Accurate assembly of thiophene-bridged titanium-oxo clusters with photocatalytic amine oxidation activity
Nai, Haoran; Hou, Jinle; Li, Jinyu; Ma, Xiaoxi; Yang, Yujia; Qu, Konggang; Huang, Xianqiang; Li, Lianzhi; RSC Advances 14 (2024) 7924–7931; doi:10.1039/D4RA00117F

data_7248285
_publ_section_title
;
 Accurate assembly of thiophene-bridged titanium-oxo clusters with
 photocatalytic amine oxidation activity
;
_journal_issue                   11
_journal_name_full               'RSC Advances'
_journal_page_first              7924
_journal_page_last               7931
_journal_paper_doi               10.1039/D4RA00117F
_journal_volume                  14
_journal_year                    2024
_chemical_formula_moiety         'C80 H167 N4 O36 S Ti10'
_chemical_formula_sum            'C80 H167 N4 O36 S Ti10'
_chemical_formula_weight         2272.23
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-11-16
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-12-27 deposited with the CCDC.	2024-02-21 downloaded from the CCDC.
;
_cell_angle_alpha                74.614(3)
_cell_angle_beta                 75.671(3)
_cell_angle_gamma                74.331(3)
_cell_formula_units_Z            2
_cell_length_a                   16.5980(5)
_cell_length_b                   18.4583(6)
_cell_length_c                   20.9945(7)
_cell_measurement_reflns_used    22408
_cell_measurement_temperature    213.00(10)
_cell_measurement_theta_max      75.9530
_cell_measurement_theta_min      2.9770
_cell_volume                     5863.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      213.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     92.00 178.00   1.00    2.00    --  105.98  15.00  60.00   86
  2  \w     94.00 178.00   1.00    2.00    --  105.98  30.00 -60.00   84
  3  \w    105.00 131.00   1.00    2.00    --  105.98  90.00 -86.00   26
  4  \w    139.00 170.00   1.00    2.00    --  105.98  90.00 -86.00   31
  5  \w    -76.00  19.00   1.00    0.25    --  -48.21  90.00 -86.00   95
  6  \w    -66.00 -21.00   1.00    2.00    --  -91.75 125.00-150.00   45
  7  \w    -25.00  27.00   1.00    0.25    --  -48.21  19.00-150.00   52
  8  \w    -22.00  27.00   1.00    0.25    --  -48.21  19.00 -90.00   49
  9  \w    -79.00 -36.00   1.00    2.00    --  -91.75  90.00 -86.00   43
 10  \w    -69.00 -21.00   1.00    2.00    --  -91.75  61.00 120.00   48
 11  \w    -49.00 -20.00   1.00    2.00    --  -91.75  45.00 120.00   29
 12  \w   -119.00 -73.00   1.00    0.25    --  -48.21-125.00-150.00   46
 13  \w   -120.00 -73.00   1.00    0.25    --  -48.21-125.00 -90.00   47
 14  \w   -166.00 -79.00   1.00    2.00    --  -91.75 -30.00-150.00   87
 15  \w   -159.00 -85.00   1.00    2.00    --  -91.75 -94.00  30.00   74
 16  \w   -140.00 -79.00   1.00    2.00    --  -91.75 -90.00 159.00   61
 17  \w    -17.00  27.00   1.00    0.25    --   48.21 -19.00-120.00   44
 18  \w     34.00 112.00   1.00    2.00    --  105.98-125.00 -30.00   78
 19  \w     33.00 106.00   1.00    2.00    --  105.98 -94.00 -30.00   73
 20  \w     33.00 105.00   1.00    2.00    --  105.98 -77.00 -30.00   72
 21  \w     37.00  96.00   1.00    2.00    --  105.98 -94.00-150.00   59
 22  \w     34.00 104.00   1.00    2.00    --  105.98 -94.00-120.00   70
 23  \w     45.00 112.00   1.00    2.00    --  105.98-125.00  90.00   67
 24  \w     35.00 104.00   1.00    2.00    --  105.98 -94.00 120.00   69
 25  \w     33.00  62.00   1.00    2.00    --  105.98 -94.00  90.00   29
 26  \w    -20.00  54.00   1.00    0.25    --   48.21 -90.00 159.00   74
 27  \w     43.00 103.00   1.00    2.00    --  105.98 -90.00 159.00   60
 28  \w     70.00 102.00   1.00    2.00    --  105.98 -94.00  90.00   32
 29  \w     33.00  71.00   1.00    2.00    --  105.98 -61.00 150.00   38
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0596833000
_diffrn_orient_matrix_UB_12      0.0380638000
_diffrn_orient_matrix_UB_13      0.0566406000
_diffrn_orient_matrix_UB_21      -0.0116272000
_diffrn_orient_matrix_UB_22      -0.0798010000
_diffrn_orient_matrix_UB_23      0.0424650000
_diffrn_orient_matrix_UB_31      0.0770788000
_diffrn_orient_matrix_UB_32      -0.0072910000
_diffrn_orient_matrix_UB_33      0.0315650000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0560
_diffrn_reflns_av_unetI/netI     0.0551
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            63279
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         2.544
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.239
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47216
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.119a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_description       block
_exptl_crystal_F_000             2398
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.821
_refine_diff_density_min         -0.816
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1448
_refine_ls_number_reflns         20665
_refine_ls_number_restraints     691
_refine_ls_restrained_S_all      1.093
_refine_ls_R_factor_all          0.0796
_refine_ls_R_factor_gt           0.0631
_refine_ls_shift/su_max          0.038
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0968P)^2^+5.6909P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1663
_refine_ls_wR_factor_ref         0.1774
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16260
_reflns_number_total             20665
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ra00117f2.cif
_cod_data_source_block           Ti10
_cod_original_cell_volume        5863.0(4)
_cod_database_code               7248285
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         TiSCNO
_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
 C80-C79 = C96-C79 = C81-C79 = C79-C91
 1.5 with sigma of 0.01
 C97-C78 = C78-C76 = C77-C76 = C97-C77
 1.5 with sigma of 0.01
 O30-C76 = O30-C97
 1.45 with sigma of 0.01
 C78-C77
 2.5 with sigma of 0.01
 C90-C65 = C90-C66 = C99-C64 = C64-C100
 1.55 with sigma of 0.01
 C101-C102
 2.55 with sigma of 0.01
 C97-C101 = C97-C102 = C77-C76 = C78-C76
 1.55 with sigma of 0.01
 C29-C28 = C89-C94 = C28-C27 = C93-C89
 1.5 with sigma of 0.01
 C20-C19 = C40-C22 = C88-C22 = C19-C21
 1.5 with sigma of 0.01
 C96-C91
 2.5 with sigma of 0.01
 C88-C40
 2.5 with sigma of 0.01
 C98-C37 = C18-C16 = C37-C85 = C17-C16
 1.5 with sigma of 0.01
 C87-C86 = C12-C10 = C11-C10 = C86-C92
 1.5 with sigma of 0.01
 C62-C61 = C61-C23 = C63-C61 = C61-C95
 1.5 with sigma of 0.01
 O29-C91
 2.5 with sigma of 0.01
 C96-O29
 2.5 with sigma of 0.01
 C69-C68
 2.5 with sigma of 0.01
 C67-C69 = C68-C67
 1.5 with sigma of 0.01
 C9-C8
 2.5 with sigma of 0.01
 C8-C7 = C9-C7
 1.5 with sigma of 0.01
 C93-C94
 2.5 with sigma of 0.01
 O14-C88
 2.5 with sigma of 0.01
 O14-C40
 2.5 with sigma of 0.01
 O14-C22
 1.45 with sigma of 0.01
 O16-C94
 2.35 with sigma of 0.01
 O16-C89
 1.45 with sigma of 0.01
 O16-C93
 2.35 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O29 \\sim C79 \\sim C80 \\sim C81 \\sim C91 \\sim C96: within 1.7A with sigma
of 0.004 and sigma for terminal atoms of 0.008 within 1.7A
O26 \\sim C70 \\sim C71 \\sim C72: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
O16 \\sim C27 \\sim C28 \\sim C29 \\sim C89 \\sim C93 \\sim C94: within 1.7A
with sigma of 0.004 and sigma for terminal atoms of 0.008 within 1.7A
O14 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C40 \\sim C88: within 1.7A
with sigma of 0.004 and sigma for terminal atoms of 0.008 within 1.7A
O20 \\sim C24 \\sim C25 \\sim C26: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.008 within 1.7A
O13 \\sim C16 \\sim C17 \\sim C18 \\sim C37 \\sim C85 \\sim C98: within 1.7A
with sigma of 0.004 and sigma for terminal atoms of 0.008 within 1.7A
O11 \\sim C10 \\sim C11 \\sim C12 \\sim C86 \\sim C87 \\sim C92: within 1.7A
with sigma of 0.004 and sigma for terminal atoms of 0.008 within 1.7A
O25 \\sim C61 \\sim C62 \\sim C63 \\sim C23 \\sim C95: within 1.7A with sigma
of 0.004 and sigma for terminal atoms of 0.008 within 1.7A
O31 \\sim C67 \\sim C68 \\sim C69: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.008 within 1.7A
O28 \\sim C73 \\sim C74 \\sim C75: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.008 within 1.7A
O24 \\sim C82 \\sim C83 \\sim C84: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.008 within 1.7A
O10 \\sim C7 \\sim C8 \\sim C9: within 2A with sigma of 0.002 and sigma for
terminal atoms of 0.004 within 2A
C64 \\sim C99 \\sim C66 \\sim C65 \\sim C100 \\sim C90 \\sim O27: within 2A
with sigma of 0.002 and sigma for terminal atoms of 0.004 within 2A
C76 \\sim C77 \\sim C78 \\sim C97 \\sim C101 \\sim C102 \\sim O30: within 2A
with sigma of 0.002 and sigma for terminal atoms of 0.004 within 2A
4. Others
 Sof(C89)=Sof(H89)=Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(H93C)=Sof(C94)=Sof(H94A)=
 Sof(H94B)=Sof(H94C)=1-FVAR(1)
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29A)=
 Sof(H29B)=Sof(H29C)=FVAR(1)
 Sof(C22)=Sof(H22)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C88)=Sof(H88A)=
 Sof(H88B)=Sof(H88C)=1-FVAR(2)
 Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21)=Sof(H21A)=
 Sof(H21B)=Sof(H21C)=FVAR(2)
 Sof(C37)=Sof(H37)=Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(H85C)=Sof(C98)=Sof(H98A)=
 Sof(H98B)=Sof(H98C)=1-FVAR(3)
 Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18)=Sof(H18A)=
 Sof(H18B)=Sof(H18C)=FVAR(3)
 Sof(C86)=Sof(H86)=Sof(C87)=Sof(H87A)=Sof(H87B)=Sof(H87C)=Sof(C92)=Sof(H92A)=
 Sof(H92B)=Sof(H92C)=1-FVAR(4)
 Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C12)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=FVAR(4)
 Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(H91C)=Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(H96C)=
 1-FVAR(5)
 Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=
 FVAR(5)
 Sof(H61A)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C95)=Sof(H95A)=Sof(H95B)=
 Sof(H95C)=1-FVAR(6)
 Sof(H61)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C63)=Sof(H63A)=Sof(H63B)=
 Sof(H63C)=FVAR(6)
 Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=
 Sof(C90)=Sof(H90)=1-FVAR(7)
 Sof(C64)=Sof(H64)=Sof(C100)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C99)=Sof(H99A)=
 Sof(H99B)=Sof(H99C)=FVAR(7)
 Sof(C97)=Sof(H97)=Sof(C101)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C102)=Sof(H10G)=
 Sof(H10H)=Sof(H10I)=1-FVAR(8)
 Sof(C76)=Sof(H76)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=Sof(C78)=Sof(H78A)=
 Sof(H78B)=Sof(H78C)=FVAR(8)
5.a Ternary CH refined with riding coordinates:
 C7(H7), C10(H10), C13(H13), C16(H16), C19(H19), C26(H26), C28(H28), C30(H30),
 C33(H33), C36(H36), C41(H41), C52(H52), C55(H55), C58(H58), C61(H61),
 C61(H61A), C64(H64), C67(H67), C70(H70), C73(H73), C76(H76), C82(H82),
 C22(H22), C37(H37), C86(H86), C89(H89), C90(H90), C97(H97)
5.b Me refined with riding coordinates:
 C80(H80A,H80B,H80C), C81(H81A,H81B,H81C)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2)
5.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C24(H24A,H24B,H24C), C25(H25A,
 H25B,H25C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C),
 C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C38(H38A,H38B,
 H38C), C39(H39A,H39B,H39C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C46(H46A,
 H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C51(H51A,H51B,H51C),
 C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C56(H56A,H56B,H56C), C57(H57A,H57B,
 H57C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C62(H62A,H62B,H62C), C63(H63A,
 H63B,H63C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C68(H68A,H68B,H68C),
 C69(H69A,H69B,H69C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C74(H74A,H74B,
 H74C), C75(H75A,H75B,H75C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C83(H83A,
 H83B,H83C), C84(H84A,H84B,H84C), C23(H23A,H23B,H23C), C40(H40A,H40B,H40C),
 C85(H85A,H85B,H85C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C91(H91A,H91B,
 H91C), C92(H92A,H92B,H92C), C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C95(H95A,
 H95B,H95C), C96(H96A,H96B,H96C), C98(H98A,H98B,H98C), C100(H10A,H10B,H10C),
 C99(H99A,H99B,H99C), C101(H10D,H10E,H10F), C102(H10G,H10H,H10I)
;
_shelx_res_checksum              22276
_shelx_hkl_checksum              96916
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.740
_oxdiff_exptl_absorpt_empirical_full_min 0.636