# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_2
_database_code_depnum_ccdc_archive 'CCDC 1503068'
_audit_update_record             
;
2017-01-20 deposited with the CCDC.
2017-01-23 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         'C4 H12 Cu N18 O5 Pb, 2(H2 O)'
_chemical_formula_sum            'C4 H16 Cu N18 O7 Pb'
_chemical_formula_weight         699.08

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'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pb Pb -3.3944 10.1111 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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, -z'

_cell_length_a                   6.8365(12)
_cell_length_b                   12.453(2)
_cell_length_c                   13.026(2)
_cell_angle_alpha                110.877(2)
_cell_angle_beta                 103.778(3)
_cell_angle_gamma                100.585(3)
_cell_volume                     961.3(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    3177
_cell_measurement_theta_min      3.02
_cell_measurement_theta_max      27.45

_exptl_crystal_description       block
_exptl_crystal_colour            blue
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.415
_exptl_crystal_F_000             666
_exptl_transmission_factor_min   0.2463
_exptl_transmission_factor_max   0.3361
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.130
_exptl_crystal_size_min          0.110
_exptl_absorpt_coefficient_mu    9.928
_shelx_estimated_absorpt_T_min   0.317
_shelx_estimated_absorpt_T_max   0.408
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   sadabs
_exptl_absorpt_special_details   ?
_exptl_special_details           
; 
SADABS v.2.10 (Bruker,2003) was used for absorption correction.
R(int) was 0.0308 after correction.
The Ratio of minimum to maximum transmission is 0.7321.
The λ/2 correction factor is 0.0015. 
;
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker SMART CCD area-detector'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            5027
_diffrn_reflns_av_unetI/netI     0.0623
_diffrn_reflns_av_R_equivalents  0.0308
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         1.773
_diffrn_reflns_theta_max         25.987
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.968
_diffrn_measured_fraction_theta_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_point_group_measured_fraction_full 0.982
_reflns_number_total             3784
_reflns_number_gt                3298
_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.

The Cu atom in the structure of complex 2 is positional 
disordered, which was split into two parts with 90% and 
10% site occupancies, respectively.
;

_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)+(0.0728P)²+1.7081P] 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_number_reflns         3664
_refine_ls_number_parameters     289
_refine_ls_number_restraints     18
_refine_ls_R_factor_all          0.0460
_refine_ls_R_factor_gt           0.0410
_refine_ls_wR_factor_ref         0.1257
_refine_ls_wR_factor_gt          0.1163
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_restrained_S_all      1.096
_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
Pb1 Pb 1.06941(5) 0.71299(3) 0.74747(3) 0.02532(14) Uani 1 1 d . . . . .
Cu1 Cu 0.47227(17) 0.22098(9) 0.74113(9) 0.0172(2) Uani 0.9 1 d . . P . .
Cu1' Cu 0.3283(14) 0.2332(7) 0.7471(8) 0.0129(17) Uani 0.1 1 d . . P . .
N5 N 0.5032(11) 0.0753(6) 0.7696(6) 0.0192(14) Uani 1 1 d . . . . .
N1 N 0.3492(11) -0.0819(6) 0.5732(6) 0.0228(15) Uani 1 1 d . . . . .
H1 H 0.3285 -0.1564 0.5299 0.027 Uiso 1 1 calc R U . . .
N10 N 0.7858(11) 0.5135(6) 0.8829(6) 0.0228(15) Uani 1 1 d . . . . .
H2 H 0.8467 0.5898 0.9163 0.027 Uiso 1 1 calc R U . . .
N15 N 0.6504(12) 0.3387(6) 0.7016(6) 0.0242(15) Uani 1 1 d . . . . .
N18 N 0.8624(11) 0.5014(6) 0.7125(6) 0.0232(15) Uani 1 1 d . . . . .
N14 N 0.5991(11) 0.3428(6) 0.9067(6) 0.0236(15) Uani 1 1 d . . . . .
N13 N 0.5738(12) 0.3280(6) 0.9990(7) 0.0267(16) Uani 1 1 d . . . . .
N4 N 0.5971(12) 0.0740(7) 0.8731(6) 0.0262(16) Uani 1 1 d . . . . .
N12 N 0.6603(12) 0.4293(6) 1.0898(6) 0.0281(16) Uani 1 1 d . . . . .
N17 N 0.8121(12) 0.4106(6) 0.6046(7) 0.0279(16) Uani 1 1 d . . . . .
N7 N 0.2244(12) 0.1391(7) 0.4919(6) 0.0272(16) Uani 1 1 d . . . . .
N11 N 0.7564(10) 0.5147(6) 1.0613(6) 0.0229(15) Uani 1 1 d . . . . .
O2 O 1.0318(10) 0.7551(5) 0.9460(6) 0.0312(14) Uani 1 1 d . . . . .
H2A H 1.1500 0.7659 0.9942 0.047 Uiso 1 1 d R U . . .
H2B H 0.9925 0.8179 0.9688 0.047 Uiso 1 1 d R U . . .
N6 N 0.3169(11) 0.1065(6) 0.5745(6) 0.0212(14) Uani 1 1 d . . . . .
O5 O 0.7093(9) 0.7064(6) 0.7068(6) 0.0314(14) Uani 1 1 d . U . . .
H5A H 0.7068 0.7738 0.7536 0.047 Uiso 1 1 d R U . . .
H5B H 0.6532 0.6540 0.7271 0.047 Uiso 1 1 d R U . . .
N9 N 0.1701(11) -0.0550(6) 0.4093(6) 0.0241(15) Uani 1 1 d . . . . .
N8 N 0.1355(12) 0.0427(7) 0.3945(6) 0.0297(17) Uani 1 1 d . . . . .
O3 O 1.0600(11) 0.9237(6) 0.7970(6) 0.0339(15) Uani 1 1 d . U . . .
H3A H 1.1038 0.9628 0.8706 0.051 Uiso 1 1 d R U . . .
H3B H 0.9340 0.9235 0.7694 0.051 Uiso 1 1 d R U . . .
C1 C 0.4486(12) -0.0394(7) 0.6910(7) 0.0180(16) Uani 1 1 d . U . . .
N16 N 0.6811(13) 0.3151(6) 0.5988(6) 0.0289(17) Uani 1 1 d . . . . .
C2 C 0.2818(12) -0.0104(7) 0.5222(7) 0.0187(16) Uani 1 1 d . . . . .
C3 C 0.7657(12) 0.4533(7) 0.7701(7) 0.0174(15) Uani 1 1 d . . . . .
C4 C 0.7123(12) 0.4576(7) 0.9481(7) 0.0194(16) Uani 1 1 d . . . . .
O4 O 0.9241(11) 0.6648(6) 0.5280(6) 0.0403(17) Uani 1 1 d . . . . .
H4A H 1.0210 0.6569 0.4979 0.060 Uiso 1 1 d R U . . .
H4B H 0.8806 0.7227 0.5221 0.060 Uiso 1 1 d R U . . .
N2 N 0.5077(12) -0.1106(6) 0.7397(6) 0.0278(16) Uani 1 1 d . . . . .
N3 N 0.6012(13) -0.0342(7) 0.8547(6) 0.0308(17) Uani 1 1 d . . . . .
O1 O 0.1763(12) 0.2668(8) 0.7426(8) 0.068(3) Uani 1 1 d . . . . .
H1A H 0.2031 0.3281 0.8058 0.101 Uiso 1 1 d R U . . .
H1B H 0.0714 0.2135 0.7365 0.101 Uiso 1 1 d R U . . .
O7 O 0.7502(10) 0.8655(6) 1.0061(5) 0.0304(14) Uani 1 1 d . . . . .
O6 O 0.3542(12) 0.5518(7) 0.6825(7) 0.0464(19) Uani 1 1 d . . . . .
H6A H 0.3407 0.5298 0.7359 0.070 Uiso 1 1 d R U . . .
H7A H 0.6834 0.7999 1.0041 0.070 Uiso 1 1 d R U . . .
H7B H 0.6895 0.8839 0.9535 0.070 Uiso 1 1 d R U . . .
H6B H 0.2649 0.5072 0.6153 0.070 Uiso 1 1 d 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
Pb1 O5 2.371(6) . ?
Pb1 O3 2.486(6) . ?
Pb1 O2 2.536(7) . ?
Pb1 N18 2.573(7) . ?
Pb1 O4 2.593(7) . ?
Cu1 Cu1' 1.040(9) . ?
Cu1 N14 2.000(7) . ?
Cu1 N6 2.003(7) . ?
Cu1 N5 2.014(7) . ?
Cu1 N15 2.019(7) . ?
Cu1 O1 2.204(8) . ?
Cu1' O1 1.186(12) . ?
Cu1' N14 2.197(12) . ?
Cu1' N6 2.212(11) . ?
Cu1' H1A 1.6590 . ?
Cu1' H1B 1.6924 . ?
N5 C1 1.345(10) . ?
N5 N4 1.355(10) . ?
N1 C2 1.368(11) . ?
N1 C1 1.374(10) . ?
N1 H1 0.8600 . ?
N10 C3 1.350(10) . ?
N10 C4 1.398(10) . ?
N10 H2 0.8600 . ?
N15 N16 1.341(10) . ?
N15 C3 1.342(10) . ?
N18 C3 1.330(10) . ?
N18 N17 1.367(10) . ?
N14 N13 1.325(10) . ?
N14 C4 1.333(10) . ?
N13 N12 1.291(10) . ?
N4 N3 1.289(11) . ?
N12 N11 1.358(10) . ?
N17 N16 1.317(10) . ?
N7 N8 1.303(11) . ?
N7 N6 1.343(10) . ?
N11 C4 1.316(11) . ?
O2 H2A 0.8500 . ?
O2 H2B 0.8499 . ?
N6 C2 1.314(10) . ?
O5 H5A 0.8499 . ?
O5 H5B 0.8501 . ?
N9 C2 1.335(11) . ?
N9 N8 1.351(11) . ?
O3 H3A 0.8500 . ?
O3 H3B 0.8501 . ?
C1 N2 1.327(11) . ?
O4 H4A 0.8500 . ?
O4 H4B 0.8499 . ?
N2 N3 1.365(10) . ?
O1 H1A 0.8499 . ?
O1 H1B 0.8499 . ?
O7 H7A 0.8482 . ?
O7 H7B 0.8398 . ?
O6 H6A 0.8500 . ?
O6 H6B 0.8500 . ?

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
O5 Pb1 O3 73.5(2) . . ?
O5 Pb1 O2 79.4(2) . . ?
O3 Pb1 O2 83.3(2) . . ?
O5 Pb1 N18 73.1(2) . . ?
O3 Pb1 N18 144.7(2) . . ?
O2 Pb1 N18 79.6(2) . . ?
O5 Pb1 O4 73.7(2) . . ?
O3 Pb1 O4 89.7(2) . . ?
O2 Pb1 O4 153.0(2) . . ?
N18 Pb1 O4 91.7(2) . . ?
Cu1' Cu1 N14 86.5(5) . . ?
Cu1' Cu1 N6 87.3(5) . . ?
N14 Cu1 N6 173.4(3) . . ?
Cu1' Cu1 N5 108.8(5) . . ?
N14 Cu1 N5 97.6(3) . . ?
N6 Cu1 N5 86.5(3) . . ?
Cu1' Cu1 N15 116.6(5) . . ?
N14 Cu1 N15 86.8(3) . . ?
N6 Cu1 N15 94.1(3) . . ?
N5 Cu1 N15 134.5(3) . . ?
Cu1' Cu1 O1 8.7(6) . . ?
N14 Cu1 O1 87.2(3) . . ?
N6 Cu1 O1 86.3(3) . . ?
N5 Cu1 O1 117.3(4) . . ?
N15 Cu1 O1 108.1(4) . . ?
Cu1 Cu1' O1 163.7(11) . . ?
Cu1 Cu1' N14 65.3(5) . . ?
O1 Cu1' N14 114.9(7) . . ?
Cu1 Cu1' N6 64.7(5) . . ?
O1 Cu1' N6 112.4(7) . . ?
N14 Cu1' N6 130.0(5) . . ?
Cu1 Cu1' H1A 146.6 . . ?
O1 Cu1' H1A 29.2 . . ?
N14 Cu1' H1A 85.8 . . ?
N6 Cu1' H1A 140.1 . . ?
Cu1 Cu1' H1B 164.9 . . ?
O1 Cu1' H1B 27.9 . . ?
N14 Cu1' H1B 125.7 . . ?
N6 Cu1' H1B 103.8 . . ?
H1A Cu1' H1B 48.4 . . ?
C1 N5 N4 105.1(6) . . ?
C1 N5 Cu1 128.2(6) . . ?
N4 N5 Cu1 126.6(5) . . ?
C2 N1 C1 122.6(7) . . ?
C2 N1 H1 118.7 . . ?
C1 N1 H1 118.7 . . ?
C3 N10 C4 123.1(7) . . ?
C3 N10 H2 118.4 . . ?
C4 N10 H2 118.4 . . ?
N16 N15 C3 105.5(7) . . ?
N16 N15 Cu1 125.8(5) . . ?
C3 N15 Cu1 128.7(6) . . ?
C3 N18 N17 105.4(6) . . ?
C3 N18 Pb1 136.5(5) . . ?
N17 N18 Pb1 117.6(5) . . ?
N13 N14 C4 104.9(7) . . ?
N13 N14 Cu1 126.4(6) . . ?
C4 N14 Cu1 128.5(6) . . ?
N13 N14 Cu1' 113.1(6) . . ?
C4 N14 Cu1' 130.0(6) . . ?
Cu1 N14 Cu1' 28.2(2) . . ?
N12 N13 N14 109.2(7) . . ?
N3 N4 N5 108.3(7) . . ?
N13 N12 N11 110.4(7) . . ?
N16 N17 N18 108.3(6) . . ?
N8 N7 N6 108.1(7) . . ?
C4 N11 N12 103.1(7) . . ?
Pb1 O2 H2A 109.3 . . ?
Pb1 O2 H2B 109.4 . . ?
H2A O2 H2B 109.5 . . ?
C2 N6 N7 105.8(7) . . ?
C2 N6 Cu1 130.1(6) . . ?
N7 N6 Cu1 124.1(5) . . ?
C2 N6 Cu1' 135.3(6) . . ?
N7 N6 Cu1' 109.9(6) . . ?
Cu1 N6 Cu1' 28.0(3) . . ?
Pb1 O5 H5A 106.2 . . ?
Pb1 O5 H5B 105.8 . . ?
H5A O5 H5B 106.3 . . ?
C2 N9 N8 103.3(7) . . ?
N7 N8 N9 110.6(7) . . ?
Pb1 O3 H3A 109.4 . . ?
Pb1 O3 H3B 109.2 . . ?
H3A O3 H3B 109.5 . . ?
N2 C1 N5 111.9(7) . . ?
N2 C1 N1 122.0(7) . . ?
N5 C1 N1 126.1(7) . . ?
N17 N16 N15 109.8(7) . . ?
N6 C2 N9 112.1(7) . . ?
N6 C2 N1 126.0(7) . . ?
N9 C2 N1 121.9(7) . . ?
N18 C3 N15 110.9(7) . . ?
N18 C3 N10 123.5(7) . . ?
N15 C3 N10 125.6(7) . . ?
N11 C4 N14 112.4(7) . . ?
N11 C4 N10 122.0(7) . . ?
N14 C4 N10 125.6(7) . . ?
Pb1 O4 H4A 110.0 . . ?
Pb1 O4 H4B 108.0 . . ?
H4A O4 H4B 110.1 . . ?
C1 N2 N3 103.3(6) . . ?
N4 N3 N2 111.4(7) . . ?
Cu1' O1 Cu1 7.6(5) . . ?
Cu1' O1 H1A 108.0 . . ?
Cu1 O1 H1A 107.7 . . ?
Cu1' O1 H1B 111.4 . . ?
Cu1 O1 H1B 118.1 . . ?
H1A O1 H1B 107.8 . . ?
H7A O7 H7B 114.7 . . ?
H6A O6 H6B 115.1 . . ?

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
N1 H1 N16 0.86 2.06 2.902(10) 164.4 2_656
O6 H6A N12 0.85 2.15 2.918(11) 150.9 2_667
O5 H5A N2 0.85 2.18 2.831(10) 133.4 1_565
O7 H7A N13 0.85 2.13 2.927(10) 157.6 2_667
O7 H7B N3 0.84 1.96 2.785(9) 165.7 1_565
O2 H2A N4 0.85 2.19 2.848(10) 133.9 2_767
O3 H3A O7 0.85 2.04 2.742(9) 139.7 2_777
O4 H4B N7 0.85 2.03 2.881(11) 179.8 2_666
O1 H1A N11 0.85 2.02 2.857(10) 170.5 2_667
O4 H4A N17 0.85 2.02 2.840(10) 162.8 2_766

_refine_diff_density_max         2.080
_refine_diff_density_min         -2.685
_refine_diff_density_rms         0.241

####################################################################### 
# 
# 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_1
_database_code_depnum_ccdc_archive 'CCDC 1501053'
_audit_update_record             
;
2017-01-20 deposited with the CCDC.
2017-01-23 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         'C2 H3 N9 O Pb'
_chemical_formula_sum            'C2 H3 N9 O Pb'
_chemical_formula_weight         376.32

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'
Pb Pb -3.3944 10.1111 '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'

_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                   10.6068(16)
_cell_length_b                   6.5724(10)
_cell_length_c                   11.3962(17)
_cell_angle_alpha                90
_cell_angle_beta                 112.778(2)
_cell_angle_gamma                90
_cell_volume                     732.50(19)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    2290
_cell_measurement_theta_min      2.23
_cell_measurement_theta_max      27.20

_exptl_crystal_description       block
_exptl_crystal_colour            Transparent
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    3.412
_exptl_crystal_F_000             672
_exptl_transmission_factor_min   0.4596
_exptl_transmission_factor_max   0.7455
_exptl_crystal_size_max          0.220
_exptl_crystal_size_mid          0.140
_exptl_crystal_size_min          0.090
_exptl_absorpt_coefficient_mu    23.008
_shelx_estimated_absorpt_T_min   0.081
_shelx_estimated_absorpt_T_max   0.231
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.029
_exptl_absorpt_correction_T_max  0.126
_exptl_absorpt_process_details   sadabs
_exptl_absorpt_special_details   ?
_exptl_special_details           
; 
SADABS v.2.10 (Bruker,2003) was used for absorption correction.
R(int) was 0.0374 after correction.
The Ratio of minimum to maximum transmission is 0.2302.
The λ/2 correction factor is 0.0015. 
;
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker SMART CCD area-detector'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            3754
_diffrn_reflns_av_unetI/netI     0.0425
_diffrn_reflns_av_R_equivalents  0.0374
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_theta_min         2.082
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             1437
_reflns_number_gt                1294
_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)+(0.0322P)²+1.9563P] 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     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_extinction_coef       0.0055(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         1431
_refine_ls_number_parameters     119
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0282
_refine_ls_R_factor_gt           0.0249
_refine_ls_wR_factor_ref         0.0646
_refine_ls_wR_factor_gt          0.0631
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_restrained_S_all      1.021
_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
N6 N 0.4022(6) 0.2721(9) 0.7218(5) 0.0173(12) Uani 1 1 d . . . . .
N7 N 0.3625(6) 0.2505(10) 0.8205(5) 0.0197(12) Uani 1 1 d . . . . .
N1 N 0.8244(6) 0.2593(9) 0.6734(5) 0.0176(12) Uani 1 1 d . . . . .
Pb1 Pb 1.22962(2) 0.08019(4) 0.99983(2) 0.01401(14) Uani 1 1 d . . . . .
N3 N 0.9553(6) 0.1087(9) 0.8484(6) 0.0169(13) Uani 1 1 d . . . . .
N2 N 0.9524(6) 0.1938(9) 0.7439(6) 0.0206(14) Uani 1 1 d . . . . .
C1 C 0.7503(7) 0.2059(10) 0.7390(6) 0.0119(13) Uani 1 1 d . . . . .
N9 N 0.5825(6) 0.1837(8) 0.8927(5) 0.0146(12) Uani 1 1 d . . . . .
N5 N 0.6135(6) 0.2404(9) 0.6976(5) 0.0164(12) Uani 1 1 d . U . . .
H1 H 0.5715 0.2717 0.6186 0.020 Uiso 1 1 calc R U . . .
N4 N 0.8277(6) 0.1142(8) 0.8493(5) 0.0137(12) Uani 1 1 d . . . . .
N8 N 0.4693(6) 0.1983(9) 0.9218(5) 0.0179(13) Uani 1 1 d . . . . .
C2 C 0.5361(6) 0.2299(10) 0.7703(6) 0.0111(12) Uani 1 1 d . . . . .
O1 O 1.1056(6) 0.3684(9) 1.0861(5) 0.0305(13) Uani 1 1 d . . . . .
H1A H 1.1119 0.4895 1.0628 0.046 Uiso 1 1 d R U . . .
H1B H 1.0331 0.3360 1.0966 0.046 Uiso 1 1 d 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
N6 C2 1.339(8) . ?
N6 N7 1.353(8) . ?
N6 Pb1 2.666(6) 4_465 ?
N7 N8 1.312(8) . ?
N1 C1 1.324(8) . ?
N1 N2 1.352(8) . ?
N1 Pb1 2.793(6) 2_756 ?
Pb1 N4 2.402(6) 3_757 ?
Pb1 N9 2.567(5) 3_757 ?
Pb1 N6 2.666(6) 4_666 ?
Pb1 O1 2.700(6) . ?
Pb1 N3 2.756(6) . ?
Pb1 N1 2.793(6) 2_746 ?
N3 N2 1.305(8) . ?
N3 N4 1.358(9) . ?
C1 N4 1.348(8) . ?
C1 N5 1.360(8) . ?
N9 C2 1.323(8) . ?
N9 N8 1.367(8) . ?
N9 Pb1 2.567(5) 3_757 ?
N5 C2 1.375(9) . ?
N5 H1 0.8600 . ?
N4 Pb1 2.402(6) 3_757 ?
O1 H1A 0.8500 . ?
O1 H1B 0.8500 . ?

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
C2 N6 N7 104.9(5) . . ?
C2 N6 Pb1 134.1(4) . 4_465 ?
N7 N6 Pb1 120.5(4) . 4_465 ?
N8 N7 N6 108.5(5) . . ?
C1 N1 N2 105.0(5) . . ?
C1 N1 Pb1 126.5(4) . 2_756 ?
N2 N1 Pb1 123.0(4) . 2_756 ?
N4 Pb1 N9 70.36(18) 3_757 3_757 ?
N4 Pb1 N6 77.61(18) 3_757 4_666 ?
N9 Pb1 N6 70.87(18) 3_757 4_666 ?
N4 Pb1 O1 79.53(18) 3_757 . ?
N9 Pb1 O1 134.28(17) 3_757 . ?
N6 Pb1 O1 69.59(17) 4_666 . ?
N4 Pb1 N3 89.20(18) 3_757 . ?
N9 Pb1 N3 141.37(18) 3_757 . ?
N6 Pb1 N3 137.77(18) 4_666 . ?
O1 Pb1 N3 68.61(17) . . ?
N4 Pb1 N1 93.73(18) 3_757 2_746 ?
N9 Pb1 N1 74.69(17) 3_757 2_746 ?
N6 Pb1 N1 145.43(18) 4_666 2_746 ?
O1 Pb1 N1 142.37(17) . 2_746 ?
N3 Pb1 N1 74.37(17) . 2_746 ?
N2 N3 N4 108.9(5) . . ?
N2 N3 Pb1 104.3(4) . . ?
N4 N3 Pb1 144.2(4) . . ?
N3 N2 N1 110.0(6) . . ?
N1 C1 N4 111.4(6) . . ?
N1 C1 N5 123.1(6) . . ?
N4 C1 N5 125.5(6) . . ?
C2 N9 N8 103.7(5) . . ?
C2 N9 Pb1 124.1(4) . 3_757 ?
N8 N9 Pb1 121.6(4) . 3_757 ?
C1 N5 C2 126.0(6) . . ?
C1 N5 H1 117.0 . . ?
C2 N5 H1 117.0 . . ?
C1 N4 N3 104.7(5) . . ?
C1 N4 Pb1 132.4(5) . 3_757 ?
N3 N4 Pb1 121.4(4) . 3_757 ?
N7 N8 N9 110.3(5) . . ?
N9 C2 N6 112.6(6) . . ?
N9 C2 N5 125.6(6) . . ?
N6 C2 N5 121.8(6) . . ?
Pb1 O1 H1A 115.7 . . ?
Pb1 O1 H1B 118.1 . . ?
H1A O1 H1B 117.6 . . ?

_refine_diff_density_max         2.373
_refine_diff_density_min         -1.394
_refine_diff_density_rms         0.216

