Synthesis of heteropnictogen ligands via PI transfer
Zimmermann, Lisa; Land, Michael A.; Riesinger, Christoph; Macdonald, Charles L. B.; Scheer, Manfred; Chemical Communications 61 (2025) 6973–6976; doi:10.1039/D5CC01162K

data_7134390
_publ_section_title
;
 Synthesis of heteropnictogen ligands via PI transfer
;
_journal_issue                   38
_journal_name_full               'Chemical Communications'
_journal_page_first              6973
_journal_page_last               6976
_journal_paper_doi               10.1039/D5CC01162K
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety
'C7 H5 Mo O2, C28 H20 As2 Mo4 O8 P2, C32 H12 B F24'
_chemical_formula_sum            'C67 H37 As2 B F24 Mo5 O10 P2'
_chemical_formula_weight         2160.25
_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             2024-12-19
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2024.12.18 svn.re4d4a415 for OlexSys, GUI svn.r7107)
;
_audit_update_record
;
2025-03-03 deposited with the CCDC.	2025-04-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 113.556(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.8305(5)
_cell_length_b                   20.6156(5)
_cell_length_c                   20.0687(6)
_cell_measurement_reflns_used    16403
_cell_measurement_temperature    123.01(10)
_cell_measurement_theta_max      31.9010
_cell_measurement_theta_min      2.2600
_cell_volume                     7141.5(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_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_temperature      123.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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     13.00  39.00   0.50    9.62    --    0.11  92.00-120.41   52
  2  \w    -19.00  47.00   0.50    9.62    --    0.11  19.00 120.00  132
  3  \w    -41.00  21.00   0.50    9.62    --    8.00 -25.00-127.32  124
  4  \w    -37.00   2.00   0.50    9.62    --   12.00 -30.00 -44.40   78
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0591
_diffrn_reflns_av_unetI/netI     0.0674
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            64302
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.508
_diffrn_reflns_theta_min         2.153
_exptl_absorpt_coefficient_mu    1.939
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.645
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.51a (Rigaku Oxford Diffraction, 2022)
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 red'
_exptl_crystal_density_diffrn    2.009
_exptl_crystal_description       block
_exptl_crystal_F_000             4184
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.045
_refine_diff_density_min         -0.904
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1411
_refine_ls_number_reflns         21767
_refine_ls_number_restraints     951
_refine_ls_restrained_S_all      1.205
_refine_ls_R_factor_all          0.0814
_refine_ls_R_factor_gt           0.0471
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0505P)^2^+4.8805P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1078
_refine_ls_wR_factor_ref         0.1192
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14946
_reflns_number_total             21767
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01162k3.cif
_cod_data_source_block           lz667_mo5pas_abs
_cod_depositor_comments
'Adding full bibliography for 7134388--7134391.cif.'
_cod_database_code               7134390
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C67 H37 O10 Mo5 P2 As2 B F24'
_cell_oxdiff_angle_alpha         90.042(2)
_cell_oxdiff_angle_beta          113.520(3)
_cell_oxdiff_angle_gamma         89.971(2)
_cell_oxdiff_length_a            18.8401(5)
_cell_oxdiff_length_b            20.6112(5)
_cell_oxdiff_length_c            20.0572(6)
_cell_oxdiff_measurement_reflns_used 16403
_cell_oxdiff_volume              7141.5(3)
_shelx_estimated_absorpt_t_max   0.830
_shelx_estimated_absorpt_t_min   0.643
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Mo1-O14
 3.1 with sigma of 0.04
 F14-C34 \\sim F27-C69
 with sigma of 0.02
 F16-C34 \\sim F26-C69
 with sigma of 0.02
 C8-C34 \\sim C8-C69
 with sigma of 0.02
 F19-C34 \\sim F25-C69
 with sigma of 0.02
 F14-F16 \\sim F27-F26
 with sigma of 0.04
 F14-C8 \\sim F27-C8
 with sigma of 0.04
 F14-F19 \\sim F27-F25
 with sigma of 0.04
 F16-C8 \\sim F26-C8
 with sigma of 0.04
 F16-F19 \\sim F26-F25
 with sigma of 0.04
 C8-F19 \\sim C8-F25
 with sigma of 0.04
 F18-C50 \\sim F29-C70
 with sigma of 0.02
 C18-C50 \\sim C18-C70
 with sigma of 0.02
 C50-F22 \\sim C70-F28
 with sigma of 0.02
 C50-F23 \\sim C70-F30
 with sigma of 0.02
 F18-C18 \\sim F29-C18
 with sigma of 0.04
 F18-F22 \\sim F29-F28
 with sigma of 0.04
 F18-F23 \\sim F29-F30
 with sigma of 0.04
 C18-F22 \\sim C18-F28
 with sigma of 0.04
 C18-F23 \\sim C18-F30
 with sigma of 0.04
 F22-F23 \\sim F28-F30
 with sigma of 0.04
 F13-C28 \\sim F31-C71
 with sigma of 0.02
 C2-C28 \\sim C2-C71
 with sigma of 0.02
 F17-C28 \\sim F32-C71
 with sigma of 0.02
 F20-C28 \\sim F33-C71
 with sigma of 0.02
 F13-C2 \\sim F31-C2
 with sigma of 0.04
 F13-F17 \\sim F31-F32
 with sigma of 0.04
 F13-F20 \\sim F31-F33
 with sigma of 0.04
 C2-F17 \\sim C2-F32
 with sigma of 0.04
 C2-F20 \\sim C2-F33
 with sigma of 0.04
 F17-F20 \\sim F32-F33
 with sigma of 0.04
 F7-C54 \\sim F36-C72
 with sigma of 0.02
 C27-C54 \\sim C27-C72
 with sigma of 0.02
 F21-C54 \\sim F35-C72
 with sigma of 0.02
 F24-C54 \\sim F34-C72
 with sigma of 0.02
 F7-C27 \\sim F36-C27
 with sigma of 0.04
 F7-F21 \\sim F36-F35
 with sigma of 0.04
 F7-F24 \\sim F36-F34
 with sigma of 0.04
 C27-F21 \\sim C27-F35
 with sigma of 0.04
 C27-F24 \\sim C27-F34
 with sigma of 0.04
 F21-F24 \\sim F35-F34
 with sigma of 0.04
 F9-C30 \\sim F37-C30
 with sigma of 0.02
 F10-C30 \\sim F39-C30
 with sigma of 0.02
 F12-C30 \\sim F38-C30
 with sigma of 0.02
 F8-C41 \\sim F42-C41
 with sigma of 0.02
 F11-C41 \\sim F40-C41
 with sigma of 0.02
 F15-C41 \\sim F41-C41
 with sigma of 0.02
 Mo4-C55 \\sim Mo4-C84
 with sigma of 0.02
 O10-C55 \\sim O9-C84
 with sigma of 0.02
 Mo7-C83 \\sim Mo7-C66
 with sigma of 0.02
 O11-C66 \\sim O8-C83
 with sigma of 0.02
 O7-C51 \\sim O14-C90
 with sigma of 0.02
 Mo2-C40 \\sim Mo2-C86
 with sigma of 0.04
 Mo2-C46 \\sim Mo2-C87
 with sigma of 0.04
 Mo2-C49 \\sim Mo2-C85
 with sigma of 0.04
 Mo2-C51 \\sim Mo2-C90
 with sigma of 0.04
 Mo2-C52 \\sim Mo2-C88
 with sigma of 0.04
 Mo2-C53 \\sim Mo2-C89
 with sigma of 0.04
 As1-C40 \\sim As1-C86
 with sigma of 0.04
 As1-C46 \\sim As1-C87
 with sigma of 0.04
 As1-C49 \\sim As1-C85
 with sigma of 0.04
 As1-C51 \\sim As1-C90
 with sigma of 0.04
 As1-C52 \\sim As1-C88
 with sigma of 0.04
 As1-C53 \\sim As1-C89
 with sigma of 0.04
 P1-C40 \\sim P1-C86
 with sigma of 0.04
 P1-C46 \\sim P1-C87
 with sigma of 0.04
 P1-C49 \\sim P1-C85
 with sigma of 0.04
 P1-C51 \\sim P1-C90
 with sigma of 0.04
 P1-C52 \\sim P1-C88
 with sigma of 0.04
 P1-C53 \\sim P1-C89
 with sigma of 0.04
 C35-C40 \\sim C35-C86
 with sigma of 0.04
 C35-C46 \\sim C35-C87
 with sigma of 0.04
 C35-C49 \\sim C35-C85
 with sigma of 0.04
 C35-C51 \\sim C35-C90
 with sigma of 0.04
 C35-C52 \\sim C35-C88
 with sigma of 0.04
 C35-C53 \\sim C35-C89
 with sigma of 0.04
 C40-C46 \\sim C86-C87
 with sigma of 0.04
 C40-C49 \\sim C86-C85
 with sigma of 0.04
 C40-C51 \\sim C86-C90
 with sigma of 0.04
 C40-C52 \\sim C86-C88
 with sigma of 0.04
 C40-C53 \\sim C86-C89
 with sigma of 0.04
 C46-C49 \\sim C87-C85
 with sigma of 0.04
 C46-C51 \\sim C87-C90
 with sigma of 0.04
 C46-C52 \\sim C87-C88
 with sigma of 0.04
 C46-C53 \\sim C87-C89
 with sigma of 0.04
 C49-C51 \\sim C85-C90
 with sigma of 0.04
 C49-C52 \\sim C85-C88
 with sigma of 0.04
 C49-C53 \\sim C85-C89
 with sigma of 0.04
 C51-C52 \\sim C90-C88
 with sigma of 0.04
 C51-C53 \\sim C90-C89
 with sigma of 0.04
 C52-C53 \\sim C88-C89
 with sigma of 0.04
 O3-C35 \\sim O14-C90
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F14 \\sim F16 \\sim F19 \\sim C34 \\sim F25 \\sim F26 \\sim F27 \\sim C69:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
O7 \\sim C40 \\sim C46 \\sim C49 \\sim C51 \\sim C52 \\sim C53 \\sim O14 \\sim
C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89 \\sim C90: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
F18 \\sim C50 \\sim F22 \\sim F23 \\sim F28 \\sim C70 \\sim F29 \\sim F30:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
F13 \\sim F17 \\sim F20 \\sim C28 \\sim F31 \\sim C71 \\sim F32 \\sim F33:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
F7 \\sim F21 \\sim F24 \\sim C54 \\sim F34 \\sim F35 \\sim F36 \\sim C72:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
F9 \\sim F10 \\sim F12 \\sim C30 \\sim F37 \\sim F38 \\sim F39: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
F8 \\sim F11 \\sim F15 \\sim C41 \\sim F40 \\sim F41 \\sim F42: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
C73 \\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim
C81 \\sim C82: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
C65 \\sim C83: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
C58 \\sim C84: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
As3 \\sim C67: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
As2 \\sim C68: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
Uanis(Mo8) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Sof(Mo5)=Sof(As2)=Sof(O8)=Sof(Mo7)=Sof(C56)=Sof(H56)=Sof(C57)=Sof(H57)=
 Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=Sof(C60)=Sof(H60)=Sof(O11)=Sof(C66)=
 Sof(O12)=Sof(C67)=Sof(C73)=Sof(H73)=Sof(C74)=Sof(H74)=Sof(C75)=Sof(H75)=
 Sof(C76)=Sof(H76)=Sof(C77)=Sof(H77)=Sof(C83)=1-FVAR(1)
 Sof(Mo4)=Sof(As3)=Sof(O9)=Sof(Mo6)=Sof(O10)=Sof(C55)=Sof(C61)=Sof(H61)=
 Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=Sof(C65)=Sof(H65)=
 Sof(O13)=Sof(C68)=Sof(C78)=Sof(H78)=Sof(C79)=Sof(H79)=Sof(C80)=Sof(H80)=
 Sof(C81)=Sof(H81)=Sof(C82)=Sof(H82)=Sof(C84)=FVAR(1)
 Sof(H29A)=Sof(H33A)=Sof(Mo8)=1-FVAR(2)
 Sof(Mo3)=Sof(H29)=Sof(H33)=FVAR(2)
 Sof(O14)=Sof(C85)=Sof(H85)=Sof(C86)=Sof(H86)=Sof(C87)=Sof(H87)=Sof(C88)=
 Sof(H88)=Sof(C89)=Sof(H89)=Sof(C90)=1-FVAR(3)
 Sof(O7)=Sof(C40)=Sof(H40)=Sof(C46)=Sof(H46)=Sof(C49)=Sof(H49)=Sof(C51)=
 Sof(C52)=Sof(H52)=Sof(C53)=Sof(H53)=FVAR(3)
 Fixed Sof: F7(0.48) F8(0.49) F9(0.81) F10(0.81) F11(0.49) F12(0.81) F13(0.68)
 F14(0.75) F15(0.49) F16(0.75) F17(0.68) F18(0.73) F19(0.75) F20(0.68)
 C28(0.68) C34(0.75) F21(0.48) C50(0.73) F22(0.73) F23(0.73) F24(0.48)
 C54(0.48) F25(0.25) F26(0.25) F27(0.25) C69(0.25) F28(0.27) C70(0.27)
 F29(0.27) F30(0.27) F31(0.32) C71(0.32) F32(0.32) F33(0.32) F34(0.52)
 F35(0.52) F36(0.52) C72(0.52) F37(0.19) F38(0.19) F39(0.19) F40(0.51)
 F41(0.51) F42(0.51)
 Fixed X: O14(0.738165) C90(0.747622)
 Fixed Y: O14(-0.179708) C90(-0.183105)
 Fixed Z: O14(1.288046) C90(1.235412)
5.a Ternary CH refined with riding coordinates:
 C29(H29), C29(H29A), C33(H33), C33(H33A)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C9(H9), C10(H10), C11(H11), C14(H14), C16(H16),
 C21(H21), C23(H23), C24(H24), C25(H25), C31(H31), C37(H37), C39(H39), C40(H40),
  C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C47(H47), C49(H49),
 C52(H52), C53(H53), C56(H56), C57(H57), C58(H58), C59(H59), C60(H60), C61(H61),
  C62(H62), C63(H63), C64(H64), C65(H65), C73(H73), C74(H74), C75(H75),
 C76(H76), C77(H77), C78(H78), C79(H79), C80(H80), C81(H81), C82(H82), C85(H85),
  C86(H86), C87(H87), C88(H88), C89(H89)
5.c Fitted pentagon refined as free rotating group:
 C56(C57,C58,C59,C60), C61(C62,C63,C64,C65), C85(C86,C87,C88,C89)
;
_shelx_res_checksum              92844
_shelx_hkl_checksum              53585
_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 3.887
_oxdiff_exptl_absorpt_empirical_full_min 0.429