Defying the inverse energy gap law: a vacuum-evaporable Fe(II) low-spin complex with a long-lived LIESST state
Tuczek, Felix; Grunwald, Jan; Torres, Jorge; Buchholz, Axel; Nather, Christian; Spieker, Lea; Gruber, Manuel; Rohlf, Sebastian; Thakur, Sangeeta; Wende, Heiko; Plass, Winfried; Kuch, Wolfgang; Chemical Science  (2023) –; doi:10.1039/D3SC00561E

data_1569229
_publ_section_title
;
 Defying the inverse energy gap law: a vacuum-evaporable Fe(II) low-spin
 complex with a long-lived LIESST state
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D3SC00561E
_journal_year                    2023
_chemical_formula_moiety         'C28 H20 Fe N6'
_chemical_formula_sum            'C28 H20 Fe N6'
_chemical_formula_weight         496.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-16
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_audit_update_record
;
2022-12-27 deposited with the CCDC.	2023-05-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.054(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   28.5552(4)
_cell_length_b                   13.9204(2)
_cell_length_c                   16.0184(2)
_cell_measurement_reflns_used    25165
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      78.1350
_cell_measurement_theta_min      3.1870
_cell_volume                     6202.76(15)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.987
_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   -115.00 -56.00   0.50    5.18    --  -47.54 -77.00-120.00  118
  2  \w   -119.00 -94.00   0.50    5.18    --  -47.54-125.00   0.00   50
  3  \w    -62.00  23.00   0.50    5.18    --  -47.54  57.00-180.00  170
  4  \w     10.00  69.00   0.50    5.18    --   47.54 -76.00 -23.00  118
  5  \w    -24.00  24.00   0.50    5.18    --   47.54 -19.00   0.00   96
  6  \w    -24.00  98.00   0.50    5.18    --   47.54   0.00  30.00  244
  7  \w     48.00  92.00   0.50    5.18    --   47.54-125.00-180.00   88
  8  \w   -110.00 -85.00   0.50   20.72    --  -91.75 -95.00 150.00   50
  9  \w    -50.00 -21.00   0.50   20.72    --  -91.75  45.00 -60.00   58
 10  \w    -51.00 -21.00   0.50   20.72    --  -91.75  45.00  60.00   60
 11  \w     46.00  92.00   0.50   20.72    --  113.25 -77.00  60.00   92
 12  \w     43.00 105.00   0.50   20.72    --  113.25-125.00 -60.00  124
 13  \w    101.00 176.00   0.50   20.72    --  113.25  45.00-180.00  150
 14  \w     50.00  85.00   0.50   20.72    --  113.25 -95.00  30.00   70
 15  \w    109.00 174.00   0.50   20.72    --  113.25  15.00 -60.00  130
 16  \w     45.00  70.00   0.50   20.72    --  113.25 -61.00 120.00   50
 17  \w    106.00 164.00   0.50   20.72    --  113.25  30.00   0.00  116
 18  \w    101.00 165.00   0.50   20.72    --  113.25  45.00  60.00  128
 19  \w    148.00 175.00   0.50   20.72    --  113.25  30.00  30.00   54
 20  \w     44.00  78.00   0.50   20.72    --  113.25-125.00   0.00   68
 21  \w     51.00  89.00   0.50   20.72    --  113.25 -77.00  90.00   76
 22  \w     81.00 106.00   0.50   20.72    --  113.25 -95.00 -30.00   50
 23  \w     64.00 104.00   0.50   20.72    --  113.25 -95.00-180.00   80
 24  \w     44.00  73.00   0.50   20.72    --  113.25-125.00 120.00   58
 25  \w     86.00 111.00   0.50   20.72    --  113.25-125.00 120.00   50
 26  \w     43.00 111.00   0.50   20.72    --  113.25-125.00 -90.00  136
 27  \w     42.00  67.00   0.50   20.72    --  113.25 -61.00 -30.00   50
 28  \w    110.00 139.00   0.50   20.72    --  113.25  30.00  30.00   58
 29  \w     43.00  68.00   0.50   20.72    --  113.25-105.00 -63.00   50
 30  \w     72.00 104.00   0.50   20.72    --  113.25-105.00 -63.00   64
 31  \w     79.00 106.00   0.50   20.72    --  113.25 -95.00   0.00   54
 32  \w     45.00  70.00   0.50   20.72    --  113.25 -61.00   0.00   50
 33  \w     42.00  67.00   0.50   20.72    --  113.25 -61.00 -90.00   50
 34  \w     43.00  69.00   0.50   20.72    --  113.25 -61.00-180.00   52
 35  \w     71.00 106.00   0.50   20.72    --  113.25 -95.00  60.00   70
 36  \w     42.00  71.00   0.50   20.72    --  113.25 -95.00   0.00   58
 37  \w     86.00 117.00   0.50   20.72    --  113.25-132.00 -94.12   62
 38  \w    117.00 175.00   0.50   20.72    --  113.25  45.00 120.00  116
 39  \w     42.00  85.00   0.50   20.72    --  113.25 -95.00 150.00   86
 40  \w     46.00  82.00   0.50   20.72    --  113.25-132.00 -94.12   72
 41  \w     86.00 111.00   0.50   20.72    --  113.25-125.00   0.00   50
 42  \w    119.00 175.00   0.50   20.72    --  113.25  45.00-120.00  112
 43  \w    104.00 139.00   0.50   20.72    --  113.25  30.00 120.00   70
 44  \w     48.00 111.00   0.50   20.72    --  113.25-125.00-180.00  126
 45  \w     43.00  69.00   0.50   20.72    --  113.25 -77.00-180.00   52
 46  \w     80.00 105.00   0.50   20.72    --  113.25 -77.00-150.00   50
 47  \w     74.00 125.00   0.50   20.72    --  113.25-144.00-123.94  102
 48  \w     72.00 105.00   0.50   20.72    --  113.25-125.00  90.00   66
 49  \w    121.00 163.00   0.50   20.72    --  113.25  45.00 150.00   84
 50  \w     43.00 108.00   0.50   20.72    --  113.25-108.00 -25.48  130
;
_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      0.0356403000
_diffrn_orient_matrix_UB_12      0.0821698000
_diffrn_orient_matrix_UB_13      -0.0034647000
_diffrn_orient_matrix_UB_21      0.0293752000
_diffrn_orient_matrix_UB_22      -0.0672127000
_diffrn_orient_matrix_UB_23      -0.0450683000
_diffrn_orient_matrix_UB_31      -0.0305736000
_diffrn_orient_matrix_UB_32      0.0312797000
_diffrn_orient_matrix_UB_33      -0.0877613000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0326
_diffrn_reflns_av_unetI/netI     0.0146
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            41621
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.308
_diffrn_reflns_theta_min         3.177
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.072
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65752
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark black'
_exptl_crystal_density_diffrn    1.063
_exptl_crystal_description       block
_exptl_crystal_F_000             2048
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.533
_refine_diff_density_min         -0.515
_refine_diff_density_rms         0.078
_refine_ls_extinction_coef       0.00015(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     317
_refine_ls_number_reflns         6703
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0565
_refine_ls_R_factor_gt           0.0543
_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^)+(0.1103P)^2^+3.8169P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1644
_refine_ls_wR_factor_ref         0.1667
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6178
_reflns_number_total             6703
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc00561e3.cif
_cod_data_source_block           felix220
_cod_database_code               1569229
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C28H20FeN6
_chemical_oxdiff_usercomment     'Jan Grunwald  jg228'
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13),
 C14(H14), C22(H22), C23(H23), C24(H24), C27(H27), C28(H28), C29(H29), C30(H30),
  C32(H32), C33(H33), C34(H34)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              17429
_shelx_hkl_checksum              43282
_shelx_fab_checksum              93015
_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 1.238
_oxdiff_exptl_absorpt_empirical_full_min 0.835