Bis(amidinate) ligands in early lanthanide chemistry - synthesis, structures, and hydroamination catalysis.
Kazeminejad, Neda; Munzel, Denise; Gamer, Michael T.; Roesky, Peter W.; Chemical communications (Cambridge, England) 53 (2017) 1060–1063; doi:10.1039/c6cc08958e

data_7119279
_publ_section_title
;
 Bis(amidinate) ligands in early lanthanide chemistry - synthesis,
 structures, and hydroamination catalysis.
;
_journal_issue                   6
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              1060
_journal_page_last               1063
_journal_paper_doi               10.1039/c6cc08958e
_journal_volume                  53
_journal_year                    2017
_chemical_formula_moiety         '2(C96 H104 La2 N10 O2 Si4), 9(C7 H8)'
_chemical_formula_sum            'C255 H280 La4 N20 O4 Si8'
_chemical_formula_weight         4467.32
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yac'
_space_group_name_H-M_alt        'P 1 2/n 1'
_symmetry_space_group_name_Hall  '-P 2yac'
_symmetry_space_group_name_H-M   'P 1 2/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-12-01
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_audit_update_record
;
2016-12-02 deposited with the CCDC.
2016-12-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.338(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   20.8963(9)
_cell_length_b                   22.8615(8)
_cell_length_c                   25.1772(10)
_cell_measurement_reflns_used    44720
_cell_measurement_temperature    150
_cell_measurement_theta_max      27.77
_cell_measurement_theta_min      1.78
_cell_volume                     11993.2(8)
_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    'SHELXT-2014/7 (Sheldrick, 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'image plate (34cm diameter)'
_diffrn_detector_area_resol_mean 6.67
_diffrn_detector_type            'STOE image plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device       'two-circle goniometer'
_diffrn_measurement_device_type  'STOE IPDS 2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_collimation    '0.5mm monocapillary'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1342
_diffrn_reflns_av_unetI/netI     0.1045
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            76389
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.266
_diffrn_reflns_theta_min         1.782
_diffrn_source                   'sealed tube, 12x0.4mm long-fine focus'
_exptl_absorpt_coefficient_mu    0.796
_exptl_absorpt_correction_T_max  0.9990
_exptl_absorpt_correction_T_min  0.9951
_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    1.237
_exptl_crystal_description       plate
_exptl_crystal_F_000             4640
_exptl_crystal_size_max          0.247
_exptl_crystal_size_mid          0.167
_exptl_crystal_size_min          0.033
_refine_diff_density_max         3.549
_refine_diff_density_min         -1.671
_refine_diff_density_rms         0.168
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1183
_refine_ls_number_reflns         23699
_refine_ls_number_restraints     291
_refine_ls_restrained_S_all      1.099
_refine_ls_R_factor_all          0.2382
_refine_ls_R_factor_gt           0.1308
_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^)+(0.1003P)^2^+213.5015P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2810
_refine_ls_wR_factor_ref         0.3663
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12174
_reflns_number_total             23699
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc08958e2.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 7119278--7119283.cif.'
_cod_database_code               7119279
_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
 C116-C117
 1.51 with sigma of 0.02
 C123-C124
 1.51 with sigma of 0.02
 C109-C110
 1.51 with sigma of 0.02
 C216-C217
 1.51 with sigma of 0.02
 C223-C224
 1.51 with sigma of 0.02
 C209-C210
 1.51 with sigma of 0.02
 C117-C118 \\sim C120-C121 \\sim C121-C122 \\sim C122-C117
 with sigma of 0.02
 C117-C121 \\sim C122-C120 \\sim C118-C122 \\sim C118-C120
 with sigma of 0.04
 C116-C122 \\sim C116-C118
 with sigma of 0.04
 C124-C129 \\sim C129-C128 \\sim C126-C125 \\sim C125-C124
 with sigma of 0.02
 C124-C126 \\sim C124-C128 \\sim C129-C125 \\sim C128-C126
 with sigma of 0.04
 C123-C125 \\sim C123-C129
 with sigma of 0.04
 C110-C115 \\sim C115-C114 \\sim C112-C111 \\sim C111-C110
 with sigma of 0.02
 C110-C112 \\sim C110-C114 \\sim C115-C111 \\sim C114-C112
 with sigma of 0.04
 C109-C111 \\sim C109-C115
 with sigma of 0.04
 C217-C222 \\sim C222-C221 \\sim C221-C220 \\sim C220-C219 \\sim C219-C218
\\sim C218-C217
 with sigma of 0.02
 C217-C219 \\sim C217-C221 \\sim C218-C220 \\sim C222-C218 \\sim C221-C219
\\sim C222-C220
 with sigma of 0.04
 C216-C218 \\sim C216-C222
 with sigma of 0.04
 C224-C225 \\sim C225-C226 \\sim C228-C229 \\sim C229-C224
 with sigma of 0.02
 C224-C228 \\sim C224-C226 \\sim C225-C229 \\sim C226-C228
 with sigma of 0.04
 C223-C229 \\sim C223-C225
 with sigma of 0.04
 C210-C215 \\sim C215-C214 \\sim C214-C213 \\sim C213-C212 \\sim C212-C211
\\sim C211-C210
 with sigma of 0.02
 C210-C212 \\sim C210-C214 \\sim C211-C213 \\sim C215-C211 \\sim C214-C212
\\sim C215-C213
 with sigma of 0.04
 C209-C211 \\sim C209-C215
 with sigma of 0.04
3. Restrained planarity
 C116, C117, C122, C121, C120, C118
 with sigma of 0.1
 C125, C123, C124, C126, C128, C129
 with sigma of 0.1
 C110, C115, C114, C112, C111, C109
 with sigma of 0.1
 C216, C217, C218, C219, C220, C221, C222
 with sigma of 0.1
 C223, C224, C225, C226, C228, C229
 with sigma of 0.1
 C209, C210, C211, C212, C213, C214, C215
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C24 \\sim C25 \\sim C26 \\sim C28: within 1.7A with sigma of 0.008 and sigma
for terminal atoms of 0.016
C17 \\sim C18 \\sim C19 \\sim C21: within 1.7A with sigma of 0.008 and sigma
for terminal atoms of 0.016
C2 \\sim C7 \\sim O1 \\sim C8 \\sim C13: within 1.7A with sigma of 0.004 and
sigma for terminal atoms of 0.016
C116 \\sim C117 \\sim C122 \\sim C121 \\sim C120 \\sim C118: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C125 \\sim C123 \\sim C124 \\sim C125 \\sim C126 \\sim C127 \\sim C128 \\sim
C129: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C110 \\sim C115 \\sim C114 \\sim C112 \\sim C111 \\sim C109: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
O2 \\sim C50 \\sim C54 \\sim C55 \\sim C61 \\sim C57 \\sim C56: within 1.7A
with sigma of 0.004 and sigma for terminal atoms of 0.008
C216 \\sim C217 \\sim C218 \\sim C219 \\sim C220 \\sim C221 \\sim C222: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C223 \\sim C224 \\sim C225 \\sim C226 \\sim C228 \\sim C229: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C209 \\sim C210 \\sim C215: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C86 \\sim C87 \\sim C88 \\sim C90: within 1.7A with sigma of 0.008 and sigma
for terminal atoms of 0.016
5. Rigid body (RIGU) restrains
 C116, C117, C122, C121, C120, C118
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C125, C123, C124, C126, C128, C129
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C110, C115, C114, C112, C111, C109
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C216, C217, C218, C219, C220, C221, C222
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C223, C224, C225, C226, C228, C229
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C209, C210, C211, C212, C213, C214, C215
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: C223(0.5) H22A(0.5) H22B(0.5) H22C(0.5) C224(0.5) C225(0.5)
 H225(0.5) C226(0.5) H226(0.5) C227(0.5) H227(0.5) C228(0.5) H228(0.5)
 C229(0.5) H229(0.5) C216(0.5) H21D(0.5) H21E(0.5) H21F(0.5) C217(0.5)
 C218(0.5) H218(0.5) C219(0.5) H219(0.5) C220(0.5) H220(0.5) C221(0.5)
 H221(0.5) C222(0.5) H222(0.5) C209(0.5) H20A(0.5) H20B(0.5) H20C(0.5)
 C210(0.5) C215(0.5) H215(0.5) C214(0.5) H214(0.5) C213(0.5) H213(0.5)
 C212(0.5) H212(0.5) C211(0.5) H211(0.5) C104(0.5) H10D(0.5) H10E(0.5)
 H10F(0.5) C110(0.5) C115(0.5) H115(0.5) C114(0.5) H114(0.5) C113(0.5)
 H113(0.5) C112(0.5) H112(0.5) C111(0.5) H111(0.5) C109(0.5) H10A(0.5)
 H10B(0.5) H10C(0.5) C123(0.5) H12A(0.5) H12B(0.5) H12C(0.5) C124(0.5)
 C125(0.5) H125(0.5) C126(0.5) H126(0.5) C127(0.5) H127(0.5) C128(0.5)
 H128(0.5) C129(0.5) H129(0.5) C116(0.5) H11A(0.5) H11B(0.5) H11C(0.5)
 C117(0.5) C122(0.5) H122(0.5) C121(0.5) H121(0.5) C120(0.5) H120(0.5)
 C119(0.5) H119(0.5) C118(0.5) H118(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C10(H10), C11(H11), C12(H12), C16(H16), C17(H17),
 C19(H19), C20(H20), C23(H23), C24(H24), C26(H26), C27(H27), C30(H30), C31(H31),
  C33(H33), C34(H34), C37(H37), C38(H38), C40(H40), C41(H41), C51(H51),
 C52(H52), C53(H53), C60(H60), C59(H59), C58(H58), C64(H64), C65(H65), C67(H67),
  C68(H68), C71(H71), C72(H72), C74(H74), C75(H75), C78(H78), C79(H79),
 C81(H81), C82(H82), C85(H85), C86(H86), C88(H88), C89(H89), C225(H225),
 C226(H226), C227(H227), C228(H228), C229(H229), C218(H218), C219(H219),
 C220(H220), C221(H221), C222(H222), C99(H99), C100(H100), C101(H101),
 C102(H102), C103(H103), C215(H215), C214(H214), C213(H213), C212(H212),
 C211(H211), C106(H106), C107(H107), C108(H108), C115(H115), C114(H114),
 C113(H113), C112(H112), C111(H111), C125(H125), C126(H126), C127(H127),
 C128(H128), C129(H129), C122(H122), C121(H121), C120(H120), C119(H119),
 C118(H118)
7.b Fitted hexagon refined as free rotating group:
 C61(C60,C59,C58,C57,C56), C224(C225,C226,C227,C228,C229), C217(C218,C219,C220,
 C221,C222), C210(C215,C214,C213,C212,C211), C110(C115,C114,C113,C112,C111),
 C124(C125,C126,C127,C128,C129), C117(C122,C121,C120,C119,C118)
7.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C28(H28A,H28B,H28C), C35(H35A,H35B,H35C), C42(H42A,H42B,
 H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,
 H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C69(H69A,H69B,H69C),
 C76(H76A,H76B,H76C), C83(H83A,H83B,H83C), C90(H90A,H90B,H90C), C91(H91A,H91B,
 H91C), C92(H92A,H92B,H92C), C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C95(H95A,
 H95B,H95C), C96(H96A,H96B,H96C), C223(H22A,H22B,H22C), C216(H21D,H21E,H21F),
 C97(H97A,H97B,H97C), C209(H20A,H20B,H20C), C104(H10D,H10E,H10F), C109(H10A,
 H10B,H10C), C123(H12A,H12B,H12C), C116(H11A,H11B,H11C)
;
_shelx_res_checksum              49635
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'