# Electronic Supplementary Material (ESI) for CrystEngComm.
# This journal is © The Royal Society of Chemistry 2023

####################################################################### 
# 
# 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_aaa_pl
_database_code_depnum_ccdc_archive 'CCDC 2233509'
loop_
_audit_author_name
_audit_author_address
'Yoichi Habata'
;Toho University
Japan
;
_audit_update_record             
;
2022-12-30 deposited with the CCDC.	2023-03-16 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C44 H44 N4'
_chemical_formula_sum            'C44 H44 N4'
_chemical_formula_weight         628.83

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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_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'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   10.825(5)
_cell_length_b                   18.151(8)
_cell_length_c                   9.211(4)
_cell_angle_alpha                90
_cell_angle_beta                 97.156(8)
_cell_angle_gamma                90
_cell_volume                     1795.7(14)
_cell_formula_units_Z            2
_cell_measurement_temperature    120(2)
_cell_measurement_reflns_used    292
_cell_measurement_theta_min      2.94
_cell_measurement_theta_max      14.30

_exptl_crystal_description       PLATE
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.163
_exptl_crystal_F_000             672
_exptl_transmission_factor_min   0.5659
_exptl_transmission_factor_max   0.7457
_exptl_crystal_size_max          0.244
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.065
_exptl_absorpt_coefficient_mu    0.068
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5659
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      120(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            10326
_diffrn_reflns_av_unetI/netI     0.2073
_diffrn_reflns_av_R_equivalents  0.1711
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_theta_min         1.896
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             3530
_reflns_number_gt                1394
_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-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_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)+(0.0566P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3530
_refine_ls_number_parameters     217
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.2119
_refine_ls_R_factor_gt           0.0755
_refine_ls_wR_factor_ref         0.1969
_refine_ls_wR_factor_gt          0.1391
_refine_ls_goodness_of_fit_ref   1.008
_refine_ls_restrained_S_all      1.008
_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
N1 N 0.9570(3) -0.04109(19) 0.7973(4) 0.0284(9) Uani 1 1 d . . . . .
N2 N 0.9783(3) 0.12624(19) 0.8917(4) 0.0264(9) Uani 1 1 d . . . . .
C1 C 0.8715(4) 0.0213(2) 0.7596(5) 0.0329(12) Uani 1 1 d . . . . .
H1A H 0.7859 0.0023 0.7330 0.039 Uiso 1 1 calc R U . . .
H1B H 0.8964 0.0475 0.6737 0.039 Uiso 1 1 calc R U . . .
C2 C 0.8726(4) 0.0749(2) 0.8868(4) 0.0277(11) Uani 1 1 d . . . . .
H2A H 0.7938 0.1032 0.8764 0.033 Uiso 1 1 calc R U . . .
H2B H 0.8784 0.0470 0.9798 0.033 Uiso 1 1 calc R U . . .
C3 C 1.0217(4) 0.1535(2) 1.0399(5) 0.0316(12) Uani 1 1 d . . . . .
H3A H 0.9487 0.1636 1.0917 0.038 Uiso 1 1 calc R U . . .
H3B H 1.0668 0.2006 1.0322 0.038 Uiso 1 1 calc R U . . .
C4 C 1.1070(4) 0.0993(2) 1.1292(5) 0.0303(11) Uani 1 1 d . . . . .
H4A H 1.1611 0.0756 1.0637 0.036 Uiso 1 1 calc R U . . .
H4B H 1.1615 0.1270 1.2044 0.036 Uiso 1 1 calc R U . . .
C5 C 1.0101(4) -0.0696(2) 0.6698(5) 0.0331(12) Uani 1 1 d . . . . .
H5A H 1.0667 -0.1109 0.7021 0.040 Uiso 1 1 calc R U . . .
H5B H 1.0609 -0.0303 0.6322 0.040 Uiso 1 1 calc R U . . .
C6 C 0.9185(4) -0.0958(2) 0.5481(5) 0.0283(11) Uani 1 1 d . . . . .
C7 C 0.8454(4) -0.1139(2) 0.4472(5) 0.0294(11) Uani 1 1 d . . . . .
C8 C 0.7571(4) -0.1332(3) 0.3217(5) 0.0290(11) Uani 1 1 d . . . . .
C9 C 0.7180(4) -0.2057(3) 0.2988(5) 0.0366(12) Uani 1 1 d . . . . .
H9A H 0.7473 -0.2427 0.3675 0.044 Uiso 1 1 calc R U . . .
C10 C 0.6356(4) -0.2242(3) 0.1751(6) 0.0420(13) Uani 1 1 d . . . . .
H10A H 0.6106 -0.2740 0.1582 0.050 Uiso 1 1 calc R U . . .
C11 C 0.5910(4) -0.1703(3) 0.0780(5) 0.0426(14) Uani 1 1 d . . . . .
H11A H 0.5339 -0.1826 -0.0053 0.051 Uiso 1 1 calc R U . . .
C12 C 0.6286(4) -0.0984(3) 0.1010(5) 0.0434(14) Uani 1 1 d . . . . .
H12A H 0.5967 -0.0613 0.0338 0.052 Uiso 1 1 calc R U . . .
C13 C 0.7131(4) -0.0796(3) 0.2218(5) 0.0355(12) Uani 1 1 d . . . . .
H13A H 0.7405 -0.0300 0.2355 0.043 Uiso 1 1 calc R U . . .
C14 C 0.9530(4) 0.1873(2) 0.7892(5) 0.0316(12) Uani 1 1 d . . . . .
H14A H 0.9285 0.1669 0.6901 0.038 Uiso 1 1 calc R U . . .
H14B H 1.0309 0.2156 0.7865 0.038 Uiso 1 1 calc R U . . .
C15 C 0.8544(4) 0.2384(2) 0.8249(5) 0.0289(11) Uani 1 1 d . . . . .
C16 C 0.7749(4) 0.2788(2) 0.8540(5) 0.0288(11) Uani 1 1 d . . . . .
C17 C 0.6757(4) 0.3275(2) 0.8850(5) 0.0248(10) Uani 1 1 d . . . . .
C18 C 0.6175(4) 0.3735(2) 0.7778(5) 0.0349(12) Uani 1 1 d . . . . .
H18A H 0.6459 0.3753 0.6844 0.042 Uiso 1 1 calc R U . . .
C19 C 0.5171(4) 0.4175(2) 0.8065(5) 0.0376(13) Uani 1 1 d . . . . .
H19A H 0.4765 0.4485 0.7321 0.045 Uiso 1 1 calc R U . . .
C20 C 0.4775(4) 0.4158(3) 0.9424(5) 0.0364(12) Uani 1 1 d . . . . .
H20A H 0.4085 0.4450 0.9614 0.044 Uiso 1 1 calc R U . . .
C21 C 0.5370(4) 0.3721(2) 1.0512(5) 0.0334(12) Uani 1 1 d . . . . .
H21A H 0.5103 0.3724 1.1456 0.040 Uiso 1 1 calc R U . . .
C22 C 0.6356(4) 0.3275(2) 1.0246(5) 0.0320(11) Uani 1 1 d . . . . .
H22A H 0.6759 0.2972 1.1002 0.038 Uiso 1 1 calc R U . . .


_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
N1 C5 1.465(5) . ?
N1 C4 1.473(5) 3_757 ?
N1 C1 1.477(5) . ?
N2 C14 1.459(5) . ?
N2 C2 1.472(5) . ?
N2 C3 1.473(5) . ?
C1 C2 1.521(5) . ?
C1 H1A 0.9900 . ?
C1 H1B 0.9900 . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C3 C4 1.520(6) . ?
C3 H3A 0.9900 . ?
C3 H3B 0.9900 . ?
C4 N1 1.473(5) 3_757 ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
C5 C6 1.479(6) . ?
C5 H5A 0.9900 . ?
C5 H5B 0.9900 . ?
C6 C7 1.190(6) . ?
C7 C8 1.447(6) . ?
C8 C13 1.383(6) . ?
C8 C9 1.390(6) . ?
C9 C10 1.398(6) . ?
C9 H9A 0.9500 . ?
C10 C11 1.373(6) . ?
C10 H10A 0.9500 . ?
C11 C12 1.375(6) . ?
C11 H11A 0.9500 . ?
C12 C13 1.392(6) . ?
C12 H12A 0.9500 . ?
C13 H13A 0.9500 . ?
C14 C15 1.482(6) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C15 C16 1.187(5) . ?
C16 C17 1.447(6) . ?
C17 C18 1.384(6) . ?
C17 C22 1.407(5) . ?
C18 C19 1.400(6) . ?
C18 H18A 0.9500 . ?
C19 C20 1.374(6) . ?
C19 H19A 0.9500 . ?
C20 C21 1.373(6) . ?
C20 H20A 0.9500 . ?
C21 C22 1.384(6) . ?
C21 H21A 0.9500 . ?
C22 H22A 0.9500 . ?

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
C5 N1 C4 111.6(3) . 3_757 ?
C5 N1 C1 112.3(3) . . ?
C4 N1 C1 109.9(3) 3_757 . ?
C14 N2 C2 112.3(3) . . ?
C14 N2 C3 110.9(3) . . ?
C2 N2 C3 113.5(3) . . ?
N1 C1 C2 111.4(4) . . ?
N1 C1 H1A 109.3 . . ?
C2 C1 H1A 109.3 . . ?
N1 C1 H1B 109.3 . . ?
C2 C1 H1B 109.3 . . ?
H1A C1 H1B 108.0 . . ?
N2 C2 C1 111.1(3) . . ?
N2 C2 H2A 109.4 . . ?
C1 C2 H2A 109.4 . . ?
N2 C2 H2B 109.4 . . ?
C1 C2 H2B 109.4 . . ?
H2A C2 H2B 108.0 . . ?
N2 C3 C4 112.7(4) . . ?
N2 C3 H3A 109.1 . . ?
C4 C3 H3A 109.1 . . ?
N2 C3 H3B 109.1 . . ?
C4 C3 H3B 109.1 . . ?
H3A C3 H3B 107.8 . . ?
N1 C4 C3 115.1(4) 3_757 . ?
N1 C4 H4A 108.5 3_757 . ?
C3 C4 H4A 108.5 . . ?
N1 C4 H4B 108.5 3_757 . ?
C3 C4 H4B 108.5 . . ?
H4A C4 H4B 107.5 . . ?
N1 C5 C6 115.4(4) . . ?
N1 C5 H5A 108.4 . . ?
C6 C5 H5A 108.4 . . ?
N1 C5 H5B 108.4 . . ?
C6 C5 H5B 108.4 . . ?
H5A C5 H5B 107.5 . . ?
C7 C6 C5 177.1(5) . . ?
C6 C7 C8 177.7(5) . . ?
C13 C8 C9 119.5(4) . . ?
C13 C8 C7 120.0(4) . . ?
C9 C8 C7 120.5(4) . . ?
C8 C9 C10 120.2(5) . . ?
C8 C9 H9A 119.9 . . ?
C10 C9 H9A 119.9 . . ?
C11 C10 C9 119.7(5) . . ?
C11 C10 H10A 120.1 . . ?
C9 C10 H10A 120.1 . . ?
C10 C11 C12 120.2(5) . . ?
C10 C11 H11A 119.9 . . ?
C12 C11 H11A 119.9 . . ?
C11 C12 C13 120.6(5) . . ?
C11 C12 H12A 119.7 . . ?
C13 C12 H12A 119.7 . . ?
C8 C13 C12 119.8(5) . . ?
C8 C13 H13A 120.1 . . ?
C12 C13 H13A 120.1 . . ?
N2 C14 C15 114.5(4) . . ?
N2 C14 H14A 108.6 . . ?
C15 C14 H14A 108.6 . . ?
N2 C14 H14B 108.6 . . ?
C15 C14 H14B 108.6 . . ?
H14A C14 H14B 107.6 . . ?
C16 C15 C14 179.4(5) . . ?
C15 C16 C17 178.1(5) . . ?
C18 C17 C22 119.2(4) . . ?
C18 C17 C16 120.7(4) . . ?
C22 C17 C16 120.1(4) . . ?
C17 C18 C19 120.3(4) . . ?
C17 C18 H18A 119.8 . . ?
C19 C18 H18A 119.8 . . ?
C20 C19 C18 119.7(5) . . ?
C20 C19 H19A 120.1 . . ?
C18 C19 H19A 120.1 . . ?
C21 C20 C19 120.5(4) . . ?
C21 C20 H20A 119.8 . . ?
C19 C20 H20A 119.8 . . ?
C20 C21 C22 120.7(4) . . ?
C20 C21 H21A 119.7 . . ?
C22 C21 H21A 119.7 . . ?
C21 C22 C17 119.6(4) . . ?
C21 C22 H22A 120.2 . . ?
C17 C22 H22A 120.2 . . ?

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
C5 N1 C1 C2 -149.0(3) . . . . ?
C4 N1 C1 C2 86.1(4) 3_757 . . . ?
C14 N2 C2 C1 81.2(4) . . . . ?
C3 N2 C2 C1 -152.1(4) . . . . ?
N1 C1 C2 N2 82.4(4) . . . . ?
C14 N2 C3 C4 -151.4(3) . . . . ?
C2 N2 C3 C4 81.1(4) . . . . ?
N2 C3 C4 N1 -83.6(5) . . . 3_757 ?
C4 N1 C5 C6 65.4(5) 3_757 . . . ?
C1 N1 C5 C6 -58.6(5) . . . . ?
C13 C8 C9 C10 0.5(6) . . . . ?
C7 C8 C9 C10 -178.1(4) . . . . ?
C8 C9 C10 C11 -1.7(7) . . . . ?
C9 C10 C11 C12 1.1(7) . . . . ?
C10 C11 C12 C13 0.6(7) . . . . ?
C9 C8 C13 C12 1.1(6) . . . . ?
C7 C8 C13 C12 179.8(4) . . . . ?
C11 C12 C13 C8 -1.7(7) . . . . ?
C2 N2 C14 C15 66.7(5) . . . . ?
C3 N2 C14 C15 -61.4(5) . . . . ?
C22 C17 C18 C19 -2.3(7) . . . . ?
C16 C17 C18 C19 176.5(4) . . . . ?
C17 C18 C19 C20 1.0(7) . . . . ?
C18 C19 C20 C21 1.1(7) . . . . ?
C19 C20 C21 C22 -1.8(7) . . . . ?
C20 C21 C22 C17 0.5(7) . . . . ?
C18 C17 C22 C21 1.6(6) . . . . ?
C16 C17 C22 C21 -177.2(4) . . . . ?

_refine_diff_density_max         0.265
_refine_diff_density_min         -0.324
_refine_diff_density_rms         0.066



# start Validation Reply Form
_vrf_PLAT026_aaa_pl              
;
PROBLEM: Ratio Observed / Unique Reflections (too) Low .. 39% Check.
RESPONSE: Crystals were relatively small and weakly diffracting, hence 
not all high-angle reflections were observed. A few junk reflections were
 also removed using R-LATT. 
;
# end Validation Reply Form
####################################################################### 
# 
# 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_triplebond_cyclen_Ligand
_database_code_depnum_ccdc_archive 'CCDC 2233510'
loop_
_audit_author_name
_audit_author_address
'Yoichi Habata'
;Toho University
Japan
;
_audit_update_record             
;
2023-02-06 deposited with the CCDC.	2023-03-16 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C44 H44 N4, C2 H3 N'
_chemical_formula_sum            'C46 H47 N5'
_chemical_formula_weight         669.89

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'

_space_group_crystal_system      tetragonal
_space_group_IT_number           104
_space_group_name_H-M_alt        'P 4 n c'
_space_group_name_Hall           'P 4 -2n'

_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, z'
'-x, -y, z'
'y, -x, z'
'-x+1/2, y+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'x+1/2, -y+1/2, z+1/2'
'y+1/2, x+1/2, z+1/2'

_cell_length_a                   14.404(7)
_cell_length_b                   14.404(7)
_cell_length_c                   9.018(8)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1871(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    120(2)
_cell_measurement_reflns_used    588
_cell_measurement_theta_min      2.66
_cell_measurement_theta_max      17.02

_exptl_crystal_description       BLOCK
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.189
_exptl_crystal_F_000             716
_exptl_transmission_factor_min   0.5862
_exptl_transmission_factor_max   0.7457
_exptl_crystal_size_max          0.265
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.106
_exptl_absorpt_coefficient_mu    0.070
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5862
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      120(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            9633
_diffrn_reflns_av_unetI/netI     0.1216
_diffrn_reflns_av_R_equivalents  0.1687
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         1.999
_diffrn_reflns_theta_max         25.997
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_point_group_measured_fraction_full 0.971
_reflns_number_total             1794
_reflns_number_gt                840
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.818
_reflns_Friedel_fraction_max     0.939
_reflns_Friedel_fraction_full    0.939

_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-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_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)+(0.0984P)²+0.4239P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
; 
 Flack x determined using 253 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   ?
_chemical_absolute_configuration ?
_refine_ls_number_reflns         1794
_refine_ls_number_parameters     118
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.1918
_refine_ls_R_factor_gt           0.0786
_refine_ls_wR_factor_ref         0.2340
_refine_ls_wR_factor_gt          0.1657
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_restrained_S_all      1.072
_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
N1 N 0.0514(4) 0.1379(4) 0.0804(8) 0.0463(16) Uani 1 1 d . . . . .
C1 C 0.1130(5) 0.1027(5) -0.0360(9) 0.048(2) Uani 1 1 d . . . . .
H1A H 0.1471 0.1555 -0.0805 0.057 Uiso 1 1 calc R U . . .
H1B H 0.0749 0.0739 -0.1150 0.057 Uiso 1 1 calc R U . . .
C2 C -0.0319(5) 0.1824(5) 0.0206(11) 0.051(2) Uani 1 1 d . . . . .
H2A H -0.0138 0.2242 -0.0616 0.062 Uiso 1 1 calc R U . . .
H2B H -0.0608 0.2208 0.0990 0.062 Uiso 1 1 calc R U . . .
C5 C 0.0995(6) 0.1985(5) 0.1851(11) 0.055(2) Uani 1 1 d . . . . .
H5A H 0.1532 0.1642 0.2262 0.066 Uiso 1 1 calc R U . . .
H5B H 0.0568 0.2119 0.2685 0.066 Uiso 1 1 calc R U . . .
C6 C 0.1333(6) 0.2877(6) 0.1253(10) 0.054(3) Uani 1 1 d . . . . .
C7 C 0.1534(5) 0.3626(6) 0.0800(14) 0.059(2) Uani 1 1 d . . . . .
C8 C 0.1747(5) 0.4544(5) 0.0289(12) 0.056(2) Uani 1 1 d . . . . .
C9 C 0.2470(6) 0.5049(6) 0.0925(11) 0.059(2) Uani 1 1 d . . . . .
H9A H 0.2842 0.4776 0.1678 0.071 Uiso 1 1 calc R U . . .
C10 C 0.2646(7) 0.5942(6) 0.0464(14) 0.077(3) Uani 1 1 d . . . . .
H10A H 0.3145 0.6283 0.0886 0.092 Uiso 1 1 calc R U . . .
C11 C 0.2106(7) 0.6335(6) -0.0595(15) 0.078(3) Uani 1 1 d . . . . .
H11A H 0.2217 0.6959 -0.0885 0.093 Uiso 1 1 calc R U . . .
C12 C 0.1406(7) 0.5845(7) -0.1251(15) 0.083(4) Uani 1 1 d . . . . .
H12A H 0.1035 0.6131 -0.1993 0.099 Uiso 1 1 calc R U . . .
C13 C 0.1234(6) 0.4947(6) -0.0850(14) 0.072(3) Uani 1 1 d . . . . .
H13A H 0.0766 0.4600 -0.1345 0.087 Uiso 1 1 calc R U . . .
N3 N 0.0000 0.0000 0.644(2) 0.080(5) Uani 1 4 d S T P . .
C23 C 0.0000 0.0000 0.518(2) 0.047(4) Uani 1 4 d S T P . .
C24 C 0.0000 0.0000 0.366(2) 0.088(7) Uani 1 4 d S T P . .
H24A H 0.0035 0.0643 0.3298 0.106 Uiso 0.25 1 d R U P . .
H24B H -0.0571 -0.0289 0.3298 0.106 Uiso 0.25 1 d R U P . .
H24C H 0.0539 -0.0348 0.3298 0.106 Uiso 0.25 1 d R U 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
N1 C5 1.461(10) . ?
N1 C2 1.463(10) . ?
N1 C1 1.464(10) . ?
C1 C2 1.517(10) 4 ?
C1 H1A 0.9900 . ?
C1 H1B 0.9900 . ?
C2 C1 1.517(10) 2 ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C5 C6 1.475(12) . ?
C5 H5A 0.9900 . ?
C5 H5B 0.9900 . ?
C6 C7 1.189(11) . ?
C7 C8 1.434(13) . ?
C8 C13 1.393(14) . ?
C8 C9 1.394(12) . ?
C9 C10 1.375(12) . ?
C9 H9A 0.9500 . ?
C10 C11 1.355(15) . ?
C10 H10A 0.9500 . ?
C11 C12 1.366(14) . ?
C11 H11A 0.9500 . ?
C12 C13 1.365(13) . ?
C12 H12A 0.9500 . ?
C13 H13A 0.9500 . ?
N3 C23 1.13(2) . ?
C23 C24 1.37(3) . ?
C24 H24A 0.9827 . ?
C24 H24B 0.9776 . ?
C24 H24C 0.9797 . ?

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
C5 N1 C2 111.5(6) . . ?
C5 N1 C1 112.6(6) . . ?
C2 N1 C1 112.6(7) . . ?
N1 C1 C2 113.0(7) . 4 ?
N1 C1 H1A 109.0 . . ?
C2 C1 H1A 109.0 4 . ?
N1 C1 H1B 109.0 . . ?
C2 C1 H1B 109.0 4 . ?
H1A C1 H1B 107.8 . . ?
N1 C2 C1 112.8(6) . 2 ?
N1 C2 H2A 109.0 . . ?
C1 C2 H2A 109.0 2 . ?
N1 C2 H2B 109.0 . . ?
C1 C2 H2B 109.0 2 . ?
H2A C2 H2B 107.8 . . ?
N1 C5 C6 116.1(7) . . ?
N1 C5 H5A 108.3 . . ?
C6 C5 H5A 108.3 . . ?
N1 C5 H5B 108.3 . . ?
C6 C5 H5B 108.3 . . ?
H5A C5 H5B 107.4 . . ?
C7 C6 C5 174.5(9) . . ?
C6 C7 C8 177.7(10) . . ?
C13 C8 C9 118.9(8) . . ?
C13 C8 C7 120.5(8) . . ?
C9 C8 C7 120.6(9) . . ?
C10 C9 C8 120.1(9) . . ?
C10 C9 H9A 120.0 . . ?
C8 C9 H9A 120.0 . . ?
C11 C10 C9 119.8(9) . . ?
C11 C10 H10A 120.1 . . ?
C9 C10 H10A 120.1 . . ?
C10 C11 C12 120.9(9) . . ?
C10 C11 H11A 119.6 . . ?
C12 C11 H11A 119.6 . . ?
C13 C12 C11 120.6(11) . . ?
C13 C12 H12A 119.7 . . ?
C11 C12 H12A 119.7 . . ?
C12 C13 C8 119.6(10) . . ?
C12 C13 H13A 120.2 . . ?
C8 C13 H13A 120.2 . . ?
N3 C23 C24 180.0 . . ?
C23 C24 H24A 109.4 . . ?
C23 C24 H24B 109.5 . . ?
H24A C24 H24B 109.4 . . ?
C23 C24 H24C 109.5 . . ?
H24A C24 H24C 109.3 . . ?
H24B C24 H24C 109.7 . . ?

_refine_diff_density_max         0.161
_refine_diff_density_min         -0.226
_refine_diff_density_rms         0.054





# start Validation Reply Form 
_vrf_PLAT340_triplebond_cyclen_Ligand 
; 
PROBLEM: Low Bond Precision on  C-C Bonds ..........0.01473 Ang. 
RESPONSE: Crystallographic data for atoms of bad crystal quality has 
 a larger temperature factor (displacement from the equilibrium 
position due to thermal vibration). In other words, since the standard 
 deviation of the positions of carbon atoms is large, the standard 
deviation of the distance between atoms is also large. 
;
# end Validation Reply Form 
