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_7715536
_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 N10 Ni, 2(Cl O4)'
_chemical_formula_sum            'C22 H18 Cl2 N10 Ni O8'
_chemical_formula_weight         680.07
_chemical_name_systematic
;
Bis[2,6-di{pyrazol-1-yl}pyridine]nickel(II) diperchlorate
;
_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             2023-08-04
_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                 97.645(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.5069(3)
_cell_length_b                   8.5670(2)
_cell_length_c                   18.8513(7)
_cell_measurement_reflns_used    9067
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      29.4450
_cell_measurement_theta_min      2.2260
_cell_volume                     1361.64(8)
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3095
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.886
_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    -65.00   3.00   1.00    4.00    --    9.61 -25.00 131.00   68
  2  \w    -16.00  82.00   1.00    4.00    --    9.61  25.00 -64.00   98
  3  \w     -3.00  46.00   1.00    4.00    --    9.61 -99.00  90.00   49
  4  \w    -41.00  20.00   1.00    4.00    --   -9.92 -77.00  30.00   61
  5  \w    -35.00  19.00   1.00    4.00    --   -9.92 -77.00 120.00   54
  6  \w    -11.00  15.00   1.00    4.00    --   -9.92  77.00 -60.00   26
  7  \w    -30.00  -1.00   1.00    4.00    --   -9.92  77.00 -30.00   29
;
_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      0.0765238000
_diffrn_orient_matrix_UB_12      -0.0224817000
_diffrn_orient_matrix_UB_13      0.0163992000
_diffrn_orient_matrix_UB_21      -0.0309395000
_diffrn_orient_matrix_UB_22      -0.0147471000
_diffrn_orient_matrix_UB_23      0.0324864000
_diffrn_orient_matrix_UB_31      -0.0161423000
_diffrn_orient_matrix_UB_32      -0.0783148000
_diffrn_orient_matrix_UB_33      -0.0108346000
_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  0.0340
_diffrn_reflns_av_unetI/netI     0.0514
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.886
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            15835
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.860
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.749
_diffrn_reflns_theta_min         2.180
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.976
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.555
_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            blue
_exptl_crystal_density_diffrn    1.659
_exptl_crystal_description       'rectangular prism'
_exptl_crystal_F_000             692
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: nitromethane/diethyl ether'
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.283
_refine_diff_density_min         -0.518
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
;
 Flack x determined using 2507 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     409
_refine_ls_number_reflns         6658
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0392
_refine_ls_R_factor_gt           0.0351
_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^)+(0.0215P)^2^+0.4088P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0659
_refine_ls_wR_factor_ref         0.0686
_reflns_Friedel_coverage         0.827
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.831
_reflns_number_gt                6197
_reflns_number_total             6658
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00443d2.cif
_cod_data_source_block           mh5clo4
_cod_depositor_comments
'Adding full bibliography for 7715536--7715541.cif.'
_cod_database_code               7715536
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C44  H36  Cl4  N20  Ni2  O16  '
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 Cl3A-O40A
 1.44286 with sigma of 0.02
 Cl3A-O41A
 1.44286 with sigma of 0.02
 Cl3A-O42A
 1.44286 with sigma of 0.02
 Cl3A-O43A
 1.44286 with sigma of 0.02
 O40A-O41A
 2.35619 with sigma of 0.02
 O40A-O42A
 2.35619 with sigma of 0.02
 O40A-O43A
 2.35619 with sigma of 0.02
 O41A-O42A
 2.35619 with sigma of 0.02
 O41A-O43A
 2.35619 with sigma of 0.02
 O42A-O43A
 2.35619 with sigma of 0.02
 Cl3B-O40B
 1.44286 with sigma of 0.02
 Cl3B-O41B
 1.44286 with sigma of 0.02
 Cl3B-O42B
 1.44286 with sigma of 0.02
 Cl3B-O43B
 1.44286 with sigma of 0.02
 O40B-O41B
 2.35619 with sigma of 0.02
 O40B-O42B
 2.35619 with sigma of 0.02
 O40B-O43B
 2.35619 with sigma of 0.02
 O41B-O42B
 2.35619 with sigma of 0.02
 O41B-O43B
 2.35619 with sigma of 0.02
 O42B-O43B
 2.35619 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(DFIX)=1(DFIX)=1(DFIX)=
 1(DFIX)=1(DFIX)=1(DFIX)=1.633*FVAR(2)
 Fixed Sof: Cl3A(0.71) O40A(0.71) O41A(0.71) O42A(0.71) O43A(0.71) Cl3B(0.29)
 O40B(0.29) O41B(0.29) O42B(0.29) O43B(0.29)
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              83786
_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 1.316
_oxdiff_exptl_absorpt_empirical_full_min 0.796