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_7709788
_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         'C54 H50 N4 O10 Sb, F6 P, 1[C5H12], 1[C5H12]'
_chemical_formula_sum            'C69 H86 F6 N4 O10 P Sb'
_chemical_formula_weight         1398.13
_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             2021-11-19
_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                 90.6426(8)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   15.21938(12)
_cell_length_b                   25.80070(18)
_cell_length_c                   45.1560(4)
_cell_measurement_reflns_used    37097
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      80.1160
_cell_measurement_theta_min      3.3750
_cell_volume                     17730.3(2)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.972
_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    -38.00  -9.00   0.50    1.00    --  -47.13  39.00  20.00   58
  2  \w    -89.00 -34.00   0.50    1.00    --  -47.13 -39.00-133.00  110
  3  \w     -8.00  33.00   0.50    1.00    --   47.13 -39.00-133.00   82
  4  \w     35.00 115.00   0.50    1.00    --   47.13  39.00  20.00  160
  5  \w   -128.00 -79.00   0.50    4.00    --  -91.75 -39.00-133.00   98
  6  \w    -54.00 -29.00   0.50    4.00    --  -91.75  39.00  20.00   50
  7  \w    120.00 178.00   0.50    4.00    --  113.25  39.00  20.00  116
  8  \w    -28.00  15.00   0.50    1.00    --   47.13 -19.00 150.00   86
  9  \w    -27.00  14.00   0.50    1.00    --   47.13 -19.00  90.00   82
 10  \w    -45.00 -20.00   0.50    4.00    --  -91.75  30.00-150.00   50
 11  \w    -58.00 -26.00   0.50    4.00    --  -91.75  45.00 150.00   64
 12  \w    -60.00 -20.00   0.50    4.00    --  -91.75  45.00-150.00   80
 13  \w     59.00  94.00   0.50    4.00    --  113.25 -77.00-180.00   70
 14  \w     46.00  94.00   0.50    4.00    --  113.25 -77.00  90.00   96
 15  \w     53.00  95.00   0.50    4.00    --  113.25 -77.00-120.00   84
 16  \w     43.00  86.00   0.50    4.00    --  113.25 -77.00-150.00   86
 17  \w     68.00  94.00   0.50    4.00    --  113.25 -94.00 -60.00   52
 18  \w     95.00 174.00   0.50    4.00    --  113.25  77.00 -30.00  158
 19  \w     42.00  97.00   0.50    4.00    --  113.25 -94.00 150.00  110
 20  \w    105.00 157.00   0.50    4.00    --  113.25  30.00 -90.00  104
 21  \w     43.00  90.00   0.50    4.00    --  113.25 -77.00 -60.00   94
 22  \w     47.00  72.00   0.50    4.00    --  113.25 -77.00 120.00   50
 23  \w     43.00  75.00   0.50    4.00    --  113.25 -77.00 -90.00   64
 24  \w     49.00  94.00   0.50    4.00    --  113.25 -77.00   0.00   90
 25  \w     56.00  81.00   0.50    4.00    --  113.25 -94.00 120.00   50
 26  \w     99.00 171.00   0.50    4.00    --  113.25  15.00 150.00  144
 27  \w    100.00 125.00   0.50    4.00    --  113.25  15.00-120.00   50
 28  \w    131.00 156.00   0.50    4.00    --  113.25  15.00-120.00   50
 29  \w     44.00  93.00   0.50    4.00    --  113.25 -77.00 150.00   98
;
_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      0.0918445000
_diffrn_orient_matrix_UB_12      0.0160545000
_diffrn_orient_matrix_UB_13      0.0113339000
_diffrn_orient_matrix_UB_21      -0.0196470000
_diffrn_orient_matrix_UB_22      -0.0245199000
_diffrn_orient_matrix_UB_23      0.0303299000
_diffrn_orient_matrix_UB_31      0.0378175000
_diffrn_orient_matrix_UB_32      -0.0520026000
_diffrn_orient_matrix_UB_33      -0.0107721000
_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  0.0423
_diffrn_reflns_av_unetI/netI     0.0375
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       57
_diffrn_reflns_limit_l_min       -56
_diffrn_reflns_number            73318
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.514
_diffrn_reflns_theta_min         3.372
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.694
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60208
_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            'clear pale red'
_exptl_crystal_density_diffrn    1.571
_exptl_crystal_description       block
_exptl_crystal_F_000             8736
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.580
_refine_diff_density_min         -1.135
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1059
_refine_ls_number_reflns         18893
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0500
_refine_ls_R_factor_gt           0.0471
_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^)+(0.0552P)^2^+67.4350P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1225
_refine_ls_wR_factor_ref         0.1243
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17625
_reflns_number_total             18893
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00675h2.cif
_cod_data_source_block           str0789lt150kcu34mm_auto
_cod_database_code               7709788
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C54 H50 N4 O10F6PSb'
_shelx_estimated_absorpt_t_max   0.955
_shelx_estimated_absorpt_t_min   0.735
_reflns_odcompleteness_completeness 99.21
_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
 O2A-C24B
 1.35 with sigma of 0.01
 O10-C54C
 1.35 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C54C) = Uanis(C54)
4. Others
 Sof(C24B)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C54C)=Sof(H54D)=Sof(H54E)=
 Sof(H54F)=1-FVAR(1)
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C24A)=Sof(H24A)=Sof(H24B)=
 Sof(H24C)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C8(H8), C12(H12), C13(H13), C17(H17), C18(H18),
 C22(H22), C24(H24), C26(H26), C28(H28), C30(H30), C32(H32), C34(H34), C36(H36),
  C38(H38), C40(H40), C42(H42), C44(H44), C2A(H2A), C3A(H3A), C7A(H7A),
 C8A(H8A), C12A(H12A), C14A(H14A), C16A(H16A), C18A(H18A), C20A(H20A),
 C22A(H22A)
5.b Idealised Me refined as rotating group:
 C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,
 H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C52(H52A,
 H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C23A(H23A,H23B,H23C),
 C24A(H24A,H24B,H24C), C25A(H25A,H25B,H25C), C26A(H26A,H26B,H26C), C27A(H27A,
 H27B,H27C), C24B(H24D,H24E,H24F), C54C(H54D,H54E,H54F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 940 electrons were
found in a volume of 3404\%A^3 in 1 void per unit cell.
This is consistent with the presence of 
2[C5H12] per Formula Unit which account for 1008 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              86547
_shelx_fab_checksum              23397
_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 1.489
_oxdiff_exptl_absorpt_empirical_full_min 0.595