Controlling optoelectronic properties and aggregation of planar dipoles through symmetry-preserving modifications
García-Calvo, José; Modino-Montes, María; Romero-Muñiz, Ignacio; Torres, Tomás; Chemical Science  (2025) –; doi:10.1039/D5SC06682D

data_1576315
_publ_section_title
;
 Controlling optoelectronic properties and aggregation of planar dipoles
 through symmetry-preserving modifications
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC06682D
_journal_year                    2025
_chemical_formula_moiety         'C65 H53 F12 N O6'
_chemical_formula_sum            'C65 H53 F12 N O6'
_chemical_formula_weight         1172.08
_chemical_name_systematic        '14bc-mmm 250K  / 4a'
_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             2025-07-09
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2025-08-30 deposited with the CCDC.	2025-11-14 downloaded from the CCDC.
;
_cell_angle_alpha                106.197(2)
_cell_angle_beta                 92.734(2)
_cell_angle_gamma                96.796(2)
_cell_formula_units_Z            2
_cell_length_a                   8.6217(2)
_cell_length_b                   18.0300(4)
_cell_length_c                   18.8439(3)
_cell_measurement_reflns_used    13119
_cell_measurement_temperature    250.00(10)
_cell_measurement_theta_max      68.1080
_cell_measurement_theta_min      2.4380
_cell_volume                     2783.21(11)
_computing_cell_refinement       'CrysAlisPro 1.171.43.144a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.144a (release 23-01-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.43.144a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      250.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.999
_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   -112.00 -23.00   0.50    0.27    --  -88.35 125.00-180.00  178
  2  \w    -62.00 -22.00   0.50    0.27    --  -95.50 138.00 -90.93   80
  3  \w   -121.00 -66.00   0.50    0.27    --  -95.50 138.00 -90.93  110
  4  \w   -124.00 -93.00   0.50    0.27    --  -95.50 143.00  26.10   62
  5  \w   -124.00 -23.00   0.50    0.27    --  -95.50 142.00  69.49  202
  6  \w   -100.00 -69.00   0.50    0.27    --  -88.35  77.00  60.00   62
  7  \w    -62.00 -23.00   0.50    0.27    --  -88.35  77.00  60.00   78
  8  \w    -32.00  -6.00   0.50    0.27    --  -88.35  30.00 120.00   52
  9  \w    -31.00  -6.00   0.50    0.27    --  -88.35  30.00  60.00   50
 10  \w    -21.00   4.00   0.50    0.27    --  -47.32  28.00 -93.00   50
 11  \w    -31.00  -6.00   0.50    0.27    --  -88.35  30.00-150.00   50
 12  \w    -32.00  -6.00   0.50    0.27    --  -88.35  30.00 -90.00   52
 13  \w    -46.00  -9.00   0.50    0.27    --  -88.35  45.00-120.00   74
 14  \w   -154.00-128.00   0.50    0.27    --  -88.35 -61.00 -90.00   52
 15  \w   -114.00 -66.00   0.50    0.27    --  -88.35 -61.00 -90.00   96
 16  \w   -165.00 -57.00   0.50    0.27    --  -88.35 -28.00 105.00  216
 17  \w   -125.00 -98.00   0.50    0.27    --  -47.32 -28.00 105.00   54
 18  \w    -34.00  30.00   0.50    0.27    --   46.07 -28.00 105.00  128
 19  \w     29.00  54.00   0.50    0.27    --  105.50 -61.00 -30.00   50
 20  \w     44.00  70.00   0.50    0.27    --  113.15 -77.00 -60.00   52
 21  \w     73.00  98.00   0.50    0.27    --  113.15 -77.00 -60.00   50
 22  \w     45.00  92.00   0.50    0.27    --  113.15 -77.00-120.00   94
 23  \w     43.00  68.00   0.50    0.27    --  113.15 -61.00-120.00   50
 24  \w     25.00  51.00   0.50    0.27    --  105.50 -45.00 -90.00   52
 25  \w     25.00  54.00   0.50    0.27    --  105.50 -45.00-150.00   58
 26  \w     26.00  52.00   0.50    0.27    --  105.50 -45.00 -60.00   52
 27  \w     25.00  54.00   0.50    0.27    --  105.50 -45.00   0.00   58
 28  \w     25.00  50.00   0.50    0.27    --  105.50 -45.00  30.00   50
 29  \w     25.00  53.00   0.50    0.27    --  105.50 -45.00  60.00   56
 30  \w     40.00  96.00   0.50    0.27    --  113.15 -95.00 120.00  112
 31  \w     31.00  83.00   0.50    0.27    --  105.50-125.00 120.00  104
 32  \w     56.00  96.00   0.50    0.27    --  105.50 -95.00  30.00   80
 33  \w     85.00 112.00   0.50    0.27    --  113.15-125.00 -60.00   54
 34  \w     20.00 104.00   0.50    0.27    --   46.07-125.00-180.00  168
 35  \w     33.00 103.00   0.50    0.27    --  105.50 -95.00-150.00  140
 36  \w     46.00  88.00   0.50    0.27    --  113.15 -95.00-180.00   84
 37  \w    103.00 128.00   0.50    0.27    --  113.15  28.00 -93.00   50
 38  \w    119.00 175.00   0.50    0.27    --  105.50  45.00-180.00  112
 39  \w     86.00 116.00   0.50    0.27    --  105.50  45.00-180.00   60
 40  \w     79.00 131.00   0.50    0.27    --  105.50  28.00 -93.00  104
 41  \w    141.00 173.00   0.50    0.27    --  105.50  28.00 -93.00   64
 42  \w     10.00 129.00   0.50    0.27    --   46.07  28.00 -93.00  238
 43  \w     75.00 104.00   0.50    0.27    --  105.50  77.00   0.00   58
 44  \w    118.00 176.00   0.50    0.27    --  113.15  45.00 150.00  116
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0139852000
_diffrn_orient_matrix_UB_12      -0.0704548000
_diffrn_orient_matrix_UB_13      0.0315432000
_diffrn_orient_matrix_UB_21      0.1794550000
_diffrn_orient_matrix_UB_22      0.0023623000
_diffrn_orient_matrix_UB_23      0.0032466000
_diffrn_orient_matrix_UB_31      0.0146772000
_diffrn_orient_matrix_UB_32      0.0556707000
_diffrn_orient_matrix_UB_33      0.0793372000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0350
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            33941
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.332
_diffrn_reflns_theta_min         2.450
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.995
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.747
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.144a (Rigaku Oxford Diffraction, 2024)
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 intense red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   intense
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.399
_exptl_crystal_description       needle
_exptl_crystal_F_000             1212
_exptl_crystal_recrystallization_method 'obtained from ethanol'
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.623
_refine_diff_density_min         -0.657
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     844
_refine_ls_number_reflns         10206
_refine_ls_number_restraints     960
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.1023
_refine_ls_R_factor_gt           0.0822
_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^)+(0.1332P)^2^+2.3240P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2369
_refine_ls_wR_factor_ref         0.2557
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7546
_reflns_number_total             10206
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06682d2.cif
_cod_data_source_block           04337
_cod_original_cell_volume        2783.21(10)
_cod_database_code               1576315
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C65H53F12NO6
_chemical_oxdiff_usercomment     '14bc-mmm 250K'
_shelx_estimated_absorpt_t_max   0.961
_shelx_estimated_absorpt_t_min   0.833
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C24A-C25A = C25A-C26A = C26A-C27A = C27A-C28A
 1.45 with sigma of 0.02
 C24B-C25B = C25B-C26B = C26B-C27B = C27B-C28B
 1.45 with sigma of 0.02
 C29A-C30A = C30A-C31A = C31A-C32A = C32A-C33A
 1.45 with sigma of 0.02
 C29B-C30B = C30B-C31B = C31B-C32B = C32B-C33B
 1.45 with sigma of 0.02
 C40-F1A = C40-F1B = C40-F2A = C40-F2B = C40-F3A = C40-F3B
 1.33 with sigma of 0.02
 C41-F4A = C41-F4B = C41-F5A = C41-F5B = C41-F6A = C41-F6B
 1.33 with sigma of 0.02
 C48-F7A = C48-F7B = C48-F8A = C48-F8B = C48-F9A = C48-F9B
 1.33 with sigma of 0.02
 C49-F10A = C49-F10B = C49-F11A = C49-F11B = C49-F12A = C49-F12B
 1.33 with sigma of 0.02
 C23-C25A = C24A-C26A = C25A-C27A = C26A-C28A
 2.5 with sigma of 0.04
 C23-C25B = C24B-C26B = C25B-C27B = C26B-C28B
 2.5 with sigma of 0.04
 C29A-C31A = C30A-C32A = C29B-C31B = C30B-C32B = C31A-C33A = C31B-C33B
 2.5 with sigma of 0.04
 F1A-F2A = F2A-F3A = F3A-F1A = F1B-F2B = F2B-F3B = F3B-F1B
 2.05 with sigma of 0.04
 F4A-F5A = F5A-F6A = F6A-F4A = F4B-F5B = F5B-F6B = F6B-F4B
 2.05 with sigma of 0.04
 F7A-F8A = F8A-F9A = F9A-F7A = F7B-F8B = F8B-F9B = F9B-F7B
 2.05 with sigma of 0.04
 F10A-F11A = F11A-F12A = F12A-F10A = F10B-F11B = F11B-F12B = F12B-F10B
 2.05 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(F3B) = Uanis(F1B) = Uanis(F2B) = Uanis(F1A) = Uanis(F2A) = Uanis(F3A)
Uanis(F5B) = Uanis(F5A) = Uanis(F4A) = Uanis(F4B) = Uanis(F6A) = Uanis(F6B)
Uanis(F8A) = Uanis(F7A) = Uanis(F9A) = Uanis(F8B) = Uanis(F7B) = Uanis(F9B)
Uanis(F11B) = Uanis(F10A) = Uanis(F10B) = Uanis(F11A) = Uanis(F12A) =
Uanis(F12B)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H23B)=Sof(C24B)=Sof(H24C)=Sof(H24D)=Sof(C25B)=Sof(H25C)=Sof(H25D)=
 Sof(C26B)=Sof(H26C)=Sof(H26D)=Sof(C27B)=Sof(H27C)=Sof(H27D)=Sof(C28B)=
 Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29B)=Sof(H29C)=Sof(H29D)=Sof(C30B)=
 Sof(H30C)=Sof(H30D)=Sof(C31B)=Sof(H31C)=Sof(H31D)=Sof(C32B)=Sof(H32C)=
 Sof(H32D)=Sof(C33B)=Sof(H33D)=Sof(H33E)=Sof(H33F)=1-FVAR(1)
 Sof(H23A)=Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(C25A)=Sof(H25A)=Sof(H25B)=
 Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(C27A)=Sof(H27A)=Sof(H27B)=Sof(C28A)=
 Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29A)=Sof(H29A)=Sof(H29B)=Sof(C30A)=
 Sof(H30A)=Sof(H30B)=Sof(C31A)=Sof(H31A)=Sof(H31B)=Sof(C32A)=Sof(H32A)=
 Sof(H32B)=Sof(C33A)=Sof(H33A)=Sof(H33B)=Sof(H33C)=FVAR(1)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=1-FVAR(2)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(2)
 Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(3)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(3)
 Sof(F7B)=Sof(F8B)=Sof(F9B)=1-FVAR(4)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=FVAR(4)
 Sof(F10B)=Sof(F11B)=Sof(F12B)=1-FVAR(5)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C23(H23A), C23(H23B)
6.b Secondary CH2 refined with riding coordinates:
 C24A(H24A,H24B), C25A(H25A,H25B), C26A(H26A,H26B), C27A(H27A,H27B), C29A(H29A,
 H29B), C30A(H30A,H30B), C31A(H31A,H31B), C32A(H32A,H32B), C24B(H24C,H24D),
 C25B(H25C,H25D), C26B(H26C,H26D), C27B(H27C,H27D), C29B(H29C,H29D), C30B(H30C,
 H30D), C31B(H31C,H31D), C32B(H32C,H32D)
6.c Me refined with riding coordinates:
 C28A(H28A,H28B,H28C), C33A(H33A,H33B,H33C), C28B(H28D,H28E,H28F), C33B(H33D,
 H33E,H33F)
6.d Aromatic/amide H refined with riding coordinates:
 C7(H7), C11(H11), C14(H14), C16(H16), C18(H18), C20(H20), C35(H35), C37(H37),
 C39(H39), C43(H43), C45(H45), C47(H47), C51(H51), C53(H53), C55(H55), C59(H59),
  C61(H61), C63(H63)
6.e Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C64(H64A,H64B,H64C), C65(H65A,H65B,
 H65C)
;
_shelx_res_checksum              8971
_olex2_exptl_crystal_mounting_method 'placed on a MiTeGen micromount'
_olex2_submission_original_sample_id 04337
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.280
_oxdiff_exptl_absorpt_empirical_full_min 0.826