Synthesis and Characterisation of Lanthanide N-Trimethylsilyl and -Mesityl Functionalised Bis(iminophosphorano)methanides and -Methanediides
Marshall, G.; Wooles, A.J.; Mills, D.P.; Lewis, W.; Blake, A.J.; Liddle, S.T.; Inorganics 1 (2013) 46–69; doi:10.3390/inorganics1010046

data_1556459
_publ_section_title
;
 Synthesis and Characterisation of Lanthanide N-Trimethylsilyl and
 -Mesityl Functionalised Bis(iminophosphorano)methanides and
 -Methanediides
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_journal_name_full               Inorganics
_journal_page_first              46
_journal_page_last               69
_journal_paper_doi               10.3390/inorganics1010046
_journal_volume                  1
_journal_year                    2013
_chemical_formula_moiety         'C49 H59 Gd I2 N4 P2, 2 (C7 H8)'
_chemical_formula_sum            'C63 H75 Gd I2 N4 P2'
_chemical_formula_weight         1361.26
_space_group_crystal_system      orthorhombic
_space_group_IT_number           64
_space_group_name_Hall           '-C 2ac 2'
_space_group_name_H-M_alt        'C m c e'
_atom_sites_solution_hydrogens   'geom, Me from difmap'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   26.770(2)
_cell_length_b                   18.9186(16)
_cell_length_c                   22.445(2)
_cell_measurement_reflns_used    6824
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      27.12
_cell_measurement_theta_min      2.15
_cell_volume                     11367.3(16)
_computing_cell_refinement       'Bruker SAINT version 6.36A (Bruker, 2000)'
_computing_data_collection       'Bruker SMART version 5.625 (Bruker, 2001)'
_computing_data_reduction        'Bruker SAINT; SHELXTL (Sheldrick, 2008)'
_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
;
_diffrn_ambient_temperature      90(2)
_diffrn_detector_area_resol_mean 8.366
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0458
_diffrn_reflns_av_unetI/netI     0.0356
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            34384
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.461
_diffrn_reflns_theta_min         2.368
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.353
_exptl_absorpt_correction_T_max  0.4305
_exptl_absorpt_correction_T_min  0.3452
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2007/2 (Bruker,2007) was used for absorption correction.
wR2(int) was 0.0781 before and 0.0477 after correction.
The Ratio of minimum to maximum transmission is 0.8019.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            COLOURLESS
_exptl_crystal_density_diffrn    1.591
_exptl_crystal_description       BLOCK
_exptl_crystal_F_000             5448
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.30
_refine_diff_density_min         -0.63
_refine_diff_density_rms         0.11
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.04
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     413
_refine_ls_number_reflns         6604
_refine_ls_number_restraints     154
_refine_ls_restrained_S_all      1.03
_refine_ls_R_factor_all          0.0483
_refine_ls_R_factor_gt           0.0314
_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^)+(0.040P)^2^+0.307P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0687
_refine_ls_wR_factor_ref         0.0758
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                5170
_reflns_number_total             6604
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            inorganics-01-00046-s001.cif
_cod_data_source_block           6b
_cod_original_cell_volume        11367.4(17)
_cod_original_sg_symbol_Hall     '-C 2bc 2'
_cod_original_sg_symbol_H-M      'C m c a'
_cod_database_code               1556459
_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
2. Restrained distances
 C86-C81 \\sim C82-C81 \\sim C83-C82 \\sim C84-C83 \\sim C85-C84 \\sim C86-C85
 with sigma of 0.02
 C81-C83 \\sim C82-C84 \\sim C83-C85 \\sim C84-C86 \\sim C85-C81 \\sim C86-C82
 with sigma of 0.02
 C72-C73 \\sim C62-C63
 with sigma of 0.02
 C73-C74 \\sim C63-C64
 with sigma of 0.02
 C72-C74 \\sim C62-C64
 with sigma of 0.02
 C71-C72 \\sim C61-C62
 with sigma of 0.02
 C71-C73 \\sim C61-C63
 with sigma of 0.02
 C74-C75 \\sim C64-C65
 with sigma of 0.02
 C73-C75 \\sim C63-C65
 with sigma of 0.02
3. Restrained planarity
 C62, C63, C64, C61, C65
 with sigma of 0.1
 C72, C73, C71, C74, C75
 with sigma of 0.1
4. Rigid bond restraints
 C84, C83, C82, C87, C81, C86, C85
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C63, C62, C64, C61, C65
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C72, C73, C71, C74, C75
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C86 \\sim C81 \\sim C82 \\sim C85 \\sim C83 \\sim C84: within 1.7A with 
sigma of 0.04 and sigma for terminal atoms of 0.08
C63 \\sim C61 \\sim C65 \\sim C62 \\sim C64: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
C72 \\sim C74 \\sim C73 \\sim C71 \\sim C75: within 1.7A with sigma of 
0.04 and sigma for terminal atoms of 0.08
6. Others
 Sof(C73)=Sof(H73)=Sof(C74)=Sof(H74)=1-FVAR(1)
 Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C72)=Sof(C75)=Sof(H75)=0.5*(1-
 FVAR(2))
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=Sof(C62)=Sof(C65)=Sof(H65)=0.5*FVAR(2)
 Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=FVAR(1)
 Fixed Sof: C25(0.5) H25A(0.5) H25B(0.5) C26(0.5) H25C(0.5) H26(0.5) C81(0.5)
 H81(0.5) C82(0.5) C83(0.5) H83(0.5) C84(0.5) H84(0.5) C85(0.5) H85(0.5)
 C86(0.5) H86(0.5) C87(0.5) H87A(0.5) H87B(0.5) H87C(0.5)
7.a Ternary CH refined with riding coordinates:
 C1(H1)
7.b Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C26(H25C,H26)
7.c Me refined with riding coordinates:
 C61(H61A,H61B,H61C), C71(H71A,H71B,H71C)
7.d Aromatic/amide H refined with riding coordinates:
 C5(H5), C8(H8), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C18(H18),
 C19(H19), C20(H20), C21(H21), C22(H22), C63(H63), C64(H64), C65(H65), C73(H73),
  C74(H74), C75(H75), C81(H81), C83(H83), C84(H84), C85(H85), C86(H86)
7.e Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C7(H7A,H7B,H7C), C10(H10A,H10B,H10C), C23(H23A,H23B,H23C),
 C24(H24A,H24B,H24C), C87(H87A,H87B,H87C)
;