Magnesium-mediated arylation of amines via C-F bond activation of fluoroarenes.
Bole, Leonie J.; Davin, Laia; Kennedy, Alan R.; McLellan, Ross; Hevia, Eva; Chemical communications (Cambridge, England) 55 (2019) 4339–4342; doi:10.1039/c9cc01670h

data_7125367
_publ_section_title
;
 Magnesium-mediated arylation of amines via C-F bond activation of
 fluoroarenes.
;
_journal_issue                   30
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              4339
_journal_page_last               4342
_journal_paper_doi               10.1039/c9cc01670h
_journal_volume                  55
_journal_year                    2019
_chemical_formula_moiety         'C70 H90 Mg2 N10, C7 H8'
_chemical_formula_sum            'C77 H98 Mg2 N10'
_chemical_formula_weight         1212.27
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-02-15
_audit_creation_method
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Olex2 1.2
(compiled Jan 19 2015 12:28:14 for OlexSys, GUI svn.r4998)
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_audit_update_record
;
2019-01-30 deposited with the CCDC.	2019-03-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.872(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.0738(4)
_cell_length_b                   14.2398(5)
_cell_length_c                   19.0456(6)
_cell_measurement_reflns_used    7182
_cell_measurement_temperature    123.4
_cell_measurement_theta_max      30.1087
_cell_measurement_theta_min      3.0488
_cell_volume                     3541.2(2)
_computing_cell_refinement
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CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
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_computing_data_collection
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CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
;
_computing_data_reduction
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CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
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_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      123.4
_diffrn_detector_area_resol_mean 16.0727
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_details
;
  1 omega  -37.00   47.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       20.9636  -37.0000  -30.0000 84

  2 omega   24.00   74.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       20.9636   64.0000   89.0000 50

  3 omega   31.00   75.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       20.9636   37.0000 -180.0000 44

  4 omega  -78.00  -33.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -21.9011  179.0000  120.0000 45

  5 omega   -9.00   20.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       20.9636   77.0000  -30.0000 29
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0380287000
_diffrn_orient_matrix_UB_12      -0.0344254000
_diffrn_orient_matrix_UB_13      0.0082979000
_diffrn_orient_matrix_UB_21      0.0009486000
_diffrn_orient_matrix_UB_22      0.0137178000
_diffrn_orient_matrix_UB_23      0.0358179000
_diffrn_orient_matrix_UB_31      -0.0389248000
_diffrn_orient_matrix_UB_32      -0.0331540000
_diffrn_orient_matrix_UB_33      0.0062169000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0249
_diffrn_reflns_av_unetI/netI     0.0413
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            18999
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.999
_diffrn_reflns_theta_min         3.055
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.083
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92990
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.137
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             1308
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.617
_refine_diff_density_min         -0.371
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     442
_refine_ls_number_reflns         9058
_refine_ls_number_restraints     120
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0704
_refine_ls_R_factor_gt           0.0497
_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^)+(0.0544P)^2^+1.4945P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1173
_refine_ls_wR_factor_ref         0.1297
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6862
_reflns_number_total             9058
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc01670h2.cif
_cod_data_source_block           ld384
_cod_database_code               7125367
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.68
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.82
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C36-C42 = C36A-C42A
 1.47 with sigma of 0.01
 C41A-C42A = C37A-C42A = C41-C42 = C37-C42
 2.48 with sigma of 0.01
3. Rigid bond restraints
 C42A, C36A, C37A, C38A, C39A, C40A, C41A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C42, C36, C37, C38, C39, C40, C41
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C42A \\sim C36A \\sim C37A \\sim C38A \\sim C39A \\sim C40A \\sim C41A: within
1.7A with sigma of 0.02 and sigma for terminal atoms of 0.02
C42 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.02
Uanis(C42) = Uanis(C42A)
Uanis(C36) = Uanis(C36A)
Uanis(C37) = Uanis(C37A)
Uanis(C38) = Uanis(C38A)
Uanis(C39) = Uanis(C39A)
Uanis(C40) = Uanis(C40A)
Uanis(C41) = Uanis(C41A)
5. Others
 Fixed Sof: C42(0.33) H42A(0.33) H42B(0.33) H42C(0.33) C36(0.33) C37(0.33)
 H37(0.33) C38(0.33) H38(0.33) C39(0.33) H39(0.33) C40(0.33) H40(0.33)
 C41(0.33) H41(0.33) C42A(0.17) H42D(0.17) H42E(0.17) H42F(0.17) C36A(0.17)
 C37A(0.17) H37A(0.17) C38A(0.17) H38A(0.17) C39A(0.17) H39A(0.17) C40A(0.17)
 H40A(0.17) C41A(0.17) H41A(0.17)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24(H24), C27(H27)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22), C31(H31),
 C32(H32), C33(H33), C34(H34), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41),
  C37A(H37A), C38A(H38A), C39A(H39A), C40A(H40A), C41A(H41A)
6.c Fitted hexagon refined as free rotating group:
 C36(C37,C38,C39,C40,C41), C36A(C37A,C38A,C39A,C40A,C41A)
6.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C42(H42A,H42B,H42C),
 C42A(H42D,H42E,H42F)
;
_shelx_res_checksum              72448
_olex2_submission_original_sample_id LD384
_olex2_submission_special_instructions 'No special instructions were received'