Improving Spin Crossover Characteristics in Heteroleptic [FeIII(qsal-5-I)(qsal-5-OMe)]A Complexes
Díaz-Torres, Raúl; Gómez-Coca, Silvia; Ruiz, Eliseo; Harding, Phimphaka; Harding, David J.; Dalton Transactions  (2023) –; doi:10.1039/D3DT02503A

data_7714339
_publ_section_title
;
 Improving Spin Crossover Characteristics in Heteroleptic
 [FeIII(qsal-5-I)(qsal-5-OMe)]A Complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02503A
_journal_year                    2023
_chemical_formula_moiety         'C33 H23 Fe I N4 O3, B F4, 1.1[CH4O]'
_chemical_formula_sum            'C34.1 H27.4 B F4 Fe I N4 O4.1'
_chemical_formula_weight         828.36
_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             2023-09-20
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-10-13 deposited with the CCDC.	2023-10-28 downloaded from the CCDC.
;
_cell_angle_alpha                104.192(5)
_cell_angle_beta                 99.345(4)
_cell_angle_gamma                94.337(4)
_cell_formula_units_Z            2
_cell_length_a                   10.8316(5)
_cell_length_b                   12.4983(6)
_cell_length_c                   12.8260(8)
_cell_measurement_reflns_used    8625
_cell_measurement_temperature    300.00(10)
_cell_measurement_theta_max      66.5240
_cell_measurement_theta_min      3.6000
_cell_volume                     1648.87(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      300.00(10)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.984
_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     -9.00  78.00   0.50    3.00    --   40.91-106.00 155.00  174
  2  \w     29.00 107.00   0.50   11.50    --   96.59-106.00 155.00  156
  3  \w     83.00 157.00   0.50   11.50    --   96.59 106.00-105.00  148
  4  \w    -78.00   9.00   0.50    3.00    --  -40.91 106.00-105.00  174
  5  \w   -104.00 -25.00   0.50    3.00    --  -40.91 -50.00 120.00  158
  6  \w   -104.00 -25.00   0.50    3.00    --  -40.91 -50.00-180.00  158
  7  \w    -50.00  27.00   0.50    3.00    --  -40.91  25.00 150.00  154
  8  \w    -53.00  23.00   0.50    3.00    --  -40.91  37.00   0.00  152
  9  \w   -105.00 -29.00   0.50    3.00    --  -40.91 -37.00 -60.00  152
 10  \w     16.00  42.00   0.50    3.00    --   40.91  76.00  56.38   52
 11  \w     29.00 105.00   0.50    3.00    --   40.91  37.00-150.00  152
 12  \w     19.00 114.00   0.50    3.00    --   40.91  12.00  60.00  190
 13  \w     16.00  42.00   0.50    3.00    --   40.91  79.00  26.46   52
 14  \w     16.00  42.00   0.50    3.00    --   40.91  80.00 -42.19   52
 15  \w     14.00  97.00   0.50    3.00    --   40.91-138.00 -30.00  166
 16  \w     16.00  42.00   0.50    3.00    --   40.91  78.00  59.30   52
 17  \w     15.00  42.00   0.50    3.00    --   40.91  82.00-118.48   54
 18  \w    -22.00  57.00   0.50    3.00    --   40.91 -50.00   0.00  158
 19  \w     15.00  42.00   0.50    3.00    --   40.91  81.00 -73.30   54
 20  \w     32.00 109.00   0.50    3.00    --   40.91  25.00 120.00  154
 21  \w     16.00  42.00   0.50    3.00    --   40.91  80.00 119.17   52
 22  \w     16.00  42.00   0.50    3.00    --   40.91  76.00   1.93   52
 23  \w     16.00  42.00   0.50    3.00    --   40.91  78.00-145.78   52
 24  \w     15.00  42.00   0.50    3.00    --   40.91  77.00 167.78   54
 25  \w     31.00 106.00   0.50   11.50    --   96.59 -33.00  60.00  150
 26  \w     84.00 157.00   0.50   11.50    --   96.59  42.00 -60.00  146
 27  \w     32.00 109.00   0.50   11.50    --   96.59-117.00 -60.00  154
 28  \w     33.00 126.00   0.50   11.50    --   96.59-144.00-150.00  186
 29  \w     27.00 105.00   0.50   11.50    --   96.59 -96.00 -90.00  156
 30  \w     33.00 115.00   0.50   11.50    --   96.59 -59.00 120.00  164
 31  \w     88.00 157.00   0.50   11.50    --   96.59  25.00  90.00  138
 32  \w     32.00 109.00   0.50   11.50    --   96.59-117.00 120.00  154
 33  \w     32.00 122.00   0.50   11.50    --   96.59 -77.00 150.00  180
 34  \w     78.00 157.00   0.50   11.50    --   96.59  59.00   0.00  158
 35  \w     78.00 157.00   0.50   11.50    --   96.59  59.00-120.00  158
 36  \w     77.00 157.00   0.50   11.50    --   96.59  63.00 -37.32  160
 37  \w     27.00 105.00   0.50   11.50    --   96.59 -96.00-150.00  156
 38  \w     29.00 105.00   0.50   11.50    --   96.59 -25.00  90.00  152
 39  \w     33.00 115.00   0.50   11.50    --   96.59 -59.00  30.00  164
 40  \w     33.00 115.00   0.50   11.50    --   96.59 -59.00-120.00  164
 41  \w     32.00 109.00   0.50   11.50    --   96.59-117.00   0.00  154
 42  \w     32.00 122.00   0.50   11.50    --   96.59 -77.00   0.00  180
 43  \w     75.00 157.00   0.50   11.50    --   96.59  68.00  90.00  164
 44  \w     81.00 157.00   0.50   11.50    --   96.59  50.00  60.00  152
 45  \w     32.00 109.00   0.50   11.50    --   96.59-117.00  60.00  154
 46  \w     80.00 157.00   0.50   11.50    --   96.59  51.00  22.20  154
 47  \w     32.00 122.00   0.50   11.50    --   96.59 -77.00 -60.00  180
 48  \w     81.00 157.00   0.50   11.50    --   96.59 117.00   0.00  152
 49  \w     84.00 157.00   0.50   11.50    --   96.59  96.00-180.00  146
 50  \w    -50.00  27.00   0.50    3.00    --  -40.91  25.00  60.00  154
 51  \w   -104.00 -21.00   0.50    3.00    --  -40.91 -63.00   0.00  166
 52  \w   -104.00 -21.00   0.50    3.00    --  -40.91 -63.00 -90.00  166
 53  \w   -104.00 -25.00   0.50    3.00    --  -40.91 -50.00-150.00  158
 54  \w   -104.00 -21.00   0.50    3.00    --  -40.91 -63.00  60.00  166
 55  \w   -114.00 -19.00   0.50    3.00    --  -40.91 -12.00  90.00  190
 56  \w    -22.00  57.00   0.50    3.00    --   40.91 -50.00 120.00  158
 57  \w     16.00  42.00   0.50    3.00    --   40.91  80.00 -84.59   52
 58  \w     15.00  42.00   0.50    3.00    --   40.91  82.00 139.34   54
 59  \w     15.00  42.00   0.50    3.00    --   40.91  81.00 165.48   54
 60  \w     16.00  42.00   0.50    3.00    --   40.91  78.00  88.12   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0638
_diffrn_reflns_av_unetI/netI     0.0396
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            24963
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.685
_diffrn_reflns_theta_min         3.619
_exptl_absorpt_coefficient_mu    11.615
_exptl_absorpt_correction_T_max  0.584
_exptl_absorpt_correction_T_min  0.180
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (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            'dull dark black'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.668
_exptl_crystal_description       block
_exptl_crystal_F_000             826
_exptl_crystal_size_max          0.211
_exptl_crystal_size_mid          0.184
_exptl_crystal_size_min          0.055
_refine_diff_density_max         0.435
_refine_diff_density_min         -1.057
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     438
_refine_ls_number_reflns         5991
_refine_ls_number_restraints     20
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0903
_refine_ls_R_factor_gt           0.0769
_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^)+(0.1713P)^2^+0.2822P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2366
_refine_ls_wR_factor_ref         0.2512
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4522
_reflns_number_total             5991
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02503a2.cif
_cod_data_source_block           rdt133-300k
_cod_original_formula_sum        'C34.10 H27.40 B F4 Fe I N4 O4.10'
_cod_database_code               7714339
_shelx_shelxl_version_number     2018/3
_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
2. Restrained distances
 O3-C13
 1.38 with sigma of 0.02
 O3-C33
 1.42 with sigma of 0.02
 O4-C34
 1.42 with sigma of 0.02
 O4-C29
 1.38 with sigma of 0.02
 C11-C12 \\sim C11-C12A
 with sigma of 0.02
 C12-C13 \\sim C12A-C13A
 with sigma of 0.02
 C13-C14 \\sim C13A-C14A
 with sigma of 0.02
 C13-O3 \\sim C13A-O3
 with sigma of 0.02
 C13-I1 \\sim C13A-I1
 with sigma of 0.02
 C14-C15 \\sim C14A-C15A
 with sigma of 0.02
 C15-C16 \\sim C15A-C16
 with sigma of 0.02
 C11-C13 \\sim C11-C13A
 with sigma of 0.04
 C12-C14 \\sim C12A-C14A
 with sigma of 0.04
 C12-O3 \\sim C12A-O3
 with sigma of 0.04
 C12-I1 \\sim C12A-I1
 with sigma of 0.04
 C13-C15 \\sim C13A-C15A
 with sigma of 0.04
 C14-C16 \\sim C14A-C16
 with sigma of 0.04
 C14-O3 \\sim C14A-O3
 with sigma of 0.04
 C14-I1 \\sim C14A-I1
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uiso(O3) = Uiso(C33)
4. Rigid body (RIGU) restrains
 C29, O4, C34
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C13, O3, C33
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: C12(0.4) H12(0.4) C13(0.4) C14(0.4) H14(0.4) C15(0.6) H15(0.6)
 I2(0.4) O3(0.4) C33(0.4) H33A(0.4) H33B(0.4) H33C(0.4) I1(0.6) O4(0.6)
 C34(0.6) H34A(0.6) H34B(0.6) H34C(0.6) C12A(0.6) H12A(0.6) C13A(0.6) C14A(0.6)
 H14A(0.6) C15A(0.4) H15A(0.4)
6.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), C12A(H12A), C14A(H14A), C15A(H15A)
6.b Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C34(H34A,H34B,H34C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 40 electrons were 
found in a volume of 188\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1.1[CH4O] per Asymmetric Unit 
which account for 40 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              38644
_shelx_fab_checksum              36486
_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
;