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#$Date: 2025-06-19 04:22:11 +0300 (Thu, 19 Jun 2025) $
#$Revision: 300128 $
#$URL: file:///home/coder/svn-repositories/cod/cif/7/25/05/7250562.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_7250562
loop_
_publ_author_name
'Liu, Huimin'
'Zhuang, Zeyan'
'Hou, Yawen'
'Zhu, Yujiao'
'Xu, Ruofeng'
'Chen, Bin'
'Hu, Rong'
'Zhao, Zujin'
_publ_section_title
;
 Oxidation reduces spin-orbital coupling to achieve robust fluorescent
 emission in halogen substituted
 dithieno[3,2-b:2′,3′-d]thiophene
;
_journal_name_full               'Physical Chemistry Chemical Physics'
_journal_paper_doi               10.1039/D5CP01121C
_journal_year                    2025
_chemical_formula_moiety         'C8 H2 Cl2 O2 S3'
_chemical_formula_sum            'C8 H2 Cl2 O2 S3'
_chemical_formula_weight         297.18
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2019/2
_audit_update_record
;
2024-08-21 deposited with the CCDC.	2025-06-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.26(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.031(3)
_cell_length_b                   6.9802(14)
_cell_length_c                   9.3455(19)
_cell_measurement_reflns_used    4193
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      3.5
_cell_volume                     1025.6(4)
_computing_cell_refinement       RAPID-AUTO
_computing_data_collection       'RAPID-AUTO (Rigaku, 1998)'
_computing_data_reduction        'CrystalStructure (Rigaku/MSC, 2004)'
_computing_molecular_graphics    'ORTEPII (Johnson, 1976)'
_computing_publication_material  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_structure_solution    'SHELXL-2016/6 (Sheldrick, 2016)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Rigaku R-AXIS RAPID'
_diffrn_measurement_method       'ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0722
_diffrn_reflns_av_unetI/netI     0.1067
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            3862
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.013
_diffrn_reflns_theta_max         25.013
_diffrn_reflns_theta_min         3.193
_exptl_absorpt_coefficient_mu    1.213
_exptl_absorpt_correction_T_max  0.812
_exptl_absorpt_correction_T_min  0.723
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'ABSCOR (Higashi, 1995)'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.925
_exptl_crystal_description       block
_exptl_crystal_F_000             592
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: DCM'
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.599
_refine_diff_density_min         -0.440
_refine_diff_density_rms         0.105
_refine_ls_extinction_coef       0.055(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     70
_refine_ls_number_reflns         902
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0386
_refine_ls_R_factor_gt           0.0353
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[σ²(Fo²)+(0.0432P)²+0.2085P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0855
_refine_ls_wR_factor_ref         0.0874
_reflns_Friedel_coverage         0.000
_reflns_number_gt                837
_reflns_number_total             902
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            d5cp01121c2.cif
_cod_data_source_block           tref
_cod_original_sg_symbol_H-M      'C 2/c'
_cod_database_code               7250562
_shelx_shelxl_version_number     2019/2
_shelx_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_shelx_res_file
;
TITL tref_a.res in C2/c
    tref.res
    created by SHELXL-2019/2 at 15:42:43 on 15-Dec-2023
REM Old TITL tref in C2/c
REM SHELXT solution in C2/c: R1 0.130, Rweak 0.004, Alpha 0.026
REM <I/s> 0.940 for 89 systematic absences, Orientation as input
REM Formula found by SHELXT: C8 N2 S2 Cl3
CELL 0.71073 16.031 6.9802 9.3455 90 101.261 90
ZERR 4 0.0032 0.0014 0.0019 0 0.03 0
LATT 7
SYMM -X,+Y,0.5-Z
SFAC C H O S Cl
UNIT 32 8 8 12 8

L.S. 20
PLAN  5
ACTA
CONF
HTAB
BOND $H
SHEL 999 0.84
OMIT   -16   0   8
OMIT     1   3  11
OMIT    -5   1   3
OMIT    -4   2   1
OMIT     4   0   4
list 4
fmap 2
MORE -1
REM <olex2.extras>
REM <HklSrc "%.\\tref.hkl">
REM </olex2.extras>
WGHT    0.043200    0.208500
EXTI    0.055064
FVAR       0.23107
S1    4    0.594381    0.650731    0.414054    11.00000    0.03361    0.02454 =
         0.03934   -0.00346    0.00628   -0.00369
S2    4    0.500000    0.122562    0.250000    10.50000    0.04049    0.02014 =
         0.03367    0.00000    0.00049    0.00000
CL1   5    0.733298    0.544394    0.658484    11.00000    0.04087    0.05429 =
         0.04177   -0.00640   -0.00217   -0.01094
O1    3    0.446412    0.015473    0.326665    11.00000    0.06038    0.03945 =
         0.05186    0.01230    0.00083   -0.02217
C1    1    0.628046    0.292994    0.481303    11.00000    0.03144    0.02996 =
         0.03191    0.00336    0.00749    0.00056
AFIX  43
H1A   2    0.652268    0.182504    0.527255    11.00000   -1.20000
AFIX   0
C2    1    0.652910    0.476093    0.520215    11.00000    0.02771    0.03687 =
         0.02964   -0.00033    0.00593   -0.00397
C3    1    0.534566    0.478199    0.312504    11.00000    0.02710    0.02289 =
         0.03141   -0.00087    0.00861   -0.00132
C4    1    0.560419    0.297995    0.361462    11.00000    0.03048    0.02432 =
         0.03112    0.00066    0.00720   -0.00124

HKLF 4




REM  tref_a.res in C2/c
REM wR2 = 0.0874, GooF = S = 1.086, Restrained GooF = 1.086 for all data
REM R1 = 0.0353 for 837 Fo > 4sig(Fo) and 0.0386 for all 902 data
REM 70 parameters refined using 0 restraints

END

WGHT      0.0463      0.1878

REM No hydrogen bonds found for HTAB generation

REM Highest difference peak  0.599,  deepest hole -0.440,  1-sigma level  0.105
Q1    1   0.6321  0.5620  0.4684  11.00000  0.05    0.60
Q2    1   0.5604  0.5616  0.3492  11.00000  0.05    0.54
Q3    1   0.5343  0.2101  0.3081  11.00000  0.05    0.48
Q4    1   0.5493  0.3686  0.3383  11.00000  0.05    0.41
Q5    1   0.5000  0.5401  0.2500  10.50000  0.05    0.39
;
_shelx_res_checksum              2283
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
S1 S 0.59438(3) 0.65073(7) 0.41405(6) 0.0326(3) Uani 1 1 d . . . . .
S2 S 0.500000 0.12256(9) 0.250000 0.0324(3) Uani 1 2 d S T P . .
Cl1 Cl 0.73330(4) 0.54439(9) 0.65848(6) 0.0470(3) Uani 1 1 d . . . . .
O1 O 0.44641(11) 0.0155(2) 0.32667(19) 0.0519(5) Uani 1 1 d . . . . .
C1 C 0.62805(13) 0.2930(3) 0.4813(2) 0.0309(5) Uani 1 1 d . . . . .
H1A H 0.652268 0.182504 0.527255 0.037 Uiso 1 1 calc R U . . .
C2 C 0.65291(13) 0.4761(3) 0.5202(2) 0.0314(5) Uani 1 1 d . . . . .
C3 C 0.53457(12) 0.4782(3) 0.3125(2) 0.0267(5) Uani 1 1 d . . . . .
C4 C 0.56042(13) 0.2980(3) 0.3615(2) 0.0285(5) Uani 1 1 d . . . . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
S1 0.0336(4) 0.0245(4) 0.0393(4) -0.00346(19) 0.0063(3) -0.00369(19)
S2 0.0405(5) 0.0201(4) 0.0337(5) 0.000 0.0005(4) 0.000
Cl1 0.0409(4) 0.0543(5) 0.0418(4) -0.0064(2) -0.0022(3) -0.0109(3)
O1 0.0604(11) 0.0394(9) 0.0519(10) 0.0123(7) 0.0008(9) -0.0222(8)
C1 0.0314(11) 0.0300(10) 0.0319(12) 0.0034(8) 0.0075(9) 0.0006(8)
C2 0.0277(10) 0.0369(11) 0.0296(11) -0.0003(9) 0.0059(9) -0.0040(9)
C3 0.0271(10) 0.0229(10) 0.0314(11) -0.0009(7) 0.0086(9) -0.0013(8)
C4 0.0305(11) 0.0243(10) 0.0311(11) 0.0007(8) 0.0072(9) -0.0012(8)
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C3 S1 C2 90.26(10) . . ?
O1 S2 O1 117.07(15) . 2_655 ?
O1 S2 C4 112.32(9) . . ?
O1 S2 C4 110.06(10) 2_655 . ?
O1 S2 C4 110.06(10) . 2_655 ?
O1 S2 C4 112.32(9) 2_655 2_655 ?
C4 S2 C4 92.37(13) . 2_655 ?
C2 C1 C4 109.26(18) . . ?
C2 C1 H1A 125.4 . . ?
C4 C1 H1A 125.4 . . ?
C1 C2 Cl1 126.95(17) . . ?
C1 C2 S1 114.17(17) . . ?
Cl1 C2 S1 118.89(11) . . ?
C4 C3 C3 113.76(12) . 2_655 ?
C4 C3 S1 111.12(16) . . ?
C3 C3 S1 135.10(7) 2_655 . ?
C3 C4 C1 115.18(17) . . ?
C3 C4 S2 110.04(16) . . ?
C1 C4 S2 134.74(14) . . ?
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
S1 C3 1.707(2) . ?
S1 C2 1.728(2) . ?
S2 O1 1.4319(15) . ?
S2 O1 1.4320(15) 2_655 ?
S2 C4 1.769(2) . ?
S2 C4 1.769(2) 2_655 ?
Cl1 C2 1.705(2) . ?
C1 C2 1.367(3) . ?
C1 C4 1.399(3) . ?
C1 H1A 0.9300 . ?
C3 C4 1.375(3) . ?
C3 C3 1.445(4) 2_655 ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C4 C1 C2 Cl1 -179.37(14) . . . . ?
C4 C1 C2 S1 0.6(2) . . . . ?
C3 S1 C2 C1 -0.36(15) . . . . ?
C3 S1 C2 Cl1 179.60(13) . . . . ?
C2 S1 C3 C4 0.01(14) . . . . ?
C2 S1 C3 C3 -178.5(3) . . . 2_655 ?
C3 C3 C4 C1 179.21(18) 2_655 . . . ?
S1 C3 C4 C1 0.3(2) . . . . ?
C3 C3 C4 S2 1.1(2) 2_655 . . . ?
S1 C3 C4 S2 -177.81(8) . . . . ?
C2 C1 C4 C3 -0.6(3) . . . . ?
C2 C1 C4 S2 176.95(14) . . . . ?
O1 S2 C4 C3 -113.23(15) . . . . ?
O1 S2 C4 C3 114.43(15) 2_655 . . . ?
C4 S2 C4 C3 -0.39(9) 2_655 . . . ?
O1 S2 C4 C1 69.1(2) . . . . ?
O1 S2 C4 C1 -63.2(2) 2_655 . . . ?
C4 S2 C4 C1 -178.0(2) 2_655 . . . ?
