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_7715539
_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 Fe0.5 N10 Ni0.5, 2(Cl O4)'
_chemical_formula_sum            'C22 H18 Cl2 Fe0.5 N10 Ni0.5 O8'
_chemical_formula_weight         678.64
_chemical_name_systematic
'Bis[2,6-di(pyrazol-1-yl)pyridine]iron(II) bis[2,6-di(pyrazol-1-yl)pyridine]-nickel(II) ditetrafluoroborate 0.50:0.50 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             2024-02-12
_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                 96.371(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.5567(7)
_cell_length_b                   8.6233(6)
_cell_length_c                   19.2053(15)
_cell_measurement_reflns_used    4032
_cell_measurement_temperature    300.00(10)
_cell_measurement_theta_max      26.35
_cell_measurement_theta_min      2.12
_cell_volume                     1408.35(19)
_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      air
_diffrn_ambient_temperature      300.00(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 0.851
_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    -58.00  16.00   1.00   60.00    --    9.61 -30.00-142.00   74
  2  \w     -5.00  83.00   1.00   60.00    --    9.61  30.00  18.00   88
  3  \w     -9.00  46.00   1.00   60.00    --    9.61 -99.00-180.00   55
  4  \w    -37.00  18.00   1.00   60.00    --  -10.00  77.00-150.00   55
;
_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      -0.0200198000
_diffrn_orient_matrix_UB_12      0.0146991000
_diffrn_orient_matrix_UB_13      -0.0362284000
_diffrn_orient_matrix_UB_21      0.0747707000
_diffrn_orient_matrix_UB_22      -0.0276861000
_diffrn_orient_matrix_UB_23      -0.0069574000
_diffrn_orient_matrix_UB_31      -0.0310797000
_diffrn_orient_matrix_UB_32      -0.0760539000
_diffrn_orient_matrix_UB_33      -0.0044490000
_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  0.0308
_diffrn_reflns_av_unetI/netI     0.0558
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.851
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            11743
_diffrn_reflns_point_group_measured_fraction_full 0.942
_diffrn_reflns_point_group_measured_fraction_max 0.780
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.766
_diffrn_reflns_theta_min         2.134
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.867
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.797
_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            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.600
_exptl_crystal_description       plate
_exptl_crystal_F_000             690
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile/diethyl ether'
_exptl_crystal_size_max          0.125
_exptl_crystal_size_mid          0.118
_exptl_crystal_size_min          0.041
_refine_diff_density_max         0.313
_refine_diff_density_min         -0.298
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 1511 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.019(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     422
_refine_ls_number_reflns         6235
_refine_ls_number_restraints     62
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0765
_refine_ls_R_factor_gt           0.0532
_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^)+(0.0463P)^2^+0.1990P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1074
_refine_ls_wR_factor_ref         0.1210
_reflns_Friedel_coverage         0.725
_reflns_Friedel_fraction_full    0.878
_reflns_Friedel_fraction_max     0.698
_reflns_number_gt                4681
_reflns_number_total             6235
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00443d2.cif
_cod_data_source_block           mh722rt
_cod_depositor_comments
'Adding full bibliography for 7715536--7715541.cif.'
_cod_original_formula_sum        'C22 H18 Cl2 Fe0.50 N10 Ni0.50 O8'
_cod_database_code               7715539
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C22H18Cl2Fe0.5N10Ni0.5O8
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 Cl3A-O35A = Cl3A-O36A = Cl3A-O37A = Cl3A-O38A
 1.44284 with sigma of 0.02
 Cl3B-O35B = Cl3B-O36B = Cl3B-O37B = Cl3B-O38B
 1.44284 with sigma of 0.02
 Cl3B-O35C = Cl3B-O36C = Cl3B-O37C = Cl3B-O38C
 1.44284 with sigma of 0.02
 Cl39-O40A = Cl39-O41A = Cl39-O42A = Cl39-O43A
 1.44284 with sigma of 0.02
 Cl39-O40B = Cl39-O41B = Cl39-O42B = Cl39-O43B
 1.44284 with sigma of 0.02
 Cl39-O40C = Cl39-O41C = Cl39-O42C = Cl39-O43C
 1.44284 with sigma of 0.02
 O35A-O36A = O35A-O37A = O35A-O38A = O36A-O37A = O36A-O38A = O37A-O38A
 2.356158 with sigma of 0.02
 O35B-O36B = O35B-O37B = O35B-O38B = O36B-O37B = O36B-O38B = O37B-O38B
 2.356158 with sigma of 0.02
 O35C-O36C = O35C-O37C = O35C-O38C = O36C-O37C = O36C-O38C = O37C-O38C
 2.356158 with sigma of 0.02
 O40A-O41A = O40A-O42A = O40A-O43A = O41A-O42A = O41A-O43A = O42A-O43A
 2.356158 with sigma of 0.02
 O40B-O41B = O40B-O42B = O40B-O43B = O41B-O42B = O41B-O43B = O42B-O43B
 2.356158 with sigma of 0.02
 O40C-O41C = O40C-O42C = O40C-O43C = O41C-O42C = O41C-O43C = O42C-O43C
 2.356158 with sigma of 0.02
 N13-O38C
 -3 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Fe1) = Uanis(Ni1)
4. Others
 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)
 X(Fe1)=X(Ni1)=FVAR(2)
 Y(Fe1)=Y(Ni1)=FVAR(3)
 Z(Fe1)=Z(Ni1)=FVAR(4)
 Fixed Sof: Fe1(0.5) Ni1(0.5) Cl3A(0.5) O35A(0.5) O36A(0.5) O37A(0.5)
 O38A(0.5) Cl3B(0.5) O35B(0.35) O36B(0.35) O37B(0.35) O38B(0.35) O35C(0.15)
 O36C(0.15) O37C(0.15) O38C(0.15) O40A(0.45) O41A(0.45) O42A(0.45) O43A(0.45)
 O40B(0.15) O41B(0.15) O42B(0.15) O43B(0.15) O40C(0.4) O41C(0.4) O42C(0.4)
 O43C(0.4)
5.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              93861
_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 1.725
_oxdiff_exptl_absorpt_empirical_full_min 0.692