Antimony(+5) Ion Induced Tunable Intramolecular Charge Transfer in Hypervalent Antimony(V) Porphyrins
Holzer, Noah; Sharma, Jatan K.; Peterson, Steven; Bayard, Brandon J.; Nesterov, Vladimir; Karr, Paul A.; D'Souza, Francis; Poddutoori, Prashanth K.; Dalton Transactions  (2022) –; doi:10.1039/D2DT00675H

data_7709786
_publ_section_title
;
 Antimony(+5) Ion Induced Tunable Intramolecular Charge Transfer in
 Hypervalent Antimony(V) Porphyrins
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00675H
_journal_year                    2022
_chemical_formula_moiety         'C50 H42 N4 O6 Sb, F6 P, 2(C3 H6 O)'
_chemical_formula_sum            'C56 H54 F6 N4 O8 P Sb'
_chemical_formula_weight         1177.75
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-22
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_audit_update_record
;
2021-12-26 deposited with the CCDC.	2022-03-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 132.011(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   30.6284(7)
_cell_length_b                   10.75280(10)
_cell_length_c                   20.9262(5)
_cell_measurement_reflns_used    30397
_cell_measurement_temperature    219.99(11)
_cell_measurement_theta_max      79.8850
_cell_measurement_theta_min      2.8950
_cell_volume                     5120.8(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (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      219.99(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.991
_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     51.00  76.00   0.50    0.50    --   46.88  55.00   4.00   50
  2  \w     93.00 119.00   0.50    0.50    --   46.88  77.00 -30.00   52
  3  \w     43.00 112.00   0.50    0.50    --   46.88  37.00 150.00  138
  4  \w    109.00 145.00   0.50    0.50    --  113.25 125.00-120.00   72
  5  \w    -29.00   4.00   0.50    0.50    --   46.88 -19.00-120.00   66
  6  \w    -26.00  53.00   0.50    0.50    --   46.88 -55.00-138.00  158
  7  \w     91.00 160.00   0.50    0.50    --  113.25  77.00  30.00  138
  8  \w     90.00 126.00   0.50    0.50    --  113.25  77.00  60.00   72
  9  \w    134.00 174.00   0.50    0.50    --  113.25  77.00  60.00   80
 10  \w     90.00 143.00   0.50    0.50    --  113.25  77.00 120.00  106
 11  \w     96.00 172.00   0.50    0.50    --  113.25  61.00 120.00  152
 12  \w    119.00 144.00   0.50    0.50    --  113.25  77.00  90.00   50
 13  \w     90.00 117.00   0.50    0.50    --  113.25  77.00  90.00   54
 14  \w     97.00 142.00   0.50    0.50    --  113.25  61.00 150.00   90
 15  \w     98.00 177.00   0.50    0.50    --  113.25  61.00  90.00  158
 16  \w     98.00 166.00   0.50    0.50    --  113.25  61.00  60.00  136
 17  \w    100.00 177.00   0.50    0.50    --  113.25  55.00   4.00  154
 18  \w    118.00 144.00   0.50    0.50    --  113.25  45.00 150.00   52
 19  \w    128.00 161.00   0.50    0.50    --  113.25  61.00 -30.00   66
 20  \w    109.00 147.00   0.50    0.50    --  113.25  61.00 -60.00   76
 21  \w    122.00 175.00   0.50    0.50    --  113.25  45.00 -90.00  106
 22  \w    130.00 170.00   0.50    0.50    --  113.25  61.00-180.00   80
 23  \w    101.00 152.00   0.50    0.50    --  113.25  30.00  60.00  102
 24  \w    132.00 158.00   0.50    0.50    --  113.25  15.00 120.00   52
 25  \w     41.00  84.00   0.50    0.50    --  113.25 -77.00 -60.00   86
 26  \w     43.00  96.00   0.50    0.50    --  113.25 -77.00-120.00  106
 27  \w     50.00  82.00   0.50    0.50    --  113.25 -77.00-150.00   64
 28  \w     41.00  66.00   0.50    0.50    --  113.25 -77.00-180.00   50
 29  \w     41.00  87.00   0.50    0.50    --  113.25 -77.00 -90.00   92
 30  \w     42.00  92.00   0.50    0.50    --  113.25 -77.00 -30.00  100
 31  \w     58.00  96.00   0.50    0.50    --  113.25 -77.00  30.00   76
 32  \w     47.00  98.00   0.50    0.50    --  113.25 -94.00  90.00  102
 33  \w     59.00 112.00   0.50    0.50    --  113.25-125.00   0.00  106
 34  \w     46.00  78.00   0.50    0.50    --  113.25-125.00 -90.00   64
 35  \w     43.00  93.00   0.50    0.50    --  113.25-125.00 -60.00  100
 36  \w     56.00 112.00   0.50    0.50    --  113.25-125.00-120.00  112
 37  \w     45.00 112.00   0.50    0.50    --  113.25-125.00-150.00  134
 38  \w     86.00 111.00   0.50    0.50    --  113.25-125.00-180.00   50
 39  \w     42.00  69.00   0.50    0.50    --  113.25-125.00-180.00   54
 40  \w     44.00  83.00   0.50    0.50    --  113.25 -94.00  30.00   78
 41  \w   -121.00 -90.00   0.50    0.50    --  -46.88-125.00  30.00   62
 42  \w   -106.00 -80.00   0.50    0.50    --  -91.75 -61.00 120.00   52
 43  \w   -111.00 -85.00   0.50    0.50    --  -91.75 -61.00  90.00   52
 44  \w   -103.00 -74.00   0.50    0.50    --  -91.75 -61.00  60.00   58
 45  \w   -104.00 -78.00   0.50    0.50    --  -91.75 -55.00  97.36   52
 46  \w   -103.00 -78.00   0.50    0.50    --  -91.75 -45.00 120.00   50
 47  \w   -164.00-116.00   0.50    0.50    --  -91.75 -61.00  60.00   96
 48  \w   -164.00-138.00   0.50    0.50    --  -91.75 -30.00 120.00   52
 49  \w   -107.00 -81.00   0.50    0.50    --  -91.75 -30.00 120.00   52
 50  \w   -113.00 -87.00   0.50    0.50    --  -91.75 -55.00-138.00   52
 51  \w   -163.00-137.00   0.50    0.50    --  -91.75 -55.00-138.00   52
 52  \w   -119.00 -60.00   0.50    0.50    --  -46.88 -55.00-138.00  118
 53  \w    -60.00  25.00   0.50    0.50    --  -46.88  55.00   4.00  170
 54  \w    -41.00 -16.00   0.50    0.50    --  -91.75  30.00 150.00   50
 55  \w    -49.00 -19.00   0.50    0.50    --  -91.75  55.00   4.00   60
 56  \w    -43.00 -18.00   0.50    0.50    --  -91.75  30.00   0.00   50
 57  \w    -44.00 -16.00   0.50    0.50    --  -91.75  30.00-150.00   56
 58  \w    -60.00 -24.00   0.50    0.50    --  -91.75  45.00-180.00   72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0573228000
_diffrn_orient_matrix_UB_12      0.0381230000
_diffrn_orient_matrix_UB_13      -0.0221619000
_diffrn_orient_matrix_UB_21      -0.0350848000
_diffrn_orient_matrix_UB_22      -0.0874479000
_diffrn_orient_matrix_UB_23      -0.0784791000
_diffrn_orient_matrix_UB_31      0.0082781000
_diffrn_orient_matrix_UB_32      -0.1068272000
_diffrn_orient_matrix_UB_33      0.0562640000
_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  0.0376
_diffrn_reflns_av_unetI/netI     0.0200
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            40217
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.336
_diffrn_reflns_theta_min         3.885
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.277
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70079
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.120a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_density_diffrn    1.528
_exptl_crystal_description       plate
_exptl_crystal_F_000             2408
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.783
_refine_diff_density_min         -1.162
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     381
_refine_ls_number_reflns         5552
_refine_ls_number_restraints     170
_refine_ls_restrained_S_all      1.287
_refine_ls_R_factor_all          0.0396
_refine_ls_R_factor_gt           0.0369
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0646P)^2^+7.9688P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1038
_refine_ls_wR_factor_ref         0.1060
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5120
_reflns_number_total             5552
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00675h2.cif
_cod_data_source_block           str0792lt220kcu34mm_auto
_cod_original_cell_volume        5120.8(3)
_cod_database_code               7709786
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H42 N4 O6 F6 PSb'
_shelx_estimated_absorpt_t_max   0.858
_shelx_estimated_absorpt_t_min   0.709
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 P1-F1 = P1-F2 = P1-F3 = P1-F4 = P1-F5 = P1-F6
 1.65 with sigma of 0.02
 F2-F3
 2.2 with sigma of 0.02
 F1-F3 \\sim F2-F4 \\sim F6-F5
 with sigma of 0.05
 P1-F1 \\sim P1-F2 \\sim P1-F3 \\sim P1-F4 \\sim P1-F5 \\sim P1-F6
 with sigma of 0.02
 F1-F2 \\sim F1-F4 \\sim F1-F5 \\sim F1-F6 \\sim F3-F2 \\sim F3-F4 \\sim F3-F5
\\sim F3-F6
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
P1 \\sim F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 P1, F1, F2, F3, F4, F5, F6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: P1(0.5) F1(0.5) F2(0.5) F3(0.5) F4(0.5) F5(0.5) F6(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C8(H8), C12(H12), C13(H13), C15(H15), C16(H16),
 C18(H18), C19(H19), C21(H21), C22(H22)
6.b Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C2A(H2AA,H2AB,
 H2AC), C3A(H3AA,H3AB,H3AC)
;
_shelx_res_checksum              90907
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.839
_oxdiff_exptl_absorpt_empirical_full_min 0.619