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_1575809
_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         'C19 H19 F24 N2 O5 Ti'
_chemical_formula_sum            'C19 H19 F24 N2 O5 Ti'
_chemical_formula_weight         859.26
_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             2024-02-01
_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                 97.922(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.4959(3)
_cell_length_b                   12.8299(3)
_cell_length_c                   16.1978(3)
_cell_measurement_reflns_used    13980
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      30.0110
_cell_measurement_theta_min      2.0260
_cell_volume                     2983.73(11)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.105a 64-bit (release 11-01-2024))'
_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)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(3)
_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 0.847
_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      6.00  55.00   0.50   80.75    --    8.73-115.00  17.00   98
  2  \w    -89.00 -40.00   0.50   80.75    --   -7.72 -19.00 120.00   98
  3  \w    -60.00   8.00   0.50   80.75    --   -7.72 -57.00  60.00  136
  4  \w     -7.00  39.00   0.50   80.75    --    8.73  57.00 120.00   92
  5  \w    -72.00 -40.00   0.50   80.75    --    8.73 -19.00 -30.00   64
  6  \w    -72.00 -40.00   0.50   80.75    --    8.73 -19.00 -60.00   64
  7  \w     -4.00  46.00   0.50   80.75    --    8.73 -99.00-120.00  100
  8  \w    -72.00 -40.00   0.50   80.75    --    8.73 -19.00 -90.00   64
  9  \w    -89.00 -40.00   0.50   80.75    --   -7.72 -19.00-150.00   98
 10  \w    -72.00 -40.00   0.50   80.75    --    8.73 -19.00-180.00   64
 11  \w     -4.00  21.00   0.50   80.75    --    8.73 -99.00 120.00   50
 12  \w    -72.00 -40.00   0.50   80.75    --    8.73 -19.00 150.00   64
;
_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      0.0034443000
_diffrn_orient_matrix_UB_12      0.0252454000
_diffrn_orient_matrix_UB_13      0.0392616000
_diffrn_orient_matrix_UB_21      -0.0110367000
_diffrn_orient_matrix_UB_22      0.0483099000
_diffrn_orient_matrix_UB_23      -0.0202716000
_diffrn_orient_matrix_UB_31      -0.0480352000
_diffrn_orient_matrix_UB_32      -0.0092766000
_diffrn_orient_matrix_UB_33      0.0012031000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0380
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.847
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            42310
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.847
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.364
_diffrn_reflns_theta_min         2.030
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.473
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77844
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.913
_exptl_crystal_description       plate
_exptl_crystal_F_000             1700
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.798
_refine_diff_density_min         -0.771
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     504
_refine_ls_number_reflns         7621
_refine_ls_number_restraints     189
_refine_ls_restrained_S_all      1.135
_refine_ls_R_factor_all          0.0679
_refine_ls_R_factor_gt           0.0460
_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^)+(0.0515P)^2^+3.8871P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1111
_refine_ls_wR_factor_ref         0.1206
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5793
_reflns_number_total             7621
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00688k2.cif
_cod_data_source_block           flga076_autored
_cod_depositor_comments
'Adding full bibliography for 1575809--1575816.cif.'
_cod_database_code               1575809
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C76 H88 F96 N8 O20 Ti4 '
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.945
_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) groups
2. Restrained distances
 O4-H4
 0.87 with sigma of 0.01
 C10-H4
 1.903468 with sigma of 0.02
 Ti1-H4
 2.610627 with sigma of 0.02
 C10-C11 \\sim C10A-C11
 with sigma of 0.02
 C10-C12 \\sim C10A-C12
 with sigma of 0.02
 C11-F20 \\sim C11-F20A
 with sigma of 0.02
 C11-F21 \\sim C11-F21A
 with sigma of 0.02
 C11-F19 \\sim C11-F19A
 with sigma of 0.02
 C12-C10 \\sim C12-C10A
 with sigma of 0.01
 O4-C10 \\sim O4-C10A
 with sigma of 0.01
 C11-C10 \\sim C11-C10A
 with sigma of 0.01
 F19-C11 \\sim F20A-C11 \\sim F20-C11 \\sim F21-C11 \\sim F19A-C11
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C11 \\sim F20 \\sim F21 \\sim F19 \\sim F19A \\sim F20A \\sim F21A \\sim C10
\\sim C10A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
4. Rigid body (RIGU) restrains
 C11, F20, F21, F19, F19A, F20A, F21A, C10A, C10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C10A)=Sof(F19A)=Sof(F20A)=Sof(F21A)=1-FVAR(1)
 Sof(C10)=Sof(F20)=Sof(F21)=Sof(F19)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C4(H4A), C7(H7), C15(H15)
6.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B)
6.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C)
;
_shelx_res_checksum              37256
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id FLGA076
_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 1.324
_oxdiff_exptl_absorpt_empirical_full_min 0.763