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_7706323
_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         'C36 H30 N12 Zn, 2(F6 P1)'
_chemical_formula_sum            'C36 H30 F12 N12 P2 Zn'
_chemical_formula_weight         986.03
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_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
_cell_angle_beta                 91.9320(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.58526(12)
_cell_length_b                   10.68649(11)
_cell_length_c                   27.0840(3)
_cell_measurement_reflns_used    34499
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      74.1330
_cell_measurement_theta_min      3.2460
_cell_volume                     3929.79(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      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix-Arc
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_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     88.00 113.20   0.30    0.69    --   75.25  59.00  51.54   84
  2  \w     91.00 116.50   0.30    0.69    --   75.25  47.00  93.34   85
  3  \w     65.00 117.20   0.30    0.69    --   75.25  22.00  56.40  174
  4  \w     90.00 115.50   0.30    0.69    --   75.25  45.00 -28.02   85
  5  \w     90.00 115.20   0.30    0.69    --   75.25  51.00-100.04   84
  6  \w     88.00 113.50   0.30    0.69    --   75.25  35.00-173.22   85
  7  \w     72.00  97.80   0.30    0.69    --   75.25  19.00-156.71   86
  8  \w     65.00  90.80   0.30    0.69    --   75.25  22.00-122.65   86
  9  \w     73.00 116.20   0.30    0.69    --   75.25  21.00 -52.10  144
 10  \w     47.00  72.80   0.30    0.69    --   75.25  16.00 -49.38   86
 11  \w     78.00 108.00   0.30    0.69    --   75.25   8.00 -53.52  100
 12  \w     48.00  73.80   0.30    0.69    --   75.25  14.00  40.36   86
 13  \w     84.00 115.20   0.30    0.69    --   75.25  21.00 158.24  104
 14  \w     67.00 104.80   0.30    0.69    --   75.25  21.00 131.38  126
 15  \w     80.00 108.20   0.30    0.69    --   75.25  14.00  40.36   94
 16  \w     81.00 106.20   0.30    0.69    --   75.25   3.00 -25.97   84
 17  \w     44.00  72.50   0.30    0.69    --   75.25   4.00 -97.76   95
 18  \w     45.00  96.00   0.30    0.69    --   75.25   6.00-167.51  170
 19  \w     43.00  68.20   0.30    0.69    --   75.25   3.00 -25.97   84
 20  \w     73.00 100.00   0.30    0.69    --   69.88   0.00 150.00   90
 21  \w     36.00  60.90   0.30    0.69    --   69.88   0.00 150.00   83
 22  \w    -58.00 -26.20   0.30    0.69    --  -52.43 -15.00 120.00  106
 23  \w    -86.00 -59.00   0.30    0.69    --  -52.43   0.00   0.00   90
 24  \w    -52.00 -19.00   0.30    0.69    --  -52.43   0.00   0.00  110
 25  \w     37.00  62.50   0.30    0.69    --   75.25 -60.00 -47.17   85
 26  \w     35.00  60.50   0.30    0.69    --   75.25 -53.00-159.96   85
 27  \w     35.00  59.90   0.30    0.69    --   75.25 -56.00   2.17   83
 28  \w     35.00  59.90   0.30    0.69    --   75.25 -53.00 118.49   83
 29  \w     35.00  60.50   0.30    0.69    --   75.25 -54.00 170.58   85
 30  \w     47.00  72.20   0.30    0.69    --   75.25 -89.00 144.98   84
 31  \w     36.00  79.20   0.30    0.69    --   68.73-125.00 -30.00  144
 32  \w     45.00  82.80   0.30    0.69    --   68.73-125.00 -90.00  126
 33  \w     69.00  96.00   0.30    0.69    --   75.25-126.00-134.00   90
 34  \w     78.00 103.80   0.30    0.69    --   75.25-157.00-172.23   86
 35  \w     62.00  87.80   0.30    0.69    --   75.25-116.00-128.42   86
 36  \w     37.00  85.00   0.30    0.69    --   69.88-125.00-180.00  160
 37  \w     66.00  91.20   0.30    0.69    --   75.25-112.00 -99.88   84
 38  \w     50.00  75.80   0.30    0.69    --   75.25-120.00   6.54   86
 39  \w     60.00  85.20   0.30    0.69    --   75.25-114.00  80.81   84
 40  \w     40.00  85.00   0.30    0.69    --   68.73-125.00  90.00  150
 41  \w     58.00  89.50   0.30    0.69    --   75.25-108.00 117.19  105
 42  \w     71.00  96.20   0.30    0.69    --   75.25-117.00 149.97   84
 43  \w     44.00  91.10   0.30    0.69    --   75.25-110.00 156.49  157
 44  \w     39.00  70.80   0.30    0.69    --   75.25-100.00 117.49  106
 45  \w     59.90  84.20   0.30    0.69    --   75.25-103.00  90.05   81
 46  \w     41.00  66.80   0.30    0.69    --   75.25-101.00  56.42   86
 47  \w     50.00  75.80   0.30    0.69    --   75.25 -90.00 154.07   86
 48  \w     53.00  78.80   0.30    0.69    --   75.25 -99.00 -52.05   86
 49  \w     38.00  62.90   0.30    0.69    --   75.25-105.00-150.46   83
 50  \w     44.00  78.80   0.30    0.69    --   75.25 -99.00-168.59  116
;
_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      0.0422425000
_diffrn_orient_matrix_UB_12      -0.0799307000
_diffrn_orient_matrix_UB_13      0.0430365000
_diffrn_orient_matrix_UB_21      -0.0201330000
_diffrn_orient_matrix_UB_22      0.1072632000
_diffrn_orient_matrix_UB_23      0.0362723000
_diffrn_orient_matrix_UB_31      -0.1034301000
_diffrn_orient_matrix_UB_32      -0.0535475000
_diffrn_orient_matrix_UB_33      0.0084281000
_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  0.0299
_diffrn_reflns_av_unetI/netI     0.0152
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            52508
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.472
_diffrn_reflns_theta_min         3.255
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.581
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.384
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.667
_exptl_crystal_description       block
_exptl_crystal_F_000             1992
_exptl_crystal_size_max          0.236
_exptl_crystal_size_mid          0.062
_exptl_crystal_size_min          0.059
_refine_diff_density_max         0.915
_refine_diff_density_min         -0.750
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     724
_refine_ls_number_reflns         8008
_refine_ls_number_restraints     806
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0539
_refine_ls_R_factor_gt           0.0505
_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^)+(0.0759P)^2^+4.3906P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1400
_refine_ls_wR_factor_ref         0.1429
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7297
_reflns_number_total             8008
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt03828h2.cif
_cod_data_source_block           9_ZnL7_PF6
_cod_depositor_comments
'Adding full bibliography for 7706322--7706338.cif.'
_cod_original_cell_volume        3929.78(7)
_cod_database_code               7706323
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C36 H30 F12 N12 P2 Zn2'
_reflns_odcompleteness_completeness 99.59
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
 P3-F13 \\sim P3-F16 \\sim P3-F14 \\sim P3-F15 \\sim P3-F17 \\sim P3-F18
 with sigma of 0.02
 P2-F7 \\sim P2-F9 \\sim P2-F12 \\sim P2-F11 \\sim P2-F10 \\sim P2-F8
 with sigma of 0.02
 P4-F23 \\sim P4-F21 \\sim P4-F19 \\sim P4-F20 \\sim P4-F24 \\sim P4-F22
 with sigma of 0.02
 F15-F17 \\sim F15-F13 \\sim F15-F14 \\sim F15-F18 \\sim F17-F16 \\sim F17-F13
\\sim F17-F18 \\sim F16-F13
 \\sim F16-F14 \\sim F16-F18 \\sim F13-F14 \\sim F14-F18
 with sigma of 0.04
 F11-F12 \\sim F11-F10 \\sim F11-F8 \\sim F11-F9 \\sim F12-F10 \\sim F12-F9
\\sim F12-F7 \\sim F10-F8 ~
 F10-F7 \\sim F8-F9 \\sim F8-F7 \\sim F9-F7
 with sigma of 0.04
 F21-F22 \\sim F21-F23 \\sim F21-F20 \\sim F21-F19 \\sim F24-F19 \\sim F24-F20
\\sim F24-F22 \\sim F24-F23
 \\sim F19-F20 \\sim F19-F23 \\sim F22-F20 \\sim F22-F23
 with sigma of 0.04
 N47A-C48A \\sim N47B-C48B \\sim N47A-C46A \\sim N47B-C46B
 with sigma of 0.02
 N6B-C44B \\sim N6A-C44A \\sim N6B-C48B \\sim N6A-C48A
 with sigma of 0.02
 C45B-C46B \\sim C46A-C45A \\sim C45A-C44A \\sim C44B-C45B
 with sigma of 0.02
 Zn1-N6A \\sim Zn1-N6B
 with sigma of 0.02
 C44B-C42 \\sim C44A-C42
 with sigma of 0.02
3. Restrained planarity
 C44A, N6A, C48A, N47A, C45A, C46A
 with sigma of 0.1
 C44B, N6B, C48B, N47B, C46B, C45B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
F3 \\sim F19 \\sim F4 \\sim F6 \\sim F23 \\sim F24 \\sim F5 \\sim F22 \\sim F1
\\sim F2 \\sim F20 \\sim F21: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C44B \\sim C44A \\sim C46B \\sim C46A \\sim C45B \\sim C45A \\sim N47B \\sim
N47A \\sim C48B \\sim C48A \\sim N6B \\sim N6A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
Uanis(P2) = Uanis(P3)
Uanis(P1) = Uanis(P4)
Uanis(C48B) = Uanis(C48A)
Uanis(C44B) = Uanis(C44A)
Uanis(N6A) = Uanis(N6B)
5. Rigid body (RIGU) restrains
 F11, P2, F9, F10, F12, F7, F8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F16, P3, F13, F18, F15, F17, F14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P4, F22, F20, F24, F21, F19, F23
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F19, P4, F22, F20, F21, F24, F23
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C44B, N6B, C48B, N47B, C46B, C45B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C44A, N6A, C48A, N47A, C46A, C45A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(P3)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(F16)=Sof(F17)=Sof(F18)=1-FVAR(1)
 Sof(P2)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(P1)=1-FVAR(2)
 Sof(P4)=Sof(F19)=Sof(F20)=Sof(F22)=Sof(F23)=Sof(F24)=Sof(F21)=FVAR(2)
 Sof(N47A)=Sof(C45A)=Sof(H45A)=Sof(C46A)=Sof(H46A)=Sof(C48A)=Sof(H48A)=
 Sof(N6A)=Sof(C44A)=1-FVAR(3)
 Sof(N6B)=Sof(C44B)=Sof(C48B)=Sof(H48B)=Sof(N47B)=Sof(C46B)=Sof(H46B)=
 Sof(C45B)=Sof(H45B)=FVAR(3)
7.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C17(H17), C18(H18), C20(H20), C22(H22),
 C23(H23), C24(H24), C25(H25), C31(H31), C32(H32), C34(H34), C36(H36), C37(H37),
  C38(H38), C39(H39), C45A(H45A), C46A(H46A), C48B(H48B), C46B(H46B),
 C45B(H45B), C48A(H48A)
7.b Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C28(H28A,H28B,H28C), C43(H43A,H43B,H43C)
;
_shelx_res_checksum              73994
_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 1.367
_oxdiff_exptl_absorpt_empirical_full_min 0.763