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_4089694
_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
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_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 Ce O16 Si4, C1 H2 Cl2'
_chemical_formula_sum            'C49 H111 Ce Cl2 O16 Si4'
_chemical_formula_weight         1279.75
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_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             2014-06-30
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_cell_angle_alpha                75.471(2)
_cell_angle_beta                 81.717(2)
_cell_angle_gamma                60.894(2)
_cell_formula_units_Z            2
_cell_length_a                   13.684(2)
_cell_length_b                   13.866(2)
_cell_length_c                   21.622(3)
_cell_measurement_reflns_used    9950
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.686
_cell_measurement_theta_min      2.200
_cell_volume                     3468.7(9)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_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 0.990
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0362
_diffrn_reflns_av_unetI/netI     0.0468
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            49573
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.735
_diffrn_reflns_theta_min         1.704
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.856
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.5855
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0693 before and 0.0482 after correction.
The Ratio of minimum to maximum transmission is 0.7850.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear yellowish white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.225
_exptl_crystal_description       block
_exptl_crystal_F_000             1362
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.33
_refine_diff_density_max         1.690
_refine_diff_density_min         -3.246
_refine_diff_density_rms         0.158
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.203
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     834
_refine_ls_number_reflns         19341
_refine_ls_number_restraints     1026
_refine_ls_restrained_S_all      1.189
_refine_ls_R_factor_all          0.0837
_refine_ls_R_factor_gt           0.0737
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+35.2360P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1871
_refine_ls_wR_factor_ref         0.1916
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17052
_reflns_number_total             19341
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om501047g_si_001.cif
_cod_data_source_block           cesilox
_cod_original_cell_volume        3468.6(10)
_cod_database_code               4089694
_shelxl_version_number           2013-4
_olex2_refinement_description
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1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, {H27A,H27B,H27C} of C27, {H26A,H26B,H26C} of C26, {H29A,
  H29B,H29C} of C29, {H42A,H42B,H42C} of C42
 At 1.5 times of:
  All O(H) groups, {H56A,H56B,H56C} of C56, {H52A,H52B,H52C} of C52, {H54A,
  H54B,H54C} of C54, {H36A,H36B,H36C} of C36, {H38A,H38B,H38C} of C38, {H37A,
  H37B,H37C} of C37, {H48A,H48B,H48C} of C48, {H10A,H10B,H10C} of C10, {H12A,
  H12B,H12C} of C12, {H5A,H5B,H5C} of C5, {H3A,H3B,H3C} of C3, {H7A,H7B,H7C} of
  C7, {H8A,H8B,H8C} of C8, {H46A,H46B,H46C} of C46, {H43A,H43B,H43C} of C43,
  {H45A,H45B,H45C} of C45, {H17A,H17B,H17C} of C17, {H2A,H2B,H2C} of C2, {H11A,
  H11B,H11C} of C11, {H4A,H4B,H4C} of C4, {H24A,H24B,H24C} of C24, {H39A,H39B,
  H39C} of C39, {H25A,H25B,H25C} of C25, {H59A,H59B,H59C} of C59, {H40A,H40B,
  H40C} of C40, {H23A,H23B,H23C} of C23, {H61A,H61B,H61C} of C61, {H49A,H49B,
  H49C} of C49, {H50A,H50B,H50C} of C50, {H60A,H60B,H60C} of C60, {H34A,H34B,
  H34C} of C34, {H30A,H30B,H30C} of C30, {H33A,H33B,H33C} of C33, {H57A,H57B,
  H57C} of C57, {H55A,H55B,H55C} of C55, {H53A,H53B,H53C} of C53, {H21A,H21B,
  H21C} of C21, {H13A,H13B,H13C} of C13
2. Restrained distances
 O1-H1
 0.87 with sigma of 0.01
 Si3-H1
 2.09382 with sigma of 0.02
 Ce1-H1
 3.284256 with sigma of 0.02
 C44-C45 \\sim C44-C43 \\sim C44-C46
 with sigma of 0.0001
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=1-FVAR(1)
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=
 Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=FVAR(1)
 Sof(O15)=Sof(C31)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C30)=Sof(H30A)=
 Sof(H30B)=Sof(H30C)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=1-FVAR(2)
 Sof(O14)=Sof(C35)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C38)=Sof(H38A)=
 Sof(H38B)=Sof(H38C)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=FVAR(2)
 Uiso(H16A)=Uiso(H16B)=Uiso(H16C)=Uiso(H14A)=Uiso(H14B)=Uiso(H14C)=Uiso(H20A)=
 Uiso(H20B)=Uiso(H20C)=FVAR(3)
 Sof(O8)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C18)=1-FVAR(4)
 Sof(O9)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C19)=Sof(C13)=Sof(H13A)=
 Sof(H13B)=Sof(H13C)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(4)
 Sof(Cl1)=Sof(Cl4)=Sof(C63)=Sof(H63A)=Sof(H63B)=1-FVAR(5)
 Sof(Cl2)=Sof(Cl3)=Sof(C62)=Sof(H62A)=Sof(H62B)=FVAR(5)
6.a Free rotating group:
 O8(C16,H16A,H16B,H16C,C14,H14A,H14B,H14C,C20,H20A,H20B,H20C,C18)
6.b Secondary CH2 refined with riding coordinates:
 C62(H62A,H62B), C63(H63A,H63B)
6.c Idealised Me refined as rotating group:
 C60(H60A,H60B,H60C), C50(H50A,H50B,H50C), C49(H49A,H49B,H49C), C61(H61A,H61B,
 H61C), C23(H23A,H23B,H23C), C40(H40A,H40B,H40C), C59(H59A,H59B,H59C), C25(H25A,
 H25B,H25C), C42(H42A,H42B,H42C), C39(H39A,H39B,H39C), C24(H24A,H24B,H24C),
 C4(H4A,H4B,H4C), C11(H11A,H11B,H11C), C2(H2A,H2B,H2C), C17(H17A,H17B,H17C),
 C29(H29A,H29B,H29C), C26(H26A,H26B,H26C), C45(H45A,H45B,H45C), C43(H43A,H43B,
 H43C), C46(H46A,H46B,H46C), C8(H8A,H8B,H8C), C7(H7A,H7B,H7C), C3(H3A,H3B,H3C),
 C5(H5A,H5B,H5C), C12(H12A,H12B,H12C), C10(H10A,H10B,H10C), C48(H48A,H48B,H48C),
  C27(H27A,H27B,H27C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C36(H36A,H36B,
 H36C), C54(H54A,H54B,H54C), C52(H52A,H52B,H52C), C56(H56A,H56B,H56C), C34(H34A,
 H34B,H34C), C30(H30A,H30B,H30C), C33(H33A,H33B,H33C), C57(H57A,H57B,H57C),
 C55(H55A,H55B,H55C), C53(H53A,H53B,H53C), C13(H13A,H13B,H13C), C21(H21A,H21B,
 H21C)
;