Rational design of Fe catalysts for olefin aziridination through DFT-based mechanistic analysis
Patra, Ranjan; Coin, Guillaume; Castro, Ludovic; Dubourdeaux, Patrick; Clémancey, Martin; Pécaut, Jacques; Lebrun, Colette; Maldivi, Pascale; Latour, Jean-Marc; Catal. Sci. Technol.  (2017) –; doi:10.1039/C7CY01283G

data_1547134
_publ_section_title
;
 Rational design of Fe catalysts for olefin aziridination through
 DFT-based mechanistic analysis
;
_journal_name_full               'Catal. Sci. Technol.'
_journal_paper_doi               10.1039/C7CY01283G
_journal_year                    2017
_chemical_formula_moiety
'C30 H24 Cl4 Fe N4 O2, C4 H8 O, 0.25(C6.44 H14.44 O0.44)'
_chemical_formula_sum            'C35.61 H35.61 Cl4 Fe N4 O3.11'
_chemical_formula_weight         767.08
_chemical_name_systematic
(Bis-(4,6-dichlorophenolato)-2-methylpyridine)amine)iron(II)-bis-pyridine
_chemical_properties_physical    ', Air-sensitive'
_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   mixed
_audit_creation_date             2017-03-23
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2017-06-13 deposited with the CCDC.
2017-08-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 118.213(14)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   27.042(3)
_cell_length_b                   10.5667(9)
_cell_length_c                   28.273(3)
_cell_measurement_reflns_used    4473
_cell_measurement_temperature    149(1)
_cell_measurement_theta_max      25.7090
_cell_measurement_theta_min      3.2030
_cell_volume                     7119.1(16)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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
;
SUPERFLIP program (Palatinus, L. & Chapuis, G. J. Appl. Cryst., 2007,
 40, 786-790)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9653
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
  1 omega  -22.00   68.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       -0.6250   57.0000  -30.0000 90

  2 omega  -17.00  100.00   1.0000  110.0000
omega____ theta____ kappa____ phi______ frames
    -       55.5052  -19.0000   90.0000 117

  3 omega  -16.00   97.00   1.0000  110.0000
omega____ theta____ kappa____ phi______ frames
    -       55.5052  -99.0000  -60.0000 113

  4 omega   26.00  125.00   1.0000  110.0000
omega____ theta____ kappa____ phi______ frames
    -       55.5052   77.0000 -120.0000 99

  5 omega -118.00  -95.00   1.0000  110.0000
omega____ theta____ kappa____ phi______ frames
    -      -56.7552  -99.0000  -90.0000 23
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0058000000
_diffrn_orient_matrix_UB_12      0.0054030000
_diffrn_orient_matrix_UB_13      0.0218762000
_diffrn_orient_matrix_UB_21      -0.0290262000
_diffrn_orient_matrix_UB_22      0.0066536000
_diffrn_orient_matrix_UB_23      -0.0182344000
_diffrn_orient_matrix_UB_31      -0.0033938000
_diffrn_orient_matrix_UB_32      -0.0665549000
_diffrn_orient_matrix_UB_33      -0.0000115000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1725
_diffrn_reflns_av_unetI/netI     0.1757
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            44150
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         2.094
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.766
_exptl_absorpt_correction_T_max  0.909
_exptl_absorpt_correction_T_min  0.533
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'translucent light yellow'
_exptl_crystal_density_diffrn    1.431
_exptl_crystal_description       needle
_exptl_crystal_F_000             3169
_exptl_crystal_size_max          0.9185
_exptl_crystal_size_mid          0.1311
_exptl_crystal_size_min          0.0689
_refine_diff_density_max         0.703
_refine_diff_density_min         -0.691
_refine_diff_density_rms         0.120
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.975
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     937
_refine_ls_number_reflns         14374
_refine_ls_number_restraints     181
_refine_ls_restrained_S_all      0.972
_refine_ls_R_factor_all          0.1563
_refine_ls_R_factor_gt           0.0877
_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^)+(0.1034P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2009
_refine_ls_wR_factor_ref         0.2240
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7487
_reflns_number_total             14374
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cy01283g2.cif
_cod_data_source_block           rp21
_cod_original_cell_volume        7119.0(15)
_cod_database_code               1547134
_chemical_oxdiff_formula         'Fe O2 Cl4 N3 C30 H30'
_reflns_odcompleteness_completeness 98.39
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C71-C74B
 2.3 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O62B \\sim C65B \\sim C67 \\sim O62 \\sim C68 \\sim C67B \\sim C68B \\sim C66
\\sim C66B \\sim C65: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O71B \\sim C71 \\sim C72 \\sim C73 \\sim C73B \\sim C74B: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O61) \\sim Ueq, Uanis(N2) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C7) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Sof(O62)=Sof(C65)=Sof(H5AA)=Sof(H6AA)=Sof(C66)=Sof(H7AA)=Sof(H8AA)=Sof(C67)=
 Sof(H9AA)=Sof(H0BA)=Sof(C68)=Sof(H1BA)=Sof(H2BA)=1-FVAR(1)
 Sof(O62B)=Sof(C65B)=Sof(H3BA)=Sof(H4BA)=Sof(C66B)=Sof(H5BA)=Sof(H6BA)=
 Sof(C67B)=Sof(H7BA)=Sof(H8BA)=Sof(C68B)=Sof(H9BA)=Sof(H0CA)=FVAR(1)
 Sof(H4CA)=Sof(H5CA)=Sof(H8CA)=Sof(H9CA)=Sof(O71B)=Sof(C74B)=Sof(H2DA)=
 Sof(H3DA)=Sof(C73B)=Sof(H4DA)=Sof(H5DA)=1-FVAR(2)
 Sof(H1CA)=Sof(H2CA)=Sof(H3CA)=Sof(H6CA)=Sof(H7CA)=Sof(C73)=Sof(H0DA)=
 Sof(H1DA)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C8(HD,HE), C15(HH,HI), C31(H31A,H31B), C38(H38A,H38B), C45(H45A,H45B), C61(HX,
 HY), C62(HZ,H0AA), C63(H1AA,H2AA), C64(H3AA,H4AA), C65(H5AA,H6AA), C66(H7AA,
 H8AA), C67(H9AA,H0BA), C68(H1BA,H2BA), C65B(H3BA,H4BA), C66B(H5BA,H6BA),
 C67B(H7BA,H8BA), C68B(H9BA,H0CA), C71(H4CA,H5CA), C72(H6CA,H7CA), C72(H8CA,
 H9CA), C73(H0DA,H1DA), C74B(H2DA,H3DA), C73B(H4DA,H5DA)
5.b Aromatic/amide H refined with riding coordinates:
 C3(HB), C5(HC), C10(HF), C12(HG), C17(HJ), C18(HK), C19(HL), C20(HM), C21(HN),
  C22(HO), C23(HP), C24(HQ), C25(HR), C26(HS), C27(HT), C28(HU), C29(HV),
 C30(HW), C33(H33), C35(H35), C40(H40), C42(H42), C47(H47), C48(H48), C49(H49),
 C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C55(H55), C56(H56), C57(H57),
  C58(H58), C59(H59), C60(H60)
5.c Idealised Me refined as rotating group:
 C71(H1CA,H2CA,H3CA)
;
_shelx_shelxl_version_number     2016/6
_olex2_submission_special_instructions 'No special instructions were received'