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_7709923
_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_absolute_configuration unk
_chemical_formula_moiety         'C60 H138 K N16 Nd O P4, C4 H10 O'
_chemical_formula_sum            'C64 H148 K N16 Nd O2 P4'
_chemical_formula_weight         1481.20
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-08-20
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_audit_update_record
;
2021-10-11 deposited with the CCDC.	2022-04-01 downloaded from the CCDC.
;
_cell_angle_alpha                96.467(7)
_cell_angle_beta                 104.784(7)
_cell_angle_gamma                110.524(7)
_cell_formula_units_Z            2
_cell_length_a                   13.798(3)
_cell_length_b                   13.807(3)
_cell_length_c                   24.382(4)
_cell_measurement_reflns_used    9012
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      30.47
_cell_measurement_theta_min      2.59
_cell_volume                     4100.0(15)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(1)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0360
_diffrn_reflns_av_unetI/netI     0.0488
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            88316
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.585
_diffrn_reflns_theta_min         2.410
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.810
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7972
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1247 before and 0.0645 after correction.
The Ratio of minimum to maximum transmission is 0.7972.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.200
_exptl_crystal_description       prism
_exptl_crystal_F_000             1598
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.248
_exptl_crystal_size_min          0.208
_refine_diff_density_max         1.377
_refine_diff_density_min         -1.018
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Twinning involves inversion, so Flack parameter cannot be determined
;
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1660
_refine_ls_number_reflns         32769
_refine_ls_number_restraints     1268
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0383
_refine_ls_R_factor_gt           0.0363
_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^)+(0.0001P)^2^+6.9143P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0786
_refine_ls_wR_factor_ref         0.0801
_reflns_Friedel_coverage         1.000
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                31931
_reflns_number_total             32769
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00758d2.cif
_cod_data_source_block           ntr-nd-tp
_cod_original_cell_volume        4100.3(14)
_cod_database_code               7709923
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.850
_shelx_estimated_absorpt_t_min   0.733
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.476(13)
 0.476(7) 0.022(8) 0.026(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C3S_1-O1S_1
 C3S_2-O1S_2
 C3S_3-O1S_3
 C3S_4-O1S_4
 2.3917 with sigma of 0.002
 O1S_1-C2S_1
 O1S_2-C2S_2
 O1S_3-C2S_3
 O1S_4-C2S_4
 1.4204 with sigma of 0.001
 O1S_1-C4S_1
 O1S_2-C4S_2
 O1S_3-C4S_3
 O1S_4-C4S_4
 1.4204 with sigma of 0.001
 O1S_1-C5S_1
 O1S_2-C5S_2
 O1S_3-C5S_3
 O1S_4-C5S_4
 2.3917 with sigma of 0.002
 C2S_1-C3S_1
 C2S_2-C3S_2
 C2S_3-C3S_3
 C2S_4-C3S_4
 1.5202 with sigma of 0.001
 C4S_1-C2S_1
 C4S_2-C2S_2
 C4S_3-C2S_3
 C4S_4-C2S_4
 2.3753 with sigma of 0.002
 C5S_1-C4S_1
 C5S_2-C4S_2
 C5S_3-C4S_3
 C5S_4-C4S_4
 1.5202 with sigma of 0.001
4. Uiso/Uaniso restraints and constraints
Uanis(O1S_2) \\sim Ueq, Uanis(C2S_2) \\sim Ueq, Uanis(C4S_2) \\sim Ueq,
Uanis(C3S_2) \\sim Ueq, Uanis(C5S_2) \\sim Ueq, Uanis(O1S_1) \\sim Ueq,
Uanis(C2S_1) \\sim Ueq, Uanis(C4S_1) \\sim Ueq, Uanis(C3S_1) \\sim Ueq,
Uanis(C5S_1) \\sim Ueq, Uanis(O1S_4) \\sim Ueq, Uanis(C2S_4) \\sim Ueq,
Uanis(C4S_4) \\sim Ueq, Uanis(C3S_4) \\sim Ueq, Uanis(C5S_4) \\sim Ueq,
Uanis(O1S_3) \\sim Ueq, Uanis(C2S_3) \\sim Ueq, Uanis(C4S_3) \\sim Ueq,
Uanis(C3S_3) \\sim Ueq, Uanis(C5S_3) \\sim Ueq: with sigma of 0.004 and sigma
for terminal atoms of 0.008
5. Rigid body (RIGU) restrains
 N1, P1, N3, N4, N5, C13, C3, C1, C8, C2, C121, C14, C16, C9, C10, C11, C5, C6,
  C7
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 N8, P3, N9, N30, N35, C27, C28, C29, C31, C36, C39, C109, C119, C120, C32,
 C33, C34, C38, C40
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 N8, P3
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C45, P4, N10, N11, N46, N51, C41, C44, C47, C52, C53, C12, C42, C43, C48, C49,
  C50, C115, C118
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 N13, P5, N14, N16, N18, C54, C57, C58, C59, C62, C64, C15, C55, C56, C17, C60,
  C61, C63, C65
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 N19, P6, N20, N21, N22, C66, C72, C67, C68, C76, C78, C73, C74, C75, C69, C70,
  C71, C77, C79
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 N23, P7, N24, N25, N26, C80, C86, C81, C82, C90, C92, C87, C88, C89, C83, C84,
  C85, C91, C93
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 N27, P8, N28, N29, N17, C94, C98, C99, C101, C103, C111, C95, C96, C97, C100,
 C102, C104, C105, C106
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 O1S_1, C2S_1, C3S_1, C4S_1, C5S_1
 O1S_2, C2S_2, C3S_2, C4S_2, C5S_2
 O1S_3, C2S_3, C3S_3, C4S_3, C5S_3
 O1S_4, C2S_4, C3S_4, C4S_4, C5S_4
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
6. Same fragment restrains
{O1S_2, C2S_2, C3S_2, C4S_2, C5S_2}
{O1S_3, C2S_3, C3S_3, C4S_3, C5S_3}
{O1S_4, C2S_4, C3S_4, C4S_4, C5S_4}
as
{O1S_1, C2S_1, C3S_1, C4S_1, C5S_1} sigma for 1-2: 0.002 1-3: 0.004
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C4(H4A,H4B), C13(H13A,H13B), C3(H3A,H3B), C18(H18A,
 H18B), C19(H19A,H19B), C28(H28A,H28B), C29(H29A,H29B), C36(H36A,H36B),
 C39(H39A,H39B), C44(H44A,H44B), C45(H45A,H45B), C52(H52A,H52B), C53(H53A,H53B),
  C113(H11G,H11H), C57(H57A,H57B), C58(H58A,H58B), C62(H62A,H62B), C64(H64A,
 H64B), C66(H66A,H66B), C67(H67A,H67B), C76(H76A,H76B), C78(H78A,H78B),
 C80(H80A,H80B), C81(H81A,H81B), C90(H90A,H90B), C92(H92A,H92B), C98(H98A,H98B),
  C99(H99A,H99B), C101(H10J,H10K), C111(H11U,H11V), C2S(H2SA,H2SB), C4S(H4SA,
 H4SB), C2S(H2SA,H2SB), C4S(H4SA,H4SB), C2S(H2SA,H2SB), C4S(H4SA,H4SB),
 C2S(H2SA,H2SB), C4S(H4SA,H4SB)
7.b Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C),
 C16(H16A,H16B,H16C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C24(H24A,H24B,
 H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C), C34(H34A,H34B,H34C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C),
 C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C48(H48A,H48B,
 H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C109(H10D,H10E,H10F),
 C112(H11D,H11E,H11F), C114(H11I,H11J,H11K), C115(H11L,H11M,H11N), C118(H11O,
 H11P,H11Q), C119(H11R,H11S,H11T), C120(H12D,H12E,H12F), C15(H15A,H15B,H15C),
 C17(H17A,H17B,H17C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C60(H60A,H60B,
 H60C), C61(H61A,H61B,H61C), C63(H63A,H63B,H63C), C65(H65A,H65B,H65C), C69(H69A,
 H69B,H69C), C70(H70A,H70B,H70C), C71(H71A,H71B,H71C), C73(H73A,H73B,H73C),
 C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C77(H77A,H77B,H77C), C79(H79A,H79B,
 H79C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C85(H85A,H85B,H85C), C87(H87A,
 H87B,H87C), C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C91(H91A,H91B,H91C),
 C93(H93A,H93B,H93C), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C), C97(H97A,H97B,
 H97C), C100(H10G,H10H,H10I), C102(H10L,H10M,H10N), C104(H10O,H10P,H10Q),
 C105(H10R,H10S,H10T), C106(H10U,H10V,H10W), C3S(H3SA,H3SB,H3SC), C5S(H5SA,H5SB,
 H5SC), C3S(H3SA,H3SB,H3SC), C5S(H5SA,H5SB,H5SC), C3S(H3SA,H3SB,H3SC), C5S(H5SA,
 H5SB,H5SC), C3S(H3SA,H3SB,H3SC), C5S(H5SA,H5SB,H5SC)
;
_shelx_res_checksum              6289
_shelx_hkl_checksum              38240
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_special_instructions 'No special instructions were received'