In-Plane Thorium(IV), Uranium(IV), and Neptunium(IV) Expanded Porphyrin Complexes.
Brewster, 2nd, James T; Mangel, Daniel N.; Gaunt, Andrew J.; Saunders, Douglas P.; Zafar, Hadiqa; Lynch, Vincent M.; Boreen, Michael A.; Garner, Mary E.; Goodwin, Conrad A. P.; Settineri, Nicholas S.; Arnold, John; Sessler, Jonathan L.; Journal of the American Chemical Society  (2019) –; doi:10.1021/jacs.9b09123

data_4127305
_publ_section_title
;
 In-Plane Thorium(IV), Uranium(IV), and Neptunium(IV) Expanded Porphyrin
 Complexes.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b09123
_journal_year                    2019
_chemical_formula_moiety         'C112 H112 Cl2 N12 O Th2'
_chemical_formula_sum            'C112 H112 Cl2 N12 O Th2'
_chemical_formula_weight         2177.11
_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'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.4740(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.5656(4)
_cell_length_b                   28.2946(7)
_cell_length_c                   16.5351(2)
_cell_measurement_reflns_used    40538
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      78.8980
_cell_measurement_theta_min      3.6130
_cell_volume                     10547.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.991
_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    -42.00   4.00   0.50    6.29    --    0.00 -77.00 -60.00   92
  2  \w    -10.00  28.00   0.50    6.29    --    0.00 -99.00  30.00   76
  3  \w     32.00 113.00   0.50   15.00    --  106.00-119.00 -47.00  162
  4  \w     99.00 125.00   0.50   15.00    --  106.00 -77.00 -60.00   52
  5  \w     77.00 102.00   0.50   15.00    --  106.00-111.00 -90.00   50
  6  \w     48.00  74.00   0.50   15.00    --  106.00 -77.00 -60.00   52
  7  \w     38.00  72.00   0.50   15.00    --  106.00-111.00 -90.00   68
  8  \w     36.00 120.00   0.50   15.00    --  106.00 -61.00 -30.00  168
  9  \w     61.00 100.00   0.50   15.00    --  106.00 -77.00  90.00   78
 10  \w     66.00 109.00   0.50   15.00    --  106.00 -94.00 150.00   86
 11  \w     86.00 128.00   0.50   15.00    --  106.00-158.00 157.00   84
 12  \w     50.00 111.00   0.50   15.00    --  106.00 -61.00 150.00  122
 13  \w     35.00  96.00   0.50   15.00    --  106.00-111.00   0.00  122
 14  \w     35.00  66.00   0.50   15.00    --  106.00 -30.00   0.00   62
 15  \w     31.00  73.00   0.50   15.00    --  106.00 -45.00 -30.00   84
 16  \w     38.00  74.00   0.50   15.00    --  106.00 -45.00 -90.00   72
 17  \w     30.00  66.00   0.50   15.00    --  106.00 -30.00-150.00   72
 18  \w     30.00  66.00   0.50   15.00    --  106.00 -30.00-180.00   72
 19  \w     93.00 168.00   0.50   15.00    --  106.00  61.00-180.00  150
 20  \w    106.00 144.00   0.50   15.00    --  106.00 179.00 -30.00   76
 21  \w    103.00 128.00   0.50   15.00    --  106.00 119.00  37.00   50
 22  \w     93.00 171.00   0.50   15.00    --  106.00  61.00 120.00  156
 23  \w     57.00  96.00   0.50   15.00    --  106.00 179.00 -30.00   78
 24  \w     50.00 131.00   0.50   15.00    --  106.00 158.00-168.00  162
 25  \w     16.00  43.00   0.50    6.29    --    0.00  77.00-120.00   54
 26  \w    -20.00  43.00   0.50    6.29    --    0.00  77.00-180.00  126
 27  \w    -20.00  45.00   0.50    6.29    --    0.00  77.00 -60.00  130
 28  \w    -20.00  45.00   0.50    6.29    --    0.00  77.00  30.00  130
 29  \w    -57.00 -30.00   0.50    6.29    --    0.00 148.00  27.68   54
 30  \w   -113.00 -26.00   0.50   15.00    -- -100.00 119.00  37.00  174
 31  \w    -64.00 -38.00   0.50   15.00    -- -100.00  61.00  60.00   52
 32  \w    -54.00 -29.00   0.50   15.00    -- -100.00  45.00  30.00   50
 33  \w    -79.00 -53.00   0.50   15.00    -- -100.00  61.00 150.00   52
 34  \w   -112.00 -25.00   0.50   15.00    -- -100.00 111.00  30.00  174
 35  \w    -57.00 -32.00   0.50   15.00    -- -100.00 146.00-101.16   50
 36  \w    -64.00 -31.00   0.50   15.00    -- -100.00 144.00-139.18   66
 37  \w    -73.00 -25.00   0.50   15.00    -- -100.00 111.00-180.00   96
 38  \w    -80.00 -26.00   0.50   15.00    -- -100.00  45.00-180.00  108
 39  \w    -98.00 -63.00   0.50   15.00    -- -100.00 141.00-160.90   70
 40  \w   -130.00-104.00   0.50   15.00    -- -100.00 141.00-160.90   52
 41  \w   -132.00 -95.00   0.50   15.00    -- -100.00 144.00-139.18   74
 42  \w   -133.00 -83.00   0.50   15.00    -- -100.00 146.00-101.16  100
 43  \w   -140.00 -34.00   0.50   15.00    -- -100.00 158.00-168.00  212
 44  \w    -45.00 -10.00   0.50    6.29    --    0.00 -77.00-180.00   70
 45  \w     32.00  69.00   0.50   15.00    --  106.00-111.00 -30.00   74
 46  \w     33.00  74.00   0.50   15.00    --  106.00 -45.00 150.00   82
 47  \w     30.00  58.00   0.50   15.00    --  106.00 -94.00 150.00   56
 48  \w     35.00 111.00   0.50   15.00    --  106.00-111.00 150.00  152
 49  \w    -88.00 -59.00   0.50   15.00    -- -100.00 179.00  60.00   58
 50  \w   -131.00-105.00   0.50   15.00    -- -100.00 143.00  44.10   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0022259000
_diffrn_orient_matrix_UB_12      0.0537255000
_diffrn_orient_matrix_UB_13      -0.0147341000
_diffrn_orient_matrix_UB_21      0.0630244000
_diffrn_orient_matrix_UB_22      -0.0049722000
_diffrn_orient_matrix_UB_23      -0.0314128000
_diffrn_orient_matrix_UB_31      -0.0264022500
_diffrn_orient_matrix_UB_32      -0.0071946500
_diffrn_orient_matrix_UB_33      -0.0865513000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0722
_diffrn_reflns_av_unetI/netI     0.0403
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            63689
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.245
_diffrn_reflns_theta_min         3.124
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.898
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71041
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic blackish violet'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   blackish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.371
_exptl_crystal_description       plank
_exptl_crystal_F_000             4360
_exptl_crystal_preparation       'By JTB.'
_exptl_crystal_recrystallization_method 'From hexanes.'
_exptl_crystal_size_max          0.264
_exptl_crystal_size_mid          0.056
_exptl_crystal_size_min          0.03
_refine_diff_density_max         4.091
_refine_diff_density_min         -1.080
_refine_diff_density_rms         0.178
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     592
_refine_ls_number_reflns         9566
_refine_ls_number_restraints     585
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0618
_refine_ls_R_factor_gt           0.0527
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1061P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1476
_refine_ls_wR_factor_ref         0.1523
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7713
_reflns_number_total             9566
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b09123_si_003.cif
_cod_data_source_block           jtb_0101_ucb_2nd
_cod_database_code               4127305
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Th N C Cl H'
_shelx_estimated_absorpt_t_max   0.756
_shelx_estimated_absorpt_t_min   0.180
_reflns_odcompleteness_completeness 98.59
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C6(H6A,H6B), C18(H18A,H18B), C21(H21A,H21B), C36(H36A,H36B),
 C39(H39A,H39B), C51(H51A,H51B), C54(H54A,H54B)
3.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C25(H25), C26(H26),
 C27(H27), C30(H30), C31(H31), C32(H32), C44(H44), C45(H45), C46(H46), C47(H47),
  C48(H48)
3.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C7(H7A,H7B,H7C), C19(H19A,H19B,H19C), C22(H22A,H22B,H22C),
 C37(H37A,H37B,H37C), C40(H40A,H40B,H40C), C52(H52A,H52B,H52C), C55(H55A,H55B,
 H55C)
;
_shelx_res_checksum              85639
_shelx_hkl_checksum              45326
_shelx_fab_checksum              94762
_olex2_exptl_crystal_mounting_method 'On a cryoloop, coated in oil.'
_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 1.982
_oxdiff_exptl_absorpt_empirical_full_min 0.467