Tuning spin-crossover transition temperatures in non-symmetrical homoleptic meridional/facial [Fe(didentate)<sub>3</sub>]<sup>2+</sup> complexes: what for and who cares about it?
Deorukhkar, Neel; Besnard, Céline; Guénée, Laure; Piguet, Claude; Dalton transactions (Cambridge, England : 2003) 50 (2021) 1206–1223; doi:10.1039/d0dt03828h

data_7706336
_publ_section_title
;
 Tuning spin-crossover transition temperatures in non-symmetrical
 homoleptic meridional/facial [Fe(didentate)<sub>3</sub>]<sup>2+</sup>
 complexes: what for and who cares about it?
;
_journal_issue                   4
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1206
_journal_page_last               1223
_journal_paper_doi               10.1039/d0dt03828h
_journal_volume                  50
_journal_year                    2021
_chemical_formula_moiety
'2(C36 H30 Fe N12), 0.562(Cl O4), 3.438(F6 P), C H4 O'
_chemical_formula_sum            'C73 H64 Cl0.56 F20.63 Fe2 N24 O3.25 P3.44'
_chemical_formula_weight         1959.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-04-14
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2020-10-30 deposited with the CCDC.	2020-12-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.075(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.0452(4)
_cell_length_b                   21.4963(4)
_cell_length_c                   19.0632(5)
_cell_measurement_reflns_used    15258
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      66.9030
_cell_measurement_theta_min      2.3230
_cell_volume                     7727.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.53a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.53a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.53a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix-Arc
_diffrn_measured_fraction_theta_full 0.973
_diffrn_measured_fraction_theta_max 0.953
_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    -67.00 -17.00   0.50   80.00    --  -52.43 125.00-150.00  100
  2  \w    -60.00 -35.00   0.50   80.00    --  -52.43 125.00  60.00   50
  3  \w    -70.00 -22.00   0.50   80.00    --  -52.43 125.00 120.00   96
  4  \w    -48.00 -23.00   0.50   80.00    --  -52.43 125.00   0.00   50
  5  \w    -76.00 -25.00   0.50   80.00    --  -52.43 125.00 -90.00  102
  6  \w    -93.00 -25.00   0.50   80.00    --  -52.43 -15.00 150.00  136
  7  \w    -88.00 -25.00   0.50   80.00    --  -52.43 -15.00  30.00  126
  8  \w     54.00 103.00   0.50   80.00    --   66.75  15.00   0.00   98
  9  \w     70.00 107.00   0.50   80.00    --   66.75  15.00  90.00   74
 10  \w     38.00  72.00   0.50   80.00    --   66.75  15.00-150.00   68
 11  \w     34.00  68.00   0.50   80.00    --   66.75-125.00  60.00   68
 12  \w     49.00  90.00   0.50   80.00    --   66.75-125.00-180.00   82
 13  \w     36.00  62.00   0.50   80.00    --   66.75-125.00  30.00   52
 14  \w     58.00  92.00   0.50   80.00    --   66.75-125.00   0.00   68
 15  \w     47.00  73.00   0.50   80.00    --   66.75-125.00 120.00   52
 16  \w     72.00 109.00   0.50   80.00    --   66.75  15.00-120.00   74
 17  \w     45.00  71.00   0.50   80.00    --   66.75  15.00-120.00   52
 18  \w     47.00 100.00   0.50   80.00    --   66.75  15.00 150.00  106
 19  \w     36.00  91.00   0.50   80.00    --   66.75-125.00 -60.00  110
 20  \w     52.00  79.00   0.50   80.00    --   66.75-125.00 150.00   54
 21  \w     69.00 107.00   0.50   80.00    --   66.75  15.00  30.00   76
 22  \w     46.00  71.00   0.50   80.00    --   66.75-125.00 -30.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0195758000
_diffrn_orient_matrix_UB_12      0.0553510000
_diffrn_orient_matrix_UB_13      0.0448568000
_diffrn_orient_matrix_UB_21      -0.0734688000
_diffrn_orient_matrix_UB_22      -0.0290137000
_diffrn_orient_matrix_UB_23      0.0030070000
_diffrn_orient_matrix_UB_31      0.0298118000
_diffrn_orient_matrix_UB_32      -0.0351413000
_diffrn_orient_matrix_UB_33      0.0681124000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0572
_diffrn_reflns_av_unetI/netI     0.0597
_diffrn_reflns_Laue_measured_fraction_full 0.973
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            56784
_diffrn_reflns_point_group_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.252
_diffrn_reflns_theta_min         3.116
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.911
_exptl_absorpt_correction_T_max  0.948
_exptl_absorpt_correction_T_min  0.708
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.53a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.684
_exptl_crystal_description       prism
_exptl_crystal_F_000             3979
_exptl_crystal_size_max          0.082
_exptl_crystal_size_mid          0.037
_exptl_crystal_size_min          0.022
_refine_diff_density_max         1.204
_refine_diff_density_min         -0.710
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1227
_refine_ls_number_reflns         14030
_refine_ls_number_restraints     207
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.1190
_refine_ls_R_factor_gt           0.0764
_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^)+(0.1098P)^2^+11.5216P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2007
_refine_ls_wR_factor_ref         0.2256
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8942
_reflns_number_total             14030
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt03828h2.cif
_cod_data_source_block           13_FeL7PF6ClO4
_cod_depositor_comments
'Adding full bibliography for 7706322--7706338.cif.'
_cod_database_code               7706336
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula
'C73 H61 Cl0.551 F20.691 Fe2 N24 O3.206 P3.449'
_reflns_odcompleteness_completeness 97.45
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_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
 P4-F20 = P4-F21 = P4-F19 = P4-F22 = P4-F24 = P4-F23
 1.6 with sigma of 0.02
 Cl1-O2 = Cl1-O4 = Cl1-O1 = Cl1-O3
 1.5 with sigma of 0.02
 F24-F20
 2.24 with sigma of 0.04
 O2-O3
 2.45 with sigma of 0.04
 F21-F23
 2.24 with sigma of 0.04
 F21-F19
 2.24 with sigma of 0.04
 F19-F20
 2.24 with sigma of 0.04
 F24-F23
 2.24 with sigma of 0.04
 O2-O3 = O2-O4 = O3-O4 = O1-O2 = O1-O3 = O1-O4
 2.45 with sigma of 0.04
 F22-F23
 2.24 with sigma of 0.04
 F22-F21
 2.24 with sigma of 0.04
 F21-F20
 2.24 with sigma of 0.04
 F20-F22
 2.24 with sigma of 0.04
 F23-F19
 2.24 with sigma of 0.04
 F24-F19
 2.24 with sigma of 0.04
 F24-F22
 2.24 with sigma of 0.04
 O2-O4
 2.45 with sigma of 0.04
 O4-O3
 2.45 with sigma of 0.04
 P4-F23 \\sim P4-F22 \\sim P4-F20 \\sim P4-F19 \\sim P4-F24 \\sim P4-F21
 with sigma of 0.02
 O36-C37A \\sim O38-C37B
 with sigma of 0.02
 F23-F22 \\sim F23-F19 \\sim F23-F24 \\sim F23-F21 \\sim F20-F22 \\sim F20-F19
\\sim F20-F24 \\sim F20-F21
 with sigma of 0.04
 F23-F20 \\sim F22-F19 \\sim F21-F24
 with sigma of 0.05
3. Uiso/Uaniso restraints and constraints
O36 \\sim C37A \\sim O38 \\sim C37B: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Cl1 \\sim O1 \\sim O2 \\sim O3 \\sim O4: within 1A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1A
Cl1 \\sim O1 \\sim O2 \\sim O3 \\sim O4 \\sim P4 \\sim F19 \\sim F20 \\sim F21
\\sim F22 \\sim F23 \\sim F24: within 1A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 1A
4. Rigid body (RIGU) restrains
 O38, C37B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P4, F19, F20, F21, F22, F23, F24
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O36, C37A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(P4)=Sof(F19)=Sof(F20)=Sof(F21)=Sof(F22)=Sof(F23)=Sof(F24)=1-FVAR(1)
 Sof(Cl1)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(O4)=FVAR(1)
 Sof(O38)=Sof(H38)=Sof(C37B)=Sof(H37D)=Sof(H37E)=Sof(H37F)=1-FVAR(2)
 Sof(O36)=Sof(H36)=Sof(C37A)=Sof(H37A)=Sof(H37B)=Sof(H37C)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C13(H13),
 C14(H14), C15(H15), C16(H16), C21(H21), C22(H22), C23(H23), C25(H25), C26(H26),
  C27(H27), C28(H28), C33(H33), C34(H34), C35(H35), C2B(H2B), C3B(H3B),
 C4B(H4B), C5B(H5B), C9B(H9B), C10B(H10B), C11B(H11B), C13B(H13B), C14B(H14B),
 C15B(H15B), C16B(H16B), C21B(H21B), C22B(H22B), C23B(H23B), C25B(H25B),
 C26B(H26B), C27B(H27B), C28B(H28B), C33B(H33B), C34B(H34B), C35B(H35B)
6.b Tetrahedral OH refined with riding coordinates:
 O38(H38)
6.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C18(H18A,H18B,H18C), C30(H30A,H30B,H30C), C7B(H7BA,H7BB,
 H7BC), C18B(H18D,H18E,H18F), C30B(H30D,H30E,H30F), C37A(H37A,H37B,H37C),
 C37B(H37D,H37E,H37F)
6.d Idealised tetrahedral OH refined as rotating group:
 O36(H36)
;
_shelx_res_checksum              79371
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.397
_oxdiff_exptl_absorpt_empirical_full_min 0.675