Rotation-Triggered Transmetalation on a Heterobimetallic Cu/Al <i>N</i>-Phosphine-Oxide-Substituted Imidazolylidene Complex.
Asada, Takahiro; Hoshimoto, Yoichi; Ogoshi, Sensuke; Journal of the American Chemical Society 142 (2020) 9772–9784; doi:10.1021/jacs.0c03252

data_4134978
_publ_section_title
;
 Rotation-Triggered Transmetalation on a Heterobimetallic Cu/Al
 <i>N</i>-Phosphine-Oxide-Substituted Imidazolylidene Complex.
;
_journal_issue                   21
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9772
_journal_page_last               9784
_journal_paper_doi               10.1021/jacs.0c03252
_journal_volume                  142
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C27 H46 Cu N2 O2 P, C4 H8 O'
_chemical_formula_sum            'C31 H54 Cu N2 O3 P'
_chemical_formula_weight         597.30
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_Int_Tables_number      33
_atom_sites_solution_primary     dual
_audit_creation_date             2019-08-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.7593(3)
_cell_length_b                   13.3807(2)
_cell_length_c                   21.4965(3)
_cell_measurement_reflns_used    37387
_cell_measurement_temperature    123.15
_cell_measurement_theta_max      74.1040
_cell_measurement_theta_min      3.7130
_cell_volume                     6834.08(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      123.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9798
_diffrn_measured_fraction_theta_max 0.9798
_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    -65.00  31.00   0.50    0.05    --  -42.80  59.00 -61.00  192
  2  \w   -109.00 -21.00   0.50    0.05    --  -42.80 -59.00 157.00  176
  3  \w     86.00 112.00   0.50    0.05    --   42.80  59.00 -61.00   52
  4  \w     25.00  70.00   0.50    0.05    --   42.80  59.00 -61.00   90
  5  \w     54.00  89.00   0.50    0.16    --   76.50  59.00 -61.00   70
  6  \w     26.00  51.00   0.50    0.16    --   76.50 -59.00 157.00   50
  7  \w   -170.00 -84.00   0.50    0.16    -- -106.00 -59.00 157.00  172
  8  \w   -127.00 -32.00   0.50    0.16    -- -106.00  59.00 -61.00  190
  9  \w    -95.00 -16.00   0.50    0.05    --  -42.80 125.00 -90.00  158
 10  \w    -55.00  31.00   0.50    0.05    --  -42.80  57.00-180.00  172
 11  \w    -94.00 -69.00   0.50    0.05    --  -42.80 125.00 120.00   50
 12  \w    -27.00  -1.00   0.50    0.05    --  -42.80  57.00  60.00   52
 13  \w    -41.00 -16.00   0.50    0.05    --  -42.80 125.00 120.00   50
 14  \w    -16.00   9.00   0.50    0.05    --   42.80 -59.00 157.00   50
 15  \w     71.00 133.00   0.50    0.16    --   76.50 125.00-150.00  124
 16  \w     73.00 120.00   0.50    0.16    --   76.50 125.00-180.00   94
 17  \w   -115.00 -70.00   0.50    0.16    -- -106.00 125.00 120.00   90
 18  \w   -117.00 -40.00   0.50    0.16    -- -106.00 125.00  30.00  154
 19  \w    -75.00 -34.00   0.50    0.16    -- -106.00  57.00 150.00   82
 20  \w   -122.00 -96.00   0.50    0.16    -- -106.00 -37.00   0.00   52
 21  \w   -132.00 -97.00   0.50    0.16    -- -106.00 -37.00-150.00   70
 22  \w   -167.00-112.00   0.50    0.16    -- -106.00 -19.00  90.00  110
 23  \w   -134.00 -32.00   0.50    0.16    -- -106.00  77.00 -60.00  204
 24  \w   -177.00-143.00   0.50    0.16    -- -106.00 -57.00-180.00   68
 25  \w   -177.00 -91.00   0.50    0.16    -- -106.00 -37.00-120.00  172
 26  \w    -93.00 -49.00   0.50    0.16    -- -106.00 125.00  90.00   88
 27  \w    -67.00 -38.00   0.50    0.16    -- -106.00 125.00   0.00   58
 28  \w   -138.00 -92.00   0.50    0.16    -- -106.00 -57.00-180.00   92
 29  \w   -177.00-116.00   0.50    0.16    -- -106.00 -99.00 -60.00  122
 30  \w   -117.00 -92.00   0.50    0.16    -- -106.00 125.00-180.00   50
 31  \w   -153.00 -79.00   0.50    0.16    -- -106.00 -77.00 -30.00  148
 32  \w   -117.00 -71.00   0.50    0.16    -- -106.00 125.00   0.00   92
 33  \w   -169.00 -81.00   0.50    0.16    -- -106.00-125.00-120.00  176
 34  \w   -173.00-106.00   0.50    0.16    -- -106.00 -99.00   0.00  134
 35  \w   -111.00 -32.00   0.50    0.16    -- -106.00 125.00 -60.00  158
 36  \w   -128.00-103.00   0.50    0.16    -- -106.00  57.00 150.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0303548000
_diffrn_orient_matrix_UB_12      -0.0058651000
_diffrn_orient_matrix_UB_13      0.0632555000
_diffrn_orient_matrix_UB_21      0.0335142000
_diffrn_orient_matrix_UB_22      -0.0913445000
_diffrn_orient_matrix_UB_23      -0.0229669000
_diffrn_orient_matrix_UB_31      0.0464818000
_diffrn_orient_matrix_UB_32      0.0697416000
_diffrn_orient_matrix_UB_33      -0.0247210000
_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  0.1048
_diffrn_reflns_av_unetI/netI     0.0505
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            63548
_diffrn_reflns_theta_full        68.2500
_diffrn_reflns_theta_max         68.25
_diffrn_reflns_theta_min         3.72
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.572
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78717
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.43a (Rigaku Oxford Diffraction, 2019)
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    1.1610
_exptl_crystal_description       block
_exptl_crystal_F_000             2568.8090
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.7779
_refine_diff_density_min         -1.2935
_refine_diff_density_rms         0.0932
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   -0.01(4)
_refine_ls_d_res_high            0.8300
_refine_ls_d_res_low             11.8797
_refine_ls_goodness_of_fit_ref   1.2656
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    156
_refine_ls_number_parameters     712
_refine_ls_number_reflns         12279
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.2656
_refine_ls_R_factor_all          0.0905
_refine_ls_R_factor_gt           0.0805
_refine_ls_shift/su_max          0.0003
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2384
_refine_ls_wR_factor_ref         0.2845
_reflns_Friedel_coverage         0.961
_reflns_limit_h_max              28
_reflns_limit_h_min              -28
_reflns_limit_k_max              16
_reflns_limit_k_min              -16
_reflns_limit_l_max              25
_reflns_limit_l_min              -25
_reflns_number_gt                10996
_reflns_number_total             12279
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            ja0c03252_si_002.cif
_cod_data_source_block           4a
_cod_depositor_comments
;
Adding full bibliography for 4134972--4134984.cif.

2025-07-29
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C62 H108 Cu2 N4 O6 P2'
_cod_original_formula_weight         1194.61
_cod_original_formula_moiety         '2(C27 H46 Cu N2 O2 P), 2(C4 H8 O)'
_cod_original_formula_units_Z            4
_cod_original_sg_symbol_Hall     ' P 2c -2n'
_cod_database_code               4134978
_chemical_oxdiff_formula         'C27 H46 Cu1 N2 O2 P1'
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.795127
 0.204873
2. 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
3.a Ternary CH refined with riding coordinates:
 C54(H54), C51(H51), C27(H27), C24(H24)
3.b Secondary CH2 refined with riding coordinates:
 C80(H80a,H80b), C84(H84a,H84b), C77(H77a,H77b), C79(H79a,H79b), C81(H81a,
 H81b), C78(H78a,H78b), C83(H83a,H83b), C82(H82a,H82b)
3.c Aromatic/amide H refined with riding coordinates:
 C39(H39), C10(H10), C40(H40), C5(H5), C7(H7), C33(H33), C6(H6), C34(H34),
 C32(H32), C11(H11)
3.d Idealised Me refined as rotating group:
 C16(H16a,H16b,H16c), C43(H43a,H43b,H43c), C17(H17a,H17b,H17c), C48(H48a,H48b,
 H48c), C46(H46a,H46b,H46c), C21(H21a,H21b,H21c), C19(H19a,H19b,H19c), C22(H22a,
 H22b,H22c), C44(H44a,H44b,H44c), C29(H29a,H29b,H29c), C20(H20a,H20b,H20c),
 C64(H64a,H64b,H64c), C49(H49a,H49b,H49c), C59(H59a,H59b,H59c), C65(H65a,H65b,
 H65c), C47(H47a,H47b,H47c), C66(H66a,H66b,H66c), C53(H53a,H53b,H53c), C28(H28a,
 H28b,H28c), C26(H26a,H26b,H26c), C56(H56a,H56b,H56c), C25(H25a,H25b,H25c),
 C60(H60a,H60b,H60c), C61(H61a,H61b,H61c), C52(H52a,H52b,H52c), C55(H55a,H55b,
 H55c)
;
_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 2.087
_oxdiff_exptl_absorpt_empirical_full_min 0.539