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_1569266
_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             2020-04-16
_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                91.9059(9)
_cell_angle_beta                 107.5608(12)
_cell_angle_gamma                99.8600(11)
_cell_formula_units_Z            4
_cell_length_a                   12.73249(18)
_cell_length_b                   13.82045(16)
_cell_length_c                   20.0000(2)
_cell_measurement_reflns_used    26528
_cell_measurement_temperature    100.0(5)
_cell_measurement_theta_max      68.4480
_cell_measurement_theta_min      3.6810
_cell_volume                     3292.26(7)
_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      100.0(5)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.990
_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    -82.00   2.00   0.50    0.20    --  -40.91 114.00-179.00  168
  2  \w   -111.00 -41.00   0.50    0.20    --  -40.91-177.00 -47.00  140
  3  \w   -116.00 -37.00   0.50    0.20    --  -40.91 177.00 -42.00  158
  4  \w     -2.00  83.00   0.50    0.20    --   40.91-114.00  89.00  170
  5  \w     37.00 116.00   0.50    0.20    --   40.91-177.00 -47.00  158
  6  \w     82.00 157.00   0.50    0.80    --   96.59 114.00-179.00  150
  7  \w     37.00 150.00   0.50    0.80    --   96.59-177.00 -47.00  226
  8  \w     31.00 108.00   0.50    0.80    --   96.59-114.00  89.00  154
  9  \w     41.00 145.00   0.50    0.80    --   96.59 177.00 -42.00  208
 10  \w   -105.00 -29.00   0.50    0.20    --  -40.91 -37.00 -30.00  152
 11  \w   -105.00 -29.00   0.50    0.20    --  -40.91 -37.00-120.00  152
 12  \w    -61.00  23.00   0.50    0.20    --  -40.91  63.00 120.00  168
 13  \w   -105.00 -29.00   0.50    0.20    --  -40.91 -37.00  90.00  152
 14  \w    -61.00  23.00   0.50    0.20    --  -40.91  63.00-150.00  168
 15  \w    -57.00  22.00   0.50    0.20    --  -40.91  50.00-150.00  158
 16  \w    -53.00  23.00   0.50    0.20    --  -40.91  37.00 120.00  152
 17  \w    -22.00  57.00   0.50    0.20    --   40.91 -50.00 -30.00  158
 18  \w    -23.00  61.00   0.50    0.20    --   40.91 -63.00-120.00  168
 19  \w     29.00 105.00   0.50    0.20    --   40.91  37.00 -60.00  152
 20  \w     21.00 105.00   0.50    0.20    --   40.91  63.00 -30.00  168
 21  \w    -23.00  53.00   0.50    0.20    --   40.91 -37.00 -60.00  152
 22  \w     40.00 112.00   0.50    0.20    --   40.91 177.00 -42.00  144
 23  \w     14.00  97.00   0.50    0.20    --   40.91-138.00   0.00  166
 24  \w     32.00 109.00   0.50    0.20    --   40.91  25.00  60.00  154
 25  \w     26.00 110.00   0.50    0.80    --   96.59 -17.00-120.00  168
 26  \w     33.00 126.00   0.50    0.80    --   96.59-144.00  90.00  186
 27  \w     81.00 157.00   0.50    0.80    --   96.59 117.00-150.00  152
 28  \w     81.00 157.00   0.50    0.80    --   96.59 117.00 -30.00  152
 29  \w     32.00 122.00   0.50    0.80    --   96.59 -77.00  90.00  180
 30  \w    102.00 157.00   0.50    0.80    --   96.59  96.00 150.00  110
 31  \w     29.00  93.00   0.50    0.80    --   96.59 -96.00  90.00  128
 32  \w     48.00 108.00   0.50    0.80    --   96.59 -68.00-120.00  120
 33  \w     56.00 105.00   0.50    0.80    --   96.59 -33.00   0.00   98
 34  \w     41.00  85.00   0.50    0.80    --   96.59-117.00  30.00   88
 35  \w     38.00 105.00   0.50    0.80    --   96.59 -25.00  90.00  134
 36  \w     80.00 109.00   0.50    0.80    --   96.59-117.00   0.00   58
 37  \w     33.00 109.00   0.50    0.80    --   96.59-117.00 -90.00  152
 38  \w     58.00  98.00   0.50    0.80    --   96.59 -33.00-120.00   80
 39  \w     29.00  85.00   0.50    0.80    --   96.59 -25.00-180.00  112
 40  \w    106.00 148.00   0.50    0.80    --   96.59  96.00-150.00   84
 41  \w    102.00 156.00   0.50    0.80    --   96.59  50.00-150.00  108
 42  \w     64.00 104.00   0.50    0.80    --   96.59 -96.00 -90.00   80
 43  \w    101.00 126.00   0.50    0.80    --   96.59-144.00-120.00   50
 44  \w    103.00 150.00   0.50    0.80    --   96.59  96.00  60.00   94
 45  \w     62.00  88.00   0.50    0.80    --   96.59-144.00-120.00   52
 46  \w     90.00 156.00   0.50    0.80    --   96.59  33.00 150.00  132
 47  \w     78.00 114.00   0.50    0.80    --   96.59 -59.00 -90.00   72
 48  \w     33.00  67.00   0.50    0.80    --   96.59 -59.00 -90.00   68
 49  \w     81.00 156.00   0.50    0.80    --   96.59 144.00 150.00  150
 50  \w    125.00 151.00   0.50    0.80    --   96.59  96.00 -90.00   52
 51  \w     28.00  54.00   0.50    0.80    --   96.59 -96.00 -90.00   52
 52  \w     38.00 113.00   0.50    0.80    --   96.59 -50.00  60.00  150
 53  \w     69.00 139.00   0.50    0.80    --   96.59   8.00 150.00  140
;
_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      -0.0153842000
_diffrn_orient_matrix_UB_12      -0.0699640000
_diffrn_orient_matrix_UB_13      0.0561247000
_diffrn_orient_matrix_UB_21      -0.0420759000
_diffrn_orient_matrix_UB_22      -0.0879968000
_diffrn_orient_matrix_UB_23      -0.0567753000
_diffrn_orient_matrix_UB_31      0.1212584000
_diffrn_orient_matrix_UB_32      -0.0163702000
_diffrn_orient_matrix_UB_33      0.0144202000
_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  0.1165
_diffrn_reflns_av_unetI/netI     0.0745
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            44074
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.602
_diffrn_reflns_theta_min         2.327
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    18.889
_exptl_absorpt_correction_T_max  0.301
_exptl_absorpt_correction_T_min  0.031
_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    1.873
_exptl_crystal_description       block
_exptl_crystal_F_000             1820
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.529
_exptl_crystal_size_mid          0.207
_exptl_crystal_size_min          0.091
_refine_diff_density_max         3.462
_refine_diff_density_min         -2.421
_refine_diff_density_rms         0.264
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     891
_refine_ls_number_reflns         12042
_refine_ls_number_restraints     144
_refine_ls_restrained_S_all      1.007
_refine_ls_R_factor_all          0.0715
_refine_ls_R_factor_gt           0.0675
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1402P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1757
_refine_ls_wR_factor_ref         0.1815
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10730
_reflns_number_total             12042
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01495a2.cif
_cod_data_source_block           rdt54c-100k-new
_cod_depositor_comments
'Adding full bibliography for 1569262--1569271.cif.'
_cod_database_code               1569266
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         C34H28FeI2N5O7
_chemical_oxdiff_usercomment     'From RT to 100K'
_reflns_odcompleteness_completeness 99.97
_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. Rigid body (RIGU) restrains
 C59, C60, C61, C62, C63, C64
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C43, C44, C45, C46, C47, C48
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C11, C12, C13, C14, C15, C16
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C27, C28, C29, C30, C31, C32
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3.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)
3.b Idealised Me refined as rotating group:
 C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C68(H68A,H68B,
 H68C)
3.c Idealised tetrahedral OH refined as rotating group:
 O8(H8), O9(H9), O13(H13), O14(H14A)
;
_shelx_res_checksum              48893
_shelx_hkl_checksum              67508
_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 2.959
_oxdiff_exptl_absorpt_empirical_full_min 0.519