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_7706337
_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 N12 Ni), 2.96(Cl O4), 1.04(F6 P)'
_chemical_formula_sum            'C72 H60 Cl2.96 F6.24 N24 Ni2 O11.84 P1.04'
_chemical_formula_weight         1824.00
_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             2020-07-07
_audit_creation_method
;
Olex2 1.3
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_audit_update_record
;
2020-10-30 deposited with the CCDC.	2020-12-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.5966(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.9538(2)
_cell_length_b                   21.5853(3)
_cell_length_c                   19.0060(3)
_cell_measurement_reflns_used    30735
_cell_measurement_temperature    120.01(12)
_cell_measurement_theta_max      71.2480
_cell_measurement_theta_min      3.0430
_cell_volume                     7688.44(18)
_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      120.01(12)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix-Arc
_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    -85.00 -24.00   0.50   25.00    --  -52.43   0.00-180.00  122
  2  \w    -80.00 -24.00   0.50   25.00    --  -52.43   0.00 120.00  112
  3  \w    -75.00 -38.00   0.50   25.00    --  -52.43 125.00  30.00   74
  4  \w    -66.00 -40.00   0.50   25.00    --  -52.43 125.00 -90.00   52
  5  \w    -76.00 -36.00   0.50   25.00    --  -52.43 125.00 -30.00   80
  6  \w    -62.00 -35.00   0.50   25.00    --  -52.43 125.00 120.00   54
  7  \w    -79.00 -18.00   0.50   25.00    --  -52.43   0.00  60.00  122
  8  \w    -60.00 -26.00   0.50   25.00    --  -52.43 -15.00-120.00   68
  9  \w     39.00  68.00   0.50   25.00    --   68.73-125.00-180.00   58
 10  \w     47.00  73.00   0.50   25.00    --   68.73-125.00  30.00   52
 11  \w     43.00  69.00   0.50   25.00    --   68.73-125.00 120.00   52
 12  \w     37.00  79.00   0.50   25.00    --   68.73-125.00  60.00   84
 13  \w     48.00 109.00   0.50   25.00    --   68.73  15.00-120.00  122
 14  \w     37.00  75.00   0.50   25.00    --   68.73-125.00 -30.00   76
 15  \w     55.00  89.00   0.50   25.00    --   68.73-125.00   0.00   68
 16  \w     54.00  80.00   0.50   25.00    --   68.73-125.00-150.00   52
 17  \w     69.00  94.00   0.50   25.00    --   69.88-125.00  60.00   50
 18  \w     37.00 104.00   0.50   25.00    --   69.88   0.00-150.00  134
 19  \w     41.00  79.00   0.50   25.00    --   69.88-125.00  30.00   76
 20  \w     65.00 103.00   0.50   25.00    --   69.88  15.00 -90.00   76
 21  \w     37.00  95.00   0.50   25.00    --   69.88-125.00  90.00  116
 22  \w     47.00  72.00   0.50   25.00    --   69.88-125.00 120.00   50
 23  \w     54.00  87.00   0.50   25.00    --   69.88  15.00-180.00   66
 24  \w     41.00  89.00   0.50   25.00    --   69.88   0.00  90.00   96
 25  \w     48.00 112.00   0.50   25.00    --   69.88  15.00 120.00  128
;
_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      -0.0357917000
_diffrn_orient_matrix_UB_12      0.0610736000
_diffrn_orient_matrix_UB_13      0.0172936000
_diffrn_orient_matrix_UB_21      -0.0230488000
_diffrn_orient_matrix_UB_22      0.0118839000
_diffrn_orient_matrix_UB_23      -0.0800421000
_diffrn_orient_matrix_UB_31      -0.0702612000
_diffrn_orient_matrix_UB_32      -0.0350962000
_diffrn_orient_matrix_UB_33      0.0031648000
_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  0.0279
_diffrn_reflns_av_unetI/netI     0.0249
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            67327
_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         71.738
_diffrn_reflns_theta_min         3.071
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.570
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.729
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.576
_exptl_crystal_description       block
_exptl_crystal_F_000             3731
_exptl_crystal_size_max          0.092
_exptl_crystal_size_mid          0.073
_exptl_crystal_size_min          0.043
_refine_diff_density_max         1.121
_refine_diff_density_min         -0.697
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1219
_refine_ls_number_reflns         14753
_refine_ls_number_restraints     980
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0635
_refine_ls_R_factor_gt           0.0536
_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^)+(0.0642P)^2^+10.9632P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1396
_refine_ls_wR_factor_ref         0.1454
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12338
_reflns_number_total             14753
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt03828h2.cif
_cod_data_source_block           10_NiL7
_cod_depositor_comments
'Adding full bibliography for 7706322--7706338.cif.'
_cod_original_cell_volume        7688.46(19)
_cod_database_code               7706337
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula
'C72 H60 Cl2.963 F6.225 N24 Ni2 O11.85 P1.037'
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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
2. Restrained distances
 O1-O2 \\sim O1-O3 \\sim O1-O4 \\sim O2-O3 \\sim O2-O4 \\sim O3-O4
 with sigma of 0.04
 Cl5-O17 \\sim Cl5-O18 \\sim Cl5-O20 \\sim Cl5-O19
 with sigma of 0.02
 F7-F10 \\sim F7-F11 \\sim F7-F8 \\sim F7-F9 \\sim F12-F8 \\sim F12-F9 \\sim
F12-F10 \\sim F12-F11 \\sim F8-F9
 \\sim F9-F11 \\sim F11-F10 \\sim F10-F8
 with sigma of 0.04
 P2-F9 \\sim P2-F7 \\sim P2-F8 \\sim P2-F10 \\sim P2-F11 \\sim P2-F12
 with sigma of 0.02
 O17-O20 \\sim O17-O19 \\sim O17-O18 \\sim O18-O19 \\sim O18-O20 \\sim O19-O20
 with sigma of 0.04
 P1-F1 \\sim P1-F2 \\sim P1-F5 \\sim P1-F4 \\sim P1-F3 \\sim P1-F6
 with sigma of 0.02
 F1-F2 \\sim F1-F3 \\sim F1-F4 \\sim F1-F5 \\sim F6-F2 \\sim F6-F3 \\sim F6-F4
\\sim F6-F5 \\sim F2-F3 \\sim F3-F4
 \\sim F4-F5 \\sim F5-F2
 with sigma of 0.04
 Cl4-O13 \\sim Cl4-O16 \\sim Cl4-O15 \\sim Cl4-O14
 with sigma of 0.02
 O13-O14 \\sim O13-O15 \\sim O13-O16 \\sim O14-O15 \\sim O14-O16 \\sim O15-O16
 with sigma of 0.04
 Cl1-O1 \\sim Cl1-O2 \\sim Cl1-O3 \\sim Cl1-O4
 with sigma of 0.02
 O5-O6 \\sim O5-O8 \\sim O5-O7 \\sim O6-O7 \\sim O6-O8 \\sim O7-O8
 with sigma of 0.04
 Cl2-O5 \\sim Cl2-O8 \\sim Cl2-O6 \\sim Cl2-O7
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl4 \\sim O13 \\sim O14 \\sim O15 \\sim O16 \\sim P2 \\sim F7 \\sim F8 \\sim F9
\\sim F10 \\sim F11 \\sim F12: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Cl5 \\sim O17 \\sim O18 \\sim O19 \\sim O20 \\sim P1 \\sim F1 \\sim F2 \\sim F3
\\sim F4 \\sim F5 \\sim F6: 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 \\sim Cl2 \\sim O5 \\sim O6 \\sim O7
\\sim O8: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
Uanis(Cl4) = Uanis(P2)
Uanis(O14) = Uanis(F7)
Uanis(P1) = Uanis(Cl5)
Uanis(O18) = Uanis(F3)
4. Rigid body (RIGU) restrains
 P2, F7, F8, F9, F10, F11, F12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P1, F1, F2, F3, F4, F5, F6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl5, O17, O18, O19, O20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl4, O13, O14, O15, O16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl2, O5, O6, O7, O8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1, O1, O2, O3, O4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Cl2)=Sof(O5)=Sof(O6)=Sof(O7)=Sof(O8)=1-FVAR(1)
 Sof(Cl1)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(O4)=FVAR(1)
 Sof(P1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=1-FVAR(2)
 Sof(Cl5)=Sof(O17)=Sof(O18)=Sof(O19)=Sof(O20)=FVAR(2)
 Sof(P2)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=1-FVAR(3)
 Sof(Cl4)=Sof(O13)=Sof(O14)=Sof(O15)=Sof(O16)=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)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              37365
_shelx_fab_checksum              7932
_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 1.117
_oxdiff_exptl_absorpt_empirical_full_min 0.897