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_1547629
_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         'C16 H9 F6 N5 O4 S'
_chemical_formula_sum            'C16 H9 F6 N5 O4 S'
_chemical_formula_weight         481.34
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2016-02-02
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-04-13 deposited with the CCDC.
2017-09-27 downloaded from the CCDC.
;
_cell_angle_alpha                89.810(2)
_cell_angle_beta                 71.081(2)
_cell_angle_gamma                68.037(2)
_cell_formula_units_Z            2
_cell_length_a                   8.8724(4)
_cell_length_b                   9.8446(5)
_cell_length_c                   12.3483(6)
_cell_measurement_reflns_used    8691
_cell_measurement_temperature    295
_cell_measurement_theta_max      30.17
_cell_measurement_theta_min      2.66
_cell_volume                     937.66(8)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      295
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0330
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            21041
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.251
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.268
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.7045
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/3 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.1296 before and 0.0473 after correction.
The Ratio of minimum to maximum transmission is 0.9442.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellowish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.705
_exptl_crystal_description       needle
_exptl_crystal_F_000             484
_exptl_crystal_size_max          0.422
_exptl_crystal_size_mid          0.304
_exptl_crystal_size_min          0.212
_refine_diff_density_max         0.445
_refine_diff_density_min         -0.442
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     353
_refine_ls_number_reflns         3830
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0523
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0500P)^2^+0.4370P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1029
_refine_ls_wR_factor_ref         0.1115
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3090
_reflns_number_total             3830
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc03366d2.cif
_cod_data_source_block           mo_d8v1126_0m-a
_cod_database_code               1547629
_shelxl_version_number           2014/6
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Others
 Sof(F6)=Sof(F4A)=Sof(F5A)=1-FVAR(1)
 Sof(F4)=Sof(F5)=Sof(F6A)=FVAR(1)
 Sof(F3A)=Sof(F1A)=Sof(F2A)=1-FVAR(2)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(2)
3.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C7(H7), C13(H13), C15(H15), C17(H17)
;
_shelx_res_checksum              31089
_olex2_submission_special_instructions 'No special instructions were received'