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_7123424
_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         'C94 H104 Co2 Mg N6 O4 P6'
_chemical_formula_sum            'C94 H104 Co2 Mg N6 O4 P6'
_chemical_formula_weight         1709.82
_chemical_name_systematic        2
_chemical_properties_physical    Air-sensitive,Moisture-sensitive,Hygroscopic
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   35.2041(4)
_cell_length_b                   18.5349(2)
_cell_length_c                   13.28584(19)
_cell_measurement_reflns_used    6681
_cell_measurement_temperature    174(3)
_cell_measurement_theta_max      72.8730
_cell_measurement_theta_min      3.4490
_cell_volume                     8669.07(18)
_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
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4115
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.969
_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    -70.00  31.00   1.00    8.89    --  -42.36  57.00   0.00  101
  2  \w    108.00 178.00   1.00   29.59    --  105.13  45.00-180.00   70
  3  \w     92.00 158.00   1.00   29.59    --  105.13  45.00 -60.00   66
  4  \w     73.00 166.00   1.00   29.59    --  105.13 125.00   0.00   93
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0365681000
_diffrn_orient_matrix_UB_12      -0.0101619000
_diffrn_orient_matrix_UB_13      0.0619953000
_diffrn_orient_matrix_UB_21      0.0213494000
_diffrn_orient_matrix_UB_22      -0.0509524000
_diffrn_orient_matrix_UB_23      0.0721023000
_diffrn_orient_matrix_UB_31      0.0109886000
_diffrn_orient_matrix_UB_32      0.0649093000
_diffrn_orient_matrix_UB_33      0.0663614000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0390
_diffrn_reflns_av_unetI/netI     0.0504
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       43
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            18064
_diffrn_reflns_point_group_measured_fraction_full 0.745
_diffrn_reflns_point_group_measured_fraction_max 0.715
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.167
_diffrn_reflns_theta_min         3.463
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.543
_exptl_absorpt_correction_T_max  0.234
_exptl_absorpt_correction_T_min  0.103
_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    1.310
_exptl_crystal_description       block
_exptl_crystal_F_000             3592
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.365
_exptl_crystal_size_mid          0.259
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.412
_refine_diff_density_min         -0.368
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.026(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1099
_refine_ls_number_reflns         12435
_refine_ls_number_restraints     55
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0539
_refine_ls_R_factor_gt           0.0455
_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^)+(0.0659P)^2^+0.7926P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1141
_refine_ls_wR_factor_ref         0.1235
_reflns_Friedel_coverage         0.412
_reflns_Friedel_fraction_full    0.474
_reflns_Friedel_fraction_max     0.437
_reflns_number_gt                10867
_reflns_number_total             12435
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc01496a2.cif
_cod_data_source_block           2
_cod_original_cell_volume        8669.08(18)
_cod_database_code               7123424
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C94 H104 Co2 Mg1 N6 O4 P6'
_chemical_oxdiff_usercomment     SA370
_shelx_estimated_absorpt_t_max   0.396
_shelx_estimated_absorpt_t_min   0.288
_reflns_odcompleteness_completeness 98.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 O91-C95 \\sim O91-C92
 with sigma of 0.02
 O91'-C95' \\sim O91'-C92'
 with sigma of 0.02
 C95-C94 \\sim C94-C93 \\sim C93-C92
 with sigma of 0.02
 C95'-C94' \\sim C94'-C93' \\sim C93'-C92'
 with sigma of 0.02
 C92-C94 \\sim C93-C95
 with sigma of 0.02
 C92'-C94' \\sim C93'-C95'
 with sigma of 0.02
 O91-C93 \\sim O91-C94
 with sigma of 0.02
 O91'-C93' \\sim O91'-C94'
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O91 \\sim O91' \\sim C92 \\sim C92' \\sim C93 \\sim C93' \\sim C94 \\sim C94'
\\sim C95 \\sim C95': within 1A with sigma of 0.002 and sigma for terminal
atoms of 0.002
O61 \\sim O61' \\sim C62 \\sim C62' \\sim C63 \\sim C63' \\sim C64 \\sim C64'
\\sim C65 \\sim C65': within 1A with sigma of 0.002 and sigma for terminal
atoms of 0.002
4. Others
 Sof(O61')=Sof(C62')=Sof(H62C)=Sof(H62D)=Sof(C63')=Sof(H63C)=Sof(H63D)=
 Sof(C64')=Sof(H64C)=Sof(H64D)=Sof(C65')=Sof(H65C)=Sof(H65D)=Sof(O71')=
 Sof(C72')=Sof(H72C)=Sof(H72D)=Sof(C73')=Sof(H73C)=Sof(H73D)=Sof(C74')=
 Sof(H74C)=Sof(H74D)=Sof(C75')=Sof(H75C)=Sof(H75D)=Sof(O81')=Sof(C82')=
 Sof(H82C)=Sof(H82D)=Sof(C83')=Sof(H83C)=Sof(H83D)=Sof(C84')=Sof(H84C)=
 Sof(H84D)=Sof(C85')=Sof(H85C)=Sof(H85D)=Sof(O91')=Sof(C92')=Sof(H92C)=
 Sof(H92D)=Sof(C93')=Sof(H93C)=Sof(H93D)=Sof(C94')=Sof(H94C)=Sof(H94D)=
 Sof(C95')=Sof(H95C)=Sof(H95D)=1-FVAR(1)
 Sof(O61)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(C64)=
 Sof(H64A)=Sof(H64B)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(O71)=Sof(C72)=Sof(H72A)=
 Sof(H72B)=Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(C75)=
 Sof(H75A)=Sof(H75B)=Sof(O81)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(C83)=Sof(H83A)=
 Sof(H83B)=Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(O91)=
 Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(C94)=Sof(H94A)=
 Sof(H94B)=Sof(C95)=Sof(H95A)=Sof(H95B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C2A(H2AA,H2AB), C2B(H2BA,H2BB), C4A(H4AA,H4AB), C4B(H4BA,H4BB), C6A(H6AA,
 H6AB), C6B(H6BA,H6BB), C62(H62A,H62B), C62'(H62C,H62D), C63(H63A,H63B),
 C63'(H63C,H63D), C64(H64A,H64B), C64'(H64C,H64D), C65(H65A,H65B), C65'(H65C,
 H65D), C72(H72A,H72B), C72'(H72C,H72D), C73(H73A,H73B), C73'(H73C,H73D),
 C74(H74A,H74B), C74'(H74C,H74D), C75(H75A,H75B), C75'(H75C,H75D), C82(H82A,
 H82B), C82'(H82C,H82D), C83(H83A,H83B), C83'(H83C,H83D), C84(H84A,H84B),
 C84'(H84C,H84D), C85(H85A,H85B), C85'(H85C,H85D), C92(H92A,H92B), C92'(H92C,
 H92D), C93(H93A,H93B), C93'(H93C,H93D), C94(H94A,H94B), C94'(H94C,H94D),
 C95(H95A,H95B), C95'(H95C,H95D)
5.b Aromatic/amide H refined with riding coordinates:
 C9A(H9A), C9B(H9B), C10A(H10A), C10B(H10B), C11A(H11A), C11B(H11B),
 C12A(H12A), C12B(H12B), C13A(H13A), C13B(H13B), C15A(H15A), C15B(H15B),
 C16A(H16A), C16B(H16B), C17A(H17A), C17B(H17B), C18A(H18A), C18B(H18B),
 C19A(H19A), C19B(H19B), C21A(H21A), C21B(H21B), C22A(H22A), C22B(H22B),
 C23A(H23A), C23B(H23B), C24A(H24A), C24B(H24B), C25A(H25A), C25B(H25B),
 C27A(H27A), C27B(H27B), C28A(H28A), C28B(H28B), C29A(H29A), C29B(H29B),
 C30A(H30A), C30B(H30B), C31A(H31A), C31B(H31B), C33A(H33A), C33B(H33B),
 C34A(H34A), C34B(H34B), C35A(H35A), C35B(H35B), C36A(H36A), C36B(H36B),
 C37A(H37A), C37B(H37B), C39A(H39A), C39B(H39B), C40A(H40A), C40B(H40B),
 C41A(H41A), C41B(H41B), C42A(H42A), C42B(H42B), C43A(H43A), C43B(H43B)
;
_shelx_res_checksum              75311
_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 1.193
_oxdiff_exptl_absorpt_empirical_full_min 0.869