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_7709640
_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         'C46 H38 Fe N6 O2 S2, 2(Cl O4), C H3 N O2'
_chemical_formula_sum            'C47 H41 Cl2 Fe N7 O12 S2'
_chemical_formula_weight         1086.74
_chemical_name_systematic
'[2,6-Bis((R)-4-phenyl-4,5-dihydrothiazol-2-yl)pyridine]- [2,6-Bis((S)-4-phenyl-4,5-dihydroxazol-2-yl)pyridine]iron(II) diperchlorate nitromethane 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
_audit_creation_date             2020-11-06
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2022-01-10 deposited with the CCDC.	2022-03-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.775(1)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.9689(2)
_cell_length_b                   12.0094(1)
_cell_length_c                   16.2339(2)
_cell_measurement_reflns_used    12737
_cell_measurement_temperature    125.0(1)
_cell_measurement_theta_max      72.15
_cell_measurement_theta_min      4.40
_cell_volume                     2325.35(5)
_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      125.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3095
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.970
_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    -22.00  22.00   1.00    2.32    --  -41.04  37.00 120.00   44
  2  \w    -36.00  33.00   1.00    2.32    --  -41.04  37.00 -60.00   69
  3  \w   -113.00 -26.00   1.00    2.32    --  -41.04 -57.00-150.00   87
  4  \w    -61.00  29.00   1.00    2.32    --  -41.04  57.00   0.00   90
  5  \w     12.00  50.00   1.00    2.32    --   41.04  63.00 -57.89   38
  6  \w    -24.00  62.00   1.00    2.32    --   41.04 -57.00-180.00   86
  7  \w     74.00 100.00   1.00    9.29    --  103.83  63.00-127.77   26
  8  \w     74.00 100.00   1.00    9.29    --  103.83  64.00 -97.46   26
  9  \w     31.00 120.00   1.00    9.29    --  103.83 -65.00-132.36   89
 10  \w     76.00 132.00   1.00    9.29    --  103.83  61.00 -60.00   56
 11  \w     79.00 106.00   1.00    9.29    --  103.83  61.00 -90.00   27
 12  \w     62.00  89.00   1.00    9.29    --  103.83 -64.00 115.82   27
 13  \w     47.00  98.00   1.00    9.29    --  103.83 -65.00 162.50   51
 14  \w     79.00 175.00   1.00    9.29    --  103.83  61.00   0.00   96
 15  \w     62.00 144.00   1.00    9.29    --  103.83 -15.00  30.00   82
 16  \w     70.00  97.00   1.00    9.29    --  103.83 -63.00  15.61   27
 17  \w     51.00 131.00   1.00    9.29    --  103.83 -64.00  60.57   80
 18  \w     76.00 112.00   1.00    9.29    --  103.83  55.00 -64.30   36
 19  \w     59.00 109.00   1.00    9.29    --  103.83 -65.00 145.60   50
 20  \w     77.00 169.00   1.00    9.29    --  103.83  61.00-120.00   92
 21  \w     78.00 177.00   1.00    9.29    --  103.83  45.00  60.00   99
 22  \w     70.00  95.00   1.00    9.29    --  103.83 -65.00-163.73   25
 23  \w     67.00 100.00   1.00    9.29    --  103.83 -64.00  99.01   33
 24  \w     32.00  93.00   1.00    9.29    --  103.83 -65.00 -25.64   61
 25  \w     68.00  95.00   1.00    9.29    --  103.83 -65.00 -73.92   27
 26  \w     35.00  62.00   1.00    9.29    --  103.83 -65.00 -85.89   27
;
_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      0.1230195000
_diffrn_orient_matrix_UB_12      -0.0382923000
_diffrn_orient_matrix_UB_13      0.0013951000
_diffrn_orient_matrix_UB_21      -0.0359084000
_diffrn_orient_matrix_UB_22      -0.1201650000
_diffrn_orient_matrix_UB_23      0.0178290000
_diffrn_orient_matrix_UB_31      -0.0160120000
_diffrn_orient_matrix_UB_32      -0.0235847000
_diffrn_orient_matrix_UB_33      -0.0935281000
_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  0.0368
_diffrn_reflns_av_unetI/netI     0.0424
_diffrn_reflns_Laue_measured_fraction_full 0.970
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            20842
_diffrn_reflns_point_group_measured_fraction_full 0.943
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        72.000
_diffrn_reflns_theta_max         72.475
_diffrn_reflns_theta_min         3.706
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.120
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.708
_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            violet
_exptl_crystal_density_diffrn    1.552
_exptl_crystal_description       'rectangular prism'
_exptl_crystal_F_000             1120
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: nitromethane/diethyl ether'
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.663
_refine_diff_density_min         -0.427
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Flack x determined using 3530 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     632
_refine_ls_number_reflns         8622
_refine_ls_number_restraints     52
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0380
_refine_ls_R_factor_gt           0.0359
_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^)+(0.0540P)^2^+0.8479P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0901
_refine_ls_wR_factor_ref         0.0920
_reflns_Friedel_coverage         0.849
_reflns_Friedel_fraction_full    0.914
_reflns_Friedel_fraction_max     0.908
_reflns_number_gt                8263
_reflns_number_total             8622
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00393g2.cif
_cod_data_source_block           ns408
_cod_database_code               7709640
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 98.42
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 Cl63-O64A = Cl63-O65A = Cl63-O66A = Cl63-O67A
 1.44017 with sigma of 0.02
 Cl63-O64B = Cl63-O65B = Cl63-O66B = Cl63-O67B
 1.44017 with sigma of 0.02
 O64A-O65A = O64A-O66A = O64A-O67A = O65A-O66A = O65A-O67A = O66A-O67A
 2.351798 with sigma of 0.02
 O64B-O65B = O64B-O66B = O64B-O67B = O65B-O66B = O65B-O67B = O66B-O67B
 2.351798 with sigma of 0.02
 C13A-C14A \\sim C14A-C15A \\sim C15A-C16A \\sim C16A-C17A \\sim C17A-C18A
\\sim C13A-C18A
 with sigma of 0.01
 C13B-C14B \\sim C14B-C15B \\sim C15B-C16B \\sim C16B-C17B \\sim C17B-C18B
\\sim C13B-C18B
 with sigma of 0.01
 C10-C13A \\sim C10-C13B
 with sigma of 0.01
3. Others
 1(DFIX)=1(DFIX)=FVAR(1)
 1(DFIX)=1(DFIX)=1.633*FVAR(2)
 Fixed Sof: H10(0.5) H10A(0.5) C13A(0.5) C14A(0.5) H14A(0.5) C15A(0.5)
 H15A(0.5) C16A(0.5) H16A(0.5) C17A(0.5) H17A(0.5) C18A(0.5) H18A(0.5)
 C13B(0.5) C14B(0.5) H14B(0.5) C15B(0.5) H15B(0.5) C16B(0.5) H16B(0.5)
 C17B(0.5) H17B(0.5) C18B(0.5) H18B(0.5) O64A(0.5) O65A(0.5) O66A(0.5)
 O67A(0.5) O64B(0.5) O65B(0.5) O66B(0.5) O67B(0.5)
4.a Ternary CH refined with riding coordinates:
 C10(H10), C10(H10A), C21(H21), C38(H38), C49(H49)
4.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C22(H22A,H22B), C39(H39A,H39B), C50(H50A,H50B)
4.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C14A(H14A), C15A(H15A), C16A(H16A), C17A(H17A),
 C18A(H18A), C14B(H14B), C15B(H15B), C16B(H16B), C17B(H17B), C18B(H18B),
 C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C32(H32), C33(H33), C34(H34),
  C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C53(H53), C54(H54),
 C55(H55), C56(H56), C57(H57)
4.d Idealised Me refined as rotating group:
 C68(H68A,H68B,H68C)
;
_shelx_res_checksum              72857
_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 1.523
_oxdiff_exptl_absorpt_empirical_full_min 0.678