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_1570456
_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         '2(C378 H448 Br4 O74 Ti16)'
_chemical_formula_sum            'C756 H896 Br8 O148 Ti32'
_chemical_formula_weight         14522.75
_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             2023-02-04
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-08-09 deposited with the CCDC.	2023-11-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.147(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   39.278(7)
_cell_length_b                   32.838(6)
_cell_length_c                   37.800(6)
_cell_measurement_reflns_used    5312
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      50.974
_cell_measurement_theta_min      2.348
_cell_volume                     44134(13)
_computing_cell_refinement       'SAINT V8.40C (?, 2016)'
_computing_data_collection       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_reduction        'SAINT V8.40C (?, 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      150.00
_diffrn_detector                 'Image Plate'
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 0.753
_diffrn_measured_fraction_theta_max 0.948
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku R-AXIS Spider'
_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_unetI/netI     0.1118
_diffrn_reflns_Laue_measured_fraction_full 0.753
_diffrn_reflns_Laue_measured_fraction_max 0.948
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -43
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            42512
_diffrn_reflns_point_group_measured_fraction_full 0.753
_diffrn_reflns_point_group_measured_fraction_max 0.948
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         48.177
_diffrn_reflns_theta_min         1.593
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           2.86
_diffrn_source_power             0.1997996
_diffrn_source_target            Mo
_diffrn_source_voltage           69.86
_exptl_absorpt_coefficient_mu    2.186
_exptl_absorpt_correction_T_max  0.485
_exptl_absorpt_correction_T_min  0.320
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_density_diffrn    1.093
_exptl_crystal_description       block
_exptl_crystal_F_000             15200
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.210
_refine_diff_density_min         -0.893
_refine_diff_density_rms         0.133
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.206
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2318
_refine_ls_number_reflns         42512
_refine_ls_number_restraints     1936
_refine_ls_restrained_S_all      1.217
_refine_ls_R_factor_all          0.1732
_refine_ls_R_factor_gt           0.1388
_refine_ls_shift/su_max          0.025
_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^+150.0000P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3612
_refine_ls_wR_factor_ref         0.3814
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25585
_reflns_number_total             42512
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06046b2.cif
_cod_data_source_block           Ti16L4-1-HBra
_cod_depositor_comments
'Adding full bibliography for 1570454--1570469.cif.'
_cod_original_cell_volume        44135(13)
_cod_database_code               1570456
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.560
_shelx_estimated_absorpt_t_min   0.408
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.636(2)
 0.364(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C041-C01R = C041-C46 = C041-C10 = C041-C11
 1.54 with sigma of 0.01
 C58-C054 = C58-C44 = C58-C8 = C58-C30
 1.54 with sigma of 0.01
 C37-C49
 1.45 with sigma of 0.01
 C9-C49
 2.2 with sigma of 0.01
 C28-C49
 2.2 with sigma of 0.01
 C52-C26
 2.2 with sigma of 0.01
 C24-C6
 2.2 with sigma of 0.01
 C32-C24
 2.2 with sigma of 0.01
 C30-C8
 2.2 with sigma of 0.01
 C19-C54
 2.2 with sigma of 0.01
 C36-C04J
 1.54 with sigma of 0.01
 C61-C35 = C35-C03A = C31-C35 = C22-C35
 1.54 with sigma of 0.01
 C2-C4
 1.54 with sigma of 0.01
 C41-C12 = C41-C14 = C41-C15
 1.54 with sigma of 0.01
 C17-C38
 1.54 with sigma of 0.01
 C1-C5
 1.5 with sigma of 0.01
 C5-C3
 1.5 with sigma of 0.01
 C1-C3
 2.5 with sigma of 0.01
 O2-C5
 1.5 with sigma of 0.01
 C3A-C2A
 1.5 with sigma of 0.01
 O3-C2A
 2.2 with sigma of 0.01
 C1A-C2A
 1.5 with sigma of 0.01
 O1-C1
 2.2 with sigma of 0.01
 O1A-C1A
 2.2 with sigma of 0.01
 O1A-C2A
 1.5 with sigma of 0.01
 C28-C37
 1.5 with sigma of 0.01
 C16-C23
 2.5 with sigma of 0.01
 C61A-C35
 1.5 with sigma of 0.01
 H042-H50A
 2 with sigma of 0.01
 H30B-H44B
 2 with sigma of 0.01
 H03P-H69A
 2 with sigma of 0.01
 H42C-H45B
 2 with sigma of 0.01
 C44-C8 \\sim C8-C30 \\sim C44-C30
 with sigma of 0.01
 C41-C15 \\sim C41-C33
 with sigma of 0.02
 C41-C12 \\sim C41-C39
 with sigma of 0.02
 C41-C14 \\sim C41-C43
 with sigma of 0.02
 C7-C19 \\sim C7-C52
 with sigma of 0.02
 C7-C51 \\sim C7-C53
 with sigma of 0.02
 C7-C54 \\sim C7-C26
 with sigma of 0.02
 C48-C62 \\sim C48-C6
 with sigma of 0.02
 C48-C18 \\sim C48-C32
 with sigma of 0.02
 C48-C25 \\sim C48-C24
 with sigma of 0.02
 C18-C62 \\sim C62-C25 \\sim C25-C18
 with sigma of 0.02
 C14-C12 \\sim C12-C15 \\sim C15-C14
 with sigma of 0.02
 C32-C6 \\sim C6-C24 \\sim C24-C32
 with sigma of 0.02
 C19-C54 \\sim C54-C51 \\sim C51-C19
 with sigma of 0.02
 C56-C57 \\sim C57-C50 \\sim C50-C56
 with sigma of 0.02
 C8-C30 \\sim C30-C44 \\sim C44-C8
 with sigma of 0.02
 C49-C9 \\sim C9-C28 \\sim C28-C49
 with sigma of 0.02
 C39-C43 \\sim C43-C33 \\sim C33-C39
 with sigma of 0.02
 C53-C26 \\sim C26-C52 \\sim C52-C53
 with sigma of 0.02
 C2-O3 \\sim C2-O1
 with sigma of 0.01
 C04-C18 \\sim C04-C62 \\sim C04-C25
 with sigma of 0.01
 C31-C22 \\sim C22-C61 \\sim C31-C61
 with sigma of 0
4. Restrained planarity
 C04, C04H, C02O, C48
 with sigma of 0.01
5. Rigid bond restraints
 C61A, C35
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
6. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Uanis(C3A) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C50)
\\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C16) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
7. Rigid body (RIGU) restrains
 C12, C14, C15
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C39, C43, C33
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C52, C53, C26
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C19, C51, C54
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C24, C32, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
8. Same fragment restrains
{C04, C48, C24, C6, C32} sigma for 1-2: 0.01, 1-3: 0.04
as in
{C04, C48, C25, C18, C62}
9. Others
 Sof(Br2A)=Sof(H05C)=Sof(H05D)=1-FVAR(1)
 Sof(Br2)=Sof(H05A)=Sof(H05B)=FVAR(1)
 Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=1-FVAR(2)
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(2)
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=1-FVAR(3)
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=FVAR(3)
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=1-FVAR(4)
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=
 Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=FVAR(4)
 Sof(O1A)=Sof(C2A)=Sof(H2A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C3A)=
 Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=1-FVAR(5)
 Sof(O2)=Sof(C5)=Sof(H5)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C3)=Sof(H3A)=
 Sof(H3B)=Sof(H3C)=FVAR(5)
 Sof(C61A)=Sof(H61D)=Sof(H61E)=Sof(H61F)=Sof(C31A)=Sof(H31D)=Sof(H31E)=
 Sof(H31F)=Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=1-FVAR(6)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=FVAR(6)
 Fixed X: C6(0.51654) C31(0.32513) C22(0.34233)
 Fixed Y: C31(0.40906) C22(0.3807)
 Fixed Z: C6(0.69969) C31(0.54083) C22(0.491381)
10.a Riding coordinates:
 C45(H45A,H45B,H45C), C05E(H05Q,H05R,H05S), C13(H13A,H13B,H13C), C20(H20A,H20B,
 H20C), C42(H42A,H42B,H42C), C56(H56A,H56B,H56C), C16(H16A,H16B,H16C), C17(H17A,
 H17B,H17C), C49(H49A,H49B,H49C), C8(H8A,H8B,H8C), C29(H29A,H29B,H29C),
 C19(H19A,H19B,H19C), C39(H39A,H39B,H39C), C54(H54A,H54B,H54C), C26(H26A,H26B,
 H26C), C24(H24A,H24B,H24C), C6(H6A,H6B,H6C), C32(H32A,H32B,H32C), C31(H31A,
 H31B,H31C), C61(H61A,H61B,H61C), C63(H63A,H63B,H63C), C1(H1A,H1B,H1C), C3(H3A,
 H3B,H3C), C3A(H3AA,H3AB,H3AC), C61A(H61D,H61E,H61F), C31A(H31D,H31E,H31F),
 C22A(H22D,H22E,H22F)
10.b Ternary CH refined with riding coordinates:
 C05Y(H05Z), C5(H5), C2A(H2A)
10.c Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C026(H02A,H02B), C029(H02C,H02D), C02N(H02G,H02H), C02P(H02I,
 H02J), C02X(H02L,H02N), C02Y(H02P,H02Q), C037(H03A,H03B), C03F(H03D,H03F),
 C03M(H03G,H03H), C03S(H03I,H03J), C03V(H03K,H03M), C040(H04A,H04B), C048(H04C,
 H04D), C04O(H04G,H04I), C04Q(H04J,H04K), C051(H05A,H05B), C051(H05C,H05D)
10.d Aromatic/amide H refined with riding coordinates:
 C019(H019), C01N(H01N), C02E(H02E), C02F(H02F), C02K(H02K), C02M(H02M),
 C02O(H02O), C02U(H02U), C02W(H02W), C030(H030), C036(H036), C03B(H03C),
 C03E(H03E), C03L(H03L), C03N(H03N), C03P(H03P), C03Q(H03Q), C03U(H03U),
 C03Y(H03Y), C03Z(H03Z), C042(H042), C044(H044), C045(H045), C047(H047),
 C049(H049), C04C(H04E), C04E(H04F), C04H(H04H), C04S(H04S), C04U(H04U),
 C04W(H04W), C04Y(H04Y)
10.e Idealised Me refined as rotating group:
 C02Z(H02R,H02S,H02T), C46(H46A,H46B,H46C), C055(H05E,H05F,H05G), C10(H10A,
 H10B,H10C), C059(H05H,H05I,H05J), C60(H60A,H60B,H60C), C05B(H05K,H05L,H05M),
 C05C(H05N,H05O,H05P), C12(H12A,H12B,H12C), C05G(H05T,H05U,H05V), C14(H14A,H14B,
 H14C), C05W(H05W,H05X,H05Y), C28(H28A,H28B,H28C), C59(H59A,H59B,H59C),
 C11(H11A,H11B,H11C), C06C(H06A,H06B,H06C), C06E(H06D,H06E,H06F), C06G(H06G,
 H06H,H06I), C50(H50A,H50B,H50C), C57(H57A,H57B,H57C), C15(H15A,H15B,H15C),
 C9(H9A,H9B,H9C), C23(H23A,H23B,H23C), C30(H30A,H30B,H30C), C44(H44A,H44B,H44C),
  C21(H21A,H21B,H21C), C51(H51A,H51B,H51C), C43(H43A,H43B,H43C), C33(H33A,H33B,
 H33C), C34(H34A,H34B,H34C), C69(H69A,H69B,H69C), C53(H53A,H53B,H53C), C52(H52A,
 H52B,H52C), C25(H25A,H25B,H25C), C18(H18A,H18B,H18C), C62(H62A,H62B,H62C),
 C36(H36A,H36B,H36C), C22(H22A,H22B,H22C), C1A(H1AA,H1AB,H1AC)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              46827
_shelx_fab_checksum              42205
_olex2_submission_special_instructions 'No special instructions were received'