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_1569270
_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, 2(C H4 O), N O3'
_chemical_formula_sum            'C34 H28 Fe I2 N5 O7'
_chemical_formula_weight         928.26
_chemical_melting_point          ?
_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
_atom_sites_solution_secondary   difmap
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-11-16 deposited with the CCDC.	2023-06-01 downloaded from the CCDC.
;
_cell_angle_alpha                91.9450(10)
_cell_angle_beta                 107.6440(10)
_cell_angle_gamma                100.0190(10)
_cell_formula_units_Z            4
_cell_length_a                   12.7132(2)
_cell_length_b                   13.7693(2)
_cell_length_c                   19.9776(3)
_cell_measurement_reflns_used    32302
_cell_measurement_temperature    10.0
_cell_measurement_theta_max      32.1180
_cell_measurement_theta_min      3.0290
_cell_volume                     3267.76(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      10.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1852
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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     36.00  95.00   1.00    2.50    --   30.28 -19.00 -30.00   59
  2  \w     26.00  75.00   1.00    2.50    --   30.28 -99.00-180.00   49
  3  \w    -24.00   3.00   1.00    2.50    --   30.28 -99.00-180.00   27
  4  \w    -26.00  61.00   1.00    2.50    --   30.28 -38.00-180.00   87
  5  \w     -3.00  96.00   1.00    2.50    --   30.28  77.00-150.00   99
  6  \w     42.00 108.00   1.00    2.50    --   30.28 178.00-120.00   66
  7  \w      1.00  93.00   1.00    2.50    --   30.28  77.00 -60.00   92
  8  \w     -1.00 104.00   1.00    2.50    --   30.28  38.00 150.00  105
  9  \w    -17.00  60.00   1.00    2.50    --   30.28 -77.00  30.00   77
 10  \w    -45.00   2.00   1.00    2.50    --   30.28 -19.00 -30.00   47
 11  \w    -99.00  -5.00   1.00    2.50    --  -28.56 -57.00   0.00   94
 12  \w    -33.00  -1.00   1.00    2.50    --   30.28 130.00   2.10   32
 13  \w   -111.00 -32.00   1.00    2.50    --  -28.56 178.00-150.00   79
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0134850000
_diffrn_orient_matrix_UB_12      -0.0429589000
_diffrn_orient_matrix_UB_13      -0.0238954000
_diffrn_orient_matrix_UB_21      -0.0368141000
_diffrn_orient_matrix_UB_22      0.0231039000
_diffrn_orient_matrix_UB_23      -0.0258320000
_diffrn_orient_matrix_UB_31      0.0449870000
_diffrn_orient_matrix_UB_32      0.0195116000
_diffrn_orient_matrix_UB_33      -0.0127187000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0315
_diffrn_reflns_av_unetI/netI     0.0312
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            52595
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.000
_diffrn_reflns_theta_min         3.108
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.409
_exptl_absorpt_correction_T_max  0.764
_exptl_absorpt_correction_T_min  0.590
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.95a (Rigaku Oxford Diffraction, 2021)
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            'dark black'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.887
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    none
_exptl_crystal_description       block
_exptl_crystal_F_000             1820
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.372
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.209
_refine_diff_density_max         1.914
_refine_diff_density_min         -1.471
_refine_diff_density_rms         0.120
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     931
_refine_ls_number_reflns         14257
_refine_ls_number_restraints     89
_refine_ls_restrained_S_all      1.101
_refine_ls_R_factor_all          0.0355
_refine_ls_R_factor_gt           0.0295
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0323P)^2^+6.2162P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0701
_refine_ls_wR_factor_ref         0.0728
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12588
_reflns_number_total             14257
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01495a2.cif
_cod_data_source_block           FeqsalDark10K
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value 'not measured' was changed
to '?' -- the value is undefined or not given.

data item '_exptl_crystal_density_meas' value 'not measured' was
changed to '?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1569262--1569271.cif.
;
_cod_database_code               1569270
_chemical_oxdiff_formula         'C34 H28 Fe I2 N5 O7'
_shelx_estimated_absorpt_t_max   0.633
_shelx_estimated_absorpt_t_min   0.468
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_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
 I1A-C4
 2.09 with sigma of 0.005
 I4-C52 = I2A_$1-C20_$1 = I2_$1-C20_$1 = I1_$1-C4_$1
 2.09 with sigma of 0.01
 I3A-C36
 2.09 with sigma of 0.001
 I3-C36 = I4A-C52
 2.09 with sigma of 0.001
 I2A-C21
 2.95 with sigma of 0.01
 C19-I2A
 2.95 with sigma of 0.01
 I4A-C51
 2.95 with sigma of 0.01
 I4A-C53
 2.95 with sigma of 0.01
 I3A-C37
 2.95 with sigma of 0.01
 I3A-C35
 2.95 with sigma of 0.005
 I3-C35
 2.95 with sigma of 0.01
3. Restrained planarity
 I3A, C37, C36, C38, C35
 with sigma of 0.025
4. Uiso/Uaniso restraints and constraints
I1A \\sim I1: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
I4A \\sim I4: within 2A with sigma of 0.0001 and sigma for terminal atoms of
0.0002
I2A \\sim I2: within 2A with sigma of 0.0001 and sigma for terminal atoms of
0.0002
I3 \\sim I3A: within 2A with sigma of 0.0005 and sigma for terminal atoms of
0.001
Uanis(I4A) \\sim Ueq, Uanis(I2A) \\sim Ueq, Uanis(I1A) \\sim Ueq, Uanis(I4)
\\sim Ueq, Uanis(I2) \\sim Ueq, Uanis(I1) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(I3) \\sim Ueq, Uanis(I3A) \\sim Ueq: with sigma of 0.0005 and sigma for
terminal atoms of 0.001
5. Others
 Sof(I4)=1-FVAR(1)
 Sof(I4A)=FVAR(1)
 Sof(I2A)=1-FVAR(2)
 Sof(I2)=FVAR(2)
 Sof(I1)=1-FVAR(3)
 Sof(I1A)=FVAR(3)
 Sof(I3A)=1-FVAR(4)
 Sof(I3)=FVAR(4)
6.a Aromatic/amide H refined with riding coordinates:
 C62(H62), C64(H64), C37(H37), C39(H39), C46(H46), C50(H50), C31(H31),
 C15(H15), C58(H58), C57(H57), C7(H7), C41(H41), C26(H26), C59(H59), C5(H5),
 C3(H3), C2(H2), C16(H16), C27(H27), C19(H19), C25(H25), C53(H53), C63(H63),
 C35(H35), C43(H43), C51(H51), C47(H47), C55(H55), C34(H34), C23(H23), C9(H9),
 C42(H42), C30(H30), C11(H11), C32(H32), C10(H10), C18(H18), C14(H14), C21(H21),
  C48(H48)
6.b Idealised Me refined as rotating group:
 C68(H68A,H68B,H68C), C67(H67A,H67B,H67C), C66(H66A,H66B,H66C), C65(H65A,H65B,
 H65C)
6.c Idealised tetrahedral OH refined as rotating group:
 O8(H8), O14(H14A), O13(H13), O9(H9A)
;
_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 1.044
_oxdiff_exptl_absorpt_empirical_full_min 0.967