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_1575816
_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         'C24 H32 F24 N4 O6 Ti2, 0.5(C7 H8)'
_chemical_formula_sum            'C27.5 H36 F24 N4 O6 Ti2'
_chemical_formula_weight         1070.40
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   24.66436(10)
_cell_length_b                   12.04568(5)
_cell_length_c                   62.6972(3)
_cell_measurement_reflns_used    155756
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      77.8660
_cell_measurement_theta_min      2.2620
_cell_volume                     18627.27(14)
_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)'
_computing_structure_solution
;
Superflip  (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_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 0.990
_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    -25.00  54.00   0.50    6.15    --   36.74 -63.00-152.00  158
  2  \w      8.00  59.00   0.50    6.15    --   36.74  57.00 161.00  102
  3  \w    -39.00  45.00   0.50    6.15    --   36.74 -57.00  20.00  168
  4  \w     37.00 102.00   0.50    6.15    --   36.74-129.00 147.00  130
  5  \w    -54.00  43.00   0.50    6.15    --  -37.99  63.00 -15.00  194
  6  \w    -45.00  45.00   0.50    6.15    --  -37.99  57.00 161.00  180
  7  \w     -7.00  45.00   0.50    6.15    --   75.23 -57.00  20.00  104
  8  \w     37.00 102.00   0.50    6.15    --   75.23-129.00 147.00  130
  9  \w    106.00 155.00   0.50    6.15    --   75.23  57.00 161.00   98
 10  \w   -156.00 -92.00   0.50    6.15    --  -75.58 -63.00-152.00  128
 11  \w    -76.00 -15.00   0.50    6.15    --  -75.58 129.00-139.00  122
 12  \w    -45.00   7.00   0.50    6.15    --  -75.58  57.00 161.00  104
 13  \w    -54.00   5.00   0.50    6.15    --  -75.58  63.00 -15.00  118
 14  \w     37.00 102.00   0.50    6.15    --   85.26-129.00 147.00  130
 15  \w      5.00  54.00   0.50    6.15    --   85.26 -63.00-152.00   98
 16  \w      3.00  45.00   0.50    6.15    --   85.26 -57.00  20.00   84
 17  \w    -45.00  -3.00   0.50    6.15    --  -86.16  57.00 161.00   84
 18  \w   -177.00 -83.00   0.50    6.15    --  -97.69 -57.00  20.00  188
 19  \w    -54.00 -17.00   0.50    6.15    --  -97.69  63.00 -15.00   74
 20  \w    -45.00 -15.00   0.50    6.15    --  -97.69  57.00 161.00   60
 21  \w   -177.00 -92.00   0.50    6.15    --  -97.69 -63.00-152.00  170
 22  \w   -151.00 -88.00   0.50    6.15    --  -97.69-129.00 147.00  126
 23  \w    110.00 156.00   0.50    6.15    --  122.23 129.00-139.00   92
 24  \w    105.00 156.00   0.50    6.15    --  122.23  57.00 161.00  102
 25  \w      7.00  60.00   0.50    6.15    --   36.74  57.00-120.00  106
 26  \w     19.00  47.00   0.50    6.15    --  -37.99  19.00-150.00   56
 27  \w     19.00  47.00   0.50    6.15    --  -37.99  19.00 -60.00   56
 28  \w    -55.00 -17.00   0.50    6.15    --  -97.69  64.00  90.00   76
 29  \w    -67.00 -21.00   0.50    6.15    --  -97.69  77.00-180.00   92
 30  \w    -67.00 -21.00   0.50    6.15    --  -97.69  77.00  90.00   92
 31  \w    -66.00 -15.00   0.50    6.15    --  -97.69 111.00 -90.00  102
 32  \w     92.00 156.00   0.50    6.15    --  122.23  50.00  90.00  128
 33  \w     92.00 156.00   0.50    6.15    --  122.23  50.00 -90.00  128
 34  \w     92.00 156.00   0.50    6.15    --  122.23  50.00 -60.00  128
 35  \w     46.00  75.00   0.50    6.15    --  122.23 -77.00 -60.00   58
 36  \w     38.00  92.00   0.50    6.15    --  122.23-111.00  30.00  108
 37  \w     38.00  92.00   0.50    6.15    --  122.23-111.00-180.00  108
 38  \w     46.00  75.00   0.50    6.15    --  122.23 -77.00 -90.00   58
 39  \w     46.00  75.00   0.50    6.15    --  122.23 -77.00 120.00   58
 40  \w     46.00  75.00   0.50    6.15    --  122.23 -77.00 -30.00   58
 41  \w     92.00 156.00   0.50    6.15    --  122.23  50.00-180.00  128
 42  \w     46.00  75.00   0.50    6.15    --  122.23 -77.00 150.00   58
 43  \w      7.00  60.00   0.50    6.15    --   36.74  57.00  30.00  106
 44  \w      7.00  60.00   0.50    6.15    --   36.74  57.00 -30.00  106
 45  \w      7.00  60.00   0.50    6.15    --   36.74  57.00  90.00  106
 46  \w     19.00  47.00   0.50    6.15    --  -37.99  19.00  90.00   56
 47  \w     19.00  47.00   0.50    6.15    --  -37.99  19.00 120.00   56
 48  \w     19.00  47.00   0.50    6.15    --  -37.99  19.00  60.00   56
 49  \w     19.00  47.00   0.50    6.15    --  -37.99  19.00 -90.00   56
 50  \w     53.00 156.00   0.50    6.15    --   85.26  45.00-120.00  206
 51  \w   -166.00 -35.00   0.50    6.15    --  -86.16 -30.00  90.00  262
;
_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      -0.0046330000
_diffrn_orient_matrix_UB_12      0.1275531000
_diffrn_orient_matrix_UB_13      -0.0003721000
_diffrn_orient_matrix_UB_21      0.0457211000
_diffrn_orient_matrix_UB_22      0.0082864000
_diffrn_orient_matrix_UB_23      0.0166620000
_diffrn_orient_matrix_UB_31      0.0422779000
_diffrn_orient_matrix_UB_32      0.0049478000
_diffrn_orient_matrix_UB_33      -0.0180588000
_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  0.0416
_diffrn_reflns_av_unetI/netI     0.0185
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       78
_diffrn_reflns_limit_l_min       -79
_diffrn_reflns_number            212795
_diffrn_reflns_point_group_measured_fraction_full 0.952
_diffrn_reflns_point_group_measured_fraction_max 0.919
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.596
_diffrn_reflns_theta_min         2.819
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.189
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.213
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.105a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.527
_exptl_crystal_description       block
_exptl_crystal_F_000             8592
_exptl_crystal_size_max          0.422
_exptl_crystal_size_mid          0.261
_exptl_crystal_size_min          0.142
_refine_diff_density_max         0.584
_refine_diff_density_min         -0.545
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.401(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2244
_refine_ls_number_reflns         36848
_refine_ls_number_restraints     68
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0590
_refine_ls_R_factor_gt           0.0588
_refine_ls_shift/su_max          0.031
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0717P)^2^+42.4529P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1529
_refine_ls_wR_factor_ref         0.1530
_reflns_Friedel_coverage         0.838
_reflns_Friedel_fraction_full    0.902
_reflns_Friedel_fraction_max     0.846
_reflns_number_gt                36691
_reflns_number_total             36848
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00688k2.cif
_cod_data_source_block           flgb024_autored
_cod_depositor_comments
'Adding full bibliography for 1575809--1575816.cif.'
_cod_original_formula_sum        'C27.50 H36 F24 N4 O6 Ti2'
_cod_database_code               1575816
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C30 H40 F24 N4 O6 Ti2'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.599(6)
 0.401(6)
2. 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
3. Restrained distances
 C98-C97 \\sim C99-C98 \\sim C99-C100 \\sim C101-C100 \\sim C102-C101 \\sim
C97-C102 \\sim C106-C105 ~
 C107-C106 \\sim C108-C107 \\sim C109-C108 \\sim C109-C104 \\sim C105-C104
 with sigma of 0.01
 C110-C104 \\sim C97-C103
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C100) = Uanis(C99) = Uanis(C98) = Uanis(C101) = Uanis(C109) = Uanis(C104)
= Uanis(C107) = Uanis(C108) = Uanis(C106) = Uanis(C105) = Uanis(C110) =
Uanis(C102) = Uanis(C97) = Uanis(C103)
5.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C10(H10A,H10B), C16(H16A,H16B), C22(H22A,H22B), C28(H28A,H28B),
 C34(H34A,H34B), C40(H40A,H40B), C46(H46A,H46B), C52(H52A,H52B), C58(H58A,H58B),
  C64(H64A,H64B), C70(H70A,H70B), C76(H76A,H76B), C82(H82A,H82B), C88(H88A,
 H88B), C94(H94A,H94B)
5.b Aromatic/amide H refined with riding coordinates:
 C98(H98), C99(H99), C100(H100), C101(H101), C102(H102), C105(H105),
 C106(H106), C107(H107), C108(H108), C109(H109)
5.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C47(H47A,H47B,H47C),
 C48(H48A,H48B,H48C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C59(H59A,H59B,
 H59C), C60(H60A,H60B,H60C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C71(H71A,
 H71B,H71C), C72(H72A,H72B,H72C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C),
 C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C89(H89A,H89B,H89C), C90(H90A,H90B,
 H90C), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C), C103(H10C,H10D,H10E),
 C110(H11D,H11E,H11F)
;
_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 FLGB024
_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 1.434
_oxdiff_exptl_absorpt_empirical_full_min 0.758