Design strategy for tautomerization-based small panchromatic molecules
Tanioka, Masaru; Kitamura, Fumino; Oyama, Masaya; Chen, Shiyu; Ohishi, Yuki; Yamada, Tsuyoshi; Matsuya, Yuji; Chemical Communications 61 (2025) 9298–9301; doi:10.1039/D5CC01507C

data_7134578
_publ_section_title
;
 Design strategy for tautomerization-based small panchromatic molecules
;
_journal_issue                   51
_journal_name_full               'Chemical Communications'
_journal_page_first              9298
_journal_page_last               9301
_journal_paper_doi               10.1039/D5CC01507C
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         '2(C H Cl3), C24 H19 N O4'
_chemical_formula_sum            'C26 H21 Cl6 N O4'
_chemical_formula_weight         624.14
_chemical_name_common            'compound 2'
_chemical_name_systematic        'bridged rhodol'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-05-13
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-05-19 deposited with the CCDC.	2025-05-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   24.0040(6)
_cell_length_b                   7.00530(10)
_cell_length_c                   31.8407(7)
_cell_measurement_reflns_used    8109
_cell_measurement_temperature    103.15
_cell_measurement_theta_max      67.9070
_cell_measurement_theta_min      2.7290
_cell_volume                     5354.18(19)
_computing_cell_refinement       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      103.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.983
_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    -28.00  21.00   0.50   10.25    --  -41.44  58.00  28.00   98
  2  \w    -24.00   1.00   0.50   10.25    --  -41.44  72.00 161.00   50
  3  \w    -56.00 -28.00   0.50   40.98    --  -95.43  58.00  28.00   56
  4  \w    -47.00   4.00   0.50   10.25    --  -41.44  94.00-101.00  102
  5  \w    -53.00 -23.00   0.50   40.98    --  -95.43  94.00-101.00   60
  6  \w    -28.00  29.00   0.50   10.25    --  -41.44  21.00-180.00  114
  7  \w    -24.00  41.00   0.50   10.25    --   41.75 -43.00 -60.00  130
  8  \w     -7.00  19.00   0.50   10.25    --   41.75 -58.00-112.00   52
  9  \w     29.00  57.00   0.50   40.98    --   95.75 -50.00 -90.00   56
 10  \w     31.00  76.00   0.50   40.98    --   95.75 -68.00 -30.00   90
 11  \w     30.00  57.00   0.50   40.98    --   95.75 -50.00  30.00   54
 12  \w     35.00  62.00   0.50   40.98    --   95.75 -59.00  60.00   54
 13  \w     29.00  54.00   0.50   40.98    --   95.75 -50.00 120.00   50
 14  \w     29.00  57.00   0.50   40.98    --   95.75 -50.00  90.00   56
 15  \w     81.00 106.00   0.50   40.98    --   95.75 -94.00 147.00   50
 16  \w     50.00  76.00   0.50   40.98    --   95.75 -94.00 147.00   52
 17  \w    122.00 160.00   0.50   40.98    --   95.75  33.00  90.00   76
 18  \w     88.00 158.00   0.50   40.98    --   95.75  72.00 161.00  140
 19  \w     84.00 112.00   0.50   40.98    --   95.75  33.00  90.00   56
 20  \w     64.00  90.00   0.50   10.25    --   41.75  72.00 161.00   52
 21  \w     40.00  65.00   0.50   10.25    --   41.75  58.00  28.00   50
 22  \w     32.00  57.00   0.50   40.98    --   95.75 -50.00-180.00   50
 23  \w    -53.00 -28.00   0.50   10.25    --  -41.44 -72.00  31.00   50
 24  \w    -89.00 -64.00   0.50   10.25    --  -41.44 -58.00-112.00   50
 25  \w   -121.00 -96.00   0.50   40.98    --  -95.43 -58.00-112.00   50
 26  \w   -109.00 -83.00   0.50   10.25    --  -41.44-138.00 -30.00   52
 27  \w    -90.00 -65.00   0.50   10.25    --  -41.44-138.00  60.00   50
 28  \w     -1.00  24.00   0.50   10.25    --   41.75 -94.00 147.00   50
 29  \w    -83.00 -58.00   0.50   40.98    --  -95.43  72.00 161.00   50
 30  \w    -76.00 -31.00   0.50   40.98    --  -95.43  68.00-120.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0689
_diffrn_reflns_av_unetI/netI     0.0606
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            17269
_diffrn_reflns_point_group_measured_fraction_full 0.784
_diffrn_reflns_point_group_measured_fraction_max 0.776
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.494
_diffrn_reflns_theta_min         2.776
_exptl_absorpt_coefficient_mu    6.153
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.897
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.80a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.549
_exptl_crystal_description       block
_exptl_crystal_F_000             2544
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CHCl3/Et2O'
_exptl_crystal_size_max          0.149
_exptl_crystal_size_mid          0.123
_exptl_crystal_size_min          0.051
_refine_diff_density_max         0.787
_refine_diff_density_min         -0.399
_refine_diff_density_rms         0.141
_refine_ls_abs_structure_details
;
 Flack x determined using 2122 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.139(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     746
_refine_ls_number_reflns         7655
_refine_ls_number_restraints     307
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0916
_refine_ls_R_factor_gt           0.0863
_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^)+(0.1782P)^2^+2.3647P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2323
_refine_ls_wR_factor_ref         0.2397
_reflns_Friedel_coverage         0.549
_reflns_Friedel_fraction_full    0.569
_reflns_Friedel_fraction_max     0.561
_reflns_number_gt                6875
_reflns_number_total             7655
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01507c4.cif
_cod_data_source_block           exp_121
_cod_depositor_comments
'Adding full bibliography for 7134578--7134579.cif.'
_cod_database_code               7134578
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H N O Cl'
_diffrn_oxdiff_digest_hkl
;
01e9505d364543f3bb1259de83aa84d8fb793c
;
_olex2_refinement_description
;
1. Restrained distances
 C2-Cl6 = C2-Cl4 = C2-Cl5
 1.78 with sigma of 0.02
 C1-Cl2 = C1-Cl3 = C1-Cl1
 1.78 with sigma of 0.02
 C2-Cl6 \\sim C2-Cl4 \\sim C2-Cl5
 with sigma of 0.02
 Cl6-Cl4 \\sim Cl4-Cl5 \\sim Cl5-Cl6
 with sigma of 0.04
 C2-Cl6 \\sim C2'-Cl6'
 with sigma of 0.02
 C2-Cl4 \\sim C2'-Cl4'
 with sigma of 0.02
 C2-Cl5 \\sim C2'-Cl5'
 with sigma of 0.02
 Cl6-Cl4 \\sim Cl6'-Cl4'
 with sigma of 0.04
 Cl6-Cl5 \\sim Cl6'-Cl5'
 with sigma of 0.04
 Cl4-Cl5 \\sim Cl4'-Cl5'
 with sigma of 0.04
 C1-Cl2 \\sim C1-Cl3 \\sim C1-Cl1
 with sigma of 0.02
 Cl2-Cl3 \\sim Cl3-Cl1 \\sim Cl1-Cl2
 with sigma of 0.04
 C1-Cl2 \\sim C1'-Cl2'
 with sigma of 0.02
 C1-Cl3 \\sim C1'-Cl3'
 with sigma of 0.02
 C1-Cl1 \\sim C1'-Cl1'
 with sigma of 0.02
 Cl2-Cl3 \\sim Cl2'-Cl3'
 with sigma of 0.04
 Cl2-Cl1 \\sim Cl2'-Cl1'
 with sigma of 0.04
 Cl3-Cl1 \\sim Cl3'-Cl1'
 with sigma of 0.04
2. Uiso/Uaniso restraints and constraints
C2 \\sim Cl4 \\sim Cl5 \\sim Cl6: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C2' \\sim Cl4' \\sim Cl5' \\sim Cl6' \\sim C2 \\sim Cl4 \\sim Cl5 \\sim Cl6:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C1 \\sim Cl1 \\sim Cl2 \\sim Cl3: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C1 \\sim Cl1 \\sim Cl2 \\sim Cl3 \\sim C1' \\sim Cl1' \\sim Cl2' \\sim Cl3':
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
3. Rigid body (RIGU) restrains
 C2, Cl4, Cl5, Cl6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2', Cl4', Cl5', Cl6', C2, Cl4, Cl5, Cl6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1, Cl1, Cl2, Cl3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, Cl1, Cl2, Cl3, C1', Cl1', Cl2', Cl3'
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Others
 Sof(Cl4')=Sof(C2')=Sof(H2')=Sof(Cl6')=Sof(Cl5')=1-FVAR(1)
 Sof(C2)=Sof(H2)=Sof(Cl6)=Sof(Cl4)=Sof(Cl5)=FVAR(1)
 Sof(C1')=Sof(H1')=Sof(Cl2')=Sof(Cl1')=Sof(Cl3')=1-FVAR(2)
 Sof(C1)=Sof(H1)=Sof(Cl2)=Sof(Cl3)=Sof(Cl1)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C3(H3), C4(H4), C2(H2), C2'(H2'), C1(H1), C1'(H1')
5.b Secondary CH2 refined with riding coordinates:
 C21A(H21A,H21B), C23A(H23A,H23B), C21B(H21C,H21D), C23B(H23C,H23D)
5.c Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C2A(H2AA), C18B(H18B), C2B(H2B), C15A(H15A), C16A(H16A), C5B(H5B),
 C5A(H5A), C12A(H12A), C17B(H17B), C15B(H15B), C4B(H4B), C17A(H17A), C12B(H12B),
  C16B(H16B), C18A(H18A)
5.d Tetrahedral OH refined with riding coordinates:
 O2A(H2A)
5.e Idealised Me refined as rotating group:
 C22A(H22A,H22B,H22C), C22B(H22D,H22E,H22F), C24A(H24A,H24B,H24C), C24B(H24D,
 H24E,H24F)
5.f Idealised tetrahedral OH refined as rotating group:
 O3B(H3B)
;
_shelx_res_checksum              52861
_shelx_hkl_checksum              43098
_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 1.855
_oxdiff_exptl_absorpt_empirical_full_min 0.582