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_7048063
_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(B F4), C H3 N O2'
_chemical_formula_sum            'C27 H27 B2 F8 Fe N13 O2 S2'
_chemical_formula_weight         859.20
_chemical_name_systematic
'Iron(II) bis(N-methyl-2,6-bis(pyrazol-1-yl)pyridine-4-carbothioamide ) tetrafluorobroate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-09-05
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.03.02 svn.r3394 for Rigaku Oxford Diffraction, GUI svn.r5318)
;
_audit_update_record
;
2018-08-07 deposited with the CCDC.
2018-11-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.7390(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.25830(10)
_cell_length_b                   40.8625(4)
_cell_length_c                   10.80570(10)
_cell_measurement_reflns_used    13112
_cell_measurement_temperature    329.98(12)
_cell_measurement_theta_max      77.0310
_cell_measurement_theta_min      4.2520
_cell_volume                     3633.97(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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      329.98(12)
_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     17.00  71.00   0.50    1.60    --    0.57  19.00 -30.00  108
  2  \w     10.00  60.00   0.50    1.60    --    0.57  38.00-120.00  100
  3  \w     35.00  83.00   0.50    6.20    --  104.00 -45.00 -30.00   96
  4  \w     71.00 100.00   0.50    6.20    --  104.00 -94.00   0.00   58
  5  \w     37.00  64.00   0.50    6.20    --  104.00 -30.00 120.00   54
  6  \w     38.00 110.00   0.50    6.20    --  104.00 -77.00 120.00  144
  7  \w     34.00  59.00   0.50    6.20    --  104.00 -30.00   0.00   50
  8  \w     34.00  61.00   0.50    6.20    --  104.00 -15.00  30.00   54
  9  \w     37.00  65.00   0.50    6.20    --  104.00 -15.00   0.00   56
 10  \w    104.00 175.00   0.50    6.20    --  104.00  45.00 -60.00  142
 11  \w    130.00 169.00   0.50    6.20    --  104.00  77.00 -30.00   78
 12  \w     93.00 122.00   0.50    6.20    --  104.00  77.00 -30.00   58
 13  \w    134.00 175.00   0.50    6.20    --  104.00 125.00 150.00   82
 14  \w     93.00 119.00   0.50    6.20    --  104.00 125.00 150.00   52
 15  \w     33.00 108.00   0.50    6.20    --  104.00 -94.00-150.00  150
 16  \w     34.00  59.00   0.50    6.20    --  104.00 -30.00-180.00   50
 17  \w    -67.00 -11.00   0.50    1.60    --    0.57 -38.00  60.00  112
 18  \w    -54.00 -23.00   0.50    6.20    --  -82.50  30.00 -60.00   62
 19  \w     34.00 108.00   0.50    6.20    --  104.00 -94.00 120.00  148
;
_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      -0.0306834000
_diffrn_orient_matrix_UB_12      0.0289053000
_diffrn_orient_matrix_UB_13      -0.0904374000
_diffrn_orient_matrix_UB_21      -0.0524653000
_diffrn_orient_matrix_UB_22      -0.0241098000
_diffrn_orient_matrix_UB_23      -0.1053812000
_diffrn_orient_matrix_UB_31      -0.1770384000
_diffrn_orient_matrix_UB_32      0.0021407000
_diffrn_orient_matrix_UB_33      0.0343974000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0196
_diffrn_reflns_av_unetI/netI     0.0215
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -49
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            20884
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.238
_diffrn_reflns_theta_min         4.246
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.207
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.408
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
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_density_diffrn    1.570
_exptl_crystal_F_000             1744
_exptl_crystal_size_max          0.329
_exptl_crystal_size_mid          0.106
_exptl_crystal_size_min          0.062
_refine_diff_density_max         0.498
_refine_diff_density_min         -0.358
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     555
_refine_ls_number_reflns         6617
_refine_ls_number_restraints     205
_refine_ls_restrained_S_all      1.138
_refine_ls_R_factor_all          0.0441
_refine_ls_R_factor_gt           0.0393
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0624P)^2^+1.3133P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1076
_refine_ls_wR_factor_ref         0.1111
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5910
_reflns_number_total             6617
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt03240h2.cif
_cod_data_source_block           ma-ctabpp-02a_cu_330k
_cod_depositor_comments
'Adding full bibliography for 7048061--7048070.cif.'
_cod_database_code               7048063
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'C27 H27 B2 F8 Fe N13 O2 S2'
_diffrn_oxdiff_ac3_digest_frames
;
01fa820f014a25903a845a8cfea8142a710165429a0
;
_diffrn_oxdiff_ac3_digest_hkl
;
012e2ea6832b43c8494dc5cd3d332851769231
;
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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
 F01B-B01G \\sim F4-B01G \\sim F2-B01G \\sim F01J-B01G \\sim F01H-B01G \\sim
F01K-B01G \\sim F016-B01G
 \\sim F01C-B01D \\sim F3-B01D \\sim F017-B01D \\sim F1-B01D \\sim F00E-B01D
\\sim F01E-B01D \\sim F0AA-B01D
 with sigma of 0.01
3. Rigid body (RIGU) restrains
 F016, B01G, F01J, F01B, F01H, F01K, F4, F2, F016, B01G, F01J, B01G, F01B,
 B01G, F01H, B01G, F01K, B01G, F4, B01G, F2, B01G
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1, F00E, B01D, F0AA, F017, F3, F01E, F01C, F00E, B01D, F0AA, B01D, F017,
 B01D, F3, B01D, F01E, B01D, F1, B01D, F01C, B01D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F01H)=Sof(F2)=Sof(F4)=1-FVAR(1)
 Sof(F01B)=Sof(F01J)=Sof(F01K)=FVAR(1)
 Sof(F1)=Sof(F0AA)=Sof(F3)=1-FVAR(2)
 Sof(F017)=Sof(F01C)=Sof(F01E)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C00J(H00J), N00K(H00K), N00L(H00L), C00M(H00M), C00O(H00O), C00Q(H00Q),
 C00R(H00R), C00S(H00S), C00T(H00T), C00V(H00V), C00W(H00W), C00X(H00X),
 C00Y(H00Y), C00Z(H00Z), C010(H010), C011(H011), C013(H013), C014(H014)
5.b Idealised Me refined as rotating group:
 C019(H01A,H01B,H01C), C01A(H01D,H01E,H01F), C01I(H01G,H01H,H01I)
;
_shelx_res_checksum              29849
_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 1.374
_oxdiff_exptl_absorpt_empirical_full_min 0.747