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_4131256
_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
'0.8(C47 H94 B Fe2 N8 P4), 0.8(C32 H12 B F24), 0.4(F), 0.4(C6 H5)'
_chemical_formula_sum            'C65.43 H86.4 B1.6 F19.6 Fe1.6 N6.4 P3.2'
_chemical_formula_weight         1540.76
_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'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-01-16
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.7535(8)
_cell_angle_gamma                90
_cell_formula_units_Z            10
_cell_length_a                   26.3521(3)
_cell_length_b                   22.42897(19)
_cell_length_c                   35.7607(3)
_cell_measurement_reflns_used    80955
_cell_measurement_temperature    90
_cell_measurement_theta_max      68.7350
_cell_measurement_theta_min      2.3240
_cell_volume                     21134.6(3)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      90
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device_type  'Rigaku Saturn70 CCD'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0609
_diffrn_reflns_av_unetI/netI     0.0293
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            321948
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.586
_diffrn_reflns_theta_min         1.677
_exptl_absorpt_coefficient_mu    3.506
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59710
_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    1.211
_exptl_crystal_description       cube
_exptl_crystal_F_000             7978
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.2
_platon_squeeze_details
'The unit cell contains 21 highly disordered fluorobenzene molecules which were removed through the squeeze program.'
_refine_diff_density_max         1.362
_refine_diff_density_min         -0.994
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2320
_refine_ls_number_reflns         38825
_refine_ls_number_restraints     211
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0965
_refine_ls_R_factor_gt           0.0855
_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^)+(0.1330P)^2^+42.1630P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2310
_refine_ls_wR_factor_ref         0.2421
_reflns_Friedel_coverage         0.000
_reflns_number_gt                32701
_reflns_number_total             38825
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b01982_si_002.cif
_cod_data_source_block           4
_cod_original_cell_volume        21134.5(3)
_cod_original_formula_sum
'C65.43 H86.40 B1.60 F19.60 Fe1.60 N6.40 P3.20'
_cod_database_code               4131256
_shelxl_version_number           2014-3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, 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
 C183-C186 \\sim C215-C186
 with sigma of 0.005
 C309-C100 \\sim C284-C100
 with sigma of 0.005
 C32A-C282 \\sim C32-C282 \\sim C31A-C282 \\sim C31-C282
 with sigma of 0.005
 C334-C18 \\sim C17-C18 \\sim C275-C18 \\sim C1A-C18
 with sigma of 0.005
 C374-C140 \\sim C2-C140
 with sigma of 0.005
 C14-C93A \\sim C434-C93A
 with sigma of 0.005
 C170-F92 \\sim C170-F137 \\sim C170-F136
 with sigma of 0.005
 C244-F174 \\sim C244-F110 \\sim C244-F164
 with sigma of 0.005
 C142-F116 \\sim C142-F47 \\sim C142-F88
 with sigma of 0.005
 C172-C12 \\sim C136-C4 \\sim C255-C195 \\sim C298-C217
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
C2 \\sim C374: within 2A with sigma of 0.004 and sigma for terminal atoms of
0.008
C17 \\sim C334: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.005
C275 \\sim C1A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.005
C409 \\sim C257 \\sim C354: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C2CA \\sim C2CB: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004
C2CA \\sim C2CB \\sim P7 \\sim C1 \\sim C2BA: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
C354 \\sim C409 \\sim C257: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C3AA \\sim C217 \\sim P28 \\sim C195: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01
C423 \\sim C343 \\sim C332 \\sim C382 \\sim C446 \\sim C328: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C328 \\sim C423 \\sim C343 \\sim C332 \\sim C446 \\sim C382: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C7AA \\sim C47 \\sim C128: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
C434 \\sim C14 \\sim C93A: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
C374 \\sim C140 \\sim C2: within 2A with sigma of 0.002 and sigma for terminal
atoms of 0.004
C298 \\sim C217: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C257 \\sim C409 \\sim C354: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
C359 \\sim C43 \\sim C220: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(C265) = Uanis(C32A) = Uanis(C32)
Uanis(C268) = Uanis(C31A) = Uanis(C31)
Uanis(C200) = Uanis(C282)
4. Same fragment restrains
{P20, C3, C2CA, P7} sigma for 1-2: 0.001, 1-3: 0.001
as
{P24, C42, C176, P2}
5. Others
 Sof(H28C)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C31A)=Sof(H31G)=
 Sof(H31H)=Sof(H31I)=1-FVAR(1)
 Sof(C282)=Sof(H282)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C31)=Sof(H31D)=
 Sof(H31E)=Sof(H31F)=FVAR(1)
 Sof(H14C)=Sof(H14D)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=1-FVAR(2)
 Sof(H14A)=Sof(H14B)=Sof(C374)=Sof(H37A)=Sof(H37B)=Sof(H37C)=FVAR(2)
 Sof(H328)=Sof(F4A)=1-FVAR(3)
 Sof(F4)=Sof(H423)=FVAR(3)
 Sof(H24F)=Sof(H24G)=Sof(C34A)=Sof(H34D)=Sof(H34E)=Sof(H34F)=1-FVAR(4)
 Sof(H24D)=Sof(H24E)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(4)
 Sof(C2CB)=Sof(H2CC)=Sof(H2CD)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=1-FVAR(5)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C2CA)=Sof(H2CA)=Sof(H2CB)=FVAR(5)
 Sof(C14)=Sof(H14H)=Sof(H14I)=Sof(H14J)=Sof(H93C)=Sof(H93D)=1-FVAR(6)
 Sof(C434)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(H93A)=Sof(H93B)=FVAR(6)
 Sof(C17)=Sof(H17C)=Sof(H17D)=Sof(H17E)=Sof(H18D)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=
 Sof(H1AC)=1-FVAR(7)
 Sof(C275)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C334)=Sof(H33A)=Sof(H33B)=
 Sof(H33C)=Sof(H18)=FVAR(7)
6.a Ternary CH refined with riding coordinates:
 C207(H207), C224(H224), C22(H22), C43(H43), C91(H91), C100(H100), B114(H114),
 C200(H200), C282(H282), C282(H28C), B164(H164), C186(H186), C213(H213),
 C257(H257), C18(H18), C18(H18D)
6.b Secondary CH2 refined with riding coordinates:
 C42(H42A,H42B), C176(H17A,H17B), C3(H3A,H3B), C2CA(H2CA,H2CB), C88(H88A,H88B),
  C12(H12A,H12B), C60(H60A,H60B), C66(H66A,H66B), C6BA(H6BA,H6BB), C0AA(H0AA,
 H0AB), C3AA(H3AC,H3AD), C2BA(H2BA,H2BB), C1(H1A,H1B), C4(H4A,H4B), C16(H16D,
 H16E), C19(H19A,H19B), C24(H24D,H24E), C24(H24F,H24G), C28(H28A,H28B),
 C45(H45A,H45B), C112(H11A,H11B), C140(H14A,H14B), C140(H14C,H14D), C195(H19F,
 H19G), C2CB(H2CC,H2CD), C3A(H3AA,H3AB), C93A(H93A,H93B), C93A(H93C,H93D)
6.c Aromatic/amide H refined with riding coordinates:
 C62(H62), C4BA(H4BA), C101(H101), C113(H113), C119(H119), C150(H150),
 C152(H152), C154(H154), C166(H166), C167(H167), C8AA(H8AA), C15(H15),
 C0CA(H0CA), C30(H30), C44(H44), C50(H50), C2AA(H2AA), C74(H74), C77(H77),
 C92(H92), C99(H99), C125(H125), C188(H188), C228(H228), C236(H236), C47(H47),
 C89(H89), C121(H121), C180(H180), C187(H187), C217(H217), C328(H328),
 C446(H446), C382(H382), C332(H332), C343(H343), C423(H423)
6.d Idealised Me refined as rotating group:
 C4AA(H4AA,H4AB,H4AC), C164(H16A,H16B,H16C), C189(H18A,H18B,H18C), C212(H21A,
 H21B,H21C), C36(H36A,H36B,H36C), C63(H63A,H63B,H63C), C72(H72A,H72B,H72C),
 C84(H84A,H84B,H84C), C87(H87A,H87B,H87C), C265(H26A,H26B,H26C), C268(H26D,H26E,
 H26F), C136(H13A,H13B,H13C), C144(H14K,H14L,H14M), C146(H14E,H14F,H14G),
 C147(H14N,H14O,H14P), C32(H32A,H32B,H32C), C31(H31D,H31E,H31F), C172(H17F,H17G,
 H17H), C183(H18E,H18F,H18G), C190(H19C,H19D,H19E), C204(H20A,H20B,H20C),
 C215(H21D,H21E,H21F), C220(H22A,H22B,H22C), C229(H22D,H22E,H22F), C234(H23A,
 H23B,H23C), C248(H24A,H24B,H24C), C255(H25A,H25B,H25C), C275(H27A,H27B,H27C),
 C284(H28D,H28E,H28F), C298(H29A,H29B,H29C), C309(H30A,H30B,H30C), C311(H31A,
 H31B,H31C), C334(H33A,H33B,H33C), C34(H34A,H34B,H34C), C351(H35A,H35B,H35C),
 C354(H35D,H35E,H35F), C359(H35G,H35H,H35I), C374(H37A,H37B,H37C), C409(H40A,
 H40B,H40C), C434(H43A,H43B,H43C), C32A(H32D,H32E,H32F), C31A(H31G,H31H,H31I),
 C2(H2A,H2B,H2C), C34A(H34D,H34E,H34F), C14(H14H,H14I,H14J), C17(H17C,H17D,
 H17E), C1A(H1AA,H1AB,H1AC)
;
_olex2_submission_special_instructions 'No special instructions were received'