Anionic 1-Aza-3,4-diphospholides as redox active ligands
Suter, Riccardo; Gilliard, Robert J.; Iskandarov, Javad; Benkő, Zoltan; Wörle, Michael; Grützmacher, Hansjörg; Inorganica Chimica Acta 520 (2021) 120274–; doi:10.1016/j.ica.2021.120274

data_1566184
_publ_section_title
;
 Anionic 1-Aza-3,4-diphospholides as redox active ligands
;
_journal_name_full               'Inorganica Chimica Acta'
_journal_page_first              120274
_journal_paper_doi               10.1016/j.ica.2021.120274
_journal_volume                  520
_journal_year                    2021
_chemical_formula_moiety         'C48 H62 Fe2 N2 O4 P4, 0.5(C6 H6), C4 H8 O1'
_chemical_formula_sum            'C55 H73 Fe2 N2 O5 P4'
_chemical_formula_weight         1077.73
_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
_atom_sites_solution_primary     direct
_cell_angle_alpha                90
_cell_angle_beta                 98.503(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.8927(4)
_cell_length_b                   24.8383(5)
_cell_length_c                   13.7936(5)
_cell_measurement_reflns_used    7637
_cell_measurement_temperature    106.11(10)
_cell_measurement_theta_max      26.9410
_cell_measurement_theta_min      1.5450
_cell_volume                     5385.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    OLEX2
_computing_publication_material  OLEX2
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      106.11(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0839
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -16.00  22.00   1.00   13.00    --  -17.98 -99.00 -60.00   38
  2  \w     -4.00  22.00   1.00   13.00    --  -17.98 -99.00  60.00   26
  3  \w    -49.00  38.00   1.00   13.00    --   18.45 -57.00 150.00   87
  4  \w    -45.00  42.00   1.00   13.00    --   18.45 -77.00  60.00   87
  5  \w     34.00  68.00   1.00   13.00    --   18.45 179.00  30.00   34
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0263928000
_diffrn_orient_matrix_UB_12      0.0031332000
_diffrn_orient_matrix_UB_13      -0.0458502000
_diffrn_orient_matrix_UB_21      -0.0352292000
_diffrn_orient_matrix_UB_22      -0.0098205000
_diffrn_orient_matrix_UB_23      0.0208470000
_diffrn_orient_matrix_UB_31      -0.0099032000
_diffrn_orient_matrix_UB_32      0.0266165000
_diffrn_orient_matrix_UB_33      0.0130607000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0439
_diffrn_reflns_av_unetI/netI     0.0638
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            26338
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.348
_diffrn_reflns_theta_min         1.533
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.706
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94582
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.329
_exptl_crystal_description       block
_exptl_crystal_F_000             2276
_exptl_crystal_recrystallization_method
'crystallized from a benzene/THF mixture'
_exptl_crystal_size_max          0.331
_exptl_crystal_size_mid          0.263
_exptl_crystal_size_min          0.193
_refine_diff_density_max         1.676
_refine_diff_density_min         -1.273
_refine_diff_density_rms         0.088
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     648
_refine_ls_number_reflns         9864
_refine_ls_number_restraints     169
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0943
_refine_ls_R_factor_gt           0.0704
_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^)+(0.0671P)^2^+16.6346P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1675
_refine_ls_wR_factor_ref         0.1813
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                7476
_reflns_number_total             9864
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            4-syn.cif
_cod_data_source_block           rs5122
_cod_database_code               1566184
_chemical_oxdiff_formula         Fe1P4N2O2C50H50
_shelx_estimated_absorpt_t_max   0.876
_shelx_estimated_absorpt_t_min   0.800
_reflns_odcompleteness_completeness 99.97
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C47-C46 \\sim C47-C43 \\sim C44-C43 \\sim C44-C45 \\sim C46-C45 \\sim
C43A-C44A \\sim C44A-C45A ~
 C45A-C46A \\sim C47A-C46A \\sim C43A-C47A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uiso(C53A) = Uiso(C58A) = Uiso(C57A) = Uiso(C56A) = Uiso(C55A) = Uiso(C54A)
Uiso(C53) = Uiso(C58) = Uiso(C57) = Uiso(C56) = Uiso(C55) = Uiso(C54)
Uiso(C50A) = Uiso(C49A) = Uiso(O5A) = Uiso(C52A) = Uiso(C51A)
Uiso(O5) = Uiso(C52) = Uiso(C51) = Uiso(C50) = Uiso(C49)
4. Rigid body (RIGU) restrains
 Fe1, O4, O4A, C43, C43A, C44, C44A, C45, C45A, C46, C46A, C47, C47A, C48, C48A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O4A)=Sof(C43A)=Sof(H43A)=Sof(C44A)=Sof(H44A)=Sof(C45A)=Sof(H45A)=
 Sof(C46A)=Sof(H46A)=Sof(C47A)=Sof(H47A)=Sof(C48A)=Sof(O5A)=Sof(C49A)=Sof(H49C)=
 Sof(H49D)=Sof(C50A)=Sof(H50C)=Sof(H50D)=Sof(C51A)=Sof(H51C)=Sof(H51D)=
 Sof(C52A)=Sof(H52C)=Sof(H52D)=1-FVAR(1)
 Sof(O4)=Sof(C43)=Sof(H43)=Sof(C44)=Sof(H44)=Sof(C45)=Sof(H45)=Sof(C46)=
 Sof(H46)=Sof(C47)=Sof(H47)=Sof(C48)=Sof(O5)=Sof(C49)=Sof(H49A)=Sof(H49B)=
 Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C52)=Sof(H52A)=
 Sof(H52B)=FVAR(1)
 Sof(C56)=Sof(H56)=Sof(C53)=Sof(H53)=Sof(C54)=Sof(H54)=Sof(C55)=Sof(H55)=
 Sof(C57)=Sof(H57)=Sof(C58)=Sof(H58)=0.5*(1-FVAR(3))
 Sof(C56A)=Sof(H56A)=Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(H54A)=Sof(C55A)=
 Sof(H55A)=Sof(C57A)=Sof(H57A)=Sof(C58A)=Sof(H58A)=0.5*FVAR(3)
6.a Free rotating group:
 C56(C53,C54,C55,C57,C58), C56A(C53A,C54A,C55A,C57A,C58A), O5(C49,C50,C51,C52),
  O5A(C49A,C50A,C51A,C52A)
6.b Ternary CH refined with riding coordinates:
 C13(H13), C16(H16), C37(H37), C40(H40), C46A(H46A), C47A(H47A)
6.c Secondary CH2 refined with riding coordinates:
 C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B), C49A(H49C,
 H49D), C50A(H50C,H50D), C51A(H51C,H51D), C52A(H52C,H52D)
6.d Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26),
 C33(H33), C34(H34), C35(H35), C43(H43), C43A(H43A), C44(H44), C44A(H44A),
 C45(H45), C45A(H45A), C46(H46), C47(H47), C56(H56), C53(H53), C54(H54),
 C55(H55), C57(H57), C58(H58), C56A(H56A), C53A(H53A), C54A(H54A), C55A(H55A),
 C57A(H57A), C58A(H58A)
6.e Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C14(H14A,H14B,H14C),
 C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C28(H28A,H28B,
 H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C38(H38A,H38B,H38C), C39(H39A,
 H39B,H39C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C)
;
_shelx_res_checksum              83182
_shelx_hkl_checksum              71487
_olex2_exptl_crystal_mounting_method tip-mounted
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.083
_oxdiff_exptl_absorpt_empirical_full_min 0.939