Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex.
Rice, Natalie T.; Popov, Ivan A.; Russo, Dominic R.; Bacsa, John; Batista, Enrique R.; Yang, Ping; Telser, Joshua; La Pierre, Henry S.; Journal of the American Chemical Society 141 (2019) 13222–13233; doi:10.1021/jacs.9b06622

data_4127824
_publ_section_title
;
 Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium
 Complex.
;
_journal_issue                   33
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13222
_journal_page_last               13233
_journal_paper_doi               10.1021/jacs.9b06622
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         '2(C56 H128 K4 N16 P4), 0.5(C8 H20 O2)'
_chemical_formula_sum            'C116 H266 K8 N32 O P8'
_chemical_formula_weight         2686.15
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-11
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.3668(12)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   22.6075(3)
_cell_length_b                   14.13495(15)
_cell_length_c                   24.5014(3)
_cell_measurement_reflns_used    83982
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      38.0810
_cell_measurement_theta_min      2.1650
_cell_volume                     7549.65(16)
_computing_cell_refinement       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.43c (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_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 HyPix
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_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      7.00  59.00   0.50    6.98    --   27.43  19.00 -30.00  104
  2  \w     10.00 101.00   0.50    6.98    --   27.43  77.00 -60.00  182
  3  \w     53.00 100.00   0.50    6.98    --   27.43 150.00  -2.00   94
  4  \w     39.00  65.00   0.50    6.98    --   27.43 178.00  60.00   52
  5  \w      4.00  95.00   0.50    6.98    --   27.43  77.00  90.00  182
  6  \w      2.00 101.00   0.50    6.98    --   27.43  77.00-150.00  198
  7  \w     39.00  66.00   0.50   12.00    --   27.43 178.00-150.00   54
  8  \w    -64.00 -38.00   0.50   12.00    --  -27.43 123.00-164.00   52
  9  \w   -101.00 -59.00   0.50   12.00    --  -27.43 178.00-120.00   84
 10  \w    -71.00 -44.00   0.50   12.00    --  -27.43 150.00  -2.00   54
 11  \w     51.00  77.00   0.50   12.00    --   27.43-123.00 115.00   52
 12  \w     38.00 102.00   0.50   12.00    --   27.43-178.00  90.00  128
 13  \w     34.00  59.00   0.50   12.00    --   27.43-150.00 -46.00   50
 14  \w     19.00  45.00   0.50   12.00    --   27.43-123.00 115.00   52
 15  \w    -54.00 -28.00   0.50   12.00    --  -27.43 -77.00   0.00   52
 16  \w   -100.00 -77.00   0.50   12.00    --  -27.43 -77.00   0.00   46
;
_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      0.0005657000
_diffrn_orient_matrix_UB_12      0.0452192000
_diffrn_orient_matrix_UB_13      -0.0124020000
_diffrn_orient_matrix_UB_21      -0.0063895000
_diffrn_orient_matrix_UB_22      -0.0211914000
_diffrn_orient_matrix_UB_23      -0.0271687000
_diffrn_orient_matrix_UB_31      -0.0319094000
_diffrn_orient_matrix_UB_32      0.0050560000
_diffrn_orient_matrix_UB_33      -0.0028867000
_diffrn_radiation_monochromator  'multilayer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0812
_diffrn_reflns_av_unetI/netI     0.0508
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            207068
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         36.318
_diffrn_reflns_theta_min         1.868
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.367
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.321
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.43c (Rigaku Oxford Diffraction, 2018)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.182
_exptl_crystal_description       block
_exptl_crystal_F_000             2932
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.47
_exptl_crystal_size_mid          0.427
_exptl_crystal_size_min          0.333
_refine_diff_density_max         0.699
_refine_diff_density_min         -0.599
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     797
_refine_ls_number_reflns         36590
_refine_ls_number_restraints     417
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0550
_refine_ls_R_factor_gt           0.0392
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0526P)^2^+0.6449P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0996
_refine_ls_wR_factor_ref         0.1054
_reflns_Friedel_coverage         0.000
_reflns_number_gt                28895
_reflns_number_total             36590
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b06622_si_003.cif
_cod_data_source_block           drr-2-017
_cod_database_code               4127824
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C236  H492  K16  N66  P16  '
_shelx_estimated_absorpt_t_max   0.888
_shelx_estimated_absorpt_t_min   0.847
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     36.23
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C3S-C4S
 1.51 with sigma of 0.004
 C3S-C4S = C1S-C2S
 1.51 with sigma of 0.01
 O1S-C1S = O1S-C3S
 1.42 with sigma of 0.01
 C4S-C3S \\sim C1S-C2S
 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
C1S \\sim C2S \\sim C3S \\sim C4S: within 2A with sigma of 0.004 and sigma for
terminal atoms of 0.008
4. Rigid body (RIGU) restrains
 C11D, C12D, N4D
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 C13D, C14D, N4D
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 C7D, C8D, C9D, C10D, N3D
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 C1D, C2D, N2D, N3D
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 C3D, C4D, C5D, C6D, N2D
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 C7C, C8C, C9C, C10C, N3C
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 C1C, C2C, C3C, C4C, C5C, C6C, N2C, N3C
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 C11C, C12C, C13C, C14C, N4C
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 C3B, C4B, C5B, C6B, N2B
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 C1B, C2B, N2B, N3B
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C7B, C8B, C9B, C10B, N3B
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C11B, C12B, N4B
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C13B, C14B, N4B
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C1, C2, N2, N3
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C3, C4, C5, C6, N2
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C7, C8, C9, C10, N3
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C11, C12, N4
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C13, C14, N4
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C1S, C2S, C3S, C4S, O1S
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
5. Others
 Fixed Sof: C1S(0.5) H1SA(0.5) H1SB(0.5) C2S(0.5) H2SA(0.5) H2SB(0.5)
 H2SC(0.5) C3S(0.5) H3SA(0.5) H3SB(0.5) C4S(0.5) H4SA(0.5) H4SB(0.5) H4SC(0.5)
 Fixed X: O1S(0.5)
 Fixed Y: O1S(1)
 Fixed Z: O1S(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C11(H11A,H11B), C13(H13A,H13B), C1D(H1DA,H1DB),
 C2D(H2DA,H2DB), C11D(H11C,H11D), C13D(H13C,H13D), C1C(H1CA,H1CB), C2C(H2CA,
 H2CB), C11C(H11E,H11F), C13C(H13E,H13F), C1B(H1BA,H1BB), C2B(H2BA,H2BB),
 C11B(H11G,H11H), C13B(H13G,H13H), C1S(H1SA,H1SB), C3S(H3SA,H3SB)
6.b Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,
 H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C),
 C4D(H4DA,H4DB,H4DC), C5D(H5DA,H5DB,H5DC), C6D(H6DA,H6DB,H6DC), C8D(H8DA,H8DB,
 H8DC), C9D(H9DA,H9DB,H9DC), C10D(H10D,H10E,H10F), C12D(H12D,H12E,H12F),
 C14D(H14D,H14E,H14F), C4C(H4CA,H4CB,H4CC), C5C(H5CA,H5CB,H5CC), C6C(H6CA,H6CB,
 H6CC), C8C(H8CA,H8CB,H8CC), C9C(H9CA,H9CB,H9CC), C10C(H10G,H10H,H10I),
 C12C(H12G,H12H,H12I), C14C(H14G,H14H,H14I), C4B(H4BA,H4BB,H4BC), C5B(H5BA,H5BB,
 H5BC), C6B(H6BA,H6BB,H6BC), C8B(H8BA,H8BB,H8BC), C9B(H9BA,H9BB,H9BC),
 C10B(H10J,H10K,H10L), C12B(H12J,H12K,H12L), C14B(H14J,H14K,H14L), C2S(H2SA,
 H2SB,H2SC), C4S(H4SA,H4SB,H4SC)
;
_shelx_res_checksum              98689
_shelx_hkl_checksum              60478
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id DRR-2-017
_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 1.530
_oxdiff_exptl_absorpt_empirical_full_min 0.624