A convenient route to mixed cationic group 13/14/15 compounds
Ackermann, Matthias T.; Seidl, Michael; Grande, Riccardo; Zhou, Yuqiao; Ferguson, Michael J.; Timoshkin, Alexey Y.; Rivard, Eric; Scheer, Manfred; Chemical Science 14 (2023) 2313–2317; doi:10.1039/D2SC06594K

data_1568314
_publ_section_title
;
 A convenient route to mixed cationic group 13/14/15 compounds
;
_journal_issue                   9
_journal_name_full               'Chemical Science'
_journal_page_first              2313
_journal_page_last               2317
_journal_paper_doi               10.1039/D2SC06594K
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C54 H80 As B2 Ge N4, C F3 O3 S, 0.8(C H2 Cl2)'
_chemical_formula_sum            'C55.8 H81.6 As B2 Cl1.6 F3 Ge N4 O3 S'
_chemical_formula_weight         1171.36
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-08-22
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2022.06.10 svn.r3fa896fb for OlexSys, GUI svn.r6535)
;
_audit_update_record
;
2022-11-15 deposited with the CCDC.	2023-01-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.9603(7)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   35.2609(2)
_cell_length_b                   10.43718(8)
_cell_length_c                   35.8116(3)
_cell_measurement_reflns_used    58294
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.6500
_cell_measurement_theta_min      2.5270
_cell_volume                     12671.50(17)
_computing_cell_refinement       'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.984
_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     36.00 108.00   0.50    1.20    --   65.12  15.00  30.00  144
  2  \w     48.00 120.00   0.50    1.20    --   76.81  15.00  90.00  144
  3  \w     59.00  98.00   0.50    1.20    --   76.81  15.00  30.00   78
  4  \w     65.00  99.00   0.50    1.20    --   65.12   0.00 -30.00   68
  5  \w     30.00  60.00   0.50    1.20    --   65.12   0.00 -30.00   60
  6  \w     51.00  77.00   0.50    1.20    --   76.81  15.00 -90.00   52
  7  \w     79.00 108.00   0.50    1.20    --   76.81  15.00 -90.00   58
  8  \w     46.00 107.00   0.50    1.20    --   76.81   0.00-180.00  122
  9  \w     33.00  75.00   0.50    1.20    --   65.12-111.00 -95.00   84
 10  \w     77.00 103.00   0.50    1.20    --   76.81-125.00-120.00   52
 11  \w     36.00  98.00   0.50    1.20    --   76.81-125.00-150.00  124
 12  \w     35.00  70.00   0.50    1.20    --   76.81-125.00-120.00   70
 13  \w     43.00 101.00   0.50    1.20    --   76.81-125.00 -60.00  116
 14  \w     42.00 102.00   0.50    1.20    --   76.81-125.00 -30.00  120
 15  \w     57.00 103.00   0.50    1.20    --   76.81-125.00  30.00   92
 16  \w     44.00 100.00   0.50    1.20    --   76.81-125.00 150.00  112
 17  \w     49.00 100.00   0.50    1.20    --   76.81-125.00  90.00  102
 18  \w     38.00  63.00   0.50    1.20    --   72.93-111.00 -95.00   50
 19  \w     46.00  93.00   0.50    1.20    --   76.81-111.00 -95.00   94
 20  \w     55.00 103.00   0.50    1.20    --   76.81-125.00   0.00   96
 21  \w     37.00 101.00   0.50    1.20    --   76.81-125.00  60.00  128
 22  \w    -92.00 -31.00   0.50    1.20    --  -66.48   0.00-180.00  122
 23  \w    -65.00 -29.00   0.50    1.20    --  -66.48 125.00-120.00   72
 24  \w    -94.00 -51.00   0.50    1.20    --  -67.47 125.00 -90.00   86
 25  \w    -82.00 -56.00   0.50    1.20    --  -66.48 111.00  -1.00   52
 26  \w    -75.00 -29.00   0.50    1.20    --  -67.47 111.00  -1.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0143509000
_diffrn_orient_matrix_UB_12      0.0964129000
_diffrn_orient_matrix_UB_13      0.0257121000
_diffrn_orient_matrix_UB_21      -0.0230421000
_diffrn_orient_matrix_UB_22      -0.1076188000
_diffrn_orient_matrix_UB_23      0.0135354000
_diffrn_orient_matrix_UB_31      0.0364336000
_diffrn_orient_matrix_UB_32      -0.0301485000
_diffrn_orient_matrix_UB_33      0.0340361000
_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  0.0497
_diffrn_reflns_av_unetI/netI     0.0379
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -41
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            130860
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.046
_diffrn_reflns_theta_min         2.539
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.569
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.649
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.118a (Rigaku Oxford Diffraction, 2021)
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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.228
_exptl_crystal_description       block
_exptl_crystal_F_000             4909
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.744
_refine_diff_density_min         -0.939
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1756
_refine_ls_number_reflns         25685
_refine_ls_number_restraints     1150
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0857
_refine_ls_R_factor_gt           0.0734
_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^)+(0.0864P)^2^+31.4566P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1925
_refine_ls_wR_factor_ref         0.1992
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21418
_reflns_number_total             25685
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06594k2.cif
_cod_data_source_block           ma376_2_mp_abs_gaus
_cod_depositor_comments
'Adding full bibliography for 1568311--1568314.cif.'
_cod_original_cell_volume        12671.53(16)
_cod_original_formula_sum        'C55.80 H81.60 As B2 Cl1.60 F3 Ge N4 O3 S'
_cod_database_code               1568314
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C55 H80 B2 F3 Ge N4 O3 As S Cl2'
_shelx_estimated_absorpt_t_max   0.927
_shelx_estimated_absorpt_t_min   0.669
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H,H) groups, All C(H) groups, All C(H,H) groups, All Ge(H,H) groups,
  All As(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C28-B2B
 1.6 with sigma of 0.01
 C112-F9 = C112-F7 = C112-F8
 1.35 with sigma of 0.02
 Cl4-C114 = Cl2-C113 = Cl10-C42 = Cl3-C114 = Cl1-C113 = Cl9-C42
 1.75 with sigma of 0.02
 F9-F7 = F7-F8 = F8-F9
 2.15 with sigma of 0.04
 Ge2B-B3B \\sim Ge2C-B3C \\sim Ge2A-B3A
 with sigma of 0.02
 As2A-B4A \\sim As2A-B3A \\sim As2C-B3C \\sim As2B-B3B \\sim As2C-B4C \\sim
As2B-B5B
 with sigma of 0.01
 C81A-C79 \\sim C81B-C79
 with sigma of 0.02
 Ge2A-C82 \\sim Ge2B-C55 \\sim Ge2C-C55
 with sigma of 0.02
 C82-B5B \\sim C55-B4A
 with sigma of 0.02
 C94A-C95A \\sim C94A-C96A \\sim C95B-C94B \\sim C96B-C94B
 with sigma of 0.02
 S3-O7 \\sim S3-O9 \\sim S3-O8
 with sigma of 0.02
 O7-O9 \\sim O9-O8 \\sim O7-O8
 with sigma of 0.04
 C112-O7 \\sim C112-O9 \\sim C112-O8
 with sigma of 0.04
 C41B-C40 \\sim C41A-C40 \\sim C42A-C40 \\sim C42B-C40
 with sigma of 0.02
 As1A-B1A \\sim As1C-B1C \\sim As1B-B1B \\sim As1D-B1D
 with sigma of 0.01
 As1A-B2A \\sim As1C-B2C \\sim As1B-B2B \\sim As1D-B2D
 with sigma of 0.02
 Ge1B-B1B \\sim Ge1D-B1D \\sim Ge1A-B1A \\sim Ge1C-B1C
 with sigma of 0.01
 C1-B2A \\sim C1-B2C \\sim C28-B2D \\sim C28-B2B
 with sigma of 0.02
 Ge1B-C1 \\sim Ge1D-C1 \\sim Ge1A-C28 \\sim Ge1C-C28
 with sigma of 0.01
 C52-C48 \\sim C54A-C52 \\sim C53A-C52
 with sigma of 0.02
 S3-F9 \\sim S3-F7 \\sim S3-F8
 with sigma of 0.04
 Cl8-C116 \\sim Cl6-C115 \\sim Cl7-C116 \\sim Cl5-C115
 with sigma of 0.02
 S3-C112 \\sim S2-C111
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
B5B \\sim B4C \\sim Ge2A \\sim As2C \\sim B3A \\sim As2B \\sim B3B \\sim B3C
\\sim As2A \\sim Ge2C \\sim Ge2B \\sim B4A: within 2.4A with sigma of 0.01 and
sigma for terminal atoms of 0.01 within 2.4A
C112 \\sim F9 \\sim F7 \\sim F8 \\sim S3 \\sim O7 \\sim O9 \\sim O8 \\sim Cl7
\\sim C116 \\sim Cl8 \\sim C115 \\sim Cl5 \\sim Cl6: within 1.9A with sigma of
0.01 and sigma for terminal atoms of 0.01 within 1.9A
Ge1B \\sim B2A \\sim B2C \\sim Ge1D \\sim As1A \\sim As1C \\sim B1B \\sim B1D
\\sim As1D \\sim As1B \\sim Ge1C \\sim B1A \\sim B1C \\sim Ge1A \\sim B2B \\sim
B2D: within 2.4A with sigma of 0.01 and sigma for terminal atoms of 0.01 within
2.4A
C42A \\sim C42B \\sim C40 \\sim C41A \\sim C41B: within 1.7A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 1.7A
C52 \\sim C53A \\sim C53B \\sim C54A \\sim C54B: within 1.7A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 1.7A
Cl2 \\sim C113 \\sim Cl1 \\sim Cl9 \\sim C42 \\sim C114 \\sim Cl10 \\sim Cl4
\\sim Cl3: within 1.9A with sigma of 0.01 and sigma for terminal atoms of 0.01
within 1.9A
Uanis(B5B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.001
Uanis(B1A) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.01
Uanis(B1C) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(B2D) = Uanis(B2B)
4. Others
 Sof(C96A)=Sof(H96A)=Sof(H96B)=Sof(H96C)=Sof(C95A)=Sof(H95A)=Sof(H95B)=
 Sof(H95C)=Sof(C94A)=Sof(H94A)=1-FVAR(1)
 Sof(C94B)=Sof(H94B)=Sof(C96B)=Sof(H96D)=Sof(H96E)=Sof(H96F)=Sof(C95B)=
 Sof(H95D)=Sof(H95E)=Sof(H95F)=FVAR(1)
 Sof(H10A)=1-FVAR(2)
 Sof(H103)=FVAR(2)
 Fixed Sof: Ge2A(0.55) H2AC(0.55) H2AD(0.55) Ge1C(0.18) H1CA(0.18) H1CB(0.18)
 As2A(0.55) H2AE(0.55) H2AF(0.55) Ge2B(0.37) H2BC(0.37) H2BD(0.37) S2(0.89)
 As2B(0.37) H2BE(0.37) H2BF(0.37) Ge1B(0.2) H1BA(0.2) H1BB(0.2) As1B(0.2)
 H1BC(0.2) H1BD(0.2) F6(0.89) F4(0.89) O4(0.89) O5(0.89) F5(0.89) O6(0.89)
 H40(0.39) H40A(0.61) H79(0.41) H79A(0.59) H52(0.55) H52A(0.45) C111(0.89)
 B3A(0.55) H3AA(0.55) H3AB(0.55) C42B(0.39) H42A(0.39) H42B(0.39) H42C(0.39)
 C41B(0.39) H41A(0.39) H41B(0.39) H41C(0.39) C105(0.48) H10K(0.48) H10L(0.48)
 H10M(0.48) C81B(0.41) H81A(0.41) H81B(0.41) H81C(0.41) C54A(0.55) H54A(0.55)
 H54B(0.55) H54C(0.55) C53A(0.55) H53A(0.55) H53B(0.55) H53C(0.55) As1D(0.07)
 H1DA(0.07) H1DB(0.07) Ge1A(0.55) H1AA(0.55) H1AB(0.55) B4A(0.55) H4AA(0.55)
 H4AB(0.55) B3B(0.37) H3BA(0.37) H3BB(0.37) B5B(0.37) H5BA(0.37) H5BB(0.37)
 As2C(0.08) H2CC(0.08) H2CD(0.08) Cl5(0.5) Cl6(0.5) C115(0.5) H11D(0.5)
 H11E(0.5) Cl7(0.25) Cl8(0.25) C116(0.25) H11F(0.25) H11G(0.25) C112(0.11)
 F9(0.11) F7(0.11) F8(0.11) S3(0.11) O7(0.11) O9(0.11) O8(0.11) C54B(0.45)
 H54D(0.45) H54E(0.45) H54F(0.45) C53B(0.45) H53D(0.45) H53E(0.45) H53F(0.45)
 B2A(0.55) H2AA(0.55) H2AB(0.55) Cl2(0.3) Cl1(0.3) C113(0.3) H11H(0.3)
 H11I(0.3) Cl10(0.3) Cl9(0.3) C42(0.3) H42G(0.3) H42H(0.3) Cl4(0.25) Cl3(0.25)
 C114(0.25) H11J(0.25) H11K(0.25) B1A(0.55) H1AC(0.55) H1AD(0.55) B1B(0.2)
 H1BE(0.2) H1BF(0.2) As1A(0.55) H1AE(0.55) H1AF(0.55) B2B(0.2) H2BA(0.2)
 H2BB(0.2) B1C(0.18) H1CC(0.18) H1CD(0.18) As1C(0.18) H1CE(0.18) H1CF(0.18)
 B3C(0.08) H3CA(0.08) H3CB(0.08) Ge2C(0.08) H2CE(0.08) H2CF(0.08) B4C(0.08)
 H4CA(0.08) H4CB(0.08) C106(0.52) H10N(0.52) H10O(0.52) H10P(0.52) B2C(0.18)
 H2CA(0.18) H2CB(0.18) Ge1D(0.07) H1DC(0.07) H1DD(0.07) B1D(0.07) H1DE(0.07)
 H1DF(0.07) B2D(0.07) H2DA(0.07) H2DB(0.07) C41A(0.61) H41D(0.61) H41E(0.61)
 H41F(0.61) C42A(0.61) H42D(0.61) H42E(0.61) H42F(0.61) C81A(0.59) H81D(0.59)
 H81E(0.59) H81F(0.59)
 Fixed X: B4C(0.906528) B2C(0.63462) B2D(0.54329)
 Fixed Y: B4C(0.341961) B2C(0.476548) B2D(0.593201)
 Fixed Z: B4C(0.60163) B2C(0.31523) B2D(0.36261)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C91(H91), C67(H67), C37(H37), C40(H40), C40(H40A),
 C107(H107), C64(H64), C49(H49), C25(H25), C76(H76), C103(H103), C103(H10A),
 C79(H79), C79(H79A), C52(H52), C52(H52A), C22(H22), C94B(H94B), C94A(H94A)
5.b Secondary CH2 refined with riding coordinates:
 Ge2A(H2AC,H2AD), Ge1C(H1CA,H1CB), As2A(H2AE,H2AF), Ge2B(H2BC,H2BD), As2B(H2BE,
 H2BF), Ge1B(H1BA,H1BB), As1B(H1BC,H1BD), B3A(H3AA,H3AB), As1D(H1DA,H1DB),
 Ge1A(H1AA,H1AB), B4A(H4AA,H4AB), B3B(H3BA,H3BB), B5B(H5BA,H5BB), As2C(H2CC,
 H2CD), C115(H11D,H11E), C116(H11F,H11G), B2A(H2AA,H2AB), C113(H11H,H11I),
 C42(H42G,H42H), C114(H11J,H11K), B1A(H1AC,H1AD), B1B(H1BE,H1BF), As1A(H1AE,
 H1AF), B2B(H2BA,H2BB), B1C(H1CC,H1CD), As1C(H1CE,H1CF), B3C(H3CA,H3CB),
 Ge2C(H2CE,H2CF), B4C(H4CA,H4CB), B2C(H2CA,H2CB), Ge1D(H1DC,H1DD), B1D(H1DE,
 H1DF), B2D(H2DA,H2DB)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C2(H2), C12(H12), C8(H8), C56(H56), C57(H57), C29(H29), C30(H30),
 C87(H87), C7(H7), C99(H99), C88(H88), C84(H84), C83(H83), C35(H35), C101(H101),
  C74(H74), C20(H20), C62(H62), C100(H100), C34(H34), C33(H33), C73(H73),
 C47(H47), C60(H60), C89(H89), C72(H72), C46(H46), C61(H61), C45(H45), C18(H18),
  C19(H19)
5.d Idealised Me refined as rotating group:
 C027(H02A,H02B,H02C), C11(H11A,H11B,H11C), C15(H15A,H15B,H15C), C65(H65A,H65B,
 H65C), C14(H14A,H14B,H14C), C69(H69A,H69B,H69C), C66(H66A,H66B,H66C), C92(H92A,
 H92B,H92C), C26(H26A,H26B,H26C), C78(H78A,H78B,H78C), C93(H93A,H93B,H93C),
 C39(H39A,H39B,H39C), C77(H77A,H77B,H77C), C38(H38A,H38B,H38C), C68(H68A,H68B,
 H68C), C108(H10B,H10C,H10D), C51(H51A,H51B,H51C), C50(H50A,H50B,H50C),
 C80(H80A,H80B,H80C), C27(H27A,H27B,H27C), C24(H24A,H24B,H24C), C42B(H42A,H42B,
 H42C), C109(H10E,H10F,H10G), C23(H23A,H23B,H23C), C104(H10H,H10I,H10J),
 C41B(H41A,H41B,H41C), C105(H10K,H10L,H10M), C81B(H81A,H81B,H81C), C96A(H96A,
 H96B,H96C), C54A(H54A,H54B,H54C), C95A(H95A,H95B,H95C), C53A(H53A,H53B,H53C),
 C96B(H96D,H96E,H96F), C95B(H95D,H95E,H95F), C54B(H54D,H54E,H54F), C53B(H53D,
 H53E,H53F), C106(H10N,H10O,H10P), C41A(H41D,H41E,H41F), C42A(H42D,H42E,H42F),
 C81A(H81D,H81E,H81F)
;
_shelx_res_checksum              30658
_shelx_hkl_checksum              66849
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 4.027
_oxdiff_exptl_absorpt_empirical_full_min 0.493