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_7134391
_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         'C35 H25 Mo5 O10 P2 Sb2, C32 H12 B F24'
_chemical_formula_sum            'C67 H37 B F24 Mo5 O10 P2 Sb2'
_chemical_formula_weight         2253.91
_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             2025-01-16
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2025.01.10 svn.r16582094 for OlexSys, GUI svn.r7115)
;
_audit_update_record
;
2025-03-03 deposited with the CCDC.	2025-04-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 113.3230(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.9232(2)
_cell_length_b                   20.7180(2)
_cell_length_c                   20.1171(2)
_cell_measurement_reflns_used    52717
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      74.9490
_cell_measurement_theta_min      2.5260
_cell_volume                     7242.47(14)
_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_environment      N~2~
_diffrn_ambient_temperature      123.00(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 0.998
_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     66.00 120.00   0.50    0.17    --   79.75  23.00-161.24  108
  2  \w    101.00 126.00   0.50    0.17    --   79.75  23.00-128.49   50
  3  \w     81.00 120.00   0.50    0.17    --   79.75  21.00-134.48   78
  4  \w     49.00 103.00   0.50    0.17    --   63.24  15.00-150.00  108
  5  \w     78.00 108.00   0.50    0.17    --   63.24  15.00 -90.00   60
  6  \w     48.00  93.00   0.50    0.17    --   79.75   4.00-149.22   90
  7  \w     68.00 110.00   0.50    0.17    --   79.75   1.00 -34.13   84
  8  \w     74.00 100.00   0.50    0.17    --   79.75  23.00 130.22   52
  9  \w     82.00 112.00   0.50    0.17    --   79.75  22.00 147.43   60
 10  \w     54.00  85.00   0.50    0.17    --   79.75  19.00 134.64   62
 11  \w     44.00  69.00   0.50    0.17    --   79.75  -4.00 -31.66   50
 12  \w     62.00  98.00   0.50    0.17    --   79.75-128.00-106.37   72
 13  \w     43.00  68.00   0.50    0.17    --   63.24-146.00-118.00   50
 14  \w     44.00  69.00   0.50    0.17    --   75.99-126.00  48.00   50
 15  \w     31.00  75.00   0.50    0.17    --   63.24-126.00  48.00   88
 16  \w     41.00 110.00   0.50    0.17    --   79.75-129.00 124.34  138
 17  \w     44.00  69.00   0.50    0.17    --   75.65-126.00  48.00   50
 18  \w     27.00  81.00   0.50    0.17    --   63.24-125.00 -60.00  108
 19  \w     43.00 106.00   0.50    0.17    --   79.75-124.00  79.05  126
 20  \w     52.00  77.00   0.50    0.17    --   75.65 -95.00 120.00   50
 21  \w     39.00  78.00   0.50    0.17    --   79.75-118.00  62.55   78
 22  \w     46.00  71.00   0.50    0.17    --   63.24 -95.00 -60.00   50
 23  \w     31.00  57.00   0.50    0.17    --   63.24 -95.00-150.00   52
 24  \w     40.00  81.00   0.50    0.17    --   79.75  -4.00 -95.38   82
 25  \w     66.00  91.00   0.50    0.17    --   75.65 146.00 -67.00   50
 26  \w    -65.00 -40.00   0.50    0.17    --  -63.74 146.00 -67.00   50
 27  \w    -99.00 -74.00   0.50    0.17    --  -73.72 146.00 -67.00   50
 28  \w   -101.00 -76.00   0.50    0.17    --  -76.64 146.00 -67.00   50
 29  \w   -107.00 -73.00   0.50    0.17    --  -78.25 127.00 -35.01   68
 30  \w   -113.00 -87.00   0.50    0.17    --  -78.25 136.00  44.06   52
 31  \w    -70.00 -40.00   0.50    0.17    --  -73.72 125.00   0.00   60
 32  \w   -108.00 -82.00   0.50    0.17    --  -78.25 129.00  89.02   52
 33  \w    -98.00 -61.00   0.50    0.17    --  -73.72 126.00 125.00   74
 34  \w    -57.00 -32.00   0.50    0.17    --  -63.74 126.00 125.00   50
 35  \w    -70.00 -45.00   0.50    0.17    --  -76.64 126.00 125.00   50
 36  \w   -100.00 -61.00   0.50    0.17    --  -78.25 116.00 147.87   78
 37  \w    -76.00 -44.00   0.50    0.17    --  -78.25 113.00  86.61   64
 38  \w    -97.00 -60.00   0.50    0.17    --  -78.25 113.00  96.02   74
 39  \w    -88.00 -63.00   0.50    0.17    --  -78.25  98.00  92.46   50
 40  \w    -81.00 -44.00   0.50    0.17    --  -78.25  98.00  79.57   74
 41  \w    -80.00 -42.00   0.50    0.17    --  -78.25  97.00 179.52   76
 42  \w    -72.00 -46.00   0.50    0.17    --  -78.25 121.00  44.15   52
 43  \w    -81.00 -56.00   0.50    0.17    --  -78.25  87.00 101.94   50
 44  \w    -89.00 -63.00   0.50    0.17    --  -78.25 101.00  40.77   52
 45  \w    -97.00 -72.00   0.50    0.17    --  -73.72 125.00   0.00   50
 46  \w    -77.00 -52.00   0.50    0.17    --  -78.25  90.00 -59.72   50
 47  \w    -64.00 -39.00   0.50    0.17    --  -78.25  62.00  23.36   50
 48  \w    -61.00 -36.00   0.50    0.17    --  -78.25  56.00   5.38   50
 49  \w    -60.00 -35.00   0.50    0.17    --  -78.25  56.00 174.70   50
 50  \w    -61.00 -36.00   0.50    0.17    --  -78.25  56.00 128.87   50
 51  \w   -108.00 -35.00   0.50    0.17    --  -63.74 -15.00   0.00  146
 52  \w   -107.00 -77.00   0.50    0.17    --  -76.64-126.00  48.00   60
 53  \w   -110.00 -85.00   0.50    0.17    --  -73.72-146.00-118.00   50
 54  \w   -112.00 -87.00   0.50    0.17    --  -76.64-146.00-118.00   50
;
_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      -0.0508065000
_diffrn_orient_matrix_UB_12      -0.0040169000
_diffrn_orient_matrix_UB_13      -0.0815376000
_diffrn_orient_matrix_UB_21      -0.0024593000
_diffrn_orient_matrix_UB_22      -0.0740709000
_diffrn_orient_matrix_UB_23      0.0055606000
_diffrn_orient_matrix_UB_31      -0.0725973000
_diffrn_orient_matrix_UB_32      0.0052773000
_diffrn_orient_matrix_UB_33      0.0165736000
_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  0.0439
_diffrn_reflns_av_unetI/netI     0.0275
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            112565
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.163
_diffrn_reflns_theta_min         2.543
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    14.185
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.654
_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    2.067
_exptl_crystal_description       block
_exptl_crystal_F_000             4328
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.182
_refine_diff_density_min         -1.091
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1303
_refine_ls_number_reflns         14709
_refine_ls_number_restraints     592
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0508
_refine_ls_R_factor_gt           0.0419
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0622P)^2^+11.8346P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1129
_refine_ls_wR_factor_ref         0.1181
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12354
_reflns_number_total             14709
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01162k3.cif
_cod_data_source_block           lz747_cu1_abs
_cod_depositor_comments
'Adding full bibliography for 7134388--7134391.cif.'
_cod_original_cell_volume        7242.46(14)
_cod_database_code               7134391
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C67 H37 O10 Mo3 P2 Sb2 B F24'
_cell_oxdiff_angle_alpha         90.0194(11)
_cell_oxdiff_angle_beta          113.3168(14)
_cell_oxdiff_angle_gamma         90.0170(11)
_cell_oxdiff_length_a            18.9247(3)
_cell_oxdiff_length_b            20.7155(2)
_cell_oxdiff_length_c            20.1170(3)
_cell_oxdiff_measurement_reflns_used 52716
_cell_oxdiff_volume              7242.48(17)
_shelx_estimated_absorpt_t_max   0.483
_shelx_estimated_absorpt_t_min   0.210
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 O10-C67
 1.2 with sigma of 0.02
 Mo6-C69
 2 with sigma of 0.02
 O11-C69
 1.2 with sigma of 0.02
 F31-C23 = F33-C23 = F32-C23
 1.33 with sigma of 0.02
 C75-C76 = C75-C79 = C76-C77 = C77-C78 = C78-C79
 1.42 with sigma of 0.02
 Mo5-C67
 2 with sigma of 0.02
 C70-C71 = C70-C74 = C71-C72 = C72-C73 = C73-C74
 1.42 with sigma of 0.02
 O13-C80
 1.2 with sigma of 0.02
 Mo4-C80
 2 with sigma of 0.02
 F25-C34 = F26-C34 = F27-C34
 1.33 with sigma of 0.02
 F30-C26 = F28-C26 = F29-C26
 1.33 with sigma of 0.02
 F35-C45 = F34-C45 = F36-C45
 1.33 with sigma of 0.02
 F35-C45 = F36-C45 = F34-C45
 1.33 with sigma of 0.02
 F23A-C41 = F21A-C41 = F24A-C41
 1.33 with sigma of 0.02
 F32-F33
 2.2 with sigma of 0.04
 F33-F31
 2.2 with sigma of 0.04
 C75-C77 = C75-C78 = C76-C78 = C77-C79
 2.29 with sigma of 0.04
 C70-C72 = C70-C73 = C71-C73 = C72-C74
 2.29 with sigma of 0.04
 F25-F26
 2.2 with sigma of 0.04
 F26-F27
 2.2 with sigma of 0.04
 F27-F25
 2.2 with sigma of 0.04
 F30-F28
 2.2 with sigma of 0.04
 F28-F29
 2.2 with sigma of 0.04
 F29-F30
 2.2 with sigma of 0.04
 F31-F32
 2.2 with sigma of 0.04
 F34-F36
 2.2 with sigma of 0.04
 F36-F35
 2.2 with sigma of 0.04
 F35-F34
 2.2 with sigma of 0.04
 F21A-F24A
 2.2 with sigma of 0.04
 F24A-F23A
 2.2 with sigma of 0.04
 F23A-F21A
 2.2 with sigma of 0.04
 C76-C77 \\sim C75-C76 \\sim C77-C78 \\sim C75-C79 \\sim C78-C79
 with sigma of 0.02
 C77-C79 \\sim C76-C78 \\sim C75-C78 \\sim C75-C77 \\sim C76-C79
 with sigma of 0.04
 C71-C72 \\sim C70-C71 \\sim C72-C73 \\sim C70-C74 \\sim C73-C74
 with sigma of 0.02
 C72-C74 \\sim C71-C73 \\sim C70-C73 \\sim C70-C72 \\sim C71-C74
 with sigma of 0.04
3. Restrained planarity
 C75, C76, C77, C78, C79
 with sigma of 0.1
 C70, C71, C72, C73, C74
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C69 \\sim Sb2: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
F8 \\sim F9 \\sim F10 \\sim C23 \\sim F31 \\sim F32 \\sim F33: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C67 \\sim Sb3: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C54 \\sim C75: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
F12 \\sim F18 \\sim F20 \\sim C34 \\sim F25 \\sim F26 \\sim F27: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
F16 \\sim F17 \\sim F19 \\sim C26 \\sim F28 \\sim F29 \\sim F30: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
F7 \\sim F15 \\sim F22 \\sim C45 \\sim F34 \\sim F35 \\sim F36: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
F21 \\sim F23 \\sim C41 \\sim F24 \\sim F21A \\sim F24A \\sim F23A: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
Uanis(C69) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
5. Rigid body (RIGU) restrains
 C75, C76, C77, C78, C79
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C70, C71, C72, C73, C74
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(Mo6)=Sof(Sb3)=Sof(O11)=Sof(O12)=Sof(C68)=Sof(C69)=Sof(C70)=Sof(H70)=
 Sof(C71)=Sof(H71)=Sof(C72)=Sof(H72)=Sof(C73)=Sof(H73)=Sof(C74)=Sof(H74)=
 Sof(C75)=Sof(H75)=Sof(C76)=Sof(H76)=Sof(C77)=Sof(H77)=Sof(C78)=Sof(H78)=
 Sof(C79)=Sof(H79)=Sof(O13)=Sof(C80)=Sof(Mo7)=Sof(P3)=1-FVAR(1)
 Sof(Mo4)=Sof(Sb2)=Sof(Mo5)=Sof(P2)=Sof(C54)=Sof(O8)=Sof(O9)=Sof(C56)=Sof(H56)=
 Sof(C57)=Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=Sof(C60)=Sof(H60)=
 Sof(C61)=Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=Sof(C65)=
 Sof(H65)=Sof(C66)=Sof(H66)=Sof(C67)=Sof(O10)=FVAR(1)
 Sof(F25)=Sof(F26)=Sof(F27)=1-FVAR(2)
 Sof(F12)=Sof(F18)=Sof(F20)=FVAR(2)
 Sof(F28)=Sof(F29)=Sof(F30)=1-FVAR(3)
 Sof(F16)=Sof(F17)=Sof(F19)=FVAR(3)
 Sof(F31)=Sof(F32)=Sof(F33)=1-FVAR(4)
 Sof(F8)=Sof(F9)=Sof(F10)=FVAR(4)
 Sof(F34)=Sof(F35)=Sof(F36)=1-FVAR(5)
 Sof(F7)=Sof(F15)=Sof(F22)=FVAR(5)
 Sof(F21A)=Sof(F24A)=Sof(F23A)=1-FVAR(6)
 Sof(F21)=Sof(F23)=Sof(F24)=FVAR(6)
7.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C5(H5), C9(H9), C12(H12), C13(H13), C15(H15), C19(H19),
 C20(H20), C22(H22), C24(H24), C29(H29), C32(H32), C33(H33), C36(H36), C38(H38),
  C39(H39), C42(H42), C43(H43), C46(H46), C48(H48), C49(H49), C50(H50),
 C51(H51), C52(H52), C53(H53), C55(H55), C56(H56), C57(H57), C58(H58), C59(H59),
  C60(H60), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66), C70(H70),
 C71(H71), C72(H72), C73(H73), C74(H74), C75(H75), C76(H76), C77(H77), C78(H78),
  C79(H79)
7.b Fitted pentagon refined as free rotating group:
 C56(C57,C58,C59,C60), C62(C63,C64,C65,C66)
;
_shelx_res_checksum              52977
_shelx_hkl_checksum              12449
_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 2.403
_oxdiff_exptl_absorpt_empirical_full_min 0.684