# Supplementary Material (ESI) for Chemical Communications
# This journal is (c) The Royal Society of Chemistry 2008

data_global
_journal_name_full               Chem.Commun.

_journal_coden_Cambridge         0182
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Spencer Williams'
_publ_contact_author_email       SJWILL@UNIMELB.EDU.AU

_publ_section_title              
;
'Click' Cycloaddition Catalysts: Copper(I) and
Copper(II) tris-(Triazolylmethyl)amine Complexes
;
loop_
_publ_author_name
'Spencer Williams'
'Paul Donnelly'
'Jonathan M White'
'Steven C Zammit'
'Shannon D. Zanatta'

data_pdsw
_database_code_depnum_ccdc_archive 'CCDC 671781'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            'Cu(ii) complex with TBTA'
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C10 H8 Cl0.50 Cu0.33 N3.33'
_chemical_formula_weight         213.77

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu -1.9646 0.5888 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_space_group_name_H-M   'I 21/a -3'
_symmetry_cell_setting           cubic

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

_cell_length_a                   17.6375(2)
_cell_length_b                   17.6375(2)
_cell_length_c                   17.6375(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     5486.70(11)
_cell_formula_units_Z            24
_cell_measurement_temperature    130(2)
_cell_measurement_reflns_used    1080
_cell_measurement_theta_min      3.5486
_cell_measurement_theta_max      73.1262

_exptl_crystal_description       ?
_exptl_crystal_colour            ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.553
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2628
_exptl_absorpt_coefficient_mu    2.810
_exptl_absorpt_correction_T_min  0.32933
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.32.5 (release 08-05-2007 CrysAlis171 .NET)
(compiled May 8 2007,13:10:02)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      130(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_radiation_source         'Enhance (Cu) X-ray Source'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Oxford Xcalibur'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean 16.0711
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            8136
_diffrn_reflns_av_R_equivalents  0.0773
_diffrn_reflns_av_sigmaI/netI    0.1073
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_theta_min         4.34
_diffrn_reflns_theta_max         64.87
_reflns_number_total             1524
_reflns_number_gt                575
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger. The structure is mixed charge
complex with LCu(I)Cl and LCu(II)Cl sharing a single Cl- counterion. Initial
solution in space group P2(1)-3 revealed two complexes and a chloride ion which
was found to be disordered over two sites consistent with the symmetry of the
Pa-3 space group, therefore refinement was performed in the centrosymmetric
space group with the chloride assigned half the occupancy required to fulfill
overall stoichiometry.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.1783P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         1524
_refine_ls_number_parameters     130
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1969
_refine_ls_R_factor_gt           0.0919
_refine_ls_wR_factor_ref         0.3260
_refine_ls_wR_factor_gt          0.2532
_refine_ls_goodness_of_fit_ref   0.966
_refine_ls_restrained_S_all      0.966
_refine_ls_shift/su_max          0.012
_refine_ls_shift/su_mean         0.002

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 0.5993(7) 0.1786(8) 0.2940(9) 0.108(5) Uani 1 1 d . . .
H1A H 0.5639 0.1633 0.3333 0.129 Uiso 1 1 calc R . .
H1B H 0.5937 0.1448 0.2510 0.129 Uiso 1 1 calc R . .
C2 C 0.5850(7) 0.2624(8) 0.2700(8) 0.099(4) Uani 1 1 d . . .
C3 C 0.5192(6) 0.3018(8) 0.2549(7) 0.084(4) Uani 1 1 d . . .
H3 H 0.4698 0.2887 0.2677 0.101 Uiso 1 1 calc R . .
C4 C 0.4954(6) 0.4249(6) 0.1910(9) 0.100(5) Uani 1 1 d . . .
H4A H 0.4428 0.4087 0.1908 0.120 Uiso 1 1 calc R . .
H4B H 0.5095 0.4369 0.1392 0.120 Uiso 1 1 calc R . .
C5 C 0.5026(7) 0.4937(8) 0.2379(12) 0.107(6) Uani 1 1 d . . .
C6 C 0.5461(7) 0.5537(9) 0.2180(12) 0.133(7) Uani 1 1 d . . .
H6 H 0.5694 0.5540 0.1707 0.160 Uiso 1 1 calc R . .
C7 C 0.5574(10) 0.6184(9) 0.2691(16) 0.176(11) Uani 1 1 d . . .
H7 H 0.5904 0.6575 0.2565 0.212 Uiso 1 1 calc R . .
C8 C 0.5170(12) 0.6193(11) 0.3373(19) 0.183(11) Uani 1 1 d . . .
H8 H 0.5197 0.6602 0.3704 0.219 Uiso 1 1 calc R . .
C9 C 0.4706(13) 0.5529(15) 0.3538(16) 0.186(9) Uani 1 1 d . . .
H9 H 0.4441 0.5521 0.3993 0.224 Uiso 1 1 calc R . .
C10 C 0.4639(12) 0.4934(9) 0.3077(16) 0.144(8) Uani 1 1 d . . .
H10 H 0.4339 0.4523 0.3215 0.172 Uiso 1 1 calc R . .
N1 N 0.6435(4) 0.3020(5) 0.2406(5) 0.059(2) Uani 1 1 d . . .
N3 N 0.5429(5) 0.3623(5) 0.2183(6) 0.076(3) Uani 1 1 d . . .
N2 N 0.6183(5) 0.3618(5) 0.2085(6) 0.076(3) Uani 1 1 d . . .
N4 N 0.6774(4) 0.1774(4) 0.3226(4) 0.045(3) Uani 1 3 d S . .
Cl1 Cl 0.81990(15) 0.31990(15) 0.18010(15) 0.0724(13) Uani 1 3 d S . .
Cu1 Cu 0.74678(7) 0.24678(7) 0.25322(7) 0.0548(8) Uani 1 3 d S . .
Cl2 Cl 0.0417(3) 0.0417(3) 0.0417(3) 0.074(2) Uani 0.50 3 d SP . .

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 0.067(8) 0.107(10) 0.149(13) 0.037(9) -0.008(8) -0.003(7)
C2 0.081(8) 0.106(10) 0.109(10) 0.033(8) 0.028(7) 0.034(8)
C3 0.048(6) 0.098(9) 0.106(9) 0.011(8) -0.001(6) 0.012(6)
C4 0.072(8) 0.062(7) 0.167(14) 0.018(8) -0.041(8) 0.015(6)
C5 0.055(7) 0.074(9) 0.19(2) 0.004(10) 0.014(9) 0.009(7)
C6 0.047(7) 0.094(10) 0.26(2) 0.001(12) 0.031(10) 0.014(7)
C7 0.088(11) 0.077(10) 0.36(3) -0.073(15) 0.069(16) 0.014(8)
C8 0.116(16) 0.104(15) 0.33(4) -0.034(19) -0.027(18) 0.016(12)
C9 0.17(2) 0.141(19) 0.25(3) 0.03(2) 0.028(19) 0.012(18)
C10 0.140(16) 0.067(11) 0.22(2) -0.019(12) -0.019(18) 0.036(10)
N1 0.050(5) 0.059(5) 0.069(5) -0.002(4) 0.001(4) 0.017(4)
N3 0.064(6) 0.059(5) 0.105(7) 0.001(5) -0.027(5) 0.005(5)
N2 0.069(6) 0.068(6) 0.091(7) -0.009(5) -0.011(5) -0.005(5)
N4 0.045(3) 0.045(3) 0.045(3) 0.004(3) 0.004(3) -0.004(3)
Cl1 0.0724(13) 0.0724(13) 0.0724(13) 0.0037(13) 0.0037(13) -0.0037(13)
Cu1 0.0548(8) 0.0548(8) 0.0548(8) -0.0029(7) -0.0029(7) 0.0029(7)
Cl2 0.074(2) 0.074(2) 0.074(2) 0.005(3) 0.005(3) 0.005(3)

_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 N4 1.467(13) . ?
C1 C2 1.557(17) . ?
C2 N1 1.349(15) . ?
C2 C3 1.379(15) . ?
C3 N3 1.315(15) . ?
C4 N3 1.467(13) . ?
C4 C5 1.48(2) . ?
C5 C6 1.353(18) . ?
C5 C10 1.41(3) . ?
C6 C7 1.47(2) . ?
C7 C8 1.40(3) . ?
C8 C9 1.46(3) . ?
C9 C10 1.33(3) . ?
N1 N2 1.278(11) . ?
N1 Cu1 2.078(7) . ?
N3 N2 1.341(13) . ?
N4 C1 1.467(13) 8_645 ?
N4 C1 1.467(13) 11_556 ?
N4 Cu1 2.120(11) . ?
Cl1 Cu1 2.233(5) . ?
Cu1 N1 2.078(7) 8_645 ?
Cu1 N1 2.078(7) 11_556 ?

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
N4 C1 C2 105.0(10) . . ?
N1 C2 C3 107.9(11) . . ?
N1 C2 C1 118.2(10) . . ?
C3 C2 C1 131.8(13) . . ?
N3 C3 C2 103.7(10) . . ?
N3 C4 C5 112.7(11) . . ?
C6 C5 C10 120.3(17) . . ?
C6 C5 C4 123.2(18) . . ?
C10 C5 C4 116.4(14) . . ?
C5 C6 C7 121.7(18) . . ?
C8 C7 C6 117.9(18) . . ?
C7 C8 C9 117(2) . . ?
C10 C9 C8 124(3) . . ?
C9 C10 C5 119(2) . . ?
N2 N1 C2 109.4(9) . . ?
N2 N1 Cu1 137.7(7) . . ?
C2 N1 Cu1 112.7(7) . . ?
C3 N3 N2 111.9(9) . . ?
C3 N3 C4 126.2(10) . . ?
N2 N3 C4 121.9(10) . . ?
N1 N2 N3 107.0(9) . . ?
C1 N4 C1 109.4(7) 8_645 . ?
C1 N4 C1 109.4(7) 8_645 11_556 ?
C1 N4 C1 109.4(7) . 11_556 ?
C1 N4 Cu1 109.6(7) 8_645 . ?
C1 N4 Cu1 109.6(7) . . ?
C1 N4 Cu1 109.6(7) 11_556 . ?
N1 Cu1 N1 117.03(14) 8_645 . ?
N1 Cu1 N1 117.03(14) 8_645 11_556 ?
N1 Cu1 N1 117.03(14) . 11_556 ?
N1 Cu1 N4 80.0(2) 8_645 . ?
N1 Cu1 N4 80.0(2) . . ?
N1 Cu1 N4 80.0(2) 11_556 . ?
N1 Cu1 Cl1 100.0(2) 8_645 . ?
N1 Cu1 Cl1 100.0(2) . . ?
N1 Cu1 Cl1 100.0(2) 11_556 . ?
N4 Cu1 Cl1 180.0(4) . . ?

_diffrn_measured_fraction_theta_max 0.973
_diffrn_reflns_theta_full        64.87
_diffrn_measured_fraction_theta_full 0.973
_refine_diff_density_max         0.751
_refine_diff_density_min         -0.399
_refine_diff_density_rms         0.105

# Attachment 'Cu_I_.cif'

data_jmwpd19
_database_code_depnum_ccdc_archive 'CCDC 671782'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            'Cu(i) complex with TBTA'
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C31.50 H33.50 B Cu F4 N10.50 O0.50'
_chemical_formula_weight         717.54

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'
B B 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           ?
_symmetry_space_group_name_H-M   ?

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

_cell_length_a                   16.3055(11)
_cell_length_b                   15.7883(10)
_cell_length_c                   25.4248(16)
_cell_angle_alpha                90.00
_cell_angle_beta                 96.7850(10)
_cell_angle_gamma                90.00
_cell_volume                     6499.4(7)
_cell_formula_units_Z            8
_cell_measurement_temperature    130(2)
_cell_measurement_reflns_used    4889
_cell_measurement_theta_min      2.32
_cell_measurement_theta_max      26.01
_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_min          0.14
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_max          0.15
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.467
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2960
_exptl_absorpt_coefficient_mu    0.738
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      130(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  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            16902
_diffrn_reflns_av_R_equivalents  0.0507
_diffrn_reflns_av_sigmaI/netI    0.0541
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_theta_min         1.61
_diffrn_reflns_theta_max         25.00
_reflns_number_total             5746
_reflns_number_gt                4554
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ 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/[\s^2^(Fo^2^)+(0.0512P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         5746
_refine_ls_number_parameters     462
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0506
_refine_ls_R_factor_gt           0.0389
_refine_ls_wR_factor_ref         0.0983
_refine_ls_wR_factor_gt          0.0947
_refine_ls_goodness_of_fit_ref   0.978
_refine_ls_restrained_S_all      0.978
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.41081(16) 0.01053(16) 0.08947(10) 0.0269(6) Uani 1 1 d . . .
H1A H 0.3957 -0.0050 0.0527 0.032 Uiso 1 1 calc R . .
H1B H 0.3682 -0.0104 0.1097 0.032 Uiso 1 1 calc R . .
C2 C 0.49223(15) -0.02959(15) 0.10960(9) 0.0218(6) Uani 1 1 d . . .
C3 C 0.52712(16) -0.10497(15) 0.09815(10) 0.0247(6) Uani 1 1 d . . .
H3 H 0.5067 -0.1444 0.0727 0.030 Uiso 1 1 calc R . .
C4 C 0.66053(16) -0.17739(16) 0.13611(11) 0.0289(6) Uani 1 1 d . . .
H4A H 0.6380 -0.2277 0.1179 0.035 Uiso 1 1 calc R . .
H4B H 0.6750 -0.1916 0.1732 0.035 Uiso 1 1 calc R . .
C5 C 0.73711(15) -0.15002(15) 0.11278(10) 0.0246(6) Uani 1 1 d . . .
C6 C 0.80100(17) -0.10932(17) 0.14440(11) 0.0328(7) Uani 1 1 d . . .
H6 H 0.7969 -0.1001 0.1801 0.039 Uiso 1 1 calc R . .
C7 C 0.87021(18) -0.0827(2) 0.12277(12) 0.0421(8) Uani 1 1 d . . .
H7 H 0.9125 -0.0554 0.1440 0.051 Uiso 1 1 calc R . .
C8 C 0.87739(19) -0.09603(18) 0.06998(13) 0.0400(8) Uani 1 1 d . . .
H8 H 0.9241 -0.0775 0.0556 0.048 Uiso 1 1 calc R . .
C9 C 0.8150(2) -0.13701(17) 0.03853(12) 0.0386(8) Uani 1 1 d . . .
H9 H 0.8198 -0.1466 0.0029 0.046 Uiso 1 1 calc R . .
C10 C 0.74523(18) -0.16388(17) 0.05988(11) 0.0329(7) Uani 1 1 d . . .
H10 H 0.7034 -0.1915 0.0385 0.040 Uiso 1 1 calc R . .
C11 C 0.45689(16) 0.14518(16) 0.05390(10) 0.0264(6) Uani 1 1 d . . .
H11A H 0.4156 0.1676 0.0269 0.032 Uiso 1 1 calc R . .
H11B H 0.4906 0.1050 0.0372 0.032 Uiso 1 1 calc R . .
C12 C 0.51030(15) 0.21625(16) 0.07741(10) 0.0227(6) Uani 1 1 d . . .
C13 C 0.53948(16) 0.28730(16) 0.05492(10) 0.0281(6) Uani 1 1 d . . .
H13 H 0.5270 0.3061 0.0202 0.034 Uiso 1 1 calc R . .
C14 C 0.64286(18) 0.39955(16) 0.09231(12) 0.0360(7) Uani 1 1 d . . .
H14A H 0.6718 0.4103 0.1272 0.043 Uiso 1 1 calc R . .
H14B H 0.6088 0.4485 0.0819 0.043 Uiso 1 1 calc R . .
C15 C 0.70516(16) 0.38630(15) 0.05288(11) 0.0289(6) Uani 1 1 d . . .
C16 C 0.69330(18) 0.42585(18) 0.00418(12) 0.0412(8) Uani 1 1 d . . .
H16 H 0.6480 0.4612 -0.0040 0.049 Uiso 1 1 calc R . .
C17 C 0.74834(19) 0.41335(19) -0.03250(12) 0.0422(8) Uani 1 1 d . . .
H17 H 0.7407 0.4413 -0.0649 0.051 Uiso 1 1 calc R . .
C18 C 0.81404(17) 0.35984(17) -0.02103(13) 0.0365(7) Uani 1 1 d . . .
H18 H 0.8504 0.3505 -0.0460 0.044 Uiso 1 1 calc R . .
C19 C 0.82651(17) 0.31961(17) 0.02768(12) 0.0344(7) Uani 1 1 d . . .
H19 H 0.8713 0.2835 0.0355 0.041 Uiso 1 1 calc R . .
C20 C 0.77240(16) 0.33319(16) 0.06457(11) 0.0304(6) Uani 1 1 d . . .
H20 H 0.7811 0.3066 0.0974 0.037 Uiso 1 1 calc R . .
C21 C 0.34300(15) 0.14399(16) 0.10926(9) 0.0249(6) Uani 1 1 d . . .
H21A H 0.2939 0.1194 0.0899 0.030 Uiso 1 1 calc R . .
H21B H 0.3446 0.2036 0.1002 0.030 Uiso 1 1 calc R . .
C22 C 0.33898(15) 0.13474(15) 0.16785(10) 0.0217(6) Uani 1 1 d . . .
C23 C 0.27248(16) 0.13119(16) 0.19599(10) 0.0251(6) Uani 1 1 d . . .
C25 C 0.26311(16) 0.13192(17) 0.29535(10) 0.0285(6) Uani 1 1 d . . .
H25A H 0.3038 0.1339 0.3264 0.034 Uiso 1 1 calc R . .
H25B H 0.2310 0.0805 0.2972 0.034 Uiso 1 1 calc R . .
C26 C 0.20651(16) 0.20796(17) 0.29543(10) 0.0271(6) Uani 1 1 d . . .
C27 C 0.23209(18) 0.28759(18) 0.28157(10) 0.0346(7) Uani 1 1 d . . .
H27 H 0.2849 0.2948 0.2719 0.042 Uiso 1 1 calc R . .
C28 C 0.1796(2) 0.3570(2) 0.28200(11) 0.0431(8) Uani 1 1 d . . .
H28 H 0.1974 0.4105 0.2729 0.052 Uiso 1 1 calc R . .
C29 C 0.1008(2) 0.3463(2) 0.29602(12) 0.0508(9) Uani 1 1 d . . .
H29 H 0.0649 0.3921 0.2953 0.061 Uiso 1 1 calc R . .
C30 C 0.07581(19) 0.2674(2) 0.31099(13) 0.0500(9) Uani 1 1 d . . .
H30 H 0.0235 0.2605 0.3215 0.060 Uiso 1 1 calc R . .
C31 C 0.12822(17) 0.19821(19) 0.31050(11) 0.0378(7) Uani 1 1 d . . .
H31 H 0.1107 0.1451 0.3203 0.045 Uiso 1 1 calc R . .
C32 C 0.5000 0.6479(3) 0.7500 0.082(2) Uani 1 2 d S . .
H32A H 0.5506 0.6682 0.7387 0.124 Uiso 0.50 1 calc PR . .
H32B H 0.4952 0.6682 0.7851 0.124 Uiso 0.50 1 calc PR . .
H32C H 0.4542 0.6682 0.7261 0.124 Uiso 0.50 1 calc PR . .
C33 C 0.4314(2) 0.5126(2) 0.76514(13) 0.0567(10) Uani 1 1 d . . .
H33 H 0.4423 0.4554 0.7715 0.068 Uiso 0.50 1 calc PR . .
N1 N 0.54344(12) 0.00767(12) 0.14909(8) 0.0227(5) Uani 1 1 d . . .
N2 N 0.60832(13) -0.04158(13) 0.16286(8) 0.0249(5) Uani 1 1 d . . .
N3 N 0.59729(13) -0.11005(12) 0.13149(8) 0.0237(5) Uani 1 1 d . . .
N4 N 0.54483(12) 0.21363(13) 0.12884(8) 0.0229(5) Uani 1 1 d . . .
N5 N 0.59413(13) 0.27958(13) 0.13905(8) 0.0269(5) Uani 1 1 d . . .
N6 N 0.59031(13) 0.32418(13) 0.09412(8) 0.0269(5) Uani 1 1 d . . .
N7 N 0.38878(12) 0.13151(12) 0.25148(8) 0.0203(5) Uani 1 1 d . . .
N8 N 0.30579(12) 0.12988(12) 0.24735(8) 0.0224(5) Uani 1 1 d . . .
N9 N 0.41600(12) 0.10194(12) 0.09405(8) 0.0208(5) Uani 1 1 d . . .
N10 N 0.40899(12) 0.13383(12) 0.20253(8) 0.0195(5) Uani 1 1 d . . .
N11 N 0.5000 0.5561(2) 0.7500 0.0492(10) Uani 1 2 d S . .
O1 O 0.3614(3) 0.5317(3) 0.77186(16) 0.0459(11) Uani 0.50 1 d P . .
Cu Cu 0.526729(18) 0.123183(18) 0.182941(11) 0.02043(11) Uani 1 1 d . . .
B B 0.4525(2) 0.3783(2) 0.91223(15) 0.0388(8) Uani 1 1 d . . .
F1 F 0.36857(11) 0.38108(11) 0.90566(8) 0.0587(5) Uani 1 1 d . . .
F2' F 0.4384(7) 0.3550(5) 0.8495(3) 0.069(4) Uani 0.286(8) 1 d P . .
F2 F 0.4897(2) 0.4070(3) 0.87201(14) 0.0673(17) Uani 0.714(8) 1 d P . .
F3 F 0.47531(19) 0.43331(18) 0.95790(12) 0.0407(9) Uani 0.714(8) 1 d P . .
F3' F 0.4931(5) 0.4435(5) 0.9151(8) 0.111(9) Uani 0.286(8) 1 d P . .
F4 F 0.48136(11) 0.30000(10) 0.92999(7) 0.0536(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 0.0238(15) 0.0270(15) 0.0287(15) -0.0034(12) -0.0017(11) 0.0009(11)
C2 0.0201(14) 0.0200(14) 0.0251(14) -0.0023(11) 0.0021(11) -0.0012(10)
C3 0.0231(14) 0.0227(15) 0.0280(15) -0.0048(11) 0.0025(11) -0.0010(11)
C4 0.0255(15) 0.0182(14) 0.0422(17) -0.0004(12) 0.0005(12) 0.0070(11)
C5 0.0236(14) 0.0170(14) 0.0325(15) -0.0010(11) 0.0002(11) 0.0082(11)
C6 0.0290(16) 0.0370(18) 0.0317(16) -0.0018(13) 0.0012(12) 0.0003(12)
C7 0.0295(17) 0.046(2) 0.049(2) 0.0005(15) -0.0019(14) -0.0004(14)
C8 0.0333(18) 0.0357(18) 0.053(2) 0.0175(15) 0.0147(15) 0.0151(14)
C9 0.053(2) 0.0339(18) 0.0305(16) 0.0074(13) 0.0136(15) 0.0194(15)
C10 0.0394(18) 0.0255(16) 0.0315(16) -0.0025(12) -0.0058(13) 0.0106(13)
C11 0.0231(14) 0.0338(16) 0.0226(14) -0.0005(11) 0.0033(11) 0.0042(11)
C12 0.0216(14) 0.0242(14) 0.0227(14) 0.0029(11) 0.0046(11) 0.0062(11)
C13 0.0281(15) 0.0281(16) 0.0290(15) 0.0071(12) 0.0074(12) 0.0082(12)
C14 0.0428(18) 0.0178(15) 0.0510(19) 0.0018(13) 0.0204(15) -0.0022(12)
C15 0.0300(16) 0.0157(14) 0.0430(17) 0.0012(12) 0.0130(13) -0.0035(11)
C16 0.0379(18) 0.0309(17) 0.058(2) 0.0156(15) 0.0193(15) 0.0116(13)
C17 0.047(2) 0.0366(18) 0.0462(19) 0.0135(15) 0.0191(15) 0.0028(15)
C18 0.0301(16) 0.0264(16) 0.056(2) -0.0074(14) 0.0189(14) -0.0041(12)
C19 0.0222(15) 0.0255(16) 0.054(2) -0.0089(14) -0.0015(13) -0.0023(12)
C20 0.0314(16) 0.0221(15) 0.0372(16) -0.0031(12) 0.0016(13) -0.0046(12)
C21 0.0208(14) 0.0306(16) 0.0226(14) 0.0001(11) 0.0004(11) 0.0038(11)
C22 0.0198(13) 0.0208(14) 0.0242(14) -0.0010(11) 0.0008(10) 0.0037(10)
C23 0.0235(14) 0.0278(15) 0.0240(14) 0.0006(11) 0.0032(11) 0.0028(11)
C25 0.0204(14) 0.0414(17) 0.0246(14) 0.0042(12) 0.0067(11) 0.0002(12)
C26 0.0229(15) 0.0395(17) 0.0192(13) -0.0034(12) 0.0031(11) 0.0025(12)
C27 0.0325(16) 0.0438(19) 0.0285(15) 0.0052(13) 0.0072(12) 0.0043(14)
C28 0.058(2) 0.0401(19) 0.0305(17) 0.0008(13) 0.0027(15) 0.0132(15)
C29 0.051(2) 0.064(2) 0.0368(18) -0.0103(17) 0.0037(15) 0.0305(18)
C30 0.0311(18) 0.071(3) 0.050(2) -0.0162(18) 0.0142(15) 0.0115(17)
C31 0.0281(16) 0.048(2) 0.0387(17) -0.0082(14) 0.0088(13) 0.0011(13)
C32 0.164(7) 0.037(3) 0.051(3) 0.000 0.032(4) 0.000
C33 0.046(2) 0.070(3) 0.054(2) 0.0235(18) 0.0072(17) 0.0010(19)
N1 0.0194(12) 0.0204(12) 0.0276(12) -0.0021(9) 0.0000(9) 0.0025(9)
N2 0.0232(12) 0.0197(12) 0.0312(12) -0.0018(10) 0.0004(9) 0.0030(9)
N3 0.0221(12) 0.0175(12) 0.0312(12) -0.0023(9) 0.0027(9) 0.0016(9)
N4 0.0225(12) 0.0225(12) 0.0240(12) 0.0015(9) 0.0040(9) -0.0018(9)
N5 0.0286(13) 0.0224(12) 0.0308(13) 0.0018(10) 0.0082(10) -0.0020(10)
N6 0.0300(13) 0.0187(12) 0.0344(13) 0.0041(10) 0.0138(10) 0.0029(9)
N7 0.0159(11) 0.0226(12) 0.0228(11) 0.0008(9) 0.0035(8) 0.0018(8)
N8 0.0159(11) 0.0286(13) 0.0230(11) 0.0022(9) 0.0038(9) 0.0023(9)
N9 0.0179(11) 0.0199(12) 0.0246(11) -0.0025(9) 0.0021(9) 0.0033(8)
N10 0.0171(11) 0.0227(12) 0.0187(11) 0.0007(9) 0.0024(8) 0.0024(8)
N11 0.077(3) 0.038(2) 0.033(2) 0.000 0.007(2) 0.000
O1 0.037(3) 0.052(3) 0.049(3) 0.005(2) 0.003(2) -0.008(2)
Cu 0.01868(18) 0.02085(19) 0.02173(18) -0.00026(13) 0.00224(12) 0.00038(13)
B 0.034(2) 0.028(2) 0.055(2) 0.0026(17) 0.0060(17) 0.0062(16)
F1 0.0349(11) 0.0493(12) 0.0883(15) 0.0025(10) -0.0083(10) -0.0009(8)
F2' 0.101(8) 0.050(6) 0.059(5) 0.013(4) 0.025(5) 0.007(5)
F2 0.078(3) 0.079(4) 0.052(2) 0.016(2) 0.032(2) 0.012(3)
F3 0.0492(17) 0.0271(16) 0.0429(19) -0.0113(12) -0.0065(13) 0.0018(11)
F3' 0.031(5) 0.032(5) 0.26(3) -0.011(8) -0.033(9) -0.010(4)
F4 0.0654(13) 0.0272(10) 0.0605(12) -0.0064(8) -0.0245(10) 0.0095(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 N9 1.450(3) . ?
C1 C2 1.505(3) . ?
C2 N1 1.361(3) . ?
C2 C3 1.365(3) . ?
C3 N3 1.343(3) . ?
C4 N3 1.476(3) . ?
C4 C5 1.508(4) . ?
C5 C10 1.384(4) . ?
C5 C6 1.395(4) . ?
C6 C7 1.378(4) . ?
C7 C8 1.377(4) . ?
C8 C9 1.379(4) . ?
C9 C10 1.384(4) . ?
C11 N9 1.454(3) . ?
C11 C12 1.500(3) . ?
C12 N4 1.362(3) . ?
C12 C13 1.370(3) . ?
C13 N6 1.351(3) . ?
C14 N6 1.470(3) . ?
C14 C15 1.523(4) . ?
C15 C16 1.380(4) . ?
C15 C20 1.384(4) . ?
C16 C17 1.383(4) . ?
C17 C18 1.368(4) . ?
C18 C19 1.385(4) . ?
C19 C20 1.378(4) . ?
C21 N9 1.455(3) . ?
C21 C22 1.506(3) . ?
C22 N10 1.358(3) . ?
C22 C23 1.369(3) . ?
C23 N8 1.354(3) . ?
C25 N8 1.475(3) . ?
C25 C26 1.514(3) . ?
C26 C27 1.383(4) . ?
C26 C31 1.384(4) . ?
C27 C28 1.392(4) . ?
C28 C29 1.383(4) . ?
C29 C30 1.378(5) . ?
C30 C31 1.388(4) . ?
C32 N11 1.450(6) . ?
C33 O1 1.213(5) . ?
C33 N11 1.404(4) . ?
N1 N2 1.326(3) . ?
N1 Cu 2.049(2) . ?
N2 N3 1.343(3) . ?
N4 N5 1.322(3) . ?
N4 Cu 2.028(2) . ?
N5 N6 1.337(3) . ?
N7 N10 1.325(3) . ?
N7 N8 1.345(3) . ?
N7 Cu 2.038(2) 2_655 ?
N10 Cu 2.0464(19) . ?
N11 C33 1.404(4) 2_656 ?
Cu N7 2.038(2) 2_655 ?
B F3' 1.221(8) . ?
B F2 1.328(4) . ?
B F1 1.360(4) . ?
B F4 1.379(4) . ?
B F3 1.463(5) . ?
B F2' 1.625(10) . ?
F2' F2 1.260(10) . ?
F2 F3' 1.233(16) . ?
F3 F3' 1.169(18) . ?

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
N9 C1 C2 110.5(2) . . ?
N1 C2 C3 107.4(2) . . ?
N1 C2 C1 120.6(2) . . ?
C3 C2 C1 131.9(2) . . ?
N3 C3 C2 105.2(2) . . ?
N3 C4 C5 111.4(2) . . ?
C10 C5 C6 118.8(3) . . ?
C10 C5 C4 121.0(2) . . ?
C6 C5 C4 120.1(2) . . ?
C7 C6 C5 120.1(3) . . ?
C8 C7 C6 120.7(3) . . ?
C7 C8 C9 119.7(3) . . ?
C8 C9 C10 120.1(3) . . ?
C9 C10 C5 120.7(3) . . ?
N9 C11 C12 111.4(2) . . ?
N4 C12 C13 107.5(2) . . ?
N4 C12 C11 121.0(2) . . ?
C13 C12 C11 131.3(2) . . ?
N6 C13 C12 105.0(2) . . ?
N6 C14 C15 110.2(2) . . ?
C16 C15 C20 119.4(3) . . ?
C16 C15 C14 119.6(2) . . ?
C20 C15 C14 121.0(3) . . ?
C15 C16 C17 120.5(3) . . ?
C18 C17 C16 119.9(3) . . ?
C17 C18 C19 120.1(3) . . ?
C20 C19 C18 119.9(3) . . ?
C19 C20 C15 120.2(3) . . ?
N9 C21 C22 110.6(2) . . ?
N10 C22 C23 108.5(2) . . ?
N10 C22 C21 120.8(2) . . ?
C23 C22 C21 130.6(2) . . ?
N8 C23 C22 104.6(2) . . ?
N8 C25 C26 111.4(2) . . ?
C27 C26 C31 119.2(3) . . ?
C27 C26 C25 121.2(2) . . ?
C31 C26 C25 119.6(2) . . ?
C26 C27 C28 120.6(3) . . ?
C29 C28 C27 119.8(3) . . ?
C30 C29 C28 119.7(3) . . ?
C29 C30 C31 120.4(3) . . ?
C26 C31 C30 120.3(3) . . ?
O1 C33 N11 135.2(4) . . ?
N2 N1 C2 109.99(19) . . ?
N2 N1 Cu 123.55(16) . . ?
C2 N1 Cu 126.45(16) . . ?
N1 N2 N3 105.58(19) . . ?
N2 N3 C3 111.78(19) . . ?
N2 N3 C4 119.3(2) . . ?
C3 N3 C4 128.9(2) . . ?
N5 N4 C12 109.7(2) . . ?
N5 N4 Cu 123.71(16) . . ?
C12 N4 Cu 126.57(17) . . ?
N4 N5 N6 106.3(2) . . ?
N5 N6 C13 111.5(2) . . ?
N5 N6 C14 119.0(2) . . ?
C13 N6 C14 129.4(2) . . ?
N10 N7 N8 106.66(18) . . ?
N10 N7 Cu 123.44(15) . 2_655 ?
N8 N7 Cu 129.75(15) . 2_655 ?
N7 N8 C23 111.12(19) . . ?
N7 N8 C25 120.2(2) . . ?
C23 N8 C25 128.5(2) . . ?
C1 N9 C11 116.01(19) . . ?
C1 N9 C21 115.7(2) . . ?
C11 N9 C21 115.5(2) . . ?
N7 N10 C22 109.08(19) . . ?
N7 N10 Cu 124.82(15) . . ?
C22 N10 Cu 125.72(16) . . ?
C33 N11 C33 121.4(4) . 2_656 ?
C33 N11 C32 119.3(2) . . ?
C33 N11 C32 119.3(2) 2_656 . ?
N4 Cu N7 111.77(8) . 2_655 ?
N4 Cu N10 108.85(8) . . ?
N7 Cu N10 111.01(7) 2_655 . ?
N4 Cu N1 107.74(8) . . ?
N7 Cu N1 106.89(8) 2_655 . ?
N10 Cu N1 110.52(8) . . ?
F3' B F2 57.7(9) . . ?
F3' B F1 120.6(5) . . ?
F2 B F1 116.0(3) . . ?
F3' B F4 125.1(5) . . ?
F2 B F4 112.9(3) . . ?
F1 B F4 111.6(3) . . ?
F3' B F3 50.7(9) . . ?
F2 B F3 108.2(3) . . ?
F1 B F3 103.6(3) . . ?
F4 B F3 103.2(3) . . ?
F3' B F2' 105.2(9) . . ?
F2 B F2' 49.2(4) . . ?
F1 B F2' 82.1(4) . . ?
F4 B F2' 97.0(3) . . ?
F3 B F2' 155.0(4) . . ?
F2 F2' B 53.0(4) . . ?
F3' F2 F2' 131.7(7) . . ?
F3' F2 B 56.8(6) . . ?
F2' F2 B 77.8(4) . . ?
F3' F3 B 53.9(4) . . ?
F3 F3' B 75.4(9) . . ?
F3 F3' F2 140.6(8) . . ?
B F3' F2 65.5(6) . . ?

_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         0.718
_refine_diff_density_min         -0.255
_refine_diff_density_rms         0.059