# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 2014

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_Complex-1

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C6 H18 Cu5 N18'
_chemical_formula_sum            'C6 H18 Cu5 N18'
_chemical_formula_weight         660.08

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'
Cu Cu 0.3201 1.2651 '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/n'
_space_group_name_Hall           '-P 2yn'

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

_cell_length_a                   9.2061(11)
_cell_length_b                   11.3907(15)
_cell_length_c                   9.9910(18)
_cell_angle_alpha                90
_cell_angle_beta                 107.692(16)
_cell_angle_gamma                90
_cell_volume                     998.1(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       block
_exptl_crystal_colour            blue
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.196
_exptl_crystal_F_000             650
_exptl_transmission_factor_min   0.402
_exptl_transmission_factor_max   0.590
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.10
_exptl_absorpt_coefficient_mu    5.276
_shelx_estimated_absorpt_T_min   0.597
_shelx_estimated_absorpt_T_max   0.711
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'fine-focus sealed tube'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 15.9853
_diffrn_reflns_number            5050
_diffrn_reflns_av_unetI/netI     0.0716
_diffrn_reflns_av_R_equivalents  0.0572
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.931
_diffrn_reflns_theta_max         24.984
_diffrn_reflns_theta_full        25.000
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measured_fraction_theta_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_point_group_measured_fraction_full 0.977
_reflns_number_total             1714
_reflns_number_gt                1289
_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       'X-calibur S oxford'
_computing_cell_refinement       'X-calibur S SAINT'
_computing_data_reduction        'X-calibur S SAINT'
_computing_structure_solution    'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'Oxford SHELXTL'
_computing_publication_material  'Oxford 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)+(0.0808P)²+5.1036P] 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     SHELXL
_refine_ls_extinction_coef       .
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         1714
_refine_ls_number_parameters     137
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0883
_refine_ls_R_factor_gt           0.0643
_refine_ls_wR_factor_ref         0.1687
_refine_ls_wR_factor_gt          0.1518
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_restrained_S_all      1.017
_refine_ls_shift/su_max          0.015
_refine_ls_shift/su_mean         0.015

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
Cu1 Cu 0.04467(12) 0.71856(10) 0.97732(12) 0.0317(4) Uani 1 1 d . . . . .
Cu2 Cu 1.0000 0.5000 1.5000 0.0339(5) Uani 1 2 d S . P . .
Cu3 Cu 0.47493(12) 0.42473(10) 1.15717(14) 0.0429(5) Uani 1 1 d . . . . .
N9 N 0.4897(8) 0.1715(7) 1.0465(9) 0.0337(19) Uani 1 1 d . . . . .
N6 N -0.1315(8) 0.8307(7) 0.8970(8) 0.039(2) Uani 1 1 d . . . . .
H6A H -0.0999 0.8911 0.8566 0.058 Uiso 1 1 calc R U . . .
H6B H -0.1658 0.8568 0.9658 0.058 Uiso 1 1 calc R U . . .
H6C H -0.2062 0.7934 0.8334 0.058 Uiso 1 1 calc R U . . .
N2 N 0.2750(9) 0.9019(6) 1.1734(8) 0.0324(19) Uani 1 1 d . . . . .
C8 C 0.6741(11) 0.4645(8) 1.2910(10) 0.032(2) Uani 1 1 d . . . . .
N7 N 0.2177(9) 0.6054(7) 1.0502(9) 0.039(2) Uani 1 1 d . . . . .
N8 N 0.7912(9) 0.4854(6) 1.3680(9) 0.0356(19) Uani 1 1 d . . . . .
C9 C 0.4751(10) 0.2679(9) 1.0760(11) 0.035(2) Uani 1 1 d . . . . .
N3 N 0.3982(9) 0.9419(7) 1.2009(10) 0.044(2) Uani 1 1 d . . . . .
C7 C 0.3181(11) 0.5405(8) 1.0850(10) 0.033(2) Uani 1 1 d . . . . .
N4 N -0.0676(8) 0.6472(7) 1.1022(9) 0.0354(19) Uani 1 1 d . . . . .
H4A H -0.1504 0.6102 1.0496 0.053 Uiso 1 1 calc R U . . .
H4B H -0.0949 0.7037 1.1513 0.053 Uiso 1 1 calc R U . . .
H4C H -0.0070 0.5963 1.1609 0.053 Uiso 1 1 calc R U . . .
N5 N 0.1289(9) 0.7556(7) 0.8180(8) 0.036(2) Uani 1 1 d . . . . .
H5A H 0.2277 0.7725 0.8524 0.055 Uiso 1 1 calc R U . . .
H5B H 0.0795 0.8170 0.7700 0.055 Uiso 1 1 calc R U . . .
H5C H 0.1166 0.6938 0.7611 0.055 Uiso 1 1 calc R U . . .
N1 N 0.1511(9) 0.8647(7) 1.1524(9) 0.042(2) Uani 1 1 d . . . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cu1 0.0176(6) 0.0336(7) 0.0414(8) 0.0081(5) 0.0052(5) 0.0042(4)
Cu2 0.0161(8) 0.0307(9) 0.0476(11) 0.0069(8) -0.0011(7) -0.0026(6)
Cu3 0.0206(7) 0.0340(7) 0.0604(10) -0.0055(6) -0.0081(6) 0.0052(5)
N9 0.019(4) 0.030(4) 0.048(5) -0.011(4) 0.004(4) -0.002(3)
N6 0.025(4) 0.048(5) 0.040(5) 0.011(4) 0.006(4) 0.013(4)
N2 0.025(5) 0.027(4) 0.041(5) -0.008(4) 0.003(4) 0.003(3)
C8 0.031(5) 0.025(4) 0.032(6) -0.002(4) -0.002(4) 0.005(4)
N7 0.025(4) 0.045(5) 0.046(5) 0.009(4) 0.006(4) 0.006(4)
N8 0.024(4) 0.033(4) 0.044(5) 0.000(4) 0.003(4) -0.003(3)
C9 0.015(4) 0.047(6) 0.038(6) -0.004(5) 0.001(4) -0.007(4)
N3 0.027(5) 0.044(5) 0.059(6) -0.010(5) 0.009(4) -0.005(4)
C7 0.027(5) 0.032(5) 0.032(6) 0.002(4) -0.002(4) 0.000(4)
N4 0.023(4) 0.036(4) 0.047(5) 0.002(4) 0.010(4) -0.002(3)
N5 0.033(5) 0.029(4) 0.046(5) -0.003(4) 0.010(4) -0.001(3)
N1 0.029(5) 0.042(5) 0.054(6) -0.013(4) 0.009(4) -0.005(4)

_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
Cu1 N7 2.006(8) . ?
Cu1 N5 2.016(8) . ?
Cu1 N4 2.018(7) . ?
Cu1 N6 2.029(7) . ?
Cu1 N1 2.398(8) . ?
Cu2 N8 1.980(8) 3_768 ?
Cu2 N8 1.980(8) . ?
Cu2 N9 2.017(8) 2_657 ?
Cu2 N9 2.017(8) 4_666 ?
Cu3 C7 1.926(9) . ?
Cu3 C9 1.962(11) . ?
Cu3 C8 1.966(10) . ?
N9 C9 1.155(12) . ?
N9 Cu2 2.017(8) 2_647 ?
N2 N3 1.175(11) . ?
N2 N1 1.174(11) . ?
C8 N8 1.143(12) . ?
N7 C7 1.152(12) . ?

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
N7 Cu1 N5 88.1(3) . . ?
N7 Cu1 N4 90.9(3) . . ?
N5 Cu1 N4 164.8(3) . . ?
N7 Cu1 N6 178.0(3) . . ?
N5 Cu1 N6 90.5(3) . . ?
N4 Cu1 N6 90.0(3) . . ?
N7 Cu1 N1 94.5(3) . . ?
N5 Cu1 N1 105.1(3) . . ?
N4 Cu1 N1 90.1(3) . . ?
N6 Cu1 N1 87.2(3) . . ?
N8 Cu2 N8 180.0 3_768 . ?
N8 Cu2 N9 88.2(3) 3_768 2_657 ?
N8 Cu2 N9 91.8(3) . 2_657 ?
N8 Cu2 N9 91.8(3) 3_768 4_666 ?
N8 Cu2 N9 88.2(3) . 4_666 ?
N9 Cu2 N9 180.0 2_657 4_666 ?
C7 Cu3 C9 124.3(4) . . ?
C7 Cu3 C8 122.3(4) . . ?
C9 Cu3 C8 111.9(4) . . ?
C9 N9 Cu2 175.3(8) . 2_647 ?
N3 N2 N1 176.4(10) . . ?
N8 C8 Cu3 178.5(8) . . ?
C7 N7 Cu1 176.3(8) . . ?
C8 N8 Cu2 172.6(7) . . ?
N9 C9 Cu3 170.3(9) . . ?
N7 C7 Cu3 173.7(9) . . ?
N2 N1 Cu1 122.7(7) . . ?


_shelx_res_file                  
;
TITL DS-255 in P2(1)/n
CELL  0.71073   9.2061  11.3907   9.9910   90.000  107.692   90.000
ZERR     2.00   0.0011   0.0015   0.0018    0.000    0.016    0.000
LATT   1
SYMM  1/2 - X, 1/2 + Y, 1/2 - Z
SFAC  C    H    N    CU
UNIT  12   36   36   10
MERG   2
OMIT    -2.00  50.00
FMAP   2
PLAN   20
ACTA    50.00
BOND
CONF
L.S.   4
WGHT    0.080800    5.103600
EXTI    0.000000
FVAR       2.31490
MOLE    1
CU1   4    0.044669    0.718557    0.977315    11.00000    0.01763    0.03357 =
         0.04139    0.00806    0.00520    0.00419
CU2   4    1.000000    0.500000    1.500000    10.50000    0.01607    0.03068 =
         0.04763    0.00693   -0.00113   -0.00263
CU3   4    0.474925    0.424734    1.157169    11.00000    0.02064    0.03398 =
         0.06038   -0.00554   -0.00808    0.00516
N9    3    0.489660    0.171511    1.046524    11.00000    0.01905    0.03045 =
         0.04789   -0.01101    0.00444   -0.00199
N6    3   -0.131536    0.830678    0.896996    11.00000    0.02490    0.04845 =
         0.03973    0.01122    0.00600    0.01256
AFIX 137
H6A   2   -0.099901    0.891054    0.856600    11.00000   -1.50000
H6B   2   -0.165775    0.856807    0.965795    11.00000   -1.50000
H6C   2   -0.206237    0.793365    0.833355    11.00000   -1.50000
AFIX   0
N2    3    0.274999    0.901948    1.173417    11.00000    0.02486    0.02681 =
         0.04094   -0.00765    0.00311    0.00274
C8    1    0.674087    0.464502    1.290967    11.00000    0.03063    0.02487 =
         0.03161   -0.00244   -0.00247    0.00461
N7    3    0.217657    0.605399    1.050160    11.00000    0.02483    0.04474 =
         0.04586    0.00906    0.00642    0.00553
N8    3    0.791212    0.485449    1.367977    11.00000    0.02430    0.03337 =
         0.04435    0.00046    0.00312   -0.00257
C9    1    0.475110    0.267914    1.075996    11.00000    0.01515    0.04747 =
         0.03805   -0.00431    0.00058   -0.00683
N3    3    0.398202    0.941908    1.200853    11.00000    0.02706    0.04400 =
         0.05897   -0.00952    0.00945   -0.00480
C7    1    0.318128    0.540459    1.084994    11.00000    0.02690    0.03193 =
         0.03185    0.00194   -0.00186    0.00029
N4    3   -0.067586    0.647204    1.102243    11.00000    0.02311    0.03570 =
         0.04726    0.00222    0.01044   -0.00186
AFIX 137
H4A   2   -0.150390    0.610151    1.049614    11.00000   -1.50000
H4B   2   -0.094914    0.703661    1.151307    11.00000   -1.50000
H4C   2   -0.006973    0.596324    1.160918    11.00000   -1.50000
AFIX   0
N5    3    0.128897    0.755625    0.817958    11.00000    0.03276    0.02932 =
         0.04559   -0.00315    0.00955   -0.00097
AFIX 137
H5A   2    0.227691    0.772459    0.852356    11.00000   -1.50000
H5B   2    0.079535    0.816988    0.770029    11.00000   -1.50000
H5C   2    0.116646    0.693792    0.761142    11.00000   -1.50000
AFIX   0
N1    3    0.151082    0.864744    1.152357    11.00000    0.02874    0.04159 =
         0.05392   -0.01288    0.00882   -0.00477
HKLF    4

REM  DS-255 in P2(1)/n
REM R1 =  0.0643 for    1289 Fo > 4sig(Fo)  and  0.0883 for all    1714 data
REM    137 parameters refined using      0 restraints

END

WGHT      0.0810      3.3088

REM Highest difference peak  2.084,  deepest hole -1.136,  1-sigma level  0.182
Q1    1   1.0440  0.4111  1.4561  11.00000  0.05    2.08
Q2    1   0.4783  0.4912  1.2028  11.00000  0.05    1.07
Q3    1   0.5452  0.4355  1.1139  11.00000  0.05    0.95
Q4    1   0.0075  0.7768  0.9203  11.00000  0.05    0.89
Q5    1   0.1186  0.7281  0.9191  11.00000  0.05    0.84
Q6    1  -0.0339  0.7206  1.0262  11.00000  0.05    0.82
Q7    1   0.0081  0.6601  0.9143  11.00000  0.05    0.70
Q8    1   0.4509  0.2391  1.0103  11.00000  0.05    0.66
Q9    1   0.4706  0.5184  1.0833  11.00000  0.05    0.64
Q10   1   1.0533  0.4412  1.5735  11.00000  0.05    0.63
Q11   1   1.0979  0.4984  1.4591  11.00000  0.05    0.59
Q12   1   0.5306  0.3739  1.2302  11.00000  0.05    0.57
Q13   1   0.5169  0.2678  1.0626  11.00000  0.05    0.57
Q14   1   0.4201  0.3617  1.0918  11.00000  0.05    0.57
Q15   1   0.0968  0.7850  1.0413  11.00000  0.05    0.54
Q16   1   0.0040  0.7839  1.1613  11.00000  0.05    0.54
Q17   1   0.4766  0.2978  1.1490  11.00000  0.05    0.50
Q18   1  -0.0197  0.9297  0.7969  11.00000  0.05    0.50
Q19   1  -0.0092  0.5482  1.0462  11.00000  0.05    0.50
Q20   1   0.4941  0.9035  1.3068  11.00000  0.05    0.47
;
_shelx_res_checksum              81882
_database_code_depnum_ccdc_archive 'CCDC 971692'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_Complex-2

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'Cu H6 N8'
_chemical_formula_sum            'Cu H6 N8'
_chemical_formula_weight         181.67

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
N N 0.0061 0.0033 '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'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_H-M_alt        'P n m a'
_space_group_name_Hall           '-P 2ac 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'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z'
'x+1/2, -y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'x, -y-1/2, z'
'-x-1/2, y-1/2, z-1/2'

_cell_length_a                   6.3785(7)
_cell_length_b                   7.4502(15)
_cell_length_c                   12.6761(15)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     602.38(16)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    1293
_cell_measurement_theta_min      3.1657
_cell_measurement_theta_max      29.1744

_exptl_crystal_description       needle
_exptl_crystal_colour            green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.003
_exptl_crystal_F_000             364
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.10
_exptl_absorpt_coefficient_mu    3.546
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.65151
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Enhance (Mo) X-ray Source'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            3654
_diffrn_reflns_av_unetI/netI     0.0263
_diffrn_reflns_av_R_equivalents  0.0396
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         3.172
_diffrn_reflns_theta_max         24.973
_diffrn_reflns_theta_full        25.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             575
_reflns_number_gt                528
_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       'X-calibur S oxford'
_computing_cell_refinement       'X-calibur S SAINT'
_computing_data_reduction        'X-calibur S SAINT'
_computing_structure_solution    'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'Oxford SHELXTL'
_computing_publication_material  'Oxford 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)+(0.0398P)²+0.1485P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         575
_refine_ls_number_parameters     64
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0301
_refine_ls_R_factor_gt           0.0267
_refine_ls_wR_factor_ref         0.0719
_refine_ls_wR_factor_gt          0.0692
_refine_ls_goodness_of_fit_ref   1.124
_refine_ls_restrained_S_all      1.120
_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
Cu1 Cu 0.22661(7) 0.2500 0.35990(4) 0.0221(2) Uani 1 2 d S T P . .
N1 N 0.3442(7) 0.2500 0.6568(3) 0.0446(11) Uani 1 2 d S T P . .
N2 N 0.2371(5) 0.2500 0.5841(3) 0.0258(8) Uani 1 2 d S T P . .
N3 N 0.1195(5) 0.2500 0.5120(3) 0.0324(9) Uani 1 2 d S T P . .
N4 N 0.3551(5) 0.2500 0.2104(3) 0.0256(8) Uani 1 2 d S T P . .
N5 N 0.2330(5) 0.2500 0.1397(3) 0.0258(10) Uani 1 2 d S T P . .
N6 N 0.1170(6) 0.2500 0.0704(3) 0.0452(11) Uani 1 2 d S T P . .
N7 N 0.2297(4) -0.0147(4) 0.3623(2) 0.0301(7) Uani 1 1 d D . . . .
H7A H 0.198(4) -0.052(7) 0.2982(15) 0.081(16) Uiso 1 1 d D . . . .
H7B H 0.358(3) -0.046(6) 0.379(2) 0.079(15) Uiso 1 1 d D . . . .
H7C H 0.139(4) -0.059(5) 0.4080(18) 0.068(13) Uiso 1 1 d D . . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cu1 0.0263(4) 0.0222(3) 0.0177(3) 0.000 0.00319(19) 0.000
N1 0.045(3) 0.061(3) 0.028(2) 0.000 -0.003(2) 0.000
N2 0.027(2) 0.026(2) 0.025(2) 0.000 0.0097(17) 0.000
N3 0.0277(19) 0.051(3) 0.0188(19) 0.000 0.0040(17) 0.000
N4 0.0227(18) 0.038(2) 0.0166(18) 0.000 0.0000(16) 0.000
N5 0.020(2) 0.033(2) 0.024(2) 0.000 0.0072(17) 0.000
N6 0.026(2) 0.087(4) 0.022(2) 0.000 -0.0046(19) 0.000
N7 0.0332(17) 0.0262(16) 0.0309(17) 0.0022(12) 0.0029(12) 0.0000(11)

_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
Cu1 N7 1.973(3) . ?
Cu1 N7 1.973(3) 7_565 ?
Cu1 N3 2.045(3) . ?
Cu1 N4 2.064(3) . ?
N1 N2 1.146(6) . ?
N2 N3 1.183(5) . ?
N4 N5 1.188(5) . ?
N5 N6 1.148(5) . ?
N7 H7A 0.883(10) . ?
N7 H7B 0.879(10) . ?
N7 H7C 0.883(10) . ?

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
N7 Cu1 N7 177.92(17) . 7_565 ?
N7 Cu1 N3 89.38(8) . . ?
N7 Cu1 N3 89.37(8) 7_565 . ?
N7 Cu1 N4 90.57(8) . . ?
N7 Cu1 N4 90.57(8) 7_565 . ?
N3 Cu1 N4 176.12(13) . . ?
N1 N2 N3 177.2(4) . . ?
N2 N3 Cu1 121.1(3) . . ?
N5 N4 Cu1 115.6(3) . . ?
N6 N5 N4 179.2(4) . . ?
Cu1 N7 H7A 107(3) . . ?
Cu1 N7 H7B 106(3) . . ?
H7A N7 H7B 111(3) . . ?
Cu1 N7 H7C 112(3) . . ?
H7A N7 H7C 110(3) . . ?
H7B N7 H7C 110(3) . . ?

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
N7 H7A N1 0.883(10) 2.34(2) 3.175(4) 159(4) 2_554
N7 H7B N1 0.879(10) 2.48(3) 3.243(5) 146(4) 5_656
N7 H7C N3 0.883(10) 2.403(16) 3.252(4) 161(3) 5_556

_refine_diff_density_max         0.470
_refine_diff_density_min         -0.379
_refine_diff_density_rms         0.088

_shelxl_version_number           2013-4

_shelx_res_file                  
;
TITL TS-2- in Pnma
CELL  0.71073   6.3785   7.4502  12.6761   90.000   90.000   90.000
ZERR     4.00   0.0007   0.0015   0.0015    0.000    0.000    0.000
LATT   1
SYMM  1/2 - X, - Y, 1/2 + Z
SYMM  - X, 1/2 + Y, - Z
SYMM  1/2 + X, 1/2 - Y, 1/2 - Z
SFAC  N  H  Cu
UNIT  32  24 4

sadi h7a h7b h7a h7c h7b h7c
dfix 0.890 0.01 n7 h7a n7 h7b n7 h7c

OMIT  -3.00
L.S.   10
acta 50
wpdb -2
list 4
OMIT -2 50
bond $h
rem conf
more 2
EQIV $1 -x+1/2, -y, z-1/2
HTAB N7 N1_$1
EQIV $2 -x+1, -y, -z+1
HTAB N7 N1_$2
EQIV $3 -x, -y, -z+1
HTAB N7 N3_$3
FMAP   2
PLAN   10

WGHT    0.039800    0.148500
FVAR       4.11639
CU1   3    0.226613    0.250000    0.359900    10.50000    0.02634    0.02218 =
         0.01775    0.00000    0.00319    0.00000
N1    1    0.344161    0.250000    0.656756    10.50000    0.04464    0.06125 =
         0.02805    0.00000   -0.00262    0.00000
N2    1    0.237065    0.250000    0.584133    10.50000    0.02650    0.02615 =
         0.02489    0.00000    0.00971    0.00000
N3    1    0.119486    0.250000    0.511994    10.50000    0.02771    0.05076 =
         0.01877    0.00000    0.00395    0.00000
N4    1    0.355097    0.250000    0.210430    10.50000    0.02274    0.03755 =
         0.01656    0.00000    0.00001    0.00000
N5    1    0.232997    0.250000    0.139675    10.50000    0.02018    0.03335 =
         0.02383    0.00000    0.00719    0.00000
N6    1    0.116998    0.250000    0.070407    10.50000    0.02627    0.08744 =
         0.02178    0.00000   -0.00464    0.00000
N7    1    0.229719   -0.014734    0.362252    11.00000    0.03321    0.02625 =
         0.03088    0.00216    0.00292   -0.00003
H7A   2    0.197616   -0.052219    0.298201    11.00000    0.08116
H7B   2    0.358229   -0.045816    0.379475    11.00000    0.07858
H7C   2    0.138961   -0.058913    0.407992    11.00000    0.06768
HKLF    4

REM  TS-2- in Pnma
REM R1 =  0.0267 for     528 Fo > 4sig(Fo)  and  0.0301 for all     575 data
REM     64 parameters refined using      6 restraints

END

WGHT      0.0353      0.2060

REM Highest difference peak  0.470,  deepest hole -0.379,  1-sigma level  0.088
Q1    1   0.2260 -0.2500  0.4094  10.50000  0.05    0.47
Q2    1   0.1106  0.2500  0.0341  10.50000  0.05    0.35
Q3    1   0.4676  0.2500  0.2339  10.50000  0.05    0.32
Q4    1   0.5005  0.3821  0.2456  11.00000  0.05    0.31
Q5    1  -0.0002  0.2500  0.4812  10.50000  0.05    0.28
Q6    1  -0.0043  0.2861  0.0831  11.00000  0.05    0.28
Q7    1   0.4113  0.2500  0.6959  10.50000  0.05    0.27
Q8    1   0.1692  0.3226  0.4671  11.00000  0.05    0.24
Q9    1   0.4752  0.0488  0.4437  11.00000  0.05    0.21
Q10   1   0.2254  0.2500  0.6780  10.50000  0.05    0.21
;
_shelx_res_checksum              9909
_database_code_depnum_ccdc_archive 'CCDC 989191'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_Complex-3

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C4 H9 Cu3 N7'
_chemical_formula_sum            'C4 H9 Cu3 N7'
_chemical_formula_weight         345.80

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'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   P21/n
_symmetry_space_group_name_Hall  -P2yn

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   9.3703(3)
_cell_length_b                   12.6234(3)
_cell_length_c                   9.3981(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 98.559(3)
_cell_angle_gamma                90.00
_cell_volume                     1099.27(6)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    7223
_cell_measurement_theta_min      3.2145
_cell_measurement_theta_max      32.6361

_exptl_crystal_description       Needle
_exptl_crystal_colour            Blue
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.21
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.089
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             676
_exptl_absorpt_coefficient_mu    5.723
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.2971
_exptl_absorpt_correction_T_max  0.3795
_exptl_absorpt_process_details   
;
CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.33.31 (release 08-01-2009 CrysAlis171 .NET)
(compiled Jan  8 2009,16:24:04)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Goniometer KM4/Xcalibur, detector: Sapphire3'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 15.9948
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            7291
_diffrn_reflns_av_R_equivalents  0.0374
_diffrn_reflns_av_sigmaI/netI    0.0229
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         3.23
_diffrn_reflns_theta_max         25.00
_reflns_number_total             1921
_reflns_number_gt                1820
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.31 (release 08-01-2009 CrysAlis171 .NET)
(compiled Jan  8 2009,16:24:04)
;
_computing_cell_refinement       
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.31 (release 08-01-2009 CrysAlis171 .NET)
(compiled Jan  8 2009,16:24:04)
;
_computing_data_reduction        
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.31 (release 08-01-2009 CrysAlis171 .NET)
(compiled Jan  8 2009,16:24:04)
;
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Oxford SHELXTL'
_computing_publication_material  'Oxford SHELXTL'

_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0000P)²+61.7879P] 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         1921
_refine_ls_number_parameters     130
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0910
_refine_ls_R_factor_gt           0.0890
_refine_ls_wR_factor_ref         0.2177
_refine_ls_wR_factor_gt          0.2171
_refine_ls_goodness_of_fit_ref   1.294
_refine_ls_restrained_S_all      1.294
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.4453(19) 0.0488(13) 0.6800(17) 0.028(4) Uani 1 1 d . . .
C2 C 0.1240(15) -0.0339(11) 0.2889(15) 0.017(3) Uani 1 1 d . . .
N6 N 0.6235(19) 0.3210(14) 1.0738(16) 0.047(4) Uani 1 1 d . . .
H6A H 0.6897 0.3625 1.0388 0.071 Uiso 1 1 calc R . .
H6B H 0.6628 0.2939 1.1605 0.071 Uiso 1 1 calc R . .
H6C H 0.5446 0.3604 1.0845 0.071 Uiso 1 1 calc R . .
C5 C -0.1693(16) 0.0481(12) 0.0528(16) 0.021(3) Uani 1 1 d . . .
N1 N 0.4740(16) 0.1066(11) 0.7756(15) 0.033(3) Uani 1 1 d . . .
N2 N 0.2124(17) -0.0360(11) 0.3894(16) 0.033(3) Uani 1 1 d . . .
C6 C 0.4180(15) -0.2044(11) 0.5724(15) 0.018(3) Uani 1 1 d . . .
N3 N -0.0603(15) -0.2059(11) 0.0894(13) 0.029(3) Uani 1 1 d . . .
N4 N 0.4213(15) 0.1479(12) 1.0659(15) 0.032(3) Uani 1 1 d . . .
H4A H 0.3379 0.1858 1.0478 0.048 Uiso 1 1 calc R . .
H4B H 0.4604 0.1560 1.1599 0.048 Uiso 1 1 calc R . .
H4C H 0.4022 0.0782 1.0473 0.048 Uiso 1 1 calc R . .
N5 N 0.6890(18) 0.2676(12) 0.7962(17) 0.039(4) Uani 1 1 d . . .
H5A H 0.6741 0.2318 0.7112 0.059 Uiso 1 1 calc R . .
H5B H 0.7839 0.2633 0.8348 0.059 Uiso 1 1 calc R . .
H5C H 0.6641 0.3367 0.7806 0.059 Uiso 1 1 calc R . .
N7 N 0.7332(14) 0.0995(11) 1.0270(14) 0.026(3) Uani 1 1 d . . .
Cu1 Cu 0.3769(2) -0.05548(16) 0.5404(2) 0.0322(6) Uani 1 1 d . . .
Cu2 Cu 0.56508(18) 0.20204(13) 0.93577(18) 0.0152(4) Uani 1 1 d . . .
Cu3 Cu -0.0176(2) -0.05388(15) 0.1183(2) 0.0282(5) Uani 1 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
C1 0.038(10) 0.024(8) 0.020(8) 0.013(7) -0.006(7) -0.007(7)
C2 0.015(7) 0.015(7) 0.017(7) -0.003(6) -0.009(6) -0.003(6)
N6 0.053(10) 0.060(11) 0.033(8) -0.014(8) 0.024(8) -0.015(9)
C5 0.017(8) 0.018(7) 0.021(8) -0.006(6) -0.013(6) 0.004(6)
N1 0.038(8) 0.024(7) 0.033(8) -0.011(6) -0.006(6) -0.003(6)
N2 0.049(9) 0.018(7) 0.034(8) -0.009(6) 0.012(7) -0.005(6)
C6 0.020(7) 0.015(7) 0.019(7) 0.001(6) 0.002(6) 0.001(6)
N3 0.036(8) 0.033(8) 0.018(6) 0.004(6) 0.010(6) 0.007(7)
N4 0.032(8) 0.036(8) 0.028(7) -0.005(6) 0.006(6) 0.000(6)
N5 0.049(10) 0.031(8) 0.040(9) 0.004(7) 0.016(7) 0.002(7)
N7 0.018(7) 0.032(8) 0.030(7) 0.005(6) 0.007(6) -0.011(6)
Cu1 0.0298(11) 0.0180(10) 0.0438(13) -0.0058(9) -0.0113(9) 0.0013(8)
Cu2 0.0158(8) 0.0136(8) 0.0162(8) -0.0017(7) 0.0019(6) -0.0005(7)
Cu3 0.0405(12) 0.0194(10) 0.0219(10) 0.0029(8) -0.0050(8) 0.0018(8)

_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 1.16(2) . ?
C1 Cu1 1.901(17) . ?
C2 N2 1.160(19) . ?
C2 Cu3 1.940(13) . ?
N6 Cu2 2.006(16) . ?
N6 H6A 0.9100 . ?
N6 H6B 0.9100 . ?
N6 H6C 0.9100 . ?
C5 N7 1.118(19) 1_454 ?
C5 Cu3 1.949(14) . ?
C5 Cu3 2.549(16) 3 ?
N1 Cu2 2.016(13) . ?
N2 Cu1 1.949(16) . ?
C6 N3 1.16(2) 4_656 ?
C6 Cu1 1.933(15) . ?
N3 C6 1.16(2) 4 ?
N3 Cu3 1.971(15) . ?
N4 Cu2 2.066(14) . ?
N4 H4A 0.9100 . ?
N4 H4B 0.9100 . ?
N4 H4C 0.9100 . ?
N5 Cu2 2.051(15) . ?
N5 H5A 0.9100 . ?
N5 H5B 0.9100 . ?
N5 H5C 0.9100 . ?
N7 C5 1.118(19) 1_656 ?
N7 Cu2 2.119(14) . ?
Cu1 Cu1 2.896(5) 3_656 ?
Cu3 C5 2.549(16) 3 ?
Cu3 Cu3 2.669(4) 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 Cu1 170.9(15) . . ?
N2 C2 Cu3 171.0(13) . . ?
Cu2 N6 H6A 109.5 . . ?
Cu2 N6 H6B 109.5 . . ?
H6A N6 H6B 109.5 . . ?
Cu2 N6 H6C 109.5 . . ?
H6A N6 H6C 109.5 . . ?
H6B N6 H6C 109.5 . . ?
N7 C5 Cu3 170.6(15) 1_454 . ?
N7 C5 Cu3 117.6(12) 1_454 3 ?
Cu3 C5 Cu3 71.4(5) . 3 ?
C1 N1 Cu2 168.5(15) . . ?
C2 N2 Cu1 170.8(13) . . ?
N3 C6 Cu1 178.4(14) 4_656 . ?
C6 N3 Cu3 178.4(13) 4 . ?
Cu2 N4 H4A 109.5 . . ?
Cu2 N4 H4B 109.5 . . ?
H4A N4 H4B 109.5 . . ?
Cu2 N4 H4C 109.5 . . ?
H4A N4 H4C 109.5 . . ?
H4B N4 H4C 109.5 . . ?
Cu2 N5 H5A 109.5 . . ?
Cu2 N5 H5B 109.5 . . ?
H5A N5 H5B 109.5 . . ?
Cu2 N5 H5C 109.5 . . ?
H5A N5 H5C 109.5 . . ?
H5B N5 H5C 109.5 . . ?
C5 N7 Cu2 167.7(13) 1_656 . ?
C1 Cu1 C6 121.8(6) . . ?
C1 Cu1 N2 124.3(6) . . ?
C6 Cu1 N2 110.7(6) . . ?
C1 Cu1 Cu1 69.3(5) . 3_656 ?
C6 Cu1 Cu1 111.3(4) . 3_656 ?
N2 Cu1 Cu1 108.8(4) . 3_656 ?
N6 Cu2 N1 167.1(7) . . ?
N6 Cu2 N5 89.2(6) . . ?
N1 Cu2 N5 88.9(6) . . ?
N6 Cu2 N4 90.2(6) . . ?
N1 Cu2 N4 90.2(6) . . ?
N5 Cu2 N4 173.3(6) . . ?
N6 Cu2 N7 94.6(7) . . ?
N1 Cu2 N7 98.3(6) . . ?
N5 Cu2 N7 92.7(6) . . ?
N4 Cu2 N7 94.0(5) . . ?
C2 Cu3 C5 123.5(6) . . ?
C2 Cu3 N3 109.9(6) . . ?
C5 Cu3 N3 118.4(6) . . ?
C2 Cu3 C5 93.9(5) . 3 ?
C5 Cu3 C5 108.6(5) . 3 ?
N3 Cu3 C5 94.9(5) . 3 ?
C2 Cu3 Cu3 117.9(4) . 3 ?
C5 Cu3 Cu3 64.8(5) . 3 ?
N3 Cu3 Cu3 115.4(4) . 3 ?
C5 Cu3 Cu3 43.8(3) 3 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
Cu1 C1 N1 Cu2 138(8) . . . . ?
Cu3 C2 N2 Cu1 38(16) . . . . ?
N1 C1 Cu1 C6 -70(10) . . . . ?
N1 C1 Cu1 N2 88(9) . . . . ?
N1 C1 Cu1 Cu1 -173(10) . . . 3_656 ?
N3 C6 Cu1 C1 153(49) 4_656 . . . ?
N3 C6 Cu1 N2 -8(50) 4_656 . . . ?
N3 C6 Cu1 Cu1 -129(49) 4_656 . . 3_656 ?
C2 N2 Cu1 C1 151(8) . . . . ?
C2 N2 Cu1 C6 -49(9) . . . . ?
C2 N2 Cu1 Cu1 74(8) . . . 3_656 ?
C1 N1 Cu2 N6 129(6) . . . . ?
C1 N1 Cu2 N5 47(7) . . . . ?
C1 N1 Cu2 N4 -139(7) . . . . ?
C1 N1 Cu2 N7 -45(7) . . . . ?
C5 N7 Cu2 N6 -112(6) 1_656 . . . ?
C5 N7 Cu2 N1 67(6) 1_656 . . . ?
C5 N7 Cu2 N5 -23(6) 1_656 . . . ?
C5 N7 Cu2 N4 157(6) 1_656 . . . ?
N2 C2 Cu3 C5 165(9) . . . . ?
N2 C2 Cu3 N3 17(9) . . . . ?
N2 C2 Cu3 C5 -80(9) . . . 3 ?
N2 C2 Cu3 Cu3 -118(9) . . . 3 ?
N7 C5 Cu3 C2 -88(8) 1_454 . . . ?
Cu3 C5 Cu3 C2 108.0(6) 3 . . . ?
N7 C5 Cu3 N3 57(8) 1_454 . . . ?
Cu3 C5 Cu3 N3 -106.5(5) 3 . . . ?
N7 C5 Cu3 C5 164(8) 1_454 . . 3 ?
Cu3 C5 Cu3 C5 0.0 3 . . 3 ?
N7 C5 Cu3 Cu3 164(8) 1_454 . . 3 ?
C6 N3 Cu3 C2 -56(44) 4 . . . ?
C6 N3 Cu3 C5 155(44) 4 . . . ?
C6 N3 Cu3 C5 40(44) 4 . . 3 ?
C6 N3 Cu3 Cu3 81(44) 4 . . 3 ?

_diffrn_measured_fraction_theta_max 0.993
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.993
_refine_diff_density_max         2.358
_refine_diff_density_min         -1.382
_refine_diff_density_rms         0.276
_database_code_depnum_ccdc_archive 'CCDC 952627'
