Spectroscopic and Electrochemical Characterization of a Pr4+ Imidophosphorane Complex and the Redox Chemistry of Nd3+ and Dy3+ Complexes
Rice, Natalie T.; Popov, Ivan A.; Carlson, Rebbeca; Greer, Samuel M.; Boggiano, Andrew C.; Stein, Benjamin William; Bacsa, John; Batista, Enrique R.; Yang, Ping; La Pierre, Henry Storms; Dalton Transactions  (2022) –; doi:10.1039/D2DT00758D

data_7709921
_publ_section_title
;
 Spectroscopic and Electrochemical Characterization of a Pr4+
 Imidophosphorane Complex and the Redox Chemistry of Nd3+ and Dy3+
 Complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00758D
_journal_year                    2022
_chemical_formula_moiety         'C60 H138 Dy K N16 O P4'
_chemical_formula_sum            'C60 H138 Dy K N16 O P4'
_chemical_formula_weight         1425.34
_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             2020-09-07
_audit_creation_method
;
Olex2 1.3-dev
(compiled 2020.07.30 svn.rde3f2a17 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2021-10-07 deposited with the CCDC.	2022-04-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.536(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.4405(10)
_cell_length_b                   15.8568(7)
_cell_length_c                   25.4452(16)
_cell_measurement_reflns_used    9615
_cell_measurement_temperature    130(2)
_cell_measurement_theta_max      33.17
_cell_measurement_theta_min      2.37
_cell_volume                     8236.7(7)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_collection       'APEX2  v2016.5-1 (Bruker, 2014)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 1.3-dev (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-dev (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      130(2)
_diffrn_detector_area_resol_mean 7.495
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker D8 VENTURE diffractometer'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirror'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0486
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            167230
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         36.349
_diffrn_reflns_theta_min         2.037
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.079
_exptl_absorpt_correction_T_max  0.7471
_exptl_absorpt_correction_T_min  0.4861
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1234 before and 0.0918 after correction.
The Ratio of minimum to maximum transmission is 0.6506.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.149
_exptl_crystal_description       prism
_exptl_crystal_F_000             3052
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.402
_exptl_crystal_size_mid          0.292
_exptl_crystal_size_min          0.275
_refine_diff_density_max         2.454
_refine_diff_density_min         -1.512
_refine_diff_density_rms         0.113
_refine_ls_extinction_coef       0.00021(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     446
_refine_ls_number_reflns         19958
_refine_ls_number_restraints     88
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0437
_refine_ls_R_factor_gt           0.0401
_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^)+(0.0346P)^2^+29.1972P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0998
_refine_ls_wR_factor_ref         0.1015
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18518
_reflns_number_total             19958
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00758d2.cif
_cod_data_source_block           ntr-04-086_130k
_cod_database_code               7709921
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.756
_shelx_estimated_absorpt_t_min   0.671
_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
 C29-C30
 1.5202 with sigma of 0.002
 C31-C29
 2.3753 with sigma of 0.002
 O1-C29
 1.42 with sigma of 0.01
 C31-C32
 1.52 with sigma of 0.01
 O1-C31
 1.42 with sigma of 0.01
 O1-C30 = O1-C32
 2.3917 with sigma of 0.01
 C5-H5C \\sim C5-H5B \\sim C6-H6C \\sim C22-H22C \\sim C22-H22B \\sim C23-H23B
\\sim C24-H24C \\sim C18-
 H18C \\sim C20-H20B
 with sigma of 0.0002
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1A
Uanis(C31) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uiso(H6B) = Uiso(H6A)
Uiso(H26B) = Uiso(H26A) = Uiso(H26C)
4. Rigid body (RIGU) restrains
 C1, N1
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C1, C2
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C2, N2
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C3, C5
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 C3, C6
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 N1, C3
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 C3, C4
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 C15, H6C
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 N6, H6C
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C7, C10
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 C7, C9
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C7, C8
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 N2, C7
 with sigma for 1-2 distances of 0.0004 and sigma for 1-3 distances of 0.0004
 C11, C12
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C13, C14
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 N5, C15
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 H20C, C21, H23C, H24A, H22C, N6
 with sigma for 1-2 distances of 0.0006 and sigma for 1-3 distances of 0.0006
 C29, C30
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 O1, C29
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C31, C32
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 O1, C31
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
5. Others
 Fixed Sof: C30(0.5) H30A(0.5) H30B(0.5) H30C(0.5) C29(0.5) H29A(0.5)
 H29B(0.5) C31(0.5) H31A(0.5) H31B(0.5) C32(0.5) H32A(0.5) H32B(0.5) H32C(0.5)
 O1(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C31(H31A,H31B)
6.b Secondary CH2 refined with riding coordinates and stretchable bonds:
 C1(H1A,H1B), C2(H2A,H2B), C11(H11A,H11B), C13(H13A,H13B), C15(H15A,H15B),
 C16(H16A,H16B), C27(H27A,H27B), C25(H25A,H25B)
6.c Idealised Me refined with riding coordinates and stretchable bonds:
 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), C22(H22A,H22B,H22C),
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C18(H18A,H18B,
 H18C), C20(H20A,H20B,H20C)
6.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C19(H19A,H19B,H19C), C28(H28A,H28B,H28C), C30(H30A,H30B,
 H30C), C32(H32A,H32B,H32C)
;
_smtbx_masks_void_probe_radius   0.6
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              47777
_shelx_hkl_checksum              13953
_shelx_fab_checksum              53828
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone'
_olex2_submission_special_instructions 'No special instructions were received'