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_7709639
_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_formula_moiety         'C30 H22 Fe N6, 2(Cl O4), 2(C2 H3 N)'
_chemical_formula_sum            'C34 H28 Cl2 Fe N8 O8'
_chemical_formula_weight         803.39
_chemical_name_systematic
'Bis[2,2':6',2''-terpyridine]iron(II) diperchlorate bis-acetonitrile solvate'
_space_group_crystal_system      tetragonal
_space_group_IT_number           78
_space_group_name_Hall           'P 4cw'
_space_group_name_H-M_alt        'P 43'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-01-07
_audit_creation_method
;
Olex2 1.5
(compiled 2021.07.19 svn.r715e62df for OlexSys, GUI svn.r6383)
;
_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            8
_cell_length_a                   12.2320(1)
_cell_length_b                   12.2320(1)
_cell_length_c                   47.2452(6)
_cell_measurement_reflns_used    11009
_cell_measurement_temperature    130.01(10)
_cell_measurement_theta_max      72.34
_cell_measurement_theta_min      4.55
_cell_volume                     7068.91(12)
_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 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_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 0.993
_diffrn_measured_fraction_theta_max 0.988
_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    -78.00 -36.00   0.75   31.17    --  -41.04 -49.00  41.00   56
  2  \w   -127.00  29.00   0.75   31.17    --  -41.04   0.00-120.00  208
  3  \w     78.00 161.25   0.75  124.69    --  103.83  30.00 120.00  111
  4  \w     78.00 105.00   0.75  124.69    --  103.83  61.00  60.00   36
  5  \w    128.00 175.25   0.75  124.69    --  103.83  61.00  60.00   63
  6  \w     80.00 106.25   0.75  124.69    --  103.83  45.00 150.00   35
  7  \w     50.00 122.00   0.75  124.69    --  103.83 -45.00 -60.00   96
  8  \w    115.00 162.25   0.75  124.69    --  103.83  45.00 150.00   63
  9  \w     94.00 129.25   0.75  124.69    --  103.83 -45.00-150.00   47
 10  \w     39.00 127.50   0.75  124.69    --  103.83 -45.00  60.00  118
;
_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      0.0323274000
_diffrn_orient_matrix_UB_12      0.1057358000
_diffrn_orient_matrix_UB_13      0.0156294000
_diffrn_orient_matrix_UB_21      -0.0691187000
_diffrn_orient_matrix_UB_22      -0.0354287000
_diffrn_orient_matrix_UB_23      0.0256642000
_diffrn_orient_matrix_UB_31      0.1002199000
_diffrn_orient_matrix_UB_32      -0.0585616000
_diffrn_orient_matrix_UB_33      0.0126445000
_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  0.0394
_diffrn_reflns_av_unetI/netI     0.0530
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       57
_diffrn_reflns_limit_l_min       -58
_diffrn_reflns_number            27682
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        72.000
_diffrn_reflns_theta_max         72.568
_diffrn_reflns_theta_min         3.613
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.361
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.695
_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    1.510
_exptl_crystal_description       fragment
_exptl_crystal_F_000             3296
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile/diethyl ether'
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.522
_refine_diff_density_min         -0.728
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
;
 Flack x determined using 5318 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     948
_refine_ls_number_reflns         13607
_refine_ls_number_restraints     44
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0550
_refine_ls_R_factor_gt           0.0514
_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^)+(0.0607P)^2^+6.0907P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1258
_refine_ls_wR_factor_ref         0.1289
_reflns_Friedel_coverage         0.939
_reflns_Friedel_fraction_full    0.960
_reflns_Friedel_fraction_max     0.953
_reflns_number_gt                12827
_reflns_number_total             13607
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00393g2.cif
_cod_data_source_block           ns522
_cod_original_cell_volume        7068.91(15)
_cod_database_code               7709639
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl4A-O49A
 1.42624 with sigma of 0.02
 Cl4A-O50A
 1.42624 with sigma of 0.02
 Cl4A-O51A
 1.42624 with sigma of 0.02
 Cl4A-O52A
 1.42624 with sigma of 0.02
 O49A-O50A
 2.32905 with sigma of 0.02
 O49A-O51A
 2.32905 with sigma of 0.02
 O49A-O52A
 2.32905 with sigma of 0.02
 O50A-O51A
 2.32905 with sigma of 0.02
 O50A-O52A
 2.32905 with sigma of 0.02
 O51A-O52A
 2.32905 with sigma of 0.02
 Cl4B-O49B
 1.42624 with sigma of 0.02
 Cl4B-O50B
 1.42624 with sigma of 0.02
 Cl4B-O51B
 1.42624 with sigma of 0.02
 Cl4B-O52B
 1.42624 with sigma of 0.02
 O49B-O50B
 2.32905 with sigma of 0.02
 O49B-O51B
 2.32905 with sigma of 0.02
 O49B-O52B
 2.32905 with sigma of 0.02
 O50B-O51B
 2.32905 with sigma of 0.02
 O50B-O52B
 2.32905 with sigma of 0.02
 O51B-O52B
 2.32905 with sigma of 0.02
 Cl5A-O54A
 1.42624 with sigma of 0.02
 Cl5A-O55A
 1.42624 with sigma of 0.02
 Cl5A-O56A
 1.42624 with sigma of 0.02
 Cl5A-O57A
 1.42624 with sigma of 0.02
 O54A-O55A
 2.32905 with sigma of 0.02
 O54A-O56A
 2.32905 with sigma of 0.02
 O54A-O57A
 2.32905 with sigma of 0.02
 O55A-O56A
 2.32905 with sigma of 0.02
 O55A-O57A
 2.32905 with sigma of 0.02
 O56A-O57A
 2.32905 with sigma of 0.02
 Cl5B-O54B
 1.42624 with sigma of 0.02
 Cl5B-O55B
 1.42624 with sigma of 0.02
 Cl5B-O56B
 1.42624 with sigma of 0.02
 Cl5B-O57B
 1.42624 with sigma of 0.02
 O54B-O55B
 2.32905 with sigma of 0.02
 O54B-O56B
 2.32905 with sigma of 0.02
 O54B-O57B
 2.32905 with sigma of 0.02
 O55B-O56B
 2.32905 with sigma of 0.02
 O55B-O57B
 2.32905 with sigma of 0.02
 O56B-O57B
 2.32905 with sigma of 0.02
 C67A-C68A
 1.48 with sigma of 0.02
 C68A-N69A
 1.15 with sigma of 0.02
 C67A-N69A
 2.63 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O49B \\sim O50B \\sim O51B \\sim O52B: within 2A with sigma of 0.001 and sigma
for terminal atoms of 0.002 within 2A
O54B \\sim O55B \\sim O56B \\sim O57B: within 2A with sigma of 0.001 and sigma
for terminal atoms of 0.002 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)=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)=1.633*FVAR(2)
 Fixed Sof: Cl4A(0.65) O49A(0.65) O50A(0.65) O51A(0.65) O52A(0.65) Cl4B(0.35)
 O49B(0.35) O50B(0.35) O51B(0.35) O52B(0.35) Cl5A(0.75) O57A(0.75) O54A(0.75)
 O55A(0.75) O56A(0.75) Cl5B(0.25) O54B(0.25) O55B(0.25) O56B(0.25) O57B(0.25)
 C67A(0.5) H67A(0.5) H67B(0.5) H67C(0.5) C68A(0.5) N69A(0.5) C67B(0.5)
 H67D(0.5) H67E(0.5) H67F(0.5) C68B(0.5) N69B(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C5A(H5A), C6A(H6A), C10A(H10A), C11A(H11A), C12A(H12A), C13A(H13A),
 C16A(H16A), C17A(H17A), C18A(H18A), C19A(H19A), C22A(H22A), C23A(H23A),
 C24A(H24A), C28A(H28A), C29A(H29A), C30A(H30A), C31A(H31A), C34A(H34A),
 C35A(H35A), C36A(H36A), C37A(H37A), C4B(H4B), C5B(H5B), C6B(H6B), C10B(H10B),
 C11B(H11B), C12B(H12B), C13B(H13B), C16B(H16B), C17B(H17B), C18B(H18B),
 C19B(H19B), C22B(H22B), C23B(H23B), C24B(H24B), C28B(H28B), C29B(H29B),
 C30B(H30B), C31B(H31B), C34B(H34B), C35B(H35B), C36B(H36B), C37B(H37B)
5.b Idealised Me refined as rotating group:
 C58(H58A,H58B,H58C), C61(H61A,H61B,H61C), C64(H64A,H64B,H64C), C67A(H67A,H67B,
 H67C), C67B(H67D,H67E,H67F)
;
_shelx_res_checksum              18045
_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 2.788
_oxdiff_exptl_absorpt_empirical_full_min 0.637