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_1570463
_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         'C386 H468 O71 Ti16, 2(C2 H3 N)'
_chemical_formula_sum            'C390 H474 N2 O71 Ti16'
_chemical_formula_weight         7092.08
_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_creation_date             2023-08-12
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-08-15 deposited with the CCDC.	2023-11-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.3290(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   39.0491(14)
_cell_length_b                   32.3507(12)
_cell_length_c                   37.9914(14)
_cell_measurement_reflns_used    9272
_cell_measurement_temperature    90.0
_cell_measurement_theta_max      51.30
_cell_measurement_theta_min      2.35
_cell_volume                     43379(3)
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_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 0.996
_diffrn_measured_fraction_theta_max 0.996
_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  0.0564
_diffrn_reflns_av_unetI/netI     0.0350
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -45
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            302985
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        51.363
_diffrn_reflns_theta_max         51.363
_diffrn_reflns_theta_min         2.350
_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    1.844
_exptl_absorpt_correction_T_max  0.7501
_exptl_absorpt_correction_T_min  0.5522
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1506 before and 0.0659 after correction.
The Ratio of minimum to maximum transmission is 0.7362.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'dull reddish red'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.086
_exptl_crystal_description       block
_exptl_crystal_F_000             14992
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.891
_refine_diff_density_min         -1.028
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2422
_refine_ls_number_reflns         35755
_refine_ls_number_restraints     366
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.1127
_refine_ls_R_factor_gt           0.0971
_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^)+(0.1953P)^2^+92.0210P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2887
_refine_ls_wR_factor_ref         0.3070
_reflns_Friedel_coverage         0.000
_reflns_number_gt                27444
_reflns_number_total             35755
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06046b2.cif
_cod_data_source_block           Ti16L4-1-postcatalysis
_cod_depositor_comments
'Adding full bibliography for 1570454--1570469.cif.'
_cod_database_code               1570463
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.608
_shelx_estimated_absorpt_t_min   0.459
_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
 C139-C33
 1.45 with sigma of 0.01
 O7-C33
 1.45 with sigma of 0.01
 Ti2-C33
 2.8 with sigma of 0.01
 O15-C33
 1.45 with sigma of 0.01
 C212-C213 = C213-C214
 1.5 with sigma of 0.02
 C209-C210 = C210-C211
 1.5 with sigma of 0.02
 C5-C159
 1.45 with sigma of 0.01
 C191-C175 \\sim C191-C56
 with sigma of 0.02
 C175-C171 \\sim C56-C173
 with sigma of 0.02
 C191-C11 \\sim C191-C89
 with sigma of 0.02
 C191-C171 \\sim C191-C173
 with sigma of 0.02
 C159-C4 \\sim C159-C5
 with sigma of 0.02
 C159-C6 \\sim C159-C1
 with sigma of 0.02
 C159-C2 \\sim C159-C3
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Ti2: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
Uanis(O29) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C191) \\sim Ueq, Uanis(C143)
\\sim Ueq, Uanis(C159) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C167) \\sim Ueq,
Uanis(C121) \\sim Ueq, Uanis(C123) \\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C63)
\\sim Ueq, Uanis(C127) \\sim Ueq, Uanis(C179) \\sim Ueq, Uanis(C171) \\sim Ueq,
Uanis(C175) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C129) \\sim Ueq, Uanis(C137)
\\sim Ueq, Uanis(C187) \\sim Ueq, Uanis(C147) \\sim Ueq, Uanis(C21) \\sim Ueq,
Uanis(C81) \\sim Ueq, Uanis(C165) \\sim Ueq, Uanis(C215) \\sim Ueq, Uanis(C164)
\\sim Ueq, Uanis(C89) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(O25) \\sim Ueq,
Uanis(O29) \\sim Ueq, Uanis(O15) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C39)
\\sim Ueq, Uanis(C173) \\sim Ueq, Uanis(C135) \\sim Ueq, Uanis(C1) \\sim Ueq,
Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim
Ueq, Uanis(C6) \\sim Ueq, Uanis(O29) \\sim Ueq, Uanis(O29A) \\sim Ueq: with
sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C209) \\sim Ueq, Uanis(C210) \\sim Ueq, Uanis(C211) \\sim Ueq,
Uanis(C214) \\sim Ueq, Uanis(C213) \\sim Ueq, Uanis(C212) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 Ti6, O27, C212, C213, C214
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O37, C211, C210, C209, Ti2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C21)=Sof(H21D)=Sof(H21E)=Sof(H21F)=1-FVAR(1)
 Sof(C167)=Sof(H16O)=Sof(H16P)=Sof(H16Q)=FVAR(1)
 Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(H95C)=1-FVAR(2)
 Sof(C189)=Sof(H18J)=Sof(H18K)=Sof(H18L)=FVAR(2)
 Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=1-FVAR(3)
 Sof(C215)=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(3)
 Sof(C164)=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(4)
 Sof(C162)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(4)
 Sof(C165)=Sof(H16L)=Sof(H16M)=Sof(H16N)=1-FVAR(5)
 Sof(C163)=Sof(H16I)=Sof(H16J)=Sof(H16K)=FVAR(5)
 Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C173)=Sof(H17K)=Sof(H17L)=
 Sof(H17M)=Sof(C89)=Sof(H89A)=Sof(H89B)=Sof(H89C)=1-FVAR(6)
 Sof(C171)=Sof(H17H)=Sof(H17I)=Sof(H17J)=Sof(C175)=Sof(H17N)=Sof(H17O)=
 Sof(H17P)=Sof(C11)=Sof(H11J)=Sof(H11K)=Sof(H11L)=FVAR(6)
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=1-FVAR(7)
 Sof(C121)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(7)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C5)=
 Sof(H5A)=Sof(H5B)=Sof(H5C)=1-FVAR(8)
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C4)=
 Sof(H4A)=Sof(H4B)=Sof(H4C)=FVAR(8)
 Sof(O29A)=1-FVAR(9)
 Sof(O29)=FVAR(9)
 Fixed Sof: O7(0.5) O15(0.5) O31(0.5) C33(0.5) O133(0.5) C135(0.5) C17(0.5)
 H17E(0.5) H17F(0.5) H17G(0.5) C139(0.5) H13F(0.5) H13G(0.5) H13H(0.5) O37(0.5)
 C209(0.5) H20P(0.5) H20Q(0.5) H20R(0.5) C210(0.5) C212(0.5) H21G(0.5)
 H21H(0.5) H21I(0.5) C214(0.5) H21J(0.5) H21K(0.5) H21L(0.5) C211(0.5)
 H21M(0.5) H21N(0.5) H21O(0.5) C213(0.5)
6.a Riding coordinates:
 C169(H16R,H16S,H16T), C209(H20P,H20Q,H20R)
6.b Ternary CH refined with riding coordinates:
 C39(H39), C208(H208)
6.c Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C34(H34A,H34B), C38(H38A,H38B), C48(H48A,H48B), C62(H62A,
 H62B), C82(H82A,H82B), C94(H94A,H94B), C130(H13A,H13B), C142(H14A,H14B),
 C144(H14C,H14D), C170(H17A,H17B), C176(H17C,H17D), C151(H15A,H15B), C157(H15C,
 H15D), C161(H16G,H16H), C87(H87A,H87B)
6.d Aromatic/amide H refined with riding coordinates:
 C14(H14), C36(H36), C54(H54), C70(H70), C76(H76), C80(H80), C88(H88),
 C100(H100), C102(H102), C114(H114), C120(H120), C122(H122), C132(H132),
 C136(H136), C146(H146), C150(H150), C156(H156), C158(H158), C160(H160),
 C168(H168), C174(H174), C9(H9), C73(H73), C155(H155), C41(H41), C83(H83),
 C43(H43), C45(H45), C181(H181), C187(H187), C99(H99), C203(H203)
6.e Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C162(H16A,H16B,H16C), C164(H16D,H16E,H16F), C180(H18A,
 H18B,H18C), C182(H18D,H18E,H18F), C188(H18G,H18H,H18I), C190(H19A,H19B,H19C),
 C192(H19D,H19E,H19F), C196(H19G,H19H,H19I), C198(H19J,H19K,H19L), C200(H20A,
 H20B,H20C), C202(H20D,H20E,H20F), C105(H10A,H10B,H10C), C107(H10D,H10E,H10F),
 C27(H27A,H27B,H27C), C109(H10G,H10H,H10I), C111(H11A,H11B,H11C), C113(H11D,
 H11E,H11F), C57(H57A,H57B,H57C), C115(H11G,H11H,H11I), C29(H29A,H29B,H29C),
 C59(H59A,H59B,H59C), C121(H12A,H12B,H12C), C61(H61A,H61B,H61C), C123(H12D,H12E,
 H12F), C31(H31A,H31B,H31C), C63(H63A,H63B,H63C), C127(H12G,H12H,H12I),
 C129(H12J,H12K,H12L), C17(H17E,H17F,H17G), C137(H13C,H13D,H13E), C139(H13F,
 H13G,H13H), C141(H14E,H14F,H14G), C143(H14H,H14I,H14J), C75(H75A,H75B,H75C),
 C215(H21A,H21B,H21C), C81(H81A,H81B,H81C), C163(H16I,H16J,H16K), C165(H16L,
 H16M,H16N), C167(H16O,H16P,H16Q), C21(H21D,H21E,H21F), C171(H17H,H17I,H17J),
 C173(H17K,H17L,H17M), C175(H17N,H17O,H17P), C11(H11J,H11K,H11L), C89(H89A,H89B,
 H89C), C179(H17Q,H17R,H17S), C91(H91A,H91B,H91C), C189(H18J,H18K,H18L),
 C95(H95A,H95B,H95C), C112(H11M,H11N,H11O), C193(H19M,H19N,H19O), C97(H97A,H97B,
 H97C), C195(H19P,H19Q,H19R), C25(H25A,H25B,H25C), C201(H20G,H20H,H20I),
 C101(H10J,H10K,H10L), C51(H51A,H51B,H51C), C205(H20J,H20K,H20L), C103(H10M,
 H10N,H10O), C207(H20M,H20N,H20O), C212(H21G,H21H,H21I), C214(H21J,H21K,H21L),
 C211(H21M,H21N,H21O), C2(H2A,H2B,H2C), C6(H6A,H6B,H6C), C4(H4A,H4B,H4C),
 C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              13478
_shelx_fab_checksum              73511
_olex2_submission_special_instructions 'No special instructions were received'