Molecular cyclo-P3 complexes of the rare-earth elements via a one-pot reaction and selective reduction
Hauser, Adrian; Münzfeld, Luca; Schlittenhardt, Sören; Köppe, Ralf; Uhlmann, Cedric; Rauska, Ulf-Christian; Ruben, Mario; Roesky, Peter W.; Chemical Science 14 (2023) 2149–2158; doi:10.1039/D2SC06730G

data_1568523
_publ_section_title
;
 Molecular cyclo-P3 complexes of the rare-earth elements via a one-pot
 reaction and selective reduction
;
_journal_issue                   8
_journal_name_full               'Chemical Science'
_journal_page_first              2149
_journal_page_last               2158
_journal_paper_doi               10.1039/D2SC06730G
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C102 H140 K N6 O2 P3 Y2, 2(C7 H8)'
_chemical_formula_sum            'C116 H156 K N4 O4 P3 Y2'
_chemical_formula_weight         1980.27
_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             2022-04-15
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-12-02 deposited with the CCDC.	2023-02-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 119.7260(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   31.5819(6)
_cell_length_b                   24.1585(4)
_cell_length_c                   16.5122(3)
_cell_measurement_reflns_used    32053
_cell_measurement_temperature    180
_cell_measurement_theta_max      64.25
_cell_measurement_theta_min      2.82
_cell_volume                     10940.5(4)
_computing_cell_refinement       'X-Area Recipe 1.37.0.0 (STOE, 2021)'
_computing_data_collection       'X-Area Pilatus3_SV 1.31.175.0 (STOE, 2021)'
_computing_data_reduction
;
X-Area Integrate 1.78.0.0 (STOE, 2020)
X-Area LANA 1.78.0.0 (STOE, 2020)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      180
_diffrn_detector                 EIGER4M
_diffrn_detector_area_resol_mean 13.33
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.941
_diffrn_measurement_details
;
 986 frames, detector distance = 80 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '1.2 0.6 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Ga K\a'
_diffrn_radiation_wavelength     1.34143
_diffrn_reflns_av_R_equivalents  0.0253
_diffrn_reflns_av_unetI/netI     0.0328
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.941
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            34539
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.941
_diffrn_reflns_theta_full        53.597
_diffrn_reflns_theta_max         64.079
_diffrn_reflns_theta_min         2.821
_diffrn_source                   'Metaljet D2'
_diffrn_source_current           3.57
_diffrn_source_power             0.250
_diffrn_source_voltage           70
_exptl_absorpt_coefficient_mu    1.706
_exptl_absorpt_correction_T_max  0.5492
_exptl_absorpt_correction_T_min  0.1330
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens, "The Evaluation of Absorption and Extinction in Single-Crystal
Structure Analysis", published in: F. R. Ahmed (Editor), "Crystallographic
Computing", Munksgaard, Copenhagen (1970), 255 - 270. Afterwards scaling of
reflection intensities was performed within STOE LANA. J. Koziskova, F. Hahn,
J. Richter, J. Kozisek, Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136-140.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.202
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             4216
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.083
_exptl_crystal_size_min          0.02
_exptl_crystal_size_rad          0.100
_refine_diff_density_max         2.835
_refine_diff_density_min         -1.438
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     673
_refine_ls_number_reflns         12995
_refine_ls_number_restraints     181
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0867
_refine_ls_R_factor_gt           0.0646
_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^)+(0.1360P)^2^+10.8069P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1946
_refine_ls_wR_factor_ref         0.2127
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9421
_reflns_number_total             12995
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06730g3.cif
_cod_data_source_block           ah174
_cod_database_code               1568523
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.716
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C16A-C17 \\sim C17B-C17 \\sim C17A-C17 \\sim C18B-C17 \\sim C18A-C17 \\sim
C16B-C17
 with sigma of 0.05
 C48A-C49 \\sim C48B-C49 \\sim C46B-C47B \\sim C46A-C47A
 with sigma of 0.05
 O2-C49 \\sim O2-C46B \\sim O2-C46A
 with sigma of 0.05
 C48B-C47B \\sim C48A-C47A
 with sigma of 0.05
 C42A-C40A \\sim C40A-C41A \\sim C40B-C41B \\sim C42B-C40B
 with sigma of 0.05
3. Uiso/Uaniso restraints and constraints
C19 \\sim C20 \\sim C21 \\sim C18: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.001 within 2A
C46A \\sim C47A \\sim C48A \\sim C49 \\sim O2: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
O2 \\sim C49 \\sim C48B \\sim C47B \\sim C46B: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C56 \\sim C50 \\sim C55 \\sim C54 \\sim C53 \\sim C52 \\sim C51: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C33 \\sim C31 \\sim C32: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C40B \\sim C41B \\sim C42B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C42A \\sim C40A \\sim C41A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
4. Others
 Fixed Sof: C16A(0.7) H16A(0.7) H16B(0.7) H16C(0.7) C46A(0.5) H46A(0.5)
 H46B(0.5) C17A(0.7) H17A(0.7) H17B(0.7) H17C(0.7) C18A(0.7) H18A(0.7)
 H18B(0.7) H18C(0.7) C18B(0.3) H18D(0.3) H18E(0.3) H18F(0.3) C17B(0.3)
 H17D(0.3) H17E(0.3) H17F(0.3) C16B(0.3) H16D(0.3) H16E(0.3) H16F(0.3)
 C47A(0.5) H47A(0.5) H47B(0.5) C48B(0.5) H48A(0.5) H48B(0.5) H49C(0.5)
 H49D(0.5) H49A(0.5) H49B(0.5) C46B(0.5) H46C(0.5) H46D(0.5) C47B(0.5)
 H47C(0.5) H47D(0.5) C48A(0.5) H48C(0.5) H48D(0.5) C40B(0.5) H40B(0.5)
 C41B(0.5) H41A(0.5) H41B(0.5) H41C(0.5) C42B(0.5) H42A(0.5) H42B(0.5)
 H42C(0.5) C42A(0.5) H42D(0.5) H42E(0.5) H42F(0.5) C40A(0.5) H40A(0.5)
 C41A(0.5) H41D(0.5) H41E(0.5) H41F(0.5)
5.a Ternary CH refined with riding coordinates:
 C28(H28), C31(H31), C43(H43), C40B(H40B), C40A(H40A)
5.b Secondary CH2 refined with riding coordinates:
 C46A(H46A,H46B), C47A(H47A,H47B), C48B(H48A,H48B), C49(H49C,H49D), C49(H49A,
 H49B), C46B(H46C,H46D), C47B(H47C,H47D), C48A(H48C,H48D)
5.c Me refined with riding coordinates:
 C56(H56A,H56B,H56C), C41B(H41A,H41B,H41C), C42B(H42A,H42B,H42C), C42A(H42D,
 H42E,H42F), C41A(H41D,H41E,H41F)
5.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C26(H26), C9(H9), C5(H5), C24(H24), C11(H11), C25(H25), C36(H36),
 C38(H38), C37(H37), C55(H55), C54(H54), C53(H53), C52(H52), C51(H51)
5.e Fitted hexagon refined as free rotating group:
 C50(C55,C54,C53,C52,C51)
5.f Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C30(H30A,H30B,H30C), C33(H33A,H33B,
 H33C), C29(H29A,H29B,H29C), C20(H20A,H20B,H20C), C44(H44A,H44B,H44C), C21(H21A,
 H21B,H21C), C19(H19A,H19B,H19C), C32(H32A,H32B,H32C), C45(H45A,H45B,H45C),
 C16A(H16A,H16B,H16C), C17A(H17A,H17B,H17C), C18A(H18A,H18B,H18C), C18B(H18D,
 H18E,H18F), C17B(H17D,H17E,H17F), C16B(H16D,H16E,H16F)
;
_shelx_res_checksum              22026
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in mineral oil'
_olex2_submission_special_instructions 'No special instructions were received'
_stoe_detector_distance          '80.0 mm'
_stoe_detector_pixelsize_x       '0.075 mm'
_stoe_detector_pixelsize_y       '0.075 mm'
_stoe_detector_size_x            '15.5 cm'
_stoe_detector_size_y            '16.2 cm'
_stoe_evaluation_integration_a   16.0
_stoe_evaluation_integration_b   0.4
_stoe_evaluation_integration_ems 0.014
_stoe_evaluation_lana_bis_l_even_max -
_stoe_evaluation_lana_bis_l_odd_max -
_stoe_evaluation_lana_bos_l_even_max 4
_stoe_evaluation_lana_bos_l_odd_max 1
_stoe_evaluation_lana_completeness 94.1
_stoe_evaluation_lana_dxs_max_order 1
_stoe_evaluation_lana_dys_max_order -
_stoe_evaluation_lana_fs_max_order 3
_stoe_evaluation_lana_max_2theta_available 128.2
_stoe_evaluation_lana_max_2theta_desired 128.2
_stoe_evaluation_lana_mean_redundancy 2.7
_stoe_evaluation_lana_number_refls_after_or 35163
_stoe_evaluation_lana_number_refls_outliers 4246
_stoe_evaluation_lana_number_refls_total 39409
_stoe_evaluation_lana_number_refls_unique 12997
_stoe_evaluation_lana_number_refls_written 35163
_stoe_evaluation_lana_or_c1      0.035
_stoe_evaluation_lana_or_c2      0
_stoe_evaluation_lana_or_c3      0
_stoe_evaluation_lana_or_c4      0.7
_stoe_evaluation_lana_point_group 2/m
_stoe_evaluation_lana_table
;
2Theta          11.6   25.4   39.2   53.0   66.8   80.6   94.4  108.2  122.0
<Resolution>    5.48   2.90   1.92   1.49   1.22   1.04   0.91   0.83   0.77
N(total)          81    561   2025   5928   7409   7089   7657   5559   3100
<Redundancy>     1.5    1.8    2.5    4.1    3.6    2.9    2.8    2.1    1.6
Complet. [%%]    71.1   89.8   97.7  100.0   99.9   97.1   99.4   94.8   77.9
<I/sigma>      249.4  124.8   67.8   34.4   19.7   10.9    6.2    4.4    3.3
R(int)         0.009  0.009  0.012  0.015  0.020  0.033  0.057  0.083  0.122
;
_stoe_measurement_identifier     AH174
_stoe_measurement_max_exposure_per_frame '2.0 s'
_stoe_measurement_mean_exposure_per_frame '2.0 s'
_stoe_measurement_min_exposure_per_frame '2.0 s'
_stoe_measurement_total_exposure_time '33 min'
_stoe_measurement_total_frame_number 986
_stoe_measurement_total_run_number 18
_stoe_measurement_tube_power     '250 W'