Ring Expansion vs. Addition – Reactivity of a cyclo-P4 Complex Towards Pnictogenium Cations
Riesinger, Christoph; Erhard, Alexander; Scheer, Manfred; Chemical Communications  (2023) –; doi:10.1039/D3CC03369D

data_7131939
_publ_section_title
;
 Ring Expansion vs. Addition -- Reactivity of a cyclo-P4 Complex Towards
 Pnictogenium Cations
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC03369D
_journal_year                    2023
_chemical_formula_moiety         'C27 H43 As O2 P4 Ta, Al C16 F36 O4'
_chemical_formula_sum            'C46 H45 Al As F37 O6 P4 Ta'
_chemical_formula_weight         1803.55
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-03-15
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-07-10 deposited with the CCDC.	2023-07-26 downloaded from the CCDC.
;
_cell_angle_alpha                79.473(2)
_cell_angle_beta                 79.942(2)
_cell_angle_gamma                85.7070(10)
_cell_formula_units_Z            2
_cell_length_a                   10.4865(2)
_cell_length_b                   14.5949(3)
_cell_length_c                   21.4991(5)
_cell_measurement_reflns_used    43399
_cell_measurement_temperature    122.98(14)
_cell_measurement_theta_max      66.7530
_cell_measurement_theta_min      4.0260
_cell_volume                     3182.19(12)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_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      122.98(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 4.2047
_diffrn_detector_type            TitanS2
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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     12.00  37.00   1.00    1.00    --    0.00-121.00 -49.00   25
  2  \w     35.00  64.00   1.00    1.00    --    0.00-152.00 150.00   29
  3  \w     80.00 105.00   1.00    4.00    --   86.50 152.00-166.00   25
  4  \w     39.00  64.00   1.00    4.00    --   86.50-152.00 150.00   25
  5  \w     94.00 119.00   1.00    4.00    --   86.50 121.00  33.00   25
  6  \w     37.00  62.00   1.00    4.00    --   86.50-121.00 -49.00   25
  7  \w   -123.00 -96.00   1.00    4.00    --  -90.00 152.00-166.00   27
  8  \w   -146.00-121.00   1.00    4.00    --  -90.00-152.00 150.00   25
  9  \w    -79.00 -52.00   1.00    4.00    --  -90.00 121.00  33.00   27
 10  \w   -156.00-131.00   1.00    4.00    --  -90.00-121.00 -49.00   25
 11  \w     40.00  65.00   1.00    1.00    --    0.00 178.00   0.00   25
 12  \w    -42.00  28.00   1.00    1.00    --    0.00 -77.00-120.00   70
 13  \w    -42.00  15.00   1.00    1.00    --    0.00 -77.00 150.00   57
 14  \w    -31.00  20.00   1.00    1.00    --    0.00  77.00  90.00   51
 15  \w    -22.00  16.00   1.00    1.00    --    0.00  77.00   0.00   38
 16  \w    -78.00 -37.00   1.00    4.00    --  -90.00  77.00 120.00   41
 17  \w    -94.00 -47.00   1.00    4.00    --  -90.00  30.00-150.00   47
 18  \w   -171.00-105.00   1.00    4.00    --  -90.00 -94.00  60.00   66
 19  \w   -109.00 -67.00   1.00    4.00    --  -90.00 125.00  90.00   42
 20  \w   -107.00 -28.00   1.00    4.00    --  -90.00 125.00 -60.00   79
 21  \w    -90.00 -23.00   1.00    4.00    --  -90.00 116.00   4.26   67
 22  \w    -40.00 -12.00   1.00    4.00    --  -90.00 101.00 100.44   28
 23  \w   -150.00-103.00   1.00    4.00    --  -90.00 -61.00  60.00   47
 24  \w   -111.00 -81.00   1.00    4.00    --  -90.00 125.00-180.00   30
 25  \w   -103.00 -53.00   1.00    4.00    --  -90.00  77.00-120.00   50
 26  \w   -134.00 -97.00   1.00    4.00    --  -90.00-125.00  60.00   37
 27  \w    -67.00 -25.00   1.00    4.00    --  -90.00  77.00  30.00   42
 28  \w   -136.00 -67.00   1.00    4.00    --  -90.00 -45.00 120.00   69
 29  \w   -159.00-102.00   1.00    4.00    --  -90.00 -61.00 -60.00   57
 30  \w   -159.00-132.00   1.00    4.00    --  -90.00 -45.00-180.00   27
 31  \w    -94.00 -69.00   1.00    4.00    --  -90.00 -45.00-180.00   25
 32  \w   -107.00 -41.00   1.00    4.00    --  -90.00 125.00 150.00   66
 33  \w    -83.00 -38.00   1.00    4.00    --  -90.00 148.00 177.97   45
 34  \w    -90.00 -48.00   1.00    4.00    --  -90.00 101.00 100.44   42
 35  \w   -103.00 -32.00   1.00    4.00    --  -90.00 101.00  66.33   71
 36  \w   -108.00 -71.00   1.00    4.00    --  -90.00 137.00  87.42   37
 37  \w   -114.00 -89.00   1.00    4.00    --  -90.00  45.00  30.00   25
 38  \w   -104.00 -77.00   1.00    4.00    --  -90.00  45.00 120.00   27
 39  \w    -76.00 -43.00   1.00    4.00    --  -90.00  45.00 120.00   33
 40  \w    -91.00 -64.00   1.00    4.00    --  -90.00  47.00 -70.04   27
 41  \w    -90.00 -49.00   1.00    4.00    --  -90.00 125.00-120.00   41
 42  \w    -97.00 -64.00   1.00    4.00    --  -90.00 -65.00 -48.40   33
 43  \w   -121.00 -89.00   1.00    4.00    --  -90.00  77.00  30.00   32
 44  \w   -153.00-124.00   1.00    4.00    --  -90.00 -65.00 -48.40   29
 45  \w   -152.00-125.00   1.00    4.00    --  -90.00 -45.00  90.00   27
 46  \w   -103.00 -78.00   1.00    4.00    --  -90.00  99.00 -12.79   25
 47  \w    -67.00 -40.00   1.00    4.00    --  -90.00  99.00 -12.79   27
 48  \w   -107.00 -59.00   1.00    4.00    --  -90.00 100.00 133.64   48
 49  \w    -46.00 -21.00   1.00    4.00    --  -90.00  47.00 -70.04   25
 50  \w    -77.00 -50.00   1.00    4.00    --  -90.00  15.00 -60.00   27
 51  \w   -145.00-120.00   1.00    4.00    --  -90.00-125.00 -30.00   25
 52  \w   -161.00-123.00   1.00    4.00    --  -90.00-125.00 120.00   38
 53  \w   -170.00-105.00   1.00    4.00    --  -90.00 -94.00-180.00   65
 54  \w   -164.00-105.00   1.00    4.00    --  -90.00 -94.00  30.00   59
 55  \w    -97.00 -70.00   1.00    4.00    --  -90.00 125.00 -30.00   27
 56  \w   -129.00 -97.00   1.00    4.00    --  -90.00 148.00 177.97   32
 57  \w   -150.00 -97.00   1.00    4.00    --  -90.00 -61.00 -30.00   53
 58  \w   -108.00 -83.00   1.00    4.00    --  -90.00 114.00 -52.85   25
 59  \w    -87.00 -62.00   1.00    4.00    --  -90.00  61.00-120.00   25
 60  \w   -108.00 -83.00   1.00    4.00    --  -90.00  61.00  60.00   25
 61  \w   -121.00 -89.00   1.00    4.00    --  -90.00 -45.00   0.00   32
 62  \w   -129.00-104.00   1.00    4.00    --  -90.00 -70.00  10.79   25
 63  \w    -94.00 -45.00   1.00    4.00    --  -90.00  77.00 -90.00   49
 64  \w    -93.00 -68.00   1.00    4.00    --  -90.00  77.00  90.00   25
 65  \w   -125.00 -66.00   1.00    4.00    --  -90.00  15.00-180.00   59
 66  \w    -94.00 -68.00   1.00    4.00    --  -90.00  15.00   0.00   26
 67  \w   -157.00-130.00   1.00    4.00    --  -90.00 -45.00   0.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dualflex, TitanS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0136659000
_diffrn_orient_matrix_UB_12      -0.0025844000
_diffrn_orient_matrix_UB_13      0.0728126000
_diffrn_orient_matrix_UB_21      0.1317033000
_diffrn_orient_matrix_UB_22      0.0454001000
_diffrn_orient_matrix_UB_23      -0.0101050000
_diffrn_orient_matrix_UB_31      -0.0690833000
_diffrn_orient_matrix_UB_32      0.0973727000
_diffrn_orient_matrix_UB_33      -0.0074440000
_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  0.0361
_diffrn_reflns_av_unetI/netI     0.0227
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            55899
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        66.937
_diffrn_reflns_theta_max         66.937
_diffrn_reflns_theta_min         3.426
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.282
_exptl_absorpt_correction_T_max  0.908
_exptl_absorpt_correction_T_min  0.216
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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 intense orange'
_exptl_crystal_density_diffrn    1.882
_exptl_crystal_description       block
_exptl_crystal_F_000             1762
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.196
_exptl_crystal_size_min          0.124
_refine_diff_density_max         3.411
_refine_diff_density_min         -0.983
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1268
_refine_ls_number_reflns         11297
_refine_ls_number_restraints     404
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0392
_refine_ls_R_factor_gt           0.0389
_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^)+(0.0564P)^2^+7.9316P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1024
_refine_ls_wR_factor_ref         0.1026
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11169
_reflns_number_total             11297
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc03369d2.cif
_cod_data_source_block           cr888_cua_abs
_cod_database_code               7131939
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C50H53O6AlF37P4AsTa
_shelx_estimated_absorpt_t_max   0.510
_shelx_estimated_absorpt_t_min   0.246
_reflns_odcompleteness_completeness 99.12
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Restrained distances
 C43-C11
 1.53 with sigma of 0.02
 C49-C9
 1.53 with sigma of 0.02
 C39A-F36A
 1.33 with sigma of 0.02
 F17A-C39A = F7A-C39A
 1.33 with sigma of 0.02
 O3-C11
 2.4 with sigma of 0.04
 F17A-F7A
 2.2 with sigma of 0.04
 F7A-F36A
 2.2 with sigma of 0.04
 F36A-F17A
 2.2 with sigma of 0.04
2. Uiso/Uaniso restraints and constraints
C3 \\sim C33: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
C47 \\sim C2: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
C11 \\sim C35: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
C45 \\sim C37: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
F3 \\sim F16: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
C43 \\sim C29 \\sim C37 \\sim C45 \\sim C23 \\sim C41 \\sim C11 \\sim C35:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
C47 \\sim C2 \\sim C5 \\sim C25 \\sim C33 \\sim C3 \\sim C9 \\sim C49: within
1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
F19 \\sim F32: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
F37 \\sim F24 \\sim F42 \\sim F39 \\sim F41 \\sim F48: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
F5 \\sim F44: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
F46 \\sim F46A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
C39A \\sim C39: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
C19A \\sim C19 \\sim F30A \\sim F30 \\sim F2A \\sim F2 \\sim F40A \\sim F40:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
F56A \\sim F56 \\sim C21A \\sim F35A \\sim C21 \\sim F10 \\sim F35: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
F26A \\sim F26: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
3. Others
 Sof(F9)=Sof(F37)=Sof(F19)=Sof(F39)=Sof(F5)=Sof(F41)=Sof(F21)=Sof(F43)=Sof(O3)=
 Sof(F11)=Sof(C43)=Sof(C11)=Sof(C45)=Sof(C23)=1-FVAR(1)
 Sof(F12)=Sof(F24)=Sof(F32)=Sof(F42)=Sof(F44)=Sof(F48)=Sof(F50)=Sof(F15)=
 Sof(O5)=Sof(F31)=Sof(C29)=Sof(C35)=Sof(C37)=Sof(C41)=FVAR(1)
 Sof(F45)=Sof(F23)=Sof(F47)=Sof(F3)=Sof(F49)=Sof(F25)=Sof(F51)=Sof(O7)=
 Sof(F13)=Sof(F53)=Sof(C47)=Sof(C3)=Sof(C49)=Sof(C25)=1-FVAR(2)
 Sof(F1)=Sof(F4)=Sof(F14)=Sof(F16)=Sof(F34)=Sof(F52)=Sof(F54)=Sof(O2)=Sof(F29)=
 Sof(F33)=Sof(C2)=Sof(C33)=Sof(C9)=Sof(C5)=FVAR(2)
 Sof(F6A)=Sof(F28A)=Sof(F20A)=Sof(F18A)=Sof(F46A)=Sof(F22A)=Sof(F26A)=Sof(F8A)=
 Sof(F38A)=1-FVAR(3)
 Sof(F6)=Sof(F8)=Sof(F18)=Sof(F20)=Sof(F22)=Sof(F26)=Sof(F28)=Sof(F38)=
 Sof(F46)=FVAR(3)
 Sof(F30A)=Sof(F36A)=Sof(F40A)=Sof(F56A)=Sof(F7A)=Sof(F2A)=Sof(F17A)=Sof(F35A)=
 Sof(C19A)=Sof(C39A)=Sof(C21A)=1-FVAR(4)
 Sof(F30)=Sof(F36)=Sof(F40)=Sof(F56)=Sof(F7)=Sof(F2)=Sof(F17)=Sof(F35)=
 Sof(C19)=Sof(C39)=Sof(C21)=FVAR(4)
 Fixed X: C2(0.170609)
 Fixed Y: C2(-0.04276)
 Fixed Z: C2(0.81342)
4.a Ternary CH refined with riding coordinates:
 C32(H32), C44(H44)
4.b Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C42(H42A,H42B), C36(H36A,H36B), C46(H46A,H46B), C38(H38A,
 H38B), C40(H40A,H40B), C54(H54A,H54B), C48(H48A,H48B), C50(H50A,H50B),
 C52(H52A,H52B)
4.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C10(H10)
4.d Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C14(H14A,H14B,
 H14C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 48 electrons were 
found in a volume of 224\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
0.4[C6H4F2] per Asymmetric Unit 
which account for 46 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              12250
_shelx_hkl_checksum              7259
_shelx_fab_checksum              92893
_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 1.731
_oxdiff_exptl_absorpt_empirical_full_min 0.685