05W,H05X), C68(H68A,H68B), C85(H85A,
 H85B), C88(H88A,H88B), C95(H95A,H95B), C102(H10A,H10B), C108(H10C,H10D),
 C123(H12F,H12G), C137(H13G,H13H), C141(H14A,H14B)
5.d Aromatic/amide H refined with riding coordinates:
 C02G(H02G), C03C(H03C), C03G(H03G), C03K(H03K), C03L(H03L), C03P(H03P),
 C03S(H03S), C04X(H04X), C7(H7), C11(H11), C14(H14), C16(H16), C25(H25),
 C025(H025), C27(H27), C033(H033), C38(H38), C44(H44), C047(H047), C55(H55),
 C56(H56), C70(H70), C72(H72), C83(H83), C86(H86), C87(H87), C90(H90), C92(H92),
  C97(H97), C99(H99), C106(H106), C112(H112)
5.e Idealised Me refined as rotating group:
 C04J(H04A,H04B,H04C), C04P(H04F,H04G,H04H), C05G(H05E,H05F,H05G), C05K(H05H,
 H05I,H05J), C05N(H05K,H05L,H05M), C05W(H05N,H05O,H05P), C05Z(H05Q,H05R,H05S),
 C06J(H06A,H06B,H06C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C40(H40A,H40B,H40C), C41(H41A,
 H41B,H41C), C43(H43A,H43B,H43C), C48(H48A,H48B,H48C), C052(H05T,H05U,H05V),
 C60(H60A,H60B,H60C), C4(H4A,H4B,H4C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C),
  C67(H67A,H67B,H67C), C117(H11A,H11B,H11C), C119(H11D,H11E,H11F), C121(H12C,
 H12D,H12E), C131(H13D,H13E,H13F), C142(H14C,H14D,H14E), C122(H12H,H12I,H12J),
 C61(H61A,H61B,H61C), C144(H14F,H14G,H14H), C17(H17A,H17B,H17C), C51(H51A,H51B,
 H51C), C77(H77A,H77B,H77C), C79(H79A,H79B,H79C), C115(H11G,H11H,H11I),
 C118(H11J,H11K,H11L), C125(H12K,H12L,H12M), C130(H13I,H13J,H13K), C138(H13R,
 H13S,H13T), C63(H63A,H63B,H63C), C62(H62A,H62B,H62C), C19A(H19A,H19B,H19C),
 C24A(H24A,H24B,H24C), C35(H35A,H35B,H35C), C47(H47A,H47B,H47C), C50(H50A,H50B,
 H50C), C78(H78A,H78B,H78C), C80(H80A,H80B,H80C), C110(H11M,H11N,H11O),
 C113(H11P,H11Q,H11R), C116(H11S,H11T,H11U), C120(H12Q,H12R,H12S), C124(H12T,
 H12U,H12V), C126(H12W,H12X,H12Y), C127(H12Z,H,HA), C52(H52A,H52B,H52C),
 C75(H75A,H75B,H75C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              66584
_shelx_fab_checksum              2619
_olex2_submission_special_instructions 'No special instructions were received'