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_7709645
_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 H28 Fe N8 S2, 2(Cl O4), 2(C2 H3 N)'
_chemical_formula_sum            'C38 H34 Cl2 Fe N10 O8 S2'
_chemical_formula_weight         949.62
_chemical_name_systematic
'[2,6-Bis((R)-4-phenyl-4,5-dihydrothiazol-2-yl)pyridine]-[2,6-di(pyrazol-1-yl)pyridine]iron(II) diperchlorateacetonitrile solvate'
_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
_audit_creation_date             2021-05-07
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.8452(1)
_cell_length_b                   20.3285(3)
_cell_length_c                   22.9238(4)
_cell_measurement_reflns_used    6606
_cell_measurement_temperature    130.00(10)
_cell_measurement_theta_max      72.2840
_cell_measurement_theta_min      4.4020
_cell_volume                     4121.92(11)
_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 0.986
_diffrn_measured_fraction_theta_max 0.981
_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   -112.00 -33.00   1.00    1.50    --  -41.04 -57.00-150.00   79
  2  \w   -113.00 -16.00   1.00    1.50    --  -41.04 -57.00 -90.00   97
  3  \w     18.00  44.00   1.00    1.50    --   41.04 -37.00-180.00   26
  4  \w     67.00 178.00   1.00    6.00    --  103.83  15.00 -30.00  111
  5  \w     77.00 169.00   1.00    6.00    --  103.83  61.00 120.00   92
  6  \w     77.00 120.00   1.00    6.00    --  103.83 -63.00-132.43   43
  7  \w     96.00 163.00   1.00    6.00    --  103.83  45.00-120.00   67
  8  \w     33.00 133.00   1.00    6.00    --  103.83 -63.00-173.36  100
;
_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      -0.0175131000
_diffrn_orient_matrix_UB_12      0.0060774000
_diffrn_orient_matrix_UB_13      -0.0667046000
_diffrn_orient_matrix_UB_21      -0.1620052000
_diffrn_orient_matrix_UB_22      -0.0273725000
_diffrn_orient_matrix_UB_23      0.0044085000
_diffrn_orient_matrix_UB_31      -0.0615767000
_diffrn_orient_matrix_UB_32      0.0703231000
_diffrn_orient_matrix_UB_33      0.0074212000
_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  0.0461
_diffrn_reflns_av_unetI/netI     0.0647
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            15685
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        72.000
_diffrn_reflns_theta_max         72.484
_diffrn_reflns_theta_min         3.857
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.630
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.445
_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            brown
_exptl_crystal_density_diffrn    1.530
_exptl_crystal_description       plate
_exptl_crystal_F_000             1952
_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          0.05
_refine_diff_density_max         0.325
_refine_diff_density_min         -0.352
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Flack x determined using 2604 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     573
_refine_ls_number_reflns         7950
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0504
_refine_ls_R_factor_gt           0.0412
_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^)+(0.0318P)^2^+1.8280P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0903
_refine_ls_wR_factor_ref         0.0945
_reflns_Friedel_coverage         0.770
_reflns_Friedel_fraction_full    0.970
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                6996
_reflns_number_total             7950
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00393g2.cif
_cod_data_source_block           ns537
_cod_database_code               7709645
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.76
_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
 1.4313 with sigma of 0.02
 Cl4A-O48A
 1.4313 with sigma of 0.02
 Cl4A-O49A
 1.4313 with sigma of 0.02
 Cl4A-O50A
 1.4313 with sigma of 0.02
 Cl4B-O47B
 1.4313 with sigma of 0.02
 Cl4B-O48B
 1.4313 with sigma of 0.02
 Cl4B-O49B
 1.4313 with sigma of 0.02
 Cl4B-O50B
 1.4313 with sigma of 0.02
 O47A-O48A
 2.337313 with sigma of 0.02
 O47A-O49A
 2.337313 with sigma of 0.02
 O47A-O50A
 2.337313 with sigma of 0.02
 O48A-O49A
 2.337313 with sigma of 0.02
 O48A-O50A
 2.337313 with sigma of 0.02
 O49A-O50A
 2.337313 with sigma of 0.02
3. Others
 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)=1.633*FVAR(2)
 Fixed Sof: Cl4A(0.73) O47A(0.73) O48A(0.73) O49A(0.73) O50A(0.73) Cl4B(0.27)
 O47B(0.27) O48B(0.27) O49B(0.27) O50B(0.27)
4.a Ternary CH refined with riding coordinates:
 C10(H10), C21(H21)
4.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C22(H22A,H22B)
4.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18),
 C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C32(H32), C33(H33), C34(H34),
  C38(H38), C39(H39), C40(H40), C43(H43), C44(H44), C45(H45)
4.d Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C59(H59A,H59B,H59C)
;
_shelx_res_checksum              53524
_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 2.261
_oxdiff_exptl_absorpt_empirical_full_min 0.561