Exploring untapped potential of the molecular precursor approach to control fluorine-doping in mesostructured titania for acid catalysis
Elgayar, Fouad; Jeanneau, Erwann; Bargiela, Pascal; Mesbah, Adel; Essayem, Nadine; Mishra, Shashank; Catalysis Science & Technology 15 (2025) 6744–6756; doi:10.1039/D5CY00688K

data_1575815
_publ_section_title
;
 Exploring untapped potential of the molecular precursor approach to
 control fluorine-doping in mesostructured titania for acid catalysis
;
_journal_issue                   22
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              6744
_journal_page_last               6756
_journal_paper_doi               10.1039/D5CY00688K
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C37 H59 F24 N5 O17 Ti5, 0.5(C H Cl3)'
_chemical_formula_sum            'C37.5 H59.5 Cl1.5 F24 N5 O17 Ti5'
_chemical_formula_weight         1601.07
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-05-14
_audit_creation_method
;
Olex2 1.5-ac6-015
(compiled 2023.12.04 svn.r209d9fb2 for Rigaku Oxford Diffraction, GUI svn.r6873)
;
_audit_update_record
;
2025-02-19 deposited with the CCDC.	2025-09-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.7420(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.49510(10)
_cell_length_b                   13.28940(10)
_cell_length_c                   32.9588(2)
_cell_measurement_reflns_used    55330
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      78.0760
_cell_measurement_theta_min      2.6720
_cell_volume                     6763.66(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.120a 64-bit (release 16-04-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-015 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-015 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.956
_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     34.00 126.00   0.50    0.92    --   47.49  22.00 -95.00  184
  2  \w   -127.00 -35.00   0.50    0.92    --  -48.74 -22.00  98.00  184
  3  \w   -155.00 -71.00   0.50    3.68    --  -84.50 -22.00  98.00  168
  4  \w     87.00 155.00   0.50    3.68    --  100.60  22.00 -95.00  136
  5  \w     97.00 155.00   0.50    3.68    --  111.29  22.00 -95.00  116
  6  \w    -30.00  19.00   0.50    0.92    --   47.49 -38.00   0.00   98
  7  \w     18.00  80.00   0.50    0.92    --   47.49 -99.00-180.00  124
  8  \w    -19.00  29.00   0.50    0.92    --  -48.74  38.00-120.00   96
  9  \w    -19.00  29.00   0.50    0.92    --  -48.74  38.00  30.00   96
 10  \w    -51.00 -11.00   0.50    3.68    --  -84.50  61.00-120.00   80
 11  \w    -51.00 -11.00   0.50    3.68    --  -84.50  61.00  90.00   80
 12  \w    -51.00 -11.00   0.50    3.68    --  -84.50  61.00-150.00   80
 13  \w    -51.00 -11.00   0.50    3.68    --  -84.50  61.00  30.00   80
 14  \w    -51.00 -11.00   0.50    3.68    --  -84.50  61.00-180.00   80
 15  \w    -67.00 -17.00   0.50    3.68    --  -84.50  77.00 -30.00  100
 16  \w     33.00  92.00   0.50    3.68    --  100.60 -95.00 -60.00  118
 17  \w    112.00 172.00   0.50    3.68    --  100.60 125.00 120.00  120
 18  \w     33.00  92.00   0.50    3.68    --  100.60 -95.00 120.00  118
 19  \w    124.00 178.00   0.50    3.68    --  111.29  77.00 -90.00  108
 20  \w     44.00  92.00   0.50    3.68    --  111.29 -95.00  30.00   96
 21  \w     85.00 136.00   0.50    3.68    --  111.29  15.00-150.00  102
 22  \w     85.00 136.00   0.50    3.68    --  111.29  15.00 -60.00  102
 23  \w     44.00  75.00   0.50    3.68    --  111.29 -77.00-150.00   62
 24  \w     85.00 136.00   0.50    3.68    --  111.29  15.00-120.00  102
 25  \w     44.00  75.00   0.50    3.68    --  111.29 -77.00-120.00   62
 26  \w     44.00  75.00   0.50    3.68    --  111.29 -77.00-180.00   62
 27  \w    124.00 178.00   0.50    3.68    --  111.29  77.00  90.00  108
 28  \w     39.00 125.00   0.50    0.92    --   47.49  38.00-180.00  172
 29  \w   -126.00 -40.00   0.50    0.92    --  -48.74 -38.00-120.00  172
 30  \w   -126.00 -40.00   0.50    0.92    --  -48.74 -38.00  30.00  172
 31  \w   -126.00 -40.00   0.50    0.92    --  -48.74 -38.00 -60.00  172
 32  \w   -126.00 -40.00   0.50    0.92    --  -48.74 -38.00 -30.00  172
 33  \w   -136.00 -59.00   0.50    3.68    --  -84.50 -15.00   0.00  154
 34  \w     74.00 136.00   0.50    3.68    --  100.60  15.00   0.00  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0362585000
_diffrn_orient_matrix_UB_12      0.0329045000
_diffrn_orient_matrix_UB_13      -0.0428867000
_diffrn_orient_matrix_UB_21      -0.0922379000
_diffrn_orient_matrix_UB_22      0.0011082000
_diffrn_orient_matrix_UB_23      0.0142477000
_diffrn_orient_matrix_UB_31      0.0116789000
_diffrn_orient_matrix_UB_32      0.1111405000
_diffrn_orient_matrix_UB_33      0.0125530000
_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  0.0392
_diffrn_reflns_av_unetI/netI     0.0208
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            85609
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.394
_diffrn_reflns_theta_min         2.691
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.520
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50859
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.105a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.572
_exptl_crystal_description       block
_exptl_crystal_F_000             3228
_exptl_crystal_size_max          0.247
_exptl_crystal_size_mid          0.134
_exptl_crystal_size_min          0.066
_refine_diff_density_max         2.126
_refine_diff_density_min         -0.710
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     834
_refine_ls_number_reflns         13869
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0503
_refine_ls_R_factor_gt           0.0488
_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^)+(0.0806P)^2^+11.9727P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1390
_refine_ls_wR_factor_ref         0.1404
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13138
_reflns_number_total             13869
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00688k2.cif
_cod_data_source_block           ga75_autored
_cod_depositor_comments
'Adding full bibliography for 1575809--1575816.cif.'
_cod_original_formula_sum        'C37.50 H59.50 Cl1.50 F24 N5 O17 Ti5'
_cod_database_code               1575815
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C150 H238 Cl6 F96 N20 O68 Ti20 '
_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. Others
 Fixed Sof: Cl1(0.5) Cl2(0.5) Cl3(0.5) C38(0.5) H38(0.5)
3.a Ternary CH refined with riding coordinates:
 C16(H16), C24(H24), C32(H32), C35(H35), C38(H38)
3.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B),
 C8(H8A,H8B), C9(H9A,H9B), C11(H11A,H11B), C12(H12A,H12B), C14(H14A,H14B),
 C15(H15A,H15B), C19(H19A,H19B), C20(H20A,H20B), C22(H22A,H22B), C23(H23A,H23B),
  C27(H27A,H27B), C28(H28A,H28B), C30(H30A,H30B), C31(H31A,H31B)
3.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C10(H10A,H10B,H10C), C13(H13A,H13B,H13C), C21(H21A,H21B,
 H21C), C29(H29A,H29B,H29C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id GA75
_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 1.576
_oxdiff_exptl_absorpt_empirical_full_min 0.665