Redox mediated dimerisation of a cyclo-As8 complex
Riesinger, Christoph; Scheer, Manfred; Chemical Science 16 (2025) 8807–8811; doi:10.1039/D5SC01685A

data_1574359
_publ_section_title
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 Redox mediated dimerisation of a cyclo-As8 complex
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_journal_issue                   20
_journal_name_full               'Chemical Science'
_journal_page_first              8807
_journal_page_last               8811
_journal_paper_doi               10.1039/D5SC01685A
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety
'C39 H61 As12.5 Ta3, F3 Sb0.5, Al C36 F46 O3, 0.25(C6 H4 F2), 2[C6H14]'
_chemical_formula_sum            'C88.5 H90 Al As12.5 F49.5 O3 Sb0.5 Ta3'
_chemical_formula_weight         3709.30
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2024-11-20
_audit_creation_method
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Olex2 1.5-alpha
(compiled 2024.11.02 svn.r19aeb66f for OlexSys, GUI svn.r7078)
;
_audit_update_record
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2025-02-06 deposited with the CCDC.	2025-04-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.6410(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   24.4761(3)
_cell_length_b                   36.8173(5)
_cell_length_c                   28.1239(3)
_cell_measurement_reflns_used    23645
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      73.7750
_cell_measurement_theta_min      4.0180
_cell_volume                     24907.9(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.27a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.41.27a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.41.27a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 4.2047
_diffrn_detector_type            TitanS2
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.961
_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    -35.00 124.00   1.00   10.00    --   44.62   0.00-180.00  159
  2  \w     26.00  83.00   1.00   45.00    --  104.50 -94.00-150.00   57
  3  \w     37.00  93.00   1.00   45.00    --  104.50 -61.00  90.00   56
  4  \w     31.00  56.00   1.00   45.00    --  104.50 -30.00  60.00   25
  5  \w    106.00 176.00   1.00   45.00    --  104.50  77.00  60.00   70
  6  \w     35.00  72.00   1.00   45.00    --  104.50 -45.00-150.00   37
  7  \w     34.00  72.00   1.00   45.00    --  104.50 -45.00  30.00   38
  8  \w     94.00 178.00   1.00   45.00    --  104.50  30.00 -30.00   84
  9  \w     55.00  85.00   1.00   45.00    --  104.50 -61.00 -30.00   30
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'GV1000, TitanS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0016574000
_diffrn_orient_matrix_UB_12      0.0010805000
_diffrn_orient_matrix_UB_13      -0.0550607000
_diffrn_orient_matrix_UB_21      -0.0483252000
_diffrn_orient_matrix_UB_22      0.0274677000
_diffrn_orient_matrix_UB_23      -0.0057616000
_diffrn_orient_matrix_UB_31      0.0419412000
_diffrn_orient_matrix_UB_32      0.0315206000
_diffrn_orient_matrix_UB_33      0.0068493000
_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  0.0399
_diffrn_reflns_av_unetI/netI     0.0467
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            47169
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.846
_diffrn_reflns_theta_min         3.588
_diffrn_source                   'gradient vaccum rotating-anode X-ray tube'
_diffrn_source_type              'GV1000 (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.396
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.088
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.27a (Rigaku Oxford Diffraction, 2019)
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            'dark brown'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.978
_exptl_crystal_description       stick
_exptl_crystal_F_000             14084
_exptl_crystal_size_max          0.319
_exptl_crystal_size_mid          0.121
_exptl_crystal_size_min          0.042
_refine_diff_density_max         2.508
_refine_diff_density_min         -2.288
_refine_diff_density_rms         0.218
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1408
_refine_ls_number_reflns         24241
_refine_ls_number_restraints     145
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0603
_refine_ls_R_factor_gt           0.0558
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1059P)^2^+51.1868P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1491
_refine_ls_wR_factor_ref         0.1540
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21703
_reflns_number_total             24241
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01685a2.cif
_cod_data_source_block           cr395_cua
_cod_depositor_comments
'Adding full bibliography for 1574358--1574360.cif.'
_cod_original_formula_sum        'C88.50 H90 Al As12.50 F49.50 O3 Sb0.50 Ta3'
_cod_database_code               1574359
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C181 H180 O6 F106 As26 Ta6 Sb'
_chemical_oxdiff_usercomment     'side product?'
_diffrn_oxdiff_digest_hkl
;
01b877d4ee1671a2aa440635b28253d980b82c
;
_reflns_odcompleteness_completeness 99.06
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
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
 C7-C2
 1.3 with sigma of 0.02
 C2-F8 \\sim C3-F9
 with sigma of 0.02
 C2-C7 \\sim C6-C7 \\sim C2-C3 \\sim C5-C6 \\sim C4-C5 \\sim C3-C4
 with sigma of 0.02
 C2-F9 \\sim C4-F9 \\sim C3-F8 \\sim C7-F8
 with sigma of 0.04
 C5-C7 \\sim C4-C6 \\sim C3-C5 \\sim C2-C4 \\sim C3-C7 \\sim C2-C6
 with sigma of 0.04
3. Restrained planarity
 C2, C3, C4, C5, C6, C7, F8, F9
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim F8 \\sim F9: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C2, C3, C4, C5, C6, C7, F8, F9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F9, F8, C2, C3, C7, C6, C5, C4
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
6. Others
 Fixed Sof: As0F(0.5) As0G(0.5) As1(0.5) As2(0.5) As3(0.5) As92(0.5) C2(0.25)
 C7(0.25) H7(0.25) C6(0.25) H6(0.25) C5(0.25) H5(0.25) C4(0.25) H4(0.25)
 C3(0.25) F8(0.25) F9(0.25) As4(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C01Z(H01Z), C021(H021), C022(H022), C025(H025), C02M(H02M), C02S(H02S),
 C02U(H02U), C031(H031), C039(H039), C7(H7), C6(H6), C5(H5), C4(H4)
7.b Fitted hexagon refined as free rotating group:
 C2(C7,C6,C5,C4,C3)
7.c Idealised Me refined as rotating group:
 C020(H02A,H02B,H02C), C024(H02D,H02E,H02F), C02L(H02G,H02H,H02I), C02O(H02J,
 H02K,H02L), C02T(H02N,H02O,H02P), C02V(H02Q,H02R,H02T), C02Z(H02V,H02W,H02X),
 C030(H03A,H03B,H03C), C033(H03D,H03E,H03F), C03I(H03G,H03H,H03I), C03M(H03J,
 H03K,H03L), C03N(H03M,H03N,H03O), C03P(H03P,H03Q,H03R), C03R(H03S,H03T,H03U),
 C03T(H03V,H03W,H03X), C03Y(H03Y,H,HA), C03Z(H03Z,HB,HC), C040(H04A,H04B,H04C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 792 electrons were 
found in a volume of 5538\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[C6H14] per Asymmetric Unit 
which account for 800 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.4
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              82813
_shelx_fab_checksum              51653
_olex2_date_sample_data_collection 2020-02-10
_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 1.646
_oxdiff_exptl_absorpt_empirical_full_min 0.494