Enantiopure Amidinate Complexes of the Rare-Earth Elements
Brunner, Tobias S.; Benndorf, Paul; Gamer, Michael T.; Knöfel, Nicolai; Gugau, Katharina; Roesky, Peter W.; Organometallics 35 (2016) 3474–; doi:10.1021/acs.organomet.6b00523

data_4088883
_publ_contact_author
;
      Prof. Dr. Peter W. Roesky
      Karlsruher Institut fuer Technologie (KIT), CS
      Institut fuer Anorganische Chemie (AOC)
      Lehrstuhl fuer Anorganische Funktionsmaterialien
      Engesserstr. 15, Geb. 30.45
      76131 Karlsruhe 
      Bundesrepublik Deutschland
;
_publ_section_title
;
 Enantiopure Amidinate Complexes of the Rare-Earth Elements
;
_journal_issue                   20
_journal_name_full               Organometallics
_journal_page_first              3474
_journal_paper_doi               10.1021/acs.organomet.6b00523
_journal_volume                  35
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C49 H73 Lu N4 Si2, 0.5(C5 H12)'
_chemical_formula_sum            'C51.5 H79 Lu N4 Si2'
_chemical_formula_weight         985.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-06-17
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.408(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.7416(7)
_cell_length_b                   11.4890(2)
_cell_length_c                   43.5432(14)
_cell_measurement_reflns_used    43498
_cell_measurement_temperature    200
_cell_measurement_theta_max      26.14
_cell_measurement_theta_min      1.53
_cell_volume                     10534.5(5)
_computing_cell_refinement       'STOE X-AREA, PLATON (A.L.Spek, 2009)'
_computing_data_collection       'STOE X-AREA'
_computing_data_reduction        'STOE X-RED & LANA, PLATON (A.L.Spek, 2009)'
_computing_molecular_graphics    'Diamond 2/3, Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'MS Word, Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-2014/7 (Sheldrick, 2015)'
_diffrn_ambient_temperature      200
_diffrn_detector                 'image plate (34cm diameter)'
_diffrn_detector_area_resol_mean 6.67
_diffrn_detector_type            'STOE image plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device       'two-circle goniometer'
_diffrn_measurement_device_type  STOE-IPDS2-200K
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_collimation    '0.5mm monocapillary'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0860
_diffrn_reflns_av_unetI/netI     0.0775
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       53
_diffrn_reflns_limit_l_min       -53
_diffrn_reflns_number            104944
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.151
_diffrn_reflns_theta_min         1.528
_diffrn_source                   'sealed tube, 12x0.4mm long-fine focus'
_exptl_absorpt_coefficient_mu    1.955
_exptl_absorpt_correction_T_max  0.8390
_exptl_absorpt_correction_T_min  0.5978
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   'STOE X-RED & X-SHAPE'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.243
_exptl_crystal_description       needle
_exptl_crystal_F_000             4120
_exptl_crystal_size_max          0.552
_exptl_crystal_size_mid          0.256
_exptl_crystal_size_min          0.074
_refine_diff_density_max         0.518
_refine_diff_density_min         -1.296
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 5069 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.026(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.874
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1498
_refine_ls_number_reflns         20655
_refine_ls_number_restraints     829
_refine_ls_restrained_S_all      0.868
_refine_ls_R_factor_all          0.0692
_refine_ls_R_factor_gt           0.0356
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0286P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0597
_refine_ls_wR_factor_ref         0.0673
_reflns_Friedel_coverage         0.880
_reflns_Friedel_fraction_full    0.979
_reflns_Friedel_fraction_max     0.969
_reflns_number_gt                14107
_reflns_number_total             20655
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00523_si_002.cif
_cod_data_source_block           11
_cod_original_formula_sum        'C51.50 H79 Lu N4 Si2'
_cod_database_code               4088883
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 N5-C55
 1.48 with sigma of 0.02
 C23A-C22
 1.55 with sigma of 0.02
 N6-C63
 1.48 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(N5) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C94)
\\sim Ueq, Uanis(C110) \\sim Ueq, Uanis(C111) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C23B) = Uanis(C23A)
4. Rigid body (RIGU) restrains
 C35A, C36A, C37A, C38A, C39A, C40A, C41A, C42A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C35B, C36B, C37B, C38B, C39B, C40B, C41B, C42B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N5, C55, C56, C57, C58, C59, C60, C61, C62
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C106, C107, C108, C109, C110, C111
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C206, C207, C208, C209, C210, C211
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C22, C26, C23A, C24A, C25A, C23B, C24B, C25B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C76, C77, C78, C79, C80, C81, C82, C83
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N7, N8, C71, C72, C73, C74, C75
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C6A, C7A, C8A, C9A, C10A, C11A, C12A, C13A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C6B, C7B, C8B, C9B, C10B, C11B, C12B, C13B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Si5, C120, C121, C122, C123
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Si2A, C43, C47A, C48A, C49A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Si2B, C43, C47B, C48B, C49B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Si3, Si4, C92, C93, C94, C95, C96, C97, C98
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N5, N6, C50, C51, C52, C53, C54, C55, C56
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C63, C64, C65, C66, C67, C68, C69, C70
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N6, C63, C65
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N8, C71, C84, C85, C86
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C300, C301, C303, C302, C304
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C23B)=1-FVAR(1)
 Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C23A)=FVAR(1)
 Fixed Sof: Si2A(0.5) Si2B(0.5) H43(0.5) H43A(0.5) C6A(0.5) H6A(0.5) C7A(0.5)
 H7AA(0.5) H7AB(0.5) H7AC(0.5) C8A(0.5) C9A(0.5) H9A(0.5) C10A(0.5) H10A(0.5)
 C11A(0.5) H11A(0.5) C12A(0.5) H12A(0.5) C13A(0.5) H13A(0.5) C24A(0.5)
 H24A(0.5) H24B(0.5) H24C(0.5) C25A(0.5) H25A(0.5) H25B(0.5) H25C(0.5)
 C35A(0.5) H35A(0.5) C36A(0.5) H36A(0.5) H36B(0.5) H36C(0.5) C37A(0.5)
 C42A(0.5) H42A(0.5) C41A(0.5) H41A(0.5) C40A(0.5) H40A(0.5) C39A(0.5)
 H39A(0.5) C38A(0.5) H38A(0.5) C47A(0.5) H47A(0.5) H47B(0.5) H47C(0.5)
 C48A(0.5) H48A(0.5) H48B(0.5) H48C(0.5) C49A(0.5) H49A(0.5) H49B(0.5)
 H49C(0.5) C6B(0.5) H6B(0.5) C7B(0.5) H7BA(0.5) H7BB(0.5) H7BC(0.5) C8B(0.5)
 C9B(0.5) H9B(0.5) C10B(0.5) H10B(0.5) C11B(0.5) H11B(0.5) C12B(0.5) H12B(0.5)
 C13B(0.5) H13B(0.5) C24B(0.5) H24D(0.5) H24E(0.5) H24F(0.5) C25B(0.5)
 H25D(0.5) H25E(0.5) H25F(0.5) C35B(0.5) H35B(0.5) C36B(0.5) H36D(0.5)
 H36E(0.5) H36F(0.5) C37B(0.5) C42B(0.5) H42B(0.5) C41B(0.5) H41B(0.5)
 C40B(0.5) H40B(0.5) C39B(0.5) H39B(0.5) C38B(0.5) H38B(0.5) C47B(0.5)
 H47D(0.5) H47E(0.5) H47F(0.5) C48B(0.5) H48D(0.5) H48E(0.5) H48F(0.5)
 C49B(0.5) H49D(0.5) H49E(0.5) H49F(0.5) Lu2(0.5) Si3(0.5) Si4(0.5) N5(0.5)
 N6(0.5) N7(0.5) N8(0.5) C50(0.5) C51(0.5) C52(0.5) H52A(0.5) H52B(0.5)
 H52C(0.5) C53(0.5) H53A(0.5) H53B(0.5) H53C(0.5) C54(0.5) H54A(0.5) H54B(0.5)
 H54C(0.5) C55(0.5) H55(0.5) C56(0.5) H56A(0.5) H56B(0.5) H56C(0.5) C57(0.5)
 C62(0.5) H62(0.5) C61(0.5) H61(0.5) C60(0.5) H60(0.5) C59(0.5) H59(0.5)
 C58(0.5) H58(0.5) C63(0.5) H63(0.5) C64(0.5) H64A(0.5) H64B(0.5) H64C(0.5)
 C65(0.5) C66(0.5) H66(0.5) C67(0.5) H67(0.5) C68(0.5) H68(0.5) C69(0.5)
 H69(0.5) C70(0.5) H70(0.5) C71(0.5) C72(0.5) C73(0.5) H73A(0.5) H73B(0.5)
 H73C(0.5) C74(0.5) H74A(0.5) H74B(0.5) H74C(0.5) C75(0.5) H75A(0.5) H75B(0.5)
 H75C(0.5) C76(0.5) H76(0.5) C77(0.5) H77A(0.5) H77B(0.5) H77C(0.5) C78(0.5)
 C83(0.5) H83(0.5) C82(0.5) H82(0.5) C81(0.5) H81(0.5) C80(0.5) H80(0.5)
 C79(0.5) H79(0.5) C84(0.5) H84(0.5) C85(0.5) H85A(0.5) H85B(0.5) H85C(0.5)
 C86(0.5) C91(0.5) H91(0.5) C90(0.5) H90(0.5) C89(0.5) H89(0.5) C88(0.5)
 H88(0.5) C87(0.5) H87(0.5) C92(0.5) H92(0.5) C93(0.5) H93A(0.5) H93B(0.5)
 H93C(0.5) C94(0.5) H94A(0.5) H94B(0.5) H94C(0.5) C95(0.5) H95A(0.5) H95B(0.5)
 H95C(0.5) C96(0.5) H96A(0.5) H96B(0.5) H96C(0.5) C97(0.5) H97A(0.5) H97B(0.5)
 H97C(0.5) C98(0.5) H98A(0.5) H98B(0.5) H98C(0.5) H104(0.5) H10L(0.5) C120(0.5)
 H120(0.5) C106(0.5) C107(0.5) H107(0.5) C108(0.5) H108(0.5) C109(0.5)
 H109(0.5) C110(0.5) H110(0.5) C111(0.5) H111(0.5) C206(0.5) C211(0.5)
 H211(0.5) C210(0.5) H210(0.5) C209(0.5) H209(0.5) C208(0.5) H208(0.5)
 C207(0.5) H207(0.5)
6.a Free rotating group:
 C300(C301,C302,C303,C304)
6.b Ternary CH refined with riding coordinates:
 C14(H14), C27(H27), C43(H43), C43(H43A), C6A(H6A), C35A(H35A), C6B(H6B),
 C35B(H35B), C55(H55), C63(H63), C76(H76), C84(H84), C92(H92), C104(H104),
 C104(H10L), C112(H112), C120(H120)
6.c Secondary CH2 refined with riding coordinates:
 C301(H30D,H30E), C302(H30F,H30G), C303(H30H,H30I)
6.d Me refined with riding coordinates:
 C26(H26A,H26B,H26C), C26(H26D,H26E,H26F)
6.e Aromatic/amide H refined with riding coordinates:
 C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C30(H30), C31(H31),
 C32(H32), C33(H33), C34(H34), C9A(H9A), C10A(H10A), C11A(H11A), C12A(H12A),
 C13A(H13A), C42A(H42A), C41A(H41A), C40A(H40A), C39A(H39A), C38A(H38A),
 C9B(H9B), C10B(H10B), C11B(H11B), C12B(H12B), C13B(H13B), C42B(H42B),
 C41B(H41B), C40B(H40B), C39B(H39B), C38B(H38B), C62(H62), C61(H61), C60(H60),
 C59(H59), C58(H58), C66(H66), C67(H67), C68(H68), C69(H69), C70(H70), C83(H83),
  C82(H82), C81(H81), C80(H80), C79(H79), C91(H91), C90(H90), C89(H89),
 C88(H88), C87(H87), C115(H115), C116(H116), C117(H117), C118(H118), C119(H119),
  C107(H107), C108(H108), C109(H109), C110(H110), C111(H111), C211(H211),
 C210(H210), C209(H209), C208(H208), C207(H207)
6.f Fitted hexagon refined as free rotating group:
 C8A(C9A,C10A,C11A,C12A,C13A), C37A(C42A,C41A,C40A,C39A,C38A), C8B(C9B,C10B,
 C11B,C12B,C13B), C37B(C42B,C41B,C40B,C39B,C38B), C57(C62,C61,C60,C59,C58),
 C65(C66,C67,C68,C69,C70), C78(C83,C82,C81,C80,C79), C86(C91,C90,C89,C88,C87),
 C206(C211,C210,C209,C208,C207)
6.g Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C15(H15A,H15B,H15C),
 C28(H28A,H28B,H28C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,
 H46C), C7A(H7AA,H7AB,H7AC), C24A(H24A,H24B,H24C), C25A(H25A,H25B,H25C),
 C36A(H36A,H36B,H36C), C47A(H47A,H47B,H47C), C48A(H48A,H48B,H48C), C49A(H49A,
 H49B,H49C), C7B(H7BA,H7BB,H7BC), C24B(H24D,H24E,H24F), C25B(H25D,H25E,H25F),
 C36B(H36D,H36E,H36F), C47B(H47D,H47E,H47F), C48B(H48D,H48E,H48F), C49B(H49D,
 H49E,H49F), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C),
 C56(H56A,H56B,H56C), C64(H64A,H64B,H64C), C73(H73A,H73B,H73C), C74(H74A,H74B,
 H74C), C75(H75A,H75B,H75C), C77(H77A,H77B,H77C), C85(H85A,H85B,H85C), C93(H93A,
 H93B,H93C), C94(H94A,H94B,H94C), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C),
 C97(H97A,H97B,H97C), C98(H98A,H98B,H98C), C101(H10C,H10D,H10E), C102(H10F,H10G,
 H10H), C103(H10I,H10J,H10K), C105(H10M,H10N,H10O), C113(H11C,H11D,H11E),
 C121(H12C,H12D,H12E), C122(H12F,H12G,H12H), C123(H12I,H12J,H12K), C300(H30A,
 H30B,H30C), C304(H30J,H30K,H30L)
;
_shelx_res_checksum              25334
_shelx_hkl_checksum              35758
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'