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_7130334
_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         'C66 H99 Al Cu N2 O2 P, C3 H7'
_chemical_formula_sum            'C69 H106 Al Cu N2 O2 P'
_chemical_formula_weight         1117.04
_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     dual
_audit_creation_date             2022-01-21
_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                90
_cell_angle_beta                 92.351(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.8505(2)
_cell_length_b                   23.4691(4)
_cell_length_c                   20.3996(3)
_cell_measurement_reflns_used    12831
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      76.3410
_cell_measurement_theta_min      4.1920
_cell_volume                     6625.49(18)
_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      150.01(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 0.986
_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   -112.00 -15.00   1.00    1.00    --  -41.65 -57.00   0.00   97
  2  \w     -5.00  20.00   1.00    1.00    --  -41.65  19.00 -60.00   25
  3  \w    -41.00  26.00   1.00    1.00    --  -41.65  57.00 150.00   67
  4  \w     -2.00  32.00   1.00    1.00    --  -41.65  19.00  90.00   34
  5  \w      2.00  31.00   1.00    1.00    --  -41.65  37.00-150.00   29
  6  \w     -4.00  22.00   1.00    1.00    --  -41.65  19.00 -30.00   26
  7  \w     41.00  68.00   1.00    2.75    --  111.00 -45.00   0.00   27
  8  \w     40.00  70.00   1.00    2.75    --  111.00 -45.00-120.00   30
  9  \w     41.00  72.00   1.00    2.75    --  111.00 -45.00 -30.00   31
 10  \w     69.00  94.00   1.00    2.75    --  111.00 178.00 120.00   25
 11  \w    113.00 139.00   1.00    2.75    --  111.00 178.00 120.00   26
 12  \w     43.00  70.00   1.00    2.75    --  111.00 -45.00-180.00   27
 13  \w     40.00  70.00   1.00    2.75    --  111.00 -45.00 -90.00   30
 14  \w    112.00 165.00   1.00    2.75    --  111.00  77.00-120.00   53
 15  \w     41.00  67.00   1.00    2.75    --  111.00 -45.00 -60.00   26
 16  \w     63.00  89.00   1.00    2.75    --  111.00 178.00  30.00   26
 17  \w     59.00  90.00   1.00    2.75    --  111.00 -61.00 -60.00   31
 18  \w    104.00 141.00   1.00    2.75    --  111.00 111.00-180.00   37
 19  \w    112.00 146.00   1.00    2.75    --  111.00 178.00  30.00   34
 20  \w    104.00 154.00   1.00    2.75    --  111.00 111.00 -30.00   50
 21  \w     63.00  88.00   1.00    2.75    --  111.00 -61.00   0.00   25
 22  \w     44.00  69.00   1.00    2.75    --  111.00 -45.00-150.00   25
 23  \w    123.00 161.00   1.00    2.75    --  111.00  15.00-180.00   38
 24  \w     41.00  67.00   1.00    2.75    --  111.00 -45.00  30.00   26
 25  \w     64.00  91.00   1.00    2.75    --  111.00 -61.00-180.00   27
 26  \w     41.00  93.00   1.00    2.75    --  111.00 -61.00  90.00   52
 27  \w    -87.00 -83.00   1.00    1.00    --  -41.65 125.00-120.00    4
;
_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      0.0129841000
_diffrn_orient_matrix_UB_12      -0.0511224000
_diffrn_orient_matrix_UB_13      0.0468900000
_diffrn_orient_matrix_UB_21      0.0944954000
_diffrn_orient_matrix_UB_22      -0.0159958000
_diffrn_orient_matrix_UB_23      -0.0327997000
_diffrn_orient_matrix_UB_31      0.0573844000
_diffrn_orient_matrix_UB_32      0.0379324000
_diffrn_orient_matrix_UB_33      0.0493939000
_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  0.0314
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            37124
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.261
_diffrn_reflns_theta_min         3.708
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.135
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81758
_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    1.120
_exptl_crystal_description       block
_exptl_crystal_F_000             2428
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.650
_refine_diff_density_min         -0.541
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     773
_refine_ls_number_reflns         13709
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0539
_refine_ls_R_factor_gt           0.0426
_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^)+(0.0606P)^2^+2.5084P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1115
_refine_ls_wR_factor_ref         0.1211
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11337
_reflns_number_total             13709
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc02578g2.cif
_cod_data_source_block           4-Et
_cod_database_code               7130334
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C60 H80 Al1 O3 N2 P1 Cu1'
_shelx_estimated_absorpt_t_max   0.805
_shelx_estimated_absorpt_t_min   0.727
_reflns_odcompleteness_completeness 99.54
_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
C1B \\sim C1A \\sim C23: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
C101 \\sim C100 \\sim C102: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
3. Others
 Sof(C70A)=Sof(H70D)=Sof(H70E)=Sof(H70F)=Sof(C68A)=Sof(H68D)=Sof(H68E)=
 Sof(H68F)=Sof(C69A)=Sof(H69D)=Sof(H69E)=Sof(H69F)=1-FVAR(1)
 Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=
 Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=FVAR(1)
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C1B)=
 Sof(H1BA)=Sof(H1BB)=1-FVAR(2)
 Sof(C102)=Sof(H10A)=Sof(H10B)=Sof(C101)=Sof(H10C)=Sof(H10D)=Sof(C100)=
 Sof(H10E)=Sof(H10F)=Sof(H10G)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C48(H48), C51(H51), C36(H36), C40(H40)
4.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C3(H3A,H3B), C102(H10A,H10B), C101(H10C,H10D), C1A(H1AA,H1AB),
 C1B(H1BA,H1BB)
4.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C19(H19), C21(H21), C10(H10), C32(H32), C46(H46), C34(H34),
 C44(H44), C45(H45), C33(H33)
4.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C28(H28A,H28B,H28C), C53(H53A,H53B,
 H53C), C39(H39A,H39B,H39C), C29(H29A,H29B,H29C), C52(H52A,H52B,H52C), C27(H27A,
 H27B,H27C), C60(H60A,H60B,H60C), C50(H50A,H50B,H50C), C49(H49A,H49B,H49C),
 C7(H7A,H7B,H7C), C59(H59A,H59B,H59C), C4(H4A,H4B,H4C), C56(H56A,H56B,H56C),
 C41(H41A,H41B,H41C), C61(H61A,H61B,H61C), C37(H37A,H37B,H37C), C55(H55A,H55B,
 H55C), C70(H70A,H70B,H70C), C57(H57A,H57B,H57C), C63(H63A,H63B,H63C), C68(H68A,
 H68B,H68C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C69(H69A,H69B,H69C),
 C38(H38A,H38B,H38C), C100(H10E,H10F,H10G), C70A(H70D,H70E,H70F), C68A(H68D,
 H68E,H68F), C69A(H69D,H69E,H69F), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              42043
_shelx_hkl_checksum              32856
_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 1.312
_oxdiff_exptl_absorpt_empirical_full_min 0.685