Copper catalyzed benzylic sp<sup>3</sup> C-H alkenylation.
Chen, Ting-An; Staples, Richard J.; Warren, Timothy H.; Chemical science 15 (2024) 17685–17690; doi:10.1039/d4sc03430a

data_1572624
_publ_section_title
;
 Copper catalyzed benzylic sp<sup>3</sup> C-H alkenylation.
;
_journal_issue                   42
_journal_name_full               'Chemical science'
_journal_page_first              17685
_journal_page_last               17690
_journal_paper_doi               10.1039/d4sc03430a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C62 H76 Cu2 F12 N4'
_chemical_formula_sum            'C62 H76 Cu2 F12 N4'
_chemical_formula_weight         1232.34
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2024-01-29
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-01-29 deposited with the CCDC.	2024-09-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.0395(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.6807(2)
_cell_length_b                   16.85029(18)
_cell_length_c                   20.0632(2)
_cell_measurement_reflns_used    23083
_cell_measurement_temperature    99.9(5)
_cell_measurement_theta_max      79.1310
_cell_measurement_theta_min      2.1870
_cell_volume                     5973.54(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.119a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(5)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    100.00 126.00   0.50    0.15    --  113.25  69.00  46.00   52
  2  \w    132.00 157.00   0.50    0.15    --  113.25  77.00  60.00   50
  3  \w    147.00 177.00   0.50    0.15    --  113.25  61.00  90.00   60
  4  \w    133.00 176.00   0.50    0.15    --  113.25  69.00  46.00   86
  5  \w    129.00 158.00   0.50    0.15    --  113.25  61.00  30.00   58
  6  \w    128.00 178.00   0.50    0.15    --  113.25  77.00   0.00  100
  7  \w    142.00 168.00   0.50    0.15    --  113.25  61.00 120.00   52
  8  \w    127.00 168.00   0.50    0.15    --  113.25  61.00 -30.00   82
  9  \w    126.00 177.00   0.50    0.15    --  113.25  77.00 -60.00  102
 10  \w    137.00 162.00   0.50    0.15    --  113.25  77.00 -90.00   50
 11  \w    135.00 160.00   0.50    0.15    --  113.25  61.00-180.00   50
 12  \w    126.00 178.00   0.50    0.15    --  113.25  45.00 -60.00  104
 13  \w    101.00 158.00   0.50    0.15    --  113.25  30.00-120.00  114
 14  \w    150.00 175.00   0.50    0.15    --  113.25  30.00   0.00   50
 15  \w    102.00 139.00   0.50    0.15    --  113.25  30.00 150.00   74
 16  \w    101.00 127.00   0.50    0.15    --  113.25  30.00 176.28   52
 17  \w    102.00 134.00   0.50    0.15    --  113.25  15.00 150.00   64
 18  \w    153.00 178.00   0.50    0.15    --  113.25  15.00 150.00   50
 19  \w    101.00 140.00   0.50    0.15    --  113.25  30.00   0.00   78
 20  \w    101.00 174.00   0.50    0.15    --  113.25  30.00-150.00  146
 21  \w    103.00 157.00   0.50    0.15    --  113.25  30.00-180.00  108
 22  \w    -67.00  19.00   0.50    0.05    --  -47.86  69.00  46.00  172
 23  \w    -25.00  15.00   0.50    0.05    --  -47.86  19.00 -60.00   80
 24  \w    -26.00  21.00   0.50    0.05    --  -47.86  19.00  30.00   94
 25  \w    -17.00   8.00   0.50    0.05    --  -47.86  19.00  60.00   50
 26  \w     53.00 105.00   0.50    0.15    --  113.25-125.00  90.00  104
 27  \w     71.00 108.00   0.50    0.15    --  113.25-125.00  30.00   74
 28  \w     43.00  69.00   0.50    0.15    --  113.25-125.00  30.00   52
 29  \w     48.00  76.00   0.50    0.15    --  113.25-125.00   0.00   56
 30  \w     47.00 107.00   0.50    0.15    --  113.25-125.00 -60.00  120
 31  \w     83.00 108.00   0.50    0.15    --  113.25-125.00   0.00   50
 32  \w     42.00  80.00   0.50    0.15    --  113.25 -94.00  30.00   76
 33  \w     72.00  98.00   0.50    0.15    --  113.25 -94.00  90.00   52
 34  \w     43.00  69.00   0.50    0.15    --  113.25 -94.00 120.00   52
 35  \w    -19.00   6.00   0.50    0.05    --   47.86 -19.00  30.00   50
 36  \w     15.00  48.00   0.50    0.05    --   47.86 -69.00 -86.00   66
 37  \w     42.00  67.00   0.50    0.15    --  113.25 -69.00 -86.00   50
 38  \w     43.00  69.00   0.50    0.15    --  113.25 -61.00 -90.00   52
 39  \w     42.00  69.00   0.50    0.15    --  113.25 -61.00-120.00   54
 40  \w     42.00  67.00   0.50    0.15    --  113.25 -61.00-180.00   50
 41  \w     44.00  69.00   0.50    0.15    --  113.25 -61.00 -60.00   50
 42  \w     43.00  70.00   0.50    0.15    --  113.25 -61.00-150.00   54
 43  \w     42.00  68.00   0.50    0.15    --  113.25 -61.00   0.00   52
 44  \w     43.00  68.00   0.50    0.15    --  113.25 -61.00  60.00   50
 45  \w     42.00  67.00   0.50    0.15    --  113.25 -61.00 120.00   50
 46  \w     43.00  68.00   0.50    0.15    --  113.25 -61.00 150.00   50
 47  \w    113.00 158.00   0.50    0.15    --  113.25 125.00 120.00   90
 48  \w    113.00 157.00   0.50    0.15    --  113.25 125.00 150.00   88
 49  \w    109.00 142.00   0.50    0.15    --  113.25 125.00  60.00   66
 50  \w    149.00 174.00   0.50    0.15    --  113.25 125.00  60.00   50
 51  \w    -47.00 -20.00   0.50    0.15    --  -91.75  45.00-120.00   54
 52  \w    -74.00 -33.00   0.50    0.05    --  -47.86 125.00-180.00   82
 53  \w    -82.00 -30.00   0.50    0.05    --  -47.86 125.00 -60.00  104
 54  \w    -77.00 -52.00   0.50    0.15    --  -91.75  69.00  46.00   50
 55  \w    -78.00 -37.00   0.50    0.05    --  -47.86 125.00 150.00   82
 56  \w   -127.00-100.00   0.50    0.15    --  -91.75 -15.00 150.00   54
 57  \w   -125.00 -89.00   0.50    0.15    --  -91.75 -30.00 150.00   72
 58  \w   -150.00 -82.00   0.50    0.15    --  -91.75 -29.00 125.69  136
 59  \w   -133.00 -79.00   0.50    0.15    --  -91.75 -27.00  98.69  108
 60  \w   -142.00-117.00   0.50    0.15    --  -91.75 -69.00 -86.00   50
 61  \w   -113.00 -88.00   0.50    0.15    --  -91.75 -30.00-180.00   50
 62  \w   -116.00 -37.00   0.50    0.05    --  -47.86 -69.00 -86.00  158
 63  \w   -163.00-138.00   0.50    0.15    --  -91.75 -94.00  30.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0372158000
_diffrn_orient_matrix_UB_12      0.0667334000
_diffrn_orient_matrix_UB_13      -0.0398398000
_diffrn_orient_matrix_UB_21      0.0782896000
_diffrn_orient_matrix_UB_22      -0.0247837000
_diffrn_orient_matrix_UB_23      0.0290873000
_diffrn_orient_matrix_UB_31      0.0094475000
_diffrn_orient_matrix_UB_32      -0.0574357000
_diffrn_orient_matrix_UB_33      -0.0588495000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0346
_diffrn_reflns_av_unetI/netI     0.0192
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            47112
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.824
_diffrn_reflns_theta_min         3.625
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.556
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95022
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.119a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.370
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2568
_exptl_crystal_recrystallization_method 'used as received'
_exptl_crystal_size_max          0.264
_exptl_crystal_size_mid          0.245
_exptl_crystal_size_min          0.167
_refine_diff_density_max         0.639
_refine_diff_density_min         -0.824
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     382
_refine_ls_number_reflns         6459
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0380
_refine_ls_R_factor_gt           0.0371
_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^)+(0.0391P)^2^+10.2187P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0921
_refine_ls_wR_factor_ref         0.0928
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6255
_reflns_number_total             6459
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03430a2.cif
_cod_data_source_block           tc-10122021-tc-5-13
_cod_depositor_comments
'Adding full bibliography for 1572623--1572624.cif.'
_cod_original_cell_volume        5973.56(11)
_cod_database_code               1572624
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C78H132Cu2F12N4
_chemical_oxdiff_usercomment     Tc-5-13
_reflns_odcompleteness_completeness 97.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
2. Uiso/Uaniso restraints and constraints
Uanis(C2) = Uanis(C2B)
3. Others
 Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(C2B)=Sof(H2B)=1-FVAR(1)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C2(H2), C2B(H2B), C14(H14), C17(H17), C26(H26), C29(H29)
4.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C10(H10), C11(H11), C12(H12), C22(H22), C23(H23), C24(H24)
4.c X=CH2 refined with riding coordinates:
 C1(H1A,H1B), C1B(H1BA,H1BB)
4.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C)
;
_shelx_res_checksum              6916
_shelx_hkl_checksum              24714
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a nylon loop with paratone oil'
_olex2_submission_original_sample_id Tc-5-13
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.134
_oxdiff_exptl_absorpt_empirical_full_min 0.884