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_1575811
_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 H34 F12 N4 O6 Ti2'
_chemical_formula_sum            'C20 H34 F12 N4 O6 Ti2'
_chemical_formula_weight         750.31
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-28
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2025-02-28 deposited with the CCDC.	2025-09-17 downloaded from the CCDC.
;
_cell_angle_alpha                67.895(2)
_cell_angle_beta                 79.245(2)
_cell_angle_gamma                63.170(2)
_cell_formula_units_Z            1
_cell_length_a                   9.5425(2)
_cell_length_b                   9.6023(2)
_cell_length_c                   9.9370(2)
_cell_measurement_reflns_used    19689
_cell_measurement_temperature    100.00(17)
_cell_measurement_theta_max      77.1810
_cell_measurement_theta_min      4.7890
_cell_volume                     752.63(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.124a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 44.93a 64-bit (release 10-02-2025))'
_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      100.00(17)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.943
_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     27.00  54.00   0.50    0.05    --   42.00  64.00-144.87   54
  2  \w     11.00  37.00   0.50    0.05    --   30.00  72.00-167.09   52
  3  \w     22.00  49.00   0.50    0.05    --   38.00  67.00-108.60   54
  4  \w     22.00  49.00   0.50    0.05    --   38.00  67.00 -60.97   54
  5  \w     27.00  56.00   0.50    0.05    --   42.00  63.00   5.09   58
  6  \w     32.00  58.00   0.50    0.05    --   46.00  62.00 117.02   52
  7  \w     26.00  54.00   0.50    0.05    --   42.00  65.00 164.94   56
  8  \w     28.00  58.00   0.50    0.05    --   42.00  62.00  92.58   60
  9  \w     33.00  59.00   0.50    0.05    --   46.00  60.00  46.35   52
 10  \w     33.00  59.00   0.50    0.05    --   46.00  59.00 -29.40   52
 11  \w     87.00 136.00   0.50    0.12    --   99.76  15.00 -60.00   98
 12  \w    121.00 178.00   0.50    0.12    --  111.05  77.00 -60.00  114
 13  \w     98.00 136.00   0.50    0.12    --  111.05  15.00 -30.00   76
 14  \w     98.00 136.00   0.50    0.12    --  111.05  15.00 -90.00   76
 15  \w     87.00 136.00   0.50    0.12    --   99.76  15.00  30.00   98
 16  \w    121.00 169.00   0.50    0.12    --   99.76  77.00 120.00   96
 17  \w     98.00 136.00   0.50    0.12    --  111.05  15.00 120.00   76
 18  \w     31.00  82.00   0.50    0.12    --   99.76 -81.00 131.00  102
 19  \w     29.00  92.00   0.50    0.12    --   99.76 -95.00 120.00  126
 20  \w     40.00  92.00   0.50    0.12    --  111.05 -95.00  60.00  104
 21  \w     40.00  92.00   0.50    0.12    --  111.05 -95.00  30.00  104
 22  \w     31.00 100.00   0.50    0.12    --   99.76-125.00   0.00  138
 23  \w     40.00  92.00   0.50    0.12    --  111.05 -95.00 -60.00  104
 24  \w     40.00  92.00   0.50    0.12    --  111.05 -95.00-120.00  104
 25  \w     29.00  92.00   0.50    0.12    --   99.76 -95.00-150.00  126
 26  \w     40.00  92.00   0.50    0.12    --  111.05 -95.00 -90.00  104
 27  \w     40.00  92.00   0.50    0.12    --  111.05 -95.00 -30.00  104
 28  \w     42.00  82.00   0.50    0.12    --  111.05 -81.00 131.00   80
 29  \w     40.00  92.00   0.50    0.12    --  111.05 -95.00 150.00  104
 30  \w     40.00  92.00   0.50    0.12    --  111.05 -95.00  90.00  104
 31  \w     31.00  75.00   0.50    0.12    --   99.76 -77.00  30.00   88
 32  \w      0.00  72.00   0.50    0.05    --   49.03 -81.00 131.00  144
 33  \w     42.00  75.00   0.50    0.12    --  111.05 -77.00  30.00   66
 34  \w    120.00 178.00   0.50    0.12    --  111.05  81.00-105.00  116
 35  \w    120.00 169.00   0.50    0.12    --   99.76  81.00-105.00   98
 36  \w     -6.00  20.00   0.50    0.05    --   18.00  83.00 111.19   52
 37  \w    -67.00  19.00   0.50    0.05    --  -50.53  81.00-105.00  172
 38  \w    -51.00  -8.00   0.50    0.12    --  -81.95  61.00-150.00   86
 39  \w    -66.00 -13.00   0.50    0.12    --  -81.95  81.00-105.00  106
 40  \w    -51.00  -8.00   0.50    0.12    --  -81.95  61.00   0.00   86
 41  \w    -51.00  -8.00   0.50    0.12    --  -81.95  61.00 120.00   86
 42  \w   -151.00 -99.00   0.50    0.12    --  -81.95 -81.00 131.00  104
 43  \w   -164.00 -79.00   0.50    0.12    --  -90.25 -61.00  86.77  170
 44  \w   -164.00 -79.00   0.50    0.12    --  -90.25 -61.00  14.09  170
 45  \w   -165.00 -79.00   0.50    0.12    --  -90.25 -59.00 -13.02  172
 46  \w   -164.00 -79.00   0.50    0.12    --  -90.25 -61.00 -29.34  170
 47  \w   -165.00 -79.00   0.50    0.12    --  -90.25 -58.00-106.81  172
 48  \w   -164.00 -81.00   0.50    0.12    --  -90.25 -63.00-148.65  166
 49  \w   -126.00 -79.00   0.50    0.05    --  -50.53 -57.00-180.00   94
 50  \w   -151.00 -99.00   0.50    0.12    --  -81.95 -77.00-120.00  104
 51  \w   -126.00 -79.00   0.50    0.05    --  -50.53 -57.00-120.00   94
 52  \w   -165.00 -79.00   0.50    0.12    --  -90.25 -57.00 -89.85  172
 53  \w   -166.00 -79.00   0.50    0.12    --  -90.25 -56.00-171.86  174
 54  \w   -166.00 -79.00   0.50    0.12    --  -90.25 -56.00  94.98  174
 55  \w   -165.00 -79.00   0.50    0.12    --  -90.25 -58.00 119.82  172
 56  \w   -165.00 -79.00   0.50    0.12    --  -90.25 -60.00 137.31  172
 57  \w   -166.00 -79.00   0.50    0.12    --  -90.25 -55.00 141.82  174
 58  \w   -158.00 -71.00   0.50    0.12    --  -82.00 -55.00 176.15  174
 59  \w   -126.00 -79.00   0.50    0.05    --  -50.53 -57.00 120.00   94
 60  \w   -166.00 -80.00   0.50    0.12    --  -90.25 -54.00  62.22  172
 61  \w   -158.00 -71.00   0.50    0.12    --  -82.00 -54.00 147.03  174
 62  \w   -162.00 -75.00   0.50    0.12    --  -86.00 -54.00  37.97  174
 63  \w   -150.00 -63.00   0.50    0.05    --  -74.00 -54.00 -47.21  174
 64  \w   -166.00 -80.00   0.50    0.12    --  -90.25 -53.00 -75.50  172
 65  \w   -154.00 -68.00   0.50    0.12    --  -78.00 -53.00-125.80  172
 66  \w   -150.00 -63.00   0.50    0.05    --  -74.00 -54.00  -6.02  174
 67  \w   -154.00 -68.00   0.50    0.12    --  -78.00 -53.00 154.37  172
 68  \w   -150.00 -64.00   0.50    0.05    --  -74.00 -53.00 101.42  172
 69  \w   -154.00 -95.00   0.50    0.12    --  -78.00 -51.00  44.46  118
 70  \w   -166.00 -79.00   0.50    0.12    --  -90.25 -55.00  23.00  174
 71  \w   -162.00 -76.00   0.50    0.12    --  -86.00 -53.00-173.23  172
 72  \w   -150.00 -65.00   0.50    0.05    --  -74.00 -51.00 -92.04  170
 73  \w   -167.00 -83.00   0.50    0.12    --  -90.25 -47.00-141.25  168
 74  \w   -154.00 -69.00   0.50    0.12    --  -78.00 -51.00 -71.88  170
 75  \w   -151.00 -66.00   0.50    0.05    --  -74.00 -47.00-165.70  170
 76  \w   -154.00 -69.00   0.50    0.12    --  -78.00 -51.00 -27.37  170
 77  \w   -159.00 -75.00   0.50    0.12    --  -81.95 -45.00-120.00  168
 78  \w   -151.00 -66.00   0.50    0.05    --  -74.00 -47.00  50.18  170
 79  \w   -151.00 -66.00   0.50    0.05    --  -74.00 -48.00  69.72  170
 80  \w   -151.00 -65.00   0.50    0.05    --  -74.00 -50.00 125.56  172
 81  \w   -136.00 -69.00   0.50    0.12    --  -81.95 -15.00 120.00  134
;
_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      0.0516507000
_diffrn_orient_matrix_UB_12      -0.0057343000
_diffrn_orient_matrix_UB_13      0.1406255000
_diffrn_orient_matrix_UB_21      -0.1712116000
_diffrn_orient_matrix_UB_22      0.1080063000
_diffrn_orient_matrix_UB_23      0.0323214000
_diffrn_orient_matrix_UB_31      -0.0276336000
_diffrn_orient_matrix_UB_32      -0.1570461000
_diffrn_orient_matrix_UB_33      0.0848019000
_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  0.0326
_diffrn_reflns_av_unetI/netI     0.0153
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.943
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            27862
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.892
_diffrn_reflns_theta_min         4.804
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.595
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52592
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.655
_exptl_crystal_description       plate
_exptl_crystal_F_000             382
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.593
_refine_diff_density_min         -0.528
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     231
_refine_ls_number_reflns         3068
_refine_ls_number_restraints     57
_refine_ls_restrained_S_all      1.113
_refine_ls_R_factor_all          0.0332
_refine_ls_R_factor_gt           0.0330
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0542P)^2^+0.4671P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0918
_refine_ls_wR_factor_ref         0.0920
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3029
_reflns_number_total             3068
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00688k2.cif
_cod_data_source_block           flgb71_autored
_cod_depositor_comments
'Adding full bibliography for 1575809--1575816.cif.'
_cod_database_code               1575811
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H34 F12 N4 O6 Ti2'
_shelx_estimated_absorpt_t_max   0.530
_shelx_estimated_absorpt_t_min   0.313
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N2-C8A \\sim N2-C8B \\sim N2-C7A \\sim N2-C7B \\sim N2-C10A \\sim N2-C10B
 with sigma of 0.01
 C8A-C9 \\sim C8B-C9 \\sim C7B-C6 \\sim C7A-C6
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C7A \\sim C7B \\sim C8A \\sim C8B \\sim C10A \\sim C10B: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(H6B)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H9BC)=
 Sof(H9BD)=Sof(C10A)=Sof(H10A)=Sof(H10B)=Sof(H10C)=1-FVAR(1)
 Sof(H6A)=Sof(C7B)=Sof(H7BA)=Sof(H7BB)=Sof(C8B)=Sof(H8BA)=Sof(H8BB)=Sof(H9AA)=
 Sof(H9AB)=Sof(C10B)=Sof(H10D)=Sof(H10E)=Sof(H10F)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C3(H3)
5.b Secondary CH2 refined with riding coordinates:
 C7A(H7AA,H7AB), C7B(H7BA,H7BB), C8A(H8AA,H8AB), C8B(H8BA,H8BB), C9(H9AA,H9AB),
  C9(H9BC,H9BD)
5.c Aromatic/amide H refined with riding coordinates:
 C6(H6A), C6(H6B)
5.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C10A(H10A,H10B,H10C), C10B(H10D,H10E,H10F)
;
_shelx_res_checksum              6599
_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 1.511
_oxdiff_exptl_absorpt_empirical_full_min 0.605