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_7130331
_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         'C70 H101 Al Cu N2 O P, C6 H14'
_chemical_formula_sum            'C76 H115 Al Cu N2 O P'
_chemical_formula_weight         1194.18
_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             2022-02-22
_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                97.054(5)
_cell_angle_beta                 94.267(4)
_cell_angle_gamma                115.698(6)
_cell_formula_units_Z            2
_cell_length_a                   13.2005(7)
_cell_length_b                   13.5410(10)
_cell_length_c                   22.7180(11)
_cell_measurement_reflns_used    6175
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      74.3810
_cell_measurement_theta_min      3.6450
_cell_volume                     3594.3(4)
_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      150.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.982
_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 -42.00   1.00   30.00    --  -42.53 -57.00 120.00   70
  2  \w     -1.00  27.00   1.00   30.00    --  -42.53  19.00 -60.00   28
  3  \w     -4.00  36.00   1.00   30.00    --  -42.53  19.00  60.00   40
  4  \w     -4.00  35.00   1.00   30.00    --  -42.53  19.00 -90.00   39
  5  \w     -4.00  33.00   1.00   30.00    --  -42.53  19.00   0.00   37
  6  \w    -11.00  26.00   1.00   30.00    --  -42.53  38.00  30.00   37
  7  \w     61.00 116.00   1.00   30.00    --   42.53 178.00 -60.00   55
  8  \w     71.00 120.00   1.00   30.00    --   42.53-178.00-150.00   49
  9  \w     77.00 102.00   1.00   30.00    --   42.53 178.00  90.00   25
 10  \w     61.00 128.00   1.00   30.00    --   42.53 178.00  60.00   67
 11  \w     99.00 135.00   1.00   40.00    --  111.00  15.00 150.00   36
 12  \w     61.00  92.00   1.00   40.00    --  111.00 -61.00  60.00   31
 13  \w     38.00  72.00   1.00   40.00    --  111.00 -77.00  60.00   34
 14  \w     41.00  71.00   1.00   40.00    --  111.00 -45.00  90.00   30
 15  \w     49.00  84.00   1.00   40.00    --  111.00 -61.00 -60.00   35
 16  \w     73.00 106.00   1.00   40.00    --  111.00 -95.00-150.00   33
 17  \w     37.00 109.00   1.00   40.00    --  111.00-112.00-161.39   72
 18  \w     44.00  72.00   1.00   40.00    --  111.00 -45.00-120.00   28
 19  \w     86.00 112.00   1.00   40.00    --  111.00-125.00 150.00   26
 20  \w     42.00  68.00   1.00   40.00    --  111.00-125.00 120.00   26
 21  \w     53.00  94.00   1.00   40.00    --  111.00-125.00 -60.00   41
 22  \w     43.00  71.00   1.00   40.00    --  111.00 -45.00   0.00   28
 23  \w    130.00 168.00   1.00   40.00    --  111.00  30.00  30.00   38
 24  \w     32.00  65.00   1.00   40.00    --  111.00 -95.00-150.00   33
 25  \w     91.00 178.00   1.00   40.00    --  111.00  45.00-120.00   87
 26  \w     47.00  91.00   1.00   40.00    --  111.00 -61.00-150.00   44
 27  \w    108.00 145.00   1.00   40.00    --  111.00  45.00-180.00   37
 28  \w     84.00 174.00   1.00   40.00    --  111.00  61.00 -30.00   90
 29  \w     89.00 157.00   1.00   40.00    --  111.00  30.00 -60.00   68
 30  \w     30.00  58.00   1.00   40.00    --  111.00 -95.00 -30.00   28
 31  \w     91.00 116.00   1.00   40.00    --  111.00  30.00  30.00   25
 32  \w     98.00 134.00   1.00   40.00    --  111.00 125.00 -90.00   36
 33  \w     43.00  86.00   1.00   40.00    --  111.00 -61.00-180.00   43
 34  \w     62.00  89.00   1.00   40.00    --  111.00 -95.00  30.00   27
 35  \w    135.00 162.00   1.00   40.00    --  111.00 125.00 -90.00   27
 36  \w     42.00  71.00   1.00   40.00    --  111.00 -45.00  60.00   29
 37  \w     79.00 106.00   1.00   40.00    --  111.00 -95.00 -30.00   27
 38  \w     46.00  72.00   1.00   40.00    --  111.00 -45.00 -30.00   26
 39  \w     62.00 125.00   1.00   40.00    --  111.00-142.00 -14.89   63
 40  \w     80.00 112.00   1.00   40.00    --  111.00-125.00 120.00   32
 41  \w     67.00 120.00   1.00   40.00    --  111.00  15.00  90.00   53
 42  \w     77.00 102.00   1.00   40.00    --  111.00-125.00-180.00   25
 43  \w     85.00 127.00   1.00   40.00    --  111.00-146.00 113.74   42
 44  \w     62.00 108.00   1.00   40.00    --  111.00-109.00 -22.92   46
;
_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      -0.1250294000
_diffrn_orient_matrix_UB_12      -0.0423279000
_diffrn_orient_matrix_UB_13      -0.0271031000
_diffrn_orient_matrix_UB_21      0.0187360000
_diffrn_orient_matrix_UB_22      -0.0653785000
_diffrn_orient_matrix_UB_23      -0.0550572000
_diffrn_orient_matrix_UB_31      -0.0337568000
_diffrn_orient_matrix_UB_32      -0.1018054000
_diffrn_orient_matrix_UB_33      0.0316257000
_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  0.0821
_diffrn_reflns_av_unetI/netI     0.0807
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            40061
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.388
_diffrn_reflns_theta_min         3.678
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.064
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74643
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.103
_exptl_crystal_description       block
_exptl_crystal_F_000             1300
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.01
_refine_diff_density_max         3.171
_refine_diff_density_min         -0.783
_refine_diff_density_rms         0.145
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.217
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     822
_refine_ls_number_reflns         14807
_refine_ls_number_restraints     118
_refine_ls_restrained_S_all      1.217
_refine_ls_R_factor_all          0.1628
_refine_ls_R_factor_gt           0.1253
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3156
_refine_ls_wR_factor_ref         0.3547
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9554
_reflns_number_total             14807
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc02578g2.cif
_cod_data_source_block           3-PrPh
_cod_database_code               7130331
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H70 Al1 N2 O1 P1 Cu1'
_shelx_estimated_absorpt_t_max   0.989
_shelx_estimated_absorpt_t_min   0.901
_reflns_odcompleteness_completeness 99.46
_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. Restrained distances
 C1A-C1B = C1B-C1C = C1C-C1D = C1D-C1E = C1E-C1F
 1.52 with sigma of 0.02
 C1B-C1D = C1C-C1E
 2.54 with sigma of 0.04
 C1A-C1C = C1D-C1F
 2.53 with sigma of 0.04
 C1A-C1B \\sim C1B-C1C \\sim C1C-C1D \\sim C1D-C1E \\sim C1E-C1F
 with sigma of 0.02
 C1A-C1C \\sim C1C-C1E \\sim C1B-C1D \\sim C1D-C1F
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C1K \\sim C1J \\sim C1I \\sim C1H \\sim C71 \\sim C1G: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 2A
C1A \\sim C1B \\sim C1C \\sim C1D \\sim C1E \\sim C1F: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 2A
C17 \\sim C16: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
4. Rigid body (RIGU) restrains
 C1A, C1B, C1C, C1D, C1E, C1F
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C1C, C1D, C1E, C1F
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C1G)=Sof(H1GA)=Sof(H1GB)=Sof(H1GC)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(C1H)=
 Sof(H1HA)=Sof(H1HB)=Sof(C1I)=Sof(H1IA)=Sof(H1IB)=Sof(C1J)=Sof(H1JA)=Sof(H1JB)=
 Sof(C1K)=Sof(H1KA)=Sof(H1KB)=Sof(H1KC)=1-FVAR(1)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(C1C)=
 Sof(H1CA)=Sof(H1CB)=Sof(C1D)=Sof(H1DA)=Sof(H1DB)=Sof(C1E)=Sof(H1EA)=Sof(H1EB)=
 Sof(C1F)=Sof(H1FA)=Sof(H1FB)=Sof(H1FC)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C33(H33), C30(H30), C45(H45), C42(H42)
6.b Secondary CH2 refined with riding coordinates:
 C62(H62A,H62B), C63(H63A,H63B), C1B(H1BA,H1BB), C1C(H1CA,H1CB), C1D(H1DA,
 H1DB), C1E(H1EA,H1EB), C71(H71A,H71B), C1H(H1HA,H1HB), C1I(H1IA,H1IB),
 C1J(H1JA,H1JB)
6.c Me refined with riding coordinates:
 C1A(H1AA,H1AB,H1AC), C1F(H1FA,H1FB,H1FC)
6.d Aromatic/amide H refined with riding coordinates:
 C11(H11), C66(H66), C4(H4), C28(H28), C2(H2), C70(H70), C38(H38), C27(H27),
 C26(H26), C13(H13), C69(H69), C67(H67), C40(H40), C39(H39), C68(H68)
6.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C35(H35A,H35B,H35C), C47(H47A,H47B,H47C),
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C46(H46A,H46B,
 H46C), C44(H44A,H44B,H44C), C55(H55A,H55B,H55C), C64(H64A,H64B,H64C), C17(H17A,
 H17B,H17C), C19(H19A,H19B,H19C), C54(H54A,H54B,H54C), C57(H57A,H57B,H57C),
 C58(H58A,H58B,H58C), C43(H43A,H43B,H43C), C51(H51A,H51B,H51C), C50(H50A,H50B,
 H50C), C53(H53A,H53B,H53C), C18(H18A,H18B,H18C), C23(H23A,H23B,H23C), C21(H21A,
 H21B,H21C), C49(H49A,H49B,H49C), C22(H22A,H22B,H22C), C59(H59A,H59B,H59C),
 C1G(H1GA,H1GB,H1GC), C1K(H1KA,H1KB,H1KC)
;
_shelx_res_checksum              1234
_shelx_hkl_checksum              68222
_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 1.290
_oxdiff_exptl_absorpt_empirical_full_min 0.721