# Supplementary Material (ESI) for Journal of Materials Chemistry
# This journal is (C) The Royal Society of Chemistry 2007


data_global
_journal_name_full               J.Mater.Chem.

_journal_coden_Cambridge         1145

_publ_contact_author_name        'J. Veciana'
_publ_contact_author_address     
;
Institut de Ciencia de Materials
de Barcelona (CSIC)
Campus de la U.A.B. Bellaterra
Cerdanyola
Barcelona
08193
SPAIN
;

_publ_contact_author_email       VECIANAJ@ICMAB.ES

_publ_section_title              
;
A Hexacarboxylic Open-shell Building Block: Synthesis,
Structure and Magnetism of a Three-Dimensional Metal-Radical Framework
;
loop_
_publ_author_name
'J. Veciana'
'Agustin Camon'
'F. Luis'
'D. Maspoch'
'Nans Roques'
'Concepcio Rovira'
;
D.Ruiz-Molina
;
'Klaus Wurst'

data_rn59
_database_code_depnum_ccdc_archive 'CCDC 659802'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C89.60 H76.40 Cl18 Cu6 N6 O43'
_chemical_formula_weight         2944.51

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'
Cl Cl 0.1484 0.1585 '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           trigonal
_symmetry_space_group_name_H-M   R-3c

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'y, x, -z+1/2'
'x-y, -y, -z+1/2'
'-x, -x+y, -z+1/2'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'y+2/3, x+1/3, -z+5/6'
'x-y+2/3, -y+1/3, -z+5/6'
'-x+2/3, -x+y+1/3, -z+5/6'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'y+1/3, x+2/3, -z+7/6'
'x-y+1/3, -y+2/3, -z+7/6'
'-x+1/3, -x+y+2/3, -z+7/6'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-y, -x, z-1/2'
'-x+y, y, z-1/2'
'x, x-y, z-1/2'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-y+2/3, -x+1/3, z-1/6'
'-x+y+2/3, y+1/3, z-1/6'
'x+2/3, x-y+1/3, z-1/6'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'
'-y+1/3, -x+2/3, z+1/6'
'-x+y+1/3, y+2/3, z+1/6'
'x+1/3, x-y+2/3, z+1/6'

_cell_length_a                   22.3534(4)
_cell_length_b                   22.3534(3)
_cell_length_c                   41.1462(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     17805.2(4)
_cell_formula_units_Z            6
_cell_measurement_temperature    233(2)
_cell_measurement_reflns_used    61114
_cell_measurement_theta_min      1.0
_cell_measurement_theta_max      25.0

_exptl_crystal_description       prism
_exptl_crystal_colour            black
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.648
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             8880
_exptl_absorpt_coefficient_mu    1.546
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      233(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  'Nonius KappaCCD'
_diffrn_measurement_method       'phi- and omega-scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            33151
_diffrn_reflns_av_R_equivalents  0.0406
_diffrn_reflns_av_sigmaI/netI    0.0187
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_theta_min         1.82
_diffrn_reflns_theta_max         25.00
_reflns_number_total             3483
_reflns_number_gt                2907
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       COLLECT
_computing_cell_refinement       ?
_computing_data_reduction        'DENZO and SCALEPACK'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
Highly disordered structure of the triphenylmethan radical. There are
two positions of the phenyl and one carboxylat group. The phenyl rings
and carboxyl groups has common positions at C6, C7, C8 and O1. The ratio
O2, C1, C4, C5, C9, Cl1, Cl2, Cl3 to O2A, C1A, C4A, C5A, C9A, Cl1A, Cl2A,
Cl3A is around 4:1. The minor part were only refined isotropically. This
disorder leads for the Cu environment, coordinated with a well ordered
carboxylic function (C2, O3 and O4) and the disordered functions (C1, O1,
O2 and C1A, O1, O2A), to a 'trans' conformation (O4-Cu1-O2) for the major
and a 'cis' conformation (O4-Cu1-O2A) for the minor part.
This disorder causes also a disordered network of hydrogen bonded solvent
molecules around th Cu core. The THF molecule belongs to the major part and
is bonded to O6. It superposes with O2A and were refined with an occupancy
of 0.4, because it lies nearby a twofold rotation axis and split into two
positions, whereas C15, refined with occupancy of 0.8, is a common atom of
both orientations. The water molecule O7 (major part) bonds to O6 and O2
and is only partial filled (occupancy around 0.4), whereas O8 with occupancy
of O.2 and bonded to O6 and O2A belongs to the minor part. Maybe the the
real occupation is higher, because around this position there is place for
a water molecule of the major network, bonding to THF, O7 and O6.
At least a single, not bonded water molecule O9 with occupancy of 0.16667
lies nearby of the position -3 (Wyckoff later 6b, see also International
Tables of Crystallography). Hydrogen atoms for the water and THF molecules
were not found and not refined.
;

_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^)+(0.1194P)^2^+138.0242P] 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    'constr, omitted at water and THF molecules'
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3483
_refine_ls_number_parameters     316
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0772
_refine_ls_R_factor_gt           0.0656
_refine_ls_wR_factor_ref         0.1973
_refine_ls_wR_factor_gt          0.1883
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_restrained_S_all      1.062
_refine_ls_shift/su_max          0.003
_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
Cu1 Cu 0.43100(3) 0.00655(3) 0.156185(17) 0.0485(3) Uani 1 1 d . . .
N1 N 0.5159(3) 0.0678(3) 0.13039(13) 0.0543(12) Uani 1 1 d . . .
O1 O 0.4618(2) 0.0751(2) 0.19073(10) 0.0539(10) Uani 1 1 d D . .
O3 O 0.40139(18) 0.25568(18) 0.29222(9) 0.0429(8) Uani 1 1 d . . .
O4 O 0.4153(2) 0.1764(2) 0.31822(10) 0.0576(11) Uani 1 1 d . . .
O5 O 0.3600(3) -0.0569(3) 0.18703(14) 0.107(2) Uani 1 1 d . . .
O6 O 0.3598(4) 0.0339(4) 0.12812(18) 0.112(2) Uani 1 1 d . . .
C2 C 0.4274(3) 0.2178(3) 0.29569(12) 0.0400(11) Uani 1 1 d . . .
C3 C 0.6667 0.3333 0.2468(2) 0.0362(18) Uani 1 3 d S . .
C6 C 0.4768(2) 0.2230(2) 0.26900(12) 0.0355(10) Uani 1 1 d . . .
C7 C 0.5456(2) 0.2756(2) 0.26854(11) 0.0296(9) Uani 1 1 d . B .
C8 C 0.5932(2) 0.2787(2) 0.24550(11) 0.0324(10) Uani 1 1 d . . .
C10 C 0.5126(3) 0.0851(4) 0.10001(18) 0.0634(17) Uani 1 1 d . . .
H10 H 0.4692 0.0730 0.0912 0.076 Uiso 1 1 calc . . .
C11 C 0.5714(4) 0.1209(4) 0.08056(17) 0.0658(17) Uani 1 1 d . . .
H11 H 0.5676 0.1333 0.0592 0.079 Uiso 1 1 calc . . .
C12 C 0.6352(3) 0.1376(3) 0.09329(18) 0.0588(16) Uani 1 1 d . . .
C13 C 0.6377(3) 0.1196(4) 0.12552(17) 0.0622(17) Uani 1 1 d . . .
H13 H 0.6802 0.1311 0.1352 0.075 Uiso 1 1 calc . . .
C14 C 0.5773(3) 0.0848(4) 0.14306(16) 0.0632(17) Uani 1 1 d . . .
H14 H 0.5794 0.0727 0.1647 0.076 Uiso 1 1 calc . . .
Cl1 Cl 0.36809(9) 0.10936(11) 0.24300(6) 0.0519(5) Uani 0.80 1 d P A 1
Cl2 Cl 0.57193(12) 0.33393(13) 0.30034(6) 0.0363(6) Uani 0.80 1 d P B 1
Cl3 Cl 0.61900(10) 0.22965(11) 0.18930(6) 0.0469(5) Uani 0.80 1 d P A 1
O2 O 0.4493(4) 0.1543(3) 0.16591(15) 0.083(2) Uani 0.80 1 d P A 1
C1 C 0.4671(3) 0.1308(4) 0.18922(16) 0.0436(15) Uani 0.80 1 d P A 1
C4 C 0.4966(3) 0.1777(3) 0.21847(15) 0.0339(13) Uani 0.80 1 d P A 1
C5 C 0.4531(3) 0.1753(4) 0.2433(2) 0.0321(15) Uani 0.80 1 d P A 1
C9 C 0.5658(3) 0.2294(4) 0.22003(19) 0.0318(15) Uani 0.80 1 d P A 1
O7 O 0.2999(15) 0.1066(13) 0.1575(4) 0.155(9) Uani 0.40 1 d P C 1
O10 O 0.2414(18) -0.0690(17) 0.1077(12) 0.33(4) Uani 0.40 1 d P D 1
C15 C 0.1508(16) -0.1443(13) 0.0765(9) 0.216(12) Uani 0.80 1 d P D 1
C16 C 0.1942(15) -0.0716(17) 0.0873(11) 0.122(13) Uani 0.40 1 d P D 1
C17 C 0.238(2) -0.1311(18) 0.1070(8) 0.117(9) Uani 0.40 1 d P D 1
Cl1A Cl 0.3780(10) 0.0948(10) 0.2553(5) 0.119(7) Uiso 0.20 1 d P A 2
Cl2A Cl 0.5697(6) 0.3459(5) 0.2939(2) 0.029(3) Uiso 0.20 1 d P B 2
Cl3A Cl 0.6244(5) 0.2132(6) 0.1995(3) 0.056(3) Uiso 0.20 1 d P A 2
O2A O 0.520(2) 0.059(2) 0.2186(10) 0.117(11) Uiso 0.20 1 d PD A 2
C1A C 0.487(2) 0.088(2) 0.2168(8) 0.096(13) Uiso 0.20 1 d PD A 2
C4A C 0.5062(16) 0.1577(17) 0.2332(8) 0.051(7) Uiso 0.20 1 d P A 2
C5A C 0.459(2) 0.165(2) 0.2534(9) 0.044(12) Uiso 0.20 1 d P A 2
C9A C 0.5706(15) 0.2159(15) 0.2291(7) 0.023(7) Uiso 0.20 1 d P A 2
O8 O 0.235(2) -0.005(4) 0.1022(14) 0.20(3) Uani 0.20 1 d P E 2
O9 O 0.663(3) 0.361(2) 0.0606(6) 0.080(9) Uani 0.17 1 d P . .

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 0.0407(4) 0.0383(4) 0.0565(5) -0.0154(3) 0.0105(3) 0.0122(3)
N1 0.045(3) 0.046(3) 0.064(3) -0.013(2) 0.011(2) 0.016(2)
O1 0.054(2) 0.045(2) 0.054(2) -0.0176(18) 0.0041(18) 0.0172(18)
O3 0.0393(19) 0.043(2) 0.050(2) 0.0001(16) 0.0127(16) 0.0235(17)
O4 0.069(3) 0.057(2) 0.053(2) 0.009(2) 0.016(2) 0.036(2)
O5 0.091(4) 0.067(3) 0.088(4) -0.023(3) 0.045(3) -0.016(3)
O6 0.117(5) 0.132(6) 0.124(5) -0.021(4) -0.018(4) 0.090(5)
C2 0.034(3) 0.035(3) 0.044(3) -0.007(2) 0.004(2) 0.012(2)
C3 0.024(2) 0.024(2) 0.061(5) 0.000 0.000 0.0119(12)
C6 0.031(2) 0.036(3) 0.039(2) -0.005(2) 0.0048(19) 0.016(2)
C7 0.031(2) 0.027(2) 0.033(2) -0.0089(18) -0.0007(18) 0.0162(19)
C8 0.027(2) 0.026(2) 0.043(3) -0.0038(19) 0.0017(19) 0.0126(19)
C10 0.047(3) 0.064(4) 0.079(5) 0.008(3) 0.012(3) 0.027(3)
C11 0.060(4) 0.066(4) 0.080(4) 0.017(3) 0.019(3) 0.038(3)
C12 0.050(3) 0.037(3) 0.086(5) 0.003(3) 0.016(3) 0.019(3)
C13 0.049(3) 0.063(4) 0.064(4) -0.013(3) 0.008(3) 0.021(3)
C14 0.056(4) 0.059(4) 0.059(4) -0.014(3) 0.013(3) 0.018(3)
Cl1 0.0245(8) 0.0499(11) 0.0593(12) -0.0210(9) 0.0045(8) 0.0021(7)
Cl2 0.0437(11) 0.0333(11) 0.0307(11) -0.0083(9) -0.0047(8) 0.0182(9)
Cl3 0.0453(10) 0.0434(10) 0.0448(11) -0.0063(9) 0.0196(8) 0.0168(9)
O2 0.128(6) 0.072(4) 0.056(3) -0.020(3) -0.029(4) 0.054(4)
C1 0.041(4) 0.041(4) 0.041(4) -0.012(3) 0.004(3) 0.015(3)
C4 0.031(3) 0.030(3) 0.037(3) -0.009(3) 0.000(3) 0.012(3)
C5 0.023(3) 0.034(4) 0.030(4) -0.005(3) 0.001(3) 0.008(3)
C9 0.033(4) 0.032(4) 0.031(4) 0.003(3) 0.007(3) 0.017(3)
O7 0.25(3) 0.162(19) 0.087(12) 0.033(12) 0.027(14) 0.13(2)
O10 0.22(4) 0.13(2) 0.61(10) 0.00(4) -0.27(5) 0.06(2)
C15 0.23(3) 0.137(18) 0.28(3) 0.02(2) 0.01(3) 0.089(18)
C16 0.067(15) 0.091(19) 0.19(4) 0.05(2) -0.026(19) 0.026(14)
C17 0.13(3) 0.11(2) 0.097(19) 0.010(17) -0.017(18) 0.05(2)
O8 0.09(3) 0.33(8) 0.23(5) 0.18(6) 0.06(3) 0.14(4)
O9 0.13(3) 0.09(3) 0.054(13) 0.007(15) -0.01(2) 0.08(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 O1 1.947(4) . ?
Cu1 O3 1.955(3) 28 ?
Cu1 O5 1.972(5) . ?
Cu1 N1 2.001(5) . ?
Cu1 O6 2.282(7) . ?
N1 C10 1.322(9) . ?
N1 C14 1.333(9) . ?
O1 C1A 1.18(3) . ?
O1 C1 1.192(8) . ?
O3 C2 1.252(6) . ?
O3 Cu1 1.955(3) 34 ?
O4 C2 1.241(6) . ?
C2 C6 1.520(7) . ?
C3 C8 1.478(4) 2_655 ?
C3 C8 1.478(4) . ?
C3 C8 1.478(4) 3_665 ?
C6 C5A 1.32(4) . ?
C6 C7 1.394(7) . ?
C6 C5 1.404(8) . ?
C7 C8 1.400(6) . ?
C7 Cl2 1.730(5) . ?
C7 Cl2A 1.733(12) . ?
C8 C9A 1.40(3) . ?
C8 C9 1.418(8) . ?
C10 C11 1.399(9) . ?
C11 C12 1.385(9) . ?
C12 C13 1.395(10) . ?
C12 C12 1.467(12) 18_654 ?
C13 C14 1.378(9) . ?
Cl1 C5 1.726(7) . ?
Cl3 C9 1.734(6) . ?
O2 C1 1.251(9) . ?
C1 C4 1.514(8) . ?
C4 C5 1.393(9) . ?
C4 C9 1.395(9) . ?
O10 C16 1.32(4) . ?
O10 C17 1.35(5) . ?
C15 C17 1.32(4) 16_544 ?
C15 C16 1.48(4) . ?
C15 C15 1.58(5) 16_544 ?
C16 C17 1.30(5) 16_544 ?
C17 C16 1.30(5) 16_544 ?
C17 C15 1.32(4) 16_544 ?
Cl1A C5A 1.71(4) . ?
Cl3A C9A 1.73(3) . ?
O2A C1A 1.22(3) . ?
C1A C4A 1.54(5) . ?
C4A C9A 1.39(4) . ?
C4A C5A 1.41(5) . ?
O9 O9 1.15(4) 3_665 ?
O9 O9 1.15(4) 2_655 ?

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
O1 Cu1 O3 169.19(18) . 28 ?
O1 Cu1 O5 86.39(19) . . ?
O3 Cu1 O5 92.45(18) 28 . ?
O1 Cu1 N1 90.42(18) . . ?
O3 Cu1 N1 88.63(17) 28 . ?
O5 Cu1 N1 168.6(3) . . ?
O1 Cu1 O6 100.3(2) . . ?
O3 Cu1 O6 90.5(2) 28 . ?
O5 Cu1 O6 95.8(3) . . ?
N1 Cu1 O6 95.6(3) . . ?
C10 N1 C14 119.1(5) . . ?
C10 N1 Cu1 122.0(4) . . ?
C14 N1 Cu1 118.4(5) . . ?
C1A O1 C1 90(2) . . ?
C1A O1 Cu1 143(2) . . ?
C1 O1 Cu1 126.5(5) . . ?
C2 O3 Cu1 113.8(3) . 34 ?
O4 C2 O3 126.0(5) . . ?
O4 C2 C6 118.5(5) . . ?
O3 C2 C6 115.5(4) . . ?
C8 C3 C8 119.88(5) 2_655 . ?
C8 C3 C8 119.88(5) 2_655 3_665 ?
C8 C3 C8 119.88(5) . 3_665 ?
C5A C6 C7 118.8(18) . . ?
C5A C6 C5 21.9(15) . . ?
C7 C6 C5 117.9(4) . . ?
C5A C6 C2 115.4(18) . . ?
C7 C6 C2 121.9(4) . . ?
C5 C6 C2 120.1(5) . . ?
C6 C7 C8 122.9(4) . . ?
C6 C7 Cl2 116.2(3) . . ?
C8 C7 Cl2 120.8(3) . . ?
C6 C7 Cl2A 117.9(5) . . ?
C8 C7 Cl2A 118.6(5) . . ?
Cl2 C7 Cl2A 13.2(3) . . ?
C7 C8 C9A 113.0(12) . . ?
C7 C8 C9 116.1(4) . . ?
C9A C8 C9 21.4(10) . . ?
C7 C8 C3 121.3(5) . . ?
C9A C8 C3 122.6(12) . . ?
C9 C8 C3 122.5(5) . . ?
N1 C10 C11 122.3(6) . . ?
C12 C11 C10 119.0(6) . . ?
C11 C12 C13 117.8(6) . . ?
C11 C12 C12 121.9(8) . 18_654 ?
C13 C12 C12 120.2(8) . 18_654 ?
C14 C13 C12 119.4(6) . . ?
N1 C14 C13 122.4(6) . . ?
O1 C1 O2 126.4(6) . . ?
O1 C1 C4 117.6(6) . . ?
O2 C1 C4 116.0(6) . . ?
C5 C4 C9 117.6(6) . . ?
C5 C4 C1 120.1(5) . . ?
C9 C4 C1 122.0(6) . . ?
C4 C5 C6 122.1(5) . . ?
C4 C5 Cl1 118.5(5) . . ?
C6 C5 Cl1 119.4(5) . . ?
C4 C9 C8 123.1(6) . . ?
C4 C9 Cl3 116.3(5) . . ?
C8 C9 Cl3 120.5(5) . . ?
C16 O10 C17 108(3) . . ?
C17 C15 C16 55(2) 16_544 . ?
C17 C15 C15 99(2) 16_544 16_544 ?
C16 C15 C15 105(2) . 16_544 ?
C17 C16 O10 108(4) 16_544 . ?
C17 C16 C15 56(3) 16_544 . ?
O10 C16 C15 108(3) . . ?
C16 C17 C15 69(3) 16_544 16_544 ?
C16 C17 O10 110(4) 16_544 . ?
C15 C17 O10 120(3) 16_544 . ?
O1 C1A O2A 105(4) . . ?
O1 C1A C4A 121(3) . . ?
O2A C1A C4A 125(3) . . ?
C9A C4A C5A 116(3) . . ?
C9A C4A C1A 122(3) . . ?
C5A C4A C1A 122(3) . . ?
C6 C5A C4A 122(3) . . ?
C6 C5A Cl1A 123(3) . . ?
C4A C5A Cl1A 115(3) . . ?
C4A C9A C8 125(3) . . ?
C4A C9A Cl3A 118(2) . . ?
C8 C9A Cl3A 117.6(19) . . ?
O9 O9 O9 60.000(15) 3_665 2_655 ?

_diffrn_measured_fraction_theta_max 0.995
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.995
_refine_diff_density_max         0.917
_refine_diff_density_min         -0.789
_refine_diff_density_rms         0.125

# Attachment '_2__Veciana.CIF'

data_cor2
_database_code_depnum_ccdc_archive 'CCDC 659803'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C98 H94 Cl18 Cu6 N6 O40'
_chemical_formula_weight         3015.13

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'
Cl Cl 0.1484 0.1585 '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           trigonal
_symmetry_space_group_name_H-M   R-3c

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'y, x, -z+1/2'
'x-y, -y, -z+1/2'
'-x, -x+y, -z+1/2'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'y+2/3, x+1/3, -z+5/6'
'x-y+2/3, -y+1/3, -z+5/6'
'-x+2/3, -x+y+1/3, -z+5/6'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'y+1/3, x+2/3, -z+7/6'
'x-y+1/3, -y+2/3, -z+7/6'
'-x+1/3, -x+y+2/3, -z+7/6'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-y, -x, z-1/2'
'-x+y, y, z-1/2'
'x, x-y, z-1/2'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-y+2/3, -x+1/3, z-1/6'
'-x+y+2/3, y+1/3, z-1/6'
'x+2/3, x-y+1/3, z-1/6'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'
'-y+1/3, -x+2/3, z+1/6'
'-x+y+1/3, y+2/3, z+1/6'
'x+1/3, x-y+2/3, z+1/6'

_cell_length_a                   22.4479(5)
_cell_length_b                   22.4479(7)
_cell_length_c                   41.1720(6)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     17967.3(7)
_cell_formula_units_Z            6
_cell_measurement_temperature    233(2)
_cell_measurement_reflns_used    32557
_cell_measurement_theta_min      1.0
_cell_measurement_theta_max      24.0

_exptl_crystal_description       prism
_exptl_crystal_colour            blue
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.672
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             9144
_exptl_absorpt_coefficient_mu    1.532
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      233(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  'Nonius KappaCCD'
_diffrn_measurement_method       'phi- and omega-scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            30126
_diffrn_reflns_av_R_equivalents  0.0532
_diffrn_reflns_av_sigmaI/netI    0.0221
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_theta_min         1.44
_diffrn_reflns_theta_max         23.75
_reflns_number_total             3046
_reflns_number_gt                2583
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       COLLECT
_computing_cell_refinement       ?
_computing_data_reduction        'DENZO and SCALEPACK'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
Hydrogen atoms at the oxygen atoms from the coordinated water and ethanol
molecule O5 and O6 were refined with bond restraint (d=0.85 angs.).
Hydrogen atoms of solvent water and ethanol (O7 and O8) were omitted.
;

_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^)+(0.0767P)^2^+136.9081P] 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    'constr, refined at O5 and O6'
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3046
_refine_ls_number_parameters     272
_refine_ls_number_restraints     5
_refine_ls_R_factor_all          0.0624
_refine_ls_R_factor_gt           0.0506
_refine_ls_wR_factor_ref         0.1409
_refine_ls_wR_factor_gt          0.1336
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_restrained_S_all      1.074
_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
Cu1 Cu 0.43312(3) 0.00822(3) 0.156307(13) 0.0344(2) Uani 1 1 d D . .
Cl1 Cl 0.36727(6) 0.11099(7) 0.24129(3) 0.0510(4) Uani 1 1 d . . .
Cl2 Cl 0.56780(6) 0.33249(6) 0.30080(3) 0.0394(3) Uani 1 1 d . . .
Cl3 Cl 0.61925(7) 0.23066(7) 0.19077(3) 0.0445(4) Uani 1 1 d . . .
N1 N 0.5164(2) 0.0708(2) 0.13004(9) 0.0362(10) Uani 1 1 d . . .
O1 O 0.46511(18) 0.07758(18) 0.19079(8) 0.0407(9) Uani 1 1 d . . .
O2 O 0.4522(3) 0.1578(2) 0.16517(10) 0.0640(12) Uani 1 1 d D . .
O3 O 0.39979(17) 0.25422(17) 0.29281(8) 0.0355(8) Uani 1 1 d . . .
O4 O 0.4103(2) 0.17102(19) 0.31697(8) 0.0486(9) Uani 1 1 d . . .
O5 O 0.3646(3) -0.0542(2) 0.18788(10) 0.0661(13) Uani 1 1 d D . .
H5A H 0.374(5) -0.040(5) 0.2075(10) 0.14(4) Uiso 1 1 d D . .
H5B H 0.336(5) -0.0970(17) 0.187(3) 0.19(6) Uiso 1 1 d D . .
C1 C 0.4689(3) 0.1351(3) 0.18849(12) 0.0379(12) Uani 1 1 d . . .
C2 C 0.4243(2) 0.2148(2) 0.29553(11) 0.0324(11) Uani 1 1 d . . .
C3 C 0.6667 0.3333 0.2529(2) 0.040(2) Uani 1 3 d S . .
H3 H 0.6667 0.3333 0.2769 0.048 Uiso 1 3 calc S . .
C4 C 0.4967(2) 0.1807(2) 0.21843(11) 0.0320(11) Uani 1 1 d . . .
C5 C 0.4526(2) 0.1761(2) 0.24310(11) 0.0336(11) Uani 1 1 d . . .
C6 C 0.4745(2) 0.2217(2) 0.26879(10) 0.0292(10) Uani 1 1 d . . .
C7 C 0.5435(2) 0.2741(2) 0.26924(10) 0.0263(9) Uani 1 1 d . . .
C8 C 0.5918(2) 0.2792(2) 0.24615(11) 0.0259(10) Uani 1 1 d . . .
C9 C 0.5659(2) 0.2307(2) 0.22120(11) 0.0296(10) Uani 1 1 d . . .
C10 C 0.5127(3) 0.0880(3) 0.09949(12) 0.0411(12) Uani 1 1 d . . .
H10 H 0.4692 0.0744 0.0906 0.049 Uiso 1 1 calc . . .
C11 C 0.5704(3) 0.1251(3) 0.08030(12) 0.0428(12) Uani 1 1 d . . .
H11 H 0.5663 0.1370 0.0589 0.051 Uiso 1 1 calc . . .
C12 C 0.6349(3) 0.1443(3) 0.09354(12) 0.0386(12) Uani 1 1 d . . .
C13 C 0.6380(3) 0.1283(3) 0.12540(12) 0.0447(13) Uani 1 1 d . . .
H13 H 0.6807 0.1422 0.1353 0.054 Uiso 1 1 calc . . .
C14 C 0.5778(3) 0.0914(3) 0.14276(12) 0.0451(13) Uani 1 1 d . . .
H14 H 0.5805 0.0804 0.1645 0.054 Uiso 1 1 calc . . .
O6 O 0.3701(2) 0.0453(2) 0.12934(10) 0.0575(10) Uani 1 1 d D . .
H6O H 0.393(3) 0.0853(17) 0.1384(16) 0.12(3) Uiso 1 1 d D . .
C15 C 0.2999(4) 0.0138(5) 0.1359(3) 0.115(3) Uani 1 1 d . . .
H15A H 0.2933 0.0038 0.1592 0.138 Uiso 1 1 calc . . .
H15B H 0.2769 -0.0304 0.1245 0.138 Uiso 1 1 calc . . .
C16 C 0.2661(5) 0.0513(7) 0.1274(3) 0.127(4) Uani 1 1 d . . .
H16A H 0.2178 0.0245 0.1331 0.190 Uiso 1 1 calc . . .
H16B H 0.2704 0.0601 0.1042 0.190 Uiso 1 1 calc . . .
H16C H 0.2871 0.0946 0.1390 0.190 Uiso 1 1 calc . . .
O7 O 0.4362(5) 0.0000 0.2500 0.164(6) Uani 1 2 d S . .
C17 C 0.5030(7) 0.0000 0.2500 0.152(8) Uani 1 2 d S . .
C18 C 0.5576(12) 0.0624(13) 0.2612(6) 0.129(8) Uani 0.50 1 d P . .
O8 O 0.6667 0.3333 0.1018(5) 0.100(6) 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
Cu1 0.0341(4) 0.0313(4) 0.0340(4) -0.0067(2) 0.0052(2) 0.0135(3)
Cl1 0.0259(7) 0.0490(8) 0.0607(9) -0.0190(6) 0.0040(6) 0.0055(6)
Cl2 0.0402(7) 0.0370(7) 0.0365(7) -0.0154(5) -0.0049(5) 0.0158(6)
Cl3 0.0386(7) 0.0432(8) 0.0469(7) -0.0067(5) 0.0167(6) 0.0168(6)
N1 0.036(2) 0.036(2) 0.037(2) -0.0048(18) 0.0048(18) 0.018(2)
O1 0.050(2) 0.036(2) 0.0324(18) -0.0083(15) 0.0021(15) 0.0180(17)
O2 0.092(3) 0.058(3) 0.052(2) -0.014(2) -0.019(2) 0.045(3)
O3 0.0347(19) 0.0363(19) 0.0377(18) -0.0001(14) 0.0086(14) 0.0195(16)
O4 0.060(2) 0.051(2) 0.041(2) 0.0111(18) 0.0169(17) 0.033(2)
O5 0.065(3) 0.055(3) 0.044(2) -0.002(2) 0.017(2) 0.004(2)
C1 0.036(3) 0.040(3) 0.038(3) -0.006(2) 0.004(2) 0.018(2)
C2 0.028(2) 0.034(3) 0.032(2) -0.004(2) 0.0020(19) 0.013(2)
C3 0.022(3) 0.022(3) 0.077(6) 0.000 0.000 0.0110(13)
C4 0.027(3) 0.030(3) 0.034(3) -0.009(2) 0.000(2) 0.011(2)
C5 0.022(2) 0.032(3) 0.039(3) -0.007(2) -0.001(2) 0.007(2)
C6 0.026(2) 0.032(3) 0.030(2) -0.0041(19) 0.0028(19) 0.015(2)
C7 0.028(2) 0.025(2) 0.027(2) -0.0076(18) -0.0044(18) 0.014(2)
C8 0.019(2) 0.019(2) 0.039(2) -0.0003(18) 0.0003(18) 0.0092(18)
C9 0.027(2) 0.030(3) 0.033(2) -0.0020(19) 0.0081(19) 0.015(2)
C10 0.035(3) 0.046(3) 0.044(3) 0.001(2) 0.002(2) 0.021(3)
C11 0.040(3) 0.044(3) 0.046(3) 0.008(2) 0.005(2) 0.022(3)
C12 0.038(3) 0.032(3) 0.045(3) -0.001(2) 0.007(2) 0.017(2)
C13 0.036(3) 0.056(3) 0.038(3) -0.006(2) 0.000(2) 0.020(3)
C14 0.043(3) 0.052(3) 0.037(3) -0.003(2) 0.005(2) 0.022(3)
O6 0.048(2) 0.069(3) 0.064(3) -0.009(2) -0.003(2) 0.035(2)
C15 0.056(5) 0.112(8) 0.178(10) 0.003(7) -0.004(6) 0.043(5)
C16 0.098(7) 0.178(11) 0.142(9) 0.074(8) 0.037(6) 0.098(8)
O7 0.156(7) 0.305(18) 0.081(6) 0.045(8) 0.023(4) 0.153(9)
C17 0.107(8) 0.21(2) 0.174(17) 0.078(17) 0.039(8) 0.105(12)
C18 0.084(14) 0.14(2) 0.133(17) 0.005(15) -0.029(13) 0.035(14)
O8 0.096(9) 0.096(9) 0.107(13) 0.000 0.000 0.048(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 O3 1.946(3) 28 ?
Cu1 O1 1.959(3) . ?
Cu1 O5 1.966(4) . ?
Cu1 N1 2.003(4) . ?
Cu1 O6 2.259(4) . ?
Cl1 C5 1.735(5) . ?
Cl2 C7 1.730(4) . ?
Cl3 C9 1.734(4) . ?
N1 C14 1.323(7) . ?
N1 C10 1.330(6) . ?
O1 C1 1.255(6) . ?
O2 C1 1.229(6) . ?
O3 C2 1.259(6) . ?
O3 Cu1 1.946(3) 34 ?
O4 C2 1.239(6) . ?
C1 C4 1.522(7) . ?
C2 C6 1.527(6) . ?
C3 C8 1.529(5) 2_655 ?
C3 C8 1.529(5) . ?
C3 C8 1.529(5) 3_665 ?
C4 C5 1.386(7) . ?
C4 C9 1.394(7) . ?
C5 C6 1.380(6) . ?
C6 C7 1.400(6) . ?
C7 C8 1.402(6) . ?
C8 C9 1.395(6) . ?
C10 C11 1.385(7) . ?
C11 C12 1.397(7) . ?
C12 C13 1.371(7) . ?
C12 C12 1.494(10) 18_654 ?
C13 C14 1.379(7) . ?
O6 C15 1.394(10) . ?
C15 C16 1.432(13) . ?
O7 C17 1.500(18) . ?
C17 C18 1.40(2) 5 ?
C17 C18 1.40(2) . ?
O8 O8 1.52(4) 16_544 ?

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
O3 Cu1 O1 168.98(15) 28 . ?
O3 Cu1 O5 92.49(17) 28 . ?
O1 Cu1 O5 86.13(17) . . ?
O3 Cu1 N1 89.81(15) 28 . ?
O1 Cu1 N1 89.48(15) . . ?
O5 Cu1 N1 168.6(2) . . ?
O3 Cu1 O6 94.59(15) 28 . ?
O1 Cu1 O6 96.41(16) . . ?
O5 Cu1 O6 100.2(2) . . ?
N1 Cu1 O6 90.74(16) . . ?
C14 N1 C10 118.5(4) . . ?
C14 N1 Cu1 118.4(3) . . ?
C10 N1 Cu1 122.8(3) . . ?
C1 O1 Cu1 124.9(3) . . ?
C2 O3 Cu1 113.7(3) . 34 ?
O2 C1 O1 127.4(5) . . ?
O2 C1 C4 117.5(5) . . ?
O1 C1 C4 115.1(5) . . ?
O4 C2 O3 126.4(4) . . ?
O4 C2 C6 118.4(4) . . ?
O3 C2 C6 115.1(4) . . ?
C8 C3 C8 116.8(2) 2_655 . ?
C8 C3 C8 116.8(2) 2_655 3_665 ?
C8 C3 C8 116.8(2) . 3_665 ?
C5 C4 C9 117.8(4) . . ?
C5 C4 C1 120.4(4) . . ?
C9 C4 C1 121.7(4) . . ?
C6 C5 C4 122.0(4) . . ?
C6 C5 Cl1 119.5(3) . . ?
C4 C5 Cl1 118.5(3) . . ?
C5 C6 C7 117.9(4) . . ?
C5 C6 C2 120.4(4) . . ?
C7 C6 C2 121.8(4) . . ?
C6 C7 C8 123.0(4) . . ?
C6 C7 Cl2 116.3(3) . . ?
C8 C7 Cl2 120.6(3) . . ?
C9 C8 C7 115.6(4) . . ?
C9 C8 C3 128.1(5) . . ?
C7 C8 C3 116.1(5) . . ?
C4 C9 C8 123.4(4) . . ?
C4 C9 Cl3 115.6(3) . . ?
C8 C9 Cl3 121.0(3) . . ?
N1 C10 C11 122.6(5) . . ?
C10 C11 C12 118.4(4) . . ?
C13 C12 C11 118.2(5) . . ?
C13 C12 C12 120.2(6) . 18_654 ?
C11 C12 C12 121.4(6) . 18_654 ?
C12 C13 C14 119.4(5) . . ?
N1 C14 C13 122.8(5) . . ?
C15 O6 Cu1 118.3(5) . . ?
O6 C15 C16 116.8(9) . . ?
C18 C17 C18 136(3) 5 . ?
C18 C17 O7 112.0(13) 5 . ?
C18 C17 O7 112.0(13) . . ?

_diffrn_measured_fraction_theta_max 0.997
_diffrn_reflns_theta_full        23.75
_diffrn_measured_fraction_theta_full 0.997
_refine_diff_density_max         0.927
_refine_diff_density_min         -0.517
_refine_diff_density_rms         0.095