Isolation of singlet carbene derived 2-arsa-1,3-butadiene radical cations and dications.
Sharma, Mahendra K.; Blomeyer, Sebastian; Neumann, Beate; Stammler, Hans-Georg; Hinz, Alexander; van Gastel, Maurice; Ghadwal, Rajendra S.; Chemical communications (Cambridge, England) 56 (2020) 3575–3578; doi:10.1039/d0cc00624f

data_7126050
_publ_section_title
;
 Isolation of singlet carbene derived 2-arsa-1,3-butadiene radical cations
 and dications.
;
_journal_issue                   24
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              3575
_journal_page_last               3578
_journal_paper_doi               10.1039/d0cc00624f
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety         'C54 H72 As N3, 2(Cl4 Ga1)'
_chemical_formula_sum            'C54 H72 As Cl8 Ga2 N3'
_chemical_formula_weight         1261.10
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-14
_audit_creation_method
;
Olex2 1.3-dev
(compiled 2019.03.18 svn.r3573 for OlexSys, GUI svn.r5757)
;
_audit_update_record
;
2019-11-19 deposited with the CCDC.	2020-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.8893(4)
_cell_length_b                   26.1136(4)
_cell_length_c                   24.2536(4)
_cell_measurement_reflns_used    30043
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      72.0000
_cell_measurement_theta_min      3.3360
_cell_volume                     11963.5(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.51a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.51a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.51a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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    -59.00  32.00   1.00   12.50    --  -38.50  37.00 -90.00   91
  2  \w    -59.00  33.00   1.00   12.50    --  -38.50  37.00  30.00   92
  3  \w    -91.00  -5.00   1.00   12.50    --  -38.50 125.00  90.00   86
  4  \w   -116.00  -5.00   1.00   12.50    --  -38.50 -19.00-150.00  111
  5  \w    -54.00 -13.00   1.00   12.50    --  -38.50 -57.00-180.00   41
  6  \w     13.00 109.00   1.00   12.50    --   42.70  77.00 -30.00   96
  7  \w     14.00  93.00   1.00   12.50    --   42.70  77.00  30.00   79
  8  \w     23.00  83.00   1.00   12.50    --   42.70-125.00 -30.00   60
  9  \w     26.00  73.00   1.00   12.50    --   42.70-125.00  90.00   47
 10  \w     13.00  78.00   1.00   12.50    --   42.70  77.00-180.00   65
 11  \w     15.00 114.00   1.00   12.50    --   42.70  77.00  90.00   99
 12  \w     62.00  89.00   1.00   12.50    --   42.70  77.00 -90.00   27
 13  \w     13.00  46.00   1.00   12.50    --   42.70  77.00 -90.00   33
 14  \w     22.00  72.00   1.00   12.50    --   42.70  37.00 -30.00   50
 15  \w     81.00 177.00   1.00   50.00    --  111.00  77.00 120.00   96
 16  \w     42.00 119.00   1.00   50.00    --  111.00-126.00 -57.82   77
 17  \w    137.00 164.00   1.00   50.00    --  111.00  75.00-100.38   27
 18  \w     83.00 110.00   1.00   50.00    --  111.00  68.00 -68.94   27
 19  \w     87.00 156.00   1.00   50.00    --  111.00  54.00 107.98   69
 20  \w     81.00 108.00   1.00   50.00    --  111.00  75.00-100.38   27
 21  \w     82.00 109.00   1.00   50.00    --  111.00  71.00  -7.45   27
 22  \w     81.00 177.00   1.00   50.00    --  111.00  77.00 -90.00   96
 23  \w     82.00 107.00   1.00   50.00    --  111.00  77.00  90.00   25
 24  \w     89.00 115.00   1.00   50.00    --  111.00  45.00 150.00   26
 25  \w     81.00 178.00   1.00   50.00    --  111.00  77.00 -30.00   97
 26  \w     81.00 150.00   1.00   50.00    --  111.00  77.00-150.00   69
 27  \w     81.00 157.00   1.00   50.00    --  111.00  77.00  30.00   76
 28  \w     31.00 109.00   1.00   50.00    --  111.00 -94.00 -30.00   78
 29  \w     83.00 109.00   1.00   50.00    --  111.00  69.00 110.80   26
 30  \w     81.00 178.00   1.00   50.00    --  111.00  77.00 150.00   97
 31  \w    115.00 140.00   1.00   50.00    --  111.00 -77.00  90.00   25
 32  \w     41.00  95.00   1.00   50.00    --  111.00 -77.00  90.00   54
 33  \w     82.00 145.00   1.00   50.00    --  111.00  71.00  18.21   63
 34  \w     85.00 122.00   1.00   50.00    --  111.00  59.00 -19.22   37
 35  \w     85.00 111.00   1.00   50.00    --  111.00  61.00 -30.00   26
 36  \w     85.00 178.00   1.00   50.00    --  111.00  61.00-120.00   93
 37  \w     81.00 143.00   1.00   50.00    --  111.00  77.00   0.00   62
 38  \w     45.00  90.00   1.00   50.00    --  111.00 -94.00  30.00   45
 39  \w     85.00 111.00   1.00   50.00    --  111.00  61.00  60.00   26
 40  \w     85.00 117.00   1.00   50.00    --  111.00  61.00-180.00   32
 41  \w     83.00 109.00   1.00   50.00    --  111.00  70.00-158.37   26
 42  \w     81.00 107.00   1.00   50.00    --  111.00  77.00-180.00   26
 43  \w    111.00 178.00   1.00   50.00    --  111.00  77.00-180.00   67
 44  \w     81.00 107.00   1.00   50.00    --  111.00  77.00-120.00   26
 45  \w     85.00 111.00   1.00   50.00    --  111.00  61.00  90.00   26
 46  \w     85.00 111.00   1.00   50.00    --  111.00  61.00 -90.00   26
 47  \w     81.00 107.00   1.00   50.00    --  111.00  77.00  60.00   26
 48  \w     81.00 107.00   1.00   50.00    --  111.00  77.00 -60.00   26
 49  \w     85.00 112.00   1.00   50.00    --  111.00  59.00  -1.73   27
 50  \w     85.00 112.00   1.00   50.00    --  111.00  61.00 150.00   27
 51  \w     92.00 153.00   1.00   50.00    --  111.00  44.00 -34.96   61
 52  \w     41.00 102.00   1.00   50.00    --  111.00-125.00 -90.00   61
 53  \w     41.00 118.00   1.00   50.00    --  111.00-125.00-150.00   77
 54  \w     57.00 111.00   1.00   50.00    --  111.00-125.00 -30.00   54
 55  \w     44.00 118.00   1.00   50.00    --  111.00-125.00 120.00   74
 56  \w     84.00 110.00   1.00   50.00    --  111.00  65.00-158.09   26
 57  \w     85.00 121.00   1.00   50.00    --  111.00  59.00  69.39   36
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0752544000
_diffrn_orient_matrix_UB_12      -0.0227147000
_diffrn_orient_matrix_UB_13      0.0007467000
_diffrn_orient_matrix_UB_21      -0.0025458000
_diffrn_orient_matrix_UB_22      0.0063060000
_diffrn_orient_matrix_UB_23      0.0631155000
_diffrn_orient_matrix_UB_31      -0.0313346000
_diffrn_orient_matrix_UB_32      0.0540896000
_diffrn_orient_matrix_UB_33      -0.0070204000
_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  0.1217
_diffrn_reflns_av_unetI/netI     0.0466
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            141043
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.241
_diffrn_reflns_theta_min         3.385
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.283
_exptl_absorpt_correction_T_max  0.976
_exptl_absorpt_correction_T_min  0.408
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.51a (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            'clear green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.400
_exptl_crystal_description       plate
_exptl_crystal_F_000             5184
_exptl_crystal_size_max          0.244
_exptl_crystal_size_mid          0.169
_exptl_crystal_size_min          0.045
_refine_diff_density_max         1.246
_refine_diff_density_min         -0.726
_refine_diff_density_rms         0.119
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     661
_refine_ls_number_reflns         10879
_refine_ls_number_restraints     92
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0850
_refine_ls_R_factor_gt           0.0676
_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/[\s^2^(Fo^2^)+(0.0793P)^2^+44.6112P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1669
_refine_ls_wR_factor_ref         0.1792
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8619
_reflns_number_total             10879
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc00624f2.cif
_cod_data_source_block           compound4a
_cod_depositor_comments
'Adding full bibliography for 7126045--7126050.cif.'
_cod_database_code               7126050
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C54H72AsCl8Ga2N3
_diffrn_oxdiff_digest_frames
;
0100d2e35c0ccb61a6c026838f2be4c61503074fd5f
;
_diffrn_oxdiff_digest_hkl
;
01d511cffb48b30dc04e1377353e1a219764eb
;
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Ga1-Cl1 \\sim Ga1B-Cl1B \\sim Ga1-Cl4 \\sim Ga1B-Cl4B \\sim Ga1-Cl2 \\sim
Ga1B-Cl2B \\sim Ga2B-Cl7B ~
 Ga2-Cl7 \\sim Ga2-Cl8 \\sim Ga2B-Cl8B \\sim Ga2-Cl6 \\sim Ga2B-Cl6B \\sim
Ga2B-Cl5B \\sim Ga2-Cl5
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Ga1B) = Uanis(Ga1)
Uanis(Cl4B) = Uanis(Cl4)
Uanis(Cl2B) = Uanis(Cl2)
Uanis(Cl1) = Uanis(Cl1B)
Uanis(Ga2B) = Uanis(Ga2)
Uanis(Cl8B) = Uanis(Cl8)
Uanis(Cl6) = Uanis(Cl6B)
Uanis(Cl5B) = Uanis(Cl5)
Uanis(Cl3) = Uanis(Cl3B)
Uanis(Cl7B) = Uanis(Cl7)
4. Others
 1*[Sof(Ga1)+Sof(Cl1)+Sof(Cl2)+Sof(Cl3)+Sof(Cl4)+Sof(Ga1B)+Sof(Cl1B)+Sof(Cl2B)+
 Sof(Cl3B)+Sof(Cl4B)]-1*[Sof(Ga2)+Sof(Cl5)+Sof(Cl6)+Sof(Cl7)+Sof(Cl8)+Sof(Ga2B)+
 Sof(Cl5B)+Sof(Cl6B)+Sof(Cl7B)+Sof(Cl8B)]=0 with esd of 0
 Sof(Ga1B)=Sof(Cl1B)=Sof(Cl2B)=Sof(Cl3B)=Sof(Cl4B)=1-FVAR(1)
 Sof(Ga1)=Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=Sof(Cl4)=FVAR(1)
 Sof(Ga2B)=Sof(Cl5B)=Sof(Cl6B)=Sof(Cl7B)=Sof(Cl8B)=1-FVAR(2)
 Sof(Ga2)=Sof(Cl5)=Sof(Cl6)=Sof(Cl7)=Sof(Cl8)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C23(H23), C26(H26), C49(H49), C52(H52)
5.b Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C8(H8), C9(H9), C19(H19), C20(H20), C21(H21),
 C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C45(H45), C46(H46), C47(H47)
5.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,
 H28B,H28C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C),
 C42(H42A,H42B,H42C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C53(H53A,H53B,
 H53C), C54(H54A,H54B,H54C)
;
_shelx_res_checksum              78425
_olex2_date_sample_data_collection 2019-04-26
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.287
_oxdiff_exptl_absorpt_empirical_full_min 0.533