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_7714333
_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, N O3, 1.6(C H4 O)'
_chemical_formula_sum            'C34.6 H29.4 Fe I N5 O7.6'
_chemical_formula_weight         819.58
_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                79.464(4)
_cell_angle_beta                 69.435(5)
_cell_angle_gamma                69.693(5)
_cell_formula_units_Z            2
_cell_length_a                   11.9974(7)
_cell_length_b                   12.4166(6)
_cell_length_c                   12.9275(5)
_cell_measurement_reflns_used    6643
_cell_measurement_temperature    300(2)
_cell_measurement_theta_max      67.7880
_cell_measurement_theta_min      3.6200
_cell_volume                     1686.91(16)
_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 1.5 (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 n/a (Sheldrick, 2015)'
_diffrn_ambient_temperature      300(2)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.993
_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   -106.00 -32.00   0.50    0.65    --  -40.91 -32.00 -77.00  148
  2  \w     32.00 107.00   0.50    0.65    --   40.91  32.00  81.00  150
  3  \w     31.00 105.00   0.50    2.70    --   96.59 -32.00 -77.00  148
  4  \w     88.00 157.00   0.50    2.70    --   96.59  32.00  81.00  138
  5  \w   -104.00 -25.00   0.50    0.65    --  -40.91 -50.00  60.00  158
  6  \w    -66.00  24.00   0.50    0.65    --  -40.91  77.00  30.00  180
  7  \w   -104.00 -25.00   0.50    0.65    --  -40.91 -50.00-180.00  158
  8  \w    -49.00  25.00   0.50    0.65    --  -40.91  32.00  81.00  148
  9  \w    -97.00 -14.00   0.50    0.65    --  -40.91 138.00 120.00  166
 10  \w     29.00 105.00   0.50    0.65    --   40.91  37.00 150.00  152
 11  \w     15.00  42.00   0.50    0.65    --   40.91  81.00 -36.83   54
 12  \w     16.00  42.00   0.50    0.65    --   40.91  76.00  18.19   52
 13  \w    -23.00  71.00   0.50    0.65    --   40.91 -91.00-180.00  188
 14  \w     16.00  42.00   0.50    0.65    --   40.91  78.00-106.99   52
 15  \w     29.00 105.00   0.50    0.65    --   40.91  37.00-120.00  152
 16  \w     15.00  42.00   0.50    0.65    --   40.91  81.00  99.07   54
 17  \w    -25.00  50.00   0.50    0.65    --   40.91 -32.00 -77.00  150
 18  \w     15.00  42.00   0.50    0.65    --   40.91  81.00 -63.41   54
 19  \w     29.00 105.00   0.50    0.65    --   40.91  37.00 -60.00  152
 20  \w    -27.00  50.00   0.50    0.65    --   40.91 -25.00-180.00  154
 21  \w     16.00  42.00   0.50    0.65    --   40.91  78.00  52.11   52
 22  \w     15.00  42.00   0.50    0.65    --   40.91  82.00 -18.60   54
 23  \w     34.00 110.00   0.50    2.70    --   96.59 -42.00   0.00  152
 24  \w     26.00 110.00   0.50    2.70    --   96.59 -17.00  60.00  168
 25  \w     31.00 124.00   0.50    2.70    --   96.59 -86.00   0.00  186
 26  \w     33.00 126.00   0.50    2.70    --   96.59-144.00-150.00  186
 27  \w     34.00 113.00   0.50    2.70    --   96.59 -50.00  60.00  158
 28  \w     32.00 109.00   0.50    2.70    --   96.59-117.00  30.00  154
 29  \w     81.00 157.00   0.50    2.70    --   96.59 117.00   0.00  152
 30  \w     34.00 110.00   0.50    2.70    --   96.59 -42.00 150.00  152
 31  \w     88.00 157.00   0.50    2.70    --   96.59  25.00   0.00  138
 32  \w     77.00 157.00   0.50    2.70    --   96.59  62.00  99.45  160
 33  \w     29.00 105.00   0.50    2.70    --   96.59 -25.00-180.00  152
 34  \w     83.00 157.00   0.50    2.70    --   96.59  17.00-120.00  148
 35  \w     33.00 118.00   0.50    2.70    --   96.59 -68.00   0.00  170
 36  \w     32.00 109.00   0.50    2.70    --   96.59-117.00   0.00  154
 37  \w     32.00 109.00   0.50    2.70    --   96.59-117.00  90.00  154
 38  \w     88.00 157.00   0.50    2.70    --   96.59  25.00 120.00  138
 39  \w     32.00 109.00   0.50    2.70    --   96.59-117.00 -90.00  154
 40  \w     32.00 122.00   0.50    2.70    --   96.59 -77.00-180.00  180
 41  \w     88.00 157.00   0.50    2.70    --   96.59  25.00-120.00  138
 42  \w     32.00 109.00   0.50    2.70    --   96.59-117.00 -60.00  154
 43  \w     88.00 157.00   0.50    2.70    --   96.59  25.00  30.00  138
 44  \w     32.00 109.00   0.50    2.70    --   96.59-117.00 -30.00  154
 45  \w     27.00 105.00   0.50    2.70    --   96.59 -96.00 -30.00  156
 46  \w     32.00 109.00   0.50    2.70    --   96.59-117.00 150.00  154
 47  \w     32.00 109.00   0.50    2.70    --   96.59-117.00-150.00  154
 48  \w   -104.00 -21.00   0.50    0.65    --  -40.91 -63.00   0.00  166
 49  \w   -104.00 -21.00   0.50    0.65    --  -40.91 -63.00 120.00  166
;
_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  0.1094
_diffrn_reflns_av_unetI/netI     0.0803
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            19710
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.682
_diffrn_reflns_theta_min         3.661
_exptl_absorpt_coefficient_mu    11.264
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.12791
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.76a (Rigaku Oxford Diffraction, 2020)
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    1.614
_exptl_crystal_description       block
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.629
_exptl_crystal_size_mid          0.255
_exptl_crystal_size_min          0.064
_refine_diff_density_max         1.016
_refine_diff_density_min         -0.959
_refine_diff_density_rms         0.120
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.105
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     454
_refine_ls_number_reflns         6140
_refine_ls_number_restraints     33
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.1282
_refine_ls_R_factor_gt           0.0894
_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^)+(0.1704P)^2^+0.8955P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2582
_refine_ls_wR_factor_ref         0.2999
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3804
_reflns_number_total             6140
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02503a2.cif
_cod_data_source_block           rdt82-300k
_cod_original_cell_volume        1686.90(16)
_cod_original_formula_sum        'C34.60 H29.40 Fe I N5 O7.60'
_cod_database_code               7714333
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.533
_shelx_estimated_absorpt_t_min   0.053
_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
 C13-O3
 1.38 with sigma of 0.02
 C29-O4
 1.38 with sigma of 0.02
 C29A-O4
 1.38 with sigma of 0.02
 O4-C33
 1.42 with sigma of 0.02
 O3-C36
 1.42 with sigma of 0.02
 O3-C13
 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
 C27-C28 \\sim C27-C28A
 with sigma of 0.02
 C28-C29 \\sim C28A-C29A
 with sigma of 0.02
 C29-C30 \\sim C29A-C30A
 with sigma of 0.02
 C29-I2 \\sim C29A-I2
 with sigma of 0.02
 C29-O4 \\sim C29A-O4
 with sigma of 0.02
 C30-C31 \\sim C30A-C31A
 with sigma of 0.02
 C31-C32 \\sim C31A-C32
 with sigma of 0.02
 C27-C29 \\sim C27-C29A
 with sigma of 0.04
 C28-C30 \\sim C28A-C30A
 with sigma of 0.04
 C28-I2 \\sim C28A-I2
 with sigma of 0.04
 C28-O4 \\sim C28A-O4
 with sigma of 0.04
 C29-C31 \\sim C29A-C31A
 with sigma of 0.04
 C30-C32 \\sim C30A-C32
 with sigma of 0.04
 C30-I2 \\sim C30A-I2
 with sigma of 0.04
 C30-O4 \\sim C30A-O4
 with sigma of 0.04
3. Rigid bond restraints
 O4, C33
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O8, C34
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
O8 \\sim C34: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uiso(C33) = Uiso(O4)
Uiso(O3) = Uiso(C36)
5. Rigid body (RIGU) restrains
 O4, C33
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O8, C34
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Fixed Sof: C12(0.5) H12(0.5) C13(0.5) C14(0.5) H14(0.5) C15(0.5) H15(0.5)
 C28(0.5) H28(0.5) C29(0.5) C30(0.5) H30(0.5) C31(0.5) H31(0.5) I2(0.5) O3(0.5)
 C36(0.5) H36A(0.5) H36B(0.5) H36C(0.5) I1(0.5) O4(0.5) C33(0.5) H33A(0.5)
 H33B(0.5) H33C(0.5) O8(0.8) H8(0.8) C34(0.8) H34A(0.8) H34B(0.8) H34C(0.8)
 O9(0.8) H9(0.8) C35(0.8) H35A(0.8) H35B(0.8) H35C(0.8) C12A(0.5) H12A(0.5)
 C13A(0.5) C14A(0.5) H14A(0.5) C15A(0.5) H15A(0.5) C28A(0.5) H28A(0.5)
 C29A(0.5) C30A(0.5) H30A(0.5) C31A(0.5) H31A(0.5)
7.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), C28A(H28A),
 C30A(H30A), C31A(H31A)
7.b Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,
 H35C)
7.c Idealised tetrahedral OH refined as rotating group:
 O8(H8), O9(H9)
;
_shelx_res_checksum              52082
_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
;