Heteroleptic iron(ii) complexes of chiral 2,6-bis(oxazolin-2-yl)-pyridine (PyBox) and 2,6-bis(thiazolin-2-yl)pyridine ligands – the interplay of two different ligands on the metal ion spin sate
Shahid, Namrah; Burrows, Kay E.; Pask, Christopher M.; Cespedes, Oscar; Howard, Mark J.; McGowan, Patrick C.; Halcrow, Malcolm A.; Dalton Transactions  (2022) –; doi:10.1039/D2DT00393G

data_7709643
_publ_section_title
;
 Heteroleptic iron(ii) complexes of chiral 2,6-bis(oxazolin-2-yl)-pyridine
 (PyBox) and 2,6-bis(thiazolin-2-yl)pyridine ligands -- the interplay of
 two different ligands on the metal ion spin sate
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00393G
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety
'C36 H36 Fe N8 S2, 2(Cl O4), C2 H3 N, C4 H10 O'
_chemical_formula_sum            'C42 H49 Cl2 Fe N9 O9 S2'
_chemical_formula_weight         1014.77
_chemical_name_systematic
'[2,6-Bis((S)-4-isopropyl-4,5-dihydrothiazol-2-yl)pyridine]-[2,6-bis(1H-benzimidazol-2-yl)pyridine]iron(II) diperchlorateacetonitrile diethyl ether solvate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-03-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-01-10 deposited with the CCDC.	2022-03-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.649(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.0025(3)
_cell_length_b                   24.0613(9)
_cell_length_c                   11.2550(5)
_cell_measurement_reflns_used    4830
_cell_measurement_temperature    130.00(10)
_cell_measurement_theta_max      71.35
_cell_measurement_theta_min      4.47
_cell_volume                     2335.76(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_molecular_graphics    'X-Seed (Barbour, 2001)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      130.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3095
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.966
_diffrn_measured_fraction_theta_max 0.966
_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    -36.00  30.00   1.00   30.00    --  -41.04  37.00-120.00   66
  2  \w   -112.00 -65.00   1.00   30.00    --  -41.04 -57.00 150.00   47
  3  \w     12.00  99.00   1.00   30.00    --   41.04  64.00 -94.92   87
  4  \w    -25.00   4.00   1.00   30.00    --   41.04 -37.00-150.00   29
  5  \w     30.00  67.00   1.00   30.00    --   41.04 -57.00  90.00   37
  6  \w     28.00 127.00   1.00  120.00    --  102.56 -30.00-120.00   99
  7  \w     70.00  98.00   1.00  120.00    --  102.56 -65.00 159.03   28
  8  \w     51.00 109.00   1.00  120.00    --  102.56 -65.00 129.50   58
  9  \w     34.00 124.00   1.00  120.00    --  102.56 -65.00  46.85   90
 10  \w     78.00 169.00   1.00  120.00    --  102.56  45.00  60.00   91
 11  \w     81.00 111.00   1.00  120.00    --  102.56 -45.00 -90.00   30
 12  \w     76.00 101.00   1.00  120.00    --  102.56 -64.00  94.17   25
 13  \w    -68.00 -27.00   1.00   30.00    --  -41.29  57.00-150.00   41
 14  \w     10.00  48.00   1.00   30.00    --   41.29  19.00-120.00   38
 15  \w     15.00  41.00   1.00   30.00    --   41.29  57.00 -90.00   26
 16  \w     15.00  81.00   1.00   30.00    --   41.29  57.00-180.00   66
 17  \w     19.00  61.00   1.00   30.00    --   41.29  57.00-120.00   42
 18  \w    -14.00  53.00   1.00   30.00    --   41.29 -37.00-150.00   67
 19  \w     73.00  99.00   1.00  120.00    --  102.56  61.00 -90.00   26
 20  \w     73.00  99.00   1.00  120.00    --  102.56  65.00-120.30   26
 21  \w     74.00  99.00   1.00  120.00    --  102.56  57.00-123.78   25
 22  \w     73.00 109.00   1.00  120.00    --  102.56  61.00-180.00   36
 23  \w     81.00 115.00   1.00  120.00    --  102.56  45.00-150.00   34
 24  \w     73.00  98.00   1.00  120.00    --  102.56  61.00 120.00   25
 25  \w    124.00 151.00   1.00  120.00    --  102.56  61.00 150.00   27
 26  \w     73.00  99.00   1.00  120.00    --  102.56  61.00-150.00   26
 27  \w    140.00 166.00   1.00  120.00    --  102.56  63.00-163.07   26
 28  \w     73.00  98.00   1.00  120.00    --  102.56  61.00-120.00   25
 29  \w     77.00 148.00   1.00  120.00    --  102.56  45.00 150.00   71
 30  \w     73.00  98.00   1.00  120.00    --  102.56  61.00 150.00   25
 31  \w     78.00 104.00   1.00  120.00    --  102.56  61.00  90.00   26
 32  \w    102.00 128.00   1.00  120.00    --  102.56 -45.00 -90.00   26
 33  \w     73.00 118.00   1.00  120.00    --  102.56  61.00 -60.00   45
 34  \w     78.00 103.00   1.00  120.00    --  102.56  45.00-120.00   25
 35  \w     78.00 103.00   1.00  120.00    --  102.56  45.00-180.00   25
 36  \w     81.00 119.00   1.00  120.00    --  102.56  45.00 120.00   38
 37  \w     74.00 100.00   1.00  120.00    --  102.56  63.00-163.07   26
 38  \w     76.00 102.00   1.00  120.00    --  102.56  48.00-115.86   26
 39  \w     47.00  73.00   1.00  120.00    --  102.56 -64.00  80.92   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1520993000
_diffrn_orient_matrix_UB_12      0.0105255000
_diffrn_orient_matrix_UB_13      -0.1030420000
_diffrn_orient_matrix_UB_21      0.0903483000
_diffrn_orient_matrix_UB_22      0.0001691000
_diffrn_orient_matrix_UB_23      -0.0974420000
_diffrn_orient_matrix_UB_31      -0.0250382000
_diffrn_orient_matrix_UB_32      -0.0631189000
_diffrn_orient_matrix_UB_33      -0.0174087000
_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  0.0763
_diffrn_reflns_av_unetI/netI     0.0905
_diffrn_reflns_Laue_measured_fraction_full 0.966
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            21424
_diffrn_reflns_point_group_measured_fraction_full 0.909
_diffrn_reflns_point_group_measured_fraction_max 0.909
_diffrn_reflns_theta_full        71.978
_diffrn_reflns_theta_max         71.978
_diffrn_reflns_theta_min         3.674
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.011
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.462
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.443
_exptl_crystal_description       needle
_exptl_crystal_F_000             1056
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile/diethyl ether'
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.429
_refine_diff_density_min         -0.700
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details
;
 Flack x determined using 2324 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.009(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     586
_refine_ls_number_reflns         8331
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0690
_refine_ls_R_factor_gt           0.0522
_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^)+(0.0487P)^2^+0.0738P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1197
_refine_ls_wR_factor_ref         0.1322
_reflns_Friedel_coverage         0.836
_reflns_Friedel_fraction_full    0.850
_reflns_Friedel_fraction_max     0.850
_reflns_number_gt                6911
_reflns_number_total             8331
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00393g2.cif
_cod_data_source_block           ns532_a
_cod_original_cell_volume        2335.75(16)
_cod_database_code               7709643
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 98.52
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C61A-C62A
 1.52 with sigma of 0.02
 C64A-C65A
 1.52 with sigma of 0.02
 C62A-O63A
 1.43 with sigma of 0.02
 O63A-C64A
 1.43 with sigma of 0.02
 C62A-C64A
 2.34 with sigma of 0.02
 C61A-O63A
 2.42 with sigma of 0.02
 O63A-C65A
 2.42 with sigma of 0.02
 C61B-C62B
 1.52 with sigma of 0.02
 C64B-C65B
 1.52 with sigma of 0.02
 C62B-O63B
 1.43 with sigma of 0.02
 O63B-C64B
 1.43 with sigma of 0.02
 C62B-C64B
 2.34 with sigma of 0.02
 C61B-O63B
 2.42 with sigma of 0.02
 O63B-C65B
 2.42 with sigma of 0.02
3. Others
 Fixed Sof: C61A(0.5) H61A(0.5) H61B(0.5) H61C(0.5) C62A(0.5) H62A(0.5)
 H62B(0.5) O63A(0.5) C64A(0.5) H64A(0.5) H64B(0.5) C65A(0.5) H65A(0.5)
 H65B(0.5) H65C(0.5) C61B(0.5) H61D(0.5) H61E(0.5) H61F(0.5) C62B(0.5)
 H62C(0.5) H62D(0.5) O63B(0.5) C64B(0.5) H64C(0.5) H64D(0.5) C65B(0.5)
 H65D(0.5) H65E(0.5) H65F(0.5)
4.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C18(H18), C21(H21)
4.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C19(H19A,H19B), C62A(H62A,H62B), C64A(H64A,H64B), C62B(H62C,
 H62D), C64B(H64C,H64D)
4.c Me refined with riding coordinates:
 C61A(H61A,H61B,H61C), C65A(H65A,H65B,H65C), C61B(H61D,H61E,H61F), C65B(H65D,
 H65E,H65F)
4.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C26(H26), C27(H27), C28(H28), C33(H33), C34(H34),
 C35(H35), C36(H36), N38(H38), C42(H42), C43(H43), C44(H44), C45(H45), N47(H47)
4.e Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C58(H58A,H58B,H58C)
;
_shelx_res_checksum              50535
_olex2_date_sample_data_collection 2021-03-17
_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 5.203
_oxdiff_exptl_absorpt_empirical_full_min 0.534