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_4003726
_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             2020-04-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                61.743(10)
_cell_angle_beta                 83.250(8)
_cell_angle_gamma                70.312(8)
_cell_formula_units_Z            2
_cell_length_a                   11.7635(10)
_cell_length_b                   12.7160(12)
_cell_length_c                   13.2423(14)
_cell_measurement_reflns_used    3849
_cell_measurement_temperature    335.00(10)
_cell_measurement_theta_max      26.8720
_cell_measurement_theta_min      2.4240
_cell_volume                     1640.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.63a (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      air
_diffrn_ambient_temperature      335.00(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 1.000
_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    -41.00  25.00   0.50    3.50    --   12.29 -57.00  30.00  132
  2  \w     -2.00  34.00   0.50    3.50    --   12.29 -99.00  30.00   72
  3  \w     -2.00  45.00   0.50    3.50    --   12.29 -99.00  90.00   94
  4  \w     -2.00  49.00   0.50    3.50    --   12.29 -99.00 150.00  102
  5  \w    -56.00  41.00   0.50    3.50    --   12.29 -80.00 -82.00  194
  6  \w      0.00  26.00   0.50    3.50    --   12.29 -19.00 -90.00   52
  7  \w    -15.00  15.00   0.50    3.50    --  -11.00 -80.00 -82.00   60
  8  \w     -2.00  50.00   0.50    3.50    --   12.29 -99.00 -90.00  104
  9  \w     -8.00  87.00   0.50    3.50    --   12.29  19.00-120.00  190
 10  \w     38.00  63.00   0.50    3.50    --  -11.00  57.00-180.00   50
 11  \w    -11.00  14.00   0.50    3.50    --  -11.00  57.00-180.00   50
 12  \w    -56.00 -31.00   0.50    3.50    --   12.29 -19.00 -90.00   50
 13  \w    -55.00 -25.00   0.50    3.50    --  -11.00 -80.00 -82.00   60
 14  \w     11.00  60.00   0.50    3.50    --   12.29  57.00  60.00   98
 15  \w    -16.00  41.00   0.50    3.50    --   12.29  80.00  40.00  114
 16  \w     -6.00  59.00   0.50    3.50    --   12.29  77.00 150.00  130
;
_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      -0.0529667000
_diffrn_orient_matrix_UB_12      0.0145774000
_diffrn_orient_matrix_UB_13      0.0289730000
_diffrn_orient_matrix_UB_21      0.0239859000
_diffrn_orient_matrix_UB_22      -0.0583230000
_diffrn_orient_matrix_UB_23      0.0496814000
_diffrn_orient_matrix_UB_31      0.0270351000
_diffrn_orient_matrix_UB_32      0.0293025000
_diffrn_orient_matrix_UB_33      0.0199920000
_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  0.2307
_diffrn_reflns_av_unetI/netI     0.1785
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_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       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            38800
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.282
_diffrn_reflns_theta_min         1.905
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.575
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56964
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.63a (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    1.436
_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         0.363
_refine_diff_density_min         -0.405
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.960
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     445
_refine_ls_number_reflns         8130
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      0.962
_refine_ls_R_factor_all          0.1964
_refine_ls_R_factor_gt           0.0776
_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^)+(0.0718P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1792
_refine_ls_wR_factor_ref         0.2426
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3246
_reflns_number_total             8130
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm0c03396_si_004.cif
_cod_data_source_block           sjcm19ar22_17_335_00
_cod_database_code               4003726
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C37 H31 N6 O4 Fe1 S1'
_shelx_estimated_absorpt_t_max   0.597
_shelx_estimated_absorpt_t_min   0.393
_reflns_odcompleteness_completeness 80.42
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     35.70
_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. Uiso/Uaniso restraints and constraints
Uanis(C37) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
3. Rigid body (RIGU) restrains
 C36, N6, C37, H37A, H37B, H37C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Aromatic/amide H refined with riding coordinates:
 C25(H25), C16(H16), C8(H8), C19(H19), C23(H23), C33(H33), C20(H20), C27(H27),
 C3(H3), C15(H15), C6(H6), C2(H2), C10(H10), C12(H12), C28(H28), C31(H31),
 C29(H29), C11(H11), C32(H32), C14(H14)
4.b Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C5(H5A,H5B,H5C), C37(H37A,H37B,H37C)
;
_shelx_res_checksum              67977
_shelx_hkl_checksum              38926
_olex2_exptl_crystal_mounting_method 'Paratone oil'
_olex2_submission_original_sample_id Sjcm19ar22_17_335_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 3.667
_oxdiff_exptl_absorpt_empirical_full_min 0.356