Synthesis and Characterization of Rare Earth Siloxide Complexes, M[OSi(OtBu)3]3(L)x where L is HOSi(OtBu)3 and x = 0 or 1
Lapadula, Giuseppe; Conley, Matthew P.; Copéret, Christophe; Andersen, Richard A.; Organometallics 34 (2014) 2271–; doi:10.1021/om501047g

data_4089695
_publ_section_title
;
 Synthesis and Characterization of Rare Earth Siloxide Complexes,
 M[OSi(OtBu)3]3(L)x where L is HOSi(OtBu)3 and x = 0 or 1
;
_journal_issue                   11
_journal_name_full               Organometallics
_journal_page_first              2271
_journal_paper_doi               10.1021/om501047g
_journal_volume                  34
_journal_year                    2014
_chemical_formula_moiety         'C48 H109 Eu O16 Si4, C H2 Cl2'
_chemical_formula_sum            'C49 H111 Cl2 Eu O16 Si4'
_chemical_formula_weight         1291.59
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-08-14
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                75.5109(17)
_cell_angle_beta                 81.1199(17)
_cell_angle_gamma                60.5631(15)
_cell_formula_units_Z            2
_cell_length_a                   13.7651(15)
_cell_length_b                   13.8406(15)
_cell_length_c                   21.602(2)
_cell_measurement_reflns_used    9970
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.975
_cell_measurement_theta_min      2.201
_cell_volume                     3467.8(6)
_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
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.795
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0284
_diffrn_reflns_av_unetI/netI     0.0539
_diffrn_reflns_Laue_measured_fraction_full 0.795
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            31650
_diffrn_reflns_point_group_measured_fraction_full 0.791
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         23.256
_diffrn_reflns_theta_min         0.974
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    1.104
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6016
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0718 before and 0.0502 after correction.
The Ratio of minimum to maximum transmission is 0.8063.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.237
_exptl_crystal_description       block
_exptl_crystal_F_000             1372
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.27
_refine_diff_density_max         1.534
_refine_diff_density_min         -0.855
_refine_diff_density_rms         0.088
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.44(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1129
_refine_ls_number_reflns         19837
_refine_ls_number_restraints     1582
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0498
_refine_ls_R_factor_gt           0.0413
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0384P)^2^+8.3645P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0967
_refine_ls_wR_factor_ref         0.1012
_reflns_Friedel_coverage         0.988
_reflns_Friedel_fraction_full    0.786
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                17533
_reflns_number_total             19837
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om501047g_si_001.cif
_cod_data_source_block           eusiloxide_0m
_cod_depositor_comments
;

2020-07-06
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C98 H222 Cl4 Eu2 O32 Si8'
_cod_original_formula_weight         2583.18
_cod_original_formula_moiety         '2(C48 H109 Eu O16 Si4), 2(C H2 Cl2)'
_cod_original_formula_units_Z            1
_cod_original_cell_volume        3467.8(7)
_cod_database_code               4089695
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All O(H) groups, {H14A,H14B,H14C} of C14A, {H23D,H23E,H23F} of C23B, {H30A,
  H30B,H30C} of C30A, {H15D,H15E,H15F} of C15B, {H12A,H12B,H12C} of C12A, {H8AA,
  H8AB,H8AC} of C8A, {H17D,H17E,H17F} of C17B, {H10A,H10B,H10C} of C10B, {H15A,
  H15B,H15C} of C15A, {H20D,H20E,H20F} of C20B, {H13A,H13B,H13C} of C13B, {H9AA,
  H9AB,H9AC} of C9A, {H24D,H24E,H24F} of C24B, {H7BA,H7BB,H7BC} of C7B, {H11A,
  H11B,H11C} of C11A, {H32A,H32B,H32C} of C32A, {H18A,H18B,H18C} of C18A, {H2AA,
  H2AB,H2AC} of C2A, {H16D,H16E,H16F} of C16B, {H44A,H44B,H44C} of C44A, {H34D,
  H34E,H34F} of C34B, {H38A,H38B,H38C} of C38A, {H31D,H31E,H31F} of C31B, {H16A,
  H16B,H16C} of C16A, {H42A,H42B,H42C} of C42A, {H23A,H23B,H23C} of C23A, {H21D,
  H21E,H21F} of C21B, {H20A,H20B,H20C} of C20A, {H26D,H26E,H26F} of C26B, {H6BA,
  H6BB,H6BC} of C6B, {H31A,H31B,H31C} of C31A, {H27D,H27E,H27F} of C27B, {H44D,
  H44E,H44F} of C44B, {H46D,H46E,H46F} of C46B, {H33A,H33B,H33C} of C33A, {H48D,
  H48E,H48F} of C48B, {H34A,H34B,H34C} of C34A, {H28D,H28E,H28F} of C28B, {H42D,
  H42E,H42F} of C42B, {H5AA,H5AB,H5AC} of C5A, {H11D,H11E,H11F} of C11B, {H39D,
  H39E,H39F} of C39B, {H17A,H17B,H17C} of C17A, {H47D,H47E,H47F} of C47B, {H8BA,
  H8BB,H8BC} of C8B, {H4BA,H4BB,H4BC} of C4B, {H40D,H40E,H40F} of C40B, {H18D,
  H18E,H18F} of C18B, {H35D,H35E,H35F} of C35B, {H28A,H28B,H28C} of C28A, {H6AA,
  H6AB,H6AC} of C6A, {H38D,H38E,H38F} of C38B, {H43A,H43B,H43C} of C43A, {H32D,
  H32E,H32F} of C32B, {H40A,H40B,H40C} of C40A, {H39A,H39B,H39C} of C39A, {H35A,
  H35B,H35C} of C35A
 At 1.1 times of:
  {H3EA,H3EB} of C3E
 At 1.2 times of:
  {H43D,H43E,H43F} of C43B, {H36A,H36B,H36C} of C36B, {H12D,H12E,H12F} of
  C12B, {H47A,H47B,H47C} of C47A, {H24A,H24B,H24C} of C24A, {H48A,H48B,H48C} of
  C48A, {H26A,H26B,H26C} of C26A, {H3BA,H3BB,H3BC} of C3B, {H2PA,H2PB} of C2P,
  {H30D,H30E,H30F} of C30B, {H21A,H21B,H21C} of C21A, {H27A,H27B,H27C} of C27A,
  {H3AA,H3AB,H3AC} of C3A, {H46A,H46B,H46C} of C46A, {H4AA,H4AB,H4AC} of C4A,
  {H2BA,H2BB,H2BC} of C2B
2. Restrained distances
 O2A-H2A
 0.85 with sigma of 0.01
 O5B-H5B
 0.85 with sigma of 0.01
 C35B-C34B
 2.2 with sigma of 0.02
 C32B-C31B
 2.3 with sigma of 0.02
 C31B-C32B = C32B-C30B
 2.4 with sigma of 0.02
 Si4A-H2A
 2.07815 with sigma of 0.02
 Eu1A-H2A
 3.151192 with sigma of 0.02
 Si4-H5B
 2.060723 with sigma of 0.02
 Eu1B-H5B
 3.126202 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.00001 and sigma for 1-3 distances of 0.00001
4. Uiso/Uaniso restraints and constraints
C27A \\sim C25A \\sim C28A \\sim C26A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C4A \\sim C1A \\sim C3A \\sim C2A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C17A \\sim C18A \\sim C20A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C23A \\sim C22A \\sim C24A \\sim C21A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C31B \\sim C32B \\sim C29B \\sim C30B: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(O2A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C37B) \\sim Ueq, Uanis(O1B) \\sim Ueq, Uanis(C44A) \\sim Ueq, Uanis(C42A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C13B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C16A) \\sim Ueq, Uanis(C30A) \\sim Ueq, Uanis(C13B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C30A) \\sim Ueq, Uanis(C16A) \\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(O2A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C3A) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C4A) \\sim Ueq, Uanis(C2A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C10B) \\sim Ueq, Uanis(C9B) \\sim Ueq, Uanis(C12B) \\sim Ueq, Uanis(C11B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C16B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C40A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O12A) \\sim Ueq, Uanis(C17A) \\sim Ueq, Uanis(C30A) \\sim Ueq, Uanis(O13A) \\sim Ueq, Uanis(O1B) \\sim Ueq, Uanis(O13B) \\sim Ueq, Uanis(C25B) \\sim Ueq, Uanis(C36B) \\sim Ueq, Uanis(C23A) \\sim Ueq, Uanis(C21A) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(O7A) \\sim Ueq, Uanis(C6B) \\sim Ueq, Uanis(C5B) \\sim Ueq, Uanis(C7B) \\sim Ueq, Uanis(C8B) \\sim Ueq, Uanis(C2B) \\sim Ueq, Uanis(C1B) \\sim Ueq, Uanis(C30B) \\sim Ueq, Uanis(C32B) \\sim Ueq, Uanis(C31B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C43A) = Uanis(C41A) = Uanis(C42A) = Uanis(C44A)
Uanis(C13A) = Uanis(C15A) = Uanis(C16A) = Uanis(C14A)
Uanis(C1B) = Uanis(C2B) = Uanis(C3B) = Uanis(C4B)
Uanis(O1B) = Uanis(O14B)
Uanis(C32A) = Uanis(C29A) = Uanis(C31A) = Uanis(C30A)
Uanis(C6A) = Uanis(C7A) = Uanis(C8A) = Uanis(C5A)
Uanis(C25B) = Uanis(C27B) = Uanis(C26B) = Uanis(C28B)
Uanis(C29A) = Uanis(C31A) = Uanis(C30A) = Uanis(C32A)
Uanis(C45B) = Uanis(C48B) = Uanis(C47B) = Uanis(C46B)
Uanis(O12A) = Uanis(O11A)
Uanis(C27A) = Uanis(C26A) = Uanis(C25A) = Uanis(C28A)
Uanis(C21B) = Uanis(C22B) = Uanis(C23B) = Uanis(C24B)
Uanis(C40A) = Uanis(C39A) = Uanis(C37A) = Uanis(C38A)
Uanis(C17A) = Uanis(C19A) = Uanis(C18A) = Uanis(C20A)
Uanis(C33B) = Uanis(C35B) = Uanis(C34B) = Uanis(C36B)
Uanis(C33B) = Uanis(C36B) = Uanis(C34B) = Uanis(C35B)
Uanis(C36B) = Uanis(C33B) = Uanis(C34B) = Uanis(C35B)
Uanis(C21A) = Uanis(C23A) = Uanis(C22A) = Uanis(C24A)
5.a Secondary CH2 refined with riding coordinates:
 C2P(H2PA,H2PB), C3E(H3EA,H3EB)
5.b Idealised Me refined as rotating group:
 C18B(H18D,H18E,H18F), C20A(H20A,H20B,H20C), C17A(H17A,H17B,H17C), C39B(H39D,
 H39E,H39F), C20B(H20D,H20E,H20F), C40B(H40D,H40E,H40F), C17B(H17D,H17E,H17F),
 C15A(H15A,H15B,H15C), C32A(H32A,H32B,H32C), C16A(H16A,H16B,H16C), C18A(H18A,
 H18B,H18C), C8B(H8BA,H8BB,H8BC), C38B(H38D,H38E,H38F), C21B(H21D,H21E,H21F),
 C23B(H23D,H23E,H23F), C14A(H14A,H14B,H14C), C31A(H31A,H31B,H31C), C16B(H16D,
 H16E,H16F), C24B(H24D,H24E,H24F), C12A(H12A,H12B,H12C), C15B(H15D,H15E,H15F),
 C9A(H9AA,H9AB,H9AC), C13B(H13A,H13B,H13C), C36B(H36A,H36B,H36C), C7B(H7BA,H7BB,
 H7BC), C30A(H30A,H30B,H30C), C8A(H8AA,H8AB,H8AC), C3A(H3AA,H3AB,H3AC),
 C11A(H11A,H11B,H11C), C4B(H4BA,H4BB,H4BC), C6A(H6AA,H6AB,H6AC), C6B(H6BA,H6BB,
 H6BC), C2B(H2BA,H2BB,H2BC), C28B(H28D,H28E,H28F), C48A(H48A,H48B,H48C),
 C34B(H34D,H34E,H34F), C31B(H31D,H31E,H31F), C26B(H26D,H26E,H26F), C47A(H47A,
 H47B,H47C), C26A(H26A,H26B,H26C), C4A(H4AA,H4AB,H4AC), C35B(H35D,H35E,H35F),
 C28A(H28A,H28B,H28C), C46A(H46A,H46B,H46C), C3B(H3BA,H3BB,H3BC), C32B(H32D,
 H32E,H32F), C27B(H27D,H27E,H27F), C27A(H27A,H27B,H27C), C30B(H30D,H30E,H30F),
 C44B(H44D,H44E,H44F), C23A(H23A,H23B,H23C), C44A(H44A,H44B,H44C), C42A(H42A,
 H42B,H42C), C24A(H24A,H24B,H24C), C38A(H38A,H38B,H38C), C21A(H21A,H21B,H21C),
 C39A(H39A,H39B,H39C), C43A(H43A,H43B,H43C), C5A(H5AA,H5AB,H5AC), C33A(H33A,
 H33B,H33C), C42B(H42D,H42E,H42F), C11B(H11D,H11E,H11F), C48B(H48D,H48E,H48F),
 C47B(H47D,H47E,H47F), C46B(H46D,H46E,H46F), C34A(H34A,H34B,H34C), C43B(H43D,
 H43E,H43F), C35A(H35A,H35B,H35C), C10B(H10A,H10B,H10C), C40A(H40A,H40B,H40C),
 C2A(H2AA,H2AB,H2AC), C12B(H12D,H12E,H12F)
;
_shelxl_version_number           2013-2