Testing the Push-Pull Hypothesis: Lewis Acid Augmented N<sub>2</sub> Activation at Iron.
Geri, Jacob B.; Shanahan, James P.; Szymczak, Nathaniel K.; Journal of the American Chemical Society 139 (2017) 5952–5956; doi:10.1021/jacs.7b01982

data_4131254
_publ_section_title
;
 Testing the Push-Pull Hypothesis: Lewis Acid Augmented N<sub>2</sub>
 Activation at Iron.
;
_journal_issue                   16
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5952
_journal_page_last               5956
_journal_paper_doi               10.1021/jacs.7b01982
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C37.82 H48 B F15 Fe N2 P4, 2.5(C7 H8)'
_chemical_formula_sum            'C55.32 H68 B F15 Fe N2 P4'
_chemical_formula_weight         1236.49
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-10-15
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                89.5764(14)
_cell_angle_beta                 84.6591(17)
_cell_angle_gamma                83.2243(19)
_cell_formula_units_Z            2
_cell_length_a                   12.6573(4)
_cell_length_b                   13.9154(3)
_cell_length_c                   16.4180(3)
_cell_measurement_reflns_used    24124
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      69.0500
_cell_measurement_theta_min      2.7000
_cell_volume                     2859.04(12)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (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    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.965
_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   -110.00  70.00   1.00    1.00    --  -20.00   0.00-180.00  180
  2  \w    -45.00   0.00   1.00    1.00    --  -20.00  72.00   0.00   45
  3  \w    -45.00   0.00   1.00    1.00    --  -20.00  72.00   0.00   45
  4  \w    -25.00  43.00   1.00    1.00    --  -20.00  36.00 120.00   68
  5  \w    -45.00   0.00   1.00    1.00    --  -20.00  72.00-180.00   45
  6  \w   -173.00-128.00   1.00    3.00    --  -92.00 -36.00 120.00   45
  7  \w   -133.00 -88.00   1.00    3.00    --  -92.00 -36.00 -60.00   45
  8  \w   -104.00 -59.00   1.00    3.00    --  -92.00  36.00  60.00   45
  9  \w   -122.00 -77.00   1.00    3.00    --  -92.00 -72.00  60.00   45
 10  \w   -174.00 -78.00   1.00    3.00    --  -92.00 -72.00-120.00   96
 11  \w    -93.00 -35.00   1.00    3.00    --  -92.00  36.00-120.00   58
 12  \w   -176.00 -77.00   1.00    3.00    --  -92.00 -72.00 -60.00   99
 13  \w   -147.00 -75.00   1.00    3.00    --  -92.00 -72.00-180.00   72
 14  \w   -176.00 -77.00   1.00    3.00    --  -92.00 -72.00 120.00   99
 15  \w   -177.00-116.00   1.00    3.00    --  -92.00 -36.00  60.00   61
 16  \w    -87.00  -9.00   1.00    3.00    --  -92.00  36.00 -60.00   78
 17  \w   -102.00 -14.00   1.00    3.00    --  -92.00  36.00   0.00   88
 18  \w   -102.00 -21.00   1.00    3.00    --  -92.00  72.00 120.00   81
 19  \w   -175.00-104.00   1.00    3.00    --  -92.00 -36.00   0.00   71
 20  \w   -104.00 -52.00   1.00    3.00    --  -92.00  72.00  60.00   52
 21  \w   -109.00 -14.00   1.00    3.00    --  -92.00  72.00-120.00   95
 22  \w   -105.00 -24.00   1.00    3.00    --  -92.00  36.00-120.00   81
 23  \w   -105.00  -2.00   1.00    3.00    --  -92.00  36.00-180.00  103
 24  \w   -106.00  -2.00   1.00    3.00    --  -92.00  72.00 -60.00  104
 25  \w   -106.00  -2.00   1.00    3.00    --  -92.00  72.00 -60.00  104
 26  \w   -107.00 -29.00   1.00    3.00    --  -92.00  72.00   0.00   78
 27  \w   -117.00 -72.00   1.00    3.00    --  -92.00  72.00 180.00   45
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0727275000
_diffrn_orient_matrix_UB_12      -0.0624267000
_diffrn_orient_matrix_UB_13      0.0550458000
_diffrn_orient_matrix_UB_21      -0.0071142000
_diffrn_orient_matrix_UB_22      -0.0894409000
_diffrn_orient_matrix_UB_23      -0.0530676000
_diffrn_orient_matrix_UB_31      0.0990655000
_diffrn_orient_matrix_UB_32      0.0230855000
_diffrn_orient_matrix_UB_33      -0.0550968000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0605
_diffrn_reflns_av_unetI/netI     0.0352
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            42581
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.348
_diffrn_reflns_theta_min         2.703
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.945
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60392
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.436
_exptl_crystal_description       block
_exptl_crystal_F_000             1280
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.14
_refine_diff_density_max         1.145
_refine_diff_density_min         -0.917
_refine_diff_density_rms         0.098
_refine_ls_extinction_coef       0.0046(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     762
_refine_ls_number_reflns         10331
_refine_ls_number_restraints     144
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0609
_refine_ls_R_factor_gt           0.0595
_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^)+(0.0995P)^2^+3.2234P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1592
_refine_ls_wR_factor_ref         0.1610
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9955
_reflns_number_total             10331
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b01982_si_002.cif
_cod_data_source_block           2
_cod_original_cell_volume        2859.04(11)
_cod_database_code               4131254
_chemical_oxdiff_formula         C38H48BF15FeN2P4(C7H8)2
_reflns_odcompleteness_completeness 96.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.22
_olex2_refinement_description
;
1. 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
2. Restrained distances
 C044-C049 \\sim C028-C034 \\sim C048-C030 \\sim C063-C020 \\sim C045-C036
\\sim C057-C042 \\sim C056-
 C038 \\sim C1-C046 \\sim C067-C046
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1 \\sim C046 \\sim C067: within 2A with sigma of 0.002 and sigma for terminal
atoms of 0.004
4. Rigid body (RIGU) restrains
 C2, C3, C3AA, C4, C4AA, C5, C7, C7, C7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Same fragment restrains
{C054, C062, C050, C060, C051, C047, C064} sigma for 1-2: 0.02, 1-3: 0.04
as
{C2, C3, C3AA, C4, C4AA, C5, C7}
{C054, C062, C050, C060, C051, C047, C064} sigma for 1-2: 0.02, 1-3: 0.04
as
{C2A, C3A, C3AB, C4A, C4AB, C5A, C7A}
6. Others
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(H04H)=Sof(H04I)=1-FVAR(1)
 Sof(C046)=Sof(H04J)=Sof(H04K)=Sof(C067)=Sof(H06H)=Sof(H06I)=Sof(H06J)=FVAR(1)
 Fixed Sof: C2A(0.5) C3A(0.5) H3A(0.5) C3AB(0.5) H3AB(0.5) C4A(0.5) H4AB(0.5)
 H4AC(0.5) H4AD(0.5) C4AB(0.5) H4AE(0.5) C5A(0.5) H5A(0.5) C7A(0.5) H7A(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C020(H02A,H02B), C024(H02C,H02D), C028(H02E,H02F), C030(H03A,H03B), C035(H03F,
 H03G), C036(H03H,H03I), C038(H03J,H03K), C042(H04A,H04B), C044(H04C,H04D),
 C046(H04J,H04K), C046(H04H,H04I), C065(H06D,H06E), C066(H06F,H06G)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C3AA(H3AA), C4AA(H4AA), C5(H5), C7(H7), C3A(H3A), C3AB(H3AB),
 C4AB(H4AE), C5A(H5A), C7A(H7A), C062(H062), C050(H050), C051(H051), C047(H047),
  C064(H064)
7.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C034(H03C,H03D,H03E), C045(H04E,H04F,H04G), C048(H04L,H04M,
 H04N), C049(H04O,H04P,H04Q), C056(H05A,H05B,H05C), C057(H05D,H05E,H05F),
 C063(H06A,H06B,H06C), C067(H06H,H06I,H06J), C4(H4A,H4B,H4C), C4A(H4AB,H4AC,
 H4AD), C060(H06K,H06L,H06M)
;
_shelx_res_checksum              18872
_shelx_hkl_checksum              23743
_shelx_shelxl_version_number     2014/7
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.734
_oxdiff_exptl_absorpt_empirical_full_min 0.615