Catalyst Design for Alkene Epoxidation by Molecular Analogues of Heterogeneous Titanium-Silicalite Catalysts
Solé-Daura, Albert; Zhang, Teng; Fouilloux, Hugo; Robert, Carine; Thomas, Christophe M.; Chamoreau, Lise-Marie; Carbó, Jorge J.; Proust, Anna; Guillemot, Geoffroy; Poblet, Josep M.; ACS Catalysis  (2020) 4737–; doi:10.1021/acscatal.9b05147

data_4517546
_publ_section_title
;
 Catalyst Design for Alkene Epoxidation by Molecular Analogues of
 Heterogeneous Titanium-Silicalite Catalysts
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              4737
_journal_paper_doi               10.1021/acscatal.9b05147
_journal_year                    2020
_chemical_formula_moiety         'C12 H28 O37 Sb Si3 Ti W9, 3(C24 H52 N)'
_chemical_formula_sum            'C84 H184 N3 O37 Sb Si3 Ti W9'
_chemical_formula_weight         3736.90
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-10-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.112(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.7721(8)
_cell_length_b                   28.9182(12)
_cell_length_c                   23.5633(10)
_cell_measurement_reflns_used    9066
_cell_measurement_temperature    200
_cell_measurement_theta_max      33.07
_cell_measurement_theta_min      2.19
_cell_volume                     12110.0(9)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      200
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0457
_diffrn_reflns_av_unetI/netI     0.0322
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            186544
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.239
_diffrn_reflns_theta_min         0.864
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.890
_exptl_absorpt_correction_T_max  0.3352
_exptl_absorpt_correction_T_min  0.2569
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0804 before and 0.0510 after correction. The Ratio of minimum to maximum transmission is 0.7664. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.050
_exptl_crystal_description       prism
_exptl_crystal_F_000             7144
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         6.859
_refine_diff_density_min         -3.110
_refine_diff_density_rms         0.286
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1257
_refine_ls_number_reflns         32760
_refine_ls_number_restraints     101
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.0824
_refine_ls_R_factor_gt           0.0571
_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^)+442.4271P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1143
_refine_ls_wR_factor_ref         0.1341
_reflns_Friedel_coverage         0.000
_reflns_number_gt                27078
_reflns_number_total             32760
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b05147_si_002.cif
_cod_data_source_block           tz455b_0m
_cod_database_code               4517546
_shelx_shelxl_version_number     2017/1
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.8609(6)
 0.1391(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
 C5-C6
 1.54 with sigma of 0.02
 C305-C304
 1.54 with sigma of 0.02
 C316-C317
 1.54 with sigma of 0.02
 C315-C317
 2.54 with sigma of 0.04
 C316-C318
 2.54 with sigma of 0.04
 C204-C205 \\sim C205-C206
 with sigma of 0.02
 C4-C5 \\sim C5-C6
 with sigma of 0.02
 C303-C304 \\sim C305-C306
 with sigma of 0.02
 C313-C314 \\sim C315-C316 \\sim C317-C318
 with sigma of 0.015
4. Uiso/Uaniso restraints and constraints
C217 \\sim C218: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C314 \\sim C315 \\sim C316 \\sim C317 \\sim C318: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 C114, C115, C116, C117
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C4, C5, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C214, C215, C216, C217, C218
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C315, C316, C317, C318
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Ternary CH refined with riding coordinates:
 C10(H10)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C4(H4A,H4B), C5(H5A,H5B), C7(H7A,H7B), C8(H8A,H8B),
 C301(H30A,H30B), C302(H30C,H30D), C303(H30E,H30F), C304(H30G,H30H), C305(H30I,
 H30J), C307(H30N,H30O), C308(H30P,H30Q), C309(H30R,H30S), C310(H31A,H31B),
 C311(H31C,H31D), C313(H31H,H31I), C314(H31J,H31K), C315(H31L,H31M), C316(H31N,
 H31O), C317(H31P,H31Q), C319(H31U,H31V), C320(H32A,H32B), C321(H32C,H32D),
 C322(H32E,H32F), C323(H32G,H32H), C101(H10A,H10B), C102(H10C,H10D), C103(H10E,
 H10F), C104(H104,H10H), C105(H10G,H10I), C107(H10L,H10N), C108(H10O,H10P),
 C109(H10Q,H10R), C110(H11D,H11E), C111(H11F,H11G), C112(H11H,H11I), C113(H11J,
 H11K), C114(H11L,H11M), C115(H11N,H11O), C116(H11P,H11Q), C118(H118,H11V),
 C119(H11U,H11W), C120(H12D,H12E), C121(H121,H12G), C122(H12H,H12I), C201(H20A,
 H20B), C202(H20C,H20D), C203(H20E,H20F), C204(H20G,H20H), C205(H20I,H20J),
 C207(H20N,H20O), C208(H20P,H20Q), C209(H20R,H20S), C210(H21A,H21B), C211(H21C,
 H21D), C213(H21H,H21I), C214(H21J,H21K), C215(H21L,H21M), C216(H21N,H21O),
 C217(H21P,H21Q), C219(H21U,H21V), C220(H220,H22B), C221(H22C,H22D), C222(H22E,
 H22F), C223(H22G,H22H)
6.c Me refined with riding coordinates:
 C3(H3A,H3B,H3C), C11(H11A,H11B,H11C), C318(H31R,H31S,H31T), C218(H21R,H21S,
 H21T)
6.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C9(H9A,H9B,H9C), C12(H12A,H12B,H12C), C306(H30K,H30L,H30M),
 C312(H31E,H31F,H31G), C324(H32I,H32J,H32K), C106(H10J,H10K,H10M), C117(H11R,
 H11S,H11T), C123(H12J,H12K,H12L), C124(H12F,H12M,H12N), C206(H20K,H20L,H20M),
 C212(H21E,H21F,H21G), C224(H22I,H22J,H22K)
;
_shelx_res_checksum              34767
_shelx_hkl_checksum              28792
_olex2_submission_special_instructions 'No special instructions were received'