Activating a high-spin iron(II) complex to thermal spin-crossover with an inert non-isomorphous molecular dopant.
Halcrow, Malcolm A.; Vasili, Hari Babu; Pask, Christopher M.; Kulak, Alexander N.; Cespedes, Oscar; Dalton transactions (Cambridge, England : 2003) 53 (2024) 6983–6992; doi:10.1039/d4dt00443d

data_7715541
_publ_section_title
;
 Activating a high-spin iron(II) complex to thermal spin-crossover with an
 inert non-isomorphous molecular dopant.
;
_journal_issue                   16
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              6983
_journal_page_last               6992
_journal_paper_doi               10.1039/d4dt00443d
_journal_volume                  53
_journal_year                    2024
_chemical_absolute_configuration ab
_chemical_formula_moiety         'C22 H18 Fe0.76 N10 Ni0.24, 2(Cl O4)'
_chemical_formula_sum            'C22 H18 Cl2 Fe0.76 N10 Ni0.24 O8'
_chemical_formula_weight         677.90
_chemical_name_systematic
'Bis[2,6-di(pyrazol-1-yl)pyridine]iron(II) bis[2,6-di(pyrazol-1-yl)pyridine]-nickel(II) ditetrafluoroborate 0.76:0.24 solid solution'
_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             2024-01-31
_audit_creation_method
;
Olex2 1.5
(compiled 2021.07.19 svn.r715e62df for OlexSys, GUI svn.r6383)
;
_audit_update_record
;
2024-02-13 deposited with the CCDC.	2024-03-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.424(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.4873(5)
_cell_length_b                   8.5486(5)
_cell_length_c                   18.6946(10)
_cell_measurement_reflns_used    5286
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      29.2810
_cell_measurement_theta_min      2.1770
_cell_volume                     1341.74(13)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'XSEED (Barbour, 2020)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELX-TL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3095
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.862
_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    -77.00   8.00   1.00   30.00    --   -9.84 -52.00 165.00   85
  2  \w    -31.00  28.00   1.00   30.00    --   -9.84  52.00 -49.00   59
  3  \w    -13.00  29.00   1.00   30.00    --    9.45 -99.00  60.00   42
  4  \w    -42.00 -16.00   1.00   30.00    --    9.45 -77.00   0.00   26
  5  \w    -36.00  20.00   1.00   30.00    --   -9.84  77.00   0.00   56
;
_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      -0.0553844000
_diffrn_orient_matrix_UB_12      0.0020910000
_diffrn_orient_matrix_UB_13      0.0249103000
_diffrn_orient_matrix_UB_21      -0.0079886000
_diffrn_orient_matrix_UB_22      -0.0825646000
_diffrn_orient_matrix_UB_23      -0.0023760000
_diffrn_orient_matrix_UB_31      0.0631872000
_diffrn_orient_matrix_UB_32      -0.0085358000
_diffrn_orient_matrix_UB_33      0.0290868000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0347
_diffrn_reflns_av_unetI/netI     0.0602
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.862
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            10773
_diffrn_reflns_point_group_measured_fraction_full 0.925
_diffrn_reflns_point_group_measured_fraction_max 0.758
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.736
_diffrn_reflns_theta_min         2.203
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.868
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.866
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.678
_exptl_crystal_description       lath
_exptl_crystal_F_000             689
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile/diethyl ether'
_exptl_crystal_size_max          0.135
_exptl_crystal_size_mid          0.051
_exptl_crystal_size_min          0.039
_refine_diff_density_max         0.486
_refine_diff_density_min         -0.507
_refine_diff_density_rms         0.095
_refine_ls_abs_structure_details
;
 Flack x determined using 1895 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.018(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     388
_refine_ls_number_reflns         5799
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.0532
_refine_ls_R_factor_gt           0.0487
_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^)+(0.0145P)^2^+2.1932P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0911
_refine_ls_wR_factor_ref         0.0931
_reflns_Friedel_coverage         0.655
_reflns_Friedel_fraction_full    0.839
_reflns_Friedel_fraction_max     0.640
_reflns_number_gt                5420
_reflns_number_total             5799
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00443d2.cif
_cod_data_source_block           mh723
_cod_depositor_comments
'Adding full bibliography for 7715536--7715541.cif.'
_cod_database_code               7715541
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C22H18Cl2Fe0.73N10Ni0.27O8
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(Fe1) = Uanis(Ni1)
3. Others
 X(Fe1)=X(Ni1)=FVAR(1)
 Y(Fe1)=Y(Ni1)=FVAR(2)
 Z(Fe1)=Z(Ni1)=FVAR(3)
 Fixed Sof: Fe1(0.76) Ni1(0.24)
4.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12), C15(H15), C16(H16),
 C17(H17), C20(H20), C21(H21), C22(H22), C26(H26), C27(H27), C28(H28), C31(H31),
  C32(H32), C33(H33)
;
_shelx_res_checksum              76699
_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 1.280
_oxdiff_exptl_absorpt_empirical_full_min 0.820