"Catch and release" of the Cp<sup>N3</sup> ligand using cobalt: dissociation, protonation, and C-H bond thermochemistry.
Luhach, Sanju; Lalancette, Roger A.; Prokopchuk, Demyan E.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 18865–18872; doi:10.1039/d4dt01560f

data_7716383
_publ_section_title
;
 "Catch and release" of the Cp<sup>N3</sup> ligand using cobalt:
 dissociation, protonation, and C-H bond thermochemistry.
;
_journal_issue                   47
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              18865
_journal_page_last               18872
_journal_paper_doi               10.1039/d4dt01560f
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         '2(B F4), C24 H29 N3, C2 H3 N'
_chemical_formula_sum            'C26 H32 B2 F8 N4'
_chemical_formula_weight         574.17
_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
_audit_creation_date             2024-02-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-05-27 deposited with the CCDC.	2024-06-18 downloaded from the CCDC.
;
_cell_angle_alpha                79.8160(11)
_cell_angle_beta                 84.9985(9)
_cell_angle_gamma                73.8252(12)
_cell_formula_units_Z            4
_cell_length_a                   10.38703(12)
_cell_length_b                   14.8503(2)
_cell_length_c                   19.1230(2)
_cell_measurement_reflns_used    34997
_cell_measurement_temperature    99.9(4)
_cell_measurement_theta_max      77.4040
_cell_measurement_theta_min      2.3230
_cell_volume                     2786.09(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXL-2018/3 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(4)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.959
_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    -76.00  26.00   0.50    0.25    --  -46.79  89.00 -17.00  204
  2  \w    -20.00  76.00   0.50    0.25    --   46.79 -89.00-133.00  192
  3  \w    -80.00 -19.00   0.50    1.01    --  -91.75  89.00 -17.00  122
  4  \w     37.00 105.00   0.50    1.01    --  109.46 -89.00-133.00  136
  5  \w    101.00 178.00   0.50    1.01    --  109.46  89.00 -17.00  154
  6  \w   -120.00 -82.00   0.50    0.25    --  -46.79 -57.00-180.00   76
  7  \w    -41.00  27.00   0.50    0.25    --  -46.79  38.00 -90.00  136
  8  \w    -37.00  29.00   0.50    0.25    --  -46.79  19.00 150.00  132
  9  \w   -119.00 -32.00   0.50    0.25    --  -46.79 -45.00-120.07  174
 10  \w    -29.00  52.00   0.50    0.25    --   46.79 -19.00 -60.00  162
 11  \w     82.00 120.00   0.50    0.25    --   46.79  57.00  90.00   76
 12  \w     82.00 120.00   0.50    0.25    --   46.79  57.00 -30.00   76
 13  \w    -41.00 -15.00   0.50    1.01    --  -91.75  15.00 -30.00   52
 14  \w    -41.00 -15.00   0.50    1.01    --  -91.75  15.00 -60.00   52
 15  \w    -41.00 -15.00   0.50    1.01    --  -91.75  15.00   0.00   52
 16  \w    -41.00 -15.00   0.50    1.01    --  -91.75  15.00-150.00   52
 17  \w    -41.00 -15.00   0.50    1.01    --  -91.75  15.00 120.00   52
 18  \w   -162.00 -87.00   0.50    1.01    --  -91.75-125.00 -60.00  150
 19  \w    -46.00 -19.00   0.50    1.01    --  -91.75  45.00 -90.00   54
 20  \w    -46.00 -19.00   0.50    1.01    --  -91.75  45.00   0.00   54
 21  \w    -62.00 -19.00   0.50    1.01    --  -91.75  61.00 -60.00   86
 22  \w    -41.00 -15.00   0.50    1.01    --  -91.75  15.00  30.00   52
 23  \w    -41.00 -15.00   0.50    1.01    --  -91.75  15.00  90.00   52
 24  \w   -164.00 -79.00   0.50    1.01    --  -91.75 -89.00-133.00  170
 25  \w   -164.00-100.00   0.50    1.01    --  -91.75 -77.00 -30.00  128
 26  \w   -164.00 -87.00   0.50    1.01    --  -91.75 -59.00 -70.83  154
 27  \w    -41.00 -15.00   0.50    1.01    --  -91.75  15.00 -90.00   52
 28  \w     37.00 105.00   0.50    1.01    --  109.46 -95.00   0.00  136
 29  \w     37.00  77.00   0.50    1.01    --  109.46 -61.00 120.00   80
 30  \w     37.00  77.00   0.50    1.01    --  109.46 -61.00 -90.00   80
 31  \w     37.00 105.00   0.50    1.01    --  109.46 -95.00 150.00  136
 32  \w     94.00 178.00   0.50    1.01    --  109.46  30.00 120.00  168
 33  \w     40.00 111.00   0.50    1.01    --  109.46-125.00 -60.00  142
 34  \w     37.00 105.00   0.50    1.01    --  109.46 -95.00 -30.00  136
 35  \w     40.00 111.00   0.50    1.01    --  109.46-125.00  90.00  142
 36  \w     37.00 105.00   0.50    1.01    --  109.46 -95.00 -60.00  136
 37  \w     37.00  77.00   0.50    1.01    --  109.46 -61.00-150.00   80
 38  \w     39.00 106.00   0.50    1.01    --  109.46 -97.00  72.31  134
 39  \w     37.00 105.00   0.50    1.01    --  109.46 -95.00-120.00  136
 40  \w     37.00 105.00   0.50    1.01    --  109.46 -95.00 120.00  136
 41  \w     37.00  77.00   0.50    1.01    --  109.46 -61.00  90.00   80
 42  \w     37.00  77.00   0.50    1.01    --  109.46 -61.00 -30.00   80
 43  \w     37.00 105.00   0.50    1.01    --  109.46 -95.00-180.00  136
 44  \w     95.00 178.00   0.50    1.01    --  109.46  45.00-180.00  166
 45  \w     37.00  77.00   0.50    1.01    --  109.46 -61.00 150.00   80
 46  \w     31.00 120.00   0.50    0.25    --   46.79  53.00 -13.27  178
 47  \w     31.00 108.00   0.50    0.25    --   46.79  54.00 162.59  154
 48  \w     31.00 120.00   0.50    0.25    --   46.79  54.00  68.39  178
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0260268000
_diffrn_orient_matrix_UB_12      -0.0988323000
_diffrn_orient_matrix_UB_13      0.0185707000
_diffrn_orient_matrix_UB_21      -0.0666648000
_diffrn_orient_matrix_UB_22      0.0159276000
_diffrn_orient_matrix_UB_23      -0.0716682000
_diffrn_orient_matrix_UB_31      0.1369858000
_diffrn_orient_matrix_UB_32      -0.0441579000
_diffrn_orient_matrix_UB_33      -0.0350576000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0417
_diffrn_reflns_av_unetI/netI     0.0290
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            53954
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         78.159
_diffrn_reflns_theta_min         2.349
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.022
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.771
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.369
_exptl_crystal_description       parallelepiped
_exptl_crystal_F_000             1192
_exptl_crystal_size_max          0.157
_exptl_crystal_size_mid          0.112
_exptl_crystal_size_min          0.108
_refine_diff_density_max         0.619
_refine_diff_density_min         -0.587
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     833
_refine_ls_number_reflns         11457
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0473
_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^)+(0.0576P)^2^+1.1142P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1149
_refine_ls_wR_factor_ref         0.1188
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10165
_reflns_number_total             11457
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01560f3.cif
_cod_data_source_block           230623ral_sk_88_100k
_cod_depositor_comments
'Adding full bibliography for 7716380--7716384.cif.'
_cod_original_cell_volume        2786.11(6)
_cod_database_code               7716383
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C26H32B2F8N4
_chemical_oxdiff_usercomment     ACN/ETHER
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(F5) \\sim Ueq, Uanis(F8) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
3. Others
 Sof(F14A)=Sof(F15A)=Sof(F13A)=Sof(F16A)=1-FVAR(1)
 Sof(F16)=Sof(F15)=Sof(F13)=Sof(F14)=FVAR(1)
 Sof(F5A)=Sof(F7A)=Sof(F8A)=Sof(F6A)=1-FVAR(2)
 Sof(F6)=Sof(F7)=Sof(F5)=Sof(F8)=FVAR(2)
 Sof(F9A)=Sof(F11A)=Sof(F12A)=1-FVAR(3)
 Sof(F9)=Sof(F11)=Sof(F12)=FVAR(3)
4.a Ternary CH refined with riding coordinates:
 C2(H2), C10(H10), C26(H26), C34(H34)
4.b Secondary CH2 refined with riding coordinates:
 C32(H32A,H32B), C33(H33A,H33B), C8(H8A,H8B), C9(H9A,H9B)
4.c Aromatic/amide H refined with riding coordinates:
 C38(H38), C42(H42), C41(H41), C39(H39), C40(H40), C20(H20), C24(H24),
 C22(H22), C23(H23), C21(H21), C14(H14), C18(H18), C17(H17), C15(H15), C16(H16),
  C48(H48), C44(H44), C47(H47), C46(H46), C45(H45), N1(H1), N4(H4)
4.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C30(H30A,H30B,H30C), C50(H50A,H50B,H50C), C52(H52A,H52B,
 H52C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C12(H12A,H12B,H12C), C11(H11A,H11B,
 H11C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C)
;
_shelx_res_checksum              34396
_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 1.705
_oxdiff_exptl_absorpt_empirical_full_min 0.712