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_7130332
_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         'C49 H67 Al N2 O, C3 H7'
_chemical_formula_sum            'C52 H74 Al N2 O'
_chemical_formula_weight         770.11
_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             2021-09-30
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-03-11 deposited with the CCDC.	2022-06-22 downloaded from the CCDC.
;
_cell_angle_alpha                99.705(4)
_cell_angle_beta                 104.191(3)
_cell_angle_gamma                98.075(4)
_cell_formula_units_Z            2
_cell_length_a                   13.0581(5)
_cell_length_b                   13.3038(7)
_cell_length_c                   14.3490(5)
_cell_measurement_reflns_used    11065
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      76.5480
_cell_measurement_theta_min      4.0670
_cell_volume                     2338.58(18)
_computing_cell_refinement       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_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      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5035
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.983
_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     -3.00  29.00   1.00    5.00    --  -41.11  19.00-120.00   32
  2  \w     -4.00  38.00   1.00    5.00    --  -41.11  19.00 120.00   42
  3  \w    -19.00  30.00   1.00    5.00    --  -41.11  37.00-180.00   49
  4  \w     -5.00  37.00   1.00    5.00    --  -41.11  19.00 -30.00   42
  5  \w    -18.00  28.00   1.00    5.00    --  -41.11  37.00 -90.00   46
  6  \w    -50.00  -9.00   1.00    5.00    --  -41.11 125.00   0.00   41
  7  \w     -4.00  36.00   1.00    5.00    --  -41.11  19.00  30.00   40
  8  \w     18.00  74.00   1.00    5.00    --   41.11 -99.00 -30.00   56
  9  \w     39.00  74.00   1.00    5.00    --   41.11-125.00 -90.00   35
 10  \w     43.00 100.00   1.00    5.00    --   41.11-134.00 150.00   57
 11  \w     58.00  90.00   1.00   21.00    --  112.00 -61.00  90.00   32
 12  \w     36.00  92.00   1.00   21.00    --  112.00-111.00  30.00   56
 13  \w    111.00 169.00   1.00   21.00    --  112.00 111.00-180.00   58
 14  \w     70.00 109.00   1.00   21.00    --  112.00-111.00 -60.00   39
 15  \w     37.00 109.00   1.00   21.00    --  112.00-111.00  60.00   72
 16  \w    132.00 175.00   1.00   21.00    --  112.00  77.00   0.00   43
 17  \w     40.00  71.00   1.00   21.00    --  112.00 -61.00-120.00   31
 18  \w     99.00 149.00   1.00   21.00    --  112.00  45.00  60.00   50
 19  \w    119.00 162.00   1.00   21.00    --  112.00  77.00 120.00   43
 20  \w    109.00 137.00   1.00   21.00    --  112.00 178.00 -90.00   28
 21  \w     52.00 109.00   1.00   21.00    --  112.00-111.00 -90.00   57
 22  \w     67.00  93.00   1.00   21.00    --  112.00 178.00 -90.00   26
 23  \w     37.00  90.00   1.00   21.00    --  112.00-111.00 -30.00   53
 24  \w     40.00  74.00   1.00   21.00    --  112.00 -61.00 -60.00   34
 25  \w     43.00  69.00   1.00   21.00    --  112.00-111.00 150.00   26
 26  \w     84.00 109.00   1.00   21.00    --  112.00-111.00 150.00   25
 27  \w     66.00 109.00   1.00   21.00    --  112.00-111.00 120.00   43
 28  \w     73.00 108.00   1.00   21.00    --  112.00-111.00-150.00   35
 29  \w     91.00 162.00   1.00   21.00    --  112.00  45.00-180.00   71
 30  \w     39.00  64.00   1.00   21.00    --  112.00 -45.00 150.00   25
 31  \w     53.00 109.00   1.00   21.00    --  112.00-111.00   0.00   56
 32  \w     39.00  84.00   1.00   21.00    --  112.00-111.00-120.00   45
 33  \w     75.00 109.00   1.00   21.00    --  112.00-111.00  90.00   34
 34  \w     41.00  70.00   1.00   21.00    --  112.00 -45.00  30.00   29
 35  \w     39.00  64.00   1.00   21.00    --  112.00 -45.00  60.00   25
 36  \w     43.00  69.00   1.00   21.00    --  112.00 -45.00  90.00   26
 37  \w     59.00 168.00   1.00   21.00    --  112.00  15.00 -30.00  109
 38  \w     82.00 133.00   1.00   21.00    --  112.00  15.00 150.00   51
;
_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      -0.0320660000
_diffrn_orient_matrix_UB_12      -0.0332645000
_diffrn_orient_matrix_UB_13      -0.1129992000
_diffrn_orient_matrix_UB_21      -0.0279152000
_diffrn_orient_matrix_UB_22      0.1074508000
_diffrn_orient_matrix_UB_23      -0.0083355000
_diffrn_orient_matrix_UB_31      0.1164362000
_diffrn_orient_matrix_UB_32      0.0408347000
_diffrn_orient_matrix_UB_33      0.0001105000
_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  0.0303
_diffrn_reflns_av_unetI/netI     0.0390
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            23697
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.808
_diffrn_reflns_theta_min         3.556
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.649
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91137
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.117a (Rigaku Oxford Diffraction, 2021)
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    1.094
_exptl_crystal_description       plate
_exptl_crystal_F_000             842
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.005
_refine_diff_density_max         0.376
_refine_diff_density_min         -0.320
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     554
_refine_ls_number_reflns         9701
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0558
_refine_ls_R_factor_gt           0.0430
_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^)+(0.0560P)^2^+0.5412P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1091
_refine_ls_wR_factor_ref         0.1187
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7911
_reflns_number_total             9701
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc02578g2.cif
_cod_data_source_block           (NON)Al-Et
_cod_database_code               7130332
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H60 Al1 N2 O1'
_shelx_estimated_absorpt_t_max   0.997
_shelx_estimated_absorpt_t_min   0.994
_reflns_odcompleteness_completeness 99.72
_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
C22A \\sim C24A \\sim C23A: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C21 \\sim C24A \\sim C22A \\sim C23A: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 2A
3. Others
 Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C22A)=Sof(H22D)=Sof(H22E)=
 Sof(H22F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(1)
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C34(H34), C46(H46), C43(H43), C31(H31)
4.b Secondary CH2 refined with riding coordinates:
 C49(H49A,H49B), C102(H10A,H10B), C101(H10C,H10D)
4.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C13(H13), C11(H11), C3(H3), C39(H39), C27(H27), C41(H41), C29(H29),
 C28(H28), C40(H40)
4.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C44(H44A,H44B,H44C), C35(H35A,H35B,
 H35C), C8(H8A,H8B,H8C), C47(H47A,H47B,H47C), C18(H18A,H18B,H18C), C48(H48A,
 H48B,H48C), C33(H33A,H33B,H33C), C36(H36A,H36B,H36C), C45(H45A,H45B,H45C),
 C19(H19A,H19B,H19C), C32(H32A,H32B,H32C), C100(H10E,H10F,H10G), C20(H20A,H20B,
 H20C), C24(H24A,H24B,H24C), C23(H23A,H23B,H23C), C22(H22A,H22B,H22C),
 C23A(H23D,H23E,H23F), C22A(H22D,H22E,H22F), C24A(H24D,H24E,H24F)
;
_shelx_res_checksum              62810
_shelx_hkl_checksum              94392
_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 1.189
_oxdiff_exptl_absorpt_empirical_full_min 0.879