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_7714338
_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
'C32.93 H22.79 Fe I1.07 N4 O2.93, C F3 O3 S, C H4 O'
_chemical_formula_sum            'C34.93 H26.79 F3 Fe I1.07 N4 O6.93 S'
_chemical_formula_weight         894.12
_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                71.125(2)
_cell_angle_beta                 86.434(2)
_cell_angle_gamma                67.786(2)
_cell_formula_units_Z            2
_cell_length_a                   11.9334(2)
_cell_length_b                   12.6849(2)
_cell_length_c                   13.1443(4)
_cell_measurement_reflns_used    16052
_cell_measurement_temperature    280.00(10)
_cell_measurement_theta_max      68.3610
_cell_measurement_theta_min      3.5290
_cell_volume                     1738.87(8)
_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      280.00(10)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.993
_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   -105.00 -55.00   0.50    0.25    --  -40.91-160.00 -15.00  100
  2  \w   -110.00 -26.00   0.50    0.25    --  -40.91 160.00  15.00  168
  3  \w    -84.00   0.00   0.50    0.25    --  -40.91 117.00-136.00  168
  4  \w      0.00  84.00   0.50    0.25    --   40.91-117.00 136.00  168
  5  \w     55.00 105.00   0.50    0.25    --   40.91 160.00  15.00  100
  6  \w     26.00 111.00   0.50    0.25    --   40.91-160.00 -15.00  170
  7  \w     32.00 109.00   0.50    0.95    --   96.59-117.00 136.00  154
  8  \w     32.00 135.00   0.50    0.95    --   96.59-160.00 -15.00  206
  9  \w     81.00 157.00   0.50    0.95    --   96.59 117.00-136.00  152
 10  \w     54.00 157.00   0.50    0.95    --   96.59 160.00  15.00  206
 11  \w   -104.00 -25.00   0.50    0.25    --  -40.91 -50.00 -30.00  158
 12  \w    -57.00  22.00   0.50    0.25    --  -40.91  50.00   0.00  158
 13  \w   -105.00 -29.00   0.50    0.25    --  -40.91 -37.00  60.00  152
 14  \w   -109.00 -32.00   0.50    0.25    --  -40.91 -25.00  90.00  154
 15  \w     29.00 105.00   0.50    0.25    --   40.91  37.00-150.00  152
 16  \w    -27.00  50.00   0.50    0.25    --   40.91 -25.00 -30.00  154
 17  \w     15.00  42.00   0.50    0.25    --   40.91  81.00-161.59   54
 18  \w     16.00  42.00   0.50    0.25    --   40.91  78.00  -3.88   52
 19  \w     16.00  42.00   0.50    0.25    --   40.91  78.00 -27.04   52
 20  \w    -13.00  77.00   0.50    0.25    --   40.91-104.00  90.00  180
 21  \w    -23.00  53.00   0.50    0.25    --   40.91 -37.00-180.00  152
 22  \w     16.00  42.00   0.50    0.25    --   40.91  79.00  27.59   52
 23  \w     29.00 105.00   0.50    0.25    --   40.91  37.00-180.00  152
 24  \w     31.00 106.00   0.50    0.95    --   96.59 -33.00 -30.00  150
 25  \w     31.00 124.00   0.50    0.95    --   96.59 -86.00 -30.00  186
 26  \w     29.00 105.00   0.50    0.95    --   96.59 -25.00 -90.00  152
 27  \w     33.00 118.00   0.50    0.95    --   96.59 -68.00 150.00  170
 28  \w     27.00 105.00   0.50    0.95    --   96.59 -96.00 150.00  156
 29  \w     34.00 110.00   0.50    0.95    --   96.59 -42.00  60.00  152
 30  \w     84.00 157.00   0.50    0.95    --   96.59  42.00-150.00  146
 31  \w     87.00 157.00   0.50    0.95    --   96.59  33.00 -60.00  140
 32  \w     33.00 126.00   0.50    0.95    --   96.59-144.00-150.00  186
 33  \w     33.00 118.00   0.50    0.95    --   96.59 -68.00 -30.00  170
 34  \w     33.00 126.00   0.50    0.95    --   96.59-144.00 120.00  186
 35  \w     34.00 110.00   0.50    0.95    --   96.59 -42.00 150.00  152
 36  \w     32.00 109.00   0.50    0.95    --   96.59-117.00 -30.00  154
 37  \w     81.00 157.00   0.50    0.95    --   96.59  50.00-120.00  152
 38  \w     34.00 110.00   0.50    0.95    --   96.59 -42.00 -30.00  152
 39  \w     84.00 157.00   0.50    0.95    --   96.59  42.00-180.00  146
 40  \w     87.00 157.00   0.50    0.95    --   96.59  33.00  60.00  140
 41  \w     27.00 105.00   0.50    0.95    --   96.59 -96.00 -60.00  156
 42  \w     83.00 157.00   0.50    0.95    --   96.59  77.00  90.00  148
 43  \w     84.00 157.00   0.50    0.95    --   96.59  96.00 -30.00  146
 44  \w     33.00 115.00   0.50    0.95    --   96.59 -59.00 -90.00  164
 45  \w     33.00 126.00   0.50    0.95    --   96.59-144.00 -60.00  186
 46  \w     84.00 157.00   0.50    0.95    --   96.59  42.00 150.00  146
 47  \w   -104.00 -21.00   0.50    0.25    --  -40.91 -63.00-150.00  166
 48  \w   -104.00 -21.00   0.50    0.25    --  -40.91 -63.00  30.00  166
 49  \w   -105.00 -29.00   0.50    0.25    --  -40.91 -37.00-120.00  152
 50  \w    -50.00  27.00   0.50    0.25    --  -40.91  25.00-120.00  154
 51  \w     16.00  42.00   0.50    0.25    --   40.91  78.00 145.14   52
 52  \w     15.00  42.00   0.50    0.25    --   40.91  77.00-121.29   54
 53  \w     16.00  42.00   0.50    0.25    --   40.91  80.00-176.12   52
 54  \w     21.00 105.00   0.50    0.25    --   40.91  62.00-102.68  168
 55  \w     15.00  42.00   0.50    0.25    --   40.91  82.00 -69.17   54
 56  \w     25.00 104.00   0.50    0.25    --   40.91  50.00   0.00  158
 57  \w     16.00  42.00   0.50    0.25    --   40.91  79.00  70.39   52
 58  \w     16.00  42.00   0.50    0.25    --   40.91  79.00  60.35   52
 59  \w     16.00  42.00   0.50    0.25    --   40.91  76.00 114.71   52
 60  \w     16.00  42.00   0.50    0.25    --   40.91  76.00 -74.63   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  0.1143
_diffrn_reflns_av_unetI/netI     0.0537
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            27210
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.459
_diffrn_reflns_theta_min         3.562
_exptl_absorpt_coefficient_mu    12.119
_exptl_absorpt_correction_T_max  0.358
_exptl_absorpt_correction_T_min  0.044
_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            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.708
_exptl_crystal_description       block
_exptl_crystal_F_000             891
_exptl_crystal_size_max          0.465
_exptl_crystal_size_mid          0.289
_exptl_crystal_size_min          0.139
_refine_diff_density_max         0.951
_refine_diff_density_min         -0.675
_refine_diff_density_rms         0.100
_refine_ls_extinction_coef       0.0026(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     516
_refine_ls_number_reflns         6347
_refine_ls_number_restraints     120
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0713
_refine_ls_R_factor_gt           0.0670
_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^)+(0.0823P)^2^+3.1525P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1819
_refine_ls_wR_factor_ref         0.1850
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5670
_reflns_number_total             6347
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02503a2.cif
_cod_data_source_block           rdt135c-280k
_cod_original_cell_volume        1738.87(7)
_cod_database_code               7714338
_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, All O(H) groups
2. Restrained distances
 C33-O3
 1.5 with sigma of 0.02
 C13-O3
 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-C29A
 1.38 with sigma of 0.02
 C34-O4
 1.42 with sigma of 0.02
 I1-C13 \\sim I1-C13A
 with sigma of 0.02
 C16-C15 \\sim C16-C15A
 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
 C15-C14 \\sim C15A-C14A
 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
 I1-C12 \\sim I1-C12A
 with sigma of 0.04
 I1-C14 \\sim I1-C14A
 with sigma of 0.04
 C16-C14 \\sim C16-C14A
 with sigma of 0.04
 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
 C15-C13 \\sim C15A-C13A
 with sigma of 0.04
 C14-O3 \\sim C14A-O3
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O3 \\sim C33: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
Uiso(O3) = Uiso(C33)
4. Rigid body (RIGU) restrains
 O3, C33
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C16, C11, C12A, C15A, C13A, C14A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16, C11, C12, C13, C14, C15
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C32, C27
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27, C32, C31A, C30A, C29A, C28A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: I2(0.59) O3(0.52) C12A(0.52) H12A(0.52) C33(0.52) H33A(0.52)
 H33B(0.52) H33C(0.52) C15A(0.52) H15A(0.52) C13A(0.52) C14A(0.52) H14A(0.52)
 I1(0.48) O4(0.41) C12(0.48) H12(0.48) C13(0.48) C14(0.48) H14(0.48) C15(0.48)
 H15(0.48) C34(0.41) H34A(0.41) H34B(0.41) H34C(0.41)
6.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C6(H6), C23(H23), C3(H3), C7(H7), C5(H5), C2(H2), C22(H22), C19(H19),
 C10(H10), C21(H21), C18(H18), C26(H26), C17(H17), C12A(H12A), C15A(H15A),
 C14A(H14A), C12(H12), C14(H14), C15(H15), C28A(H28A), C30A(H30A), C31A(H31A)
6.b Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C36(H36A,H36B,H36C)
6.c Idealised tetrahedral OH refined as rotating group:
 O8(H8)
;
_shelx_res_checksum              811
_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
;