Exceptionally high temperature spin crossover in amide-functionalised 2,6-bis(pyrazol-1-yl)pyridine iron(ii) complex revealed by variable temperature Raman spectroscopy and single crystal X-ray diffraction.
Attwood, Max; Akutsu, Hiroki; Martin, Lee; Blundell, Toby J.; Le Maguere, Pierre; Turner, Scott S.; Dalton transactions (Cambridge, England : 2003) 50 (2021) 11843–11851; doi:10.1039/d1dt01743h

data_7707940
_publ_section_title
;
 Exceptionally high temperature spin crossover in amide-functionalised
 2,6-bis(pyrazol-1-yl)pyridine iron(ii) complex revealed by variable
 temperature Raman spectroscopy and single crystal X-ray diffraction.
;
_journal_issue                   34
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              11843
_journal_page_last               11851
_journal_paper_doi               10.1039/d1dt01743h
_journal_volume                  50
_journal_year                    2021
_chemical_formula_moiety         'C24 H20 Fe N12 O2, 2(B F4)'
_chemical_formula_sum            'C24 H20 B2 F8 Fe N12 O2'
_chemical_formula_weight         737.99
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_audit_update_record
;
2021-05-25 deposited with the CCDC.	2021-07-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.460(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.3506(6)
_cell_length_b                   33.3034(10)
_cell_length_c                   10.8189(8)
_cell_measurement_reflns_used    5586
_cell_measurement_temperature    499.99(10)
_cell_measurement_theta_max      73.8620
_cell_measurement_theta_min      4.4700
_cell_volume                     3213.9(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.3a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.3a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.3a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      499.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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    -61.00  22.00   0.50   12.00    --  -49.80  57.00-120.00  166
  2  \w    -43.00 -14.00   0.50   57.00    --  -84.25 125.00  60.00   58
  3  \w    -91.00 -63.00   0.50   57.00    --  -84.25 125.00  60.00   56
  4  \w    -93.00 -57.00   0.50   12.00    --  -49.80   0.00  90.00   72
  5  \w   -123.00 -91.00   0.50   57.00    --  -84.25   0.00  90.00   64
  6  \w   -119.00 -73.00   0.50   12.00    --  -49.80-125.00-120.00   92
  7  \w   -118.00 -91.00   0.50   12.00    --  -49.80-125.00-150.00   54
  8  \w    -82.00 -51.00   0.50   12.00    --  -49.80   0.00-150.00   62
  9  \w     36.00  73.00   0.50   57.00    --  105.75 -57.00 -30.00   74
 10  \w     40.00  83.00   0.50   57.00    --  105.75 -57.00   0.00   86
 11  \w     43.00  83.00   0.50   57.00    --  105.75 -57.00  60.00   80
 12  \w     52.00 111.00   0.50   57.00    --  105.75 -19.00  90.00  118
 13  \w     79.00 105.00   0.50   57.00    --  105.75   0.00  90.00   52
 14  \w     37.00  62.00   0.50   57.00    --  105.75 -37.00  90.00   50
 15  \w     34.00  59.00   0.50   57.00    --  105.75 -37.00  60.00   50
 16  \w     39.00 103.00   0.50   57.00    --  105.75-125.00  30.00  128
 17  \w     45.00  83.00   0.50   57.00    --  105.75 -57.00-120.00   76
 18  \w     46.00  86.00   0.50   57.00    --  105.75 -57.00-150.00   80
 19  \w     73.00 111.00   0.50   57.00    --  105.75   0.00-120.00   76
 20  \w     34.00  59.00   0.50   57.00    --  105.75 -37.00-180.00   50
 21  \w     36.00  61.00   0.50   57.00    --  105.75 -37.00-150.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1501753000
_diffrn_orient_matrix_UB_12      0.0227918000
_diffrn_orient_matrix_UB_13      -0.0445478000
_diffrn_orient_matrix_UB_21      -0.0017112000
_diffrn_orient_matrix_UB_22      0.0028905000
_diffrn_orient_matrix_UB_23      0.1415233000
_diffrn_orient_matrix_UB_31      0.0853409000
_diffrn_orient_matrix_UB_32      0.0401949000
_diffrn_orient_matrix_UB_33      0.0150369000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0432
_diffrn_reflns_av_unetI/netI     0.0465
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            18409
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.076
_diffrn_reflns_theta_max         67.076
_diffrn_reflns_theta_min         4.485
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.595
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54078
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.3a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark brown'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.525
_exptl_crystal_description       block
_exptl_crystal_F_000             1488
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.208
_exptl_crystal_size_mid          0.137
_exptl_crystal_size_min          0.073
_refine_diff_density_max         0.233
_refine_diff_density_min         -0.230
_refine_diff_density_rms         0.044
_refine_ls_extinction_coef       0.00052(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.008
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     499
_refine_ls_number_reflns         5715
_refine_ls_number_restraints     108
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0858
_refine_ls_R_factor_gt           0.0575
_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^)+(0.1302P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1712
_refine_ls_wR_factor_ref         0.1988
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3434
_reflns_number_total             5715
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt01743h2.cif
_cod_data_source_block           cambpp-01a_500k_manual
_cod_depositor_comments
'Adding full bibliography for 7707940--7707943.cif.'
_cod_original_cell_volume        3213.9(3)
_cod_database_code               7707940
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C24 H20 B2 F8 Fe N12 O2'
_chemical_oxdiff_usercomment     'ruby test crystal'
_reflns_odcompleteness_completeness 99.57
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
2. Restrained distances
 F00L-B019 \\sim F00K-B019 \\sim F2-B019 \\sim F015-B019 \\sim F01E-B019 \\sim
F00R-B019 \\sim F01D-B019
 with sigma of 0.01
 F0AA-B01A \\sim F00P-B01A \\sim F01C-B01A \\sim F0-B01A \\sim F014-B01A \\sim
F1-B01A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
F00K \\sim F00L \\sim F01D \\sim F01E \\sim F015 \\sim F2: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02
F01C \\sim F1 \\sim F014 \\sim F0 \\sim F016 \\sim F0AA: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(F0AA)=Sof(F0)=Sof(F1)=1-FVAR(1)
 Sof(F014)=Sof(F016)=Sof(F01C)=FVAR(1)
 Sof(F00L)=Sof(F2)=Sof(F01E)=1-FVAR(2)
 Sof(F00K)=Sof(F015)=Sof(F01D)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C00H(H00H), C00J(H00J), C00N(H00N), C00O(H00O), C00Q(H00Q), C00S(H00S),
 C00V(H00V), C00W(H00W), C00X(H00X), C010(H010), C011(H011), C012(H012),
 C013(H013), C017(H017), C018(H018), C01B(H01B)
5.b X=CH2 refined with riding coordinates:
 N00M(H00A,H00B), N00Y(H00C,H00D)
;
_shelx_res_checksum              7946
_shelx_hkl_checksum              74985
_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 2.284
_oxdiff_exptl_absorpt_empirical_full_min 0.633