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_7715537
_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_formula_moiety         'C22 H18 Fe N10, 2(Cl O4)'
_chemical_formula_sum            'C22 H18 Cl2 Fe N10 O8'
_chemical_formula_weight         677.21
_chemical_name_systematic
; 
Bis-[2,6-dipyrazol-1-ylpyridine]iron(II) diperchlorate
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-11-09
_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                 99.014(1)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.5206(2)
_cell_length_b                   9.3323(1)
_cell_length_c                   20.1872(2)
_cell_measurement_reflns_used    7619
_cell_measurement_temperature    300(1)
_cell_measurement_theta_max      72.73
_cell_measurement_theta_min      2.19
_cell_volume                     2701.80(5)
_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 0.998
_diffrn_measured_fraction_theta_max 0.982
_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    -72.00  31.00   1.00    1.50    --  -38.50  86.00  55.00  103
  2  \w    -10.00  76.00   1.00    1.50    --   42.71 -86.00 -62.00   86
  3  \w    101.00 178.00   1.00    6.00    --  103.10  86.00  55.00   77
  4  \w     28.00 137.00   1.00    6.00    --  103.10 -86.00 -62.00  109
  5  \w    -59.00  33.00   1.00    1.50    --  -38.50  37.00-180.00   92
  6  \w     22.00 114.00   1.00    1.50    --   42.71  37.00 -30.00   92
  7  \w    103.00 174.00   1.00    6.00    --  103.10  77.00  30.00   71
  8  \w    103.00 174.00   1.00    6.00    --  103.10  77.00 120.00   71
  9  \w     35.00 112.00   1.00    6.00    --  103.10-125.00 120.00   77
 10  \w     77.00 172.00   1.00    6.00    --  103.10  61.00   0.00   95
 11  \w     82.00 176.00   1.00    6.00    --  103.10  30.00-150.00   94
 12  \w     82.00 176.00   1.00    6.00    --  103.10  30.00   0.00   94
 13  \w    103.00 174.00   1.00    6.00    --  103.10  77.00-150.00   71
 14  \w     18.00 111.00   1.00    1.50    --   42.71  57.00-150.00   93
 15  \w     18.00 111.00   1.00    1.50    --   42.71  57.00  30.00   93
 16  \w     18.00 111.00   1.00    1.50    --   42.71  57.00 150.00   93
 17  \w      6.00  80.00   1.00    1.50    --   42.71 -99.00-180.00   74
 18  \w     18.00 111.00   1.00    1.50    --   42.71  57.00  90.00   93
;
_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      -0.0368595000
_diffrn_orient_matrix_UB_12      0.1497652000
_diffrn_orient_matrix_UB_13      -0.0227067000
_diffrn_orient_matrix_UB_21      0.0515949000
_diffrn_orient_matrix_UB_22      -0.0087785000
_diffrn_orient_matrix_UB_23      -0.0610454000
_diffrn_orient_matrix_UB_31      -0.0866525000
_diffrn_orient_matrix_UB_32      -0.0689508000
_diffrn_orient_matrix_UB_33      -0.0415825000
_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  0.0491
_diffrn_reflns_av_unetI/netI     0.0290
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            12271
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.883
_diffrn_reflns_theta_min         4.435
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.904
_exptl_absorpt_correction_T_max  0.989
_exptl_absorpt_correction_T_min  0.194
_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            yellow
_exptl_crystal_density_diffrn    1.665
_exptl_crystal_description       plate
_exptl_crystal_F_000             1376
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: nitromethane/diethyl ether'
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.617
_refine_diff_density_min         -0.302
_refine_diff_density_rms         0.059
_refine_ls_extinction_coef       0.00090(17)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     242
_refine_ls_number_reflns         2655
_refine_ls_number_restraints     64
_refine_ls_restrained_S_all      1.123
_refine_ls_R_factor_all          0.0451
_refine_ls_R_factor_gt           0.0428
_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^)+(0.0826P)^2^+2.2754P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1240
_refine_ls_wR_factor_ref         0.1266
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2490
_reflns_number_total             2656
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00443d2.cif
_cod_data_source_block           mh87rt
_cod_depositor_comments
'Adding full bibliography for 7715536--7715541.cif.'
_cod_database_code               7715537
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C22 H18 Cl2 Fe1 N10 O8'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 O19A-O20A
 2.31708 with sigma of 0.02
 O19A-O21A
 2.31708 with sigma of 0.02
 O19A-O22A
 2.31708 with sigma of 0.02
 O20A-O21A
 2.31708 with sigma of 0.02
 O20A-O22A
 2.31708 with sigma of 0.02
 O21A-O22A
 2.31708 with sigma of 0.02
 Cl1B-O19B
 1.41891 with sigma of 0.02
 Cl1B-O20B
 1.41891 with sigma of 0.02
 Cl1B-O21B
 1.41891 with sigma of 0.02
 Cl1B-O22B
 1.41891 with sigma of 0.02
 O19B-O20B
 2.31708 with sigma of 0.02
 O19B-O21B
 2.31708 with sigma of 0.02
 O19B-O22B
 2.31708 with sigma of 0.02
 O20B-O21B
 2.31708 with sigma of 0.02
 O20B-O22B
 2.31708 with sigma of 0.02
 O21B-O22B
 2.31708 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O19A) \\sim Ueq, Uanis(O20A) \\sim Ueq, Uanis(O21A) \\sim Ueq,
Uanis(O22A) \\sim Ueq, Uanis(O19B) \\sim Ueq, Uanis(O20B) \\sim Ueq,
Uanis(O21B) \\sim Ueq, Uanis(O22B) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.004
4. Others
 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)=1.633*FVAR(2)
 Fixed Sof: Cl1A(0.5) O19A(0.5) O20A(0.5) O21A(0.5) O22A(0.5) Cl1B(0.5)
 O19B(0.5) O20B(0.5) O21B(0.5) O22B(0.5)
 Fixed X: Fe1(0)
 Fixed Z: Fe1(0.25)
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)
;
_shelx_res_checksum              89453
_olex2_submission_special_instructions 'No special instructions were received'