Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004

data_global
_journal_name_full               'Dalton Trans.'

_journal_coden_Cambridge         0222

_publ_contact_author_name        'Prof Rita Delgado'
_publ_contact_author_address     
;
Chemistry Division
ITQB
Apartado 127
Oeiras
2781-901
PORTUGAL
;

_publ_contact_author_email       DELGADO@ITQB.UNL.PT

_publ_section_title              
;
Ditopic hexaazamacrocycles containing pyridine:
synthesis, protonation and complexation studies
;
loop_
_publ_author_name
'Rita Delgado'
'Judite Costa'
'Michael Drew'
'Vitor Felix'
'Feng Li'

data_compound_1
_database_code_depnum_ccdc_archive 'CCDC 252426'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            (Cu2((20)Py2N4)(H2O)4).(CU(H2O)6).4SO4.2H2O
_chemical_formula_moiety         ?
_chemical_formula_sum            'C20 H56 Cu3 N6 O25 S3'
_chemical_formula_weight         1067.51

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'
S S 0.1246 0.1234 '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/c

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

_cell_length_a                   12.644(14)
_cell_length_b                   22.780(24)
_cell_length_c                   13.771(15)
_cell_angle_alpha                90.00
_cell_angle_beta                 93.780(10)
_cell_angle_gamma                90.00
_cell_volume                     3958(7)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_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    1.792
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2212
_exptl_absorpt_coefficient_mu    1.853
_exptl_absorpt_correction_type   'Empirical (DIFABS)'
_exptl_absorpt_correction_T_min  0.788
_exptl_absorpt_correction_T_max  1.000

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      293(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  'MAR research image plate system'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            10697
_diffrn_reflns_av_R_equivalents  0.0293
_diffrn_reflns_av_sigmaI/netI    0.0454
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         1.85
_diffrn_reflns_theta_max         25.98
_reflns_number_total             6214
_reflns_number_gt                4355
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        'W. Kabsch, J. Appl. Crystallogr. 21,916,1983'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'PLATON (Spek, 1999)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'

_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 w=1/[\s^2^(Fo^2^)+(0.1206P)^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         6214
_refine_ls_number_parameters     592
_refine_ls_number_restraints     38
_refine_ls_R_factor_all          0.0957
_refine_ls_R_factor_gt           0.0612
_refine_ls_wR_factor_ref         0.1871
_refine_ls_wR_factor_gt          0.1698
_refine_ls_goodness_of_fit_ref   1.123
_refine_ls_restrained_S_all      1.119
_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_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.33109(6) 0.04645(3) 0.04191(5) 0.0292(2) Uani 1 d . . .
N1 N 0.3132(4) 0.1306(2) 0.0466(4) 0.0297(12) Uani 1 d . . .
C2 C 0.2141(5) 0.1527(3) 0.0338(4) 0.0351(16) Uani 1 d . . .
C3 C 0.1323(6) 0.1091(3) -0.0017(5) 0.0433(17) Uani 1 d . . .
H3A H 0.1223 0.1110 -0.0720 0.052 Uiso 1 calc R . .
H3B H 0.0652 0.1181 0.0253 0.052 Uiso 1 calc R . .
N4 N 0.1679(4) 0.0477(2) 0.0292(4) 0.0318(12) Uani 1 d . . .
H4 H 0.1465 0.0226 -0.0196 0.038 Uiso 1 calc R . .
C5 C 0.1156(5) 0.0287(3) 0.1192(4) 0.0364(16) Uani 1 d . . .
H5A H 0.1274 -0.0130 0.1300 0.044 Uiso 1 calc R . .
H5B H 0.0398 0.0353 0.1105 0.044 Uiso 1 calc R . .
C6 C 0.1622(6) 0.0638(3) 0.2088(4) 0.0406(17) Uani 1 d . . .
H6A H 0.2366 0.0541 0.2205 0.049 Uiso 1 calc R . .
H6B H 0.1572 0.1055 0.1945 0.049 Uiso 1 calc R . .
C7 C 0.1052(5) 0.0511(3) 0.3001(4) 0.0344(15) Uani 1 d . . .
H7A H 0.0297 0.0578 0.2877 0.041 Uiso 1 calc R . .
H7B H 0.1157 0.0103 0.3188 0.041 Uiso 1 calc R . .
N8 N 0.1484(4) 0.0908(2) 0.3812(4) 0.0333(12) Uani 1 d . . .
H8 H 0.1173 0.0788 0.4356 0.040 Uiso 1 calc R . .
C9 C 0.1137(6) 0.1528(3) 0.3641(5) 0.0451(17) Uani 1 d . . .
H9A H 0.0759 0.1663 0.4189 0.054 Uiso 1 calc R . .
H9B H 0.0657 0.1546 0.3063 0.054 Uiso 1 calc R . .
C10 C 0.2077(6) 0.1923(3) 0.3514(4) 0.0359(15) Uani 1 d . . .
N11 N 0.3014(4) 0.1692(2) 0.3795(4) 0.0322(12) Uani 1 d . . .
C12 C 0.3905(5) 0.2005(3) 0.3785(4) 0.0323(14) Uani 1 d . . .
C13 C 0.4896(6) 0.1688(3) 0.4193(6) 0.0491(19) Uani 1 d . . .
H13A H 0.5459 0.1743 0.3756 0.059 Uiso 1 calc R . .
H13B H 0.5127 0.1857 0.4818 0.059 Uiso 1 calc R . .
N14 N 0.4698(4) 0.1047(2) 0.4315(4) 0.0351(12) Uani 1 d . . .
H14 H 0.4858 0.0987 0.4961 0.042 Uiso 1 calc R . .
C15 C 0.5489(7) 0.0682(3) 0.3845(6) 0.053(2) Uani 1 d . . .
H15A H 0.6168 0.0747 0.4198 0.063 Uiso 1 calc R . .
H15B H 0.5302 0.0274 0.3947 0.063 Uiso 1 calc R . .
C16 C 0.5653(7) 0.0752(4) 0.2801(6) 0.060(2) Uani 1 d . . .
H16A H 0.5883 0.1150 0.2679 0.072 Uiso 1 calc R . .
H16B H 0.6206 0.0486 0.2621 0.072 Uiso 1 calc R . .
C17 C 0.4673(7) 0.0628(3) 0.2199(6) 0.057(2) Uani 1 d . . .
H17A H 0.4126 0.0898 0.2382 0.068 Uiso 1 calc R . .
H17B H 0.4439 0.0234 0.2340 0.068 Uiso 1 calc R . .
N18 N 0.4788(4) 0.0682(2) 0.1088(4) 0.0440(15) Uani 1 d . . .
H18 H 0.5300 0.0436 0.0893 0.053 Uiso 1 calc R . .
C19 C 0.4987(6) 0.1288(3) 0.0788(6) 0.0478(19) Uani 1 d . . .
H19A H 0.5278 0.1288 0.0153 0.057 Uiso 1 calc R . .
H19B H 0.5500 0.1470 0.1249 0.057 Uiso 1 calc R . .
C20 C 0.3973(5) 0.1635(3) 0.0742(4) 0.0349(15) Uani 1 d . . .
C21 C 0.1983(7) 0.2108(3) 0.0543(5) 0.0468(19) Uani 1 d . . .
H21 H 0.1304 0.2267 0.0472 0.056 Uiso 1 calc R . .
C22 C 0.2837(8) 0.2463(3) 0.0859(5) 0.054(2) Uani 1 d . . .
H22 H 0.2734 0.2858 0.0996 0.065 Uiso 1 calc R . .
C23 C 0.3840(7) 0.2217(3) 0.0965(5) 0.0450(19) Uani 1 d . . .
H23 H 0.4418 0.2444 0.1186 0.054 Uiso 1 calc R . .
C24 C 0.2008(6) 0.2501(3) 0.3209(5) 0.0434(17) Uani 1 d . . .
H24 H 0.1354 0.2665 0.3018 0.052 Uiso 1 calc R . .
C25 C 0.2918(7) 0.2831(3) 0.3189(5) 0.056(2) Uani 1 d . . .
H25 H 0.2885 0.3219 0.2980 0.068 Uiso 1 calc R . .
C26 C 0.3879(6) 0.2581(3) 0.3482(5) 0.0431(18) Uani 1 d . . .
H26 H 0.4501 0.2798 0.3474 0.052 Uiso 1 calc R . .
Cu2 Cu 0.30855(6) 0.08741(3) 0.41559(5) 0.0319(2) Uani 1 d . . .
O101 O 0.3441(4) -0.03856(19) 0.0531(3) 0.0389(11) Uani 1 d D . .
H10A H 0.354(4) -0.056(2) 0.107(2) 0.047 Uiso 1 d D . .
H10B H 0.286(3) -0.049(3) 0.024(4) 0.047 Uiso 1 d D . .
O102 O 0.3631(5) 0.0392(2) -0.1144(3) 0.0523(14) Uani 1 d D . .
H10C H 0.403(4) 0.054(3) -0.156(4) 0.063 Uiso 1 d D . .
H10D H 0.302(2) 0.054(3) -0.122(5) 0.063 Uiso 1 d D . .
O201 O 0.3134(4) 0.00198(19) 0.4221(4) 0.0469(12) Uani 1 d D . .
H20A H 0.273(4) -0.013(3) 0.462(3) 0.056 Uiso 1 d D . .
H20B H 0.375(2) 0.006(3) 0.448(4) 0.056 Uiso 1 d D . .
O202 O 0.2932(5) 0.0938(3) 0.5765(4) 0.0600(15) Uani 1 d D . .
H20C H 0.236(3) 0.110(3) 0.588(5) 0.072 Uiso 1 d D . .
H20D H 0.343(3) 0.106(3) 0.616(5) 0.072 Uiso 1 d D . .
Cu3 Cu 0.18064(7) -0.24581(3) 0.15725(5) 0.0346(2) Uani 1 d . . .
O301 O 0.0717(4) -0.25317(19) 0.2582(3) 0.0411(11) Uani 1 d D . .
H30A H 0.045(5) -0.2257(15) 0.291(4) 0.049 Uiso 1 d D . .
H30B H 0.074(6) -0.2844(13) 0.292(3) 0.049 Uiso 1 d D . .
O302 O 0.2902(6) -0.2365(3) 0.0563(4) 0.0690(17) Uani 1 d D . .
H30C H 0.321(7) -0.209(2) 0.090(4) 0.083 Uiso 1 d D . .
H30D H 0.270(7) -0.222(3) 0.001(3) 0.083 Uiso 1 d D . .
O303 O 0.1756(5) -0.1559(2) 0.1775(4) 0.0618(15) Uani 1 d D . .
H30L H 0.187(7) -0.1225(19) 0.152(6) 0.074 Uiso 1 d D . .
H30K H 0.142(6) -0.140(3) 0.224(5) 0.074 Uiso 1 d D . .
O304 O 0.0592(5) -0.2406(2) 0.0391(4) 0.0532(13) Uani 1 d D . .
H30E H 0.044(6) -0.2716(14) 0.007(4) 0.064 Uiso 1 d D . .
H30F H 0.056(6) -0.2111(15) 0.001(3) 0.064 Uiso 1 d D . .
O305 O 0.3150(5) -0.2642(2) 0.2579(4) 0.0634(16) Uani 1 d D . .
H30G H 0.296(7) -0.285(2) 0.304(3) 0.076 Uiso 1 d D . .
H30H H 0.332(7) -0.2303(15) 0.280(4) 0.076 Uiso 1 d D . .
O306 O 0.1720(5) -0.3364(2) 0.1356(4) 0.0642(16) Uani 1 d D . .
H30I H 0.174(7) -0.356(3) 0.083(2) 0.077 Uiso 1 d D . .
H30J H 0.183(7) -0.360(2) 0.183(3) 0.077 Uiso 1 d D . .
S1 S 0.16553(13) -0.12213(6) -0.11216(11) 0.0310(4) Uani 1 d . . .
O11 O 0.1622(4) -0.0773(2) -0.0371(3) 0.0512(13) Uani 1 d . . .
O12 O 0.0695(4) -0.1588(2) -0.1108(3) 0.0457(12) Uani 1 d . . .
O13 O 0.1683(5) -0.0947(2) -0.2085(3) 0.0605(16) Uani 1 d . . .
O14 O 0.2589(4) -0.1611(2) -0.0943(4) 0.0528(13) Uani 1 d . . .
S2 S -0.02146(14) -0.37822(7) -0.13330(12) 0.0397(4) Uani 1 d . . .
O21 O -0.1272(5) -0.3560(4) -0.1514(7) 0.141(4) Uani 1 d . . .
O22 O 0.0120(8) -0.3999(3) -0.2260(6) 0.124(3) Uani 1 d . . .
O23 O 0.0466(6) -0.3309(3) -0.1035(5) 0.097(2) Uani 1 d . . .
O24 O -0.0225(5) -0.4253(2) -0.0611(4) 0.0675(16) Uani 1 d . . .
S3 S 0.44659(13) -0.11131(6) 0.28182(11) 0.0333(4) Uani 1 d . . .
O31 O 0.5262(11) -0.1126(4) 0.2174(10) 0.230(8) Uani 1 d . . .
O32 O 0.4821(10) -0.0734(3) 0.3581(6) 0.148(4) Uani 1 d . . .
O33 O 0.3536(6) -0.0869(4) 0.2352(8) 0.145(4) Uani 1 d . . .
O34 O 0.4282(5) -0.1698(2) 0.3223(4) 0.0683(16) Uani 1 d . . .
O501 O 0.2622(5) -0.3400(3) -0.0462(4) 0.0682(16) Uani 1 d D . .
H50A H 0.301(5) -0.333(4) -0.093(4) 0.082 Uiso 1 d D . .
H50B H 0.209(4) -0.360(4) -0.067(5) 0.082 Uiso 1 d D . .
O502 O 0.1639(6) 0.0253(3) -0.1946(5) 0.083(2) Uani 1 d D . .
H50C H 0.183(9) 0.017(3) -0.251(4) 0.100 Uiso 1 d D . .
H50D H 0.167(8) 0.0622(8) -0.186(6) 0.100 Uiso 1 d D . .
O503 O 0.1610(5) -0.4680(3) 0.0354(4) 0.0659(16) Uani 1 d D . .
H50E H 0.123(5) -0.499(2) 0.034(6) 0.079 Uiso 1 d D . .
H50F H 0.138(6) -0.444(3) -0.009(5) 0.079 Uiso 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 0.0287(5) 0.0301(4) 0.0290(4) -0.0022(3) 0.0039(3) 0.0014(3)
N1 0.030(3) 0.027(2) 0.032(3) -0.002(2) 0.007(2) 0.000(2)
C2 0.040(4) 0.041(4) 0.025(3) 0.006(3) 0.005(3) 0.003(3)
C3 0.035(4) 0.044(4) 0.052(4) 0.006(3) 0.013(3) 0.016(3)
N4 0.020(3) 0.043(3) 0.033(3) -0.004(2) 0.002(2) 0.002(2)
C5 0.028(4) 0.044(4) 0.039(4) -0.003(3) 0.010(3) -0.009(3)
C6 0.031(4) 0.059(4) 0.033(4) -0.003(3) 0.009(3) -0.015(3)
C7 0.032(4) 0.036(3) 0.035(4) 0.002(3) -0.002(3) -0.007(3)
N8 0.029(3) 0.036(3) 0.035(3) -0.001(2) 0.008(2) -0.002(2)
C9 0.040(5) 0.043(4) 0.051(4) -0.007(3) -0.003(3) 0.011(3)
C10 0.043(5) 0.036(3) 0.028(3) -0.002(2) 0.000(3) 0.007(3)
N11 0.035(3) 0.029(3) 0.032(3) -0.001(2) 0.001(2) 0.001(2)
C12 0.028(4) 0.035(3) 0.034(3) -0.007(3) 0.004(3) 0.000(3)
C13 0.035(5) 0.039(4) 0.073(5) -0.018(3) 0.006(4) -0.010(3)
N14 0.029(3) 0.047(3) 0.029(3) 0.000(2) -0.003(2) 0.008(2)
C15 0.058(6) 0.042(4) 0.060(5) -0.008(3) 0.014(4) -0.009(4)
C16 0.053(6) 0.074(6) 0.052(5) -0.016(4) -0.005(4) -0.004(4)
C17 0.058(6) 0.053(4) 0.058(5) 0.010(4) -0.003(4) -0.004(4)
N18 0.033(4) 0.038(3) 0.061(4) -0.017(3) 0.002(3) 0.007(3)
C19 0.029(4) 0.062(5) 0.053(5) -0.010(3) 0.006(3) -0.017(3)
C20 0.031(4) 0.042(4) 0.031(3) 0.001(3) 0.001(3) -0.009(3)
C21 0.057(5) 0.044(4) 0.041(4) 0.009(3) 0.014(4) 0.017(4)
C22 0.082(7) 0.034(4) 0.047(5) 0.004(3) 0.018(4) 0.012(4)
C23 0.067(6) 0.035(4) 0.033(4) 0.001(3) 0.006(4) -0.018(4)
C24 0.055(5) 0.044(4) 0.029(4) 0.004(3) -0.010(3) 0.014(3)
C25 0.092(7) 0.036(4) 0.042(4) 0.009(3) 0.015(4) -0.005(4)
C26 0.051(5) 0.041(4) 0.037(4) -0.003(3) 0.004(4) -0.017(3)
Cu2 0.0303(5) 0.0292(4) 0.0359(5) 0.0000(3) -0.0010(4) 0.0005(3)
O101 0.047(3) 0.033(2) 0.036(3) 0.0041(19) -0.008(2) 0.001(2)
O102 0.064(4) 0.063(3) 0.031(3) 0.004(2) 0.013(3) -0.003(3)
O201 0.043(3) 0.029(2) 0.069(3) 0.004(2) 0.007(3) -0.005(2)
O202 0.039(3) 0.102(5) 0.039(3) -0.008(3) 0.005(3) 0.013(3)
Cu3 0.0357(5) 0.0378(4) 0.0307(5) 0.0038(3) 0.0046(4) 0.0015(3)
O301 0.052(3) 0.036(2) 0.035(3) 0.0026(18) 0.004(2) 0.008(2)
O302 0.071(5) 0.079(4) 0.057(4) 0.019(3) 0.005(3) 0.018(3)
O303 0.075(4) 0.047(3) 0.066(4) 0.001(3) 0.021(3) -0.009(3)
O304 0.064(4) 0.052(3) 0.044(3) 0.004(2) 0.007(3) -0.005(3)
O305 0.082(5) 0.058(3) 0.051(3) 0.006(3) 0.009(3) -0.022(3)
O306 0.094(5) 0.065(3) 0.034(3) -0.002(2) 0.012(3) 0.011(3)
S1 0.0314(10) 0.0315(8) 0.0306(8) -0.0017(6) 0.0051(7) -0.0004(6)
O11 0.061(4) 0.049(3) 0.044(3) -0.016(2) -0.003(3) -0.005(2)
O12 0.039(3) 0.044(3) 0.055(3) -0.009(2) 0.011(2) -0.008(2)
O13 0.096(5) 0.047(3) 0.040(3) 0.007(2) 0.017(3) 0.000(3)
O14 0.038(3) 0.065(3) 0.055(3) 0.001(2) -0.002(2) 0.015(2)
S2 0.0388(11) 0.0336(8) 0.0475(10) 0.0044(7) 0.0087(8) -0.0042(7)
O21 0.043(5) 0.170(8) 0.209(10) 0.134(8) -0.002(5) 0.001(5)
O22 0.197(9) 0.080(5) 0.108(6) -0.004(4) 0.099(6) -0.008(5)
O23 0.156(7) 0.058(4) 0.073(4) 0.001(3) -0.014(4) -0.052(4)
O24 0.067(4) 0.063(4) 0.073(4) 0.023(3) 0.016(3) 0.004(3)
S3 0.0324(10) 0.0322(8) 0.0358(9) -0.0010(6) 0.0060(7) -0.0039(7)
O31 0.305(16) 0.092(6) 0.327(15) 0.061(8) 0.273(14) 0.038(8)
O32 0.272(13) 0.062(4) 0.095(6) -0.009(4) -0.098(7) -0.009(6)
O33 0.064(5) 0.138(7) 0.222(11) 0.107(7) -0.067(6) -0.030(5)
O34 0.073(4) 0.054(3) 0.078(4) 0.023(3) 0.001(3) -0.016(3)
O501 0.062(4) 0.091(5) 0.053(3) -0.008(3) 0.016(3) -0.002(3)
O502 0.110(6) 0.047(3) 0.087(5) 0.007(3) -0.032(4) -0.006(4)
O503 0.071(5) 0.058(3) 0.070(4) 0.005(3) 0.012(3) 0.006(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
Cu1 N1 1.933(5) . ?
Cu1 O101 1.949(5) . ?
Cu1 N4 2.059(6) . ?
Cu1 N18 2.087(6) . ?
Cu1 O102 2.222(5) . ?
N1 C20 1.335(8) . ?
N1 C2 1.351(8) . ?
C2 C21 1.371(9) . ?
C2 C3 1.494(10) . ?
C3 N4 1.520(8) . ?
C3 H3A 0.9700 . ?
C3 H3B 0.9700 . ?
N4 C5 1.506(7) . ?
N4 H4 0.9100 . ?
C5 C6 1.554(9) . ?
C5 H5A 0.9700 . ?
C5 H5B 0.9700 . ?
C6 C7 1.518(8) . ?
C6 H6A 0.9700 . ?
C6 H6B 0.9700 . ?
C7 N8 1.512(8) . ?
C7 H7A 0.9700 . ?
C7 H7B 0.9700 . ?
N8 C9 1.493(8) . ?
N8 Cu2 2.050(6) . ?
N8 H8 0.9100 . ?
C9 C10 1.509(10) . ?
C9 H9A 0.9700 . ?
C9 H9B 0.9700 . ?
C10 N11 1.331(8) . ?
C10 C24 1.384(9) . ?
N11 C12 1.334(8) . ?
N11 Cu2 1.928(5) . ?
C12 C26 1.377(9) . ?
C12 C13 1.521(10) . ?
C13 N14 1.493(8) . ?
C13 H13A 0.9700 . ?
C13 H13B 0.9700 . ?
N14 C15 1.482(8) . ?
N14 Cu2 2.073(6) . ?
N14 H14 0.9100 . ?
C15 C16 1.475(11) . ?
C15 H15A 0.9700 . ?
C15 H15B 0.9700 . ?
C16 C17 1.472(11) . ?
C16 H16A 0.9700 . ?
C16 H16B 0.9700 . ?
C17 N18 1.551(10) . ?
C17 H17A 0.9700 . ?
C17 H17B 0.9700 . ?
N18 C19 1.469(9) . ?
N18 H18 0.9100 . ?
C19 C20 1.503(10) . ?
C19 H19A 0.9700 . ?
C19 H19B 0.9700 . ?
C20 C23 1.374(9) . ?
C21 C22 1.395(11) . ?
C21 H21 0.9300 . ?
C22 C23 1.386(12) . ?
C22 H22 0.9300 . ?
C23 H23 0.9300 . ?
C24 C25 1.375(11) . ?
C24 H24 0.9300 . ?
C25 C26 1.377(11) . ?
C25 H25 0.9300 . ?
C26 H26 0.9300 . ?
Cu2 O201 1.949(5) . ?
Cu2 O202 2.242(5) . ?
Cu2 H20B 2.07(7) . ?
O101 H10A 0.845(10) . ?
O101 H10B 0.844(10) . ?
O102 H10C 0.850(10) . ?
O102 H10D 0.851(10) . ?
O201 H20A 0.847(10) . ?
O201 H20B 0.845(10) . ?
O202 H20C 0.849(10) . ?
O202 H20D 0.846(10) . ?
Cu3 O301 2.027(5) . ?
Cu3 O302 2.037(6) . ?
Cu3 O303 2.069(6) . ?
Cu3 O306 2.088(6) . ?
Cu3 O305 2.161(7) . ?
Cu3 O304 2.165(6) . ?
O301 H30A 0.853(10) . ?
O301 H30B 0.850(10) . ?
O302 H30C 0.858(10) . ?
O302 H30D 0.856(10) . ?
O303 H30L 0.85(2) . ?
O303 H30K 0.86(2) . ?
O304 H30E 0.849(10) . ?
O304 H30F 0.853(10) . ?
O305 H30G 0.849(10) . ?
O305 H30H 0.851(10) . ?
O306 H30I 0.852(10) . ?
O306 H30J 0.854(10) . ?
S1 O11 1.455(5) . ?
S1 O13 1.469(5) . ?
S1 O12 1.475(5) . ?
S1 O14 1.484(5) . ?
S2 O23 1.423(6) . ?
S2 O21 1.436(7) . ?
S2 O22 1.457(7) . ?
S2 O24 1.463(5) . ?
S3 O31 1.385(7) . ?
S3 O32 1.411(7) . ?
S3 O33 1.416(7) . ?
S3 O34 1.469(5) . ?
O501 H50A 0.853(10) . ?
O501 H50B 0.849(10) . ?
O502 H50C 0.849(10) . ?
O502 H50D 0.848(10) . ?
O503 H50E 0.849(10) . ?
O503 H50F 0.847(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
N1 Cu1 O101 173.16(19) . . ?
N1 Cu1 N4 82.5(2) . . ?
O101 Cu1 N4 95.7(2) . . ?
N1 Cu1 N18 81.5(2) . . ?
O101 Cu1 N18 97.6(2) . . ?
N4 Cu1 N18 153.7(2) . . ?
N1 Cu1 O102 97.78(19) . . ?
O101 Cu1 O102 89.02(19) . . ?
N4 Cu1 O102 99.4(2) . . ?
N18 Cu1 O102 103.3(2) . . ?
C20 N1 C2 122.9(5) . . ?
C20 N1 Cu1 118.2(4) . . ?
C2 N1 Cu1 118.3(4) . . ?
N1 C2 C21 118.6(7) . . ?
N1 C2 C3 114.2(5) . . ?
C21 C2 C3 127.1(7) . . ?
C2 C3 N4 109.6(6) . . ?
C2 C3 H3A 109.8 . . ?
N4 C3 H3A 109.8 . . ?
C2 C3 H3B 109.8 . . ?
N4 C3 H3B 109.8 . . ?
H3A C3 H3B 108.2 . . ?
C5 N4 C3 110.9(4) . . ?
C5 N4 Cu1 114.7(4) . . ?
C3 N4 Cu1 108.3(4) . . ?
C5 N4 H4 107.6 . . ?
C3 N4 H4 107.6 . . ?
Cu1 N4 H4 107.6 . . ?
N4 C5 C6 109.9(5) . . ?
N4 C5 H5A 109.7 . . ?
C6 C5 H5A 109.7 . . ?
N4 C5 H5B 109.7 . . ?
C6 C5 H5B 109.7 . . ?
H5A C5 H5B 108.2 . . ?
C7 C6 C5 112.5(5) . . ?
C7 C6 H6A 109.1 . . ?
C5 C6 H6A 109.1 . . ?
C7 C6 H6B 109.1 . . ?
C5 C6 H6B 109.1 . . ?
H6A C6 H6B 107.8 . . ?
N8 C7 C6 109.2(5) . . ?
N8 C7 H7A 109.8 . . ?
C6 C7 H7A 109.8 . . ?
N8 C7 H7B 109.8 . . ?
C6 C7 H7B 109.8 . . ?
H7A C7 H7B 108.3 . . ?
C9 N8 C7 111.2(5) . . ?
C9 N8 Cu2 110.3(4) . . ?
C7 N8 Cu2 116.9(4) . . ?
C9 N8 H8 105.9 . . ?
C7 N8 H8 105.9 . . ?
Cu2 N8 H8 105.9 . . ?
N8 C9 C10 110.9(5) . . ?
N8 C9 H9A 109.5 . . ?
C10 C9 H9A 109.5 . . ?
N8 C9 H9B 109.5 . . ?
C10 C9 H9B 109.5 . . ?
H9A C9 H9B 108.0 . . ?
N11 C10 C24 120.1(6) . . ?
N11 C10 C9 115.0(5) . . ?
C24 C10 C9 124.7(6) . . ?
C10 N11 C12 121.4(5) . . ?
C10 N11 Cu2 118.9(4) . . ?
C12 N11 Cu2 119.6(4) . . ?
N11 C12 C26 120.6(6) . . ?
N11 C12 C13 114.7(5) . . ?
C26 C12 C13 124.5(6) . . ?
N14 C13 C12 111.4(5) . . ?
N14 C13 H13A 109.3 . . ?
C12 C13 H13A 109.3 . . ?
N14 C13 H13B 109.3 . . ?
C12 C13 H13B 109.3 . . ?
H13A C13 H13B 108.0 . . ?
C15 N14 C13 112.1(5) . . ?
C15 N14 Cu2 122.3(5) . . ?
C13 N14 Cu2 110.2(4) . . ?
C15 N14 H14 103.3 . . ?
C13 N14 H14 103.3 . . ?
Cu2 N14 H14 103.3 . . ?
C16 C15 N14 120.5(7) . . ?
C16 C15 H15A 107.2 . . ?
N14 C15 H15A 107.2 . . ?
C16 C15 H15B 107.2 . . ?
N14 C15 H15B 107.2 . . ?
H15A C15 H15B 106.8 . . ?
C17 C16 C15 111.2(7) . . ?
C17 C16 H16A 109.4 . . ?
C15 C16 H16A 109.4 . . ?
C17 C16 H16B 109.4 . . ?
C15 C16 H16B 109.4 . . ?
H16A C16 H16B 108.0 . . ?
C16 C17 N18 114.2(6) . . ?
C16 C17 H17A 108.7 . . ?
N18 C17 H17A 108.7 . . ?
C16 C17 H17B 108.7 . . ?
N18 C17 H17B 108.7 . . ?
H17A C17 H17B 107.6 . . ?
C19 N18 C17 112.4(5) . . ?
C19 N18 Cu1 105.3(4) . . ?
C17 N18 Cu1 106.1(4) . . ?
C19 N18 H18 110.9 . . ?
C17 N18 H18 110.9 . . ?
Cu1 N18 H18 110.9 . . ?
N18 C19 C20 110.2(5) . . ?
N18 C19 H19A 109.6 . . ?
C20 C19 H19A 109.6 . . ?
N18 C19 H19B 109.6 . . ?
C20 C19 H19B 109.6 . . ?
H19A C19 H19B 108.1 . . ?
N1 C20 C23 119.9(6) . . ?
N1 C20 C19 112.2(6) . . ?
C23 C20 C19 127.9(6) . . ?
C2 C21 C22 120.2(7) . . ?
C2 C21 H21 119.9 . . ?
C22 C21 H21 119.9 . . ?
C23 C22 C21 118.9(6) . . ?
C23 C22 H22 120.6 . . ?
C21 C22 H22 120.6 . . ?
C20 C23 C22 119.4(7) . . ?
C20 C23 H23 120.3 . . ?
C22 C23 H23 120.3 . . ?
C25 C24 C10 119.3(7) . . ?
C25 C24 H24 120.3 . . ?
C10 C24 H24 120.3 . . ?
C24 C25 C26 119.4(6) . . ?
C24 C25 H25 120.3 . . ?
C26 C25 H25 120.3 . . ?
C25 C26 C12 119.0(7) . . ?
C25 C26 H26 120.5 . . ?
C12 C26 H26 120.5 . . ?
N11 Cu2 O201 167.7(2) . . ?
N11 Cu2 N8 82.8(2) . . ?
O201 Cu2 N8 94.3(2) . . ?
N11 Cu2 N14 82.7(2) . . ?
O201 Cu2 N14 99.0(2) . . ?
N8 Cu2 N14 165.1(2) . . ?
N11 Cu2 O202 100.8(2) . . ?
O201 Cu2 O202 91.3(2) . . ?
N8 Cu2 O202 94.4(2) . . ?
N14 Cu2 O202 91.8(2) . . ?
N11 Cu2 H20B 158.5(9) . . ?
O201 Cu2 H20B 24.1(7) . . ?
N8 Cu2 H20B 117.8(8) . . ?
N14 Cu2 H20B 76.2(8) . . ?
O202 Cu2 H20B 84.5(17) . . ?
Cu1 O101 H10A 124(4) . . ?
Cu1 O101 H10B 100(4) . . ?
H10A O101 H10B 110.9(18) . . ?
Cu1 O102 H10C 140(5) . . ?
Cu1 O102 H10D 83(5) . . ?
H10C O102 H10D 109.1(18) . . ?
Cu2 O201 H20A 114(5) . . ?
Cu2 O201 H20B 86(5) . . ?
H20A O201 H20B 110.4(18) . . ?
Cu2 O202 H20C 111(5) . . ?
Cu2 O202 H20D 123(5) . . ?
H20C O202 H20D 110.2(18) . . ?
O301 Cu3 O302 178.8(2) . . ?
O301 Cu3 O303 87.79(19) . . ?
O302 Cu3 O303 91.0(2) . . ?
O301 Cu3 O306 89.1(2) . . ?
O302 Cu3 O306 92.1(2) . . ?
O303 Cu3 O306 175.2(3) . . ?
O301 Cu3 O305 94.9(2) . . ?
O302 Cu3 O305 85.2(3) . . ?
O303 Cu3 O305 97.8(2) . . ?
O306 Cu3 O305 86.1(2) . . ?
O301 Cu3 O304 92.3(2) . . ?
O302 Cu3 O304 87.8(3) . . ?
O303 Cu3 O304 91.2(2) . . ?
O306 Cu3 O304 85.3(2) . . ?
O305 Cu3 O304 168.8(2) . . ?
Cu3 O301 H30A 128(4) . . ?
Cu3 O301 H30B 116(4) . . ?
H30A O301 H30B 108.8(18) . . ?
Cu3 O302 H30C 90(6) . . ?
Cu3 O302 H30D 118(6) . . ?
H30C O302 H30D 107.6(18) . . ?
Cu3 O303 H30L 145(6) . . ?
Cu3 O303 H30K 122(6) . . ?
H30L O303 H30K 93(7) . . ?
Cu3 O304 H30E 118(5) . . ?
Cu3 O304 H30F 121(5) . . ?
H30E O304 H30F 109.3(18) . . ?
Cu3 O305 H30G 110(6) . . ?
Cu3 O305 H30H 102(6) . . ?
H30G O305 H30H 109.2(18) . . ?
Cu3 O306 H30I 129(5) . . ?
Cu3 O306 H30J 121(5) . . ?
H30I O306 H30J 108.8(18) . . ?
O11 S1 O13 110.3(3) . . ?
O11 S1 O12 109.0(3) . . ?
O13 S1 O12 108.7(3) . . ?
O11 S1 O14 111.2(3) . . ?
O13 S1 O14 109.8(3) . . ?
O12 S1 O14 107.8(3) . . ?
O23 S2 O21 108.7(5) . . ?
O23 S2 O22 107.7(4) . . ?
O21 S2 O22 106.8(6) . . ?
O23 S2 O24 113.1(4) . . ?
O21 S2 O24 109.1(4) . . ?
O22 S2 O24 111.3(4) . . ?
O31 S3 O32 106.3(8) . . ?
O31 S3 O33 109.5(8) . . ?
O32 S3 O33 108.1(6) . . ?
O31 S3 O34 111.3(4) . . ?
O32 S3 O34 108.9(4) . . ?
O33 S3 O34 112.4(4) . . ?
H50A O501 H50B 109.1(18) . . ?
H50C O502 H50D 109.8(18) . . ?
H50E O503 H50F 109.8(18) . . ?

_diffrn_measured_fraction_theta_max 0.800
_diffrn_reflns_theta_full        25.98
_diffrn_measured_fraction_theta_full 0.800
_refine_diff_density_max         0.997
_refine_diff_density_min         -0.735
_refine_diff_density_rms         0.127
#==END

data_compound_2
_database_code_depnum_ccdc_archive 'CCDC 252427'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            
(Cu2((20)Py2N4)(CH3CN)4).(Ni((20)Py2N4)).(SO4)2(CLO4)2.0.25H2O
_chemical_formula_moiety         ?
_chemical_formula_sum            'C68 H104 Cl8 Cu2 N22 Ni2 O33'
_chemical_formula_weight         2285.83

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
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'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ni Ni 0.3393 1.1124 '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'
'-x, -y, z+1/2'
'x, -y, z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, z'
'-x+1/2, -y+1/2, z+1/2'
'x+1/2, -y+1/2, z+1/2'
'-x, -y, -z'
'x, -y, -z'
'x, y, -z-1/2'
'-x, y, -z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, -z'
'x+1/2, y+1/2, -z-1/2'
'-x+1/2, y+1/2, -z-1/2'

_cell_length_a                   44.912(53)
_cell_length_b                   12.707(14)
_cell_length_c                   17.266(19)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     9854(19)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_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    1.541
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             4720
_exptl_absorpt_coefficient_mu    1.107
_exptl_absorpt_correction_type   'Empirical (DIFABS)'
_exptl_absorpt_correction_T_min  0.711
_exptl_absorpt_correction_T_max  1.000

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      293(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  'MAR research image plate system'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            9095
_diffrn_reflns_av_R_equivalents  0.1041
_diffrn_reflns_av_sigmaI/netI    0.0765
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_h_max       55
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_theta_min         2.04
_diffrn_reflns_theta_max         26.10
_reflns_number_total             5038
_reflns_number_gt                3078
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        'W. Kabsch, J. Appl. Crystallogr. 21,916,1983'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'PLATON (Spek, 1999)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'

_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 w=1/[\s^2^(Fo^2^)+(0.1696P)^2^+82.4281P] 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         5038
_refine_ls_number_parameters     316
_refine_ls_number_restraints     19
_refine_ls_R_factor_all          0.2008
_refine_ls_R_factor_gt           0.1258
_refine_ls_wR_factor_ref         0.3624
_refine_ls_wR_factor_gt          0.3246
_refine_ls_goodness_of_fit_ref   1.141
_refine_ls_restrained_S_all      1.143
_refine_ls_shift/su_max          0.028
_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_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Ni1 Ni 0.18392(4) 0.5000 0.0000 0.0608(6) Uani 1 d S . .
N11 N 0.2285(3) 0.5000 0.0000 0.060(3) Uani 1 d S . .
C12 C 0.2428(2) 0.4831(9) 0.0678(6) 0.068(3) Uani 1 d . . .
C13 C 0.2738(3) 0.4822(9) 0.0678(11) 0.099(5) Uani 1 d . . .
H13 H 0.2840 0.4696 0.1136 0.119 Uiso 1 calc R . .
C14 C 0.2894(5) 0.5000 0.0000 0.131(12) Uani 1 d S . .
H14 H 0.3101 0.5000 0.0000 0.158 Uiso 1 calc SR . .
C15 C 0.2215(4) 0.4662(11) 0.1347(6) 0.106(6) Uani 1 d . . .
H15A H 0.2306 0.4195 0.1722 0.128 Uiso 1 calc R . .
H15B H 0.2177 0.5331 0.1600 0.128 Uiso 1 calc R . .
N16 N 0.1932(3) 0.4213(9) 0.1091(6) 0.087(3) Uani 1 d . . .
H16 H 0.1789 0.4399 0.1437 0.105 Uiso 1 calc R . .
C17 C 0.1958(4) 0.3002(13) 0.1088(12) 0.150(9) Uani 1 d . . .
H17A H 0.1928 0.2735 0.1609 0.180 Uiso 1 calc R . .
H17B H 0.2155 0.2798 0.0919 0.180 Uiso 1 calc R . .
C18 C 0.1711(5) 0.2497(12) 0.0513(10) 0.122(6) Uani 1 d . . .
H18A H 0.1669 0.1776 0.0664 0.146 Uiso 1 calc R . .
H18B H 0.1527 0.2895 0.0546 0.146 Uiso 1 calc R . .
C19 C 0.1814(4) 0.2520(11) -0.0213(13) 0.122(6) Uani 1 d . . .
H19A H 0.1727 0.1945 -0.0505 0.147 Uiso 1 calc R . .
H19B H 0.2028 0.2420 -0.0206 0.147 Uiso 1 calc R . .
N20 N 0.1744(2) 0.3519(7) -0.0599(7) 0.085(3) Uani 1 d . . .
H20 H 0.1861 0.3530 -0.1029 0.102 Uiso 1 calc R . .
C21 C 0.1433(3) 0.3568(10) -0.0896(7) 0.085(4) Uani 1 d . . .
H21A H 0.1346 0.2869 -0.0886 0.102 Uiso 1 calc R . .
H21B H 0.1435 0.3809 -0.1429 0.102 Uiso 1 calc R . .
C22 C 0.0782(4) 0.5000 0.0000 0.099(7) Uani 1 d S . .
H22 H 0.0574 0.5000 0.0000 0.118 Uiso 1 calc SR . .
C23 C 0.0937(3) 0.4279(13) -0.0406(8) 0.093(4) Uani 1 d . . .
H23 H 0.0836 0.3762 -0.0682 0.111 Uiso 1 calc R . .
C24 C 0.1247(3) 0.4299(9) -0.0416(7) 0.068(3) Uani 1 d . . .
N25 N 0.1393(3) 0.5000 0.0000 0.064(3) Uani 1 d S . .
Cu1 Cu 0.06132(4) 0.10616(13) 0.2500 0.0514(5) Uani 1 d S . .
N41 N 0.0538(2) 0.2537(8) 0.2500 0.040(2) Uani 1 d S . .
C42 C 0.0503(2) 0.3048(7) 0.3177(6) 0.050(2) Uani 1 d . . .
C43 C 0.0411(2) 0.4070(8) 0.3187(7) 0.062(3) Uani 1 d . . .
H43 H 0.0383 0.4418 0.3655 0.074 Uiso 1 calc R . .
C44 C 0.0360(3) 0.4581(11) 0.2500 0.059(4) Uani 1 d S . .
H44 H 0.0291 0.5271 0.2500 0.071 Uiso 1 calc SR . .
C45 C 0.0586(2) 0.2383(8) 0.3865(6) 0.063(3) Uani 1 d . . .
H45A H 0.0790 0.2536 0.4017 0.076 Uiso 1 calc R . .
H45B H 0.0457 0.2553 0.4298 0.076 Uiso 1 calc R . .
N46 N 0.05582(17) 0.1248(6) 0.3676(4) 0.053(2) Uani 1 d . . .
H46 H 0.0715 0.0920 0.3905 0.064 Uiso 1 calc R . .
C47 C 0.0285(2) 0.0771(8) 0.4017(5) 0.056(3) Uani 1 d . . .
H47A H 0.0280 0.0909 0.4569 0.068 Uiso 1 calc R . .
H47B H 0.0289 0.0014 0.3942 0.068 Uiso 1 calc R . .
C48 C 0.0000 0.1232(11) 0.3631(8) 0.054(3) Uani 1 d S . .
H48A H 0.0000 0.1064 0.3083 0.065 Uiso 1 calc SR . .
H48B H 0.0000 0.1992 0.3684 0.065 Uiso 1 calc SR . .
N200 N 0.0610(3) -0.0459(11) 0.2500 0.073(4) Uiso 1 d SD . .
C201 C 0.0658(5) -0.1354(11) 0.2500 0.122(8) Uiso 1 d SD . .
C202 C 0.0701(7) -0.2495(12) 0.2500 0.181(13) Uiso 1 d SD . .
H20A H 0.0910 -0.2651 0.2495 0.218 Uiso 1 calc SR . .
H20B H 0.0609 -0.2793 0.2048 0.218 Uiso 0.50 calc PR . .
H20C H 0.0612 -0.2791 0.2956 0.218 Uiso 0.50 calc PR . .
Cl1 Cl 0.0000 -0.3021(4) 0.4193(3) 0.0751(12) Uani 1 d SD . .
O11 O 0.0000 -0.344(3) 0.4938(11) 0.265(15) Uani 1 d SD . .
O12 O 0.0000 -0.1949(8) 0.4161(14) 0.30(2) Uani 1 d SD . .
O13 O -0.0205(5) -0.353(2) 0.3763(16) 0.337(16) Uani 1 d D . .
Cl2 Cl 0.12531(8) 0.4311(4) 0.2500 0.0703(11) Uani 1 d SD . .
O21 O 0.1205(2) 0.3711(9) 0.1828(5) 0.118(4) Uani 1 d D . .
O22 O 0.1055(3) 0.5156(10) 0.2500 0.118(5) Uani 1 d SD . .
O23 O 0.15493(18) 0.4700(9) 0.2500 0.075(3) Uani 1 d SD . .
Cl3 Cl 0.11335(12) 0.0000 0.5000 0.173(4) Uani 1 d SD . .
O31 O 0.1135(7) 0.0935(14) 0.4581(15) 0.160(10) Uiso 0.50 d PD . .
O32 O 0.1374(4) 0.012(2) 0.5501(13) 0.157(10) Uiso 0.50 d PD . .
O33 O 0.0963(8) 0.077(2) 0.537(2) 0.205(14) Uiso 0.50 d PD . .
O34 O 0.0825(3) 0.0000 0.5000 0.41(3) Uiso 1 d SD . .
Cl4 Cl 0.28583(14) 0.2561(4) 0.2500 0.0986(16) Uani 1 d SD . .
O41 O 0.3078(3) 0.1794(12) 0.2500 0.121(5) Uani 1 d SD . .
O42 O 0.2703(4) 0.2385(13) 0.3189(9) 0.225(9) Uani 1 d D . .
O43 O 0.2924(7) 0.3629(9) 0.2500 0.213(12) Uani 1 d SD . .
N100 N 0.1098(3) 0.1246(13) 0.2500 0.094(5) Uiso 1 d SD . .
C101 C 0.1330(4) 0.0850(19) 0.2500 0.29(3) Uiso 1 d SD . .
C102 C 0.1635(5) 0.044(3) 0.2500 0.39(4) Uiso 1 d SD . .
H10A H 0.1718 0.0508 0.1990 0.471 Uiso 0.50 calc PR . .
H10B H 0.1634 -0.0282 0.2651 0.471 Uiso 0.50 calc PR . .
H10C H 0.1754 0.0842 0.2859 0.471 Uiso 0.50 calc PR . .
O400 O 0.0000(5) -0.158(4) 0.279(6) 0.36(5) Uiso 0.50 d SPR . .

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
Ni1 0.0532(10) 0.0668(12) 0.0625(12) 0.0209(10) 0.000 0.000
N11 0.057(7) 0.084(9) 0.038(6) -0.015(6) 0.000 0.000
C12 0.077(7) 0.069(7) 0.057(7) -0.005(5) -0.026(6) 0.021(6)
C13 0.082(9) 0.045(7) 0.170(17) -0.010(8) -0.062(10) 0.004(6)
C14 0.066(13) 0.060(13) 0.27(4) 0.011(19) 0.000 0.000
C15 0.208(18) 0.079(9) 0.032(6) -0.010(6) -0.016(9) 0.066(11)
N16 0.091(7) 0.109(9) 0.062(6) 0.020(6) 0.025(6) 0.038(7)
C17 0.113(11) 0.125(14) 0.21(2) 0.129(15) -0.058(13) -0.020(10)
C18 0.20(2) 0.076(10) 0.093(12) 0.002(9) 0.008(13) -0.003(11)
C19 0.107(11) 0.065(9) 0.20(2) 0.027(11) -0.007(12) 0.009(8)
N20 0.095(7) 0.060(6) 0.101(8) 0.021(6) 0.031(7) 0.002(5)
C21 0.126(11) 0.067(7) 0.062(8) -0.004(6) 0.006(8) -0.002(8)
C22 0.067(11) 0.18(2) 0.050(11) 0.021(13) 0.000 0.000
C23 0.078(8) 0.138(13) 0.061(8) 0.021(8) -0.003(7) -0.034(8)
C24 0.069(7) 0.068(7) 0.066(7) 0.015(6) 0.003(6) -0.009(6)
N25 0.053(6) 0.044(7) 0.095(10) 0.007(7) 0.000 0.000
Cu1 0.0564(10) 0.0486(10) 0.0492(10) 0.000 0.000 0.0115(8)
N41 0.045(5) 0.047(6) 0.030(5) 0.000 0.000 -0.004(4)
C42 0.046(5) 0.048(6) 0.058(6) -0.006(5) -0.006(4) -0.004(4)
C43 0.061(6) 0.053(6) 0.071(7) -0.021(6) -0.004(5) -0.002(5)
C44 0.060(8) 0.038(7) 0.081(11) 0.000 0.000 -0.003(6)
C45 0.071(6) 0.070(7) 0.048(6) -0.004(5) -0.018(5) -0.008(5)
N46 0.056(5) 0.061(5) 0.043(4) 0.002(4) -0.011(4) 0.009(4)
C47 0.075(7) 0.054(6) 0.040(5) 0.007(4) -0.002(5) 0.008(5)
C48 0.058(8) 0.051(8) 0.054(8) 0.007(6) 0.000 0.000
Cl1 0.074(2) 0.078(3) 0.074(3) -0.024(2) 0.000 0.000
O11 0.28(3) 0.37(4) 0.15(2) 0.11(2) 0.000 0.000
O12 0.68(7) 0.087(14) 0.15(2) -0.020(13) 0.000 0.000
O13 0.33(3) 0.28(2) 0.40(4) -0.10(2) -0.20(3) -0.039(19)
Cl2 0.051(2) 0.102(3) 0.058(2) 0.000 0.000 -0.016(2)
O21 0.095(7) 0.151(10) 0.108(8) -0.055(7) 0.005(6) -0.035(6)
O22 0.075(8) 0.112(11) 0.169(16) 0.000 0.000 0.019(8)
O23 0.061(6) 0.109(9) 0.055(6) 0.000 0.000 -0.029(6)
Cl3 0.053(3) 0.274(10) 0.192(8) 0.152(8) 0.000 0.000
Cl4 0.129(4) 0.070(3) 0.097(4) 0.000 0.000 0.038(3)
O41 0.132(12) 0.134(13) 0.098(10) 0.000 0.000 0.057(10)
O42 0.27(2) 0.179(15) 0.225(17) 0.027(12) 0.150(15) 0.086(14)
O43 0.35(4) 0.090(14) 0.20(2) 0.000 0.000 -0.025(17)

_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
Ni1 N11 2.004(12) . ?
Ni1 N25 2.005(12) . ?
Ni1 N16 2.173(10) . ?
Ni1 N16 2.173(10) 10_565 ?
Ni1 N20 2.189(11) . ?
Ni1 N20 2.189(11) 10_565 ?
N11 C12 1.352(11) . ?
N11 C12 1.352(11) 10_565 ?
C12 C13 1.390(17) . ?
C12 C15 1.516(18) . ?
C13 C14 1.382(19) . ?
C14 C13 1.382(19) 10_565 ?
C15 N16 1.461(18) . ?
N16 C17 1.543(19) . ?
C17 C18 1.62(2) . ?
C18 C19 1.34(2) . ?
C19 N20 1.467(17) . ?
N20 C21 1.491(16) . ?
C21 C24 1.500(17) . ?
C22 C23 1.348(17) 10_565 ?
C22 C23 1.348(17) . ?
C23 C24 1.392(17) . ?
C24 N25 1.319(13) . ?
N25 C24 1.319(13) 10_565 ?
Cu1 N41 1.904(10) . ?
Cu1 N200 1.932(14) . ?
Cu1 N46 2.059(8) 11_556 ?
Cu1 N46 2.059(8) . ?
Cu1 N100 2.190(14) . ?
N41 C42 1.347(11) . ?
N41 C42 1.347(11) 11_556 ?
C42 C43 1.364(13) . ?
C42 C45 1.506(14) . ?
C43 C44 1.370(13) . ?
C44 C43 1.370(13) 11_556 ?
C45 N46 1.485(13) . ?
N46 C47 1.490(12) . ?
C47 C48 1.557(12) . ?
C48 C47 1.557(12) 2 ?
N200 C201 1.1573(16) . ?
C201 C202 1.4633(19) . ?
Cl1 O13 1.350(9) . ?
Cl1 O13 1.350(9) 2 ?
Cl1 O12 1.363(9) . ?
Cl1 O11 1.395(10) . ?
Cl2 O22 1.395(8) . ?
Cl2 O21 1.405(7) . ?
Cl2 O21 1.405(7) 11_556 ?
Cl2 O23 1.419(7) . ?
Cl3 O34 1.386(10) . ?
Cl3 O32 1.391(10) . ?
Cl3 O32 1.391(10) 10_556 ?
Cl3 O31 1.391(10) . ?
Cl3 O31 1.391(10) 10_556 ?
Cl3 O33 1.397(10) 10_556 ?
Cl3 O33 1.397(10) . ?
O31 O33 1.59(4) . ?
O31 O32 1.72(3) 10_556 ?
O32 O31 1.72(3) 10_556 ?
O32 O32 1.76(4) 10_556 ?
O33 O34 1.32(4) . ?
O34 O33 1.32(4) 10_556 ?
Cl4 O41 1.386(8) . ?
Cl4 O43 1.389(9) . ?
Cl4 O42 1.398(9) 11_556 ?
Cl4 O42 1.398(9) . ?
N100 C101 1.1578(15) . ?
C101 C102 1.4638(18) . ?
O400 O400 1.0(2) 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
N11 Ni1 N25 180.0 . . ?
N11 Ni1 N16 78.9(3) . . ?
N25 Ni1 N16 101.1(3) . . ?
N11 Ni1 N16 78.9(3) . 10_565 ?
N25 Ni1 N16 101.1(3) . 10_565 ?
N16 Ni1 N16 157.9(6) . 10_565 ?
N11 Ni1 N20 101.2(3) . . ?
N25 Ni1 N20 78.8(3) . . ?
N16 Ni1 N20 92.9(4) . . ?
N16 Ni1 N20 91.4(4) 10_565 . ?
N11 Ni1 N20 101.2(3) . 10_565 ?
N25 Ni1 N20 78.8(3) . 10_565 ?
N16 Ni1 N20 91.4(4) . 10_565 ?
N16 Ni1 N20 92.9(4) 10_565 10_565 ?
N20 Ni1 N20 157.6(6) . 10_565 ?
C12 N11 C12 123.3(13) . 10_565 ?
C12 N11 Ni1 118.3(7) . . ?
C12 N11 Ni1 118.3(7) 10_565 . ?
N11 C12 C13 118.4(12) . . ?
N11 C12 C15 112.4(10) . . ?
C13 C12 C15 129.2(12) . . ?
C14 C13 C12 120.4(16) . . ?
C13 C14 C13 119(2) 10_565 . ?
N16 C15 C12 112.0(9) . . ?
C15 N16 C17 109.0(10) . . ?
C15 N16 Ni1 104.4(8) . . ?
C17 N16 Ni1 118.1(10) . . ?
N16 C17 C18 110.2(11) . . ?
C19 C18 C17 109.1(18) . . ?
C18 C19 N20 111.7(15) . . ?
C19 N20 C21 113.1(11) . . ?
C19 N20 Ni1 119.2(11) . . ?
C21 N20 Ni1 108.0(7) . . ?
N20 C21 C24 111.0(10) . . ?
C23 C22 C23 117.7(19) 10_565 . ?
C22 C23 C24 120.8(15) . . ?
N25 C24 C23 120.2(12) . . ?
N25 C24 C21 116.2(10) . . ?
C23 C24 C21 123.6(12) . . ?
C24 N25 C24 120.4(13) . 10_565 ?
C24 N25 Ni1 119.8(7) . . ?
C24 N25 Ni1 119.8(7) 10_565 . ?
N41 Cu1 N200 169.4(5) . . ?
N41 Cu1 N46 82.3(2) . 11_556 ?
N200 Cu1 N46 96.5(2) . 11_556 ?
N41 Cu1 N46 82.3(2) . . ?
N200 Cu1 N46 96.5(2) . . ?
N46 Cu1 N46 160.9(4) 11_556 . ?
N41 Cu1 N100 94.0(5) . . ?
N200 Cu1 N100 96.6(6) . . ?
N46 Cu1 N100 96.1(2) 11_556 . ?
N46 Cu1 N100 96.1(2) . . ?
C42 N41 C42 120.4(11) . 11_556 ?
C42 N41 Cu1 119.7(6) . . ?
C42 N41 Cu1 119.7(6) 11_556 . ?
N41 C42 C43 120.4(10) . . ?
N41 C42 C45 112.6(8) . . ?
C43 C42 C45 126.9(9) . . ?
C42 C43 C44 119.4(10) . . ?
C43 C44 C43 119.7(13) 11_556 . ?
N46 C45 C42 110.5(8) . . ?
C45 N46 C47 112.2(8) . . ?
C45 N46 Cu1 108.6(6) . . ?
C47 N46 Cu1 116.2(6) . . ?
N46 C47 C48 110.8(8) . . ?
C47 C48 C47 110.5(11) . 2 ?
C201 N200 Cu1 169.0(14) . . ?
N200 C201 C202 177(2) . . ?
O13 Cl1 O13 86(2) . 2 ?
O13 Cl1 O12 117.3(14) . . ?
O13 Cl1 O12 117.3(14) 2 . ?
O13 Cl1 O11 108.8(18) . . ?
O13 Cl1 O11 108.8(18) 2 . ?
O12 Cl1 O11 115(2) . . ?
O22 Cl2 O21 108.6(6) . . ?
O22 Cl2 O21 108.6(6) . 11_556 ?
O21 Cl2 O21 111.4(10) . 11_556 ?
O22 Cl2 O23 109.2(8) . . ?
O21 Cl2 O23 109.4(5) . . ?
O21 Cl2 O23 109.4(5) 11_556 . ?
O34 Cl3 O32 140.8(11) . . ?
O34 Cl3 O32 140.8(11) . 10_556 ?
O32 Cl3 O32 78(2) . 10_556 ?
O34 Cl3 O31 90.2(13) . . ?
O32 Cl3 O31 103.0(18) . . ?
O32 Cl3 O31 76.6(16) 10_556 . ?
O34 Cl3 O31 90.2(13) . 10_556 ?
O32 Cl3 O31 76.6(16) . 10_556 ?
O32 Cl3 O31 103.0(18) 10_556 10_556 ?
O31 Cl3 O31 180(2) . 10_556 ?
O34 Cl3 O33 56.8(18) . 10_556 ?
O32 Cl3 O33 142(2) . 10_556 ?
O32 Cl3 O33 93(2) 10_556 10_556 ?
O31 Cl3 O33 111(2) . 10_556 ?
O31 Cl3 O33 69.4(19) 10_556 10_556 ?
O34 Cl3 O33 56.8(18) . . ?
O32 Cl3 O33 93(2) . . ?
O32 Cl3 O33 142(2) 10_556 . ?
O31 Cl3 O33 69.4(19) . . ?
O31 Cl3 O33 111(2) 10_556 . ?
O33 Cl3 O33 114(4) 10_556 . ?
Cl3 O31 O33 55.5(10) . . ?
Cl3 O31 O32 51.7(9) . 10_556 ?
O33 O31 O32 105.5(13) . 10_556 ?
Cl3 O32 O31 51.7(9) . 10_556 ?
Cl3 O32 O32 50.8(11) . 10_556 ?
O31 O32 O32 77.4(17) 10_556 10_556 ?
O34 O33 Cl3 61.1(10) . . ?
O34 O33 O31 84.5(19) . . ?
Cl3 O33 O31 55.1(10) . . ?
O33 O34 O33 124(2) . 10_556 ?
O33 O34 Cl3 62.0(10) . . ?
O33 O34 Cl3 62.0(10) 10_556 . ?
O41 Cl4 O43 122.4(16) . . ?
O41 Cl4 O42 104.0(8) . 11_556 ?
O43 Cl4 O42 105.3(10) . 11_556 ?
O41 Cl4 O42 104.0(8) . . ?
O43 Cl4 O42 105.3(10) . . ?
O42 Cl4 O42 117(2) 11_556 . ?
C101 N100 Cu1 148.1(16) . . ?
N100 C101 C102 174.9(17) . . ?

_diffrn_measured_fraction_theta_max 0.490
_diffrn_reflns_theta_full        26.10
_diffrn_measured_fraction_theta_full 0.490
_refine_diff_density_max         1.052
_refine_diff_density_min         -0.722
_refine_diff_density_rms         0.127