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_4003722
_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                61.782(5)
_cell_angle_beta                 83.994(4)
_cell_angle_gamma                70.307(5)
_cell_formula_units_Z            2
_cell_length_a                   12.3403(7)
_cell_length_b                   12.4634(7)
_cell_length_c                   12.6799(6)
_cell_measurement_reflns_used    10305
_cell_measurement_temperature    315.00(10)
_cell_measurement_theta_max      28.6440
_cell_measurement_theta_min      2.2980
_cell_volume                     1614.40(18)
_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      315.00(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 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    -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      -0.0501209000
_diffrn_orient_matrix_UB_12      0.0158005000
_diffrn_orient_matrix_UB_13      0.0297638000
_diffrn_orient_matrix_UB_21      0.0223864000
_diffrn_orient_matrix_UB_22      -0.0601691000
_diffrn_orient_matrix_UB_23      0.0518550000
_diffrn_orient_matrix_UB_31      0.0270194000
_diffrn_orient_matrix_UB_32      0.0283664000
_diffrn_orient_matrix_UB_33      0.0217490000
_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  0.1215
_diffrn_reflns_av_unetI/netI     0.0890
_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            39021
_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         28.281
_diffrn_reflns_theta_min         2.163
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.584
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62467
_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    1.460
_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         0.484
_refine_diff_density_min         -0.788
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     452
_refine_ls_number_reflns         8010
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0905
_refine_ls_R_factor_gt           0.0582
_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^)+(0.0561P)^2^+0.5278P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1429
_refine_ls_wR_factor_ref         0.1603
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5525
_reflns_number_total             8010
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm0c03396_si_004.cif
_cod_data_source_block           sjcm19ar22_13_315_00
_cod_original_cell_volume        1614.40(17)
_cod_database_code               4003722
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C37 H31 N6 O4 Fe1 S1'
_shelx_estimated_absorpt_t_max   0.593
_shelx_estimated_absorpt_t_min   0.388
_reflns_odcompleteness_completeness 86.27
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     34.68
_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
 C1A-N7
 1.137 with sigma of 0.01
 C1A-C1B
 1.456 with sigma of 0.01
 C1B-N7
 2.593 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N7 \\sim C1A \\sim C1B: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(C36) = Uanis(C1A)
Uanis(N6) = Uanis(N7)
Uanis(C37) = Uanis(C1B)
4. Rigid body (RIGU) restrains
 N7, C1A, C1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C36(0.8) N6(0.8) C37(0.8) H37A(0.8) H37B(0.8) H37C(0.8) N7(0.2)
 C1A(0.2) C1B(0.2) H1BA(0.2) H1BB(0.2) H1BC(0.2)
6.a Free rotating group:
 N7(C1A,C1B)
6.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C25(H25), C6(H6), C23(H23), C19(H19), C2(H2), C20(H20), C3(H3),
 C33(H33), C16(H16), C12(H12), C27(H27), C10(H10), C15(H15), C14(H14), C31(H31),
  C11(H11), C32(H32), C29(H29), C28(H28)
6.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C5(H5A,H5B,H5C), C37(H37A,H37B,H37C), C1B(H1BA,H1BB,H1BC)
;
_shelx_res_checksum              86733
_shelx_hkl_checksum              62661
_olex2_exptl_crystal_mounting_method 'Paratone oil'
_olex2_submission_original_sample_id Sjcm19ar22_13_315_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 4.860
_oxdiff_exptl_absorpt_empirical_full_min 0.442