Nickel-Catalyzed Skeletal Transformation of Tropone Derivatives via C–C Bond Activation: Catalyst-Controlled Access to Diverse Ring Systems
Kodama, Takuya; Saito, Kanako; Tobisu, Mamoru; Chemical Science  (2022) –; doi:10.1039/D2SC01394K

data_1566746
_publ_section_title
;
 Nickel-Catalyzed Skeletal Transformation of Tropone Derivatives via C--C
 Bond Activation: Catalyst-Controlled Access to Diverse Ring Systems
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC01394K
_journal_year                    2022
_chemical_formula_moiety         'C69 H76 Ni O P2'
_chemical_formula_sum            'C69 H76 Ni O P2'
_chemical_formula_weight         1041.94
_chemical_properties_physical    Air-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-02-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-10-14 deposited with the CCDC.	2022-04-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.0390(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   33.7405(2)
_cell_length_b                   13.53070(10)
_cell_length_c                   24.6084(2)
_cell_measurement_reflns_used    49740
_cell_measurement_temperature    123
_cell_measurement_theta_max      76.3760
_cell_measurement_theta_min      3.6840
_cell_volume                     10849.75(14)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      123
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9980
_diffrn_measured_fraction_theta_max 0.9644
_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    -92.00  -9.00   0.50    0.15    --  -47.45 118.00 168.00  166
  2  \w    -64.00 -33.00   0.50    0.61    -- -106.00  37.00  60.00   62
  3  \w   -112.00 -40.00   0.50    0.61    -- -106.00 118.00 168.00  144
  4  \w   -112.00 -87.00   0.50    0.61    -- -106.00  37.00  60.00   50
  5  \w   -118.00 -35.00   0.50    0.15    --  -47.45 -37.00 -30.00  166
  6  \w    -61.00 -33.00   0.50    0.61    -- -106.00  57.00-150.00   56
  7  \w    -60.00 -34.00   0.50    0.61    -- -106.00 125.00-120.00   52
  8  \w   -111.00 -85.00   0.50    0.61    -- -106.00 125.00-120.00   52
  9  \w   -116.00 -55.00   0.50    0.61    -- -106.00 125.00 -60.00  122
 10  \w   -121.00 -86.00   0.50    0.61    -- -106.00  57.00-150.00   70
 11  \w   -118.00 -40.00   0.50    0.61    -- -106.00  37.00-150.00  156
 12  \w   -139.00 -60.00   0.50    0.61    -- -106.00 158.00 -38.00  158
 13  \w   -177.00-104.00   0.50    0.61    -- -106.00 -19.00  60.00  146
 14  \w   -172.00-108.00   0.50    0.61    -- -106.00 -57.00   0.00  128
 15  \w    -97.00 -71.00   0.50    0.15    --  -47.45-125.00 120.00   52
 16  \w   -102.00 -70.00   0.50    0.15    --  -47.45-125.00 150.00   64
 17  \w   -108.00 -83.00   0.50    0.15    --  -47.45-158.00 -71.00   50
 18  \w    -86.00 -60.00   0.50    0.61    -- -106.00-158.00 -71.00   52
 19  \w     48.00  73.00   0.50    0.15    --   47.45-118.00  81.00   50
 20  \w     35.00  60.00   0.50    0.61    --   70.50-118.00  81.00   50
 21  \w     47.00  72.00   0.50    0.15    --   47.45-158.00 -71.00   50
 22  \w     59.00  84.00   0.50    0.61    --   70.50-158.00 -71.00   50
 23  \w     75.00 113.00   0.50    0.61    --   70.50 118.00 168.00   76
 24  \w     72.00 119.00   0.50    0.15    --   47.45 125.00 120.00   94
 25  \w     71.00 120.00   0.50    0.15    --   47.45 125.00  90.00   98
 26  \w     80.00 105.00   0.50    0.15    --   47.45 158.00 -38.00   50
 27  \w     71.00  96.00   0.50    0.61    --   70.50 158.00 -38.00   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      0.0060379000
_diffrn_orient_matrix_UB_12      -0.0641548000
_diffrn_orient_matrix_UB_13      0.0532730000
_diffrn_orient_matrix_UB_21      -0.0035072000
_diffrn_orient_matrix_UB_22      0.0927892000
_diffrn_orient_matrix_UB_23      0.0347139000
_diffrn_orient_matrix_UB_31      -0.0467501000
_diffrn_orient_matrix_UB_32      -0.0152329000
_diffrn_orient_matrix_UB_33      -0.0126986000
_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  0.0352
_diffrn_reflns_av_unetI/netI     0.0289
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            88681
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.590
_diffrn_reflns_theta_min         3.537
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.407
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63513
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.276
_exptl_crystal_description       prism
_exptl_crystal_F_000             4448
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.218
_exptl_crystal_size_min          0.104
_refine_diff_density_max         1.558
_refine_diff_density_min         -0.854
_refine_diff_density_rms         0.068
_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     1315
_refine_ls_number_reflns         21988
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0582
_refine_ls_R_factor_gt           0.0531
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0690P)^2^+14.0169P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1383
_refine_ls_wR_factor_ref         0.1423
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19674
_reflns_number_total             21988
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01394k2.cif
_cod_data_source_block           190519_tk01-120-1_toluene
_cod_depositor_comments
;

2025-05-14
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C138 H152 Ni2 O2 P4'
_cod_original_formula_weight         2083.89
_cod_original_formula_moiety         '2(C69 H76 Ni O P2)'
_cod_original_formula_units_Z            4
_cod_database_code               1566746
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C69 H76 O1 P2 Ni1'
_chemical_oxdiff_usercomment
'190519_TK01-120-1_Toluene_yellow C69 H76 O1 P2 Ni1'
_diffrn_oxdiff_ac3_digest_frames
;
010b24c746d3f0fbe1bc77ea34e8f272de00076e94f
;
_diffrn_oxdiff_ac3_digest_hkl
;
012326fb4e807852e2a077bd17231f53e9b5c0
;
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3), C13(H13), C19(H19), C31(H31), C41(H41), C25(H25), C47(H47), C53(H53)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C24(H24A,H24B), C8(H8A,H8B), C36(H36A,H36B),
 C4(H4A,H4B), C52(H52A,H52B), C20(H20A,H20B), C22(H22A,H22B), C23(H23A,H23B),
 C39(H39A,H39B), C50(H50A,H50B), C32(H32A,H32B), C38(H38A,H38B), C56(H56A,H56B),
  C48(H48A,H48B), C7(H7A,H7B), C30(H30A,H30B), C6(H6A,H6B), C35(H35A,H35B),
 C51(H51A,H51B), C5(H5A,H5B), C42(H42A,H42B), C46(H46A,H46B), C54(H54A,H54B),
 C29(H29A,H29B), C57(H57A,H57B), C21(H21A,H21B), C49(H49A,H49B), C58(H58A,H58B),
  C34(H34A,H34B), C55(H55A,H55B), C33(H33A,H33B), C28(H28A,H28B), C26(H26A,
 H26B), C43(H43A,H43B), C27(H27A,H27B), C45(H45A,H45B), C44(H44A,H44B),
 C16(H16A,H16B), C15(H15A,H15B), C17(H17A,H17B), C14(H14A,H14B), C18(H18A,H18B)
2.c Aromatic/amide H refined with riding coordinates:
 C71(H71), C93(H93), C62(H62), C86(H86), C77(H77), C87(H87), C102(H102),
 C85(H85), C92(H92), C65(H65), C81(H81), C106(H106), C137(H137), C64(H64),
 C89(H89), C70(H70), C115(H115), C108(H108), C83(H83), C114(H114), C63(H63),
 C98(H98), C109(H109), C80(H80), C90(H90), C112(H112), C91(H91), C84(H84),
 C101(H101), C100(H100), C78(H78), C107(H107), C69(H69), C121(H121), C133(H133),
  C136(H136), C68(H68), C125(H125), C99(H99), C113(H113), C135(H135), C79(H79),
 C146(H146), C142(H142), C123(H123), C122(H122), C130(H130), C131(H131),
 C129(H129), C124(H124), C134(H134), C145(H145), C127(H127), C143(H143),
 C144(H144), C128(H128)
;
_shelx_res_checksum              81998
_shelx_hkl_checksum              62197
_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 1.323
_oxdiff_exptl_absorpt_empirical_full_min 0.608