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_1575814
_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, C7 H8'
_chemical_formula_sum            'C31 H40 F24 N4 O6 Ti2'
_chemical_formula_weight         1116.47
_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     dual
_audit_creation_date             2024-04-03
_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                   24.6382(2)
_cell_length_b                   12.05520(10)
_cell_length_c                   62.6466(4)
_cell_measurement_reflns_used    144940
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      77.1580
_cell_measurement_theta_min      2.8030
_cell_volume                     18607.2(2)
_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  (Sheldrick, 2015)'
_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 0.962
_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    -67.00   9.00   0.38    1.42    --  -46.35  92.00 -49.00  200
  2  \w   -128.00 -30.72   0.38    1.42    --  -46.35 -31.00   7.00  256
  3  \w   -167.00 -72.00   0.38    8.00    --  -87.71 -31.00   7.00  250
  4  \w   -154.00 -92.06   0.38    8.00    --  -87.71-124.00 -53.00  163
  5  \w    -66.00 -17.74   0.38    8.00    --  -87.71  92.00 -49.00  127
  6  \w     34.00  98.22   0.38    8.00    --  101.89-124.00 -53.00  169
  7  \w     41.00  91.16   0.38    8.00    --  111.66 -92.00-162.00  132
  8  \w    -35.00  18.20   0.38    1.42    --   45.10 -38.00  60.00  140
  9  \w    -19.00  33.06   0.38    1.42    --  -46.35  38.00 -60.00  137
 10  \w     33.00  73.66   0.38    8.00    --  101.89 -77.00 -60.00  107
 11  \w    124.00 170.36   0.38    8.00    --  101.89  77.00 -30.00  122
 12  \w    124.00 170.36   0.38    8.00    --  101.89  77.00   0.00  122
 13  \w    124.00 170.36   0.38    8.00    --  101.89  77.00 -90.00  122
 14  \w    124.00 170.36   0.38    8.00    --  101.89  77.00  60.00  122
 15  \w     33.00  73.66   0.38    8.00    --  101.89 -77.00 150.00  107
 16  \w     42.00  73.92   0.38    8.00    --  111.66 -77.00 -30.00   84
 17  \w     42.00  73.92   0.38    8.00    --  111.66 -77.00  90.00   84
 18  \w     42.00  73.92   0.38    8.00    --  111.66 -77.00-150.00   84
 19  \w    109.00 176.64   0.38    8.00    --  111.66  61.00  30.00  178
 20  \w     42.00  73.92   0.38    8.00    --  111.66 -77.00  60.00   84
 21  \w     42.00  73.92   0.38    8.00    --  111.66 -77.00 120.00   84
 22  \w     30.00 125.00   0.38    1.42    --   45.10  38.00-150.00  250
 23  \w     30.00 125.00   0.38    1.42    --   45.10  38.00 150.00  250
 24  \w   -127.00 -32.00   0.38    1.42    --  -46.35 -38.00-150.00  250
 25  \w   -127.00 -32.00   0.38    1.42    --  -46.35 -38.00 -90.00  250
 26  \w    -66.00 -18.88   0.38    8.00    --  -87.71  77.00-150.00  124
 27  \w   -167.00 -74.66   0.38    8.00    --  -87.71 -45.00-180.00  243
 28  \w   -167.00 -74.66   0.38    8.00    --  -87.71 -45.00-150.00  243
 29  \w   -136.00 -41.00   0.38    8.00    --  -87.71 -15.00 -90.00  250
 30  \w   -167.00 -74.66   0.38    8.00    --  -87.71 -45.00 -90.00  243
 31  \w   -136.00 -41.00   0.38    8.00    --  -87.71 -15.00  60.00  250
 32  \w     30.00  91.94   0.38    8.00    --  101.89 -95.00  60.00  163
 33  \w     88.00 177.30   0.38    8.00    --  101.89  45.00-180.00  235
 34  \w     30.00  91.94   0.38    8.00    --  101.89 -95.00 120.00  163
 35  \w     62.00 135.34   0.38    8.00    --  111.66  15.00 -60.00  193
 36  \w     62.00 135.34   0.38    8.00    --  111.66  15.00 150.00  193
 37  \w     39.00  91.06   0.38    8.00    --  111.66 -95.00  30.00  137
 38  \w     30.00 125.00   0.38    1.42    --   45.10  38.00  60.00  250
 39  \w   -127.00 -32.00   0.38    1.42    --  -46.35 -38.00 150.00  250
 40  \w   -127.00 -32.00   0.38    1.42    --  -46.35 -38.00 -30.00  250
 41  \w    -74.00 -13.96   0.38    1.42    --  -46.35 125.00 120.00  158
 42  \w   -167.00 -74.66   0.38    8.00    --  -87.71 -45.00  60.00  243
 43  \w   -167.00 -74.66   0.38    8.00    --  -87.71 -45.00 -60.00  243
 44  \w   -167.00-119.12   0.38    8.00    --  -87.71 -45.00 -30.00  126
 45  \w     37.00 100.08   0.38    8.00    --  111.66-125.00   0.00  166
;
_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      0.0149994000
_diffrn_orient_matrix_UB_12      -0.1240522000
_diffrn_orient_matrix_UB_13      -0.0001244000
_diffrn_orient_matrix_UB_21      0.0557199000
_diffrn_orient_matrix_UB_22      0.0284683000
_diffrn_orient_matrix_UB_23      -0.0097297000
_diffrn_orient_matrix_UB_31      0.0240842000
_diffrn_orient_matrix_UB_32      0.0115176000
_diffrn_orient_matrix_UB_33      0.0225830000
_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  0.0637
_diffrn_reflns_av_unetI/netI     0.0377
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       77
_diffrn_reflns_limit_l_min       -67
_diffrn_reflns_number            222714
_diffrn_reflns_point_group_measured_fraction_full 0.948
_diffrn_reflns_point_group_measured_fraction_max 0.884
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.539
_diffrn_reflns_theta_min         2.821
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.220
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.483
_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    1.594
_exptl_crystal_description       plate
_exptl_crystal_F_000             8992
_exptl_crystal_size_max          0.164
_exptl_crystal_size_mid          0.128
_exptl_crystal_size_min          0.032
_refine_diff_density_max         0.389
_refine_diff_density_min         -0.470
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.044(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2580
_refine_ls_number_reflns         35000
_refine_ls_number_restraints     918
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0540
_refine_ls_R_factor_gt           0.0513
_refine_ls_shift/su_max          0.046
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0478P)^2^+30.7986P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1233
_refine_ls_wR_factor_ref         0.1253
_reflns_Friedel_coverage         0.821
_reflns_Friedel_fraction_full    0.895
_reflns_Friedel_fraction_max     0.804
_reflns_number_gt                33296
_reflns_number_total             35000
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00688k2.cif
_cod_data_source_block           flgb021_2
_cod_depositor_comments
'Adding full bibliography for 1575809--1575816.cif.'
_cod_database_code               1575814
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C488 H620 F412 N84 O40 Ti32 '
_shelx_estimated_absorpt_t_max   0.877
_shelx_estimated_absorpt_t_min   0.544
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.956(5)
 0.044(5)
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
 C127-C125
 1.51 with sigma of 0.02
 C125-C128 = C125-C131 = C132-C130
 1.39 with sigma of 0.02
 C128-C132 = C130-C129 = C129-C131
 1.38 with sigma of 0.02
 C127-C128 = C127-C131
 2.52 with sigma of 0.04
 C125-C132
 2.42 with sigma of 0.04
 C125-C129
 2.41 with sigma of 0.04
 C128-C130
 2.39 with sigma of 0.04
 C132-C129 = C130-C131
 2.4 with sigma of 0.04
 C125-C128 \\sim C128-C132 \\sim C132-C130 \\sim C130-C129 \\sim C129-C131
\\sim C131-C125
 with sigma of 0.02
 C125-C129 \\sim C125-C132 \\sim C131-C130 \\sim C128-C131 \\sim C132-C129
\\sim C128-C130
 with sigma of 0.04
 C127-C131 \\sim C127-C128
 with sigma of 0.04
 C127-C125 \\sim C124-C118
 with sigma of 0.02
 C125-C128 \\sim C118-C119
 with sigma of 0.02
 C125-C131 \\sim C118-C123
 with sigma of 0.02
 C128-C132 \\sim C119-C120
 with sigma of 0.02
 C132-C130 \\sim C120-C121
 with sigma of 0.02
 C130-C129 \\sim C121-C122
 with sigma of 0.02
 C129-C131 \\sim C122-C123
 with sigma of 0.02
 C127-C128 \\sim C124-C119
 with sigma of 0.04
 C127-C131 \\sim C124-C123
 with sigma of 0.04
 C125-C132 \\sim C118-C120
 with sigma of 0.04
 C125-C129 \\sim C118-C122
 with sigma of 0.04
 C128-C130 \\sim C119-C121
 with sigma of 0.04
 C128-C131 \\sim C119-C123
 with sigma of 0.04
 C132-C129 \\sim C120-C122
 with sigma of 0.04
 C130-C131 \\sim C121-C123
 with sigma of 0.04
 C125-C127 \\sim C118-C124
 with sigma of 0.01
 C125-C131 \\sim C118-C123 \\sim C118-C119 \\sim C119-C120 \\sim C132-C128
\\sim C129-C130 \\sim C122-
 C121 \\sim C132-C130 \\sim C122-C123 \\sim C129-C131 \\sim C125-C128 \\sim
C121-C120
 with sigma of 0.01
 C113-C114 \\sim C1B-C1C
 with sigma of 0.02
 C113-C112 \\sim C1B-C1D
 with sigma of 0.02
 C114-C115 \\sim C1C-C1E
 with sigma of 0.02
 C115-C116 \\sim C1E-C1A
 with sigma of 0.02
 C112-C111 \\sim C1D-C1F
 with sigma of 0.02
 C111-C116 \\sim C1F-C1A
 with sigma of 0.02
 C113-C115 \\sim C1B-C1E
 with sigma of 0.04
 C113-C111 \\sim C1B-C1F
 with sigma of 0.04
 C114-C112 \\sim C1C-C1D
 with sigma of 0.04
 C114-C116 \\sim C1C-C1A
 with sigma of 0.04
 C115-C111 \\sim C1E-C1F
 with sigma of 0.04
 C112-C116 \\sim C1D-C1A
 with sigma of 0.04
 C112-C117 \\sim C1D-C1G
 with sigma of 0.04
 C116-C117 \\sim C1A-C1G
 with sigma of 0.04
 C115-C116 \\sim C1E-C1A \\sim C1F-C1A \\sim C111-C116 \\sim C1F-C1D \\sim
C111-C112 \\sim C112-C113 ~
 C1D-C1B \\sim C1C-C1B \\sim C114-C113 \\sim C115-C114 \\sim C1E-C1C
 with sigma of 0.01
 C111-C117 \\sim C1F-C1G
 with sigma of 0.01
4. Restrained planarity
 C127, C125, C128, C132, C130, C129, C131
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C127 \\sim C125 \\sim C128 \\sim C132 \\sim C130 \\sim C129 \\sim C131: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C128 \\sim C127 \\sim C125 \\sim C131 \\sim C132 \\sim C129 \\sim C130 \\sim
C118 \\sim C124 \\sim C119 \\sim C123 \\sim C120 \\sim C122 \\sim C121: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C116 \\sim C113 \\sim C114 \\sim C112 \\sim C115 \\sim C111 \\sim C117 \\sim
C1A \\sim C1E \\sim C1F \\sim C1C \\sim C1D \\sim C1G \\sim C1B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
6. Rigid body (RIGU) restrains
 C127, C125, C128, C132, C130, C129, C131
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C124, C118, C119, C120, C121, C122, C123
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C125, C127, C128, C131, C132, C129, C130, C124, C118, C119, C123, C120, C122,
 C121
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C113, C114, C115, C112, C111, C116, C117
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1B, C1C, C1E, C1D, C1F, C1A, C1G
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C116, C113, C114, C112, C115, C111, C117, C1A, C1E, C1F, C1C, C1D, C1G, C1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(C124)=Sof(H12G)=Sof(H12H)=Sof(H12I)=Sof(C118)=Sof(C119)=Sof(H119)=
 Sof(C123)=Sof(H123)=Sof(C120)=Sof(H120)=Sof(C122)=Sof(H122)=Sof(C121)=
 Sof(H121)=1-FVAR(1)
 Sof(C127)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C125)=Sof(C128)=Sof(H128)=
 Sof(C132)=Sof(H132)=Sof(C130)=Sof(H130)=Sof(C129)=Sof(H129)=Sof(C131)=
 Sof(H131)=FVAR(1)
 Sof(C1A)=Sof(H1A)=Sof(C1B)=Sof(H1B)=Sof(C1C)=Sof(H1C)=Sof(C1D)=Sof(H1D)=
 Sof(C1E)=Sof(H1E)=Sof(C1F)=Sof(C1G)=Sof(H1GA)=Sof(H1GB)=Sof(H1GC)=1-FVAR(2)
 Sof(C113)=Sof(H113)=Sof(C114)=Sof(H114)=Sof(C115)=Sof(H115)=Sof(C112)=
 Sof(H112)=Sof(C111)=Sof(C116)=Sof(H116)=Sof(C117)=Sof(H11G)=Sof(H11H)=
 Sof(H11I)=FVAR(2)
8.a Secondary CH2 refined with riding coordinates:
 C58(H58A,H58B), C52(H52A,H52B), C40(H40A,H40B), C70(H70A,H70B), C64(H64A,
 H64B), C94(H94A,H94B), C82(H82A,H82B), C88(H88A,H88B), C4(H4A,H4B), C76(H76A,
 H76B), C16(H16A,H16B), C46(H46A,H46B), C28(H28A,H28B), C10(H10A,H10B),
 C34(H34A,H34B), C22(H22A,H22B)
8.b Aromatic/amide H refined with riding coordinates:
 C105(H105), C109(H109), C99(H99), C98(H98), C113(H113), C106(H106),
 C114(H114), C115(H115), C101(H101), C102(H102), C108(H108), C100(H100),
 C107(H107), C112(H112), C116(H116), C128(H128), C132(H132), C130(H130),
 C129(H129), C131(H131), C119(H119), C123(H123), C120(H120), C122(H122),
 C121(H121), C1A(H1A), C1B(H1B), C1C(H1C), C1D(H1D), C1E(H1E)
8.c Idealised Me refined as rotating group:
 C59(H59A,H59B,H59C), C96(H96A,H96B,H96C), C65(H65A,H65B,H65C), C71(H71A,H71B,
 H71C), C35(H35A,H35B,H35C), C60(H60A,H60B,H60C), C11(H11A,H11B,H11C), C66(H66A,
 H66B,H66C), C53(H53A,H53B,H53C), C41(H41A,H41B,H41C), C95(H95A,H95B,H95C),
 C72(H72A,H72B,H72C), C6(H6A,H6B,H6C), C36(H36A,H36B,H36C), C77(H77A,H77B,H77C),
  C48(H48A,H48B,H48C), C83(H83A,H83B,H83C), C89(H89A,H89B,H89C), C47(H47A,H47B,
 H47C), C54(H54A,H54B,H54C), C90(H90A,H90B,H90C), C5(H5A,H5B,H5C), C78(H78A,
 H78B,H78C), C42(H42A,H42B,H42C), C30(H30A,H30B,H30C), C84(H84A,H84B,H84C),
 C23(H23A,H23B,H23C), C103(H10C,H10D,H10E), C12(H12A,H12B,H12C), C18(H18A,H18B,
 H18C), C24(H24A,H24B,H24C), C110(H11D,H11E,H11F), C29(H29A,H29B,H29C),
 C17(H17A,H17B,H17C), C117(H11G,H11H,H11I), C127(H12D,H12E,H12F), C124(H12G,
 H12H,H12I), C1G(H1GA,H1GB,H1GC)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              20956
_shelx_fab_checksum              52157
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id FLGB021_2
_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 1.690
_oxdiff_exptl_absorpt_empirical_full_min 0.580