C(sp<sup>3</sup>)-H Fluorination with a Copper(II)/(III) Redox Couple.
Bower, Jamey K.; Cypcar, Andrew D.; Henriquez, Brenda; Stieber, S Chantal E; Zhang, Shiyu; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c02583

data_4134781
_publ_section_title
;
 C(sp<sup>3</sup>)-H Fluorination with a Copper(II)/(III) Redox Couple.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c02583
_journal_year                    2020
_chemical_formula_moiety
'C31 H37 Cu F N3 O2, C36 H30 N P2, 5(C4 H8 O)'
_chemical_formula_sum            'C87 H107 Cu F N4 O7 P2'
_chemical_formula_weight         1465.24
_chemical_name_systematic
;   
 Bis(triphenylphosphoranylidene)ammonium [N,N'-Bis(2,6-diisopropylphenyl)-
 2,6-pyridinedicarboxamido] copper fluoride tetrahydrofuran solvate
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-01-25
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.0248(16)
_cell_length_b                   17.643(2)
_cell_length_c                   30.044(3)
_cell_measurement_reflns_used    9858
_cell_measurement_temperature    100
_cell_measurement_theta_max      23.809
_cell_measurement_theta_min      2.238
_cell_volume                     7964.1(15)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2016)'
_computing_data_collection       'APEX3 v2017.3-0 (Bruker, 2017)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Nonius Kappa APEX II'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0531
_diffrn_reflns_av_unetI/netI     0.0481
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            97748
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.328
_diffrn_reflns_theta_min         1.338
_diffrn_source                   'sealed tube'
_diffrn_source_type              fine-focus
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.373
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6484
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 
 wR2(int) was 0.0671 before and 0.0630 after correction. 
 The Ratio of minimum to maximum transmission is 0.8699.
 The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.222
_exptl_crystal_description       block
_exptl_crystal_F_000             3124
_exptl_crystal_recrystallization_method
; 
 Grown from a concentrated solution of THF
layered with diethyl ether at -35 degrees C.
;
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.203
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.386
_refine_diff_density_min         -0.334
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 5736 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     947
_refine_ls_number_reflns         16194
_refine_ls_number_restraints     90
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0491
_refine_ls_R_factor_gt           0.0396
_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^)+(0.0653P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0989
_refine_ls_wR_factor_ref         0.1030
_reflns_Friedel_coverage         0.833
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                14115
_reflns_number_total             16194
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c02583_si_002.cif
_cod_data_source_block           pdacufppn
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_original_cell_volume        7964.3(15)
_cod_database_code               4134781
_shelx_shelxl_version_number     2018/1
_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. Shared sites
{C5F, O1E}
3. Uiso/Uaniso restraints and constraints
Uanis(O1F) = Uanis(O1G)
Uanis(C1F) = Uanis(C4G)
Uanis(C4F) = Uanis(C3G)
Uanis(C2F) = Uanis(C1G)
Uanis(C3F) = Uanis(C2G)
Uanis(C5F) = Uanis(O1E)
Uanis(C1E) = Uanis(O0AA)
4. Rigid body (RIGU) restrains
 O1F, C1F, C2F, C3F, C4F, O1G, C1G, C2G, C3G, C4G
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Same fragment restrains
{O1C, C2C, C3C, C4C, C5C} sigma for 1-2: 0.02, 1-3: 0.04
as
{O1F, C1F, C2F, C3F, C4F}
{O1C, C2C, C3C, C4C, C5C} sigma for 1-2: 0.02, 1-3: 0.04
as
{O1G, C1G, C2G, C3G, C4G}
6. Others
 Sof(O1G)=Sof(C1G)=Sof(H1GA)=Sof(H1GB)=Sof(C2G)=Sof(H2GA)=Sof(H2GB)=Sof(C3G)=
 Sof(H3GA)=Sof(H3GB)=Sof(C4G)=Sof(H4GA)=Sof(H4GB)=1-FVAR(1)
 Sof(O1F)=Sof(C1F)=Sof(H1FA)=Sof(H1FB)=Sof(C2F)=Sof(H2FA)=Sof(H2FB)=Sof(C3F)=
 Sof(H3FA)=Sof(H3FB)=Sof(C4F)=Sof(H4FA)=Sof(H4FB)=FVAR(1)
 Sof(H2AC)=Sof(H2AD)=Sof(H0AC)=Sof(H0AD)=Sof(O0AA)=Sof(C5F)=Sof(H5FA)=
 Sof(H5FB)=1-FVAR(2)
 Sof(H2AA)=Sof(H2AB)=Sof(H0AA)=Sof(H0AB)=Sof(O1E)=Sof(C1E)=Sof(H1EA)=Sof(H1EB)=
 FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C16(H16), C26(H26), C13(H13), C29(H29)
7.b Secondary CH2 refined with riding coordinates:
 C2D(H2DA,H2DB), C4D(H4DA,H4DB), C1D(H1DA,H1DB), C3D(H3DA,H3DB), C1F(H1FA,
 H1FB), C2F(H2FA,H2FB), C3F(H3FA,H3FB), C4F(H4FA,H4FB), C2AA(H2AA,H2AB),
 C2AA(H2AC,H2AD), C0AA(H0AA,H0AB), C0AA(H0AC,H0AD), C1AA(H1AA,H1AB), C1E(H1EA,
 H1EB), C5F(H5FA,H5FB), C2C(H2CA,H2CB), C3C(H3CA,H3CB), C4C(H4CA,H4CB),
 C5C(H5CA,H5CB), C2B(H2BA,H2BB), C1B(H1BA,H1BB), C3B(H3BA,H3BB), C4B(H4BA,H4BB),
  C1G(H1GA,H1GB), C2G(H2GA,H2GB), C3G(H3GA,H3GB), C4G(H4GA,H4GB)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C22(H22), C9(H9), C10(H10), C11(H11), C24(H24), C2(H2),
 C23(H23), C28A(H28D), C20A(H20A), C18A(H18D), C2A(H2A), C29A(H29A), C12A(H12A),
  C6A(H6A), C3A(H3A), C27A(H27D), C30A(H30D), C26A(H26A), C5A(H5A), C32A(H32A),
 C23A(H23A), C35A(H35A), C17A(H17D), C24A(H24A), C10A(H10A), C15A(H15D),
 C11A(H11A), C16A(H16A), C33A(H33A), C36A(H36A), C22A(H22A), C21A(H21A),
 C4A(H4A), C34A(H34A), C14A(H14D), C9A(H9A), C8A(H8A)
7.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C31(H31A,H31B,H31C), C18(H18A,H18B,H18C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C), C14(H14A,H14B,H14C), C30(H30A,H30B,H30C), C17(H17A,
 H17B,H17C)
;
_shelx_res_checksum              8612
_shelx_hkl_checksum              48420
_olex2_exptl_crystal_mounting_method
'Mounted on a MiTeGen mount with Paratone oil'
_olex2_submission_original_sample_id '[PPN]PDACuF'
_olex2_submission_special_instructions 'No special instructions were received'