The impact of whole-molecule disorder on spin-crossover in a family of isomorphous molecular crystals
Sephton, Holly E.; Watson, Rhiannon L.; Shahid, Namrah; Vasili, Hari Babu; Baker, Daniel L.; Saha, Dipankar; Capel Berdiell, Izar; Pask, Christopher M.; Cespedes, Oscar; Halcrow, Malcolm A.; Chemical Science 16 (2025) 9203–9212; doi:10.1039/D5SC00090D

data_1574389
_publ_section_title
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 The impact of whole-molecule disorder on spin-crossover in a family of
 isomorphous molecular crystals
;
_journal_issue                   21
_journal_name_full               'Chemical Science'
_journal_page_first              9203
_journal_page_last               9212
_journal_paper_doi               10.1039/D5SC00090D
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ab
_chemical_formula_moiety         'C24 H22 Fe N10, 2(Cl O4)'
_chemical_formula_sum            'C24 H22 Cl2 Fe N10 O8'
_chemical_formula_weight         705.26
_chemical_name_systematic
Bis[2-{4-methylpyrazol-1-yl}-6-{pyrazol-1-yl}pyridine]iron(II)di(perchlorate)
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-05-17
_audit_creation_method
;
Olex2 1.5
(compiled 2021.07.19 svn.r715e62df for OlexSys, GUI svn.r6383)
;
_audit_update_record
;
2024-12-17 deposited with the CCDC.	2025-04-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.553(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.0570(3)
_cell_length_b                   9.1234(2)
_cell_length_c                   18.0236(4)
_cell_measurement_reflns_used    6018
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      27.97
_cell_measurement_theta_min      1.10
_cell_volume                     1476.38(7)
_computing_cell_refinement       'XIA2 0.4.0.438-g4431aaa (Winter, 2010)'
_computing_data_collection       'GDA - generic data acquisition software'
_computing_data_reduction        'XIA2 0.4.0.438-g4431aaa (Winter, 2010)'
_computing_molecular_graphics    'XSEED (Barbour, 2020)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Fluid Film Devices'
_diffrn_measurement_method       'shutterless scans'
_diffrn_radiation_monochromator  'silicon 111'
_diffrn_radiation_source         'Diamond Light Source station I19'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.68890
_diffrn_reflns_av_R_equivalents  0.0387
_diffrn_reflns_av_unetI/netI     0.0443
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            18774
_diffrn_reflns_point_group_measured_fraction_full 0.946
_diffrn_reflns_point_group_measured_fraction_max 0.892
_diffrn_reflns_theta_full        24.820
_diffrn_reflns_theta_max         28.997
_diffrn_reflns_theta_min         1.105
_exptl_absorpt_coefficient_mu    0.700
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.906
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
;
DIALS 3.dev.728-gc72b5fc4a
Scaling & analysis of unmerged intensities, absorption correction 
using spherical harmonics
;
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.586
_exptl_crystal_description       fragment
_exptl_crystal_F_000             720
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: nitromethane/diethyl ether'
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.423
_refine_diff_density_min         -0.457
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 1735 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.004(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     565
_refine_ls_number_reflns         7684
_refine_ls_number_restraints     193
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0807
_refine_ls_R_factor_gt           0.0560
_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^)+(0.0961P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1542
_refine_ls_wR_factor_ref         0.1690
_reflns_Friedel_coverage         0.701
_reflns_Friedel_fraction_full    0.889
_reflns_Friedel_fraction_max     0.780
_reflns_number_gt                4957
_reflns_number_total             7684
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00090d2.cif
_cod_data_source_block           RW5_100d
_cod_depositor_comments
'Adding full bibliography for 1574389--1574393.cif.'
_cod_database_code               1574389
_shelx_shelxl_version_number     2018/3
_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
 Cl3A-O37A
 1.43955 with sigma of 0.02
 Cl3A-O38A
 1.43955 with sigma of 0.02
 Cl3A-O39A
 1.43955 with sigma of 0.02
 Cl3A-O40A
 1.43955 with sigma of 0.02
 Cl3B-O37B
 1.43955 with sigma of 0.02
 Cl3B-O38B
 1.43955 with sigma of 0.02
 Cl3B-O39B
 1.43955 with sigma of 0.02
 Cl3B-O40B
 1.43955 with sigma of 0.02
 O37A-O38A
 2.350785 with sigma of 0.02
 O37A-O39A
 2.350785 with sigma of 0.02
 O37A-O40A
 2.350785 with sigma of 0.02
 O38A-O39A
 2.350785 with sigma of 0.02
 O38A-O40A
 2.350785 with sigma of 0.02
 O39A-O40A
 2.350785 with sigma of 0.02
 O37B-O38B
 2.350785 with sigma of 0.02
 O37B-O39B
 2.350785 with sigma of 0.02
 O37B-O40B
 2.350785 with sigma of 0.02
 O38B-O39B
 2.350785 with sigma of 0.02
 O38B-O40B
 2.350785 with sigma of 0.02
 O39B-O40B
 2.350785 with sigma of 0.02
 Cl4A-O42A
 1.43955 with sigma of 0.02
 Cl4A-O43A
 1.43955 with sigma of 0.02
 Cl4A-O44A
 1.43955 with sigma of 0.02
 Cl4A-O45A
 1.43955 with sigma of 0.02
 Cl4B-O42B
 1.43955 with sigma of 0.02
 Cl4B-O43B
 1.43955 with sigma of 0.02
 Cl4B-O44B
 1.43955 with sigma of 0.02
 Cl4B-O45B
 1.43955 with sigma of 0.02
 O42A-O43A
 2.350785 with sigma of 0.02
 O42A-O44A
 2.350785 with sigma of 0.02
 O42A-O45A
 2.350785 with sigma of 0.02
 O43A-O44A
 2.350785 with sigma of 0.02
 O43A-O45A
 2.350785 with sigma of 0.02
 O44A-O45A
 2.350785 with sigma of 0.02
 O42B-O43B
 2.350785 with sigma of 0.02
 O42B-O44B
 2.350785 with sigma of 0.02
 O42B-O45B
 2.350785 with sigma of 0.02
 O43B-O44B
 2.350785 with sigma of 0.02
 O43B-O45B
 2.350785 with sigma of 0.02
 O44B-O45B
 2.350785 with sigma of 0.02
 N2A-C3A \\sim N2A-C7A \\sim N2B-C3B \\sim N2B-C7B
 with sigma of 0.01
 N19A-C20A \\sim N19A-C24A \\sim N19B-C20B \\sim N19B-C24B
 with sigma of 0.01
 C20A-C21A \\sim C23A-C24A \\sim C20B-C21B \\sim C23B-C24B
 with sigma of 0.01
 C21A-C22A \\sim C22A-C23A \\sim C21B-C22B \\sim C22B-C23B
 with sigma of 0.01
 C20A-N25A \\sim C24A-N30A \\sim C20B-N25B \\sim C24B-N30B
 with sigma of 0.01
 N8A-N9A \\sim N13A-N14A \\sim N8B-N9B \\sim N13B-N14B
 with sigma of 0.01
 N25A-N26A \\sim N30A-N31A \\sim N25B-N26B \\sim N30B-N31B
 with sigma of 0.01
 N9A-C10A \\sim N14A-C15A \\sim N9B-C10B \\sim N14B-C15B
 with sigma of 0.01
 N8A-C11A \\sim N9A-C11A \\sim N8B-C11B \\sim N9B-C11B
 with sigma of 0.01
 N8A-C10A \\sim N9A-C12A \\sim N8B-C10B \\sim N9B-C12B
 with sigma of 0.01
 N13A-C16A \\sim N14A-C16A \\sim N13B-C16B \\sim N14B-C16B
 with sigma of 0.01
 N13A-C15A \\sim N14A-C17A \\sim N13B-C15B \\sim N14B-C17B
 with sigma of 0.01
 N25A-C28A \\sim N26A-C28A \\sim N25B-C28B \\sim N26B-C28B
 with sigma of 0.01
 N25A-C27A \\sim N26A-C29A \\sim N25B-C27B \\sim N26B-C29B
 with sigma of 0.01
 N26A-C27A \\sim N31A-C32A \\sim N26B-C27B \\sim N31B-C32B
 with sigma of 0.01
 N30A-C33A \\sim N31A-C33A \\sim N30B-C33B \\sim N31B-C33B
 with sigma of 0.01
 N30A-C32A \\sim N31A-C34A \\sim N30B-C32B \\sim N31B-C34B
 with sigma of 0.01
 N8A-C12A \\sim N13A-C17A \\sim N8B-C12B \\sim N13B-C17B
 with sigma of 0.01
 N25A-C29A \\sim N30A-C34A \\sim N25B-C29B \\sim N30B-C34B
 with sigma of 0.01
 C10A-C11A \\sim C15A-C16A \\sim C10B-C11B \\sim C15B-C16B
 with sigma of 0.01
 C27A-C28A \\sim C32A-C33A \\sim C27B-C28B \\sim C32B-C33B
 with sigma of 0.01
 C11A-C12A \\sim C16A-C17A \\sim C11B-C12B \\sim C16B-C17B
 with sigma of 0.01
 C28A-C29A \\sim C33A-C34A \\sim C28B-C29B \\sim C33B-C34B
 with sigma of 0.01
 C11A-C18A \\sim C28B-C35A \\sim C16B-C18B \\sim C33B-C35B
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
N25B \\sim N26B \\sim C27B \\sim C28B \\sim C29B: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01 within 2A
Cl3A \\sim Cl3B: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
4. Others
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=FVAR(1)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1.633*FVAR(2)
 Fixed Sof: Fe1A(0.5) Fe1B(0.25) Fe1C(0.25) N2A(0.6) C3A(0.6) C4A(0.6)
 H4A(0.6) C5A(0.6) H5A(0.6) C6A(0.6) H6A(0.6) C7A(0.6) N8A(0.6) N9A(0.6)
 C10A(0.6) H10A(0.6) C11A(0.6) C12A(0.6) H12A(0.6) N13A(0.6) N14A(0.6)
 C15A(0.6) H15A(0.6) C16A(0.6) H16A(0.6) C17A(0.6) H17A(0.6) C18A(0.6)
 H18A(0.6) H18B(0.6) H18C(0.6) N19A(0.8) C20A(0.8) C21A(0.8) H21A(0.8)
 C22A(0.8) H22A(0.8) C23A(0.8) H23A(0.8) C24A(0.8) N25A(0.8) N26A(0.8)
 C27A(0.8) H27A(0.8) C28A(0.8) C29A(0.8) H29A(0.8) N30A(0.8) N31A(0.8)
 C32A(0.8) H32A(0.8) C33A(0.8) H33A(0.8) C34A(0.8) H34A(0.8) C35A(0.8)
 H35A(0.8) H35B(0.8) H35C(0.8) N2B(0.4) C3B(0.4) C4B(0.4) H4B(0.4) C5B(0.4)
 H5B(0.4) C6B(0.4) H6B(0.4) C7B(0.4) N8B(0.4) N9B(0.4) C10B(0.4) H10B(0.4)
 C11B(0.4) H11B(0.4) C12B(0.4) H12B(0.4) N13B(0.4) N14B(0.4) C15B(0.4)
 H15B(0.4) C16B(0.4) C17B(0.4) H17B(0.4) C18B(0.4) H18D(0.4) H18E(0.4)
 H18F(0.4) N19B(0.2) C20B(0.2) C21B(0.2) H21B(0.2) C22B(0.2) H22B(0.2)
 C23B(0.2) H23B(0.2) C24B(0.2) N25B(0.2) N26B(0.2) C27B(0.2) H27B(0.2)
 C28B(0.2) H28B(0.2) C29B(0.2) H29B(0.2) N30B(0.2) N31B(0.2) C32B(0.2)
 H32B(0.2) C33B(0.2) C34B(0.2) H34B(0.2) C35B(0.2) H35D(0.2) H35E(0.2)
 H35F(0.2) Cl3A(0.5) O37A(0.5) O38A(0.5) O39A(0.5) O40A(0.5) Cl3B(0.5)
 O37B(0.5) O38B(0.5) O39B(0.5) O40B(0.5) Cl4A(0.5) O42A(0.5) O43A(0.5)
 O44A(0.5) O45A(0.5) Cl4B(0.5) O42B(0.5) O43B(0.5) O44B(0.5) O45B(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C5A(H5A), C6A(H6A), C10A(H10A), C12A(H12A), C15A(H15A), C16A(H16A),
 C17A(H17A), C21A(H21A), C22A(H22A), C23A(H23A), C27A(H27A), C29A(H29A),
 C32A(H32A), C33A(H33A), C34A(H34A), C4B(H4B), C5B(H5B), C6B(H6B), C10B(H10B),
 C11B(H11B), C12B(H12B), C15B(H15B), C17B(H17B), C21B(H21B), C22B(H22B),
 C23B(H23B), C27B(H27B), C28B(H28B), C29B(H29B), C32B(H32B), C34B(H34B)
5.b Idealised Me refined as rotating group:
 C18A(H18A,H18B,H18C), C35A(H35A,H35B,H35C), C18B(H18D,H18E,H18F), C35B(H35D,
 H35E,H35F)
;
_shelx_res_checksum              26869
_olex2_submission_special_instructions 'No special instructions were received'