Thiosemicarbazone organocatalysis: tetrahydropyranylation and 2-deoxygalactosylation reactions and kinetics-based mechanistic investigation
Larsen, Dennis; Langhorn, Line M.; Akselsen, Olivia M.; Nielsen, Bjarne E.; Pittelkow, Michael; Chem. Sci.  (2017) –; doi:10.1039/C7SC03366D

data_1547627
_publ_section_title
;
 Thiosemicarbazone organocatalysis: tetrahydropyranylation and
 2-deoxygalactosylation reactions and kinetics-based mechanistic
 investigation
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC03366D
_journal_year                    2017
_chemical_formula_moiety         'C18 H9 F12 N3 S'
_chemical_formula_sum            'C18 H9 F12 N3 S'
_chemical_formula_weight         527.34
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-03-06
_audit_creation_method
;
Olex2 1.2
(compiled 2014.02.28 svn.r2900 for OlexSys, GUI svn.r4781)
;
_audit_update_record
;
2016-04-13 deposited with the CCDC.
2017-09-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.153(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   4.7617(3)
_cell_length_b                   31.515(3)
_cell_length_c                   13.2597(10)
_cell_measurement_reflns_used    4204
_cell_measurement_temperature    122.15
_cell_measurement_theta_max      27.91
_cell_measurement_theta_min      3.14
_cell_volume                     1988.4(3)
_computing_cell_refinement       'SAINT (Bruker, 2013)'
_computing_data_collection       'APEX2 (Bruker, 2013)'
_computing_data_reduction        'SAINT (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2013)'
_diffrn_ambient_temperature      122.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0397
_diffrn_reflns_av_unetI/netI     0.0417
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            11072
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.348
_diffrn_reflns_theta_min         2.474
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.286
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6445
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0772 before and 0.0538 after correction.
The Ratio of minimum to maximum transmission is 0.8643.
The \l/2 correction factor is 0.0000.
;
_exptl_crystal_density_diffrn    1.762
_exptl_crystal_description       prism
_exptl_crystal_F_000             1048
_exptl_crystal_size_max          0.246
_exptl_crystal_size_mid          0.177
_exptl_crystal_size_min          0.078
_refine_diff_density_max         0.694
_refine_diff_density_min         -0.379
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     314
_refine_ls_number_reflns         3629
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0722
_refine_ls_R_factor_gt           0.0531
_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^)+(0.0290P)^2^+4.6900P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1135
_refine_ls_wR_factor_ref         0.1207
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2848
_reflns_number_total             3629
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc03366d2.cif
_cod_data_source_block           mo_d8v218_0m
_cod_database_code               1547627
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.933
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C8(H8), C13(H13), C14(H14), C17(H17), C18(H18)
;
_shelx_res_checksum              78262
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'