Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides
Kiernicki, John J.; Shanahan, James P.; Zeller, Matthias; Szymczak, Nathaniel K.; Chemical Science  (2019) –; doi:10.1039/C9SC00561G

data_1550976
_publ_section_title
;
 Tuning ligand field strength with pendent Lewis acids: access to high
 spin iron hydrides
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC00561G
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C86 H126 B4 Fe2 N14, 3.272(C H2 Cl2)'
_chemical_formula_sum            'C89.49 H132.99 B4 Cl6.99 Fe2 N14'
_chemical_formula_weight         1807.60
_chemical_properties_physical    Air-sensitive,Moisture-sensitive,Hygroscopic
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2016/6
_audit_update_record
;
2018-12-10 deposited with the CCDC.    2019-04-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.451(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.7395(8)
_cell_length_b                   31.7053(18)
_cell_length_c                   22.0966(13)
_cell_measurement_reflns_used    9636
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      34.9680
_cell_measurement_theta_min      3.0484
_cell_volume                     10325.9(10)
_computing_cell_refinement       'SAINT V8.37A (Bruker, 2016)'
_computing_data_collection       'Apex3 v2016.9-0 (Bruker, 2016)'
_computing_data_reduction        'SAINT V8.37A (Bruker, 2016)'
_computing_structure_refinement
;  
SHELXL-2016/6 (Sheldrick, 2015, 2016), 
SHELXLE Rev714 (H\"ubschle et al., 2011)
;
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker AXS D8 Quest CMOS diffractometer'
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_monochromator  'Triumph curved graphite crystal'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0425
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            123502
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.282
_diffrn_reflns_theta_min         3.048
_diffrn_source                   'sealed tube X-ray source'
_exptl_absorpt_coefficient_mu    0.508
_exptl_absorpt_correction_T_max  0.7469
_exptl_absorpt_correction_T_min  0.6303
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 SADABS 2016/2: Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D.,
 J. Appl. Cryst. 48 (2015) 3-10
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.162
_exptl_crystal_description       block
_exptl_crystal_F_000             3834.8
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.540
_exptl_crystal_size_mid          0.520
_exptl_crystal_size_min          0.390
_refine_diff_density_max         0.628
_refine_diff_density_min         -0.518
_refine_diff_density_rms         0.084
_refine_ls_abs_structure_details
;
The structure exhibits pseudo-inversion and pseudo-twofold symmetry 
emulating space group C2/c. The higher symmetry is broken by ordering of 
the borabicyclononane of B1 and B3. Refined as an inversion twin.

Dichloromethane solvate molecules are extensively disordered. All 
methylene chloride moieties were restrained to have similar geometries. 
Uij components of ADPs were restrained to be similar for atoms closer to 
each other than 2.0 Angstrom. A weak anti-bumping restraint was applied to 
keep solvate H atoms from approaching main moiety H atoms too closely. 
Atoms Cl8 and C92 and atoms Cl16 and C97 were constrained to share a site 
and ADP. Due to the extensive and sequential disorder no attempts were 
made to match occupancy rates and occupancies for all solvate molecules 
were independently refined. Occupancies refined to values between 0.800(6)
and 0.059(5).
;
_refine_ls_abs_structure_Flack   0.445(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.125
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1314
_refine_ls_number_reflns         24774
_refine_ls_number_restraints     808
_refine_ls_restrained_S_all      1.183
_refine_ls_R_factor_all          0.0697
_refine_ls_R_factor_gt           0.0627
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+45.5669P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1346
_refine_ls_wR_factor_ref         0.1400
_reflns_Friedel_coverage         0.999
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                23021
_reflns_number_total             24774
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc00561g2.cif
_cod_data_source_block           JK217_0m
_cod_database_code               1550976
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_min   0.771
_shelx_estimated_absorpt_t_max   0.826
_shelx_res_checksum              7502