Ligand symmetry significantly affects spin crossover behaviour in isomeric [Fe(pybox)<sub>2</sub>]<sup>2+</sup> complexes.
Wang, Run-Guo; Meng, Yin-Shan; Gao, Fang-Fang; Gao, Wan-Qing; Liu, Chun-Hua; Li, Anyang; Liu, Tao; Zhu, Yuan-Yuan; Dalton transactions (Cambridge, England : 2003) 50 (2021) 3369–3378; doi:10.1039/d0dt03978k

data_7706563
_publ_section_title
;
 Ligand symmetry significantly affects spin crossover behaviour in
 isomeric [Fe(pybox)<sub>2</sub>]<sup>2+</sup> complexes.
;
_journal_issue                   9
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              3369
_journal_page_last               3378
_journal_paper_doi               10.1039/d0dt03978k
_journal_volume                  50
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_compound_source        no
_chemical_formula_moiety         'C46 H38 Fe N6 O4, 2(Cl O4)'
_chemical_formula_sum            'C47 H42 Cl2 Fe N6 O13'
_chemical_formula_weight         1025.61
_chemical_name_common            2(ClO4)-MeOH-153K
_chemical_name_systematic        2(ClO4)-MeOH-153K
_chemical_properties_physical    Air-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-01-20
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2021-01-20 deposited with the CCDC.	2021-01-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.389(2)
_cell_length_b                   12.886(3)
_cell_length_c                   30.629(6)
_cell_measurement_reflns_used    12210
_cell_measurement_temperature    153.15
_cell_measurement_theta_max      27.4816
_cell_measurement_theta_min      1.3297
_cell_volume                     4495.1(16)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2008)'
_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_temperature      153.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'MM007HF + CCD (Saturn724+)'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0366
_diffrn_reflns_av_unetI/netI     0.0401
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            26929
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.471
_diffrn_reflns_theta_min         2.478
_diffrn_source                   'Rotating Anode'
_exptl_absorpt_coefficient_mu    0.530
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7736
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2008)'
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    1.515
_exptl_crystal_description       block
_exptl_crystal_F_000             2120
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: methanol'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_platon_squeeze_details
;
A solvent mask was calculated and 88 electrons were 
found in a volume of 263\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of [CH4O] per Formula Unit, 
which account for 72 electrons per unit cell.
;
_refine_diff_density_max         0.403
_refine_diff_density_min         -0.430
_refine_diff_density_rms         0.086
_refine_ls_abs_structure_details
;
 Flack x determined using 3491 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.051(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     710
_refine_ls_number_reflns         10196
_refine_ls_number_restraints     166
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0538
_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^)+(0.0640P)^2^+1.6391P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1343
_refine_ls_wR_factor_ref         0.1377
_reflns_Friedel_coverage         0.788
_reflns_Friedel_fraction_full    0.990
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                9655
_reflns_number_total             10196
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt03978k2.cif
_cod_data_source_block           2045171
_cod_depositor_comments
'Adding full bibliography for 7706562--7706567.cif.'
_cod_original_cell_volume        4495.3(16)
_cod_database_code               7706563
_shelx_shelxl_version_number     2018/3
_exptl_absorpt_special_details
;
    Higashi, T. (1995). Program for Absorption Correction.
    Rigaku Corporation, Tokyo, Japan.
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C18A-C22A \\sim C18B-C22B
 with sigma of 0.04
 O9A-O12A \\sim O9B-O11B
 with sigma of 0.04
 O12A-O11A \\sim O11B-O12B
 with sigma of 0.04
 O2-C16A \\sim O2-C16B
 with sigma of 0.02
 N3-C17A \\sim N3-C17B
 with sigma of 0.02
 O10A-O12A \\sim O10B-O11B
 with sigma of 0.04
 Cl2A-O12A \\sim Cl2B-O11B
 with sigma of 0.04
 C17A-C23A \\sim C17B-C23B
 with sigma of 0.04
 C20A-C22A \\sim C20B-C22B
 with sigma of 0.04
 C17A-C18A \\sim C17B-C18B
 with sigma of 0.02
 C18A-C19A \\sim C18B-C19B
 with sigma of 0.02
 C18A-C23A \\sim C18B-C23B
 with sigma of 0.02
 C16A-C17A \\sim C16B-C17B
 with sigma of 0.02
 C19A-C21A \\sim C19B-C21B
 with sigma of 0.04
 C20A-C21A \\sim C20B-C21B
 with sigma of 0.02
 C21A-C23A \\sim C21B-C23B
 with sigma of 0.04
 C21A-C22A \\sim C21B-C22B
 with sigma of 0.02
 C19A-C20A \\sim C19B-C20B
 with sigma of 0.02
 C22A-C23A \\sim C22B-C23B
 with sigma of 0.02
 C18A-C20A \\sim C18B-C20B
 with sigma of 0.04
 C19A-C23A \\sim C19B-C23B
 with sigma of 0.04
 O2-C17A \\sim O2-C17B
 with sigma of 0.04
 N3-C16A \\sim N3-C16B
 with sigma of 0.04
 N3-C18A \\sim N3-C18B
 with sigma of 0.04
 C16A-C18A \\sim C16B-C18B
 with sigma of 0.04
 C17A-C19A \\sim C17B-C19B
 with sigma of 0.04
 Cl2A-O10A \\sim Cl2B-O10B
 with sigma of 0.02
 O10A-O11A \\sim O10B-O12B
 with sigma of 0.04
 O9A-O11A \\sim O9B-O12B
 with sigma of 0.04
 Cl2A-O11A \\sim Cl2B-O12B
 with sigma of 0.04
 Cl2A-O9A \\sim Cl2B-O9B
 with sigma of 0.02
 O9A-O10A \\sim O9B-O10B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(O11B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 O12B, Cl2B, O9B, O10B, O11B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O11B, Cl2B, O9B, O10B, O12B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C16A, C17A, C18A, C19A, C20A, C21A, C22A, C23A, C16B, C17B, C18B, C19B, C20B,
 C21B, C22B, C23B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C16B)=Sof(H16C)=Sof(H16D)=Sof(C17B)=Sof(H17B)=Sof(C18B)=Sof(C19B)=
 Sof(H19B)=Sof(C20B)=Sof(H20B)=Sof(C21B)=Sof(H21B)=Sof(C22B)=Sof(H22B)=
 Sof(C23B)=Sof(H23B)=1-FVAR(1)
 Sof(C16A)=Sof(H16A)=Sof(H16B)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(C19A)=
 Sof(H19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=
 Sof(C23A)=Sof(H23A)=FVAR(1)
 Fixed Sof: Cl2A(0.75) O9A(0.75) O10A(0.75) O12A(0.75) O11A(0.75) Cl2B(0.25)
 O9B(0.25) O10B(0.25) O11B(0.25) O12B(0.25)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C17A(H17A), C30(H30), C40(H40), C17B(H17B)
6.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C16A(H16A,H16B), C31(H31A,H31B), C39(H39A,H39B), C16B(H16C,H16D)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C11(H11), C12(H12), C13(H13),
 C19A(H19A), C20A(H20A), C21A(H21A), C22A(H22A), C23A(H23A), C25(H25), C26(H26),
  C27(H27), C28(H28), C29(H29), C34(H34), C35(H35), C36(H36), C42(H42),
 C43(H43), C44(H44), C45(H45), C46(H46), C19B(H19B), C20B(H20B), C21B(H21B),
 C22B(H22B), C23B(H23B)
6.d Fitted hexagon refined as free rotating group:
 C18A(C19A,C20A,C21A,C22A,C23A)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              80482
_shelx_fab_checksum              48980
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'