Three-Way Switchable Single-Crystal-to-Single-Crystal Solvatomorphic Spin Crossover in a Molecular Cocrystal
Zuluaga, Andrés Reyes; Brock, Aidan J.; Pfrunder, Michael C.; Phonsri, Wasinee; Murray, Keith S.; Harding, Phimphaka; Micallef, Aaron S.; Mullen, Kathleen M.; Clegg, Jack K.; Harding, David J.; McMurtrie, John C.; Chemistry of Materials  (2020) –; doi:10.1021/acs.chemmater.0c03396

data_4003791
_publ_section_title
;
 Three-Way Switchable Single-Crystal-to-Single-Crystal Solvatomorphic Spin
 Crossover in a Molecular Cocrystal
;
_journal_name_full               'Chemistry of Materials'
_journal_paper_doi               10.1021/acs.chemmater.0c03396
_journal_year                    2020
_chemical_formula_moiety         'C6 F3 I3, C34 H26 Fe N4 O4, C N S, H2 O'
_chemical_formula_sum            'C41 H28 F3 Fe I3 N5 O5 S'
_chemical_formula_weight         1196.29
_chemical_name_systematic
'bis(4-methoxy-2-(((quinolin-8-yl)imino)methyl)phenolato)-iron(iii) thiocyanate (2,4,5-tetrafluoro-1,3,5-triiodobenzene) monhydrate'
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-07-03
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                83.747(2)
_cell_angle_beta                 77.8010(10)
_cell_angle_gamma                89.2370(10)
_cell_formula_units_Z            2
_cell_length_a                   11.7164(2)
_cell_length_b                   12.4037(2)
_cell_length_c                   14.2131(2)
_cell_measurement_reflns_used    23174
_cell_measurement_temperature    240.01(10)
_cell_measurement_theta_max      29.7530
_cell_measurement_theta_min      2.3260
_cell_volume                     2006.79(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      240.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -17.00  34.00   0.50    1.00    --    7.84  93.00-131.00  102
  2  \w    -13.00  38.00   0.50    1.00    --    7.84 -93.00 117.00  102
  3  \w    -43.00 -16.00   0.50    1.00    --   -9.41  93.00-131.00   54
  4  \w    -42.00 -16.00   0.50    1.00    --    7.84 -57.00 -30.00   52
  5  \w      0.00  37.00   0.50    1.00    --    7.84 -99.00 -90.00   74
  6  \w    -59.00  22.00   0.50    1.00    --    7.84 -57.00  60.00  162
  7  \w    -18.00  75.00   0.50    1.00    --    7.84  77.00   0.00  186
  8  \w      5.00  36.00   0.50    1.00    --    7.84 -99.00   0.00   62
  9  \w     -7.00  79.00   0.50    1.00    --    7.84  57.00  60.00  172
 10  \w      3.00  40.00   0.50    1.00    --    7.84 -99.00-180.00   74
 11  \w    -61.00 -36.00   0.50    1.00    --    7.84 153.00-168.43   50
 12  \w    -26.00  68.00   0.50    1.00    --   -9.41  37.00 150.00  188
 13  \w    -30.00  49.00   0.50    1.00    --   -9.41  77.00 150.00  158
 14  \w      6.00  31.00   0.50    1.00    --   -9.41  93.00-131.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0300643000
_diffrn_orient_matrix_UB_12      -0.0055202000
_diffrn_orient_matrix_UB_13      -0.0480532000
_diffrn_orient_matrix_UB_21      -0.0149566000
_diffrn_orient_matrix_UB_22      -0.0559480000
_diffrn_orient_matrix_UB_23      0.0068076000
_diffrn_orient_matrix_UB_31      -0.0520487000
_diffrn_orient_matrix_UB_32      0.0122057000
_diffrn_orient_matrix_UB_33      -0.0168082000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0544
_diffrn_reflns_av_unetI/netI     0.0394
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            50011
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.280
_diffrn_reflns_theta_min         2.057
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.802
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33616
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.61a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark brown'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.980
_exptl_crystal_description       block
_exptl_crystal_F_000             1154
_exptl_crystal_preparation       'Combined equal ratios of starting materials'
_exptl_crystal_recrystallization_method 'Slow evaporation of the solvent'
_exptl_crystal_size_max          2
_exptl_crystal_size_mid          1
_exptl_crystal_size_min          1
_refine_diff_density_max         1.049
_refine_diff_density_min         -1.124
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     537
_refine_ls_number_reflns         9953
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0584
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0382P)^2^+2.6886P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0924
_refine_ls_wR_factor_ref         0.1007
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7536
_reflns_number_total             9953
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm0c03396_si_006.cif
_cod_data_source_block           sjcm19ar19_27_240_00
_cod_database_code               4003791
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.166
_shelx_estimated_absorpt_t_min   0.071
_reflns_odcompleteness_completeness 83.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     33.36
_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, All O(H,H) groups
2. Restrained distances
 N5-H5E
 1.962 with sigma of 0.02
3.a Free rotating group:
 O5(H5D,H5E)
3.b Aromatic/amide H refined with riding coordinates:
 C25(H25), C8(H8), C23(H23), C19(H19), C33(H33), C2(H2), C6(H6), C10(H10),
 C27(H27), C16(H16), C28(H28), C3(H3), C20(H20), C12(H12), C29(H29), C31(H31),
 C32(H32), C14(H14), C11(H11), C15(H15)
3.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C5(H5A,H5B,H5C)
;
_shelx_res_checksum              55638
_shelx_hkl_checksum              91144
_olex2_exptl_crystal_mounting_method 'Paratone oil'
_olex2_submission_original_sample_id Sjcm19ar19_27_240_00
_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 2.701
_oxdiff_exptl_absorpt_empirical_full_min 0.632