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_1569263
_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
'2(C16 H10 Fe0.5 I N2 O), 2(N0.5 O1.5), 4(C0.5 H2 O0.5)'
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2020-04-21
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.10.09 svn.r3662 for Rigaku Oxford Diffraction, GUI svn.r5959)
;
_audit_update_record
;
2022-11-16 deposited with the CCDC.	2023-06-01 downloaded from the CCDC.
;
_cell_angle_alpha                91.9250(10)
_cell_angle_beta                 107.4830(10)
_cell_angle_gamma                99.8440(10)
_cell_formula_units_Z            4
_cell_length_a                   12.75940(10)
_cell_length_b                   13.8795(2)
_cell_length_c                   20.0074(3)
_cell_measurement_reflns_used    34878
_cell_measurement_temperature    150.0(5)
_cell_measurement_theta_max      68.3220
_cell_measurement_theta_min      3.6800
_cell_volume                     3316.13(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.76a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.76a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.76a (Rigaku OD, 2020)'
_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 2016/4 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT n/a (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0(5)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.992
_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   -104.00 -57.00   0.50    0.25    --  -40.91-157.00  21.00   94
  2  \w   -109.00 -24.00   0.50    0.25    --  -40.91 157.00  56.00  170
  3  \w    -85.00  -2.00   0.50    0.25    --  -40.91 119.00 -98.00  166
  4  \w      2.00  86.00   0.50    0.25    --   40.91-119.00 176.00  168
  5  \w     24.00 110.00   0.50    0.25    --   40.91-157.00  21.00  172
  6  \w     57.00 105.00   0.50    0.25    --   40.91 157.00  56.00   96
  7  \w     80.00 157.00   0.50    0.70    --   96.59 119.00 -98.00  154
  8  \w     32.00 133.00   0.50    0.70    --   96.59-157.00  21.00  202
  9  \w     33.00 109.00   0.50    0.70    --   96.59-119.00 176.00  152
 10  \w     56.00 157.00   0.50    0.70    --   96.59 157.00  56.00  202
 11  \w   -109.00 -32.00   0.50    0.25    --  -40.91 -25.00 150.00  154
 12  \w   -105.00 -29.00   0.50    0.25    --  -40.91 -37.00  30.00  152
 13  \w   -109.00 -32.00   0.50    0.25    --  -40.91 -25.00-180.00  154
 14  \w   -109.00 -32.00   0.50    0.25    --  -40.91 -25.00 -90.00  154
 15  \w    -61.00  23.00   0.50    0.25    --  -40.91  63.00-150.00  168
 16  \w   -104.00 -25.00   0.50    0.25    --  -40.91 -50.00-120.00  158
 17  \w    -41.00 -15.00   0.50    0.25    --  -40.91 -77.00 126.52   52
 18  \w     32.00 109.00   0.50    0.25    --   40.91  25.00 150.00  154
 19  \w     16.00  42.00   0.50    0.25    --   40.91  80.00  11.53   52
 20  \w     16.00  42.00   0.50    0.25    --   40.91  80.00-110.30   52
 21  \w     16.00  42.00   0.50    0.25    --   40.91  76.00 -81.64   52
 22  \w    -23.00  53.00   0.50    0.25    --   40.91 -37.00 -30.00  152
 23  \w    -23.00  53.00   0.50    0.25    --   40.91 -37.00-150.00  152
 24  \w     14.00  97.00   0.50    0.25    --   40.91-138.00-180.00  166
 25  \w     15.00  42.00   0.50    0.25    --   40.91  82.00  43.82   54
 26  \w    -27.00  50.00   0.50    0.25    --   40.91 -25.00  60.00  154
 27  \w     15.00  42.00   0.50    0.25    --   40.91  82.00  74.70   54
 28  \w     16.00  42.00   0.50    0.25    --   40.91  79.00-147.61   52
 29  \w     15.00  42.00   0.50    0.25    --   40.91  81.00   5.79   54
 30  \w     29.00 105.00   0.50    0.70    --   96.59 -25.00 -90.00  152
 31  \w     74.00 157.00   0.50    0.70    --   96.59  74.00 -53.04  166
 32  \w     31.00 124.00   0.50    0.70    --   96.59 -86.00 150.00  186
 33  \w     33.00 115.00   0.50    0.70    --   96.59 -59.00 -90.00  164
 34  \w     32.00 109.00   0.50    0.70    --   96.59-117.00  90.00  154
 35  \w     83.00 157.00   0.50    0.70    --   96.59  77.00-150.00  148
 36  \w     88.00 157.00   0.50    0.70    --   96.59  25.00-180.00  138
 37  \w     32.00 109.00   0.50    0.70    --   96.59-117.00 120.00  154
 38  \w     33.00 115.00   0.50    0.70    --   96.59 -59.00   0.00  164
 39  \w     75.00 157.00   0.50    0.70    --   96.59  68.00-120.00  164
 40  \w     81.00 157.00   0.50    0.70    --   96.59  50.00  90.00  152
 41  \w     84.00 157.00   0.50    0.70    --   96.59  42.00 120.00  146
 42  \w     75.00 157.00   0.50    0.70    --   96.59  68.00-180.00  164
 43  \w     27.00 105.00   0.50    0.70    --   96.59 -96.00 -60.00  156
 44  \w     33.00 115.00   0.50    0.70    --   96.59 -59.00 -30.00  164
 45  \w     33.00 126.00   0.50    0.70    --   96.59-144.00 -30.00  186
 46  \w     33.00 118.00   0.50    0.70    --   96.59 -68.00 150.00  170
 47  \w     33.00 126.00   0.50    0.70    --   96.59-144.00 -90.00  186
 48  \w     84.00 157.00   0.50    0.70    --   96.59  42.00 150.00  146
 49  \w     75.00 157.00   0.50    0.70    --   96.59  68.00 -90.00  164
 50  \w     32.00 109.00   0.50    0.70    --   96.59-117.00 150.00  154
 51  \w     34.00 113.00   0.50    0.70    --   96.59 -50.00 120.00  158
 52  \w     27.00 105.00   0.50    0.70    --   96.59 -96.00   0.00  156
 53  \w     83.00 157.00   0.50    0.70    --   96.59  77.00 150.00  148
 54  \w     33.00 109.00   0.50    0.70    --   96.59-117.00 -30.00  152
 55  \w     89.00 144.00   0.50    0.70    --   96.59  66.00-162.16  110
;
_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      0.0253758000
_diffrn_orient_matrix_UB_12      -0.0635999000
_diffrn_orient_matrix_UB_13      0.0624361000
_diffrn_orient_matrix_UB_21      0.0563310000
_diffrn_orient_matrix_UB_22      0.0932298000
_diffrn_orient_matrix_UB_23      0.0506228000
_diffrn_orient_matrix_UB_31      -0.1131675000
_diffrn_orient_matrix_UB_32      0.0076666000
_diffrn_orient_matrix_UB_33      0.0104841000
_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  0.1407
_diffrn_reflns_av_unetI/netI     0.0646
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            49547
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.553
_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    18.753
_exptl_absorpt_correction_T_max  0.112
_exptl_absorpt_correction_T_min  0.014
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.76a (Rigaku Oxford Diffraction, 2020)
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_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.859
_exptl_crystal_description       block
_exptl_crystal_F_000             1820
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.701
_exptl_crystal_size_mid          0.394
_exptl_crystal_size_min          0.317
_refine_diff_density_max         1.526
_refine_diff_density_min         -2.389
_refine_diff_density_rms         0.232
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     891
_refine_ls_number_reflns         12129
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0603
_refine_ls_R_factor_gt           0.0579
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1099P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1419
_refine_ls_wR_factor_ref         0.1447
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11125
_reflns_number_total             12129
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01495a2.cif
_cod_data_source_block           rdt54e-150k-slowcool
_cod_depositor_comments
'Adding full bibliography for 1569262--1569271.cif.'
_cod_database_code               1569263
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         C34H28FeI2N5O7
_chemical_oxdiff_usercomment     'From RT to 150K slow (10 K/h)'
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5), C6(H6), C7(H7), C10(H10), C12(H12), C14(H14),
 C15(H15), C17(H17), C18(H18), C19(H19), C21(H21), C22(H22), C23(H23), C26(H26),
  C28(H28), C30(H30), C31(H31), C33(H33), C34(H34), C35(H35), C37(H37),
 C38(H38), C39(H39), C42(H42), C44(H44), C46(H46), C47(H47), C49(H49), C50(H50),
  C51(H51), C53(H53), C54(H54), C55(H55), C58(H58), C60(H60), C62(H62), C63(H63)
2.b Idealised Me refined as rotating group:
 C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C68(H68A,H68B,
 H68C)
2.c Idealised tetrahedral OH refined as rotating group:
 O11(H11), O12(H12A), O13(H13), O14(H14A)
;
_shelx_res_checksum              24365
_shelx_hkl_checksum              33178
_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 5.257
_oxdiff_exptl_absorpt_empirical_full_min 0.460