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_4003758
_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         'C34 H26 Fe N4 O4, C N S, C2 H3 N'
_chemical_formula_sum            'C37 H29 Fe N6 O4 S'
_chemical_formula_weight         709.57
_chemical_name_systematic
'bis(4-methoxy-2-(((quinolin-8-yl)imino)methyl)phenolato)-iron(iii) thiocyanate acetonitrile solvate'
_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     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                61.827(10)
_cell_angle_beta                 83.958(8)
_cell_angle_gamma                70.162(8)
_cell_formula_units_Z            2
_cell_length_a                   12.3363(10)
_cell_length_b                   12.3705(12)
_cell_length_c                   12.5962(13)
_cell_measurement_reflns_used    4515
_cell_measurement_temperature    249.9(2)
_cell_measurement_theta_max      30.7650
_cell_measurement_theta_min      2.2550
_cell_volume                     1590.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.37a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.37a (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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      249.9(2)
_diffrn_detector                 'CCD plate'
_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      4.00  40.00   0.50    2.00    --    9.19-101.00 102.00   72
  2  \w    -26.00  18.00   0.50    2.00    --    9.19 101.00-153.00   88
  3  \w    -50.00  19.00   0.50    2.00    --  -10.75 101.00-153.00  138
  4  \w      4.00  35.00   0.50    2.00    --    9.19 -99.00-180.00   62
  5  \w    -67.00 -14.00   0.50    2.00    --    9.19 -37.00 -90.00  106
  6  \w    -42.00  26.00   0.50    2.00    --    9.19 -77.00 -90.00  136
  7  \w     39.00  65.00   0.50    2.00    --    9.19  57.00 -30.00   52
  8  \w     -4.00  24.00   0.50    2.00    --    9.19 -37.00 -90.00   56
  9  \w    -11.00  83.00   0.50    2.00    --    9.19  57.00  60.00  188
 10  \w      5.00  47.00   0.50    2.00    --    9.19 -99.00  30.00   84
 11  \w     12.00  57.00   0.50    2.00    --  -10.75  77.00 150.00   90
 12  \w    -19.00  64.00   0.50    2.00    --  -10.75  57.00   0.00  166
 13  \w    -38.00   6.00   0.50    2.00    --  -10.75  77.00 150.00   88
 14  \w    -22.00   3.00   0.50    2.00    --  -10.75 -77.00  60.00   50
 15  \w    -78.00 -53.00   0.50    2.00    --  -10.75 -77.00  60.00   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      -0.0542221000
_diffrn_orient_matrix_UB_12      0.0497289000
_diffrn_orient_matrix_UB_13      -0.0230748000
_diffrn_orient_matrix_UB_21      0.0272576000
_diffrn_orient_matrix_UB_22      0.0395354000
_diffrn_orient_matrix_UB_23      -0.0474897000
_diffrn_orient_matrix_UB_31      -0.0083751000
_diffrn_orient_matrix_UB_32      -0.0267063000
_diffrn_orient_matrix_UB_33      -0.0362030000
_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  0.1927
_diffrn_reflns_av_unetI/netI     0.1575
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            34502
_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         28.282
_diffrn_reflns_theta_min         2.263
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.593
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29893
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.37a (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    1.482
_exptl_crystal_description       needle
_exptl_crystal_F_000             734
_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         0.882
_refine_diff_density_min         -0.536
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.977
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     464
_refine_ls_number_reflns         7888
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      0.978
_refine_ls_R_factor_all          0.1583
_refine_ls_R_factor_gt           0.0825
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1047P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1964
_refine_ls_wR_factor_ref         0.2439
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3848
_reflns_number_total             7888
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm0c03396_si_003.cif
_cod_data_source_block           sjcm19ar07_31_250_00
_cod_database_code               4003758
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C30 H20 N4 O4 F4 I2 S1'
_shelx_estimated_absorpt_t_max   0.589
_shelx_estimated_absorpt_t_min   0.384
_reflns_odcompleteness_completeness 83.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     33.39
_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. Shared sites
{C36A, C36}
3. Restrained distances
 N6-C36 \\sim N6A-C36A
 with sigma of 0.02
 C36-H37a \\sim C36A-H37a
 with sigma of 0.04
 C36-H37c \\sim C36A-H37c
 with sigma of 0.04
 C36-C37 \\sim C36A-C37A
 with sigma of 0.02
 C36-H37b \\sim C36A-H37b
 with sigma of 0.04
 C37-H37a \\sim C37A-H37a
 with sigma of 0.02
 C37-H37b \\sim C37A-H37b
 with sigma of 0.02
 C37-H37c \\sim C37A-H37c
 with sigma of 0.02
 N6-C37 \\sim N6A-C37A
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
Uanis(C36A) = Uanis(C36)
5. Others
 Fixed Sof: N6(0.75) C36(0.75) C37(0.75) H37a(0.75) H37b(0.75) H37c(0.75)
 N6A(0.25) C36A(0.25) C37A(0.25) H37d(0.25) H37e(0.25) H37f(0.25)
6.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C23(H23), C25(H25), C3(H3), C2(H2), C6(H6), C10(H10), C19(H19),
 C12(H12), C16(H16), C15(H15), C20(H20), C11(H11), C27(H27), C33(H33), C28(H28),
  C14(H14), C32(H32), C31(H31), C29(H29)
6.b Idealised Me refined as rotating group:
 C5(H5a,H5b,H5c), C22(H22a,H22b,H22c), C37(H37a,H37b,H37c), C37A(H37d,H37e,H37f)
;
_shelx_res_checksum              61419
_shelx_hkl_checksum              94501
_olex2_exptl_crystal_mounting_method 'Paratone oil'
_olex2_submission_original_sample_id Sjcm19ar07_31_250_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 4.211
_oxdiff_exptl_absorpt_empirical_full_min 0.260