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_1570465
_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
'C374 H434 F12 O72 Ti16, 4(C2 H3 N), 12[H2O], 10[H2O]'
_chemical_formula_sum            'C382 H450 F12 N4 O72 Ti16'
_chemical_formula_weight         7243.83
_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             2023-04-21
_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                 121.984(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   54.372(7)
_cell_length_b                   20.162(2)
_cell_length_c                   50.494(7)
_cell_measurement_reflns_used    9673
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      44.35
_cell_measurement_theta_min      2.88
_cell_volume                     46951(10)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_device_type  'Bruker PHOTON III'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34138
_diffrn_reflns_av_R_equivalents  0.0618
_diffrn_reflns_av_unetI/netI     0.0683
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       54
_diffrn_reflns_limit_h_min       -57
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       53
_diffrn_reflns_limit_l_min       -52
_diffrn_reflns_number            106571
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        45.104
_diffrn_reflns_theta_max         45.104
_diffrn_reflns_theta_min         2.443
_diffrn_source_current           3.57
_diffrn_source_power             0.24972149999999999
_diffrn_source_voltage           69.95
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.823
_exptl_absorpt_correction_T_max  0.585
_exptl_absorpt_correction_T_min  0.284
_exptl_absorpt_correction_type   multi-scan
_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    1.025
_exptl_crystal_description       block
_exptl_crystal_F_000             15224
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.978
_refine_diff_density_min         -0.540
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2516
_refine_ls_number_reflns         28404
_refine_ls_number_restraints     2173
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.1304
_refine_ls_R_factor_gt           0.0902
_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          0.2705
_refine_ls_wR_factor_ref         0.3036
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15908
_reflns_number_total             28404
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06046b2.cif
_cod_data_source_block           Ti16L4-2-HTfa
_cod_depositor_comments
'Adding full bibliography for 1570454--1570469.cif.'
_cod_original_cell_volume        46950(10)
_cod_database_code               1570465
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.611
_shelx_estimated_absorpt_t_min   0.463
_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, All O(H,H) groups
2. Restrained distances
 O2-C12
 1.5 with sigma of 0.01
 C04R-C065
 1.35 with sigma of 0.01
 C23-C20
 1.5 with sigma of 0.01
 C1-C61
 2.2 with sigma of 0.01
 C1-C2
 2.2 with sigma of 0.01
 C64-C61
 1.5 with sigma of 0.01
 C18-C20
 1.5 with sigma of 0.01
 C73-C74
 2.2 with sigma of 0.01
 C18-C21
 2.3 with sigma of 0.01
 C3-C65
 2.2 with sigma of 0.01
 C71-C45
 1.5 with sigma of 0.01
 C71-C73
 1.5 with sigma of 0.01
 C71-C24
 1.5 with sigma of 0.01
 C71-C74
 1.5 with sigma of 0.01
 C48-C12
 1.5 with sigma of 0.01
 C68-O1
 1.5 with sigma of 0.01
 C76-C90
 1.5 with sigma of 0.01
 C69-O1
 2.5 with sigma of 0.01
 C49-C12
 1.5 with sigma of 0.01
 C68-C69
 1.5 with sigma of 0.01
 C77-C68
 1.5 with sigma of 0.01
 C39-C25
 2.2 with sigma of 0.01
 C7-C4 \\sim C7-C3
 with sigma of 0.02
 C7-C6 \\sim C7-C5
 with sigma of 0.02
 C43-C41 \\sim C43-C25
 with sigma of 0.02
 C43-C38 \\sim C43-C42
 with sigma of 0.02
 C43-C40 \\sim C43-C39
 with sigma of 0.02
 C31-C30 \\sim C31-C26
 with sigma of 0.02
 C31-C29 \\sim C31-C28
 with sigma of 0.02
 C31-C27 \\sim C31-C19
 with sigma of 0.02
 C62-C83 \\sim C63-C83
 with sigma of 0.02
 C80-C83 \\sim C81-C83
 with sigma of 0.02
 C82-C83 \\sim C8-C83
 with sigma of 0.02
 C10-C13 \\sim C46-C13
 with sigma of 0.02
 C11-C13 \\sim C47-C13
 with sigma of 0.02
 C13-C14 \\sim C13-C44
 with sigma of 0.02
 C37-C34 \\sim C37-C9
 with sigma of 0.02
 C37-C35 \\sim C37-C36
 with sigma of 0.02
 C37-C33 \\sim C37-C32
 with sigma of 0.02
 C71-C24 \\sim C71-C74
 with sigma of 0.02
 C71-C54 \\sim C71-C55
 with sigma of 0.02
 C71-C50 \\sim C71-C73
 with sigma of 0.02
 C60-C64 \\sim C1-C64
 with sigma of 0.02
 C58-C64 \\sim C61-C64
 with sigma of 0.02
 C64-C66 \\sim C64-C67
 with sigma of 0.02
 F1-C05J \\sim F2-C05J
 with sigma of 0.02
 F5-C05J \\sim F6-C05J
 with sigma of 0.02
 F3-C05J \\sim F4-C05J
 with sigma of 0.02
 C56-C76 \\sim C51-C76
 with sigma of 0.02
 C76-C52 \\sim C76-C53
 with sigma of 0.02
 C76-C75 \\sim C76-C15
 with sigma of 0.02
 C16-C20 \\sim C17-C20
 with sigma of 0.02
 C21-C20 \\sim C22-C20
 with sigma of 0.02
 C18-C20 \\sim C23-C20
 with sigma of 0.02
3. Rigid bond restraints
 C65, C7
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C69 \\sim C68 \\sim C77 \\sim O1: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C22 \\sim C16 \\sim C17 \\sim C18 \\sim C23 \\sim C20 \\sim C21: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C101: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
C89: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C65 \\sim C86 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C71 \\sim C24 \\sim C50 \\sim C54 \\sim C73 \\sim C74 \\sim C55: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C64 \\sim C58 \\sim C60 \\sim C66 \\sim C61 \\sim C1 \\sim C67: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
F1 \\sim F3 \\sim F5 \\sim F2 \\sim F4 \\sim F6: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
C76 \\sim C75 \\sim C52 \\sim C56 \\sim C15 \\sim C51 \\sim C53: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C8 \\sim C62 \\sim C63 \\sim C80 \\sim C81 \\sim C82 \\sim C83: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C43 \\sim C38 \\sim C40 \\sim C41 \\sim C25 \\sim C39 \\sim C42: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C37 \\sim C33 \\sim C34 \\sim C35 \\sim C9 \\sim C32 \\sim C36: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C31 \\sim C27 \\sim C29 \\sim C30 \\sim C19 \\sim C26 \\sim C28: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C13 \\sim C10 \\sim C11 \\sim C14 \\sim C44 \\sim C46 \\sim C47: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C16 \\sim C17 \\sim C18 \\sim C23 \\sim C21 \\sim C22 \\sim C20: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C71) \\sim Ueq, Uanis(C01B) \\sim Ueq, Uanis(C01C) \\sim Ueq, Uanis(C01F)
\\sim Ueq, Uanis(C01G) \\sim Ueq, Uanis(C01H) \\sim Ueq, Uanis(C01I) \\sim Ueq,
Uanis(C01J) \\sim Ueq, Uanis(C01K) \\sim Ueq, Uanis(C01L) \\sim Ueq,
Uanis(C01N) \\sim Ueq, Uanis(C01O) \\sim Ueq, Uanis(C01P) \\sim Ueq,
Uanis(C01Q) \\sim Ueq, Uanis(C01R) \\sim Ueq, Uanis(C01S) \\sim Ueq,
Uanis(C01T) \\sim Ueq, Uanis(C01U) \\sim Ueq, Uanis(C01V) \\sim Ueq,
Uanis(C01W) \\sim Ueq, Uanis(C01X) \\sim Ueq, Uanis(C01Y) \\sim Ueq,
Uanis(C01Z) \\sim Ueq, Uanis(C02A) \\sim Ueq, Uanis(C02B) \\sim Ueq,
Uanis(C02C) \\sim Ueq, Uanis(C02D) \\sim Ueq, Uanis(C02E) \\sim Ueq,
Uanis(C02G) \\sim Ueq, Uanis(C02H) \\sim Ueq, Uanis(C02I) \\sim Ueq,
Uanis(C02J) \\sim Ueq, Uanis(C02K) \\sim Ueq, Uanis(C02L) \\sim Ueq,
Uanis(C02M) \\sim Ueq, Uanis(C02N) \\sim Ueq, Uanis(C02O) \\sim Ueq,
Uanis(C02P) \\sim Ueq, Uanis(C02Q) \\sim Ueq, Uanis(C02R) \\sim Ueq,
Uanis(C02S) \\sim Ueq, Uanis(C02T) \\sim Ueq, Uanis(C02U) \\sim Ueq,
Uanis(C02V) \\sim Ueq, Uanis(C02W) \\sim Ueq, Uanis(C02X) \\sim Ueq,
Uanis(C02Y) \\sim Ueq, Uanis(C02Z) \\sim Ueq, Uanis(C03A) \\sim Ueq,
Uanis(C03B) \\sim Ueq, Uanis(C03C) \\sim Ueq, Uanis(C03D) \\sim Ueq,
Uanis(C03E) \\sim Ueq, Uanis(C03F) \\sim Ueq, Uanis(C03G) \\sim Ueq,
Uanis(C03H) \\sim Ueq, Uanis(C03I) \\sim Ueq, Uanis(C03J) \\sim Ueq,
Uanis(C03K) \\sim Ueq, Uanis(C03L) \\sim Ueq, Uanis(C03M) \\sim Ueq,
Uanis(C03N) \\sim Ueq, Uanis(C03P) \\sim Ueq, Uanis(C03Q) \\sim Ueq,
Uanis(C03R) \\sim Ueq, Uanis(C03S) \\sim Ueq, Uanis(C03T) \\sim Ueq,
Uanis(C03U) \\sim Ueq, Uanis(C03V) \\sim Ueq, Uanis(C03W) \\sim Ueq,
Uanis(C03X) \\sim Ueq, Uanis(C03Y) \\sim Ueq, Uanis(C03Z) \\sim Ueq,
Uanis(C04A) \\sim Ueq, Uanis(C04E) \\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(C2)
\\sim Ueq, Uanis(C04K) \\sim Ueq, Uanis(C04L) \\sim Ueq, Uanis(C04N) \\sim Ueq,
Uanis(C04O) \\sim Ueq, Uanis(C04P) \\sim Ueq, Uanis(C04R) \\sim Ueq,
Uanis(C04T) \\sim Ueq, Uanis(C89) \\sim Ueq, Uanis(C04V) \\sim Ueq, Uanis(C04W)
\\sim Ueq, Uanis(C04Y) \\sim Ueq, Uanis(C05A) \\sim Ueq, Uanis(C05C) \\sim Ueq,
Uanis(C05E) \\sim Ueq, Uanis(C05F) \\sim Ueq, Uanis(C05G) \\sim Ueq,
Uanis(C05I) \\sim Ueq, Uanis(C05J) \\sim Ueq, Uanis(C05L) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C05T) \\sim Ueq, Uanis(C05U) \\sim Ueq,
Uanis(C18) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C12)
\\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C020) \\sim Ueq, Uanis(C021) \\sim Ueq,
Uanis(C022) \\sim Ueq, Uanis(C023) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C024)
\\sim Ueq, Uanis(C025) \\sim Ueq, Uanis(C026) \\sim Ueq, Uanis(C027) \\sim Ueq,
Uanis(C028) \\sim Ueq, Uanis(C029) \\sim Ueq, Uanis(C030) \\sim Ueq, Uanis(C31)
\\sim Ueq, Uanis(C031) \\sim Ueq, Uanis(C032) \\sim Ueq, Uanis(C033) \\sim Ueq,
Uanis(C034) \\sim Ueq, Uanis(C035) \\sim Ueq, Uanis(C036) \\sim Ueq,
Uanis(C037) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C038) \\sim Ueq, Uanis(C039)
\\sim Ueq, Uanis(C040) \\sim Ueq, Uanis(C041) \\sim Ueq, Uanis(C042) \\sim Ueq,
Uanis(C43) \\sim Ueq, Uanis(C043) \\sim Ueq, Uanis(C044) \\sim Ueq, Uanis(C45)
\\sim Ueq, Uanis(C045) \\sim Ueq, Uanis(C046) \\sim Ueq, Uanis(C047) \\sim Ueq,
Uanis(C48) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C050) \\sim Ueq, Uanis(C83)
\\sim Ueq, Uanis(C053) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C057) \\sim Ueq,
Uanis(C058) \\sim Ueq, Uanis(C061) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C77)
\\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C065) \\sim Ueq, Uanis(C90) \\sim Ueq,
Uanis(C91) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C94)
\\sim Ueq, Uanis(C95) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C75) \\sim Ueq,
Uanis(C62) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C6) \\sim Ueq,
Uanis(C86) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C29)
\\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C34) \\sim Ueq,
Uanis(C35) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41)
\\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C54) \\sim Ueq,
Uanis(C56) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C66)
\\sim Ueq, Uanis(C81) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C74) \\sim Ueq,
Uanis(C15) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C65)
\\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C3) \\sim Ueq,
Uanis(C63) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C28)
\\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C39) \\sim Ueq,
Uanis(C42) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C47)
\\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C55) \\sim Ueq,
Uanis(C61) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C04I)
\\sim Ueq, Uanis(C04X) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C59) \\sim Ueq,
Uanis(C17) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C84)
\\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C85) \\sim Ueq,
Uanis(C78) \\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(N58) \\sim Ueq, Uanis(F6)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C6, C86, C4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C38, C40, C41
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C25, C39, C42
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27, C29, C30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C19, C26, C28
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C62, C80, C82
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C81, C8, C63
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C10, C11, C14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C44, C46, C47
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C33, C34, C35
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C9, C32, C36
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C24, C50, C54
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C73, C74, C55
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C58, C60, C66
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C61, C1, C67
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1, F3, F5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F2, F4, F6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C75, C52, C56
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C15, C51, C53
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16, C21, C18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C17, C22, C23
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=1-FVAR(1)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C86)=Sof(H86A)=Sof(H86B)=Sof(H86C)=
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=FVAR(1)
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=
 Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=1-FVAR(2)
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=FVAR(2)
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=1-FVAR(3)
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(3)
 Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=1-FVAR(4)
 Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=
 Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=FVAR(4)
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=1-FVAR(5)
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(5)
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=1-FVAR(6)
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=FVAR(6)
 Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=
 Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=1-FVAR(7)
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=FVAR(7)
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=
 Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=1-FVAR(8)
 Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=
 Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=FVAR(8)
 Sof(F2)=Sof(F4)=Sof(F6)=1-FVAR(9)
 Sof(F1)=Sof(F3)=Sof(F5)=FVAR(9)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=1-FVAR(10)
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=
 Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=FVAR(10)
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=1-FVAR(11)
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=FVAR(11)
 Fixed Sof: C69(0.5) H69A(0.5) H69B(0.5) H69C(0.5) C12(0.5) H12(0.5) C48(0.5)
 H48A(0.5) H48B(0.5) H48C(0.5) C49(0.5) H49A(0.5) H49B(0.5) H49C(0.5) C68(0.5)
 H68(0.5) C77(0.5) H77A(0.5) H77B(0.5) H77C(0.5)
7.a Riding coordinates:
 C04W(H04C,H04D,H04F), C05C(H05C,H05D,H05E), C05F(H05G,H05H,H05I), C05I(H05J,
 H05K,H05L), C05L(H05M,H05N,H05O), C16(H16A,H16B,H16C), C21(H21A,H21B,H21C),
 C05T(H05P,H05Q,H05R), C05U(H05S,H05T,H05U), C18(H18A,H18B,H18C), C69(H69A,H69B,
 H69C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C050(H05V,H05W,H05X),
 C053(H05Y,H,HA), C057(H05Z,HB,HC), C058(H05,HD,HE), C061(H06A,H06B,H06C),
 C77(H77A,H77B,H77C), C24(H24A,H24B,H24C), C75(H75A,H75B,H75C), C62(H62A,H62B,
 H62C), C80(H80A,H80B,H80C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C14(H14A,
 H14B,H14C), C82(H82A,H82B,H82C), C6(H6A,H6B,H6C), C86(H86A,H86B,H86C), C4(H4A,
 H4B,H4C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C38(H38A,H38B,
 H38C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C50(H50A,H50B,H50C), C52(H52A,
 H52B,H52C), C54(H54A,H54B,H54C), C56(H56A,H56B,H56C), C58(H58A,H58B,H58C),
 C60(H60A,H60B,H60C), C66(H66A,H66B,H66C), C81(H81A,H81B,H81C), C73(H73A,H73B,
 H73C), C74(H74A,H74B,H74C), C15(H15A,H15B,H15C), C9(H9A,H9B,H9C), C8(H8A,H8B,
 H8C), C65(H65A,H65B,H65C), C19(H19A,H19B,H19C), C5(H5A,H5B,H5C), C3(H3A,H3B,
 H3C), C63(H63A,H63B,H63C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,
 H28B,H28C), C32(H32A,H32B,H32C), C36(H36A,H36B,H36C), C39(H39A,H39B,H39C),
 C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C), C47(H47A,H47B,
 H47C), C51(H51A,H51B,H51C), C53(H53A,H53B,H53C), C55(H55A,H55B,H55C), C61(H61A,
 H61B,H61C), C1(H1A,H1B,H1C), C67(H67A,H67B,H67C), C04I(H04I,H04J,H04K),
 C59(H59A,H59B,H59C), C17(H17A,H17B,H17C), C23(H23A,H23B,H23C), C22(H22A,H22B,
 H22C), C84(H84A,H84B,H84C), C72(H72A,H72B,H72C), C70(H70A,H70B,H70C)
7.b Rotating group:
 O00I(H00A,H00B), O014(H01A,H01B)
7.c Ternary CH refined with riding coordinates:
 C12(H12), C68(H68)
7.d Secondary CH2 refined with riding coordinates:
 C01T(H01C,H01D), C01V(H01E,H01F), C02E(H02A,H02B), C02J(H02C,H02E), C02L(H02F,
 H02G), C02M(H02H,H02I), C02O(H02J,H02L), C02W(H02M,H02N), C02Z(H02O,H02P),
 C03D(H03B,H03C), C03Y(H03D,H03F), C04A(H04A,H04B), C05A(H05A,H05B), C024(H02Q,
 H02R), C029(H02T,H02U), C046(H04G,H04H)
7.e Aromatic/amide H refined with riding coordinates:
 C01U(H01U), C01W(H01W), C02D(H02D), C02K(H02K), C02S(H02S), C03A(H03A),
 C03E(H03E), C03G(H03G), C03I(H03I), C03K(H03K), C03P(H03P), C03R(H03R),
 C03T(H03T), C03U(H03U), C03V(H03V), C03W(H03W), C04E(H04E), C04N(H04N),
 C04T(H04T), C04V(H04V), C05E(H05F), C020(H020), C030(H030), C036(H036),
 C037(H037), C038(H038), C039(H039), C042(H042), C044(H044), C065(H065),
 C91(H91), C95(H95)
7.f Fitted hexagon refined as free rotating group:
 C90(C91,C92,C93,C94,C95)
7.g Idealised Me refined as rotating group:
 C85(H85A,H85B,H85C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              44559
_shelx_fab_checksum              1309
_olex2_submission_special_instructions 'No special instructions were received'