Spin-crossover iron (II) complex showing thermal hysteresis around room temperature with symmetry breaking and an unusually high T(LIESST) of 120 K.
Clemente Leon, Miguel; García-López, Víctor; Palacios-Corella, Mario; Cardona-Serra, Salvador; Coronado, Eugenio; Chemical Communications  (2019) –; doi:10.1039/C9CC05988A

data_7124157
_publ_section_title
;
 Spin-crossover iron (II) complex showing thermal hysteresis around room
 temperature with symmetry breaking and an unusually high T(LIESST) of 120
 K.
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC05988A
_journal_year                    2019
_chemical_formula_moiety
'2(C39 H23 Cl Fe2 N15 O16), 4(Cl O4), 3(C3 H6 O), 2(O)'
_chemical_formula_sum            'C87 H74 Cl6 Fe4 N30 O53'
_chemical_formula_weight         2823.86
_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   geom
_audit_creation_date             2019-08-28
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-08-28 deposited with the CCDC.    2019-09-12 downloaded from the CCDC.
;
_cell_angle_alpha                96.056(3)
_cell_angle_beta                 112.125(4)
_cell_angle_gamma                104.778(4)
_cell_formula_units_Z            1
_cell_length_a                   14.6268(6)
_cell_length_b                   15.0615(6)
_cell_length_c                   15.2862(6)
_cell_measurement_reflns_used    6069
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      24.5180
_cell_measurement_theta_min      3.6830
_cell_volume                     2939.0(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      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0267
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.872
_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    -84.00   7.00   1.00   22.50    --  -14.89 -57.00  30.00   91
  2  \w    -84.00   7.00   1.00   22.50    --  -14.89 -57.00-180.00   91
  3  \w    -79.00  -2.00   1.00   22.50    --  -14.89 -62.00 130.29   77
  4  \w    -83.00   3.00   1.00   22.50    --  -14.89 -68.00 -50.01   86
  5  \w    -53.00  37.00   1.00   22.50    --   15.67 -58.00-129.86   90
  6  \w    -53.00  38.00   1.00   22.50    --   15.67 -68.00  84.68   91
  7  \w    -53.00  37.00   1.00   22.50    --   15.67 -57.00 -60.00   90
  8  \w    -32.00  37.00   1.00   22.50    --   15.67 -57.00   0.00   69
  9  \w    -48.00  40.00   1.00   22.50    --   15.67 -67.00 153.65   88
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0396090000
_diffrn_orient_matrix_UB_12      0.0070640000
_diffrn_orient_matrix_UB_13      -0.0170541000
_diffrn_orient_matrix_UB_21      -0.0120221000
_diffrn_orient_matrix_UB_22      -0.0494845000
_diffrn_orient_matrix_UB_23      -0.0138845000
_diffrn_orient_matrix_UB_31      -0.0366001000
_diffrn_orient_matrix_UB_32      -0.0002511000
_diffrn_orient_matrix_UB_33      -0.0464673000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0880
_diffrn_reflns_av_unetI/netI     0.1527
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.872
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            43662
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.872
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.010
_diffrn_reflns_theta_min         3.306
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.728
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91801
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.595
_exptl_crystal_description       prism
_exptl_crystal_F_000             1436
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.284
_refine_diff_density_min         -0.916
_refine_diff_density_rms         0.115
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     893
_refine_ls_number_reflns         12366
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.1863
_refine_ls_R_factor_gt           0.0954
_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^)+(0.1412P)^2^+1.6213P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2362
_refine_ls_wR_factor_ref         0.3061
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6106
_reflns_number_total             12366
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc05988a3.cif
_cod_data_source_block           vg180bot_a
_cod_database_code               7124157
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.918
_reflns_odcompleteness_completeness 99.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O25-C41
 1.2 with sigma of 0.02
 O26A-C44
 1.2 with sigma of 0.02
 O26B-C44
 1.2 with sigma of 0.02
 C42-C41 \\sim C41-C40
 with sigma of 0.02
3. Restrained planarity
 O25, C40, C41, C42
 with sigma of 0.1
4. Others
 Fixed Sof: O18A(0.5) O18B(0.5) O19A(0.5) O19B(0.5) O20A(0.5) O20B(0.5)
 O22A(0.5) O22B(0.5) O23A(0.5) O23B(0.5) O24A(0.5) O24B(0.5) O25(0.5) O26A(0.5)
 O26B(0.5) C40(0.5) H40A(0.5) H40B(0.5) H40C(0.5) C41(0.5) C42(0.5) H42A(0.5)
 H42B(0.5) H42C(0.5) C45A(0.5) H45A(0.5) H45B(0.5) H45C(0.5) C45B(0.5)
 H45D(0.5) H45E(0.5) H45F(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1A), C3(H3), C5(H5), C6(H6), C7(H7), C9(H9), C11(H11), C14(H14), C16(H16),
  C18(H18), C19(H19), C20(H20), C22(H22), C24(H24), C27(H27), C29(H29),
 C31(H31), C32(H32), C33(H33), C35(H35), C37(H37)
5.b Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C45A(H45A,H45B,
 H45C), C45B(H45D,H45E,H45F)
5.c Idealised tetrahedral OH refined as rotating group:
 O1(H1), O4(H4)
;
_shelx_res_checksum              2877
_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 1.152
_oxdiff_exptl_absorpt_empirical_full_min 0.866