Bidirectional photoswitchability in an iron(iii) spin crossover complex: symmetry-breaking and solvent effects.
Díaz-Torres, Raúl; Chastanet, Guillaume; Collet, Eric; Trzop, Elzbieta; Harding, Phimphaka; Harding, David J.; Chemical science 14 (2023) 7185–7191; doi:10.1039/d3sc01495a

data_1569265
_publ_section_title
;
 Bidirectional photoswitchability in an iron(iii) spin crossover complex:
 symmetry-breaking and solvent effects.
;
_journal_issue                   26
_journal_name_full               'Chemical science'
_journal_page_first              7185
_journal_page_last               7191
_journal_paper_doi               10.1039/d3sc01495a
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C32 H20 Fe I2 N4 O2, N O3, 2(C H4 O)'
_chemical_formula_sum            'C34 H28 Fe I2 N5 O7'
_chemical_formula_weight         928.26
_chemical_properties_physical    Light-sensitive,Photo-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-03-25
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-11-16 deposited with the CCDC.	2023-06-01 downloaded from the CCDC.
;
_cell_angle_alpha                92.0011(4)
_cell_angle_beta                 107.5267(5)
_cell_angle_gamma                99.7927(5)
_cell_formula_units_Z            4
_cell_length_a                   12.75426(7)
_cell_length_b                   13.88144(8)
_cell_length_c                   20.01371(9)
_cell_measurement_reflns_used    58867
_cell_measurement_temperature    149.7(6)
_cell_measurement_theta_max      69.1680
_cell_measurement_theta_min      3.6940
_cell_volume                     3315.63(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.72a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.72a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.72a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2016/4 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.7(6)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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    -24.00  67.00   0.50    2.50    --   40.91 -81.00  72.00  182
  2  \w     80.00 157.00   0.50   10.00    --   98.15  81.00-165.00  154
  3  \w     33.00 124.00   0.50   10.00    --   98.15 -81.00  72.00  182
  4  \w    -48.00  -2.00   0.50    2.50    --    0.00 124.00-127.65   92
  5  \w    -33.00  -4.00   0.50    2.50    --   16.00 126.00  18.75   58
  6  \w    -28.00  -2.00   0.50    2.50    --   20.00 124.00 176.23   52
  7  \w    -10.00  17.00   0.50    2.50    --   24.00 101.00 -75.30   54
  8  \w     -3.00  23.00   0.50    2.50    --   28.00  96.00  54.81   52
  9  \w      4.00  33.00   0.50    2.50    --   32.00  87.00  -0.10   58
 10  \w      2.00  28.00   0.50    2.50    --   32.00  91.00-113.51   52
 11  \w      2.00  28.00   0.50    2.50    --   32.00  91.00 -49.28   52
 12  \w      2.00  28.00   0.50    2.50    --   32.00  91.00 139.06   52
 13  \w      2.00  28.00   0.50    2.50    --   32.00  91.00 177.95   52
 14  \w      9.00  35.00   0.50    2.50    --   36.00  85.00 -77.36   52
 15  \w      9.00  37.00   0.50    2.50    --   36.00  84.00  88.66   56
 16  \w    -77.00  17.00   0.50    2.50    --  -40.91 104.00 -90.00  188
 17  \w    -66.00  24.00   0.50    2.50    --  -40.91  81.00-165.00  180
 18  \w    -97.00 -11.00   0.50    2.50    --  -40.91 138.00 -90.00  172
 19  \w     11.00  97.00   0.50    2.50    --   40.91-138.00 120.00  172
 20  \w     11.00  97.00   0.50    2.50    --   40.91-138.00 -60.00  172
 21  \w     19.00  45.00   0.50    2.50    --   44.00  81.00-127.05   52
 22  \w     18.00  45.00   0.50    2.50    --   44.00  82.00 -35.73   54
 23  \w     18.00  45.00   0.50    2.50    --   44.00  82.00 156.51   54
 24  \w     19.00  45.00   0.50    2.50    --   44.00  79.00 -71.72   52
 25  \w     19.00  45.00   0.50    2.50    --   44.00  81.00  47.55   52
 26  \w     19.00  45.00   0.50    2.50    --   44.00  81.00-168.21   52
 27  \w     19.00  45.00   0.50    2.50    --   44.00  80.00-150.54   52
 28  \w     19.00  45.00   0.50    2.50    --   44.00  80.00 116.18   52
 29  \w     19.00  45.00   0.50    2.50    --   44.00  81.00  -6.65   52
 30  \w     19.00  45.00   0.50    2.50    --   44.00  81.00  17.33   52
 31  \w     18.00  45.00   0.50    2.50    --   44.00  82.00 134.83   54
 32  \w     19.00  45.00   0.50    2.50    --   44.00  81.00  80.75   52
 33  \w     24.00 112.00   0.50    2.50    --   48.00  75.00 122.08  176
 34  \w     27.00 117.00   0.50    2.50    --   52.00  77.00  63.71  180
 35  \w     27.00 117.00   0.50    2.50    --   52.00  77.00  33.94  180
 36  \w     28.00 116.00   0.50    2.50    --   52.00  75.00 163.39  176
 37  \w     28.00 116.00   0.50    2.50    --   52.00  75.00 -16.34  176
 38  \w     33.00 120.00   0.50    2.50    --   56.00  72.00-148.50  174
 39  \w     31.00 121.00   0.50    2.50    --   56.00  77.00 -81.11  180
 40  \w     31.00 121.00   0.50    2.50    --   56.00  76.00-110.81  180
 41  \w     37.00 124.00   0.50    2.50    --   60.00  73.00  84.42  174
 42  \w     37.00 124.00   0.50    2.50    --   60.00  74.00-134.01  174
 43  \w     39.00 129.00   0.50    2.50    --   64.00  76.00 125.81  180
 44  \w     40.00 128.00   0.50    2.50    --   64.00  75.00  20.46  176
 45  \w     41.00 128.00   0.50    2.50    --   64.00  73.00 109.07  174
 46  \w     39.00 129.00   0.50    2.50    --   64.00  76.00 175.45  180
 47  \w     39.00 129.00   0.50    2.50    --   64.00  77.00-109.22  180
 48  \w     39.00 129.00   0.50    2.50    --   64.00  77.00  36.15  180
 49  \w     39.00 129.00   0.50    2.50    --   64.00  76.00  -8.59  180
 50  \w     39.00 129.00   0.50    2.50    --   64.00  76.00 -52.67  180
 51  \w     50.00 136.00   0.50   10.00    --   72.00  70.00  34.79  172
 52  \w     50.00 136.00   0.50   10.00    --   72.00  71.00  53.26  172
 53  \w     52.00 136.00   0.50   10.00    --   72.00  64.00 126.44  168
 54  \w     47.00 137.00   0.50   10.00    --   72.00  77.00 133.59  180
 55  \w     49.00 136.00   0.50   10.00    --   72.00  72.00-124.57  174
 56  \w     51.00 141.00   0.50   10.00    --   76.00  76.00 -63.17  180
 57  \w     51.00 141.00   0.50   10.00    --   76.00  77.00 156.82  180
 58  \w     52.00 140.00   0.50   10.00    --   76.00  75.00 -98.65  176
 59  \w     51.00 141.00   0.50   10.00    --   76.00  76.00-165.87  180
 60  \w     58.00 144.00   0.50   10.00    --   80.00  71.00-114.61  172
 61  \w     62.00 148.00   0.50   10.00    --   84.00  69.00  33.19  172
 62  \w     64.00 148.00   0.50   10.00    --   84.00  64.00 127.64  168
 63  \w     77.00 157.00   0.50   10.00    --   98.15  68.00 120.00  160
 64  \w     73.00 157.00   0.50   10.00    --   98.15  77.00-120.00  168
 65  \w     28.00 109.00   0.50   10.00    --   98.15 -96.00  60.00  162
 66  \w     73.00 157.00   0.50   10.00    --   98.15  77.00 -60.00  168
 67  \w     80.00 157.00   0.50   10.00    --   98.15  59.00 150.00  154
 68  \w     80.00 157.00   0.50   10.00    --   98.15  59.00 -60.00  154
 69  \w     33.00 107.00   0.50   10.00    --   98.15 -33.00  30.00  148
 70  \w     80.00 157.00   0.50   10.00    --   98.15  59.00-120.00  154
 71  \w     73.00 157.00   0.50   10.00    --   98.15  77.00-180.00  168
 72  \w     80.00 157.00   0.50   10.00    --   98.15  59.00  90.00  154
 73  \w     80.00 157.00   0.50   10.00    --   98.15  59.00  30.00  154
 74  \w     34.00 113.00   0.50   10.00    --   98.15-117.00  60.00  158
 75  \w     33.00 107.00   0.50   10.00    --   98.15 -33.00-150.00  148
 76  \w     80.00 157.00   0.50   10.00    --   98.15  59.00 -90.00  154
 77  \w     73.00 157.00   0.50   10.00    --   98.15  77.00 -30.00  168
 78  \w     80.00 157.00   0.50   10.00    --   98.15  59.00  60.00  154
 79  \w     78.00 157.00   0.50   10.00    --   98.15  64.00  -2.52  158
 80  \w     73.00 157.00   0.50   10.00    --   98.15  77.00  30.00  168
 81  \w     73.00 157.00   0.50   10.00    --   98.15  77.00  60.00  168
 82  \w     73.00 157.00   0.50   10.00    --   98.15  77.00  90.00  168
 83  \w     34.00 120.00   0.50   10.00    --   98.15 -68.00 120.00  172
 84  \w     35.00 111.00   0.50   10.00    --   98.15 -42.00 120.00  152
 85  \w     75.00 157.00   0.50   10.00    --   98.15  73.00 164.04  164
 86  \w     77.00 157.00   0.50   10.00    --   98.15  68.00 -30.00  160
 87  \w     73.00 157.00   0.50   10.00    --   98.15  77.00 150.00  168
 88  \w     73.00 157.00   0.50   10.00    --   98.15  77.00-150.00  168
 89  \w     28.00 109.00   0.50   10.00    --   98.15 -96.00 120.00  162
 90  \w     73.00 157.00   0.50   10.00    --   98.15  77.00 120.00  168
 91  \w     35.00 130.00   0.50   10.00    --   98.15-144.00 -60.00  190
 92  \w     35.00 117.00   0.50   10.00    --   98.15 -59.00-120.00  164
 93  \w     35.00 130.00   0.50   10.00    --   98.15-144.00  60.00  190
 94  \w     73.00 157.00   0.50   10.00    --   98.15  77.00 -90.00  168
 95  \w     73.00 157.00   0.50   10.00    --   98.15  77.00   0.00  168
 96  \w     35.00 130.00   0.50   10.00    --   98.15-144.00  30.00  190
 97  \w     28.00 109.00   0.50   10.00    --   98.15 -96.00 -90.00  162
 98  \w     -4.00  22.00   0.50    2.50    --   28.00  97.00-137.76   52
 99  \w     -3.00  24.00   0.50    2.50    --   28.00  95.00-112.06   54
100  \w      3.00  32.00   0.50    2.50    --   32.00  90.00  88.28   58
101  \w      4.00  33.00   0.50    2.50    --   32.00  87.00  30.43   58
102  \w      9.00  35.00   0.50    2.50    --   36.00  85.00-133.91   52
103  \w      9.00  35.00   0.50    2.50    --   36.00  85.00-167.50   52
104  \w     14.00  45.00   0.50    2.50    --   40.00  82.00 124.37   62
105  \w    -61.00  23.00   0.50    2.50    --  -40.91  63.00 150.00  168
106  \w    -27.00  71.00   0.50    2.50    --   40.91 -91.00 -30.00  196
107  \w     18.00  45.00   0.50    2.50    --   44.00  82.00-110.59   54
108  \w     19.00  41.50   0.50    2.50    --   44.00  79.00 -48.45   45
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0372605000
_diffrn_orient_matrix_UB_12      0.0667663000
_diffrn_orient_matrix_UB_13      0.0480705000
_diffrn_orient_matrix_UB_21      -0.1205487000
_diffrn_orient_matrix_UB_22      -0.0239344000
_diffrn_orient_matrix_UB_23      -0.0509928000
_diffrn_orient_matrix_UB_31      -0.0268743000
_diffrn_orient_matrix_UB_32      -0.0880928000
_diffrn_orient_matrix_UB_33      0.0407473000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0844
_diffrn_reflns_av_unetI/netI     0.0336
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            95849
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.333
_diffrn_reflns_theta_min         2.325
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    18.756
_exptl_absorpt_correction_T_max  0.867
_exptl_absorpt_correction_T_min  0.315
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.860
_exptl_crystal_description       block
_exptl_crystal_F_000             1820
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.158
_exptl_crystal_size_mid          0.053
_exptl_crystal_size_min          0.04
_refine_diff_density_max         2.384
_refine_diff_density_min         -1.657
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     891
_refine_ls_number_reflns         12346
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0396
_refine_ls_R_factor_gt           0.0368
_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^)+(0.0660P)^2^+3.5015P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1008
_refine_ls_wR_factor_ref         0.1026
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11370
_reflns_number_total             12346
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01495a2.cif
_cod_data_source_block           nut10-150k
_cod_depositor_comments
'Adding full bibliography for 1569262--1569271.cif.'
_cod_database_code               1569265
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C34H28FeI2N5O7
_shelx_estimated_absorpt_t_max   0.521
_shelx_estimated_absorpt_t_min   0.156
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1.a Aromatic/amide H refined with riding coordinates:
 C28(H28), C58(H58), C10(H10), C60(H60), C26(H26), C44(H44), C35(H35),
 C42(H42), C3(H3), C1(H1), C12(H12), C7(H7), C14(H14), C33(H33), C47(H47),
 C39(H39), C46(H46), C15(H15), C51(H51), C18(H18), C19(H19), C49(H49), C55(H55),
  C23(H23), C53(H53), C17(H17), C50(H50), C22(H22), C62(H62), C38(H38),
 C21(H21), C31(H31), C34(H34), C6(H6), C2(H2), C37(H37), C54(H54), C63(H63),
 C5(H5), C30(H30)
1.b Idealised Me refined as rotating group:
 C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C65(H65A,H65B,
 H65C)
1.c Idealised tetrahedral OH refined as rotating group:
 O8(H8), O13(H13), O9(H9), O14(H14A)
;
_shelx_res_checksum              74162
_shelx_hkl_checksum              62170
_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 5.202
_oxdiff_exptl_absorpt_empirical_full_min 0.404