Catalytic regioselective construction of phenylthio- and phenoxyldifluoroalkyl tetrazoles from difluorodiazoketones
Shi, Hong-Song; Li, Shuo-Han; Zhang, Fa-Guang; Ma, Jun-An; Chemical Communications  (2021) –; doi:10.1039/D1CC05890H

data_7129315
_publ_section_title
;
 Catalytic regioselective construction of phenylthio- and
 phenoxyldifluoroalkyl tetrazoles from difluorodiazoketones
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC05890H
_journal_year                    2021
_chemical_formula_moiety         'C15 H12 F2 N4 O2 S'
_chemical_formula_sum            'C15 H12 F2 N4 O2 S'
_chemical_formula_weight         350.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'I -2ya'
_space_group_name_H-M_alt        'I 1 a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-01-11
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2021-10-17 deposited with the CCDC.	2021-11-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.428(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.4470(4)
_cell_length_b                   26.496(4)
_cell_length_c                   11.3845(12)
_cell_measurement_reflns_used    3430
_cell_measurement_temperature    293.15
_cell_measurement_theta_max      24.5630
_cell_measurement_theta_min      1.9970
_cell_volume                     1604.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     -7.00  40.00   0.50    6.00    --    5.00  14.00  60.00   94
  2  \w    -24.00  79.00   0.50    6.00    --   -9.60  55.00   0.00  206
  3  \w    -58.00 -32.00   0.50    6.00    --   -9.60  43.00  90.00   52
  4  \w    -25.00  77.00   0.50    6.00    --   -9.60  55.00-120.00  204
  5  \w    -99.00 -62.00   0.50    6.00    --   -9.60  43.00 150.00   74
  6  \w    -47.00  55.00   0.50    6.00    --   -9.60  43.00 150.00  204
  7  \w    -79.00 -50.00   0.50    6.00    --   -9.60  55.00-120.00   58
  8  \w     -7.00  19.00   0.50    6.00    --   -9.60  43.00  90.00   52
  9  \w    -26.00  78.00   0.50    6.00    --   -9.60  55.00 120.00  208
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0679207000
_diffrn_orient_matrix_UB_12      -0.0231596000
_diffrn_orient_matrix_UB_13      -0.0101111000
_diffrn_orient_matrix_UB_21      0.0059094000
_diffrn_orient_matrix_UB_22      -0.0468294000
_diffrn_orient_matrix_UB_23      -0.0036328000
_diffrn_orient_matrix_UB_31      0.0118748000
_diffrn_orient_matrix_UB_32      0.0117096000
_diffrn_orient_matrix_UB_33      0.0471622000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0328
_diffrn_reflns_av_unetI/netI     0.0371
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            10241
_diffrn_reflns_point_group_measured_fraction_full 0.892
_diffrn_reflns_point_group_measured_fraction_max 0.892
_diffrn_reflns_theta_full        25.025
_diffrn_reflns_theta_max         25.025
_diffrn_reflns_theta_min         1.986
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.239
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93210
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.450
_exptl_crystal_description       block
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.876
_refine_diff_density_min         -0.595
_refine_diff_density_rms         0.115
_refine_ls_abs_structure_details
;
 Flack x determined using 869 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.13(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     195
_refine_ls_number_reflns         2544
_refine_ls_number_restraints     98
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0969
_refine_ls_R_factor_gt           0.0879
_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^)+(0.1803P)^2^+4.6897P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2488
_refine_ls_wR_factor_ref         0.2626
_reflns_Friedel_coverage         0.777
_reflns_Friedel_fraction_full    0.784
_reflns_Friedel_fraction_max     0.784
_reflns_number_gt                2258
_reflns_number_total             2544
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc05890h2.cif
_cod_data_source_block           exp_1250
_cod_database_code               7129315
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.940
_reflns_odcompleteness_completeness 98.49
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2. Rigid bond restraints
 C00K, C8, C3, C4, C2, C00J
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 F002, F007
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C00K \\sim C8 \\sim C3 \\sim C4 \\sim C2 \\sim C00J: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 2A
Uanis(C00K) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4)
\\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C00J) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(F002) \\sim Ueq, Uanis(F007) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
4.a Aromatic/amide H refined with riding coordinates:
 C00F(H00F), C00I(H00I), C00H(H00H), C00A(H00A), C00E(H00E), C2(H2),
 C00K(H00K), C8(H8), C3(H3), C4(H4)
4.b Fitted hexagon refined as free rotating group:
 C00F(C00I,C00H,C00C,C00A,C00E), C2(C00J,C00K,C8,C3,C4)
4.c Idealised tetrahedral OH refined as rotating group:
 O003(H003), O1(H1)
;
_shelx_res_checksum              81761
_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 1.048
_oxdiff_exptl_absorpt_empirical_full_min 0.942