Azothiophene-Based Molecular Switches: Influence of Substituent Position and Solvent Environment on Photophysical Behaviour
Zhang, Xin; Kotoulas, Konstantinos T.; Bandaranayake, P.M. Anuththaara; Chathumalee, Dilani; Ehsan, Nuha; Huddleston, Patrick R.; Wallis, John D.; Perry, Carole Celia; Physical Chemistry Chemical Physics  (2025) –; doi:10.1039/D5CP03027G

data_7251352
_publ_section_title
;
 Azothiophene-Based Molecular Switches: Influence of Substituent Position
 and Solvent Environment on Photophysical Behaviour
;
_journal_name_full               'Physical Chemistry Chemical Physics'
_journal_paper_doi               10.1039/D5CP03027G
_journal_year                    2025
_chemical_formula_moiety         'C12 H10 N2 O4 S2'
_chemical_formula_sum            'C12 H10 N2 O4 S2'
_chemical_formula_weight         310.34
_chemical_melting_point          475
_chemical_name_common
;
orange polymorph
;
_chemical_name_systematic
;
2,2'-Bis(methoxycarbonyl)-3,3'-azothiophene
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-07-15
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-06-06 deposited with the CCDC.	2025-11-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.546(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.0514(2)
_cell_length_b                   7.63966(18)
_cell_length_c                   9.7827(2)
_cell_measurement_reflns_used    5542
_cell_measurement_temperature    120
_cell_measurement_theta_max      77.2260
_cell_measurement_theta_min      5.9270
_cell_volume                     654.79(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120
_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 0.924
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_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  0.0273
_diffrn_reflns_av_unetI/netI     0.0158
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.924
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            7403
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.924
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.924
_diffrn_reflns_theta_min         5.957
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.844
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.310
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.92a (Rigaku Oxford Diffraction, 2023)
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            orange-red
_exptl_crystal_density_diffrn    1.574
_exptl_crystal_description       'cut block'
_exptl_crystal_F_000             320
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: THF'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.362
_refine_diff_density_min         -0.318
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     124
_refine_ls_number_reflns         1323
_refine_ls_number_restraints     38
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0349
_refine_ls_R_factor_gt           0.0339
_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^)+(0.0569P)^2^+0.3241P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0935
_refine_ls_wR_factor_ref         0.0946
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1265
_reflns_number_total             1323
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cp03027g2.cif
_cod_data_source_block           PRHdiesterorange
_cod_database_code               7251352
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.655
_shelx_estimated_absorpt_t_min   0.435
_olex2_refinement_description
;
A second orientation of the molecule across a different centre of
symmetry (4.3 per cent) was included in the refinement.
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
 S1-C1 \\sim S1A-C1A
 with sigma of 0.02
 S1-C4 \\sim S1A-C4A
 with sigma of 0.02
 O1-C5 \\sim O1A-C5A
 with sigma of 0.02
 O2-C5 \\sim O2A-C5A
 with sigma of 0.02
 O2-C6 \\sim O2A-C6A
 with sigma of 0.02
 N1-C2 \\sim N1A-C2A
 with sigma of 0.02
 C1-C2 \\sim C1A-C2A
 with sigma of 0.02
 C1-C5 \\sim C1A-C5A
 with sigma of 0.02
 C2-C3 \\sim C2A-C3A
 with sigma of 0.02
 C3-H3 \\sim C3A-H3A
 with sigma of 0.02
 C3-C4 \\sim C3A-C4A
 with sigma of 0.02
 C4-H4 \\sim C4A-H4A
 with sigma of 0.02
 C6-H6A \\sim C6A-H6AA
 with sigma of 0.02
 C6-H6B \\sim C6A-H6AB
 with sigma of 0.02
 C6-H6C \\sim C6A-H6AC
 with sigma of 0.02
 S1-C2 \\sim S1A-C2A
 with sigma of 0.04
 S1-C3 \\sim S1A-C3A
 with sigma of 0.04
 S1-H4 \\sim S1A-H4A
 with sigma of 0.04
 S1-C5 \\sim S1A-C5A
 with sigma of 0.04
 O1-O2 \\sim O1A-O2A
 with sigma of 0.04
 O1-C1 \\sim O1A-C1A
 with sigma of 0.04
 O2-C1 \\sim O2A-C1A
 with sigma of 0.04
 O2-H6A \\sim O2A-H6AA
 with sigma of 0.04
 O2-H6B \\sim O2A-H6AB
 with sigma of 0.04
 O2-H6C \\sim O2A-H6AC
 with sigma of 0.04
 N1-C1 \\sim N1A-C1A
 with sigma of 0.04
 N1-C3 \\sim N1A-C3A
 with sigma of 0.04
 C1-C3 \\sim C1A-C3A
 with sigma of 0.04
 C1-C4 \\sim C1A-C4A
 with sigma of 0.04
 C2-H3 \\sim C2A-H3A
 with sigma of 0.04
 C2-C4 \\sim C2A-C4A
 with sigma of 0.04
 C2-C5 \\sim C2A-C5A
 with sigma of 0.04
 C3-H4 \\sim C3A-H4A
 with sigma of 0.04
 H3-C4 \\sim H3A-C4A
 with sigma of 0.04
 C5-C6 \\sim C5A-C6A
 with sigma of 0.04
 H6A-H6B \\sim H6AA-H6AB
 with sigma of 0.04
 H6A-H6C \\sim H6AA-H6AC
 with sigma of 0.04
 H6B-H6C \\sim H6AB-H6AC
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(S1) = Uanis(S1A)
Uanis(O1) = Uanis(O1A)
Uanis(O2) = Uanis(O2A)
Uanis(N1) = Uanis(N1A)
Uanis(C1) = Uanis(C1A)
Uanis(C2) = Uanis(C2A)
Uanis(C3) = Uanis(C3A)
Uanis(C4) = Uanis(C4A)
Uanis(C5) = Uanis(C5A)
Uanis(C6) = Uanis(C6A)
4. Others
 Sof(S1A)=Sof(C4A)=Sof(H4A)=Sof(C1A)=Sof(C3A)=Sof(H3A)=Sof(C2A)=Sof(C5A)=
 Sof(N1A)=Sof(O1A)=Sof(O2A)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=1-FVAR(1)
 Sof(S1)=Sof(O1)=Sof(O2)=Sof(N1)=Sof(C1)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=
 Sof(H4)=Sof(C5)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C4A(H4A), C3A(H3A)
5.b Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C6A(H6AA,H6AB,H6AC)
;
_shelx_res_checksum              88347
_olex2_submission_special_instructions 'No special instructions were received'