Mononuclear Fe(III) Schiff base antipyrine complexes for catalytic hydrogen generation.
Cropley, Jessica D.; Mitchell, Amanda C.; Fritsch, Nicole A.; Ho, Marissa; Wells, Timothy D.; Reynolds, Todd M.; Brennessel, William W.; McNamara, William R.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 15421–15426; doi:10.1039/d4dt01876a

data_7716945
_publ_section_title
;
 Mononuclear Fe(III) Schiff base antipyrine complexes for catalytic
 hydrogen generation.
;
_journal_issue                   37
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              15421
_journal_page_last               15426
_journal_paper_doi               10.1039/d4dt01876a
_journal_volume                  53
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H28 Cl2 Fe N6 O2, Cl'
_chemical_formula_sum            'C26 H28 Cl3 Fe N6 O2'
_chemical_formula_weight         618.74
_chemical_name_common            FeBAME
_chemical_name_systematic
'Iron (III) N,N?- bis(4-antipyrlmethylidene)ethylenediamine dichloride'
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Hygroscopic,Oxygen-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-11-28
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-12-19 deposited with the CCDC.	2024-09-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   18.0494(2)
_cell_length_b                   26.5169(2)
_cell_length_c                   28.1081(2)
_cell_measurement_reflns_used    50494
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.6990
_cell_measurement_theta_min      3.3470
_cell_volume                     13452.9(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.980
_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   -119.00 -67.00   0.50    3.87    --  -47.05-135.00-128.00  104
  2  \w     72.00 120.00   0.50    3.87    --   47.05 160.00   9.00   96
  3  \w    -14.00  28.00   0.50    3.87    --  -47.05  19.00-120.00   84
  4  \w    -14.00  28.00   0.50    3.87    --  -47.05  19.00 150.00   84
  5  \w    -14.00  28.00   0.50    3.87    --  -47.05  19.00 120.00   84
  6  \w    -14.00  28.00   0.50    3.87    --  -47.05  19.00-150.00   84
  7  \w    -62.00  25.00   0.50    3.87    --  -47.05  57.00-180.00  174
  8  \w     24.00 116.00   0.50    3.87    --   47.05  77.00 120.00  184
  9  \w   -166.00 -76.00   0.50   15.49    --  -91.75 -11.00 -92.00  180
 10  \w    -93.00 -19.00   0.50   15.49    --  -91.75 135.00 117.00  148
 11  \w    -47.00 -20.00   0.50   15.49    --  -91.75  45.00  60.00   54
 12  \w     89.00 178.00   0.50   15.49    --  113.25 135.00 117.00  178
 13  \w     45.00 109.00   0.50   15.49    --  113.25-117.00 131.00  128
 14  \w     97.00 178.00   0.50   15.49    --  113.25  61.00-180.00  162
 15  \w     42.00  76.00   0.50   15.49    --  113.25 -61.00-120.00   68
 16  \w     42.00  76.00   0.50   15.49    --  113.25 -61.00-150.00   68
 17  \w     44.00 111.00   0.50   15.49    --  113.25-125.00 120.00  134
 18  \w     44.00 111.00   0.50   15.49    --  113.25-125.00 -90.00  134
 19  \w     42.00  76.00   0.50   15.49    --  113.25 -61.00   0.00   68
 20  \w     42.00 106.00   0.50   15.49    --  113.25 -94.00 150.00  128
 21  \w    100.00 178.00   0.50   15.49    --  113.25  15.00  60.00  156
 22  \w    101.00 178.00   0.50   15.49    --  113.25  30.00-120.00  154
 23  \w     42.00 106.00   0.50   15.49    --  113.25 -94.00  30.00  128
 24  \w     44.00 111.00   0.50   15.49    --  113.25-125.00-180.00  134
 25  \w     42.00  76.00   0.50   15.49    --  113.25 -61.00 -90.00   68
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0841018000
_diffrn_orient_matrix_UB_12      -0.0082975000
_diffrn_orient_matrix_UB_13      0.0051406000
_diffrn_orient_matrix_UB_21      0.0079608000
_diffrn_orient_matrix_UB_22      0.0007576000
_diffrn_orient_matrix_UB_23      0.0545561000
_diffrn_orient_matrix_UB_31      -0.0122165000
_diffrn_orient_matrix_UB_32      0.0575051000
_diffrn_orient_matrix_UB_33      0.0000600000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0465
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            136133
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         81.549
_diffrn_reflns_theta_min         3.353
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.032
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51928
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.222
_exptl_crystal_description       plate
_exptl_crystal_F_000             5104
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Methanol, Ethyl Acetate'
_exptl_crystal_size_max          0.241
_exptl_crystal_size_mid          0.209
_exptl_crystal_size_min          0.081
_refine_diff_density_max         0.745
_refine_diff_density_min         -0.614
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.052(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1452
_refine_ls_number_reflns         28760
_refine_ls_number_restraints     99
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0577
_refine_ls_R_factor_gt           0.0493
_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^)+(0.0570P)^2^+13.5146P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1240
_refine_ls_wR_factor_ref         0.1295
_reflns_Friedel_coverage         0.838
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.951
_reflns_number_gt                25201
_reflns_number_total             28760
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01876a2.cif
_cod_data_source_block           cwmwm18
_cod_depositor_comments
'Adding full bibliography for 7716945--7716947.cif.'
_cod_database_code               7716945
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.641
_shelx_estimated_absorpt_t_min   0.324
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.948(4)
 0.052(4)
2. 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
3. Restrained distances
 N17-C72 \\sim N17-C72'
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 1.2A
5. Same fragment restrains
{C100, C101, C102, C103, C104, C99} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C00', C01', C02', C03', C04', C99'}
{C99, C104, C103, C102, C101, C100} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C99, C100, C101, C102, C103, C104}
6. Others
 Sof(C00')=Sof(H00')=Sof(C01')=Sof(H01')=Sof(C02')=Sof(H02')=Sof(C03')=
 Sof(H03')=Sof(C04')=Sof(H04')=Sof(C99')=1-FVAR(1)
 Sof(C99)=Sof(C100)=Sof(H100)=Sof(C101)=Sof(H101)=Sof(C102)=Sof(H102)=
 Sof(C103)=Sof(H103)=Sof(C104)=Sof(H104)=FVAR(1)
 Sof(C72')=Sof(H72D)=Sof(H72E)=Sof(H72F)=1-FVAR(2)
 Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=FVAR(2)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C53(H53A,H53B), C54(H54A,H54B), C27(H27A,H27B),
 C28(H28A,H28B), C79(H79A,H79B), C80(H80A,H80B)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C22(H22),
 C23(H23), C24(H24), C25(H25), C26(H26), C55(H55), C62(H62), C63(H63), C64(H64),
  C65(H65), C66(H66), C67(H67), C74(H74), C75(H75), C76(H76), C77(H77),
 C78(H78), C29(H29), C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41),
  C48(H48), C49(H49), C50(H50), C51(H51), C52(H52), C00'(H00'), C01'(H01'),
 C02'(H02'), C03'(H03'), C04'(H04'), C81(H81), C88(H88), C89(H89), C90(H90),
 C91(H91), C92(H92), C93(H93), C100(H100), C101(H101), C102(H102), C103(H103),
 C104(H104)
7.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C),
 C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C71(H71A,H71B,H71C), C72(H72A,H72B,
 H72C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C45(H45A,H45B,H45C), C46(H46A,
 H46B,H46C), C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C97(H97A,H97B,H97C),
 C98(H98A,H98B,H98C), C72'(H72D,H72E,H72F)
;
_shelx_res_checksum              20604
_shelx_hkl_checksum              28305
_shelx_fab_checksum              27722
_olex2_submission_original_sample_id cwmwm18
_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 1.536
_oxdiff_exptl_absorpt_empirical_full_min 0.737