A Well-Defined Isocyano Analogue of HCo(CO)4. 1: Synthesis, Decomposition, and Catalytic 1,1-Hydrogenation of Isocyanides
Carpenter, Alex E.; Rheingold, Arnold L.; Figueroa, Joshua S.; Organometallics 35 (2016) 2309–; doi:10.1021/acs.organomet.6b00297

data_4088672
_publ_section_title
;
 A Well-Defined Isocyano Analogue of HCo(CO)4. 1: Synthesis,
 Decomposition, and Catalytic 1,1-Hydrogenation of Isocyanides
;
_journal_issue                   14
_journal_name_full               Organometallics
_journal_page_first              2309
_journal_paper_doi               10.1021/acs.organomet.6b00297
_journal_volume                  35
_journal_year                    2016
_chemical_formula_moiety
'C80 H85 Co N4, 0.5(C7 H8), 0.45(C5 H12), 0.125(C4 H8 O), 0.25(C2 H3 N)'
_chemical_formula_sum            'C85.625 H93.375 Co N4.25 O0.125'
_chemical_formula_weight         1242.94
_chemical_melting_point          ?
_chemical_name_common            CoH(t-BuNC)(CNArMes2)3
_chemical_name_systematic
; 
 'hydridotetrakis(2,6-dimesitylphenylioscyanide)(tert-butylisocyanide)cobalt'
;
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-08-21
_audit_creation_method
; 
Olex2 1.2-beta 
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862) 
;
_cell_angle_alpha                88.505(2)
_cell_angle_beta                 84.345(2)
_cell_angle_gamma                86.6950(10)
_cell_formula_units_Z            4
_cell_length_a                   14.7093(6)
_cell_length_b                   20.7346(8)
_cell_length_c                   24.4314(11)
_cell_measurement_reflns_used    9994
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.892
_cell_measurement_theta_min      2.502
_cell_volume                     7401.2(5)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 8.0
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0874
_diffrn_reflns_av_unetI/netI     0.0810
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            97111
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.439
_diffrn_reflns_theta_min         2.348
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.278
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6942
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; 
SADABS-2008/1 (Bruker,2008) was used for absorption correction. 
wR2(int) was 0.1501 before and 0.0509 after correction. 
The Ratio of minimum to maximum transmission is 0.9316. 
The \l/2 correction factor is 0.0015. 
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.115
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Block
_exptl_crystal_F_000             2660
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.062
_refine_diff_density_min         -0.804
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1710
_refine_ls_number_reflns         27144
_refine_ls_number_restraints     31
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1150
_refine_ls_R_factor_gt           0.0631
_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^)+(0.0881P)^2^+5.4052P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1545
_refine_ls_wR_factor_ref         0.1802
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17471
_reflns_number_total             27144
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00297_si_002.cif
_cod_data_source_block           jfig715_0m
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value 'Not measured' was changed
to '?' -- the value is undefined or not given.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 

2026-05-15
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_weight         2485.89
_cod_original_formula_moiety
'2(C80 H85 Co N4), C7 H8, C2.25 H5.25, 0.25(C4 H8 O), 0.5(C2 H3 N)'
_cod_original_formula_units_Z            2
_cod_original_formula_sum        'C171.25 H186.75 Co2 N8.50 O0.25'
_cod_database_code               4088672
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.973
_shelx_estimated_absorpt_t_min   0.947
_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 
 C11S-O1S = O1S-C8S 
 1.4 with sigma of 0.02 
 C11S-C10S = C9S-C8S 
 1.35 with sigma of 0.02 
3. Uiso/Uaniso restraints and constraints 
Uanis(C26B) \\sim Ueq, Uanis(C24B) \\sim Ueq, Uanis(C23B) \\sim Ueq, 
Uanis(C25B) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2 
Uanis(C3S) = Uanis(C4S) = Uanis(C5S) = Uanis(C6S) = Uanis(C8S) 
Uanis(C9S) = Uanis(C8S) = Uanis(C11S) = Uanis(C10S) = Uanis(O1S) 
Uanis(C8S) = Uanis(C6S) = Uanis(C5S) = Uanis(C4S) = Uanis(C3S) 
Uanis(C7S) = Uanis(C6S) = Uanis(C5S) = Uanis(C4S) = Uanis(C3S) 
4. Rigid body (RIGU) restrains 
 C11S, C10S, C9S 
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004 
 C3S, C4S, C5S, C6S 
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004 
5. Others 
 Fixed Sof: C3S(0.25) H3SA(0.25) H3SB(0.25) H3SC(0.25) C4S(0.5) H4SA(0.5) 
 H4SB(0.5) C5S(0.25) H5SA(0.25) H5SB(0.25) C6S(0.5) H6SA(0.5) H6SB(0.5) 
 C7S(0.5) H7SA(0.5) H7SB(0.5) H7SC(0.5) O1S(0.25) C8S(0.25) H8SA(0.25) 
 H8SB(0.25) C9S(0.25) H9SA(0.25) H9SB(0.25) C10S(0.5) H10A(0.5) H10B(0.5) 
 C11S(0.25) H11A(0.25) H11B(0.25) N1S(0.5) C1S(0.5) H1SA(0.5) H1SB(0.5) 
 H1SC(0.5) C2S(0.5) 
6.a Secondary CH2 refined with riding coordinates: 
 C4S(H4SA,H4SB), C5S(H5SA,H5SB), C6S(H6SA,H6SB), C8S(H8SA,H8SB), C9S(H9SA, 
 H9SB), C10S(H10A,H10B), C11S(H11A,H11B) 
6.b Aromatic/amide H refined with riding coordinates: 
 C7B(H7B), C8B(H8B), C9B(H9B), C14B(H14B), C17B(H17B), C23B(H23B), C26B(H26B), 
 C31B(H31B), C32B(H32B), C33B(H33B), C38B(H38B), C41B(H41B), C47B(H47B), 
 C50B(H50B), C55B(H55B), C56B(H56B), C57B(H57B), C62B(H62B), C65B(H65B), 
 C71B(H71B), C74B(H74B), C7A(H7A), C8A(H8A), C9A(H9A), C14A(H14A), C17A(H17A), 
 C23A(H23A), C26A(H26A), C31A(H31A), C32A(H32A), C33A(H33A), C38A(H38A), 
 C41A(H41A), C47A(H47A), C50A(H50A), C55A(H55A), C56A(H56A), C57A(H57A), 
 C62A(H62A), C65A(H65A), C71A(H71A), C74A(H74A), C148(H148), C154(H154), 
 C169(H169), C172(H172), C173(H173) 
6.c Idealised Me refined with everything fixed: 
 C7S(H7SA,H7SB,H7SC) 
6.d Idealised Me refined as rotating group: 
 C13B(H13A,H13B,H13C), C16B(H16A,H16B,H16C), C19B(H19A,H19B,H19C), C22B(H22A, 
 H22B,H22C), C25B(H25A,H25B,H25C), C28B(H28A,H28B,H28C), C37B(H37A,H37B,H37C), 
 C40B(H40A,H40B,H40C), C43B(H43A,H43B,H43C), C46B(H46A,H46B,H46C), C49B(H49A, 
 H49B,H49C), C52B(H52A,H52B,H52C), C61B(H61A,H61B,H61C), C64B(H64A,H64B,H64C), 
 C67B(H67A,H67B,H67C), C70B(H70A,H70B,H70C), C73B(H73A,H73B,H73C), C76B(H76A, 
 H76B,H76C), C77B(H77A,H77B,H77C), C79B(H79A,H79B,H79C), C80B(H80A,H80B,H80C), 
 C13A(H13D,H13E,H13F), C16A(H16D,H16E,H16F), C19A(H19D,H19E,H19F), C22A(H22D, 
 H22E,H22F), C25A(H25D,H25E,H25F), C28A(H28D,H28E,H28F), C37A(H37D,H37E,H37F), 
 C40A(H40D,H40E,H40F), C43A(H43D,H43E,H43F), C46A(H46D,H46E,H46F), C49A(H49D, 
 H49E,H49F), C52A(H52D,H52E,H52F), C61A(H61D,H61E,H61F), C64A(H64D,H64E,H64F), 
 C67A(H67D,H67E,H67F), C70A(H70D,H70E,H70F), C73A(H73D,H73E,H73F), C76A(H76D, 
 H76E,H76F), C78A(H78A,H78B,H78C), C79A(H79D,H79E,H79F), C80A(H80D,H80E,H80F), 
 C174(H17C,H17D,H17E), C3S(H3SA,H3SB,H3SC), C1S(H1SA,H1SB,H1SC) 
;
_shelx_res_checksum              30282
_shelx_hkl_checksum              39891
_olex2_submission_special_instructions 'No special instructions were received'