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_1570464
_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         'C364 H422 N2 Na2 O70 Ti16, 2(C2 H3 N)'
_chemical_formula_sum            'C368 H428 N4 Na2 O70 Ti16'
_chemical_formula_weight         6839.50
_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   geom
_audit_block_doi                 10.5517/ccdc.csd.cc2bzp01
_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                 114.933(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   38.447(2)
_cell_length_b                   32.9077(17)
_cell_length_c                   37.172(2)
_cell_measurement_reflns_used    9389
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      52.14
_cell_measurement_theta_min      3.34
_cell_volume                     42647(4)
_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      150.0
_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 0.936
_diffrn_measured_fraction_theta_max 0.985
_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  0.0895
_diffrn_reflns_av_unetI/netI     0.0675
_diffrn_reflns_Laue_measured_fraction_full 0.936
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -45
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            217747
_diffrn_reflns_point_group_measured_fraction_full 0.936
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         52.317
_diffrn_reflns_theta_min         2.379
_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
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.878
_exptl_absorpt_correction_T_max  0.2987
_exptl_absorpt_correction_T_min  0.1954
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1407 before and 0.0861 after correction.
The Ratio of minimum to maximum transmission is 0.6542.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.065
_exptl_crystal_description       block
_exptl_crystal_F_000             14392
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.882
_refine_diff_density_min         -0.537
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2132
_refine_ls_number_reflns         36156
_refine_ls_number_restraints     60
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.1047
_refine_ls_R_factor_gt           0.0904
_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^)+(0.1448P)^2^+170.1562P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2599
_refine_ls_wR_factor_ref         0.2706
_reflns_Friedel_coverage         0.000
_reflns_number_gt                27929
_reflns_number_total             36156
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06046b2.cif
_cod_data_source_block           Ti16L4-1-NaOH
_cod_depositor_comments
'Adding full bibliography for 1570454--1570469.cif.'
_cod_original_cell_volume        42646(4)
_cod_database_code               1570464
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.603
_shelx_estimated_absorpt_t_min   0.454
_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. Uiso/Uaniso restraints and constraints
C5 \\sim N2 \\sim Na1A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C6 \\sim C7 \\sim C8 \\sim C9: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C1 \\sim C2 \\sim C3 \\sim C4: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(N2) \\sim Ueq, Uanis(Na1) \\sim Ueq, Uanis(O1) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: Na1(0.5) Na1A(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C02A(H02A,H02B), C02D(H02C,H02D), C02S(H02E,H02G), C02V(H02H,H02I), C02Z(H02J,
 H02K), C03C(H03B,H03C), C03F(H03E,H03F), C03J(H03G,H03H), C03O(H03J,H03K),
 C03R(H03L,H03O), C03S(H03P,H03Q), C022(H02M,H02N), C024(H02O,H02P), C034(H03R,
 H03S), C046(H04P,H04Q), C049(H04S,H04T)
4.b Aromatic/amide H refined with riding coordinates:
 C01G(H01G), C01K(H01K), C01Q(H01Q), C01S(H01S), C02F(H02F), C02L(H02L),
 C02R(H02R), C02T(H02T), C02U(H02U), C02X(H02X), C03A(H03A), C03D(H03D),
 C03I(H03I), C03M(H03M), C03N(H03N), C03T(H03T), C03W(H03W), C03X(H03X),
 C03Y(H03Y), C03Z(H03Z), C04D(H04D), C04K(H04K), C04O(H04O), C04R(H04R),
 C04V(H04V), C035(H035), C036(H036), C041(H041), C042(H042), C044(H044),
 C048(H048), C050(H050)
4.c Idealised Me refined as rotating group:
 C04A(H04A,H04B,H04C), C04J(H04E,H04F,H04G), C04M(H04H,H04I,H04J), C04Z(H04L,
 H04M,H04N), C05A(H05A,H05B,H05C), C05D(H05D,H05E,H05F), C8(H8A,H8B,H8C),
 C05F(H05G,H05H,H05I), C05G(H05J,H05K,H05L), C05J(H05M,H05N,H05O), C05K(H05P,
 H05Q,H05R), C05L(H05S,H05T,H05U), C05M(H05V,H05W,H05X), C05N(H05Y,H,HA),
 C05P(H05Z,HB,HC), C05Q(H05,HD,HE), C05S(H1,HF,HG), C05T(H2,HH,HI), C05U(H3,HJ,
 HK), C05W(H4,HL,HM), C05X(H5,HN,HO), C05Y(H6,HP,HQ), C06A(H06A,H06B,H06C),
 C06B(H06D,H06E,H06F), C06D(H06G,H06H,H06I), C06E(H06J,H06K,H06L), C7(H7A,H7B,
 H7C), C3(H3A,H3B,H3C), C06H(H06M,H06N,H06O), C06J(H06P,H06Q,H06R), C06K(H06S,
 H06T,H06U), C06N(H06V,H06W,H06X), C06Q(H06Y,HR,HS), C6(H6A,H6B,H6C), C06T(H06Z,
 HT,HU), C1(H1A,H1B,H1C), C06W(H06,HV,HW), C4(H4A,H4B,H4C), C053(H7,HX,HY),
 C054(H8,HZ,H19), C055(H9,H20,H21), C056(H10,H22,H23), C058(H11,H24,H25),
 C060(H12,H26,H27), C062(H13,H28,H29), C064(H14,H30,H31), C065(H15,H32,H33),
 C067(H16,H34,H35), C069(H17,H36,H37), C05I(H18,H38,H39)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              81133
_shelx_fab_checksum              49585
_olex2_submission_special_instructions 'No special instructions were received'