# Electronic Supplementary Material (ESI) for Dalton Transactions
# This journal is © The Royal Society of Chemistry 2013

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#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
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# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
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#  data retrieval see:
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#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
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data_z

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C45 H33 Cu3 Mo4 N18 O12'
_chemical_formula_sum            'C45 H33 Cu3 Mo4 N18 O12'
_chemical_formula_weight         1592.30

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'
Mo Mo -1.6832 0.6857 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Hexagonal
_symmetry_space_group_name_H-M   P6(3)/m
_symmetry_space_group_name_Hall  '-P 6c'

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

_cell_length_a                   15.1265(4)
_cell_length_b                   15.1265(4)
_cell_length_c                   12.5331(10)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     2483.5(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    1496
_cell_measurement_theta_min      2.69
_cell_measurement_theta_max      24.99

_exptl_crystal_description       block
_exptl_crystal_colour            violet
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.08
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.129
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1560
_exptl_absorpt_coefficient_mu    2.321
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.7681
_exptl_absorpt_correction_T_max  0.8361
_exptl_absorpt_process_details   '(SADABS; Sheldrick, 2003)'

_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  'multiwire proportional'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean 0
_diffrn_standards_number         0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_decay_%        0
_diffrn_reflns_number            15771
_diffrn_reflns_av_R_equivalents  0.0640
_diffrn_reflns_av_sigmaI/netI    0.0296
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         2.69
_diffrn_reflns_theta_max         24.99
_reflns_number_total             1496
_reflns_number_gt                1244
_reflns_threshold_expression     I>2\s(I)

_computing_data_collection       'APEX2 (Bruker, 2004)'
_computing_cell_refinement       'SAINT-Plus (Bruker, 2001)'
_computing_data_reduction        SAINT-Plus
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'SHELXTL (Bruker, 2001)'
_computing_publication_material  SHELXTL

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

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.4720P)^2^+5.0805P] 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    noref
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         1496
_refine_ls_number_parameters     141
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0674
_refine_ls_R_factor_gt           0.0592
_refine_ls_wR_factor_ref         0.1364
_refine_ls_wR_factor_gt          0.1048
_refine_ls_goodness_of_fit_ref   0.997
_refine_ls_restrained_S_all      0.997
_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
C1 C 0.1647(8) 0.7051(8) 0.5594(8) 0.025(2) Uani 1 1 d . . .
C2 C 0.0763(9) 0.6550(10) 0.5012(10) 0.034(3) Uani 1 1 d . . .
H2 H 0.0572 0.6021 0.4526 0.041 Uiso 1 1 calc R . .
C3 C 0.0205(9) 0.7042(12) 0.5337(14) 0.044(4) Uani 1 1 d . . .
H3 H -0.0458 0.6862 0.5143 0.052 Uiso 1 1 calc R . .
C4 C 0.2513(7) 0.6855(8) 0.5593(8) 0.020(2) Uani 1 1 d . . .
C5 C 0.3535(8) 0.7659(8) 0.5586(9) 0.026(2) Uani 1 1 d . . .
H5 H 0.3665 0.8329 0.5578 0.031 Uiso 1 1 calc R . .
C6 C 0.4810(12) 0.9510(11) 0.7500 0.0433(10) Uani 1 2 d S . .
H6 H 0.4784 0.8882 0.7500 0.028 Uiso 1 2 calc SR . .
C7 C 0.5678(12) 1.0420(13) 0.7500 0.027(3) Uani 1 2 d S . .
H7 H 0.6339 1.0526 0.7500 0.033 Uiso 1 2 calc SR . .
C8 C 0.5415(11) 1.1150(11) 0.7500 0.016(3) Uani 1 2 d S . .
C9 C 0.6032(13) 1.2258(11) 0.7500 0.022(3) Uani 1 2 d S . .
C10 C 0.5617(11) 1.2897(12) 0.7500 0.027(4) Uani 1 2 d S . .
H10 H 0.4911 1.2605 0.7500 0.033 Uiso 1 2 calc SR . .
Cu1 Cu 0.25208(14) 0.86029(13) 0.7500 0.0265(10) Uani 1 2 d S . .
Mo2 Mo 0.17861(16) 1.06242(16) 0.7500 0.0503(9) Uani 1 2 d S . .
Mo1 Mo 0.0000 1.0000 0.5000 0.0763(17) Uani 1 6 d S . .
N2 N 0.1705(7) 0.7836(7) 0.6199(8) 0.024(2) Uani 1 1 d . . .
N1 N 0.0807(7) 0.7784(8) 0.5951(9) 0.034(2) Uani 1 1 d . . .
H1 H 0.0649 0.8220 0.6189 0.041 Uiso 1 1 calc R . .
N3 N 0.3970(10) 0.9628(10) 0.7500 0.027(3) Uani 1 2 d S . .
N4 N 0.4374(10) 1.0641(9) 0.7500 0.0423(10) Uani 1 2 d S . .
O2 O 0.3063(13) 1.1534(14) 0.7500 0.098(8) Uani 1 2 d S . .
O3 O 0.1678(17) 0.9448(15) 0.7500 0.081(6) Uani 1 2 d S . .
O1 O 0.1227(12) 1.0757(11) 0.612(3) 0.0420(10) Uani 1 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
C1 0.028(6) 0.020(5) 0.027(5) 0.006(4) 0.005(4) 0.013(5)
C2 0.018(6) 0.029(6) 0.055(7) -0.002(6) -0.006(5) 0.012(5)
C3 0.017(6) 0.047(8) 0.076(10) -0.007(7) -0.010(6) 0.023(6)
C4 0.012(5) 0.021(5) 0.023(5) 0.005(4) 0.003(3) 0.005(4)
C5 0.013(5) 0.020(5) 0.045(6) 0.002(4) 0.000(4) 0.008(4)
C6 0.040(3) 0.035(2) 0.040(3) -0.004(2) 0.017(2) 0.000(2)
C7 0.025(8) 0.031(10) 0.032(8) 0.000 0.000 0.018(7)
C8 0.014(7) 0.019(7) 0.009(6) 0.000 0.000 0.004(6)
C9 0.033(8) 0.011(7) 0.029(7) 0.000 0.000 0.016(7)
C10 0.010(7) 0.025(9) 0.053(10) 0.000 0.000 0.013(6)
Cu1 0.0156(13) 0.0135(13) 0.0501(17) 0.000 0.000 0.0071(9)
Mo2 0.0372(18) 0.054(2) 0.051(2) -0.0125(17) 0.0135(16) 0.0155(16)
Mo1 0.0369(15) 0.0369(15) 0.155(5) 0.000 0.000 0.0185(8)
N2 0.021(5) 0.015(4) 0.040(5) 0.001(4) 0.001(4) 0.014(4)
N1 0.023(5) 0.033(6) 0.055(6) 0.000(5) -0.005(4) 0.021(5)
N3 0.010(6) 0.017(6) 0.055(8) 0.000 0.000 0.007(5)
N4 0.038(2) 0.033(2) 0.037(3) -0.0081(19) 0.015(2) -0.0041(19)
O2 0.032(9) 0.052(11) 0.22(3) 0.000 0.000 0.032(9)
O3 0.064(12) 0.041(10) 0.153(19) 0.000 0.000 0.037(9)
O1 0.038(2) 0.036(2) 0.035(3) -0.0127(19) 0.016(2) -0.0015(19)

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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 N2 1.375(14) . ?
C1 C2 1.372(16) . ?
C1 C4 1.480(14) . ?
C2 C3 1.436(18) . ?
C2 H2 0.9300 . ?
C3 N1 1.288(18) . ?
C3 H3 0.9300 . ?
C4 C5 1.370(15) 2_665 ?
C4 C5 1.410(14) . ?
C5 C4 1.370(15) 3_565 ?
C5 H5 0.9300 . ?
C6 N3 1.37(2) . ?
C6 C7 1.35(2) . ?
C6 H6 0.9300 . ?
C7 C8 1.35(2) . ?
C7 H7 0.9300 . ?
C8 N4 1.364(19) . ?
C8 C9 1.45(2) . ?
C9 C10 1.39(2) . ?
C9 C10 1.41(2) 2_775 ?
C10 C9 1.41(2) 3_575 ?
C10 H10 0.9300 . ?
Cu1 N3 1.952(13) . ?
Cu1 N2 2.024(10) . ?
Cu1 N2 2.024(10) 10_557 ?
Cu1 O3 2.211(17) . ?
Mo2 O3 1.704(17) . ?
Mo2 O2 1.722(18) . ?
Mo2 O1 1.98(3) . ?
Mo2 O1 1.98(3) 10_557 ?
Mo1 O1 2.14(2) . ?
Mo1 O1 2.14(2) 2_675 ?
Mo1 O1 2.14(2) 7_576 ?
Mo1 O1 2.14(2) 9_666 ?
Mo1 O1 2.14(2) 8_456 ?
Mo1 O1 2.14(2) 3_465 ?
N2 N1 1.356(13) . ?
N1 H1 0.8600 . ?
N3 N4 1.336(19) . ?

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
N2 C1 C2 113.1(10) . . ?
N2 C1 C4 119.6(10) . . ?
C2 C1 C4 127.2(10) . . ?
C3 C2 C1 103.1(11) . . ?
C3 C2 H2 128.4 . . ?
C1 C2 H2 128.4 . . ?
N1 C3 C2 106.1(10) . . ?
N1 C3 H3 126.9 . . ?
C2 C3 H3 126.9 . . ?
C5 C4 C5 117.8(11) 2_665 . ?
C5 C4 C1 120.5(9) 2_665 . ?
C5 C4 C1 121.7(10) . . ?
C4 C5 C4 122.2(11) 3_565 . ?
C4 C5 H5 118.9 3_565 . ?
C4 C5 H5 118.9 . . ?
N3 C6 C7 111.2(12) . . ?
N3 C6 H6 124.4 . . ?
C7 C6 H6 124.4 . . ?
C8 C7 C6 107.5(14) . . ?
C8 C7 H7 126.2 . . ?
C6 C7 H7 126.2 . . ?
C7 C8 N4 105.6(14) . . ?
C7 C8 C9 131.4(14) . . ?
N4 C8 C9 123.0(15) . . ?
C10 C9 C10 117.5(15) . 2_775 ?
C10 C9 C8 123.2(15) . . ?
C10 C9 C8 119.3(13) 2_775 . ?
C9 C10 C9 122.5(15) . 3_575 ?
C9 C10 H10 118.7 . . ?
C9 C10 H10 118.7 3_575 . ?
N3 Cu1 N2 125.2(3) . . ?
N3 Cu1 N2 125.2(3) . 10_557 ?
N2 Cu1 N2 107.4(5) . 10_557 ?
N3 Cu1 O3 106.5(7) . . ?
N2 Cu1 O3 88.2(4) . . ?
N2 Cu1 O3 88.2(4) 10_557 . ?
O3 Mo2 O2 108.5(9) . . ?
O3 Mo2 O1 106.5(6) . . ?
O2 Mo2 O1 106.5(6) . . ?
O3 Mo2 O1 106.5(6) . 10_557 ?
O2 Mo2 O1 106.5(6) . 10_557 ?
O1 Mo2 O1 121.8(15) . 10_557 ?
O1 Mo1 O1 81.8(11) . 2_675 ?
O1 Mo1 O1 180.000(4) . 7_576 ?
O1 Mo1 O1 98.2(11) 2_675 7_576 ?
O1 Mo1 O1 98.2(11) . 9_666 ?
O1 Mo1 O1 98.2(11) 2_675 9_666 ?
O1 Mo1 O1 81.8(11) 7_576 9_666 ?
O1 Mo1 O1 98.2(11) . 8_456 ?
O1 Mo1 O1 180.000(3) 2_675 8_456 ?
O1 Mo1 O1 81.8(11) 7_576 8_456 ?
O1 Mo1 O1 81.8(11) 9_666 8_456 ?
O1 Mo1 O1 81.8(11) . 3_465 ?
O1 Mo1 O1 81.8(11) 2_675 3_465 ?
O1 Mo1 O1 98.2(11) 7_576 3_465 ?
O1 Mo1 O1 180.000(4) 9_666 3_465 ?
O1 Mo1 O1 98.2(11) 8_456 3_465 ?
C1 N2 N1 101.2(9) . . ?
C1 N2 Cu1 134.1(8) . . ?
N1 N2 Cu1 121.6(8) . . ?
C3 N1 N2 116.1(10) . . ?
C3 N1 H1 122.0 . . ?
N2 N1 H1 122.0 . . ?
C6 N3 N4 103.2(12) . . ?
C6 N3 Cu1 130.0(11) . . ?
N4 N3 Cu1 126.8(10) . . ?
N3 N4 C8 112.6(13) . . ?
Mo2 O3 Cu1 145.3(13) . . ?
Mo2 O1 Mo1 144.8(8) . . ?

_diffrn_measured_fraction_theta_max 0.973
_diffrn_reflns_theta_full        24.99
_diffrn_measured_fraction_theta_full 0.973
_refine_diff_density_max         0.999
_refine_diff_density_min         -1.483
_refine_diff_density_rms         0.108
_database_code_depnum_ccdc_archive 'CCDC 933413'