Catalytic N2 Reduction to Silylamines and Thermodynamics of N2 Binding at Square Planar Fe.
Prokopchuk, Demyan E.; Wiedner, Eric S.; Walter, Eric D.; Popescu, Codrina V.; Piro, Nicholas A.; Kassel, W. Scott; Bullock, R. Morris; Mock, Michael T.; Journal of the American Chemical Society 139 (2017) 9291–9301; doi:10.1021/jacs.7b04552

data_4126322
_publ_section_title
;
 Catalytic N2 Reduction to Silylamines and Thermodynamics of N2 Binding at
 Square Planar Fe.
;
_journal_issue                   27
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9291
_journal_page_last               9301
_journal_paper_doi               10.1021/jacs.7b04552
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C44 H46 Br2 Fe N2 P4'
_chemical_formula_sum            'C44 H46 Br2 Fe N2 P4'
_chemical_formula_weight         942.38
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-07-31
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.374(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.2513(9)
_cell_length_b                   15.1785(12)
_cell_length_c                   46.440(4)
_cell_measurement_reflns_used    9232
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.240
_cell_measurement_theta_min      2.267
_cell_volume                     7881.9(11)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0869
_diffrn_reflns_av_unetI/netI     0.0472
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       65
_diffrn_reflns_limit_l_min       -65
_diffrn_reflns_number            228280
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.034
_diffrn_reflns_theta_min         1.324
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.609
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6123
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1042 before and 0.0832 after correction. The Ratio of minimum to maximum transmission is 0.8207. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.588
_exptl_crystal_description       plate
_exptl_crystal_F_000             3840
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.907
_refine_diff_density_min         -0.780
_refine_diff_density_rms         0.180
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     956
_refine_ls_number_reflns         23213
_refine_ls_number_restraints     866
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0863
_refine_ls_R_factor_gt           0.0778
_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^)+(0.1493P)^2^+49.1097P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2221
_refine_ls_wR_factor_ref         0.2297
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20245
_reflns_number_total             23213
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b04552_si_003.cif
_cod_data_source_block           pnl195
_cod_database_code               4126322
_shelx_estimated_absorpt_t_max   0.780
_shelx_estimated_absorpt_t_min   0.422
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7362(12) 0.2638(12)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(C13A) \\sim Ueq, Uanis(C6) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C13A, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Secondary CH2 refined with riding coordinates:
 C30A(H30A,H30B), C27A(H27A,H27B), C29(H29C,H29D), C26(H26C,H26D), C31A(H31A,
 H31B), C31(H31C,H31D), C28(H28C,H28D), C28A(H28A,H28B), C25(H25C,H25D),
 C32(H32C,H32D), C27(H27C,H27D), C30(H30C,H30D), C29A(H29A,H29B), C32A(H32A,
 H32B), C26A(H26A,H26B), C25A(H25A,H25B)
6.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C18(H18), C40A(H40A), C14A(H14A), C43(H43), C42A(H42A), C36(H36),
 C41(H41), C22(H22), C43A(H43A), C44A(H44A), C16A(H16A), C4(H4), C20A(H20A),
 C20(H20), C37A(H37A), C23(H23), C41A(H41A), C5A(H5A), C36A(H36A), C37(H37),
 C16(H16), C4A(H4A), C35(H35), C14(H14), C6A(H6A), C12A(H12A), C10(H10),
 C38A(H38A), C21(H21), C17A(H17A), C40(H40), C23A(H23A), C42(H42), C35A(H35A),
 C34(H34), C8A(H8A), C2A(H2A), C11A(H11A), C38(H38), C22A(H22A), C10A(H10A),
 C11(H11), C9(H9), C9A(H9A), C24(H24), C3A(H3A), C12(H12), C18A(H18A), C17(H17),
  C44(H44), C34A(H34A), C24A(H24A), C21A(H21A), C3(H3), C8(H8), C2(H2),
 C15(H15), C15A(H15A), C5(H5)
;
_shelx_res_checksum              12663
_shelx_hkl_checksum              37253
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'