Electrophilic Difluoro(phenylthio)methylation: Generation, Stability, and Reactivity of α-Fluorocarbocations.
Betterley, Nolan M.; Surawatanawong, Panida; Prabpai, Samran; Kongsaeree, Palangpon; Kuhakarn, Chutima; Pohmakotr, Manat; Reutrakul, Vichai; Organic letters 15 (2013) 5666–5669; doi:10.1021/ol402631t

data_1513109
_publ_section_title
;
 Electrophilic Difluoro(phenylthio)methylation: Generation, Stability, and
 Reactivity of \a-Fluorocarbocations.
;
_journal_issue                   22
_journal_name_full               'Organic letters'
_journal_page_first              5666
_journal_page_last               5669
_journal_paper_doi               10.1021/ol402631t
_journal_volume                  15
_journal_year                    2013
_chemical_absolute_configuration unk
_chemical_compound_source        synthesis
_chemical_formula_moiety         'F5 Sb, F11 Sb2, 3(C7 H10 N2), C7 H11 N2'
_chemical_formula_sum            'C28 H40 F16 N8 Sb3'
_chemical_formula_weight         1157.52
_chemical_properties_physical    moisture-sensitive
_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_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_cell_angle_alpha                103.8730(18)
_cell_angle_beta                 95.0740(18)
_cell_angle_gamma                107.1520(19)
_cell_formula_units_Z            10
_cell_length_a                   18.4920(6)
_cell_length_b                   22.2250(7)
_cell_length_c                   26.2530(10)
_cell_measurement_reflns_used    2783
_cell_measurement_temperature    150(2)
_cell_volume                     9860.6(6)
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_collection       KappaCCD
_computing_data_reduction
'Denzo and Scalepak (Otwinowski & Minor, 1997)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution
'SIR97(Cascarano al.,Acta Cryst.,1996,A52,C-79)'
_diffrn_ambient_temperature      150(2)
_diffrn_measured_fraction_theta_full 0.888
_diffrn_measured_fraction_theta_max 0.942
_diffrn_measurement_device       KappaCCD
_diffrn_measurement_device_type  KappaCCD
_diffrn_measurement_method       CCD
_diffrn_orient_matrix_type       X=UH
_diffrn_orient_matrix_UB_11      -0.02091
_diffrn_orient_matrix_UB_12      -0.13653
_diffrn_orient_matrix_UB_13      0.11820
_diffrn_orient_matrix_UB_21      0.01250
_diffrn_orient_matrix_UB_22      -0.05081
_diffrn_orient_matrix_UB_23      -0.05647
_diffrn_orient_matrix_UB_31      0.04647
_diffrn_orient_matrix_UB_32      0.00100
_diffrn_orient_matrix_UB_33      0.00938
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_wavelength_id  all
_diffrn_reflns_av_R_equivalents  0.0716
_diffrn_reflns_av_unetI/netI     0.1046
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            61411
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         24.717
_diffrn_reflns_theta_min         2.922
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    2.147
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.949
_exptl_crystal_description       Prism
_exptl_crystal_F_000             5606
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.10
_refine_diff_density_max         3.543
_refine_diff_density_min         -1.959
_refine_diff_density_rms         0.268
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.971
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2671
_refine_ls_number_reflns         31688
_refine_ls_number_restraints     197
_refine_ls_restrained_S_all      0.972
_refine_ls_R_factor_all          0.1213
_refine_ls_R_factor_gt           0.0801
_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^)+(0.1349P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1946
_refine_ls_wR_factor_ref         0.2136
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20023
_reflns_number_total             31688
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol402631t_si_002.cif
_cod_data_source_block           Sb2F11-SbF5-DMAP
_cod_database_code               1513109
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C245-C278
 1.36 with sigma of 0.02
 Sb11-F67A \\sim Sb11-F67B
 with sigma of 0.02
 Sb11-F67A \\sim Sb7-F67A
 with sigma of 0.02
 Sb11-F67B \\sim Sb7-F67B
 with sigma of 0.02
 Sb7-F67A \\sim Sb7-F67B
 with sigma of 0.02
 Sb4-F1A \\sim Sb4-F1B
 with sigma of 0.02
 Sb4-F1A \\sim Sb14-F1A
 with sigma of 0.02
 Sb4-F1B \\sim Sb14-F1B
 with sigma of 0.02
 Sb14-F1A \\sim Sb14-F1B
 with sigma of 0.02
 Sb7-F2A \\sim Sb7-F2B
 with sigma of 0.02
 F3A-Sb14 \\sim F3B-Sb14
 with sigma of 0.02
 F6A-Sb12 \\sim F6B-Sb12
 with sigma of 0.02
 F7A-Sb8 \\sim F7B-Sb8
 with sigma of 0.02
 F8A-Sb13 \\sim F8B-Sb13
 with sigma of 0.02
 F9A-Sb13 \\sim F9B-Sb13
 with sigma of 0.02
 F10A-Sb8 \\sim F10B-Sb8
 with sigma of 0.02
 F10A-Sb13 \\sim F10B-Sb13
 with sigma of 0.02
 F10A-Sb8 \\sim F10A-Sb13
 with sigma of 0.02
 F10B-Sb8 \\sim F10B-Sb13
 with sigma of 0.02
 F11A-Sb4 \\sim F11B-Sb4
 with sigma of 0.02
 F12A-Sb14 \\sim F12B-Sb14
 with sigma of 0.02
 F13A-Sb14 \\sim F13B-Sb14
 with sigma of 0.02
 F14A-Sb4 \\sim F14B-Sb4
 with sigma of 0.02
 F15A-Sb13 \\sim F15B-Sb13
 with sigma of 0.02
 F16A-Sb13 \\sim F16B-Sb13
 with sigma of 0.02
 F17A-Sb13 \\sim F17B-Sb13
 with sigma of 0.02
 F18A-Sb4 \\sim F18B-Sb4
 with sigma of 0.02
3. Rigid bond restraints
 N225, C223, N225, C277
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C246, C145
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Sb11, F67A, Sb11, F67B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Sb11, F67A, Sb7, F67A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Sb11, F67B, Sb7, F67B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Sb7, F67A, Sb7, F67B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Sb4, F1A, Sb4, F1B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Sb4, F1A, Sb14, F1A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Sb4, F1B, Sb14, F1B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Sb14, F1A, Sb14, F1B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Sb7, F2A, Sb7, F2B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F3A, Sb14, F3B, Sb14
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F6A, Sb12, F6B, Sb12
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F7A, Sb8, F7B, Sb8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F8A, Sb13, F8B, Sb13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F9A, Sb13, F9B, Sb13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F10A, Sb8, F10B, Sb8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F10A, Sb13, F10B, Sb13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F10A, Sb8, F10A, Sb13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F10B, Sb8, F10B, Sb13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F11A, Sb4, F11B, Sb4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F12A, Sb14, F12B, Sb14
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 F13A, Sb14, F13B, Sb14
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F14A, Sb4, F14B, Sb4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F15A, Sb13, F15B, Sb13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F16A, Sb13, F16B, Sb13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F17A, Sb13, F17B, Sb13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F18B, Sb4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
N225 \\sim C223 \\sim N225 \\sim C277: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
C246 \\sim C145: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
Sb11 \\sim F67A \\sim Sb11 \\sim F67B: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
Sb11 \\sim F67A \\sim Sb7 \\sim F67A: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
Sb11 \\sim F67B \\sim Sb7 \\sim F67B: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
Sb7 \\sim F67A \\sim Sb7 \\sim F67B: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
Sb4 \\sim F1A \\sim Sb4 \\sim F1B: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
Sb4 \\sim F1A \\sim Sb14 \\sim F1A: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
Sb4 \\sim F1B \\sim Sb14 \\sim F1B: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
Sb14 \\sim F1A \\sim Sb14 \\sim F1B: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
Sb7 \\sim F2A \\sim Sb7 \\sim F2B: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F3A \\sim Sb14 \\sim F3B \\sim Sb14: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F6A \\sim Sb12 \\sim F6B \\sim Sb12: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F7A \\sim Sb8 \\sim F7B \\sim Sb8: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F8A \\sim Sb13 \\sim F8B \\sim Sb13: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F9A \\sim Sb13 \\sim F9B \\sim Sb13: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F10A \\sim Sb8 \\sim F10B \\sim Sb8: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F10A \\sim Sb13 \\sim F10B \\sim Sb13: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F10A \\sim Sb8 \\sim F10A \\sim Sb13: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F10B \\sim Sb8 \\sim F10B \\sim Sb13: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F11A \\sim Sb4 \\sim F11B \\sim Sb4: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F12A \\sim Sb14 \\sim F12B \\sim Sb14: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 1.9
F13A \\sim Sb14 \\sim F13B \\sim Sb14: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F14A \\sim Sb4 \\sim F14B \\sim Sb4: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F15A \\sim Sb13 \\sim F15B \\sim Sb13: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F16A \\sim Sb13 \\sim F16B \\sim Sb13: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F17A \\sim Sb13 \\sim F17B \\sim Sb13: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
F18B \\sim Sb4: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 1.9
Uanis(F18A) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(F12B) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
5. Others
 Fixed Sof: F67A(0.35543) F67B(0.64044) F1A(0.62788) F1B(0.22561) F2A(0.66484)
 F2B(0.27593) F3A(0.41692) F3B(0.54085) F6A(0.56863) F6B(0.42862) F7A(0.5505)
 F7B(0.46144) F8A(0.59812) F8B(0.3872) F9A(0.51725) F9B(0.41779) F10A(0.33233)
 F10B(0.66764) F11A(0.34646) F11B(0.65354) F12A(0.55424) F12B(0.44576)
 F13A(0.36218) F13B(0.63782) F14A(0.39583) F14B(0.60417) F15A(0.52093)
 F15B(0.47907) F16A(0.42321) F16B(0.57679) F17A(0.49858) F17B(0.50152)
 F18A(0.31188) F18B(0.68812)
6.a Aromatic/amide H refined with riding coordinates:
 N111(H111), N130(H130), C136(H136), C142(H142), C147(H147), C148(H148),
 C149(H149), C152(H152), C155(H155), C156(H156), C159(H159), C160(H160),
 C161(H161), C163(H163), C164(H164), C173(H173), C175(H175), C176(H176),
 C186(H186), C187(H187), C188(H188), C189(H189), C194(H194), C205(H205),
 C206(H206), C207(H207), C209(H209), C210(H210), C211(H211), C212(H212),
 C214(H214), C215(H215), C218(H218), C221(H221), C223(H223), C226(H226),
 C227(H227), C228(H228), C231(H231), C234(H234), C236(H236), C240(H240),
 C241(H241), C243(H243), C244(H244), C245(H245), C246(H246), C248(H248),
 C250(H250), C252(H252), C253(H253), C255(H255), C258(H258), C260(H260),
 C263(H263), C265(H265), C266(H266), C268(H268), C269(H269), C275(H275),
 C65(H65), C70(H70), C74(H74), N75(H75), C77(H77), N78(H78), C80(H80), N82(H82),
  C87(H87), C90(H90), C92(H92), C97(H97), C108(H108), C112(H112), C113(H113),
 C115(H115), C120(H120), C121(H121), C122(H122), C126(H126), C128(H128),
 C131(H131), C166(H166), C278(H278), C279(H279)
6.b Idealised Me refined as rotating group:
 C153(H15A,H15B,H15C), C171(H17D,H17E,H17F), C177(H17A,H17B,H17C), C179(H17G,
 H17H,H17I), C181(H18A,H18B,H18C), C183(H18G,H18H,H18I), C184(H18D,H18E,H18F),
 C190(H19D,H19E,H19F), C196(H19G,H19H,H19I), C197(H19A,H19B,H19C), C200(H20D,
 H20E,H20F), C201(H20G,H20H,H20I), C204(H20A,H20B,H20C), C208(H20J,H20K,H20L),
 C216(H21A,H21B,H21C), C224(H22A,H22B,H22C), C230(H23J,H23K,H23L), C232(H23M,
 H23N,H23O), C233(H23P,H23Q,H23R), C235(H23D,H23E,H23F), C237(H23G,H23H,H23I),
 C238(H23A,H23B,H23C), C247(H24D,H24E,H24F), C249(H24A,H24B,H24C), C256(H25D,
 H25E,H25F), C257(H25G,H25H,H25I), C259(H25A,H25B,H25C), C261(H26G,H26H,H26I),
 C262(H26J,H26K,H26L), C264(H26D,H26E,H26F), C267(H26A,H26B,H26C), C270(H27A,
 H27B,H27C), C48(H48A,H48B,H48C), C73(H73A,H73B,H73C), C96(H96A,H96B,H96C),
 C114(H11A,H11B,H11C), C123(H12A,H12B,H12C), C124(H12D,H12E,H12F), C132(H13A,
 H13B,H13C), C277(H27D,H27E,H27F)
;
_shelx_hkl_checksum              89477
_shelx_res_checksum              27107
_shelxl_version_number           2013-4