Synthesis of C2-Symmetric gem-Difluoromethylenated Angular Triquinanes.
Thaharn, Watcharaporn; Soorukram, Darunee; Kuhakarn, Chutima; Reutrakul, Vichai; Pohmakotr, Manat; The Journal of organic chemistry  (2017) –; doi:10.1021/acs.joc.7b02777

data_4033292
_publ_section_title
;
 Synthesis of C2-Symmetric gem-Difluoromethylenated Angular Triquinanes.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.7b02777
_journal_year                    2017
_chemical_formula_moiety         'C21 H26 F4 O2'
_chemical_formula_sum            'C20.5 H26 F3.85 O2'
_chemical_formula_weight         377.61
_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     dual
_audit_creation_date             2017-07-25
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.3640(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.5396(3)
_cell_length_b                   22.9076(9)
_cell_length_c                   10.1423(4)
_cell_measurement_reflns_used    9510
_cell_measurement_temperature    100
_cell_measurement_theta_max      72.230
_cell_measurement_theta_min      5.795
_cell_volume                     1860.05(12)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker PHOTON 100 area detector'
_diffrn_detector_area_resol_mean 10.5
_diffrn_detector_type            'PHOTON area detector'
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device       'four-circle KAPPA diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_collimation    '0.5 mm'
_diffrn_radiation_monochromator  'graphiteDouble Bounce Multilayer Mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0296
_diffrn_reflns_av_unetI/netI     0.0213
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            20564
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.300
_diffrn_reflns_theta_min         6.747
_diffrn_source                   'microfocus sealed x-ray tube'
_diffrn_source_type              'Incoatec I\mus'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.943
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.6585
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0746 before and 0.0573 after correction. The Ratio of minimum to maximum transmission is 0.8738. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.348
_exptl_crystal_description       block
_exptl_crystal_F_000             799
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.344
_refine_diff_density_min         -0.217
_refine_diff_density_rms         0.039
_refine_ls_extinction_coef       0.0149(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     314
_refine_ls_number_reflns         3594
_refine_ls_number_restraints     156
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0404
_refine_ls_R_factor_gt           0.0398
_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^)+(0.0359P)^2^+1.1745P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0958
_refine_ls_wR_factor_ref         0.0962
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3524
_reflns_number_total             3594
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b02777_si_003.cif
_cod_data_source_block           vw020959
_cod_original_formula_sum        'C20.50 H26 F3.85 O2'
_cod_database_code               4033292
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
F4A \\sim F3A \\sim C8 \\sim C21A \\sim C7A \\sim C19B \\sim C7B \\sim C19A
\\sim C21B \\sim F4B \\sim F3B \\sim C20A \\sim C20B: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.005
3. Others
 Sof(H6BC)=Sof(H6BD)=1-FVAR(1)
 Sof(H6AA)=Sof(H6AB)=FVAR(1)
 Fixed Sof: F4A(0.5) F3A(0.5) C21A(0.5) H21A(0.5) H21B(0.5) H21C(0.5)
 C20A(0.5) H20A(0.5) H20B(0.5) H20C(0.5) C7A(0.5) H7A(0.5) C19B(0.5) H19B(0.5)
 C7B(0.5) H7B(0.5) C19A(0.5) H19A(0.5) C20B(0.5) H20D(0.5) H20E(0.5) H20F(0.5)
 C21B(0.5) H21D(0.5) H21E(0.5) H21F(0.5) F4B(0.5) F3B(0.5)
4.a Ternary CH refined with riding coordinates:
 C16(H16), C3(H3), C7A(H7A), C19B(H19B), C7B(H7B), C19A(H19A)
4.b Secondary CH2 refined with riding coordinates:
 C6(H6AA,H6AB), C6(H6BC,H6BD), C4(H4A,H4B)
4.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C11(H11), C13(H13), C12(H12)
4.d Idealised Me refined as rotating group:
 C21A(H21A,H21B,H21C), C20A(H20A,H20B,H20C), C17(H17A,H17B,H17C), C18(H18A,
 H18B,H18C), C20B(H20D,H20E,H20F), C21B(H21D,H21E,H21F)
;
_shelx_res_checksum              99297
_shelx_hkl_checksum              23244
_olex2_submission_special_instructions 'No special instructions were received'