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_7709641
_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 ab
_chemical_formula_moiety         'C34 H46 Fe N6 O2 S2, 2(Cl O4), C2 H3 N'
_chemical_formula_sum            'C36 H49 Cl2 Fe N7 O10 S2'
_chemical_formula_weight         930.69
_chemical_name_systematic
'[2,6-Bis((S)-4-isopropyl-4,5-dihydrothiazol-2-yl)pyridine]- [2,6-Bis((R)-4-isopropyl-4,5-dihydroxazol-2-yl)pyridine]iron(II) diperchlorate acetonitrile 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             2021-01-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2022-01-10 deposited with the CCDC.	2022-03-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.246(1)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.3515(1)
_cell_length_b                   18.6328(3)
_cell_length_c                   20.5925(3)
_cell_measurement_reflns_used    18190
_cell_measurement_temperature    130.01(10)
_cell_measurement_theta_max      72.21
_cell_measurement_theta_min      4.73
_cell_volume                     4256.42(10)
_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      130.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3095
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.959
_diffrn_measured_fraction_theta_max 0.954
_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    -17.00  14.00   1.00    7.50    --  -41.04  57.00  30.00   31
  2  \w    -68.00 -42.00   1.00    7.50    --  -41.04  57.00  30.00   26
  3  \w    -31.00  68.00   1.00    7.50    --   41.04 -57.00-150.00   99
  4  \w     12.00 105.00   1.00    7.50    --   41.04  64.00  37.53   93
  5  \w     43.00 101.00   1.00    7.50    --   41.04  57.00 120.00   58
  6  \w     12.00 114.00   1.00    7.50    --   41.04  64.00 -13.71  102
  7  \w     13.00  65.00   1.00    7.50    --   41.04  57.00 -60.00   52
  8  \w     13.00 101.00   1.00    7.50    --   41.04  63.00 -46.38   88
  9  \w     83.00 110.00   1.00   25.00    --  103.83 -65.00 -22.33   27
 10  \w     68.00  95.00   1.00   25.00    --  103.83 -65.00 153.71   27
 11  \w     64.00  91.00   1.00   25.00    --  103.83 -65.00-137.97   27
 12  \w     29.00 126.00   1.00   25.00    --  103.83 -30.00  60.00   97
 13  \w     76.00 101.00   1.00   25.00    --  103.83 -65.00 -39.15   25
 14  \w     54.00 121.00   1.00   25.00    --  103.83 -65.00-164.73   67
 15  \w     79.00 106.00   1.00   25.00    --  103.83 -30.00-180.00   27
 16  \w     22.00 123.00   1.00   25.00    --  103.83 -15.00 -90.00  101
 17  \w     31.00 110.00   1.00   25.00    --  103.83 -65.00 -58.41   79
 18  \w     60.00 108.00   1.00   25.00    --  103.83 -65.00  27.34   48
 19  \w     70.00 100.00   1.00   25.00    --  103.83 -65.00 171.15   30
 20  \w     68.00 102.00   1.00   25.00    --  103.83 -65.00-110.33   34
 21  \w     47.00 120.00   1.00   25.00    --  103.83 -30.00 -30.00   73
 22  \w     75.00 100.00   1.00   25.00    --  103.83 -65.00 -12.51   25
 23  \w     27.00 144.00   1.00   25.00    --  103.83 -15.00 150.00  117
 24  \w     74.00 101.00   1.00   25.00    --  103.83 -65.00-120.68   27
 25  \w     68.00 100.00   1.00   25.00    --  103.83 -65.00 122.52   32
 26  \w     59.00  84.00   1.00   25.00    --  103.83 -65.00  -6.12   25
 27  \w     72.00  97.00   1.00   25.00    --  103.83 -65.00 -14.03   25
 28  \w     69.00 106.00   1.00   25.00    --  103.83 -65.00  76.51   37
;
_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      -0.0834829000
_diffrn_orient_matrix_UB_12      -0.0317396000
_diffrn_orient_matrix_UB_13      -0.0621753000
_diffrn_orient_matrix_UB_21      -0.0448959000
_diffrn_orient_matrix_UB_22      0.0759489000
_diffrn_orient_matrix_UB_23      -0.0222162000
_diffrn_orient_matrix_UB_31      0.1015469000
_diffrn_orient_matrix_UB_32      0.0074164000
_diffrn_orient_matrix_UB_33      -0.0387520000
_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  0.0358
_diffrn_reflns_av_unetI/netI     0.0391
_diffrn_reflns_Laue_measured_fraction_full 0.959
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            37789
_diffrn_reflns_point_group_measured_fraction_full 0.943
_diffrn_reflns_point_group_measured_fraction_max 0.937
_diffrn_reflns_theta_full        72.000
_diffrn_reflns_theta_max         72.461
_diffrn_reflns_theta_min         3.985
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.445
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.306
_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    1.452
_exptl_crystal_description       plate
_exptl_crystal_F_000             1944
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile/diethyl ether'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.806
_refine_diff_density_min         -0.718
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details
;
 Flack x determined using 6491 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.009(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1072
_refine_ls_number_reflns         15763
_refine_ls_number_restraints     98
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0608
_refine_ls_R_factor_gt           0.0586
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0917P)^2^+5.0965P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1545
_refine_ls_wR_factor_ref         0.1571
_reflns_Friedel_coverage         0.902
_reflns_Friedel_fraction_full    0.925
_reflns_Friedel_fraction_max     0.919
_reflns_number_gt                15143
_reflns_number_total             15763
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00393g2.cif
_cod_data_source_block           ns467
_cod_database_code               7709641
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 97.33
_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
 Cl4A-O47A
 1.42819 with sigma of 0.02
 Cl4A-O48A
 1.42819 with sigma of 0.02
 Cl4A-O49A
 1.42819 with sigma of 0.02
 Cl4A-O50A
 1.42819 with sigma of 0.02
 Cl4B-O47B
 1.42819 with sigma of 0.02
 Cl4B-O48B
 1.42819 with sigma of 0.02
 Cl4B-O49B
 1.42819 with sigma of 0.02
 Cl4B-O50B
 1.42819 with sigma of 0.02
 O47A-O48A
 2.332234 with sigma of 0.02
 O47A-O49A
 2.332234 with sigma of 0.02
 O47A-O50A
 2.332234 with sigma of 0.02
 O48A-O49A
 2.332234 with sigma of 0.02
 O48A-O50A
 2.332234 with sigma of 0.02
 O49A-O50A
 2.332234 with sigma of 0.02
 Cl5A-O52A
 1.42819 with sigma of 0.02
 Cl5A-O53A
 1.42819 with sigma of 0.02
 Cl5A-O54A
 1.42819 with sigma of 0.02
 Cl5A-O55A
 1.42819 with sigma of 0.02
 Cl5B-O52B
 1.42819 with sigma of 0.02
 Cl5B-O53B
 1.42819 with sigma of 0.02
 Cl5B-O54B
 1.42819 with sigma of 0.02
 Cl5B-O55B
 1.42819 with sigma of 0.02
 O52A-O53A
 2.332234 with sigma of 0.02
 O52A-O54A
 2.332234 with sigma of 0.02
 O52A-O55A
 2.332234 with sigma of 0.02
 O53A-O54A
 2.332234 with sigma of 0.02
 O53A-O55A
 2.332234 with sigma of 0.02
 O54A-O55A
 2.332234 with sigma of 0.02
 O52B-O53B
 2.332234 with sigma of 0.02
 O52B-O54B
 2.332234 with sigma of 0.02
 O52B-O55B
 2.332234 with sigma of 0.02
 O53B-O54B
 2.332234 with sigma of 0.02
 O53B-O55B
 2.332234 with sigma of 0.02
 O54B-O55B
 2.332234 with sigma of 0.02
 Cl5C-O57A
 1.42819 with sigma of 0.02
 Cl5C-O58A
 1.42819 with sigma of 0.02
 Cl5C-O59A
 1.42819 with sigma of 0.02
 Cl5C-O60A
 1.42819 with sigma of 0.02
 Cl5D-O57B
 1.42819 with sigma of 0.02
 Cl5D-O58B
 1.42819 with sigma of 0.02
 Cl5D-O59B
 1.42819 with sigma of 0.02
 Cl5D-O60B
 1.42819 with sigma of 0.02
 O57A-O58A
 2.332234 with sigma of 0.02
 O57A-O59A
 2.332234 with sigma of 0.02
 O57A-O60A
 2.332234 with sigma of 0.02
 O58A-O59A
 2.332234 with sigma of 0.02
 O58A-O60A
 2.332234 with sigma of 0.02
 O59A-O60A
 2.332234 with sigma of 0.02
 Cl6A-O62A
 1.42819 with sigma of 0.02
 Cl6A-O63A
 1.42819 with sigma of 0.02
 Cl6A-O64A
 1.42819 with sigma of 0.02
 Cl6A-O65A
 1.42819 with sigma of 0.02
 Cl6B-O62B
 1.42819 with sigma of 0.02
 Cl6B-O63B
 1.42819 with sigma of 0.02
 Cl6B-O64B
 1.42819 with sigma of 0.02
 Cl6B-O65B
 1.42819 with sigma of 0.02
 Cl6C-O62C
 1.42819 with sigma of 0.02
 Cl6C-O63C
 1.42819 with sigma of 0.02
 Cl6C-O64C
 1.42819 with sigma of 0.02
 O62A-O63A
 2.332234 with sigma of 0.02
 O62A-O64A
 2.332234 with sigma of 0.02
 O62A-O65A
 2.332234 with sigma of 0.02
 O63A-O64A
 2.332234 with sigma of 0.02
 O63A-O65A
 2.332234 with sigma of 0.02
 O64A-O65A
 2.332234 with sigma of 0.02
 O62B-O63B
 2.332234 with sigma of 0.02
 O62B-O64B
 2.332234 with sigma of 0.02
 O63B-O64B
 2.332234 with sigma of 0.02
 O63B-O65B
 2.332234 with sigma of 0.02
 O64B-O65B
 2.332234 with sigma of 0.02
 O62C-O63C
 2.332234 with sigma of 0.02
 O62C-O64C
 2.332234 with sigma of 0.02
 O63C-O64C
 2.332234 with sigma of 0.02
 C66A-C67
 1.48 with sigma of 0.02
 C67-N68A
 1.15 with sigma of 0.02
 C66A-N68A
 2.63 with sigma of 0.02
 C66B-C67
 1.48 with sigma of 0.02
 C67-N68B
 1.15 with sigma of 0.02
 C66B-N68B
 2.63 with sigma of 0.02
 C69A-C70
 1.48 with sigma of 0.02
 C70-N71A
 1.15 with sigma of 0.02
 C69A-N71A
 2.63 with sigma of 0.02
 C69B-C70
 1.48 with sigma of 0.02
 C70-N71B
 1.15 with sigma of 0.02
 C69B-N71B
 2.63 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl6A \\sim O62A \\sim O63A \\sim O64A \\sim O65A: within 2A with sigma of 0.002
and sigma for terminal atoms of 0.004 within 2A
Cl6B \\sim O62B \\sim O63B \\sim O64B \\sim O65B: within 2A with sigma of 0.002
and sigma for terminal atoms of 0.004 within 2A
Cl6C \\sim O62C \\sim O63C \\sim O64C \\sim O65C: within 2A with sigma of 0.002
and sigma for terminal atoms of 0.004 within 2A
4. Others
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=FVAR(1)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=
 1(DFIX)=1(DFIX)=1.633*FVAR(2)
 Fixed Sof: Cl4A(0.67) O47A(0.67) O48A(0.67) O49A(0.67) O50A(0.67) Cl4B(0.33)
 O47B(0.33) O48B(0.33) O49B(0.33) O50B(0.33) Cl5A(0.43) O52A(0.43) O53A(0.43)
 O54A(0.43) O55A(0.43) Cl5B(0.57) O52B(0.57) O53B(0.57) O54B(0.57) O55B(0.57)
 Cl5C(0.53) O57A(0.53) O58A(0.53) O59A(0.53) O60A(0.53) Cl5D(0.47) O57B(0.47)
 O58B(0.47) O59B(0.47) O60B(0.47) Cl6A(0.34) O62A(0.34) O63A(0.34) O64A(0.34)
 O65A(0.34) Cl6B(0.33) O62B(0.33) O63B(0.33) O64B(0.33) O65B(0.33) Cl6C(0.33)
 O62C(0.33) O63C(0.33) O64C(0.33) O65C(0.33) C66A(0.52) H66A(0.52) H66B(0.52)
 H66C(0.52) N68A(0.52) C66B(0.48) H66D(0.48) H66E(0.48) H66F(0.48) N68B(0.48)
 C69A(0.59) H69A(0.59) H69B(0.59) H69C(0.59) N71A(0.59) C69B(0.41) H69D(0.41)
 H69E(0.41) H69F(0.41) N71B(0.41)
5.a Ternary CH refined with riding coordinates:
 C10A(H10A), C13A(H13A), C18A(H18A), C21A(H21A), C32A(H32A), C35A(H35A),
 C40A(H40A), C43A(H43A), C10B(H10B), C13B(H13B), C18B(H18B), C21B(H21B),
 C32B(H32B), C35B(H35B), C40B(H40B), C43B(H43B)
5.b Secondary CH2 refined with riding coordinates:
 C11A(H11A,H11B), C19A(H19A,H19B), C33A(H33A,H33B), C41A(H41A,H41B), C11B(H11C,
 H11D), C19B(H19C,H19D), C33B(H33C,H33D), C41B(H41C,H41D)
5.c Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C5A(H5A), C6A(H6A), C26A(H26A), C27A(H27A), C28A(H28A), C4B(H4B),
 C5B(H5B), C6B(H6B), C26B(H26B), C27B(H27B), C28B(H28B)
5.d Idealised Me refined as rotating group:
 C14A(H14A,H14B,H14C), C15A(H15A,H15B,H15C), C22A(H22A,H22B,H22C), C23A(H23A,
 H23B,H23C), C36A(H36A,H36B,H36C), C37A(H37A,H37B,H37C), C44A(H44A,H44B,H44C),
 C45A(H45A,H45B,H45C), C14B(H14D,H14E,H14F), C15B(H15D,H15E,H15F), C22B(H22D,
 H22E,H22F), C23B(H23D,H23E,H23F), C36B(H36D,H36E,H36F), C37B(H37D,H37E,H37F),
 C44B(H44D,H44E,H44F), C45B(H45D,H45E,H45F), C66A(H66A,H66B,H66C), C66B(H66D,
 H66E,H66F), C69A(H69A,H69B,H69C), C69B(H69D,H69E,H69F)
;
_shelx_res_checksum              68589
_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 2.678
_oxdiff_exptl_absorpt_empirical_full_min 0.580