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_7707943
_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(Cl O4)'
_chemical_formula_sum            'C24 H20 Cl2 Fe N12 O10'
_chemical_formula_weight         763.27
_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             2019-08-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-05-25 deposited with the CCDC.	2021-07-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.721(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4886(4)
_cell_length_b                   32.6089(8)
_cell_length_c                   10.5004(4)
_cell_measurement_reflns_used    4558
_cell_measurement_temperature    293(1)
_cell_measurement_theta_max      27.4560
_cell_measurement_theta_min      3.1320
_cell_volume                     3058.4(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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      293(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9832
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.843
_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    -51.00  20.00   1.00  325.00    --   16.00 -57.00-120.00   71
  2  \w     -1.00  79.00   1.00  325.00    --   16.00  57.00  90.00   80
  3  \w     44.00  70.00   1.00  325.00    --   16.00  57.00-180.00   26
  4  \w      9.00  64.00   1.00  325.00    --   16.00  37.00-180.00   55
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0464302000
_diffrn_orient_matrix_UB_12      0.0076159000
_diffrn_orient_matrix_UB_13      0.0352984000
_diffrn_orient_matrix_UB_21      0.0637995000
_diffrn_orient_matrix_UB_22      0.0081581000
_diffrn_orient_matrix_UB_23      0.0506895000
_diffrn_orient_matrix_UB_31      -0.0089543000
_diffrn_orient_matrix_UB_32      0.0186657000
_diffrn_orient_matrix_UB_33      -0.0365370000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0349
_diffrn_reflns_av_unetI/netI     0.0579
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.843
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -43
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            15661
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.843
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.302
_diffrn_reflns_theta_min         3.129
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.745
_exptl_absorpt_correction_T_max  0.961
_exptl_absorpt_correction_T_min  0.891
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.658
_exptl_crystal_description       block
_exptl_crystal_F_000             1552
_exptl_crystal_size_max          0.216
_exptl_crystal_size_mid          0.092
_exptl_crystal_size_min          0.065
_refine_diff_density_max         0.483
_refine_diff_density_min         -0.439
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     498
_refine_ls_number_reflns         7053
_refine_ls_number_restraints     347
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.0963
_refine_ls_R_factor_gt           0.0633
_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^)+(0.0261P)^2^+3.6544P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1055
_refine_ls_wR_factor_ref         0.1164
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5152
_reflns_number_total             7053
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt01743h2.cif
_cod_data_source_block           c-bppconh2mecn
_cod_depositor_comments
'Adding full bibliography for 7707940--7707943.cif.'
_cod_database_code               7707943
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C24 H20 Cl2 O10 Fe1 N12'
_reflns_odcompleteness_completeness 99.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
2. Restrained distances
 Cl03-O10 \\sim Cl03-O1AA \\sim Cl03-O7 \\sim Cl03-O0AA \\sim Cl03-O9 \\sim
Cl03-O2AA \\sim Cl03-O8 ~
 Cl02-O4B \\sim Cl02-O5 \\sim Cl02-O3B \\sim Cl02-O3 \\sim Cl02-O5B \\sim
Cl02-O4 \\sim Cl02-O6
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl02 \\sim Cl02 \\sim Cl02 \\sim Cl02 \\sim Cl02 \\sim Cl02 \\sim Cl02 \\sim O6
\\sim O3B \\sim O4B \\sim O5B \\sim Cl03 \\sim Cl03 \\sim Cl03 \\sim Cl03 \\sim
Cl03 \\sim Cl03 \\sim Cl03 \\sim Cl03 \\sim O8 \\sim O7 \\sim O9 \\sim O10
\\sim O0AA \\sim O1AA \\sim O2AA \\sim O3 \\sim O4 \\sim O5: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 Cl02, Cl02, Cl02, Cl02, Cl02, Cl02, Cl02, O6, O3B, O4B, O5B, Cl03, Cl03, Cl03,
  Cl03, Cl03, Cl03, Cl03, Cl03, O8, O7, O9, O10, O0AA, O1AA, O2AA, O3, O4, O5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O7)=Sof(O9)=Sof(O10)=1-FVAR(1)
 Sof(O0AA)=Sof(O1AA)=Sof(O2AA)=FVAR(1)
 Sof(O3B)=Sof(O4B)=Sof(O5B)=1-FVAR(2)
 Sof(O3)=Sof(O4)=Sof(O5)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5), C7(H7), C9(H9), C10(H10), C11(H11), C13(H13),
 C14(H14), C15(H15), C17(H17), C19(H19), C21(H21), C22(H22), C23(H23)
6.b X=CH2 refined with riding coordinates:
 N11(H11A,H11B), N12(H12A,H12B)
;
_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 1.018
_oxdiff_exptl_absorpt_empirical_full_min 0.981