Activation of an Open Shell, Carbyne-Bridged Diiron Complex Toward Binding of Dinitrogen.
Arnett, Charles H.; Agapie, Theodor; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c01896

data_4135001
_publ_section_title
;
 Activation of an Open Shell, Carbyne-Bridged Diiron Complex Toward
 Binding of Dinitrogen.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c01896
_journal_year                    2020
_chemical_formula_moiety         'C55 H80 Fe2 N2 P6, C5 H12'
_chemical_formula_sum            'C60 H92 Fe2 N2 P6'
_chemical_formula_weight         1138.87
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-12-21
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.364(7)
_cell_length_b                   18.351(4)
_cell_length_c                   29.604(5)
_cell_measurement_reflns_used    9289
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      80.08
_cell_measurement_theta_min      2.98
_cell_volume                     11606(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'XS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0980
_diffrn_reflns_av_unetI/netI     0.0422
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            174786
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         80.707
_diffrn_reflns_theta_min         2.985
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.864
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.5663
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS-2016/2 (Bruker, 2016/2) was used.'
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.304
_exptl_crystal_description       block
_exptl_crystal_F_000             4864
_exptl_crystal_size_max          0.371
_exptl_crystal_size_mid          0.268
_exptl_crystal_size_min          0.161
_refine_diff_density_max         0.643
_refine_diff_density_min         -0.515
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.134
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     682
_refine_ls_number_reflns         12333
_refine_ls_number_restraints     140
_refine_ls_restrained_S_all      1.131
_refine_ls_R_factor_all          0.0883
_refine_ls_R_factor_gt           0.0703
_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^)+(0.0244P)^2^+49.2136P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1317
_refine_ls_wR_factor_ref         0.1406
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10260
_reflns_number_total             12333
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01896_si_001.cif
_cod_data_source_block           v19198
_cod_database_code               4135001
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.452
_shelx_estimated_absorpt_t_min   0.220
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H64A,H64B,H1} of C64, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H,H,H,H) groups, {H1A,H1B,H1C} of C1, {H49A,H49B,H49C} of C49,
  {H22A,H22B,H22C} of C22, {H48A,H48B,H48C} of C48, {H25A,H25B,H25C} of C25,
  {H46A,H46B,H46C} of C46, {H19A,H19B,H19C} of C19, {H20A,H20B,H20C} of C20,
  {H45A,H45B,H45C} of C45, {H23A,H23B,H23C} of C23, {H28A,H28B,H28C} of C28,
  {H51A,H51B,H51C} of C51, {H54A,H54B,H54C} of C54, {H55A,H55B,H55C} of C55,
  {H26A,H26B,H26C} of C26, {H52A,H52B,H52C} of C52, {H29A,H29B,H29C} of C29,
  {H56A,H56B,H56C} of C56
2. Rigid bond restraints
 C56, C57, C61, C62, C63, C64, C59, C60
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C56 \\sim C61 \\sim C57 \\sim C63 \\sim C62 \\sim C64 \\sim C59 \\sim C60:
within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 1.7A
4. Rigid body (RIGU) restrains
 C56, C61, C57, C63, C62, C64, C59, C60
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(C63)=Sof(H63A)=
 Sof(H63B)=1-FVAR(1)
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(C64)=Sof(H64A)=
 Sof(H64B)=FVAR(1)
 Sof(H60A)=Sof(H60B)=Sof(H60C)=1-FVAR(2)
 Sof(H60D)=Sof(H60E)=Sof(H60F)=FVAR(2)
6.a Everything fixed:
 H1
6.b Ternary CH refined with riding coordinates:
 C44(H44), C21(H21), C24(H24), C47(H47), C18(H18), C27(H27), C50(H50), C53(H53)
6.c Secondary CH2 refined with riding coordinates:
 C59(H59A,H59B), C61(H61A,H61B), C57(H57A,H57B), C62(H62A,H62B), C63(H63A,
 H63B), C64(H64A,H64B)
6.d Aromatic/amide H refined with riding coordinates:
 C5(H5), C4(H4), C39(H39), C7(H7), C16(H16), C35(H35), C42(H42), C34(H34),
 C30(H30), C40(H40), C13(H13), C8(H8), C9(H9), C41(H41), C10(H10), C14(H14),
 C15(H15), C33(H33), C36(H36)
6.e Idealised Me refined with riding coordinates:
 C56(H56A,H56B,H56C)
6.f Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C46(H46A,H46B,H46C), C49(H49A,H49B,H49C), C25(H25A,H25B,
 H25C), C22(H22A,H22B,H22C), C48(H48A,H48B,H48C), C45(H45A,H45B,H45C), C20(H20A,
 H20B,H20C), C23(H23A,H23B,H23C), C19(H19A,H19B,H19C), C51(H51A,H51B,H51C),
 C28(H28A,H28B,H28C), C55(H55A,H55B,H55C), C54(H54A,H54B,H54C), C26(H26A,H26B,
 H26C), C52(H52A,H52B,H52C), C29(H29A,H29B,H29C), C60(H60D,H60E,H60F), C60(H60A,
 H60B,H60C)
;
_shelx_res_checksum              66993
_shelx_hkl_checksum              4153
_olex2_submission_special_instructions 'No special instructions were received'