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#$Date: 2016-03-22 21:12:29 +0200 (Tue, 22 Mar 2016) $
#$Revision: 179015 $
#$URL: svn://www.crystallography.net/cod/cif/4/12/13/4121344.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4121344
loop_
_publ_author_name
'Jerome R. Robinson'
'Zachary Gordon'
'Corwin H. Booth'
'Patrick J. Carroll'
'Patrick J. Walsh'
'Eric J. Schelter'
_publ_section_title
;
 Tuning Reactivity and Electronic Properties through Ligand Reorganization
 within a Cerium Heterobimetallic Framework
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              19016
_journal_page_last               19024
_journal_paper_doi               10.1021/ja410688w
_journal_volume                  135
_journal_year                    2013
_chemical_absolute_configuration syn
_chemical_formula_sum            'C72 H72 Br Ce Li3 N6 O6'
_chemical_formula_weight         1358.21
_space_group_IT_number           173
_symmetry_cell_setting           hexagonal
_symmetry_Int_Tables_number      173
_symmetry_space_group_name_Hall  'P 6c'
_symmetry_space_group_name_H-M   'P 63'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_formula_units_Z            2
_cell_length_a                   15.1330(5)
_cell_length_b                   15.1330(5)
_cell_length_c                   19.5974(9)
_cell_measurement_temperature    143(1)
_cell_volume                     3886.7(3)
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      143(1)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'CCD Area Detector'
_diffrn_measurement_device_type  'Bruker APEXII'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0377
_diffrn_reflns_av_sigmaI/netI    0.0381
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            42014
_diffrn_reflns_theta_full        27.56
_diffrn_reflns_theta_max         27.56
_diffrn_reflns_theta_min         1.87
_exptl_absorpt_coefficient_mu    1.147
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5947
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   '(SADABS; Sheldrick, 2007)'
_exptl_crystal_density_diffrn    1.161
_exptl_crystal_F_000             1392
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.06
_refine_diff_density_max         2.322
_refine_diff_density_min         -2.434
_refine_diff_density_rms         0.125
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.16(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.137
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         5979
_refine_ls_number_restraints     192
_refine_ls_restrained_S_all      1.166
_refine_ls_R_factor_all          0.1342
_refine_ls_R_factor_gt           0.1022
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.0815P)²+22.5832P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2571
_refine_ls_wR_factor_ref         0.2690
_reflns_number_gt                3644
_reflns_number_total             5979
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja410688w_si_002_02.cif
_cod_data_source_block           UP4031
_cod_original_sg_symbol_H-M      'P 63 '
_cod_database_code               4121344
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'x-y, x, z+1/2'
'-y, x-y, z'
'-x, -y, z+1/2'
'-x+y, -x, z'
'y, -x+y, z+1/2'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
Ce1 Ce 0.0000 0.0000 0.78256(8) 0.0651(4) Uani 1 3 d SU
Br1 Br 0.0000 0.0000 0.93035(12) 0.0603(5) Uani 1 3 d SU
O1 O 0.0639(5) 0.1381(6) 0.7090(6) 0.076(3) Uani 1 1 d U
O2 O 0.1716(5) 0.0831(5) 0.8015(6) 0.077(3) Uani 1 1 d U
N1 N 0.2909(11) -0.0365(14) 0.8060(10) 0.125(6) Uani 1 1 d DU
H1 H 0.2706 -0.1022 0.7946 0.166 Uiso 1 1 calc R
N2 N 0.3221(10) 0.0324(13) 0.6686(10) 0.109(5) Uani 1 1 d DU
H2 H 0.3593 0.1009 0.6611 0.145 Uiso 1 1 calc R
C1 C 0.1480(8) 0.1745(9) 0.6716(9) 0.069(3) Uani 1 1 d U
C2 C 0.1348(8) 0.1472(8) 0.6032(10) 0.073(3) Uani 1 1 d U
H2A H 0.0689 0.1078 0.5864 0.098 Uiso 1 1 calc R
C3 C 0.2183(11) 0.1772(10) 0.5583(9) 0.085(4) Uani 1 1 d U
H3 H 0.2081 0.1611 0.5122 0.113 Uiso 1 1 calc R
C4 C 0.3178(9) 0.2325(10) 0.5861(10) 0.080(4) Uani 1 1 d U
C5 C 0.4042(11) 0.2567(10) 0.5454(10) 0.091(4) Uani 1 1 d U
H5 H 0.3949 0.2370 0.4998 0.121 Uiso 1 1 calc R
C6 C 0.4999(12) 0.3077(13) 0.5709(12) 0.096(5) Uani 1 1 d U
H6 H 0.5556 0.3243 0.5428 0.128 Uiso 1 1 calc R
C7 C 0.5140(10) 0.3345(11) 0.6379(12) 0.096(5) Uani 1 1 d U
H7 H 0.5798 0.3675 0.6557 0.127 Uiso 1 1 calc R
C8 C 0.4333(11) 0.3139(10) 0.6796(11) 0.089(4) Uani 1 1 d U
H8 H 0.4464 0.3366 0.7246 0.119 Uiso 1 1 calc R
C9 C 0.3335(9) 0.2611(10) 0.6578(10) 0.085(5) Uani 1 1 d U
C10 C 0.2469(9) 0.2357(8) 0.6995(10) 0.072(4) Uani 1 1 d U
C11 C 0.2568(7) 0.2596(7) 0.7741(10) 0.068(4) Uani 1 1 d U
C12 C 0.3024(8) 0.3630(10) 0.7947(12) 0.084(4) Uani 1 1 d U
C13 C 0.3290(9) 0.4430(9) 0.7499(9) 0.083(4) Uani 1 1 d U
H13 H 0.3177 0.4305 0.7034 0.111 Uiso 1 1 calc R
C14 C 0.3743(10) 0.5466(11) 0.7755(13) 0.098(5) Uani 1 1 d U
H14 H 0.3933 0.6004 0.7452 0.131 Uiso 1 1 calc R
C15 C 0.3887(13) 0.5647(13) 0.8416(12) 0.102(5) Uani 1 1 d U
H15 H 0.4161 0.6312 0.8575 0.135 Uiso 1 1 calc R
C16 C 0.3635(13) 0.4860(15) 0.8875(11) 0.106(5) Uani 1 1 d U
H16 H 0.3753 0.4996 0.9339 0.141 Uiso 1 1 calc R
C17 C 0.3206(10) 0.3865(10) 0.8636(12) 0.087(4) Uani 1 1 d U
C18 C 0.2918(13) 0.3118(16) 0.9074(11) 0.101(6) Uani 1 1 d U
H18 H 0.3052 0.3290 0.9533 0.135 Uiso 1 1 calc R
C19 C 0.2413(11) 0.2061(12) 0.8903(11) 0.092(5) Uani 1 1 d U
H19 H 0.2215 0.1560 0.9236 0.122 Uiso 1 1 calc R
C20 C 0.2229(9) 0.1811(11) 0.8205(9) 0.072(4) Uani 1 1 d U
C21 C 0.3955(14) 0.0255(16) 0.7783(12) 0.137(7) Uani 1 1 d DU
H21A H 0.4202 0.0976 0.7856 0.182 Uiso 1 1 calc R
H21B H 0.4417 0.0078 0.8009 0.182 Uiso 1 1 calc R
C22 C 0.3899(15) 0.0031(17) 0.7049(11) 0.123(7) Uani 1 1 d DU
H22A H 0.3644 -0.0693 0.6986 0.164 Uiso 1 1 calc R
H22B H 0.4579 0.0399 0.6854 0.164 Uiso 1 1 calc R
C23 C 0.273(2) -0.037(2) 0.8787(13) 0.160(10) Uani 1 1 d DU
H23A H 0.3221 -0.0480 0.9030 0.240 Uiso 1 1 calc R
H23B H 0.2056 -0.0907 0.8894 0.240 Uiso 1 1 calc R
H23C H 0.2808 0.0274 0.8920 0.240 Uiso 1 1 calc R
C24 C 0.2926(16) -0.0164(18) 0.6020(12) 0.147(9) Uani 1 1 d DU
H24A H 0.3228 -0.0584 0.5953 0.221 Uiso 1 1 calc R
H24B H 0.3159 0.0349 0.5671 0.221 Uiso 1 1 calc R
H24C H 0.2197 -0.0578 0.5998 0.221 Uiso 1 1 calc R
Li1 Li 0.2075(17) 0.0083(19) 0.7414(14) 0.075(6) Uani 1 1 d U
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Li Li -0.0003 0.0001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ce Ce -0.2486 2.6331 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
O2 Ce1 O2 117.39(17) . 3
O2 Ce1 O2 117.39(17) . 5
O2 Ce1 O2 117.39(17) 3 5
O2 Ce1 O1 150.7(4) . 3
O2 Ce1 O1 75.9(3) 3 3
O2 Ce1 O1 71.1(3) 5 3
O2 Ce1 O1 75.9(3) . .
O2 Ce1 O1 71.1(3) 3 .
O2 Ce1 O1 150.7(4) 5 .
O1 Ce1 O1 85.3(4) 3 .
O2 Ce1 O1 71.1(3) . 5
O2 Ce1 O1 150.7(4) 3 5
O2 Ce1 O1 75.9(3) 5 5
O1 Ce1 O1 85.3(4) 3 5
O1 Ce1 O1 85.3(4) . 5
O2 Ce1 Br1 80.6(3) . .
O2 Ce1 Br1 80.6(3) 3 .
O2 Ce1 Br1 80.6(3) 5 .
O1 Ce1 Br1 128.5(3) 3 .
O1 Ce1 Br1 128.5(3) . .
O1 Ce1 Br1 128.5(3) 5 .
O2 Ce1 Li1 147.3(5) . 5
O2 Ce1 Li1 95.3(5) 3 5
O2 Ce1 Li1 36.0(6) 5 5
O1 Ce1 Li1 35.3(6) 3 5
O1 Ce1 Li1 119.7(6) . 5
O1 Ce1 Li1 81.3(5) 5 5
Br1 Ce1 Li1 104.7(5) . 5
O2 Ce1 Li1 36.0(6) . .
O2 Ce1 Li1 147.3(5) 3 .
O2 Ce1 Li1 95.3(5) 5 .
O1 Ce1 Li1 119.7(6) 3 .
O1 Ce1 Li1 81.3(5) . .
O1 Ce1 Li1 35.3(6) 5 .
Br1 Ce1 Li1 104.7(5) . .
Li1 Ce1 Li1 113.8(4) 5 .
O2 Ce1 Li1 95.3(5) . 3
O2 Ce1 Li1 36.0(6) 3 3
O2 Ce1 Li1 147.3(5) 5 3
O1 Ce1 Li1 81.3(5) 3 3
O1 Ce1 Li1 35.3(6) . 3
O1 Ce1 Li1 119.7(6) 5 3
Br1 Ce1 Li1 104.7(5) . 3
Li1 Ce1 Li1 113.8(4) 5 3
Li1 Ce1 Li1 113.8(4) . 3
C1 O1 Li1 131.4(10) . 3
C1 O1 Ce1 126.9(7) . .
Li1 O1 Ce1 98.8(9) 3 .
C20 O2 Li1 130.9(11) . .
C20 O2 Ce1 121.8(7) . .
Li1 O2 Ce1 99.0(8) . .
C23 N1 C21 120(2) . .
C23 N1 Li1 116.8(16) . .
C21 N1 Li1 101.4(14) . .
C24 N2 C22 111.1(15) . .
C24 N2 Li1 119.8(14) . .
C22 N2 Li1 104.6(13) . .
O1 C1 C2 116.4(11) . .
O1 C1 C10 122.5(15) . .
C2 C1 C10 121.0(13) . .
C1 C2 C3 122.2(12) . .
C4 C3 C2 117.8(15) . .
C5 C4 C3 120.6(17) . .
C5 C4 C9 118.4(13) . .
C3 C4 C9 120.9(13) . .
C6 C5 C4 121.8(19) . .
C5 C6 C7 119.5(18) . .
C6 C7 C8 121.3(17) . .
C7 C8 C9 122.7(19) . .
C8 C9 C10 124.9(18) . .
C8 C9 C4 116.2(15) . .
C10 C9 C4 118.9(13) . .
C1 C10 C9 118.9(16) . .
C1 C10 C11 118.8(13) . .
C9 C10 C11 121.9(12) . .
C20 C11 C12 122.1(18) . .
C20 C11 C10 119.2(11) . .
C12 C11 C10 118.7(14) . .
C13 C12 C17 117.3(14) . .
C13 C12 C11 123.7(19) . .
C17 C12 C11 118.9(16) . .
C12 C13 C14 120.1(18) . .
C15 C14 C13 120.2(17) . .
C14 C15 C16 120.9(17) . .
C15 C16 C17 119(2) . .
C18 C17 C16 119(2) . .
C18 C17 C12 118.6(15) . .
C16 C17 C12 122.1(17) . .
C17 C18 C19 125.1(19) . .
C20 C19 C18 117.0(17) . .
O2 C20 C11 122.2(15) . .
O2 C20 C19 119.7(14) . .
C11 C20 C19 118.1(15) . .
C22 C21 N1 106.9(18) . .
C21 C22 N2 111.6(17) . .
O1 Li1 O2 90.7(10) 5 .
O1 Li1 N1 131.2(14) 5 .
O2 Li1 N1 102.4(14) . .
O1 Li1 N2 115.0(15) 5 .
O2 Li1 N2 140.1(14) . .
N1 Li1 N2 83.7(9) . .
O1 Li1 Ce1 45.9(6) 5 .
O2 Li1 Ce1 45.0(5) . .
N1 Li1 Ce1 124.7(12) . .
N2 Li1 Ce1 151.4(11) . .
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
Ce1 O2 2.280(7) .
Ce1 O2 2.280(7) 3
Ce1 O2 2.280(7) 5
Ce1 O1 2.314(9) 3
Ce1 O1 2.314(9) .
Ce1 O1 2.314(9) 5
Ce1 Br1 2.896(3) .
Ce1 Li1 3.18(2) 5
Ce1 Li1 3.18(2) .
Ce1 Li1 3.18(2) 3
O1 C1 1.328(15) .
O1 Li1 1.86(3) 3
O2 C20 1.337(16) .
O2 Li1 1.89(3) .
N1 C23 1.450(17) .
N1 C21 1.481(16) .
N1 Li1 2.12(3) .
N2 C24 1.455(18) .
N2 C22 1.488(15) .
N2 Li1 2.13(3) .
C1 C2 1.39(2) .
C1 C10 1.418(17) .
C2 C3 1.41(2) .
C3 C4 1.416(19) .
C4 C5 1.41(2) .
C4 C9 1.45(2) .
C5 C6 1.35(2) .
C6 C7 1.36(2) .
C7 C8 1.37(2) .
C8 C9 1.38(2) .
C9 C10 1.42(2) .
C10 C11 1.50(2) .
C11 C20 1.376(18) .
C11 C12 1.417(18) .
C12 C13 1.38(2) .
C12 C17 1.39(2) .
C13 C14 1.45(2) .
C14 C15 1.32(3) .
C15 C16 1.39(3) .
C16 C17 1.39(2) .
C17 C18 1.31(2) .
C18 C19 1.43(2) .
C19 C20 1.41(2) .
C21 C22 1.471(17) .
Li1 O1 1.86(3) 5
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.333 0.333 0.978 472 98 ' '
2 0.333 0.667 0.478 472 98 ' '
3 0.333 0.667 0.948 7 0 ' '
4 0.667 0.333 0.448 7 0 ' '
