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_7706327
_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
'0.5(C36 H30 N12 Ni), C18 H15 Cl0.5 N6 Ni0.5 O2, 1.5(Cl O4)'
_chemical_formula_sum            'C36 H30 Cl2 N12 Ni O8'
_chemical_formula_weight         888.33
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-12-01
_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                90.232(3)
_cell_angle_beta                 93.788(3)
_cell_angle_gamma                90.093(3)
_cell_formula_units_Z            4
_cell_length_a                   14.6645(6)
_cell_length_b                   14.5548(6)
_cell_length_c                   17.0631(6)
_cell_measurement_reflns_used    13198
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      68.7780
_cell_measurement_theta_min      2.5600
_cell_volume                     3633.9(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'SHELXS (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4670
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_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    -29.00  -2.00   1.00    2.50    --  -38.13 125.00 -90.00   27
  2  \w    -61.00  -2.00   1.00    2.50    --  -38.13 125.00-150.00   59
  3  \w   -117.00  -7.00   1.00    2.50    --  -38.13 -38.00  30.00  110
  4  \w   -101.00  -8.00   1.00    2.50    --  -38.13 -38.00 120.00   93
  5  \w     11.00  61.00   1.00    2.50    --   38.13 -99.00   0.00   50
  6  \w     57.00  91.00   1.00    2.50    --   38.13-125.00  60.00   34
  7  \w     59.00  97.00   1.00    2.50    --   38.13-125.00 -60.00   38
  8  \w    109.00 136.00   1.00   10.00    --  100.00 111.00 -90.00   27
  9  \w     87.00 113.00   1.00   10.00    --  100.00-111.00  60.00   26
 10  \w     23.00  98.00   1.00   10.00    --  100.00 -61.00  30.00   75
 11  \w     29.00 131.00   1.00   10.00    --  100.00 -45.00-180.00  102
 12  \w    100.00 168.00   1.00   10.00    --  100.00 111.00 -30.00   68
 13  \w     73.00 151.00   1.00   10.00    --  100.00 178.00  90.00   78
 14  \w    139.00 175.00   1.00   10.00    --  100.00 111.00 -90.00   36
 15  \w     78.00 107.00   1.00   10.00    --  100.00 -30.00 -30.00   29
 16  \w     38.00  65.00   1.00   10.00    --  100.00-111.00  60.00   27
 17  \w    110.00 175.00   1.00   10.00    --  100.00  45.00-150.00   65
 18  \w     19.00 108.00   1.00   10.00    --  100.00-111.00 150.00   89
 19  \w     30.00  66.00   1.00   10.00    --  100.00-111.00-150.00   36
 20  \w     80.00 113.00   1.00   10.00    --  100.00-111.00 -90.00   33
 21  \w     68.00 109.00   1.00   10.00    --  100.00 -94.00  30.00   41
 22  \w     20.00  99.00   1.00   10.00    --  100.00 -94.00-180.00   79
 23  \w     61.00 137.00   1.00   10.00    --  100.00 178.00 120.00   76
 24  \w    139.00 172.00   1.00   10.00    --  100.00  61.00-120.00   33
 25  \w     73.00 109.00   1.00   10.00    --  100.00  45.00   0.00   36
 26  \w     33.00 178.00   1.00   10.00    --  100.00 -15.00-180.00  145
 27  \w     62.00 125.00   1.00   10.00    --  100.00 -77.00-150.00   63
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0675600251
_diffrn_orient_matrix_UB_12      0.0738403980
_diffrn_orient_matrix_UB_13      0.0331025331
_diffrn_orient_matrix_UB_21      -0.0529637486
_diffrn_orient_matrix_UB_22      0.0738246815
_diffrn_orient_matrix_UB_23      -0.0487127597
_diffrn_orient_matrix_UB_31      -0.0609519950
_diffrn_orient_matrix_UB_32      0.0173504804
_diffrn_orient_matrix_UB_33      0.0686929290
_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  0.0420
_diffrn_reflns_av_unetI/netI     0.0468
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            32057
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         68.975
_diffrn_reflns_theta_min         2.595
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.752
_exptl_absorpt_correction_T_max  0.868
_exptl_absorpt_correction_T_min  0.726
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.624
_exptl_crystal_description       prism
_exptl_crystal_F_000             1824
_exptl_crystal_size_max          0.186
_exptl_crystal_size_mid          0.114
_exptl_crystal_size_min          0.076
_refine_diff_density_max         0.646
_refine_diff_density_min         -0.881
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.110
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1247
_refine_ls_number_reflns         13338
_refine_ls_number_restraints     254
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.0905
_refine_ls_R_factor_gt           0.0841
_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^)+(0.0308P)^2^+15.9116P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1817
_refine_ls_wR_factor_ref         0.1860
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12173
_reflns_number_total             13338
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt03828h2.cif
_cod_data_source_block           3_NiL6ClO4solv
_cod_depositor_comments
'Adding full bibliography for 7706322--7706338.cif.'
_cod_original_cell_volume        3634.0(2)
_cod_database_code               7706327
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C36 H30 Cl2 N12 Ni O8 '
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.29
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.664(2)
 0.336(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(O13A) = Uanis(O13B)
4. Rigid body (RIGU) restrains
 C67A, N22A, C66A, C65A, C64A, C63A, C62A, C61A, N21A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N24A, C69A, N23A, C72A, C71A, C70A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C69B, N23B, C72B, C71B, C70B, N24B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N21B, C67B, N22B, C66B, C65B, C64B, C63B, C62B, C61B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{N21B, N22B, N23B, N24B, C61B, C62B, C63B, C64B, C65B, C66B, C67B, C68B, C69B,
C70B, C71B, C72B} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N21A, N22A, N23A, N24A, C61A, C62A, C63A, C64A, C65A, C66A, C67A, C68A, C69A,
C70A, C71A, C72A}
6. Others
 Sof(N21B)=Sof(N22B)=Sof(N23B)=Sof(N24B)=Sof(C61B)=Sof(C62B)=Sof(H62B)=
 Sof(C63B)=Sof(H63B)=Sof(C64B)=Sof(H64B)=Sof(C65B)=Sof(H65B)=Sof(C66B)=
 Sof(C67B)=Sof(C68B)=Sof(H68D)=Sof(H68E)=Sof(H68F)=Sof(C69B)=Sof(C70B)=
 Sof(H70B)=Sof(C71B)=Sof(H71B)=Sof(C72B)=Sof(H72B)=1-FVAR(1)
 Sof(N21A)=Sof(N22A)=Sof(N23A)=Sof(N24A)=Sof(C61A)=Sof(C62A)=Sof(H62A)=
 Sof(C63A)=Sof(H63A)=Sof(C64A)=Sof(H64A)=Sof(C65A)=Sof(H65A)=Sof(C66A)=
 Sof(C67A)=Sof(C68A)=Sof(H68A)=Sof(H68B)=Sof(H68C)=Sof(C69A)=Sof(C70A)=
 Sof(H70A)=Sof(C71A)=Sof(H71A)=Sof(C72A)=Sof(H72A)=FVAR(1)
 Sof(Cl4B)=Sof(O13B)=Sof(O14B)=Sof(O15B)=1-FVAR(2)
 Sof(Cl4A)=Sof(O15A)=Sof(O13A)=Sof(O14A)=FVAR(2)
7.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), C22(H22), C23(H23), C24(H24), C26(H26), C27(H27),
  C28(H28), C29(H29), C34(H34), C35(H35), C36(H36), C38(H38), C39(H39),
 C40(H40), C41(H41), C46(H46), C47(H47), C48(H48), C50(H50), C51(H51), C52(H52),
  C53(H53), C58(H58), C59(H59), C60(H60), C62A(H62A), C63A(H63A), C64A(H64A),
 C65A(H65A), C70A(H70A), C71A(H71A), C72A(H72A), C62B(H62B), C63B(H63B),
 C64B(H64B), C65B(H65B), C70B(H70B), C71B(H71B), C72B(H72B)
7.b Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C20(H20A,H20B,H20C), C32(H32A,H32B,H32C), C44(H44A,H44B,
 H44C), C56(H56A,H56B,H56C), C68A(H68A,H68B,H68C), C68B(H68D,H68E,H68F)
;
_shelx_res_checksum              38354
_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 1.496
_oxdiff_exptl_absorpt_empirical_full_min 0.713