Dinitrogen activation by a phosphido-bridged binuclear cobalt complex
Li, Hai-Jun; Feng, Rui; Wang, Gao-Xiang; Wei, Junnian; Xi, Zhenfeng; Dalton Transactions  (2022) –; doi:10.1039/D2DT03320H

data_7711676
_publ_section_title
;
 Dinitrogen activation by a phosphido-bridged binuclear cobalt complex
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT03320H
_journal_year                    2022
_chemical_formula_moiety
'C48 H90 Co2 N4 P4, C18 H36 K N2 O6, 3(C4 H10 O)'
_chemical_formula_sum            'C78 H156 Co2 K N6 O9 P4'
_chemical_formula_weight         1602.92
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-07-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-07-31 deposited with the CCDC.	2022-10-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.471(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.9250(7)
_cell_length_b                   18.5369(4)
_cell_length_c                   17.6376(4)
_cell_measurement_reflns_used    20563
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      29.7600
_cell_measurement_theta_min      2.5370
_cell_volume                     9196.7(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.995
_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    -86.00  36.00   0.50    6.69    --  -13.00 -38.00  90.00  244
  2  \w    -76.00 -20.00   0.50    6.69    --   13.00 -82.00  90.00  112
  3  \w     -4.00  22.00   0.50    6.69    --   13.00 -82.00  90.00   52
  4  \w    -15.00  91.00   0.50    6.69    --   13.00  57.00 -90.00  212
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0006412000
_diffrn_orient_matrix_UB_12      0.0359949000
_diffrn_orient_matrix_UB_13      0.0133305000
_diffrn_orient_matrix_UB_21      0.0155690000
_diffrn_orient_matrix_UB_22      0.0107186000
_diffrn_orient_matrix_UB_23      -0.0236260000
_diffrn_orient_matrix_UB_31      -0.0198497000
_diffrn_orient_matrix_UB_32      0.0073147000
_diffrn_orient_matrix_UB_33      -0.0311710000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0217
_diffrn_reflns_av_unetI/netI     0.0239
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            33343
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.482
_diffrn_reflns_theta_min         2.375
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.527
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70538
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.33c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dull dark red'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.158
_exptl_crystal_description       block
_exptl_crystal_F_000             3484
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.535
_refine_diff_density_min         -0.339
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     600
_refine_ls_number_reflns         10505
_refine_ls_number_restraints     696
_refine_ls_restrained_S_all      1.122
_refine_ls_R_factor_all          0.0506
_refine_ls_R_factor_gt           0.0419
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0461P)^2^+14.0122P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1071
_refine_ls_wR_factor_ref         0.1121
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9007
_reflns_number_total             10505
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03320h2.cif
_cod_data_source_block           exp_9082
_cod_database_code               7711676
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N P O Co K'
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.974
_reflns_odcompleteness_completeness 99.64
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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
 C40-C41 = O5-C40 = O5-C39 = C38-C39
 1.54 with sigma of 0.01
 C41-O5
 2.5 with sigma of 0.04
 C40-C39
 2.5 with sigma of 0.04
 O5-C38
 2.5 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C39 \\sim C41 \\sim C40 \\sim C38 \\sim O5 \\sim H41A \\sim H41B \\sim H41C
\\sim H38C \\sim H40A \\sim H40B \\sim H39A \\sim H39B: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
C41 \\sim C40 \\sim C39 \\sim O5 \\sim C38: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 1.7A
All non-hydrogen atoms have similar U: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 2A
Uanis(C41) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(C39)
\\sim Ueq, Uanis(C38) \\sim Ueq: with sigma of 0.05 and sigma for terminal
atoms of 0.1
4. Others
 Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(C1A)=Sof(H1A)=Sof(C7A)=Sof(H7A)=Sof(C12A)=
 Sof(H12C)=Sof(H12D)=Sof(P1A)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(C5A)=Sof(H5AA)=
 Sof(H5AB)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C4A)=
 Sof(H4AA)=Sof(H4AB)=Sof(C11A)=Sof(H11A)=Sof(H11B)=Sof(C10A)=Sof(H10C)=
 Sof(H10D)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=1-FVAR(1)
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C1)=Sof(H1)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C3)=
 Sof(H3A)=Sof(H3B)=Sof(C7)=Sof(H7)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C12)=Sof(H12A)=
 Sof(H12B)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(P1)=Sof(C10)=
 Sof(H10A)=Sof(H10B)=Sof(C11)=Sof(H11C)=Sof(H11D)=Sof(C9)=Sof(H9A)=Sof(H9B)=
 FVAR(1)
 Fixed Sof: C39(0.5) H39A(0.5) H39B(0.5) C41(0.5) H41A(0.5) H41B(0.5)
 H41C(0.5) C40(0.5) H40A(0.5) H40B(0.5) C38(0.5) H38A(0.5) H38B(0.5) H38C(0.5)
 O5(0.5)
5.a Ternary CH refined with riding coordinates:
 C13(H13), C19(H19), C1(H1), C7(H7), C1A(H1A), C7A(H7A)
5.b Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B), C32(H32A,H32B), C18(H18A,H18B), C28(H28A,H28B), C14(H14A,
 H14B), C25(H25A,H25B), C33(H33A,H33B), C30(H30A,H30B), C29(H29A,H29B),
 C26(H26A,H26B), C27(H27A,H27B), C24(H24A,H24B), C15(H15A,H15B), C17(H17A,H17B),
  C16(H16A,H16B), C22(H22A,H22B), C23(H23A,H23B), C20(H20A,H20B), C21(H21A,
 H21B), C35(H35A,H35B), C36(H36A,H36B), C2(H2A,H2B), C8(H8A,H8B), C3(H3A,H3B),
 C6(H6A,H6B), C12(H12A,H12B), C9A(H9AA,H9AB), C4(H4A,H4B), C5(H5A,H5B),
 C12A(H12C,H12D), C6A(H6AA,H6AB), C5A(H5AA,H5AB), C2A(H2AA,H2AB), C3A(H3AA,
 H3AB), C4A(H4AA,H4AB), C10(H10A,H10B), C11A(H11A,H11B), C11(H11C,H11D), C9(H9A,
 H9B), C10A(H10C,H10D), C8A(H8AA,H8AB), C39(H39A,H39B), C40(H40A,H40B)
5.c Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C37(H37A,H37B,H37C), C41(H41A,H41B,H41C), C38(H38A,H38B,
 H38C)
;
_shelx_res_checksum              49926
_shelx_hkl_checksum              47675
_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 1.481
_oxdiff_exptl_absorpt_empirical_full_min 0.730