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_1568313
_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
'2(C54 H80 B2 Ge N4 P), 2(C F3 O3 S), 0.65(C H2 Cl2), 1[CH2Cl2]'
_chemical_formula_sum            'C111.65 H163.3 B4 Cl3.3 F6 Ge2 N8 O6 P2 S2'
_chemical_formula_weight         2259.06
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2021-10-25
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2022-11-15 deposited with the CCDC.	2023-01-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.9250(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   35.1849(3)
_cell_length_b                   10.44010(10)
_cell_length_c                   35.7996(3)
_cell_measurement_reflns_used    40320
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.5300
_cell_measurement_theta_min      2.5310
_cell_volume                     12645.7(2)
_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 2018/2 (Sheldrick, 2018)'
_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 0.994
_diffrn_measured_fraction_theta_max 0.993
_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     34.00 106.00   0.50    2.50    --   64.79   9.00-132.00  144
  2  \w   -107.00 -36.00   0.50    2.50    --  -66.86  -9.00  53.00  142
  3  \w   -108.00 -36.00   0.50    2.50    --  -67.57  -9.00  53.00  144
  4  \w     46.00 117.00   0.50    2.50    --   76.70   9.00-132.00  142
  5  \w     23.00  91.00   0.50    2.50    --   64.79-125.00  90.00  136
  6  \w   -110.00 -37.00   0.50    2.50    --  -66.86 -15.00-180.00  146
  7  \w    -93.00 -25.00   0.50    2.50    --  -66.86 125.00 150.00  136
  8  \w    -94.00 -26.00   0.50    2.50    --  -67.57 125.00 -90.00  136
  9  \w     42.00 114.00   0.50    2.50    --   72.89   9.00-132.00  144
 10  \w     44.00 116.00   0.50    2.50    --   72.89  15.00 150.00  144
 11  \w     35.00 103.00   0.50    2.50    --   76.70-125.00 -30.00  136
 12  \w     35.00 103.00   0.50    2.50    --   76.70-125.00   0.00  136
 13  \w     47.00 120.00   0.50    2.50    --   76.70  15.00  90.00  146
 14  \w     35.00 103.00   0.50    2.50    --   76.70-125.00  30.00  136
 15  \w     35.00 103.00   0.50    2.50    --   76.70-125.00 -90.00  136
 16  \w     35.00 103.00   0.50    2.50    --   76.70-125.00 -60.00  136
;
_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      0.0431483000
_diffrn_orient_matrix_UB_12      -0.0131847000
_diffrn_orient_matrix_UB_13      0.0247783000
_diffrn_orient_matrix_UB_21      -0.0136895000
_diffrn_orient_matrix_UB_22      0.0099312000
_diffrn_orient_matrix_UB_23      0.0372652000
_diffrn_orient_matrix_UB_31      -0.0048382000
_diffrn_orient_matrix_UB_32      -0.1466229000
_diffrn_orient_matrix_UB_33      0.0002841000
_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  0.0655
_diffrn_reflns_av_unetI/netI     0.0651
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            122947
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.072
_diffrn_reflns_theta_min         2.567
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.251
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.731
_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    1.187
_exptl_crystal_description       plate
_exptl_crystal_F_000             4773
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.905
_refine_diff_density_min         -1.283
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1680
_refine_ls_number_reflns         23845
_refine_ls_number_restraints     972
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.1081
_refine_ls_R_factor_gt           0.0762
_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^)+(0.0948P)^2^+22.9912P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1957
_refine_ls_wR_factor_ref         0.2096
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17054
_reflns_number_total             23845
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06594k2.cif
_cod_data_source_block           ma295_2_mp_cut_abs
_cod_depositor_comments
'Adding full bibliography for 1568311--1568314.cif.'
_cod_original_formula_sum        'C111.65 H163.30 B4 Cl3.30 F6 Ge2 N8 O6 P2 S2'
_cod_database_code               1568313
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C56H82B2F3GeN4O3PSCl2
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.701
_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 P(H,H) groups,
  All Ge(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C1-B2B = C28-B2A
 1.75 with sigma of 0.02
 B2C-C28
 1.75 with sigma of 0.02
 P1B-B2B
 1.92 with sigma of 0.02
 F6B-F5B = F5B-F4B = F4B-F6B
 2.1 with sigma of 0.02
 F4B-C1A = F5B-C1A = F6B-C1A
 1.35 with sigma of 0.02
 P2C-B4C = P2B-B4B = P2B-B3B = P2D-B3D = P2C-B3C = P2A-B3A = P2D-B4D = P2A-B4A
 1.93 with sigma of 0.02
 P2A-B3A
 1.93 with sigma of 0.01
 B1C-B2C
 3 with sigma of 0.04
 S2B-F6B \\sim S2B-F5B \\sim S2B-F4B
 with sigma of 0.04
 Ge1C-B1C \\sim Ge1A-B1A \\sim Ge1B-B1B
 with sigma of 0.02
 C1-B2B \\sim C28-B2A \\sim C28-B2C
 with sigma of 0.02
 Ge1B-C28 \\sim Ge1A-C1 \\sim Ge1C-C1
 with sigma of 0.02
 P1A-B1A \\sim P1C-B1C \\sim P1B-B1B \\sim P1A-B2A \\sim P1C-B2C
 with sigma of 0.02
 C1A-F6B \\sim C1A-F5B \\sim C1A-F4B
 with sigma of 0.02
 S2B-O6B \\sim S2B-O5B \\sim S2B-O4B
 with sigma of 0.02
 C52-B4A \\sim C52-B4D \\sim C79-B4B \\sim C79-B4C
 with sigma of 0.02
 Ge2C-B3C \\sim Ge2B-B3B \\sim Ge2D-B3D \\sim Ge2A-B3A
 with sigma of 0.02
 Ge2C-C52 \\sim Ge2B-C52 \\sim Ge2A-C79 \\sim Ge2D-C79
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Ge1A \\sim Ge1B \\sim P1A \\sim P1B \\sim B2A \\sim B1A \\sim Ge1C \\sim B2B
\\sim B1B \\sim B1C \\sim P1C \\sim B2C: within 2.3A with sigma of 0.01 and
sigma for terminal atoms of 0.01 within 2.3A
B4A \\sim P2A \\sim P2B \\sim B3D \\sim Ge2B \\sim B3B \\sim Ge2C \\sim P2C
\\sim B3A \\sim B3C \\sim B4D \\sim P2D \\sim Ge2A \\sim B4C \\sim B4B \\sim
Ge2D: within 2.3A with sigma of 0.01 and sigma for terminal atoms of 0.01
within 2.3A
C25A \\sim C25B \\sim C26A \\sim C26B \\sim C27B \\sim C27A: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
C38A \\sim C38B \\sim C39B \\sim C39A \\sim C37: within 1.7A with sigma of 0.01
and sigma for terminal atoms of 0.01 within 1.7A
S2B \\sim O4B \\sim O6B \\sim C1A \\sim F6B \\sim F5B \\sim F4B \\sim O5B:
within 1.9A with sigma of 0.01 and sigma for terminal atoms of 0.01 within 1.9A
C104 \\sim C106 \\sim C103 \\sim C107 \\sim C105: within 1.7A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 1.7A
C93B \\sim C93A \\sim C91 \\sim C92B \\sim C92A: within 1.7A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 1.7A
C110 \\sim Cl1A \\sim C111 \\sim Cl2B \\sim Cl2A \\sim Cl1B: within 1.9A with
sigma of 0.02 and sigma for terminal atoms of 0.02 within 1.9A
Uanis(C37) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(P1B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(B2B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(S2B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(P2D) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(B4D) = Uanis(B4A)
4. Others
 Sof(C1A)=Sof(F6B)=Sof(F5B)=Sof(F4B)=Sof(S2B)=Sof(O6B)=Sof(O5B)=Sof(O4B)=1-
 FVAR(1)
 Sof(S2A)=Sof(F5A)=Sof(O5A)=Sof(F6A)=Sof(O4A)=Sof(F4A)=Sof(O6A)=Sof(C109)=
 FVAR(1)
 Fixed Sof: Ge1A(0.66) H1AA(0.66) H1AB(0.66) Ge2A(0.45) H2AA(0.45) H2AB(0.45)
 B4A(0.45) H4AA(0.45) H4AB(0.45) Ge1B(0.28) H1BA(0.28) H1BB(0.28) P1A(0.66)
 H1AC(0.66) H1AD(0.66) P2A(0.45) H2AC(0.45) H2AD(0.45) H37(0.46) H37A(0.54)
 H91(0.6) H91A(0.4) P1B(0.28) H1BC(0.28) H1BD(0.28) H103(0.47) H10A(0.53)
 C25A(0.63) H25A(0.63) P2B(0.25) H2BA(0.25) H2BB(0.25) C39A(0.46) H39A(0.46)
 H39B(0.46) H39C(0.46) C26A(0.63) H26A(0.63) H26B(0.63) H26C(0.63) C93A(0.6)
 H93A(0.6) H93B(0.6) H93C(0.6) C92A(0.6) H92A(0.6) H92B(0.6) H92C(0.6)
 C38A(0.46) H38A(0.46) H38B(0.46) H38C(0.46) C27A(0.63) H27A(0.63) H27B(0.63)
 H27C(0.63) B3D(0.15) H3DA(0.15) H3DB(0.15) C107(0.47) H10H(0.47) H10I(0.47)
 H10J(0.47) C106(0.47) H10K(0.47) H10L(0.47) H10M(0.47) Cl1A(0.4) Cl2A(0.4)
 C110(0.4) H11D(0.4) H11E(0.4) Cl2B(0.25) Cl1B(0.25) C111(0.25) H11F(0.25)
 H11G(0.25) C38B(0.54) H38D(0.54) H38E(0.54) H38F(0.54) C39B(0.54) H39D(0.54)
 H39E(0.54) H39F(0.54) C27B(0.37) H27D(0.37) H27E(0.37) H27F(0.37) C25B(0.37)
 H25B(0.37) C26B(0.37) H26D(0.37) H26E(0.37) H26F(0.37) B2A(0.66) H2AE(0.66)
 H2AF(0.66) B1A(0.66) H1AE(0.66) H1AF(0.66) C105(0.53) H10N(0.53) H10O(0.53)
 H10P(0.53) C104(0.53) H10Q(0.53) H10R(0.53) H10S(0.53) C93B(0.4) H93D(0.4)
 H93E(0.4) H93F(0.4) C92B(0.4) H92D(0.4) H92E(0.4) H92F(0.4) Ge2B(0.25)
 H2BC(0.25) H2BD(0.25) B3B(0.25) H3BA(0.25) H3BB(0.25) Ge1C(0.06) H1CA(0.06)
 H1CB(0.06) B2B(0.28) H2BE(0.28) H2BF(0.28) B4C(0.15) H4CA(0.15) H4CB(0.15)
 B4B(0.25) H4BA(0.25) H4BB(0.25) Ge2C(0.15) H2CA(0.15) H2CB(0.15) Ge2D(0.15)
 H2DA(0.15) H2DB(0.15) P2C(0.15) H2CC(0.15) H2CD(0.15) B3A(0.45) H3AA(0.45)
 H3AB(0.45) B3C(0.15) H3CA(0.15) H3CB(0.15) B4D(0.15) H4DA(0.15) H4DB(0.15)
 P2D(0.15) H2DC(0.15) H2DD(0.15) B1B(0.28) H1BE(0.28) H1BF(0.28) B1C(0.06)
 H1CC(0.06) H1CD(0.06) P1C(0.06) H1CE(0.06) H1CF(0.06) B2C(0.06) H2CE(0.06)
 H2CF(0.06)
 Fixed X: B4D(0.63123)
 Fixed Y: B4D(0.4527)
 Fixed Z: B4D(0.323461)
5.a Ternary CH refined with riding coordinates:
 C73(H73), C22(H22), C76(H76), C46(H46), C88(H88), C49(H49), C37(H37),
 C37(H37A), C91(H91), C91(H91A), C61(H61), C10(H10), C13(H13), C02S(H02S),
 C100(H100), C64(H64), C103(H103), C103(H10A), C25A(H25A), C25B(H25B)
5.b Secondary CH2 refined with riding coordinates:
 Ge1A(H1AA,H1AB), Ge2A(H2AA,H2AB), B4A(H4AA,H4AB), Ge1B(H1BA,H1BB), P1A(H1AC,
 H1AD), P2A(H2AC,H2AD), P1B(H1BC,H1BD), P2B(H2BA,H2BB), B3D(H3DA,H3DB),
 C110(H11D,H11E), C111(H11F,H11G), B2A(H2AE,H2AF), B1A(H1AE,H1AF), Ge2B(H2BC,
 H2BD), B3B(H3BA,H3BB), Ge1C(H1CA,H1CB), B2B(H2BE,H2BF), B4C(H4CA,H4CB),
 B4B(H4BA,H4BB), Ge2C(H2CA,H2CB), Ge2D(H2DA,H2DB), P2C(H2CC,H2CD), B3A(H3AA,
 H3AB), B3C(H3CA,H3CB), B4D(H4DA,H4DB), P2D(H2DC,H2DD), B1B(H1BE,H1BF),
 B1C(H1CC,H1CD), P1C(H1CE,H1CF), B2C(H2CE,H2CF)
5.c Aromatic/amide H refined with riding coordinates:
 C54(H54), C53(H53), C71(H71), C30(H30), C29(H29), C69(H69), C80(H80),
 C81(H81), C18(H18), C70(H70), C3(H3), C6(H6), C20(H20), C19(H19), C2(H2),
 C8(H8), C86(H86), C57(H57), C33(H33), C44(H44), C84(H84), C7(H7), C42(H42),
 C35(H35), C34(H34), C96(H96), C43(H43), C98(H98), C85(H85), C59(H59), C58(H58),
  C97(H97)
5.d Idealised Me refined as rotating group:
 C75(H75A,H75B,H75C), C51(H51A,H51B,H51C), C78(H78A,H78B,H78C), C74(H74A,H74B,
 H74C), C47(H47A,H47B,H47C), C24(H24A,H24B,H24C), C77(H77A,H77B,H77C), C63(H63A,
 H63B,H63C), C48(H48A,H48B,H48C), C23(H23A,H23B,H23C), C90(H90A,H90B,H90C),
 C03E(H03A,H03B,H03C), C14(H14A,H14B,H14C), C89(H89A,H89B,H89C), C39A(H39A,H39B,
 H39C), C03I(H03D,H03E,H03F), C50(H50A,H50B,H50C), C15(H15A,H15B,H15C),
 C101(H10B,H10C,H10D), C102(H10E,H10F,H10G), C62(H62A,H62B,H62C), C12(H12A,H12B,
 H12C), C66(H66A,H66B,H66C), C26A(H26A,H26B,H26C), C93A(H93A,H93B,H93C),
 C65(H65A,H65B,H65C), C11(H11A,H11B,H11C), C92A(H92A,H92B,H92C), C38A(H38A,H38B,
 H38C), C27A(H27A,H27B,H27C), C107(H10H,H10I,H10J), C106(H10K,H10L,H10M),
 C38B(H38D,H38E,H38F), C39B(H39D,H39E,H39F), C27B(H27D,H27E,H27F), C26B(H26D,
 H26E,H26F), C105(H10N,H10O,H10P), C104(H10Q,H10R,H10S), C93B(H93D,H93E,H93F),
 C92B(H92D,H92E,H92F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 172 electrons were 
found in a volume of 984\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
1[CH2Cl2] per Asymmetric Unit 
which account for 168 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              24386
_shelx_hkl_checksum              18945
_shelx_fab_checksum              73981
_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 7.070
_oxdiff_exptl_absorpt_empirical_full_min 0.338