Dithienoarsinines: stable and planar π-extended arsabenzenes.
Sumida, Akifumi; Saeki, Akinori; Matsuo, Kyohei; Naka, Kensuke; Imoto, Hiroaki; Chemical science 16 (2025) 1126–1135; doi:10.1039/d4sc06590e

data_1573232
_publ_section_title
;
 Dithienoarsinines: stable and planar &#x3c0;-extended arsabenzenes.
;
_journal_issue                   3
_journal_name_full               'Chemical science'
_journal_page_first              1126
_journal_page_last               1135
_journal_paper_doi               10.1039/d4sc06590e
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         '1(C9 H5 As S2)'
_chemical_formula_sum            'C9 H5 As S2'
_chemical_formula_weight         252.17
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yac'
_space_group_name_H-M_alt        'P 1 n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-29
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-09-20 deposited with the CCDC.	2024-11-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.535(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.1248(3)
_cell_length_b                   11.3296(6)
_cell_length_c                   12.9122(7)
_cell_measurement_reflns_used    2737
_cell_measurement_temperature    100
_cell_measurement_theta_max      31.8040
_cell_measurement_theta_min      3.1600
_cell_volume                     891.82(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.91a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.91a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.91a (Rigaku OD, 2023)'
_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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -74.00  -4.00   0.40    0.60    --   30.00  54.00  30.00  175
  2  \w    -48.00 112.00   0.40    0.60    --   30.00  54.00-180.00  400
  3  \w    -59.00  93.00   0.40    0.60    --   30.00  54.00 -90.00  380
;
_diffrn_measurement_device       'two-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Mini (JP)'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0573826000
_diffrn_orient_matrix_UB_12      -0.0255137000
_diffrn_orient_matrix_UB_13      -0.0448179000
_diffrn_orient_matrix_UB_21      0.1000903000
_diffrn_orient_matrix_UB_22      -0.0059346000
_diffrn_orient_matrix_UB_23      -0.0229354000
_diffrn_orient_matrix_UB_31      0.0152480000
_diffrn_orient_matrix_UB_32      -0.0568659000
_diffrn_orient_matrix_UB_33      0.0225795000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0275
_diffrn_reflns_av_unetI/netI     0.0360
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            6527
_diffrn_reflns_point_group_measured_fraction_full 0.749
_diffrn_reflns_point_group_measured_fraction_max 0.729
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.557
_diffrn_reflns_theta_min         3.170
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.212
_exptl_absorpt_correction_T_max  0.766
_exptl_absorpt_correction_T_min  0.588
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.91a (Rigaku Oxford Diffraction, 2023)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.878
_exptl_crystal_description       block
_exptl_crystal_F_000             496
_exptl_crystal_size_max          0.848
_exptl_crystal_size_mid          0.477
_exptl_crystal_size_min          0.289
_refine_diff_density_max         0.403
_refine_diff_density_min         -0.423
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.498(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     316
_refine_ls_number_reflns         2998
_refine_ls_number_restraints     270
_refine_ls_restrained_S_all      0.998
_refine_ls_R_factor_all          0.0339
_refine_ls_R_factor_gt           0.0299
_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^)+(0.0435P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0712
_refine_ls_wR_factor_ref         0.0737
_reflns_Friedel_coverage         0.455
_reflns_Friedel_fraction_full    0.497
_reflns_Friedel_fraction_max     0.457
_reflns_number_gt                2775
_reflns_number_total             2998
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06590e2.cif
_cod_data_source_block           3b
_cod_depositor_comments
'Adding full bibliography for 1573224--1573235.cif.'
_cod_database_code               1573232
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHSAs
_chemical_oxdiff_usercomment     ' '
_shelx_estimated_absorpt_t_max   0.376
_shelx_estimated_absorpt_t_min   0.125
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.502(15)
 0.498(15)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3. Restrained distances
 As1A-C1A \\sim As1B-C5B
 with sigma of 0.02
 C15A-C16A \\sim C17B-C18B
 with sigma of 0.02
 As1A-C5A \\sim As1B-C1B
 with sigma of 0.02
 C11A-C13A \\sim C13B-C11B
 with sigma of 0.02
 S2A-C2A \\sim S2B-C4B
 with sigma of 0.02
 C10A-C11A \\sim C14B-C13B
 with sigma of 0.02
 S2A-C7A \\sim S2B-C9B
 with sigma of 0.02
 C18A-C13A \\sim C16B-C11B
 with sigma of 0.02
 S1A-C4A \\sim S1B-C2B
 with sigma of 0.02
 S1A-C9A \\sim S1B-C7B
 with sigma of 0.02
 C17A-C13A \\sim C15B-C11B
 with sigma of 0.02
 C3A-C2A \\sim C3B-C4B
 with sigma of 0.02
 C3A-C4A \\sim C3B-C2B
 with sigma of 0.02
 S4A-C16A \\sim S4B-C18B
 with sigma of 0.02
 C8A-C5A \\sim C6B-C1B
 with sigma of 0.02
 C8A-C9A \\sim C6B-C7B
 with sigma of 0.02
 C6A-C1A \\sim C8B-C5B
 with sigma of 0.02
 As2A-C13A \\sim As2B-C11B
 with sigma of 0.02
 C6A-C7A \\sim C8B-C9B
 with sigma of 0.02
 C12A-S4A \\sim C12B-S4B
 with sigma of 0.02
 S3A-C14A \\sim S3B-C10B
 with sigma of 0.02
 C1A-C2A \\sim C5B-C4B
 with sigma of 0.02
 C5A-C4A \\sim C1B-C2B
 with sigma of 0.02
 C17A-C18A \\sim C15B-C16B
 with sigma of 0.02
 As2A-C17A \\sim As2B-C15B
 with sigma of 0.02
 As1A-C8A \\sim As1B-C6B
 with sigma of 0.02
 As1A-C6A \\sim As1B-C8B
 with sigma of 0.02
 As1A-C2A \\sim As1B-C4B
 with sigma of 0.02
 C12A-C14A \\sim C12B-C10B
 with sigma of 0.02
 As1A-C4A \\sim As1B-C2B
 with sigma of 0.02
 S4A-C15A \\sim S4B-C17B
 with sigma of 0.02
 S2A-C3A \\sim S2B-C3B
 with sigma of 0.02
 S2A-C6A \\sim S2B-C8B
 with sigma of 0.02
 S2A-C1A \\sim S2B-C5B
 with sigma of 0.02
 C10A-C16A \\sim C14B-C18B
 with sigma of 0.02
 S1A-C3A \\sim S1B-C3B
 with sigma of 0.02
 S1A-C8A \\sim S1B-C6B
 with sigma of 0.02
 S1A-C5A \\sim S1B-C1B
 with sigma of 0.02
 C15A-C10A \\sim C17B-C14B
 with sigma of 0.02
 C3A-C1A \\sim C3B-C5B
 with sigma of 0.02
 C3A-C5A \\sim C3B-C1B
 with sigma of 0.02
 C17A-C14A \\sim C15B-C10B
 with sigma of 0.02
 C8A-C4A \\sim C6B-C2B
 with sigma of 0.02
 C6A-C2A \\sim C8B-C4B
 with sigma of 0.02
 C14A-C13A \\sim C10B-C11B
 with sigma of 0.02
 As2A-C15A \\sim As2B-C17B
 with sigma of 0.02
 C1A-C5A \\sim C5B-C1B
 with sigma of 0.02
 As2A-C11A \\sim As2B-C13B
 with sigma of 0.02
 C1A-C7A \\sim C5B-C9B
 with sigma of 0.02
 C12A-S3A \\sim C12B-S3B
 with sigma of 0.02
 C2A-C4A \\sim C4B-C2B
 with sigma of 0.02
 C12A-C10A \\sim C12B-C14B
 with sigma of 0.02
 C2A-C7A \\sim C4B-C9B
 with sigma of 0.02
 S3A-C17A \\sim S3B-C15B
 with sigma of 0.02
 C5A-C9A \\sim C1B-C7B
 with sigma of 0.02
 S4A-C10A \\sim S4B-C14B
 with sigma of 0.02
 C15A-C11A \\sim C17B-C13B
 with sigma of 0.02
 C4A-C9A \\sim C2B-C7B
 with sigma of 0.02
 C18A-C14A \\sim C16B-C10B
 with sigma of 0.02
 C10A-C14A \\sim C14B-C10B
 with sigma of 0.02
 C11A-C16A \\sim C13B-C18B
 with sigma of 0.02
 As2A-C10A \\sim As2B-C14B
 with sigma of 0.02
 As2A-C14A \\sim As2B-C10B
 with sigma of 0.02
 C12A-C11A \\sim C12B-C13B
 with sigma of 0.02
 C12A-C13A \\sim C12B-C11B
 with sigma of 0.02
 S3A-C18A \\sim S3B-C16B
 with sigma of 0.02
 S3A-C13A \\sim S3B-C11B
 with sigma of 0.02
 S4A-C11A \\sim S4B-C13B
 with sigma of 0.02
4. Restrained planarity
 As2B, C14B, C10B, C17B, C13B, C15B, C11B, H17B, C18B, C12B, S4B, H15B, C16B,
 S3B, H18B, H12B, H16B
 with sigma of 0.1
 As1B, C5B, C1B, C8B, C4B, C6B, C2B, H8B, C9B, S2B, C3B, H6B, C7B, S1B, H9B,
 H3B, H7B
 with sigma of 0.1
5. Rigid body (RIGU) restrains
 As2A, C12A, S4A, C15A, C10A, C11A, C14A, C16A, C13A, S3A, C17A, C18A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 As2B, C12B, S4B, C17B, C14B, C13B, C10B, C11B, C18B, S3B, C15B, C16B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 As1B, S2B, S1B, C3B, C6B, C8B, C5B, C4B, C1B, C2B, C9B, C7B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 As1A, S2A, C3A, C6A, C1A, C2A, C5A, C4A, C7A, S1A, C8A, C9A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Others
 Sof(As1B)=Sof(S2B)=Sof(S1B)=Sof(C3B)=Sof(H3B)=Sof(C6B)=Sof(H6B)=Sof(C8B)=
 Sof(H8B)=Sof(C5B)=Sof(C4B)=Sof(C1B)=Sof(C2B)=Sof(C7B)=Sof(H7B)=Sof(C9B)=
 Sof(H9B)=1-FVAR(1)
 Sof(As1A)=Sof(S2A)=Sof(S1A)=Sof(C3A)=Sof(H3A)=Sof(C8A)=Sof(H8A)=Sof(C6A)=
 Sof(H6A)=Sof(C1A)=Sof(C2A)=Sof(C5A)=Sof(C4A)=Sof(C9A)=Sof(H9A)=Sof(C7A)=
 Sof(H7A)=FVAR(1)
 Sof(As2B)=Sof(C12B)=Sof(H12B)=Sof(S3B)=Sof(S4B)=Sof(C17B)=Sof(H17B)=Sof(C15B)=
 Sof(H15B)=Sof(C16B)=Sof(H16B)=Sof(C14B)=Sof(C13B)=Sof(C10B)=Sof(C11B)=
 Sof(C18B)=Sof(H18B)=1-FVAR(2)
 Sof(As2A)=Sof(C12A)=Sof(H12A)=Sof(S3A)=Sof(S4A)=Sof(C15A)=Sof(H15A)=Sof(C17A)=
 Sof(H17A)=Sof(C18A)=Sof(H18A)=Sof(C10A)=Sof(C11A)=Sof(C14A)=Sof(C16A)=
 Sof(H16A)=Sof(C13A)=FVAR(2)
7.a Aromatic/amide H refined with riding coordinates:
 C12A(H12A), C3A(H3A), C15A(H15A), C17A(H17A), C8A(H8A), C6A(H6A), C18A(H18A),
 C16A(H16A), C9A(H9A), C7A(H7A), C3B(H3B), C6B(H6B), C8B(H8B), C7B(H7B),
 C9B(H9B), C12B(H12B), C17B(H17B), C15B(H15B), C16B(H16B), C18B(H18B)
;
_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 1.401
_oxdiff_exptl_absorpt_empirical_full_min 0.721