Above room temperature spin crossover in thioamide-functionalised 2,6-bis(pyrazol-1-yl)pyridine iron(ii) complexes.
Attwood, Max; Akutsu, Hiroki; Martin, Lee; Cruickshank, Dyanne; Turner, Scott S.; Dalton transactions (Cambridge, England : 2003) 48 (2018) 90–98; doi:10.1039/c8dt03240h

data_7048065
_publ_section_title
;
 Above room temperature spin crossover in thioamide-functionalised
 2,6-bis(pyrazol-1-yl)pyridine iron(ii) complexes.
;
_journal_issue                   1
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              90
_journal_page_last               98
_journal_paper_doi               10.1039/c8dt03240h
_journal_volume                  48
_journal_year                    2018
_chemical_formula_moiety         'C26 H24 Fe N12 S2, 2(Cl O4)'
_chemical_formula_sum            'C26 H24 Cl2 Fe N12 O8 S2'
_chemical_formula_weight         823.44
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-09-07 deposited with the CCDC.
2018-11-09 downloaded from the CCDC.
;
_cell_angle_alpha                81.158(2)
_cell_angle_beta                 86.276(2)
_cell_angle_gamma                89.446(2)
_cell_formula_units_Z            2
_cell_length_a                   8.2808(2)
_cell_length_b                   10.2621(3)
_cell_length_c                   20.5898(5)
_cell_measurement_reflns_used    11677
_cell_measurement_temperature    369.99(10)
_cell_measurement_theta_max      77.3220
_cell_measurement_theta_min      4.2960
_cell_volume                     1725.24(8)
_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      369.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -12.00  55.00   0.50    4.00    --   49.80 -19.00 -60.00  134
  2  \w     38.00 109.00   0.50   16.25    --  105.75 -99.00 -60.00  142
  3  \w     74.00 101.00   0.50   16.25    --  105.75 -99.00   0.00   54
  4  \w     70.00 102.00   0.50   16.25    --  105.75 -19.00  90.00   64
  5  \w     55.00 109.00   0.50   16.25    --  105.75 -99.00  90.00  108
  6  \w     71.00 108.00   0.50   16.25    --  105.75 -99.00 150.00   74
  7  \w     34.00  68.00   0.50   16.25    --  105.75 -99.00 150.00   68
  8  \w     34.00  59.00   0.50   16.25    --  105.75 -37.00 120.00   50
  9  \w     35.00  67.00   0.50   16.25    --  105.75 -19.00  90.00   64
 10  \w     34.00  82.00   0.50   16.25    --  105.75 -57.00  60.00   96
 11  \w     34.00  59.00   0.50   16.25    --  105.75 -99.00   0.00   50
 12  \w     41.00  85.00   0.50   16.25    --  105.75 -57.00 -30.00   88
 13  \w     65.00 102.00   0.50   16.25    --  105.75   0.00 -90.00   74
 14  \w    104.00 147.00   0.50   16.25    --  105.75  19.00 -90.00   86
 15  \w     81.00 107.00   0.50   16.25    --  105.75 -77.00-150.00   52
 16  \w     66.00 112.00   0.50   16.25    --  105.75   0.00-180.00   92
 17  \w     49.00  86.00   0.50   16.25    --  105.75 -57.00-150.00   74
 18  \w     34.00  59.00   0.50   16.25    --  105.75 -37.00 -60.00   50
 19  \w     34.00  62.00   0.50   16.25    --  105.75 -37.00   0.00   56
 20  \w     37.00  62.00   0.50   16.25    --  105.75 -37.00 -30.00   50
 21  \w     35.00  60.00   0.50   16.25    --  105.75 -37.00 -90.00   50
 22  \w     34.00  62.00   0.50   16.25    --  105.75 -37.00-180.00   56
 23  \w     38.00  72.00   0.50   16.25    --  105.75 -57.00-180.00   68
 24  \w    124.00 175.00   0.50   16.25    --  105.75 125.00-180.00  102
 25  \w    -47.00  19.00   0.50    4.00    --  -49.80  37.00-180.00  132
 26  \w    -53.00 -19.00   0.50   16.25    --  -84.25  77.00-120.00   68
 27  \w    -88.00 -12.00   0.50   16.25    --  -84.25  19.00   0.00  152
 28  \w    -65.00  20.00   0.50    4.00    --  -49.80  77.00  30.00  170
 29  \w    -97.00 -46.00   0.50    4.00    --  -49.80   0.00  30.00  102
 30  \w   -109.00 -79.00   0.50   16.25    --  -84.25 -19.00  30.00   60
 31  \w   -128.00 -97.00   0.50   16.25    --  -84.25   0.00 120.00   62
 32  \w   -153.00-113.00   0.50   16.25    --  -84.25 -19.00  30.00   80
 33  \w   -118.00 -85.00   0.50    4.00    --  -49.80-125.00 120.00   66
 34  \w   -104.00 -79.00   0.50    4.00    --  -49.80-125.00  60.00   50
 35  \w   -112.00 -87.00   0.50    4.00    --  -49.80-125.00  30.00   50
 36  \w    -97.00 -62.00   0.50   16.25    --  -84.25  77.00-120.00   70
;
_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      -0.0596044000
_diffrn_orient_matrix_UB_12      0.1387440000
_diffrn_orient_matrix_UB_13      0.0097974000
_diffrn_orient_matrix_UB_21      -0.0543072000
_diffrn_orient_matrix_UB_22      -0.0528886000
_diffrn_orient_matrix_UB_23      0.0721426000
_diffrn_orient_matrix_UB_31      0.1680933000
_diffrn_orient_matrix_UB_32      0.0321645000
_diffrn_orient_matrix_UB_33      0.0213763000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0191
_diffrn_reflns_av_unetI/netI     0.0210
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            18366
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.601
_diffrn_reflns_theta_max         66.601
_diffrn_reflns_theta_min         4.566
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.640
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.418
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.3a (Rigaku Oxford Diffraction, 2018)
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            'dark brown'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.585
_exptl_crystal_description       block
_exptl_crystal_F_000             840
_exptl_crystal_size_max          0.249
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.055
_refine_diff_density_max         0.502
_refine_diff_density_min         -0.610
_refine_diff_density_rms         0.052
_refine_ls_extinction_coef       0.0008(2)
_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   1.088
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     494
_refine_ls_number_reflns         6085
_refine_ls_number_restraints     58
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.0510
_refine_ls_R_factor_gt           0.0468
_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^)+(0.0856P)^2^+0.6531P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1401
_refine_ls_wR_factor_ref         0.1439
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5401
_reflns_number_total             6085
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt03240h2.cif
_cod_data_source_block           cambpp-02b
_cod_depositor_comments
'Adding full bibliography for 7048061--7048070.cif.'
_cod_database_code               7048065
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C26 H24 Cl2 Fe N12 O9 S'
_reflns_odcompleteness_completeness 99.93
_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) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H1
 0.86 with sigma of 0.01
 Cl2-O11 \\sim Cl2-O10 \\sim Cl2-O6 \\sim Cl2-O7 \\sim Cl2-O8 \\sim Cl2-O5
\\sim Cl2-O9
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
O11 \\sim O6 \\sim O7 \\sim O8 \\sim O9 \\sim O10: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: O8(0.5) O6(0.5) O10(0.5) O11(0.5) O9(0.5) O7(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 N7(H7), C4(H4), C17(H17), C18(H18), C5(H5), C8(H8), C10(H10), C9(H9),
 C24(H24), C26(H26), C11(H11), C23(H23), C12(H12), C22(H22), C21(H21), C13(H13),
  C25(H25)
5.b Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              47373
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.331
_oxdiff_exptl_absorpt_empirical_full_min 0.713