Calix[8]arene-constructed stable polyoxo-titanium clusters for efficient CO2 photoreduction
Li, Ning; Liu, Jing-Jing; Sun, Jia-Wei; Dong, Bao-Xia; Dong, Long-Zhang; Yao, Su-Juan; Xin, Zhifeng; Li, Shun-Li; Lan, Ya-Qian; Green Chemistry 22 (2020) 5325–5332; doi:10.1039/D0GC01497D

data_7240906
_publ_section_title
;
 Calix[8]arene-constructed stable polyoxo-titanium clusters for efficient
 CO2 photoreduction
;
_journal_issue                   16
_journal_name_full               'Green Chemistry'
_journal_page_first              5325
_journal_page_last               5332
_journal_paper_doi               10.1039/D0GC01497D
_journal_volume                  22
_journal_year                    2020
_chemical_formula_moiety         'C71 H76 O15 Ti4'
_chemical_formula_sum            'C71 H76 O15 Ti4'
_chemical_formula_weight         1360.92
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-01-14
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2020-04-25 deposited with the CCDC.	2020-07-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.786(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.731(8)
_cell_length_b                   16.579(7)
_cell_length_c                   21.872(10)
_cell_measurement_reflns_used    2478
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      26.38
_cell_measurement_theta_min      2.35
_cell_volume                     6672(5)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      296.15
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0714
_diffrn_reflns_av_unetI/netI     0.0969
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            30619
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         1.551
_diffrn_source                   'sealed tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.527
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6267
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0693 before and 0.0595 after correction. The Ratio of minimum to maximum transmission is 0.8408. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear dark brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.355
_exptl_crystal_description       plate
_exptl_crystal_F_000             2840
_exptl_crystal_size_max          0.082
_exptl_crystal_size_mid          0.053
_exptl_crystal_size_min          0.031
_refine_diff_density_max         0.431
_refine_diff_density_min         -0.294
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     930
_refine_ls_number_reflns         11619
_refine_ls_number_restraints     724
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.1416
_refine_ls_R_factor_gt           0.0677
_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^)+(0.0759P)^2^+2.6102P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1446
_refine_ls_wR_factor_ref         0.1765
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6343
_reflns_number_total             11619
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0gc01497d2.cif
_cod_data_source_block           mo_b8_0m
_cod_depositor_comments
;Adding full bibliography for 7240906--7240907.cif.

 Adding full bibliography for 7240906--7240907.cif.
;
_cod_database_code               7240906
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.958
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H57B,H57,H57A} of C57, All C(H,H) groups
 At 1.5 times of:
  All O(H,H) groups, {H62A,H62B,H62C} of C62A, {H61D,H61E,H61F} of C61B,
  {H62D,H62E,H62F} of C62B, {H70A,H70B,H70C} of C70A, {H71A,H71B,H71C} of C71A,
  {H59G,H59H,H59I} of C59A, {H70D,H70E,H70F} of C70B, {H59D,H59E,H59F} of C59B,
  {H58D,H58E,H58F} of C58B, {H58G,H58H,H58I} of C58C, {H71D,H71E,H71F} of C71B,
  {H59A,H59B,H59C} of C59C, {H61A,H61B,H61C} of C61A, {H64A,H64B,H64C} of C64,
  {H67A,H67B,H67C} of C67, {H65A,H65B,H65C} of C65, {H68A,H68B,H68C} of C68,
  {H58A,H58B,H58C} of C58A
2. Restrained distances
 C58C-C57 = C58A-C57 = C58B-C57 = C59A-C57 = C59C-C57 = C57-C59B
 1.5 with sigma of 0.02
 C58C-C58B
 2.4 with sigma of 0.02
 O16-C69A = O16-C69B
 1.45 with sigma of 0.02
 O16-H16
 0.85 with sigma of 0.01
 O16-H16A
 0.85 with sigma of 0.01
 C69A-H16
 1.873066 with sigma of 0.02
 C69B-H16A
 1.908627 with sigma of 0.02
 Ti4-H16A
 2.61823 with sigma of 0.02
 Ti4-H16
 2.630569 with sigma of 0.02
3. Rigid bond restraints
 Ti4, O15
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41
\\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49
\\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57
\\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C58A \\sim
C59C \\sim C60A \\sim C61A \\sim C62A \\sim C69A \\sim C71A \\sim C71B \\sim
C58B \\sim C59B \\sim C60B \\sim C61B \\sim C62B \\sim C69B \\sim C70A \\sim
C70B \\sim C58C \\sim C59A \\sim O1 \\sim O2 \\sim O3 \\sim O4 \\sim O5 \\sim
O7 \\sim O8 \\sim O9 \\sim O10 \\sim O11 \\sim O12 \\sim O13 \\sim O14 \\sim
O15 \\sim O16: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
5. Others
 1*[Sof(C58A)+Sof(H58A)+Sof(H58B)+Sof(H58C)+Sof(C59C)+Sof(H59A)+Sof(H59B)+
 Sof(H59C)]+1*[Sof(C58B)+Sof(H58D)+Sof(H58E)+Sof(H58F)+Sof(C59B)+Sof(H59D)+
 Sof(H59E)+Sof(H59F)]+1*[Sof(C58C)+Sof(H58G)+Sof(H58H)+Sof(H58I)+Sof(C59A)+
 Sof(H59G)+Sof(H59H)+Sof(H59I)]=1 with esd of 0.0001
 Sof(H16A)=Sof(C69B)=Sof(H69B)=Sof(C70A)=Sof(H70A)=Sof(H70B)=Sof(H70C)=
 Sof(C70B)=Sof(H70D)=Sof(H70E)=Sof(H70F)=1-FVAR(1)
 Sof(H16)=Sof(C69A)=Sof(H69A)=Sof(C71A)=Sof(H71A)=Sof(H71B)=Sof(H71C)=
 Sof(C71B)=Sof(H71D)=Sof(H71E)=Sof(H71F)=FVAR(1)
 Sof(C60B)=Sof(H60B)=Sof(C61B)=Sof(H61D)=Sof(H61E)=Sof(H61F)=Sof(C62B)=
 Sof(H62D)=Sof(H62E)=Sof(H62F)=1-FVAR(2)
 Sof(C60A)=Sof(H60A)=Sof(C61A)=Sof(H61A)=Sof(H61B)=Sof(H61C)=Sof(C62A)=
 Sof(H62A)=Sof(H62B)=Sof(H62C)=FVAR(2)
 Sof(C58A)=Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C59C)=Sof(H59A)=Sof(H59B)=
 Sof(H59C)=FVAR(3)
 Sof(C58B)=Sof(H58D)=Sof(H58E)=Sof(H58F)=Sof(C59B)=Sof(H59D)=Sof(H59E)=
 Sof(H59F)=FVAR(4)
 Sof(C58C)=Sof(H58G)=Sof(H58H)=Sof(H58I)=Sof(C59A)=Sof(H59G)=Sof(H59H)=
 Sof(H59I)=FVAR(5)
 Fixed Sof: H57B(0.33333) H57(0.33333) H57A(0.33333)
6.a Ternary CH refined with riding coordinates:
 C57(H57B), C57(H57), C57(H57A), C63(H63), C66(H66), C60A(H60A), C69A(H69A),
 C60B(H60B), C69B(H69B)
6.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C14(H14A,H14B), C21(H21A,H21B), C28(H28A,H28B), C35(H35A,H35B),
 C42(H42A,H42B), C49(H49A,H49B), C56(H56A,H56B)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C16(H16B), C17(H17),
 C18(H18), C23(H23), C24(H24), C25(H25), C30(H30), C31(H31), C32(H32), C37(H37),
  C38(H38), C39(H39), C44(H44), C45(H45), C46(H46), C51(H51), C52(H52), C53(H53)
6.d Idealised Me refined as rotating group:
 C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C67(H67A,H67B,H67C), C68(H68A,H68B,
 H68C), C58A(H58A,H58B,H58C), C59C(H59A,H59B,H59C), C61A(H61A,H61B,H61C),
 C62A(H62A,H62B,H62C), C71A(H71A,H71B,H71C), C71B(H71D,H71E,H71F), C58B(H58D,
 H58E,H58F), C59B(H59D,H59E,H59F), C61B(H61D,H61E,H61F), C62B(H62D,H62E,H62F),
 C70A(H70A,H70B,H70C), C70B(H70D,H70E,H70F), C58C(H58G,H58H,H58I), C59A(H59G,
 H59H,H59I)
;
_shelx_res_checksum              52768
_olex2_submission_special_instructions 'No special instructions were received'