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_7706331
_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), 1.502(F6 P), 2.498(B F4), C H4 O'
_chemical_formula_sum            'C73 H64 B2.5 F19 Fe2 N24 O P1.5'
_chemical_formula_weight         1839.80
_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             2020-11-25
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2020-12-05 deposited with the CCDC.	2020-12-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.0140(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.82600(10)
_cell_length_b                   21.23850(10)
_cell_length_c                   18.88290(10)
_cell_measurement_reflns_used    48819
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      74.0550
_cell_measurement_theta_min      3.1130
_cell_volume                     7476.33(7)
_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 0.992
_diffrn_measured_fraction_theta_max 0.978
_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     39.00  64.00   0.50   11.42    --   32.00  79.00-176.07   50
  2  \w    -83.00 -27.00   0.50   11.42    --  -52.43 -15.00-180.00  112
  3  \w    -81.00 -26.00   0.50   11.42    --  -52.43   0.00  60.00  110
  4  \w     34.00  94.00   0.50   11.42    --   68.73-125.00 120.00  120
  5  \w     36.00  72.00   0.50   11.42    --   68.73-125.00  30.00   72
  6  \w     82.00 109.00   0.50   11.42    --   69.88  15.00  60.00   54
  7  \w     43.00  75.00   0.50   11.42    --   69.88-140.00-106.00   64
  8  \w     50.00  76.00   0.50   11.42    --   69.88  15.00  60.00   52
  9  \w     41.00  90.00   0.50   11.42    --   69.88-125.00 -60.00   98
 10  \w     52.00  97.00   0.50   11.42    --   75.25-118.00  91.31   90
 11  \w     42.00  67.00   0.50   11.42    --   75.25 -89.00 -45.35   50
 12  \w     62.00  88.00   0.50   11.42    --   75.25-127.00  24.53   52
 13  \w     42.00  72.00   0.50   11.42    --   75.25-119.00 -39.94   60
 14  \w     66.00 119.00   0.50   11.42    --   75.25  21.00 161.85  106
 15  \w     78.00 108.00   0.50   11.42    --   75.25-139.00 -97.01   60
 16  \w     63.00  97.00   0.50   11.42    --   75.25-117.00  79.29   68
 17  \w     82.00 116.00   0.50   11.42    --   75.25-153.00 167.69   68
 18  \w     38.00  90.00   0.50   11.42    --   75.25-108.00  45.47  104
 19  \w     80.00 108.00   0.50   11.42    --   75.25   4.00 175.05   56
 20  \w     70.00  96.00   0.50   11.42    --   75.25-116.00 105.90   52
 21  \w     66.00  91.00   0.50   11.42    --   75.25-109.00-140.86   50
 22  \w     46.00 107.00   0.50   11.42    --   75.25  11.00-117.47  122
 23  \w     55.00 101.00   0.50   11.42    --   75.25-129.00 173.37   92
 24  \w     50.00  91.00   0.50   11.42    --   75.25-123.00  38.29   82
 25  \w     43.00  75.00   0.50   11.42    --   75.25   4.00 175.05   64
 26  \w     36.00  61.00   0.50   11.42    --   75.25 -59.00 -13.69   50
 27  \w     42.00  87.00   0.50   11.42    --   75.25-107.00 -99.69   90
 28  \w     50.00  75.00   0.50   11.42    --   75.25  16.00  35.22   50
 29  \w     86.00 112.00   0.50   11.42    --   75.25  21.00 105.23   52
 30  \w     46.00  71.00   0.50   11.42    --   75.25-100.00  81.88   50
 31  \w     40.00  65.00   0.50   11.42    --   75.25 -97.00  20.76   50
 32  \w     58.00  96.00   0.50   11.42    --   75.25-116.00-108.58   76
 33  \w     71.00  96.00   0.50   11.42    --   75.25-115.00 139.37   50
 34  \w     93.00 118.00   0.50   11.42    --   75.25  16.00  35.22   50
 35  \w     90.00 117.00   0.50   11.42    --   75.25  51.00-140.29   54
 36  \w     53.00  97.00   0.50   11.42    --   75.25-118.00-174.11   88
 37  \w     88.00 113.00   0.50   11.42    --   75.25  35.00   9.70   50
 38  \w     48.00  89.00   0.50   11.42    --   75.25   3.00-101.75   82
 39  \w     64.00  90.00   0.50   11.42    --   75.25  21.00  14.62   52
 40  \w     46.00  71.00   0.50   11.42    --   75.25-117.00 -48.87   50
 41  \w     39.00  65.00   0.50   11.42    --   75.25-110.00-115.72   52
;
_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      -0.0420961000
_diffrn_orient_matrix_UB_12      -0.0159204000
_diffrn_orient_matrix_UB_13      0.0620501000
_diffrn_orient_matrix_UB_21      -0.0125264000
_diffrn_orient_matrix_UB_22      0.0706839000
_diffrn_orient_matrix_UB_23      0.0116624000
_diffrn_orient_matrix_UB_31      -0.0699961000
_diffrn_orient_matrix_UB_32      -0.0030420000
_diffrn_orient_matrix_UB_33      -0.0529709000
_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  0.0268
_diffrn_reflns_av_unetI/netI     0.0189
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            96589
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.447
_diffrn_reflns_theta_min         3.105
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.412
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.429
_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    1.635
_exptl_crystal_description       needle
_exptl_crystal_F_000             3744
_exptl_crystal_size_max          0.217
_exptl_crystal_size_mid          0.056
_exptl_crystal_size_min          0.031
_refine_diff_density_max         1.136
_refine_diff_density_min         -0.416
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1253
_refine_ls_number_reflns         14949
_refine_ls_number_restraints     395
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0430
_refine_ls_R_factor_gt           0.0379
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0595P)^2^+4.9100P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1023
_refine_ls_wR_factor_ref         0.1056
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13422
_reflns_number_total             14949
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt03828h2.cif
_cod_data_source_block           12_FeL7PF6BF4
_cod_depositor_comments
'Adding full bibliography for 7706322--7706338.cif.'
_cod_original_formula_sum        'C73 H64 B2.50 F19 Fe2 N24 O P1.50'
_cod_database_code               7706331
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C73 H64 B2 F20 Fe2 N24 O1 P2'
_reflns_odcompleteness_completeness 96.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.85
_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
 B4-F25 = B4-F28 = B4-F26 = B4-F27
 1.42 with sigma of 0.02
 F5B-F6B \\sim F5B-F7B \\sim F5B-F8B \\sim F6B-F7B \\sim F6B-F8B \\sim F7B-F8B
 with sigma of 0.04
 F25-F28 \\sim F28-F26 \\sim F26-F27 \\sim F27-F25 \\sim F28-F27 \\sim F25-F26
 with sigma of 0.04
 F22-B3 \\sim F24-B3 \\sim F21-B3 \\sim F23-B3
 with sigma of 0.02
 F22-F24 \\sim F24-F23 \\sim F23-F21 \\sim F23-F22 \\sim F22-F21 \\sim F21-F24
 with sigma of 0.04
 B4-F25 \\sim B4-F28 \\sim B4-F26 \\sim B4-F27
 with sigma of 0.02
 O1-C1S \\sim O2-C2S
 with sigma of 0.02
 F6A-B2A \\sim F5A-B2A \\sim F8A-B2A \\sim F7A-B2A
 with sigma of 0.02
 F5A-F6A \\sim F5A-F7A \\sim F5A-F8A \\sim F6A-F7A \\sim F6A-F8A \\sim F7A-F8A
 with sigma of 0.04
 F5B-B2B \\sim F6B-B2B \\sim F7B-B2B \\sim F8B-B2B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
B4 \\sim F25 \\sim F28 \\sim F26 \\sim F27: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C2S \\sim C1S: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
O2 \\sim O1: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
F5A \\sim F5B \\sim F6A \\sim F6B \\sim F7A \\sim F7B \\sim F8A \\sim F8B \\sim
B2A \\sim B2B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(P1) = Uanis(B3)
Uanis(F5B) = Uanis(F6A)
Uanis(B2A) = Uanis(B2B)
Uanis(B4) = Uanis(PB)
Uanis(F19) = Uanis(F26)
4. Rigid body (RIGU) restrains
 F24, B3, F23, F21, F22
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 B4, F25, F28, F26, F27
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2, C2S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1, C1S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F5B, F6B, F7B, F8B, B2B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F5A, F6A, F7A, F8A, B2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F25, B4, F28, F26, F27
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(F5B)=Sof(F6B)=Sof(F7B)=Sof(F8B)=Sof(B2B)=Sof(O1)=Sof(H1)=Sof(C1S)=
 Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=1-FVAR(1)
 Sof(F5A)=Sof(F6A)=Sof(F7A)=Sof(F8A)=Sof(B2A)=Sof(O2)=Sof(H2A)=Sof(C2S)=
 Sof(H2SA)=Sof(H2SB)=Sof(H2SC)=FVAR(1)
 Sof(B3)=Sof(F24)=Sof(F23)=Sof(F21)=Sof(F22)=1-FVAR(2)
 Sof(P1)=Sof(F14)=Sof(F9)=Sof(F13)=Sof(F10)=Sof(F12)=Sof(F11)=FVAR(2)
 Sof(B4)=Sof(F25)=Sof(F28)=Sof(F26)=Sof(F27)=1-FVAR(3)
 Sof(PB)=Sof(F18)=Sof(F17)=Sof(F19)=Sof(F20)=Sof(F16)=Sof(F15)=FVAR(3)
6.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C10(H10), C11(H11), C12(H12), C14(H14),
 C15(H15), C16(H16), C17(H17), C21(H21), C22(H22), C23(H23), C26(H26), C27(H27),
  C28(H28), C29(H29), C34(H34), C35(H35), C36(H36), C2B(H2B), C3B(H3B),
 C4B(H4B), C5B(H5B), C10B(H10B), C11B(H11B), C12B(H12B), C14B(H14B), C15B(H15B),
  C16B(H16B), C17B(H17B), C21B(H21B), C22B(H22B), C23B(H23B), C26B(H26B),
 C27B(H27B), C28B(H28B), C29B(H29B), C34B(H34B), C35B(H35B), C36B(H36B)
6.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C24(H24A,H24B,H24C), C31(H31A,H31B,H31C), C7B(H7BA,H7BB,
 H7BC), C24B(H24D,H24E,H24F), C31B(H31D,H31E,H31F), C2S(H2SA,H2SB,H2SC),
 C1S(H1SA,H1SB,H1SC)
6.c Idealised tetrahedral OH refined as rotating group:
 O2(H2A), O1(H1)
;
_shelx_res_checksum              58162
_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 1.919
_oxdiff_exptl_absorpt_empirical_full_min 0.779