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_1569230
_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 N6 Zn, C H2 Cl2'
_chemical_formula_sum            'C29 H22 Cl2 N6 Zn'
_chemical_formula_weight         590.79
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-17
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2022-12-27 deposited with the CCDC.	2023-05-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.0880(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.95270(10)
_cell_length_b                   13.24570(10)
_cell_length_c                   19.3402(2)
_cell_measurement_reflns_used    32448
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.0210
_cell_measurement_theta_min      3.2870
_cell_volume                     2539.58(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.115a (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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_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   -120.00 -73.00   0.50    1.50    --  -47.79-125.00-180.00   94
  2  \w   -120.00 -25.00   0.50    1.50    --  -47.79 -77.00  60.00  190
  3  \w    -43.00  25.00   0.50    1.50    --  -47.79  38.00  90.00  136
  4  \w    -26.00  28.00   0.50    1.50    --  -47.79  19.00   0.00  108
  5  \w    -85.00 -13.00   0.50    1.50    --  -47.79 125.00 120.00  144
  6  \w    -51.00 -20.00   0.50    6.00    --  -91.75  45.00 -90.00   62
  7  \w   -163.00 -69.00   0.50    6.00    --  -91.75 -77.00-150.00  188
  8  \w     42.00 105.00   0.50    6.00    --  113.25 -77.00 -60.00  126
  9  \w    101.00 178.00   0.50    6.00    --  113.25  45.00 150.00  154
 10  \w     95.00 178.00   0.50    6.00    --  113.25 125.00  90.00  166
 11  \w     42.00 106.00   0.50    6.00    --  113.25 -95.00  30.00  128
 12  \w    100.00 178.00   0.50    6.00    --  113.25  15.00-150.00  156
 13  \w     42.00  71.00   0.50    6.00    --  113.25 -61.00 -30.00   58
 14  \w     95.00 178.00   0.50    6.00    --  113.25 125.00-120.00  166
 15  \w     42.00 105.00   0.50    6.00    --  113.25 -77.00 -30.00  126
 16  \w    104.00 178.00   0.50    6.00    --  113.25  93.00  64.00  148
 17  \w    100.00 178.00   0.50    6.00    --  113.25  15.00  60.00  156
 18  \w    100.00 178.00   0.50    6.00    --  113.25  15.00  30.00  156
 19  \w     42.00  71.00   0.50    6.00    --  113.25 -61.00  60.00   58
 20  \w     42.00 105.00   0.50    6.00    --  113.25 -77.00  60.00  126
 21  \w     42.00 105.00   0.50    6.00    --  113.25 -77.00  30.00  126
 22  \w     42.00  71.00   0.50    6.00    --  113.25 -61.00  90.00   58
 23  \w     42.00 111.00   0.50    6.00    --  113.25-125.00 -60.00  138
 24  \w     42.00  71.00   0.50    6.00    --  113.25 -61.00 150.00   58
 25  \w   -120.00 -25.00   0.50    1.50    --  -47.79 -77.00   0.00  190
 26  \w   -120.00 -33.00   0.50    1.50    --  -47.79 -57.00 -60.00  174
 27  \w   -120.00 -33.00   0.50    1.50    --  -47.79 -57.00 120.00  174
 28  \w   -120.00 -33.00   0.50    1.50    --  -47.79 -57.00-150.00  174
 29  \w   -120.00 -33.00   0.50    1.50    --  -47.79 -57.00 -90.00  174
 30  \w   -163.00 -69.00   0.50    6.00    --  -91.75 -77.00 -90.00  188
 31  \w   -163.00 -69.00   0.50    6.00    --  -91.75 -77.00 150.00  188
 32  \w   -163.00 -69.00   0.50    6.00    --  -91.75 -77.00 120.00  188
 33  \w    101.00 178.00   0.50    6.00    --  113.25  45.00-120.00  154
 34  \w     42.00  79.50   0.50    6.00    --  113.25-125.00 -90.00   75
;
_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      0.0433695000
_diffrn_orient_matrix_UB_12      0.1060893000
_diffrn_orient_matrix_UB_13      0.0259037000
_diffrn_orient_matrix_UB_21      -0.1404208000
_diffrn_orient_matrix_UB_22      0.0166489000
_diffrn_orient_matrix_UB_23      0.0257914000
_diffrn_orient_matrix_UB_31      0.0505897000
_diffrn_orient_matrix_UB_32      -0.0446365000
_diffrn_orient_matrix_UB_33      0.0711189000
_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  0.0189
_diffrn_reflns_av_unetI/netI     0.0087
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            39393
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.971
_diffrn_reflns_theta_min         4.050
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.533
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88375
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.115a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark orange'
_exptl_crystal_density_diffrn    1.545
_exptl_crystal_description       block
_exptl_crystal_F_000             1208
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.025
_refine_diff_density_min         -0.764
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     343
_refine_ls_number_reflns         5469
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0392
_refine_ls_R_factor_gt           0.0390
_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^)+(0.0581P)^2^+3.8026P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1113
_refine_ls_wR_factor_ref         0.1114
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5433
_reflns_number_total             5469
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc00561e3.cif
_cod_data_source_block           felix221
_cod_database_code               1569230
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C29H22N6Cl2Zn
_chemical_oxdiff_usercomment     'Jan Grunwald  jg256'
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C41(H41A,H41B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C12(H12), C13(H13),
 C14(H14), C21(H21), C22(H22), C23(H23), C24(H24), C27(H27), C28(H28), C29(H29),
  C32(H32), C33(H33), C34(H34)
;
_shelx_res_checksum              31894
_shelx_hkl_checksum              18924
_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 1.192
_oxdiff_exptl_absorpt_empirical_full_min 0.910