Robust and Porous β-Diketiminate-Functionalized Metal-Organic Frameworks for Earth-Abundant-Metal-Catalyzed C-H Amination and Hydrogenation.
Thacker, Nathan C.; Lin, Zekai; Zhang, Teng; Gilhula, James C.; Abney, Carter W.; Lin, Wenbin; Journal of the American Chemical Society 138 (2016) 3501–3509; doi:10.1021/jacs.5b13394

data_4130052
_publ_section_title
;
 Robust and Porous \b-Diketiminate-Functionalized Metal-Organic Frameworks
 for Earth-Abundant-Metal-Catalyzed C-H Amination and Hydrogenation.
;
_journal_issue                   10
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3501
_journal_page_last               3509
_journal_paper_doi               10.1021/jacs.5b13394
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         'C17 H18 Cl2 Fe N2'
_chemical_formula_sum            'C17 H18 Cl2 Fe N2'
_chemical_formula_weight         377.08
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-11-28
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.473(9)
_cell_length_b                   22.252(19)
_cell_length_c                   7.486(6)
_cell_measurement_reflns_used    823
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      11.75
_cell_measurement_theta_min      2.32
_cell_volume                     1745(3)
_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    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.603
_diffrn_measured_fraction_theta_max 0.917
_diffrn_measurement_device_type  'synchrotron, beamline 15-ID, APEX2 detector'
_diffrn_measurement_method       'phi scans'
_diffrn_radiation_type           'synchrotron radiation'
_diffrn_radiation_wavelength     0.41328
_diffrn_reflns_av_R_equivalents  0.1795
_diffrn_reflns_av_unetI/netI     0.1309
_diffrn_reflns_Laue_measured_fraction_full 0.603
_diffrn_reflns_Laue_measured_fraction_max 0.917
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -5
_diffrn_reflns_number            9212
_diffrn_reflns_point_group_measured_fraction_full 0.528
_diffrn_reflns_point_group_measured_fraction_max 0.812
_diffrn_reflns_theta_full        14.357
_diffrn_reflns_theta_max         12.386
_diffrn_reflns_theta_min         1.250
_diffrn_source                   'synchrotron radiation'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.228
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.436
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             776
_refine_diff_density_max         0.280
_refine_diff_density_min         -0.339
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Flack x determined using 292 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.0(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     195
_refine_ls_number_reflns         1664
_refine_ls_number_restraints     152
_refine_ls_restrained_S_all      0.989
_refine_ls_R_factor_all          0.1104
_refine_ls_R_factor_gt           0.0551
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0332P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1016
_refine_ls_wR_factor_ref         0.1159
_reflns_Friedel_coverage         0.616
_reflns_Friedel_fraction_full    0.439
_reflns_Friedel_fraction_max     0.684
_reflns_number_gt                981
_reflns_number_total             1664
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b13394_si_003.cif
_cod_data_source_block           fe_nacnac_cl_a
_cod_database_code               4130052
_shelxl_version_number           2013-3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-C6A \\sim N1-C6
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C12) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C5) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 Fe1, Cl1, Cl2, N2, C2, C3, C4, C5, C12, C13, C14, C15, C16, C17, N1, C1
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
5. Same fragment restrains
{C6, C7, C8, C9, C10, C11} sigma for 1-2: 0.02, 1-3: 0.04
as
{C6A, C7A, C8A, C9A, C10A, C11A}
6. Others
 Fixed Sof: C6(0.5) C7(0.5) H7(0.5) C8(0.5) H8(0.5) C9(0.5) H9(0.5) C10(0.5)
 H10(0.5) C11(0.5) H11(0.5) C6A(0.5) C7A(0.5) H7A(0.5) C8A(0.5) H8A(0.5)
 C9A(0.5) H9A(0.5) C10A(0.5) H10A(0.5) C11A(0.5) H11A(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
7.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C15(H15), C16(H16), C17(H17), C7(H7), C8(H8), C9(H9),
 C10(H10), C11(H11), C7A(H7A), C8A(H8A), C9A(H9A), C10A(H10A), C11A(H11A)
7.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C5(H5A,H5B,H5C)
;
_shelx_res_checksum              38689
_shelx_hkl_checksum              90907
_olex2_submission_special_instructions 'No special instructions were received'