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_1570468
_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         'C392 H480 O72 Ti16, 2(C2 H3 N)'
_chemical_formula_sum            'C396 H486 N2 O72 Ti16'
_chemical_formula_weight         7192.24
_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.cc2bznww
_audit_creation_date             2022-05-01
_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                 115.461(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   39.1900(19)
_cell_length_b                   32.5046(16)
_cell_length_c                   38.1646(18)
_cell_measurement_reflns_used    9787
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      52.852
_cell_measurement_theta_min      3.106
_cell_volume                     43894(4)
_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 2013/2 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_detector                 'Image Plate'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 0.976
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku R-AXIS SPIDER IP'
_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  0.0589
_diffrn_reflns_av_unetI/netI     0.0387
_diffrn_reflns_Laue_measured_fraction_full 0.976
_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       37
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            285986
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         53.086
_diffrn_reflns_theta_min         2.339
_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
_exptl_absorpt_coefficient_mu    1.921
_exptl_absorpt_correction_T_max  0.7505
_exptl_absorpt_correction_T_min  0.5862
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1116 before and 0.0708 after correction.
The Ratio of minimum to maximum transmission is 0.7811.
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    1.088
_exptl_crystal_description       block
_exptl_crystal_F_000             15216
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.982
_refine_diff_density_min         -1.242
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2343
_refine_ls_number_reflns         38766
_refine_ls_number_restraints     326
_refine_ls_restrained_S_all      1.136
_refine_ls_R_factor_all          0.1168
_refine_ls_R_factor_gt           0.0999
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.1855P)^2^+95.7495P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2974
_refine_ls_wR_factor_ref         0.3146
_reflns_Friedel_coverage         0.000
_reflns_number_gt                29181
_reflns_number_total             38766
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06046b2.cif
_cod_data_source_block           Ti16L4-1
_cod_depositor_comments
'Adding full bibliography for 1570454--1570469.cif.'
_cod_database_code               1570468
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.597
_shelx_estimated_absorpt_t_min   0.447
_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
 C102-C105
 2.2 with sigma of 0.01
 C101-C97
 2.5 with sigma of 0.01
 C04E-C108 \\sim C04E-C89
 with sigma of 0.02
 C04E-C92 \\sim C04E-C90
 with sigma of 0.02
 C04E-C103 \\sim C04E-C93
 with sigma of 0.02
 C94-C102 \\sim C94-C91
 with sigma of 0.02
 C94-C105 \\sim C94-C96
 with sigma of 0.02
 C94-C104 \\sim C94-C98
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C102 \\sim C91: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C97 \\sim C101 \\sim C106 \\sim C107: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C86 \\sim C85 \\sim C87 \\sim C88: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C43 \\sim C44 \\sim C45 \\sim O7: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C95)
\\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C40) \\sim Ueq,
Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C58)
\\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(C93) \\sim Ueq,
Uanis(C108) \\sim Ueq, Uanis(C89) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C92)
\\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C57) \\sim Ueq,
Uanis(C56) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C63)
\\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C109) \\sim Ueq,
Uanis(C45) \\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(C104)
\\sim Ueq, Uanis(C98) \\sim Ueq, Uanis(C105) \\sim Ueq, Uanis(C96) \\sim Ueq,
Uanis(C102) \\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C85)
\\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C97) \\sim Ueq,
Uanis(C101) \\sim Ueq, Uanis(C106) \\sim Ueq, Uanis(C107) \\sim Ueq,
Uanis(C101) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O1) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Others
 Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(H93C)=Sof(C89)=Sof(H89A)=Sof(H89B)=Sof(H89C)=
 Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(H90C)=1-FVAR(1)
 Sof(C108)=Sof(H10J)=Sof(H10K)=Sof(H10L)=Sof(C92)=Sof(H92A)=Sof(H92B)=
 Sof(H92C)=Sof(C103)=Sof(H10M)=Sof(H10N)=Sof(H10O)=FVAR(1)
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=1-FVAR(2)
 Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=FVAR(2)
 Sof(C10A)=Sof(H10R)=Sof(H10S)=Sof(H10T)=1-FVAR(3)
 Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(H95C)=FVAR(3)
 Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(H96C)=Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(H91C)=
 Sof(C98)=Sof(H98A)=Sof(H98B)=Sof(H98C)=1-FVAR(4)
 Sof(C104)=Sof(H10U)=Sof(H10V)=Sof(H10W)=Sof(C102)=Sof(H10X)=Sof(H10Y)=Sof(HJ)=
 Sof(C105)=Sof(H10Z)=Sof(HK)=Sof(HL)=FVAR(4)
 Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=1-FVAR(5)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=FVAR(5)
5.a Riding coordinates:
 C101(H10G,H10H,H10I)
5.b Ternary CH refined with riding coordinates:
 C043(H043), C04W(H04W)
5.c Secondary CH2 refined with riding coordinates:
 C018(H01A,H01B), C01F(H01C,H01D), C021(H02A,H02B), C024(H02C,H02D), C39(H39A,
 H39B), C029(H02E,H02F), C02A(H02G,H02H), C71(H71A,H71B), C02W(H02J,H02K),
 C030(H03A,H03B), C03D(H03D,H03E), C79(H79A,H79B), C03I(H03G,H03H), C18(H18A,
 H18B), C11(H11A,H11B), C100(H10P,H10Q)
5.d Aromatic/amide H refined with riding coordinates:
 C51(H51), C01S(H01S), C47(H47), C02B(H02I), C6(H6), C02O(H02O), C02P(H02P),
 C02R(H02R), C02S(H02S), C34(H34), C67(H67), C032(H032), C10(H10), C039(H039),
 C03A(H03C), C03F(H03F), C33(H33), C68(H68), C03N(H03N), C03P(H03P), C75(H75),
 C03U(H03U), C03X(H03X), C040(H040), C23(H23), C82(H82), C80(H80), C047(H047),
 C15(H15), C20(H20), C73(H73), C13(H13)
5.e Idealised Me refined as rotating group:
 C83(H83A,H83B,H83C), C04G(H04A,H04B,H04C), C04I(H04D,H04E,H04F), C04M(H04G,
 H04H,H04I), C04O(H04J,H04K,H04L), C04P(H04M,H04N,H04O), C2(H2A,H2B,H2C),
 C3(H3A,H3B,H3C), C04T(H04P,H04Q,H04R), C04V(H04S,H04T,H04U), C4(H4A,H4B,H4C),
 C04Y(H04V,H04X,H04Y), C053(H05A,H05B,H05C), C054(H05D,H05E,H05F), C055(H2,H,
 HA), C55(H55A,H55B,H55C), C059(H05G,H05H,H05I), C05A(H05J,H05K,H05L),
 C05C(H05M,H05N,H05O), C52(H52A,H52B,H52C), C05E(H05P,H05Q,H05R), C05G(H05S,
 H05T,H05U), C30(H30A,H30B,H30C), C54(H54A,H54B,H54C), C05L(H05V,H05W,H05X),
 C32(H32A,H32B,H32C), C05S(H05Y,HB,HC), C05T(H05Z,HD,HE), C05U(H05,HF,HG),
 C05W(H1,HH,HI), C58(H58A,H58B,H58C), C41(H41A,H41B,H41C), C85(H85A,H85B,H85C),
 C97(H97A,H97B,H97C), C61(H61A,H61B,H61C), C57(H57A,H57B,H57C), C43(H43A,H43B,
 H43C), C28(H28A,H28B,H28C), C95(H95A,H95B,H95C), C107(H10A,H10B,H10C),
 C99(H99A,H99B,H99C), C59(H59A,H59B,H59C), C86(H86A,H86B,H86C), C88(H88A,H88B,
 H88C), C109(H10D,H10E,H10F), C31(H31A,H31B,H31C), C60(H60A,H60B,H60C),
 C64(H64A,H64B,H64C), C40(H40A,H40B,H40C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C108(H10J,H10K,H10L), C92(H92A,H92B,H92C), C103(H10M,H10N,H10O),
 C93(H93A,H93B,H93C), C89(H89A,H89B,H89C), C90(H90A,H90B,H90C), C63(H63A,H63B,
 H63C), C45(H45A,H45B,H45C), C10A(H10R,H10S,H10T), C104(H10U,H10V,H10W),
 C102(H10X,H10Y,HJ), C105(H10Z,HK,HL), C96(H96A,H96B,H96C), C91(H91A,H91B,H91C),
  C98(H98A,H98B,H98C), C31A(H31D,H31E,H31F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              99198
_shelx_fab_checksum              44708
_olex2_submission_special_instructions 'No special instructions were received'