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_7714340
_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         'C34 H26 Fe N4 O4, C F3 O3 S, 0.9[CH2Cl2]'
_chemical_formula_sum            'C36 H28 Cl2 F3 Fe N4 O7 S'
_chemical_formula_weight         844.43
_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             2023-09-19
_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                74.641(3)
_cell_angle_beta                 80.008(3)
_cell_angle_gamma                63.540(4)
_cell_formula_units_Z            2
_cell_length_a                   12.3692(5)
_cell_length_b                   12.4482(4)
_cell_length_c                   12.9361(5)
_cell_measurement_reflns_used    14442
_cell_measurement_temperature    280.01(10)
_cell_measurement_theta_max      68.2950
_cell_measurement_theta_min      3.5170
_cell_volume                     1715.93(13)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      280.01(10)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.991
_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    -92.00 -10.00   0.50    1.04    --  -40.91 130.00-107.00  164
  2  \w    -97.00 -14.00   0.50    1.04    --  -40.91 139.00  66.00  166
  3  \w     14.00  97.00   0.50    1.04    --   40.91-139.00   6.00  166
  4  \w     10.00  92.00   0.50    1.04    --   40.91-130.00-179.00  164
  5  \w     34.00 122.00   0.50    4.18    --   96.90-139.00   6.00  176
  6  \w     69.00 157.00   0.50    4.18    --   96.90 139.00  66.00  176
  7  \w     34.00 115.00   0.50    4.18    --   96.90-130.00-179.00  162
  8  \w     74.00 157.00   0.50    4.18    --   96.90 130.00-107.00  166
  9  \w   -109.00 -32.00   0.50    1.04    --  -40.91 -25.00 -90.00  154
 10  \w   -109.00 -32.00   0.50    1.04    --  -40.91 -25.00 -60.00  154
 11  \w    -53.00  23.00   0.50    1.04    --  -40.91  37.00   0.00  152
 12  \w    -50.00  27.00   0.50    1.04    --  -40.91  25.00 -60.00  154
 13  \w    -13.00  77.00   0.50    1.04    --   40.91-104.00  90.00  180
 14  \w     25.00 104.00   0.50    1.04    --   40.91  50.00  30.00  158
 15  \w    -23.00  53.00   0.50    1.04    --   40.91 -37.00-150.00  152
 16  \w     14.00  97.00   0.50    1.04    --   40.91-138.00-120.00  166
 17  \w    -22.00  57.00   0.50    1.04    --   40.91 -50.00 -30.00  158
 18  \w     32.00 109.00   0.50    1.04    --   40.91  25.00-180.00  154
 19  \w     29.00 105.00   0.50    1.04    --   40.91  37.00 -90.00  152
 20  \w    -22.00  57.00   0.50    1.04    --   40.91 -50.00 150.00  158
 21  \w     25.00 104.00   0.50    1.04    --   40.91  50.00  60.00  158
 22  \w     34.00 116.00   0.50    4.18    --   96.90 -59.00-150.00  164
 23  \w     67.00 157.00   0.50    4.18    --   96.90 144.00  30.00  180
 24  \w     81.00 157.00   0.50    4.18    --   96.90  50.00 -60.00  152
 25  \w     27.00 105.00   0.50    4.18    --   96.90 -96.00   0.00  156
 26  \w     32.00 109.00   0.50    4.18    --   96.90-117.00 120.00  154
 27  \w     34.00 110.00   0.50    4.18    --   96.90 -42.00-120.00  152
 28  \w     78.00 157.00   0.50    4.18    --   96.90  59.00 -30.00  158
 29  \w     26.00 111.00   0.50    4.18    --   96.90 -17.00 -60.00  170
 30  \w     34.00 113.00   0.50    4.18    --   96.90 -50.00 150.00  158
 31  \w     84.00 157.00   0.50    4.18    --   96.90  42.00   0.00  146
 32  \w     31.00 124.00   0.50    4.18    --   96.90 -86.00 150.00  186
 33  \w     33.00 118.00   0.50    4.18    --   96.90 -68.00 -30.00  170
 34  \w     88.00 157.00   0.50    4.18    --   96.90  33.00  30.00  138
 35  \w     32.00 109.00   0.50    4.18    --   96.90-117.00 -90.00  154
 36  \w     84.00 157.00   0.50    4.18    --   96.90  42.00 -90.00  146
 37  \w     32.00 106.00   0.50    4.18    --   96.90 -33.00  30.00  148
 38  \w     26.00 111.00   0.50    4.18    --   96.90 -17.00  90.00  170
 39  \w     27.00 105.00   0.50    4.18    --   96.90 -96.00 120.00  156
 40  \w     32.00 109.00   0.50    4.18    --   96.90-117.00   0.00  154
 41  \w     34.00 110.00   0.50    4.18    --   96.90 -42.00 -30.00  152
 42  \w     88.00 157.00   0.50    4.18    --   96.90  33.00-120.00  138
 43  \w     34.00 113.00   0.50    4.18    --   96.90 -50.00 120.00  158
 44  \w   -104.00 -21.00   0.50    1.04    --  -40.91 -63.00-180.00  166
 45  \w   -104.00 -21.00   0.50    1.04    --  -40.91 -63.00  90.00  166
 46  \w   -104.00 -21.00   0.50    1.04    --  -40.91 -63.00 150.00  166
 47  \w   -104.00 -21.00   0.50    1.04    --  -40.91 -63.00 -60.00  166
 48  \w   -104.00 -21.00   0.50    1.04    --  -40.91 -63.00-120.00  166
 49  \w   -104.00 -21.00   0.50    1.04    --  -40.91 -63.00-150.00  166
 50  \w   -104.00 -21.00   0.50    1.04    --  -40.91 -63.00  60.00  166
 51  \w   -104.00 -21.00   0.50    1.04    --  -40.91 -63.00 -90.00  166
 52  \w     21.00 105.00   0.50    1.04    --   40.91  63.00  90.00  168
;
_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  0.0757
_diffrn_reflns_av_unetI/netI     0.0437
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -14
_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            27182
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.590
_diffrn_reflns_theta_min         3.551
_exptl_absorpt_coefficient_mu    6.180
_exptl_absorpt_correction_T_max  0.831
_exptl_absorpt_correction_T_min  0.370
_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    1.634
_exptl_crystal_description       needle
_exptl_crystal_F_000             862
_exptl_crystal_size_max          0.494
_exptl_crystal_size_mid          0.057
_exptl_crystal_size_min          0.038
_refine_diff_density_max         0.451
_refine_diff_density_min         -0.657
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     517
_refine_ls_number_reflns         6272
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0508
_refine_ls_R_factor_gt           0.0458
_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^)+(0.0803P)^2^+0.3787P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1272
_refine_ls_wR_factor_ref         0.1310
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5583
_reflns_number_total             6272
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02503a2.cif
_cod_data_source_block           rdt285-280k
_cod_database_code               7714340
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl1-C36A
 1.76 with sigma of 0.02
 C36A-Cl2A
 1.76 with sigma of 0.02
 Cl1-C36A \\sim Cl1A-C36B
 with sigma of 0.02
 C36A-Cl2A \\sim C36B-Cl2B
 with sigma of 0.02
 Cl1-Cl2A \\sim Cl1A-Cl2B
 with sigma of 0.04
3. Rigid body (RIGU) restrains
 Cl1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl2A, C36A, Cl1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1, C36A, Cl2A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 Cl1A, C36B, Cl2B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4. Others
 Sof(Cl1A)=Sof(C36B)=Sof(H36C)=Sof(H36D)=Sof(Cl2B)=1-FVAR(1)
 Sof(Cl1)=Sof(C36A)=Sof(H36A)=Sof(H36B)=Sof(Cl2A)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C36A(H36A,H36B), C36B(H36C,H36D)
5.b 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), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24), C27(H27),
  C29(H29), C31(H31), C32(H32)
5.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C34(H34A,H34B,H34C)
;
_shelx_res_checksum              37934
_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
- Detector area scaling
;