# Supplementary Material (ESI) for Chemical Communications
# This journal is (c) The Royal Society of Chemistry 2010

data_global
_journal_name_full               Chem.Commun.

_journal_coden_Cambridge         0182

_publ_contact_author_name        'Zhou, Hong-Cai'
_publ_contact_author_email       zhouh@tamu.edu

_publ_section_title              
;
Introduction of Cavities up to 4 nm into a Hierarchically-Assembled
Metal-Organic Framework Using an Angular, Tetratopic Ligand
;
loop_
_publ_author_name
'Wenjuan Zhuang'
'Shengqian Ma'
'Xi-Sen Wang'
'Da-Qiang Yuan'
;
Jian-Rong Li
;
'Dan Zhao'
'Hong-Cai Zhou'

# Attachment '- Revised_Crystallographic file.cif'

data_PCN_21
_database_code_depnum_ccdc_archive 'CCDC 735398'
#TrackingRef '- Revised_Crystallographic file.cif'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C41 H28 Cu2 O10'
_chemical_formula_weight         807.71

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0015 0.0009 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3240 0.8257 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0056 0.0036 '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'

_symmetry_cell_setting           Cubic
_symmetry_space_group_name_H-M   'I m -3 m'

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

_cell_length_a                   67.283(10)
_cell_length_b                   67.283(10)
_cell_length_c                   67.283(10)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     304590(78)
_cell_formula_units_Z            96
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    9069
_cell_measurement_theta_min      2.1515
_cell_measurement_theta_max      9.8455

_exptl_crystal_description       prism
_exptl_crystal_colour            green
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    0.423
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             39552
_exptl_absorpt_coefficient_mu    0.187
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9852
_exptl_absorpt_correction_T_max  0.9907
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      173(2)
_diffrn_radiation_wavelength     0.41328
_diffrn_radiation_type           synchrotron
_diffrn_radiation_source         'APS 15-ID'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'SMART APEXII CCD area detector'
_diffrn_measurement_method       omega
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            263037
_diffrn_reflns_av_R_equivalents  0.1786
_diffrn_reflns_av_sigmaI/netI    0.0534
_diffrn_reflns_limit_h_min       -56
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_k_min       -56
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_l_min       -55
_diffrn_reflns_limit_l_max       55
_diffrn_reflns_theta_min         0.75
_diffrn_reflns_theta_max         9.92
_reflns_number_total             8388
_reflns_number_gt                6501
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2 Version 1.0-27 (Bruker, 2004)'
_computing_cell_refinement       'Bruker SAINT version 7.12A (Bruker, 2004)'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_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 crystal has a very weak diffraction, therefore not many high angle
reflections have been detected. PCN-21 has a complicated porous structure
with unusually large cavities; the solvent accessible volume in the
dehydrated structure is 79.3 % calculated from PLATON software.
The cavities in the framework are filled with many disordered solvent
molecules, which can not be located. Hence reflect on a high R(int)
value. In the refinement we used SQEEZE procedure to remove solvent electron
density from cavities which give a smaller final R(int) and R-value compared
with the original R(int) and R-value.
;

_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^)+(0.0841P)^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    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         8388
_refine_ls_number_parameters     499
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0675
_refine_ls_R_factor_gt           0.0487
_refine_ls_wR_factor_ref         0.1313
_refine_ls_wR_factor_gt          0.1244
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_restrained_S_all      1.008
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000

# SQUEEZE RESULTS (APPEND TO CIF)
# Note: Data are Listed for all Voids in the P1 Unit Cell
# i.e. Centre of Gravity, Solvent Accessible Volume,
# Recovered number of Electrons in the Void and
# Details about the Squeezed Material
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.017 -0.004 -0.003 241851 94536 ' '

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 0.122880(12) 0.5000 0.314840(12) 0.0681(3) Uani 1 2 d S . .
Cu2 Cu 0.095250(12) 0.5000 0.342426(12) 0.0728(3) Uani 1 2 d S . .
Cu3 Cu 0.099146(12) 0.266207(9) 0.266207(9) 0.0727(3) Uani 1 2 d S . .
Cu4 Cu 0.063531(11) 0.254706(8) 0.254706(8) 0.0664(3) Uani 1 2 d S . .
O1 O 0.10630(6) 0.47913(5) 0.30323(5) 0.0765(10) Uani 1 1 d . . .
O2 O 0.08229(6) 0.48002(5) 0.32669(6) 0.0915(13) Uani 1 1 d . . .
O3 O 0.08790(7) 0.29315(5) 0.26404(5) 0.0818(11) Uani 1 1 d . . .
O4 O 0.05800(6) 0.28331(6) 0.25431(5) 0.0742(10) Uani 1 1 d . . .
O5 O 0.10499(6) 0.23816(7) 0.26673(5) 0.0897(13) Uani 1 1 d . . .
O6 O 0.07442(7) 0.22830(5) 0.25683(5) 0.0845(12) Uani 1 1 d . . .
O7 O 0.01987(5) 0.16851(6) 0.36407(5) 0.0779(11) Uani 1 1 d . . .
O8 O 0.02007(5) 0.14544(6) 0.38806(7) 0.0971(13) Uani 1 1 d . . .
O9 O 0.14537(6) 0.5000 0.29161(6) 0.0878(14) Uani 1 2 d S . .
O10 O 0.07293(8) 0.5000 0.36617(8) 0.1322(19) Uani 1 2 d S . .
O11 O 0.12819(7) 0.27580(6) 0.27580(6) 0.1217(18) Uani 1 2 d S . .
O12 O 0.03421(6) 0.24593(5) 0.24593(5) 0.1024(16) Uani 1 2 d S . .
C1 C 0.09039(10) 0.47325(7) 0.31182(11) 0.0686(16) Uani 1 1 d . . .
C2 C 0.07914(13) 0.45701(9) 0.30051(9) 0.0837(16) Uani 1 1 d . . .
C3 C 0.08848(8) 0.44415(12) 0.28708(11) 0.0843(15) Uani 1 1 d . . .
H3 H 0.1023 0.4456 0.2846 0.101 Uiso 1 1 calc R . .
C4 C 0.07812(13) 0.42959(9) 0.27757(8) 0.0837(17) Uani 1 1 d . . .
H4 H 0.0849 0.4211 0.2685 0.100 Uiso 1 1 calc R . .
C5 C 0.05768(12) 0.42689(10) 0.28085(11) 0.090(2) Uani 1 1 d . . .
C6 C 0.04889(9) 0.43994(13) 0.29331(12) 0.106(2) Uani 1 1 d . . .
H6 H 0.0349 0.4391 0.2951 0.127 Uiso 1 1 calc R . .
C7 C 0.05899(14) 0.45427(10) 0.30353(9) 0.105(2) Uani 1 1 d . . .
H7 H 0.0521 0.4624 0.3128 0.126 Uiso 1 1 calc R . .
C8 C 0.04632(11) 0.41083(12) 0.26957(8) 0.0892(19) Uani 1 1 d . . .
C9 C 0.05353(9) 0.39155(13) 0.26830(10) 0.0870(19) Uani 1 1 d . . .
H9 H 0.0657 0.3882 0.2746 0.104 Uiso 1 1 calc R . .
C10 C 0.04305(10) 0.37694(12) 0.25776(8) 0.0708(16) Uani 1 1 d . . .
C11 C 0.02654(11) 0.38285(9) 0.24908(8) 0.0751(15) Uani 1 1 d . . .
H11 H 0.0196 0.3730 0.2417 0.090 Uiso 1 1 calc R . .
C12 C 0.01782(9) 0.40218(11) 0.24941(8) 0.0767(19) Uani 1 1 d U . .
C13 C 0.02797(10) 0.41562(10) 0.25984(10) 0.093(2) Uani 1 1 d . . .
H13 H 0.0229 0.4288 0.2609 0.112 Uiso 1 1 calc R . .
C14 C 0.0000 0.40828(9) 0.23945(10) 0.0654(19) Uani 1 2 d S . .
H14A H 0.0000 0.4027 0.2258 0.078 Uiso 1 2 calc SR . .
H14B H 0.0000 0.4229 0.2383 0.078 Uiso 1 2 calc SR . .
C15 C 0.05073(12) 0.35684(11) 0.25761(8) 0.0754(15) Uani 1 1 d . . .
C16 C 0.07017(13) 0.35198(12) 0.26051(8) 0.0974(19) Uani 1 1 d . . .
H16 H 0.0796 0.3623 0.2627 0.117 Uiso 1 1 calc R . .
C17 C 0.07648(9) 0.33263(16) 0.26033(8) 0.0992(18) Uani 1 1 d . . .
H17 H 0.0902 0.3297 0.2620 0.119 Uiso 1 1 calc R . .
C18 C 0.06272(13) 0.31711(10) 0.25768(7) 0.0648(14) Uani 1 1 d . . .
C19 C 0.04386(12) 0.32197(11) 0.25528(8) 0.0841(18) Uani 1 1 d . . .
H19 H 0.0342 0.3118 0.2536 0.101 Uiso 1 1 calc R . .
C20 C 0.03795(8) 0.34120(15) 0.25521(8) 0.0894(17) Uani 1 1 d . . .
H20 H 0.0242 0.3440 0.2534 0.107 Uiso 1 1 calc R . .
C21 C 0.07004(11) 0.29661(11) 0.25892(8) 0.0688(15) Uani 1 1 d . . .
C22 C 0.09249(14) 0.22545(10) 0.26126(8) 0.077(2) Uani 1 1 d . . .
C23 C 0.09886(12) 0.20426(13) 0.26150(9) 0.0810(18) Uani 1 1 d . . .
C24 C 0.11768(13) 0.19907(12) 0.26873(9) 0.1059(19) Uani 1 1 d . . .
H24 H 0.1262 0.2092 0.2735 0.127 Uiso 1 1 calc R . .
C25 C 0.12419(9) 0.17947(15) 0.26909(10) 0.112(2) Uani 1 1 d . . .
H25 H 0.1370 0.1763 0.2741 0.134 Uiso 1 1 calc R . .
C26 C 0.11192(13) 0.16451(11) 0.26208(9) 0.0849(18) Uani 1 1 d . . .
C27 C 0.09301(12) 0.16945(12) 0.25543(8) 0.0948(17) Uani 1 1 d . . .
H27 H 0.0842 0.1593 0.2511 0.114 Uiso 1 1 calc R . .
C28 C 0.08686(10) 0.18943(14) 0.25514(8) 0.0832(16) Uani 1 1 d . . .
H28 H 0.0740 0.1926 0.2504 0.100 Uiso 1 1 calc R . .
C29 C 0.11739(9) 0.14264(11) 0.26279(7) 0.0835(17) Uani 1 1 d . . .
C30 C 0.13707(8) 0.13707(8) 0.26161(10) 0.082(2) Uani 1 2 d S . .
H30 H 0.1470 0.1470 0.2600 0.099 Uiso 1 2 calc SR . .
C31 C 0.10314(9) 0.12773(12) 0.26573(7) 0.0910(18) Uani 1 1 d . . .
H31 H 0.0895 0.1314 0.2666 0.109 Uiso 1 1 calc R . .
C32 C 0.10808(12) 0.10808(12) 0.26743(11) 0.085(3) Uani 1 2 d S . .
C33 C 0.09287(10) 0.09287(10) 0.27276(14) 0.092(2) Uani 1 2 d S . .
H33A H 0.0967 0.0799 0.2670 0.110 Uiso 0.50 1 calc PR . .
H33B H 0.0799 0.0967 0.2670 0.110 Uiso 0.50 1 calc PR . .
C34 C 0.09085(7) 0.09085(7) 0.29488(14) 0.081(2) Uani 1 2 d S . .
C35 C 0.07856(7) 0.10340(7) 0.30552(13) 0.0936(18) Uani 1 1 d . . .
H35 H 0.0705 0.1126 0.2985 0.112 Uiso 1 1 calc R . .
C36 C 0.07765(10) 0.10304(10) 0.32597(11) 0.0962(19) Uani 1 1 d . . .
C37 C 0.09041(9) 0.09041(9) 0.33555(14) 0.117(3) Uani 1 2 d S . .
H37 H 0.0905 0.0905 0.3497 0.140 Uiso 1 2 calc SR . .
C38 C 0.06448(10) 0.11556(12) 0.33654(11) 0.0839(18) Uani 1 1 d . . .
C39 C 0.05628(11) 0.10930(9) 0.35400(14) 0.117(2) Uani 1 1 d . . .
H39 H 0.0590 0.0962 0.3586 0.140 Uiso 1 1 calc R . .
C40 C 0.04413(10) 0.12150(15) 0.36516(8) 0.111(2) Uani 1 1 d . . .
H40 H 0.0391 0.1168 0.3775 0.133 Uiso 1 1 calc R . .
C41 C 0.03910(10) 0.14068(11) 0.35864(13) 0.0899(19) Uani 1 1 d . . .
C42 C 0.04655(10) 0.14693(9) 0.34120(12) 0.0900(19) Uani 1 1 d . . .
H42 H 0.0434 0.1597 0.3361 0.108 Uiso 1 1 calc R . .
C43 C 0.05896(10) 0.13407(15) 0.33073(8) 0.0967(17) Uani 1 1 d . . .
H43 H 0.0640 0.1387 0.3184 0.116 Uiso 1 1 calc R . .
C44 C 0.02546(8) 0.15282(11) 0.37158(11) 0.0782(17) Uani 1 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cu1 0.0716(6) 0.0545(6) 0.0782(6) 0.000 -0.0123(5) 0.000
Cu2 0.0730(6) 0.0623(6) 0.0831(7) 0.000 -0.0065(5) 0.000
Cu3 0.0687(6) 0.0747(4) 0.0747(4) 0.0071(5) 0.0110(3) 0.0110(3)
Cu4 0.0737(6) 0.0627(4) 0.0627(4) 0.0069(4) 0.0124(3) 0.0124(3)
O1 0.085(3) 0.063(3) 0.082(3) -0.0008(18) -0.015(2) -0.008(2)
O2 0.089(3) 0.074(3) 0.111(3) -0.024(2) 0.005(2) -0.003(2)
O3 0.079(3) 0.063(3) 0.104(3) 0.0017(18) 0.004(2) 0.009(2)
O4 0.079(3) 0.047(3) 0.097(3) -0.0019(18) 0.0001(19) 0.007(2)
O5 0.097(3) 0.074(3) 0.099(3) 0.004(2) 0.000(2) 0.020(2)
O6 0.082(3) 0.074(3) 0.098(3) 0.0184(19) 0.008(2) 0.028(2)
O7 0.067(3) 0.076(3) 0.091(3) -0.015(2) 0.0102(19) 0.022(2)
O8 0.098(3) 0.101(3) 0.092(3) 0.004(2) 0.013(2) 0.027(2)
O9 0.083(3) 0.105(4) 0.076(3) 0.000 0.003(3) 0.000
O10 0.138(5) 0.147(5) 0.111(4) 0.000 0.022(3) 0.000
O11 0.081(4) 0.142(3) 0.142(3) 0.010(4) -0.001(2) -0.001(2)
O12 0.076(3) 0.115(2) 0.115(2) 0.012(3) -0.010(2) -0.010(2)
C1 0.080(5) 0.011(4) 0.114(6) -0.006(4) -0.014(5) -0.013(4)
C2 0.092(7) 0.070(5) 0.089(5) 0.000(5) 0.007(4) 0.003(5)
C3 0.088(5) 0.069(4) 0.095(5) -0.005(4) 0.009(5) -0.012(5)
C4 0.102(7) 0.050(4) 0.098(4) -0.019(3) -0.007(4) -0.012(4)
C5 0.054(6) 0.081(6) 0.134(6) 0.009(5) 0.002(4) 0.017(5)
C6 0.053(4) 0.102(5) 0.162(6) -0.055(5) -0.009(5) -0.008(5)
C7 0.076(6) 0.101(6) 0.138(6) -0.047(4) 0.015(5) -0.017(4)
C8 0.081(6) 0.074(6) 0.113(5) -0.048(4) 0.009(4) -0.055(5)
C9 0.083(5) 0.053(5) 0.126(5) 0.010(4) 0.016(4) 0.030(5)
C10 0.066(5) 0.045(6) 0.102(4) -0.020(4) -0.020(3) -0.021(5)
C11 0.066(5) 0.048(5) 0.111(5) -0.006(3) -0.009(4) 0.001(4)
C12 0.054(4) 0.088(5) 0.089(4) -0.028(3) -0.027(3) -0.042(5)
C13 0.028(4) 0.118(6) 0.134(5) 0.016(5) -0.004(4) 0.020(4)
C14 0.059(6) 0.064(5) 0.073(5) -0.020(4) 0.000 0.000
C15 0.069(6) 0.034(6) 0.123(5) -0.004(3) -0.004(3) -0.007(6)
C16 0.060(6) 0.066(7) 0.167(6) -0.001(4) -0.016(4) 0.003(4)
C17 0.066(5) 0.076(6) 0.156(6) -0.006(4) -0.004(3) 0.023(6)
C18 0.082(6) 0.035(6) 0.077(4) -0.001(3) 0.013(3) 0.006(6)
C19 0.051(6) 0.050(7) 0.151(5) -0.011(3) -0.003(3) 0.024(4)
C20 0.063(5) 0.059(5) 0.146(5) -0.015(3) -0.015(3) 0.023(6)
C21 0.068(6) 0.054(6) 0.084(4) -0.005(3) 0.017(3) 0.000(5)
C22 0.128(8) 0.037(6) 0.066(4) 0.005(3) 0.034(4) 0.052(6)
C23 0.056(5) 0.107(8) 0.080(4) 0.014(4) 0.010(3) 0.004(6)
C24 0.103(7) 0.076(6) 0.138(5) 0.015(4) -0.001(5) 0.028(4)
C25 0.076(5) 0.091(7) 0.168(6) 0.017(5) -0.015(4) -0.002(6)
C26 0.081(6) 0.076(7) 0.098(4) 0.029(4) 0.024(4) 0.057(6)
C27 0.093(6) 0.070(7) 0.122(5) 0.006(3) -0.021(4) 0.033(4)
C28 0.079(5) 0.076(5) 0.094(4) 0.012(4) 0.007(4) 0.043(6)
C29 0.061(5) 0.095(7) 0.095(4) 0.016(3) 0.005(3) 0.041(6)
C30 0.063(3) 0.063(3) 0.121(7) 0.021(3) 0.021(3) 0.029(6)
C31 0.048(5) 0.123(7) 0.103(4) 0.013(4) 0.004(3) 0.018(5)
C32 0.067(4) 0.067(4) 0.122(7) 0.010(4) 0.010(4) 0.056(7)
C33 0.075(4) 0.075(4) 0.124(9) 0.004(4) 0.004(4) 0.022(5)
C34 0.086(4) 0.086(4) 0.071(7) 0.016(3) 0.016(3) 0.026(6)
C35 0.066(4) 0.077(4) 0.138(7) 0.003(4) 0.039(4) 0.047(3)
C36 0.107(5) 0.108(6) 0.073(6) 0.005(5) 0.043(5) 0.044(5)
C37 0.116(5) 0.116(5) 0.119(8) 0.033(4) 0.033(4) 0.091(7)
C38 0.103(5) 0.068(6) 0.080(6) 0.029(5) 0.034(5) 0.048(4)
C39 0.135(6) 0.095(5) 0.120(6) 0.028(5) 0.054(5) 0.048(5)
C40 0.107(5) 0.146(7) 0.081(5) 0.011(6) 0.046(4) 0.054(5)
C41 0.090(5) 0.070(6) 0.109(7) 0.001(5) -0.015(6) 0.034(5)
C42 0.111(5) 0.093(5) 0.066(5) 0.022(5) 0.036(4) 0.031(5)
C43 0.104(5) 0.113(7) 0.073(5) 0.007(6) 0.027(4) 0.020(4)
C44 0.041(4) 0.090(6) 0.104(6) -0.006(6) 0.008(4) 0.033(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 O7 1.953(4) 41 ?
Cu1 O7 1.953(4) 83 ?
Cu1 O1 1.956(4) . ?
Cu1 O1 1.956(4) 57_565 ?
Cu1 O9 2.175(4) . ?
Cu1 Cu2 2.6270(12) . ?
Cu2 O2 1.920(4) . ?
Cu2 O2 1.920(4) 57_565 ?
Cu2 O8 1.936(4) 41 ?
Cu2 O8 1.936(4) 83 ?
Cu2 O10 2.193(5) . ?
Cu3 O5 1.928(4) . ?
Cu3 O5 1.928(4) 70 ?
Cu3 O3 1.970(4) . ?
Cu3 O3 1.970(4) 70 ?
Cu3 O11 2.157(5) . ?
Cu3 Cu4 2.6343(12) . ?
Cu4 O6 1.927(4) 70 ?
Cu4 O6 1.927(4) . ?
Cu4 O4 1.961(4) 70 ?
Cu4 O4 1.961(4) . ?
Cu4 O12 2.142(4) . ?
O1 C1 1.279(6) . ?
O2 C1 1.227(6) . ?
O3 C21 1.271(6) . ?
O4 C21 1.246(6) . ?
O5 C22 1.254(7) . ?
O6 C22 1.267(7) . ?
O7 C44 1.229(6) . ?
O7 Cu1 1.953(4) 84 ?
O8 C44 1.268(6) . ?
O8 Cu2 1.936(4) 84 ?
C1 C2 1.532(7) . ?
C2 C7 1.384(7) . ?
C2 C3 1.400(7) . ?
C3 C4 1.362(6) . ?
C3 H3 0.9500 . ?
C4 C5 1.405(7) . ?
C4 H4 0.9500 . ?
C5 C6 1.351(7) . ?
C5 C8 1.526(7) . ?
C6 C7 1.365(7) . ?
C6 H6 0.9500 . ?
C7 H7 0.9500 . ?
C8 C9 1.388(7) . ?
C8 C13 1.434(7) . ?
C9 C10 1.402(7) . ?
C9 H9 0.9500 . ?
C10 C11 1.316(6) . ?
C10 C15 1.448(7) . ?
C11 C12 1.427(7) . ?
C11 H11 0.9500 . ?
C12 C13 1.333(7) . ?
C12 C14 1.434(7) . ?
C13 H13 0.9500 . ?
C14 C12 1.434(7) 54 ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C15 C16 1.362(7) . ?
C15 C20 1.369(6) . ?
C16 C17 1.369(7) . ?
C16 H16 0.9500 . ?
C17 C18 1.407(7) . ?
C17 H17 0.9500 . ?
C18 C19 1.321(6) . ?
C18 C21 1.467(7) . ?
C19 C20 1.353(6) . ?
C19 H19 0.9500 . ?
C20 H20 0.9500 . ?
C22 C23 1.488(8) . ?
C23 C28 1.353(6) . ?
C23 C24 1.401(7) . ?
C24 C25 1.390(7) . ?
C24 H24 0.9500 . ?
C25 C26 1.384(7) . ?
C25 H25 0.9500 . ?
C26 C27 1.389(7) . ?
C26 C29 1.518(7) . ?
C27 C28 1.406(7) . ?
C27 H27 0.9500 . ?
C28 H28 0.9500 . ?
C29 C30 1.379(6) . ?
C29 C31 1.402(7) . ?
C30 C29 1.379(6) 68 ?
C30 H30 0.9500 . ?
C31 C32 1.368(7) . ?
C31 H31 0.9500 . ?
C32 C31 1.368(7) 68 ?
C32 C33 1.490(10) . ?
C33 C34 1.501(9) . ?
C33 H33A 0.9900 . ?
C33 H33B 0.9900 . ?
C34 C35 1.382(6) . ?
C34 C35 1.382(6) 68 ?
C35 C36 1.377(7) . ?
C35 H35 0.9500 . ?
C36 C37 1.369(8) . ?
C36 C38 1.415(7) . ?
C37 C36 1.369(8) 68 ?
C37 H37 0.9500 . ?
C38 C43 1.357(7) . ?
C38 C39 1.364(7) . ?
C39 C40 1.381(7) . ?
C39 H39 0.9500 . ?
C40 C41 1.404(7) . ?
C40 H40 0.9500 . ?
C41 C42 1.344(7) . ?
C41 C44 1.506(8) . ?
C42 C43 1.394(7) . ?
C42 H42 0.9500 . ?
C43 H43 0.9500 . ?

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
O7 Cu1 O7 86.39(18) 41 83 ?
O7 Cu1 O1 167.68(18) 41 . ?
O7 Cu1 O1 89.67(13) 83 . ?
O7 Cu1 O1 89.66(13) 41 57_565 ?
O7 Cu1 O1 167.67(18) 83 57_565 ?
O1 Cu1 O1 91.76(18) . 57_565 ?
O7 Cu1 O9 95.70(15) 41 . ?
O7 Cu1 O9 95.70(15) 83 . ?
O1 Cu1 O9 96.31(15) . . ?
O1 Cu1 O9 96.30(15) 57_565 . ?
O7 Cu1 Cu2 85.00(13) 41 . ?
O7 Cu1 Cu2 85.00(13) 83 . ?
O1 Cu1 Cu2 83.03(12) . . ?
O1 Cu1 Cu2 83.03(12) 57_565 . ?
O9 Cu1 Cu2 179.03(12) . . ?
O2 Cu2 O2 88.9(2) . 57_565 ?
O2 Cu2 O8 169.63(19) . 41 ?
O2 Cu2 O8 90.44(15) 57_565 41 ?
O2 Cu2 O8 90.44(15) . 83 ?
O2 Cu2 O8 169.63(19) 57_565 83 ?
O8 Cu2 O8 88.4(2) 41 83 ?
O2 Cu2 O10 95.20(17) . . ?
O2 Cu2 O10 95.20(17) 57_565 . ?
O8 Cu2 O10 95.16(17) 41 . ?
O8 Cu2 O10 95.16(17) 83 . ?
O2 Cu2 Cu1 86.09(13) . . ?
O2 Cu2 Cu1 86.09(13) 57_565 . ?
O8 Cu2 Cu1 83.54(13) 41 . ?
O8 Cu2 Cu1 83.54(13) 83 . ?
O10 Cu2 Cu1 178.18(15) . . ?
O5 Cu3 O5 89.7(2) . 70 ?
O5 Cu3 O3 168.66(19) . . ?
O5 Cu3 O3 89.38(14) 70 . ?
O5 Cu3 O3 89.38(14) . 70 ?
O5 Cu3 O3 168.65(19) 70 70 ?
O3 Cu3 O3 89.35(18) . 70 ?
O5 Cu3 O11 95.90(17) . . ?
O5 Cu3 O11 95.90(17) 70 . ?
O3 Cu3 O11 95.44(16) . . ?
O3 Cu3 O11 95.44(16) 70 . ?
O5 Cu3 Cu4 84.45(13) . . ?
O5 Cu3 Cu4 84.44(13) 70 . ?
O3 Cu3 Cu4 84.21(13) . . ?
O3 Cu3 Cu4 84.21(13) 70 . ?
O11 Cu3 Cu4 179.51(17) . . ?
O6 Cu4 O6 89.54(19) 70 . ?
O6 Cu4 O4 168.04(18) 70 70 ?
O6 Cu4 O4 89.25(13) . 70 ?
O6 Cu4 O4 89.25(13) 70 . ?
O6 Cu4 O4 168.03(18) . . ?
O4 Cu4 O4 89.46(18) 70 . ?
O6 Cu4 O12 96.68(16) 70 . ?
O6 Cu4 O12 96.68(16) . . ?
O4 Cu4 O12 95.28(15) 70 . ?
O4 Cu4 O12 95.29(15) . . ?
O6 Cu4 Cu3 84.45(13) 70 . ?
O6 Cu4 Cu3 84.45(13) . . ?
O4 Cu4 Cu3 83.59(12) 70 . ?
O4 Cu4 Cu3 83.58(12) . . ?
O12 Cu4 Cu3 178.40(15) . . ?
C1 O1 Cu1 121.3(4) . . ?
C1 O2 Cu2 120.5(4) . . ?
C21 O3 Cu3 123.5(4) . . ?
C21 O4 Cu4 125.3(4) . . ?
C22 O5 Cu3 121.7(4) . . ?
C22 O6 Cu4 121.5(4) . . ?
C44 O7 Cu1 121.2(4) . 84 ?
C44 O8 Cu2 122.8(4) . 84 ?
O2 C1 O1 128.7(5) . . ?
O2 C1 C2 116.8(6) . . ?
O1 C1 C2 114.2(6) . . ?
C7 C2 C3 116.9(5) . . ?
C7 C2 C1 120.4(7) . . ?
C3 C2 C1 122.7(8) . . ?
C4 C3 C2 121.2(5) . . ?
C4 C3 H3 119.4 . . ?
C2 C3 H3 119.4 . . ?
C3 C4 C5 121.4(5) . . ?
C3 C4 H4 119.3 . . ?
C5 C4 H4 119.3 . . ?
C6 C5 C4 116.2(6) . . ?
C6 C5 C8 123.4(7) . . ?
C4 C5 C8 120.3(7) . . ?
C5 C6 C7 123.6(6) . . ?
C5 C6 H6 118.2 . . ?
C7 C6 H6 118.2 . . ?
C6 C7 C2 120.5(5) . . ?
C6 C7 H7 119.7 . . ?
C2 C7 H7 119.7 . . ?
C9 C8 C13 118.9(5) . . ?
C9 C8 C5 121.2(8) . . ?
C13 C8 C5 120.0(8) . . ?
C8 C9 C10 120.7(6) . . ?
C8 C9 H9 119.7 . . ?
C10 C9 H9 119.7 . . ?
C11 C10 C9 115.9(6) . . ?
C11 C10 C15 125.5(6) . . ?
C9 C10 C15 118.6(7) . . ?
C10 C11 C12 128.0(5) . . ?
C10 C11 H11 116.0 . . ?
C12 C11 H11 116.0 . . ?
C13 C12 C11 114.6(5) . . ?
C13 C12 C14 118.7(6) . . ?
C11 C12 C14 126.7(6) . . ?
C12 C13 C8 121.9(6) . . ?
C12 C13 H13 119.0 . . ?
C8 C13 H13 119.0 . . ?
C12 C14 C12 113.5(6) . 54 ?
C12 C14 H14A 108.9 . . ?
C12 C14 H14A 108.9 54 . ?
C12 C14 H14B 108.9 . . ?
C12 C14 H14B 108.9 54 . ?
H14A C14 H14B 107.7 . . ?
C16 C15 C20 115.8(5) . . ?
C16 C15 C10 124.5(7) . . ?
C20 C15 C10 119.6(8) . . ?
C15 C16 C17 121.7(5) . . ?
C15 C16 H16 119.2 . . ?
C17 C16 H16 119.2 . . ?
C16 C17 C18 120.2(5) . . ?
C16 C17 H17 119.9 . . ?
C18 C17 H17 119.9 . . ?
C19 C18 C17 117.6(5) . . ?
C19 C18 C21 124.2(7) . . ?
C17 C18 C21 118.0(8) . . ?
C18 C19 C20 121.3(5) . . ?
C18 C19 H19 119.3 . . ?
C20 C19 H19 119.3 . . ?
C19 C20 C15 123.3(5) . . ?
C19 C20 H20 118.3 . . ?
C15 C20 H20 118.3 . . ?
O4 C21 O3 123.4(6) . . ?
O4 C21 C18 116.3(6) . . ?
O3 C21 C18 120.3(6) . . ?
O5 C22 O6 127.5(5) . . ?
O5 C22 C23 117.2(7) . . ?
O6 C22 C23 115.1(7) . . ?
C28 C23 C24 117.7(6) . . ?
C28 C23 C22 122.1(7) . . ?
C24 C23 C22 120.2(8) . . ?
C25 C24 C23 121.8(6) . . ?
C25 C24 H24 119.1 . . ?
C23 C24 H24 119.1 . . ?
C26 C25 C24 119.7(6) . . ?
C26 C25 H25 120.1 . . ?
C24 C25 H25 120.1 . . ?
C25 C26 C27 118.8(5) . . ?
C25 C26 C29 123.3(8) . . ?
C27 C26 C29 117.7(8) . . ?
C26 C27 C28 120.2(6) . . ?
C26 C27 H27 119.9 . . ?
C28 C27 H27 119.9 . . ?
C23 C28 C27 121.7(6) . . ?
C23 C28 H28 119.2 . . ?
C27 C28 H28 119.2 . . ?
C30 C29 C31 118.1(5) . . ?
C30 C29 C26 119.6(6) . . ?
C31 C29 C26 122.2(5) . . ?
C29 C30 C29 121.2(7) 68 . ?
C29 C30 H30 119.4 68 . ?
C29 C30 H30 119.4 . . ?
C32 C31 C29 122.5(6) . . ?
C32 C31 H31 118.7 . . ?
C29 C31 H31 118.7 . . ?
C31 C32 C31 117.6(8) 68 . ?
C31 C32 C33 121.1(4) 68 . ?
C31 C32 C33 121.1(4) . . ?
C32 C33 C34 111.3(7) . . ?
C32 C33 H33A 109.4 . . ?
C34 C33 H33A 109.4 . . ?
C32 C33 H33B 109.4 . . ?
C34 C33 H33B 109.4 . . ?
H33A C33 H33B 108.0 . . ?
C35 C34 C35 117.6(8) . 68 ?
C35 C34 C33 120.8(4) . . ?
C35 C34 C33 120.8(4) 68 . ?
C36 C35 C34 122.2(6) . . ?
C36 C35 H35 118.9 . . ?
C34 C35 H35 118.9 . . ?
C37 C36 C35 117.0(6) . . ?
C37 C36 C38 121.7(6) . . ?
C35 C36 C38 121.3(5) . . ?
C36 C37 C36 123.8(9) 68 . ?
C36 C37 H37 118.1 68 . ?
C36 C37 H37 118.1 . . ?
C43 C38 C39 114.9(6) . . ?
C43 C38 C36 125.0(7) . . ?
C39 C38 C36 120.1(7) . . ?
C38 C39 C40 121.6(6) . . ?
C38 C39 H39 119.2 . . ?
C40 C39 H39 119.2 . . ?
C39 C40 C41 121.3(6) . . ?
C39 C40 H40 119.4 . . ?
C41 C40 H40 119.4 . . ?
C42 C41 C40 118.1(6) . . ?
C42 C41 C44 124.2(7) . . ?
C40 C41 C44 117.7(8) . . ?
C41 C42 C43 118.1(5) . . ?
C41 C42 H42 121.0 . . ?
C43 C42 H42 121.0 . . ?
C38 C43 C42 126.1(6) . . ?
C38 C43 H43 117.0 . . ?
C42 C43 H43 117.0 . . ?
O7 C44 O8 127.5(6) . . ?
O7 C44 C41 114.5(7) . . ?
O8 C44 C41 117.9(6) . . ?

_diffrn_measured_fraction_theta_max 0.992
_diffrn_reflns_theta_full        9.92
_diffrn_measured_fraction_theta_full 0.992
_refine_diff_density_max         0.147
_refine_diff_density_min         -0.269
_refine_diff_density_rms         0.033