Cobalt-triphos dinitrogen complexes: activation and silyl-functionalisation of N2
Apps, Samantha; Miller, Philip; Long, Nicholas J.; Chemical Communications  (2019) –; doi:10.1039/C9CC01496A

data_7123426
_publ_section_title
;
 Cobalt-triphos dinitrogen complexes: activation and
 silyl-functionalisation of N2
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC01496A
_journal_year                    2019
_chemical_formula_moiety         'C66 H62 Co2 N2 P6, 2(C4 H8 O)'
_chemical_formula_sum            'C74 H78 Co2 N2 O2 P6'
_chemical_formula_weight         1331.06
_chemical_name_systematic        4
_chemical_properties_physical    Air-sensitive,Moisture-sensitive,Hygroscopic
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-02-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-02-14 deposited with the CCDC.    2019-05-10 downloaded from the CCDC.
;
_cell_angle_alpha                66.762(6)
_cell_angle_beta                 87.116(5)
_cell_angle_gamma                88.787(6)
_cell_formula_units_Z            1
_cell_length_a                   11.2875(8)
_cell_length_b                   11.4069(8)
_cell_length_c                   13.6863(8)
_cell_measurement_reflns_used    2671
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      28.1610
_cell_measurement_theta_min      2.6450
_cell_volume                     1617.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0382
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.807
_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    -40.00  54.00   1.00    5.91    --  -13.33  77.00-120.00   94
  2  \w    -79.00  13.00   1.00    5.91    --  -13.33 -77.00 120.00   92
  3  \w     -2.00  82.00   1.00    5.91    --   14.43  57.00  30.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0425901000
_diffrn_orient_matrix_UB_12      0.0420639000
_diffrn_orient_matrix_UB_13      0.0084463000
_diffrn_orient_matrix_UB_21      0.0462648000
_diffrn_orient_matrix_UB_22      0.0401761000
_diffrn_orient_matrix_UB_23      0.0017108000
_diffrn_orient_matrix_UB_31      -0.0021200000
_diffrn_orient_matrix_UB_32      0.0345832000
_diffrn_orient_matrix_UB_33      -0.0557986000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0383
_diffrn_reflns_av_unetI/netI     0.0777
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.807
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            9470
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.807
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.190
_diffrn_reflns_theta_min         2.482
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.710
_exptl_absorpt_correction_T_max  0.952
_exptl_absorpt_correction_T_min  0.714
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.367
_exptl_crystal_description       block
_exptl_crystal_F_000             696
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.63
_exptl_crystal_size_mid          0.43
_exptl_crystal_size_min          0.064
_refine_diff_density_max         1.018
_refine_diff_density_min         -0.718
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     409
_refine_ls_number_reflns         6404
_refine_ls_number_restraints     57
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0773
_refine_ls_R_factor_gt           0.0534
_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^)+(0.0634P)^2^+0.5884P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1266
_refine_ls_wR_factor_ref         0.1445
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4848
_reflns_number_total             6404
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc01496a2.cif
_cod_data_source_block           4
_cod_database_code               7123426
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C66 H62 Co2 N2 P6'
_chemical_oxdiff_usercomment     SA199
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.663
_reflns_odcompleteness_completeness 99.13
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 O41-C42 \\sim O41-C45 \\sim O41A-C42A \\sim O41A-C45A
 with sigma of 0.02
 C42-C43 \\sim C43-C44 \\sim C44-C45 \\sim C42A-C43A \\sim C43A-C44A \\sim
C44A-C45A
 with sigma of 0.02
 O41-C43 \\sim O41-C44 \\sim O41A-C43A \\sim O41A-C44A
 with sigma of 0.02
 C42-C44 \\sim C43-C45 \\sim C42A-C44A \\sim C43A-C45A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim O41A \\sim C42A \\sim C43A
\\sim C44A \\sim C45A: within 1A with sigma of 0.02 and sigma for terminal
atoms of 0.02
4. Others
 Sof(O41A)=Sof(C42A)=Sof(H42C)=Sof(H42D)=Sof(C43A)=Sof(H43C)=Sof(H43D)=
 Sof(C44A)=Sof(H44C)=Sof(H44D)=Sof(C45A)=Sof(H45C)=Sof(H45D)=1-FVAR(1)
 Sof(O41)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(C44)=
 Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=Sof(H45B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C4(H4A,H4B), C6(H6A,H6B), C42(H42A,H42B), C43(H43A,H43B),
 C44(H44A,H44B), C45(H45A,H45B), C42A(H42C,H42D), C43A(H43C,H43D), C44A(H44C,
 H44D), C45A(H45C,H45D)
5.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15), C16(H16), C17(H17),
 C18(H18), C19(H19), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C27(H27),
  C28(H28), C29(H29), C30(H30), C31(H31), C33(H33), C34(H34), C35(H35),
 C36(H36), C37(H37)
;
_shelx_res_checksum              9305
_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 1.240
_oxdiff_exptl_absorpt_empirical_full_min 0.822