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_7120297
_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         'C15 H41 Fe N2 P4 Si, C32 H12 B F24'
_chemical_formula_sum            'C47 H53 B F24 Fe N2 P4 Si'
_chemical_formula_weight         1320.54
_chemical_name_systematic        '[Fe(dmpe)2N2(SiMe3)][BArF4] '
_chemical_properties_physical    ', Air-sensitive,Moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_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                 89.9978(15)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.0435(3)
_cell_length_b                   37.6295(6)
_cell_length_c                   18.3435(4)
_cell_measurement_reflns_used    14175
_cell_measurement_temperature    173.00(14)
_cell_measurement_theta_max      27.8720
_cell_measurement_theta_min      2.5750
_cell_volume                     11764.4(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_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_temperature      173(2)
_diffrn_detector_area_resol_mean 16.0382
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.846
_diffrn_measurement_details
;
  1 omega  -39.00   51.00   0.3000    4.4150
omega____ theta____ kappa____ phi______ frames
    -      -13.1782   77.0000    0.0000 300

  2 omega  -81.00   11.10   0.3000    4.4150
omega____ theta____ kappa____ phi______ frames
    -      -13.1782  -77.0000 -120.0000 307

  3 omega   -2.00   82.00   0.3000    4.4150
omega____ theta____ kappa____ phi______ frames
    -       14.2719   57.0000  150.0000 280
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0236140000
_diffrn_orient_matrix_UB_12      -0.0018238000
_diffrn_orient_matrix_UB_13      0.0316266000
_diffrn_orient_matrix_UB_21      0.0336487000
_diffrn_orient_matrix_UB_22      -0.0047463000
_diffrn_orient_matrix_UB_23      0.0205688000
_diffrn_orient_matrix_UB_31      0.0064362000
_diffrn_orient_matrix_UB_32      0.0181462000
_diffrn_orient_matrix_UB_33      0.0085497000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0256
_diffrn_reflns_av_unetI/netI     0.0400
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.846
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_k_min       -49
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            66244
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.846
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.297
_diffrn_reflns_theta_min         2.286
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.496
_exptl_absorpt_correction_T_max  0.869
_exptl_absorpt_correction_T_min  0.812
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
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)
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.491
_exptl_crystal_F_000             5360
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: Et2O'
_exptl_crystal_size_max          0.6217
_exptl_crystal_size_mid          0.4827
_exptl_crystal_size_min          0.3315
_refine_diff_density_max         1.446
_refine_diff_density_min         -0.610
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1528
_refine_ls_number_reflns         24747
_refine_ls_number_restraints     731
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.1067
_refine_ls_R_factor_gt           0.0779
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1075P)^2^+26.4649P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2048
_refine_ls_wR_factor_ref         0.2281
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17516
_reflns_number_total             24747
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc04188h2.cif
_cod_data_source_block           ash1527
_cod_original_cell_volume        11764.3(3)
_cod_database_code               7120297
_chemical_oxdiff_formula         'C188 H212 B4 F96 Fe4 N8 P16 Si4'
_chemical_oxdiff_usercomment     LDFeN2DFBw
_reflns_odcompleteness_completeness 96.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
 F22A-C62 \\sim F24-C62 \\sim F23A-C62 \\sim F22-C62 \\sim F24A-C62 \\sim
F23-C62
 with sigma of 0.02
 F45-C93 \\sim F44A-C93 \\sim F43-C93 \\sim F45A-C93 \\sim F44-C93 \\sim
F43A-C93
 with sigma of 0.02
 F30-C70 \\sim F29A-C70 \\sim F28-C70 \\sim F30A-C70 \\sim F29-C70 \\sim
F28A-C70
 with sigma of 0.02
 F21-C61 \\sim F20A-C61 \\sim F19-C61 \\sim F21A-C61 \\sim F20-C61 \\sim
F19A-C61
 with sigma of 0.02
 F4-C38 \\sim F6A-C38 \\sim F5-C38 \\sim F4A-C38 \\sim F6-C38 \\sim F5A-C38
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F7 \\sim F8 \\sim F9
\\sim F10 \\sim F11 \\sim F12 \\sim F13 \\sim F14 \\sim F15 \\sim F16 \\sim F17
\\sim F18 \\sim F19 \\sim F20 \\sim F21 \\sim F22 \\sim F23 \\sim F24 \\sim F25
\\sim F26 \\sim F27 \\sim F28 \\sim F29 \\sim F30 \\sim F31 \\sim F32 \\sim F33
\\sim F34 \\sim F35 \\sim F36 \\sim F37 \\sim F38 \\sim F39 \\sim F40 \\sim F41
\\sim F42 \\sim F43 \\sim F44 \\sim F45 \\sim F46 \\sim F47 \\sim F48 \\sim
F23A \\sim F24A \\sim F22A \\sim F44A \\sim F43A \\sim F45A \\sim F29A \\sim
F30A \\sim F28A \\sim F20A \\sim F21A \\sim F19A \\sim F5A \\sim F6A \\sim F4A:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 C62, F24, F23A, F22, F24A, F23, F22A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C93, F44A, F43, F45A, F44, F43A, F45
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C70, F30, F29A, F28, F30A, F29, F28A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C61, F20A, F19, F21A, F20, F19A, F21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C38, F4, F6A, F5, F4A, F6, F5A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C45, F8, F9, F7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C46, F12, F10, F11
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C53, F15, F13, F14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C54, F18, F16, F17
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C37, F2, F3, F1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C69, F26, F25, F27
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C94, F48, F46, F47
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C77, F32, F31, F33
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C78, F35, F34, F36
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C86, F40, F41, F42
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C85, F39, F37, F38
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, C27, P8, C23, C22, P7, C25, C24, C20, C21, P6, C17, C16, P5, C18, C19,
 C3, C4, P2, C2, C1, P1, C5, C6, C12, C11, P3, C7, C8, C10, P4, C9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F23A)=Sof(F24A)=Sof(F22A)=1-FVAR(1)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(1)
 Sof(F44A)=Sof(F43A)=Sof(F45A)=1-FVAR(2)
 Sof(F43)=Sof(F44)=Sof(F45)=FVAR(2)
 Sof(F29A)=Sof(F30A)=Sof(F28A)=1-FVAR(3)
 Sof(F28)=Sof(F29)=Sof(F30)=FVAR(3)
 Sof(F20A)=Sof(F21A)=Sof(F19A)=1-FVAR(4)
 Sof(F19)=Sof(F20)=Sof(F21)=FVAR(4)
 Sof(F5A)=Sof(F6A)=Sof(F4A)=1-FVAR(5)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(5)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C7(H7A,H7B), C8(H8A,H8B), C16(H16A,H16B), C17(H17A,
 H17B), C22(H22A,H22B), C23(H23A,H23B)
6.b Aromatic/amide H refined with riding coordinates:
 C64(H64), C66(H66), C68(H68), C72(H72), C74(H74), C76(H76), C80(H80),
 C82(H82), C84(H84), C88(H88), C90(H90), C92(H92), C32(H32), C34(H34), C36(H36),
  C40(H40), C42(H42), C44(H44), C48(H48), C50(H50), C52(H52), C56(H56),
 C58(H58), C60(H60)
6.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C9(H9A,
 H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C24(H24A,
 H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C),
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              41091
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'