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_4134778
_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 Cl Cu N3 O2, C16 H36 N, 2(C4 H8 O), 0.33(H2 O)'
_chemical_formula_sum            'C55 H89.62 Cl Cu N4 O4.31'
_chemical_formula_weight         974.87
_chemical_name_systematic
; 
 Tetrabutylammonium [N,N'-Bis(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamido]
 copper chloride tetrahydrofuran solvate
;
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-11-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.862(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.1912(4)
_cell_length_b                   26.8069(9)
_cell_length_c                   20.4707(7)
_cell_measurement_reflns_used    9994
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.102
_cell_measurement_theta_min      2.172
_cell_volume                     5492.3(3)
_computing_cell_refinement       'SAINT v8.38A (Bruker, 2017)'
_computing_data_collection       'APEX3 v2017.3-0 (Bruker, 2017)'
_computing_data_reduction        'SAINT v8.38A (Bruker, 2017)'
_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 1.000
_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  0.0376
_diffrn_reflns_av_unetI/netI     0.0184
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            155019
_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         26.394
_diffrn_reflns_theta_min         1.266
_diffrn_source                   'sealed tube'
_diffrn_source_type              fine-focus
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.493
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6438
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;    
 SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
 wR2(int) was 0.0514 before and 0.0465 after correction.
 The Ratio of minimum to maximum transmission is 0.8637.
 The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.179
_exptl_crystal_description       block
_exptl_crystal_F_000             2112
_exptl_crystal_recrystallization_method
;
 Grown from a concentrated tethydrofuran solution layered
 with diethyl ether at -35 degrees C.
;
_exptl_crystal_size_max          0.75
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.488
_refine_diff_density_min         -0.343
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     700
_refine_ls_number_reflns         11260
_refine_ls_number_restraints     141
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0453
_refine_ls_R_factor_gt           0.0371
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0485P)^2^+3.6622P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0936
_refine_ls_wR_factor_ref         0.0980
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9687
_reflns_number_total             11260
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c02583_si_003.cif
_cod_data_source_block           pdacucltba
_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_database_code               4134778
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.917
_shelx_estimated_absorpt_t_min   0.709
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C30G-C29 = C31G-C29
 1.54 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C3D) = Uanis(C3C)
Uanis(C31G) = Uanis(C30G)
Uanis(C3D) = Uanis(C3F)
Uanis(C3C) = Uanis(C2F)
4. Rigid body (RIGU) restrains
 O1D, C1D, C2D, C3D, C4D, O1C, C1C, C2C, C3C, C4C, O1E
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C29, C30, C31, C30G, C31G
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O1D, C1D, C4D, C2D, C3D, C2F, C2C, C1F, C3C, C3F, C1C, C4C, C4F, O1F, O1C
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Same fragment restrains
{O1D, C1D, C2D, C3D, C4D} sigma for 1-2: 0.02, 1-3: 0.04
as
{O1C, C1C, C2C, C3C, C4C}
{O1D, C1D, C2D, C3D, C4D} sigma for 1-2: 0.02, 1-3: 0.04
as
{O1F, C4F, C3F, C2F, C1F}
6. Others
 1*[Sof(O1D)+Sof(C1D)+Sof(H1DA)+Sof(H1DB)+Sof(C2D)+Sof(H2DA)+Sof(H2DB)+
 Sof(C3D)+Sof(H3DA)+Sof(H3DB)+Sof(C4D)+Sof(H4DA)+Sof(H4DB)]+1*[Sof(O1C)+
 Sof(C1C)+Sof(H1CA)+Sof(H1CB)+Sof(C2C)+Sof(H2CA)+Sof(H2CB)+Sof(C3C)+Sof(H3CA)+
 Sof(H3CB)+Sof(C4C)+Sof(H4CA)+Sof(H4CB)]+1*[Sof(O1F)+Sof(C4F)+Sof(H4FA)+
 Sof(H4FB)+Sof(C3F)+Sof(H3FA)+Sof(H3FB)+Sof(C2F)+Sof(H2FA)+Sof(H2FB)+Sof(C1F)+
 Sof(H1FA)+Sof(H1FB)]=1 with esd of 0
 Sof(H29A)=Sof(C30G)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31G)=Sof(H31D)=
 Sof(H31E)=Sof(H31F)=1-FVAR(1)
 Sof(H29)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31)=Sof(H31A)=Sof(H31B)=
 Sof(H31C)=FVAR(1)
 Sof(O1D)=Sof(C1D)=Sof(H1DA)=Sof(H1DB)=Sof(C2D)=Sof(H2DA)=Sof(H2DB)=Sof(C3D)=
 Sof(H3DA)=Sof(H3DB)=Sof(C4D)=Sof(H4DA)=Sof(H4DB)=FVAR(2)
 Sof(O1C)=Sof(C1C)=Sof(H1CA)=Sof(H1CB)=Sof(C2C)=Sof(H2CA)=Sof(H2CB)=Sof(C3C)=
 Sof(H3CA)=Sof(H3CB)=Sof(C4C)=Sof(H4CA)=Sof(H4CB)=FVAR(3)
 Sof(O1F)=Sof(C4F)=Sof(H4FA)=Sof(H4FB)=Sof(C3F)=Sof(H3FA)=Sof(H3FB)=Sof(C2F)=
 Sof(H2FA)=Sof(H2FB)=Sof(C1F)=Sof(H1FA)=Sof(H1FB)=FVAR(4)
 Fixed Sof: O1E(0.33333) H1EA(0.33333) H1EB(0.33333)
7.a Free rotating group:
 O1E(H1EA,H1EB)
7.b Ternary CH refined with riding coordinates:
 C13(H13), C16(H16), C26(H26), C29(H29), C29(H29A)
7.c Secondary CH2 refined with riding coordinates:
 C1A(H1AA,H1AB), C2A(H2AA,H2AB), C3A(H3AA,H3AB), C5A(H5AA,H5AB), C6A(H6AA,
 H6AB), C7A(H7AA,H7AB), C9A(H9AA,H9AB), C10A(H10A,H10B), C11A(H11A,H11B),
 C13A(H13A,H13B), C14A(H14D,H14E), C15A(H15D,H15E), C1B(H1BA,H1BB), C2B(H2BA,
 H2BB), C3B(H3BA,H3BB), C4B(H4BA,H4BB), C1D(H1DA,H1DB), C2D(H2DA,H2DB),
 C3D(H3DA,H3DB), C4D(H4DA,H4DB), C1C(H1CA,H1CB), C2C(H2CA,H2CB), C3C(H3CA,H3CB),
  C4C(H4CA,H4CB), C4F(H4FA,H4FB), C3F(H3FA,H3FB), C2F(H2FA,H2FB), C1F(H1FA,H1FB)
7.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C9(H9), C10(H10), C11(H11), C22(H22), C23(H23),
 C24(H24)
7.e Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C), C30G(H30D,H30E,H30F), C31G(H31D,H31E,H31F), C4A(H4AA,H4AB,H4AC),
 C8A(H8AA,H8AB,H8AC), C12A(H12A,H12B,H12C), C16A(H16A,H16B,H16C)
;
_shelx_res_checksum              52499
_shelx_hkl_checksum              45826
_olex2_exptl_crystal_mounting_method
'Mounted on a MiTeGen mount with Paratone oil'
_olex2_submission_original_sample_id PDACuCl[TBA]
_olex2_submission_special_instructions 'No special instructions were received'