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_1575810
_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         'C20 H36 F12 N4 O6 Ti2'
_chemical_formula_sum            'C20 H36 F12 N4 O6 Ti2'
_chemical_formula_weight         752.33
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-11-05
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2025-02-19 deposited with the CCDC.	2025-09-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.4420(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.12930(10)
_cell_length_b                   12.74100(10)
_cell_length_c                   20.1157(2)
_cell_measurement_reflns_used    19045
_cell_measurement_temperature    100.04(18)
_cell_measurement_theta_max      78.8540
_cell_measurement_theta_min      4.0940
_cell_volume                     3105.85(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.124a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.138a 64-bit (release 24-09-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.124a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-020 (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      100.04(18)
_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 0.941
_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    -42.00  -5.00   0.50    0.95    --  -81.78  38.00-180.00   74
  2  \w    -26.00  26.00   0.50    0.24    --  -51.41  19.00 -90.00  104
  3  \w    -43.00  -5.00   0.50    0.95    --  -81.78  38.00  60.00   76
  4  \w    -43.00  -7.00   0.50    0.95    --  -81.78  38.00 120.00   72
  5  \w    -27.00  25.00   0.50    0.24    --  -51.41  19.00 150.00  104
  6  \w     55.00 128.00   0.50    0.24    --   49.91-165.00  92.00  146
  7  \w     96.00 139.00   0.50    0.95    --   99.32-165.00  92.00   86
  8  \w     73.00  98.00   0.50    0.95    --  110.98-165.00  92.00   50
  9  \w     50.00  75.00   0.50    0.95    --  110.98-117.00-119.00   50
 10  \w     41.00 105.00   0.50    0.95    --  110.98 -99.00-120.00  128
 11  \w     29.00 103.00   0.50    0.95    --   99.32-117.00-119.00  148
 12  \w     29.00  99.00   0.50    0.24    --   49.91-117.00-119.00  140
 13  \w     31.00 106.00   0.50    0.95    --   99.32 -99.00  60.00  150
 14  \w     25.00  60.00   0.50    0.95    --   99.32 -57.00  90.00   70
 15  \w     38.00  64.00   0.50    0.95    --  110.98 -57.00  60.00   52
 16  \w     37.00  64.00   0.50    0.95    --  110.98 -57.00  30.00   54
 17  \w     36.00  65.00   0.50    0.95    --  110.98 -57.00   0.00   58
 18  \w     24.00  63.00   0.50    0.95    --   99.32 -57.00-120.00   78
 19  \w     39.00  64.00   0.50    0.95    --  110.98 -57.00-150.00   50
 20  \w    101.00 126.00   0.50    0.95    --  110.98  38.00-120.00   50
 21  \w    137.00 173.00   0.50    0.95    --  110.98  38.00-120.00   72
 22  \w    120.00 168.00   0.50    0.95    --   99.32  77.00 -60.00   96
 23  \w     78.00 104.00   0.50    0.24    --   49.91  77.00  30.00   52
 24  \w     87.00 112.00   0.50    0.95    --   99.32 165.00 116.00   50
 25  \w    100.00 144.00   0.50    0.95    --  110.98 117.00 -31.00   88
 26  \w    109.00 135.00   0.50    0.95    --   99.32 125.00-180.00   52
 27  \w   -153.00 -84.00   0.50    0.95    --  -81.78-117.00-119.00  138
 28  \w   -102.00 -73.00   0.50    0.24    --  -51.41-125.00 -30.00   58
 29  \w   -119.00 -47.00   0.50    0.24    --  -51.41-165.00  92.00  144
 30  \w   -137.00 -47.00   0.50    0.95    --  -81.78-165.00  92.00  180
 31  \w    -84.00  -7.00   0.50    0.24    --  -51.41 117.00 -31.00  154
;
_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      0.0647949000
_diffrn_orient_matrix_UB_12      -0.0300472000
_diffrn_orient_matrix_UB_13      -0.0614168000
_diffrn_orient_matrix_UB_21      -0.0003179000
_diffrn_orient_matrix_UB_22      0.1157207000
_diffrn_orient_matrix_UB_23      -0.0222804000
_diffrn_orient_matrix_UB_31      0.1093854000
_diffrn_orient_matrix_UB_32      0.0181701000
_diffrn_orient_matrix_UB_33      0.0400580000
_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  0.0344
_diffrn_reflns_av_unetI/netI     0.0284
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.941
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            30300
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.941
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.349
_diffrn_reflns_theta_min         4.108
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.424
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60832
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.124a (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    1.609
_exptl_crystal_description       needle
_exptl_crystal_F_000             1536
_exptl_crystal_size_max          0.143
_exptl_crystal_size_mid          0.074
_exptl_crystal_size_min          0.044
_refine_diff_density_max         0.508
_refine_diff_density_min         -0.402
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     479
_refine_ls_number_reflns         6343
_refine_ls_number_restraints     415
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0367
_refine_ls_R_factor_gt           0.0322
_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^)+(0.0432P)^2^+1.9128P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0839
_refine_ls_wR_factor_ref         0.0874
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5729
_reflns_number_total             6343
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00688k2.cif
_cod_data_source_block           flgb34_2_autored
_cod_depositor_comments
'Adding full bibliography for 1575809--1575816.cif.'
_cod_database_code               1575810
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C84 H168 F40 N20 O28 Ti8 '
_shelx_estimated_absorpt_t_max   0.812
_shelx_estimated_absorpt_t_min   0.517
_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
 N4-C19A \\sim N4-C19B \\sim N4-C20A \\sim N4-C20B \\sim N4-C18A \\sim N4-C18B
 with sigma of 0.01
 C18A-C17A \\sim C18B-C17B \\sim C17B-C16B \\sim C17A-C16A
 with sigma of 0.01
 O6-C17B \\sim O6-C17A
 with sigma of 0.01
 F10A-C16A \\sim F12B-C16B \\sim F12A-C16A \\sim F11A-C16A \\sim F10B-C16B
\\sim F11B-C16B
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
F10A \\sim F10B \\sim F11A \\sim F11B \\sim F12A \\sim F12B \\sim O6 \\sim N4
\\sim C16A \\sim C16B \\sim C17A \\sim C17B \\sim C18A \\sim C18B \\sim C19A
\\sim C19B \\sim C20A \\sim C20B: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 F10A, F10B, F11A, F11B, F12A, F12B, O6, N4, C16A, C16B, C17A, C17B, C18A,
 C18B, C19A, C19B, C20A, C20B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: F10A(0.7) F10B(0.3) F11A(0.7) F11B(0.3) F12A(0.7) F12B(0.3)
 C16A(0.7) C16B(0.3) C17A(0.7) H17A(0.7) C17B(0.3) H17B(0.3) C18A(0.7)
 H18A(0.7) H18B(0.7) C18B(0.3) H18C(0.3) H18D(0.3) C19A(0.7) H19A(0.7)
 H19B(0.7) H19C(0.7) C19B(0.3) H19D(0.3) H19E(0.3) H19F(0.3) C20A(0.7)
 H20A(0.7) H20B(0.7) H20C(0.7) C20B(0.3) H20D(0.3) H20E(0.3) H20F(0.3)
6.a Ternary CH refined with riding coordinates:
 C2(H2), C7(H7), C12(H12), C17A(H17A), C17B(H17B)
6.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C8(H8A,H8B), C13(H13A,H13B), C18A(H18A,H18B), C18B(H18C,H18D)
6.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C19A(H19A,H19B,H19C), C19B(H19D,H19E,
 H19F), C20A(H20A,H20B,H20C), C20B(H20D,H20E,H20F)
;
_shelx_res_checksum              28854
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id FLGB34
_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 1.462
_oxdiff_exptl_absorpt_empirical_full_min 0.765