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_4003753
_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             2020-04-14
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                61.878(14)
_cell_angle_beta                 84.054(10)
_cell_angle_gamma                70.267(11)
_cell_formula_units_Z            2
_cell_length_a                   12.3384(12)
_cell_length_b                   12.4127(17)
_cell_length_c                   12.6478(18)
_cell_measurement_reflns_used    3285
_cell_measurement_temperature    289.88(18)
_cell_measurement_theta_max      29.0070
_cell_measurement_theta_min      2.2750
_cell_volume                     1604.4(4)
_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      air
_diffrn_ambient_temperature      289.88(18)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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      -0.0541202000
_diffrn_orient_matrix_UB_12      0.0495609000
_diffrn_orient_matrix_UB_13      -0.0229941000
_diffrn_orient_matrix_UB_21      0.0273001000
_diffrn_orient_matrix_UB_22      0.0393001000
_diffrn_orient_matrix_UB_23      -0.0472630000
_diffrn_orient_matrix_UB_31      -0.0085144000
_diffrn_orient_matrix_UB_32      -0.0266010000
_diffrn_orient_matrix_UB_33      -0.0360425000
_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  0.2756
_diffrn_reflns_av_unetI/netI     0.2115
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_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            33779
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.281
_diffrn_reflns_theta_min         2.260
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.588
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38051
_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    1.469
_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         0.964
_refine_diff_density_min         -0.930
_refine_diff_density_rms         0.158
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.959
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     455
_refine_ls_number_reflns         7955
_refine_ls_number_restraints     71
_refine_ls_restrained_S_all      0.955
_refine_ls_R_factor_all          0.2267
_refine_ls_R_factor_gt           0.1090
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2655
_refine_ls_wR_factor_ref         0.3793
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3230
_reflns_number_total             7955
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm0c03396_si_003.cif
_cod_data_source_block           sjcm19ar07_26_290_00
_cod_database_code               4003753
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C30 H20 N4 O4 F4 I2 S1'
_shelx_estimated_absorpt_t_max   0.591
_shelx_estimated_absorpt_t_min   0.386
_reflns_odcompleteness_completeness 84.47
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     33.27
_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
 N7-C1A
 1.14 with sigma of 0.02
 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
 N7-C1B
 2.59 with sigma of 0.04
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) \\sim Ueq, Uanis(N6) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(N7)
\\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C1B) \\sim Ueq, : with sigma of 0.05 and
sigma for terminal atoms of 0.05
Uanis(N6) = Uanis(N7)
Uanis(C37) = Uanis(C1B)
Uanis(C36) = Uanis(C1A)
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
 C1A, N7, C1B, C36, N6, C37, H37A, H37B, H37C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C36(0.5) N6(0.5) C37(0.5) H37A(0.5) H37B(0.5) H37C(0.5) N7(0.5)
 C1A(0.5) C1B(0.5) H1BA(0.5) H1BB(0.5) H1BC(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C23(H23), C25(H25), C10(H10), C2(H2), C8(H8), C19(H19), C3(H3), C16(H16),
 C20(H20), C27(H27), C32(H32), C6(H6), C15(H15), C14(H14), C33(H33), C12(H12),
 C29(H29), C11(H11), C28(H28), C31(H31)
6.b 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              89221
_shelx_hkl_checksum              70548
_olex2_exptl_crystal_mounting_method 'Paratone oil'
_olex2_submission_original_sample_id Sjcm19ar07_26_290_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 3.993
_oxdiff_exptl_absorpt_empirical_full_min 0.192