# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_ldskk141208
_database_code_depnum_ccdc_archive 'CCDC 1057179'
_audit_update_record             
;
2015-03-31 deposited with the CCDC.
2015-07-29 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C27 H18 Eu N21, 3(C H4 O)'
_chemical_formula_sum            'C30 H30 Eu N21 O3'
_chemical_formula_weight         884.71

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'
Eu Eu -0.1578 3.6682 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_H-M_alt        'R -3 :H'
_space_group_name_Hall           '-R 3'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'

_cell_length_a                   16.997(5)
_cell_length_b                   16.997(5)
_cell_length_c                   21.834(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     5463(3)
_cell_formula_units_Z            6
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    4768
_cell_measurement_theta_min      2.32
_cell_measurement_theta_max      29.54

_exptl_crystal_description       prism
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.614
_exptl_crystal_F_000             2664
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.18
_exptl_absorpt_coefficient_mu    1.787
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6712
_exptl_absorpt_correction_T_max  0.7462
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      173(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            14715
_diffrn_reflns_av_unetI/netI     0.0376
_diffrn_reflns_av_R_equivalents  0.0344
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_theta_min         1.668
_diffrn_reflns_theta_max         31.005
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             3878
_reflns_number_gt                3346
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
 ?
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0340P)²+0.0202P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3878
_refine_ls_number_parameters     168
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0364
_refine_ls_R_factor_gt           0.0276
_refine_ls_wR_factor_ref         0.0622
_refine_ls_wR_factor_gt          0.0604
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_restrained_S_all      1.049
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.07804(15) -0.06900(15) 0.40715(11) 0.0293(5) Uani 1 1 d . . . . .
H1 H 0.0194 -0.1184 0.4165 0.035 Uiso 1 1 calc R U . . .
C2 C 0.15398(17) -0.04198(17) 0.44390(12) 0.0352(5) Uani 1 1 d . . . . .
H2 H 0.1572 -0.0686 0.4814 0.042 Uiso 1 1 calc R U . . .
C3 C 0.22281(15) 0.03071(16) 0.41490(11) 0.0282(5) Uani 1 1 d . . . . .
H3 H 0.2839 0.0654 0.4285 0.034 Uiso 1 1 calc R U . . .
C4 C 0.23075(13) 0.11089(14) 0.31759(10) 0.0205(4) Uani 1 1 d . . . . .
C5 C 0.32496(14) 0.16558(16) 0.31601(12) 0.0322(5) Uani 1 1 d . . . . .
H5 H 0.3623 0.1608 0.3465 0.039 Uiso 1 1 calc R U . . .
C6 C 0.36192(15) 0.22681(18) 0.26860(13) 0.0384(6) Uani 1 1 d . . . . .
H6 H 0.4260 0.2643 0.2653 0.046 Uiso 1 1 calc R U . . .
C7 C 0.30549(15) 0.23363(16) 0.22569(12) 0.0323(5) Uani 1 1 d . . . . .
H7 H 0.3302 0.2758 0.1928 0.039 Uiso 1 1 calc R U . . .
C8 C 0.21255(13) 0.17785(13) 0.23166(10) 0.0212(4) Uani 1 1 d . . . . .
C9 C 0.14675(14) 0.18193(13) 0.19079(10) 0.0212(4) Uani 1 1 d . . . . .
C10 C 0.3836(3) 0.3842(2) 0.06435(17) 0.0636(10) Uani 1 1 d . . . . .
H10A H 0.4280 0.4432 0.0471 0.095 Uiso 1 1 calc R U . . .
H10B H 0.3519 0.3412 0.0310 0.095 Uiso 1 1 calc R U . . .
H10C H 0.4150 0.3613 0.0901 0.095 Uiso 1 1 calc R U . . .
N1 N 0.09681(11) -0.01802(11) 0.35756(8) 0.0209(3) Uani 1 1 d . . . . .
N2 N 0.18748(11) 0.04409(11) 0.36296(8) 0.0197(3) Uani 1 1 d . . . . .
N3 N 0.17487(10) 0.11561(11) 0.27676(8) 0.0180(3) Uani 1 1 d . . . . .
N4 N 0.16476(13) 0.24016(13) 0.14508(10) 0.0323(4) Uani 1 1 d . . . . .
N5 N 0.08211(14) 0.21963(14) 0.12354(10) 0.0368(5) Uani 1 1 d . . . . .
N6 N 0.01775(13) 0.15142(14) 0.15503(9) 0.0318(4) Uani 1 1 d . . . . .
N7 N 0.05731(11) 0.12645(12) 0.19817(8) 0.0217(3) Uani 1 1 d . . . . .
O1 O 0.32136(16) 0.39405(13) 0.09942(12) 0.0600(6) Uani 1 1 d . . . . .
H1A H 0.2765 0.3426 0.1069 0.090 Uiso 1 1 calc R U . . .
Eu1 Eu 0.0000 0.0000 0.27527(2) 0.01387(5) Uani 1 3 d S T P . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 N1 1.322(3) . ?
C1 C2 1.389(3) . ?
C1 H1 0.9500 . ?
C2 C3 1.360(3) . ?
C2 H2 0.9500 . ?
C3 N2 1.355(3) . ?
C3 H3 0.9500 . ?
C4 N3 1.334(3) . ?
C4 C5 1.393(3) . ?
C4 N2 1.406(3) . ?
C5 C6 1.377(3) . ?
C5 H5 0.9500 . ?
C6 C7 1.387(3) . ?
C6 H6 0.9500 . ?
C7 C8 1.383(3) . ?
C7 H7 0.9500 . ?
C8 N3 1.350(3) . ?
C8 C9 1.459(3) . ?
C9 N4 1.329(3) . ?
C9 N7 1.339(3) . ?
C10 O1 1.382(4) . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?
N1 N2 1.370(2) . ?
N1 Eu1 2.5561(17) . ?
N3 Eu1 2.6184(17) . ?
N4 N5 1.351(3) . ?
N5 N6 1.321(3) . ?
N6 N7 1.343(2) . ?
N7 Eu1 2.5117(18) . ?
O1 H1A 0.8400 . ?
Eu1 N7 2.5117(18) 3 ?
Eu1 N7 2.5117(18) 2 ?
Eu1 N1 2.5561(17) 2 ?
Eu1 N1 2.5561(17) 3 ?
Eu1 N3 2.6184(17) 2 ?
Eu1 N3 2.6185(17) 3 ?

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
_geom_angle_publ_flag
N1 C1 C2 112.1(2) . . ?
N1 C1 H1 123.9 . . ?
C2 C1 H1 123.9 . . ?
C3 C2 C1 105.5(2) . . ?
C3 C2 H2 127.3 . . ?
C1 C2 H2 127.3 . . ?
N2 C3 C2 106.86(19) . . ?
N2 C3 H3 126.6 . . ?
C2 C3 H3 126.6 . . ?
N3 C4 C5 124.0(2) . . ?
N3 C4 N2 114.75(17) . . ?
C5 C4 N2 121.26(19) . . ?
C6 C5 C4 117.4(2) . . ?
C6 C5 H5 121.3 . . ?
C4 C5 H5 121.3 . . ?
C5 C6 C7 119.9(2) . . ?
C5 C6 H6 120.1 . . ?
C7 C6 H6 120.1 . . ?
C8 C7 C6 118.7(2) . . ?
C8 C7 H7 120.7 . . ?
C6 C7 H7 120.7 . . ?
N3 C8 C7 122.5(2) . . ?
N3 C8 C9 114.13(17) . . ?
C7 C8 C9 123.3(2) . . ?
N4 C9 N7 111.87(19) . . ?
N4 C9 C8 126.72(19) . . ?
N7 C9 C8 121.35(18) . . ?
O1 C10 H10A 109.5 . . ?
O1 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
O1 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
C1 N1 N2 104.14(17) . . ?
C1 N1 Eu1 134.05(14) . . ?
N2 N1 Eu1 120.78(12) . . ?
C3 N2 N1 111.41(17) . . ?
C3 N2 C4 128.95(18) . . ?
N1 N2 C4 119.63(16) . . ?
C4 N3 C8 117.49(17) . . ?
C4 N3 Eu1 122.58(13) . . ?
C8 N3 Eu1 119.66(13) . . ?
C9 N4 N5 104.27(18) . . ?
N6 N5 N4 110.07(18) . . ?
N5 N6 N7 108.45(18) . . ?
C9 N7 N6 105.34(17) . . ?
C9 N7 Eu1 120.08(13) . . ?
N6 N7 Eu1 134.35(13) . . ?
C10 O1 H1A 109.5 . . ?
N7 Eu1 N7 79.99(7) 3 . ?
N7 Eu1 N7 79.99(7) 3 2 ?
N7 Eu1 N7 79.99(7) . 2 ?
N7 Eu1 N1 88.32(6) 3 . ?
N7 Eu1 N1 125.18(5) . . ?
N7 Eu1 N1 150.07(5) 2 . ?
N7 Eu1 N1 150.07(5) 3 2 ?
N7 Eu1 N1 88.31(6) . 2 ?
N7 Eu1 N1 125.18(5) 2 2 ?
N1 Eu1 N1 76.04(6) . 2 ?
N7 Eu1 N1 125.18(5) 3 3 ?
N7 Eu1 N1 150.06(5) . 3 ?
N7 Eu1 N1 88.31(6) 2 3 ?
N1 Eu1 N1 76.04(6) . 3 ?
N1 Eu1 N1 76.04(6) 2 3 ?
N7 Eu1 N3 138.09(6) 3 2 ?
N7 Eu1 N3 73.96(5) . 2 ?
N7 Eu1 N3 63.71(5) 2 2 ?
N1 Eu1 N3 133.57(6) . 2 ?
N1 Eu1 N3 61.57(5) 2 2 ?
N1 Eu1 N3 76.14(5) 3 2 ?
N7 Eu1 N3 73.96(5) 3 . ?
N7 Eu1 N3 63.71(5) . . ?
N7 Eu1 N3 138.09(6) 2 . ?
N1 Eu1 N3 61.57(5) . . ?
N1 Eu1 N3 76.14(5) 2 . ?
N1 Eu1 N3 133.57(6) 3 . ?
N3 Eu1 N3 119.985(2) 2 . ?
N7 Eu1 N3 63.71(5) 3 3 ?
N7 Eu1 N3 138.09(6) . 3 ?
N7 Eu1 N3 73.97(5) 2 3 ?
N1 Eu1 N3 76.14(5) . 3 ?
N1 Eu1 N3 133.57(6) 2 3 ?
N1 Eu1 N3 61.57(5) 3 3 ?
N3 Eu1 N3 119.985(2) 2 3 ?
N3 Eu1 N3 119.983(2) . 3 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N1 C1 C2 C3 0.7(3) . . . . ?
C1 C2 C3 N2 -0.6(3) . . . . ?
N3 C4 C5 C6 -1.2(4) . . . . ?
N2 C4 C5 C6 177.5(2) . . . . ?
C4 C5 C6 C7 1.5(4) . . . . ?
C5 C6 C7 C8 -0.2(4) . . . . ?
C6 C7 C8 N3 -1.6(4) . . . . ?
C6 C7 C8 C9 177.3(2) . . . . ?
N3 C8 C9 N4 175.8(2) . . . . ?
C7 C8 C9 N4 -3.2(4) . . . . ?
N3 C8 C9 N7 -1.2(3) . . . . ?
C7 C8 C9 N7 179.8(2) . . . . ?
C2 C1 N1 N2 -0.5(3) . . . . ?
C2 C1 N1 Eu1 -168.45(16) . . . . ?
C2 C3 N2 N1 0.4(3) . . . . ?
C2 C3 N2 C4 179.6(2) . . . . ?
C1 N1 N2 C3 0.1(2) . . . . ?
Eu1 N1 N2 C3 170.02(14) . . . . ?
C1 N1 N2 C4 -179.24(19) . . . . ?
Eu1 N1 N2 C4 -9.3(2) . . . . ?
N3 C4 N2 C3 -169.8(2) . . . . ?
C5 C4 N2 C3 11.4(3) . . . . ?
N3 C4 N2 N1 9.4(3) . . . . ?
C5 C4 N2 N1 -169.4(2) . . . . ?
C5 C4 N3 C8 -0.5(3) . . . . ?
N2 C4 N3 C8 -179.30(17) . . . . ?
C5 C4 N3 Eu1 173.45(17) . . . . ?
N2 C4 N3 Eu1 -5.3(2) . . . . ?
C7 C8 N3 C4 2.0(3) . . . . ?
C9 C8 N3 C4 -177.00(18) . . . . ?
C7 C8 N3 Eu1 -172.18(17) . . . . ?
C9 C8 N3 Eu1 8.8(2) . . . . ?
N7 C9 N4 N5 0.3(3) . . . . ?
C8 C9 N4 N5 -176.9(2) . . . . ?
C9 N4 N5 N6 -0.5(3) . . . . ?
N4 N5 N6 N7 0.4(3) . . . . ?
N4 C9 N7 N6 -0.1(3) . . . . ?
C8 C9 N7 N6 177.30(19) . . . . ?
N4 C9 N7 Eu1 175.19(14) . . . . ?
C8 C9 N7 Eu1 -7.4(3) . . . . ?
N5 N6 N7 C9 -0.2(3) . . . . ?
N5 N6 N7 Eu1 -174.49(16) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O1 H1A N4 0.84 2.01 2.821(3) 163.1 .

_refine_diff_density_max         0.887
_refine_diff_density_min         -0.534
_refine_diff_density_rms         0.097

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
1 0.000 0.000 0.000 136.4 42.9
2 0.000 0.000 0.500 6.9 -0.4
3 0.333 0.667 0.667 137.1 42.9
4 0.333 0.667 0.167 7.0 -0.4
5 0.667 0.333 0.333 137.0 42.9
6 0.667 0.333 0.833 7.0 -0.4
_platon_squeeze_details          
;
 The residual electron density was assigned to third a molecule of the
 methanol solvent [129/18 = 7 e per asymmetric unit; third a molecule
 of CH3OH would give 6e].
;

_shelxl_version_number           2013-4


_exptl_crystal_preparation       'Magnetic properties, Luminescent'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_ldskk150120
_database_code_depnum_ccdc_archive 'CCDC 1057180'
_audit_update_record             
;
2015-03-31 deposited with the CCDC.
2015-07-29 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C27 H18 N21 Tb, 3(C H4 O)'
_chemical_formula_sum            'C30 H30 N21 O3 Tb'
_chemical_formula_weight         891.67

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'
Tb Tb -0.1723 4.1537 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_H-M_alt        'R -3 :H'
_space_group_name_Hall           '-R 3'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'

_cell_length_a                   16.980(5)
_cell_length_b                   16.980(5)
_cell_length_c                   21.806(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     5445(3)
_cell_formula_units_Z            6
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    7426
_cell_measurement_theta_min      2.33
_cell_measurement_theta_max      31.03

_exptl_crystal_description       prism
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.632
_exptl_crystal_F_000             2676
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.20
_exptl_absorpt_coefficient_mu    2.014
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6662
_exptl_absorpt_correction_T_max  0.7462
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      173(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            14660
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_av_R_equivalents  0.0291
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_theta_min         1.670
_diffrn_reflns_theta_max         31.031
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             3871
_reflns_number_gt                3514
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
 ?
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0267P)²+3.1512P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3871
_refine_ls_number_parameters     168
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0274
_refine_ls_R_factor_gt           0.0228
_refine_ls_wR_factor_ref         0.0519
_refine_ls_wR_factor_gt          0.0510
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_restrained_S_all      1.078
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 1.07106(13) 0.92443(13) 0.40639(9) 0.0263(4) Uani 1 1 d . . . . .
H1 H 1.1204 0.9833 0.4154 0.032 Uiso 1 1 calc R U . . .
C2 C 1.04488(15) 0.84834(14) 0.44366(10) 0.0311(4) Uani 1 1 d . . . . .
H2 H 1.0721 0.8455 0.4811 0.037 Uiso 1 1 calc R U . . .
C3 C 0.97174(13) 0.77894(13) 0.41473(9) 0.0246(4) Uani 1 1 d . . . . .
H3 H 0.9373 0.7178 0.4285 0.029 Uiso 1 1 calc R U . . .
C4 C 0.89032(12) 0.77056(11) 0.31757(8) 0.0176(3) Uani 1 1 d . . . . .
C5 C 0.83515(14) 0.67631(12) 0.31641(10) 0.0274(4) Uani 1 1 d . . . . .
H5 H 0.8399 0.6390 0.3470 0.033 Uiso 1 1 calc R U . . .
C6 C 0.77348(15) 0.63943(13) 0.26924(11) 0.0336(5) Uani 1 1 d . . . . .
H6 H 0.7356 0.5753 0.2662 0.040 Uiso 1 1 calc R U . . .
C7 C 0.76650(14) 0.69584(13) 0.22606(10) 0.0287(4) Uani 1 1 d . . . . .
H7 H 0.7241 0.6710 0.1933 0.034 Uiso 1 1 calc R U . . .
C8 C 0.82254(11) 0.78863(11) 0.23176(8) 0.0183(3) Uani 1 1 d . . . . .
C9 C 0.81876(11) 0.85489(12) 0.19124(8) 0.0187(3) Uani 1 1 d . . . . .
C10 C 0.6177(2) 0.6180(2) 0.06501(15) 0.0570(8) Uani 1 1 d . . . . .
H10A H 0.6481 0.6475 0.0266 0.085 Uiso 1 1 calc R U . . .
H10B H 0.5581 0.5653 0.0559 0.085 Uiso 1 1 calc R U . . .
H10C H 0.6549 0.5981 0.0872 0.085 Uiso 1 1 calc R U . . .
N1 N 1.01919(10) 0.90500(9) 0.35697(7) 0.0183(3) Uani 1 1 d . . . . .
N2 N 0.95748(10) 0.81394(9) 0.36246(7) 0.0174(3) Uani 1 1 d . . . . .
N3 N 0.88538(9) 0.82650(9) 0.27699(6) 0.0152(3) Uani 1 1 d . . . . .
N4 N 0.76029(11) 0.83743(11) 0.14557(8) 0.0279(4) Uani 1 1 d . . . . .
N5 N 0.78111(12) 0.92033(12) 0.12426(9) 0.0322(4) Uani 1 1 d . . . . .
N6 N 0.84983(12) 0.98448(11) 0.15564(8) 0.0277(4) Uani 1 1 d . . . . .
N7 N 0.87470(10) 0.94423(10) 0.19890(7) 0.0188(3) Uani 1 1 d . . . . .
O1 O 0.60656(11) 0.67952(14) 0.10099(10) 0.0535(5) Uani 1 1 d . . . . .
H1A H 0.6578 0.7232 0.1106 0.080 Uiso 1 1 calc R U . . .
Tb1 Tb 1.0000 1.0000 0.27520(2) 0.01183(4) Uani 1 3 d S T P . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 N1 1.325(2) . ?
C1 C2 1.398(3) . ?
C1 H1 0.9500 . ?
C2 C3 1.366(3) . ?
C2 H2 0.9500 . ?
C3 N2 1.362(2) . ?
C3 H3 0.9500 . ?
C4 N3 1.331(2) . ?
C4 C5 1.393(2) . ?
C4 N2 1.400(2) . ?
C5 C6 1.375(3) . ?
C5 H5 0.9500 . ?
C6 C7 1.390(3) . ?
C6 H6 0.9500 . ?
C7 C8 1.380(2) . ?
C7 H7 0.9500 . ?
C8 N3 1.356(2) . ?
C8 C9 1.457(2) . ?
C9 N4 1.331(2) . ?
C9 N7 1.338(2) . ?
C10 O1 1.393(3) . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?
N1 N2 1.372(2) . ?
N1 Tb1 2.5324(15) . ?
N3 Tb1 2.5951(15) . ?
N4 N5 1.351(2) . ?
N5 N6 1.321(2) . ?
N6 N7 1.351(2) . ?
N7 Tb1 2.4853(15) . ?
O1 H1A 0.8400 . ?
Tb1 N7 2.4852(15) 2_765 ?
Tb1 N7 2.4853(15) 3_675 ?
Tb1 N1 2.5325(15) 2_765 ?
Tb1 N1 2.5325(15) 3_675 ?
Tb1 N3 2.5952(15) 2_765 ?
Tb1 N3 2.5952(15) 3_675 ?

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
_geom_angle_publ_flag
N1 C1 C2 112.23(17) . . ?
N1 C1 H1 123.9 . . ?
C2 C1 H1 123.9 . . ?
C3 C2 C1 105.11(17) . . ?
C3 C2 H2 127.4 . . ?
C1 C2 H2 127.4 . . ?
N2 C3 C2 107.06(16) . . ?
N2 C3 H3 126.5 . . ?
C2 C3 H3 126.5 . . ?
N3 C4 C5 124.16(17) . . ?
N3 C4 N2 114.49(14) . . ?
C5 C4 N2 121.34(16) . . ?
C6 C5 C4 117.28(18) . . ?
C6 C5 H5 121.4 . . ?
C4 C5 H5 121.4 . . ?
C5 C6 C7 120.06(18) . . ?
C5 C6 H6 120.0 . . ?
C7 C6 H6 120.0 . . ?
C8 C7 C6 118.57(18) . . ?
C8 C7 H7 120.7 . . ?
C6 C7 H7 120.7 . . ?
N3 C8 C7 122.47(17) . . ?
N3 C8 C9 113.75(15) . . ?
C7 C8 C9 123.76(16) . . ?
N4 C9 N7 111.94(16) . . ?
N4 C9 C8 126.71(16) . . ?
N7 C9 C8 121.29(15) . . ?
O1 C10 H10A 109.5 . . ?
O1 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
O1 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
C1 N1 N2 104.34(14) . . ?
C1 N1 Tb1 134.06(12) . . ?
N2 N1 Tb1 120.68(10) . . ?
C3 N2 N1 111.26(15) . . ?
C3 N2 C4 129.13(15) . . ?
N1 N2 C4 119.60(14) . . ?
C4 N3 C8 117.42(15) . . ?
C4 N3 Tb1 122.75(11) . . ?
C8 N3 Tb1 119.54(11) . . ?
C9 N4 N5 104.35(15) . . ?
N6 N5 N4 110.13(15) . . ?
N5 N6 N7 108.37(15) . . ?
C9 N7 N6 105.20(14) . . ?
C9 N7 Tb1 120.18(11) . . ?
N6 N7 Tb1 134.38(11) . . ?
C10 O1 H1A 109.5 . . ?
N7 Tb1 N7 80.08(6) 2_765 . ?
N7 Tb1 N7 80.09(6) 2_765 3_675 ?
N7 Tb1 N7 80.09(6) . 3_675 ?
N7 Tb1 N1 88.16(5) 2_765 . ?
N7 Tb1 N1 125.94(5) . . ?
N7 Tb1 N1 149.24(5) 3_675 . ?
N7 Tb1 N1 125.94(5) 2_765 2_765 ?
N7 Tb1 N1 149.24(5) . 2_765 ?
N7 Tb1 N1 88.15(5) 3_675 2_765 ?
N1 Tb1 N1 75.90(6) . 2_765 ?
N7 Tb1 N1 149.24(5) 2_765 3_675 ?
N7 Tb1 N1 88.16(5) . 3_675 ?
N7 Tb1 N1 125.94(5) 3_675 3_675 ?
N1 Tb1 N1 75.90(6) . 3_675 ?
N1 Tb1 N1 75.90(6) 2_765 3_675 ?
N7 Tb1 N3 73.65(5) 2_765 . ?
N7 Tb1 N3 64.17(5) . . ?
N7 Tb1 N3 138.38(5) 3_675 . ?
N1 Tb1 N3 61.88(4) . . ?
N1 Tb1 N3 133.44(5) 2_765 . ?
N1 Tb1 N3 75.64(4) 3_675 . ?
N7 Tb1 N3 64.17(5) 2_765 2_765 ?
N7 Tb1 N3 138.38(5) . 2_765 ?
N7 Tb1 N3 73.65(5) 3_675 2_765 ?
N1 Tb1 N3 75.64(4) . 2_765 ?
N1 Tb1 N3 61.88(4) 2_765 2_765 ?
N1 Tb1 N3 133.44(5) 3_675 2_765 ?
N3 Tb1 N3 119.978(2) . 2_765 ?
N7 Tb1 N3 138.38(5) 2_765 3_675 ?
N7 Tb1 N3 73.65(5) . 3_675 ?
N7 Tb1 N3 64.17(5) 3_675 3_675 ?
N1 Tb1 N3 133.44(5) . 3_675 ?
N1 Tb1 N3 75.64(4) 2_765 3_675 ?
N1 Tb1 N3 61.88(4) 3_675 3_675 ?
N3 Tb1 N3 119.977(2) . 3_675 ?
N3 Tb1 N3 119.977(2) 2_765 3_675 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N1 C1 C2 C3 -0.6(3) . . . . ?
C1 C2 C3 N2 0.7(2) . . . . ?
N3 C4 C5 C6 1.7(3) . . . . ?
N2 C4 C5 C6 -177.50(19) . . . . ?
C4 C5 C6 C7 -1.6(3) . . . . ?
C5 C6 C7 C8 0.1(3) . . . . ?
C6 C7 C8 N3 1.5(3) . . . . ?
C6 C7 C8 C9 -177.0(2) . . . . ?
N3 C8 C9 N4 -175.66(18) . . . . ?
C7 C8 C9 N4 3.0(3) . . . . ?
N3 C8 C9 N7 1.3(2) . . . . ?
C7 C8 C9 N7 179.90(18) . . . . ?
C2 C1 N1 N2 0.2(2) . . . . ?
C2 C1 N1 Tb1 168.77(14) . . . . ?
C2 C3 N2 N1 -0.6(2) . . . . ?
C2 C3 N2 C4 -179.30(18) . . . . ?
C1 N1 N2 C3 0.2(2) . . . . ?
Tb1 N1 N2 C3 -170.19(12) . . . . ?
C1 N1 N2 C4 179.05(16) . . . . ?
Tb1 N1 N2 C4 8.6(2) . . . . ?
N3 C4 N2 C3 169.67(17) . . . . ?
C5 C4 N2 C3 -11.1(3) . . . . ?
N3 C4 N2 N1 -8.9(2) . . . . ?
C5 C4 N2 N1 170.35(17) . . . . ?
C5 C4 N3 C8 -0.1(3) . . . . ?
N2 C4 N3 C8 179.08(15) . . . . ?
C5 C4 N3 Tb1 -173.96(14) . . . . ?
N2 C4 N3 Tb1 5.3(2) . . . . ?
C7 C8 N3 C4 -1.5(3) . . . . ?
C9 C8 N3 C4 177.15(15) . . . . ?
C7 C8 N3 Tb1 172.51(15) . . . . ?
C9 C8 N3 Tb1 -8.83(19) . . . . ?
N7 C9 N4 N5 -0.3(2) . . . . ?
C8 C9 N4 N5 176.88(18) . . . . ?
C9 N4 N5 N6 0.6(2) . . . . ?
N4 N5 N6 N7 -0.7(2) . . . . ?
N4 C9 N7 N6 -0.1(2) . . . . ?
C8 C9 N7 N6 -177.44(16) . . . . ?
N4 C9 N7 Tb1 -175.34(12) . . . . ?
C8 C9 N7 Tb1 7.3(2) . . . . ?
N5 N6 N7 C9 0.5(2) . . . . ?
N5 N6 N7 Tb1 174.70(13) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O1 H1A N4 0.84 2.00 2.819(2) 165.2 .

_refine_diff_density_max         1.313
_refine_diff_density_min         -0.527
_refine_diff_density_rms         0.088

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
1 0.000 0.000 0.000 138.2 38.6
2 0.000 0.000 0.500 6.9 0.0
3 0.333 0.667 0.667 139.2 38.7
4 0.333 0.667 0.167 6.9 0.0
5 0.667 0.333 0.333 139.1 38.6
6 0.667 0.333 0.833 6.9 0.0
_platon_squeeze_details          
;
 The residual electron density was assigned to third a molecule of the
 methanol solvent [116/18 = 6 e per asymmetric unit; third a molecule
 of CH3OH would give 6e].
;

_shelxl_version_number           2013-4

