Half-sandwich bis(propiolamidinate) rare-earth metal complexes: synthesis, structure and dissociation of the cyclopentadienyl ligand via competition with an amidinate.
Xu, Ling; Wang, Yu-Chen; Zhang, Wen-Xiong; Xi, Zhenfeng; Dalton transactions (Cambridge, England : 2003) 42 (2013) 16466–16469; doi:10.1039/c3dt52179f

data_7023971
_publ_section_title
;
 Half-sandwich bis(propiolamidinate) rare-earth metal complexes:
 synthesis, structure and dissociation of the cyclopentadienyl ligand via
 competition with an amidinate.
;
_journal_issue                   47
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              16466
_journal_page_last               16469
_journal_paper_doi               10.1039/c3dt52179f
_journal_volume                  42
_journal_year                    2013
_chemical_formula_moiety         '2(C41 H41 N2 Si Y)'
_chemical_formula_sum            'C82 H82 N4 Si2 Y2'
_chemical_formula_weight         1357.51
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2013-06-17
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr  9 2013 14:06:00, GUI svn.r4458)
;
_cell_angle_alpha                90.497(2)
_cell_angle_beta                 90.033(2)
_cell_angle_gamma                93.204(2)
_cell_formula_units_Z            2
_cell_length_a                   13.1259(3)
_cell_length_b                   16.2231(5)
_cell_length_c                   16.4294(5)
_cell_measurement_reflns_used    17636
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      29.0730
_cell_measurement_theta_min      3.2240
_cell_volume                     3492.92(17)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector_area_resol_mean 10.3914
_diffrn_measured_fraction_theta_full 0.9983
_diffrn_measured_fraction_theta_max 0.8271
_diffrn_measurement_details
;
  1 omega  -64.00   36.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       10.8993  -38.0000 -120.0000 100

  2 omega  -10.00   77.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       10.8993   57.0000 -180.0000 87

  3 omega  -14.00   86.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       10.8993   77.0000  -60.0000 100

  4 omega  -16.00   72.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       10.8993   38.0000   90.0000 88

  5 omega  -63.00   40.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       10.8993  -57.0000   30.0000 103

  6 omega  -20.00   53.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       10.8993  -99.0000  150.0000 73

  7 omega  -70.00  -25.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.6805  126.0000 -131.8788 45

  8 omega  -74.00  -34.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.6805  133.0000  102.6494 40
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0142992000
_diffrn_orient_matrix_UB_12      0.0337781000
_diffrn_orient_matrix_UB_13      0.0260554000
_diffrn_orient_matrix_UB_21      0.0517885000
_diffrn_orient_matrix_UB_22      -0.0100505000
_diffrn_orient_matrix_UB_23      -0.0028136000
_diffrn_orient_matrix_UB_31      0.0065390000
_diffrn_orient_matrix_UB_32      0.0259942000
_diffrn_orient_matrix_UB_33      -0.0343106000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0715
_diffrn_reflns_av_unetI/netI     0.0637
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            52519
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.022
_diffrn_reflns_theta_min         2.925
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.735
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78296
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.291
_exptl_crystal_F_000             1416
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.938
_refine_diff_density_min         -1.043
_refine_diff_density_rms         0.115
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.144
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     863
_refine_ls_number_reflns         13686
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.144
_refine_ls_R_factor_all          0.0989
_refine_ls_R_factor_gt           0.0848
_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^)+(0.0127P)^2^+29.1785P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1825
_refine_ls_wR_factor_ref         0.1888
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11383
_reflns_number_total             13686
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c3dt52179f.txt
_cod_data_source_block           13mar11g
_cod_original_cell_volume        3492.93(16)
_cod_database_code               7023971
_chemical_oxdiff_formula         'C82 H82 N4 Si2 Y2'
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Si1A-C8A = Si1A-C6A = Si1A-C7A = Si2A-C48A = Si2A-C49A = Si2A-C47A = Si1-C8 =
 Si1-C7 = Si1-C6 = Si2-C49 = Si2-C48 = Si2-C47
 1.87 with sigma of 0.03
3. Uiso/Uaniso restraints and constraints
Uanis(Si1) = Uanis(Si1A)
Uanis(C6) = Uanis(C7A)
Uanis(C7) = Uanis(C6A)
Uanis(C8) = Uanis(C8A)
Uanis(C48) = Uanis(C48A)
Uanis(C44) = Uanis(C51)
Uanis(C47) = Uanis(C47A)
4. Others
 1*Sof(Si2)=1-1*Sof(Si2A)=1*Sof(C47)=1*Sof(H47A)=1*Sof(H47B)=1*Sof(H47C)=1-1*
 Sof(C47A)=1-1*Sof(H47D)=1-1*Sof(H47E)=1-1*Sof(H47F)=1*Sof(C48)=1*Sof(H48A)=1*
 Sof(H48B)=1*Sof(H48C)=1-1*Sof(C48A)=1-1*Sof(H48D)=1-1*Sof(H48E)=1-1*Sof(H48F)=
 1*Sof(C49)=1*Sof(H49A)=1*Sof(H49B)=1*Sof(H49C)=1-1*Sof(C49A)=1-1*Sof(H49D)=1-1*
 Sof(H49E)=1-1*Sof(H49F)
 1*Sof(Si1)=1-1*Sof(Si1A)=1*Sof(C6)=1*Sof(H6A)=1*Sof(H6B)=1*Sof(H6C)=1-1*
 Sof(C6A)=1-1*Sof(H6AA)=1-1*Sof(H6AB)=1-1*Sof(H6AC)=1*Sof(C7)=1*Sof(H7A)=1*
 Sof(H7B)=1*Sof(H7C)=1-1*Sof(C7A)=1-1*Sof(H7AA)=1-1*Sof(H7AB)=1-1*Sof(H7AC)=1*
 Sof(C8)=1*Sof(H8A)=1*Sof(H8B)=1*Sof(H8C)=1-1*Sof(C8A)=1-1*Sof(H8AA)=1-1*
 Sof(H8AB)=1-1*Sof(H8AC)
5.a Aromatic/amide H refined with riding coordinates:
 C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23),
 C24(H24), C25(H25), C26(H26), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35),
  C37(H37), C38(H38), C39(H39), C40(H40), C41(H41), C57(H57), C58(H58),
 C59(H59), C60(H60), C61(H61), C63(H63), C64(H64), C65(H65), C66(H66), C67(H67),
  C72(H72), C73(H73), C74(H74), C75(H75), C76(H76), C78(H78), C79(H79),
 C80(H80), C81(H81), C82(H82)
5.b Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C6A(H6AA,H6AB,H6AC), C7(H7A,H7B,H7C), C7A(H7AA,H7AB,H7AC),
 C8(H8A,H8B,H8C), C8A(H8AA,H8AB,H8AC), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C47(H47A,H47B,H47C), C47A(H47D,H47E,
 H47F), C48(H48A,H48B,H48C), C48A(H48D,H48E,H48F), C49(H49A,H49B,H49C),
 C49A(H49D,H49E,H49F), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C52(H52A,H52B,
 H52C), C53(H53A,H53B,H53C)
;
_shelx_estimated_absorpt_t_max   0.846
_shelx_estimated_absorpt_t_min   0.846
_shelx_hkl_checksum              23986
_shelx_res_checksum              51418
_shelxl_version_number           2013-3