Cationic silyldiazenido complexes of the Fe(diphosphine)2(N2) platform: structural and electronic models for an elusive first intermediate in N2 fixation
Piascik, Adam D.; Hill, Peter J.; Crawford, Andrew D.; Doyle, Laurence R.; Green, Jennifer; Ashley, Andrew Edward; Chem. Commun.  (2017) –; doi:10.1039/C7CC04188H

data_7120298
_publ_section_title
;
 Cationic silyldiazenido complexes of the Fe(diphosphine)2(N2) platform:
 structural and electronic models for an elusive first intermediate in N2
 fixation
;
_journal_name_full               'Chem. Commun.'
_journal_paper_doi               10.1039/C7CC04188H
_journal_year                    2017
_chemical_formula_moiety         'C23 H57 Fe N2 P4 Si, C32 H12 B F23.8'
_chemical_formula_sum            'C55 H69 B F24 Fe N2 P4 Si'
_chemical_formula_weight         1432.75
_chemical_name_systematic        '[Fe(depe)2N2(SiMe3)][BArF4] '
_chemical_properties_physical    ', Air-sensitive,Moisture-sensitive'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-09-04
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2017-05-24 deposited with the CCDC.
2017-06-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.9303(4)
_cell_length_b                   19.1287(6)
_cell_length_c                   26.3957(12)
_cell_measurement_reflns_used    4431
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      26.6900
_cell_measurement_theta_min      2.7440
_cell_volume                     6528.7(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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    'ShelXS (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.05(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0382
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.962
_diffrn_measured_fraction_theta_max 0.823
_diffrn_measurement_details
;
  1 omega  -25.00   26.00   1.0000   13.2800
omega____ theta____ kappa____ phi______ frames
    -      -13.1782  -99.0000   90.0000 51

  2 omega  -69.00   -6.00   1.0000   13.2800
omega____ theta____ kappa____ phi______ frames
    -      -13.1782  -57.0000 -150.0000 63
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0252277000
_diffrn_orient_matrix_UB_12      0.0151696000
_diffrn_orient_matrix_UB_13      -0.0211618000
_diffrn_orient_matrix_UB_21      -0.0438938000
_diffrn_orient_matrix_UB_22      -0.0071760000
_diffrn_orient_matrix_UB_23      -0.0152704000
_diffrn_orient_matrix_UB_31      -0.0211194000
_diffrn_orient_matrix_UB_32      0.0330724000
_diffrn_orient_matrix_UB_33      0.0063928000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0290
_diffrn_reflns_av_unetI/netI     0.0695
_diffrn_reflns_Laue_measured_fraction_full 0.962
_diffrn_reflns_Laue_measured_fraction_max 0.823
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            16034
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.825
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.242
_diffrn_reflns_theta_min         2.449
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.453
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94204
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.458
_exptl_crystal_F_000             2936
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Et2O'
_exptl_crystal_size_max          0.4229
_exptl_crystal_size_mid          0.3413
_exptl_crystal_size_min          0.1902
_refine_diff_density_max         0.465
_refine_diff_density_min         -0.364
_refine_diff_density_rms         0.084
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.53(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1007
_refine_ls_number_reflns         11810
_refine_ls_number_restraints     668
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0789
_refine_ls_R_factor_gt           0.0589
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0910P)^2^+1.4711P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1471
_refine_ls_wR_factor_ref         0.1666
_reflns_Friedel_coverage         0.836
_reflns_Friedel_fraction_full    0.972
_reflns_Friedel_fraction_max     0.827
_reflns_number_gt                9416
_reflns_number_total             11810
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc04188h2.cif
_cod_data_source_block           ash1517
_cod_database_code               7120298
_chemical_oxdiff_formula         'C23 H57 Fe N2 P4 Si'
_reflns_odcompleteness_completeness 98.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.47(3) 0.53(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 F21-C54 \\sim F20A-C54 \\sim F19-C54 \\sim F21A-C54 \\sim F20-C54 \\sim
F19A-C54
 with sigma of 0.02
 F13-C46 \\sim F15A-C46 \\sim F14-C46 \\sim F13A-C46 \\sim F15-C46 \\sim
F14A-C46
 with sigma of 0.02
 F4A-C31 \\sim F6-C31 \\sim F5A-C31 \\sim F4-C31 \\sim F6A-C31 \\sim F5-C31
 with sigma of 0.02
 F7A-C38 \\sim F9-C38 \\sim F8A-C38 \\sim F7-C38 \\sim F9A-C38 \\sim F8-C38
 with sigma of 0.02
 P3-C11 \\sim P3-C11A
 with sigma of 0.02
 C12-C11A \\sim C12-C11
 with sigma of 0.02
 F18-C47 \\sim F17A-C47 \\sim F16-C47 \\sim F18A-C47 \\sim F17-C47 \\sim
F16A-C47
 with sigma of 0.02
 F24-C55 \\sim F23A-C55 \\sim F22-C55 \\sim F24A-C55 \\sim F23-C55 \\sim
F22A-C55
 with sigma of 0.02
 F3A-C30 \\sim F2-C30 \\sim F1A-C30 \\sim F3-C30 \\sim F2A-C30 \\sim F1-C30
 with sigma of 0.02
 F11-C39 \\sim F12-C39 \\sim F10-C39
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F4A \\sim F5 \\sim F5A \\sim F6 \\sim F6A
\\sim F7 \\sim F7A \\sim F8 \\sim F8A \\sim F9 \\sim F9A \\sim F10 \\sim F11
\\sim F12 \\sim F13 \\sim F13A \\sim F14 \\sim F14A \\sim F15 \\sim F15A \\sim
F16 \\sim F17 \\sim F18 \\sim F19 \\sim F19A \\sim F20 \\sim F20A \\sim F21
\\sim F21A \\sim F22 \\sim F23 \\sim F24 \\sim F17A \\sim F18A \\sim F16A \\sim
F23A \\sim F24A \\sim F22A \\sim F2A \\sim F3A \\sim F1A: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 F4, F4A, F5, F5A, F6, F6A, C31
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F19, F19A, F20, F20A, F21, F21A, C54
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F13, F13A, F14, F14A, F15, F15A, C46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F7, F7A, F8, F8A, F9, F9A, C38
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C47, F18A, F17, F16A, F18, F17A, F16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C55, F22, F24A, F23, F22A, F24, F23A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C30, F2, F1A, F3, F2A, F1, F3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C39, F11, F12, F10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F4)=Sof(F5)=Sof(F6)=1-FVAR(1)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(1)
 Sof(F19)=Sof(F20)=Sof(F21)=1-FVAR(2)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=FVAR(2)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(3)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(3)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(4)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(4)
 Sof(H12C)=Sof(H12D)=Sof(C11A)=Sof(H11C)=Sof(H11D)=1-FVAR(5)
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H12A)=Sof(H12B)=FVAR(5)
 Sof(F17A)=Sof(F18A)=Sof(F16A)=1-FVAR(6)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(6)
 Sof(F23A)=Sof(F24A)=Sof(F22A)=1-FVAR(7)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(7)
 Sof(F2A)=Sof(F3A)=Sof(F1A)=1-FVAR(8)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(8)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(9)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C7(H7A,H7B), C9(H9A,H9B),
 C11(H11A,H11B), C12(H12A,H12B), C12(H12C,H12D), C13(H13A,H13B), C15(H15A,H15B),
  C17(H17A,H17B), C19(H19A,H19B), C11A(H11C,H11D)
7.b Aromatic/amide H refined with riding coordinates:
 C25(H25), C27(H27), C29(H29), C33(H33), C35(H35), C37(H37), C41(H41),
 C43(H43), C45(H45), C49(H49), C51(H51), C53(H53)
7.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C),
 C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              35121
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'