Observation of proton-transfer-coupled spin transition by single-crystal neutron-diffraction measurement.
Nakanishi, Takumi; Hori, Yuta; Shigeta, Yasuteru; Sato, Hiroyasu; Wu, Shu-Qi; Kiyanagi, Ryoji; Munakata, Koji; Ohhara, Takashi; Sato, Osamu; Physical chemistry chemical physics : PCCP 25 (2023) 12394–12400; doi:10.1039/d3cp00527e

data_7246625
_publ_section_title
;
 Observation of proton-transfer-coupled spin transition by single-crystal
 neutron-diffraction measurement.
;
_journal_issue                   17
_journal_name_full               'Physical chemistry chemical physics : PCCP'
_journal_page_first              12394
_journal_page_last               12400
_journal_paper_doi               10.1039/d3cp00527e
_journal_volume                  25
_journal_year                    2023
_chemical_formula_moiety         'C38 H32 Fe N8 O4, 2(C3 F6 N O4 S2)'
_chemical_formula_sum            'C44 H32 F12 Fe N10 O12 S4'
_chemical_formula_weight         1304.88
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2022-05-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-05-23 deposited with the CCDC.	2023-04-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 119.1357(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.84431(5)
_cell_length_b                   18.07445(13)
_cell_length_c                   18.68645(7)
_cell_measurement_reflns_used    853
_cell_measurement_temperature    350(2)
_cell_measurement_theta_max      83.3
_cell_measurement_theta_min      6.6
_cell_volume                     5264.28(5)
_computing_cell_refinement       'STARGazer (Ohhara, 2009)'
_computing_data_collection       'STARGazer (Ohhara, 2009)'
_computing_data_reduction        'STARGazer (Ohhara, 2009)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_diffrn_ambient_temperature      350.0
_diffrn_detector_area_resol_mean '4 mm'
_diffrn_measured_fraction_theta_full 0.934
_diffrn_measured_fraction_theta_max 0.934
_diffrn_measurement_device
'single-crystal diffractometer SENJU at the BL18 in the MLF of the J-PARC'
_diffrn_measurement_device_type
'time-of-flight Laue-type single crystal neutron diffractometer'
_diffrn_measurement_method       'time-of-flight Laue method'
_diffrn_radiation_type           neutrons
_diffrn_radiation_wavelength     1
_diffrn_reflns_av_R_equivalents  0.3045
_diffrn_reflns_av_unetI/netI     0.2193
_diffrn_reflns_Laue_measured_fraction_full 0.934
_diffrn_reflns_Laue_measured_fraction_max 0.934
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            26221
_diffrn_reflns_point_group_measured_fraction_full 0.934
_diffrn_reflns_point_group_measured_fraction_max 0.934
_diffrn_reflns_theta_full        32.161
_diffrn_reflns_theta_max         32.161
_diffrn_reflns_theta_min         3.482
_exptl_absorpt_coefficient_mu    1.497
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.646
_exptl_crystal_description       block
_exptl_crystal_F_000             2640
_exptl_crystal_size_max          2.5
_exptl_crystal_size_mid          2.0
_exptl_crystal_size_min          1.5
_refine_diff_density_max         0.872
_refine_diff_density_min         -0.695
_refine_diff_density_rms         0.130
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.151
_refine_ls_hydrogen_treatment    refU
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1238
_refine_ls_number_reflns         6210
_refine_ls_number_restraints     1121
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.2435
_refine_ls_R_factor_gt           0.1206
_refine_ls_shift/su_max          0.015
_refine_ls_shift/su_mean         0.001
_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          0.2902
_refine_ls_wR_factor_ref         0.3493
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2972
_reflns_number_total             6210
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cp00527e2.cif
_cod_data_source_block           fepyneutron_350k
_cod_depositor_comments
'Adding full bibliography for 7246623--7246626.cif.'
_cod_database_code               7246625
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Restrained distances
 S2-N9 = S1-N9 = S3-N10 = S4-N10
 1.58 with sigma of 0.02
 C43-C42 = C44-C43 = C40-C39 = C41-C40
 1.54 with sigma of 0.02
 S3-C42 = S4-C44 = S2-C41 = S1-C39
 1.83 with sigma of 0.02
 F8-C42 = F7-C42 = F10-C43 = F9-C43 = F11-C44 = F12-C44 = F5-C41 = F6-C41 = F3-
 C40 = F4-C40 = F1-C39 = F2-C39
 1.34 with sigma of 0.02
 S3-O10 = S3-O9 = S4-O12 = S4-O11 = S1-O6 = S2-O8 = S2-O7 = S1-O5
 1.43 with sigma of 0.02
 N9-C39 = C42-N10
 2.63 with sigma of 0.01
 N10-C44 = N9-C41
 2.63 with sigma of 0.01
 O7-N9
 2.45 with sigma of 0.01
 F7-S3 = F12-S4
 2.61 with sigma of 0.01
 F8-S3 = F11-S4
 2.61 with sigma of 0.01
 F8-C43
 2.35 with sigma of 0.01
 F7-C43
 2.35 with sigma of 0.01
 F9-C42
 2.35 with sigma of 0.01
 S1-S2 = S3-S4
 2.73 with sigma of 0.01
 C42-C44 = C39-C41
 2.6 with sigma of 0.01
 C40-S1 = C43-S4
 2.83 with sigma of 0.01
 S2-C40 = S3-C43
 2.83 with sigma of 0.01
 F1-F2 = F3-F4 = F6-F5 = F12-F11 = F9-F10 = F7-F8
 2.15 with sigma of 0.01
 F5-S2 = F1-S1
 2.61 with sigma of 0.01
 F2-S1 = F6-S2
 2.61 with sigma of 0.01
 F1-C40
 2.35 with sigma of 0.01
 F2-C40
 2.35 with sigma of 0.01
 C39-F4
 2.35 with sigma of 0.01
 C39-F3
 2.35 with sigma of 0.01
 C40-F5
 2.35 with sigma of 0.01
 C40-F6
 2.35 with sigma of 0.01
 F4-C41
 2.35 with sigma of 0.01
 O5-O6 = O8-O7 = O11-O12 = O9-O10
 2.45 with sigma of 0.01
 O7-C41
 2.6 with sigma of 0.01
 O7-N9 \\sim O7A-N9A
 with sigma of 0.01
 S1-N9 \\sim S1A-N9A
 with sigma of 0.02
 S2-F5 \\sim S2A-F5A
 with sigma of 0.01
 S2-O7 \\sim S2A-O7A
 with sigma of 0.02
 F5-F6 \\sim F5A-F6A
 with sigma of 0.01
 F5-F1 \\sim F5A-F1A
 with sigma of 0.01
 S2-N9 \\sim S2A-N9A
 with sigma of 0.02
 F5-F3 \\sim F5A-F3A
 with sigma of 0.01
 F7-C42 \\sim F7A-C42A
 with sigma of 0.02
 F5-C39 \\sim F5A-C39A
 with sigma of 0.01
 F5-C41 \\sim F5A-C41A
 with sigma of 0.01
 F5-C40 \\sim F5A-C40A
 with sigma of 0.01
 O8-O7 \\sim O8A-O7A
 with sigma of 0.01
 O6-N9 \\sim O6A-N9A
 with sigma of 0.01
 O5-N9 \\sim O5A-N9A
 with sigma of 0.01
 O8-N9 \\sim O8A-N9A
 with sigma of 0.01
 O7-C41 \\sim O7A-C41A
 with sigma of 0.01
 S3-F7 \\sim S3A-F7A
 with sigma of 0.04
 N9-C39 \\sim N9A-C39A
 with sigma of 0.01
 N9-C41 \\sim N9A-C41A
 with sigma of 0.01
 F8-F7 \\sim F8A-F7A
 with sigma of 0.04
 F7-C43 \\sim F7A-C43A
 with sigma of 0.04
 S1-O6 \\sim S1A-O6A
 with sigma of 0.02
 S1-O5 \\sim S1A-O5A
 with sigma of 0.02
 S1-C39 \\sim S1A-C39A
 with sigma of 0.02
 S2-O8 \\sim S2A-O8A
 with sigma of 0.02
 S2-C41 \\sim S2A-C41A
 with sigma of 0.02
 F6-C41 \\sim F6A-C41A
 with sigma of 0.02
 F2-C39 \\sim F2A-C39A
 with sigma of 0.02
 S1-S2 \\sim S1A-S2A
 with sigma of 0.01
 S1-F1 \\sim S1A-F1A
 with sigma of 0.01
 S1-F2 \\sim S1A-F2A
 with sigma of 0.01
 S2-F6 \\sim S2A-F6A
 with sigma of 0.01
 F1-F3 \\sim F1A-F3A
 with sigma of 0.01
 F1-F2 \\sim F1A-F2A
 with sigma of 0.01
 F1-C39 \\sim F1A-C39A
 with sigma of 0.01
 F1-C41 \\sim F1A-C41A
 with sigma of 0.01
 F4-F3 \\sim F4A-F3A
 with sigma of 0.01
 F4-C39 \\sim F4A-C39A
 with sigma of 0.01
 F4-C41 \\sim F4A-C41A
 with sigma of 0.01
 F3-C39 \\sim F3A-C39A
 with sigma of 0.01
 F3-C41 \\sim F3A-C41A
 with sigma of 0.01
 O6-O5 \\sim O6A-O5A
 with sigma of 0.01
 O6-C39 \\sim O6A-C39A
 with sigma of 0.01
 O5-C39 \\sim O5A-C39A
 with sigma of 0.01
 O8-C41 \\sim O8A-C41A
 with sigma of 0.01
 C39-C41 \\sim C39A-C41A
 with sigma of 0.01
 F4-C40 \\sim F4A-C40A
 with sigma of 0.02
 S1-C40 \\sim S1A-C40A
 with sigma of 0.01
 S2-C40 \\sim S2A-C40A
 with sigma of 0.01
 F6-C40 \\sim F6A-C40A
 with sigma of 0.01
 F1-C40 \\sim F1A-C40A
 with sigma of 0.01
 F3-C40 \\sim F3A-C40A
 with sigma of 0.01
 F2-C40 \\sim F2A-C40A
 with sigma of 0.01
 C39-C40 \\sim C39A-C40A
 with sigma of 0.01
 C40-C41 \\sim C40A-C41A
 with sigma of 0.01
 S4-O11 \\sim S4A-O11A
 with sigma of 0.02
 S4-N10 \\sim S4A-N10A
 with sigma of 0.02
 S4-O12 \\sim S4A-O12A
 with sigma of 0.02
 S4-C44 \\sim S4A-C44A
 with sigma of 0.02
 S3-O9 \\sim S3A-O9A
 with sigma of 0.02
 S3-O10 \\sim S3A-O10A
 with sigma of 0.02
 S3-N10 \\sim S3A-N10A
 with sigma of 0.02
 S3-C42 \\sim S3A-C42A
 with sigma of 0.02
 F11-C44 \\sim F11A-C44A
 with sigma of 0.02
 F12-C44 \\sim F12A-C44A
 with sigma of 0.02
 F9-C43 \\sim F9A-C43A
 with sigma of 0.02
 F8-C42 \\sim F8A-C42A
 with sigma of 0.02
 F10-C43 \\sim F10A-C43A
 with sigma of 0.02
 C44-C43 \\sim C44A-C43A
 with sigma of 0.02
 C43-C42 \\sim C43A-C42A
 with sigma of 0.02
 S4-S3 \\sim S4A-S3A
 with sigma of 0.04
 S4-F11 \\sim S4A-F11A
 with sigma of 0.04
 S4-F12 \\sim S4A-F12A
 with sigma of 0.04
 S4-C43 \\sim S4A-C43A
 with sigma of 0.04
 S3-F8 \\sim S3A-F8A
 with sigma of 0.04
 S3-C43 \\sim S3A-C43A
 with sigma of 0.04
 F11-F12 \\sim F11A-F12A
 with sigma of 0.04
 F11-C43 \\sim F11A-C43A
 with sigma of 0.04
 F12-C43 \\sim F12A-C43A
 with sigma of 0.04
 F9-F10 \\sim F9A-F10A
 with sigma of 0.04
 F9-C44 \\sim F9A-C44A
 with sigma of 0.04
 F9-C42 \\sim F9A-C42A
 with sigma of 0.04
 F8-C43 \\sim F8A-C43A
 with sigma of 0.04
 F10-C44 \\sim F10A-C44A
 with sigma of 0.04
 F10-C42 \\sim F10A-C42A
 with sigma of 0.04
 O9-O10 \\sim O9A-O10A
 with sigma of 0.04
 O9-N10 \\sim O9A-N10A
 with sigma of 0.04
 O9-C42 \\sim O9A-C42A
 with sigma of 0.04
 O10-N10 \\sim O10A-N10A
 with sigma of 0.04
 O10-C42 \\sim O10A-C42A
 with sigma of 0.04
 O11-N10 \\sim O11A-N10A
 with sigma of 0.04
 O11-O12 \\sim O11A-O12A
 with sigma of 0.04
 O11-C44 \\sim O11A-C44A
 with sigma of 0.04
 N10-O12 \\sim N10A-O12A
 with sigma of 0.04
 N10-C44 \\sim N10A-C44A
 with sigma of 0.04
 N10-C42 \\sim N10A-C42A
 with sigma of 0.04
 O12-C44 \\sim O12A-C44A
 with sigma of 0.04
 C44-C42 \\sim C44A-C42A
 with sigma of 0.04
2. Uiso/Uaniso restraints and constraints
N9A \\sim S1A \\sim S2A \\sim O6A \\sim O5A \\sim C39A \\sim O8A \\sim O7A
\\sim C41A \\sim F1A \\sim F2A \\sim C40A \\sim F5A \\sim F6A \\sim F4A \\sim
F3A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
N10A \\sim C43A \\sim F9A \\sim C44A \\sim C42A \\sim F10A \\sim S4A \\sim F11A
\\sim F12A \\sim S3A \\sim F8A \\sim F7A \\sim O11A \\sim O12A \\sim O9A \\sim
O10A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
N9 \\sim S1 \\sim O6 \\sim O5 \\sim C39 \\sim S2 \\sim F1 \\sim F2 \\sim C40
\\sim O8 \\sim O7 \\sim C41 \\sim F4 \\sim F3 \\sim F5 \\sim F6: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
F10 \\sim S4 \\sim O11 \\sim N10 \\sim O12 \\sim C44 \\sim S3 \\sim F11 \\sim
F12 \\sim C43 \\sim O9 \\sim O10 \\sim C42 \\sim F9 \\sim F8 \\sim F7: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
3. Rigid body (RIGU) restrains
 N9A, S1A, S2A, O6A, O5A, C39A, O8A, O7A, C41A, F1A, F2A, C40A, F5A, F6A, F4A,
 F3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N10A, C43A, F9A, C44A, C42A, F10A, S4A, F11A, F12A, S3A, F8A, F7A, O11A, O12A,
  O9A, O10A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N9, S1, O6, O5, C39, S2, F1, F2, C40, O8, O7, C41, F4, F3, F5, F6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F12, S4, O11, N10, O12, C44, S3, F11, C43, O9, O10, C42, F9, F10, F8, F7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N10, S4, O11, O12, C44, S3, F11, F12, C43, O9, O10, C42, F9, F10, F8, F7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(N9A)=Sof(S1A)=Sof(O6A)=Sof(O5A)=Sof(C39A)=Sof(S2A)=Sof(F1A)=Sof(F2A)=
 Sof(C40A)=Sof(O8A)=Sof(O7A)=Sof(C41A)=Sof(F4A)=Sof(F3A)=Sof(F5A)=Sof(F6A)=1-
 FVAR(1)
 Sof(S1)=Sof(S2)=Sof(F5)=Sof(F6)=Sof(F1)=Sof(F4)=Sof(F3)=Sof(F2)=Sof(O6)=
 Sof(O5)=Sof(O8)=Sof(O7)=Sof(N9)=Sof(C39)=Sof(C40)=Sof(C41)=FVAR(1)
 Sof(N10A)=Sof(S4A)=Sof(O11A)=Sof(O12A)=Sof(C44A)=Sof(S3A)=Sof(F11A)=Sof(F12A)=
 Sof(C43A)=Sof(O9A)=Sof(O10A)=Sof(C42A)=Sof(F9A)=Sof(F10A)=Sof(F8A)=Sof(F7A)=1-
 FVAR(2)
 Sof(S4)=Sof(S3)=Sof(F11)=Sof(F12)=Sof(F9)=Sof(F8)=Sof(F10)=Sof(O9)=Sof(O10)=
 Sof(O11)=Sof(F7)=Sof(N10)=Sof(O12)=Sof(C44)=Sof(C43)=Sof(C42)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C18(H3), C19(H38), C1(H19), C4(H16), C26(H30), C20(H37), C22(H35), C21(H36),
 C15(H5A), C2(H18), C11(H14), C16(H4), C14(H6), C36(H21), C8(H11), C3(H17),
 C32(H25), C10(H13), C28(H32), C27(H31), C33(H24), C9(H12), C29(H33), C34(H23)
5.b Idealised Me refined as rotating group:
 C38(H8A,H8B,H8C), C37(H27A,H27B,H27C)
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_shelx_res_checksum              9436
_olex2_submission_special_instructions 'No special instructions were received'