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_7714337
_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
'C33.185 H23.554 Fe I0.815 N4 O3.185, C N S, 0.75(C H4 O), 1.3[H2O]'
_chemical_formula_sum            'C34.94 H29.15 Fe I0.81 N5 O5.23 S'
_chemical_formula_weight         794.10
_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                66.070(3)
_cell_angle_beta                 74.702(3)
_cell_angle_gamma                73.722(3)
_cell_formula_units_Z            2
_cell_length_a                   10.7785(3)
_cell_length_b                   12.6165(4)
_cell_length_c                   13.9032(5)
_cell_measurement_reflns_used    12266
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      68.2530
_cell_measurement_theta_min      3.5050
_cell_volume                     1634.39(10)
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0(2)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.979
_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    -62.00  23.00   0.50    0.50    --  -40.91  67.00-105.00  170
  2  \w   -105.00 -20.00   0.50    0.50    --  -40.91 -67.00 120.00  170
  3  \w    -23.00  62.00   0.50    0.50    --   40.91 -67.00 120.00  170
  4  \w     33.00 118.00   0.50    2.00    --   96.59 -67.00 120.00  170
  5  \w     76.00 157.00   0.50    2.00    --   96.59  67.00-105.00  162
  6  \w    -97.00 -14.00   0.50    0.50    --  -40.91 138.00-180.00  166
  7  \w   -114.00 -19.00   0.50    0.50    --  -40.91 -12.00 -30.00  190
  8  \w    -97.00 -14.00   0.50    0.50    --  -40.91 138.00-120.00  166
  9  \w   -104.00 -25.00   0.50    0.50    --  -40.91 -50.00  30.00  158
 10  \w   -114.00 -19.00   0.50    0.50    --  -40.91 -12.00  60.00  190
 11  \w    -24.00  67.00   0.50    0.50    --   40.91 -77.00   0.00  182
 12  \w     15.00  42.00   0.50    0.50    --   40.91  81.00  88.79   54
 13  \w     15.00  42.00   0.50    0.50    --   40.91  77.00 138.74   54
 14  \w     29.00 105.00   0.50    0.50    --   40.91  37.00  30.00  152
 15  \w     15.00  42.00   0.50    0.50    --   40.91  82.00 103.67   54
 16  \w     16.00  42.00   0.50    0.50    --   40.91  80.00 -34.40   52
 17  \w     16.00  42.00   0.50    0.50    --   40.91  79.00  53.38   52
 18  \w     25.00 104.00   0.50    0.50    --   40.91  50.00 -30.00  158
 19  \w     20.00 105.00   0.50    0.50    --   40.91  67.00-105.00  170
 20  \w     16.00  42.00   0.50    0.50    --   40.91  78.00-167.82   52
 21  \w     15.00  42.00   0.50    0.50    --   40.91  82.00 148.89   54
 22  \w     34.00 113.00   0.50    2.00    --   96.59 -50.00 -90.00  158
 23  \w     32.00 109.00   0.50    2.00    --   96.59-117.00 120.00  154
 24  \w     81.00 157.00   0.50    2.00    --   96.59  50.00  90.00  152
 25  \w     34.00 110.00   0.50    2.00    --   96.59 -42.00 120.00  152
 26  \w     27.00 105.00   0.50    2.00    --   96.59 -96.00 120.00  156
 27  \w     32.00 109.00   0.50    2.00    --   96.59-117.00-150.00  154
 28  \w     33.00 126.00   0.50    2.00    --   96.59-144.00-180.00  186
 29  \w     32.00 109.00   0.50    2.00    --   96.59-117.00  90.00  154
 30  \w     81.00 157.00   0.50    2.00    --   96.59  50.00-150.00  152
 31  \w     33.00 126.00   0.50    2.00    --   96.59-144.00 -60.00  186
 32  \w     31.00 106.00   0.50    2.00    --   96.59 -33.00-180.00  150
 33  \w     83.00 157.00   0.50    2.00    --   96.59  17.00 -60.00  148
 34  \w     26.00 110.00   0.50    2.00    --   96.59 -17.00  60.00  168
 35  \w     31.00 106.00   0.50    2.00    --   96.59 -33.00  60.00  150
 36  \w     87.00 157.00   0.50    2.00    --   96.59  33.00 -30.00  140
 37  \w     31.00 106.00   0.50    2.00    --   96.59 -33.00 -30.00  150
 38  \w     33.00 126.00   0.50    2.00    --   96.59-144.00  90.00  186
 39  \w     32.00 109.00   0.50    2.00    --   96.59-117.00 -60.00  154
 40  \w     88.00 157.00   0.50    2.00    --   96.59  25.00   0.00  138
 41  \w     22.00 127.00   0.50    2.00    --   96.59  -8.00 -60.00  210
 42  \w     27.00 105.00   0.50    2.00    --   96.59 -96.00 -60.00  156
 43  \w     31.00 106.00   0.50    2.00    --   96.59 -33.00 -90.00  150
 44  \w     33.00 118.00   0.50    2.00    --   96.59 -68.00 -90.00  170
 45  \w   -104.00 -21.00   0.50    0.50    --  -40.91 -63.00 -30.00  166
 46  \w   -104.00 -21.00   0.50    0.50    --  -40.91 -63.00-180.00  166
 47  \w   -104.00 -21.00   0.50    0.50    --  -40.91 -63.00 -90.00  166
 48  \w    -63.00  32.00   0.50    0.50    --  -40.91  12.00  90.00  190
 49  \w    -61.00  23.00   0.50    0.50    --  -40.91  63.00 120.00  168
 50  \w    -41.00 -15.00   0.50    0.50    --  -40.91 -77.00 -50.36   52
 51  \w     15.00  42.00   0.50    0.50    --   40.91  82.00-155.71   54
 52  \w     25.00 104.00   0.50    0.50    --   40.91  50.00 150.00  158
 53  \w     15.00  42.00   0.50    0.50    --   40.91  81.00  11.06   54
 54  \w     16.00  42.00   0.50    0.50    --   40.91  79.00  42.94   52
 55  \w     16.00  42.00   0.50    0.50    --   40.91  78.00-113.30   52
 56  \w     16.00  42.00   0.50    0.50    --   40.91  80.00-106.05   52
 57  \w     29.00 105.00   0.50    0.50    --   40.91  37.00 -90.00  152
 58  \w     16.00  42.00   0.50    0.50    --   40.91  80.00  73.64   52
 59  \w     15.00  42.00   0.50    0.50    --   40.91  81.00 -72.53   54
 60  \w     87.00 157.00   0.50    2.00    --   96.59  33.00  60.00  140
 61  \w     88.00 157.00   0.50    2.00    --   96.59  25.00 150.00  138
;
_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  0.0836
_diffrn_reflns_av_unetI/netI     0.0432
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            25047
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.105
_diffrn_reflns_theta_min         3.530
_exptl_absorpt_coefficient_mu    10.775
_exptl_absorpt_correction_T_max  0.329
_exptl_absorpt_correction_T_min  0.081
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.76a (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    1.614
_exptl_crystal_description       block
_exptl_crystal_F_000             802
_exptl_crystal_size_max          0.412
_exptl_crystal_size_mid          0.271
_exptl_crystal_size_min          0.201
_refine_diff_density_max         1.003
_refine_diff_density_min         -1.359
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     502
_refine_ls_number_reflns         5964
_refine_ls_number_restraints     160
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0849
_refine_ls_R_factor_gt           0.0806
_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^)+(0.0972P)^2^+5.7262P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2162
_refine_ls_wR_factor_ref         0.2193
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5393
_reflns_number_total             5964
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02503a2.cif
_cod_data_source_block           rdt83-150k
_cod_original_cell_volume        1634.41(10)
_cod_database_code               7714337
_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
 C29-O4
 1.38 with sigma of 0.02
 O3-C13
 1.38 with sigma of 0.02
 O4-C29
 1.38 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
 C11-C12 \\sim C11-C12A
 with sigma of 0.02
 C12-C13 \\sim C12A-C13A
 with sigma of 0.02
 C13-I1 \\sim C13A-I1
 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
 C15-C16 \\sim C15A-C16
 with sigma of 0.02
 C15-C14 \\sim C15A-C14A
 with sigma of 0.02
 C11-C13 \\sim C11-C13A
 with sigma of 0.04
 C12-I1 \\sim C12A-I1
 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
 C13-C15 \\sim C13A-C15A
 with sigma of 0.04
 C16-C14 \\sim C16-C14A
 with sigma of 0.04
 I1-C14 \\sim I1-C14A
 with sigma of 0.04
 C14-O3 \\sim C14A-O3
 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. Uiso/Uaniso restraints and constraints
Uanis(C34) = Uanis(O4)
Uanis(C33) = Uanis(O3)
4. Rigid body (RIGU) restrains
 C29
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C13
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 S1, N5, C35
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11, C16, C12A, C13A, C14A, C15A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11, C16, C12, C13, C14, C15
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27, C32, C28A, C29A, C30A, C31A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27, C32, C28, C29, C30, C31
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O3)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15)=
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=1-FVAR(1)
 Sof(I1)=Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=
 FVAR(1)
 Sof(I2)=Sof(C28)=Sof(H28)=Sof(C29)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=1-
 FVAR(2)
 Sof(O4)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(2)
 Fixed Sof: O5(0.75) H5A(0.75) C37(0.75) H37A(0.75) H37B(0.75) H37C(0.75)
6.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5), C6(H6), C7(H7), C10(H10), C17(H17), C18(H18),
 C19(H19), C21(H21), C22(H22), C23(H23), C26(H26), C12A(H12A), C14A(H14A),
 C15A(H15A), C28A(H28A), C30A(H30A), C31A(H31A), C12(H12), C14(H14), C15(H15),
 C28(H28), C30(H30), C31(H31)
6.b Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C33(H33A,H33B,H33C), C37(H37A,H37B,H37C)
6.c Idealised tetrahedral OH refined as rotating group:
 O5(H5A)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 26 electrons were 
found in a volume of 62\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1.3[H2O] per Asymmetric Unit 
which account for 26 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              33950
_shelx_fab_checksum              21324
_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
;