#------------------------------------------------------------------------------
#$Date: 2025-06-19 03:22:11 +0200 (Thu 19 de Jun de 2025) $
#$Revision: 300128 $
#$URL: svn://www.crystallography.net/cod/cif/7/25/05/7250563.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_7250563
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 Br2 O2 S3'
_chemical_formula_sum            'C8 H2 Br2 O2 S3'
_chemical_formula_weight         386.10
_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                 99.34(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.412(3)
_cell_length_b                   6.9676(14)
_cell_length_c                   9.5683(19)
_cell_measurement_reflns_used    3203
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      3.0
_cell_volume                     1079.7(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 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.0898
_diffrn_reflns_av_unetI/netI     0.0709
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_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            4131
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.858
_diffrn_reflns_theta_max         24.858
_diffrn_reflns_theta_min         3.183
_exptl_absorpt_coefficient_mu    8.060
_exptl_absorpt_correction_T_max  0.832
_exptl_absorpt_correction_T_min  0.745
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'ABSCOR (Higashi, 1995)'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    2.375
_exptl_crystal_description       block
_exptl_crystal_F_000             736
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.910
_refine_diff_density_min         -1.116
_refine_diff_density_rms         0.236
_refine_ls_extinction_coef       0.0095(14)
_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   1.168
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     70
_refine_ls_number_reflns         933
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.168
_refine_ls_R_factor_all          0.0779
_refine_ls_R_factor_gt           0.0525
_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/[σ²(Fo²)+(0.0523P)²+19.9813P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1169
_refine_ls_wR_factor_ref         0.1686
_reflns_Friedel_coverage         0.000
_reflns_number_gt                687
_reflns_number_total             933
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            d5cp01121c2.cif
_cod_data_source_block           tref_CCDC1
_cod_original_cell_volume        1079.6(4)
_cod_original_sg_symbol_H-M      'C 2/c'
_cod_database_code               7250563
_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 07:41:05 on 26-Dec-2023
REM Old TITL tref in C2/c
REM SHELXT solution in C2/c: R1 0.189, Rweak 0.002, Alpha 0.018
REM <I/s> 0.424 for 95 systematic absences, Orientation as input
REM Formula found by SHELXT: C8 O2 S3 Br2
CELL 0.71073 16.4117 6.9676 9.5683 90 99.339 90
ZERR 4 0.0033 0.0014 0.0019 0 0.03 0
LATT 7
SYMM -X,+Y,0.5-Z
SFAC C H Br O S
UNIT 32 8 8 8 12

L.S. 30
PLAN  5
CONF
HTAB
BOND $H
list 4
MORE -1
BOND $H
fmap 2 53
acta
SHEL 999 0.845
OMIT -12 0 2
OMIT-6 6 6
REM <olex2.extras>
REM <HklSrc "%.\\tref.hkl">
REM </olex2.extras>

WGHT    0.052300   19.981298
EXTI    0.009477
FVAR       0.29491
BR1   3    0.269777    0.552124    0.346365    11.00000    0.03673    0.06327 =
         0.04812    0.00200   -0.00791    0.00847
C1    1    0.354307    0.474850    0.490827    11.00000    0.03157    0.02515 =
         0.03700    0.01458   -0.00373    0.01134
C2    1    0.377773    0.297133    0.525811    11.00000    0.02904    0.05901 =
         0.03365    0.00345    0.00236   -0.00519
AFIX  43
H2    2    0.355186    0.187873    0.478837    11.00000   -1.20000
AFIX   0
C3    1    0.441696    0.295591    0.644005    11.00000    0.03158    0.02934 =
         0.03866    0.00044    0.00674    0.00395
C4    1    0.467551    0.479181    0.688309    11.00000    0.03842    0.03917 =
         0.01994   -0.00396    0.00137    0.00277
O1    4    0.446947    0.015330    0.824488    11.00000    0.05798    0.05514 =
         0.05913    0.01838    0.00151   -0.02775
S1    5    0.410102    0.651185    0.591978    11.00000    0.02569    0.03443 =
         0.04997    0.00069   -0.00118    0.00044
S2    5    0.500000    0.122781    0.750000    10.50000    0.03956    0.03293 =
         0.04357    0.00000   -0.00561    0.00000
HKLF 4




REM  tref_a.res in C2/c
REM wR2 = 0.1686, GooF = S = 1.168, Restrained GooF = 1.168 for all data
REM R1 = 0.0525 for 687 Fo > 4sig(Fo) and 0.0779 for all 933 data
REM 70 parameters refined using 0 restraints

END

WGHT      0.0549     20.2193

REM No hydrogen bonds found for HTAB generation

REM Highest difference peak  0.910,  deepest hole -1.116,  1-sigma level  0.236
Q1    1   0.3420  0.5578  0.4458  11.00000  0.05    0.91
Q2    1   0.2190  0.7186  0.2408  11.00000  0.05    0.90
Q3    1   0.5000 -0.2062  0.7500  10.50000  0.05    0.88
Q4    1   0.2754  0.3335  0.3428  11.00000  0.05    0.85
Q5    1   0.4379  0.7844  0.6423  11.00000  0.05    0.79
;
_shelx_res_checksum              8001
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
Br1 Br 0.26978(6) 0.55212(18) 0.34636(12) 0.0510(6) Uani 1 1 d . . . . .
C1 C 0.3543(6) 0.4748(13) 0.4908(10) 0.032(2) Uani 1 1 d . . . . .
C2 C 0.3778(6) 0.2971(16) 0.5258(11) 0.041(2) Uani 1 1 d . . . . .
H2 H 0.355186 0.187873 0.478837 0.049 Uiso 1 1 calc R U . . .
C3 C 0.4417(6) 0.2956(13) 0.6440(10) 0.033(2) Uani 1 1 d . . . . .
C4 C 0.4676(6) 0.4792(14) 0.6883(9) 0.033(2) Uani 1 1 d . . . . .
O1 O 0.4469(5) 0.0153(12) 0.8245(9) 0.058(2) Uani 1 1 d . . . . .
S1 S 0.41010(14) 0.6512(3) 0.5920(3) 0.0375(7) Uani 1 1 d . . . . .
S2 S 0.500000 0.1228(5) 0.750000 0.0401(10) Uani 1 2 d S T P . .
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
Br1 0.0367(8) 0.0633(10) 0.0481(9) 0.0020(5) -0.0079(5) 0.0085(5)
C1 0.032(5) 0.025(5) 0.037(5) 0.015(4) -0.004(4) 0.011(4)
C2 0.029(5) 0.059(7) 0.034(5) 0.003(5) 0.002(4) -0.005(5)
C3 0.032(5) 0.029(5) 0.039(5) 0.000(4) 0.007(4) 0.004(4)
C4 0.038(5) 0.039(5) 0.020(4) -0.004(4) 0.001(4) 0.003(4)
O1 0.058(5) 0.055(5) 0.059(5) 0.018(4) 0.002(4) -0.028(4)
S1 0.0257(12) 0.0344(14) 0.0500(16) 0.0007(11) -0.0012(10) 0.0004(10)
S2 0.040(2) 0.0329(18) 0.044(2) 0.000 -0.0056(16) 0.000
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'
Br Br -0.2901 2.4595 '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'
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
C2 C1 S1 114.6(7) . . ?
C2 C1 Br1 127.3(8) . . ?
S1 C1 Br1 118.0(5) . . ?
C1 C2 C3 110.9(10) . . ?
C1 C2 H2 124.5 . . ?
C3 C2 H2 124.5 . . ?
C4 C3 C2 112.8(9) . . ?
C4 C3 S2 110.1(7) . . ?
C2 C3 S2 137.1(8) . . ?
C3 C4 C4 113.2(5) . 2_656 ?
C3 C4 S1 111.6(7) . . ?
C4 C4 S1 135.0(3) 2_656 . ?
C4 S1 C1 90.0(4) . . ?
O1 S2 O1 116.6(8) . 2_656 ?
O1 S2 C3 113.1(5) . 2_656 ?
O1 S2 C3 109.2(5) 2_656 2_656 ?
O1 S2 C3 109.2(5) . . ?
O1 S2 C3 113.1(5) 2_656 . ?
C3 S2 C3 93.3(6) 2_656 . ?
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
Br1 C1 1.872(8) . ?
C1 C2 1.324(13) . ?
C1 S1 1.731(10) . ?
C2 C3 1.412(13) . ?
C2 H2 0.9300 . ?
C3 C4 1.392(13) . ?
C3 S2 1.755(9) . ?
C4 C4 1.456(17) 2_656 ?
C4 S1 1.701(9) . ?
O1 S2 1.424(8) . ?
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
S1 C1 C2 C3 2.7(12) . . . . ?
Br1 C1 C2 C3 -177.8(7) . . . . ?
C1 C2 C3 C4 -3.8(12) . . . . ?
C1 C2 C3 S2 177.9(9) . . . . ?
C2 C3 C4 C4 179.0(10) . . . 2_656 ?
S2 C3 C4 C4 -2.3(13) . . . 2_656 ?
C2 C3 C4 S1 3.3(11) . . . . ?
S2 C3 C4 S1 -177.9(5) . . . . ?
C3 C4 S1 C1 -1.5(8) . . . . ?
C4 C4 S1 C1 -175.9(14) 2_656 . . . ?
C2 C1 S1 C4 -0.7(9) . . . . ?
Br1 C1 S1 C4 179.7(6) . . . . ?
C4 C3 S2 O1 116.7(8) . . . . ?
C2 C3 S2 O1 -65.0(12) . . . . ?
C4 C3 S2 O1 -111.7(8) . . . 2_656 ?
C2 C3 S2 O1 66.6(12) . . . 2_656 ?
C4 C3 S2 C3 0.8(5) . . . 2_656 ?
C2 C3 S2 C3 179.2(13) . . . 2_656 ?
