Alkyne insertion into Cu–Al bonds and selective functionalization to form copper acyl compounds
McManus, Caitilín; Crumpton, Agamemnon E.; Aldridge, Simon; Chemical Communications  (2022) –; doi:10.1039/D2CC02578G

data_7130333
_publ_section_title
;
 Alkyne insertion into Cu--Al bonds and selective functionalization to
 form copper acyl compounds
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC02578G
_journal_year                    2022
_chemical_formula_moiety         'C71 H101 Al Cu N2 O2 P'
_chemical_formula_sum            'C71 H101 Al Cu N2 O2 P'
_chemical_formula_weight         1136.02
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-02-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-03-11 deposited with the CCDC.	2022-06-22 downloaded from the CCDC.
;
_cell_angle_alpha                71.108(2)
_cell_angle_beta                 79.692(2)
_cell_angle_gamma                80.746(2)
_cell_formula_units_Z            2
_cell_length_a                   12.1884(2)
_cell_length_b                   17.4389(4)
_cell_length_c                   19.4541(5)
_cell_measurement_reflns_used    22199
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      76.0060
_cell_measurement_theta_min      4.1220
_cell_volume                     3825.54(15)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_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   -124.00 -54.00   1.00    5.00    --  -42.66   0.00 -90.00   70
  2  \w    -26.00  41.00   1.00    5.00    --  -42.66   0.00 -90.00   67
  3  \w    -22.00  10.00   1.00    5.00    --  -42.66  38.00  30.00   32
  4  \w    -44.00   3.00   1.00    5.00    --  -42.66  57.00-150.00   47
  5  \w     -5.00  22.00   1.00    5.00    --  -42.66  19.00 -60.00   27
  6  \w     70.00 128.00   1.00    5.00    --   42.66 178.00-150.00   58
  7  \w     71.00 127.00   1.00    5.00    --   42.66 178.00  60.00   56
  8  \w     94.00 121.00   1.00    5.00    --   42.66-178.00  30.00   27
  9  \w     43.00  72.00   1.00   19.00    --  111.00 -45.00-120.00   29
 10  \w     40.00 112.00   1.00   19.00    --  111.00-125.00-150.00   72
 11  \w     70.00 112.00   1.00   19.00    --  111.00-125.00 -90.00   42
 12  \w    112.00 139.00   1.00   19.00    --  111.00  77.00 -90.00   27
 13  \w     51.00  76.00   1.00   19.00    --  111.00 -61.00 -30.00   25
 14  \w     49.00  89.00   1.00   19.00    --  111.00 -61.00  90.00   40
 15  \w     41.00  69.00   1.00   19.00    --  111.00 -45.00  90.00   28
 16  \w     91.00 163.00   1.00   19.00    --  111.00  45.00  30.00   72
 17  \w     60.00  90.00   1.00   19.00    --  111.00 -61.00-150.00   30
 18  \w    108.00 177.00   1.00   19.00    --  111.00  77.00 120.00   69
 19  \w     69.00  97.00   1.00   19.00    --  111.00-125.00-120.00   28
 20  \w     43.00  99.00   1.00   19.00    --  111.00-125.00 120.00   56
 21  \w     72.00  99.00   1.00   19.00    --  111.00-125.00  60.00   27
 22  \w     84.00 121.00   1.00   19.00    --  111.00-137.00 160.32   37
 23  \w     70.00 110.00   1.00   19.00    --  111.00-125.00   0.00   40
 24  \w    118.00 156.00   1.00   19.00    --  111.00 125.00-180.00   38
 25  \w     73.00 112.00   1.00   19.00    --  111.00-125.00 -30.00   39
 26  \w     40.00  65.00   1.00   19.00    --  111.00 -45.00-150.00   25
 27  \w     36.00  64.00   1.00   19.00    --  111.00 -95.00 120.00   28
 28  \w     69.00 100.00   1.00   19.00    --  111.00 -95.00 120.00   31
 29  \w     44.00  70.00   1.00   19.00    --  111.00 -45.00-180.00   26
 30  \w    102.00 177.00   1.00   19.00    --  111.00  30.00-120.00   75
 31  \w    107.00 178.00   1.00   19.00    --  111.00  77.00 -30.00   71
 32  \w     50.00 111.00   1.00   19.00    --  111.00-125.00  90.00   61
 33  \w     42.00  68.00   1.00   19.00    --  111.00-125.00   0.00   26
 34  \w     48.00  74.00   1.00   19.00    --  111.00-137.00 160.32   26
 35  \w     40.00  65.00   1.00   19.00    --  111.00 -45.00 -90.00   25
 36  \w    106.00 135.00   1.00   19.00    --  111.00  30.00-180.00   29
 37  \w    110.00 177.00   1.00   19.00    --  111.00  45.00 -90.00   67
 38  \w     33.00  58.00   1.00   19.00    --  111.00 -95.00-150.00   25
 39  \w     73.00 102.00   1.00   19.00    --  111.00 -95.00-150.00   29
 40  \w     45.00  72.00   1.00   19.00    --  111.00 -61.00   0.00   27
 41  \w     83.00 108.00   1.00   19.00    --  111.00  15.00-150.00   25
 42  \w    131.00 156.00   1.00   19.00    --  111.00  15.00-150.00   25
 43  \w     35.00 108.00   1.00   19.00    --  111.00-104.00  -0.50   73
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0333798000
_diffrn_orient_matrix_UB_12      -0.0824778000
_diffrn_orient_matrix_UB_13      0.0558696000
_diffrn_orient_matrix_UB_21      0.0132428000
_diffrn_orient_matrix_UB_22      0.0444903000
_diffrn_orient_matrix_UB_23      0.0542497000
_diffrn_orient_matrix_UB_31      -0.1241723000
_diffrn_orient_matrix_UB_32      -0.0066193000
_diffrn_orient_matrix_UB_33      0.0327532000
_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  0.0262
_diffrn_reflns_av_unetI/netI     0.0299
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            43236
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.118
_diffrn_reflns_theta_min         3.709
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.992
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93396
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    0.986
_exptl_crystal_description       plate
_exptl_crystal_F_000             1228
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.521
_refine_diff_density_min         -0.463
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     791
_refine_ls_number_reflns         15832
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0475
_refine_ls_R_factor_gt           0.0409
_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^)+(0.0593P)^2^+1.1196P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1084
_refine_ls_wR_factor_ref         0.1148
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13666
_reflns_number_total             15832
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc02578g2.cif
_cod_data_source_block           4-PrPh
_cod_original_cell_volume        3825.54(16)
_cod_database_code               7130333
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C80 H100 Al1 O2 N2 P1 Cu1'
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.857
_reflns_odcompleteness_completeness 99.74
_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. Others
 Sof(C65A)=Sof(H65D)=Sof(H65E)=Sof(H65F)=Sof(C66A)=Sof(H66D)=Sof(H66E)=
 Sof(H66F)=Sof(C64A)=Sof(H64D)=Sof(H64E)=Sof(H64F)=1-FVAR(1)
 Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=
 Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=FVAR(1)
 Sof(C68A)=Sof(H68D)=Sof(H68E)=Sof(H68F)=Sof(C69A)=Sof(H69D)=Sof(H69E)=
 Sof(H69F)=Sof(C70A)=Sof(H70D)=Sof(H70E)=Sof(H70F)=1-FVAR(2)
 Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=
 Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=FVAR(2)
3.a Ternary CH refined with riding coordinates:
 C41(H41), C44(H44), C54(H54), C56(H56)
3.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B)
3.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C26(H26), C16(H16), C24(H24), C39(H39), C8(H8), C37(H37), C12(H12),
 C38(H38), C51(H51), C9(H9), C49(H49), C11(H11), C10(H10), C50(H50)
3.d Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C20(H20A,H20B,H20C), C31(H31A,H31B,
 H31C), C19(H19A,H19B,H19C), C6(H6A,H6B,H6C), C34(H34A,H34B,H34C), C45(H45A,
 H45B,H45C), C30(H30A,H30B,H30C), C58(H58A,H58B,H58C), C53(H53A,H53B,H53C),
 C33(H33A,H33B,H33C), C55(H55A,H55B,H55C), C46(H46A,H46B,H46C), C57(H57A,H57B,
 H57C), C28(H28A,H28B,H28C), C27(H27A,H27B,H27C), C60(H60A,H60B,H60C), C69(H69A,
 H69B,H69C), C66(H66A,H66B,H66C), C61(H61A,H61B,H61C), C64(H64A,H64B,H64C),
 C70(H70A,H70B,H70C), C62(H62A,H62B,H62C), C65(H65A,H65B,H65C), C68(H68A,H68B,
 H68C), C65A(H65D,H65E,H65F), C66A(H66D,H66E,H66F), C64A(H64D,H64E,H64F),
 C68A(H68D,H68E,H68F), C69A(H69D,H69E,H69F), C70A(H70D,H70E,H70F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              86446
_shelx_hkl_checksum              15135
_shelx_fab_checksum              11194
_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 1.227
_oxdiff_exptl_absorpt_empirical_full_min 0.759