# Electronic Supplementary Material (ESI) for Dalton Transactions
# This journal is © The Royal Society of Chemistry 2011


data_global

_journal_coden_Cambridge         222

loop_
_publ_author_name
'Kirillov, Alexander'

_publ_contact_author_name        'Kirillov, Alexander'
_publ_contact_author_email       kirillov@ist.utl.pt

_publ_section_title              
;
New Diamandoid-like [Cu3B(u-O)6] Core Self-assembled from
Bis-Tris Biobuffer for Mild Hydrocarboxylation of Alkanes
to Carboxylic Acids
;

# Attachment '- CIF-1.cif'

data_test42bds
_database_code_depnum_ccdc_archive 'CCDC 817466'
#TrackingRef '- CIF-1.cif'

_audit_update_record             
;
2011-03-14 # Formatted by publCIF
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C24 H51 B Cu3 N3 O16, 2(H2 O), B F4'
_chemical_formula_sum            'C24 H55 B2 Cu3 F4 N3 O18'
_chemical_formula_weight         961.95

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'
B B 0.0013 0.0007 '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'
F F 0.0171 0.0103 '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           cubic
_symmetry_space_group_name_H-M   'P 21 3'
_symmetry_space_group_name_Hall  'P 2ac 2ab 3'

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

_cell_length_a                   14.927(5)
_cell_length_b                   14.927(5)
_cell_length_c                   14.927(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     3326.0(19)
_cell_formula_units_Z            4
_cell_measurement_temperature    120(2)
_cell_measurement_reflns_used    14052
_cell_measurement_theta_min      1.00
_cell_measurement_theta_max      27.48

_exptl_crystal_description       block
_exptl_crystal_colour            blue
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.11
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.921
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1988
_exptl_absorpt_coefficient_mu    2.010
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.7136
_exptl_absorpt_correction_T_max  0.8092
_exptl_absorpt_process_details   'SADABS v.2.10 (Sheldrick, 2003)'

_publ_section_exptl_refinement   
;
Atoms O5 and B2 were restrained so that their <i>U^ij^</i> components
approximate to isotropic behavior. The OH hydrogen atoms were located from the
difference Fourier map but constrained to ride on their parent atom, with
<i>U</i>~iso~ = 1.5 <i>U</i>~eq~(parent atom). The hydrogen atoms of O7 and O8
were disordered over several positions. Due to the disorder the hydrogen
atoms were omitted. These H atoms were taken into account in the unit-cell
content. Other hydrogen atoms were positioned geometrically and were also
constrained to ride on their parent atoms, with C---H = 0.99 \%A, and
<i>U</i>~iso~ = 1.2 <i>U</i>~eq~(parent atom). The highest peak is located
0.39 \%A from atom H3A and the deepest hole is located 0.61 \%A from atom O6.
;

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      120(2)
_diffrn_radiation_wavelength     0.71069
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  'horizontally mounted graphite crystal'
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_device       '95mm CCD camera on \k-goniostat'
_diffrn_detector_area_resol_mean 9
_diffrn_measurement_method       '\f scans and \w scans with \k offset'
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            58449
_diffrn_reflns_av_R_equivalents  0.0640
_diffrn_reflns_av_sigmaI/netI    0.0247
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         3.05
_diffrn_reflns_theta_max         27.57
_reflns_number_total             2596
_reflns_number_gt                2355
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Collect (Bruker AXS BV, 1997-2008)'
_computing_cell_refinement       'Denzo/Scalepack (Otwinowski & Minor, 1997)'
_computing_data_reduction        'Denzo/Scalepack (Otwinowski & Minor, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Diamond v.3.1f (Brandenburg, 2008)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 2008)'

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

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0699P)^2^+3.5606P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.03(2)
_chemical_absolute_configuration unk
_refine_ls_number_reflns         2596
_refine_ls_number_parameters     163
_refine_ls_number_restraints     12
_refine_ls_R_factor_all          0.0455
_refine_ls_R_factor_gt           0.0389
_refine_ls_wR_factor_ref         0.1123
_refine_ls_wR_factor_gt          0.1078
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_restrained_S_all      1.077
_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 0.84746(3) 0.48746(3) 0.50645(3) 0.01796(14) Uani 1 1 d . . .
F1 F 0.4826(3) 0.4826(3) 0.4826(3) 0.0705(18) Uani 1 3 d S . .
F2 F 0.3574(4) 0.4783(5) 0.4143(5) 0.133(2) Uani 1 1 d . . .
O1 O 0.8489(2) 0.3696(2) 0.6192(2) 0.0323(7) Uani 1 1 d . . .
H1O H 0.8818 0.3562 0.6478 0.048 Uiso 1 1 d R . .
O2 O 0.9398(2) 0.43198(18) 0.43147(18) 0.0222(6) Uani 1 1 d . . .
O3 O 0.79916(18) 0.57631(19) 0.39236(19) 0.0221(6) Uani 1 1 d . . .
O4 O 0.73570(18) 0.5117(2) 0.5822(2) 0.0278(6) Uani 1 1 d . . .
H4 H 0.7079 0.5627 0.5968 0.042 Uiso 1 1 d R . .
O5 O 0.79786(16) 0.70214(16) 0.29786(16) 0.0188(9) Uani 1 3 d SU . .
O6 O 0.6721(3) 0.2068(3) 0.4923(3) 0.0547(10) Uani 1 1 d . . .
H6 H 0.6348 0.1592 0.4774 0.082 Uiso 1 1 d R . .
O7 O 0.63936(18) 0.63936(18) 0.63936(18) 0.0212(10) Uani 1 3 d S . .
O8 O 0.5751(2) 0.0751(2) 0.4249(2) 0.0411(15) Uani 1 3 d S . .
N1 N 0.7648(2) 0.3972(2) 0.4499(2) 0.0235(7) Uani 1 1 d . . .
C1 C 0.7158(3) 0.3590(3) 0.5289(3) 0.0276(9) Uani 1 1 d . . .
C2 C 0.7821(3) 0.3078(3) 0.5901(3) 0.0316(10) Uani 1 1 d . . .
H2A H 0.7500 0.2825 0.6424 0.038 Uiso 1 1 calc R . .
H2B H 0.8101 0.2579 0.5566 0.038 Uiso 1 1 calc R . .
C3 C 0.6393(3) 0.2949(3) 0.5063(4) 0.0407(11) Uani 1 1 d . . .
H3A H 0.5953 0.2946 0.5559 0.049 Uiso 1 1 calc R . .
H3B H 0.6083 0.3159 0.4515 0.049 Uiso 1 1 calc R . .
C4 C 0.6748(3) 0.4367(3) 0.5824(3) 0.0309(10) Uani 1 1 d . . .
H4A H 0.6171 0.4547 0.5551 0.037 Uiso 1 1 calc R . .
H4B H 0.6632 0.4174 0.6447 0.037 Uiso 1 1 calc R . .
C5 C 0.8206(3) 0.3311(3) 0.3979(3) 0.0276(9) Uani 1 1 d . . .
H5A H 0.8004 0.2695 0.4116 0.033 Uiso 1 1 calc R . .
H5B H 0.8125 0.3415 0.3329 0.033 Uiso 1 1 calc R . .
C6 C 0.9178(3) 0.3405(3) 0.4214(3) 0.0267(9) Uani 1 1 d . . .
H6A H 0.9303 0.3081 0.4780 0.032 Uiso 1 1 calc R . .
H6B H 0.9551 0.3136 0.3736 0.032 Uiso 1 1 calc R . .
C7 C 0.7047(3) 0.4477(3) 0.3869(3) 0.0277(9) Uani 1 1 d . . .
H7A H 0.6577 0.4790 0.4216 0.033 Uiso 1 1 calc R . .
H7B H 0.6749 0.4050 0.3458 0.033 Uiso 1 1 calc R . .
C8 C 0.7575(3) 0.5152(3) 0.3330(3) 0.0273(9) Uani 1 1 d . . .
H8A H 0.8035 0.4841 0.2968 0.033 Uiso 1 1 calc R . .
H8B H 0.7171 0.5478 0.2918 0.033 Uiso 1 1 calc R . .
B1 B 0.4295(4) 0.4295(4) 0.4295(4) 0.036(2) Uani 1 3 d S . .
B2 B 0.8527(3) 0.6473(3) 0.3527(3) 0.0164(12) Uani 1 3 d SU . .

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 0.0160(2) 0.0181(2) 0.0198(2) -0.00037(18) 0.00046(16) -0.00108(16)
F1 0.0705(18) 0.0705(18) 0.0705(18) -0.0096(18) -0.0096(18) -0.0096(18)
F2 0.073(3) 0.162(6) 0.165(6) -0.009(5) -0.052(4) 0.024(4)
O1 0.0317(16) 0.0318(16) 0.0334(16) 0.0038(13) -0.0082(14) -0.0005(14)
O2 0.0284(15) 0.0143(13) 0.0238(15) -0.0031(11) 0.0065(12) -0.0016(11)
O3 0.0195(13) 0.0243(14) 0.0224(14) 0.0012(11) -0.0052(11) -0.0013(11)
O4 0.0230(13) 0.0254(15) 0.0350(16) 0.0006(13) 0.0073(12) -0.0014(12)
O5 0.0188(9) 0.0188(9) 0.0188(9) 0.0082(9) -0.0082(9) 0.0082(9)
O6 0.058(2) 0.043(2) 0.063(3) -0.005(2) 0.000(2) -0.0141(18)
O7 0.0212(10) 0.0212(10) 0.0212(10) 0.0047(11) 0.0047(11) 0.0047(11)
O8 0.0411(15) 0.0411(15) 0.0411(15) 0.0063(15) 0.0063(15) -0.0063(15)
N1 0.0196(16) 0.0227(17) 0.0280(17) 0.0017(14) -0.0002(14) -0.0030(13)
C1 0.0225(19) 0.024(2) 0.036(2) 0.0007(17) 0.0062(17) -0.0028(16)
C2 0.030(2) 0.027(2) 0.038(2) 0.0104(19) 0.0038(19) -0.0058(18)
C3 0.032(2) 0.033(2) 0.057(3) 0.004(2) -0.005(2) -0.0109(19)
C4 0.023(2) 0.029(2) 0.041(2) 0.0008(19) 0.0049(18) -0.0057(17)
C5 0.035(2) 0.018(2) 0.029(2) -0.0051(16) 0.0057(17) -0.0010(17)
C6 0.030(2) 0.0169(18) 0.033(2) -0.0048(17) 0.0094(17) -0.0017(16)
C7 0.024(2) 0.030(2) 0.029(2) -0.0029(18) -0.0069(17) -0.0031(17)
C8 0.030(2) 0.026(2) 0.0255(19) -0.0021(17) -0.0103(16) 0.0014(16)
B1 0.036(2) 0.036(2) 0.036(2) -0.005(2) -0.005(2) -0.005(2)
B2 0.0164(12) 0.0164(12) 0.0164(12) 0.0044(11) -0.0044(11) 0.0044(11)

_geom_special_details            
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu1 O2 1.896(3) 5_566 yes
Cu1 O2 1.959(3) . yes
Cu1 N1 2.013(3) . yes
Cu1 O4 2.047(3) . yes
Cu1 O3 2.276(3) . yes
Cu1 O1 2.435(3) . yes
F1 B1 1.375(11) . ?
F2 B1 1.318(6) . ?
O1 C2 1.427(6) . ?
O1 H1O 0.6802 . ?
O2 C6 1.413(5) . ?
O2 Cu1 1.896(3) 4_664 yes
O3 C8 1.415(5) . ?
O3 B2 1.454(4) . yes
O4 C4 1.441(5) . ?
O4 H4 0.8944 . ?
O5 B2 1.417(8) . yes
O6 C3 1.420(7) . ?
O6 H6 0.9299 . ?
N1 C1 1.500(5) . ?
N1 C7 1.501(5) . ?
N1 C5 1.507(5) . ?
C1 C3 1.528(6) . ?
C1 C4 1.535(6) . ?
C1 C2 1.548(6) . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C3 H3A 0.9900 . ?
C3 H3B 0.9900 . ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
C5 C6 1.499(6) . ?
C5 H5A 0.9900 . ?
C5 H5B 0.9900 . ?
C6 H6A 0.9900 . ?
C6 H6B 0.9900 . ?
C7 C8 1.512(6) . ?
C7 H7A 0.9900 . ?
C7 H7B 0.9900 . ?
C8 H8A 0.9900 . ?
C8 H8B 0.9900 . ?
B1 F2 1.318(6) 3 ?
B1 F2 1.318(6) 2 ?
B2 O3 1.454(4) 5_566 ?
B2 O3 1.454(4) 4_664 ?

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
O2 Cu1 O2 93.07(17) 5_566 . ?
O2 Cu1 N1 172.77(14) 5_566 . ?
O2 Cu1 N1 84.78(13) . . yes
O2 Cu1 O4 99.80(12) 5_566 . ?
O2 Cu1 O4 164.45(12) . . yes
N1 Cu1 O4 81.38(13) . . yes
O2 Cu1 O3 103.80(11) 5_566 . ?
O2 Cu1 O3 92.39(11) . . yes
N1 Cu1 O3 83.20(13) . . yes
O4 Cu1 O3 92.98(11) . . yes
O2 Cu1 O1 94.17(11) 5_566 . ?
O2 Cu1 O1 94.78(11) . . yes
N1 Cu1 O1 79.16(12) . . yes
O4 Cu1 O1 75.71(12) . . yes
O3 Cu1 O1 160.25(10) . . yes
C2 O1 Cu1 104.5(2) . . yes
C2 O1 H1O 120.4 . . ?
Cu1 O1 H1O 130.6 . . ?
C6 O2 Cu1 122.1(2) . 4_664 ?
C6 O2 Cu1 107.8(2) . . yes
Cu1 O2 Cu1 125.15(14) 4_664 . ?
C8 O3 B2 117.1(3) . . ?
C8 O3 Cu1 103.4(2) . . ?
B2 O3 Cu1 123.8(3) . . ?
C4 O4 Cu1 112.2(3) . . ?
C4 O4 H4 111.6 . . ?
Cu1 O4 H4 131.5 . . ?
C3 O6 H6 122.5 . . ?
C1 N1 C7 113.1(3) . . ?
C1 N1 C5 115.2(3) . . ?
C7 N1 C5 109.7(3) . . ?
C1 N1 Cu1 102.9(2) . . ?
C7 N1 Cu1 107.0(3) . . ?
C5 N1 Cu1 108.3(2) . . ?
N1 C1 C3 115.4(4) . . ?
N1 C1 C4 108.4(3) . . ?
C3 C1 C4 106.8(4) . . ?
N1 C1 C2 109.9(3) . . ?
C3 C1 C2 107.4(4) . . ?
C4 C1 C2 108.7(4) . . ?
O1 C2 C1 107.9(3) . . ?
O1 C2 H2A 110.1 . . ?
C1 C2 H2A 110.1 . . ?
O1 C2 H2B 110.1 . . ?
C1 C2 H2B 110.1 . . ?
H2A C2 H2B 108.4 . . ?
O6 C3 C1 110.8(4) . . ?
O6 C3 H3A 109.5 . . ?
C1 C3 H3A 109.5 . . ?
O6 C3 H3B 109.5 . . ?
C1 C3 H3B 109.5 . . ?
H3A C3 H3B 108.1 . . ?
O4 C4 C1 109.5(3) . . ?
O4 C4 H4A 109.8 . . ?
C1 C4 H4A 109.8 . . ?
O4 C4 H4B 109.8 . . ?
C1 C4 H4B 109.8 . . ?
H4A C4 H4B 108.2 . . ?
C6 C5 N1 110.8(3) . . ?
C6 C5 H5A 109.5 . . ?
N1 C5 H5A 109.5 . . ?
C6 C5 H5B 109.5 . . ?
N1 C5 H5B 109.5 . . ?
H5A C5 H5B 108.1 . . ?
O2 C6 C5 109.9(4) . . ?
O2 C6 H6A 109.7 . . ?
C5 C6 H6A 109.7 . . ?
O2 C6 H6B 109.7 . . ?
C5 C6 H6B 109.7 . . ?
H6A C6 H6B 108.2 . . ?
N1 C7 C8 110.9(3) . . ?
N1 C7 H7A 109.5 . . ?
C8 C7 H7A 109.5 . . ?
N1 C7 H7B 109.5 . . ?
C8 C7 H7B 109.5 . . ?
H7A C7 H7B 108.1 . . ?
O3 C8 C7 109.0(3) . . ?
O3 C8 H8A 109.9 . . ?
C7 C8 H8A 109.9 . . ?
O3 C8 H8B 109.9 . . ?
C7 C8 H8B 109.9 . . ?
H8A C8 H8B 108.3 . . ?
F2 B1 F2 113.9(4) . 3 ?
F2 B1 F2 113.9(4) . 2 ?
F2 B1 F2 113.9(4) 3 2 ?
F2 B1 F1 104.5(5) . . ?
F2 B1 F1 104.5(5) 3 . ?
F2 B1 F1 104.5(5) 2 . ?
O5 B2 O3 109.8(3) . 5_566 ?
O5 B2 O3 109.8(3) . 4_664 ?
O3 B2 O3 109.1(3) 5_566 4_664 ?
O5 B2 O3 109.8(3) . . ?
O3 B2 O3 109.1(3) 5_566 . ?
O3 B2 O3 109.1(3) 4_664 . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
O1 H1O O6 0.68 2.12 2.777(5) 163.7 7_665 yes
O4 H4 O7 0.89 1.66 2.535(3) 164.9 . yes
O6 H6 O8 0.93 1.73 2.640(5) 166.6 . yes

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        27.57
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.937
_refine_diff_density_min         -0.481
_refine_diff_density_rms         0.100

# start Validation Reply Form
_vrf_PUBL417_GLOBAL              
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PROBLEM: Isolated Oxygen Atom (H-atoms Missing ?

RESPONSE: The O7 and O8 hydrogen atoms were omitted due to the disorder.
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# end Validation Reply Form